Polyamide resin composition

Abstract

Provided is a polyamide resin composition having suppressed water absorption, good productivity, and favorable mechanical properties such as flexural strength and flexural modulus.　A polyamide resin composition according to the present invention contains: a polyamide resin (A) containing two or more polyamide resins (A1), each having a constituent unit derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid; and a resin (B) having a functional group reactive with an amino group and / or a carboxyl group, wherein 2.0 to 7.0 mass% of the resin (B) having a functional group reactive with an amino group and / or a carboxyl group is contained in 100 mass% of the polyamide resin composition, and a ratio X determined by formula (1) is 4.74-5.98 in 1H-NMR of the polyamide resin composition. (The resin (B) having a functional group reactive with an amino group and / or a carboxyl group excludes the polyamide resins (A).) (1) [(i) + (ii) + (iii)] / (iii) = X (In formula (1), (i) is an integrated value of a chemical shift of 1.20 to 1.90 ppm, (ii) is an integrated value of a chemical shift of 2.05 to 2.50 ppm, and (iii) is an integrated value of a chemical shift of 3.15 to 3.50 ppm.)

Description

Polyamide resin composition

[0001] The present invention relates to a polyamide resin composition.

[0002] Polyamide resins have excellent properties as engineering plastics and are widely used in various industrial fields such as automobiles, machinery, and electric and electronic products.

[0003] Conventional polyamide resins were made from fossil fuels. With the increasing interest in recent environmental issues, environmentally friendly resins are in demand. Pentamethylenediamine can be obtained from biomass raw materials. Polyamide resin compositions containing polyamide resins having pentamethylenediamine as a constituent have been developed (see, for example, Patent Documents 1 and 2). Patent Document 1 describes a polyamide resin composition having excellent mechanical properties blended with an acid-modified polyolefin. Patent Document 2 describes a polyamide resin composition containing a polyamide resin having pentamethylenediamine and an aliphatic dicarboxylic acid having 7 or more carbon atoms as main components.

[0004] Japanese Patent Application Laid-Open No. 2010-70701 International Publication No. 2010 / 113736

[0005] Regarding polyamide resins having pentamethylenediamine as a constituent, mechanical properties and productivity are also required as in the case of other polyamide resins that have been widely used so far. In addition, polyamide resins having pentamethylenediamine as a constituent have had the problem of high water absorption. In the polyamide resin composition of Patent Document 1, the study of mechanical properties was not sufficient yet. In the polyamide resin of Patent Document 2, the balance between water absorption and mechanical properties was poor. Also, when substantially no filler was contained, the take-up of strands during melt kneading was unstable, pellets could not be produced stably, and productivity was poor. Therefore, an object of the present invention is to provide a polyamide resin composition having suppressed water absorption, good productivity, and good mechanical properties such as flexural strength and flexural modulus.

[0006] The specific means for solving the above problems are as follows: [1] A polyamide resin composition comprising a polyamide resin (A) and a resin (B) having a functional group reactive with an amino group and / or a carboxyl group, wherein the polyamide resin (A) comprises two or more polyamide resins (A1) having constituent units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid, and the polyamide resin composition contains 2.0 to 7.0% by mass of the resin (B) having a functional group reactive with an amino group and / or a carboxyl group in 100% by mass of the polyamide resin composition, and the polyamide resin composition was measured at 400 MHz using deuterated hexafluoroisopropanol as a solvent and tetramethylsilane as a reference substance. １ A polyamide resin composition having a ratio X of 4.74 or more and 5.98 or less, determined by the following formula (1) in 1H-NMR (however, the resin (B) having a functional group that reacts with the amino group and / or carboxyl group excludes the polyamide resin (A)). [(i) + (ii) + (iii)] / (iii) = X ... (1) (In equation (1), (i) is the integral value of a chemical shift of 1.20 to 1.90 ppm, (ii) is the integral value of a chemical shift of 2.05 to 2.50 ppm, and (iii) is the integral value of a chemical shift of 3.15 to 3.50 ppm.) [2] A polyamide resin composition comprising a polyamide resin (A) and a resin (B) having a functional group reactive with an amino group and / or a carboxyl group, wherein the polyamide resin (A) comprises two or more polyamide resins (A1) having constituent units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid, and the polyamide resin composition contains 2.0 to 7.0% by mass of the resin (B) having a functional group reactive with an amino group and / or a carboxyl group in 100% by mass, A polyamide resin composition in which the ratio of the number of methylene groups to the number of amide groups in the polyamide resin (A), as determined by the following formula (2), is 4.74 or more and 5.98 or less (however, the resin (B) having a functional group that reacts with the amino group and / or carboxyl group is excluded from the polyamide resin (A)). (In formula (2), the content ratio of polyamide resin (k) in the polyamide resin (A) is the ratio (mass ratio) of the polyamide resin (k) when the total polyamide resin (A) is set to 1.) [3] The polyamide resin composition according to [1] or [2], wherein the polyamide resin (A) comprises a polyamide resin (a1) having structural units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid having 6 to 8 carbon atoms, and a polyamide resin (a2) having structural units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid having 9 to 16 carbon atoms. [4] The polyamide resin composition according to [3], wherein 100% by mass of the polyamide resin composition contains 20.0 to 75.0% by mass of the polyamide resin (a1) and 20.0 to 75.0% by mass of the polyamide resin (a2). [5] A polyamide resin composition according to any one of [1] to [4], comprising 90.0 to 98.0% by mass of the polyamide resin (A) in 100% by mass of the polyamide resin composition. [6] A polyamide resin composition according to any one of [1] to [5], wherein the functional group having a functional group reactive with an amino group and / or a carboxyl group in the resin (B) is at least one selected from the group consisting of a carboxyl group and an acid anhydride group. [7] A polyamide resin composition according to any one of [1] to [6], wherein the resin in the resin (B) having a functional group reactive with an amino group and / or a carboxyl group is at least one selected from the group consisting of (ethylene and / or propylene) / α-olefin copolymers, (ethylene and / or propylene) / (α,β-unsaturated carboxylic acid ester) copolymers, and aromatic vinyl compound / conjugated diene compound block copolymers. [8] A polyamide resin composition according to any one of [1] to [7], wherein the polyamide resin (A1) having structural units derived from the reaction product of pentamethylenediamine and aliphatic dicarboxylic acid is selected from the group consisting of polyamide 56, polyamide 59, polyamide 510, polyamide 513 and polyamide 516.[9] The polyamide resin composition of [3] wherein the polyamide resin (a1) comprises polyamide 56, and the polyamide resin (a2) comprises at least one selected from the group consisting of polyamide 59, polyamide 510, polyamide 513, and polyamide 516.

[10] The polyamide resin composition of any of [1] to [9], comprising 0.10 to 0.60% by mass of a heat-resistant agent (C) in 100% by mass of the polyamide resin composition.

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

[10] , which does not contain fillers.

[12] The polyamide resin composition of any of [1] to

[11] , wherein the water absorption rate of an ISO 294-3 Type D2 test specimen of the polyamide resin composition is 3.0% or less when the specimen is immersed in water at 23°C for 24 hours.

[13] A molded article comprising the polyamide resin composition of any of [1] to

[12] .

[14] A polyamide resin composition comprising a polyamide resin (A) and a resin (B) having a functional group that reacts with an amino group and / or a carboxyl group, wherein the polyamide resin (A) comprises a polyamide resin (a1) having structural units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid having 6 to 8 carbon atoms, and a polyamide resin (a2) having structural units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid having 9 to 16 carbon atoms, wherein the polyamide resin composition comprises 20.0 to 75.0% by mass of the polyamide resin (a1), 20.0 to 75.0% by mass of the polyamide resin (a2), and 2.0 to 7.0% by mass of the resin (B) having a functional group that reacts with an amino group and / or a carboxyl group (excluding the polyamide resin (A)).

[0007] The polyamide resin composition of the present invention has suppressed water absorption, good productivity, and good mechanical properties such as flexural strength and flexural modulus.

[0008] [First aspect of the present invention] The first aspect of the present invention is a polyamide resin composition comprising a polyamide resin (A) and a resin (B) having a functional group reactive with an amino group and / or a carboxyl group, wherein the polyamide resin (A) comprises two or more polyamide resins (A1) having structural units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid, and the polyamide resin composition contains 2.0 to 7.0% by mass of the resin (B) having a functional group reactive with an amino group and / or a carboxyl group in 100% by mass of the polyamide resin composition, and the polyamide resin composition was measured at 400 MHz using deuterated hexafluoroisopropanol as a solvent and tetramethylsilane as a reference substance. １ A polyamide resin composition having a ratio X of 4.74 or more and 5.98 or less, as determined by the following formula (1) in 1H-NMR. (However, resin (B) having a functional group that reacts with the amino group and / or carboxyl group is excluded from the polyamide resin (A).) [(i) + (ii) + (iii)] / (iii) = X ... (1) (In formula (1), (i) is the integral value of a chemical shift of 1.20 to 1.90 ppm, (ii) is the integral value of a chemical shift of 2.05 to 2.50 ppm, and (iii) is the integral value of a chemical shift of 3.15 to 3.50 ppm.)

[0009] In this specification, "one type of polyamide resin" or "one type of polyamide resin" refers to polyamide resins in which the types and content of constituent units contained as monomers are the same. In this specification, the numerical values ​​listed in the numerical range are values ​​obtained by rounding the value to the nearest tenth of the stated value.

[0010] [Polyamide resin (A)] Polyamide resin (A) includes polyamide resin (A1) having structural units derived from the reaction product of pentamethylenediamine and aliphatic dicarboxylic acid, but may optionally also include polyamide 6 (A2).

[0011] <Polyamide resin (A1) having structural units derived from the reaction product of pentamethylenediamine and aliphatic dicarboxylic acid> Polyamide resin (A) contains two or more polyamide resins (A1) having structural units derived from the reaction product of pentamethylenediamine and aliphatic dicarboxylic acid. Polyamide resin (A) may contain three or more polyamide resins (A1). Polyamide resin (A1) is an aliphatic polyamide resin having structural units from a condensate of pentamethylenediamine and aliphatic dicarboxylic acid, and is preferably an aliphatic homopolyamide resin based on structural units from a condensate of pentamethylenediamine and aliphatic dicarboxylic acid. The diamine used in the polycondensation reaction of pentamethylenediamine and aliphatic dicarboxylic acid has pentamethylenediamine as an essential component, but may also contain other diamines to the extent that it does not impair the effects of the present invention. Preferably, it does not contain other diamines.

[0012] It is more preferable that 50% or more of the pentamethylenediamine in the polyamide resin (A1) is derived from biomass raw materials. Polyamide resin (A1) using biomass-derived pentamethylenediamine is an environmentally friendly material because the raw material is plant-derived. Therefore, in the embodiment in which biomass-derived pentamethylenediamine is used in the polyamide resin (A1), the polyamide resin composition of the present invention has the effect of suppressing environmental impact.

[0013] The proportion of biomass-derived carbon in the polyamide resin (A) (hereinafter also referred to as "biomass content") is preferably 50-90%, more preferably 53-88%, and even more preferably 55-85%. When the biomass content is within the above range, the environmental burden is suppressed.

[0014] The biomass content is preferably determined by the following formula (4). The content ratio of polyamide resin (k) in polyamide resin (A) is the ratio (mass ratio) of polyamide resin (k) when the total amount of polyamide resin (A) is considered as 1. The biomass content of polyamide resin (k) can be determined by calculating the percentage of biomass-derived carbon in polyamide resin (k) using radiocarbon (C14) measurement as shown in ASTM D6866-22 Method B (AMS). Catalog values ​​are also acceptable. Polyamide resin (k) refers to each type of polyamide resin in polyamide resin (A).

[0015] Examples of aliphatic dicarboxylic acids include non-alicyclic aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedionic acid, dodecanedionic acid, tridecanedionic acid, tetradecanedionic acid, pentadecanedionic acid, hexadecanedionic acid, octadecanedionic acid, and eicosanedionic acid; and alicyclic dicarboxylic acids such as 1,3- / 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4'-dicarboxylic acid, and norbornanedicarboxylic acid. Among these, non-alicyclic aliphatic dicarboxylic acids are preferred, one selected from the group consisting of adipic acid, azelaic acid, sebacic acid, and tridecanedionic acid is more preferred, and adipic acid or sebacic acid is even more preferred.

[0016] The polyamide resin (A1) having structural units derived from the reaction product of pentamethylenediamine and aliphatic dicarboxylic acid is preferably selected from the group consisting of polyamide 56, polyamide 59, polyamide 510, polyamide 513, and polyamide 516.

[0017] Preferably, the two or more polyamide resins (A1) include a polyamide resin (a1) having structural units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid having 6 to 8 carbon atoms, and a polyamide resin (a2) having structural units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid having 9 to 16 carbon atoms. A copolymerized polyamide resin having both structural units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid having 6 to 8 carbon atoms and structural units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid having 9 to 16 carbon atoms is included in polyamide resin (a2). Polyamide resins (a1) and (a2) may be used individually or in combination of two or more types.

[0018] Polyamide 56 is an example of the polyamide resin (a1).

[0019] Examples of polyamide resins (a2) include polyamide 59, polyamide 510, polyamide 513, and polyamide 516, with polyamide 510 being preferred. Polyamide 510 is an environmentally friendly material because it can use pentamethylenediamine derived from biomass raw materials, as well as sebacic acid derived from biomass raw materials, and the biomass-derived components can be 33% by mass or more, preferably 100% by mass.

[0020] The relative viscosity of one type of polyamide resin (A1) is preferably 1.5 to 5.0, more preferably 2.0 to 4.1, and even more preferably 2.4 to 3.1. Being within this range results in good moldability. The relative viscosity was measured in accordance with JIS K6920-2, by dissolving 1 g of polyamide resin in 100 ml of 96% concentrated sulfuric acid and measuring at 25°C.

[0021] The terminal amino group concentration of one type of polyamide resin (A1) is preferably 8 μmol / g or higher, more preferably 10 to 110 μmol / g, and even more preferably 12 to 70 μmol / g, as determined by neutralization titration after dissolving in a mixed solvent of phenol and methanol. Being within this range allows for good interaction with the functional group-containing resin (B), improves the compatibility between the polyamide resins, and enhances the productivity and mechanical properties of the polyamide resin composition.

[0022] The upper limit of the amount of polyamide resin (a1) blended is preferably 75.0% by mass, more preferably 73.5% by mass, and even more preferably 73.0% by mass, based on 100% by mass of the polyamide resin composition. The lower limit of the amount of polyamide resin (a1) blended is preferably 20.0% by mass, more preferably 22.5% by mass, and even more preferably 40.0% by mass, based on 100% by mass of the polyamide resin composition.

[0023] The upper limit of the amount of polyamide resin (a2) blended is preferably 75.0% by mass, more preferably 73.5% by mass, and even more preferably 55.0% by mass, based on 100% by mass of the polyamide resin composition. The lower limit of the amount of polyamide resin (a1) blended is preferably 20.0% by mass, more preferably 22.5% by mass, and even more preferably 23.0% by mass, based on 100% by mass of the polyamide resin composition.

[0024] The polyamide resin composition preferably contains 20.0 to 75.0% by mass of polyamide resin (a1) and 20.0 to 75.0% by mass of polyamide resin (a2) per 100% by mass, more preferably 22.5 to 73.5% by mass of polyamide resin (a1) and 22.5 to 73.5% by mass of polyamide resin (a2), and even more preferably 40.0 to 73.0% by mass of polyamide resin (a1) and 23.0 to 55.0% by mass of polyamide resin (a2). When the amounts of polyamide resin (a1) and polyamide resin (a2) are within the above ranges, mechanical properties are improved, water absorption is suppressed, and moldability is good.

[0025] The mass ratio of polyamide resin (a1) to polyamide resin (a2) (polyamide resin (a1) / polyamide resin (a2)) is preferably 85 / 15 to 22 / 78, more preferably 80 / 20 to 25 / 75, and even more preferably 75 / 25 to 40 / 60. When the mass ratio of polyamide resin (a1) to polyamide resin (a2) is within the above range, the mechanical properties are improved, the water absorption rate is suppressed, and the moldability is good.

[0026] The amount of polyamide resin (A1) blended is preferably 90.0 to 98.0% by mass, more preferably 92.0 to 97.5% by mass, and even more preferably 93.5 to 97.4% by mass, based on 100% by mass of the polyamide resin composition. When the amount of polyamide resin (A1) is within the above range, both excellent mechanical properties and moldability can be achieved.

[0027] The polyamide resin (A1) is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, even more preferably 99 to 100% by mass, and even more preferably 100% by mass, based on 100% by mass of polyamide resin (A).

[0028] <Polyamide 6(A2)> The polyamide resin (A) may optionally contain polyamide 6(A2). When polyamide 6(A2) is incorporated into the polyamide resin composition, it is preferable from the viewpoint of the dispersibility of various additives. Examples of polyamide 6(A2) include ring-opened polymers of ε-caprolactam.

[0029] The relative viscosity of polyamide 6(A2) is preferably 1.5 to 5.0, more preferably 1.9 to 3.9, and even more preferably 2.2 to 2.8. Being within this range results in good moldability. The relative viscosity was measured in accordance with JIS K6920-2, by dissolving 1 g of polyamide resin in 100 ml of 96% concentrated sulfuric acid and measuring at 25°C.

[0030] The terminal amino group concentration of polyamide 6(A2), as determined by neutralization titration after dissolving in a mixed solvent of phenol and methanol, is preferably 30 μmol / g or more, more preferably 30 to 110 μmol / g, and even more preferably 30 to 70 μmol / g. Being within this range does not impair the functionality and physical properties of the polyamide resin composition.

[0031] The amount of polyamide 6 (A2) added is 0 to 5.0% by mass, preferably 0.05 to 5.0% by mass, and more preferably 0.1 to 3.0% by mass, based on 100% by mass of the polyamide resin composition. When the amount of polyamide 6 (A2) is within the above range, the function and properties of the polyamide resin (A1) are not impaired. As polyamide 6 (A2) is added in small amounts, it does not affect the physical properties of the polyamide resin composition.

[0032] The polyamide resin (A) may contain aliphatic polyamide resins and aromatic polyamide resins other than components (A1) and (A2). When the aliphatic polyamide resins and aromatic polyamide resins other than components (A1) and (A2) are blended, their amount is preferably 0.01 to 2.0% by mass, more preferably 0.05 to 1.5% by mass, and more preferably 0.1 to 1.0% by mass, of 100% by mass of the polyamide resin composition, from the viewpoint of not impairing the function and properties of the polyamide resin composition.

[0033] The upper limit of the amount of polyamide resin (A) is 98.0% by mass, preferably 97.5% by mass, and more preferably 97.0% by mass, based on 100% by mass of the polyamide resin composition. The lower limit of the amount of polyamide resin (A) is 90.0% by mass, preferably 92.0% by mass, and more preferably 93.0% by mass, based on 100% by mass of the polyamide resin composition.

[0034] The amount of polyamide resin (A) blended is preferably 90.0 to 98.0% by mass, more preferably 92.0 to 97.5% by mass, and even more preferably 93.0 to 97.5% by mass, based on 100% by mass of the polyamide resin composition. When the amount of polyamide resin (A) is within the above range, the mechanical properties and moldability are improved.

[0035] <Resin (B) having a functional group that reacts with amino groups and / or carboxyl groups> The polyamide resin composition contains a resin (B) having a functional group that reacts with amino groups and / or carboxyl groups (hereinafter also referred to as "resin (B) having a functional group"). However, the resin (B) having a functional group that reacts with amino groups and / or carboxyl groups excludes polyamide resin (A). "Functional group that reacts with amino groups and / or carboxyl groups" means that the functional group is reactive with amino groups and / or carboxyl groups. Resin (B) has such a functional group. The term "reaction" is not limited to those that form covalent bonds, such as condensation reactions, but also includes interactions such as hydrogen bonds and coordination bonds.

[0036] The resin (B) having functional groups is preferably an olefin resin, polyester resin, polyether resin, or cellulose resin, with olefin resin being more preferred. An olefin resin is a resin having structural units derived from olefins, a copolymer having structural units derived from olefins is preferred, and a copolymer mainly composed of structural units derived from olefins is more preferred.

[0037] Specific examples of the resin in the functional resin (B) include at least one selected from the group consisting of (ethylene and / or propylene) / α-olefin copolymers, (ethylene and / or propylene) / (α,β-unsaturated carboxylic acid ester) copolymers, and aromatic vinyl compound / conjugated diene compound block copolymers.

[0038] The functional group having reactivity with an amino group and / or a carboxyl group refers to a functional group that forms a hydrogen bond, a coordination bond, a covalent bond, or an ionic bond with an amino group and / or a carboxyl group, and is preferably a functional group that forms a covalent bond. Since the polyamide resin has amino groups and carboxyl groups at its terminals, the functional group having reactivity with an amino group and / or a carboxyl group reacts with the amino groups and carboxyl groups of the polyamide resin, improving the compatibility between the polyamide resins, and is considered to contribute to the improvement of the productivity and mechanical properties of the polyamide resin composition. The presence of a functional group having reactivity with an amino group and / or a carboxyl group in an olefin resin having good flexural modulus is considered to contribute to the improvement of mechanical properties such as impact resistance.

[0039] Examples of the functional group of the resin (B) having a functional group include a carboxyl group, an acid anhydride group, a carboxylic acid ester group, a metal carboxylate, a carboxylic acid imide group, a carboxylic acid amide group, an epoxy group, an amino group, a carbodiimide group, etc. A carboxyl group, an acid anhydride group, and a carboxylic acid ester group are preferable, and at least one selected from the group consisting of a carboxyl group and an acid anhydride group is more preferable.

[0040] Examples of the method for introducing a functional group into an olefin resin include: (i) a method of copolymerizing a copolymerizable monomer having a functional group during the polymerization of the olefin resin; (ii) a method of introducing a functional group into the molecular chain or molecular terminal of the olefin resin using a polymerization initiator, a chain transfer agent, etc.; (iii) a method of grafting a compound (graft compound) having a functional group capable of grafting with the said functional group onto the olefin resin. These introduction methods can be used alone or in combination as appropriate.

[0041] Examples of copolymerizable monomers having the functional groups, the graft compounds, etc. include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endobicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic acid and metal salts of these carboxylic acids, monomethyl maleate, monomethyl itaconic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, and methyl methacrylate. Examples include 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo-[2.2.1]-5-hepten-2,3-dicarboxylic acid anhydride, maleimide, N-ethyl maleimide, N-butyl maleimide, N-phenyl maleimide, acrylamide, methacrylamide, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and glycidyl citraconic acid. These can be used individually or in combination of two or more. Among these, at least one selected from the group consisting of maleic anhydride, itaconic anhydride, and citraconic anhydride is preferred.

[0042] The polymerization initiator is not particularly limited, but examples include inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate; ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methylacetoacetate peroxide, and acetylacetone peroxide; hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and 2-(4-methylcyclohexyl)-propane hydroperoxide; di-t-butyl peroxide, t-butylcumyl peroxide, and di Dialkyl peroxides such as cumyl peroxide, α,α'-bis(t-butylperoxy)p-diisopropylbenzene, α,α'-bis(t-butylperoxy)p-isopropylhexine, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3, t-butylperoxyacetate, t-butylperoxydiethylacetate, t-butylperoxylaurate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl-peroxyisobutyrate, t-butylperoxypivalate, t-butylperoxyneodecanoate, 2,4,4-trimethylpentyl-2-peroxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-Trimethylcyclohexanoate, t-Butyl peroxybenzoate, t-Butyl peroxymaleic acid, t-Amyl peroxyneodecanoate, t-Amyl peroxypivalate, t-Amyl peroxy-2-ethylhexanoate, t-Amyl peroxyn-octoate, t-Amyl peroxyacetate, t-Amyl peroxyisononanoate, t-Amyl peroxybenzoate, Cumil peroxyneohexanoate, Cumil peroxyoctoate, Cumil peroxyneodecanoate, t-Hexyl peroxypivalate, t-Hexyl peroxyneohexanoate, t-Butyl peroxyisopropyl carbonate, t-Butyl peroxy Peroxy esters such as 2-ethylhexyl carbonate, n-butyl-4,4-bis(t-butylperoxy)balate, 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)octane, and other peroxyketals, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,3,5-trimethylcyclohexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,Diacyl peroxides such as 4-dichlorobenzoyl peroxide, m-toluyl peroxide, dibenzoyl peroxide, di-n-propyl peroxydicarbonate, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-t-butyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, t-butyl peroxy 2-ethylhexyl carbonate, t-amyl peroxyisopropyl carbonate, t-amyl peroxy 2-ethylhexyl carbonate, bis-( Peroxydicarbonates such as 4-t-butylcyclohexyl) peroxydicarbonate, diacetyl peroxydicarbonate, dimyristil peroxydicarbonate, di-methoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, di-allyl peroxydicarbonate, acetylcyclohexyl sulfonyl peroxide, t-butyl peroxyallyl carbonate, and other organic peroxides, 2,2'-azobisisobutyronitrile, and 2,2'-azobis(2-methylbutyronitrile) ), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis(2-methylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis[2-(hydroxymethyl)propionitrile], 4,4'-azobis(4-cyanopentanoic acid), 1,1'-azobis(cyclohexane-1-carbonitride), 1,1'- Azobis-(cyclohexane-1-carbonitride), 2,2'-azobis(2-methyl-N-2-propenylpropanamide), 1-[(1-cyano-1-methyl)azo]formamide, 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide), 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2,2'-azobis[2-methyl-N-[2-hydroxyethyl]propionamide], 2,2'-Azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis(N-N'-dimethylenebisobutylamidine) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane} dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine], and other azo compounds, etc. These can be used alone or in combination of two or more kinds.

[0043] The chain transfer agent is not particularly limited, and examples thereof include alkyl mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, t-decyl mercaptan, n-decyl mercaptan, and n-octyl mercaptan, and alkyl ester mercaptans such as 2-ethylhexyl thioglycolate.

[0044] Specific examples of the resin (B) having a functional group include (ethylene and / or propylene) / (α,β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymers, (ethylene and / or propylene) / α-olefin copolymers into which the functional group has been introduced, and (ethylene and / or propylene) / (α,β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymers into which the functional group has been introduced. These can be used alone or in combination of two or more kinds. Among these, at least one selected from the group consisting of maleic anhydride, itaconic anhydride, and citraconic anhydride may be introduced into the (ethylene and / or propylene) / (α,β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymer, and at least one selected from the group consisting of (ethylene and / or propylene) / α-olefin copolymers into which at least one selected from the group consisting of maleic anhydride, itaconic anhydride, and citraconic anhydride has been introduced is preferable.

[0045] The (ethylene and / or propylene) / (α,β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymer is a resin (B) having functional groups into which carboxyl groups and / or carboxylic acid ester groups have been introduced by method (i) above. Further functional groups may be introduced by methods (ii), (iii), etc. above.

[0046] The (ethylene and / or propylene) / α-olefin copolymer is at least one selected from the group consisting of copolymers of ethylene and α-olefins having 3 or more carbon atoms, copolymers of ethylene and propylene and α-olefins having 3 or more carbon atoms, and copolymers of propylene and α-olefins having 4 or more carbon atoms. Examples of α-olefins having 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-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 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. α-olefins having four or more carbon atoms are those among these that have four or more carbon atoms. These may be used individually or in combination of two or more.

[0047] The copolymer may also be a copolymer of multiple types of polyenes, such as non-conjugated dienes. 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-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1,4,8-decatriene (DMDT), and dicyclopene. Examples include tadiene, cyclohexadiene, cyclooctadiene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylidene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, and 2-propenyl-2,5-norbornadiene. These may be used individually or in combination of two or more.

[0048] (Ethylene and / or propylene) / (α,β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymers are polymers obtained 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., of these α,β-unsaturated carboxylic acids. These may be used individually or in combination of two or more.

[0049] Preferably, the resin (B) having a functional group is an ethylene / α-olefin copolymer into which the functional group has been introduced. From the viewpoint of mechanical strength and impact resistance when formed into a molded article, an ethylene / α-olefin copolymer into which at least one selected from the group consisting of maleic anhydride, itaconic anhydride, and citraconic anhydride has been introduced is more preferable, an ethylene / α-olefin copolymer into which maleic anhydride has been introduced is even more preferable, and an ethylene / 1-butene copolymer into which maleic anhydride has been introduced is particularly preferable.

[0050] The functional group content (functional group concentration) in the functional group-containing resin (B) is preferably greater than 25 μmol / g and less than 120 μmol / g, more preferably 35 μmol / g or more and less than 110 μmol / g, and even more preferably 40 μmol / g or more and 100 μmol / g or less, expressed as the number of moles of functional group (μmol) / mass of the functional group-containing resin (B) (g). When the functional group content is within the above range, the compatibility between polyamide resins can be improved, and the productivity and mechanical properties of the polyamide resin composition can be improved. The functional group content in the functional group-containing resin (B) is measured, for example, when the functional group is a carboxyl group, an acid anhydride group, and / or a carboxylic acid ester group, by neutralization titration with a 0.1 N KOH ethanol solution using a sample solution prepared with toluene and ethanol, with phenolphthalein as an indicator.

[0051] When two or more functional group-containing resins (B) with different functional group content are used, the functional group content in the functional group-containing resins (B) is measured by the method described above. However, if each functional group-containing resin (B) contains two or more functional group-containing resins with different functional group content, and the content of each functional group and its mixing ratio are known, the average value (average functional group content) calculated by summing the measured values ​​of the content of each functional group multiplied by its mixing ratio may also be considered as the functional group content of the functional group-containing resin (B).

[0052] The functional resin (B) preferably has a flexural modulus of 500 MPa or less, as measured in accordance with ASTM D-790. When the flexural modulus is within the above range, impact resistance can be imparted to the polyamide resin composition.

[0053] The functional resin (B) preferably has an MFR of 0.1 g / 10 min or more and 10.0 g / 10 min or less, more preferably greater than 1.0 g / 10 min and less than 5.0 g / 10 min, even more preferably greater than 1.0 g / 10 min and 3.0 g / 10 min or less, and particularly preferably greater than 1.0 g / 10 min and 2.5 g / 10 min or less, as measured in accordance with ASTM D1238 at a temperature of 230°C and a load of 2160 g. When the MFR is within the above range, the fluidity of the polyamide resin composition is not impaired and moldability is good.

[0054] The upper limit of the amount of resin (B) having functional groups is 7.0% by mass, more preferably 6.0% by mass, and more preferably 5.0% by mass, per 100% by mass of the polyamide resin composition. The lower limit of the amount of resin (B) having functional groups is 1.5% by mass, more preferably 2.0% by mass, even more preferably 2.3% by mass, and particularly preferably 2.5% by mass, per 100% by mass of the polyamide resin composition.

[0055] The specific range of the amount of resin (B) having functional groups is 2.0 to 7.0% by mass, preferably 2.3 to 6.0% by mass, and more preferably 2.5 to 5.0% by mass, based on 100% by mass of the polyamide resin composition. When the content of resin (B) having functional groups is within the above range, the productivity, moldability, and mechanical properties of the polyamide resin composition are good.

[0056] <Heat-resistant agent (C)> The polyamide resin composition preferably contains a heat-resistant agent (C) as an optional component. Here, if the functional agent is a heat-resistant agent, organic or inorganic heat-resistant agents can be used depending on the purpose, and these may be used individually or in combination of two or more types. A heat-resistant agent is a component that suppresses thermal oxidation and thermal degradation of the polyamide resin, and in this sense, it also includes what is called an antioxidant.

[0057] Examples of organic heat-resistant agents include phenolic compounds, phosphorus compounds, sulfur compounds, and nitrogen compounds. These may be used individually or in combination of two or more. Hindered phenolic organic compounds are preferred as phenolic compounds. In this specification, hindered phenol refers to a compound having a substituent at the ortho position of the hydroxyl group of phenol. Phosphorus ester compounds of hindered phenols and hypophosphorous ester compounds of hindered phenols are preferred as phosphorus compounds.

[0058] The heat-resistant agent is preferably a combination of an inorganic compound and a nitrogen-containing compound, or an inorganic compound. Examples of inorganic compounds include metal halides and inorganic compounds other than metal halides.

[0059] Metal halides are compounds of halogens and metals. Examples of halogens include fluorine, chlorine, bromine, and iodine. Examples of metals include Group 1 elements (alkali metals), Group 2 elements (alkaline earth metals), and Group 3 to Group 12 elements (e.g., transition metals). Preferably, the metal in a metal halide is a Group 1 element (alkali metal) or a Group 11 element (copper group). Examples of metal halides when the metal is a Group 1 element (alkali metal) include potassium iodide, potassium bromide, potassium chloride, sodium iodide, or sodium chloride. Examples of metal halides when the metal is a Group 11 element (copper group) include cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, and cupric iodide. More preferably, the metal halide is potassium iodide and / or cuprous iodide, and a mixture of potassium iodide and cuprous iodide is even more preferable.

[0060] Inorganic compounds other than metal halides include metals, metal oxides, metal hydroxides, metal nitrides, metal phosphate salts, metal phosphite salts, metal carbonate salts, metal silicate salts, metal titanate salts, metal borate salts, metal sulfate salts, and metal nitrate salts.

[0061] Examples of nitrogen-containing compounds include melamine, benguanamine, dimethylolurea, and cyanuric acid.

[0062] When a heat-resistant agent (C) is included, the amount of heat-resistant agent (C) is preferably 0.10 to 0.60% by mass, more preferably 0.15 to 0.55% by mass, and more preferably 0.20 to 0.50% by mass, of 100% by mass of the polyamide resin composition.

[0063] <Colorants> The polyamide resin composition may contain a colorant as an optional component. A colorant is a component whose primary function is to color the polyamide resin composition. Examples of colorants include carbon black, nigrosine, titanium dioxide, and iron oxide. These may be used individually or in combination of two or more.

[0064] <Other Optional Components> The polyamide resin composition may contain optional components other than those listed above, as long as they do not impair the effects of the present invention. Optional components include resins other than components (A) and (B), and functional additives other than component (C).

[0065] Examples of resins other than components (A) and (B) include polyolefin resins such as low-density, medium-density, and high-density polyethylene, polypropylene, and polybutene; modified polyolefin resins having functional groups not corresponding to component (B); polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyester elastomers; vinyl aromatic resins such as polystyrene, ABS resin, and AS resin; polyether resins; polyurethane resins; acrylic resins; polyimide resins; polycarbonate resins; polyacetal; polyvinyl alcohol; and rosin resins.

[0066] When resins other than components (A) and (B) are blended, their amount is preferably 0.01 to 2.0% by mass, more preferably 0.05 to 1.5% by mass, and more preferably 0.1 to 1.0% by mass, of 100% by mass of the polyamide resin composition, from the viewpoint of not impairing the functions and properties of the polyamide resin composition.

[0067] Functionality imparters include various additives commonly incorporated into polyamide resin compositions. Specific examples of functional imparters include plasticizers, foaming agents, weathering agents, crystal nucleating agents, antioxidants, crystallization accelerators, mold release agents, antistatic agents, dispersants, flame retardants, flame retardant aids, spreading agents, dyes, colorants, lubricants, and the like.

[0068] Other functional additives not mentioned above include, for example, the components described in Japanese Patent Publication No. 2002-370551. Each optional component may be a single component or a combination of two or more components.

[0069] It is preferable that the polyamide resin composition does not contain fillers, as this would increase the viscosity of the resulting composition, impair its fluidity, and worsen its moldability. "Filler-free" means substantially filler-free; specifically, the filler content is 0 to 5% by mass, preferably 0 to 0.5% by mass or less, and more preferably 0% by mass, based on 100% by mass of the polyamide resin composition.

[0070] [Polyamide resin composition] The polyamide resin composition was measured at 400 MHz using deuterated hexafluoroisopropanol as the solvent and tetramethylsilane as the reference substance. １ By setting the ratio X, determined by the following formula (1) in H-NMR, within the following range, it is possible to achieve a balance between the mechanical properties, water absorption rate, moldability, and dimensional stability of the polyamide resin composition or its molded product. The preferred range and method for determining the ratio X, determined by the following formula (1), are as follows.

[0071] In the polyamide resin composition of the present invention, the upper limit of the ratio X determined by the following formula (1) is 5.98, preferably 5.97, more preferably 5.91, and even more preferably 5.59. Also, in the polyamide resin composition, the lower limit of the ratio X determined by the following formula (1) is 4.74, preferably 4.75, more preferably 4.82, and even more preferably 4.91.

[0072] In the polyamide resin composition of the present invention, the ratio X determined by the following formula (1) is 4.74 or more and 5.98 or less, preferably 4.75 or more and 5.97 or less, more preferably 4.82 or more and 5.91 or less, and even more preferably 4.91 or more and 5.59 or less.

[0073] [(i) + (ii) + (iii)] / (iii) = X ... (1) (In equation (1), the polyamide resin composition was measured at 400 MHz using deuterated hexafluoroisopropanol as the solvent and tetramethylsilane as the reference substance.) １ In ¹H-NMR, (i) is the integral value for chemical shifts from 1.20 to 1.90 ppm, (ii) is the integral value for chemical shifts from 2.05 to 2.50 ppm, and (iii) is the integral value for chemical shifts from 3.15 to 3.50 ppm.

[0074] In polyamide resin (A), a methylene group (CH) adjacent to a carbonyl group (C=O) ２ The peak appears in the chemical shift of (ii), and is adjacent to the methylene group (CH) adjacent to the amino group (NH). ２ The peak at (iii) appears in the chemical shift of (iii) and is a methylene group (CH) that is not adjacent to a carbonyl group (C=O) or an amino group (NH). ２ The peak of (i) is presumed to appear in the chemical shift of (i). The presence of components other than the polyamide resin in the polyamide resin composition of the present invention does not affect the value of X because the peaks of these components do not overlap with the chemical shifts of (i) to (iii), or preferably, even if the peaks overlap, the amount is so small. Therefore, the value X represented by formula (1) can be said to represent the properties of the polyamide resin (A).

[0075] In other words, the value X expressed by equation (1) can be said to be the ratio of the number of methylene groups to the number of amide groups in polyamide resin (A), and the two values ​​are approximately the same. The ratio of the number of methylene groups to the number of amide groups in polyamide resin (A) can be expressed by the following equation (2). In equation (2), the content ratio of polyamide resin (k) in polyamide resin (A) is the ratio (mass ratio) of polyamide resin (k) when the total amount of polyamide resin (A) is set to 1. Polyamide resin (k) refers to each individual type of polyamide resin in polyamide resin (A).

[0076] Therefore, the ratio of the number of methylene groups to the number of amide groups is preferably 4.74 or more and 5.98 or less, more preferably 4.75 or more and 5.97 or less, even more preferably 4.82 or more and 5.91 or less, and particularly preferably 4.91 or more and 5.59 or less.

[0077] The polyamide resin composition has improved mechanical properties, suppressed water absorption, and good moldability, provided that the ratio X determined by formula (1) is within the above range, that is, the ratio of the number of methylene groups to the number of amide groups in the polyamide resin (A).

[0078] The ratio X obtained by formula (1) above and the ratio of the number of methylene groups to the number of amide groups in polyamide resin (A) can be achieved by adjusting the content of the polyamide resin (a1), polyamide resin (a2), and any other polyamide resins that constitute polyamide resin (A).

[0079] The polyamide resin composition preferably has a water absorption rate of 3.0% or less, more preferably 2.90% or less, and even more preferably 2.80% or less, when an ISO 294-3 Type D2 test specimen of the polyamide resin composition is immersed in water at 23°C for 24 hours, as determined by the following formula (3): Water absorption rate = (Weight of test specimen after immersion - Weight of test specimen before immersion) / Weight of test specimen before immersion * 100 (3)

[0080] The water absorption rate being within the above range improves mechanical properties and moldability. The water absorption rate being within the above range is adjusted by setting the value X represented by formula (1) above to a specific range for the polyamide resin (A) in the polyamide resin composition, that is, by setting the ratio of the number of methylene groups to the number of amide groups in the polyamide resin (A) to a specific range, thereby adjusting the proportion of hydrophilic amide groups in the polyamide resin.

[0081] <Method for Manufacturing Polyamide Resin Composition> There are no particular restrictions on the method for manufacturing the polyamide resin composition, as long as it can knead each component. For example, methods using a twin-screw kneader, twin-screw extruder, single-screw extruder, multi-screw extruder, etc. may be used. For example, a method in which all raw materials are mixed and then melt-kneaded using a twin-screw extruder, a method in which some raw materials are mixed, melt-kneaded, and then the remaining raw materials are mixed and melt-kneaded again, or a method in which some raw materials are mixed, and the remaining raw materials are mixed using a side feeder during melt-kneading. Any of these methods may be used.

[0082] [Uses of Polyamide Resin Compositions] Polyamide resin compositions are not particularly limited and can be used in the manufacture of molded articles using known methods such as injection molding, extrusion molding, blow molding, rotational molding, vacuum molding, and pressure molding. Furthermore, molded articles containing polyamide resin compositions can be used in parts requiring sliding properties, general merchandise, and furniture. Examples of parts requiring sliding properties include those intended for dynamic applications such as gears, cams, pulleys, bearings, bearing retainers, door checks, timing chain guides, and cable / hose support and guidance devices. They can also be used in other components requiring similar functions.

[0083] [Second Aspect of the Invention] A second aspect of the present invention is a polyamide resin composition comprising a polyamide resin (A) and a resin (B) having a functional group reactive with an amino group and / or a carboxyl group, wherein the polyamide resin (A) comprises a polyamide resin (a1) having structural units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid having 6 to 8 carbon atoms, and a polyamide resin (a2) having structural units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid having 9 to 16 carbon atoms, and the polyamide resin composition comprises 20.0 to 75.0% by mass of the polyamide resin (a1), 20.0 to 75.0% by mass of the polyamide resin (a2), and 2.0 to 7.0% by mass of the resin (B) having a functional group reactive with an amino group and / or a carboxyl group, provided that the resin (B) having a functional group reactive with an amino group and / or a carboxyl group is excluded from the polyamide resin (A).

[0084] A second aspect of the present invention preferably includes optional components similar to those in the first aspect of the present invention, such as a polyamide resin (A2) and a heat-resistant agent (C). Preferred embodiments of the polyamide resin (A), polyamide resin (A1), resin (B) having a functional group reactive with an amino group and / or a carboxyl group, polyamide resin (a1), polyamide resin (a2), and other optional components, as well as their content in the polyamide resin composition, are the same as in the first aspect of the present invention. The second aspect of the present invention satisfies the value of X in formula (1) and the number of amide groups in the polyamide resin (A) with respect to the number of methylene groups. The water absorption rate, manufacturing method, and uses of the polyamide resin composition are also the same as in the first aspect of the present invention.

[0085] [Third Aspect of the Invention] A third aspect of the present invention is a polyamide resin composition comprising a polyamide resin (A) and a resin (B) having a functional group that reacts with an amino group and / or a carboxyl group, wherein the polyamide resin (A) comprises two or more polyamide resins (A1) having structural units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid, the polyamide resin composition contains 2.0 to 7.0% by mass of the resin (B) having a functional group that reacts with an amino group and / or a carboxyl group in 100% by mass, and the ratio of the number of methylene groups to the number of amide groups in the polyamide resin (A), as determined by the following formula (2), is 4.74 or more and 5.98 or less (however, the resin (B) having a functional group that reacts with an amino group and / or a carboxyl group excludes the polyamide resin (A)). (In formula (2), the content ratio of polyamide resin (k) in polyamide resin (A) is the ratio (mass ratio) of polyamide resin (k) when the total amount of polyamide resin (A) is set to 1.)

[0086] A third aspect of the present invention preferably includes optional components similar to those in the first aspect of the present invention, such as a polyamide resin (A2) and a heat-resistant agent (C). Preferred embodiments of the polyamide resin (A), polyamide resin (A1), resin having a functional group reactive with an amino group and / or a carboxyl group (B), polyamide resin (a1), polyamide resin (a2), and other optional components, as well as their content in the polyamide resin composition, are the same as in the first aspect of the present invention. The water absorption rate, manufacturing method, and uses of the polyamide resin composition are also the same as in the first aspect of the present invention.

[0087] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0088] <<Measurement Method and Evaluation>> ○ was considered a pass, and × was considered a fail. (1) Productivity (Strand Take-Up Stability) The molten mixture of polyamide resin composition was extruded into strands using a twin-screw molten compounder, and the take-up stability was visually confirmed and evaluated according to the following criteria. ○: Small die swell, stable strand take-up possible, excellent productivity. ×: Large die swell, strand take-up impossible, poor productivity.

[0089] (2) Biomass content of polyamide resin (A) The biomass content of polyamide resin (A) in the polyamide resin composition was calculated using the following formula. The biomass content of polyamide resin (k) was determined by calculating the percentage of biomass-derived carbon in polyamide resin (k) by radiocarbon (C14) measurement as shown in ASTM D6866-22 Method B (AMS). The content ratio of polyamide resin (k) in polyamide resin (A) is the ratio (mass ratio) of polyamide resin (k) when the total amount of polyamide resin (A) is considered as 1. ○: Biomass content of 50% or more, high level of environmental consideration. ×: Biomass content of less than 50%, low level of environmental consideration.

[0090] (3) Water absorption rate A Type D2 test specimen of the polyamide resin composition prepared in accordance with ISO 294-3 was immersed in water at 23°C for 24 hours, and the water absorption rate was determined and evaluated using the following formula (3). Water absorption rate = (Weight of test specimen after immersion - Weight of test specimen before immersion) / Weight of test specimen before immersion × 100 (3) ○: Water absorption rate is 3.0% or less, water absorption is suppressed. ×: Water absorption rate is greater than 3.0%, water absorption is not suppressed.

[0091] (4) Bending strength and flexural modulus Type B test specimens of the polyamide resin composition were prepared in accordance with ISO 294-1, and bending tests were conducted in a 23°C atmosphere in accordance with ISO 178. Bending strength was evaluated according to the following criteria: ○: Bending strength of 90 MPa or more, excellent bending strength. ×: Bending strength less than 90 MPa, poor bending strength. Flexural modulus was evaluated according to the following criteria: ○: Flexural modulus of 2050 MPa or more, excellent flexural modulus. ×: Flexural modulus of 2050 MPa or less, poor flexural modulus.

[0092] The components used in the examples and comparative examples are as follows: PA56: Polyamide 56, relative viscosity 2.78, terminal amino group concentration 49.7 μmol / g, biomass content 47%, manufactured by Cathay. PA510: Polyamide 510, relative viscosity 2.57, terminal amino group concentration 14.2 μmol / g, biomass content 100%, manufactured by Cathay. Resin (1): Tuffmer (registered trademark) MH5020, maleic anhydride-modified ethylene / 1-butene copolymer, acid anhydride group concentration: 100 μmol / g, manufactured by Mitsui Chemicals, Inc. Resin (2): Tuffmer (registered trademark) MH5010, maleic anhydride-modified ethylene / 1-butene copolymer, acid anhydride group concentration: 50 μmol / g, manufactured by Mitsui Chemicals, Inc. Heat-resistant agent: Cuprous iodide / potassium iodide = 1 / 6 (mass ratio) (mixture) Spreading agent: The relative viscosity of polyoxyethylene polyhydric alcohol fatty acid ester polyamide 56 and polyamide 510 was measured in accordance with JIS K6920-2, by dissolving 1 g of polyamide resin in 100 ml of 96% concentrated sulfuric acid and measuring at 25°C. The terminal amino group concentration of polyamide 56 and polyamide 510 was determined by neutralization titration after dissolving the polyamide resin in a mixed solvent of phenol and methanol.

[0093] In Table 1, X and the number of methylene groups / amide groups are as follows. The value of X and the value of the number of methylene groups / amide groups are approximately the same. [(i) + (ii) + (iii)] / (iii) = X ... (1) (In (1), the polyamide resin composition was measured at 400 MHz using deuterated hexafluoroisopropanol as the solvent and tetramethylsilane as the reference substance. １ In ¹H-NMR, (i) is the integral value for chemical shifts from 1.20 to 1.90 ppm, (ii) is the integral value for chemical shifts from 2.05 to 2.50 ppm, and (iii) is the integral value for chemical shifts from 3.15 to 3.50 ppm.

[0094] The ratio of methylene groups to amide groups is the ratio of methylene groups to amide groups for polyamide resin (A). In formula (2), the content ratio of polyamide resin (k) in polyamide resin (A) is the ratio (mass ratio) of polyamide resin (k) when the total amount of polyamide resin (A) is set to 1.

[0095] [Examples 1-6, Comparative Examples 1-4] Each component listed in Table 1 was melt-kneaded in a TEX34αIII twin-screw kneader manufactured by Japan Steel Works Ltd. to produce the target polyamide resin composition pellets. Unless otherwise specified in the evaluation method, the obtained pellets were injection-molded at a cylinder temperature of 290°C and a mold temperature of 80°C to produce various test pieces, and their various physical properties were evaluated. For Comparative Examples 3 and 4, which had poor productivity, it was not possible to produce pellets, and therefore test pieces could not be prepared and various physical properties could not be evaluated. In Table 1, the content of each component is the value with the polyamide resin composition as 100% by mass.

[0096]

[0097] Examples 1 to 6 exhibit good productivity, biomass content, water absorption rate, flexural strength, and flexural modulus. From the viewpoint of water absorption rate, Examples 2, 5, and 6 are superior because the values ​​of formulas (1) and (2) are large. From the viewpoint of mechanical strength expressed as flexural strength and flexural modulus, Examples 1, 3, 4, and 5 are superior because the values ​​of formulas (1) and (2) are small. Comparative Example 1 uses only one type of polyamide resin, which has constituent units derived from the reaction product of pentamethylenediamine and aliphatic dicarboxylic acid, so the value X of formula (1) is lower than that of the present invention, resulting in a lower biomass content and less environmental consideration, as well as a higher water absorption rate than the examples.

[0098] Comparative Example 2 contains only one type of polyamide resin having structural units derived from the reaction product of pentamethylenediamine and aliphatic dicarboxylic acid. Therefore, the value X in formula (1) can be said to be higher than that of the present invention from the value in formula (2), and its flexural strength and flexural modulus are smaller than those of the example.

[0099] Comparative Examples 3 and 4 either do not contain resin (B) having functional groups, or contain only a small amount of it, resulting in large die swells and strands that cannot be taken up, leading to insufficient productivity.

[0100] The polyamide resin composition of the present invention is suitably used as a molded article for automotive parts, furniture, and general merchandise.

Claims

1. A polyamide resin composition comprising a polyamide resin (A) and a resin (B) having a functional group reactive with an amino group and / or a carboxyl group, wherein the polyamide resin (A) comprises two or more polyamide resins (A1) having structural units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid, and the polyamide resin composition contains 2.0 to 7.0% by mass of the resin (B) having a functional group reactive with an amino group and / or a carboxyl group in 100% by mass of the polyamide resin composition, and the polyamide resin composition was measured at 400 MHz using deuterated hexafluoroisopropanol as a solvent and tetramethylsilane as a reference substance. １ A polyamide resin composition having a ratio X of 4.74 or more and 5.98 or less, as determined by the following formula (1) in ¹H-NMR (however, resin (B) having a functional group reactive with the amino group and / or carboxyl group is excluded from polyamide resin (A)). [(i) + (ii) + (iii)] / (iii) = X ... (1) (In formula (1), (i) is the integral value of chemical shift 1.20 to 1.90 ppm, (ii) is the integral value of chemical shift 2.05 to 2.50 ppm, and (iii) is the integral value of chemical shift 3.15 to 3.50 ppm.) 2. A polyamide resin composition comprising a polyamide resin (A) and a resin (B) having a functional group that reacts with an amino group and / or a carboxyl group, wherein the polyamide resin (A) comprises two or more polyamide resins (A1) having constituent units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid, the polyamide resin composition contains 2.0 to 7.0% by mass of the resin (B) having a functional group that reacts with an amino group and / or a carboxyl group in 100% by mass, and the ratio of the number of methylene groups to the number of amide groups in the polyamide resin (A), as determined by the following formula (2), is 4.74 or more and 5.98 or less (however, the resin (B) having a functional group that reacts with an amino group and / or a carboxyl group excludes the polyamide resin (A)). (In formula (2), the content ratio of polyamide resin (k) in polyamide resin (A) is the ratio (mass ratio) of polyamide resin (k) when the total amount of polyamide resin (A) is set to 1.) 3. The polyamide resin composition according to claim 1 or 2, wherein the polyamide resin (A) comprises a polyamide resin (a1) having structural units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid having 6 to 8 carbon atoms, and a polyamide resin (a2) having structural units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid having 9 to 16 carbon atoms.

4. The polyamide resin composition according to claim 3, comprising 20.0 to 75.0% by mass of the polyamide resin (a1) and 20.0 to 75.0% by mass of the polyamide resin (a2) in 100% by mass of the polyamide resin composition.

5. The polyamide resin composition according to claim 1 or 2, wherein the polyamide resin (A) is present in an amount of 90.0 to 98.0% by mass in 100% by mass of the polyamide resin composition.

6. The polyamide resin composition according to claim 1 or 2, wherein the functional group having a functional group that is reactive with an amino group and / or a carboxyl group in the resin (B) is at least one selected from the group consisting of a carboxyl group and an acid anhydride group.

7. The polyamide resin composition according to claim 1 or 2, wherein the resin (B) having a functional group that is reactive with an amino group and / or a carboxyl group is at least one selected from the group consisting of (ethylene and / or propylene) / α-olefin copolymers, (ethylene and / or propylene) / (α,β-unsaturated carboxylic acid ester) copolymers, and aromatic vinyl compound / conjugated diene compound block copolymers.

8. The polyamide resin composition according to claim 1 or 2, wherein the polyamide resin (A1) having constituent units derived from the reaction product of pentamethylenediamine and aliphatic dicarboxylic acid is selected from the group consisting of polyamide 56, polyamide 59, polyamide 510, polyamide 513 and polyamide 516.

9. The polyamide resin composition according to claim 3, wherein the polyamide resin (a1) comprises polyamide 56, and the polyamide resin (a2) comprises at least one selected from the group consisting of polyamide 59, polyamide 510, polyamide 513, and polyamide 516.

10. The polyamide resin composition according to claim 1 or 2, comprising 0.10 to 0.60% by mass of a heat-resistant agent (C) in 100% by mass of the polyamide resin composition.

11. A polyamide resin composition according to claim 1 or 2, which does not contain fillers.

12. The polyamide resin composition according to claim 1 or 2, wherein the water absorption rate of an ISO 294-3 Type D2 test specimen of the polyamide resin composition is 3.0% or less when the test specimen is immersed in water at 23°C for 24 hours.

13. A molded article comprising the polyamide resin composition according to claim 1 or 2.

14. A polyamide resin composition comprising a polyamide resin (A) and a resin (B) having a functional group reactive with an amino group and / or a carboxyl group, wherein the polyamide resin (A) comprises a polyamide resin (a1) having structural units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid having 6 to 8 carbon atoms, and a polyamide resin (a2) having structural units derived from a reaction product of pentamethylenediamine and an aliphatic dicarboxylic acid having 9 to 16 carbon atoms, wherein the polyamide resin composition comprises 20.0 to 75.0% by mass of the polyamide resin (a1), 20.0 to 75.0% by mass of the polyamide resin (a2), and 2.0 to 7.0% by mass of the resin (B) having a functional group reactive with an amino group and / or a carboxyl group (excluding the polyamide resin (A)).

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