Resin composition, pellets, molded articles, and method for manufacturing the resin composition

Abstract

The present invention provides a resin composition, as well as pellets, molded articles, and a method for producing the resin composition. The resin composition according to this disclosure comprises a polyamide resin (A) consisting of (A1) a semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) an aliphatic polyamide resin with a higher cooling crystallization temperature than the semi-aromatic polyamide resin (A1), (B) a reinforcing agent, (C) a coloring agent, (D) an amorphous resin, and (E) a release agent, wherein the mass ratio of the content of (A1) semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) aliphatic polyamide resin satisfies (A1) / [(A2)+(A3)]>1.0, the content of (C) coloring agent is 14.0 to 30.0 parts by mass per 100 parts by mass of (A) polyamide resin, and the mass ratio of the content of (A2) polyamide 6, (A3) aliphatic polyamide resin, and (D) amorphous resin satisfies 0.3<[(A2)+(A3)] / (D)<3.3.

Description

[Technical Field]

[0001] This invention relates to resin compositions, pellets, molded articles, and methods for producing resin compositions. In particular, it relates to resin compositions mainly composed of polyamide resin. [Background technology]

[0002] Polyamide resins are widely used as various industrial materials due to their excellent processability, durability, heat resistance, and mechanical properties (Patent Documents 1-3). For a long time, aliphatic polyamide resins, such as polyamide 6, have been used as such polyamide resins. In addition, the addition of reinforcing agents is being considered to improve the mechanical strength of polyamide resins. On the other hand, colorants are sometimes added to give molded products formed from polyamide resins aesthetic appeal. Furthermore, release agents are sometimes added to improve the release properties when molding polyamide resins with molds. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2011-057977 [Patent Document 2] Japanese Patent Publication No. 2005-089588 [Patent Document 3] Japanese Patent Publication No. 2003-105196 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] However, it was found that resin compositions containing polyamide 6, reinforcing agents, colorants, and release agents tend to produce molded products with inferior appearance. Therefore, to improve the appearance of the molded products, it was considered to incorporate semi-aromatic polyamide resins. However, when semi-aromatic polyamide resins are incorporated into polyamide 6, even if the appearance improves, the solidification rate tends to decrease. Therefore, it was considered to incorporate easily crystallizable aliphatic polyamide resins such as polyamide 66. However, it has been found that molded articles formed from resin compositions with an increased proportion of such aliphatic polyamide resin may discolor or deform when used outdoors. The present invention aims to solve these problems and to provide a resin composition that can provide molded articles with a good appearance and minimal discoloration and deformation in outdoor environments, as well as pellets, molded articles, and methods for producing the resin composition. [Means for solving the problem]

[0005] Based on the above problems, the inventors conducted studies and found that the above problems were solved by the following means. [1] A polyamide resin (A) comprising (A1) a semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) an aliphatic polyamide resin having a higher cooling crystallization temperature than the (A1) semi-aromatic polyamide resin, (B) Reinforcement material, (C) Coloring agents and, (D) Amorphous resin and (E) Contains a release agent, The mass ratio of the contents of (A1) semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) aliphatic polyamide resin satisfies (A1) / [(A2)+(A3)]>1.0, (C) The coloring agent content is 14.0 to 30.0 parts by mass per 100 parts by mass of (A) polyamide resin. The mass ratio of the contents of (A2) polyamide 6, (A3) aliphatic polyamide resin, and (D) amorphous resin satisfies 0.3 < [(A2) + (A3)] / (D) < 3.3. Resin composition. [2](A1) The resin composition according to [1], wherein the semi-aromatic polyamide resin comprises a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 50 mol% or more of the diamine-derived structural unit is derived from xylylenediamine, and the composition comprises a xylylenediamine-based polyamide resin. [3] The xylylenediamine-based polyamide resin is the resin composition according to [2], wherein 70 mol% or more of the diamine-derived constituent units are derived from xylylenediamine, and 70 mol% or more of the dicarboxylic acid-derived constituent units are derived from an α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. [4] A resin composition according to any one of [1] to [3], wherein the mass ratio of (A1) semi-aromatic polyamide resin to (A2) polyamide 6 is 0.2 < (A2) / (A1) < 0.5. [5](A3) The resin composition according to any one of [1] to [4], wherein the aliphatic polyamide resin comprises polyamide 66. [6] A resin composition according to any one of [1] to [5], wherein the mass ratio of the contents of (A1) semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) aliphatic polyamide resin is 2.2 > (A1) / [(A2) + (A3)] > 1.2. [7](B) A resin composition according to any one of [1] to [6], wherein the reinforcing material comprises glass fiber and / or talc. [8] The resin composition according to any one of [1] to [7], wherein the content of (B) the reinforcing material is 100 to 230 parts by mass per 100 parts by mass of (A) the polyamide resin. [9](C) A resin composition according to any one of [1] to [8], comprising a coloring agent carbon black.

[10] (D) A resin composition according to any one of [1] to [9], wherein the amorphous resin contains styrene units.

[11] The resin composition according to any one of [1] to

[10] , wherein the cooling crystallization temperature Tc of the resin composition, as measured by a differential scanning calorimeter, is 170°C ≤ Tc ≤ 235°C.

[12] The resin composition according to any one of [1] to

[11] , wherein the release agent (E) comprises a higher fatty acid metal salt and / or an aliphatic carboxylic acid amide.

[13] (A1) The semi-aromatic polyamide resin contains diamine-derived structural units and dicarboxylic acid-derived structural units, wherein 70 mol% or more of the diamine-derived structural units are derived from xylylenediamine, and 70 mol% or more of the dicarboxylic acid-derived structural units are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms. The mass ratio of (A1) semi-aromatic polyamide resin to (A2) polyamide 6 satisfies 0.2 < (A2) / (A1) < 0.5. (A3) Aliphatic polyamide resin containing polyamide 66, The mass ratio of the contents of (A1) semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) aliphatic polyamide resin satisfies 2.2 > (A1) / [(A2) + (A3)] > 1.2. (B) The reinforcing material contains glass fiber and / or talc, (B) The reinforcing material content is 100 to 230 parts by mass per 100 parts by mass of (A) polyamide resin. (C) The coloring agent contains carbon black, (D) The amorphous resin contains styrene units, The cooling crystallization temperature Tc of the resin composition, as measured by a differential scanning calorimeter, is 170°C ≤ Tc ≤ 235°C. The resin composition according to any one of [1] to

[12] , wherein the mold release agent (E) comprises a higher fatty acid metal salt and / or an aliphatic carboxylic acid amide.

[14] The resin composition according to any one of [1] to

[13] , wherein at least one of the (A1) semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) aliphatic polyamide resin includes recycled material. A pellet of the resin composition described in any one of

[15] [1] to

[14] . A molded article formed from any one of the resin compositions described in

[16] [1] to

[14] . A molded product formed from the pellets described in

[17] and

[15] .

[18] A method for producing the resin composition according to any one of [1] to

[14] , which comprises melt-kneading a masterbatch of a colorant, in which the colorant (C) is made into a masterbatch with an amorphous resin (D), a polyamide resin (A), a reinforcing material (B), and a mold release agent (E).

Advantages of the Invention

[0006] According to the present invention, it has become possible to provide a resin composition capable of providing a molded product having good appearance and small discoloration and deformation in an outdoor environment, as well as pellets, molded products, and a method for producing the resin composition.

Embodiments for Carrying Out the Invention

[0007] Hereinafter, embodiments for carrying out the present invention (hereinafter simply referred to as "the present embodiments") will be described in detail. The following present embodiments are examples for explaining the present invention, and the present invention is not limited only to the present embodiments. In this specification, "~" is used to mean including the numerical values described before and after it as lower and upper limits. "A~B" means A or more and B or less. Further, any combination of the upper limit value and the lower limit value of the numerical values in this specification can be cited as an example of the present embodiment.

[0008] In this specification, "mass%" indicates the content ratio of a predetermined component contained in the total amount of 100 mass%.

[0009] In this specification, a "structural unit" is a unit derived from a raw material compound formed by polymerization of the raw material compound used for producing a polymer, and represents a partial structure sandwiched between arbitrary linking groups in the obtained polymer. A partial structure in which one end is a linking group and the other end is a polymerization reactive group at the terminal portion of the polymer is also included. The structural unit may be a unit directly formed by a polymerization reaction, or may be one in which a part of the unit is converted into another structure by treating the obtained polymer. In this specification, various physical property values and characteristic values are those at 23°C unless otherwise specified.

[0010] In this specification, unless otherwise specified, weight-average molecular weight and number-average molecular weight may be measured in accordance with paragraph 0047 of Japanese Patent Application Publication No. 2018-165298, which is incorporated herein by reference. If the measurement methods, etc., described in the standards shown in this specification differ from year to year, unless otherwise specified, the standards as of January 1, 2024 shall apply. If the measurement methods, etc., described in the standards shown in this specification have been discontinued as of January 1, 2024, the standards in effect at the time of discontinuation shall apply.

[0011] The resin composition of this embodiment is characterized in that it comprises a polyamide resin (A) consisting of (A1) a semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) an aliphatic polyamide resin having a higher cooling crystallization temperature than the (A1) semi-aromatic polyamide resin, (B) a reinforcing agent, (C) a coloring agent, (D) an amorphous resin, and (E) a release agent, wherein the mass ratio of the content of (A1) semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) aliphatic polyamide resin satisfies (A1) / [(A2)+(A3)]>1.0, the content of (C) coloring agent is 14.0 to 30.0 parts by mass per 100 parts by mass of (A) polyamide resin, and the mass ratio of the content of (A2) polyamide 6, (A3) aliphatic polyamide resin, and (D) amorphous resin satisfies 0.3<[(A2)+(A3)] / (D)<3.3. By adopting such a configuration, it becomes possible to provide a resin composition, pellets, and molded articles that have a good appearance and exhibit minimal discoloration and deformation in outdoor environments. In other words, by blending a semi-aromatic polyamide resin into a resin composition containing polyamide 6, a reinforcing agent, a coloring agent, and a mold release agent, the appearance of the resulting molded product could be improved. However, blending a semi-aromatic polyamide resin with polyamide 6 tends to reduce the solidification rate. Therefore, we considered blending an aliphatic polyamide resin that is prone to crystallization, such as polyamide 66. However, when the proportion of aliphatic polyamide resin in the resin composition increased, discoloration and deformation of the molded product became significant when placed in an outdoor environment. Under these circumstances, in the present invention, we found that the above problems can be solved by blending an amorphous resin and precisely adjusting the blending amounts of each component.

[0012] The embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is merely one example of an embodiment of the present invention and is not limited to these.

[0013] <(A) Polyamide resin> The resin composition of this embodiment includes (A) a polyamide resin. (A) The polyamide resin consists of (A1) a semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) an aliphatic polyamide resin with a lower cooling crystallization temperature than the (A1) semi-aromatic polyamide resin. The resin composition of this embodiment may contain only one of each of (A1) semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) aliphatic polyamide resin, or it may contain two or more of each. The resin composition of this embodiment may also contain polyamide resins other than (A) polyamide resin, i.e., (A1) semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) polyamide resins other than aliphatic polyamide resin.

[0014] <<(A1) Semi-aromatic polyamide resin>> The resin composition of this embodiment includes (A1) a semi-aromatic polyamide resin. A semi-aromatic polyamide resin is composed of diamine-derived structural units and dicarboxylic acid-derived structural units, wherein 20 to 80 mol% (preferably 30 to 80 mol%, more preferably 40 to 70 mol%) of the total structural units of the diamine-derived and dicarboxylic acid-derived structural units contain aromatic rings.

[0015] The (A1) semi-aromatic polyamide resin used in this embodiment may be recycled semi-aromatic polyamide resin (including recovered products, material recycled products, chemical recycled products, etc.), rejected products, or scraps generated when molding molded products from resin compositions.

[0016] (A1) Examples of semi-aromatic polyamide resins include terephthalic acid-based polyamide resins (polyamide 6T, polyamide 9T, polyamide 10T) and xylylenediamine-based polyamide resins described later, with xylylenediamine-based polyamide resins being preferred. Xylylenediamine-based polyamide resins contain diamine-derived structural units and dicarboxylic acid-derived structural units, wherein 50 mol% or more of the diamine-derived structural units are derived from xylylenediamine. Preferably, in xylylenediamine-based polyamide resins, 70 mol% or more of the diamine-derived structural units are derived from xylylenediamine, and 70 mol% or more of the dicarboxylic acid-derived structural units are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms.

[0017] The diamine-derived structural units of the xylylenediamine-based polyamide resin are more preferably derived from xylylenediamine (preferably para-xylylenediamine and / or meta-xylylenediamine) in an amount of 75 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and particularly most preferably 99 mol% or more.

[0018] The xylylenediamine is preferably para-xylylenediamine and / or meta-xylylenediamine. Preferably, the xylylenediamine contains 0 to 100 mol% metaxylylenediamine and 100 to 0 mol% paraxylylenediamine (however, the total of metaxylylenediamine and paraxylylenediamine does not exceed 100 mol%), more preferably 10 to 100 mol% metaxylylenediamine and 90 to 0 mol% paraxylylenediamine, even more preferably 20 to 100 mol% metaxylylenediamine and 80 to 0 mol% paraxylylenediamine, even more preferably 40 to 100 mol% metaxylylenediamine and 60 to 0 mol% paraxylylenediamine, even more preferably 60 to 100 mol% metaxylylenediamine and 40 to 0 mol% paraxylylenediamine, and even more preferably 90 to 100 mol% metaxylylenediamine and 10 to 0 mol% paraxylylenediamine. In xylylenediamine-based polyamide resins, it is preferable that the total of constituent units derived from para-xylylenediamine and meta-xylylenediamine constitutes preferably 80 mol% or more, more preferably 85 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, even more preferably 98 mol% or more, and even more preferably 99 mol% or more of the constituent units derived from diamine. The upper limit of the total of the constituent units derived from para-xylylenediamine and meta-xylylenediamine is 100 mol%.

[0019] Diamines other than meta-xylylenediamine and para-xylylenediamine that can be used as raw material diamine components for xylylenediamine-based polyamide resins include aliphatic diamines such as tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine, as well as 1,3-bis( Examples include alicyclic diamines such as aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminomethyl)decalin, and bis(aminomethyl)tricyclodecane, as well as aromatic ring-containing diamines such as bis(4-aminophenyl) ether, paraphenylenediamine, and bis(aminomethyl)naphthalene. One or more of these can be used in combination.

[0020] On the other hand, of the xylylenediamine-based polyamide resin, preferably 70 mol% or more, more preferably 75 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and especially most preferably 99 mol% or more, are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms (preferably adipic acid).

[0021] Preferred α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms for use as raw material dicarboxylic acid components in xylylenediamine-based polyamide resins include, for example, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, undecanediic acid, and 1,12-dodecanediic acid. One or more of these can be used in combination, but among these, at least one of adipic acid, sebacic acid, and 1,12-dodecanediic acid is preferred, with adipic acid and / or sebacic acid being more preferred, and adipic acid being even more preferred, since the melting point of the polyamide resin is within a range suitable for molding.

[0022] Examples of dicarboxylic acid components other than those mentioned above include phthalate compounds such as isophthalic acid, terephthalic acid, and orthophthalic acid, and isomers of naphthalenedicarboxylic acids such as 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. One or more of these can be used in combination.

[0023] It should be noted that while xylylenediamine-based polyamide resins are mainly composed of diamine-derived and dicarboxylic acid-derived structural units, they do not completely exclude other structural units, and may also contain structural units derived from lactams such as ε-caprolactam and laurolactam, and aliphatic aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid. Here, "main component" refers to the structural unit in the xylylenediamine-based polyamide resin in which the total number of diamine-derived and dicarboxylic acid-derived structural units is the largest among all structural units. In this embodiment, it is preferable that the total of diamine-derived and dicarboxylic acid-derived structural units in the xylylenediamine-based polyamide resin accounts for 90% by mass or more of the total structural units, more preferably 95% by mass or more, even more preferably 97% by mass or more, and even more preferably 99% by mass or more.

[0024] It is also preferable to use polyamide resins manufactured using biomass raw materials (biomass polyamide resins) for xylylenediamine-based polyamide resins. By using biomass polyamide resins, it is possible to reduce the environmental impact. In xylylenediamine-based polyamide resins, bio-adipic acid can be used as a biomass raw material. Alternatively, adipic acid certified under Mass Balance Certification (ISCC PLUS) can be used. Mass Balance Certification quantifies the extent to which renewable and bio-based raw materials are used in each factory or production facility, and how much of that is used in the production and shipment of products, guaranteeing quality along with the certification itself.

[0025] (A1) The cooling crystallization temperature of the semi-aromatic polyamide resin is preferably 100°C or higher, more preferably 130°C or higher, even more preferably 140°C or higher, even more preferably 150°C or higher, and also preferably 250°C or lower, more preferably 230°C or lower, even more preferably 220°C or lower, and even more preferably 210°C or lower. Setting the temperature above the lower limit tends to accelerate the solidification of the molded product during injection molding, thereby shortening the molding time. Setting the temperature below the upper limit tends to suppress the appearance of reinforcing material on the surface of the molded product, resulting in a better appearance.

[0026] <<(A2) Polyamide 6>> The resin composition of this embodiment contains (A2) polyamide 6. Polyamide 6 is a polymer of caprolactam, but a portion of it may be modified with other monomer units. The percentage of modification is preferably less than 10% by mass of polyamide 6, more preferably less than 7% by mass, even more preferably less than 5% by mass, even more preferably less than 3% by mass, and even more preferably less than 1% by mass. The polyamide 6 used in this embodiment may be recycled polyamide 6 (including recovered products, material recycled products, chemical recycled products, etc.), rejected products, or scraps generated when molding molded products from resin compositions.

[0027] <<(A3) Aliphatic polyamide resin with a higher cooling crystallization temperature than the semi-aromatic polyamide resin (A1) mentioned above>> The resin composition of this embodiment includes an aliphatic polyamide resin with a higher cooling crystallization temperature than the (A1) semi-aromatic polyamide resin. In this embodiment, the difference in cooling crystallization temperature between the (A3) aliphatic polyamide resin and the (A1) aromatic polyamide resin is preferably 5°C or more, more preferably 20°C or more, even more preferably 30°C or more, even more preferably 40°C or more, and also preferably 140°C or less, more preferably 120°C or less, even more preferably 110°C or less, and even more preferably 100°C or less. Setting the difference above the lower limit tends to accelerate the solidification of the molded product during injection molding, thereby shortening the molding time. Setting the difference below the upper limit tends to suppress the appearance of reinforcing material on the surface of the molded product, resulting in a better appearance. In this embodiment, if the resin composition contains two or more types of (A1) semi-aromatic polyamide resins and / or (A3) aliphatic polyamide resins, the crystallization temperature of the (A1) semi-aromatic polyamide resin upon cooling shall be the temperature of the resin with the highest content among (A1), and the crystallization temperature of the (A3) aliphatic polyamide resin upon cooling shall be the temperature of the resin with the highest crystallization temperature among (A3).

[0028] (A3) Aliphatic polyamide resins can be widely used as long as they are aliphatic polyamide resins with a higher cooling crystallization temperature than (A1) semi-aromatic polyamide resins. Here, an aliphatic polyamide resin means that of the total constituent units of the polyamide resin, more than 80 mol% are derived from aliphatic monomers, preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 97 mol% or more.

[0029] (A3) Examples of aliphatic polyamide resins include polyamide 4, polyamide 46, polyamide 66, polyamide 666, polyamide 610, polyamide 11, polyamide 12, etc., with polyamide 6, polyamide 66, and polyamide 666 being preferred, and polyamide 66 being more preferred.

[0030] The (A3) aliphatic polyamide resin used in this embodiment may be recycled aliphatic polyamide resin (including recovered products, material recycled products, chemical recycled products, etc.), rejected products, or scraps generated when molding molded products from resin compositions.

[0031] Furthermore, the (A) polyamide resin used in the resin composition of this embodiment is particularly preferably a blend of xylylenediamine-based polyamide resin, polyamide 6, and polyamide 66.

[0032] <<Blending ratio of (A1) semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) aliphatic polyamide resin>> In the resin composition of this embodiment, the mass ratio of the content of (A1) semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) aliphatic polyamide resin satisfies (A1) / [(A2)+(A3)]>1.0. The (A1) / [(A2)+(A3)] is preferably greater than 1.2, more preferably greater than 1.4, even more preferably greater than 1.5, even more preferably greater than 1.7, even more preferably greater than 1.9, and also preferably less than 5.0, even more preferably less than 4.0, even more preferably less than 3.0, even more preferably less than 2.5, and even more preferably less than 2.4. Setting (A1) / [(A2)+(A3)] > 1.0 tends to suppress the reinforcing material from rising to the surface of the molded product, resulting in a better appearance. Furthermore, setting 5.0 > (A1) / [(A2)+(A3)] tends to more effectively suppress discoloration and deterioration of physical properties under external environmental conditions.

[0033] In the resin composition of this embodiment, it is also preferable that the mass ratio of (A1) semi-aromatic polyamide resin to (A2) polyamide 6 satisfies 0.1 < (A2) / (A1) < 0.5. Setting 0.1 < (A2) / (A1) tends to more effectively suppress discoloration and deterioration of physical properties under external environmental conditions. Furthermore, setting (A2) / (A1) < 0.5 tends to suppress the reinforcing material from rising to the surface of the molded product, resulting in a better appearance. The aforementioned (A2) / (A1) is preferably greater than 0.2 and preferably less than 0.4.

[0034] The total amount of (A) polyamide resin in the resin composition of this embodiment is preferably 20% by mass or more, more preferably 23% by mass or more, even more preferably 25% by mass or more, even more preferably 28% by mass or more, even more preferably 30% by mass or more, even more preferably 32% by mass or more, and also preferably 50% by mass or less, preferably 48% by mass or less, more preferably 45% by mass or less, even more preferably 43% by mass or less, even more preferably 40% by mass or less, and even more preferably 38% by mass or less.

[0035] The resin composition of this embodiment may or may not contain polyamide resins other than (A) polyamide resins (i.e., (A1) semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) aliphatic polyamide resin). The resin composition of this embodiment preferably contains substantially no polyamide resins other than (A) polyamide resin. Specifically, in the resin composition of this embodiment, the content of polyamide resins other than (A) polyamide resin is preferably less than 10% by mass of the content of (A) polyamide resin in the resin composition, more preferably less than 7% by mass, even more preferably less than 5% by mass, even more preferably less than 3% by mass, and even more preferably less than 1% by mass.

[0036] <(B) Reinforcement material> The resin composition of this embodiment includes (B) a reinforcing agent. By including (B) a reinforcing agent, the mechanical strength of the resulting molded product can be improved. The reinforcing materials that can be included in the resin composition of this embodiment are those that have the effect of improving the mechanical properties of the resin composition obtained by being compounded with the resin, and commonly used reinforcing materials for plastics can be used. The reinforcing material may be organic or inorganic, but inorganic is preferred. Preferably, fibrous reinforcing materials such as glass fibers, carbon fibers, basalt fibers, wollastonite, and potassium titanate fibers can be used. In addition, granular or amorphous reinforcing materials such as talc, titanium oxide, feldspar minerals, clay, organic clay, and glass beads; and flaky reinforcing materials such as flake glass and graphite can also be used. In this embodiment, among the above, it is more preferable to include glass fibers and / or talc, and even more preferable to include glass fibers.

[0037] (B) It is more preferable to use reinforcing materials that have been surface-treated with a surface treatment agent such as a coupling agent. In particular, glass fibers to which a surface treatment agent has been applied are preferred because they have excellent durability, resistance to humid heat, resistance to hydrolysis, and resistance to thermal shock.

[0038] The glass fibers consist of glass compositions such as A glass, C glass, E glass, S glass, R glass, M glass, and D glass, with E glass (alkali-free glass) being particularly preferred. Glass fiber refers to a material whose cross-sectional shape, when cut perpendicular to its length, is circular or polygonal, exhibiting a fibrous appearance.

[0039] The glass fibers used in the resin composition of this embodiment may be single fibers or multiple single fibers twisted together. The glass fibers can take any form, including single fibers, "glass roving" made by continuously winding multiple single fibers twisted together, "chopped strands" cut to a length of 1 to 10 mm, or "milled fibers" crushed to a length of 10 to 500 μm. Such glass fibers are readily available commercially from Asahi Fiber Glass Co., Ltd. under the product names "Glasslon Chopped Strands" and "Glasslon Milled Fiber." Different forms of glass fibers can also be used in combination.

[0040] Furthermore, the glass fibers used in this embodiment may have a circular or non-circular cross-section. By using glass fibers with a non-circular cross-section, warping of the resulting molded product can be suppressed more effectively. In addition, in this embodiment, warping can be effectively suppressed even when using glass fibers with a circular cross-section.

[0041] The content of (B) reinforcing material in the resin composition of this embodiment is preferably 100 parts by mass or more, more preferably 110 parts by mass or more, more preferably 115 parts by mass or more, and even more preferably 120 parts by mass or more, per 100 parts by mass of (A) polyamide resin. The upper limit is preferably 230 parts by mass or less, more preferably 210 parts by mass or less, even more preferably 190 parts by mass or less, even more preferably 170 parts by mass or less, and even more preferably 150 parts by mass or less, per 100 parts by mass of (A) polyamide resin. The content of (B) reinforcing material in the resin composition of this embodiment is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 45% by mass or more. The upper limit is preferably 65% ​​by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less. The resin composition of this embodiment may contain only one type of (B) reinforcing material, or it may contain two or more types. If it contains two or more types, the total amount will be within the above range. Note that the amount of reinforcing material in this embodiment includes the amount of sizing agent and surface treatment agent.

[0042] <(C) Coloring agent> The resin composition of this embodiment may also contain (C) a coloring agent. By including a coloring agent, the resulting molded product can be given a color. (C) The coloring agent may be a pigment or a dye, but it is preferably a pigment. Furthermore, (C) the coloring agent may be an achromatic coloring agent or a chromatic coloring agent, with an achromatic coloring agent being preferred. A black coloring agent composed of two or more chromatic coloring agents is also preferred. In this embodiment, a preferred example is that the colorant (C) includes a black colorant (preferably a black pigment) and / or a white colorant (preferably a white pigment). Carbon black is an example of a black pigment. Examples of white pigments include zinc sulfide and titanium dioxide. It is preferable to use a masterbatch of pigments such as carbon black with a thermoplastic resin (preferably the amorphous resin described in (D) above).

[0043] The content of (C) colorant (preferably carbon black) in the resin composition of this embodiment is preferably 14.0 parts by mass or more, more preferably 14.5 parts by mass or more, even more preferably 15.0 parts by mass or more, and even more preferably 15.5 parts by mass or more, per 100 parts by mass of (A) polyamide resin. By setting it above the lower limit, the color development can be fully exhibited. Furthermore, the content of (C) colorant in the resin composition of this embodiment is preferably 30.0 parts by mass or less, more preferably 28.0 parts by mass or less, even more preferably 26.0 parts by mass or less, even more preferably 24.0 parts by mass or less, and even more preferably 20.0 parts by mass or less, per 100 parts by mass of polyamide resin. By setting it below the upper limit, problems such as mold contamination during injection molding can be effectively suppressed. The resin composition of this embodiment may contain only one type of (C) colorant, or it may contain two or more types. If it contains two or more types, it is preferable that the total amount is within the above range.

[0044] <(D) Amorphous resin> The resin composition of this embodiment includes (D) an amorphous resin. (D) As for amorphous resins, resins containing styrene units (styrene-based resins) are preferred, and resins containing acetonitrile units and styrene units (acrylonitrile styrene resins) are more preferred.

[0045] Examples of polystyrene resins include homopolymers of styrene monomers and copolymers of styrene monomers and monomers copolymerizable with styrene monomers. In copolymers of styrene monomers and copolymerizable monomers, it is preferable that 50% by mass or more of the total monomer is styrene monomer, more preferably 60% by mass or more is styrene monomer, and preferably 100% by mass or less is styrene monomer.

[0046] Styrene monomers refer to styrene and styrene having substituents, and include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromstyrene, dibromstyrene, fluorostyrene, and tribromstyrene, with styrene and α-methylstyrene being more preferred, and styrene being particularly preferred. Furthermore, among the monomers that make up styrene-based resins, monomers other than styrene-based monomers include (meth)acrylic acid ester monomers, maleimide monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide, and rubbers such as acrylic acid, methacrylic acid, and butadiene.

[0047] The styrene resin used in this embodiment may include rubber-reinforced polystyrene resin. Specific examples of rubber-reinforced polystyrene resin include acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylene propylene-rubber-styrene copolymer (AES resin), styrene-IPN type rubber copolymer, and other resins.

[0048] In this embodiment, the polystyrene resin preferably contains at least one selected from acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), and acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), more preferably contains at least one selected from AS resin, ABS resin, and ASA resin, even more preferably contains AS resin and / or ASA resin, and even more preferably contains AS resin.

[0049] The amorphous resin (D) used in this embodiment may be a virgin amorphous resin or a recycled amorphous resin. Examples of recycled amorphous resins include those obtained through material recycling, which involves crushing and washing recovered used amorphous resin molded products for reuse, and those obtained through chemical recycling (chemical decomposition). In this embodiment, material recycled products are preferred.

[0050] The content of (D) amorphous resin in the resin composition of this embodiment is preferably 5.0 parts by mass or more, more preferably 7.0 parts by mass or more, even more preferably 9.0 parts by mass or more, even more preferably 11.0 parts by mass or more, even more preferably 13.0 parts by mass or more, even more preferably 16.0 parts by mass or more, and also preferably 30.0 parts by mass or less, and more preferably 25.0 parts by mass or less, with respect to 100 parts by mass of (A) polyamide resin. Setting the content above the lower limit tends to more effectively suppress warping of the resulting molded product. Setting the content below the upper limit tends to further improve the impact resistance of the resin composition.

[0051] The resin composition of this embodiment satisfies the mass ratio of the contents of (A2) polyamide 6, (A3) aliphatic polyamide resin, and (D) amorphous resin, which is 0.3 < [(A2) + (A3)] / (D) < 3.3. By setting 0.3 < [(A2) + (A3)] / (D), the rigidity and impact resistance of the resulting molded product tend to be improved. Furthermore, by setting [(A2) + (A3)] / (D) < 3.3, discoloration and deterioration of physical properties when the resulting molded product is exposed to the external environment tend to be more effectively suppressed. The above [(A2)+(A3)] / (D) is preferably greater than 0.5, more preferably greater than 0.8, even more preferably greater than 1.0, even more preferably greater than 1.5, and also preferably less than 3.2, more preferably less than 3.0, even more preferably less than 2.8, even more preferably less than 2.5, and even more preferably less than 2.3. The resin composition of this embodiment may contain only one type of amorphous resin (D), or it may contain two or more types. When it contains two or more types, it is preferable that the total amount is within the above range.

[0052] <(E) Release agent> The resin composition of this embodiment may also contain (E) a mold release agent. (E) Examples of release agents include aliphatic carboxylic acids, higher fatty acid metal salts, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds with a number average molecular weight of 200 to 15,000, polysiloxane-based silicone oils, ketone waxes, and aliphatic carboxylic acid amides, and it is preferable to include higher fatty acid metal salts and / or aliphatic carboxylic acid amides, and it is more preferable to include aliphatic carboxylic acid amides.

[0053] The higher fatty acid metal salt is preferably a higher fatty acid metal salt with a carbon chain number of 15 to 40. The fatty acids that make up the higher fatty acid metal salts are preferably fatty acids with 18 or more carbon chains, more preferably fatty acids with 35 or fewer carbon chains, and even more preferably fatty acids with 30 or fewer carbon chains. Specific examples of fatty acids that make up the higher fatty acid metal salts include stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, and ricinoleic acid, with montanic acid being preferred. Examples of metals that make up higher fatty acid metal salts include calcium, magnesium, zinc, aluminum, barium, and lithium, with calcium being preferred. For further details regarding the release agent, please refer to paragraphs 0037-0042 of Japanese Patent Publication No. 2016-196563, paragraphs 0067-0070 of Japanese Patent Publication No. 2021-161125, and paragraphs 0048-0058 of Japanese Patent Publication No. 2016-078318, in addition to the above, and these contents are incorporated herein by reference.

[0054] The content of the mold release agent in the resin composition of this embodiment is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.2 parts by mass or more, per 100 parts by mass of (A) polyamide resin. Setting it above the lower limit tends to further improve mold release properties. Furthermore, the content of the mold release agent in the resin composition of this embodiment is preferably 2.0 parts by mass or less, more preferably 1.5 parts by mass or less, even more preferably 1.4 parts by mass or less, even more preferably 1.1 parts by mass or less, and even more preferably 0.9 parts by mass or less, per 100 parts by mass of (A) polyamide resin. Setting it below the upper limit effectively suppresses mold release agent bleed-out and gas during molding. The resin composition of this embodiment may contain only one type of (E) mold release agent, or it may contain two or more types. If it contains two or more types, it is preferable that the total amount is within the above range.

[0055] <Other ingredients> The resin composition of this embodiment may contain other components besides those mentioned above. Other components may include thermoplastic resins other than (A) polyamide resin and (D) amorphous resin, impact resistance modifiers, heat resistance stabilizers, weather resistance stabilizers, antioxidants, flame retardants, flame retardant aids, anti-dripping agents, matting agents, ultraviolet absorbers, plasticizers, antistatic agents, color inhibitors, and gelation inhibitors, as needed. Each of these additives may be present individually or in pairs or more. Details of these components can be derived from the additives described in paragraphs 0047-0103 of International Publication No. 2021 / 241471, which are incorporated herein by reference. The total amount of these other components in the resin composition of this embodiment is preferably less than 5% by mass, more preferably less than 3% by mass, and even more preferably less than 1% by mass. In this embodiment, the total amount of (A) polyamide resin, (B) reinforcing agent, (C) colorant, (D) amorphous resin, and (E) mold release agent preferably accounts for 90% by mass or more of the resin composition, more preferably 95% by mass or more, even more preferably 97% by mass or more, and even more preferably 99% by mass or more.

[0056] <Physical properties of resin compositions> The resin composition of this embodiment preferably has high mechanical strength. Specifically, it is preferable that the flexural modulus of the resin composition of this embodiment, when molded into an ISO test piece with a thickness of 4 mm, is 18,000 GPa or higher, as measured in accordance with ISO 178. There is no particular upper limit to the flexural modulus, but for example, even 20 GPa or less, or even 10 GPa or less, is sufficient to meet the required performance.

[0057] The resin composition of this embodiment preferably exhibits excellent impact resistance. Specifically, when the resin composition of this embodiment is molded into an ISO test piece with a thickness of 4 mm, the notched Charpy impact strength measured in accordance with ISO 179-2 is 25 kJ / m². 2 Preferably, it is 28 kJ / m³ 2 It is more preferable that the value be 63 kJ / m³ or higher. 2 It is even more preferable that the above values ​​are met. There is no specific upper limit for the notched Charpy impact strength, but for example, 100 kJ / m 2 Furthermore, 90 kJ / m³ 2 Even with the following, the required performance is sufficiently met. The flexural modulus and Charpy impact strength are measured according to the examples described below.

[0058] The resin composition of this embodiment preferably has a cooling crystallization temperature (Tc) of 170°C or higher, more preferably 175°C or higher, even more preferably 179°C or higher, even more preferably 181°C or higher, even more preferably 182°C or higher, and also preferably 235°C or lower, more preferably 220°C or lower, even more preferably 210°C or lower, even more preferably 200°C or lower, even more preferably 197°C or lower, and may also be 190°C or lower. If there are two or more peaks in the cooling crystallization temperature (Tc), it is preferable that at least one of the peaks satisfies the above range, and more preferably that at least the lower peak satisfies the above range. The above cooling crystallization temperature is measured according to the description in the examples below.

[0059] <Method for producing resin compositions> In this embodiment, the method for producing the resin composition is not particularly specified, and a wide range of known methods for producing thermoplastic resin compositions can be used. Specifically, the resin composition can be produced by pre-mixing each component using various mixers such as a tumbler or a Henschel mixer, and then melt-kneading them using a Banbury mixer, rolls, brabender, single-screw extruder, twin-screw extruder, kneader, etc.

[0060] Furthermore, for example, a resin composition can be manufactured by supplying the components to an extruder using a feeder, either without pre-mixing them or by pre-mixing only some of the components, and then melt-kneading them together. Furthermore, for example, a masterbatch can be obtained by pre-mixing some components, such as colorants, and supplying them to an extruder for melt-kneading. This masterbatch can then be mixed with the remaining components and melt-kneaded again to produce pellets. More specifically, the method for producing the resin composition of this embodiment preferably involves melt-kneading a masterbatch of a coloring agent (C) with an amorphous resin (D), a polyamide resin (A), a reinforcing agent (B), and a release agent (E). Furthermore, it is preferable to side-feed the reinforcing material (especially reinforcing fibers such as glass fibers).

[0061] <Applications of resin compositions and molded articles> The molded article of this embodiment is formed from the resin composition or pellets of this embodiment. The method for manufacturing the molded article of this embodiment is not particularly defined. As an example, an injection-molded article formed by injection molding is provided. For example, the molded article of this embodiment may be formed by melting and kneading each component and then directly using various molding methods, or the components may be melted and kneaded to form pellets, then melted again and molded using various molding methods.

[0062] The method for molding the molded product is not particularly limited, and conventionally known molding methods can be used. Examples include injection molding, injection compression molding, extrusion molding, shape extrusion, transfer molding, hollow molding, gas-assisted hollow molding, blow molding, extrusion blow molding, IMC (in-mold coating) molding, rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding, and pressure molding.

[0063] There are no particular restrictions on the shape of the molded product in this embodiment, and it can be appropriately selected according to the application and purpose of the molded product. Examples include plate-shaped, rod-shaped, sheet-shaped, film-shaped, cylindrical, annular, circular, elliptical, gear-shaped, polygonal, irregularly shaped, hollow, frame-shaped, box-shaped, and panel-shaped products.

[0064] The molded product of this embodiment is also preferably used for large molded products. As an example of a large molded product, it is preferable that the longest length of the molded product is 5 cm to 200 cm. Also, the total volume of the resin composition used in one molded product is 5 cm³. 3 ~100cm 3 It is preferable that this be the case.

[0065] <Application> The resin composition, pellets, and molded articles of this embodiment can be applied to various storage containers, electrical and electronic equipment components, office automation (OA) equipment components, home appliance components, mechanical mechanism components, vehicle mechanism components, and the like. It is particularly preferred for molded products used outdoors. Specifically, it is especially preferred for exterior vehicle parts such as door mirrors, door handles, and roof rails. [Examples]

[0066] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or other reasons, measurements can be taken using other instruments with equivalent performance.

[0067] 1.Raw materials The following ingredients were used. [Table 1]

[0068] <Measurement of cooling crystallization temperature (Tc)> The cooling crystallization temperature (Tc) of polyamide resins and resin compositions was measured according to differential scanning calorimetry (DSC) in accordance with ISO 3146. Specifically, a differential scanning calorimeter was used. The resin (crushed pellets) was placed in the measurement pan of the differential scanning calorimeter, and pre-treated by heating it to a temperature above its melting point at a heating rate of 10°C / min under a nitrogen atmosphere, followed by rapid cooling, before measurement. The measurement conditions were as follows: heating at a heating rate of 10°C / min, holding at 300°C for 10 minutes, and then cooling at a cooling rate of -10°C / min down to 30°C to measure the cooling crystallization temperature (Tc, unit: °C). The differential scanning calorimeter used is the "DSC-7020" manufactured by Hitachi High-Tech Science Co., Ltd.

[0069] <Adjusting the carbon black masterbatch (1)> A masterbatch was obtained by adjusting the mass ratio of carbon black (C1) (manufactured by Mitsubishi Chemical Corporation, #45) and MXD6 to 1:1 and then melt-mixing them together.

[0070] <Preparation of carbon black masterbatch (2)> Carbon black (C2) (manufactured by Mitsubishi Chemical Corporation, #960), AS resin, and barium stearate were mixed in a ratio of 50:49.5:0.5, and then melt-mixed to obtain a masterbatch.

[0071] 2. Examples 1-7, Comparative Examples 1-6 <Compound> Each component was weighed to achieve the composition shown in Tables 2 to 4 below. The components, excluding the glass fibers, were blended in a tumbler. The mixture was then fed into a twin-screw extruder (Shibaura Machine Co., Ltd., TEM26SS) from the base, melted, and then the glass fibers were side-fed to produce pellets. The temperature setting of the twin-screw extruder was 280°C. The components in Tables 2 to 4 are shown as mass ratios. In Examples 1-3 and Comparative Examples 1-6, carbon black masterbatch (1) was prepared beforehand, while in Example 4, carbon black masterbatch (2) was prepared before the compounding process. The amounts of each component shown in Tables 2-3 represent the final amounts blended into the resin composition. Furthermore, the (C3) carbon black, (D3) AS resin, and (E2) release agent in Examples 5-7 of Table 4 are those contained in the carbon black masterbatch, and the content of (C3) carbon black, (D3) AS resin, and (E2) release agent in Table 4 is shown separately from that of the carbon black masterbatch.

[0072] <Bending properties> The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours, and then ISO tensile test specimens (4 mm thick) were injection molded using an injection molding machine (NEX-140III, manufactured by Nissei Plastic Industrial Co., Ltd.) under the conditions of cylinder temperature 280°C, mold temperature 130°C, and molding cycle of 50 seconds. In accordance with ISO 178, the flexural modulus (unit: MPa) and flexural strength (unit: MPa) were measured at a temperature of 23°C.

[0073] <Charpy impact strength> The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours, and then ISO tensile test specimens (4 mm thick) were injection molded using an injection molding machine (NEX-140III, manufactured by Nissei Plastic Industrial Co., Ltd.) under the conditions of cylinder temperature 280°C, mold temperature 130°C, and molding cycle of 50 seconds. In accordance with the ISO 179 standard, Charpy impact strength (unnotched Charpy and notched Charpy) was measured at a temperature of 23°C. The unit is kJ / m 2 As shown.

[0074] <Exterior (visual inspection)> After drying the pellets obtained by the above manufacturing method at 120°C for 4 hours, test specimens measuring 100 mm × 100 mm × 1 mm thick were manufactured using an injection molding machine (Nissei Plastic Industrial Co., Ltd., "NEX-140III") under the conditions of cylinder temperature 280°C, mold temperature 130°C, and molding cycle of 50 seconds. The obtained test specimens were visually evaluated for their appearance. A: It had a glossy finish and presented a good appearance. B: There were some white areas. C: Other than A and B above, for example, if there are many white areas on the entire surface.

[0075] <Glossy Gs60> The gloss of the central part of the 100mm x 100mm x 1mm thick test specimen prepared in the appearance evaluation section above was measured according to the specular gloss measurement method (JIS Z 8741). The gloss value (Gs60) at an incident angle of 60° for each material is shown as the representative value. A gloss meter, VG7000, manufactured by Nippon Denshoku Industries Ltd., was used.

[0076] <curve> The ISO tensile test specimens (4 mm thick) prepared above were placed in a three-point bending jig so that the deflection amount of the specimens was 4.2 mm. After placement, they were left standing in an environment of 80°C and 95% humidity for 48 hours. After the test, the specimens deformed into an arch shape were left standing in a flat place, and the vertical distance from the standing place to the highest position of the specimens was taken as the amount of warp.

[0077] <Water absorption rate> The water absorption rates before and after standing for 50 hours in an atmosphere of 80°C and 95% relative humidity in the above warp test were measured, and the water absorption rate was calculated as follows. Water absorption rate = [(mass of the specimen after standing - mass of the specimen before standing) / mass of the specimen before standing] × 100 (unit: %)

[0078] <Weather resistance test> After drying the pellets obtained by the above manufacturing method at 120°C for 4 hours, a flat test specimen with a surface textured and having dimensions of 60 mm × 60 mm × 2 mm t was created using an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., "NEX-140III") under the conditions of a cylinder temperature of 280°C, a mold temperature of 130°C, and a molding cycle of 50 seconds. The flat test specimen was processed in a weather resistance tester (manufactured by Suga Test Instruments Co., Ltd., Metalinear Weather Meter M6T) for 160 hours. The test conditions were repeated 32 times for Condition 1 and Condition 2. Condition 1: Only irradiation (BPT temperature 63°C, irradiance 0.53 kW / m 2 , test time 4 hours) Condition 2: Irradiation + rainfall (tank temperature 38°C, humidity 95%RH, irradiance 0.53 kW / m 2 , test time 1 hour) The Lab* values of the test specimens before and after the test were measured using a spectrocolorimeter (SE6000, manufactured by Nippon Denshoku Industries Co., Ltd.), and ΔE* was calculated.

[0079]

Table 2

[0080]

Table 3

[0081] [Table 4]

[0082] The amounts of carbon black listed in Tables 2-4 (C1)-(C3) represent the amount of carbon black itself, not the amount of carbon black masterbatch. As is clear from the above results, molded articles formed from the resin composition of the present invention had a good appearance and excellent weather resistance (Examples 1-7). In particular, even when recycled polyamide resin was used, performance equivalent to that obtained when virgin polyamide resin was used was obtained (Examples 5-7). Furthermore, the molded articles formed from the resin composition of the present invention also exhibited excellent mechanical strength. In contrast, when (A3) aliphatic polyamide resin (an aliphatic polyamide resin with a higher cooling crystallization temperature than (A1) semi-aromatic polyamide resin) was not included (Comparative Examples 1 and 2), the warpage was greater. (A2) When polyamide 6 was not included (Comparative Example 3), the visual appearance and gloss were inferior. If (A1) / [(A2)+(A3)] > 1.0 was not satisfied (Comparative Example 1), the glossiness was inferior. When the carbon black content was low (Comparative Examples 2-4, 6, and especially Comparative Example 6), the warping was significant, and the mechanical strength was also inferior. If the condition 0.3 < [(A2) + (A3)] / (D) < 3.3 was not met (Comparative Examples 1-6), then one or more of the following were inferior: mechanical strength, appearance, weather resistance, warping, etc.

[0083] Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications are possible without departing from the intent and scope of the invention.

Claims

1. A polyamide resin (A) comprising (A1) a semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) an aliphatic polyamide resin having a higher cooling crystallization temperature than the semi-aromatic polyamide resin (A1), (B) Reinforcement material, (C) Coloring agent and, (D) Amorphous resin and (E) Contains a release agent, The mass ratio of the contents of (A1) semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) aliphatic polyamide resin satisfies (A1) / [(A2)+(A3)]>1.0, (C) The coloring agent content is 14.0 to 30.0 parts by mass per 100 parts by mass of (A) polyamide resin. The mass ratio of the contents of (A2) polyamide 6, (A3) aliphatic polyamide resin, and (D) amorphous resin satisfies 0.3 < [(A2) + (A3)] / (D) < 3.

3. (C) The coloring agent is carbon black, (D) The amorphous resin is a styrene resin and / or acrylonitrile styrene resin, (D) The content of amorphous resin is 11.0 to 30.0 parts by mass per 100 parts by mass of (A) polyamide resin. The cooling crystallization temperature of the polyamide resin was measured according to differential scanning calorimetry (DSC) in accordance with ISO 3146. The polyamide resin was pre-treated by heating it to a temperature above its melting point at a rate of 10°C / min under a nitrogen atmosphere, followed by rapid cooling. After holding the temperature at 300°C for 10 minutes at a heating rate of 10°C / min, the temperature was measured by cooling it down to 30°C at a rate of -10°C / min. Resin composition.

2. (A1) The resin composition according to claim 1, wherein the semi-aromatic polyamide resin comprises a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and the xylylenediamine-based polyamide resin comprises 50 mol% or more of the diamine-derived structural unit derived from xylylenediamine.

3. The resin composition according to claim 2, wherein the xylylenediamine-based polyamide resin has a diamine-derived structural unit of 70 mol% or more derived from xylylenediamine, and a dicarboxylic acid-derived structural unit of 70 mol% or more derived from an α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms.

4. The resin composition according to claim 1 or 2, wherein the mass ratio of (A1) semi-aromatic polyamide resin to (A2) polyamide 6 satisfies 0.2 < (A2) / (A1) < 0.

5.

5. (A3) The resin composition according to claim 1 or 2, wherein the aliphatic polyamide resin comprises polyamide 66.

6. The resin composition according to claim 1 or 2, wherein the mass ratio of the content of (A1) semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) aliphatic polyamide resin satisfies 2.2 > (A1) / [(A2) + (A3)] > 1.

2.

7. (B) The resin composition according to claim 1 or 2, wherein the reinforcing material comprises glass fiber and / or talc.

8. The resin composition according to claim 1 or 2, wherein the content of (B) the reinforcing material is 100 to 230 parts by mass per 100 parts by mass of (A) the polyamide resin.

9. The cooling crystallization temperature Tc of the resin composition, as measured by a differential scanning calorimeter, is 170°C ≤ Tc ≤ 235°C. The resin composition according to claim 1 or 2, wherein the cooling crystallization temperature Tc of the resin composition is a value measured in accordance with ISO 3146 by differential scanning calorimetry (DSC), and is the value measured after pretreatment in which the resin composition is heated in a nitrogen atmosphere at a heating rate of 10°C / min to a temperature above the melting point and rapidly cooled, then held at 300°C for 10 minutes at a heating rate of 10°C / min, and then measured down to 30°C at a cooling rate of -10°C / min.

10. The resin composition according to claim 1 or 2, wherein the mold release agent (E) comprises a higher fatty acid metal salt and / or an aliphatic carboxylic acid amide.

11. (A1) The semi-aromatic polyamide resin contains diamine-derived structural units and dicarboxylic acid-derived structural units, wherein 70 mol% or more of the diamine-derived structural units are derived from xylylenediamine, and 70 mol% or more of the dicarboxylic acid-derived structural units are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms. The mass ratio of (A1) semi-aromatic polyamide resin to (A2) polyamide 6 satisfies 0.2 < (A2) / (A1) < 0.

5. (A3) The aliphatic polyamide resin contains polyamide 66, The mass ratio of the contents of (A1) semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) aliphatic polyamide resin satisfies 2.2 > (A1) / [(A2) + (A3)] > 1.

2. (B) The reinforcing material contains glass fiber and / or talc, (B) The reinforcing material content is 100 to 230 parts by mass per 100 parts by mass of (A) polyamide resin. The cooling crystallization temperature Tc of the resin composition, as measured by differential scanning calorimeter, is 170°C ≤ Tc ≤ 235°C. The cooling crystallization temperature Tc of the resin composition is a value measured according to differential scanning calorimetry (DSC) in accordance with ISO 3146, and is the value measured after pre-treatment in which the resin composition is heated in a nitrogen atmosphere at a heating rate of 10°C / min to a temperature above the melting point, followed by rapid cooling, then held at 300°C for 10 minutes at a heating rate of 10°C / min, and finally measured down to 30°C at a cooling rate of -10°C / min. The resin composition according to claim 1, wherein the mold release agent (E) comprises a higher fatty acid metal salt and / or an aliphatic carboxylic acid amide.

12. The resin composition according to claim 1, 2, or 11, wherein at least one of the (A1) semi-aromatic polyamide resin, (A2) polyamide 6, and (A3) aliphatic polyamide resin includes recycled material.

13. Pellets of the resin composition according to claim 1, 2, 3, or 11.

14. A molded article formed from the resin composition according to claim 1, 2, 3, or 11.

15. A molded article formed from the pellets described in claim 13.

16. A method for producing a resin composition according to claim 1, 2, 3, or 11, comprising melt-kneading a masterbatch of a coloring agent (C) with an amorphous resin (D), a polyamide resin (A), a reinforcing agent (B), and a mold release agent (E).

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