Polyamide resin composition

Abstract

The present invention relates to a polyamide resin composition comprising an aliphatic polyamide resin (Aa) containing an aliphatic homopolyamide resin (A-1) and an aliphatic copolyamide resin (A-2), an aromatic polyamide resin (Ab), an ionomer (B), and a functional group-containing olefin-based resin (C), comprising 40 to 60 mass% of the aforementioned aliphatic homopolyamide resin (A-1), 10 to 40 mass% of the aforementioned aliphatic copolyamide resin (A-2), 2 to 10 mass% of the aforementioned aromatic polyamide resin (Ab), 5 to 20 mass% of the aforementioned ionomer (B), and 5 to 10 mass% of the aforementioned functional group-containing olefin-based resin (C) in 100 mass% of the polyamide resin composition, and the relative viscosity of the aforementioned aliphatic polyamide resin (Aa) determined by dissolving 1 g of the aforementioned aliphatic polyamide resin (Aa) in 100 ml of 96% sulfuric acid and measuring at 25°C according to JIS K 6920 is 3.60 to 3.85.

Description

Technical Field

[0001] This invention relates to polyamide resin compositions. Background Technology

[0002] Polyamide resins possess excellent mechanical properties, heat resistance, and chemical resistance, making them widely used as engineering plastics in various applications and through various molding methods. Among these applications is their use as blow-molded products.

[0003] Extrusion blow molding manufactures molded articles through the following steps. First, molten resin is extruded through a die using an extruder to form a preform. As the preform emerges from the die at a predetermined length, the cavity of the die closes the preform, clamping off one end. Then, expanding gas is blown into the preform, causing it to expand and come into contact with the surface of the hollow blow mold, where it cools and takes the shape of the mold. Through contact with the cold mold wall, the preform is cooled and takes the shape of the molded article.

[0004] The report addresses the issue of the fracturing of the pinched seam formed by this method. It describes how a polymer composition containing an impact modifier and a heat stabilizer is molded under specific processing conditions using a specific resin as a polyamide resin, thereby improving the mechanical strength of the pinched seam (see, for example, Patent Document 1).

[0005] It is known that polyamide resin compositions in which acid-modified impact-resistant materials are added to polyamide resins exhibit increased viscosity and excellent blow molding properties. On the other hand, it is known that polyamide resin compositions obtained by adding ionomers to polyamide resins can achieve high viscosity, are suitable for blow molding, and exhibit excellent impact resistance.

[0006] Therefore, it has been reported that polyamide resin compositions in which acid-modified impact-resistant materials and ionomers are compounded in polyamide resins simultaneously achieve blow molding properties such as suppression of preform sag and uniform wall thickness of molten resin, and improve surface appearance and impact resistance (e.g., see Patent Document 2).

[0007] In addition, it has been reported that polyamide resin compositions formulated with acid-modified impact-resistant materials and optionally ionomers, and satisfying specific mathematical formulas, exhibit excellent blow molding properties such as suppressing preform sag while maintaining the surface appearance of the molded article, and excellent impact resistance at low temperatures (for example, see Patent Document 3).

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2022-510785

[0011] Patent Document 2: International Publication No. 2020 / 049907

[0012] Patent Document 3: International Publication No. 2019 / 117072 Summary of the Invention

[0013] The problem the invention aims to solve

[0014] Patent document 1 only confirms whether the seam can be broken by hand, and further research is needed on breaking the seam.

[0015] The fractured part is prone to breakage because its central thickness is thinner than that of its surrounding area.

[0016] The objective of this invention is to provide a polyamide resin composition that improves the weld interface strength of the resin weld portion, represented by the clamping portion, in blow molding, and improves the mechanical strength by suppressing and preventing breakage by suppressing the degree of thinning of the thickness at the center of the clamping portion relative to the thickness near the clamping portion, and also suppresses the amount of preform sagging, resulting in excellent blow molding properties.

[0017] Solution for solving the problem

[0018] 1. The means for solving the problem according to the first aspect of the present invention.

[0019] The first aspect of the present invention is, for example, the following [1] to

[12] .

[0020] [1] A polyamide resin composition comprising an aliphatic polyamide resin (Aa), an aromatic polyamide resin (Ab), an ionomer (B), and a functionalized olefin resin (C), wherein the aliphatic polyamide resin (Aa) comprises an aliphatic homopolymer polyamide resin (A-1) and an aliphatic copolymer polyamide resin (A-2).

[0021] In 100% by mass of the polyamide resin composition, there are 40-60% by mass of the aliphatic homopolymer polyamide resin (A-1), 10-40% by mass of the aliphatic copolymer polyamide resin (A-2), 2-10% by mass of the aromatic polyamide resin (Ab), 5-20% by mass of the ionomer (B), and 5-10% by mass of the functionalized olefin resin (C).

[0022] According to JIS K 6920, the relative viscosity of the aliphatic polyamide resin (Aa) is 3.60~3.85 when 1g of the aliphatic polyamide resin (Aa) is dissolved in 100ml of 96% sulfuric acid and measured at 25°C.

[0023] [2] According to the polyamide resin composition of [1], the relative viscosity of the aliphatic homopolymer polyamide resin (A-1) and the relative viscosity of the aliphatic copolymer polyamide resin (A-2), measured according to JIS K 6920 by dissolving 1 g of polyamide resin in 100 ml of 96% sulfuric acid at 25°C, are 3.00 to 4.20 respectively.

[0024] [3] The polyamide resin composition according to [1] or [2], wherein the ionomer (B) is a (ethylene and / or propylene) / (α,β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymer neutralized by metal or metal ions.

[0025] [4] The polyamide resin composition according to any one of [1] to [3], wherein the functional group-containing olefin resin (C) is at least one selected from the group consisting of: (ethylene and / or propylene) / (α,β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymers optionally incorporating at least one selected from the group consisting of maleic anhydride, itaconic anhydride and citraconic anhydride; and (ethylene and / or propylene) / α-olefin copolymers incorporating at least one selected from the group consisting of maleic anhydride, itaconic anhydride and citraconic anhydride.

[0026] [5] The polyamide resin composition according to any one of [1] to [4], wherein the relative viscosity of the aliphatic polyamide resin (Aa), as determined by dissolving 1 g of the aliphatic polyamide resin (Aa) in 100 ml of 96% sulfuric acid according to JIS K 6920 and measuring it at 25°C, is 3.65 to 3.80.

[0027] [6] The polyamide resin composition according to any one of [1] to [5], wherein the content of functional groups in the functional group-containing olefin resin (C) is more than 25 μmol / g and less than 200 μmol / g.

[0028] [7] The polyamide resin composition according to any one of [1] to [6], wherein the aliphatic homopolymer polyamide resin (A-1) is at least one of the group consisting of at least one of the group consisting of polyamide 6, polyamide 11, polyamide 12, polyamide 56, polyamide 66, polyamide 510, polyamide 610, polyamide 612 and polyamide 1010.

[0029] [8] The polyamide resin composition according to any one of [1] to [7], wherein the aliphatic copolymer polyamide resin (A-2) is at least one selected from the group consisting of polyamide 56 / 6, polyamide 56 / 66, polyamide 56 / 510, polyamide 6 / 66, polyamide 6 / 12 and polyamide 6 / 66 / 12.

[0030] [9] The polyamide resin composition according to any one of [1] to [8], wherein the aromatic polyamide resin (Ab) is at least one selected from the group consisting of polyamide 6T / 6I and polyamide MXD6.

[0031]

[10] The polyamide resin composition according to any one of [1] to [9] further comprises a heat resistant agent (D) containing a phosphorus-based organic compound and two or more hindered phenolic compounds.

[0032]

[11] A molded article comprising any one of the polyamide resin compositions described in [1] to

[10] .

[0033]

[12] The molded article according to

[11] is a molded article in contact with high-pressure gas.

[0034] 2. The means for solving the problem according to the second aspect of the present invention.

[0035] The second aspect of the present invention is, for example, the following [1] to

[13] .

[0036] [1] A polyamide resin composition comprising a polyamide resin (A), an ionomer (B), and a functionalized olefin resin (C), wherein the polyamide resin (A) comprises an aliphatic homopolymer polyamide resin (A-1), an aliphatic copolymer polyamide resin (A-2), and an aromatic polyamide resin (A-3).

[0037] In 100% by weight of the polyamide resin composition, there are 40-60% by weight of the aliphatic homopolymer polyamide resin (A-1), 10-40% by weight of the aliphatic copolymer polyamide resin (A-2), 2-10% by weight of the aromatic polyamide resin (A-3), 5-20% by weight of the ionomer (B), and 5-10% by weight of the functionalized olefin resin (C).

[0038] The total content ((B) + (C)) of the ionomer (B) and the functionalized olefin resin (C) in the polyamide resin composition is 16.0% by mass or more and less than 25.0% by mass.

[0039] The mass ratio of the ionomer (B) to the functional group-containing olefin resin (C) ((B) / (C)) is greater than 0 and less than 3.50.

[0040] [2] According to the polyamide resin composition of [1], wherein the concentration of the terminal amino group of the polyamide resin (A) determined by neutralization titration in a mixed solvent of phenol and methanol is greater than 30 μmol / g and less than 70 μmol / g.

[0041] [3] The polyamide resin composition according to [1] or [2], wherein the ionomer (B) is a (ethylene and / or propylene) / (α,β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymer neutralized by metal or metal ions.

[0042] [4] The polyamide resin composition according to any one of [1] to [3], wherein the functional group-containing olefin resin (C) is at least one selected from the group consisting of: (ethylene and / or propylene) / (α,β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymers optionally incorporating at least one selected from the group consisting of maleic anhydride, itaconic anhydride and citraconic anhydride; and (ethylene and / or propylene) / α-olefin copolymers incorporating at least one selected from the group consisting of maleic anhydride, itaconic anhydride and citraconic anhydride.

[0043] [5] The polyamide resin composition according to any one of [1] to [4], wherein the total content of the ionomer (B) and the functional group-containing olefin resin (C) in the polyamide resin composition ((B)+(C)) is 16.0% by mass or more and 23.0% by mass or less.

[0044] [6] The polyamide resin composition according to any one of [1] to [5], wherein the mass ratio of the ionomer (B) to the functional group-containing olefin resin (C) ((B) / (C)) is 1.00 or more and 2.00 or less.

[0045] [7] The polyamide resin composition according to any one of [1] to [6], wherein the content of functional groups in the functional group-containing olefin resin (C) is more than 25 μmol / g and less than 200 μmol / g.

[0046] [8] The polyamide resin composition according to any one of [1] to [7], wherein the aliphatic homopolymer polyamide resin (A-1) is at least one selected from the group consisting of polyamide 6, polyamide 11, polyamide 12, polyamide 56, polyamide 66, polyamide 510, polyamide 610, polyamide 612 and polyamide 1010.

[0047] [9] The polyamide resin composition according to any one of [1] to [8], wherein the aliphatic copolymer polyamide resin (A-2) is at least one selected from the group consisting of polyamide 56 / 6, polyamide 56 / 66, polyamide 56 / 510, polyamide 6 / 66, polyamide 6 / 12 and polyamide 6 / 66 / 12.

[0048]

[10] The polyamide resin composition according to any one of [1] to [9], wherein the aromatic polyamide resin (A-3) is at least one selected from the group consisting of polyamide 6T / 6I and polyamide MXD6.

[0049]

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

[10] further comprises a heat resistant agent (D) consisting of a combination of a hindered phenolic compound and a phosphorus organic compound.

[0050]

[12] A molded article comprising any one of the polyamide resin compositions described in [1] to

[11] .

[0051]

[13] The molded article according to

[12] is a molded article in contact with high-pressure gas.

[0052] The effects of the invention

[0053] The polyamide resin composition of the present invention can improve the weld interface strength of the resin weld portion, represented by the clamping portion, in blow molding, and suppress and prevent mechanical strength such as breakage by suppressing the degree to which the thickness of the center of the clamping portion becomes thinner relative to the thickness near the clamping portion, and suppress the amount of preform sag, resulting in excellent blow molding properties. Attached Figure Description

[0054] Figure 1 This is a schematic diagram used to calculate the shape of the clamping part. Detailed Implementation

[0055] In this specification, the values ​​recorded in the numerical range are obtained by rounding the last digit of the recorded value.

[0056] 1. The first aspect of the present invention

[0057] This invention relates to a polyamide resin composition comprising an aliphatic polyamide resin (Aa), an aromatic polyamide resin (Ab), an ionomer (B), and a functionalized olefin resin (C), wherein the aliphatic polyamide resin (Aa) comprises an aliphatic homopolymer polyamide resin (A-1) and an aliphatic copolymer polyamide resin (A-2).

[0058] In 100% by mass of the polyamide resin composition, there are 40-60% by mass of the aforementioned aliphatic homopolymer polyamide resin (A-1), 10-40% by mass of the aforementioned aliphatic copolymer polyamide resin (A-2), 2-10% by mass of the aforementioned aromatic polyamide resin (Ab), 5-20% by mass of the aforementioned ionomer (B), and 5-10% by mass of the aforementioned functionalized olefin resin (C).

[0059] According to JIS K 6920, the relative viscosity of the aforementioned aliphatic polyamide resin (Aa) was 3.60~3.85 when 1g of the aforementioned aliphatic polyamide resin (Aa) was dissolved in 100ml of 96% sulfuric acid and measured at 25°C.

[0060] <Aliphatic homopolymer polyamide resin (A-1)>

[0061] The polyamide resin composition comprises an aliphatic homopolymer polyamide resin (A-1).

[0062] Aliphatic homopolymer polyamide resin (A-1) is a polyamide resin composed of a structural unit derived from an aliphatic monomer. Aliphatic homopolymer polyamide resin (A-1) can be independently composed of at least one of a lactam and an aminocarboxylic acid as a hydrolysate of the lactam, or it can be composed of a combination of an aliphatic diamine and an aliphatic dicarboxylic acid. The combination of an aliphatic diamine and an aliphatic dicarboxylic acid refers to a monomeric component composed of a condensate of an aliphatic diamine and an aliphatic dicarboxylic acid. Here, the combination of an aliphatic diamine and an aliphatic dicarboxylic acid is considered as one monomer. Aliphatic also includes alicyclic compounds.

[0063] The number of carbon atoms in a lactam is preferably 4 to 12. The number of carbon atoms in an aminocarboxylic acid is preferably 4 to 12. The number of carbon atoms in an aliphatic diamine is preferably 2 to 20, particularly preferably 4 to 12. The number of carbon atoms in an aliphatic dicarboxylic acid is preferably 2 to 20, particularly preferably 6 to 12.

[0064] Examples of lactams include ε-caprolactam, heptanolactam, undecanolactam, dodecanolactam, α-pyrrolidone, and α-piperidinone. From the viewpoint of polymerization productivity, one of the following groups is preferred: ε-caprolactam, undecanolactam, and dodecanolactam.

[0065] In addition, examples of aminocarboxylic acids include 4-aminobutyric acid, 5-aminovaleric acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. From the viewpoint of polymerization productivity, one of the following groups is preferred: 6-aminohexanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.

[0066] Examples of aliphatic diamines include ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecadecanediamine, octadecanediamine, nonadecadecanediamine, eicosanediamine, 2-methyl-1,8-octanediamine, and 2,2,4 / 2,4,4-trimethylhexamethylenediamine; 1, Alicyclic diamines such as 3- / 1,4-cyclohexyldiamine, bis(4-aminocyclohexyl)methane, bis(4-aminocyclohexyl)propane, bis(3-methyl-4-aminocyclohexyl)methane, (3-methyl-4-aminocyclohexyl)propane, 1,3- / 1,4-bisaminomethylcyclohexane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine, bis(aminopropyl)piperazine, bis(aminoethyl)piperazine, norbornenedimethyldiamine, etc.

[0067] Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, octadecanoic acid, and eicosanoic acid; and alicyclic dicarboxylic acids such as 1,3- / 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4'-dicarboxylic acid, and norbornanedicarboxylic acid.

[0068] Examples of aliphatic homopolymer polyamide resins (A-1) include polybutyrolactam (polyamide 4), polyadipamide (polyamide 46), polyadenosylbutylene (polyamide 49), polydecanoylbutylene (polyamide 410), polyvaleronylbutylene (polyamide 5), polycaprolactam (polyamide 6), polyheptylbutylene (polyamide 7), polyundecanoylbutylene (polyamide 11), polydodecanoylbutylene (polyamide 12), polyadipamide (polyamide 66), polyadipamide (polyamide 46), polydecanoylbutylene (polyamide 410), polydodecanoylbutylene (polyamide 412), polyadipamide (polyamide 56), polyadenosylbutylene (polyamide 59), polydecanoylbutylene (polyamide 510), and polydodecanoylbutylene (polyamide 512). Tridecyl dipentanediamine (polyamide 513), polynonyl hexamethylenediamine (polyamide 69), polydecyl hexamethylenediamine (polyamide 610), polydodecyl hexamethylenediamine (polyamide 612), polyadiponyl nonadiamine (polyamide 96), polynonyl nonadiamine (polyamide 99), polydecyl nonadiamine (polyamide 910), polydodecyl nonadiamine (polyamide 912), polyadiponyl decanediamine (polyamide 106), polynonyl decanediamine (polyamide 109), polydecyl decanediamine (polyamide 1010), polydodecyl decanediamine (polyamide 1012), polyadiponyl dodecanediamine (polyamide 126), polynonyl dodecanediamine (polyamide 129), polydecyl dodecanediamine (polyamide 1210), polydodecyl dodecanediamine (polyamide 1212), polyamide 122, etc. They can be used individually or in combination of two or more.

[0069] From the viewpoint of polymerization productivity, the aliphatic homopolymer polyamide resin (A-1) is preferably at least one selected from the group consisting of polyamide 6, polyamide 11, polyamide 12, polyamide 56, polyamide 66, polyamide 510, polyamide 610, polyamide 612 and polyamide 1010, more preferably at least one selected from polyamide 6, polyamide 11, polyamide 12, polyamide 610 and polyamide 612, and even more preferably polyamide 6.

[0070] The relative viscosity of the aliphatic homopolymer polyamide resin (A-1) is preferably 2.70 or higher, more preferably 2.70 to 5.00, even more preferably 2.70 to 4.50, and particularly preferably 3.00 to 4.20. If the relative viscosity is within the above range, there is a tendency for improved molding processability.

[0071] The above relative viscosity was determined according to JIS K-6920, by dissolving 1g of polyamide resin in 100ml of 96% sulfuric acid and measuring at 25°C.

[0072] In this specification, when the aliphatic homopolymer polyamide resin (A-1) contains two or more polyamide resins with different relative viscosities, the average relative viscosity (average relative viscosity) of the aliphatic homopolymer polyamide resin (A-1) is calculated by summing the values ​​obtained by multiplying the relative viscosities of each polyamide resin measured using the method described above by their mixing ratio. The average relative viscosity is approximately consistent with the measured value of the relative viscosity of the aliphatic homopolymer polyamide resin (A-1) containing two or more polyamide resins with different relative viscosities; therefore, when the mixture contains two or more polyamide resins, the measured value of this mixture can be used.

[0073] In addition, considering the concentration of their respective terminal groups and relative viscosity, at least one of the following can be appropriately added as a terminal group regulator to the aliphatic homopolymer polyamide resin (A-1): monoamines, diamines, monocarboxylic acids, and dicarboxylic acids. Examples 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; aromatic monoamines such as aniline, toluene, diphenylamine, and naphthylamine; aliphatic diamines such as hexamethylenediamine, decamethyldiamine, and dodecamethyldiamine; alicyclic diamines such as cyclohexanediamine, methylcyclohexanediamine, and isophoronediamine; aromatic diamines such as m-phenylenediamine, p-phenylenediamine, m-phenylenediamine, and p-phenylenediamine; and acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, octanoic acid, and lauric acid. Aliphatic monocarboxylic acids such as tridecanoic acid, myristic acid, palmitic acid, stearic acid, pentanoic acid, and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, methylbenzoic acid, α-naphthoic acid, β-naphthoic acid, methylnaphthoic acid, and phenylacetic acid; aliphatic dicarboxylic acids such as adipic acid, trimethyladipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, and dodecanedicarboxylic acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; and aromatic dicarboxylic acids such as isophthalic acid and 1,4 / 2,6 / 2,7-naphthalenedicarboxylic acid. One or more of these may be used. They are used in amounts within the scope of achieving the above-mentioned objectives.

[0074] The terminal amine concentration of the aliphatic homopolymer polyamide resin (A-1) is preferably 30 μmol / g or more, more preferably 30 to 50 μmol / g. When the terminal amine concentration is within the above range, it tends to have good reactivity with olefin resins containing functional groups.

[0075] The concentration of the terminal amino group mentioned above was determined by dissolving the polyamide resin in a mixed solvent of phenol and methanol and then performing a neutralization titration.

[0076] When the aliphatic homopolymer polyamide resin (A-1) contains two or more polyamide resins with different terminal amino concentrations, the average value calculated by multiplying the terminal amino concentrations of each polyamide resin (measured using the above method) by their mixing ratio is taken as the terminal amino concentration (average terminal amino concentration) of the aliphatic homopolymer polyamide resin (A-1). The average terminal amino concentration is approximately consistent with the measured value of the terminal amino concentration of the aliphatic homopolymer polyamide resin (A-1) containing two or more polyamide resins with different terminal amino concentrations; therefore, when the mixture contains two or more polyamide resins, the measured value of this mixture can be used.

[0077] The polyamide resin composition contains 40-60% by mass, preferably 42-58% by mass, of an aliphatic homopolymer polyamide resin (A-1) in 100% by mass. If the content of the aliphatic homopolymer polyamide resin (A-1) is within the above range, the moldability, mechanical properties, and heat resistance are good.

[0078] <Aliphatic Copolymer Polyamide Resin (A-2)>

[0079] The polyamide resin composition comprises an aliphatic copolyamide resin (A-2).

[0080] Aliphatic copolymer polyamide resin (A-2) is a polyamide resin composed of two or more structural units derived from two or more aliphatic monomers, and is an aliphatic polyamide resin that does not possess aromatic rings. Aliphatic copolymer polyamide resin (A-2) is a copolymer of two or more monomers selected from the group consisting of combinations of aliphatic diamines and aliphatic dicarboxylic acids, and lactams and aminocarboxylic acids. Here, the combination of aliphatic diamines and aliphatic dicarboxylic acids refers to monomer components composed of condensates of aliphatic diamines and aliphatic dicarboxylic acids. The combination of aliphatic diamines and aliphatic dicarboxylic acids is considered as a single monomer component when considering a combination of one aliphatic diamine and one aliphatic dicarboxylic acid. Aliphatic also includes alicyclic compounds.

[0081] As an aliphatic diamine, the same aliphatic diamines as those exemplified as raw materials for aliphatic homopolymer polyamides can be listed.

[0082] As an aliphatic dicarboxylic acid, the same aliphatic dicarboxylic acid as that exemplified as a raw material for aliphatic homopolymer polyamides can be listed.

[0083] As a lactam, the same lactams exemplified as those used as raw materials for aliphatic homopolymers can be listed.

[0084] In addition, as an aminocarboxylic acid, the same aminocarboxylic acid as that exemplified as a raw material for aliphatic homopolymer polyamide can be cited.

[0085] Furthermore, considering the concentration of terminal groups and relative viscosity, at least one modifier selected from the group consisting of monoamines, diamines, monocarboxylic acids, and dicarboxylic acids can be appropriately added to the aliphatic copolyamide resin (A-2) as a modifier. As a specific example, the examples illustrated in the section on aliphatic homopolymer polyamides (A-1) can be cited. They are used in amounts within the range required to achieve the aforementioned objectives.

[0086] As an aliphatic copolymer polyamide resin (A-2), specifically, examples include caprolactam / tetramethylenediaminoadipic acid copolymer (polyamide 6 / 46), caprolactam / pentamethylenediaminoadipic acid copolymer (polyamide 6 / 56), hexamethylenediaminoadipic acid / caprolactam (polyamide 56 / 6), pentamethylenediaminoadipic acid / hexamethylenediaminoadipic acid copolymer (polyamide 56 / 66), pentamethylenediaminoadipic acid / pentamethylenediaminodecanedioic acid copolymer (polyamide 56 / 510), caprolactam / hexamethylenediaminoadipic acid copolymer (polyamide 6 / 66), caprolactam / hexamethylenediaminoazelic acid copolymer (polyamide 6 / 69), caprolactam / tetramethylenediaminodecanedioic acid copolymer (polyamide 6 / 410), caprolactam / pentamethylenediaminodecanedioic acid copolymer (polyamide 6 / 510), and caprolactam / hexamethylenediaminoazelic acid copolymer (polyamide 6 / 510). Aliphatic copolymer polyamides include: 6 / 610 (methylene diaminosepiacetic acid copolymer), 6 / 611 (caprolactam / hexamethylene diaminoundecane dicarboxylic acid copolymer), 6 / 612 (caprolactam / hexamethylene diaminododecane dicarboxylic acid copolymer), 6 / 1010 (caprolactam / decamethylene diaminosepiacetic acid copolymer), 6 / 11 (caprolactam / aminoundecane acid copolymer), 6 / 12 (caprolactam / laurolactam copolymer), 6 / 66 / 12 (caprolactam / hexamethylene diaminosepiacetic acid / laurolactam copolymer), 6 / 66 / 610 (caprolactam / hexamethylene diaminosepiacetic acid / hexamethylene diaminododecane dicarboxylic acid copolymer), and 6 / 66 / 612 (caprolactam / hexamethylene diaminosepiacetic acid / hexamethylene diaminododecane dicarboxylic acid copolymer).

[0087] Aliphatic copolymer polyamide resin (A-2) can be used alone or in combination with two or more types.

[0088] Among these aliphatic copolyamide resins (A-2), at least one is preferably selected from the group consisting of polyamide 56 / 6, polyamide 56 / 66, polyamide 56 / 510, polyamide 6 / 66, polyamide 6 / 12 and polyamide 6 / 66 / 12, more preferably at least one is selected from the group consisting of polyamide 6 / 66, polyamide 6 / 12 and polyamide 6 / 66 / 12, and even more preferably polyamide 6 / 66.

[0089] The relative viscosity of the aliphatic copolymer polyamide resin (A-2) is preferably 1.80 to 5.00, more preferably 2.50 to 4.50, and even more preferably 3.00 to 4.20. If the relative viscosity is within the above range, there is a tendency for the molding processability to become better.

[0090] The above relative viscosity was determined according to JIS K-6920, by dissolving 1g of polyamide resin in 100ml of 96% sulfuric acid and measuring at 25°C.

[0091] When the aliphatic copolyamide resin (A-2) contains two or more polyamide resins with different relative viscosities, the relative viscosity is determined by the same method as described in the section on aliphatic homopolymer polyamide resin (A-1).

[0092] The terminal amino group concentration of the aliphatic copolymer polyamide resin (A-2) is preferably 30 μmol / g or more, more preferably 30 to 50 μmol / g. When the terminal amino group concentration is within the above range, it tends to have good reactivity with olefin resins containing functional groups.

[0093] The aforementioned terminal amino concentration was determined by dissolving the polyamide resin in a mixed solvent of phenol and methanol and then titrating it using neutralization.

[0094] In the case where the aliphatic copolyamide resin (A-2) contains two or more polyamide resins with different terminal amino concentrations, the terminal amino concentrations are determined by the same method as described in the section on aliphatic homopolymer polyamide resin (A-1).

[0095] The polyamide resin composition contains 10-40% by mass, preferably 12-38% by mass, and more preferably 15-35% by mass of aliphatic copolyamide resin (A-2) in 100% by mass. If the content of aliphatic copolyamide resin (A-2) is within the above range, the moldability (especially the break portion), mechanical properties (especially the toughness / ductility at low temperatures, etc.), gas barrier properties, heat resistance, hydrolysis resistance, and chemical resistance are good.

[0096] <Aliphatic polyamide resin (Aa)>

[0097] The aliphatic homopolymer polyamide resin (A-1) and aliphatic copolymer polyamide resin (A-2) contained in the polyamide resin composition, i.e., the aliphatic polyamide resin (Aa) containing aliphatic homopolymer polyamide resin (A-1) and aliphatic copolymer polyamide resin (A-2), has a relative viscosity of 3.60 to 3.85, preferably 3.65 to 3.82, more preferably 3.73 to 3.82 or 3.65 to 3.80, and particularly preferably 3.73 to 3.80. If the relative viscosity of the aliphatic polyamide resin (Aa) is less than the above range, the sag increases, resulting in poor molding; if it exceeds the above range, the shape of the pinch-off portion deteriorates and / or the weld interface strength decreases.

[0098] The polyamide resin composition, by comprising an aliphatic polyamide resin (Aa), an ionomer (B), and a functionalized olefin resin (C) of the aforementioned relative viscosities, tends to have a melt viscosity suitable for blow molding and a good shape of the cut-off portion of the blow-molded article.

[0099] The relative viscosity of the aforementioned aliphatic polyamide resin (Aa) can be determined according to JIS K6920 by dissolving 1g of aliphatic polyamide resin (Aa) in 100ml of 96% sulfuric acid and measuring it at 25°C, or it can be calculated using the following formula (I). The measured value is approximately the same as the value based on formula (I).

[0100] The relative viscosity of aliphatic polyamide resin (Aa) = ΣXi×Yi / Z(I)

[0101] (In the formula, Xi is the relative viscosity of each polyamide resin contained in the aliphatic polyamide resin (Aa), determined according to JIS K6920, by dissolving 1g of each polyamide resin contained in the aliphatic polyamide resin (Aa) in 100ml of 96% sulfuric acid and measuring it at 25°C.)

[0102] Yi represents the mass parts of each polyamide resin contained in the aliphatic polyamide resin (Aa) relative to 100 parts by mass of the polyamide resin composition.

[0103] Z represents the mass parts of aliphatic polyamide resin (Aa) relative to 100 parts by mass of the polyamide resin composition.

[0104] i represents the quantity of each polyamide resin contained in the aliphatic polyamide resin (Aa) in the polyamide resin composition.

[0105] The various polyamide resins included in aliphatic polyamide resin (Aa) refer to the polyamide resins of raw materials mixed in aliphatic polyamide resin (Aa).

[0106] Regarding the relative viscosity of the aliphatic homopolymer polyamide resin (A-1) and the relative viscosity of the aliphatic copolymer polyamide resin (A-2) contained in the aliphatic polyamide resin (Aa), it is preferably 3.00 to 4.20 for each. If the relative viscosity is within the above range, the sag is further suppressed. The respective relative viscosity was determined according to JIS K 6920, by dissolving 1 g of polyamide resin in 100 ml of 96% sulfuric acid and measuring at 25°C.

[0107] <Aromatic polyamide resin (Ab)>

[0108] Aromatic polyamide resin refers to an aromatic polyamide resin containing at least one aromatic monomer component, such as a polyamide resin obtained by polycondensation of aliphatic dicarboxylic acid and aromatic diamine, or aromatic dicarboxylic acid and aliphatic diamine, as raw materials.

[0109] Aliphatic diamines and aliphatic dicarboxylic acids, which are used as raw materials, can be the same substances as the aforementioned aliphatic polyamide resins.

[0110] Examples of aromatic diamines include m-phenylenediamine and p-phenylenediamine; examples of aromatic dicarboxylic acids include naphthalene dicarboxylic acid, terephthalic acid, isophthalic acid, and phthalic acid.

[0111] Furthermore, considering the concentration of terminal groups and relative viscosity, at least one modifier selected from the group consisting of monoamines, diamines, monocarboxylic acids, and dicarboxylic acids can be appropriately added to aromatic polyamide resins (Ab) as a modifier. As a specific example, the examples illustrated in the section on aliphatic homopolymer polyamides (A-1) can be cited. They are used in amounts within the range required to achieve the aforementioned objectives.

[0112] Specific examples of aromatic polyamide resins (Ab) include poly(p-phenylene terephthalamide) (polyamide 9T), poly(p-phenylene terephthalamide) (polyamide 6T), poly(p-phenylene isophthalamide) (polyamide 6I), poly(p-phenylene adipamide / poly(p-phenylene terephthalamide) copolymer (polyamide 66 / 6T), poly(p-phenylene terephthalamide / poly(p-phenylene hexamethylene) copolymer (polyamide 6T / 6), poly(p-phenylene adipamide / poly(p-phenylene isophthalamide) copolymer (polyamide 66 / 6I), poly(p-phenylene isophthalamide / poly(p-phenylene hexamethylene) copolymer (polyamide 6I / 6), and poly(p-phenylene dodecylamide / poly(p-phenylene terephthalamide) copolymer (polyamide 6I / 6). The following are examples of copolymers or copolymers of polyamides: amine copolymers (polyamide 12 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymers (polyamide 66 / 6T / 6I), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymers (polyamide 66 / 6 / 6I), polyhexamethylene terephthalamide / poly(terephthaloyl-2-methylpentanediamine) copolymers (polyamide 6T / M5T), polyhexamethylene adipamide (polyamide MXD6), and mixtures or copolymers thereof. Preferably, at least one copolymer is selected from the group consisting of polyamide 6T / 6I and polyamide MXD6, and more preferably, polyamide 6T / 6I.

[0113] As an aromatic polyamide (Ab) used in this invention, amorphous partially aromatic copolymer polyamide resins containing at least two aromatic monomer components are particularly useful examples. As an amorphous partially aromatic copolymer polyamide resin, an amorphous polyamide with a glass transition temperature of 100°C or higher, determined based on the peak temperature of the loss modulus at oven-dry obtained by measuring dynamic viscoelasticity, is preferred.

[0114] Here, amorphous refers to a melting heat of less than 1 cal / g as measured by differential scanning calorimetry (DSC).

[0115] The aforementioned amorphous partially aromatic copolyamide resin is preferably a resin formed from an aromatic dicarboxylic acid and an aliphatic diamine containing 40-95 mol% of terephthalic acid components and 5-60 mol% of isophthalic acid components. Preferred combinations include equimolar salts of hexamethylenediamine and terephthalic acid, and equimolar salts of hexamethylenediamine and isophthalic acid.

[0116] In addition, it is preferred that the polyamide-forming component is formed from an aliphatic diamine and an aromatic dicarboxylic acid containing isophthalic acid and terephthalic acid, comprising 99 to 60% by weight, and the polyamide component is formed from 1 to 40% by weight.

[0117] The degree of polymerization of the aromatic polyamide resin (Ab) in this invention is not particularly limited. According to JIS K6810, the relative viscosity of the aromatic polyamide resin (Ab) at a concentration of 1% in 98% sulfuric acid and at a temperature of 25°C is preferably 1.50~4.00, more preferably 1.80~3.00.

[0118] When an aromatic polyamide resin (Ab) contains two or more polyamide resins with different relative viscosities, the relative viscosity is determined by the same method as described in the section on aliphatic homopolymer polyamide resin (A-1).

[0119] The polyamide resin composition contains 2 to 10% by mass, preferably 2 to 8% by mass, and more preferably 3 to 8% by mass of aromatic polyamide resin (Ab) in 100% by mass. By keeping the content of aromatic polyamide resin (Ab) within the above range, the mechanical properties and moldability become good.

[0120] <Polyamide resin>

[0121] Examples of polyamide resin manufacturing apparatus include batch reactors, single-tank or multi-tank continuous reactors, tubular continuous reactors, single-shaft compounding extruders, and bi-shaft compounding extruders, among other known polyamide manufacturing apparatuses. Polymerization methods include known methods such as melt polymerization, solution polymerization, and solid-phase polymerization, which are carried out by repeatedly applying atmospheric pressure, reduced pressure, and increased pressure. These polymerization methods can be used individually or in appropriate combinations.

[0122] In 100% by mass of the polyamide resin composition, it is preferable to include 52-90% by mass, more preferably 60-88% by mass, even more preferably 65-86% by mass, and particularly preferably 70-85% by mass of a polyamide resin (A) comprising an aliphatic polyamide resin (Aa) and an aromatic polyamide resin (Ab). By keeping the content of polyamide resin (A) within the above range, there is a tendency for improved mechanical properties and moldability.

[0123] The relative viscosity of the polyamide resin (A) is preferably 2.70 or higher, more preferably 2.70 to 5.00, and even more preferably 2.70 to 4.50. By keeping the relative viscosity of the polyamide resin within the above range, there is a tendency for improved moldability. The relative viscosity (A) of the polyamide resin is determined using the same method as the relative viscosity of a polyamide resin containing two or more aliphatic homopolymer polyamide resins (A-1).

[0124] The concentration of terminal amino groups in the polyamide resin (A) is preferably 30 μmol / g or more, more preferably 30 to 110 μmol / g, and even more preferably more than 30 μmol / g and less than 70 μmol / g. It is believed that the terminal amino groups interact with the functional groups of the functionalized polyolefin resin in the polyamide resin composition. Therefore, it is believed that when the concentration of terminal amino groups is within the above range, it promotes the suppression of sagging by setting the melt viscosity to a value suitable for blow molding.

[0125] The aforementioned terminal amino concentration was determined using the same method as for the terminal amino concentration in polyamide resins containing two or more aliphatic homopolymer polyamide resins (A-1).

[0126] <Ionomer (B)>

[0127] The polyamide resin composition contains an ionomer (B).

[0128] Ionomers (B) are resins containing carboxyl groups, all or part of which are neutralized by metals or metal ions. When ionomers (B) are compounded, the parison characteristics during blow molding are significantly improved, while the melt viscosity does not increase significantly, thus increasing productivity.

[0129] As ionomer (B), olefin-based ionomers are preferred. The resin of the olefin-based ionomer has structural units derived from olefins and has carboxyl groups. Examples of olefin-based ionomers include copolymers of (ethylene and / or propylene) / (α,β-unsaturated carboxylic acids and / or unsaturated carboxylic acid esters) neutralized by metals or metal ions.

[0130] Ethylene and / or propylene) / (α,β-unsaturated carboxylic acids and / or unsaturated carboxylic acid esters) copolymers are polymers formed by copolymerizing ethylene and / or propylene with α,β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester monomers. Examples of α,β-unsaturated carboxylic acid monomers include acrylic acid and methacrylic acid. Examples of α,β-unsaturated carboxylic acid ester monomers include methyl esters, ethyl esters, propyl esters, butyl esters, pentyl esters, hexyl esters, heptyl esters, octyl esters, nonyl esters, decyl esters, etc. They can be used alone or in combination of two or more.

[0131] Examples of metals and metal ions used in ionomers include Na, K, Cu, Mg, Ca, Ba, Zn, Cd, Al, Fe, Co, and Ni, as well as their ions. They can be used alone or in combination of two or more, and preferably contain at least Zn (also referred to as "zinc" in this specification). Ionomers of ethylene-methacrylic acid copolymers are preferred. Commercially available olefin-based ionomers include the Himilan (registered trademark) series manufactured by Dupont-Mitsui Polychemicals Co., Ltd.

[0132] The melting point of the ionomer (B), determined by differential scanning calorimetry (DSC) according to ISO 11357-3 under a nitrogen atmosphere at a heating rate of 20°C / min, is preferably 75 to 100°C, more preferably 80 to 95°C.

[0133] Furthermore, the density of the ionomer (B), as determined by JIS K7112, is preferably 940~980 kg / m³. 3 More preferably, it is 950~970 kg / m 3 .

[0134] Furthermore, the metal ions contained in the ionomer (B) preferably contain at least zinc, and more preferably, the zinc content determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) is 3% by mass or more.

[0135] When the melting point, density, and zinc content are within the above range, it is preferred from the viewpoint of compatibility with polyamide and the stability of wall thickness caused by the expansion during blow molding.

[0136] The polyamide resin composition contains 5 to 20% by mass, preferably 8 to 18% by mass, and more preferably 14 to 18% by mass of ionomer (B) in 100% by mass. When the content of olefin-based ionomer (B) is within the above range, the low-temperature properties and preform properties in blow molding become good.

[0137] <Olefin resins containing functional groups (C)>

[0138] The polyamide resin composition comprises a functionalized olefin resin (C). The functionalized olefin resin (C) differs from the ionomer (B) in that it does not contain metals and / or metal ions.

[0139] The flexural modulus of the functionalized olefin resin (C), as determined according to ASTM D-790, is preferably 500 MPa or less. Therefore, one of the functions of the functionalized olefin resin (C) in polyamide resin compositions is its role as an impact-resistant material.

[0140] Olefin-based resins refer to resins having structural units derived from olefins, preferably copolymers having structural units derived from olefins, and more preferably copolymers with structural units mainly derived from olefins.

[0141] Examples of functional groups in olefin-based resins (C) include carboxyl groups, acid anhydride groups, carboxylic acid ester groups, carboxylic acid imide groups, carboxylic acid amide groups, and epoxy groups, with carboxyl groups, acid anhydride groups, and carboxylic acid ester groups being preferred. These functional groups are considered to have an affinity for polyamide resins, thus contributing to the improvement of the mechanical properties of the polyamide resin composition.

[0142] In addition, methods for introducing functional groups into olefin resins include: (i) copolymerizing copolymerizable monomers having functional groups during the polymerization of the olefin resin; (ii) introducing functional groups into the molecular chains or ends of the olefin resin using polymerization initiators, chain transfer agents, etc.; and (iii) grafting compounds having functional groups that can be grafted onto the olefin resin (graft compounds), etc. These methods can be used individually or in appropriate combinations.

[0143] Examples of copolymerizable monomers and graft compounds having these functional groups include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, nicotinic acid, citraconic acid, pentenoic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endogenous bicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic acid, monomethyl maleate, monomethyl itaconic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, and 2-ethylhexyl methacrylate. Ethylhexyl ester, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, endogenous bicyclic-[2.2.1]-5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, glycidyl acrylate, glycidyl methacrylate, ethyl glycidyl acrylate, itaconic acid glycidyl ester, citraconic acid glycidyl ester, etc. These can be used alone or in combination of two or more. Preferably, at least one is selected from the group consisting of maleic anhydride, itaconic anhydride, and citraconic anhydride.

[0144] As functionalized olefin resins (C), examples include (ethylene and / or propylene) / (α,β-unsaturated carboxylic acids and / or unsaturated carboxylic acid esters) copolymers, (ethylene and / or propylene) / α-olefin copolymers incorporating the aforementioned functional groups, and (ethylene and / or propylene) / (α,β-unsaturated carboxylic acids and / or unsaturated carboxylic acid esters) copolymers incorporating the aforementioned functional groups. They can be used individually or in combination of two or more. Preferably, at least one copolymer selected from the group consisting of: (ethylene and / or propylene) / (α,β-unsaturated carboxylic acids and / or unsaturated carboxylic acid esters) copolymers optionally incorporating at least one copolymer selected from the group consisting of maleic anhydride, itaconic anhydride, and citraconic anhydride; and (ethylene and / or propylene) / α-olefin copolymers incorporating at least one copolymer selected from the group consisting of maleic anhydride, itaconic anhydride, and citraconic anhydride.

[0145] (Ethylene and / or propylene) / (α,β-unsaturated carboxylic acids and / or unsaturated carboxylic acid esters) copolymers are olefinic resins (C) containing functional groups, incorporating carboxyl and / or carboxylic acid ester groups through the above-described method (i). Functional groups can be further incorporated through the above-described methods (ii), (iii), etc.

[0146] (Ethylene and / or propylene) / α-olefin copolymers are selected from at least one of the following groups: copolymers of ethylene with α-olefins having 3 or more carbon atoms, copolymers of ethylene and propylene with α-olefins having 3 or more carbon atoms, and copolymers of propylene with α-olefins having 4 or more carbon atoms.

[0147] Examples of α-olefins with 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetracene, 1-tetradecene, 1-pentadecadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. Examples of α-olefins with 4 or more carbon atoms can be listed. They can be used alone or in combination of two or more.

[0148] Alternatively, copolymers can also be copolymers formed by copolymerizing various non-conjugated dienes and other polyenes. Examples of non-conjugated dienes include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethimide-8-methyl-1,7-nonadiene, and 4,8-dimethyl-1,4,8-decanetriene (D...). MDT), dicyclopentadiene, cyclohexadiene, cyclooctadiene, 5-vinylnorbornene, 5-ethide-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylidene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornediene, etc. They can be used alone or in combination of two or more.

[0149] Ethylene and / or propylene) / (α,β-unsaturated carboxylic acids and / or unsaturated carboxylic acid esters) copolymers are polymers formed by copolymerizing ethylene and / or propylene with α,β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester monomers. Examples of α,β-unsaturated carboxylic acid monomers include acrylic acid and methacrylic acid. Examples of α,β-unsaturated carboxylic acid ester monomers include methyl esters, ethyl esters, propyl esters, butyl esters, pentyl esters, hexyl esters, heptyl esters, octyl esters, nonyl esters, decyl esters, etc. They can be used alone or in combination of two or more.

[0150] As an olefin resin (C) containing functional groups, ethylene / α-olefin copolymers incorporating the aforementioned functional groups are preferred. From the viewpoint of mechanical strength and impact resistance when the molded article is manufactured, ethylene / α-olefin copolymers incorporating at least one of the group consisting of maleic anhydride, itaconic anhydride and citraconic anhydride are more preferred. Ethylene / α-olefin copolymers incorporating maleic anhydride are even more preferred. Ethylene / 1-butene copolymers incorporating maleic anhydride are particularly preferred.

[0151] Within the limits that do not impair the function and properties of the polyamide resin composition, the functionalized olefin resin (C) may include non-functionalized olefin resins, but even if included, it is preferably less than 2% by mass in 100% by mass of the polyamide resin composition, more preferably not included.

[0152] The content of functional groups in the functional group-containing olefin resin (C), expressed as the molar number of functional groups (μmol) / the mass (g) of the functional group-containing olefin resin (C), is preferably more than 25 μmol / g and less than 200 μmol / g, more preferably more than 35 μmol / g and less than 180 μmol, and even more preferably more than 40 μmol / g and less than 150 μmol / g. When the content exceeds 25 μmol / g, a composition with high melt viscosity can be obtained, and the target wall thickness can be achieved in blow molding. In addition, if the content is less than 200 μmol / g, the melt viscosity will not be too high, the extruder load can be suppressed and molding processing can be performed well, and the instability of the shape of the molded article and the shape of the parison during extrusion molding is suppressed, and there is a tendency for the thickness of the molded body to become more uniform. The content of functional groups in olefin resins (C) containing functional groups, for example in the case of having carboxyl, anhydride and / or carboxylic acid ester groups as functional groups, is determined by neutralization titration based on 0.1 equivalents of KOH ethanol solution using a sample solution prepared with toluene and ethanol, with phenolphthalein as an indicator.

[0153] When using two or more olefin resins (C) with different functional group contents, the functional group content in the olefin resins (C) is determined by the method described above. Having determined the functional group content and mixing ratio of each olefin resin (C), the average value (average functional group content) calculated by multiplying the measured value of each functional group content by its mixing ratio is approximately consistent with the measured value. Therefore, it can also be used as the functional group content of the olefin resin (C).

[0154] For olefin resins (C) containing functional groups, according to ASTM D1238, the melt viscosity (MFR) measured at 230°C and 2160g is preferably 0.1 g / 10 min or more and 10.0 g / 10 min or less, more preferably more than 1.0 g / 10 min or less than 5.0 g / 10 min, even more preferably more than 1.0 g / 10 min or less than 3.0 g / 10 min, and particularly preferably more than 1.0 g / 10 min or less than 2.5 g / 10 min. If the MFR is 0.1 g / 10 min or more, the melt viscosity of the polyamide resin composition will not become excessively high, which, for example, can suppress instability in the shape of the extruded article and the preform during extrusion molding, and tends to result in a more uniform thickness of the molded body. Furthermore, if the MFR is 10.0 g / 10 min or less, the sag of the extruded article and the preform during blow molding will not become excessive, and there is a tendency to obtain good extruded and blow-molded articles.

[0155] The polyamide resin composition contains 5 to 10% by mass, preferably 5 to 8% by mass, of a functionalized olefin resin (C). When the content of the functionalized olefin resin (C) is within the above range, the low-temperature physical properties and the wall thickness uniformity of the blow-molded article are good.

[0156] <Heat resistant agent (D)>

[0157] The polyamide resin composition may optionally contain a heat-resistant agent.

[0158] The term "heat resistant agent (D)" refers to the component that inhibits the thermal oxidation and thermal deterioration of polyamide resin. In this context, it also includes substances known as antioxidants.

[0159] As a heat resistant agent (D), organic or inorganic heat resistant agents can be used depending on the purpose. They can be used alone or in combination of two or more.

[0160] (1) Organic heat resistant agent

[0161] Examples of organic heat-resistant agents include phenolic compounds, phosphorus-based organic compounds, sulfur-based compounds, and nitrogen-based compounds. They can be used individually or in combination of two or more.

[0162] (Phenolic compounds)

[0163] Hindered phenolic compounds are preferred examples of phenolic compounds. In this specification, a hindered phenol is a compound having a substituent at the ortho position (hereinafter also referred to as the "o position") of the hydroxyl group of the phenol. The ortho substituent is not particularly limited and can include alkyl, alkoxy, amino, and halogen groups. Among these, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl are preferred; isopropyl, sec-butyl, isobutyl, and tert-butyl, which have larger volumes, are more preferred; and tert-butyl is most preferred. Furthermore, it is preferable that both ortho positions relative to the hydroxyl group of the phenol have substituents.

[0164] Hindered phenols with a tert-butyl group at the ortho position include: N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamamide), pentaerythritol tetratetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, ethylene bis(oxoethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxellaspiro[5.5]undecane, etc. They can be used alone or in combination of two or more. Commercially available examples of these heat-resistant agents include "Irganox 245" (registered trademark), "Irganox 1010" (BASF), and "Sumilizer GA-80" (Sumitomo Chemical). They can be used individually or in combination of two or more.

[0165] (Phosphorus-based organic compounds)

[0166] As phosphorus-based organic compounds, hindered phenolic phosphite compounds and hindered phenolic hypophosphite compounds are preferred, more preferably hindered phenolic phosphite compounds having a tert-butyl group at the ortho position and more preferably hindered phenolic hypophosphite compounds having a tert-butyl group at the ortho position, and even more preferably hindered phenolic phosphite compounds having a tert-butyl group at the ortho position. Specific examples of hindered phenolic phosphite compounds having a tert-butyl group at the ortho position include tris(2,4-di-tert-butylphenyl) phosphite and bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. Specific examples of hindered phenolic hypophosphite compounds having a tert-butyl group at the ortho position include the reaction product of biphenyl, phosphorus trichloride, and 2,4-di-tert-butylphenol, with p,p,p',p'-tetra(2,4-di-tert-butylphenoxy)-4,4-biphenyldiphosphine as the main component. Commercially available examples of these heat-resistant agents include "Irgafos 168" (BASF) and "Hostanox P-EPQ" (Clariant Chemicals). They can be used individually or in combination of two or more.

[0167] (Chalcogenide compounds)

[0168] Examples of sulfide compounds include: distearate-3,3-thiodipropionate, pentaerythritol tetra(3-lauryl thiopropionate), and didodecyl(3,3'-thiodipropionate). They can be used individually or in combination of two or more.

[0169] (Nitrogen compounds)

[0170] Examples of nitrogen-based compounds include melamine, melamine cyanurate, benzoguanamine, dimethylol urea, and cyanuric acid. They can be used individually or in combination of two or more.

[0171] From the viewpoint of material coloring, hindered phenolic compounds and phosphorus-based organic compounds are preferred as organic heat resistant agents, more preferably containing phosphorus-based organic compounds and two or more hindered phenolic compounds, and even more preferably a combination of two or more hindered phenolic compounds and a hindered phenolic phosphite compound.

[0172] (2) Inorganic heat resistant agent

[0173] Inorganic heat-resistant agents used as heat-resistant agents include copper compounds and potassium halides. Examples of copper compounds include cuprous iodide, cuprous bromide, copper bromide, and copper acetate. From the perspective of heat resistance and inhibition of metal corrosion, cuprous iodide is preferred. Examples of potassium halides include potassium iodide, potassium bromide, and potassium chloride. They can be used individually or in combination of two or more.

[0174] Furthermore, it is even more effective when combined with nitrogen-based compounds such as melamine, melamine cyanurate, benzoguanamine, dimethylol urea, or cyanuric acid.

[0175] In the polyamide resin composition, the heat resistant agent (D) preferably comprises 0.10 to 3.00% by mass, more preferably 0.20 to 2.00% by mass, and even more preferably 0.50 to 1.50% by mass. If the content of the heat resistant agent is within the above range, the thermal degradation of the resin can be suppressed, thereby suppressing significant volatile gas generation and leakage during molding and use of the molded product.

[0176] <Additives>

[0177] Polyamide resin compositions may contain, depending on the purpose, appropriate functional additives such as dyes, pigments, particulate reinforcing agents, plasticizers, antioxidants, foaming agents, weathering agents, crystallizing nucleating agents, crystallizing promoters, lubricants, antistatic agents, flame retardants, flame retardant additives, colorants, spreading agents, etc., as optional components.

[0178] Preferably, at least one of the following is selected from the group consisting of a free crystallizing nucleating agent, a lubricant, and a spreading agent. Examples of nucleating agents include talc and microtalc; examples of lubricants include higher fatty acids or their metal salts, carboxylic amides, and ethylenediamide compounds; and examples of spreading agents include surfactants and waxes.

[0179] The polyamide resin composition may preferably contain 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass of optional additives in 100% by mass.

[0180] <Optional Resin>

[0181] The polyamide resin composition may contain thermoplastic resins other than polyamide resin (A), ionomer (B) and functionalized olefin resin (C).

[0182] From the viewpoint of mechanical properties and molding processability, thermoplastic resins other than polyamide resin (A), ionomer (B) and olefin resins containing functional groups (C) are preferably 5% or less by mass in 100% by mass of the polyamide resin composition, more preferably less than 2% by mass, and even more preferably not included.

[0183] [Method for manufacturing polyamide resin composition]

[0184] There are no particular limitations on the manufacturing method of the polyamide resin composition; for example, the following methods can be used.

[0185] The raw materials for each component are mixed using commonly known melt mixing machines such as single-screw extruders, twin-screw extruders, Banbury mixers, kneaders, and mixing rollers. As for the melt mixing temperature, there are no particular limitations as long as the polyamide resin is melted; 190°C to 280°C is preferred.

[0186] For example, when using a twin-screw extruder, any of the following methods can be used: a method of melting and mixing all raw materials; a method of melting and mixing a portion of raw materials, and then melting and mixing the remaining raw materials; or a method of mixing a portion of raw materials and then mixing the remaining raw materials using a side feeder during melt mixing, preferably a method of melting and mixing all raw materials.

[0187] During mixing, each component can be blended separately, multiple components can be pre-mixed and then blended, or a masterbatch can be used. In addition, the order of blending can be appropriately selected according to the melt-blending method and conditions.

[0188] [Molded Articles of Polyamide Resin Compositions and Their Uses]

[0189] Polyamide resin compositions are suitable for the manufacture of injection-molded articles based on injection molding, extrusion-molded articles based on extrusion molding, blow-molded articles based on blow molding, and rotation-molded articles based on rotational molding.

[0190] Polyamide resin compositions, particularly those exhibiting high weld strength at the clamped portion of molded articles, are suitable for use in blow molding and extrusion blow molding. There are no particular limitations on the method for manufacturing blow-molded articles from polyamide resin compositions using blow molding; known methods can be employed. Typically, blow molding is performed after forming a preform using a conventional blow molding machine. Blow molding may include the operation of a mold cavity closing around the preform and clamping off one end. This clamping can be performed before and / or after the preform has expanded.

[0191] Injection-molded products based on injection molding, extrusion-molded products based on extrusion molding, blow-molded products based on blow molding, and rotational-molded products based on rotational molding are not particularly limited. Examples include automotive parts such as chokes, air intake pipes, intake manifolds, resonators, fuel tanks, gas cans, working oil cans, fuel filling pipes, fuel delivery pipes, and various other hoses / pipes / cans, as well as mechanical parts such as power tool housings and pipes. Examples of preferred uses include electrical / electronic components such as cans, pipes, hoses, and membranes, household / office supplies, building material-related components, and furniture components.

[0192] In addition, it is suitable for components used in environments with large temperature variations, such as those requiring high heat resistance and low cold resistance, such as drive components like gears and belts in automobiles and sliding components like tire sidewalls and belts.

[0193] Among them, it is suitable for use in automotive parts, sliding parts or electrical / electronic parts.

[0194] Furthermore, the polyamide resin composition exhibits excellent gas barrier properties, making it suitable for molded articles that come into contact with high-pressure gases, such as canisters, pipes, hoses, membranes, and gaskets for containing and conveying high-pressure gases. High-pressure gas canisters are particularly preferred. There are no particular limitations on the types of gases mentioned above; examples include hydrogen, nitrogen, helium, methane, butane, and propane. Gases with low polarity are preferred, with hydrogen, nitrogen, and methane being particularly preferred.

[0195] 2. The second aspect of the present invention

[0196] A second aspect of the present invention is a polyamide resin composition comprising a polyamide resin (A), an ionomer (B), and a functionalized olefin resin (C), wherein the polyamide resin (A) comprises an aliphatic homopolymer polyamide resin (A-1), an aliphatic copolymer polyamide resin (A-2), and an aromatic polyamide resin (Ab).

[0197] In 100% by mass of the polyamide resin composition, there are 40-60% by mass of the above-mentioned aliphatic homopolymer polyamide resin (A-1), 10-40% by mass of the above-mentioned aliphatic copolymer polyamide resin (A-2), 2-10% by mass of the above-mentioned aromatic polyamide resin (Ab), 5-20% by mass of the above-mentioned ionomer (B), and 5-10% by mass of the above-mentioned functionalized olefin resin (C).

[0198] The total content ((B) + (C)) of the ionomer (B) and the functionalized olefin resin (C) in the polyamide resin composition is 16.0% by mass or more and less than 25.0% by mass.

[0199] The mass ratio of the ionomer (B) to the functional group-containing olefin resin (C) ((B) / (C)) is greater than 0 and less than 3.50.

[0200] The definitions, preferred examples, terminal amino concentrations, and contents in the polyamide resin composition of the aliphatic homopolymer polyamide resin (A-1), aliphatic copolymer polyamide resin (A-2), and aromatic polyamide resin (Ab) are the same as those of the first embodiment of the present invention, except for the preferred range of the relative viscosity of the aliphatic homopolymer polyamide resin (A-1) and the aliphatic copolymer polyamide resin (A-2).

[0201] The manufacturing method of polyamide resin (A), the content in the polyamide resin composition, the relative viscosity, and the concentration of terminal amino groups are also the same as those in the first embodiment of the present invention.

[0202] The relative viscosity of the aliphatic homopolymer polyamide resin (A-1) is preferably 2.70 or higher, more preferably 2.70 to 5.00, and even more preferably 2.70 to 4.50. If the relative viscosity is within the above range, there is a tendency for the molding processability to become better.

[0203] The relative viscosity of the aliphatic copolymer polyamide resin (A-2) is preferably 1.80 to 5.00, more preferably 2.50 to 4.50, and even more preferably 3.00 to 4.30. If the relative viscosity is within the above range, there is a tendency for improved molding processability.

[0204] The relative viscosity described above was determined according to JIS K-6920, by dissolving 1g of polyamide resin in 100ml of 96% sulfuric acid and measuring at 25°C. The method for determining the relative viscosity when two or more polyamide resins with different relative viscosities is the same as in the first embodiment of this invention.

[0205] The definitions, preferred examples, and contents of the ionomer (B) and the functional group-containing olefin resin (C) in the polyamide resin composition, as well as the content of functional groups and MFR in the functional group-containing olefin resin (C), are the same as in the first embodiment of the present invention.

[0206] In 100% by mass of the polyamide resin composition, the total content ((B)+(C)) of the above-mentioned ionomer (B) and the above-mentioned functional group-containing olefin resin (C) is 16.0% by mass or more and less than 25.0% by mass, preferably 16.0% by mass or more and less than 23.0% by mass, more preferably 17.0% by mass or more and less than 23.0% by mass or 16.0% by mass or more and less than 22.0% by mass, and particularly preferably 17.0% by mass or more and less than 20.0% by mass.

[0207] The mass ratio ((B) / (C)) of the ionomer (B) to the functionalized polyolefin resin (C) is greater than 0 and less than 3.50, preferably 1.00 or more and 2.00 or less, more preferably 1.25 or more and 2.00 or less, even more preferably 1.25 or more and less than 2.00, and particularly preferably 1.25 or more and less than 1.67.

[0208] By setting the values ​​of (B)+(C) to the above range and the values ​​of (B) / (C) to the above range, it is possible to obtain a blow-molded product with high weld interface strength, suppressed sag, and suppressed thickness at the center of the clamped portion from the thickness near the clamped portion.

[0209] When ionomer (B) is the preferred olefin-based ionomer, both are common as resins in terms of being olefin-based and have common physical properties such as being able to function as impact-resistant materials. It is believed that the two influence each other on mechanical properties, etc.

[0210] On the other hand, the ionomer (B) differs from the olefin resin (C) containing functional groups in that some or all of the carboxyl groups are neutralized by metal or metal ions. It is believed that the neutralized ionomer (B) interacts with the amide bond and terminal amino group of the polyamide resin with relatively weak forces, while the functional groups of the unneutralized olefin resin (C) interact with the terminal amino group of the polyamide resin with relatively strong forces. As a result, it is presumed that each has a different effect on physical properties such as melt viscosity.

[0211] The aforementioned characteristics are considered to be a reason for the effect produced by setting the values ​​of (B)+(C) and (B) / (C) to a specific range.

[0212] The polyamide resin composition may optionally contain a heat-resistant agent (D).

[0213] The definition and preferred examples of the heat-resistant agent (D) are the same as those of the first embodiment of the present invention.

[0214] From the viewpoint of material coloring, hindered phenolic compounds and phosphorus-based organic compounds are preferred as organic heat resistant agents, combinations of hindered phenolic compounds and phosphorus-based organic compounds are more preferred, and combinations of hindered phenolic compounds and phosphite compounds of hindered phenols are even more preferred.

[0215] The polyamide resin composition may contain optional additives and optional resins in the same manner as the first embodiment of the invention.

[0216] The method for manufacturing the polyamide resin composition is the same as that of the first embodiment of the present invention.

[0217] The molded articles of the polyamide resin composition and their uses are the same as those of the first embodiment of the present invention.

[0218] Example

[0219] The present invention will now be described in more detail by way of examples and comparative examples, but the present invention is not limited to these examples.

[0220] The methods for evaluating the physical properties of the resins and molded articles used in the examples and comparative examples are shown below.

[0221] 1. An embodiment of the first aspect of the present invention

[0222] Relative viscosity

[0223] The relative viscosity of each polyamide resin is determined according to JIS K6920, by dissolving 1g of polyamide resin in 100ml of 96% sulfuric acid at 25°C.

[0224] The relative viscosity of the mixture of aliphatic homopolymer polyamide resin (A-1) and aliphatic copolymer polyamide resin (A-2), namely aliphatic polyamide resin (Aa), is determined by the following formula (I).

[0225] The relative viscosity of aliphatic polyamide resin (Aa) = ΣXi×Yi / Z(I)

[0226] (In the formula, Xi is the relative viscosity of each polyamide resin contained in the aliphatic polyamide resin (Aa), determined according to JIS K6920, by dissolving 1g of each component contained in the aliphatic polyamide resin (Aa) in 100ml of 96% sulfuric acid and measuring at 25°C.)

[0227] Yi is the mass part of each polyamide resin contained in 100 parts by mass of the aliphatic polyamide resin (Aa) in the polyamide resin composition.

[0228] Z is the mass part of aliphatic polyamide resin (Aa) relative to 100 parts by mass of the polyamide resin composition.

[0229] i represents the quantity of each polyamide resin contained in the aliphatic polyamide resin (Aa) in the polyamide resin composition.

[0230] Specifically,

[0231] The relative viscosity of aliphatic polyamide resin (Aa) = (relative viscosity of PA6(1) × parts by mass of PA6(1) relative to 100 parts by mass of the polyamide resin composition + relative viscosity of PA6(2) × parts by mass of PA6(2) relative to 100 parts by mass of the polyamide resin composition + relative viscosity of PA6(3) × parts by mass of PA6(3) relative to 100 parts by mass of the polyamide resin composition + relative viscosity of PA6 / 66(1) × parts by mass of PA6 / 66(1) relative to 100 parts by mass of the polyamide resin composition + relative viscosity of PA6 / 66(2) × parts by mass of PA6 / 66(2) relative to 100 parts by mass of the polyamide resin composition + relative viscosity of PA6 / 66(3) × parts by mass of PA6 / 66(3) relative to 100 parts by mass of the polyamide resin composition) / parts by mass of aliphatic polyamide resin (Aa) relative to 100 parts by mass of the polyamide resin composition.

[0232] <Terminal amino group concentration>

[0233] The polyamide resin was dissolved in a mixed solvent of phenol and methanol and determined by neutralization titration.

[0234] <Weld interface strength>

[0235] The weld interface strength is calculated using the following formula based on the weld strength and tensile yield stress determined by the following method.

[0236] Weld interface strength = (weld strength of the welded part / tensile yield stress of the material) × 100

[0237] The weld strength of the above-mentioned welded joint was determined using the following method.

[0238] Two flat plates, injection molded from the polyamide resin compositions of the Examples and Comparative Examples, were joined end-to-end. The ends of the two plates were irradiated with infrared light from an infrared heater, and fused under conditions where the surface temperature of the ends was sufficiently heated but not excessively within the range of melting point +50 to 100°C. The plates were then cut into strips with the welded portion located in the center, and tensile tests were performed at 23°C according to ISO 527-1. The tensile strength at the moment of weld failure or separation was determined as the weld strength. The tensile yield stress of the above materials was determined using the following method.

[0239] For dumbbell-shaped test pieces made by injection molding of the polyamide resin compositions of the examples and comparative examples, tensile tests were performed at 23°C in accordance with ISO 527-1 to determine the tensile yield stress of the material.

[0240] <Sagging Amount>

[0241] Using a blow molding machine DA-50 (manufactured by Placo Corporation), plasticizing is performed at a barrel temperature of 260°C and a screw speed of 40 rpm. The length of the parison obtained by extruding 1000 cc of molten resin stored in the reservoir through a die head with a core diameter of 50 mm is adjusted to be 1 m. Then, the molding machine is stopped immediately after the parison is extruded from the reservoir. The length from the position of the lower end of the parison immediately after extrusion to the position where the lower end of the parison moves after 1 second after stopping is taken as the sag.

[0242] <Shape of the clamped part>

[0243] Using a DA-50 blow molding machine (manufactured by Placo Co., Ltd.), plasticizing is performed at a barrel temperature of 260°C and a screw speed of 40 rpm. 1000 cc of molten resin stored in the reservoir is extruded from a die head with a core diameter of 50 mm, resulting in a parison length of 1 m. The parison is clamped at its upper and lower ends (excluding the gas inlet nozzle) by closing the mold, which is set to 60°C. Then, compressed gas is used to expand the parison, bringing it into contact with the hollow blow mold surface. The expanded parison is cooled to the shape of the blow mold, and the blow-molded product is removed. The cross-section of the molded blow-molded product, cut perpendicularly to the clamping line, is evaluated using the value calculated by the following formula.

[0244] Shape of the pinch-off portion (%) = 100 - (t) P / ((t1+t2) / 2))×100

[0245] (t p t1 and t2 are the plate thicknesses at the center of the clamped section (interface meeting point) and the thickest parts of the plate near both sides of the clamped section.

[0246] Figure 1 t is shown schematically P t1 and t2.

[0247] Regarding the shape of the clamped portion derived from the above formula, the lower the value, the less the thickness at the center of the clamped portion becomes thinner relative to the thickness near the clamped portion. Therefore, it can be said that the lower the value, the more the thinning of the clamped portion relative to the surrounding area is suppressed, and the higher the strength of the clamped portion.

[0248] <Overall Evaluation>

[0249] The evaluation will be conducted according to the following criteria.

[0250] ◎: The values ​​for “weld interface strength”, “sag suppression” and “pinch shape” are all excellent, or one is particularly excellent, and the others are excellent or permissible.

[0251] 〇: Two of the values ​​for "weld interface strength", "sag suppression" and "pinch shape" are excellent, and one is an acceptable value.

[0252] ×: More than one of the following values ​​is not allowed: "Weld interface strength", "Suppression of sagging" and "Shape of pinch-off part".

[0253] [Examples 1-6, Comparative Examples 1-9]

[0254] The components listed in Table 1 were melt-blended using a TEX44HCT twin-screw mixer with a barrel diameter of 44mm and a discharge rate of 50kg / hrs at a screw speed of 170rpm to produce granules of the target polyamide resin composition.

[0255] The obtained granules were used for the above-mentioned physical property evaluation. The results are shown in Table 1.

[0256] It should be noted that the units of composition in the table are by mass%, and the total mass of the polyamide resin composition is set to 100%.

[0257] The abbreviations in Table 1 are as follows.

[0258] PA6(1): Polyamide 6, relative viscosity 4.08, terminal amino concentration 33 μmol / g, manufactured by UBE Corporation.

[0259] PA6(2): Polyamide 6, relative viscosity 3.50, terminal amino concentration 42 μmol / g, manufactured by UBE Corporation.

[0260] PA6(3): Polyamide 6, relative viscosity 2.98, terminal amino concentration 56 μmol / g, manufactured by UBE Corporation.

[0261] PA6 / 66(1): Polyamide 6 / 66, relative viscosity 4.05, terminal amine concentration 34 μmol / g, manufactured by UBE Corporation.

[0262] PA6 / 66(2): Polyamide 6 / 66, relative viscosity 3.39, terminal amine concentration 45 μmol / g, manufactured by UBE Corporation.

[0263] PA6 / 66(3): Polyamide 6 / 66, relative viscosity 3.04, terminal amine concentration 54 μmol / g, manufactured by UBE Corporation.

[0264] PA6T / 6I: Polyamide 6T / 6I, product name "Grivory (registered trademark) G21" manufactured by EMS-CHEMIE (Japan) Co., Ltd., terminal amino concentration = 38 μmol / g

[0265] Ionomer: An ionomer using ethylene-methacrylic acid copolymer as resin and Zn as metal ion, product name "Himilan (registered trademark) 1706" manufactured by Mitsui-DuPont Chemicals Co., Ltd.

[0266] Olefin resin containing functional groups: Maleic anhydride modified ethylene / 1-butene copolymer, product name "TAFMER (registered trademark) MH5020", manufactured by Mitsui Chemicals Co., Ltd., MFR (230℃, load 2,160g): 1.2g / 10min, anhydride concentration (concentration of functional groups): 100μmol / g

[0267] Heat resistant agent 1: Hindered phenolic compound (3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane), product name "Sumilizer (registered trademark) GA-80", manufactured by Sumitomo Chemical Co., Ltd.

[0268] Heat resistant agent 2: Hindered phenolic compound (pentaerythritol tetratetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), product name "Irganox (registered trademark) 1010", manufactured by BASF.

[0269] Heat resistant agent 3: Phosphorus-based organic compound (tris(2,4-di-tert-butylphenyl) phosphite), product name "Irgafos (registered trademark) 168", manufactured by BASF.

[0270] [Table 1]

[0271]

[0272] In Examples 1-6, the dissolution interface strength was sufficient, the sagging was suppressed, and the thickness of the cut-off portion was only slightly thinner than the surrounding thickness.

[0273] Compared to Examples 3 and 4, which contain aliphatic homopolymer polyamide resin (A-1) and aliphatic copolymer polyamide resin (A-2) composed of polyamide resin with a relative viscosity of 3.00 or higher, the sag of Examples 1 and 2 was suppressed.

[0274] In Comparative Example 1, where the relative viscosity of the aliphatic polyamide resin (Aa) is lower than the range of the present invention, the amount of sagging is significantly greater.

[0275] In Comparative Examples 2, 4-8, where the relative viscosity of the aliphatic polyamide resin (Aa) is higher than the range of the present invention, the shape value of the pinch-off portion is high, and the degree of thinning of the pinch-off portion compared to the surrounding area is high. In Comparative Example 5, where the amount of aliphatic copolymer polyamide resin (A-2) is high, the solution interface strength is further low.

[0276] In Comparative Example 3, where the relative viscosity of the aliphatic polyamide resin (Aa) is higher than the range of the present invention, the content of (A-1) is lower than the range of the present invention, and the content of the aromatic polyamide resin (Ab) is higher than the range of the present invention, the dissolution interface strength is low.

[0277] In Comparative Example 9, where the relative viscosity of the aliphatic polyamide resin (Aa) is higher than the range of the present invention and the content of the aromatic polyamide resin (Ab) is higher than the range of the present invention, the dissolution interface strength is low.

[0278] 2. Embodiment of the second aspect of the present invention

[0279] Relative viscosity

[0280] The value was determined according to JIS K6920 by dissolving 1g of polyamide resin in 100ml of 96% sulfuric acid and measuring it at 25°C.

[0281] The methods for determining the terminal amino concentration, weld interface strength, sag, and pinch-off shape are the same as those in the embodiment of the first aspect of the present invention.

[0282] <Overall Evaluation>

[0283] The evaluation will be conducted according to the following criteria.

[0284] ◎: The values ​​for "weld interface strength", "sag suppression" and "pinch shape" are all excellent.

[0285] 〇: Two of the values ​​for "weld interface strength", "sag suppression" and "pinch shape" are excellent, and one is an acceptable value.

[0286] ×: One or more of the values ​​for weld interface strength, sag suppression, and pinch-off shape are not allowed.

[0287] [Examples 7-10, Comparative Examples 10-14]

[0288] The components listed in Table 2 were melt-blended using a TEX44HCT twin-screw mixer with a barrel diameter of 44mm and a discharge rate of 50kg / hrs at a screw speed of 170rpm to produce granules of the target polyamide resin composition.

[0289] The obtained granules were used for the above-mentioned physical property evaluation. The results are shown in Table 2.

[0290] It should be noted that the units of composition in the table are by mass%, and the total mass of the polyamide resin composition is set to 100%.

[0291] The abbreviations in Table 2 are as follows.

[0292] PA6: Polyamide 6, relative viscosity 4.08, terminal amine concentration 33 μmol / g, manufactured by UBE Corporation.

[0293] PA6 / 66: Polyamide 6 / 66, relative viscosity 4.05, terminal amine concentration 34 μmol / g, manufactured by UBE Corporation.

[0294] PA6T / 6I: Polyamide 6T / 6I, product name "Grivory (registered trademark) G21" manufactured by EMS-CHEMIE (Japan) Co., Ltd., terminal amino concentration = 38 μmol / g

[0295] Ionomer: An ionomer using ethylene-methacrylic acid copolymer as resin and Zn as metal ion, product name "Himilan (registered trademark) 1706" manufactured by Mitsui-DuPont Chemicals Co., Ltd.

[0296] Olefin resin containing functional groups: Maleic anhydride modified ethylene / 1-butene copolymer, product name "TAFMER (registered trademark) MH5020", manufactured by Mitsui Chemicals Co., Ltd., MFR (230℃, load 2,160g): 1.2g / 10min, anhydride concentration (concentration of functional groups): 100μmol / g.

[0297] Heat resistant agent 1: Hindered phenolic compound (3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane), product name "Sumilizer (registered trademark) GA-80", manufactured by Sumitomo Chemical Co., Ltd.

[0298] Heat resistant agent 2: Hindered phenolic compound (pentaerythritol tetratetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), product name "Irganox (registered trademark) 1010", manufactured by BASF.

[0299] Heat resistant agent 3: Phosphorus-based organic compound (tris(2,4-di-tert-butylphenyl) phosphite), product name "Irgafos (registered trademark) 168", manufactured by BASF.

[0300] B+C: The total content of ionomer (B) and functionalized olefin resin (C) in a polyamide resin composition.

[0301] B / C: The mass ratio of ionomer (B) to functionalized olefin resin (C) in a polyamide resin composition.

[0302] [Table 2]

[0303]

[0304] In Examples 7-10, the dissolution interface strength is sufficient, the sag is suppressed, and the thickness of the cut-off portion is only slightly thinner than the surrounding thickness.

[0305] In Comparative Example 10, where the mass ratio of component (B) to component (C) ((B) / (C)) exceeds the scope of the present invention, the shape value of the clamped portion is high, and the degree to which the clamped portion is thinner compared to the surrounding area is high.

[0306] In Comparative Example 11, where the total of component (C) and component (B) ((B) + (C)) exceeds the scope of the present invention, the shape value of the clamped portion is high, and the degree to which the clamped portion is thinner compared to the surrounding area is high.

[0307] In Comparative Example 12, where the total of component (C) and component (B) ((B)+(C)) exceeds the scope of this invention and the content of (A-1) is not within the scope of this invention, the shape value of the clamped portion is high, the degree of thinning of the clamped portion compared to the vicinity is high, and the weld interface strength is low compared to Comparative Example 11.

[0308] In Comparative Example 13, where the sum of component (C) and component (B) ((B) + (C)) exceeds the scope of the present invention to a greater extent than in Comparative Examples 11 and 12, the shape value of the clamped portion is higher than in Comparative Examples 11 and 12, the clamped portion is thinner than the surrounding area, and the dissolution interface strength is lower.

[0309] In Comparative Example 14, where the total of component (C) and component (B) ((B) + (C)) is less than the scope of the present invention, the amount of drooping increases significantly.

[0310] Industrial availability

[0311] Polyamide resin compositions are suitable for use in a variety of molded articles, especially blow-molded articles, and are particularly suitable for automotive parts, sliding parts, electrical / electronic parts, and molded articles that come into contact with high-pressure gases.

[0312] Explanation of reference numerals in the attached figures

[0313] t p Thickness of the plate at the center of the clamped section (interface meeting point)

[0314] t1: The thickness of the plate at the point of greatest thickness near both sides of the break.

[0315] t2: The thickness of the plate at the point of greatest thickness near both sides of the break.

[0316] This application claims priority based on Japanese Patent Application Nos. 2024-046675 and 2024-046590. The entire disclosure of Japanese Patent Application Nos. 2024-046675 and 2024-046590 is incorporated herein by reference.

Claims

1. A polyamide resin composition comprising an aliphatic polyamide resin (Aa), an aromatic polyamide resin (Ab), an ionomer (B), and a functionalized olefin resin (C), wherein the aliphatic polyamide resin (Aa) comprises an aliphatic homopolymer polyamide resin (A-1) and an aliphatic copolymer polyamide resin (A-2). In 100% by mass of the polyamide resin composition, there are 40-60% by mass of the aliphatic homopolymer polyamide resin (A-1), 10-40% by mass of the aliphatic copolymer polyamide resin (A-2), 2-10% by mass of the aromatic polyamide resin (Ab), 5-20% by mass of the ionomer (B), and 5-10% by mass of the functionalized olefin resin (C). According to JIS K 6920, the relative viscosity of the aliphatic polyamide resin (Aa) was 3.60~3.85 when 1g of the aliphatic polyamide resin (Aa) was dissolved in 100ml of 96% sulfuric acid and measured at 25°C.

2. The polyamide resin composition according to claim 1, wherein, According to JIS K 6920, the relative viscosity of the aliphatic homopolymer polyamide resin (A-1) and the relative viscosity of the aliphatic copolymer polyamide resin (A-2) were measured at 25°C after dissolving 1g of polyamide resin in 100ml of 96% sulfuric acid. The results were 3.00~4.

20.

3. A polyamide resin composition comprising a polyamide resin (A), an ionomer (B), and a functionalized olefin resin (C), wherein the polyamide resin (A) comprises an aliphatic homopolymer polyamide resin (A-1), an aliphatic copolymer polyamide resin (A-2), and an aromatic polyamide resin (Ab). In 100% by mass of the polyamide resin composition, there are 40-60% by mass of the aliphatic homopolymer polyamide resin (A-1), 10-40% by mass of the aliphatic copolymer polyamide resin (A-2), 2-10% by mass of the aromatic polyamide resin (Ab), 5-20% by mass of the ionomer (B), and 5-10% by mass of the functionalized olefin resin (C). The total content ((B) + (C)) of the ionomer (B) and the functionalized olefin resin (C) in the polyamide resin composition is 16.0% by mass or more and less than 25.0% by mass. The mass ratio of the ionomer (B) to the functional group-containing olefin resin (C) ((B) / (C)) is greater than 0 and less than 3.

50.

4. The polyamide resin composition according to claim 1 or 3, wherein, The ionomer (B) is a copolymer of (ethylene and / or propylene) / (α,β-unsaturated carboxylic acids and / or unsaturated carboxylic acid esters) neutralized by metal or metal ions.

5. The polyamide resin composition according to claim 1 or 3, wherein, The olefin resin (C) containing functional groups is at least one selected from the group consisting of: (ethylene and / or propylene) / (α,β-unsaturated carboxylic acids and / or unsaturated carboxylic acid esters) copolymers optionally incorporating at least one selected from the group consisting of maleic anhydride, itaconic anhydride and citraconic anhydride; and (ethylene and / or propylene) / α-olefin copolymers incorporating at least one selected from the group consisting of maleic anhydride, itaconic anhydride and citraconic anhydride.

6. The polyamide resin composition according to claim 1 or 3, wherein, The functional group content in the olefin resin (C) containing functional groups is greater than 25 μmol / g and less than 200 μmol / g.

7. The polyamide resin composition according to claim 1 or 3, wherein, The aliphatic homopolymer polyamide resin (A-1) is at least one of the following: selected from the group consisting of at least one of polyamide 6, polyamide 11, polyamide 12, polyamide 56, polyamide 66, polyamide 510, polyamide 610, polyamide 612 and polyamide 1010.

8. The polyamide resin composition according to claim 1 or 3, wherein, The aliphatic copolyamide resin (A-2) is selected from at least one of the following groups: polyamide 56 / 6, polyamide 56 / 66, polyamide 56 / 510, polyamide 6 / 66, polyamide 6 / 12 and polyamide 6 / 66 / 12.

9. The polyamide resin composition according to claim 1 or 3, wherein, The aromatic polyamide resin (Ab) is selected from at least one of the groups consisting of polyamide 6T / 6I and polyamide MXD6.

10. The polyamide resin composition according to claim 3, wherein, The concentration of terminal amino groups in the polyamide resin (A), determined by dissolving it in a mixed solvent of phenol and methanol and by neutralization titration, is greater than 30 μmol / g and less than 70 μmol / g.

11. A molded article comprising the polyamide resin composition of claim 1 or 3.

12. The molded article according to claim 11, wherein it is a molded article in contact with high-pressure gas.

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