Polyamide composition and molded product

Abstract

The present invention relates to a polyamide composition and a molded article. The present invention provides a polyamide composition and a molded article using the polyamide composition, wherein the polyamide composition contains 50 to 99 parts by mass of (1A) an aliphatic polyamide containing a diamine and a dicarboxylic acid and 1 to 50 parts by mass of (1B) a semi-aromatic polyamide, wherein the (1B) semi-aromatic polyamide contains a dicarboxylic acid unit and a diamine unit, wherein the dicarboxylic acid unit contains at least 75 mol% of isophthalic acid, and the diamine unit contains at least 50 mol% of a diamine having 4 to 10 carbon atoms, wherein the polyamide composition has a tan δ peak temperature of 90°C or higher, and a weight average molecular weight Mw of the polyamide composition is 15000≤Mw≤35000.

Description

[0001] This application is a divisional application of the Chinese patent application with the application date of March 30, 2018, application number 201880020421.7, and invention name “Polyamide composition and molded article”. Technical Field

[0002] The present invention relates to a polyamide composition and a molded product.

[0003] This application claims priority based on Japanese Patent Application No. 2017-068946, filed in Japan on March 30, 2017, the contents of which are incorporated herein by reference. Background Art

[0004] Polyamides, such as polyamide 6 (hereinafter sometimes referred to as "PA6") and polyamide 66 (hereinafter sometimes referred to as "PA66"), are widely used as materials for various components in automobiles, electrical and electronic applications, industrial materials, daily necessities, and household goods due to their excellent molding processability, mechanical properties, and chemical resistance.

[0005] In recent years, the use environment of polyamide has become increasingly stringent in terms of thermal and mechanical properties, and there is a demand for polyamide materials with improved mechanical properties, especially rigidity after water absorption (hereinafter sometimes referred to as "water absorption rigidity") and rigidity under high temperature use (hereinafter sometimes referred to as "heat rigidity"), and with minimal changes in physical properties during use in any environment.

[0006] Furthermore, in order to improve productivity, molded articles using polyamide are sometimes molded under high-cycle molding conditions in which the molding temperature is increased and the mold temperature is decreased.

[0007] On the other hand, when molding is performed under high temperature conditions, there is a problem that the polyamide decomposes or changes in fluidity, making it impossible to obtain a stable molded product.

[0008] In particular, polyamides are required that exhibit excellent stability in the surface appearance of molded articles even under the aforementioned severe molding conditions.

[0009] To meet such demands, polyamide compositions comprising polyamide 66 / 6I into which an isophthalic acid component is introduced have been disclosed as materials capable of improving the surface appearance and mechanical properties of molded articles (see, for example, Patent Document 1). Furthermore, polyamide compositions comprising polyamide 6T / 6I into which terephthalic acid and isophthalic acid components are introduced have been disclosed as materials capable of improving mechanical properties, flowability, surface appearance, and the like (see, for example, Patent Documents 2 and 3).

[0010] Furthermore, as a material capable of improving the surface appearance and mechanical properties of molded articles, a polyamide composition comprising an alloy of polyamide 6T / 6I and polyamide 66 into which terephthalic acid components and isophthalic acid components are introduced has been disclosed (for example, see Patent Document 5).

[0011] Furthermore, in order to improve mechanical properties, particularly rigidity, polyamide compositions containing carbon fibers have been disclosed (see, for example, Patent Documents 4 and 5).

[0012] Prior art literature

[0013] Patent Literature

[0014] Patent Document 1: Japanese Patent Application Laid-Open No. 6-032980

[0015] Patent Document 2: Japanese Patent Application Laid-Open No. 2000-154316

[0016] Patent Document 3: Japanese Patent Application Laid-Open No. 11-349806

[0017] Patent Document 4: Japanese Patent Application Laid-Open No. 2013-119610

[0018] Patent Document 5: International Publication No. 2005 / 035664 Summary of the Invention

[0019] Problems to be solved by the invention

[0020] However, the polyamide compositions described in Patent Documents 1, 3, and 4 have improved rigidity under normal use conditions, but still have room for improvement in rigidity after water absorption (particularly Rockwell hardness).

[0021] Furthermore, the polyamide compositions produced using the production methods described in Patent Documents 2 and 5 have improved rigidity after water absorption, and the surface appearance of molded articles under typical molding conditions is improved. However, under severe molding conditions such as high-cycle molding conditions, there is a problem of reduced appearance and stability of the molded article surface.

[0022] Furthermore, in particular, in applications for automotive exterior parts, there is also the problem of color change due to exposure to harsh environments outdoors for long periods of time. This problem is difficult to solve with the polyamide compositions described in Patent Documents 1 to 5.

[0023] Thus, in the prior art, there is no known polyamide-based material that exhibits excellent rigidity (particularly Rockwell hardness) after water absorption and rigidity under high-temperature use, and exhibits minimal changes in physical properties during use under any environment. Furthermore, it is difficult to suppress the reduction in rigidity after water absorption and under high-temperature use while maintaining the balance of mechanical strength and rigidity that characterizes polyamide-based materials. Polyamide copolymers or compositions and molded articles containing polyamides that exhibit such properties are desired.

[0024] The present invention has been made in view of the above circumstances, and an object of the present invention is to stably provide a polyamide composition and a molded article having excellent mechanical properties, particularly rigidity when absorbing water (hereinafter referred to as "water-absorbed rigidity") and rigidity when used at high temperatures (hereinafter referred to as "hot rigidity"), flowability, and surface appearance.

[0025] Another object is to stably provide a polyamide composition and a molded article having excellent mechanical properties (particularly weld strength and Rockwell hardness), surface appearance, and flame retardancy.

[0026] Another object is to stably provide a polyamide composition and a molded article having excellent mechanical properties (particularly tensile strength, flexural modulus, and Charpy impact) and surface appearance.

[0027] Furthermore, a polyamide composition, developed in light of the above circumstances, is provided that can form molded articles having excellent weld strength and Rockwell hardness upon water absorption, surface appearance, and weathering discoloration resistance. Furthermore, a molded article having excellent weld strength and Rockwell hardness upon water absorption, surface appearance, and weathering discoloration resistance is provided.

[0028] Furthermore, a polyamide composition is provided, which has been achieved in view of the above circumstances and can produce a molded article having excellent pellet shape, reduced chip generation, and excellent surface appearance. Furthermore, a molded article having excellent surface appearance and using the polyamide composition is provided.

[0029] Furthermore, a polyamide composition is provided that can be formed into a molded article having excellent tensile strength, flexural modulus, surface appearance, and weathering discoloration resistance. Furthermore, a molded article comprising the polyamide composition and having excellent tensile strength, flexural modulus, surface appearance, and weathering discoloration resistance is provided.

[0030] Means used to solve problems

[0031] The present inventors have conducted intensive studies to solve the above problems and, as a result, have found that a polyamide composition containing a specific plurality of polyamides can solve the above problems, thereby completing the present invention.

[0032] That is, the present invention includes the following aspects.

[0033] The polyamide composition of the 1-1 embodiment of the present invention contains:

[0034] 50 to 99 parts by mass of (1A) an aliphatic polyamide containing a diamine and a dicarboxylic acid, and

[0035] 1 to 50 parts by mass of (1B) a semi-aromatic polyamide, wherein the (1B) semi-aromatic polyamide comprises a dicarboxylic acid unit and a diamine unit, wherein the dicarboxylic acid unit comprises at least 75 mol % of isophthalic acid, and the diamine unit comprises at least 50 mol % of a diamine having 4 to 10 carbon atoms, wherein:

[0036] The polyamide composition has a tan δ peak temperature of 90°C or higher, and

[0037] The weight average molecular weight Mw of the polyamide composition is 15000≤Mw≤35000.

[0038] In the polyamide composition of the embodiment 1-1, the total content of polyamides having a number average molecular weight Mn of 500 to 2000 is preferably 0.5% by mass to less than 2.5% by mass relative to the total amount of polyamides in the polyamide composition.

[0039] The molecular weight distribution Mw / Mn of the polyamide composition of the embodiment 1-1 is preferably 2.6 or less.

[0040] The total amount of amino terminal groups and carboxyl terminal groups expressed as equivalents relative to 1 g of polyamide in the polyamide composition of the embodiment 1-1 is preferably 100 μequivalent / g to 175 μequivalent / g.

[0041] In the polyamide composition of the embodiment 1-1, the ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} is preferably 0.25 or more and less than 0.4.

[0042] In the polyamide composition of the embodiment 1-1, the aliphatic polyamide (1A) is preferably polyamide 66 or polyamide 610.

[0043] In the semi-aromatic polyamide (1B) of the polyamide composition of the embodiment 1-1, the content of the isophthalic acid in the dicarboxylic acid unit is preferably 100 mol%.

[0044] In the polyamide composition of the embodiment 1-1, the semi-aromatic polyamide (1B) is preferably polyamide 6I.

[0045] In the polyamide composition of the embodiment 1-1, the weight average molecular weight Mw of the semi-aromatic polyamide (1B) is preferably 10,000 ≤ Mw ≤ 25,000.

[0046] In the polyamide composition of the embodiment 1-1, the molecular weight distribution Mw / Mn of the semi-aromatic polyamide (1B) is preferably 2.4 or less.

[0047] In the polyamide composition of the first-1 method described above, the difference between the weight-average molecular weight Mw(1A) of the aliphatic polyamide and the weight-average molecular weight Mw(1B) of the semi-aromatic polyamide, {Mw(1A)-Mw(1B)}, is preferably 10,000 or more.

[0048] The polyamide composition of the embodiment 1-1 preferably further contains a metal phosphite and / or a metal hypophosphite.

[0049] The polyamide composition of the above-mentioned embodiment 1-1 preferably further contains a phosphite compound.

[0050] In the polyamide composition of the first-1 method described above, it is preferable to further contain 5 to 250 parts by mass of (1C) inorganic filler material, relative to a total of 100 parts by mass of (1A) aliphatic polyamide and (1B) semi-aromatic polyamide.

[0051] The molded article of the 1-2 embodiment of the present invention is obtained by molding the polyamide composition of the 1-1 embodiment, and the surface glossiness value of the molded article is 50 or more.

[0052] The semi-aromatic polyamides of embodiments 1-3 of the present invention contain dicarboxylic acid units and diamine units, wherein the dicarboxylic acid units comprise at least 75 mol% isophthalic acid, and the diamine units comprise chain-like aliphatic diamines having 4 to 10 carbon atoms, characterized in that...

[0053] The semi-aromatic polyamide has a tan δ peak temperature of 90° C. or higher and a weight average molecular weight Mw of 10,000 ≤ Mw ≤ 35,000.

[0054] The semi-aromatic polyamides of embodiments 1-4 of the present invention contain dicarboxylic acid units and diamine units, wherein the dicarboxylic acid units comprise at least 75 mol% isophthalic acid, and the diamine units comprise chain-like aliphatic diamines having 4 to 10 carbon atoms, characterized in that...

[0055] The total amount of amino terminal groups and carboxyl terminal groups expressed as equivalents relative to 1 g of the semi-aromatic polyamide is 160 μequivalent / g to 300 μequivalent / g.

[0056] The semi-aromatic polyamide of the first to third embodiment and the first to fourth embodiment preferably has a molecular weight distribution Mw / Mn of 2.6 or less.

[0057] The polyamide composition of the embodiment 2-1 of the present invention contains:

[0058] (2A) an aliphatic polyamide comprising a diamine and a dicarboxylic acid;

[0059] (2B) a semi-aromatic polyamide comprising a dicarboxylic acid unit and a diamine unit, wherein the dicarboxylic acid unit comprises at least 75 mol % of isophthalic acid and the diamine unit comprises a chain aliphatic diamine having 4 to 10 carbon atoms;

[0060] (2C) pigments;

[0061] (2D1) flame retardants; and

[0062] (2D2) flame retardant additives,

[0063] in,

[0064] The polyamide composition has a tan δ peak temperature of 90°C or higher, and

[0065] The weight average molecular weight Mw of the polyamide composition is 10,000≤Mw≤40,000.

[0066] The polyamide composition of the 2nd embodiment of the present invention may further contain (2E) a polymer containing an α,β-unsaturated dicarboxylic acid anhydride in a structural unit.

[0067] In the polyamide composition of the 2-1 embodiment of the present invention, the total content of the (2A) aliphatic polyamide and the (2B) semi-aromatic polyamide having a number average molecular weight Mn of 500 or more and 2000 or less is preferably 0.5% by mass or more and less than 2.5% by mass relative to the total amount of all polyamides when the polyamide composition is taken as 100% by mass.

[0068] The molecular weight distribution Mw / Mn of the polyamide composition is preferably 2.4 or less.

[0069] The ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount in the polyamide composition {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} is preferably 0.1 or more and less than 0.4.

[0070] (2A) The aliphatic polyamide is preferably polyamide 66.

[0071] The content of isophthalic acid in the dicarboxylic acid units of the (2B) semi-aromatic polyamide is preferably 100 mol%.

[0072] The weight average molecular weight Mw of the (2B) semi-aromatic polyamide is preferably 10,000 ≤ Mw ≤ 25,000.

[0073] (2B) The molecular weight distribution Mw / Mn of the semi-aromatic polyamide is preferably 2.4 or less.

[0074] (2B) The Mw / VR of the semi-aromatic polyamide is preferably 1,000 or more and 2,000 or less.

[0075] (2B) The semi-aromatic polyamide is preferably polyamide 6I.

[0076] The content of the (2B) semi-aromatic polyamide is preferably 30% by mass or more and 50% by mass or less relative to 100% by mass of all the constituent components of the polyamide in the polyamide composition.

[0077] The difference between the weight average molecular weight Mw(2A) of the aliphatic polyamide (2A) and the weight average molecular weight Mw(2B) of the semi-aromatic polyamide (2B) {Mw(2A)-Mw(2B)} is preferably 10,000 or more.

[0078] (2B) The semi-aromatic polyamide is preferably capped with acetic acid.

[0079] Preferably, (2C) the pigment is a white pigment, and the content of the white pigment is 0.5% by mass or more and 5% by mass or less relative to 100% by mass of the polyamide composition.

[0080] The white pigment is preferably at least one selected from ZnS and ZnO.

[0081] Preferably, (2D1) the flame retardant is brominated polystyrene, and the content of the brominated polystyrene is 6% by mass or more and 15% by mass or less relative to 100% by mass of the polyamide composition, and

[0082] (2D2) The flame retardant is Sb2O3, and the content of Sb2O3 is more than 0.1% by mass and less than 4% by mass relative to 100% by mass of the polyamide composition.

[0083] (2E) Polymers containing α,β unsaturated dicarboxylic acid anhydrides in their constituent units are preferably maleic anhydride-modified polyphenylene ether.

[0084] The polyamide composition of the second-first embodiment of the present invention may further contain (2F) filler material.

[0085] Preferably, the filler (2F) is glass fiber, and the content of the glass fiber is 40% by mass or more and 60% by mass or less relative to 100% by mass of the polyamide composition.

[0086] The total content of (2C) the white pigment, (2D1) the flame retardant, (2D2) the flame retardant auxiliary, (2E) the polymer containing an α,β-unsaturated dicarboxylic acid anhydride in a structural unit, and (2F) the filler is preferably 60% by mass or more and 80% by mass or less, relative to 100% by mass of the polyamide composition.

[0087] The molded article of the embodiment 2-2 of the present invention is obtained by molding the polyamide composition of the embodiment 2-1 of the present invention, and the surface glossiness value of the molded article is 50 or more.

[0088] The polyamide composition of the embodiment 3-1 of the present invention contains:

[0089] (3A) an aliphatic polyamide comprising a diamine and a dicarboxylic acid;

[0090] (3B) a semi-aromatic polyamide comprising a dicarboxylic acid unit and a diamine unit, wherein the dicarboxylic acid unit comprises 50 mol % or more of isophthalic acid and the diamine unit comprises a diamine having 4 to 10 carbon atoms;

[0091] (3C1) flame retardants; and

[0092] (3C2) flame retardant additives,

[0093] in,

[0094] The tan δ peak temperature of the polyamide composition is 100°C or higher.

[0095] The weight average molecular weight Mw of the polyamide composition is 10000≤Mw≤40000, and

[0096] The halogen content in the polyamide composition is greater than 2% by mass and not more than 20% by mass relative to the total amount of the polyamide composition.

[0097] The polyamide composition of the 3-1 embodiment of the present invention may further contain (3D) a polymer containing an α,β-unsaturated dicarboxylic acid anhydride in a structural unit.

[0098] In the polyamide composition of the 3-1 embodiment of the present invention, the total content of the (3A) aliphatic polyamide and the (3B) semi-aromatic polyamide having a number average molecular weight Mn of 500 or more and 2000 or less is preferably 0.5% by mass or more and less than 2.5% by mass relative to the total amount of polyamide when the polyamide composition is taken as 100% by mass.

[0099] The molecular weight distribution Mw / Mn of the polyamide composition is preferably 2.4 or less.

[0100] The ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount in the polyamide composition {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} is preferably 0.1 or more and less than 0.5.

[0101] (3A) The aliphatic polyamide is preferably polyamide 66.

[0102] The content of isophthalic acid in the dicarboxylic acid units of the (3B) semi-aromatic polyamide is preferably 100 mol%.

[0103] The weight average molecular weight Mw of the (3B) semi-aromatic polyamide is preferably 10,000 ≤ Mw ≤ 25,000.

[0104] (3B) The molecular weight distribution Mw / Mn of the semi-aromatic polyamide is preferably 2.4 or less.

[0105] (3B) The Mw / VR of the semi-aromatic polyamide is preferably 1,000 or more and 2,000 or less.

[0106] (3B) The semi-aromatic polyamide is preferably polyamide 6I.

[0107] The content of the (3B) semi-aromatic polyamide is preferably 30% by mass or more and 50% by mass or less relative to the total amount of polyamide in the polyamide composition.

[0108] The difference between the weight average molecular weight Mw(3A) of the aliphatic polyamide (3A) and the weight average molecular weight Mw(3B) of the semi-aromatic polyamide (3B) {Mw(3A)-Mw(3B)} is preferably 10,000 or more.

[0109] The terminals of the semi-aromatic polyamide (3B) are preferably capped with acetic acid.

[0110] Preferably, the flame retardant (3C1) is brominated polystyrene, and the content of the brominated polystyrene is 6% by mass or more and 15% by mass or less relative to 100% by mass of the polyamide composition, and

[0111] (3C2) The flame retardant auxiliary agent is Sb2O3, and the content of Sb2O3 is 0.1 mass% or more and 4 mass% or less relative to 100 mass% of the polyamide composition.

[0112] (3D) The polymer containing an α,β-unsaturated dicarboxylic acid anhydride in a structural unit is preferably a maleic anhydride-modified polyphenylene ether.

[0113] The polyamide composition of the 3-1 embodiment of the present invention may further contain (3E) a filler.

[0114] Preferably, the (3E) filler is glass fiber, and the content of the glass fiber is 40% by mass or more and 60% by mass or less relative to 100% by mass of the polyamide composition.

[0115] The molded article of the 3-2 embodiment of the present invention is obtained by molding the polyamide composition of the 3-1 embodiment of the present invention, and the surface glossiness value of the molded article is 50 or more.

[0116] The polyamide composition of the 4-1 embodiment of the present invention contains:

[0117] (4A) crystalline polyamide;

[0118] (4B) an amorphous semi-aromatic polyamide comprising a dicarboxylic acid unit and a diamine unit, wherein the dicarboxylic acid unit comprises at least 75 mol % of isophthalic acid and the diamine unit comprises at least 50 mol % of a diamine having 4 to 10 carbon atoms; and

[0119] (4C) polyphenylene ether,

[0120] in,

[0121] The polyamide composition has a tan δ peak temperature of 90°C or higher, and

[0122] The weight average molecular weight Mw of the polyamide composition is 15,000≤Mw≤35,000.

[0123] The total content of polyamides having a number average molecular weight Mn of 500 or more and 2000 or less is preferably 0.5% by mass or more and less than 2.5% by mass relative to the total amount of polyamides in the polyamide composition (the total of (4A) crystalline polyamide and (4B) amorphous semi-aromatic polyamide).

[0124] Here, in the polyamide composition of the embodiment 4-1 of the present invention, the weight average molecular weight Mw and the number average molecular weight Mn of the polyamide composition are determined by the measurement methods described in the Examples below.

[0125] The molecular weight distribution Mw / Mn of the polyamide composition is preferably 2.4 or less.

[0126] The ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} is preferably 0.25 or more and less than 0.4.

[0127] (4A) The crystalline polyamide is preferably polyamide 66 or polyamide 610.

[0128] In the amorphous semi-aromatic polyamide (4B), the content of isophthalic acid in the dicarboxylic acid unit is preferably 100 mol%.

[0129] (4B) The amorphous semi-aromatic polyamide is preferably polyamide 6I.

[0130] (4B) The weight average molecular weight Mw of the amorphous semi-aromatic polyamide is preferably 10,000 ≤ Mw ≤ 25,000.

[0131] (4B) The molecular weight distribution Mw / Mn of the amorphous semi-aromatic polyamide is preferably 2.4 or less.

[0132] The difference between the weight average molecular weight Mw(4A) of the crystalline polyamide (4A) and the weight average molecular weight Mw(4B) of the amorphous semi-aromatic polyamide (4B) {Mw(4A)-Mw(4B)} is preferably 2000 or more.

[0133] The polyamide composition of the embodiment 4-1 of the present invention may further contain a metal phosphite and / or a metal hypophosphite.

[0134] Furthermore, the polyamide composition of the embodiment 4-1 of the present invention may further contain a phosphite compound.

[0135] The compatibilizer of polyamide ((4A) crystalline polyamide and (4B) amorphous semi-aromatic polyamide, hereinafter collectively referred to as polyamide) and the above-mentioned (4C) polyphenylene ether may be further contained.

[0136] The polyamide composition of the embodiment 4-1 of the present invention may further contain 5 to 250 parts by mass of an inorganic filler per 100 parts by mass of the total of (4A) crystalline polyamide, (4B) amorphous semi-aromatic polyamide, and (4C) polyphenylene ether.

[0137] The molded article of the embodiment 4-2 of the present invention is obtained by molding the polyamide composition of the embodiment 4-1 of the present invention, and the surface glossiness value of the molded article is 50 or more.

[0138] Here, the "surface glossiness value" is measured by the method described in the examples described later.

[0139] The polyamide composition of embodiment 5-1 of the present invention contains: (5A) an aliphatic polyamide, (5B) a semi-aromatic polyamide containing a diamine unit and a dicarboxylic acid unit, (5C1) a flame retardant, (5C2) a flame retardant auxiliary, (5D) a white pigment and (5E) an ultraviolet absorber, wherein the tan δ peak temperature of the above-mentioned polyamide composition is 90°C or higher, and the mass ratio (5E) / (5D) of the (5E) ultraviolet absorber to the (5D) white pigment contained in the above-mentioned polyamide composition is 0.15 or higher and less than 2.50.

[0140] In the polyamide composition of the above-mentioned embodiment 5-1, the above-mentioned (5B) semi-aromatic polyamide may contain 50 mol% or more of isophthalic acid units in all the dicarboxylic acid units constituting the above-mentioned (5B) semi-aromatic polyamide, and may contain a diamine unit having 4 to 10 carbon atoms as the above-mentioned diamine unit.

[0141] In the polyamide composition of the embodiment 5-1, the aliphatic polyamide (5A) may contain a diamine unit and a dicarboxylic acid unit.

[0142] In the polyamide composition of the embodiment 5-1, the aliphatic polyamide (5A) may be polyamide 66.

[0143] In the polyamide composition of the embodiment 5-1, the weight average molecular weight Mw of the polyamide composition may be 10,000 or more and 50,000 or less.

[0144] The polyamide composition of the embodiment 5-1 may further contain (5F) a polymer containing an α,β-unsaturated dicarboxylic acid anhydride unit.

[0145] In the polyamide composition of the embodiment 5-1, the polymer (5F) containing α,β-unsaturated dicarboxylic acid anhydride units may be a maleic anhydride-modified polyphenylene ether.

[0146] In the polyamide composition of embodiment 5-1, the total content of the polyamide having a number average molecular weight Mn of 500 or more and 2000 or less among the aliphatic polyamide (5A) and the semi-aromatic polyamide (5B) can be 0.5% by mass or more and less than 2.5% by mass relative to the total mass of the polyamide in the polyamide composition.

[0147] In the polyamide composition of the embodiment 5-1, the molecular weight distribution Mw / Mn may be 2.4 or less.

[0148] In the polyamide composition of the embodiment 5-1, the ratio of the molar amount of amino terminals to the total molar amount of amino terminals and carboxyl terminals {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} may be 0.1 or more and less than 0.5.

[0149] In the polyamide composition of the embodiment 5-1, the semi-aromatic polyamide (5B) may contain 100 mol% of isophthalic acid units in all the dicarboxylic acid units constituting the semi-aromatic polyamide (5B).

[0150] In the polyamide composition of the embodiment 5-1, the semi-aromatic polyamide (5B) may be polyamide 6I.

[0151] In the polyamide composition of the embodiment 5-1, the weight average molecular weight Mw(5B) of the semi-aromatic polyamide (5B) may be 10,000 or more and 25,000 or less.

[0152] In the polyamide composition of the embodiment 5-1, the molecular weight distribution Mw(5B) / Mn(5B) of the semi-aromatic polyamide (5B) may be 2.4 or less.

[0153] In the polyamide composition of the embodiment 5-1, the ratio Mw(5B) / VR(5B) of the molecular weight distribution Mw(5B) of the semi-aromatic polyamide (5B) to the formic acid relative viscosity VR(5B) may be 1000 or more and 2000 or less.

[0154] In the polyamide composition of the embodiment 5-1, the content of the semi-aromatic polyamide (5B) may be 30% by mass or more and 50% by mass or less relative to the total mass of the polyamide in the polyamide composition.

[0155] In the polyamide composition of embodiment 5-1, the difference {Mw(5A)-Mw(5B)} between the weight average molecular weight Mw(5A) of the aliphatic polyamide (5A) and the weight average molecular weight Mw(5B) of the semi-aromatic polyamide (5B) may be 10,000 or more.

[0156] In the polyamide composition of the embodiment 5-1, the terminal of the semi-aromatic polyamide (5B) may be capped with acetic acid.

[0157] In the polyamide composition of the embodiment 5-1, the content of the white pigment (5D) may be 0.1% by mass or more and 5% by mass or less relative to the total mass of the polyamide composition.

[0158] In the polyamide composition of the embodiment 5-1, the white pigment (5D) may be at least one selected from ZnS and ZnO.

[0159] In the polyamide composition of the embodiment 5-1, the content of the ultraviolet absorber (5E) may be 0.1% by mass or more and 5% by mass or less relative to the total mass of the polyamide composition.

[0160] In the polyamide composition of the embodiment 5-1, the ultraviolet absorber (5E) may be at least one selected from the group consisting of a benzotriazole ultraviolet absorber and a triazine ultraviolet absorber.

[0161] In the polyamide composition of the above-mentioned embodiment 5-1, the above-mentioned (5C1) flame retardant may be brominated polystyrene, and the content of the above-mentioned brominated polystyrene may be greater than 6 mass% and less than 15 mass% relative to the total mass of the above-mentioned polyamide composition; and the above-mentioned (5C2) flame retardant auxiliary agent may be Sb2O3, and the content of the above-mentioned Sb2O3 may be greater than 0.1 mass% and less than 4 mass% relative to the total mass of the above-mentioned polyamide composition.

[0162] The polyamide composition of the above-mentioned embodiment 5-1 may further contain (5G) a filler.

[0163] In the polyamide composition of the 5-1 embodiment, the filler (5G) may be glass fiber, and the content of the glass fiber may be 40% by mass or more and 60% by mass or less relative to the total mass of the polyamide composition.

[0164] The molded article of the 5-2 embodiment of the present invention is obtained by molding the polyamide composition of the 5-1 embodiment, and the surface glossiness value of the molded article is 50 or more.

[0165] The polyamide composition of embodiment 6-1 of the present invention contains: (6A) crystalline polyamide, (6B) amorphous semi-aromatic polyamide and (6C) carbon fiber, wherein the above-mentioned (6B) amorphous semi-aromatic polyamide contains 75 mol% or more of isophthalic acid units in all the dicarboxylic acid units constituting the above-mentioned (6B) amorphous semi-aromatic polyamide, and contains 50 mol% or more of diamine units having 4 or more and 10 or less carbon atoms in all the diamine units constituting the above-mentioned (6B) amorphous semi-aromatic polyamide.

[0166] In the polyamide composition of the aforementioned embodiment 6-1, the tan δ peak temperature may be 90° C. or higher.

[0167] In the polyamide composition of the embodiment 6-1, the content of the (6C) carbon fibers in the polyamide composition may be 30% by mass or more and 65% by mass or less.

[0168] In the polyamide composition of the above-mentioned embodiment 6-1, the above-mentioned (6A) crystalline polyamide can be one or more selected from the group consisting of polyamide 4 (polyα-pyrrolidone), polyamide 6 (polycaprolactam), polyamide 11 (polyundecanamide), polyamide 12 (polydodecaneamide), polyamide 46 (polybutylene adipamide), polyamide 56 (polypentamethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610 (polyhexamethylene sebacamide), polyamide 612 (polyhexamethylene dodecanoamide), polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonane terephthalamide) and copolymer polyamides containing them as constituent components.

[0169] In the polyamide composition of the embodiment 6-1, the content of the amorphous polyamide (6B) in 100 parts by mass of the total amount of the crystalline polyamide (6A) and the amorphous semi-aromatic polyamide (6B) may be 10 parts by mass or more and 50 parts by mass or less.

[0170] In the polyamide composition of the embodiment 6-1, the contents of the amorphous semi-aromatic polyamide (6B) and the carbon fibers (6C) may satisfy the relationship represented by the following formula (1).

[0171] (C) / 4<(B)<(C)…(1)

[0172] In the polyamide composition of the above-described 6-1 method, the weight-average molecular weight Mw of the polyamide composition can be 15,000 or more and 35,000 or less.

[0173] In the above (6B) amorphous semi-aromatic polyamide, the content of the above isophthalic acid in the above dicarboxylic acid unit can be 100 mol.

[0174] In the polyamide composition of the above-mentioned 6-1 method, the above-mentioned (6B) amorphous semi-aromatic polyamide can be polyamide 6I.

[0175] In the polyamide composition of the above-mentioned 6-1 method, the weight average molecular weight Mw(6B) of the above-mentioned (6B) amorphous semi-aromatic polyamide can be 10,000 or more and 25,000 or less.

[0176] In the polyamide composition of the above-mentioned 6-1 method, the molecular weight distribution Mw(6B) / Mn(6B) of the above-mentioned (6B) amorphous semi-aromatic polyamide can be 2.4 or less.

[0177] The molded article of the sixth-second embodiment of the present invention is obtained by molding the polyamide composition of the sixth-first embodiment described above.

[0178] The polyamide composition of embodiment 7-1 of the present invention contains (7A) an aliphatic polyamide, (7B) a semi-aromatic polyamide containing a diamine unit and a dicarboxylic acid unit, (7C1) a flame retardant containing a halogen element, (7C2) a flame retardant auxiliary and (7D) an ultraviolet absorber, wherein the tanδ peak temperature of the above-mentioned polyamide composition is above 90°C, and the mass ratio of the above-mentioned (7D) ultraviolet absorber to the above-mentioned halogen element contained in the above-mentioned polyamide composition {(7D) / halogen element} is greater than 0.10 and less than 0.75.

[0179] In the polyamide composition of the above-mentioned embodiment 7-1, the above-mentioned (7B) semi-aromatic polyamide may contain 50 mol% or more of isophthalic acid units in all the dicarboxylic acid units constituting the above-mentioned (7B) semi-aromatic polyamide, and may contain a diamine unit having 4 or more and 10 or less carbon atoms as the above-mentioned diamine unit.

[0180] In the polyamide composition of the above-mentioned 7-1 method, the above-mentioned (7A) aliphatic polyamide may contain diamine units and dicarboxylic acid units.

[0181] In the polyamide composition of the above-mentioned 7-1 method, the above-mentioned (7A) aliphatic polyamide may be polyamide 66.

[0182] In the polyamide composition of the embodiment 7-1, the weight average molecular weight Mw of the polyamide composition may be 10,000 or more and 50,000 or less.

[0183] The polyamide composition of the embodiment 7-1 may further contain (7E) a polymer containing α,β-unsaturated dicarboxylic acid anhydride units.

[0184] In the polyamide composition of the embodiment 7-1, the polymer (7E) containing α,β-unsaturated dicarboxylic acid anhydride units may be a maleic anhydride-modified polyphenylene ether.

[0185] In the polyamide composition of embodiment 7-1, the total content of the polyamide having a number average molecular weight Mn of 500 or more and 2000 or less among the aliphatic polyamide (7A) and the semi-aromatic polyamide (7B) can be 0.5% by mass or more and less than 2.5% by mass relative to the total mass of the polyamide in the polyamide composition.

[0186] In the polyamide composition of the embodiment 7-1, the molecular weight distribution Mw / Mn may be 2.4 or less.

[0187] In the polyamide composition of the embodiment 7-1, the ratio of the molar amount of amino terminals to the total molar amount of amino terminals and carboxyl terminals {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} may be 0.1 or more and less than 0.5.

[0188] In the polyamide composition of the embodiment 7-1, the semi-aromatic polyamide (7B) may contain 100 mol% of isophthalic acid units in all the dicarboxylic acid units constituting the semi-aromatic polyamide (7B).

[0189] In the polyamide composition of the embodiment 7-1, the semi-aromatic polyamide (7B) may be polyamide 6I.

[0190] In the polyamide composition of the embodiment 7-1, the weight average molecular weight Mw(7B) of the semi-aromatic polyamide (7B) may be 10,000 or more and 25,000 or less.

[0191] In the polyamide composition of the embodiment 7-1, the molecular weight distribution Mw(7B) / Mn(7B) of the semi-aromatic polyamide (7B) may be 2.4 or less.

[0192] In the polyamide composition of the embodiment 7-1, the ratio Mw(7B) / VR(7B) of the molecular weight distribution Mw(7B) of the semi-aromatic polyamide (7B) to the formic acid relative viscosity VR(7B) may be 1000 or more and 2000 or less.

[0193] In the polyamide composition of the embodiment 7-1, the content of the semi-aromatic polyamide (7B) may be 30% by mass or more and 50% by mass or less relative to the total mass of the polyamide in the polyamide composition.

[0194] In the polyamide composition of embodiment 7-1, the difference {Mw(7A)-Mw(7B)} between the weight average molecular weight Mw(7A) of the aliphatic polyamide (7A) and the weight average molecular weight Mw(7B) of the semi-aromatic polyamide (7B) may be 10,000 or more.

[0195] In the polyamide composition of the embodiment 7-1, the terminal of the semi-aromatic polyamide (7B) may be capped with acetic acid.

[0196] In the polyamide composition of the embodiment 7-1, the content of the ultraviolet absorber (7D) may be 0.1% by mass or more and 5% by mass or less relative to the total mass of the polyamide composition.

[0197] In the polyamide composition of the embodiment 7-1, the ultraviolet absorber (7D) may be at least one selected from the group consisting of a benzotriazole ultraviolet absorber and a triazine ultraviolet absorber.

[0198] In the polyamide composition of the above-mentioned embodiment 7-1, the above-mentioned (7C1) flame retardant may be brominated polystyrene, and the content of the above-mentioned brominated polystyrene may be greater than 6 mass% and less than 15 mass% relative to the total mass of the above-mentioned polyamide composition; and the above-mentioned (7C2) flame retardant auxiliary agent may be Sb2O3, and the content of the above-mentioned Sb2O3 may be greater than 0.1 mass% and less than 4 mass% relative to the total mass of the above-mentioned polyamide composition.

[0199] The polyamide composition of the embodiment 7-1 may further contain (7F) a filler.

[0200] In the polyamide composition of the embodiment 7-1, the filler (7F) may be glass fiber, and the content of the glass fiber may be 40% by mass or more and 60% by mass or less relative to the total mass of the polyamide composition.

[0201] The molded article of the embodiment 7-2 of the present invention is obtained by molding the polyamide composition of the embodiment 7-1, and the surface glossiness value of the molded article is 50 or more.

[0202] Effects of the Invention

[0203] According to the polyamide composition of the above embodiment, it is possible to provide a polyamide composition and a molded article having excellent mechanical properties, particularly water absorption rigidity, hot rigidity, flowability, surface appearance, and flame retardancy.

[0204] The polyamide composition of the above embodiment can form a molded article having excellent weld strength and Rockwell hardness upon water absorption, surface appearance, and weathering discoloration resistance. Furthermore, the molded article of the above embodiment has excellent weld strength and Rockwell hardness upon water absorption, surface appearance, and weathering discoloration resistance.

[0205] The polyamide composition of the embodiment described above can provide a molded article having excellent pellet shape, reduced chip generation, and excellent surface appearance. The molded article of the embodiment described above has excellent surface appearance.

[0206] The polyamide composition of the embodiment described above can be used to form a molded article having excellent tensile strength, flexural modulus, surface appearance, and weathering discoloration resistance. The molded article of the embodiment described above comprises the polyamide composition and has excellent tensile strength, flexural modulus, surface appearance, and weathering discoloration resistance. DETAILED DESCRIPTION

[0207] Hereinafter, the present invention will be described in detail.

[0208] 《Methods 1-1 to 1-4》

[0209] [Polyamide composition]

[0210] The polyamide composition of the 1-1 embodiment of the present invention comprises 50 to 99 parts by mass of (1A) an aliphatic polyamide comprising a diamine and a dicarboxylic acid (hereinafter referred to as (1A) aliphatic polyamide) and 1 to 50 parts by mass of (1B) a semi-aromatic polyamide, wherein the (1B) semi-aromatic polyamide comprises a dicarboxylic acid unit and a diamine unit, the dicarboxylic acid unit comprising at least 75 mol % of isophthalic acid, and the diamine unit comprising at least 50 mol % of a diamine having 4 to 10 carbon atoms, wherein the polyamide composition has a tan δ peak temperature of 90° C. or higher and a weight average molecular weight Mw of the polyamide composition is 15,000 ≤ Mw ≤ 35,000.

[0211] [Semi-aromatic polyamide]

[0212] The semi-aromatic polyamide of the first to third embodiments of the present invention comprises a dicarboxylic acid unit containing at least 75 mol % of isophthalic acid and a diamine unit containing a linear aliphatic diamine having 4 to 10 carbon atoms, wherein the semi-aromatic polyamide has a tan δ peak temperature of 90° C. or higher and a weight-average molecular weight Mw of 15,000 ≤ Mw ≤ 35,000.

[0213] The semi-aromatic polyamide of the first to fourth embodiments of the present invention comprises a dicarboxylic acid unit containing at least 75 mol% of isophthalic acid and a diamine unit containing a linear aliphatic diamine having 4 to 10 carbon atoms, wherein the total amount of amino terminal groups and carboxyl terminal groups, expressed as equivalents per gram of the semi-aromatic polyamide, is 160 to 300 μequivalents / g. The total amount of amino terminal groups and carboxyl terminal groups of the semi-aromatic polyamide is preferably 170 to 280 μequivalents / g, more preferably 180 to 270 μequivalents / g, and even more preferably 190 to 260 μequivalents / g.

[0214] The semi-aromatic polyamide may have a tan δ peak temperature of 90° C. or higher, a weight-average molecular weight Mw of 15,000 ≤ Mw ≤ 35,000, and a total of the amount of amino terminal groups and the amount of carboxyl terminal groups expressed as equivalents relative to 1 g of the semi-aromatic polyamide of 160 μeq / g to 300 μeq / g.

[0215] As the aforementioned semi-aromatic polyamide, the (1B) semi-aromatic polyamide described later can be used.

[0216] The semi-aromatic polyamide in the present invention may also contain inorganic fillers, additives, etc. to form a semi-aromatic polyamide composition. The semi-aromatic polyamide composition preferably contains 90% or more of the semi-aromatic polyamide.

[0217] In the above embodiment, "polyamide" refers to a polymer having an amide (-NHCO-) ​​bond in the main chain. (1A) Aliphatic polyamide and (1B) semi-aromatic polyamide are described in detail below.

[0218] ((1A) Aliphatic polyamide)

[0219] The (1A) aliphatic polyamide contained in the polyamide composition of the above manner contains (1A-a) aliphatic dicarboxylic acid units and (1A-b) aliphatic diamine units.

[0220] ((1A-a) Aliphatic dicarboxylic acid unit)

[0221] The aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit is not limited to the following, and examples thereof include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms, such as malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid.

[0222] The aliphatic dicarboxylic acid unit (1A-a) preferably contains an aliphatic dicarboxylic acid having 6 to 20 carbon atoms, as the polyamide composition tends to have better heat resistance, fluidity, toughness, low water absorption, and rigidity. The aliphatic dicarboxylic acid unit having 6 or more carbon atoms is not particularly limited, and examples thereof include adipic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid. Among these, adipic acid, sebacic acid, and dodecanedioic acid are preferred from the viewpoint of the heat resistance of the polyamide composition.

[0223] The aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit (1A-a) may be used alone or in combination of two or more.

[0224] The aliphatic polyamide (1A) may further contain units derived from trivalent or higher polycarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid, as needed. The trivalent or higher polycarboxylic acids may be used alone or in combination of two or more.

[0225] ((1A-b) Aliphatic diamine unit)

[0226] The aliphatic diamine constituting the aliphatic diamine unit (1A-b) may be linear or branched.

[0227] The linear aliphatic diamine constituting the aliphatic diamine unit is not limited to the following, and examples thereof include linear saturated aliphatic diamines having 2 to 20 carbon atoms, such as ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine.

[0228] The diamine constituting the diamine unit having a substituent branching from the main chain is not limited to the following substances, and examples thereof include branched saturated aliphatic diamines having 3 to 20 carbon atoms, such as 2-methylpentamethylenediamine (also known as 2-methyl-1,5-diaminopentane), 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyl-1,8-octanediamine (also known as 2-methyloctamethylenediamine), and 2,4-dimethyloctamethylenediamine.

[0229] Among them, 2-methylpentamethylenediamine and 2-methyl-1,8-octanediamine are preferred, and 2-methylpentamethylenediamine is more preferred. Inclusion of such an aliphatic diamine tends to provide a polyamide composition having better heat resistance and rigidity.

[0230] The number of carbon atoms in the aliphatic diamine unit (1A-b) is preferably 6 or more and 12 or less. A carbon number of 6 or more is preferred because of excellent heat resistance, while a carbon number of 12 or less is preferred because of excellent crystallinity and releasability. The carbon number of the diamine unit (1A-b) is more preferably 6 or more and 10 or less.

[0231] The aliphatic diamine (1A-b) may further contain a trivalent or higher-valent aliphatic amine such as bis(hexamethylene)triamine, as needed.

[0232] (1A-b) The aliphatic diamine may be used alone or in combination of two or more.

[0233] Specific examples of the aliphatic polyamide (1A) used in the polyamide composition of the above embodiment include polyamide 66 (PA66), polyamide 46 (PA46), and polyamide 610 (PA610). PA66 has excellent heat resistance, moldability, and toughness, and is therefore considered a suitable material for automotive parts. Long-chain aliphatic polyamides such as PA610 have excellent chemical resistance.

[0234] In the above embodiment, the amount of the aliphatic polyamide (1A) relative to 100% by mass of the total amount of polyamide in the polyamide composition is 50.0% by mass or more and 99.0% by mass or less, preferably 52.5% by mass or more and 95.0% by mass or less, more preferably 54.0% by mass or more and 90.0% by mass or less, further preferably 55.0% by mass or more and 85.0% by mass or less, even more preferably 56.0% by mass or more and 80.0% by mass or less, particularly preferably 57.0% by mass or more and 77.5% by mass or less, and most preferably 57.5% by mass or more and 75.5% by mass or less. By setting the amount of the aliphatic polyamide (A) within the above range, a polyamide composition having excellent mechanical properties, particularly water absorption rigidity, hot rigidity, and flowability, can be obtained. In addition, the polyamide composition containing components represented by the inorganic filler has an excellent surface appearance.

[0235] ((1B) semi-aromatic polyamide)

[0236] The (1B) semi-aromatic polyamide used in the above embodiment is a polyamide containing (1B-a) dicarboxylic acid units and (1B-b) diamine units, wherein the (1B-a) dicarboxylic acid units contain at least 75 mol% of isophthalic acid, and the (1B-b) diamine units contain at least 50 mol% of a diamine having 4 to 10 carbon atoms.

[0237] The total amount of the isophthalic acid units and the diamine units having 4 to 10 carbon atoms is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, and even more preferably 100 mol%, based on 100 mol% of all constituent units of the semi-aromatic polyamide (1B).

[0238] It should be noted that, in the above method, the proportion of the specified monomer units constituting (1B) semi-aromatic polyamide can be determined by nuclear magnetic resonance spectroscopy (NMR) or the like.

[0239] ((1B-a) dicarboxylic acid unit)

[0240] The (1B-a) dicarboxylic acid unit contains 75 mol% or more of isophthalic acid (based on the total moles of the dicarboxylic acid), more preferably 80 mol% to 100 mol%, further preferably 90 mol% to 100 mol%, and even more preferably 100 mol%.

[0241] By setting the ratio of the isophthalic acid units in the dicarboxylic acid units (1B-a) to 75 mol% or more, a polyamide composition can be obtained that satisfies mechanical properties, particularly water absorption rigidity, hot rigidity, flowability, surface appearance, and the like.

[0242] The dicarboxylic acid unit (1B-a) may contain an aromatic dicarboxylic acid unit, an aliphatic dicarboxylic acid unit, or an alicyclic dicarboxylic acid unit other than the isophthalic acid unit.

[0243] -Aromatic dicarboxylic acid unit-

[0244] Aromatic dicarboxylic acids, which constitute aromatic dicarboxylic acid units other than isophthalic acid units, are not limited to the following substances; examples include dicarboxylic acids having phenyl or naphthyl groups. The aromatic groups in aromatic dicarboxylic acids may be unsubstituted or substituents.

[0245] There are no particular limitations on the substituents, and examples include: alkyl groups with 1 to 4 carbon atoms, aryl groups with 6 to 10 carbon atoms, aralkyl groups with 7 to 10 carbon atoms, halogen groups such as chloro and bromo groups, silyl groups with 1 to 6 carbon atoms, and sulfonic acid groups and their salts (sodium salts, etc.).

[0246] Specifically, and not limited to the following substances, examples include: terephthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and sodium isophthalate-5-sulfonate, etc., which are aromatic dicarboxylic acids with 8 to 20 carbon atoms, either unsubstituted or substituted with specified substituents. Among these, terephthalic acid is preferred.

[0247] The aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit may be used alone or in combination of two or more.

[0248] -Aliphatic dicarboxylic acid unit-

[0249] The aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit is not limited to the following, and examples thereof include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms, such as malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid.

[0250] -Alicyclic dicarboxylic acid unit-

[0251] As for alicyclic dicarboxylic acids that constitute alicyclic dicarboxylic acid units, they are not limited to the following substances, for example, alicyclic dicarboxylic acids with 3 to 10 carbon atoms in the alicyclic structure can be listed, and alicyclic dicarboxylic acids with 5 to 10 carbon atoms in the alicyclic structure are preferred.

[0252] Examples of such alicyclic dicarboxylic acids include, but are not limited to, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid. Among these, 1,4-cyclohexanedicarboxylic acid is preferred.

[0253] In addition, the alicyclic dicarboxylic acid which comprises an alicyclic dicarboxylic acid unit may be used individually by 1 type, and may use 2 or more types together.

[0254] The alicyclic group of the alicyclic dicarboxylic acid may be unsubstituted or may have a substituent. The substituent is not limited to the following groups, and examples thereof include alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0255] As the dicarboxylic acid unit other than the isophthalic acid unit, it is preferred to contain an aromatic dicarboxylic acid unit, and more preferably to contain an aromatic dicarboxylic acid having 6 to 12 carbon atoms.

[0256] By using such a dicarboxylic acid, the polyamide composition tends to have more excellent mechanical properties, particularly water absorption rigidity, hot rigidity, fluidity, surface appearance, and the like.

[0257] In the above embodiment, the dicarboxylic acid constituting the dicarboxylic acid unit (1B-a) is not limited to the compounds described above as the dicarboxylic acid, and may be a compound equivalent to the above dicarboxylic acid.

[0258] Here, a "compound equivalent to a dicarboxylic acid" refers to a compound that can form a dicarboxylic acid structure similar to the dicarboxylic acid structure derived from the above dicarboxylic acid. Such a compound is not limited to the following substances, and examples thereof include anhydrides and halides of dicarboxylic acids.

[0259] Furthermore, the (1B) semi-aromatic polyamide may further contain a unit derived from a trivalent or higher polyvalent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid, as needed.

[0260] The trivalent or higher polyvalent carboxylic acid may be used alone or in combination of two or more.

[0261] ((1B-b) diamine unit)

[0262] The (b) diamine unit constituting the (1B) semiaromatic polyamide contains at least 50 mol% of a diamine having 4 to 10 carbon atoms. Examples thereof include, but are not limited to, aliphatic diamine units, alicyclic diamine units, and aromatic diamine units.

[0263] -Aliphatic diamine unit-

[0264] The aliphatic diamine constituting the aliphatic diamine unit is not limited to the following, and examples thereof include linear saturated aliphatic diamines having 2 to 20 carbon atoms, such as ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine. The linear saturated aliphatic diamine may have 4 to 20 carbon atoms.

[0265] -Alicyclic diamine unit-

[0266] The alicyclic diamine constituting the alicyclic diamine unit is not limited to the following, and examples thereof include 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and 1,3-cyclopentanediamine.

[0267] -Aromatic diamine unit-

[0268] As for aromatic diamines that constitute aromatic diamine units, any diamine containing aromatic compounds is not limited to the following substances, such as m-phenylenediamine.

[0269] The diamine unit constituting (1B) semi-aromatic polyamide is preferably an aliphatic diamine unit, more preferably a diamine unit having a straight-chain saturated aliphatic group with 4 to 10 carbon atoms, even more preferably a diamine unit having a straight-chain saturated aliphatic group with 6 to 10 carbon atoms, and even more preferably hexamethylenediamine.

[0270] By using such diamines, it is possible to form polyamide compositions with superior mechanical properties, especially water absorption rigidity, rigidity under high temperature use (thermal rigidity), flowability, and surface appearance.

[0271] It should be noted that diamines can be used alone or in combination of two or more.

[0272] (1B) Semi-aromatic polyamides are preferably polyamide 6I, 9I, or 10I, with polyamide 6I being the most preferred.

[0273] The (1B) semi-aromatic polyamide may further contain a trivalent or higher-valent polyvalent aliphatic amine such as bis(hexamethylene)triamine, as needed.

[0274] Three or more polyaliphatic amines can be used alone or in combination of two or more.

[0275] In the above-described manner, relative to 100% by mass of the total polyamide content in the polyamide composition, the amount of (1B) semi-aromatic polyamide is 1.0% by mass or more and 50.0% by mass or less, preferably 5.0% by mass or more and 47.5% by mass or less, more preferably 10.0% by mass or more and 46.0% by mass or less, further preferably 15.0% by mass or more and 45.0% by mass or less, even more preferably 20.0% by mass or more and 44.0% by mass or less, particularly preferably 22.5% by mass or more and 43.0% by mass or less, and most preferably 24.5% by mass or more and 42.5% by mass or less. By setting the amount of (1B) semi-aromatic polyamide within the above-described range, a polyamide composition with excellent mechanical properties, particularly water absorption rigidity, thermal rigidity, and flowability, can be obtained. Furthermore, the polyamide composition containing components such as inorganic fillers exhibits excellent surface appearance.

[0276] (lactam unit and / or aminocarboxylic acid unit)

[0277] (1A) Aliphatic polyamides and (1B) semi-aromatic polyamides may also contain lactam units and / or aminocarboxylic acid units. By containing such units, polyamides with superior toughness are tended to be obtained. It should be noted that, here, the lactam and aminocarboxylic acid constituting the lactam and aminocarboxylic acid units refer to polymerizable (condensation-polymerized) lactams and aminocarboxylic acids.

[0278] As for the lactam and aminocarboxylic acid that constitute the lactam unit and aminocarboxylic acid unit, they are not limited to the following substances, for example, lactam and aminocarboxylic acid with 4 to 14 carbon atoms are preferred, and lactam and aminocarboxylic acid with 6 to 12 carbon atoms are more preferred.

[0279] As for the lactams that constitute the lactam unit, they are not limited to the following substances, for example: butyrolactam, neopentyl lactam, ε-caprolactam, octyl lactam, heptanolactam, undecylactam and laurolactam (dodecylactam), etc.

[0280] Among them, the lactam is preferably ε-caprolactam, laurolactam, etc., and more preferably ε-caprolactam. The inclusion of such a lactam tends to result in a polyamide composition having further excellent toughness.

[0281] The aminocarboxylic acid constituting the aminocarboxylic acid unit is not limited to the following, and examples thereof include ω-aminocarboxylic acid and α,ω-amino acid, which are compounds obtained by ring-opening of lactam.

[0282] As aminocarboxylic acids, preferably linear or branched saturated aliphatic carboxylic acids having 4 to 14 carbon atoms, substituted with an amino group at the ω position. Examples of such aminocarboxylic acids include, but are not limited to, 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Other examples of aminocarboxylic acids include p-aminomethylbenzoic acid.

[0283] The lactam and aminocarboxylic acid constituting the lactam unit and the aminocarboxylic acid unit may be used alone or in combination of two or more.

[0284] The total ratio (mol %) of the lactam unit and the aminocarboxylic acid unit relative to the total amount of polyamide in the polyamide composition is preferably 0 to 20 mol %, more preferably 0 to 10 mol %, and even more preferably 0 to 5 mol %.

[0285] By setting the total ratio of the lactam unit and the aminocarboxylic acid unit within the above range, effects such as improvement in fluidity tend to be obtained.

[0286] (Capping agent)

[0287] The ends of the polyamide used in the above embodiment can be capped with a known capping agent.

[0288] Such a terminal blocking agent can also be added as a molecular weight modifier when producing polyamide from the above-mentioned dicarboxylic acid and diamine and, if necessary, lactam and / or aminocarboxylic acid.

[0289] The terminal blocking agent is not limited to the following substances, and examples thereof include monocarboxylic acids, monoamines, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacyl halides, monoesters, and monoalcohols.

[0290] Among them, monocarboxylic acids and monoamines are preferred. By using a capping agent to cap the ends of the polyamide, a polyamide composition with better thermal stability tends to be formed. In addition, the thermal stability of the molded article obtained from the polyamide composition tends to be better.

[0291] The blocking agent may be used alone or in combination of two or more.

[0292] The monocarboxylic acid that can be used as the end-capping agent is any monocarboxylic acid that is reactive with the amino group that can be present at the end of the polyamide, and is not limited to the following substances. Examples thereof include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; and aromatic monocarboxylic acids such as benzoic acid, methylbenzoic acid, α-naphthoic acid, β-naphthoic acid, methylnaphthoic acid, and phenylacetic acid.

[0293] In particular, from the viewpoint of fluidity and mechanical strength, the terminals of the semi-aromatic polyamide (1B) are preferably capped with acetic acid.

[0294] The monocarboxylic acid may be used alone or in combination of two or more.

[0295] As the monoamine that can be used as the end-capping agent, any monoamine that is reactive with the carboxyl group that can be present at the end of the polyamide is not limited to the following substances, and examples thereof include: aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; and aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine.

[0296] The monoamines may be used alone or in combination of two or more.

[0297] A polyamide composition containing a polyamide end-capped with an end-capping agent tends to be excellent in heat resistance, fluidity, toughness, low water absorption, and rigidity.

[0298] (Production Method of Polyamide)

[0299] When obtaining the polyamide in the above embodiment, the amount of dicarboxylic acid added and the amount of diamine added are preferably approximately the same in molar amount. Regarding the molar ratio, taking into account any escape of diamine from the reaction system during the polymerization reaction, the molar amount of all diamines relative to the molar amount of all dicarboxylic acids is preferably 0.9 to 1.2, more preferably 0.95 to 1.1, and even more preferably 0.98 to 1.05.

[0300] The method for producing polyamide is not limited to the following, but includes, for example, a step of polymerizing a dicarboxylic acid constituting a dicarboxylic acid unit, a diamine constituting a diamine unit, and, if necessary, a lactam and / or an aminocarboxylic acid constituting a lactam unit and / or an aminocarboxylic acid unit to obtain a polymer, preferably further comprising a step of increasing the degree of polymerization of the polyamide. Furthermore, an end-capping step of capping the ends of the obtained polymer with an end-capping agent may be included as needed.

[0301] As specific examples of methods for producing polyamide, various methods such as those shown below can be cited.

[0302] 1) A method in which an aqueous solution of a dicarboxylic acid-diamine salt or a mixture of a dicarboxylic acid and a diamine, or an aqueous suspension thereof, is heated and polymerized while maintaining the mixture in a molten state (hereinafter also referred to as "hot melt polymerization method").

[0303] 2) A method of increasing the degree of polymerization of a polyamide obtained by hot melt polymerization while maintaining it in a solid state at a temperature below its melting point (hereinafter also referred to as "hot melt polymerization / solid phase polymerization method").

[0304] 3) A method for polymerizing dicarboxylic acid-diamine salts, or mixtures of dicarboxylic acids and diamines, while maintaining a solid state (hereinafter also referred to as "solid-state polymerization").

[0305] 4) A method of polymerizing a dicarboxylic acid halide component equivalent to a dicarboxylic acid and a diamine component (hereinafter also referred to as a "solution method").

[0306] Among them, a production method including a hot melt polymerization method is preferred. When producing polyamide by the hot melt polymerization method, it is preferred to maintain the molten state until the polymerization is completed. In order to maintain the molten state, it is necessary to produce under polymerization conditions that match the composition of the polyamide. For example, the following method can be used: the polymerization pressure in the hot melt polymerization method is controlled to 14 kg / cm 2 ~25kg / cm 2 (Gauge pressure) While continuously heating, reduce the pressure in the tank to atmospheric pressure (gauge pressure 0 kg / cm²) for more than 30 minutes. 2 ).

[0307] In the method for producing polyamide, there is no particular limitation on the polymerization method, and either a batch method or a continuous method may be used.

[0308] The polymerization apparatus for producing the polyamide is not particularly limited, and a known apparatus can be used. Examples thereof include autoclave reactors, drum reactors, and extruder reactors such as kneaders.

[0309] The following describes a method for manufacturing polyamide by intermittent hot melt polymerization, but the method for manufacturing polyamide is not limited to this.

[0310] First, for example, an aqueous solution containing approximately 40% by mass to 60% by mass of the raw material components of the polyamide (dicarboxylic acid, diamine, and, as needed, lactam and / or aminocarboxylic acid) is concentrated to approximately 65% ​​by mass to approximately 90% by mass using a concentration tank operated at a temperature of 110° C. to 180° C. and a pressure of approximately 0.035 MPa to approximately 0.6 MPa (gauge pressure) to obtain a concentrated solution.

[0311] Next, the obtained concentrated solution is transferred to an autoclave, and heating is continued until the pressure in the autoclave reaches about 1.2 MPa to about 2.2 MPa (gauge pressure).

[0312] Then, in the autoclave, the pressure is maintained at about 1.2 MPa to about 2.2 MPa (gauge pressure) while removing water and / or gas components. When the temperature reaches about 220°C to about 260°C, the pressure is reduced to atmospheric pressure (gauge pressure: 0 MPa).

[0313] After reducing the pressure in the autoclave to atmospheric pressure, the pressure is reduced as needed, whereby water produced as a by-product can be efficiently removed.

[0314] The autoclave is then pressurized with an inert gas such as nitrogen, and the polyamide melt is extruded from the autoclave in the form of strands. The extruded strands are cooled and cut to obtain polyamide pellets.

[0315] (Polymer end of polyamide)

[0316] The polymer terminals of the polyamide used in the above embodiment are not particularly limited, but can be classified and defined as follows.

[0317] That is, 1) amino terminal, 2) carboxyl terminal, 3) terminal formed by a blocking agent, and 4) other terminal.

[0318] 1) The amino terminal is a polymer terminal having an amino group (-NH2 group) and is derived from the diamine unit of the raw material.

[0319] 2) The carboxyl terminal is a polymer terminal having a carboxyl group (-COOH group) and is derived from the dicarboxylic acid of the raw material.

[0320] 3) The terminal formed by the terminal blocking agent is a terminal formed when the terminal blocking agent is added during polymerization. Examples of the terminal blocking agent include the above-mentioned terminal blocking agents.

[0321] 4) Other terminals are polymer terminals not classified in the above 1) to 3), and examples thereof include terminals generated by deamination reaction of amino terminals and terminals generated by decarboxylation reaction of carboxyl terminals.

[0322] ((1A) Characteristics of Aliphatic Polyamides)

[0323] (1A) The molecular weight, melting point Tm2, ​​crystallization enthalpy ΔH, and tan δ peak temperature of the aliphatic polyamide can be specifically measured by the methods described in the examples below.

[0324] As an indicator of the molecular weight of the aliphatic polyamide (1A), Mw (weight average molecular weight) can be used. The Mw (weight average molecular weight) of the aliphatic polyamide (1A) is preferably 10,000 to 50,000, more preferably 15,000 to 45,000, further preferably 20,000 to 40,000, and further preferably 25,000 to 35,000.

[0325] When the Mw (weight average molecular weight) is within the above range, a polyamide composition having excellent mechanical properties, particularly water absorption rigidity, hot rigidity, and flowability, can be obtained. Furthermore, polyamide compositions containing components, such as inorganic fillers, exhibit excellent surface appearance. It should be noted that the Mw (weight average molecular weight) can be measured using GPC (gel permeation chromatography), as described in the following examples.

[0326] (1A) The molecular weight distribution of the aliphatic polyamide is measured using Mw (weight average molecular weight) / Mn (number average molecular weight) as an index.

[0327] (1A) The Mw (weight average molecular weight) / Mn (number average molecular weight) ratio of the aliphatic polyamide is preferably 1.8 to 2.2, more preferably 1.9 to 2.1. The lower limit of the molecular weight distribution is 1.0. By setting the Mw (weight average molecular weight) / Mn (number average molecular weight) ratio within the above range, a polyamide composition having excellent fluidity and other characteristics can be obtained. In addition, the surface appearance of a polyamide composition containing a component represented by an inorganic filler is excellent. In addition, the surface appearance of a molded article obtained from a polyamide composition containing a component represented by an inorganic filler is further improved.

[0328] As methods for controlling the Mw (weight average molecular weight) / Mn (number average molecular weight) of (1A) aliphatic polyamide within the above range, for example, there can be listed: a method of adding a known polycondensation catalyst such as phosphoric acid and sodium hypophosphite as an additive during the hot melt polymerization of polyamide; and a method of controlling polymerization conditions such as heating conditions and reduced pressure conditions.

[0329] In the above embodiment, the Mw (weight average molecular weight) / Mn (number average molecular weight) of the aliphatic polyamide (1A) can be calculated using the Mw (weight average molecular weight) and Mn (number average molecular weight) obtained by GPC (gel permeation chromatography) as described in the following Examples.

[0330] The melting point Tm2 of the aliphatic polyamide (1A) is preferably 220°C or higher, more preferably 230°C or higher, and even more preferably 240°C or higher.

[0331] The melting point Tm2 of the aliphatic polyamide (1A) is preferably 300°C or lower, more preferably 290°C or lower, further preferably 280°C or lower, and even more preferably 270°C or lower.

[0332] When the melting point Tm2 of the aliphatic polyamide (1A) is 220°C or higher, a polyamide composition having more excellent hot stiffness, etc., tends to be obtained. In addition, a molded article obtained from the polyamide composition tends to have more excellent hot stiffness, etc.

[0333] Furthermore, when the melting point Tm2 of the aliphatic polyamide (1A) is 300° C. or lower, thermal decomposition of the polyamide composition during melt processing such as extrusion and molding tends to be further suppressed.

[0334] From the perspective of mechanical properties, particularly water absorption rigidity and hot rigidity, the crystallization enthalpy ΔH of the aliphatic polyamide (1A) is preferably 30 J / g or greater, more preferably 40 J / g or greater, even more preferably 50 J / g or greater, and even more preferably 60 J / g or greater. The upper limit of the crystallization enthalpy ΔH is not particularly limited; a higher value is preferred.

[0335] Examples of an apparatus for measuring the melting point Tm2 and crystallization enthalpy ΔH of the aliphatic polyamide (1A) include Diamond-DSC manufactured by PERKIN-ELMER.

[0336] The tan δ peak temperature of the aliphatic polyamide (1A) is preferably 40°C or higher, more preferably 50°C to 110°C, even more preferably 60°C to 100°C, even more preferably 70°C to 95°C, and even more preferably 80°C to 90°C. When the tan δ peak temperature of the aliphatic polyamide (1A) is 40°C or higher, a polyamide composition having excellent water absorption rigidity and hot rigidity tends to be obtained.

[0337] (1A) The tan δ peak temperature of the aliphatic polyamide can be measured as described in the following Examples, for example, using a viscoelasticity measurement analyzer (DVE-V4 manufactured by Rheology).

[0338] ((1B) Characteristics of semi-aromatic polyamide)

[0339] The molecular weight, formic acid relative viscosity (VR(5B)), melting point Tm2, ​​crystallization enthalpy ΔH, tan δ peak temperature, amino terminal content, and carboxyl terminal content of the (1B) semi-aromatic polyamide can be specifically measured by the methods described in the Examples below.

[0340] As an indicator of the molecular weight of the semi-aromatic polyamide (1B), Mw (weight average molecular weight) can be used. The Mw (weight average molecular weight) of the semi-aromatic polyamide (1B) is preferably 10,000 to 35,000, more preferably 10,000 to 25,000, further preferably 13,000 to 24,000, further preferably 15,000 to 23,000, particularly preferably 18,000 to 22,000, and most preferably 19,000 to 21,000.

[0341] When the Mw (weight average molecular weight) is within the above range, a polyamide composition having excellent mechanical properties, particularly water absorption rigidity, hot rigidity, and flowability, can be obtained. Furthermore, polyamide compositions containing components, such as inorganic fillers, also have excellent surface appearance. It should be noted that the Mw (weight average molecular weight) can be measured using GPC (gel permeation chromatography) as described in the following examples.

[0342] The difference between the weight average molecular weight Mw(1A) of the aliphatic polyamide (1A) and the weight average molecular weight Mw(1B) of the semi-aromatic polyamide (1B), {Mw(1A)-Mw(1B)}, is preferably 10,000 or greater, more preferably 11,000 or greater, further preferably 12,000 or greater, even further preferably 13,000 or greater, and most preferably 14,000 or greater. When {Mw(1A)-Mw(1B)} is 10,000 or greater, the semi-aromatic polyamide (1B) forms micron-sized domains, enabling a composition having excellent water absorption rigidity and hot rigidity.

[0343] (1B) The molecular weight distribution of the semi-aromatic polyamide is measured using Mw (weight average molecular weight) / Mn (number average molecular weight) as an index.

[0344] The Mw (weight average molecular weight) / Mn (number average molecular weight) ratio of the (1B) semi-aromatic polyamide is preferably 2.6 or less, more preferably 2.4 or less, further preferably 1.7 to 2.4, even more preferably 1.8 to 2.3, particularly preferably 1.9 to 2.2, and most preferably 1.9 to 2.1. The lower limit of the Mw (weight average molecular weight) / Mn (number average molecular weight) ratio is 1.0. By setting the Mw (weight average molecular weight) / Mn (number average molecular weight) ratio within the above range, a polyamide composition having excellent fluidity and other properties can be obtained. In addition, a polyamide composition containing components such as inorganic fillers has an excellent surface appearance.

[0345] Methods for controlling the Mw (weight average molecular weight) / Mn (number average molecular weight) of the semi-aromatic polyamide (1B) within the above range include, for example, adding a known polycondensation catalyst such as phosphoric acid or sodium hypophosphite as an additive during the hot melt polymerization of the polyamide. Furthermore, it is important to control polymerization conditions such as heating and reduced pressure to complete the polycondensation reaction at the lowest possible temperature and in the shortest possible time. In particular, if the semi-aromatic polyamide (1B) is amorphous, it has no melting point, and therefore, it is desirable to lower the reaction temperature.

[0346] When polyamide molecular structures contain aromatic compound units, the molecular weight distribution (Mw / Mn) tends to increase with increasing molecular weight. A high molecular weight distribution indicates a high proportion of polyamide molecules with a three-dimensional molecular structure. This facilitates further three-dimensional molecular structuring during high-temperature processing, reducing flowability and deteriorating the surface appearance of polyamide compositions containing components such as inorganic fillers.

[0347] In the above embodiment, the Mw (weight average molecular weight) / Mn (number average molecular weight) of the semi-aromatic polyamide (1B) can be calculated using the Mw (weight average molecular weight) and Mn (number average molecular weight) obtained by GPC (gel permeation chromatography) as described in the following Examples.

[0348] In the above embodiment, the formic acid relative viscosity (VR) of the polyamide is the relative viscosity of a formic acid solution of the polyamide. It can be said that it is the relative viscosity obtained by comparing the viscosity of the formic acid solution of the polyamide with the viscosity of formic acid itself. In this specification, the VR is used as an indicator of the molecular weight and fluidity of the polyamide. A high VR value indicates a high molecular weight and low fluidity. VR is measured in accordance with ASTM-D789. Specifically, the VR value is measured at 25°C using a solution obtained by dissolving the polyamide to a concentration of 8.4% by mass in 90% by mass formic acid (10% by mass water). A VR value of less than 8 results in insufficient color tone and mechanical properties. A VR value of greater than 30 results in reduced fluidity and poor moldability. The VR of the semi-aromatic polyamide (2B) in the above embodiment is 8 to 30, preferably 8 to 25, more preferably 10 to 25, and even more preferably 10 to 20.

[0349] In the above embodiment, the Mw / VR of the polyamide is an indicator of molecular weight and fluidity. The Mw / VR of the (2B) semi-aromatic polyamide is preferably 1000 to 2000, more preferably 1200 to 2000, even more preferably 1400 to 2000, even more preferably 1500 to 2000, and most preferably 1500 to 1800. When the Mw / VR is less than 1000, for example, the molecular weight is reduced, resulting in insufficient mechanical properties. On the other hand, when the Mw / VR is greater than 2000, for example, the VR is reduced, which tends to increase fluidity, generate burrs during molding, and cause molding defects.

[0350] From the viewpoint of mechanical properties, particularly water absorption rigidity and hot rigidity, the crystallization enthalpy ΔH of the semi-aromatic polyamide (1B) is preferably 15 J / g or less, more preferably 10 J / g or less, further preferably 5 J / g or less, and even more preferably 0 J / g.

[0351] As a method for controlling the crystallization enthalpy ΔH of the (1B) semi-aromatic polyamide within the above range, it is possible to cite the method of increasing the ratio of the aromatic monomer to the dicarboxylic acid unit. In addition, a known method for reducing the crystallinity of the polyamide can be adopted without particular limitation. As a known method for reducing the crystallinity of the polyamide, specifically, for example, it is possible to cite the method of increasing the ratio of the meta-substituted aromatic dicarboxylic acid unit to the dicarboxylic acid unit and the method of increasing the ratio of the meta-substituted aromatic diamine unit to the diamine unit. From this viewpoint, the (1B) semi-aromatic polyamide preferably contains 50 mol% or more of isophthalic acid as the (1B-a) dicarboxylic acid unit in all the dicarboxylic acid units constituting the (1B) semi-aromatic polyamide, more preferably contains 75 mol% or more, and even more preferably contains 100 mol%.

[0352] Examples of an apparatus for measuring the crystallization enthalpy ΔH of the (1B) semi-aromatic polyamide include Diamond-DSC manufactured by PERKIN-ELMER.

[0353] The tan δ peak temperature of the (1B) semi-aromatic polyamide is preferably 90°C or higher, more preferably 100°C to 160°C, further preferably 110°C to 150°C, further preferably 120°C to 145°C, further preferably 130°C to 140°C.

[0354] To control the tan δ peak temperature of the semi-aromatic polyamide (1B) within the above range, it is necessary to increase the ratio of the aromatic monomer to the dicarboxylic acid unit. It is important to contain 75 mol% or more of isophthalic acid as the dicarboxylic acid unit, and most preferably 100 mol%.

[0355] When the semi-aromatic polyamide (1B) has a tan δ peak temperature of 90°C or higher, a polyamide composition having excellent water absorption rigidity and hot rigidity tends to be obtained. Furthermore, when the semi-aromatic polyamide (1B) has a tan δ peak temperature of 160°C or lower, the polyamide composition containing components such as inorganic fillers tends to have excellent surface appearance.

[0356] (1B) The tan δ peak temperature of the semi-aromatic polyamide can be measured as described in the following Examples, for example, using a viscoelasticity measurement analyzer (DVE-V4 manufactured by Rheology).

[0357] The amount of amino terminal groups in the semi-aromatic polyamide (1B), expressed as an equivalent weight per gram of polyamide, is preferably 5 μequiv / g to 100 μequiv / g, more preferably 10 μequiv / g to 90 μequiv / g, even more preferably 20 μequiv / g to 80 μequiv / g, even more preferably 30 μequiv / g to 70 μequiv / g, and even more preferably 40 μequiv / g to 60 μequiv / g. When the amount of amino terminal groups falls within this range, a composition exhibiting excellent color change resistance to heat and light can be obtained. The amount of amino terminal groups can be measured by neutralization titration.

[0358] The amount of carboxyl groups in the semi-aromatic polyamide (1B) is preferably 50 μequiv / g to 300 μequiv / g, more preferably 100 μequiv / g to 280 μequiv / g, further preferably 120 μequiv / g to 260 μequiv / g, even more preferably 150 μequiv / g to 250 μequiv / g, and even more preferably 180 μequiv / g to 240 μequiv / g, relative to 1 g of polyamide. When the amount of carboxyl groups is within the above range, a polyamide composition having excellent fluidity and other properties can be obtained. Furthermore, a polyamide composition containing components such as inorganic fillers has an excellent surface appearance. Furthermore, a molded article obtained from a polyamide composition containing components such as inorganic fillers has an even better surface appearance. The amount of carboxyl groups can be measured by neutralization titration.

[0359] The total amount of amino terminal groups and carboxyl terminal groups of the (1B) semi-aromatic polyamide per 1g of polyamide is preferably 150 μequiv / g to 350 μequiv / g, more preferably 160 μequiv / g to 300 μequiv / g, even more preferably 170 μequiv / g to 280 μequiv / g, even more preferably 180 μequiv / g to 270 μequiv / g, and even more preferably 190 μequiv / g to 260 μequiv / g. When the total amount of amino terminal groups and carboxyl terminal groups is within the above range, a polyamide composition having excellent fluidity and other properties can be obtained. Furthermore, polyamide compositions containing components such as inorganic fillers have excellent surface appearance. Furthermore, molded articles obtained from polyamide compositions containing components such as inorganic fillers have even better surface appearance.

[0360] The polyamide composition of the above embodiment may contain, in addition to the above-mentioned (1A) aliphatic polyamide and (1B) semi-aromatic polyamide, one or more components selected from the group consisting of an inorganic filler, a nucleating agent, a lubricant, a stabilizer, a polymer other than polyamide, a metal phosphite and / or a metal hypophosphite, and a phosphite ester compound.

[0361] ((1C) Inorganic filler)

[0362] Examples of the inorganic filler include, but are not limited to, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, clay, flaky glass, talc, kaolin, mica, hydrotalcite, calcium carbonate, magnesium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, Ketjen black, acetylene black, furnace black, carbon nanotubes, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swelling fluorine mica, and apatite.

[0363] Among them, from the viewpoint of further improving mechanical strength, at least one selected from the group consisting of glass fiber, carbon fiber, wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate fiber, aluminum borate fiber, and clay is preferred. Among them, at least one selected from the group consisting of glass fiber, carbon fiber, wollastonite, kaolin, mica, talc, calcium carbonate, and clay is more preferred.

[0364] From the viewpoint of improving toughness and the surface appearance of molded products, the number average fiber diameter of the glass fiber and carbon fiber is preferably 3 μm to 30 μm, more preferably 3 μm to 20 μm, further preferably 3 μm to 12 μm, further preferably 3 μm to 9 μm, and further preferably 4 μm to 6 μm.

[0365] By setting the number average fiber diameter of the glass fibers and carbon fibers to 30 μm or less, a polyamide composition with excellent toughness and surface appearance of the molded article can be obtained. On the other hand, by setting the fiber diameter to 3 μm or greater, a polyamide composition with an excellent balance between cost, powder handling, and physical properties (such as flowability) can be obtained. Furthermore, by setting the fiber diameter to 3 μm to 9 μm, a polyamide composition with excellent vibration fatigue resistance and sliding properties can be obtained.

[0366] Glass fibers and carbon fibers can have a perfectly circular or flat cross-section. The flat cross-section is not limited to the following shapes, and examples include: rectangular, elliptical, and cocoon-shaped with a longitudinally constricted center. As used herein, "flattening" refers to the value expressed as D2 / D1, where the major diameter of the fiber cross-section is D2 and the minor diameter of the fiber cross-section is D1 (the flattening of a perfectly circular cross-section is approximately 1).

[0367] Among glass fibers and carbon fibers, from the viewpoint of imparting excellent mechanical strength to the polyamide composition, those having a number average fiber diameter of 3 to 30 μm, a weight average fiber length of 100 to 750 μm, and an aspect ratio (L / D) of weight average fiber length (L) to number average fiber diameter (D) of 10 to 100 can be suitably used.

[0368] Furthermore, from the perspective of reducing warpage of plate-shaped molded articles and improving heat resistance, toughness, low water absorption, and heat aging resistance, the flatness is preferably 1.5 or greater, more preferably 1.5 to 10.0, even more preferably 2.5 to 10.0, and even more preferably 3.1 to 6.0. An flatness within this range is preferred because it effectively prevents breakage during mixing with other components, kneading, molding, and other processes, and the desired effects on the molded article can be fully achieved.

[0369] The thickness of glass fibers and carbon fibers with an oblateness of 1.5 or greater is not limited to the following ranges. Preferably, the minor diameter D1 of the fiber cross section is 0.5 μm to 25 μm, and the major diameter D2 of the fiber cross section is 1.25 μm to 250 μm. Within these ranges, difficulties in fiber spinning can be effectively avoided, and the strength of the molded product can be improved without reducing the contact area with the resin (polyamide). The minor diameter D1 is more preferably 3 μm to 25 μm, and the oblateness is preferably greater than 3.

[0370] These glass fibers and carbon fibers having a flatness of 1.5 or more can be produced using methods described in, for example, Japanese Patent Publication No. 3-59019, Japanese Patent Publication No. 4-13300, and Japanese Patent Publication No. 4-32775. In particular, it is preferred to use a glass fiber having a flatness of 1.5 or more produced by using a perforated plate having a large number of holes on the bottom surface or a nozzle for spinning glass fibers with a special cross-section, wherein the perforated plate is provided with a convex edge surrounding a plurality of hole outlets and extending downward from the bottom surface, and the nozzle for spinning glass fibers with a special cross-section is provided with a plurality of convex edges extending downward from the front end of the outer periphery of the nozzle having a single or multiple holes. These fibrous reinforcing materials can use the fiber bundle as roving as it is, or can be further used after being cut into chopped glass strands.

[0371] Here, the number average fiber diameter and weight average fiber length in this specification are values ​​obtained by the following method. The polyamide composition is put into an electric furnace, and the organic matter contained is incinerated. From the residue portion after the treatment, arbitrarily select 100 or more glass fibers (or carbon fibers), utilize a scanning electron microscope (SEM) to observe, measure the fiber diameters of these glass fibers (or carbon fibers), and thus obtain the number average fiber diameter. In addition, the fiber length is measured using an SEM photo of the above-mentioned 100 or more glass fibers (or carbon fibers) taken at a magnification of 1000 times, and thus obtain the weight average fiber length.

[0372] The aforementioned glass fibers and carbon fibers can be surface-treated using silane coupling agents. As for silane coupling agents, they are not limited to the following substances, but may include, for example, aminosilanes such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, epoxysilanes, and vinylsilanes. Preferably, one or more of the components listed above are selected, and more preferably, aminosilanes.

[0373] In addition, the aforementioned glass fibers and carbon fibers may also contain the following substances as bundle binders: copolymers containing unsaturated vinyl monomers containing carboxylic anhydride and unsaturated vinyl monomers other than those containing carboxylic anhydride as constituent units; epoxy compounds; polyurethane resins; acrylic homopolymers; copolymers of acrylic acid with other comonomers; and their salts with primary, secondary, and tertiary amines; as well as copolymers containing unsaturated vinyl monomers containing carboxylic anhydride and unsaturated vinyl monomers other than those containing carboxylic anhydride. Only one of these substances may be used alone, or two or more may be used in combination.

[0374] From the viewpoint of the mechanical strength of the obtained polyamide composition, the preferred binder is a copolymer containing an unsaturated vinyl monomer containing a carboxylic anhydride and unsaturated vinyl monomers other than those containing carboxylic anhydride, an epoxy compound, a polyurethane resin, or a combination thereof. More preferably, it is a copolymer containing an unsaturated vinyl monomer containing a carboxylic anhydride and unsaturated vinyl monomers other than those containing carboxylic anhydride, a polyurethane resin, or a combination thereof.

[0375] Glass fibers and carbon fibers can be obtained by applying the aforementioned sizing agent to the fibers using a known method such as a roll coater in a known production process of the fibers, and drying the produced fiber bundle to continuously react.

[0376] The fiber bundle may be used as a roving as it is, or may be further subjected to a cutting step to be used as chopped glass strands.

[0377] In terms of solid content ratio, the sizing agent is preferably applied (added) in an amount equivalent to 0.2% to 3% by mass, more preferably applied (added) in an amount equivalent to 0.3% to 2% by mass, relative to 100% by mass of the glass fiber or carbon fiber. That is, from the perspective of maintaining the bundle of the fibers, the amount of the sizing agent added is preferably 0.2% by mass or more relative to 100% by mass of the glass fiber or carbon fiber, in terms of solid content ratio. On the other hand, from the perspective of improving the thermal stability of the resulting polyamide composition, the amount of the sizing agent added is preferably 3% by mass or less. The strands can be dried after the cutting step, or they can be cut after drying.

[0378] As inorganic fillers other than glass fiber and carbon fiber, from the viewpoint of improving the strength, rigidity and surface appearance of the molded article, it is not limited to the following substances, for example, preferably wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate fiber, aluminum borate fiber, clay. More preferably, wollastonite, kaolin, mica, talc, calcium carbonate and clay, further preferably wollastonite, kaolin, mica, talc, further preferably wollastonite, mica, particularly preferably wollastonite. These inorganic fillers can be used alone or in combination of two or more.

[0379] From the viewpoint of improving toughness and the surface appearance of molded products, the average particle size of inorganic fillers other than glass fibers and carbon fibers is preferably 0.01 μm to 38 μm, more preferably 0.03 μm to 30 μm, further preferably 0.05 μm to 25 μm, further preferably 0.10 μm to 20 μm, and particularly preferably 0.15 μm to 15 μm.

[0380] By setting the average particle size of the inorganic fillers (excluding glass fibers and carbon fibers) to 38 μm or less, a polyamide composition with excellent toughness and surface appearance of the molded article can be obtained. On the other hand, by setting the average particle size to 0.1 μm or greater, a polyamide composition with an excellent balance between cost, powder handling, and physical properties (such as flowability) can be obtained.

[0381] Here, among inorganic fillers, for inorganic fillers with needle-like shapes such as wollastonite, the number average fiber diameter (hereinafter also referred to as "average fiber diameter") is used as the average particle size. In addition, when the cross section is not circular, the maximum value of its length is used as the (number average) fiber diameter.

[0382] For the weight average fiber length of the above-mentioned inorganic filler having a needle-like shape (hereinafter also referred to as "average fiber length"), it is preferred that the numerical range be calculated from the preferred range of the above-mentioned number average fiber diameter and the preferred range of the aspect ratio (L / D) of the weight average fiber length (L) to the number average fiber diameter (D) described below.

[0383] The aspect ratio (L / D) of the weight-average fiber length (L) to the number-average fiber diameter (D) of the needle-shaped inorganic filler is preferably 1.5 to 10, more preferably 2.0 to 5, and even more preferably 2.5 to 4 from the viewpoint of improving the surface appearance of the molded article and preventing wear of metal parts of injection molding machines, etc.

[0384] In addition, inorganic fillers other than glass fiber and carbon fiber can also be surface treated using silane coupling agents, titanate coupling agents, etc. As silane coupling agents, it is not limited to the following substances, for example, aminosilanes such as γ-aminopropyl triethoxysilane, γ-aminopropyl trimethoxysilane and N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-mercaptopropyl trimethoxysilane and γ-mercaptopropyl triethoxysilane, epoxy silanes, and vinyl silanes can be listed. Among them, preferably one or more of the components selected from the above-mentioned ingredients are more preferably aminosilanes. Such a surface treatment agent can be processed in advance on the surface of the inorganic filler, or it can be added when mixing polyamide and the inorganic filler. In addition, the addition amount of the surface treatment agent is preferably 0.05% to 1.5% by mass relative to 100% by mass of the inorganic filler.

[0385] The content of the inorganic filler is preferably 5 to 250 parts by mass, more preferably 30 to 250 parts by mass, further preferably 50 to 240 parts by mass, further preferably 50 to 200 parts by mass, and particularly preferably 50 to 150 parts by mass, relative to 100 parts by mass of the total amount of the polyamide.

[0386] By setting the content of the inorganic filler to 5 parts by mass or more relative to 100 parts by mass of the total polyamide amount, the strength and rigidity of the resulting polyamide composition are improved. On the other hand, by setting the content of the inorganic filler to 250 parts by mass or less relative to 100 parts by mass of the total polyamide amount, a polyamide composition having excellent extrudability and moldability can be obtained.

[0387] (Nucleating Agent)

[0388] The nucleating agent is a substance that, when added, can increase the crystallization peak temperature of the polyamide composition, reduce the difference between the extrapolated starting temperature and the extrapolated ending temperature of the crystallization peak, or make the spherulites of the resulting molded article finer or more uniform in size.

[0389] Examples of the nucleating agent include, but are not limited to, talc, boron nitride, mica, kaolin, calcium carbonate, barium sulfate, silicon nitride, carbon black, potassium titanate, and molybdenum disulfide.

[0390] The nucleating agents may be used alone or in combination of two or more.

[0391] From the viewpoint of the effect of the nucleating agent, the nucleating agent is preferably talc or boron nitride.

[0392] Furthermore, since the nucleating agent has a high effect, a nucleating agent having a number average particle size of 0.01 μm to 10 μm is preferred.

[0393] The number-average particle size of nucleating agents can be determined as follows: the molded product is dissolved in a solvent such as formic acid that can dissolve polyamide, and more than 100 nucleating agents are randomly selected from the obtained insoluble components, and observed and measured using an optical microscope, scanning electron microscope, etc.

[0394] In the polyamide composition described above, the nucleating agent content is preferably 0.001 to 1 part by mass, more preferably 0.001 to 0.5 parts by mass, and even more preferably 0.001 to 0.09 parts by mass, relative to 100 parts by mass of the polyamide composition described above.

[0395] Compared to 100 parts by mass of polyamide, by setting the nucleating agent content to 0.001 parts by mass or more, the heat resistance of the polyamide composition is improved, and compared to 100 parts by mass of polyamide, by setting the nucleating agent content to 1 part by mass or less, a polyamide composition with excellent toughness can be obtained.

[0396] (Lubricant)

[0397] Examples of the lubricant include, but are not limited to, higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, and higher fatty acid amides.

[0398] The lubricants may be used alone or in combination of two or more.

[0399] Examples of higher fatty acids include stearic acid, palmitic acid, benzolic acid, erucic acid, oleic acid, lauric acid, and linoleic acid, which are saturated or unsaturated, straight-chain or branched aliphatic monocarboxylic acids with 8 to 40 carbon atoms, with stearic acid and linoleic acid being preferred.

[0400] As the higher fatty acid, one kind may be used or two or more kinds may be used in combination.

[0401] The higher fatty acid metal salt refers to a metal salt of a higher fatty acid.

[0402] The metal element constituting the higher fatty acid metal salt is preferably a periodic table Group 1, 2, or 3 element, zinc, or aluminum, and more preferably a Group 1 or 2 element such as calcium, sodium, potassium, or magnesium, or aluminum.

[0403] Examples of higher fatty acid metal salts include, but are not limited to, calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, and calcium palmitate. Metal salts of montanic acid and stearic acid are preferred.

[0404] The higher fatty acid metal salts may be used alone or in combination of two or more.

[0405] The higher fatty acid ester refers to an esterification product of a higher fatty acid and an alcohol, and preferably an ester of an aliphatic carboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms.

[0406] The aliphatic alcohol is not limited to the following, and examples thereof include stearyl alcohol, behenyl alcohol, and lauryl alcohol.

[0407] Examples of the higher fatty acid esters include, but are not limited to, stearyl stearate and behenyl behenate.

[0408] As the higher fatty acid ester, one species may be used alone, or two or more species may be used in combination.

[0409] Higher fatty acid amide refers to an amide compound of a higher fatty acid.

[0410] Examples of the higher fatty acid amides include, but are not limited to, stearamide, oleamide, erucamide, ethylenebisstearamide, ethylenebisoleamide, N-stearyl stearamide, and N-stearyl erucamide.

[0411] As the higher fatty acid amide, stearamide, erucamide, ethylenebisstearamide and N-stearylerucamide are preferred, and ethylenebisstearamide and N-stearylerucamide are more preferred.

[0412] The higher fatty acid amides may be used alone or in combination of two or more.

[0413] From the viewpoint of the effect of improving moldability, the lubricant is preferably a higher fatty acid metal salt or a higher fatty acid amide, and more preferably a higher fatty acid metal salt.

[0414] The content of the lubricant in the polyamide composition of the above embodiment is preferably 0.001 to 1 part by mass, more preferably 0.03 to 0.5 parts by mass, relative to 100 parts by mass of the total amount of polyamide.

[0415] By setting the lubricant content within the above range, a polyamide composition having excellent releasability and plasticizing time stability as well as excellent toughness can be obtained, and an extreme decrease in the molecular weight of the polyamide due to molecular chain scission can be prevented.

[0416] (Stabilizer)

[0417] Examples of the stabilizer include, but are not limited to, phenolic heat stabilizers, phosphorus-containing heat stabilizers, amine heat stabilizers, metal salts of elements of Groups 3, 4, and 11 to 14 of the periodic table, and halides of alkali metals and alkaline earth metals.

[0418] Examples of phenolic heat stabilizers include, but are not limited to, hindered phenol compounds. Hindered phenol compounds have the property of imparting excellent heat resistance and light resistance to resins such as polyamide and fibers.

[0419] The hindered phenol compound is not limited to the following, and examples thereof include N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 3 ,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate.

[0420] These may be used alone or in combination of two or more.

[0421] In particular, from the viewpoint of improving heat aging resistance, N,N′-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)] is preferred.

[0422] When a phenolic heat stabilizer is used, the content of the phenolic heat stabilizer in the polyamide composition is preferably 0.01% to 1% by mass, more preferably 0.1% to 1% by mass, relative to 100% by mass of the polyamide composition. When the content of the phenolic heat stabilizer is within the above range, the heat aging resistance of the polyamide composition can be further improved and the amount of gas generated can be further reduced.

[0423] Phosphorus-containing heat stabilizers are not limited to the following substances, for example, pentaerythritol-type phosphite compounds, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, triisodecyl phosphite, phenyl diisodecyl phosphite, phenyl di(tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl(tridecyl) phosphite, triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,4-di-tert-butyl-5-methylphenyl) phosphite, tris(butyloxy) phosphite ethyl) ester, 4,4'-butylene-bis(3-methyl-6-tert-butylphenyl-tetra(tridecyl)) diphosphite, tetra(C12-C15 mixed alkyl)-4,4'-isopropylidene diphenyl diphosphite, 4,4'-isopropylidene bis(2-tert-butylphenyl)-bis(nonylphenyl) phosphite, tris(biphenyl) phosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite, tetra(tridecyl)-4,4'-butylene bis(3-methyl-6-tert-butylphenyl) diphosphite, tetra(C12-C15 mixed alkyl)-4,4'-isopropylidene diphenyl diphosphite, 4,4'-isopropylidene bis(2-tert-butylphenyl)-bis(nonylphenyl) phosphite, tris(biphenyl) phosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite, tetra(tridecyl)-4,4'-butylene bis(3-methyl-6-tert-butylphenyl) diphosphite, tetra(C12-C15 mixed alkyl) 15 mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tris (mono- and di-mixed nonylphenyl) phosphite, 4,4'-isopropylidene bis (2-tert-butylphenyl) di (nonylphenyl) phosphite, 9,10-dihydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, hydrogenated 4,4'-isopropylidene diphenyl polyphosphite, bis (octylphenyl) bis (4,4'-butylidene bis (3-methyl-6-tert-butylphenyl)) -1,6-hexanol diphosphite, hexa (tridecyl) - 1,1,3-Tris(2-methyl-4-hydroxy-5-tert-butylphenyl) diphosphite, tris(4,4'-isopropylidenebis(2-tert-butylphenyl)) phosphite, tris(1,3-stearoyloxyisopropyl) phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, 2,2-methylenebis(3-methyl-4,6-di-tert-butylphenyl) 2-ethylhexyl phosphite, tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4,4'-biphenylene diphosphite, and tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphite.

[0424] These may be used alone or in combination of two or more.

[0425] Of the substances listed above, from the viewpoint of further improving the heat aging resistance of the polyamide composition and reducing gas generation, pentaerythritol-type phosphite compounds and / or tris(2,4-di-tert-butylphenyl) phosphite are preferred. As for pentaerythritol-type phosphite compounds, they are not limited to the following substances, but include, for example: 2,6-di-tert-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-methyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-2-ethylhexyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-isodecyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-2-ethylhexyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-isodecyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-lauryl-pentaerythritol diphosphite. Phosphate esters, 2,6-di-tert-butyl-4-methylphenyl-isotridecyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-stearyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-cyclohexyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-benzyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-ethyl cellulose solvent-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-butylcarbitol- Pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-octylphenyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-nonylphenyl-pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-2,6-di-tert-butylphenyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl 2,4-Di-tert-butylphenyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-2,4-di-tert-octylphenyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-2-cyclohexylphenyl-pentaerythritol diphosphite, 2,6-di-tert-pentyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, bis(2,6-di-tert-pentyl-4-methylphenyl)pentaerythritol diphosphite, and bis(2,6-di-tert-octyl-4-methylphenyl)pentaerythritol diphosphite.

[0426] These may be used alone or in combination of two or more.

[0427] Among the pentaerythritol-type phosphite compounds listed above, from the viewpoint of reducing the amount of gas generated by the polyamide composition, preferably, at least one selected from the group consisting of bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-amyl-4-methylphenyl)pentaerythritol diphosphite and bis(2,6-di-tert-octyl-4-methylphenyl)pentaerythritol diphosphite is used, and more preferably, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is used.

[0428] When a phosphorus-containing heat stabilizer is used, the content of the phosphorus-containing heat stabilizer in the polyamide composition is preferably 0.01% to 1% by mass, more preferably 0.1% to 1% by mass, relative to 100% by mass of the polyamide composition. When the content of the phosphorus-containing heat stabilizer is within the above range, the heat aging resistance of the polyamide composition can be further improved and the amount of gas generated can be further reduced.

[0429] As an amine heat stabilizer, it is not limited to the following substances, for example: 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(phenylacetoxy)-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy- 2,2,6,6-Tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4-(ethylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, 4-(cyclohexylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, 4-(phenylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidinyl) carbonate, bis(2,2,6,6-tetramethyl-4-piperidinyl) oxalate, bis(2,2,6,6-tetramethyl-4-piperidinyl) malonate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate α,α'-bis(2,2,6,6-tetramethyl-4-piperidinyl) ester, bis(2,2,6,6-tetramethyl-4-piperidinyl) ester of terephthalate, 1,2-bis(2,2,6,6-tetramethyl-4-piperidinoxy)ethane, α,α'-bis(2,2,6,6-tetramethyl-4-piperidinoxy)p-xylene, bis(2,2,6,6-tetramethyl-4-piperidinyl) ester of toluene-2,4-dicarboxylate, bis(2,2,6,6-tetramethyl-4-piperidinyl) hexamethylene-1,6-dicarboxylate, tris(2,2,6,6-tetramethyl-4-piperidinyl) ester of phenyl-1,3,5-tricarboxylate Condensations of 1,6-tetramethyl-4-piperidinyl ester, tris(2,2,6,6-tetramethyl-4-piperidinyl) ester of phenyl-1,3,4-tricarboxylic acid, 1-[2-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy}butyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]2,2,6,6-tetramethylpiperidin, and condensates of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and β,β,β',β'-tetramethyl-3,9-[2,4,8,10-tetraoxaziro(5,5)undecane]diethanol. These can be used alone or in combination of two or more.

[0430] When an amine heat stabilizer is used, the content of the amine heat stabilizer in the polyamide composition is preferably 0.01% to 1% by mass, more preferably 0.1% to 1% by mass, relative to 100% by mass of the polyamide composition. When the content of the amine heat stabilizer is within the above range, the heat aging resistance of the polyamide composition can be further improved and the amount of gas generated can be further reduced.

[0431] As for metal salts of elements from Groups 3, 4, and 11-14 of the periodic table, there are no restrictions as long as they are salts of metals belonging to these groups. From the perspective of further improving the heat aging resistance of the polyamide composition, copper salts are preferred. Examples of such copper salts include, but are not limited to, copper halides (cuprous iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.), copper acetate, copper propionate, copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate, copper stearate, and copper complexes formed by coordination of copper with chelating agents such as ethylenediamine and ethylenediaminetetraacetic acid. These salts may be used alone or in combination of two or more.

[0432] Among the copper salts listed above, one or more selected from the group consisting of cuprous iodide, cuprous bromide, cupric bromide, cuprous chloride, and cupric acetate are preferred, with cuprous iodide and / or cupric acetate being more preferred. When the more preferred copper salts are used, a polyamide composition can be obtained that has excellent heat aging resistance and can effectively suppress metal corrosion of the screw or barrel during extrusion (hereinafter sometimes referred to as "metal corrosion").

[0433] When a copper salt is used, the content of the copper salt in the polyamide composition is preferably 0.01% to 0.60% by mass, more preferably 0.02% to 0.40% by mass, relative to 100% by mass of the total amount of the polyamide. When the content of the copper salt is within the above range, the heat aging resistance of the polyamide composition can be further improved, and copper precipitation and metal corrosion can be effectively suppressed.

[0434] In addition, from the viewpoint of improving the heat aging resistance of the polyamide composition, the total amount of polyamide is 10 6 The content of the copper element derived from the copper salt is preferably 10 to 2000 parts by mass, more preferably 30 to 1500 parts by mass, and even more preferably 50 to 500 parts by mass.

[0435] Examples of alkali metal and alkaline earth metal halides include, but are not limited to, potassium iodide, potassium bromide, potassium chloride, sodium iodide, sodium chloride, and mixtures thereof. Of these, potassium iodide and / or potassium bromide are preferred, with potassium iodide being more preferred, from the perspective of improving heat aging resistance and suppressing metal corrosion.

[0436] When alkali metal and alkaline earth metal halides are used, the content of the alkali metal and alkaline earth metal halide in the polyamide composition is preferably 0.05 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, relative to 100 parts by mass of the total amount of the polyamide. When the content of the alkali metal and alkaline earth metal halide is within the above range, the heat aging resistance of the polyamide composition can be further improved, and copper precipitation and metal corrosion can be effectively suppressed.

[0437] The stabilizer components described above may be used alone or in combination of two or more. Of these, a mixture of a copper salt and a halide of an alkali metal or alkaline earth metal is preferred from the viewpoint of further improving the heat aging resistance of the polyamide composition.

[0438] The ratio of copper salt to alkali metal and alkaline earth metal halide is preferably 2 / 1 to 40 / 1, more preferably 5 / 1 to 30 / 1, in terms of the molar ratio of halogen to copper (halogen / copper). Within the above range, the heat aging resistance of the polyamide composition can be further improved.

[0439] When the halogen / copper ratio is 2 / 1 or more, copper precipitation and metal corrosion can be effectively suppressed, which is suitable. On the other hand, when the halogen / copper ratio is 40 / 1 or less, mechanical properties (toughness, etc.) are hardly impaired, and corrosion of the screw of the molding machine, etc. can be prevented, which is suitable.

[0440] (Polymers other than polyamide in the above embodiment)

[0441] Examples of polymers other than the aforementioned (1A) aliphatic polyamide and (1B) semi-aromatic polyamide include, but are not limited to, polyesters, liquid crystal polyesters, polyphenylene sulfide, polyphenylene ether, polycarbonate, polyarylate, phenolic resins, and epoxy resins.

[0442] Examples of the polyester include, but are not limited to, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene terephthalate, and polyethylene naphthalate.

[0443] The content of the polymer other than polyamide in the above embodiment is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass, and even more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the total amount of polyamide. By setting the content of the polymer other than polyamide in the polyamide composition of the above embodiment within the above range, a polyamide composition having excellent heat resistance and mold releasability can be obtained.

[0444] Examples of the metal phosphite and / or metal hypophosphite include salts of phosphorous acid, hypophosphorous acid, pyrophosphorous acid, diphosphorous acid, and members of Groups 1 and 2 of the Periodic Table, manganese, zinc, aluminum, ammonia, alkylamines, cycloalkylamines, and diamines. Among these, sodium hypophosphite, calcium hypophosphite, and magnesium hypophosphite are preferred. The inclusion of the metal phosphite and / or metal hypophosphite allows for a polyamide composition having excellent extrudability and molding stability.

[0445] Examples of the phosphite compound include triphenyl phosphite and tributyl phosphite. By adding the phosphite compound, a polyamide composition having excellent extrusion processability and stable molding can be obtained.

[0446] Examples of the phosphite compound include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, triisodecyl phosphite, phenyl diisodecyl phosphite, phenyl ditridecyl phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl- 4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, 4,4'-butylene-bis(3-methyl-6-tert-butylphenyl-di(tridecyl)) phosphite, 1,1,3-tris(2-methyl-4-di(tridecyl)phosphite-5-tert-butyl-phenyl)butane, 4,4'-isopropylidenebis(phenyldialkylphosphite), tris(2,4-di-tert-butylphenyl)phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, etc.

[0447] As the phosphite compound, one type of phosphite compound may be used, or two or more types of phosphite compounds may be used in combination.

[0448] The polyamide composition of the above embodiment may further contain additives commonly used in polyamides, such as colorants such as pigments and dyes (including color masterbatches), flame retardants, fibrillating agents, fluorescent brighteners, plasticizers, antioxidants, ultraviolet absorbers, antistatic agents, flowability improvers, spreaders, elastomers, etc., within a range that does not impair the purpose of the above embodiment.

[0449] When the polyamide composition of the above embodiment contains other raw materials that may be contained in the polyamide composition as described above, the content of the other raw materials varies depending on the type of the other raw materials, the application of the polyamide composition, etc., and is therefore not particularly limited as long as the purpose of the above embodiment is not impaired.

[0450] [Method for manufacturing polyamide compositions]

[0451] As for the manufacturing method of the polyamide composition described above, there are no particular limitations as long as the manufacturing method includes a step of melt-blending the raw material components containing the above-described (1A) aliphatic polyamide and (1B) semi-aromatic polyamide. For example, a method that includes a step of melt-blending the raw material components containing the above-described polyamide using an extruder, and setting the set temperature of the extruder to below the melting peak temperature Tm2+30°C of the above-described polyamide composition.

[0452] Examples of methods for melt-kneading the raw material components containing polyamide include a method in which the polyamide is mixed with other raw materials using a drum mixer, a Henschel mixer, or the like, and the mixture is supplied to a melt kneader for kneading; and a method in which other raw materials are added to the polyamide in a molten state in a single-screw or twin-screw extruder through a side feed.

[0453] In the method of supplying the components constituting the polyamide composition to the melt-kneader, all the components may be supplied at once to the same supply port, or the components may be supplied separately from different supply ports.

[0454] The melt kneading temperature is preferably about 250° C. to 350° C. in terms of resin temperature.

[0455] The preferred melt mixing time is about 0.25 minutes to about 5 minutes.

[0456] There are no particular restrictions on the apparatus used for melt mixing; known apparatus such as single-screw or twin-screw extruders, Banbury mixers, and mixing rolls can be used.

[0457] [Physical Properties of Polyamide Composition]

[0458] The molecular weight, melting point Tm2, ​​crystallization enthalpy ΔH, and tan δ peak temperature of the polyamide composition of the above embodiment can be specifically measured by the methods described in the examples described below.

[0459] As an indicator of the molecular weight of the polyamide composition, Mw (weight-average molecular weight) can be used. The Mw (weight-average molecular weight) of the polyamide composition is 15,000 to 35,000, preferably 17,000 to 35,000, more preferably 20,000 to 35,000, further preferably 22,000 to 34,000, even more preferably 24,000 to 33,000, and most preferably 25,000 to 32,000. With an Mw (weight-average molecular weight) within the above range, polyamides with excellent mechanical properties, particularly water absorption stiffness, thermal stiffness, and flowability, can be obtained. Furthermore, polyamide compositions containing components such as inorganic fillers have excellent surface appearance.

[0460] Examples of methods for controlling the Mw of the polyamide composition to fall within the above range include using (1A) aliphatic polyamide and (1B) semi-aromatic polyamide having Mw set within the above range.

[0461] In addition, the measurement of Mw (weight average molecular weight) can be measured using GPC (gel permeation chromatography) as described in the following examples.

[0462] The total content of polyamides with a number average molecular weight (Mn) of 500 or more and 2000 or less, relative to the total amount of polyamide in the polyamide composition, is preferably 0.5% by mass or more and less than 2.5% by mass, more preferably 0.8% by mass or more and less than 2.5% by mass, further preferably 1.0% by mass or more and less than 2.5% by mass, even more preferably 1.2% by mass or more and less than 2.5% by mass, and most preferably 1.4% by mass or more and less than 2.5% by mass. By having a content of 0.5% by mass or more of polyamides with a number average molecular weight (Mn) of 500 or more and 2000 or less, excellent flowability and a superior surface appearance of the polyamide composition containing components such as inorganic fillers are achieved. Furthermore, a content of less than 2.5% by mass helps to suppress gas generation during molding.

[0463] As a method for controlling the total content of polyamides with a number average molecular weight Mn of 500 or more and 2000 or less within the above range, (1B) the molecular weight of the semi-aromatic polyamide is very important, and the weight average molecular weight Mw is preferably 10000 to 25000.

[0464] It should be noted that the total content of polyamide with a number average molecular weight Mn of 500 or more and less than 2000 relative to the total mass of polyamide was determined by elution curves under the test conditions described in the examples below using GPC.

[0465] During GPC measurement, if the composition containing (1A) aliphatic polyamide and (1B) semi-aromatic polyamide contains other components soluble in the solvent for dissolving the polyamide resin, the other components are extracted and removed using a solvent in which the polyamide is insoluble but the other components are soluble, and then GPC measurement is performed. Furthermore, if an inorganic filler or the like is insoluble in the solvent for dissolving the polyamide, it is dissolved in the solvent for dissolving the polyamide composition, and then the insoluble matter is removed by filtration, and then GPC measurement is performed.

[0466] The difference between the weight average molecular weight Mw(1A) of the aliphatic polyamide (1A) and the weight average molecular weight Mw(1B) of the semi-aromatic polyamide (1B) {Mw(1A)-Mw(1B)} is preferably 2000 or greater, more preferably 5000 or greater, further preferably 8000 or greater, even further preferably 10000 or greater, and most preferably 12000 or greater. When {Mw(1A)-Mw(1B)} is 2000 or greater, the semi-aromatic polyamide (1B) forms micron-sized domains, enabling a composition having excellent water absorption rigidity and hot rigidity.

[0467] The molecular weight distribution of the polyamide composition of the above embodiment is measured using Mw (weight average molecular weight) / Mn (number average molecular weight) as an index.

[0468] The polyamide composition of the above embodiment preferably has an Mw (weight average molecular weight) / Mn (number average molecular weight) ratio of 2.4 or less, more preferably 1.7 to 2.3, even more preferably 1.8 to 2.2, and even more preferably 1.9 to 2.1. The lower limit of the molecular weight distribution is 1.0. By ensuring that the Mw (weight average molecular weight) / Mn (number average molecular weight) ratio falls within the above range, a polyamide composition having excellent flowability and other properties can be obtained. Furthermore, polyamide compositions containing components such as inorganic fillers exhibit excellent surface appearance.

[0469] As a method for controlling the Mw (weight average molecular weight) / Mn (number average molecular weight) of the polyamide composition within the above range, it is important to control the Mw (weight average molecular weight) / Mn (number average molecular weight) of the (1B) semi-aromatic polyamide within the above range.

[0470] When a polyamide composition contains aromatic compound units in its molecular structure, its molecular weight distribution (Mw / Mn) tends to increase with increasing molecular weight. A high molecular weight distribution indicates a high proportion of polyamide molecules with a three-dimensional molecular structure. This facilitates further three-dimensional molecular structure formation during high-temperature processing, reducing flowability and deteriorating the surface appearance of polyamide compositions containing components such as inorganic fillers.

[0471] In the above embodiment, the Mw (weight average molecular weight) / Mn (number average molecular weight) of the polyamide composition is calculated using Mw (weight average molecular weight) and Mn (number average molecular weight) obtained by GPC (gel permeation chromatography) as described in the following Examples.

[0472] The melting point Tm2 of the polyamide composition is preferably 200°C or higher, more preferably 220°C to 270°C, further preferably 230°C to 265°C, further preferably 240°C to 260°C, and particularly preferably 250°C to 260°C.

[0473] When the melting point Tm2 of the polyamide composition is 200° C. or higher, a polyamide composition having more excellent rigidity (hot rigidity) and the like during use at high temperatures tends to be obtained.

[0474] Furthermore, when the melting point Tm2 of the polyamide composition is 270° C. or lower, thermal decomposition of the polyamide composition during melt processing such as extrusion and molding tends to be further suppressed.

[0475] From the perspective of mechanical properties, particularly water absorption rigidity and hot rigidity, the crystallization enthalpy ΔH of the polyamide composition is preferably 10 J / g or greater, more preferably 14 J / g or greater, even more preferably 18 J / g or greater, and even more preferably 20 J / g or greater. The upper limit of the crystallization enthalpy ΔH is not particularly limited; a higher value is preferred.

[0476] Examples of methods for controlling the crystallization enthalpy ΔH of the polyamide composition within the above range include controlling the mixing ratio of (1A) aliphatic polyamide to (1B) semi-aromatic polyamide within the above range.

[0477] Examples of an apparatus for measuring the melting point Tm2 and the crystallization enthalpy ΔH of the polyamide composition include Diamond-DSC manufactured by PERKIN-ELMER.

[0478] The tan δ peak temperature of the polyamide composition is 90° C. or higher, more preferably 100° C. or higher, further preferably 110° C. or higher, and even more preferably 120° C. or higher.

[0479] The tan δ peak temperature of the polyamide composition is preferably 150° C. or lower, more preferably 140° C. or lower, and even more preferably 130° C. or lower.

[0480] When the polyamide composition has a tan δ peak temperature of 90°C or higher, it tends to produce a polyamide composition having excellent water absorption rigidity and hot rigidity. Furthermore, when the polyamide composition has a tan δ peak temperature of 150°C or lower, the polyamide composition containing components such as inorganic fillers exhibits excellent surface appearance.

[0481] Examples of methods for controlling the tan δ peak temperature of the polyamide composition within the above range include controlling the mixing ratio of (1A) aliphatic polyamide to (1B) semi-aromatic polyamide within the above range.

[0482] The polyamide composition of the above embodiment preferably has a crystallization peak temperature Tc (°C) obtained when cooled at 20°C / min, which is 160°C to 240°C.

[0483] The crystallization peak temperature Tc (°C) of the polyamide composition is more preferably 170°C to 230°C, further preferably 180°C to 225°C, further preferably 190°C to 220°C, and particularly preferably 200°C to 215°C.

[0484] When the polyamide composition has a crystallization peak temperature Tc (°C) of 160°C or higher, a polyamide composition having excellent mold release properties during molding can be obtained. Furthermore, when the polyamide composition has a crystallization peak temperature Tc (°C) of 240°C or lower, the polyamide composition containing components such as inorganic fillers has excellent surface appearance.

[0485] The melting point and crystallization peak temperature Tc of the polyamide composition used in the above embodiment can be measured according to JIS-K7121 by the method described in Examples below.

[0486] Examples of measuring instruments for the crystallization peak temperature Tc include the Diamond-DSC manufactured by PERKIN-ELMER. Examples of methods for controlling the crystallization peak temperature Tc of the polyamide within the aforementioned range include methods for controlling the mixing ratio of (1A) aliphatic polyamide to (1B) semi-aromatic polyamide within the aforementioned range.

[0487] In the polyamide composition of the above embodiment, the ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} is preferably 0.25 or more and less than 0.4, more preferably 0.35 or more and less than 0.4, and even more preferably 0.25 or more and less than 0.35. When the ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount is 0.25 or more, corrosion of the extruder and molding machine can be suppressed. When the ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount is less than 0.4, the composition can be made to exhibit excellent color change resistance to heat and light.

[0488] The surface gloss value of the polyamide composition of the above embodiment is preferably 50 or higher, more preferably 55 or higher, and even more preferably 60 or higher. When the polyamide composition has a surface gloss value of 50 or higher, it can be suitably used as a molding material for various parts such as those for automobiles, electrical and electronic applications, industrial materials, and daily and household products.

[0489] [Molded products]

[0490] The molded article of the above embodiment is obtained by molding the above polyamide composition.

[0491] The molded article of the above embodiment is excellent in mechanical properties, particularly water absorption rigidity, hot rigidity, flowability, and surface appearance.

[0492] The molded article of the above embodiment can be obtained by molding the above polyamide composition using a known molding method, for example.

[0493] As well-known molding methods, there are not limited to the following methods, for example, commonly known plastic molding methods such as press molding, injection molding, gas-assisted injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding and melt spinning can be listed.

[0494] (use)

[0495] The molded article of the above embodiment is obtained from the above-mentioned polyamide composition and therefore has excellent moldability, mechanical strength, low water absorption, and surface appearance. Therefore, the molded article of the above embodiment can be suitably used as various components, such as sliding parts, automotive parts, electrical and electronic components, household appliance parts, OA (Office Automation) equipment parts, portable device parts, industrial equipment parts, daily necessities, and household goods, and can also be suitably used for extrusion applications. The molded article of the above embodiment is preferably used as an automotive part, electronic component, household appliance part, OA equipment part, or portable device part.

[0496] The automobile parts are not particularly limited, and examples thereof include intake system parts, cooling system parts, fuel system parts, interior parts, exterior parts, and electrical equipment parts.

[0497] There are no particular limitations on the components of the automobile air intake system, and examples thereof include intake manifolds, intercooler inlets, exhaust pipe covers, inner bushings, bearing retainers, engine mounts, engine top covers, resonators, and throttle bodies.

[0498] The automobile cooling system components are not particularly limited, and examples thereof include a chain cover, a thermostat housing, a drain pipe, a radiator tank, an alternator, and a water pipe.

[0499] There are no particular limitations on the automotive fuel system components, and examples thereof include fuel delivery pipes and gasoline tank housings.

[0500] There are no particular limitations on the automotive interior parts, and examples thereof include instrument panels, console boxes, glove boxes, steering wheels, and interior trim.

[0501] The automobile exterior parts are not particularly limited, and examples thereof include moldings, lamp housings, front grilles, fenders, side bumpers, rearview mirror brackets, and roof rails.

[0502] The automotive electrical equipment parts are not particularly limited, and examples thereof include connectors or harness connectors, motor parts, lamp sockets, sensor-mounted switches, and combination switches.

[0503] There are no particular limitations on electrical and electronic components, and examples include connectors, reflectors for light-emitting devices, switches, relays, printed wiring boards, electronic component housings, sockets, noise filters, bobbins, and motor end caps. Reflectors for light-emitting devices can be used in a wide range of applications, including light-emitting diodes (LEDs), photodiodes including optical semiconductors such as laser diodes (LDs), charge-coupled devices (CCDs), and complementary metal oxide semiconductors (CMOS) in addition to light-emitting diodes (LEDs).

[0504] The portable device component is not particularly limited, and examples thereof include housings and structures of mobile phones, smartphones, personal computers, portable game devices, digital cameras, and the like.

[0505] The industrial equipment parts are not particularly limited, and examples thereof include gears, cams, insulating blocks, valves, power tool parts, agricultural machine parts, and engine covers.

[0506] There are no particular limitations on daily necessities and household items, and examples thereof include buttons, food containers, and office furniture.

[0507] The extrusion application is not particularly limited, and the extrusion can be used for, for example, films, sheets, filaments, tubes, rods, and hollow molded products.

[0508] Among these various applications, molded articles obtained from the polyamide composition of the embodiment described above are particularly suitable for exterior structural materials. Exterior structural materials refer to mechanical parts or structural components that require both surface workability (e.g., wrinkle workability, high surface gloss, etc.) and relatively high strength and rigidity. Examples include furniture products such as table legs, chair legs, seats, cabs, and truck parts; office automation equipment such as notebook computer cases; automotive parts such as rearview mirror brackets, wheel rims, wheel covers, wipers, motor fans, seat lock parts, gears, and lampshades; electrical equipment such as pulleys, gears, and heater housings; automotive parts for other fields such as rims, spokes, saddles, saddle posts, handles, brackets, and load platforms; valve housings, nails, screws, bolts, and nuts.

[0509] Furthermore, molded articles obtained from the polyamide composition of the above embodiment have excellent surface appearance and are therefore preferably used as molded articles having a coating film formed on the surface of the molded article. The coating film can be formed by any known method, and for example, spray coating, electrostatic coating, or the like can be used. Furthermore, the coating material used for the coating is not particularly limited, as long as it is a known coating material, and melamine-crosslinked polyester polyol resin coatings, acrylic urethane coatings, and the like can be used.

[0510] The polyamide composition of the embodiment described above is suitable as a component material for automobiles due to its excellent mechanical strength, toughness, heat resistance, and vibration fatigue resistance. Furthermore, due to its excellent sliding properties, it is particularly suitable as a component material for gears and bearings. Furthermore, due to its excellent mechanical strength, toughness, and heat resistance, it is suitable as a component material for electrical and electronic applications.

[0511] Methods 2-1 to 2-2

[0512] [Polyamide composition]

[0513] The polyamide composition of the 2-1 embodiment of the present invention contains:

[0514] (2A) an aliphatic polyamide comprising a diamine and a dicarboxylic acid;

[0515] (2B) a semi-aromatic polyamide comprising a dicarboxylic acid unit and a diamine unit, wherein the dicarboxylic acid unit comprises at least 75 mol % of isophthalic acid and the diamine unit comprises a diamine having 4 to 10 carbon atoms;

[0516] (2C) pigments;

[0517] (2D1) flame retardants; and

[0518] (2D2) flame retardant additives,

[0519] in,

[0520] The polyamide composition has a tan δ peak temperature of 90°C or higher, and

[0521] The weight average molecular weight Mw of the polyamide composition is 10,000≤Mw≤40,000.

[0522] In the above embodiment, "polyamide" refers to a polymer having an amide (-NHCO-) ​​bond in the main chain. Hereinafter, (2A) aliphatic polyamide and (2B) semi-aromatic polyamide will be described in detail.

[0523] ((2A) Aliphatic polyamide)

[0524] (2A) The aliphatic polyamide is as described in relation to "(1A) the aliphatic polyamide" in the above-mentioned embodiment 1-1.

[0525] ((2B) semi-aromatic polyamide)

[0526] The (2B) semi-aromatic polyamide is the same as described in relation to the "(1B) semi-aromatic polyamide" in the above-mentioned embodiment 1-1 except for the following points.

[0527] The (2B) semi-aromatic polyamide used in the above method is a polyamide containing (2B-a) dicarboxylic acid units and (2B-b) diamine units, wherein the (2B-a) dicarboxylic acid units contain at least 75 mol% isophthalic acid, and the (2B-b) diamine units contain diamines with 4 or more and 10 or fewer carbon atoms.

[0528] The total amount of the isophthalic acid unit and the diamine unit with 4 or more and 10 or less carbon atoms, relative to 100 mol% of all the constituent units of (2B) polyamide, preferably contains at least 50 mol%, more preferably 80 mol% to 100 mol%, further preferably 90 mol% to 100 mol%, and most preferably 100 mol%.

[0529] (lactam unit and / or aminocarboxylic acid unit)

[0530] The lactam unit and / or the aminocarboxylic acid unit are as described in the above embodiment 1-1.

[0531] (Capping agent)

[0532] The ends of the polyamide used in the above embodiment can be capped with a known capping agent.

[0533] The blocking agent is as described in the above embodiment 1-1.

[0534] (Production Method of Polyamide)

[0535] The method for producing polyamide is the same as described in the above embodiment 1-1.

[0536] (Polyamide polymer ends)

[0537] For the polymer ends of polyamide, as described in method 1-1 above.

[0538] ((2A) Characteristics of Aliphatic Polyamides)

[0539] The properties of the aliphatic polyamide (2A) are the same as those described in the "properties of the aliphatic polyamide (1A)" in the above-mentioned embodiment 1-1.

[0540] ((2B) Characteristics of semi-aromatic polyamide)

[0541] The properties of the (2B) semi-aromatic polyamide are the same as those described in the "properties of the (1B) semi-aromatic polyamide" in the above-mentioned embodiment 1-1.

[0542] ((2C) Pigment)

[0543] The polyamide composition of the above embodiment contains a pigment.

[0544] Pigments are not particularly limited, and examples include dyes such as aniline black, pigments such as zinc sulfide, zinc oxide, titanium oxide, and carbon black; metal particles such as aluminum, colored aluminum, nickel, tin, copper, gold, silver, platinum, iron oxide, stainless steel, and titanium; and metallic pigments such as mica pearlescent pigments, colored graphite, colored glass fibers, and colored flake glass. Among these, zinc sulfide (ZnS) and zinc oxide (ZnO) are preferred white pigments due to their mechanical properties such as toughness, strength, and rigidity, as well as their balance between flame retardancy and color.

[0545] ((2D1) flame retardant)

[0546] As for the (2D1) flame retardant used in the above method, there are no particular restrictions as long as it contains halogen elements. Examples include chlorine-containing flame retardants and bromine-containing flame retardants.

[0547] These (2D1) flame retardants can be used in one or in combination of two or more.

[0548] Examples of the chlorine-containing flame retardant include chlorinated paraffin, chlorinated polyethylene, bis(hexachlorocyclopentadiene)cyclooctane (Dechlorane Plus 25 <registered trademark> manufactured by Occidental Chemical), and chlorohydride.

[0549] Examples of bromine-containing flame retardants include hexabromocyclododecane (HBCD), decabromodiphenyl ether (DBDPO), octabromodiphenyl ether, tetrabromobisphenol A (TBBA), bis(tribromophenoxy)ethane, bis(pentabromophenoxy)ethane (BPBPE), tetrabromobisphenol A epoxy resin (TBBA epoxy), tetrabromobisphenol A carbonate (TBBA-PC), ethylene (bis(tetrabromophthalate))imide (EBTBPI), ethylene bispentabromobiphenyl, tris(tribromophenoxy)triazine (TTBPTA), and bis(dibromopropyl)tetrabromobisphenol A (DBP-TBBA). , bis(dibromopropyl)tetrabromobisphenol S (DBP-TBBS), brominated polyphenylene ether (including poly(di)bromophenylene ether, etc.) (BrPPE), brominated polystyrene (including polydibromostyrene, polytribromostyrene, cross-linked brominated polystyrene, etc.) (BrPS), brominated cross-linked aromatic polymers, brominated epoxy resins, brominated phenoxy resins, brominated styrene-maleic anhydride polymers, tetrabromobisphenol S (TBBS), tris(tribromoneopentyl) phosphate (TTBNPP), polybromotrimethylphenyl indane (PBPI) and tris(dibromopropyl)-isocyanurate (TDBPIC), etc.

[0550] From the viewpoint of suppressing the generation of corrosive gases during melt processing such as extrusion and molding, as well as from the viewpoint of flame retardancy, toughness, and mechanical properties such as rigidity, preferred flame retardants (2D1) are brominated polyphenylene ethers (including poly(di)bromophenylene ether, etc.) and brominated polystyrenes (including polydibromostyrene, polytribromostyrene, and cross-linked brominated polystyrene, etc.), and more preferred are brominated polystyrene.

[0551] The method for producing brominated polystyrene is not particularly limited. Examples include methods of producing polystyrene by polymerizing styrene monomers and then brominating the benzene rings of the polystyrene; or producing brominated styrene monomers (bromostyrene, dibromostyrene, tribromostyrene, etc.) by polymerizing brominated styrene monomers.

[0552] The bromine content of the brominated polystyrene is preferably 55% to 75% by mass. By setting the bromine content to 55% or greater, the required bromine content for flame retardancy can be achieved with a relatively small amount of brominated polystyrene, resulting in a polyamide composition that exhibits excellent heat resistance, fluidity, toughness, low water absorption, and rigidity, as well as excellent flame retardancy, without compromising the properties of the polyamide copolymer. Furthermore, by setting the bromine content to 75% or less, thermal decomposition during melt processing such as extrusion and molding is less likely to occur, suppressing gas generation and, in turn, providing a polyamide composition with excellent resistance to heat discoloration.

[0553] ((2D2) flame retardant additive)

[0554] The polyamide composition of the above embodiment can be made into a polyamide composition having further excellent flame retardancy by containing the flame retardant auxiliary agent (2D2).

[0555] As for the (2D2) flame retardant auxiliary agent used in the above method, there is no particular limitation, and examples thereof include: antimony oxides such as antimony trioxide (Sb2O3), antimony tetroxide, antimony pentoxide, and sodium antimonate; tin oxides such as tin monoxide and tin dioxide; iron oxides such as ferric oxide and γ-iron oxide; and metal oxides such as zinc oxide, zinc borate, calcium oxide, aluminum oxide (aluminum oxide), aluminum oxide (boehmite), silicon oxide (silicon dioxide), titanium oxide, zirconium oxide, manganese oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, nickel oxide, copper oxide, and tungsten oxide; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; metal powders such as aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, tin, antimony, nickel, copper, and tungsten; metal carbonates such as zinc carbonate, calcium carbonate, magnesium carbonate, and barium carbonate; metal borates such as magnesium borate, calcium borate, and aluminum borate; and polysiloxanes, etc.

[0556] These (2D2) flame retardant auxiliary agents may be used alone or in combination of two or more.

[0557] As the flame retardant auxiliary agent (2D2) used in the above-mentioned method, from the viewpoint of flame retardancy effect, preferred are antimony oxides such as antimony trioxide, antimony tetroxide, antimony pentoxide, and sodium antimonate; magnesium hydroxide; tin oxides such as tin monoxide and tin dioxide; iron oxides such as ferric oxide and γ-iron oxide; zinc oxide and zinc borate, etc., more preferred are antimony oxides such as antimony trioxide, antimony tetroxide, and antimony pentoxide; magnesium hydroxide and zinc borate, further preferred are antimony oxides and / or magnesium hydroxide, and particularly preferred are antimony trioxide and magnesium hydroxide.

[0558] To improve the flame retardant effect, it is preferable to use (2D2) flame retardant additives with an average particle size of 0.01μm to 10μm.

[0559] The average particle size can be determined using a laser diffraction scattering particle size distribution measuring device or a precision particle size distribution measuring device.

[0560] ((2E) Polymer containing an α,β-unsaturated dicarboxylic acid anhydride in a structural unit)

[0561] The polyamide composition of the above embodiment may further contain (2E) a polymer containing an α,β-unsaturated dicarboxylic acid anhydride in its structural units. By containing (2E) a polymer containing an α,β-unsaturated dicarboxylic acid anhydride in its structural units, a polyamide composition having excellent mechanical properties such as toughness and rigidity, as well as flame retardancy, can be obtained.

[0562] Examples of the polymer (2E) containing an α,β-unsaturated dicarboxylic acid anhydride in a structural unit used in the above embodiment include polymers containing an α,β-unsaturated dicarboxylic acid anhydride as a copolymerization component and polymers modified with an α,β-unsaturated dicarboxylic acid anhydride.

[0563] Examples of the α,β-unsaturated dicarboxylic acid anhydride include compounds represented by the following general formula.

[0564]

[0565] In the above general formula, R 1 and R 2 Each independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms. 1 and R 2 They may be the same or different from each other. 1 and R 2 The same as each other.

[0566] As R 1 and R 2 As for the alkyl group having 1 to 3 carbon atoms, examples thereof include methyl, ethyl, propyl, isopropyl, etc. 1 and R 2 As for the group, a hydrogen atom or a methyl group is preferred, and a hydrogen atom is more preferred.

[0567] Examples of the α,β-unsaturated dicarboxylic acid anhydride include maleic anhydride and methylmaleic anhydride, and maleic anhydride is preferred.

[0568] Examples of the polymer containing an α,β-unsaturated dicarboxylic acid anhydride as a copolymerization component include copolymers of an aromatic vinyl compound and an α,β-unsaturated dicarboxylic acid anhydride.

[0569] Examples of polymers modified with an α,β-unsaturated dicarboxylic acid anhydride include polyphenylene ether and polypropylene modified with an α,β-unsaturated dicarboxylic acid anhydride. Maleic anhydride-modified polyphenylene ether is particularly preferred.

[0570] As the polymer containing an α,β-unsaturated dicarboxylic acid anhydride as a copolymerization component, a copolymer of an aromatic vinyl compound and an α,β-unsaturated dicarboxylic acid anhydride is preferred from the viewpoint of improving the efficiency of flame retardancy (expression with a small addition amount).

[0571] Examples of the aromatic vinyl compound used in the above embodiment include compounds represented by the following general formula.

[0572]

[0573] In the above general formula, R 3 and R 4 Each independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms, and k is an integer of 1 to 5.

[0574] Examples of the aromatic vinyl compound include styrene, α-methylstyrene, and p-methylstyrene, and styrene is preferred.

[0575] In the above embodiment, when the polymer containing an α,β-unsaturated dicarboxylic acid anhydride in its constituent units contains an aromatic vinyl compound component, it is believed that the aromatic vinyl compound component has affinity with the flame retardant (2D1) (brominated polystyrene, etc.), and the α,β-unsaturated dicarboxylic acid anhydride portion has affinity or reaction with the semi-aromatic polyamide (2B), thereby contributing to the dispersion of the flame retardant (2D1) in the polyamide matrix, thereby enabling the flame retardant to be finely dispersed.

[0576] Regarding the ratio of the aromatic vinyl compound component to the α,β-unsaturated dicarboxylic anhydride component in the copolymer of an aromatic vinyl compound and an α,β-unsaturated dicarboxylic anhydride, from the viewpoints of flame retardancy, fluidity, thermal decomposition resistance, etc., the aromatic vinyl compound component is preferably 50% to 99% by mass, and the α,β-unsaturated dicarboxylic anhydride component is preferably 1% to 50% by mass. The ratio of the α,β-unsaturated dicarboxylic anhydride component is more preferably 5% to 20% by mass, and even more preferably 8% to 15% by mass.

[0577] By setting the proportion of the α,β-unsaturated dicarboxylic acid anhydride component to 1% by mass or greater, a polyamide composition having excellent mechanical properties such as toughness and rigidity, as well as flame retardancy, can be obtained. Furthermore, by setting the proportion of the α,β-unsaturated dicarboxylic acid anhydride component to 50% by mass or less, degradation of the polyamide composition caused by the α,β-unsaturated dicarboxylic acid anhydride can be prevented.

[0578] The polymer modified with an α,β-unsaturated dicarboxylic acid anhydride is preferably a polyphenylene ether resin or a polypropylene resin modified with an α,β-unsaturated dicarboxylic acid anhydride. The content of the polymer modified with an α,β-unsaturated dicarboxylic acid anhydride is preferably from 0.05% to 5% by mass relative to 100% by mass of the polyamide composition.

[0579] ((2F) Filling material)

[0580] The polyamide composition of the above embodiment may further contain a filler (2F). By containing a filler (2F), a polyamide composition having more excellent mechanical properties such as toughness and rigidity can be obtained.

[0581] The filler (2F) is the same as described in the above-mentioned embodiment 1-1 regarding the "(1C) inorganic filler".

[0582] (Content of each ingredient)

[0583] The content of the (2C) pigment in the polyamide composition of the above embodiment is preferably from 0.5% by mass to 5% by mass, more preferably from 3% by mass to 100% by mass of the polyamide composition. In particular, from the viewpoints of color tone and mechanical properties (particularly mechanical strength), it is preferred that the (2C) pigment be a white pigment, and the content of the white pigment be from 0.5% by mass to 5% by mass, relative to 100% by mass of the polyamide composition.

[0584] The content of the flame retardant (2D1) in the polyamide composition of the embodiment described above is preferably 0.1% by mass to 30% by mass, more preferably 5% by mass to 20% by mass, and even more preferably 5% by mass to 15% by mass, relative to 100% by mass of the polyamide composition.

[0585] The content of the (2D2) flame retardant additive in the polyamide composition is preferably 0.1% to 10% by mass, more preferably 1% to 10% by mass, relative to 100% by mass of the polyamide composition. By containing the (2D2) flame retardant additive in the above range, a polyamide composition having more excellent flame retardancy can be obtained. In addition, by setting the content of the (2D2) flame retardant additive to 10% by mass or less, the viscosity during melt processing can be controlled within an appropriate range, and the increase in torque during extrusion, the decrease in moldability during molding, and the deterioration of the appearance of the molded product can be suppressed. In addition, a polyamide composition having excellent toughness, etc. can be obtained without damaging the properties of the polyamide having excellent mechanical properties such as toughness and rigidity.

[0586] By setting the content of the flame retardant auxiliary (2D2) to 0.1% by mass or greater, a polyamide composition with excellent flame retardancy can be obtained. Furthermore, by setting the content of the flame retardant (2D1) to 15% by mass or less, the generation of decomposition gases during melt kneading, the reduction in fluidity during molding, and the adhesion of contaminants to the molding die can be suppressed. Furthermore, the deterioration of mechanical properties such as toughness and rigidity, as well as the appearance of the molded product, can be suppressed.

[0587] A particularly preferred combination is: (2D1) the flame retardant is brominated polystyrene, and the content of brominated polystyrene is greater than 6 mass% and less than 15 mass% relative to 100 mass% of the polyamide composition, and (2D2) the flame retardant auxiliary is antimony trioxide (Sb2O3), and the content of antimony trioxide (Sb2O3) is greater than 0.1 mass% and less than 4 mass% relative to 100 mass% of the polyamide composition.

[0588] The content of the polymer (2E) containing an α,β-unsaturated dicarboxylic acid anhydride as a constituent unit in the polyamide composition is preferably 0.1% to 20% by mass, more preferably 0.5% to 20% by mass, even more preferably 1% to 15% by mass, and particularly preferably 2% to 10% by mass, relative to 100% by mass of the polyamide composition. By including the polymer (2E) containing an α,β-unsaturated dicarboxylic acid anhydride as a constituent unit within this range, the microdispersion effect of the flame retardant (2D1) in the polyamide composition due to compatibilization can be enhanced, resulting in a polyamide composition with excellent flame retardancy and strength. Furthermore, by setting the content of the polymer (2E) containing an α,β-unsaturated dicarboxylic acid anhydride as a constituent unit to 20% by mass or less, a polyamide composition with excellent strength and other properties can be obtained without impairing the properties of the polyamide, which has excellent mechanical properties such as toughness and rigidity.

[0589] The content of the (2F) filler in the polyamide composition is preferably 1% by mass to 80% by mass, more preferably 10% by mass to 70% by mass, further preferably 30% by mass to 70% by mass, further preferably 30% by mass to 60% by mass, and most preferably 40% by mass to 60% by mass, relative to 100% by mass of the polyamide composition.

[0590] By containing the (2F) filler within the above range, the mechanical properties of the polyamide composition such as strength and rigidity are favorably improved. Furthermore, by setting the content of the inorganic filler to 70% by mass or less, a polyamide composition having excellent moldability can be obtained.

[0591] In the above embodiment, the total content of the pigment (2C), the flame retardant (2D1), the flame retardant auxiliary (2D2), the polymer containing an α,β-unsaturated dicarboxylic acid anhydride in its structural units (2E), and the filler (2F) is preferably 10% to 100% by mass relative to 100% by mass of the polyamide composition. It is more preferably 10% to 90% by mass, even more preferably 30% to 80% by mass, and even more preferably 40% to 80% by mass. When the total content is 10% by mass or greater, a polyamide composition having excellent strength, rigidity, flame retardancy, and excellent processability, and having an appropriate melt viscosity, can be obtained.

[0592] The polyamide composition of the above embodiment may contain additives commonly used in polyamides, such as moldability improvers, degradation inhibitors, nucleating agents, stabilizers, and polymers other than the polyamide of the above embodiment, within a range not impairing the purpose of the above embodiment.

[0593] The content of the additives varies depending on the type of the additives, the application of the polyamide composition, etc., and is not particularly limited as long as it is within a range that does not impair the purpose of the above-mentioned embodiment.

[0594] (Moldability Improver)

[0595] A moldability improver may be added to the polyamide composition of the above embodiment as needed within a range that does not impair the purpose of the above embodiment. The moldability improver is the same as described above regarding the "lubricant" in the first embodiment.

[0596] (Degradation inhibitor)

[0597] A degradation inhibitor may be added to the polyamide composition of the above embodiment as needed for the purpose of preventing thermal degradation and discoloration during heating and improving heat aging resistance and weather resistance within a range that does not impair the purpose of the above embodiment.

[0598] The degradation inhibitor is not particularly limited, and examples thereof include copper compounds such as copper acetate and cuprous iodide; phenolic stabilizers such as hindered phenol compounds; phosphite stabilizers; hindered amine stabilizers; triazine stabilizers; benzotriazole stabilizers, benzophenone stabilizers, cyanoacrylate stabilizers, salicylate stabilizers; and sulfur-containing stabilizers.

[0599] Examples of the copper compound include copper acetate and cuprous iodide. Examples of the phenol stabilizer include hindered phenol compounds.

[0600] These degradation inhibitors may be used alone or in combination of two or more.

[0601] (Nucleating Agent)

[0602] The nucleating agent is as described in the above embodiment 1-1.

[0603] (Stabilizer)

[0604] The stabilizer is as described in the above embodiment 1-1.

[0605] (Other resins)

[0606] To the polyamide composition of the above embodiment, other resins may be added as needed within a range that does not impair the purpose of the above embodiment.

[0607] Such a resin is not particularly limited, and examples thereof include thermoplastic resins and rubber components described below.

[0608] Examples of thermoplastic resins include polystyrene resins such as atactic polystyrene, isotactic polystyrene, syndiotactic polystyrene, AS (acrylonitrile-styrene copolymer) resin, and ABS (acrylonitrile-butadiene-styrene copolymer) resin; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyamides other than the polyamides used in the above-mentioned embodiments; polyether resins such as polycarbonate, polyphenylene ether, polysulfone, and polyethersulfone; condensation resins such as polyphenylene sulfide and polyoxymethylene; acrylic resins such as polyacrylic acid, polyacrylate, and polymethyl methacrylate; polyolefin resins such as polyethylene, polypropylene, polybutene, and ethylene-propylene copolymer; halogen-containing vinyl compound resins such as polyvinyl chloride and polyvinylidene chloride; phenolic resins; epoxy resins, etc.

[0609] These thermoplastic resins may be used alone or in combination of two or more.

[0610] Examples of the rubber component include natural rubber, polybutadiene, polyisoprene, polyisobutylene, chloroprene rubber, polysulfide rubber, thio rubber, acrylic rubber, polyurethane rubber, silicone rubber, epichlorohydrin rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene-ethylene The present invention relates to a core-shell rubber comprising: a butadiene-propylene random copolymer, a styrene-ethylene-butene random copolymer, an ethylene-propylene copolymer (EPR), an ethylene-(1-butene) copolymer, an ethylene-(1-hexene) copolymer, an ethylene-(1-octene) copolymer, an ethylene-propylene-diene copolymer (EPDM), or a butadiene-acrylonitrile-styrene core-shell rubber (ABS), a methyl methacrylate-butadiene-styrene core-shell rubber (MBS), a methyl methacrylate-butyl acrylate-styrene core-shell rubber (MAS), an octyl acrylate-butadiene-styrene core-shell rubber (MABS), an alkyl acrylate-butadiene-acrylonitrile-styrene core-shell rubber (AABS), a butadiene-styrene core-shell rubber (SBR), a silicone-containing core-shell rubber including methyl methacrylate-butyl acrylate silicone, and the like.

[0611] These rubber components may be used alone or in combination of two or more.

[0612] (Method for producing polyamide composition)

[0613] The method for producing the polyamide composition of the above embodiment is not particularly limited as long as (2A) an aliphatic polyamide, (2B) a semi-aromatic polyamide, (2C) a pigment, (2D1) a flame retardant, (2D2) a flame retardant auxiliary, and, if necessary, (2E) a polymer containing an α,β-unsaturated dicarboxylic acid anhydride in a structural unit, and (2F) a filler are mixed.

[0614] As a method for mixing (2A) aliphatic polyamide, (2B) semi-aromatic polyamide, (2C) pigment, (2D1) flame retardant, (2D2) flame retardant auxiliary, (2E) polymer containing α,β-unsaturated dicarboxylic acid anhydride in its constituent units, and (2F) filler, for example, the following method can be cited: (2A) aliphatic polyamide, (2B) semi-aromatic polyamide, (2C) pigment, (2D1) flame retardant and optionally selected from (2D2) flame retardant auxiliary, (2E) polymer containing α,β-unsaturated dicarboxylic acid anhydride in its constituent units are mixed using a Henschel mixer or the like; A method in which (2A) an aliphatic polyamide, (2B) a semi-aromatic polyamide, (2D1) a flame retardant, and optionally (2C) a pigment, (2D2) a flame retardant aid, and / or (2E) a polymer containing an α,β-unsaturated dicarboxylic acid anhydride in its constituent units are mixed and supplied to a melt kneader for kneading using a single-screw or twin-screw extruder, using a Henschel mixer or the like, and then the mixture is supplied to a melt kneader for kneading, and then the filler (2F) is optionally added from a side feed port.

[0615] In the method of supplying the components constituting the polyamide composition to the melt-kneader, all the components may be supplied at once to the same supply port, or the components may be supplied from different supply ports.

[0616] The temperature for melt kneading is preferably about 1°C to 100°C higher than the melting point of the aliphatic polyamide (2A), and more preferably about 10°C to 50°C higher.

[0617] The shear rate in the mixer is preferably about 100 seconds -1 As described above, the average residence time during kneading is preferably about 0.5 to 5 minutes.

[0618] As an apparatus for performing melt kneading, a known apparatus such as a single-screw or twin-screw extruder, a Banbury mixer, or a melt kneading machine such as a kneading roll is preferably used.

[0619] The amount of each component added when producing the polyamide composition of the above embodiment is the same as the content of each component in the above-mentioned polyamide composition.

[0620] (Physical Properties of Polyamide Composition)

[0621] The physical properties of the polyamide composition are the same as those described in the above embodiment 1-1.

[0622] [Molded products]

[0623] By molding the polyamide resin composition of the embodiment described above, a molded article having a surface gloss value of 50 or greater can be obtained. The surface gloss value of the polyamide composition of the embodiment described above is more preferably 55 or greater, and even more preferably 60 or greater. When the polyamide composition has a surface gloss value of 50 or greater, it can be suitably used as a molding material for various parts such as those for automobiles, electrical and electronic applications, industrial materials, and daily and household products.

[0624] There are no particular limitations on the method for obtaining a molded article, and a known molding method can be used.

[0625] For example, the following molding methods can be listed: extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decorative molding, heterogeneous material molding, gas-assisted injection molding, foam injection molding, low-pressure molding, ultra-thin wall injection molding (ultra-high-speed injection molding) and in-mold composite molding (insert molding, insert-on molding).

[0626] (use)

[0627] The molded article of the 2-2 embodiment of the present invention contains the above-mentioned polyamide resin composition, has excellent mechanical properties (particularly weld strength and hardness), surface appearance, flame retardancy, etc., and can be used in various applications.

[0628] For example, it can be suitably used in the automotive field, the electrical and electronic field, the mechanical and industrial field, the office equipment field, and the aviation and aerospace field.

[0629] 《Methods 3-1 to 3-2》

[0630] [Polyamide composition]

[0631] The polyamide composition of the 3-1 embodiment of the present invention contains:

[0632] (3A) an aliphatic polyamide comprising a diamine and a dicarboxylic acid;

[0633] (3B) a semi-aromatic polyamide; the semi-aromatic polyamide comprises a dicarboxylic acid unit and a diamine unit, the dicarboxylic acid unit comprising 50 mol % or more of isophthalic acid, and the diamine unit comprising a diamine having 4 to 10 carbon atoms;

[0634] (3C1) flame retardants; and

[0635] (3C2) flame retardant additives,

[0636] in,

[0637] The tan δ peak temperature of the polyamide composition is 100°C or higher.

[0638] The weight average molecular weight Mw of the polyamide composition is 10000≤Mw≤40000, and

[0639] The halogen content is greater than 2% by mass and less than 20% by mass based on the total amount of the polyamide composition.

[0640] In the above embodiment, "polyamide" refers to a polymer having an amide (-NHCO-) ​​bond in the main chain. (3A) Aliphatic polyamide and (3B) semi-aromatic polyamide are described in detail below.

[0641] ((3A) Aliphatic polyamide)

[0642] (3A) The aliphatic polyamide is as described in relation to "(1A) the aliphatic polyamide" in the above-mentioned embodiment 1-1.

[0643] ((3B) semi-aromatic polyamide)

[0644] The (3B) semi-aromatic polyamide is the same as described in relation to the "(1B) semi-aromatic polyamide" in the above-mentioned embodiment 1-1 except for the following points.

[0645] The (3B) semi-aromatic polyamide used in the above embodiment is a polyamide containing (3B-a) dicarboxylic acid units containing 50 mol% or more of isophthalic acid and (3B-b) diamine units containing a diamine having 4 to 10 carbon atoms.

[0646] The total amount of the isophthalic acid units and the diamine units having 4 to 10 carbon atoms is preferably 50 mol% or more, more preferably 80 to 100 mol%, further preferably 90 to 100 mol%, and particularly preferably 100 mol%, based on 100 mol% of all the constituent units of the semi-aromatic polyamide (3B).

[0647] ((3B-a) dicarboxylic acid unit)

[0648] (3B-a) The dicarboxylic acid unit contains 50 mol% or more of isophthalic acid (based on the total moles of the dicarboxylic acid). The dicarboxylic acid unit preferably contains 65 mol% to 100 mol% of isophthalic acid, more preferably 70 mol% to 100 mol%, further preferably 80 mol% to 100 mol%, and particularly preferably 100 mol%.

[0649] When the ratio of the isophthalic acid unit in the dicarboxylic acid unit (3B-a) is 50 mol% or more, a polyamide composition can be obtained that satisfies all mechanical properties, particularly water absorption rigidity, hot rigidity, flowability, surface appearance, etc.

[0650] (lactam unit and / or aminocarboxylic acid unit)

[0651] The lactam unit and / or the aminocarboxylic acid unit are as described in the above embodiment 1-1.

[0652] (Capping agent)

[0653] The ends of the polyamide used in the above embodiment can be capped with a known end-capping agent.

[0654] The blocking agent is as described in the above embodiment 1-1.

[0655] (Production Method of Polyamide)

[0656] The method for producing polyamide is the same as described in the above embodiment 1-1.

[0657] (Polymer end of polyamide)

[0658] The polymer terminals of the polyamide are as described in the above embodiment 1-1.

[0659] ((3A) Characteristics of Aliphatic Polyamides)

[0660] The properties of the aliphatic polyamide (3A) are the same as those described in the "properties of the aliphatic polyamide (1A)" in the above-mentioned embodiment 1-1.

[0661] ((3B) Characteristics of semi-aromatic polyamide)

[0662] The properties of the (3B) semi-aromatic polyamide are the same as those described in the "properties of the (1B) semi-aromatic polyamide" in the above-mentioned embodiment 1-1.

[0663] ((3C1) flame retardant)

[0664] The properties of the flame retardant (3C1) are the same as those described in connection with the "flame retardant (2D1)" in the above-mentioned embodiment 2-1.

[0665] ((3C2) flame retardant additive)

[0666] The polyamide composition of the above embodiment can be made into a polyamide composition having further excellent flame retardancy by containing the flame retardant auxiliary agent (3C2).

[0667] The properties of the flame retardant auxiliary (3C2) are the same as those described in relation to the "(2D2) flame retardant auxiliary" in the above-mentioned embodiment 2-1.

[0668] ((3D) Polymer containing an α,β-unsaturated dicarboxylic acid anhydride in a structural unit)

[0669] The polyamide composition of the above embodiment may further contain (3D) a polymer containing an α,β-unsaturated dicarboxylic acid anhydride as a structural unit. By containing (3D) a polymer containing an α,β-unsaturated dicarboxylic acid anhydride as a structural unit, a polyamide composition having excellent mechanical properties such as toughness and rigidity can be obtained.

[0670] (3D) The polymer containing an α,β-unsaturated dicarboxylic acid anhydride in a structural unit is as described in the above-mentioned embodiment 2-1 regarding "(2E) The polymer containing an α,β-unsaturated dicarboxylic acid anhydride in a structural unit".

[0671] ((3E) Filling material)

[0672] The polyamide composition of the above embodiment may further contain a filler (3E). By containing a filler (3E), a polyamide composition having more excellent mechanical properties such as toughness and rigidity can be obtained.

[0673] For (3E) filler material, as described in the above-mentioned method 1-1 regarding "(1C) inorganic filler material".

[0674] (Content of each ingredient)

[0675] The content of the flame retardant (3C1) in the polyamide composition of the embodiment described above is preferably 0.1% by mass or more and 30% by mass or less, more preferably 5% by mass to 20% by mass, and even more preferably 5% by mass to 15% by mass, relative to 100% by mass of the polyamide composition.

[0676] By setting the content of the (3C1) flame retardant to 0.1% by mass or more, a polyamide composition with excellent flame retardant properties can be obtained. Furthermore, by setting the content of the (3C1) flame retardant to 15% by mass or less, the generation of decomposition gases during melt mixing, the reduction of fluidity during molding, and the adhesion of polluting substances to the molding die can be suppressed. In addition, the deterioration of mechanical properties such as toughness and rigidity, as well as the appearance of the molded product, can be suppressed.

[0677] The content of the flame retardant auxiliary (3C2) in the polyamide composition is preferably 0.1% to 10% by mass, more preferably 1% to 10% by mass, relative to 100% by mass of the polyamide composition. By containing the flame retardant auxiliary (3C2) within the above range, a polyamide composition having even better flame retardancy can be obtained.

[0678] By setting the content of the flame retardant auxiliary (3C2) to 10% by mass or less, the viscosity during melt processing can be controlled within an appropriate range, thereby suppressing increases in torque during extrusion, decreases in moldability during molding, and deterioration in the appearance of molded products. Furthermore, a polyamide composition having excellent toughness, etc., can be obtained without compromising the properties of the polyamide, which has excellent mechanical properties such as toughness and rigidity.

[0679] A particularly preferred combination is: (3C1) the flame retardant is brominated polystyrene, and the content of brominated polystyrene is 6 mass% or more and 15 mass% or less relative to 100 mass% of the polyamide composition, and (3C2) the flame retardant auxiliary is antimony trioxide (Sb2O3), and the content of antimony trioxide (Sb2O3) is 0.1 mass% or more and 4 mass% or less relative to 100 mass% of the polyamide composition.

[0680] The content of the polymer (3D) containing an α,β-unsaturated dicarboxylic acid anhydride as a constituent unit in the polyamide composition is preferably 0.1% to 20% by mass, more preferably 0.5% to 20% by mass, even more preferably 1% to 15% by mass, and particularly preferably 2% to 10% by mass, relative to 100% by mass of the polyamide composition. By including the polymer (3D) containing an α,β-unsaturated dicarboxylic acid anhydride as a constituent unit in the polyamide composition within this range, the microdispersion effect of the flame retardant (3C1) in the polyamide composition due to compatibilization can be enhanced, resulting in a polyamide composition with excellent flame retardancy and strength. Furthermore, by setting the content of the polymer (3D) containing an α,β-unsaturated dicarboxylic acid anhydride as a constituent unit to 20% by mass or less, a polyamide composition with excellent strength and other properties can be obtained without compromising the properties of the polyamide, which has excellent mechanical properties such as toughness and rigidity.

[0681] The content of the (3E) filler in the polyamide composition is preferably 1% by mass to 80% by mass, more preferably 10% by mass to 70% by mass, further preferably 30% by mass to 70% by mass, further preferably 30% by mass to 60% by mass, and most preferably 40% by mass to 60% by mass, relative to 100% by mass of the polyamide composition.

[0682] By containing the (3E) filler within the above range, the mechanical properties of the polyamide composition such as strength and rigidity are favorably improved. Furthermore, by setting the content of the inorganic filler to 70% by mass or less, a polyamide composition having excellent moldability can be obtained.

[0683] In the above embodiment, the total content of the flame retardant (3C1), the flame retardant auxiliary (3C2), the polymer containing an α,β-unsaturated dicarboxylic acid anhydride in its structural units (3D), and the filler (3E) relative to 100% by mass of the polyamide composition is preferably 10% to 90% by mass. It is more preferably 30% to 80% by mass, and even more preferably 40% to 80% by mass. By setting the total content to 10% by mass or greater, a polyamide composition having excellent strength, rigidity, flame retardancy, and other properties, as well as having an appropriate melt viscosity and excellent processability can be obtained.

[0684] The polyamide composition of the above embodiment may contain additives commonly used in polyamides, such as moldability improvers, degradation inhibitors, nucleating agents, stabilizers, and polymers other than the polyamide of the above embodiment, within a range not impairing the purpose of the above embodiment.

[0685] The content of the additives varies depending on the type of the additives, the application of the polyamide composition, etc., and is therefore not particularly limited as long as it is within a range that does not impair the purpose of the above-mentioned embodiment.

[0686] (Moldability Improver)

[0687] A moldability improver may be added to the polyamide composition of the above embodiment as needed within a range that does not impair the purpose of the above embodiment. The moldability improver is the same as described above regarding the "lubricant" in the first embodiment.

[0688] (Degradation inhibitor)

[0689] A degradation inhibitor may be added to the polyamide composition of the above embodiment as needed for the purpose of preventing thermal degradation and discoloration during heating and improving heat aging resistance and weather resistance within a range that does not impair the purpose of the above embodiment.

[0690] The degradation inhibitor is as described in the above-mentioned embodiment 2-1.

[0691] (Nucleating Agent)

[0692] The nucleating agent is as described in the above embodiment 1-1.

[0693] (Stabilizer)

[0694] The stabilizer is as described in the above embodiment 1-1.

[0695] (Other resins)

[0696] To the polyamide composition of the above embodiment, other resins may be added as needed within a range that does not impair the purpose of the above embodiment.

[0697] Such a resin is as described in the above embodiment 2-1.

[0698] (Method for producing polyamide composition)

[0699] The method for producing the polyamide composition of the above embodiment is the same as described in the above embodiment 2-1.

[0700] The amount of each component added when producing the polyamide composition of the above embodiment is the same as the content of each component in the above-mentioned polyamide composition.

[0701] (Physical Properties of Polyamide Composition)

[0702] The physical properties of the polyamide composition are the same as those described in the above embodiment 1-1.

[0703] [Molding products]

[0704] By molding the polyamide composition of the above embodiment, a molded article having a surface gloss value of 50 or greater can be obtained. The surface gloss value of the polyamide composition of the above embodiment is more preferably 55 or greater, and even more preferably 60 or greater. When the polyamide composition has a surface gloss value of 50 or greater, it can be suitably used as a molding material for various parts such as those for automobiles, electrical and electronic applications, industrial materials, and daily and household products.

[0705] There are no particular limitations on the method for obtaining a molded article, and a known molding method can be used.

[0706] For example, the following molding methods can be listed: extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decorative molding, heterogeneous material molding, gas-assisted injection molding, foam injection molding, low-pressure molding, ultra-thin wall injection molding (ultra-high-speed injection molding) and in-mold composite molding (insert molding, insert-on molding).

[0707] (use)

[0708] The molded article of the 3-2 embodiment of the present invention comprises the above-mentioned polyamide composition, has excellent mechanical properties (particularly tensile strength, flexural modulus, and Charpy impact), surface appearance, etc., and can be used in various applications.

[0709] For example, it can be suitably used in the automotive field, the electrical and electronic field, the mechanical and industrial field, the office equipment field, and the aviation and aerospace field.

[0710] 《Methods 4-1 and 4-2》

[0711] [Polyamide composition]

[0712] The polyamide composition of the fourth-first embodiment of the present invention comprises (4A) a crystalline polyamide, (4B) an amorphous semi-aromatic polyamide, and (4C) a polyphenylene ether, wherein the (4B) amorphous semi-aromatic polyamide comprises a dicarboxylic acid unit and a diamine unit, wherein the dicarboxylic acid unit comprises at least 75 mol% isophthalic acid, and the diamine unit comprises at least 50 mol% of a diamine having 4 to 10 carbon atoms, wherein the tanδ peak temperature of the polyamide composition is above 90°C.

[0713] In the above description, "polyamide" refers to a polymer having amide (-NHCO-) ​​bonds in its main chain. The following provides a detailed description of (4A) crystalline polyamide and (4B) amorphous semi-aromatic polyamide.

[0714] ((4A) Crystalline polyamide)

[0715] Crystalline polyamide refers to polyamide whose heat of fusion of crystals is 4 J / g or more when measured using a differential scanning calorimeter at 20 °C / min. It is not limited to the following substances, but includes, for example, (a) polyamides obtained by ring-opening polymerization of lactams, (b) polyamides obtained by self-condensation of ω-aminocarboxylic acids, (c) polyamides obtained by condensation of diamines and dicarboxylic acids, and copolymers thereof. One type or a mixture of two or more types of crystalline polyamide can be used.

[0716] (a) The lactams are not limited to the following substances, such as pyrrolidone, caprolactam, undecanolactam, dodecalactam, etc.

[0717] The ω-aminocarboxylic acid (b) is not limited to the following, and examples thereof include ω-amino fatty acids, which are ring-opened compounds of the lactams obtained with water. Two or more monomers of the lactams or ω-aminocarboxylic acids may be used in combination for condensation.

[0718] The diamine (monomer) of (c) is not limited to the following substances, and examples thereof include: linear aliphatic diamines such as hexamethylenediamine and pentamethylenediamine; branched aliphatic diamines such as 2-methylpentanediamine and 2-ethylhexamethylenediamine; aromatic diamines such as p-phenylenediamine and m-phenylenediamine; alicyclic diamines such as cyclohexanediamine, cyclopentanediamine and cyclooctanediamine, etc.

[0719] The dicarboxylic acid (monomer) (c) is not limited to the following, and examples thereof include aliphatic dicarboxylic acids such as adipic acid, pimelic acid, and sebacic acid; aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The diamines and dicarboxylic acids used as monomers may be condensed alone or in combination of two or more.

[0720] The crystalline polyamide (4A) may further contain units derived from trivalent or higher polycarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid, as needed. The trivalent or higher polycarboxylic acids may be used alone or in combination of two or more.

[0721] Specific examples of the (4A) crystalline polyamide used in the polyamide composition of the above embodiment include polyamide 4 (polyα-pyrrolidone), polyamide 6 (polycaprolactam), polyamide 11 (polyundecanamide), polyamide 12 (polydodecaneamide), polyamide 46 (polybutylene adipamide), polyamide 56 (polypentamethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610 (polyhexamethylene sebacamide), polyamide 612 (polyhexamethylene dodecanoamide), polyamide 6T (polyhexamethylene terephthalamide) and polyamide 9T (polynonamethylene terephthalamide), as well as copolymer polyamides containing these as constituent components.

[0722] Among them, polyamide 66 (PA66), polyamide 46 (PA46), and polyamide 610 (PA610) are preferably mentioned. PA66 is considered to be a material suitable for automotive parts due to its excellent heat resistance, moldability, and toughness. In addition, long-chain aliphatic polyamides such as PA610 are preferred due to their excellent chemical resistance.

[0723] The content of the (4A) crystalline polyamide in the polyamide composition of the above embodiment can be set to, for example, 50 mass% or more and 99 mass% or less, for example, 60 mass% or more and 95 mass% or less, for example, 70 mass% or more and 85 mass% or less, relative to the total mass of all resins contained in the polyamide composition.

[0724] ((4B) Amorphous semi-aromatic polyamide)

[0725] The (4B) semi-aromatic polyamide is as described in relation to the "(1B) semi-aromatic polyamide" in the above-mentioned embodiment 1-1.

[0726] (Capping agent)

[0727] The ends of the polyamide used in the above embodiment can be capped with a known capping agent.

[0728] The blocking agent is as described in the above embodiment 1-1.

[0729] (Production Method of Polyamide)

[0730] The method for producing polyamide is the same as described in the above embodiment 1-1.

[0731] (Polyamide polymer ends)

[0732] For the polymer ends of polyamide, as described in method 1-1 above.

[0733] ((4A) Characteristics of Crystalline Polyamide)

[0734] The properties of the crystalline polyamide (4A) are the same as those described in the "properties of the aliphatic polyamide (1A)" in the above-mentioned embodiment 1-1 except for the following points.

[0735] From the viewpoint of mechanical properties, particularly water absorption rigidity and hot rigidity, the crystallization enthalpy ΔH of the (4A) crystalline polyamide is preferably 4 J / g or more, more preferably 20 J / g or more, further preferably 30 J / g or more, further preferably 40 J / g or more, particularly preferably 50 J / g or more, and most preferably 60 J / g or more.

[0736] ((4B) Characteristics of Amorphous Semi-Aromatic Polyamide)

[0737] The properties of the amorphous semi-aromatic polyamide (4B) are the same as those described in the "properties of the semi-aromatic polyamide (1B)" in the above-mentioned embodiment 1-1 except for the following points.

[0738] The molecular weight distribution of the (4B) amorphous semi-aromatic polyamide is determined by weight average molecular weight Mw(4B) / number average molecular weight Mn(4B).

[0739] The Mw(4B) / Mn(4B) ratio of the (4B) amorphous semi-aromatic polyamide is preferably 2.4 or less, more preferably 1.7 to 2.4, even more preferably 1.8 to 2.3, even more preferably 1.9 to 2.2, and most preferably 1.9 to 2.1. The lower limit of Mw(4B) / Mn(4B) is 1.0. By adjusting the Mw(4B) / Mn(4B) ratio within the above range, a polyamide composition having excellent fluidity and other properties can be obtained. In addition, a polyamide composition containing components such as inorganic fillers has an excellent surface appearance.

[0740] As a method for controlling the Mw(4B) / Mn(4B) ratio of the amorphous semi-aromatic polyamide (4B) within the above-mentioned range, for example, a method of adding a known polycondensation catalyst such as phosphoric acid or sodium hypophosphite as an additive during the hot melt polymerization of the polyamide can be mentioned. Alternatively, polymerization conditions such as heating and reduced pressure can be controlled to complete the polycondensation reaction at the lowest possible temperature and in the shortest possible time. In particular, since the amorphous semi-aromatic polyamide (4B) does not have a melting point, it is preferable to lower the reaction temperature to control the Mw(4B) / Mn(4B) ratio within the above-mentioned range.

[0741] When polyamide molecular structures contain aromatic compound units, the molecular weight distribution (Mw(4B) / Mn(4B)) tends to increase with increasing molecular weight. Maintaining a molecular weight distribution within this range reduces the proportion of polyamide molecules with a three-dimensional molecular structure, effectively preventing the formation of a three-dimensional molecular structure during high-temperature processing, and maintaining good fluidity. This improves the surface appearance of polyamide compositions containing components such as inorganic fillers.

[0742] From the viewpoint of mechanical properties, particularly water absorption rigidity and thermal rigidity, the crystallization enthalpy ΔH of the amorphous semi-aromatic polyamide (4B) is preferably less than 4 J / g, more preferably 2 J / g or less, and even more preferably 0 J / g.

[0743] ((4C)Polyphenylene ether)

[0744] The (4C) polyphenylene ether contained in the polyamide composition of the above embodiment is a homopolymer and / or copolymer having a repeating structural unit represented by the following general formula.

[0745]

[0746] Here, in the above general formula, O represents an oxygen atom, R 41 、R 42 、R 43 and R 44 Each independently represents hydrogen, halogen, primary or secondary C1-C7 alkyl, phenyl, C1-C7 haloalkyl, C1-C7 aminoalkyl, C1-C7 hydrocarbyloxy, or halohydrocarbyloxy (however, at least two carbon atoms separate the halogen atom and the oxygen atom).

[0747] Specific examples of (4C) polyphenylene ethers include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), and poly(2,6-dichloro-1,4-phenylene ether). Polyphenylene ether copolymers such as copolymers of 2,6-dimethylphenol and other phenols (for example, copolymers with 2,3,6-trimethylphenol described in Japanese Patent Publication No. 52-17880 and copolymers with 2-methyl-6-butylphenol) can also be mentioned.

[0748] Among them, particularly preferred polyphenylene ethers include poly(2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethyl-1,4-phenol and 2,3,6-trimethyl-1,4-phenol, or a mixture thereof.

[0749] Furthermore, regarding the copolymer of 2,6-dimethyl-1,4-phenol and 2,3,6-trimethyl-1,4-phenol, when the total amount of the polyphenylene ether copolymer is 100% by mass, the copolymer preferably contains 10% to 30% by mass of 2,3,6-trimethyl-1,4-phenol, more preferably 15% to 25% by mass, and even more preferably 20% to 25% by mass.

[0750] From the viewpoint of compatibility with polyamide, the polyphenylene ether (4C) is preferably a polyphenylene ether modified with an α,β-unsaturated dicarboxylic acid anhydride.

[0751] Examples of the α,β-unsaturated dicarboxylic acid anhydride include compounds represented by the following general formula.

[0752]

[0753] In the above general formula, R 1 and R 2 Each independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms.

[0754] Examples of the α,β-unsaturated dicarboxylic acid anhydride include maleic anhydride and methylmaleic anhydride, and maleic anhydride is preferred.

[0755] The content of the α,β-unsaturated dicarboxylic acid anhydride component in the polyphenylene ether (4C) is preferably 0.1% by mass to 50% by mass, more preferably 0.2% by mass to 20% by mass, further preferably 0.3% by mass to 5% by mass, particularly preferably 0.3% by mass to 1% by mass, and most preferably 0.3% by mass to 0.8% by mass, relative to 100% by mass of the polyphenylene ether (4C).

[0756] By setting the content of the α,β-unsaturated dicarboxylic acid anhydride component to 0.1% by mass or greater, compatibility with the polyamide is improved, resulting in a polyamide composition with excellent mechanical properties such as toughness and rigidity. Furthermore, by setting the proportion of the α,β-unsaturated dicarboxylic acid anhydride component to 50% by mass or less, degradation of the polyamide composition caused by the α,β-unsaturated dicarboxylic acid anhydride can be prevented.

[0757] One of the characteristics of polyphenylene ether is that it has a low molecular weight, a narrow molecular weight distribution, and a small amount of oligomers.

[0758] The (4C) polyphenylene ether contained in the polyamide composition of the above embodiment contains 60% by mass or more, more preferably 65% ​​by mass or more, of a component having a molecular weight of 30,000 or less. When the amount of the component having a molecular weight of 30,000 or less is 60% by mass or more, excellent thin-wall flowability within a mold is achieved. Furthermore, from the perspective of maintaining the toughness of a molded article such as a connector, the upper limit of the amount of the component having a molecular weight of 30,000 or less is preferably 95% by mass, more preferably 85% by mass, and even more preferably 80% by mass.

[0759] The amount of components with a molecular weight of 30,000 or less in commonly used polyphenylene ethers is about 40% by mass in polyphenylene ethers of a generally used molecular weight and about 50% by mass in so-called low-molecular-weight polyphenylene ethers. The polyphenylene ether used in the above embodiment is a low-molecular-weight polyphenylene ether with a further reduced molecular weight.

[0760] The content of components having a molecular weight of 3000 or less in the polyphenylene ether (4C) is preferably 5% by mass or less, more preferably 4.5% by mass or less, and even more preferably 4% by mass or less. By limiting the content of components having a molecular weight of 3000 or less to 5% by mass or less, color change of the molded article during heat exposure is suppressed.

[0761] The number average molecular weight of the (4C) polyphenylene ether contained in the polyamide composition of the above embodiment is not particularly limited, but the preferred lower limit is 7000, the more preferred lower limit is 9000, and the further preferred lower limit is 10000. Furthermore, the preferred upper limit of the number average molecular weight is 15000, the more preferred upper limit is 14000, and the further preferred upper limit is 13000. To further suppress color change of the molded article after heat exposure, the lower limit of the number average molecular weight is preferably 7000 or higher, and to further improve thin-wall flowability in a mold, the upper limit of the number average molecular weight is preferably 15000 or lower.

[0762] The polyphenylene ether dispersion ratio, i.e., the ratio of weight average molecular weight to number average molecular weight (Mw / Mn), is not particularly limited, but its preferred upper limit is 2.50, and its more preferred upper limit is 2.40. Its preferred lower limit is 2.00, and its more preferred lower limit is 2.10. A dispersion ratio of 2.50 or less results in a narrow molecular weight distribution, a reduction in oligomers (low molecular weight components), or a reduction in high molecular weight components. Reducing the low molecular weight components is preferred to minimize color changes in the molded sheet after heat exposure.

[0763] The production methods of polyphenylene ether are roughly divided into two types: precipitation polymerization and solution polymerization.

[0764] The precipitation polymerization method is a polymerization method that produces a precipitate of polyphenylene ether within the above-mentioned concentration range. Specifically, in this polymerization method, as the polymerization of polyphenylene ether proceeds, a state is formed in which a material with a sufficiently high molecular weight is precipitated and a material with an insufficiently high molecular weight is dissolved. As a solvent, a mixed solvent of a good solvent for polyphenylene ether such as toluene, xylene, and ethylbenzene and a poor solvent for polyphenylene ether such as methanol and butanol can be used.

[0765] It is considered that the precipitated polyphenylene ether inhibits the movement of the molecular chain and that the catalyst dissolves in the mixed solvent, thereby causing a solid-liquid reaction and slowing down the reaction rate of further polymerization.

[0766] On the other hand, polyphenylene ether in a dissolved state whose molecular weight has not yet been sufficiently increased maintains its polymerization reaction rate, and when the polymerization progresses and the molecular weight reaches a high enough level for precipitation, the polyphenylene ether precipitates.

[0767] Furthermore, in the aforementioned polymerization form, it is believed that when a substance with a small particle size precipitates, the surface area increases during the solid-liquid reaction, thereby accelerating the reaction compared to a substance with a large particle size. Furthermore, since polyphenylene ether precipitates during the polymerization process, the viscosity within the system gradually decreases, thereby increasing the monomer concentration (phenolic compound concentration) during polymerization. Furthermore, the precipitated polyphenylene ether can be easily extracted by filtering, significantly simplifying the process.

[0768] The solution polymerization method is a polymerization method that conducts polymerization in a good solvent for polyphenylene ether and does not produce precipitation during polymerization. In solution polymerization, polyphenylene ether molecules are dissolved, and the molecular weight distribution tends to be broad. In solution polymerization, a polymerization solution containing polyphenylene ether is developed in a poor solvent for polyphenylene ether, such as methanol, to produce a powdered polyphenylene ether.

[0769] The polymerization method for the polyphenylene ether is not particularly limited, but precipitation polymerization is preferred. The precipitation polymerization method is suitable for producing low-molecular-weight polyphenylene ether having a narrow molecular weight distribution, and can produce polyphenylene ether in which the amount of components with a molecular weight of 30,000 or less is 60% by mass or more, and the amount of components with a molecular weight of 3,000 or less is 5% by mass or less.

[0770] The intrinsic viscosity (chloroform solution, measured at 30°C) of the polyphenylene ether (4C) contained in the polyamide composition of the above embodiment is not particularly limited, but is preferably in the range of 0.15 to 0.40 deciliter / g, more preferably in the range of 0.20 to 0.35 deciliter / g, even more preferably in the range of 0.25 to 0.35 deciliter / g, and particularly preferably in the range of 0.25 to 0.30 deciliter / g.

[0771] In the above embodiment, a mixture of two or more polyphenylene ethers having different intrinsic viscosities can be used. Examples of such a mixture include, but are not limited to, a mixture of a polyphenylene ether having an intrinsic viscosity of 0.40 dl / g or less and a polyphenylene ether having an intrinsic viscosity of 0.45 dl / g or greater. Even in such a case, if the intrinsic viscosity of the mixture falls within the preferred intrinsic viscosity range described above, the desired effect is more likely to be achieved, and therefore, this is more preferred.

[0772] In the above embodiment, the amount of the (4C) polyphenylene ether blended relative to 100% by mass of all resins contained in the polyamide composition is preferably from 0.5% to 30.0% by mass, more preferably from 1.0% to 15.0% by mass, even more preferably from 2.0% to 10.0% by mass, even more preferably from 3.0% to 8.0% by mass, and particularly preferably from 3.0% to 6.0% by mass. By adjusting the amount of the (4C) polyphenylene ether blended within the above range, a polyamide composition having excellent mechanical properties, particularly water absorption rigidity, hot rigidity, and flowability, can be obtained. Furthermore, polyamide compositions containing components, typified by inorganic fillers, exhibit excellent surface appearance.

[0773] In the above embodiment, a compatibilizer may be included to improve the compatibility between the polyamide and the polyphenylene ether. While there are no particular limitations on the compatibilizer that can be used in the above embodiment, it is preferred to use at least one selected from citric acid, maleic acid, itaconic acid, and their anhydrides for ease of use and affordability. Maleic acid or its anhydride is more preferred. Maleic acid or its anhydride can compatibilize the polyamide and the polyphenylene ether in relatively small amounts, thereby suppressing color changes in the molded sheet.

[0774] The content of the compatibilizer relative to 100 parts by mass of all resins contained in the polyamide composition is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass or more and 3 parts by mass or less, and even more preferably 0.2 parts by mass or more and 2 parts by mass or less. By setting the content of the compatibilizer to 0.05 parts by mass or more, compatibility with the polyamide is improved, and a polyamide composition having excellent impact resistance can be obtained. In addition, by setting the content of the compatibilizer to 5 parts by mass or less, a polyamide composition having excellent fluidity can be obtained.

[0775] The polyamide composition of the above embodiment further contains a polymer containing an α,β-unsaturated dicarboxylic acid anhydride, thereby improving the compatibility between the polyamide and the polyphenylene ether, and can be made into a polyamide composition having more excellent mechanical properties such as toughness and rigidity.

[0776] Examples of the polymer containing an α,β-unsaturated dicarboxylic acid anhydride used in the above embodiment include polymers containing an α,β-unsaturated dicarboxylic acid anhydride as a copolymerization component and polymers modified with an α,β-unsaturated dicarboxylic acid anhydride.

[0777] As the polymer containing an α,β-unsaturated dicarboxylic acid anhydride as a copolymerization component, a copolymer of an aromatic vinyl compound and an α,β-unsaturated dicarboxylic acid anhydride is preferred from the viewpoint of improving compatibility with the amorphous semi-aromatic polyamide (4B).

[0778] Examples of the aromatic vinyl compound used in the above embodiment include compounds represented by the following general formula.

[0779]

[0780] In the above general formula, R 3 and R 4 Each independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms, and k is an integer of 1 to 5.

[0781] Examples of the aromatic vinyl compound include styrene, α-methylstyrene, and p-methylstyrene, and styrene is preferred.

[0782] From the viewpoints of toughness, fluidity, thermal decomposition resistance, etc., the proportion of the α,β-unsaturated dicarboxylic acid anhydride component in the copolymer of an aromatic vinyl compound and an α,β-unsaturated dicarboxylic acid anhydride is preferably 0.1% by mass to 50% by mass, more preferably 5% by mass to 20% by mass, and even more preferably 8% by mass to 15% by mass, relative to 100% by mass of the polyamide composition.

[0783] By setting the proportion of the α,β-unsaturated dicarboxylic acid anhydride component to 0.1% by mass or greater, a polyamide composition having excellent mechanical properties such as toughness and rigidity can be obtained. Furthermore, by setting the proportion of the α,β-unsaturated dicarboxylic acid anhydride component to 50% by mass or less, degradation of the polyamide composition caused by the α,β-unsaturated dicarboxylic acid anhydride can be prevented.

[0784] As the polymer modified with an α,β-unsaturated dicarboxylic acid anhydride, a polypropylene resin modified with an α,β-unsaturated dicarboxylic acid anhydride is preferred.

[0785] The content of the polymer containing the α,β-unsaturated dicarboxylic acid anhydride is preferably 0.1 parts by mass or more and 5 parts by mass or less relative to 100 parts by mass of all resins contained in the polyamide composition.

[0786] The polyamide composition of the above embodiment may contain, in addition to the above-mentioned (4A) crystalline polyamide, (4B) amorphous semi-aromatic polyamide, and (4C) polyphenylene ether, one or more components selected from the group consisting of an inorganic filler, a nucleating agent, a lubricant, a stabilizer, a polymer other than (4A), (4B), and (4C), a metal phosphite and / or a metal hypophosphite, and a phosphite ester compound.

[0787] (Inorganic filler)

[0788] The inorganic filler is the same as described in the above-mentioned embodiment 1-1 regarding "(1C) Inorganic filler" except for the following points.

[0789] The content of the inorganic filler is preferably 5 to 250 parts by mass, more preferably 30 to 250 parts by mass, further preferably 50 to 240 parts by mass, further preferably 50 to 200 parts by mass, and particularly preferably 50 to 150 parts by mass, relative to 100 parts by mass of the total of (4A) crystalline polyamide, (4B) amorphous semi-aromatic polyamide, and (4C) polyphenylene ether.

[0790] By setting the content of the inorganic filler to 5 parts by mass or more relative to 100 parts by mass of the total of (4A) crystalline polyamide, (4B) amorphous semi-aromatic polyamide, and (4C) polyphenylene ether, the strength and rigidity of the resulting polyamide composition are improved. On the other hand, by setting the content of the inorganic filler to 250 parts by mass or less, a polyamide composition having excellent extrudability and moldability can be obtained.

[0791] (Nucleating Agent)

[0792] The nucleating agent is as described in the above embodiment 1-1.

[0793] (Lubricant)

[0794] The lubricant is the same as described in the above embodiment 1-1.

[0795] (Stabilizer)

[0796] The stabilizer is as described in the above embodiment 1-1.

[0797] (Other polymers)

[0798] Examples of polymers other than the aforementioned (4A) crystalline polyamide, (4B) amorphous semi-aromatic polyamide, and (4C) polyphenylene ether include, but are not limited to, polyesters, liquid crystal polyesters, polyphenylene sulfide, polycarbonates, polyarylates, phenolic resins, and epoxy resins.

[0799] The polyester is as described in the above embodiment 1-1.

[0800] The content of the polymer other than (4A) crystalline polyamide, (4B) amorphous semi-aromatic polyamide, and (4C) polyphenylene ether in the above embodiment is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass, and even more preferably 5 to 50 parts by mass, relative to 100 parts by mass of all resins contained in the polyamide composition. By adjusting the content of the polymer other than polyamide in the polyamide composition of the above embodiment to within the above range, a polyamide composition having excellent heat resistance and mold releasability can be obtained.

[0801] (phosphite metal salt and / or hypophosphite metal salt)

[0802] The metal phosphite and / or metal hypophosphite are as described in the above embodiment 1-1.

[0803] (Phosphite compound)

[0804] The phosphite compound is as described in the above embodiment 1-1.

[0805] The polyamide composition of the above embodiment may further contain additives commonly used in polyamide compositions, such as colorants such as pigments and dyes (including color masterbatches), flame retardants, fibrillating agents, fluorescent whitening agents, plasticizers, antioxidants, ultraviolet absorbers, antistatic agents, flowability improvers, spreaders, elastomers, etc., within a range that does not impair the purpose of the above embodiment.

[0806] When the polyamide composition of the above embodiment contains other raw materials that can be contained in the polyamide composition as described above, the content of the other raw materials varies depending on the type of the other raw materials, the application of the polyamide composition, etc., and is therefore not particularly limited as long as the purpose of the above embodiment is not impaired.

[0807] [Method for producing polyamide composition]

[0808] The method for producing the polyamide composition of the embodiment described above is not particularly limited as long as it comprises a step of melt-kneading raw material components comprising the aforementioned crystalline polyamide (4A), the amorphous semi-aromatic polyamide (4B), and the polyphenylene ether (4C). For example, a method is preferably one comprising a step of melt-kneading the raw material components comprising the aforementioned polyamide in an extruder, wherein the set temperature of the extruder is set to a melting peak temperature Tm2 of the polyamide composition described later + 30°C or less.

[0809] The details of the method for producing the polyamide composition are as described in the above-mentioned embodiment 1-1.

[0810] [Physical Properties of Polyamide Composition]

[0811] The physical properties of the polyamide composition are the same as those described in the above embodiment 1-1 except that the (1A) aliphatic polyamide is replaced by the (4A) crystalline polyamide, the (1B) semi-aromatic polyamide is replaced by the (4B) amorphous semi-aromatic polyamide, and the following points.

[0812] From the perspective of mechanical properties, particularly water absorption rigidity and hot rigidity, the crystallization enthalpy ΔH of the polyamide composition is preferably 10 J / g or greater, more preferably 14 J / g or greater, even more preferably 18 J / g or greater, and even more preferably 20 J / g or greater. The upper limit of the crystallization enthalpy ΔH is not particularly limited; a higher value is preferred.

[0813] Examples of methods for controlling the crystallization enthalpy ΔH of the polyamide composition within the above range include controlling the mixing ratio of (4A) crystalline polyamide, (4B) amorphous semi-aromatic polyamide, and (4C) polyphenylene ether within the above range.

[0814] Examples of an apparatus for measuring the melting point Tm2 and the crystallization enthalpy ΔH of the polyamide composition include Diamond-DSC manufactured by PERKIN-ELMER.

[0815] The tan δ peak temperature of the polyamide composition is 90° C. or higher, more preferably 100° C. or higher, further preferably 110° C. or higher, and even more preferably 120° C. or higher.

[0816] The tan δ peak temperature of the polyamide composition is preferably 150° C. or lower, more preferably 140° C. or lower, and even more preferably 130° C. or lower.

[0817] When the polyamide composition has a tan δ peak temperature of 90°C or higher, it tends to produce a polyamide composition having excellent water absorption rigidity and hot rigidity. Furthermore, when the polyamide composition has a tan δ peak temperature of 150°C or lower, the polyamide composition containing components such as inorganic fillers exhibits excellent surface appearance.

[0818] Examples of methods for controlling the tan δ peak temperature of the polyamide composition within the above range include controlling the blending ratio of (4A) crystalline polyamide, (4B) amorphous semi-aromatic polyamide, and (4C) polyphenylene ether within the above range.

[0819] The melting point crystallization peak temperature Tc of the polyamide composition used in the above embodiment can be measured by the method described in the examples described later in accordance with JIS-K7121.

[0820] Examples of measuring instruments for the crystallization peak temperature Tc include the Diamond-DSC manufactured by PERKIN-ELMER. Examples of methods for controlling the crystallization peak temperature Tc of polyamide within the aforementioned range include methods for controlling the blending ratio of (4A) crystalline polyamide, (4B) amorphous semi-aromatic polyamide, and (4C) polyphenylene ether within the aforementioned range.

[0821] [Molding products]

[0822] The molded article of the 4-2 embodiment of the present invention is obtained by molding the above-mentioned polyamide composition.

[0823] The molded article and its use are as described in the above-mentioned embodiment 1-2.

[0824] 《Methods 5-1 and 5-2》

[0825] Polyamide composition

[0826] The polyamide composition of the 5-1 embodiment of the present invention contains the following (5A) to (5E).

[0827] (5A) aliphatic polyamide;

[0828] (5B) semiaromatic polyamides containing diamine units and dicarboxylic acid units;

[0829] (5C1) flame retardant;

[0830] (5C2) flame retardant additives;

[0831] (5D) white pigment;

[0832] (5E) Ultraviolet absorber.

[0833] The molecular weight and tan δ peak temperature of the polyamide composition of the embodiment described above can be obtained as follows, and can be specifically measured by the method described in the examples described later.

[0834] <Weight Average Molecular Weight (Mw) of Polyamide Composition>

[0835] As an indicator of the molecular weight of the polyamide composition, the weight average molecular weight (Mw) can be used.

[0836] The weight average molecular weight (Mw) of the polyamide composition is 10,000 to 50,000, preferably 17,000 to 40,000, more preferably 20,000 to 35,000, further preferably 22,000 to 34,000, even more preferably 24,000 to 33,000, and particularly preferably 25,000 to 32,000. Other preferred embodiments include 20,000 to 38,000, 25,000 to 36,000, 27,000 to 35,000, and 29,000 to 34,000.

[0837] When the weight average molecular weight (Mw) of the polyamide composition is within the above range, a polyamide having more excellent mechanical properties, particularly water absorption rigidity, hot rigidity, and flowability, can be obtained. In addition, molded articles obtained from polyamide compositions containing components such as fillers have more excellent surface appearance.

[0838] Examples of methods for controlling the Mw of the polyamide composition to fall within the above range include using (5A) aliphatic polyamide and (5B) semi-aromatic polyamide having Mw within the ranges described below.

[0839] In addition, the measurement of Mw (weight average molecular weight) can be measured using GPC (gel permeation chromatography) as described in the examples described later.

[0840] <Total content of the polyamide having a number average molecular weight Mn of 500 or more and 2000 or less among the (5A) aliphatic polyamide and the (5B) semi-aromatic polyamide>

[0841] The total content of the aliphatic polyamide (5A) and the polyamide having a number average molecular weight Mn of 500 to 2000 among the semi-aromatic polyamide (5B) is preferably 0.5% by mass or more and less than 2.5% by mass, more preferably 0.8% by mass or more and less than 2.5% by mass, further preferably 1.0% by mass or more and less than 2.5% by mass, still further preferably 1.2% by mass or more and less than 2.5% by mass, and particularly preferably 1.4% by mass or more and less than 2.5% by mass, relative to the total mass of the polyamide in the polyamide composition. In other preferred embodiments, the total content may be 1.0% by mass or more and less than 2.0% by mass, 1.4% by mass or more and less than 1.8% by mass, or 1.6% by mass or more and less than 1.8% by mass.

[0842] When the total content of the aliphatic polyamide (5A) and the polyamide having a number average molecular weight Mn of 500 or more and 2000 or less among the semi-aromatic polyamide (5B) is at least the above lower limit, the flowability tends to be further improved, and the surface appearance of a molded article obtained from the polyamide composition containing components represented by the filler (5G) can be further improved. In addition, when the total content is less than the above upper limit, gas generation during molding tends to be more effectively suppressed.

[0843] As a method for controlling the total content of the aliphatic polyamide (5A) and the polyamide having a number average molecular weight Mn of 500 or more and 2000 or less in the semi-aromatic polyamide (5B) to fall within the above range, for example, a method of adjusting the molecular weight of the semi-aromatic polyamide (5B) can be mentioned. In this case, the weight average molecular weight (Mw(5B)) of the semi-aromatic polyamide (5B)) is preferably 10,000 or more and 25,000 or less.

[0844] The total content of the aliphatic polyamide (5A) and the polyamide having a number average molecular weight Mn of 500 to 2000 among the semi-aromatic polyamide (5B) can be determined using GPC from an elution curve under the measurement conditions in the examples described below.

[0845] Furthermore, when performing GPC measurement, if the composition containing the aliphatic polyamide (5A) and the semi-aromatic polyamide (5B) contains other components that are soluble in the solvent in which the polyamide is dissolved, the other components can be extracted and removed using a solvent in which the polyamide is insoluble but the other components are soluble, and then the GPC measurement can be performed. Furthermore, if the filler (5G) is insoluble in the solvent in which the polyamide is dissolved, the filler can be dissolved in a solvent in which the polyamide composition is dissolved, followed by filtration to remove the insoluble matter, and then the GPC measurement can be performed.

[0846] <Molecular Weight Distribution of Polyamide Composition>

[0847] The molecular weight distribution of the polyamide composition of the above embodiment is determined by weight average molecular weight (Mw) / number average molecular weight (Mn) as an index.

[0848] The weight average molecular weight (Mw) / number average molecular weight (Mn) of the polyamide composition of the above embodiment is 2.4 or less, preferably 1.0 or more and 2.4 or less, more preferably 1.7 or more and 2.3 or less, further preferably 1.8 or more and 2.2 or less, and particularly preferably 1.9 or more and 2.1 or less.

[0849] When the weight average molecular weight (Mw) / number average molecular weight (Mn) is within the above range, a polyamide composition having better fluidity, etc. is likely to be obtained. In addition, molded articles obtained from polyamide compositions containing components represented by the filler (5G) tend to have better surface appearance.

[0850] Examples of methods for controlling the weight average molecular weight (Mw) / number average molecular weight (Mn) of the polyamide composition within the above range include a method for adjusting the weight average molecular weight (Mw(5B)) / number average molecular weight (Mn(5B)) of the (5B) semi-aromatic polyamide within the range described below.

[0851] When a polyamide composition contains aromatic compound units in its molecular structure, its molecular weight distribution (Mw / Mn) tends to increase with increasing molecular weight. A high molecular weight distribution indicates a high proportion of polyamide molecules with a three-dimensional molecular structure. Therefore, by controlling the Mw / Mn ratio within the above range, the progression of three-dimensional molecular structure during high-temperature processing can be suppressed, resulting in a polyamide composition with improved flowability and other properties. Furthermore, molded articles obtained from polyamide compositions containing components such as fillers (5G) exhibit improved surface appearance.

[0852] The weight average molecular weight (Mw) / number average molecular weight (Mn) of the polyamide composition can be calculated using the weight average molecular weight (Mw) and number average molecular weight (Mn) obtained by GPC as described in Examples below.

[0853] <Tan δ Peak Temperature of Polyamide Composition>

[0854] The lower limit of the tan δ peak temperature of the polyamide composition is 90°C, preferably 105°C, more preferably 110°C, and even more preferably 115°C.

[0855] On the other hand, the upper limit of the tan δ peak temperature of the polyamide composition is preferably 150°C, more preferably 140°C, and even more preferably 130°C.

[0856] That is, the tanδ peak temperature of the polyamide composition is 90°C or higher, preferably 105°C or higher and 150°C or lower, more preferably 110°C or higher and 140°C or lower, and even more preferably 115°C or higher and 130°C or lower.

[0857] When the tanδ peak temperature of the polyamide composition is above the lower limit mentioned above, it tends to yield a polyamide composition with superior water absorption rigidity and thermal rigidity. On the other hand, when the tanδ peak temperature of the polyamide composition is below the upper limit mentioned above, molded articles obtained from polyamide compositions containing components represented by (5G) filler tend to have a superior surface appearance.

[0858] As a method for controlling the tanδ peak temperature of the polyamide composition within the above-mentioned range, for example, methods for controlling the content of (5A) aliphatic polyamide and (5B) semi-aromatic polyamide within the range described later can be listed.

[0859] <The ratio of the molar amount of the amino terminus to the total molar amount of the amino terminus and the carboxyl terminus>

[0860] In the polyamide composition described above, the ratio of the molar amount of the amino terminus to the total molar amount of the amino terminus and the carboxyl terminus {amino terminus / (amino terminus + carboxyl terminus)} is preferably 0.1 or more and less than 0.5, more preferably 0.25 or more and less than 0.45, further preferably 0.25 or more and less than 0.4, and even more preferably 0.25 or more and less than 0.35.

[0861] When the ratio of the molar amount of amino-terminal groups to the total molar amount of amino-terminal groups and carboxyl-terminal groups is above the lower limit mentioned above, it tends to be more effective in suppressing corrosion of extruders and molding machines. When the ratio of the molar amount of amino-terminal groups to the total molar amount of amino-terminal groups and carboxyl-terminal groups is less than the upper limit mentioned above, it tends to be possible to produce polyamide compositions with better color change resistance to heat and light.

[0862] <(5E) mass ratio of UV absorber to (5D) white pigment ((5E) / (5D))>

[0863] In the polyamide composition described above, the mass ratio of (5E) UV absorber to (5D) white pigment ((5E) UV absorber / (5D) white pigment) is 0.15 or more and less than 2.50, preferably 0.15 or more and less than 2.0, more preferably 0.20 or more and less than 2.0, further preferably 0.30 or more and less than 1.5, and particularly preferably 0.30 or more and less than 1.0.

[0864] When (5E) / (5D) is equal to or greater than the above lower limit, a polyamide composition having better weathering resistance and discoloration resistance can be obtained. When (5E) / (5D) is less than the above upper limit, a polyamide composition having better moldability, appearance, and mechanical properties can be obtained.

[0865] The polyamide composition of the above embodiment, by having the above-mentioned configuration, can form a molded article having excellent weld strength and Rockwell hardness when absorbing water, surface appearance, and weathering discoloration resistance.

[0866] Hereinafter, each constituent component of the polyamide composition of the above embodiment will be described in detail.

[0867] <(5A) Aliphatic Polyamide>

[0868] The aliphatic polyamide (5A) contained in the polyamide composition of the above embodiment preferably contains the following structural unit (1) or (2).

[0869] (1) Contains (5A-a) an aliphatic dicarboxylic acid unit and (5A-b) an aliphatic diamine unit.

[0870] (2) It contains at least one selected from the group consisting of (5A-c) lactam units and aminocarboxylic acid units.

[0871] [(5A-a) Aliphatic dicarboxylic acid unit]

[0872] Examples of the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit (5A-a) include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms.

[0873] Examples of the linear saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms include, but are not limited to, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid.

[0874] Examples of branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms include, but are not limited to, dimethylmalonic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, and trimethyladipic acid.

[0875] The aliphatic dicarboxylic acid constituting these (5A-a) aliphatic dicarboxylic acid units may be used alone or in combination of two or more.

[0876] Among them, the polyamide composition tends to have better heat resistance, flowability, toughness, low water absorption and rigidity. Therefore, as for the aliphatic dicarboxylic acid constituting the (5A-a) aliphatic dicarboxylic acid unit, a straight-chain saturated aliphatic dicarboxylic acid with 6 or more carbon atoms is preferred.

[0877] Preferred linear saturated aliphatic dicarboxylic acids with 6 or more carbon atoms include, for example: adipic acid, sebacic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, etc.

[0878] Among them, adipic acid, sebacic acid, or dodecanoic acid are preferred as linear saturated aliphatic dicarboxylic acids with 6 or more carbon atoms, from the viewpoint of heat resistance of the polyamide composition.

[0879] Furthermore, the aliphatic polyamide (5A) may further contain units derived from trivalent or higher polycarboxylic acids as needed, within a range that does not impair the effects of the polyamide composition of the above embodiment. Examples of trivalent or higher polycarboxylic acids include trimellitic acid, trimesic acid, and pyromellitic acid. These trivalent or higher polycarboxylic acids may be used alone or in combination of two or more.

[0880] [(5A-b) Aliphatic diamine unit]

[0881] Examples of aliphatic diamines that constitute the (5A-b) aliphatic diamine unit include linear saturated aliphatic diamines with 2 or more carbon atoms and 20 or fewer carbon atoms, or branched saturated aliphatic diamines with 3 or more carbon atoms and 20 or fewer carbon atoms.

[0882] As for straight-chain saturated aliphatic diamines with 2 or more but less than 20 carbon atoms, they are not limited to the following substances, for example: ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, etc.

[0883] As for branched saturated aliphatic diamines with 3 or more but less than 20 carbon atoms, they are not limited to the following substances, for example: 2-methylpentamethylenediamine (also known as 2-methyl-1,5-diaminopentane), 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyl-1,8-octanediamine (also known as 2-methyloctamethylenediamine), 2,4-dimethyloctamethylenediamine, etc.

[0884] These aliphatic diamines that constitute the (5A-b) aliphatic diamine unit can be used alone or in combination of two or more.

[0885] The number of carbon atoms in the aliphatic diamine constituting the aliphatic diamine unit (5A-b) is preferably 6 or more and 12 or less, more preferably 6 or more and 10 or less. When the number of carbon atoms in the aliphatic diamine constituting the aliphatic diamine unit (5A-b) is at least the lower limit, the resulting molded article has further excellent heat resistance. On the other hand, when the number of carbon atoms is at most the upper limit, the resulting molded article has further excellent crystallinity and releasability.

[0886] Preferred linear or branched saturated aliphatic diamines with 6 or more but less than 12 carbon atoms include, for example, hexamethylenediamine, 2-methylpentamethylenediamine, or 2-methyl-1,8-octanediamine.

[0887] Among these, hexamethylenediamine or 2-methylpentamethylenediamine is preferred as a straight-chain or branched saturated aliphatic diamine with 6 or more but less than 12 carbon atoms. By containing such (5A-b) aliphatic diamine units, the molded articles obtained from the polyamide composition exhibit superior heat resistance and rigidity.

[0888] Furthermore, without impairing the effect of the polyamide composition described above, (5A) the aliphatic polyamide may, as needed, contain units derived from ternary or higher polyaliphatic amines. Examples of ternary or higher polyaliphatic amines include, for instance, bis(hexamethylene)triamine.

[0889] [(5A-c) is selected from at least one of the group consisting of lactam units and aminocarboxylic acid units]

[0890] (5A) The aliphatic polyamide may contain at least one of (5A-c) selected from the group consisting of lactam units and aminocarboxylic acid units instead of the (5A-a) aliphatic dicarboxylic acid units and (5A-b) aliphatic diamine units. By containing such units, polyamides with excellent toughness are tended to be obtained.

[0891] It should be noted that the "lactam unit" and "aminocarboxylic acid unit" referred to here are the (condensed) polymerized lactam and aminocarboxylic acid.

[0892] As for lactams that constitute a lactam unit or an aminocarboxylic acid unit, they are not limited to the following substances, for example: butyrolactam, neopentyl lactam, ε-caprolactam, octyl lactam, heptanolactam, undecyl lactam, laurolactam (dodecyl lactam), etc.

[0893] Among them, as the lactam constituting the lactam unit or the aminocarboxylic acid unit, ε-caprolactam or laurolactam is preferred, and ε-caprolactam is more preferred. By containing such a lactam, the toughness of a molded article obtained from the polyamide composition tends to be further improved.

[0894] The aminocarboxylic acid constituting the aminocarboxylic acid unit is not limited to the following, and examples thereof include ω-aminocarboxylic acid and α,ω-amino acid, which are compounds obtained by ring-opening of lactam.

[0895] The aminocarboxylic acid constituting the aminocarboxylic acid unit is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms, substituted with an amino group at the ω position. Examples of such aminocarboxylic acids include, but are not limited to, 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Examples of aminocarboxylic acids include p-aminomethylbenzoic acid.

[0896] The lactam and aminocarboxylic acid constituting at least one selected from the group consisting of lactam units and aminocarboxylic acid units in (5A-c) may be used alone or in combination of two or more.

[0897] Among them, the aliphatic polyamide (5A) contained in the polyamide composition of the above embodiment is preferably a polyamide containing a dicarboxylic acid unit and a diamine unit, and more preferably polyamide 66 (PA66), from the viewpoints of mechanical properties, heat resistance, moldability, and toughness. PA66 has excellent mechanical properties, heat resistance, moldability, and toughness, and is therefore considered to be a suitable material for automotive parts.

[0898] The content of the (5A) aliphatic polyamide in the polyamide composition of the above embodiment can be, for example, 10% by mass or more and less than 100% by mass, for example, 13% by mass or more and 90% by mass or less, for example, 50% by mass or more and 70% by mass or less, for example, 55% by mass or more and 70% by mass or less, for example, 50% by mass or more and 100% by mass or less, for example, 55% by mass or more and 100% by mass or less, for example, 57% by mass or more and 100% by mass or less, relative to the total mass of the polyamide in the polyamide composition.

[0899] <(5B) Semi-aromatic polyamide>

[0900] The (5B) semi-aromatic polyamide contained in the polyamide composition of the above embodiment is a polyamide containing a diamine unit and a dicarboxylic acid unit.

[0901] The semi-aromatic polyamide (5B) preferably contains 20 mol% to 80 mol% of aromatic structural units, more preferably 30 mol% to 70 mol% of aromatic structural units, and even more preferably 40 mol% to 60 mol% of aromatic structural units, relative to the total structural units of the semi-aromatic polyamide (5B). The "aromatic structural units" herein refer to aromatic diamine units and aromatic dicarboxylic acid units.

[0902] Compared to all the dicarboxylic acid units of the (5B) semi-aromatic polyamide, the (5B) semi-aromatic polyamide is preferably a polyamide containing (5B-a) dicarboxylic acid units and (5B-b) diamine units, wherein the (5B-a) dicarboxylic acid units contain more than 50 mol% isophthalic acid units, and the (5B-b) diamine units contain diamine units with 4 or more and 10 or fewer carbon atoms.

[0903] Furthermore, at this time, relative to all the constituent units of the (5B) semi-aromatic polyamide, the total content of isophthalic acid units and diamine units with 4 or more and 10 or less carbon atoms in the (5B) semi-aromatic polyamide is preferably 50 mol% or more, more preferably 80 mol% or more and 100 mol% or less, further preferably 90 mol% or more and 100 mol% or less, and particularly preferably 100 mol%.

[0904] The ratio of the predetermined monomer units constituting the semi-aromatic polyamide (5B) can be measured by nuclear magnetic resonance spectroscopy (NMR) or the like.

[0905] [(5B-a) dicarboxylic acid unit]

[0906] The dicarboxylic acid unit (5B-a) is not particularly limited, and examples thereof include an aromatic dicarboxylic acid unit, an aliphatic dicarboxylic acid unit, and an alicyclic dicarboxylic acid unit.

[0907] Of which, as a (5B-a) dicarboxylic acid unit, relative to the total number of moles of (5B-a) dicarboxylic acid, it is preferable to contain more than 50 mol% of isophthalic acid, more preferably more than 65 mol% and less than 100 mol% of isophthalic acid, further preferably more than 70 mol% and less than 100 mol% of isophthalic acid, particularly preferably more than 80 mol% and less than 100 mol% of isophthalic acid, and most preferably 100 mol%.

[0908] When the proportion of isophthalic acid units in the (5B-a) dicarboxylic acid units is above the aforementioned lower limit, it is preferable to obtain a polyamide composition that can simultaneously satisfy mechanical properties, particularly water absorption rigidity, thermal rigidity, and flowability. Furthermore, molded articles obtained from polyamide compositions tend to have superior surface appearance.

[0909] (Aromatic dicarboxylic acid unit)

[0910] The aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit other than the isophthalic acid unit is not limited to the following, and examples thereof include dicarboxylic acids having aromatic groups such as phenyl and naphthyl. The aromatic group of the aromatic dicarboxylic acid may be unsubstituted or may have a substituent.

[0911] There are no particular restrictions on the substituent, and examples thereof include an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, a halogen group, a silyl group having 1 to 6 carbon atoms, a sulfonic acid group and its salts (sodium salts, etc.).

[0912] Examples of the alkyl group having 1 to 4 carbon atoms are not limited to the following groups, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0913] Examples of the aryl group having 6 to 10 carbon atoms are not limited to the following groups, and examples thereof include phenyl, tolyl, xylyl, and naphthyl.

[0914] Examples of the aralkyl group having 7 to 10 carbon atoms are not limited to the following groups, and examples thereof include benzyl group.

[0915] Examples of the halogen group include, but are not limited to, fluoro, chloro, bromo, and iodo groups.

[0916] The silyl group having 1 to 6 carbon atoms is not limited to the following groups, and examples thereof include a trimethylsilyl group and a tert-butyldimethylsilyl group.

[0917] Among them, as the aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit other than the isophthalic acid unit, an aromatic dicarboxylic acid having 8 to 20 carbon atoms, which is unsubstituted or substituted with a predetermined substituent, is preferred.

[0918] Specific examples of the unsubstituted or substituted aromatic dicarboxylic acid having 8 to 20 carbon atoms include, but are not limited to, terephthalic acid, naphthalene dicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalate.

[0919] The aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit may be used alone or in combination of two or more.

[0920] (aliphatic dicarboxylic acid unit)

[0921] Examples of the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms.

[0922] Examples of the linear saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms include, but are not limited to, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid.

[0923] Examples of branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms include, but are not limited to, dimethylmalonic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, and trimethyladipic acid.

[0924] (alicyclic dicarboxylic acid unit)

[0925] The alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit is not limited to the following, and examples thereof include alicyclic dicarboxylic acids having an alicyclic structure with carbon atoms of 3 or more and 10 or less. Among these, alicyclic dicarboxylic acids having carbon atoms of 5 or more and 10 or less in the alicyclic structure are preferred.

[0926] Such alicyclic dicarboxylic acids are not limited to the following, and examples thereof include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid. Among them, 1,4-cyclohexanedicarboxylic acid is preferred as the alicyclic dicarboxylic acid.

[0927] In addition, the alicyclic dicarboxylic acid which comprises an alicyclic dicarboxylic acid unit may be used individually by 1 type, and may use 2 or more types together.

[0928] The alicyclic group of the alicyclic dicarboxylic acid may be unsubstituted or may have a substituent. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include the same alkyl groups as exemplified in the "aromatic dicarboxylic acid unit" described above.

[0929] As the dicarboxylic acid units other than the isophthalic acid unit, it is preferred to contain an aromatic dicarboxylic acid unit, and more preferably to contain an aromatic dicarboxylic acid having 6 or more carbon atoms.

[0930] By using such a dicarboxylic acid, a polyamide composition that satisfies all mechanical properties, particularly water absorption rigidity, hot rigidity, flowability, etc., tends to be obtained. In addition, molded articles obtained from the polyamide composition tend to have more excellent surface appearance.

[0931] In the (5B) semi-aromatic polyamide, the dicarboxylic acid constituting the (5B-a) dicarboxylic acid unit is not limited to the compounds described above as the dicarboxylic acid, and may be a compound equivalent to the above dicarboxylic acid.

[0932] The term "compound equivalent to a dicarboxylic acid" as used herein refers to a compound that can form a dicarboxylic acid structure similar to the dicarboxylic acid structure derived from the aforementioned dicarboxylic acid. Such compounds are not limited to the following, and examples thereof include anhydrides of dicarboxylic acids and halides of dicarboxylic acids.

[0933] In addition, without compromising the effect of the polyamide composition described above, (5B) the semi-aromatic polyamide may, as needed, contain units derived from ternary or more polycarboxylic acids.

[0934] Examples of trivalent or higher polycarboxylic acids include trimellitic acid, trimesic acid, pyromellitic acid, etc. These trivalent or higher polycarboxylic acids may be used alone or in combination of two or more.

[0935] [(5B-b) diamine unit]

[0936] The diamine unit (5B-b) constituting the semi-aromatic polyamide (5B) is not particularly limited, and examples thereof include aromatic diamine units, aliphatic diamine units, and alicyclic diamine units. Among these, the diamine unit (5B-b) constituting the semi-aromatic polyamide (5B) preferably contains a diamine unit having 4 to 10 carbon atoms, and more preferably contains a diamine unit having 6 to 10 carbon atoms.

[0937] (aliphatic diamine unit)

[0938] Examples of aliphatic diamines that constitute aliphatic diamine units include linear saturated aliphatic diamines with 4 or more but less than 20 carbon atoms.

[0939] Examples of the linear saturated aliphatic diamine having 4 to 20 carbon atoms include, but are not limited to, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine.

[0940] (alicyclic diamine unit)

[0941] The alicyclic diamine constituting the alicyclic diamine unit is not limited to the following, and examples thereof include 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and 1,3-cyclopentanediamine.

[0942] (Aromatic diamine unit)

[0943] The aromatic diamine constituting the aromatic diamine unit is not limited to the following as long as it is a diamine containing an aromatic group. Specific examples of the aromatic diamine include meta-xylylenediamine.

[0944] In addition, these diamines which constitute each diamine unit may be used alone or in combination of two or more.

[0945] Among them, as the (5B-b) diamine unit, an aliphatic diamine unit is preferred, a linear saturated aliphatic diamine unit having 4 to 10 carbon atoms is more preferred, a linear saturated aliphatic diamine unit having 6 to 10 carbon atoms is further preferred, and a hexamethylenediamine unit is particularly preferred.

[0946] By using such a diamine, a polyamide composition that satisfies all mechanical properties, particularly water absorption rigidity, hot rigidity, flowability, etc., tends to be obtained. In addition, molded articles obtained from the polyamide composition tend to have more excellent surface appearance.

[0947] The semi-aromatic polyamide (5B) contained in the polyamide composition of the above embodiment is preferably polyamide 6I (poly(hexamethylene isophthalamide), polyamide 9I), or polyamide 10I, and more preferably polyamide 6I. Polyamide 6I is considered to be a suitable material for automotive parts due to its excellent heat resistance, moldability, and flame retardancy.

[0948] The content of the semi-aromatic polyamide (5B) in the polyamide composition of the above embodiment can be set to 5.0% by mass or more and 50.0% by mass or less, preferably 10.0% by mass or more and 50% by mass or less, more preferably 15.0% by mass or more and 50% by mass or less, further preferably 20.0% by mass or more and 50% by mass or less, particularly preferably 30% by mass or more and 50% by mass or less, and most preferably 30% by mass or more and 45% by mass or less, relative to the total mass of the polyamide in the polyamide composition. In other preferred embodiments, the content can be greater than 0% by mass and less than 90% by mass, or greater than 10% by mass and less than 87% by mass.

[0949] By setting the content of the semi-aromatic polyamide (5B) within the above range, the mechanical properties of the molded article obtained from the polyamide composition are further improved. In addition, by containing components such as the filler (5G), the surface appearance of the molded article obtained from the polyamide composition is further improved.

[0950] <Capping Agent>

[0951] The ends of the polyamides ((5A) aliphatic polyamide and (5B) semi-aromatic polyamide) contained in the polyamide composition described above can be capped using a known capping agent.

[0952] The blocking agent is as described in the above embodiment 1-1.

[0953] <(5A) Methods for manufacturing aliphatic polyamides and (5B) semi-aromatic polyamides>

[0954] The method for producing polyamide is the same as described in the above embodiment 1-1 except that the (1A) aliphatic polyamide is replaced by the (5A) aliphatic polyamide and the (1B) semi-aromatic polyamide is replaced by the (5B) semi-aromatic polyamide.

[0955] <Polymer Terminals of Polyamide>

[0956] For the polymer ends of polyamide, as described in method 1-1 above.

[0957] <Characteristics of Polyamide>

[0958] [(5A) Characteristics of aliphatic polyamide]

[0959] The properties of (5A) aliphatic polyamide are as described in the section on "(1A) aliphatic polyamide" in the above-mentioned method 1-1.

[0960] [(5B) Characteristics of semi-aromatic polyamide]

[0961] The properties of the (5B) semi-aromatic polyamide are the same as those described in the "properties of the (1B) semi-aromatic polyamide" in the above-mentioned embodiment 1-1 except for the following points.

[0962] (Weight average molecular weight Mw(5B) of (5B) semi-aromatic polyamide)

[0963] As an indicator of the molecular weight of (5B) semi-aromatic polyamide, the weight-average molecular weight (Mw(5B)) of (5B) semi-aromatic polyamide can be used.

[0964] The weight average molecular weight (Mw(5B)) of the (5B) semi-aromatic polyamide is preferably 10,000 to 50,000, more preferably 13,000 to 40,000, further preferably 15,000 to 25,000, particularly preferably 18,000 to 22,000, and most preferably 19,000 to 21,000.

[0965] When the weight average molecular weight (Mw(5B)) of the semi-aromatic polyamide (5B) is within the above range, a polyamide composition having further improved mechanical properties, particularly water absorption rigidity, hot rigidity, and flowability, can be obtained. Furthermore, molded articles obtained from the polyamide composition containing components such as the filler (5G) can further improve the surface appearance.

[0966] The weight average molecular weight (Mw(5B)) of the (5B) semi-aromatic polyamide can be measured using GPC.

[0967] ((5B) Tan δ Peak Temperature of Semi-aromatic Polyamide)

[0968] The tan δ peak temperature of the (5B) semi-aromatic polyamide is preferably 70°C or higher, more preferably 100°C or higher and 160°C or lower, further preferably 110°C or higher and 150°C or lower, particularly preferably 120°C or higher and 145°C or lower, and most preferably 130°C or higher and 140°C or lower.

[0969] Examples of methods for controlling the tan δ peak temperature of the semi-aromatic polyamide (5B) to fall within the above range include increasing the ratio of the aromatic monomer to the dicarboxylic acid unit. From this viewpoint, the semi-aromatic polyamide (5B) preferably contains 50 mol% or more of isophthalic acid as the dicarboxylic acid unit (5B-a), more preferably 100 mol%, of all the dicarboxylic acid units constituting the semi-aromatic polyamide (5B).

[0970] When the tan δ peak temperature of the semi-aromatic polyamide (5B) is at least the aforementioned lower limit, a polyamide composition having further excellent water absorption rigidity and hot rigidity tends to be obtained. Furthermore, when the tan δ peak temperature of the polyamide composition is at most the aforementioned upper limit, the surface appearance of a molded article obtained from the polyamide composition containing components such as the filler (5G) is further improved.

[0971] (5B) The tan δ peak temperature of the semi-aromatic polyamide can be measured using, for example, a viscoelasticity measurement analyzer (DVE-V4 manufactured by Rheology).

[0972] [Total amount of amino terminal group and carboxyl terminal group of polyamide]

[0973] The total amount of the amino terminal amount and the carboxyl terminal amount of the polyamide ((5A) aliphatic polyamide and (5B) semi-aromatic polyamide) relative to 1 g of the polyamide is 150 μ equivalent or more and 350 μ equivalent or less, preferably 160 μ equivalent or more and 330 μ equivalent or less, more preferably 170 μ equivalent or more and 320 μ equivalent or less, further preferably 180 μ equivalent or more and 300 μ equivalent or less, and particularly preferably 190 μ equivalent or more and 280 μ equivalent or less.

[0974] When the total amount of amino terminal groups and carboxyl terminal groups in the polyamide ((5A) aliphatic polyamide and (5B) semi-aromatic polyamide) is within the above range, a polyamide composition having improved flowability and other properties can be obtained. Furthermore, molded articles obtained from the polyamide composition containing components such as the filler (5G) have improved surface appearance.

[0975] <(5C1) Flame Retardant>

[0976] The flame retardant (5C1) is the same as described in connection with the "(2D1) flame retardant" in the above-mentioned embodiment 2-1.

[0977] <(5C2) Flame retardant additive>

[0978] The polyamide composition of the above embodiment can be made into a polyamide composition having further excellent flame retardancy by containing the flame retardant auxiliary agent (5C2).

[0979] The properties of the flame retardant auxiliary (5C2) are the same as those described in connection with the "(2D2) flame retardant auxiliary" in the above-mentioned embodiment 2-1.

[0980] <(5D) White Pigment>

[0981] The polyamide composition of the above embodiment contains (5D) a white pigment.

[0982] The white pigment is not particularly limited, and examples thereof include zinc sulfide, zinc oxide, titanium oxide, barium sulfate, calcium carbonate, aluminum oxide, lead carbonate, lead hydroxide, and silicon dioxide.

[0983] Among them, at least one selected from zinc sulfide (ZnS) and zinc oxide (ZnO) is preferred in view of the mechanical properties of the polyamide composition, such as toughness, strength, and rigidity, and the balance between flame retardancy and coloring.

[0984] <(5E) Ultraviolet Absorber>

[0985] The polyamide composition of the above embodiment contains (5E) an ultraviolet absorber.

[0986] The ultraviolet absorber is not particularly limited, and examples thereof include benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, benzophenone ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, salicylate ultraviolet absorbers, and oxalic acid anilide ultraviolet absorbers.

[0987] Among them, at least one selected from benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers is preferred in view of the mechanical properties of the polyamide composition, such as toughness, strength, and rigidity, and the balance between flame retardancy and coloring.

[0988] <(5F) Polymer containing α,β-unsaturated dicarboxylic acid anhydride units>

[0989] The polyamide composition of the above embodiment may further contain (5F) a polymer containing α,β-unsaturated dicarboxylic acid anhydride units in addition to the above components (5A) to (5E). The inclusion of (5F) a polymer containing α,β-unsaturated dicarboxylic acid anhydride units enables a polyamide composition having further improved mechanical properties such as toughness and rigidity.

[0990] Examples of the polymer (5F) containing an α,β-unsaturated dicarboxylic acid anhydride unit contained in the polyamide composition of the embodiment include polymers containing an α,β-unsaturated dicarboxylic acid anhydride as a copolymerization component and polymers modified with an α,β-unsaturated dicarboxylic acid anhydride.

[0991] Examples of the α,β-unsaturated dicarboxylic acid anhydride include compounds represented by the following general formula (I) (hereinafter sometimes referred to as “compound (I)”).

[0992]

[0993] In the above general formula (I), R 11 and R 12 Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 11 and R 12 They can be the same or different. 11 and R 12 Preferably they are identical to each other.

[0994] As R 11 and R 12 Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group.

[0995] Among them, as R 11 and R 12 As for the group, it is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0996] Preferred examples of compound (I) (α,β-unsaturated dicarboxylic acid anhydride) include maleic anhydride and methylmaleic anhydride. Among them, maleic anhydride is preferred as compound (I) (α,β-unsaturated dicarboxylic acid anhydride).

[0997] [Copolymer of aromatic vinyl compound and α,β-unsaturated dicarboxylic acid anhydride]

[0998] As the polymer containing an α,β-unsaturated dicarboxylic acid anhydride as a copolymerization component, a copolymer of an aromatic vinyl compound and an α,β-unsaturated dicarboxylic acid anhydride is preferred from the viewpoint of improving the efficiency of flame retardancy (expression with a small addition amount).

[0999] Examples of the aromatic vinyl compound used in the production of the copolymer of the aromatic vinyl compound and the α,β-unsaturated dicarboxylic acid anhydride include compounds represented by the following general formula (hereinafter sometimes referred to as “compound (II)”).

[1000]

[1001] In the above general formula (II), R 21 It is hydrogen or an alkyl group having 1 to 3 carbon atoms. 22 is a substituent of the benzene ring. 22 is an alkyl group having 1 to 3 carbon atoms. n21 is an integer of 0 to 5. When n21 is 0, the benzene ring is unsubstituted.

[1002] As R 21 and R 22 As for the alkyl group having 1 to 3 carbon atoms, examples include the same alkyl groups as exemplified in the above-mentioned compound (I).

[1003] Among them, R 21 Preferably, it is a hydrogen atom or a methyl group. 22 Preferred is methyl.

[1004] n21 represents R as a substituent of the benzene ring 22 n21 is preferably an integer greater than or equal to 0 and less than or equal to 1, and more preferably 0.

[1005] Preferred examples of compound (II) (aromatic vinyl compound) include styrene, α-methylstyrene, and p-methylstyrene. Among them, styrene is preferred as compound (II) (aromatic vinyl compound).

[1006] When the polymer (5F) containing α,β-unsaturated dicarboxylic acid anhydride units contains aromatic vinyl compound units, the aromatic vinyl compound units form an affinity with the flame retardant (5C1) (brominated polystyrene, etc.), while the α,β-unsaturated dicarboxylic acid anhydride units form an affinity or reaction with the semi-aromatic polyamide (5B). This is believed to facilitate the dispersion of the flame retardant (5C1) in the polyamide matrix, enabling the flame retardant to be finely dispersed.

[1007] Regarding the ratio of the aromatic vinyl compound units to the α,β-unsaturated dicarboxylic anhydride units in the copolymer of an aromatic vinyl compound and an α,β-unsaturated dicarboxylic anhydride, from the viewpoints of flame retardancy, fluidity, thermal decomposition resistance, etc. of the resulting polyamide composition, preferably, the aromatic vinyl compound units account for 50% to 99% by mass, and the α,β-unsaturated dicarboxylic anhydride units account for 1% to 50% by mass. Furthermore, the ratio of the α,β-unsaturated dicarboxylic anhydride units in the copolymer of an aromatic vinyl compound and an α,β-unsaturated dicarboxylic anhydride is more preferably 5% to 20% by mass, and even more preferably 8% to 15% by mass.

[1008] When the ratio of α,β-unsaturated dicarboxylic anhydride units in the copolymer of an aromatic vinyl compound and an α,β-unsaturated dicarboxylic anhydride is greater than the aforementioned lower limit, a polyamide composition having even better mechanical properties such as toughness and rigidity, as well as flame retardancy, can be obtained. On the other hand, when the ratio of α,β-unsaturated dicarboxylic anhydride units is less than the aforementioned upper limit, deterioration of the polyamide composition caused by the α,β-unsaturated dicarboxylic anhydride can be more effectively prevented.

[1009] [Polymer modified with α,β-unsaturated dicarboxylic acid anhydride]

[1010] Examples of polymers modified with an α,β-unsaturated dicarboxylic acid anhydride include polyphenylene ether and polypropylene modified with an α,β-unsaturated dicarboxylic acid anhydride. Among these, maleic anhydride-modified polyphenylene ether is preferred.

[1011] The content of the polymer modified with the α,β-unsaturated dicarboxylic acid anhydride is preferably 0.05% by mass or more and 5% by mass or less relative to the total mass of the polyamide composition.

[1012] <(5G) Filling Material>

[1013] The polyamide composition of the above embodiment may further contain (5G) a filler in addition to the above components (5A) to (5F). By containing the filler (5G), a polyamide composition having further excellent mechanical properties such as toughness and rigidity can be obtained.

[1014] The filler (5G) contained in the polyamide composition of the above embodiment is not particularly limited, and examples thereof include glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, flaky glass, talc, kaolin, mica, hydrotalcite, zinc carbonate, calcium monohydrogen phosphate, wollastonite, zeolite, boehmite, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, Ketjen black, acetylene black, furnace black, carbon nanotubes, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swelling fluorine mica, apatite, and the like.

[1015] These (5G) fillers may be used alone or in combination of two or more.

[1016] Among them, the filler (5G) is preferably glass fiber, carbon fiber, flaky glass, talc, kaolin, mica, calcium monohydrogen phosphate, wollastonite, carbon nanotubes, graphite, calcium fluoride, montmorillonite, swelling fluorine mica, or apatite from the viewpoints of rigidity and strength. Furthermore, the filler (5G) is more preferably glass fiber or carbon fiber. Glass fiber is further preferred.

[1017] (5G) When the filling material is glass fiber or carbon fiber, the number average fiber diameter (D) is preferably 3 μm or more and 30 μm or less. In addition, the weight average fiber length (L) is preferably 100 μm or more and 750 μm or less. In addition, the aspect ratio ((L) / (D)) of the number average fiber diameter (D) to the weight average fiber length (L) is preferably 10 or more and 100 or less. By using the glass fiber or carbon fiber having the above-mentioned structure, higher properties can be exhibited.

[1018] Furthermore, when the (5G) filler is glass fiber, the number average fiber diameter (D) is more preferably 3 μm to 30 μm. The weight average fiber length (L) is more preferably 103 μm to 500 μm. Furthermore, the aspect ratio ((L) / (D)) is more preferably 3 to 100.

[1019] (5G) The number average fiber diameter and weight average fiber length of the filler can be measured using the following method.

[1020] First, a molded article of a polyamide composition is dissolved in a polyamide-soluble solvent, such as formic acid. Next, at least 100 filler particles are randomly selected from the resulting insoluble fraction. The filler particles are then observed using an optical microscope, scanning electron microscope, or the like to determine their content.

[1021] <Contents of (5C1) to (5G) in the Polyamide Composition> [Content of (5C1) Flame Retardant]

[1022] The content of the flame retardant (5C1) in the polyamide composition of the above embodiment is preferably 0.1 mass % to 30 mass % relative to the total mass of the polyamide composition, more preferably 5 mass % to 20 mass % and even more preferably 5 mass % to 15 mass %.

[1023] By setting the content of the flame retardant (5C1) to above the aforementioned lower limit, a polyamide composition with even better flame retardancy can be obtained. On the other hand, by setting the content of the flame retardant (5C1) to below the aforementioned upper limit, the generation of decomposition gases during melt kneading, the reduction in fluidity during molding, and the adhesion of contaminants to the molding die can be more effectively suppressed. Furthermore, the deterioration of mechanical properties such as toughness and rigidity, as well as the appearance of the molded product, can be more effectively suppressed.

[1024] [(5C2) flame retardant additive content]

[1025] The content of the flame retardant auxiliary (5C2) in the polyamide composition of the above embodiment is preferably 0.1% by mass to 10% by mass, more preferably 1% by mass to 10% by mass, relative to the total mass of the polyamide composition.

[1026] By setting the content of the flame retardant auxiliary (5C2) to above the aforementioned lower limit, a polyamide composition with even better flame retardancy can be obtained. By setting the content of the flame retardant auxiliary (5C2) to below the aforementioned upper limit, the viscosity during melt processing can be controlled within an appropriate range, and an increase in torque during extrusion, a decrease in moldability during molding, and deterioration in the appearance of the molded product can be more effectively suppressed. Furthermore, a polyamide composition with even better toughness, etc., can be obtained without compromising the properties of the polyamide, which has excellent mechanical properties such as toughness and rigidity.

[1027] [Type and content of (5C1) flame retardant and (5C2) flame retardant auxiliary]

[1028] As a particularly preferred combination of the flame retardant (5C1) and the flame retardant auxiliary (5C2) contained in the polyamide composition of the above embodiment, the flame retardant (5C1) is brominated polystyrene, and the content of the brominated polystyrene is 6 mass% or more and 15 mass% or less relative to the total mass of the polyamide composition, and the flame retardant auxiliary (5C2) is antimony trioxide (Sb2O3), and the content of antimony trioxide (Sb2O3) is 0.1 mass% or more and 4 mass% or less relative to the total mass of the polyamide composition.

[1029] [(5D) White pigment content]

[1030] The content of (5D) white pigment in the polyamide composition described above is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.5% by mass or more and 5% by mass or less, relative to the total mass of the polyamide composition.

[1031] When the content of the (5D) white pigment is within the above range, the color tone and mechanical properties (particularly mechanical strength) of the obtained polyamide composition tend to be better.

[1032] [(5E) Content of UV absorber]

[1033] Relative to the total mass of the polyamide composition, the content of (5E) ultraviolet absorber in the polyamide composition of the above manner is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.3% by mass or more and 3% by mass or less, further preferably 0.4% by mass or more and 3% by mass or less, and particularly preferably 0.5% by mass or more and 3% by mass or less.

[1034] In particular, by using (5E) ultraviolet absorber as at least one of the group consisting of benzotriazole and triazine ultraviolet absorbers, and by ensuring that the content of (5E) ultraviolet absorber is within the above-mentioned range relative to the total mass of the polyamide composition, a polyamide composition with superior weather resistance and colorfastness and mechanical properties (especially mechanical strength) can be obtained.

[1035] [(5F) Content of polymer containing α,β-unsaturated dicarboxylic acid anhydride units]

[1036] When the polyamide composition of the above embodiment contains (7E) a polymer containing α,β-unsaturated dicarboxylic acid anhydride units, the content of (5F) a polymer containing α,β-unsaturated dicarboxylic acid anhydride units in the polyamide composition is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less, further preferably 1% by mass or more and 15% by mass or less, and particularly preferably 1% by mass or more and 10% by mass or less, relative to the total mass of the polyamide composition.

[1037] When the content of the polymer (5F) containing α,β-unsaturated dicarboxylic acid anhydride units is at least the above lower limit, the microdispersion effect of the flame retardant (5C1) in the polyamide composition due to compatibilization can be further enhanced. Furthermore, a polyamide composition with even greater improvements in flame retardancy and strength tends to be obtained. Furthermore, when the content of the polymer (5F) containing α,β-unsaturated dicarboxylic acid anhydride units is at most the above upper limit, a polyamide composition with even greater improvements in strength tends to be obtained without impairing the mechanical properties (particularly toughness and rigidity) of the polyamide.

[1038] [Content of (5G) filler material]

[1039] When the polyamide composition of the above embodiment contains a filler (5G), the content of the filler (5G) in the polyamide composition is preferably 1% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 70% by mass or less, further preferably 30% by mass or more and 70% by mass or less, particularly preferably 30% by mass or more and 60% by mass or less, and most preferably 40% by mass or more and 60% by mass or less, relative to the total mass of the polyamide composition.

[1040] When the content of the filler (5G) is at least the lower limit, the mechanical properties of the polyamide composition, such as strength and rigidity, tend to be further improved. On the other hand, when the content of the filler (5G) is at most the upper limit, a polyamide composition with even better moldability tends to be obtained.

[1041] In particular, when the (5G) filler is glass fiber and the content of the (5G) filler relative to the total mass of the polyamide composition is within the above range, the mechanical properties such as strength and rigidity of the polyamide composition tend to be further improved.

[1042] [Total content of (5C1) to (5G) components]

[1043] The total content of the flame retardant (5C1), the flame retardant auxiliary (5C2), the white pigment (5D), the ultraviolet absorber (5E), the polymer containing α,β-unsaturated dicarboxylic acid anhydride units (5F), and the filler (5G) in the polyamide composition of the above embodiment is preferably 10% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 80% by mass or less, and even more preferably 40% by mass or more and 75% by mass or less, relative to the total mass of the polyamide composition. When the total content of the components (5C1) to (5G) in the polyamide composition of the above embodiment is at least the above lower limit, a polyamide composition having improved strength, rigidity, and flame retardancy can be obtained. Furthermore, a polyamide composition having an appropriate melt viscosity and improved processability can be obtained.

[1044] <(5H) Other Additives>

[1045] The polyamide composition of the above embodiment may further contain (5H) other additives commonly used in polyamides, in addition to the above components (5A) to (5G), within a range that does not impair the effects of the polyamide composition of the above embodiment. Examples of the other additives (5H) include (5H1) moldability improvers and lubricants, (5H2) degradation inhibitors, (5H3) nucleating agents, (5H4) heat stabilizers, and (5H5) other resins other than the above-mentioned (5A) aliphatic polyamide and (5B) semi-aromatic polyamide.

[1046] The content of other additives (5H) in the polyamide composition described above varies depending on their type, the application of the polyamide composition, etc. Therefore, there are no particular restrictions as long as they do not impair the effect of the polyamide composition described above. For example, the total amount of other additives (6J) in the polyamide composition can be less than 50% by mass, less than 10% by mass, less than 5% by mass, and less than 1% by mass.

[1047] [(5H1) Molding modifiers and lubricants]

[1048] The moldability improver and the lubricant (5H1) are the same as those described with respect to the "lubricant" in the above-mentioned embodiment 1-1.

[1049] [(5H2) Deterioration Inhibitor]

[1050] The (5H2) degradation inhibitor contained in the polyamide composition of the above embodiment is used for the purpose of preventing thermal degradation and discoloration during heating and improving heat aging resistance.

[1051] The (5H2) degradation inhibitor is as described above with respect to the "degradation inhibitor" in the embodiment 2-1.

[1052] [(5H3) nucleating agent]

[1053] The (5H3) nucleating agent is as described above regarding the "nucleating agent" in the embodiment 1-1.

[1054] [(5H4) heat stabilizer]

[1055] The (5H4) thermal stabilizer is as described above with respect to the "stabilizer" in the embodiment 1-1.

[1056] [(5H6)Other resins]

[1057] (5H6) Other resins are as described in the above-mentioned embodiment 2-1 regarding "other resins".

[1058] <Method for manufacturing polyamide compositions>

[1059] As for the method of manufacturing the polyamide composition described above, there are no particular limitations as long as the method of mixing (5A) aliphatic polyamide with each of the above-mentioned components (5B) to (5E) and components (5F) and (5G) as needed is used.

[1060] Examples of a method for mixing the components (5A) to (5E) and, if necessary, the components (5F) and (5G) include the following method (1) or (2).

[1061] (1) A method in which the above components (5A) to (5E) and, if necessary, components (5F) and (5G) are mixed using a Henschel mixer or the like, and the mixture is supplied to a melt kneader for kneading.

[1062] (2) A method in which a mixture containing the components (5A) to (5E) and the component (5F) as required is prepared by pre-mixing the components (5A) to (5E) and the component (5F) as required using a single-screw or twin-screw extruder, feeding the mixture to a melt kneader for kneading, and then optionally adding a filler (5G) from a side feed port.

[1063] In the method of supplying the components constituting the polyamide composition to the melt-kneader, all the components may be supplied at once to the same supply port, or the components may be supplied from different supply ports.

[1064] The melt kneading temperature is preferably about 1°C higher than the melting point of the aliphatic polyamide (5A) and about 100°C lower, more preferably about 10°C higher than the melting point of the aliphatic polyamide (5A) and about 50°C lower.

[1065] The shear rate in the mixer is preferably about 100 seconds -1 In addition, the average residence time during kneading is preferably about 0.5 minutes or more and about 5 minutes or less.

[1066] As an apparatus for performing melt kneading, any known apparatus may be used, and for example, a single-screw or twin-screw extruder, a Banbury mixer, a melt kneader (kneading roll, etc.) or the like is preferably used.

[1067] The amount of each component added when producing the polyamide composition of the above embodiment is the same as the content of each component in the above-mentioned polyamide composition.

[1068] Molded Products

[1069] The molded article of the 5-2 embodiment of the present invention is obtained by molding the polyamide composition of the above embodiment.

[1070] Furthermore, the molded article of the above embodiment has a high surface glossiness. The surface glossiness of the molded article of the above embodiment is preferably 50 or greater, more preferably 55 or greater, and even more preferably 60 or greater. When the surface glossiness of the molded article is at least the above lower limit, the obtained molded article can be suitably used as various parts for automobiles, electrical and electronic applications, industrial materials, industrial materials, and daily and household products.

[1071] There are no particular limitations on the method for obtaining a molded article, and a known molding method can be used.

[1072] As well-known molding methods, for example, there are: extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decorative molding, heterogeneous material molding, gas-assisted injection molding, foam injection molding, low-pressure molding, ultra-thin-wall injection molding (ultra-high-speed injection molding), in-mold composite molding (insert molding, insert-on molding), etc.

[1073] <Purpose>

[1074] The molded article of the embodiment described above contains the polyamide composition of the embodiment described above, has excellent mechanical properties (particularly tensile strength, flexural modulus, Charpy impact), surface appearance, and the like, and can be used in various applications.

[1075] The molded article of the embodiment described above can be suitably used in, for example, the automotive field, the electrical and electronic field, the mechanical and industrial field, the office equipment field, and the aviation and aerospace field.

[1076] 《Methods 6-1 and 6-2》

[1077] Polyamide composition

[1078] The polyamide composition of the 6-1 embodiment of the present invention comprises (6A) a crystalline polyamide, (6B) an amorphous semi-aromatic polyamide, and (6C) carbon fibers. Furthermore, the amorphous semi-aromatic polyamide (6B) contains 75 mol% or more of isophthalic acid units among all the dicarboxylic acid units constituting the amorphous semi-aromatic polyamide (6B), and contains 50 mol% or more of diamine units having 4 to 10 carbon atoms among all the diamine units constituting the amorphous semi-aromatic polyamide (6B).

[1079] In addition, in this specification, "polyamide" refers to a polymer having an amide (-NHCO-) ​​bond in the main chain.

[1080] The polyamide composition of the above embodiment, containing the (6A) crystalline polyamide, (6B) amorphous semi-aromatic polyamide, and (6C) carbon fibers of the above-described configuration, can maintain excellent water absorption rigidity and hot rigidity while maintaining an excellent pellet shape and reducing the amount of chip generation. Furthermore, the use of the polyamide composition of the above embodiment can provide a molded article having an excellent surface appearance.

[1081] Each component contained in the polyamide composition of the above embodiment will be described in detail below.

[1082] <Polyamide>

[1083] The polyamide composition of the above embodiment contains (6A) a crystalline polyamide and (6B) an amorphous semi-aromatic polyamide as polyamide components. Each polyamide component will be described in detail below.

[1084] [(6A) Crystalline polyamide]

[1085] The (6A) crystalline polyamide is as described in the above-mentioned embodiment 4-1 regarding the "(4A) crystalline polyamide".

[1086] [(6B) Amorphous semi-aromatic polyamide]

[1087] The (6B) amorphous semi-aromatic polyamide contained in the polyamide composition of the above embodiment is a polyamide containing diamine units and dicarboxylic acid units. The (6B) amorphous semi-aromatic polyamide is preferably a polyamide containing dicarboxylic acid units (6B-a) and diamine units (6B-b), wherein the (6B-a) dicarboxylic acid units contain 75 mol% or more of isophthalic acid units relative to the total dicarboxylic acid units constituting the (6B) amorphous semi-aromatic polyamide, and the (6B-b) diamine units contain 50 mol% or more of diamine units having 4 to 10 carbon atoms relative to the total diamine units constituting the (6B) amorphous semi-aromatic polyamide.

[1088] In this case, the total amount of the isophthalic acid units and the diamine units having 4 to 10 carbon atoms in the amorphous semi-aromatic polyamide (6B) is preferably 80 mol% to 100 mol%, more preferably 90 mol% to 100 mol%, and even more preferably 100 mol%, relative to all the constituent units of the amorphous semi-aromatic polyamide (6B).

[1089] In this specification, the ratio of predetermined monomer units constituting the amorphous semi-aromatic polyamide (6B) can be measured by nuclear magnetic resonance spectroscopy (NMR) or the like.

[1090] ((6B-a) dicarboxylic acid unit)

[1091] The (6B-a) dicarboxylic acid unit may contain 75 mol% or more of isophthalic acid, preferably 80 mol% or more and 100 mol% or less, more preferably 90 mol% or more and 100 mol% or less, and further preferably 100 mol% relative to the total moles of the (6B-a) dicarboxylic acid.

[1092] When the ratio of the isophthalic acid unit in the dicarboxylic acid unit (6B-a) is equal to or greater than the above lower limit, a polyamide composition can be obtained that satisfies all mechanical properties, particularly water absorption rigidity, hot rigidity, fluidity, surface appearance, and the like.

[1093] The dicarboxylic acid unit (6B-a) may contain an aromatic dicarboxylic acid unit, an aliphatic dicarboxylic acid unit, or an alicyclic dicarboxylic acid unit other than the isophthalic acid unit.

[1094] (1) Aromatic dicarboxylic acid unit

[1095] Aromatic dicarboxylic acids, which constitute aromatic dicarboxylic acid units other than isophthalic acid units, are not limited to the following substances; for example, dicarboxylic acids having aromatic groups such as phenyl or naphthyl groups can be listed. The aromatic groups of aromatic dicarboxylic acids may be unsubstituted or substituent.

[1096] There are no particular restrictions on the substituent, and examples thereof include an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, a halogen group, a silyl group having 1 to 6 carbon atoms, a sulfonic acid group and its salts (sodium salts, etc.).

[1097] Examples of the alkyl group having 1 to 4 carbon atoms include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[1098] Examples of the aryl group having 6 to 10 carbon atoms are not limited to the following groups, and examples thereof include phenyl, tolyl, xylyl, and naphthyl.

[1099] Examples of the aralkyl group having 7 to 10 carbon atoms are not limited to the following groups, and examples thereof include benzyl group.

[1100] Examples of the halogen group include, but are not limited to, fluoro, chloro, bromo, and iodo groups.

[1101] The silyl group having 1 to 6 carbon atoms is not limited to the following groups, and examples thereof include a trimethylsilyl group and a tert-butyldimethylsilyl group.

[1102] Among them, the aromatic dicarboxylic acid that constitutes an aromatic dicarboxylic acid unit other than isophthalic acid unit is preferably an aromatic dicarboxylic acid with 8 or more and 20 or less carbon atoms after being unsubstituted or substituted by a specified substituent.

[1103] Specific examples of the unsubstituted or substituted aromatic dicarboxylic acid having 8 to 20 carbon atoms include, but are not limited to, terephthalic acid, naphthalene dicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalate.

[1104] The aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit may be used alone or in combination of two or more.

[1105] (2) Aliphatic dicarboxylic acid unit

[1106] Examples of the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms.

[1107] Examples of the linear saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms include, but are not limited to, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid.

[1108] Examples of branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms include, but are not limited to, dimethylmalonic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, and trimethyladipic acid.

[1109] (3) Alicyclic dicarboxylic acid unit

[1110] The alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit is not limited to the following, and examples thereof include alicyclic dicarboxylic acids having an alicyclic structure with carbon atoms of 3 or more and 10 or less. Among these, alicyclic dicarboxylic acids having an alicyclic structure with carbon atoms of 5 or more and 10 or less are preferred.

[1111] Such alicyclic dicarboxylic acids are not limited to the following, and examples thereof include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid. Among them, 1,4-cyclohexanedicarboxylic acid is preferred as the alicyclic dicarboxylic acid.

[1112] In addition, the alicyclic dicarboxylic acid which comprises an alicyclic dicarboxylic acid unit may be used individually by 1 type, and may use 2 or more types together.

[1113] The alicyclic group of the alicyclic dicarboxylic acid may be unsubstituted or may have a substituent. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include the same alkyl groups as exemplified in the above-mentioned "aromatic dicarboxylic acid unit".

[1114] As the dicarboxylic acid units other than the isophthalic acid unit, it is preferred that an aromatic dicarboxylic acid unit be contained, and it is more preferred that an aromatic dicarboxylic acid having 6 or more carbon atoms be contained.

[1115] By using such a dicarboxylic acid, the mechanical properties of the polyamide composition, particularly water absorption rigidity, hot rigidity, fluidity, surface appearance, etc., tend to be more excellent.

[1116] In the amorphous semi-aromatic polyamide (6B), the dicarboxylic acid constituting the dicarboxylic acid unit (6B-a) is not limited to the compounds described above as the dicarboxylic acids, and may be a compound equivalent to the above dicarboxylic acids.

[1117] The term "compound equivalent to a dicarboxylic acid" as used herein refers to a compound that can form a dicarboxylic acid structure similar to the dicarboxylic acid structure derived from the aforementioned dicarboxylic acid. Such compounds are not limited to the following, and examples thereof include anhydrides of dicarboxylic acids and halides of dicarboxylic acids.

[1118] Furthermore, the amorphous semi-aromatic polyamide (6B) may further contain a unit derived from a trivalent or higher-valent polycarboxylic acid as needed.

[1119] Examples of trivalent or higher polycarboxylic acids include trimellitic acid, trimesic acid, pyromellitic acid, etc. These trivalent or higher polycarboxylic acids may be used alone or in combination of two or more.

[1120] ((6B-b) diamine unit)

[1121] The (6B-b) diamine unit constituting the (6B) amorphous semi-aromatic polyamide preferably contains a diamine unit having 4 to 10 carbon atoms, more preferably a linear saturated aliphatic diamine unit having 4 to 10 carbon atoms, further preferably a linear saturated aliphatic diamine unit having 6 to 10 carbon atoms, and particularly preferably a hexamethylenediamine unit.

[1122] By using such a diamine, a polyamide composition tends to be formed that has more excellent mechanical properties, particularly water absorption rigidity, rigidity under high-temperature use (hot rigidity), fluidity, surface appearance, and the like.

[1123] In this case, the amorphous semi-aromatic polyamide (6B) may contain 50 mol% or more of diamine units having 4 to 10 carbon atoms relative to the total moles of the diamine units (6B-b).

[1124] Furthermore, the diamine other than the diamine having 4 to 10 carbon atoms constituting the amorphous semi-aromatic polyamide (6B) is not limited to the following, and examples thereof include aliphatic diamine units, alicyclic diamine units, and aromatic diamine units.

[1125] (1) Aliphatic diamine unit

[1126] Examples of the aliphatic diamine constituting the aliphatic diamine unit include linear saturated aliphatic diamines having 4 to 20 carbon atoms.

[1127] Examples of the linear saturated aliphatic diamine having 4 to 20 carbon atoms include, but are not limited to, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine.

[1128] (2) Alicyclic diamine unit

[1129] The alicyclic diamine constituting the alicyclic diamine unit is not limited to the following, and examples thereof include 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and 1,3-cyclopentanediamine.

[1130] (3) Aromatic diamine unit

[1131] The aromatic diamine constituting the aromatic diamine unit is not limited to the following as long as it is a diamine containing an aromatic group. Specific examples of the aromatic diamine include meta-xylylenediamine.

[1132] In addition, these diamines which constitute each diamine unit may be used alone or in combination of two or more.

[1133] The (6B) amorphous semi-aromatic polyamide contained in the polyamide composition of the above embodiment is preferably polyamide 6I (polyhexamethylene isophthalamide), polyamide 9I, or polyamide 10I, and more preferably polyamide 6I.

[1134] It should be noted that the (6B) amorphous semi-aromatic polyamide may further contain a trivalent or higher polyvalent aliphatic amine as needed. Examples of the trivalent or higher polyvalent aliphatic amine include bis(hexamethylene)triamine. The trivalent or higher polyvalent aliphatic amine may be used alone or in combination of two or more.

[1135] The content of the amorphous semi-aromatic polyamide (6B) in the polyamide composition of the above embodiment can be set to 5.0% by mass or more and 45.0% by mass or less, preferably 10.0% by mass or more and 42.5% by mass or less, more preferably 15.0% by mass or more and 40.0% by mass or less, further preferably 20.0% by mass or more and 37.5% by mass or less, particularly preferably 22.5% by mass or more and 35.0% by mass or less, and most preferably 22.5% by mass or more and 30.0% by mass or less, relative to 100% by mass of all the resins contained in the polyamide composition. By setting the content of the amorphous semi-aromatic polyamide (6B) within the above range, a polyamide composition having excellent mechanical properties, particularly water absorption rigidity, hot rigidity, flowability, surface appearance, etc., can be obtained.

[1136] [Capping agent]

[1137] The ends of the polyamide ((6A) crystalline polyamide and (6B) amorphous semi-aromatic polyamide) contained in the polyamide composition of the above embodiment can be capped with a known capping agent.

[1138] The blocking agent is as described in the above embodiment 1-1.

[1139] [Production method of polyamide]

[1140] The method for producing polyamide is the same as described in the above embodiment 1-1.

[1141] [Polymer terminal of polyamide]

[1142] The polymer terminal of the polyamide is as described in the above embodiment 1-1.

[1143] [(6A) Characteristics of Crystalline Polyamide]

[1144] (6A) The molecular weight, melting point Tm2, ​​and crystallization enthalpy ΔH of the crystalline polyamide can be measured by the methods described in the examples below.

[1145] The tan δ peak temperature of the crystalline polyamide (6A) can be measured by the following method.

[1146] (Weight average molecular weight Mw(6A) of crystalline polyamide (6A))

[1147] As an indicator of the molecular weight of the crystalline polyamide (6A), the weight average molecular weight Mw(6A) can be used. The weight average molecular weight Mw(6A) of the crystalline polyamide is preferably 10,000 to 50,000, more preferably 15,000 to 45,000, further preferably 20,000 to 4...

Claims

1. A polyamide composition comprising: 52.5 to 95 parts by mass of (1A) an aliphatic polyamide containing a diamine and a dicarboxylic acid, and 5 to 47.5 parts by mass of (1B) a semi-aromatic polyamide, wherein the (1B) semi-aromatic polyamide is selected from at least one of polyamide 6I, polyamide 6I / 6, and polyamide 6I / 6T, and the (1B) semi-aromatic polyamide is an amorphous polyamide, wherein: The polyamide composition has a tan δ peak temperature of 90° C. or higher, and The weight average molecular weight Mw of the polyamide composition is 15000≤Mw≤35000.

2. The polyamide composition according to claim 1, wherein The total content of polyamides having a number average molecular weight Mn of 500 or more and 2000 or less is 0.5% by mass or more and less than 2.5% by mass based on the total amount of polyamides in the polyamide composition.

3. The polyamide composition according to claim 1 or 2, wherein The molecular weight distribution Mw / Mn of the polyamide composition is 2.6 or less.

4. The polyamide composition according to claim 1 or 2, wherein The total amount of the amino terminal group and the carboxyl terminal group expressed as an equivalent relative to 1 g of the polyamide in the polyamide composition is 100 μequivalent / g to 175 μequivalent / g.

5. The polyamide composition according to claim 3, wherein The total amount of the amino terminal group and the carboxyl terminal group expressed as an equivalent relative to 1 g of the polyamide in the polyamide composition is 100 μequivalent / g to 175 μequivalent / g.

6. The polyamide composition according to any one of claims 1, 2 and 5, wherein The ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount in the polyamide composition {amino terminal amount / (amino terminal amount+carboxyl terminal amount)} is 0.25 or more and less than 0.

4.

7. The polyamide composition according to claim 3, wherein The ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount in the polyamide composition {amino terminal amount / (amino terminal amount+carboxyl terminal amount)} is 0.25 or more and less than 0.

4.

8. The polyamide composition according to claim 4, wherein The ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount in the polyamide composition {amino terminal amount / (amino terminal amount+carboxyl terminal amount)} is 0.25 or more and less than 0.

4.

9. The polyamide composition according to any one of claims 1, 2, 5, 7 to 8, wherein The (1A) aliphatic polyamide is polyamide 66 or polyamide 610.

10. The polyamide composition according to claim 3, wherein The (1A) aliphatic polyamide is polyamide 66 or polyamide 610.

11. The polyamide composition according to claim 4, wherein The (1A) aliphatic polyamide is polyamide 66 or polyamide 610.

12. The polyamide composition according to claim 6, wherein The (1A) aliphatic polyamide is polyamide 66 or polyamide 610.

13. The polyamide composition according to any one of claims 1, 2, 5, 7 to 8, 10 to 12, wherein In the (1B) semi-aromatic polyamide, the content of the isophthalic acid in the dicarboxylic acid unit is 100 mol%.

14. The polyamide composition according to claim 3, wherein In the (1B) semi-aromatic polyamide, the content of the isophthalic acid in the dicarboxylic acid unit is 100 mol%.

15. The polyamide composition according to claim 4, wherein In the (1B) semi-aromatic polyamide, the content of the isophthalic acid in the dicarboxylic acid unit is 100 mol%.

16. The polyamide composition according to claim 6, wherein In the (1B) semi-aromatic polyamide, the content of the isophthalic acid in the dicarboxylic acid unit is 100 mol%.

17. The polyamide composition according to claim 9, wherein In the (1B) semi-aromatic polyamide, the content of the isophthalic acid in the dicarboxylic acid unit is 100 mol%.

18. The polyamide composition according to any one of claims 1, 2, 5, 7 to 8, 10 to 12, 14 to 17, wherein The (1B) semi-aromatic polyamide is polyamide 6I.

19. The polyamide composition according to claim 3, wherein The (1B) semi-aromatic polyamide is polyamide 6I.

20. The polyamide composition according to claim 4, wherein The (1B) semi-aromatic polyamide is polyamide 6I.

21. The polyamide composition according to claim 6, wherein The (1B) semi-aromatic polyamide is polyamide 6I.

22. The polyamide composition according to claim 9, wherein The (1B) semi-aromatic polyamide is polyamide 6I.

23. The polyamide composition of claim 13, wherein The (1B) semi-aromatic polyamide is polyamide 6I.

24. The polyamide composition according to any one of claims 1, 2, 5, 7 to 8, 10 to 12, 14 to 17, 19 to 23, wherein The weight average molecular weight Mw of the (1B) semi-aromatic polyamide is 10000≤Mw≤25000.

25. The polyamide composition of claim 3, wherein: The weight average molecular weight Mw of the (1B) semi-aromatic polyamide is 10000≤Mw≤25000.

26. The polyamide composition of claim 4, wherein The weight average molecular weight Mw of the (1B) semi-aromatic polyamide is 10000≤Mw≤25000.

27. The polyamide composition according to claim 6, wherein The weight average molecular weight Mw of the (1B) semi-aromatic polyamide is 10000≤Mw≤25000.

28. The polyamide composition of claim 9, wherein The weight average molecular weight Mw of the (1B) semi-aromatic polyamide is 10000≤Mw≤25000.

29. The polyamide composition of claim 13, wherein The weight average molecular weight Mw of the (1B) semi-aromatic polyamide is 10000≤Mw≤25000.

30. The polyamide composition of claim 18, wherein The weight average molecular weight Mw of the (1B) semi-aromatic polyamide is 10000≤Mw≤25000.

31. The polyamide composition according to any one of claims 1, 2, 5, 7 to 8, 10 to 12, 14 to 17, 19 to 23, 25 to 30, wherein The (1B) semi-aromatic polyamide has a molecular weight distribution Mw / Mn of 2.4 or less.

32. The polyamide composition of claim 3, wherein: The (1B) semi-aromatic polyamide has a molecular weight distribution Mw / Mn of 2.4 or less.

33. The polyamide composition of claim 4, wherein The (1B) semi-aromatic polyamide has a molecular weight distribution Mw / Mn of 2.4 or less.

34. The polyamide composition of claim 6, wherein The (1B) semi-aromatic polyamide has a molecular weight distribution Mw / Mn of 2.4 or less.

35. The polyamide composition of claim 9, wherein The (1B) semi-aromatic polyamide has a molecular weight distribution Mw / Mn of 2.4 or less.

36. The polyamide composition of claim 13, wherein: The (1B) semi-aromatic polyamide has a molecular weight distribution Mw / Mn of 2.4 or less.

37. The polyamide composition of claim 18, wherein The (1B) semi-aromatic polyamide has a molecular weight distribution Mw / Mn of 2.4 or less.

38. The polyamide composition of claim 24, wherein The (1B) semi-aromatic polyamide has a molecular weight distribution Mw / Mn of 2.4 or less.

39. The polyamide composition according to any one of claims 1, 2, 5, 7 to 8, 10 to 12, 14 to 17, 19 to 23, 25 to 30, 32 to 38, wherein The difference between the weight average molecular weight Mw(1A) of the aliphatic polyamide (1A) and the weight average molecular weight Mw(1B) of the semi-aromatic polyamide (1B) {Mw(1A)-Mw(1B)} is 10,000 or more.

40. The polyamide composition of claim 3, wherein: The difference between the weight average molecular weight Mw(1A) of the aliphatic polyamide (1A) and the weight average molecular weight Mw(1B) of the semi-aromatic polyamide (1B) {Mw(1A)-Mw(1B)} is 10,000 or more.

41. The polyamide composition of claim 4, wherein The difference between the weight average molecular weight Mw(1A) of the aliphatic polyamide (1A) and the weight average molecular weight Mw(1B) of the semi-aromatic polyamide (1B) {Mw(1A)-Mw(1B)} is 10,000 or more.

42. The polyamide composition of claim 6, wherein The difference between the weight average molecular weight Mw(1A) of the aliphatic polyamide (1A) and the weight average molecular weight Mw(1B) of the semi-aromatic polyamide (1B) {Mw(1A)-Mw(1B)} is 10,000 or more.

43. The polyamide composition of claim 9, wherein The difference between the weight average molecular weight Mw(1A) of the aliphatic polyamide (1A) and the weight average molecular weight Mw(1B) of the semi-aromatic polyamide (1B) {Mw(1A)-Mw(1B)} is 10,000 or more.

44. The polyamide composition of claim 13, wherein The difference between the weight average molecular weight Mw(1A) of the aliphatic polyamide (1A) and the weight average molecular weight Mw(1B) of the semi-aromatic polyamide (1B) {Mw(1A)-Mw(1B)} is 10,000 or more.

45. The polyamide composition of claim 18, wherein The difference between the weight average molecular weight Mw(1A) of the aliphatic polyamide (1A) and the weight average molecular weight Mw(1B) of the semi-aromatic polyamide (1B) {Mw(1A)-Mw(1B)} is 10,000 or more.

46. ​​The polyamide composition of claim 24, wherein The difference between the weight average molecular weight Mw(1A) of the aliphatic polyamide (1A) and the weight average molecular weight Mw(1B) of the semi-aromatic polyamide (1B) {Mw(1A)-Mw(1B)} is 10,000 or more.

47. The polyamide composition of claim 31, wherein The difference between the weight average molecular weight Mw(1A) of the aliphatic polyamide (1A) and the weight average molecular weight Mw(1B) of the semi-aromatic polyamide (1B) {Mw(1A)-Mw(1B)} is 10,000 or more.

48. The polyamide composition according to any one of claims 1, 2, 5, 7 to 8, 10 to 12, 14 to 17, 19 to 23, 25 to 30, 32 to 38, 40 to 47, wherein The polyamide composition further contains a metal phosphite and / or a metal hypophosphite.

49. The polyamide composition of claim 3, wherein The polyamide composition further contains a metal phosphite and / or a metal hypophosphite.

50. The polyamide composition of claim 4, wherein The polyamide composition further contains a metal phosphite and / or a metal hypophosphite.

51. The polyamide composition of claim 6, wherein The polyamide composition further contains a metal phosphite and / or a metal hypophosphite.

52. The polyamide composition of claim 9, wherein The polyamide composition further contains a metal phosphite and / or a metal hypophosphite.

53. The polyamide composition of claim 13, wherein The polyamide composition further contains a metal phosphite and / or a metal hypophosphite.

54. The polyamide composition of claim 18, wherein The polyamide composition further contains a metal phosphite and / or a metal hypophosphite.

55. The polyamide composition of claim 24, wherein The polyamide composition further contains a metal phosphite and / or a metal hypophosphite.

56. The polyamide composition of claim 31, wherein The polyamide composition further contains a metal phosphite and / or a metal hypophosphite.

57. The polyamide composition of claim 39, wherein The polyamide composition further contains a metal phosphite and / or a metal hypophosphite.

58. The polyamide composition according to any one of claims 1, 2, 5, 7 to 8, 10 to 12, 14 to 17, 19 to 23, 25 to 30, 32 to 38, 40 to 47, 49 to 57, wherein The polyamide composition further contains a phosphite compound.

59. The polyamide composition of claim 3, wherein The polyamide composition further contains a phosphite compound.

60. The polyamide composition of claim 4, wherein The polyamide composition further contains a phosphite compound.

61. The polyamide composition of claim 6, wherein The polyamide composition further contains a phosphite compound.

62. The polyamide composition of claim 9, wherein The polyamide composition further contains a phosphite compound.

63. The polyamide composition of claim 13, wherein: The polyamide composition further contains a phosphite compound.

64. The polyamide composition of claim 18, wherein The polyamide composition further contains a phosphite compound.

65. The polyamide composition of claim 24, wherein The polyamide composition further contains a phosphite compound.

66. The polyamide composition of claim 31, wherein The polyamide composition further contains a phosphite compound.

67. The polyamide composition of claim 39, wherein The polyamide composition further contains a phosphite compound.

68. The polyamide composition of claim 48, wherein The polyamide composition further contains a phosphite compound.

69. The polyamide composition according to any one of claims 1, 2, 5, 7 to 8, 10 to 12, 14 to 17, 19 to 23, 25 to 30, 32 to 38, 40 to 47, 49 to 57, 59 to 68, wherein The polyamide composition further contains 5 to 250 parts by mass of (1C) an inorganic filler, based on 100 parts by mass of the total of the (1A) aliphatic polyamide and the (1B) semi-aromatic polyamide.

70. The polyamide composition of claim 3, wherein: The polyamide composition further contains 5 to 250 parts by mass of (1C) an inorganic filler, based on 100 parts by mass of the total of the (1A) aliphatic polyamide and the (1B) semi-aromatic polyamide.

71. The polyamide composition of claim 4, wherein The polyamide composition further contains 5 to 250 parts by mass of (1C) an inorganic filler, based on 100 parts by mass of the total of the (1A) aliphatic polyamide and the (1B) semi-aromatic polyamide.

72. The polyamide composition of claim 6, wherein The polyamide composition further contains 5 to 250 parts by mass of (1C) an inorganic filler, based on 100 parts by mass of the total of the (1A) aliphatic polyamide and the (1B) semi-aromatic polyamide.

73. The polyamide composition of claim 9, wherein The polyamide composition further contains 5 to 250 parts by mass of (1C) an inorganic filler, based on 100 parts by mass of the total of the (1A) aliphatic polyamide and the (1B) semi-aromatic polyamide.

74. The polyamide composition of claim 13, wherein The polyamide composition further contains 5 to 250 parts by mass of (1C) an inorganic filler, based on 100 parts by mass of the total of the (1A) aliphatic polyamide and the (1B) semi-aromatic polyamide.

75. The polyamide composition of claim 18, wherein The polyamide composition further contains 5 to 250 parts by mass of (1C) an inorganic filler, based on 100 parts by mass of the total of the (1A) aliphatic polyamide and the (1B) semi-aromatic polyamide.

76. The polyamide composition of claim 24, wherein The polyamide composition further contains 5 to 250 parts by mass of (1C) an inorganic filler, based on 100 parts by mass of the total of the (1A) aliphatic polyamide and the (1B) semi-aromatic polyamide.

77. The polyamide composition of claim 31, wherein The polyamide composition further contains 5 to 250 parts by mass of (1C) an inorganic filler, based on 100 parts by mass of the total of the (1A) aliphatic polyamide and the (1B) semi-aromatic polyamide.

78. The polyamide composition of claim 39, wherein The polyamide composition further contains 5 to 250 parts by mass of (1C) an inorganic filler, based on 100 parts by mass of the total of the (1A) aliphatic polyamide and the (1B) semi-aromatic polyamide.

79. The polyamide composition of claim 48, wherein The polyamide composition further contains 5 to 250 parts by mass of (1C) an inorganic filler, based on 100 parts by mass of the total of the (1A) aliphatic polyamide and the (1B) semi-aromatic polyamide.

80. The polyamide composition of claim 58, wherein The polyamide composition further contains 5 to 250 parts by mass of (1C) an inorganic filler, based on 100 parts by mass of the total of the (1A) aliphatic polyamide and the (1B) semi-aromatic polyamide.

81. A molded article, wherein The molded article is obtained by molding the polyamide composition according to any one of claims 1 to 80, and the surface gloss value of the molded article is 50 or more.

82. The polyamide composition according to any one of claims 1, 2, 5, 7 to 8, 10 to 12, 14 to 17, 19 to 23, 25 to 30, 32 to 38, 40 to 47, 49 to 57, 59 to 68, 70 to 80, wherein The polyamide composition further comprises: pigment, Flame retardants, and Flame retardant additive.

83. The polyamide composition of claim 3, wherein The polyamide composition further comprises: pigment, Flame retardants, and Flame retardant additive.

84. The polyamide composition of claim 4, wherein The polyamide composition further comprises: pigment, Flame retardants, and Flame retardant additive.

85. The polyamide composition of claim 6, wherein The polyamide composition further comprises: pigment, Flame retardants, and Flame retardant additive.

86. The polyamide composition of claim 9, wherein The polyamide composition further comprises: pigment, Flame retardants, and Flame retardant additive.

87. The polyamide composition of claim 13, wherein The polyamide composition further comprises: pigment, Flame retardants, and Flame retardant additive.

88. The polyamide composition of claim 18, wherein The polyamide composition further comprises: pigment, Flame retardants, and Flame retardant additive.

89. The polyamide composition of claim 24, wherein The polyamide composition further comprises: pigment, Flame retardants, and Flame retardant additive.

90. The polyamide composition of claim 31, wherein The polyamide composition further comprises: pigment, Flame retardants, and Flame retardant additive.

91. The polyamide composition of claim 39, wherein The polyamide composition further comprises: pigment, Flame retardants, and Flame retardant additive.

92. The polyamide composition of claim 48, wherein The polyamide composition further comprises: pigment, Flame retardants, and Flame retardant additive.

93. The polyamide composition of claim 58, wherein The polyamide composition further comprises: pigment, Flame retardants, and Flame retardant additive.

94. The polyamide composition of claim 69, wherein The polyamide composition further comprises: pigment, Flame retardants, and Flame retardant additive.

95. The polyamide composition according to any one of claims 1, 2, 5, 7 to 8, 10 to 12, 14 to 17, 19 to 23, 25 to 30, 32 to 38, 40 to 47, 49 to 57, 59 to 68, 70 to 80, wherein The polyamide composition further comprises: Flame retardants, and Flame retardant additives, in, The polyamide composition has a tan δ peak temperature of 100°C or higher, and The halogen content in the polyamide composition is greater than 2% by mass and less than or equal to 20% by mass based on the total amount of the polyamide composition.

96. The polyamide composition of claim 3, wherein The polyamide composition further comprises: Flame retardants, and Flame retardant additives, in, The polyamide composition has a tan δ peak temperature of 100°C or higher, and The halogen content in the polyamide composition is greater than 2% by mass and less than or equal to 20% by mass based on the total amount of the polyamide composition.

97. The polyamide composition of claim 4, wherein The polyamide composition further comprises: Flame retardants, and Flame retardant additives, in, The polyamide composition has a tan δ peak temperature of 100°C or higher, and The halogen content in the polyamide composition is greater than 2% by mass and less than or equal to 20% by mass based on the total amount of the polyamide composition.

98. The polyamide composition of claim 6, wherein The polyamide composition further comprises: Flame retardants, and Flame retardant additives, in, The polyamide composition has a tan δ peak temperature of 100°C or higher, and The halogen content in the polyamide composition is greater than 2% by mass and less than or equal to 20% by mass based on the total amount of the polyamide composition.

99. The polyamide composition of claim 9, wherein The polyamide composition further comprises: Flame retardants, and Flame retardant additives, in, The polyamide composition has a tan δ peak temperature of 100°C or higher, and The halogen content in the polyamide composition is greater than 2% by mass and less than or equal to 20% by mass based on the total amount of the polyamide composition.

100. The polyamide composition of claim 13, wherein: The polyamide composition further comprises: Flame retardants, and Flame retardant additives, in, The polyamide composition has a tan δ peak temperature of 100°C or higher, and The halogen content in the polyamide composition is greater than 2% by mass and less than or equal to 20% by mass based on the total amount of the polyamide composition.

101. The polyamide composition of claim 18, wherein The polyamide composition further comprises: Flame retardants, and Flame retardant additives, in, The polyamide composition has a tan δ peak temperature of 100°C or higher, and The halogen content in the polyamide composition is greater than 2% by mass and less than or equal to 20% by mass based on the total amount of the polyamide composition.

102. The polyamide composition of claim 24, wherein The polyamide composition further comprises: Flame retardants, and Flame retardant additives, in, The polyamide composition has a tan δ peak temperature of 100°C or higher, and The halogen content in the polyamide composition is greater than 2% by mass and less than or equal to 20% by mass based on the total amount of the polyamide composition.

103. The polyamide composition of claim 31, wherein The polyamide composition further comprises: Flame retardants, and Flame retardant additives, in, The polyamide composition has a tan δ peak temperature of 100°C or higher, and The halogen content in the polyamide composition is greater than 2% by mass and less than or equal to 20% by mass based on the total amount of the polyamide composition.

104. The polyamide composition of claim 39, wherein The polyamide composition further comprises: Flame retardants, and Flame retardant additives, in, The polyamide composition has a tan δ peak temperature of 100°C or higher, and The halogen content in the polyamide composition is greater than 2% by mass and less than or equal to 20% by mass based on the total amount of the polyamide composition.

105. The polyamide composition of claim 48, wherein The polyamide composition further comprises: Flame retardants, and Flame retardant additives, in, The polyamide composition has a tan δ peak temperature of 100°C or higher, and The halogen content in the polyamide composition is greater than 2% by mass and less than or equal to 20% by mass based on the total amount of the polyamide composition.

106. The polyamide composition of claim 58, wherein The polyamide composition further comprises: Flame retardants, and Flame retardant additives, in, The polyamide composition has a tan δ peak temperature of 100°C or higher, and The halogen content in the polyamide composition is greater than 2% by mass and less than or equal to 20% by mass based on the total amount of the polyamide composition.

107. The polyamide composition of claim 69, wherein The polyamide composition further comprises: Flame retardants, and Flame retardant additives, in, The polyamide composition has a tan δ peak temperature of 100°C or higher, and The halogen content in the polyamide composition is greater than 2% by mass and less than or equal to 20% by mass based on the total amount of the polyamide composition.

108. The polyamide composition according to any one of claims 1, 2, 5, 7 to 8, 10 to 12, 14 to 17, 19 to 23, 25 to 30, 32 to 38, 40 to 47, 49 to 57, 59 to 68, 70 to 80, wherein The polyamide composition further contains (4C) polyphenylene ether.

109. The polyamide composition of claim 3, wherein: The polyamide composition further contains (4C) polyphenylene ether.

110. The polyamide composition of claim 4, wherein The polyamide composition further contains (4C) polyphenylene ether.

111. The polyamide composition of claim 6, wherein The polyamide composition further contains (4C) polyphenylene ether.

112. The polyamide composition of claim 9, wherein The polyamide composition further contains (4C) polyphenylene ether.

113. The polyamide composition of claim 13, wherein The polyamide composition further contains (4C) polyphenylene ether.

114. The polyamide composition of claim 18, wherein The polyamide composition further contains (4C) polyphenylene ether.

115. The polyamide composition of claim 24, wherein The polyamide composition further contains (4C) polyphenylene ether.

116. The polyamide composition of claim 31, wherein The polyamide composition further contains (4C) polyphenylene ether.

117. The polyamide composition of claim 39, wherein The polyamide composition further contains (4C) polyphenylene ether.

118. The polyamide composition of claim 48, wherein The polyamide composition further contains (4C) polyphenylene ether.

119. The polyamide composition of claim 58, wherein The polyamide composition further contains (4C) polyphenylene ether.

120. The polyamide composition of claim 69, wherein The polyamide composition further contains (4C) polyphenylene ether.

121. The polyamide composition according to any one of claims 1, 2, 5, 7 to 8, 10 to 12, 14 to 17, 19 to 23, 25 to 30, 32 to 38, 40 to 47, 49 to 57, 59 to 68, 70 to 80, further comprising a flame retardant, a flame retardant auxiliary, a white pigment and an ultraviolet absorber, wherein The mass ratio of the ultraviolet absorber to the white pigment contained in the polyamide composition (ultraviolet absorber / white pigment) is 0.15 or more and less than 2.

50.

122. The polyamide composition according to claim 3, further comprising a flame retardant, a flame retardant auxiliary, a white pigment and an ultraviolet absorber, wherein: The mass ratio of the ultraviolet absorber to the white pigment contained in the polyamide composition (ultraviolet absorber / white pigment) is 0.15 or more and less than 2.

50.

123. The polyamide composition according to claim 4, further comprising a flame retardant, a flame retardant auxiliary, a white pigment and an ultraviolet absorber, wherein: The mass ratio of the ultraviolet absorber to the white pigment contained in the polyamide composition (ultraviolet absorber / white pigment) is 0.15 or more and less than 2.

50.

124. The polyamide composition according to claim 6, further comprising a flame retardant, a flame retardant auxiliary, a white pigment and an ultraviolet absorber, wherein: The mass ratio of the ultraviolet absorber to the white pigment contained in the polyamide composition (ultraviolet absorber / white pigment) is 0.15 or more and less than 2.

50.

125. The polyamide composition according to claim 9, further comprising a flame retardant, a flame retardant auxiliary, a white pigment and an ultraviolet absorber, wherein: The mass ratio of the ultraviolet absorber to the white pigment contained in the polyamide composition (ultraviolet absorber / white pigment) is 0.15 or more and less than 2.

50.

126. The polyamide composition according to claim 13, further comprising a flame retardant, a flame retardant auxiliary, a white pigment and an ultraviolet absorber, wherein: The mass ratio of the ultraviolet absorber to the white pigment contained in the polyamide composition (ultraviolet absorber / white pigment) is 0.15 or more and less than 2.

50.

127. The polyamide composition according to claim 18, further comprising a flame retardant, a flame retardant auxiliary, a white pigment and an ultraviolet absorber, wherein: The mass ratio of the ultraviolet absorber to the white pigment contained in the polyamide composition (ultraviolet absorber / white pigment) is 0.15 or more and less than 2.

50.

128. The polyamide composition according to claim 24, further comprising a flame retardant, a flame retardant auxiliary, a white pigment and an ultraviolet absorber, wherein: The mass ratio of the ultraviolet absorber to the white pigment contained in the polyamide composition (ultraviolet absorber / white pigment) is 0.15 or more and less than 2.

50.

129. The polyamide composition according to claim 31, further comprising a flame retardant, a flame retardant auxiliary, a white pigment and an ultraviolet absorber, wherein: The mass ratio of the ultraviolet absorber to the white pigment contained in the polyamide composition (ultraviolet absorber / white pigment) is 0.15 or more and less than 2.

50.

130. The polyamide composition according to claim 39, further comprising a flame retardant, a flame retardant auxiliary, a white pigment and an ultraviolet absorber, wherein: The mass ratio of the ultraviolet absorber to the white pigment contained in the polyamide composition (ultraviolet absorber / white pigment) is 0.15 or more and less than 2.

50.

131. The polyamide composition according to claim 48, further comprising a flame retardant, a flame retardant auxiliary, a white pigment and an ultraviolet absorber, wherein: The mass ratio of the ultraviolet absorber to the white pigment contained in the polyamide composition (ultraviolet absorber / white pigment) is 0.15 or more and less than 2.

50.

132. The polyamide composition according to claim 58, further comprising a flame retardant, a flame retardant auxiliary, a white pigment and an ultraviolet absorber, wherein: The mass ratio of the ultraviolet absorber to the white pigment contained in the polyamide composition (ultraviolet absorber / white pigment) is 0.15 or more and less than 2.

50.

133. The polyamide composition according to claim 69, further comprising a flame retardant, a flame retardant auxiliary, a white pigment and an ultraviolet absorber, wherein: The mass ratio of the ultraviolet absorber to the white pigment contained in the polyamide composition (ultraviolet absorber / white pigment) is 0.15 or more and less than 2.

50.

134. The polyamide composition according to any one of claims 1, 2, 5, 7 to 8, 10 to 12, 14 to 17, 19 to 23, 25 to 30, 32 to 38, 40 to 47, 49 to 57, 59 to 68, 70 to 80, wherein The polyamide composition further contains (6C) carbon fibers.

135. The polyamide composition of claim 3, wherein: The polyamide composition further contains (6C) carbon fibers.

136. The polyamide composition of claim 4, wherein The polyamide composition further contains (6C) carbon fibers.

137. The polyamide composition of claim 6, wherein The polyamide composition further contains (6C) carbon fibers.

138. The polyamide composition of claim 9, wherein The polyamide composition further contains (6C) carbon fibers.

139. The polyamide composition of claim 13, wherein The polyamide composition further contains (6C) carbon fibers.

140. The polyamide composition of claim 18, wherein The polyamide composition further contains (6C) carbon fibers.

141. The polyamide composition of claim 24, wherein The polyamide composition further contains (6C) carbon fibers.

142. The polyamide composition of claim 31, wherein The polyamide composition further contains (6C) carbon fibers.

143. The polyamide composition of claim 39, wherein The polyamide composition further contains (6C) carbon fibers.

144. The polyamide composition of claim 48, wherein The polyamide composition further contains (6C) carbon fibers.

145. The polyamide composition of claim 58, wherein The polyamide composition further contains (6C) carbon fibers.

146. The polyamide composition of claim 69, wherein The polyamide composition further contains (6C) carbon fibers.

147. The polyamide composition according to any one of claims 1, 2, 5, 7 to 8, 10 to 12, 14 to 17, 19 to 23, 25 to 30, 32 to 38, 40 to 47, 49 to 57, 59 to 68, 70 to 80, wherein The polyamide composition further contains a flame retardant containing a halogen element, a flame retardant auxiliary and an ultraviolet absorber, wherein: A mass ratio of the ultraviolet absorber to the halogen element {ultraviolet absorber / halogen element} contained in the polyamide composition is greater than 0.10 and less than 0.

75.

148. The polyamide composition of claim 3, wherein The polyamide composition further contains a flame retardant containing a halogen element, a flame retardant auxiliary and an ultraviolet absorber, wherein: A mass ratio of the ultraviolet absorber to the halogen element {ultraviolet absorber / halogen element} contained in the polyamide composition is greater than 0.10 and less than 0.

75.

149. The polyamide composition of claim 4, wherein The polyamide composition further contains a flame retardant containing a halogen element, a flame retardant auxiliary and an ultraviolet absorber, wherein: A mass ratio of the ultraviolet absorber to the halogen element {ultraviolet absorber / halogen element} contained in the polyamide composition is greater than 0.10 and less than 0.

75.

150. The polyamide composition of claim 6, wherein The polyamide composition further contains a flame retardant containing a halogen element, a flame retardant auxiliary and an ultraviolet absorber, wherein: A mass ratio of the ultraviolet absorber to the halogen element {ultraviolet absorber / halogen element} contained in the polyamide composition is greater than 0.10 and less than 0.

75.

151. The polyamide composition of claim 9, wherein The polyamide composition further contains a flame retardant containing a halogen element, a flame retardant auxiliary and an ultraviolet absorber, wherein: A mass ratio of the ultraviolet absorber to the halogen element {ultraviolet absorber / halogen element} contained in the polyamide composition is greater than 0.10 and less than 0.

75.

152. The polyamide composition of claim 13, wherein The polyamide composition further contains a flame retardant containing a halogen element, a flame retardant auxiliary and an ultraviolet absorber, wherein: A mass ratio of the ultraviolet absorber to the halogen element {ultraviolet absorber / halogen element} contained in the polyamide composition is greater than 0.10 and less than 0.

75.

153. The polyamide composition of claim 18, wherein The polyamide composition further contains a flame retardant containing a halogen element, a flame retardant auxiliary and an ultraviolet absorber, wherein: A mass ratio of the ultraviolet absorber to the halogen element {ultraviolet absorber / halogen element} contained in the polyamide composition is greater than 0.10 and less than 0.

75.

154. The polyamide composition of claim 24, wherein The polyamide composition further contains a flame retardant containing a halogen element, a flame retardant auxiliary and an ultraviolet absorber, wherein: A mass ratio of the ultraviolet absorber to the halogen element {ultraviolet absorber / halogen element} contained in the polyamide composition is greater than 0.10 and less than 0.

75.

155. The polyamide composition of claim 31, wherein The polyamide composition further contains a flame retardant containing a halogen element, a flame retardant auxiliary and an ultraviolet absorber, wherein: A mass ratio of the ultraviolet absorber to the halogen element {ultraviolet absorber / halogen element} contained in the polyamide composition is greater than 0.10 and less than 0.

75.

156. The polyamide composition of claim 39, wherein The polyamide composition further contains a flame retardant containing a halogen element, a flame retardant auxiliary and an ultraviolet absorber, wherein: A mass ratio of the ultraviolet absorber to the halogen element {ultraviolet absorber / halogen element} contained in the polyamide composition is greater than 0.10 and less than 0.

75.

157. The polyamide composition of claim 48, wherein The polyamide composition further contains a flame retardant containing a halogen element, a flame retardant auxiliary and an ultraviolet absorber, wherein: A mass ratio of the ultraviolet absorber to the halogen element {ultraviolet absorber / halogen element} contained in the polyamide composition is greater than 0.10 and less than 0.

75.

158. The polyamide composition of claim 58, wherein The polyamide composition further contains a flame retardant containing a halogen element, a flame retardant auxiliary and an ultraviolet absorber, wherein: A mass ratio of the ultraviolet absorber to the halogen element {ultraviolet absorber / halogen element} contained in the polyamide composition is greater than 0.10 and less than 0.

75.

159. The polyamide composition of claim 69, wherein The polyamide composition further contains a flame retardant containing a halogen element, a flame retardant auxiliary and an ultraviolet absorber, wherein: A mass ratio of the ultraviolet absorber to the halogen element {ultraviolet absorber / halogen element} contained in the polyamide composition is greater than 0.10 and less than 0.75.

Images