JP2022143428A - Resin composition and molding - Google Patents

Abstract

To provide a polyamide resin composition that has excellent impact resistance particularly at low temperatures and also has excellent thermal degradation resistance, and a molding thereof.SOLUTION: A resin composition contains a polyamide resin (A), a rubber-containing graft polymer having an epoxy group (B), and a polymer containing a carboxy group and/or a derivative thereof (C).SELECTED DRAWING: None

Description

The present invention relates to resin compositions and molded articles.

Polyamide resins are widely used for automobile parts, electric/electronic parts, industrial materials, etc., because they are excellent in properties such as heat deformation resistance, chemical resistance, and abrasion resistance. In particular, it is widely used as automobile parts, such as engine peripheral parts such as intake manifolds, radiator tanks, canisters and engine covers, and battery and motor peripheral parts such as heat sinks and connectors.

BACKGROUND ART In recent years, in order to improve the fuel efficiency of automobiles, weight reduction and downsizing of automobile bodies have been carried out. As a result, there is a demand for thinner resin parts, and the use environment temperature tends to rise due to the higher density of the parts. That is, there is an increasing demand for a durable material that has high impact resistance per unit volume and is less likely to deteriorate even when used for a long time under high temperature conditions of 100° C. or higher.
However, conventional polyamide resins are insufficient in impact resistance, particularly in low-temperature conditions, and in heat deterioration resistance, and their application development is currently limited.

Many proposals have been made as methods for improving the impact resistance of polyamide resins. Patent Document 2 proposes a method of blending an olefin-maleic anhydride copolymer with a polyamide resin. Further, Patent Document 3 proposes a method of blending a polyorganosiloxane-based graft copolymer with a polyamide resin.

In addition, many proposals have been made as a method for improving the heat deterioration resistance of polyamide resins. A method of blending an alkali metal compound and an ethylene-maleic anhydride copolymer with a resin has been proposed.

JP-A-59-131649 Japanese Patent Publication No. 2014-503003 JP-A-5-98115 Japanese Patent Publication No. 2008-527129 JP 2016-153459 A

However, the techniques described in Patent Documents 1 to 5 are insufficient in impact resistance, particularly in low temperature impact resistance and heat deterioration resistance.

Therefore, in the present invention, in view of the above-mentioned problems of the prior art, a polyamide resin composition and a molded article thereof, which are excellent in impact resistance, particularly in low-temperature impact resistance, and also excellent in heat deterioration resistance, are provided. intended to provide

That is, the gist of the present invention is as follows.
[1] A resin composition comprising a polyamide resin (A), a rubber-containing graft polymer (B) having an epoxy group, and a polymer (C) containing a carboxy group and/or a derivative thereof.
[2] The ratio of the rubber-containing graft polymer (B) to 100 parts by weight of the polyamide resin (A) is 0.1 to 30 parts by weight, and the ratio of the polymer (C) is 0.1 to 10 parts by weight. The resin composition according to [1], which is a part.
[3] The resin composition according to [1] or [2], wherein the rubber-containing graft polymer (B) contains at least one of polyorganosiloxane and polyalkyl(meth)acrylate as a rubber component.
[4] The resin composition according to any one of [1] to [3], wherein the polymer (C) contains a dicarboxylic anhydride group.
[5] The resin composition according to any one of [1] to [4], wherein the polymer (C) has an acid value of 1 to 2500 mgKOH/g.
[6] The resin composition according to any one of [1] to [5], wherein the polymer (C) has an acid value of 20 to 200 mgKOH/g.
[7] The polyamide resin composition according to any one of [1] to [6], wherein the polymer (C) contains an α-olefin having 10 to 80 carbon atoms as a copolymer component.
[8] A molded article containing the resin composition according to any one of [1] to [7].

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a polyamide resin composition which is excellent in impact resistance, particularly in low-temperature impact resistance, and which is also excellent in heat deterioration resistance, and a molded article thereof.

Embodiments of the present invention will be described in detail below, but the present invention is not limited to these descriptions, and other than the following examples may be appropriately modified within the scope of the present invention. In the present invention, the vinyl monomer means a compound having a polymerizable double bond, (meth)acryl means acrylic or methacrylic, and (meth)acrylic acid ester means acrylic acid ester or methacrylic acid ester. means an acid ester. Also, in this specification, the term "~" is used to include the numerical values before and after it as lower and upper limits.

The resin composition according to the present embodiment contains a polyamide resin (A), a rubber-containing graft polymer (B) containing an epoxy group, and a polymer (C) containing a carboxyl group and/or a derivative thereof. do.

[Polyamide resin (A)]
The resin composition according to this embodiment contains a polyamide resin (A). Here, a polyamide resin is a polymer having an amide bond (--NHCO--) in its main chain. The polyamide resin (A) is not particularly limited, but for example, a polyamide resin obtained by condensation polymerization of diamine and dicarboxylic acid, a polyamide resin obtained by ring-opening polymerization of lactam, and a polyamide resin obtained by self-condensation of aminocarboxylic acid. , and copolymers obtained by copolymerization of two or more types of monomers constituting these polyamide resins, and these may be used alone or in combination of two or more types. good.
When used in combination, a method of blending these polyamide resins, a method of using a polyamide resin obtained by copolymerizing a plurality of these polyamide raw materials, and the like are exemplified.

Raw materials for the polyamide resin are described below.

<Diamine>
Examples of the diamine include, but are not limited to, aliphatic diamines, alicyclic diamines, and aromatic diamines.

Examples of the aliphatic diamine include, but are not limited to, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, and decamethylene. Linear saturated aliphatic diamines having 2 to 20 carbon atoms such as diamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine; ), 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, 2,4-dimethyloctamethylenediamine, etc. branched saturated aliphatic diamine; Examples of the branched saturated aliphatic diamine include diamines having substituents branched from the main chain.

Examples of the alicyclic diamine (also referred to as alicyclic diamine) include, but are not limited to, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and 1,3-cyclohexanediamine. pentanediamine and the like.

Examples of the aromatic diamine include, but are not limited to, meta-xylylenediamine, para-xylylenediamine, meta-phenylenediamine, ortho-phenylenediamine, and para-phenylenediamine.

<Dicarboxylic acid>
Examples of the dicarboxylic acid include, but are not limited to, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids.

Examples of the aliphatic dicarboxylic acid include, but are not limited to, malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2- Diethylsuccinic acid, 2,3-diethylglutaric acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane di linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as acids, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid;

Examples of the alicyclic dicarboxylic acid include, but are not limited to, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid. Carboxylic acids are mentioned.
The number of carbon atoms in the alicyclic structure of the alicyclic carboxylic acid is not particularly limited, but is preferably 3 to 10, more preferably 5 to 10, from the viewpoint of the balance between water absorption and crystallinity of the resulting polyamide resin. is.

The alicyclic dicarboxylic acid may be unsubstituted or may have a substituent.
Examples of substituents include, but are not limited to, those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group. and the like.

Examples of the aromatic dicarboxylic acid include, but are not limited to, an unsubstituted or substituted aromatic dicarboxylic acid having 8 to 20 carbon atoms.
Examples of substituents include, but are not limited to, alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 12 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, chloro groups and bromo groups. and the like, alkylsilyl groups having 3 to 10 carbon atoms, sulfonic acid groups, and salts thereof such as sodium salts thereof.
Examples of the aromatic dicarboxylic acid include, but are not limited to, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5- and sodium sulfoisophthalic acid.

The dicarboxylic acid may further contain a polyvalent carboxylic acid having a valence of 3 or more, such as trimellitic acid, trimesic acid, pyromellitic acid, etc., as long as the object of the present embodiment is not impaired.
The above diamines and dicarboxylic acids may be used alone or in combination of two or more.

<Lactam>
Examples of the lactam include, but are not limited to, butyrolactam, pivalolactam, ε-caprolactam, caprylolactam, enantholactam, undecanolactam, and laurolactam (dodecanolactam).
Among these, from the viewpoint of toughness, ε-caprolactam, laurolactam and the like are preferable, and ε-caprolactam is more preferable.

<Aminocarboxylic acid>
Examples of the aminocarboxylic acid include, but are not limited to, the above-mentioned lactam ring-opened compounds (ω-aminocarboxylic acid, α,ω-aminocarboxylic acid, etc.).
The aminocarboxylic acid is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms, substituted with an amino group at the ω-position, from the viewpoint of increasing the crystallinity of the polyamide resin. . Examples include, but are not limited to, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. Examples of the aminocarboxylic acid include para-aminomethylbenzoic acid and the like.

Examples of the polyamide resin (A) described above include, but are not limited to, polyamide 4 (polyα-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecaneamide), polyamide 12 ( polydodecanamide), polyamide 46 (polytetramethylene adipamide), polyamide 56 (polypentamethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610 (polyhexamethylene sebacamide), polyamide 612 (polyhexamethylene dodecamide), polyamide 116 (polyundecamethylene adipamide), polyamide TMHT (trimethylhexamethylene terephthalamide), polyamide 6T (polyhexamethylene terephthalamide), polyamide 2Me-5T (poly2-methyl pentamethylene terephthalamide), polyamide 9T (polynonamethylene terephthalamide), 2Me-8T (poly-2-methyloctamethylene terephthalamide), polyamide 6I (polyhexamethyleneisophthalamide), polyamide 6C (polyhexamethylenecyclohexanedicarboxamide) , polyamide 2Me-5C (poly 2-methylpentamethylenecyclohexanedicarboxamide), polyamide 9C (polynonamethylenecyclohexanedicarboxamide), 2Me-8C (poly 2-methyloctamethylenecyclohexanedicarboxamide), polyamide PBCM12 (polybis(4- aminocyclohexyl)methandodecamide), polyamide dimethyl PBCM12 (polybis(3-methyl-aminocyclohexyl)methandodedecamide, polyamide MXD6 (polymetaxylylene adipamide), polyamide 10T (polydecamethylene terephthalamide), polyamide 11T (poly undecamethylene terephthalamide), polyamide 12T (polydodecamethylene terephthalamide), polyamide 10C (polyundodecamethylenecyclohexanedicarboxamide), polyamide 11C (polyundecamethylenecyclohexanedicarboxamide), polyamide 12C (polydodecamethylenecyclohexanedicarboxamide) and other polyamide resins.
In addition, said "Me" shows a methyl group.

In addition, when the various monomers are polymerized to produce the polyamide resin (A), a terminal blocker may be further added for molecular weight adjustment. The terminal blocking agent is not particularly limited, and known ones can be used.

Examples of terminal blocking agents include, but are not limited to, monocarboxylic acids, monoamines, acid anhydrides, monoisocyanates, monoacid halides, monoesters, and monoalcohols.
These may be used individually by 1 type, and may use 2 or more types together.

The monocarboxylic acid that can be used as a terminal blocking agent is not limited to the following as long as it has reactivity with an amino group. Examples include formic acid, acetic acid, propionic acid, butyric acid, and valeric acid. , caproic acid, caprylic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, pivalic acid, aliphatic monocarboxylic acids such as isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, aromatic monocarboxylic acids such as toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid;
These may be used individually by 1 type, and may use 2 or more types together.

The monoamine that can be used as a terminal blocker may be any one having reactivity with a carboxyl group, and is not limited to the following. Examples include methylamine, ethylamine, propylamine, butylamine, hexylamine, Aliphatic monoamines such as octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; Alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; Aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine; is mentioned.
These may be used individually by 1 type, and may use 2 or more types together.

Acid anhydrides that can be used as terminal blockers include, but are not limited to, phthalic anhydride, maleic anhydride, benzoic anhydride, acetic anhydride, hexahydrophthalic anhydride, and the like.
These may be used individually by 1 type, and may use 2 or more types together.

Examples of monoisocyanates that can be used as terminal blocking agents include, but are not limited to, phenylisocyanate, tolylisocyanate, dimethylphenylisocyanate, cyclohexylisocyanate, butylisocyanate, naphthylisocyanate, and the like.
These may be used individually by 1 type, and may use 2 or more types together.

Examples of monoacid halides that can be used as endcapping agents include, but are not limited to, benzoic acid, diphenylmethanecarboxylic acid, diphenylsulfonecarboxylic acid, diphenylsulfoxidecarboxylic acid, diphenylsulfidecarboxylic acid, diphenylethercarboxylic acid, Acids, and halogen-substituted monocarboxylic acids such as benzophenonecarboxylic acid, biphenylcarboxylic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, and monocarboxylic acids such as anthracenecarboxylic acid.
These may be used individually by 1 type, and may use 2 or more types together.

Examples of monoesters that can be used as endcapping agents include, but are not limited to, glycerin monopalmitate, glycerin monostearate, glycerin monobehenate, glycerin monomontanate, pentaerythritol monopalmitate, Pentaerythritol monostearate, pentaerythritol monobehenate, pentaerythritol monomontanate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate, sorbitan monomontanate, sorbitan dimontanate, sorbitan trimontanate, sorbitol mono palmitate, sorbitol monostearate, sorbitol monobehenate, sorbitol tribehenate, sorbitol monomontanate, sorbitol dimontanate and the like.
These may be used individually by 1 type, and may use 2 or more types together.

Monoalcohols that can be used as endcapping agents include, but are not limited to, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol. , pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, docosanol, tricosanol, tetracosanol, hexacosanol, heptakosanol, octacosanol, triacontanol (above, linear, branched) , oleyl alcohol, behenyl alcohol, phenol, cresol (o-, m-, p-form), biphenol (o-, m-, p-form), 1-naphthol, 2-naphthol and the like.
These may be used individually by 1 type, and may use 2 or more types together.

The terminal group of the polyamide resin (A) used in the present invention is not particularly limited, but generally includes an amino group or a carboxy group. The molar ratio of the amount of amino terminal groups to the amount of carboxy terminal groups in the polyamide resin (A) (molar amount of amino terminal groups/molar amount of carboxy terminal groups) is not particularly limited, but is preferably 0.05 to 1.5. , is more preferably 0.1 to 1.0, and more preferably 0.15 to 0.7. When the molar ratio of the terminal group amount is 0.05 or more, the polyamide resin (A), the rubber-containing graft polymer (B) containing an epoxy group described later, and the polymer containing a carboxy group and/or a derivative thereof are mixed during melt-kneading. The reaction with coalescence (C) becomes favorable, and the impact resistance tends to be improved. Further, when the molar ratio of the amount of terminal groups is 1.5 or less, the molded article obtained from the resin composition tends to have more excellent resistance to heat deterioration.

The amino terminal group molar amount of the polyamide is not particularly limited, but is preferably 10 to 100 μmol/g, more preferably 15 to 80 μmol/g, and even more preferably 30 to 80 μmol/g. When the amount of amino terminal groups is within the above range, the impact resistance of the resin composition tends to be more excellent.

Here, examples of methods for measuring the amount of amino terminal groups and the amount of carboxyl terminal groups in the present specification include 1H-NMR method and titration method. In the 1H-NMR method, it can be determined by integral values of characteristic signals corresponding to each terminal group. In the titration method, for amino terminal groups, a method of titrating a phenol solution of polyamide resin with 0.1N hydrochloric acid, for carboxyl terminal groups, a method of titrating a benzyl alcohol solution of polyamide resin with 0.1N sodium hydroxide, etc. is mentioned.

The method for adjusting the concentration of the terminal groups of the polyamide is not particularly limited, but includes, for example, the method using the terminal blocker described above.

[Rubber-containing graft polymer (B) having an epoxy group]
The resin composition according to the present embodiment contains a rubber-containing graft polymer (B) (hereinafter sometimes simply referred to as graft polymer (B)) having an epoxy group.
The graft polymer (B) is obtained by graft-polymerizing the vinyl monomer component (b) containing at least a vinyl monomer having an epoxy group to the polymer (β). It contains a polymer obtained by polymerizing a vinyl monomer component (b) containing a vinyl monomer having an epoxy group (hereinafter also referred to as a "graft component").

The polymer (β) is a rubber component, that is, includes a polymer having a glass transition temperature (hereinafter sometimes referred to as Tg) of 0° C. or lower. The proportion of the polymer having a Tg of 0° C. or lower in the polymer (β) is preferably 1% by mass or more, more preferably 10% by mass or more, and even more preferably 30% or more. , more preferably 50% by mass or more, particularly preferably 70% by mass or more, while the upper limit is 100% by mass.

In addition, from the viewpoint of heat deterioration resistance of the molded article, the polymer (β) includes polyorganosiloxane (β-1) (hereinafter also referred to as “rubber (β-1)”) and poly(meth)acrylate (β -2) (hereinafter also referred to as “rubber (β-2)”). In particular, it is preferable that both rubber (β-1) and rubber (β-2) are contained, since they are excellent in the effect of improving impact strength.

In the present invention, the glass transition temperature of the polymer or the like is determined by thermal analysis such as differential scanning calorimetry (DSC), dynamic viscoelasticity measurement (DMS), thermomechanical analysis (TMA), etc. Among others, Tg can be easily measured by the method for measuring Tg of a polymer described in Examples below. Since the Tg of the obtained rubber component can be predicted in advance by the FOX formula, the composition of the rubber component can be considered based on this.

The number average particle diameter of the graft polymer (B) is not particularly limited, but is preferably 10 to 1000 nm, more preferably 20 to 700 nm, still more preferably 30 to 500 nm, particularly preferably 50 to 300 nm, most preferably 70 to 250 nm. preferable. When the number average particle size is 10 nm or more, the molded article has excellent impact resistance. When the number average particle size is 1000 nm or less, the appearance smoothness of the molded article is excellent.

The method for measuring the number average particle size of the graft polymer (B) is not particularly limited, but examples thereof include methods such as dynamic light scattering, laser diffraction, centrifugal sedimentation, and observation with a transmission electron microscope.
Among them, the particle size distribution data can be easily obtained by the method described in Examples below.

The number average particle size of the graft polymer (B) can be adjusted, for example, by adjusting the amount of emulsifier when the graft polymer (B) is produced by emulsion polymerization.

The mass average particle diameter of the graft polymer (B) is not particularly limited, but is preferably 10 to 1500 nm, more preferably 20 to 1000 nm, still more preferably 30 to 800 nm, particularly preferably 50 to 500 nm, most preferably 70 to 350 nm. preferable. When the mass average particle size is 10 nm or more, the molded article has excellent impact resistance. When the mass average particle diameter is 1500 nm or less, the appearance smoothness of the molded article is excellent.

The ratio of the mass average particle size to the number average molecular weight (mass average particle size/number average molecular weight) of the graft polymer (B) is not particularly limited, but is preferably 1.00 to 5.00, more preferably 1.00 to 3.00. 00 is more preferred, 1.00 to 2.50 is more preferred, 1.00 to 1.60 is particularly preferred, and 1.00 to 1.40 is most preferred. When the ratio of the mass average particle diameter to the number average molecular weight is 1.00 to 5.00, the impact resistance of the molded article is excellent.

(Polyorganosiloxane (β-1))
Polyorganosiloxane (β-1) is a polymer containing organosiloxane (b1-1) units.
Polyorganosiloxane (β-1) can be obtained by polymerizing an organosiloxane mixture containing organosiloxane. The organosiloxane mixture may further contain optional ingredients.
Components used as necessary include a siloxane-based cross-linking agent (b1-2) (hereinafter also referred to as "cross-linking agent (b1-2)"), a siloxane-based cross-linking agent (b1-3) (hereinafter referred to as " crossing agent (b1-3)”), and at least one selected from the group consisting of a siloxane oligomer having a terminal blocking group.

Examples of the organosiloxane (b1-1) include linear organosiloxanes, alkoxysilane compounds, cyclic organosiloxanes, and the like, and any of them can be used. Among them, alkoxysilane compounds and cyclic organosiloxanes are preferred, and cyclic organosiloxanes are particularly preferred because of their high polymerization stability and high polymerization rate.

As the alkoxysilane compound, a bifunctional alkoxysilane compound is preferable, and examples thereof include dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dipropoxydimethylsilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane. These can be used individually by 1 type or in combination of 2 or more types.

As the cyclic organosiloxane, those having 3- to 7-membered rings are preferable, and examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetra Examples include methyltetraphenylcyclotetrasiloxane and octaphenylcyclotetrasiloxane. These can be used individually by 1 type or in combination of 2 or more types. Among these, octamethylcyclotetrasiloxane is preferable because the particle size distribution can be easily controlled.

The organosiloxane (b1-1) is at least one selected from the group consisting of a cyclic dimethylsiloxane and a difunctional dialkylsilane compound in order to obtain a graft polymer (B) capable of increasing the impact resistance of the molded article. is preferred.

A cyclic dimethylsiloxane is a cyclic siloxane having two methyl groups on a silicon atom, and examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These can be used individually by 1 type or in combination of 2 or more types.

A bifunctional dialkylsilane compound is a silane compound having two alkoxy groups and two alkyl groups on a silicon atom, and examples thereof include dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, and dipropoxydimethylsilane. These can be used individually by 1 type or in combination of 2 or more types.

As the cross-linking agent (b1-2), one having a siloxy group is preferred. Examples of the cross-linking agent (b1-2) include trifunctional or tetrafunctional compounds such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane. Examples include silane-based cross-linking agents. Among them, a tetrafunctional cross-linking agent is preferable, and tetraethoxysilane is more preferable.

The content of the cross-linking agent (b1-2) is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, based on 100% by mass of the organosiloxane mixture. When the content of the cross-linking agent (b1-2) is 10% by mass or less, it is possible to obtain the graft polymer (B) capable of improving the impact resistance of the molded article.

The cross-linking agent (b1-3) has a siloxy group (--Si--O--) and a functional group capable of polymerizing with a vinyl monomer.
By using the crossing agent (b1-3), the vinyl monomer component (b) can be effectively graft-polymerized, and the appearance smoothness of the molded article to which the graft polymer (B) is added can be improved.
Further, by using a crossing agent (b1-3) when using a combination of polyorganosiloxane (β-1) and poly(meth)acrylate (β-2), polyorganosiloxane (β-1) and poly It is possible to obtain a graft polymer (B) that can strengthen the bond with the (meth)acrylate (β-2) and improve the impact resistance of the molded product.

Examples of the crossing agent (b1-3) include siloxanes represented by the following formula (I).
R-Si(R1)n(OR2)(3-n) (I)
In formula (I), R1 represents a methyl group, an ethyl group, a propyl group, or a phenyl group. R2 represents an organic group such as a hydrocarbon group, preferably a methyl group, an ethyl group, a propyl group, or a phenyl group. n represents 0, 1 or 2; R represents a functional group represented by any one of formulas (I-1) to (I-4) below.
CH ₂ =C(R3)-COO-(CH ₂ )p- (I-1)
_CH2 =C( _R4 ) _-C6H4- (I-2)
CH ₂ =CH- (I-3)
HS-(CH ₂ )p- (I-4)
In these formulas, R3 and R4 each independently represent a hydrogen atom or a methyl group, and p represents an integer of 1-6.

Examples of functional groups represented by formula (I-1) include methacryloyloxyalkyl groups. Examples of siloxanes having this group include the following. β-Methacryloyloxyethyldimethoxymethylsilane, γ-Methacryloyloxypropylmethoxydimethylsilane, γ-Methacryloyloxypropyldimethoxymethylsilane, γ-Methacryloyloxypropyltrimethoxysilane, γ-Methacryloyloxypropylethoxydiethylsilane, γ-Methacryloyloxypropyl diethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane and the like.

Examples of the functional group represented by formula (I-2) include a vinylphenyl group. Siloxanes having this group include, for example, vinylphenylethyldimethoxysilane.

Examples of siloxanes having functional groups represented by formula (I-3) include vinyltrimethoxysilane and vinyltriethoxysilane.

The functional group represented by formula (I-4) includes a mercaptoalkyl group. Examples of siloxanes having this group include the following. γ-mercaptopropyldimethylsilane, γ-mercaptopropylmethoxydimethylsilane, γ-mercaptopropyldiethoxymethylsilane, γ-mercaptopropylethoxydimethylsilane, γ-mercaptopropyltrimethoxysilane and the like.

These crossing agents (b1-3) can be used singly or in combination of two or more. As the cross-linking agent (b1-3), 3-methacryloxypropylmethyldimethoxysilane is used because the graft polymer (B) having excellent reactivity with other vinyl monomer components and excellent effect of improving impact strength can be obtained. is preferred.

The content of the crossing agent (b1-3) is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on 100% by mass of the organosiloxane mixture. preferable. By setting the content of the siloxane-based graft crossing agent (b1-3) to 0.05 to 20% by mass, it is possible to obtain the graft polymer (B) having an excellent impact strength improving effect.

The number average particle size of polyorganosiloxane (β-1) is not particularly limited, but is preferably 1 to 900 nm, more preferably 10 to 600 nm, and particularly preferably 30 to 200 nm. If the number average particle size of the polyorganosiloxane (β-1) is within the range of 1-900 nm, the number average particle size of the graft polymer (B) can easily be adjusted within the range of 10-1000 nm.

The number average particle size (Dn) of the polyorganosiloxane (β-1) can be measured using the same technique as the method for measuring the number average particle size of the graft polymer (B).

(Poly(meth)acrylate polymer (β-2))
Poly(meth)acrylate (β-2) is a polymer obtained by polymerizing a vinyl monomer (b2) containing a (meth)acrylate component, and has units based on the vinyl monomer.

The vinyl monomer component (b2) constituting the poly(meth)acrylate (β-2) consists of one or more vinyl monomers, and is a (meth)acrylate monomer (hereinafter referred to as “monomer (b2 -1)”.).
The vinyl monomer component (b2) includes, in addition to the monomer (b2-1), a monofunctional monomer copolymerizable with the monomer (b2-1) (hereinafter referred to as "monomer (b2-2 )”.) and at least one selected from the group consisting of a polyfunctional monomer copolymerizable with the monomer (b2-1) (hereinafter also referred to as “monomer (b2-3)”) It may further contain seeds.
The composition ratio of the various monomers may be selected so that the Tg of the resulting polymer is 0° C. or lower.

Examples of the monomer (b2-1) include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and n-octyl acrylate; Alkyl methacrylates such as propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate and stearyl methacrylate.
Above all, it contains at least one monomer selected from the group consisting of ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and n-octyl acrylate, since the impact resistance of the molded article is improved. is preferred, and n-butyl acrylate is more preferred.
These monomers (b2-1) can be used singly or in combination of two or more.

Examples of the monomer (b2-2) include aromatic vinyl monomers such as styrene and α-methylstyrene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; and (meth)acrylic group-modified silicones. and various vinyl monomers. These monomers (b2-2) can be used singly or in combination of two or more.

Examples of the monomer (b2-3) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, ethylene glycol diacrylate and propylene glycol diacrylate. , 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, divinylbenzene, polyfunctional (meth)acrylic group-modified silicone, allyl methacrylate, triallyl cyanurate, tri Examples include allyl isocyanurate and triallyl trimellitate.
Among them, at least one selected from the group consisting of allyl methacrylate, triallyl cyanurate and triallyl isocyanurate is preferred, and allyl methacrylate is more preferred, since the molded article has better impact resistance.
These monomers (b2-3) can be used singly or in combination of two or more.

When the polymer (β) contains both the polyorganosiloxane (β-1) and the poly(meth)acrylate polymer (β-2), the production method is not particularly limited, and the polyorganosiloxane (β-1 ) or the poly(meth)acrylate polymer (β-2), the monomer components constituting the other polymer may be polymerized in the latex, or each may be polymerized separately. The resulting polyorganosiloxane (β-1) and poly(meth)acrylate polymer (β-2) polymer latexes may be mixed. A preferred method is to polymerize the vinyl monomer component (b2) constituting the poly(meth)acrylate polymer (β-2) in the presence of a latex containing siloxane (β-1).

The method of polymerizing the vinyl monomer component (b2) in the presence of the latex containing the polyorganosiloxane (β-1) is not particularly limited. A method of dropping the monomer component (b2) for polymerization, (ii) adding part of the vinyl monomer component (b2) to a latex containing polyorganosiloxane (β-1) under conditions that do not initiate polymerization. and impregnating the particles of polyorganosiloxane (β-1), polymerization is initiated, and then the remainder of the vinyl monomer component (b2) is added dropwise or all at once for polymerization, (iii) polyorganosiloxane The total amount of the vinyl monomer component (b2) is added to the latex containing siloxane (β-1) under conditions that do not initiate polymerization, and the particles of polyorganosiloxane (β-1) are impregnated, followed by polymerization. method.

As a method for producing the polymer (A), among the above, the total amount of the vinyl monomer component (b2) is added to the latex containing the polyorganosiloxane (β-1) because the impact strength of the molded product is superior. , the method of charging under conditions where polymerization does not start, impregnating particles of polyorganosiloxane (β-1), and then polymerizing is preferable.

The ratio of the monomer (b2-1) is preferably 60 to 100% by mass, preferably 70 to 99.9% by mass, based on 100% by mass of the vinyl monomer component (b2), from the viewpoint of the impact resistance of the molded article. %, more preferably 80 to 99.9% by mass, particularly preferably 90 to 99.9% by mass.

The ratio of the monomer (b2-2) is preferably 0 to 40% by mass, more preferably 0 to 30% by mass, based on 100% by mass of the vinyl monomer component (b2), from the viewpoint of the impact resistance of the molded article. More preferably, 0 to 20% by mass is more preferable, and 0 to 10% by mass is particularly preferable.

The ratio of the monomer (b2-3) is preferably 0.1 to 4% by mass with respect to 100% by mass of the vinyl monomer component (b2).
The ratio of the monomer (b2-3) is more preferably 0.1 to 2% by mass with respect to 100% by mass of the vinyl monomer component (b2) from the viewpoint of further increasing the impact resistance of the molded article. 0.1 to 1% by mass is more preferable.
The ratio of the monomer (b2-3) is more preferably 0.5 to 4% by mass with respect to 100% by mass of the vinyl monomer component (b2) from the viewpoint of further enhancing the colored appearance of the molded article. ~4% by mass is more preferred.
The ratio of the monomer (b2-3) is 100% by mass of the vinyl monomer component (b2) from the viewpoint of melt fluidity during molding and the viewpoint of balancing the colored appearance and impact resistance of the molded product. 0.3 to 3% by mass is more preferable, and 0.5 to 2.5% by mass is even more preferable.

The content of the polymer (β) in 100% by mass of the graft polymer (B) is not particularly limited, and is preferably 10 to 95% by mass, more preferably 20 to 95% by mass. , more preferably in the range of 30 to 93% by mass, and most preferably in the range of 50 to 90% by mass.

When the content of the polymer (β) is 10% by mass or more, the effect of improving the impact strength when the graft polymer (B) is added becomes better, and when it is 95% by mass or less, the graft polymer The dispersibility of (B) in the molded article becomes better, and the appearance of the obtained molded article is improved.

The content of polyorganosiloxane (β-1) in 100% by mass of polymer (β) is 0 to 100% by mass, more preferably 1 to 90% by mass, and in the range of 1 to 80% by mass. is more preferable, the range of 2 to 50% by mass is particularly preferable, and the range of 3 to 30% by mass is most preferable.

By including the polyorganosiloxane (β-1) in the graft polymer (B), the effect of improving the low-temperature impact strength when the graft polymer (B) is added is improved.

The content of the poly(meth)acrylate polymer (β-2) in 100% by mass of the polymer (β) is 0 to 100% by mass, more preferably 10 to 99% by mass, and 20 to 99% by mass. It is more preferably in the range of 50-98% by weight, most preferably in the range of 70-97% by weight.

By including the polyorganosiloxane (β-2) in the graft polymer (B), the effect of improving the impact strength and the pigment coloring property are well balanced when the graft polymer (B) is added.

(vinyl monomer (b))
The vinyl monomer component (b) contains a vinyl monomer (b-1) having an epoxy group.

Examples of the vinyl monomer (b-1) having an epoxy group include glycidyl (meth)acrylate, vinyl glycidyl ether, allyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth)acrylate, and polyalkylene glycol (meth)acrylate. Glycidyl ether, glycidyl itaconate.
Among these, glycidyl methacrylate is preferred.

Furthermore, the vinyl monomer (b) may contain another vinyl monomer (b-2) copolymerizable with the vinyl monomer (b-1) having an epoxy group.

The vinyl monomer (b-2) is not particularly limited, but examples include (meth)acrylate monomers having no epoxy group, aromatic vinyl monomers having no epoxy group, and Various vinyl-based monomers such as vinyl cyanide monomers that do not contain

(Meth)acrylate monomers having no epoxy group include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and i-butyl methacrylate; alkyl acrylates such as methyl acrylate, ethyl acrylate and n-butyl acrylate; etc.

Examples of aromatic vinyl monomers having no epoxy group include styrene, alkyl-substituted styrenes (p-methylstyrene, m-methylstyrene, o-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, etc.), alkyl-substituted isopropenylbenzene (isopropenylbenzene (α-methylstyrene), isopropenyltoluene , isopropenylethylbenzene, isopropenylpropylbenzene, isopropenylbutylbenzene, isopropenylpentylbenzene, isopropenylhexylbenzene, isopropenyloctylbenzene, etc.), 1,1-diphenylethylene and the like. Among them, styrene and α-methylstyrene are preferable because they can suppress the generation of cullet.

Vinyl cyanide monomers having no epoxy group include acrylonitrile, methacrylonitrile, ethacrylonitrile and fumaronitrile.
These can be used individually by 1 type or in combination of 2 or more types.

The content of the vinyl monomer (b-1) having an epoxy group in 100% by mass of the vinyl monomer component (b) is preferably 1% by mass or more, more preferably 3% by mass or more. On the other hand, it is preferably 80% by mass or less, more preferably 50% by mass or less, particularly preferably 30% by mass or less, and most preferably 20% by mass or less. By setting the content of the vinyl monomer (b-1) having an epoxy group to 1% by mass or more, when added to the polyamide resin, the polyamide resin (A) and a polymer containing a carboxy group and a derivative thereof described later can be obtained. By reacting with the coalescence (C), the interfacial strength with the polyamide resin (A) is improved, and the effect of improving the impact strength is excellent. Furthermore, when the content is 80% by mass or less, the presence of the vinyl monomer (b-2) or (b-3) makes it easy to seal the ends of the polyamide resin (A), and is resistant to heat deterioration. Excellent improvement effect.

The vinyl monomer constituting the vinyl monomer component (b) is selected so that the glass transition temperature of the graft component (polymer obtained by polymerizing the vinyl monomer component (b)) is 70°C or higher. is preferred. The Tg of the graft component is more preferably 80°C or higher, more preferably 90 to 105°C. If the Tg of the graft component is 70° C. or higher, the characteristics of the powder of the graft polymer (B) obtained by performing the powder recovery step after graft polymerization of the vinyl monomer component (b) (fluidity of powder properties and particle size) are improved.

Also, the Tg of the graft component can be predicted in advance by the FOX formula. At this time, the Tg value of each homopolymer obtained by polymerizing each monomer unit constituting the vinyl monomer component (b) is, for example, the value described in "POLYMER HANDBOOK" (Wiley Interscience / 1999). can be used. In addition, the Tg values of undescribed monomer components can be calculated using the BicerAno method "Prediction of Polymer Properties" (MARCEL DEKKER, 2002).

(Method for producing graft polymer (B))
The graft polymer (B) can be produced by graft polymerizing the vinyl monomer component (b) to the polymer (β).

As a method for producing the graft polymer (B), a method of adding the vinyl monomer component (b) to the latex of the polymer (β) and graft-polymerizing the vinyl monomer component (b) in the latex is preferable. . At this time, when the vinyl monomer component (b) contains a plurality of monomer components, each component may be added after being uniformly mixed, or each component may be added individually. , a plurality of solutions in which the mixing ratio of each component is changed may be added in order.

The latex of the polymer (β) is obtained by polymerizing the vinyl monomer component (b2) constituting the poly(meth)acrylate (β-2) in the presence of the latex containing the polyorganosiloxane (β-1). It is preferably manufactured by

The vinyl monomer component (b) is a crossing agent (b1-3) contained in the polyorganosiloxane (β-1) and/or a polyfunctional monomer contained in the poly(meth)acrylate (β-2) ( By chemically bonding with the unsaturated component (vinyl component) derived from b2-3), a graft polymer with the polymer (β) can be formed.

In order to improve the efficiency of this grafting, prior to the addition of the vinyl monomer component (b), for example, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate. Methacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, divinylbenzene, polyfunctional (meth)acrylic group modification Polyfunctional monomers such as silicone, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, and triallyl trimellitate can be prepolymerized.

When polymerizing the vinyl monomer component (b), a chain transfer agent may be used for the purpose of adjusting the molecular weight of the THF-soluble component.
Chain transfer agents include mercaptans such as n-dodecylmercaptan, t-dodecylmercaptan, n-octylmercaptan, n-tetradecylmercaptan, n-hexylmercaptan and n-butylmercaptan; Halogen compounds; α-methylstyrene dimer and the like. These chain transfer agents may be used alone or in combination of two or more.

The amount of the chain transfer agent to be used is preferably 0 to 2.0% by mass with respect to 100% by mass of the vinyl monomer component (b). By setting the amount of the chain transfer agent to be 2.0% by mass or less, the impact resistance of the resulting molded article is more excellent.

After the vinyl monomer component (b) is graft-polymerized, the graft polymer (B) may be recovered as powder from the obtained latex of the graft polymer (B).
When the graft polymer (B) is recovered as powder, a direct drying method such as a spray drying method or a coagulation method can be used. In the coagulation method, residual polymerization aids contained in the resulting powder, such as the emulsifier used during polymerization, its coagulation salt, and the initiator, can be reduced in the washing step after coagulation. On the other hand, in the direct drying method, the auxiliaries added during polymerization can generally remain in the resulting powder. These powder recovery methods can be appropriately selected in order to obtain a preferable residual state when the graft polymer (B) is added to the thermoplastic resin.

The spray-drying method is a method in which the latex of the graft polymer (B) is sprayed into a dryer in the form of minute droplets, which are then dried by applying a heating gas for drying. Methods for generating fine droplets include, for example, a rotating disc type, a pressure nozzle type, a two-fluid nozzle type, and a pressurized two-fluid nozzle type. The capacity of the dryer can be from small capacity for laboratory use to large capacity for industrial use. The temperature of the heating gas for drying is preferably 200°C or less, more preferably 120 to 180°C. Latices of two or more graft copolymers made separately can also be spray dried together. Further, in order to improve powder properties such as blocking and bulk density during spray drying, optional components such as silica may be added to the latex of the graft polymer (B) and spray drying may be carried out.

The coagulation method is a method of coagulating the latex of the graft polymer (B), separating the graft polymer (B), recovering it, and drying it. First, a latex of the graft polymer (B) is put into hot water in which a coagulant is dissolved, salted out, and coagulated to separate the graft polymer (B). Next, the separated wet graft polymer (B) is subjected to dehydration or the like to recover the graft polymer (B) having a reduced water content. The recovered graft polymer (B) is dried using a press dehydrator or a hot air dryer.

The coagulant includes inorganic salts such as aluminum chloride, aluminum sulfate, sodium sulfate, magnesium sulfate, sodium nitrate and calcium acetate, and acids such as sulfuric acid, with calcium acetate being particularly preferred. These coagulants can be used singly or in combination of two or more.

Without recovering the graft polymer (B) discharged from the dehydrator or extruder, it is also possible to directly send it to an extruder or molding machine for producing a resin composition and mix it with a thermoplastic resin to obtain a molded product. It is possible.

[Polymer (C) containing a carboxy group or a derivative thereof]
The resin composition according to this embodiment contains a polymer (C) containing a carboxyl group and/or a derivative thereof. Derivatives of carboxy groups include acyl halide groups, dicarboxylic anhydride groups, ester groups, amide groups, nitrile groups and the like.

Among them, the polymer (C) has excellent quality stability during storage, and has excellent reactivity with the polyamide resin (A) and the graft polymer (B), so that the effect of improving the heat deterioration resistance of the resin composition is excellent. Furthermore, it preferably contains a carboxy group and/or a dicarboxylic anhydride group, and particularly preferably contains a dicarboxylic anhydride group, because of its excellent impact resistance.

The carboxy group or derivative thereof may be on either the main chain or the side chain of the polymer (C).
When producing the polymer (C), a monomer (c-1) containing a carboxy group or a derivative thereof and another copolymerizable monomer (c-2) are used, and these are copolymerized. A polymer (C) containing a carboxy group or a derivative thereof in the main chain can be obtained. In addition, a polymer (γ) as a base material is prepared in advance, radicals are generated by an organic peroxide, a thermal decomposition method, or the like, and a monomer (c-1) containing a carboxy group or a derivative thereof is converted into a polymer ( By reacting with γ), a polymer (C) containing a carboxy group or a derivative thereof in the side chain can be obtained.

Among them, the polymer (C) has excellent reactivity with the polyamide resin (A) and the graft polymer (B), is excellent in the effect of improving the heat deterioration resistance of the resin composition, and is also excellent in impact resistance. It is preferred that the main chain contain a carboxy group or a derivative thereof.

The monomer (c-1) containing a carboxy group or a derivative thereof is not particularly limited, but (meth)acrylic acid, maleic acid, methylmaleic acid, fumaric acid, methylfumaric acid, tetrahydrophthalic acid, itaconic acid, citracone Carboxy group-containing monomers such as acid, crotonic acid, isocrotonic acid, glutaconic acid, norbornane-5-ene-2,3-dicarboxylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, 5-norbornene-2 , 3-dicarboxylic anhydride and other acid anhydride group-containing monomers. These may be used alone or in combination of two or more.

Among them, the acid anhydride group-containing monomer has excellent reactivity with the polyamide resin (A) and the graft polymer (B), so that the effect of improving the heat deterioration resistance of the resin composition is excellent, and further impact resistance The monomer (c-1) is preferably an acid anhydride group-containing monomer having 4 or more carbon atoms, while the monomer (c-1) is preferably an acid anhydride group-containing monomer having 15 or less carbon atoms. It is preferably a solid, more preferably an acid anhydride group-containing monomer having 10 or less carbon atoms, and preferably maleic anhydride.

The copolymerizable monomer (c-2) is not particularly limited, but fatty acids such as ethylene, propylene, 1-butene, 2-methyl-1-butene, pentene, hexene, 4-methyl-1-pentene, etc. cyclohexene, vinylcyclohexane, and norbornene; diene monomers such as butadiene, isoprene, hexadiene, cyclopentadiene, dicyclopentadiene, and divinylbenzene; methyl methacrylate, ethyl methacrylate, Alkyl methacrylate monomers such as n-butyl methacrylate and i-butyl methacrylate; Alkyl acrylate monomers such as methyl acrylate, ethyl acrylate and n-butyl acrylate; Aromatics such as styrene, alkyl-substituted styrene and alkyl-substituted isopropenylbenzene vinyl monomers; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile;
These can be used individually by 1 type or in combination of 2 or more types.

Among them, the monomer (c-2) is an aliphatic olefin monomer because it has excellent compatibility with the polyamide resin (A) and has excellent thermal decomposition resistance when made into a polymer (C). and more preferably an α-olefin monomer. Among them, the number of carbon atoms in the α-olefin is preferably 10 or more, more preferably 16 or more, and still more preferably 24 or more, while it is preferably 80 or less, and 72 or less. is more preferable, and 64 or less is even more preferable.

By containing an α-olefin monomer having 10 to 80 carbon atoms, the reactivity between the polymer (C) and the polyamide resin (A) is further increased, making it easier to control the melt viscosity of the resin composition. .

Components constituting the base polymer (γ) include aliphatic olefins such as ethylene, propylene, 1-butene, 2-methyl-1-butene, pentene, hexene, and 4-methyl-1-pentene; cyclohexene , vinylcyclohexane, norbornene; dienes such as butadiene, isoprene, hexadiene, cyclopentadiene, dicyclopentadiene, divinylbenzene; alkyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, etc. methacrylate; alkyl acrylate such as methyl acrylate, ethyl acrylate and n-butyl acrylate; aromatic vinyl such as styrene, alkyl-substituted styrene and alkyl-substituted isopropenylbenzene; vinyl cyanide such as acrylonitrile and methacrylonitrile.
These may be one kind of homopolymer or two or more kinds of copolymers. Further, post-treatment such as hydrogenation may be performed on the obtained polymer.

Among them, the polymer (γ) is a monomer containing an aliphatic olefin monomer because it has excellent compatibility with the polyamide resin (A) and has excellent thermal decomposition resistance when used as a polymer (C). It preferably contains a polymer derived from a monomer group, and more preferably contains a polymer derived from a monomer group containing ethylene or propylene.

The melting point of the polymer (C) is preferably 40° C. or higher and 170° C. or lower from the viewpoint of handling. If it is 40° C. or higher, the heat deformation resistance of the resin composition is hardly impaired, and if it is 170° C. or lower, it can be rapidly melted in the melt-kneading process and can be well mixed with the polyamide resin (A). From the viewpoint of handling, the temperature is preferably 50° C. or higher and 130° C. or lower, and more preferably 60° C. or higher and 90° C. or lower.

The acid value of the polymer (C) can be adjusted by the ratio of the monomer (c-1) containing a carboxy group or derivative thereof to be used, and is not particularly limited, but is preferably 1 mgKOH/g or more, and 10 mgKOH/g. more preferably 15 mgKOH/g or more, most preferably 20 mgKOH/g or more, on the other hand, preferably 2500 mgKOH/g or less, preferably 1000 mgKOH/g or less It is more preferably 500 mgKOH/g or less, particularly preferably 200 mgKOH/g or less, most preferably 200 mgKOH/g or less. By adjusting the acid value to 1 mgKOH/g or more, the reactivity with the polyamide resin (A) is improved, and the effect of adjusting the melt viscosity when the polymer (C) is added is easily obtained. In addition, by adjusting to 2500 mg KOH / g or less, the effect of increasing the melt viscosity due to the addition of the polymer (C) can be moderated, and the molding fluidity due to uncontrollable slight changes in the addition amount such as weighing errors It can suppress the influence and is excellent in handleability.

The acid value of the polymer (C) can be determined by a neutralization titration method or a potentiometric titration method, preferably by a suitable neutralization method. In the neutralization titration method, the polymer (C) is dissolved in chloroform, phenolphthalein is added as an indicator, and the solution is titrated with a potassium hydroxide ethanol solution to determine the acid value.

The molecular weight of the polymer (C) is not particularly limited, but the weight-average molecular weight is preferably 01,000 to 200,000, more preferably 01,000 to 150,000, and 0.3. It is more preferably 10,000 to 100,000, and most preferably 10,000 to 50,000.
By setting the mass average molecular weight to 01,000 or more, the thermal decomposition resistance of the polymer (C) is improved, and gas generation during molding can be suppressed. Further, by setting the mass average molecular weight to 200,000 or less, the dispersibility of the polymer (C) in the molded product is improved, and the molded product has excellent appearance smoothness.

The weight average molecular weight can be calculated using gel permeation chromatography (GPC). Specifically, a solvent in which the compound is dissolved, such as hexafluoroisopropanol, is used as the mobile phase, polymethyl methacrylate (PMMA) or polystyrene with a known molecular weight is used as the standard substance, and the column is matched to the solvent, such as hexafluoroisopropanol. In that case, using Shimadzu GLC Co., Ltd. "Shodex GPC HFIP-806M" and / or "Shodex GPC HFIP-LG", the weight average molecular weight is measured using a differential refractometer as a detector. be able to.

The form of the polymer (C) is not particularly limited, but from the point of view of ease of handling during kneading, it is preferable to use a solid such as rubber, wax, or clay that can be handled. More preferred.

[Resin composition]
The resin composition according to this embodiment contains a polyamide resin (A), a graft polymer (B), and a polymer (C).

The graft polymer (B) can improve impact resistance and heat deterioration resistance by reacting with the polyamide resin (A) and the polymer (C) during melt-kneading. The content can be arbitrarily controlled.
Further, the polymer (C) can improve heat deterioration resistance and impact resistance by reacting with the polyamide resin (A) and the graft polymer (B) during melt-kneading, and the polymer (C ) can be arbitrarily controlled by the content.

The ratio of the graft polymer (B) to 100 parts by mass of the polyamide resin (A) is not particularly limited, but is preferably 0.1 parts by mass or more, preferably 0.5 parts by mass or more, It is particularly preferably 1 part by mass or more, on the other hand, preferably 30 parts by mass or less, preferably 25 parts by mass or less, and particularly preferably 20 parts by mass or less.
By setting the content of the graft polymer (B) to 0.1 parts by mass or more, the impact resistance of the resin composition can be further improved. Further, by setting the content of the graft polymer (B) to 30 parts by mass or less, it is possible to suppress a decrease in rigidity of the resin composition.

The ratio of the polymer (C) to 100 parts by mass of the polyamide resin (A) is not particularly limited, but is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more. It is particularly preferably 0.3 parts by mass or more, on the other hand, preferably 10 parts by mass or less, preferably 8 parts by mass or less, and particularly preferably 5 parts by mass or less.
By setting the content of the polymer (C) to 0.1 parts by mass or more, the heat deterioration resistance of the resin composition can be further improved. Further, by setting the content of the polymer (C) to 10 parts by mass or less, it is possible to suppress the decrease in the melt fluidity of the resin composition.

Other additives may be added to the resin composition as long as they do not impair the effects of the present invention. Examples of such additives include fillers, heat stabilizers, antioxidants, dyes, pigments, and the like.

Examples of fillers include fibrous fillers such as glass fiber, carbon fiber, alumina fiber and ceramic fiber; whisker fillers such as calcium carbonate, zinc oxide, aluminum borate and potassium titanate; talc and mica. , clay, zeolite, glass flakes, glass beads, silica, montmorillonite, wollastonite, and other non-fibrous fillers are used. Among these, glass fiber is particularly preferred.

These fillers may be pretreated with a coupling agent such as an epoxy-based compound, an isocyanate-based compound, or an organic silane-based compound.

These fillers can be used singly or in combination, and are appropriately selected depending on the application.

Although there is no particular limitation on the amount of the filler compounded, it is generally preferably 5 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the resin composition. If the amount is 5 parts by mass or more, the rigidity is likely to be improved. From the viewpoint of achieving both rigidity and moldability, it is more preferably 10 parts by mass or more and 35 parts by mass or less, and even more preferably 15 parts by mass or less and 30 parts by mass or less.

As the heat stabilizer, a copper compound is preferable from the viewpoint of long-term thermal decomposition resistance. Specific examples of copper compounds include copper chloride, copper bromide, copper iodide, copper sulfate, copper nitrate, copper phosphate, copper acetate, and copper stearate. From the viewpoint of long-term thermal decomposition resistance, monovalent copper compounds are preferred.

Conventional antioxidants such as hindered phenol compounds and phosphorus compounds are used. In order to suppress volatilization and decomposition during melt-kneading, one having a high melting point is preferred.

Examples of dyes or pigments include inorganic pigments such as iron oxide, ultramarine blue, titanium oxide, and carbon black. Examples of organic pigments include phthalocyanine-based and anthraquinone-based blue pigments, perylene-based and quinacridone-based red pigments, and isoindolinone-based yellow pigments. Moreover, fluorescent pigments, metal powder pigments, pearl pigments, etc., can be used as special pigments. Examples of dyes include nigrosine, perinone, and anthraquinone dyes. These dyes and pigments are commercially available in various grades depending on the desired color and can be used. These can be used individually by 1 type or in combination of 2 or more types. The amount of these colorants to be added is not particularly limited, but is preferably from 0.01 to 3 parts by mass, more preferably from 0.05 to 2 parts by mass, more preferably from 0.05 to 2 parts by mass, based on 100 parts by mass of the resin composition, since the appearance is excellent. .1 to 2 parts by mass is more preferred.

In addition to additives, flame retardants (phosphorus-based, bromine-based, silicone-based, organic metal salt-based, etc.), anti-drip agents (e.g., fluorinated polyolefin, silicone and aramid fibers), lubricants (e.g., magnesium stearate, etc.) long-chain fatty acid metal salt, etc.), release agent (eg, pentaerythritol tetrastearate, etc.), nucleating agent, antistatic agent, ultraviolet absorber, amine light stabilizer, plasticizer, and the like.

(Method for producing resin composition)
The resin composition can be produced by mixing the polyamide resin (A), the graft polymer (B), the polymer (C) and, if necessary, additives.
A method for mixing each material includes a known blending method, and is not particularly limited. Examples thereof include a method of mixing and kneading with a tumbler, V-type blender, super mixer, Nauta mixer, Banbury mixer, kneading roll, single-screw extruder, twin-screw extruder, and the like.
As an example of the method for producing the resin composition of the present invention, the polyamide resin (A), the graft polymer (B) and the polymer (C), and if necessary additives are mixed using a twin-screw extruder to form strands. A method of extruding into a shape and cutting into pellets with a rotary cutter or the like can be mentioned. By this method, a pellet-shaped resin composition can be obtained.

[Molded body]
A molded article can be produced by molding the resin composition according to the present embodiment.
The molded article contains the resin composition according to the present embodiment.
The method for molding the resin composition is not particularly limited, but specific examples include extrusion molding, injection molding, blow molding, press molding, insert molding, suction blow molding, three-dimensional blow molding, and multicolor molding. . The resin composition of the present invention is particularly suitable for extrusion molding, blow molding, suction blow molding, and three-dimensional blow molding, since the melt viscosity can be easily controlled.

Molded articles can be widely used industrially as various materials in the fields of automobiles, OA equipment, home electric appliances, electrical/electronics, lifestyle/cosmetics, medical supplies, and the like. More specifically, automotive parts such as intake manifolds, radiator tanks, transmission mounts, fuel tubes, air brake tubes, ducts, and exhaust gas tubes, electrical and electronic parts such as gears, hubs, bushes, connectors, and bearing retainers. , fans, impellers and other machine parts, food packaging films, fishing lines, sports shoe soles and other daily necessities, medical packs, medical supplies such as medical catheters and pipes, and the like.

EXAMPLES The present invention will be described in more detail below with reference to manufacturing examples and examples, but the present invention is not limited to these examples. Production Examples 1 to 4 are production examples of the graft polymer (B). In addition, "part" means "mass part" and "%" means "mass %".

[Measurement of solid content]
A polymer latex having a weight of w1 is dried for 30 minutes in a hot air dryer at 180° C., the weight of the residue after drying is measured, and the solid content [%] is calculated by the following formula (e).
Solid content [%] = w2/w1 x 100 (e)

[Method for measuring particle size of graft polymer (B)]
The polymer latex to be measured was diluted with deionized water to a solid content concentration of about 3% as a sample, and the number average particle diameter was determined using the CHDF2000 particle size distribution meter manufactured by MATEC, USA, under the following conditions. Dn and mass average particle size Dw were measured.
Cartridge: Dedicated capillary cartridge for particle separation (trade name: C-202),
Carrier liquid: Dedicated carrier liquid (trade name; 2XGR500),
Liquid property of carrier liquid: Neutral,
Carrier liquid flow rate: 1.4 mL/min,
carrier liquid pressure: 4,000 psi (2,600 kPa);
Measurement temperature: 35°C,
Amount of sample used: 0.1 mL.

[Method for measuring Tg of polymer]
The Tg of the polymer was evaluated using a dynamic viscoelasticity apparatus (DMS6100, manufactured by Seiko Instruments Inc.) according to the following method.
Graft polymer (B) is compression-molded at 160° C. and 5 MPa for 10 minutes, and a test piece having a thickness of 2 mm is measured in bending mode at a frequency of 1 Hz in a temperature range of −150° C. to 180° C. The obtained peak temperature of tan δ is defined as Tg.

[Method for measuring acid value of polymer (C)]
About 0.2 g of polymer (C) was put into a 250 ml Erlenmeyer flask and the mass was measured. Then, it was dissolved in 20 ml of chloroform and titrated with 0.1 N (normal) potassium hydroxide ethanol solution using phenolphthalein as an indicator to calculate the acid value [mgKOH/g].

[Method for measuring melting point of polymer (C)]
The melting point of the polymer (C) was evaluated according to the following method using a differential scanning calorimeter (DSC) (manufactured by Seiko Instruments Inc., DSC6200).
About 10 mg of polymer (C) was placed in an aluminum sample container, heated to 200°C at a temperature increase rate of 10°C/min, held for 5 minutes, and then cooled to 0°C at a rate of 10°C/min. Subsequently, the temperature was raised again at a rate of temperature increase of 10° C./min, held for 5 minutes, and then lowered at a rate of 10° C./min. melting point.

[material]
Raw materials used in Examples and Comparative Examples are shown below.
(1) Polyamide resin (A)
PA6 (nylon 6): manufactured by Ube Industries, Ltd., product name: UBE Nylon 1022B
PA66 (nylon 66): manufactured by Toyobo Co., Ltd., product name: Gramide T-662
PA66+GF (nylon 66 containing glass fiber): manufactured by Toyobo Co., Ltd., product name: Gramide T-663G30 (containing 30% glass fiber)
(2) Polymer (C)
30M: manufactured by Mitsubishi Chemical Corporation, product name: Diacarna 30M (a copolymer of α-olefins and maleic anhydride containing multiple types of α-olefins having 28 to 58 carbon atoms as copolymer components, acid value : 90mgKOH/g, melting point 72°C)
CE2: Clariant Chemicals Co., Ltd., product name: Recolb CE2 (a copolymer of α-olefins and maleic anhydride containing multiple types of α-olefins having 28 to 58 carbon atoms in copolymerization components, acid value: 81 mg KOH/ g, melting point 74°C)
1105A: Mitsui Chemicals, Inc., product name: Hi-Wax 1105A (maleic anhydride-modified polyethylene, acid value: 60 mgKOH/g, melting point: 104°C)
2203A: Mitsui Chemicals, Inc., product name: Hi-Wax 2203A (maleic anhydride-modified polyethylene, acid value: 30 mgKOH/g, melting point: 107°C)
U1001: manufactured by Sanyo Chemical Industries, Ltd., product name: Yumex 1001 (maleic anhydride-modified polypropylene, acid value: 26 mgKOH/g, melting point: 142°C)
H12: Clariant Chemicals, product name: Recolb H12 (carboxy group-containing polyethylene oxide, acid value: 17 mgKOH/g, melting point: 104°C)
VPN233: manufactured by Emery Oleochemicals, product name: Roxol VPN233 (polyethylene, acid value: 0 mgKOH/g, melting point: 110°C)

<Production Example 1-1> (Production of polyorganosiloxane (β-1-1))
98 parts of a cyclic organosiloxane mixture (manufactured by Shin-Etsu Silicone Co., Ltd., product name: DMC, a mixture of 3- to 6-membered cyclic organosiloxanes) and 2 parts of 3-methacryloxypropylmethyldimethoxysilane (KBM-502) were mixed. to obtain 100 parts of an organosiloxane mixture. An aqueous solution prepared by dissolving 0.7 parts of sodium dodecylbenzenesulfonate (DBSNa) in 350 parts of deionized water was added to the above mixture, and after stirring at 10,000 rpm for 5 minutes with a homomixer, a pressure of 20 MPa was applied to a homogenizer. Two pressure passes resulted in a stable premixed emulsion.
Next, an aqueous solution prepared by dissolving 10 parts of dodecylbenzenesulfonic acid (DBSH) in 40 parts of deionized water is placed in a 5-liter separable flask equipped with a cooling condenser, and the aqueous solution is heated to 80°C. Then, the above emulsion was continuously added for 240 minutes for polymerization reaction, then cooled to 25° C., 5% aqueous sodium hydroxide solution was added to neutralize the reaction solution to pH 7.5, and the poly An organosiloxane latex (β-1-1) was obtained.
The solid content of the polyorganosiloxane latex (β-1-1) was 18%. The number average particle diameter (Dn) of this latex measured by a capillary particle size distribution analyzer was 46 nm, the mass average particle diameter (Dw) was 75 nm, and Dw/Dn was 1.63.

<Production Example 1-2> (Production of polyorganosiloxane (β-1-2))
Cyclic organosiloxane mixture (manufactured by Shin-Etsu Silicone Co., Ltd., product name: DMC, a mixture of 3- to 6-membered ring cyclic organosiloxane) 96 parts, tetraethoxysilane (TEOS) 2.0 parts and 3-methacryloxypropylmethyldimethoxy 2.0 parts of silane (KBM-502) were mixed to obtain 100 parts of an organosiloxane mixture. An aqueous solution prepared by dissolving 1.0 part of sodium dodecylbenzenesulfonate (DBSNa) in 250 parts of deionized water was added to the above mixture and stirred at 10,000 rpm for 5 minutes with a homomixer. Two pressure passes resulted in a stable premixed emulsion.

Next, after putting the mixed emulsion into a 5-liter separable flask equipped with a cooling condenser, the aqueous solution was heated to a temperature of 80° C., and then 0.20 parts of sulfuric acid and 49.8 parts of distilled water were added. The mixture was dosed continuously over 3 minutes. The temperature was maintained at 80° C. for 7 hours to carry out a polymerization reaction, then cooled to 25° C., a 5% aqueous sodium hydroxide solution was added to neutralize the reaction solution to pH 7.0, and polyorganosiloxane was obtained. A latex (β-1-2) was obtained.
The solid content of the polyorganosiloxane latex (β-1-2) was 28% by mass. The latex had a number average particle diameter (Dn) of 380 nm, a mass average particle diameter (Dw) of 407 nm, and a Dw/Dn of 1.07 as measured by a capillary particle size distribution analyzer.

<Production Example 2-1> (Production of rubber-containing graft polymer (B-1))
60 parts of the polyorganosiloxane latex (β-1-1) obtained in Production Example 1-1 (10 parts in terms of polymer) was collected in a 5-liter separable flask, and 160 parts of deionized water was added and mixed. did. Next, 69.9 parts of n-butyl acrylate (nBA), 0.1 part of allyl methacrylate (AMA), and 0.15 parts of t-butyl hydroperoxide are added to the separable flask, and a stream of nitrogen is passed through. The atmosphere in the flask was replaced with nitrogen, the liquid temperature was raised to 50°C, and the mixture was stirred for 1 hour.

Subsequently, 0.0005 parts of ferrous sulfate heptahydrate, 0.0015 parts of ethylenediaminetetraacetic acid disodium salt dihydrate, and 0.2 parts of sodium formaldehyde sulfoxylate (SFS) were dissolved in deionized 5 parts of water was added to initiate radical polymerization. Thereafter, the mixture was held for 1 hour to complete the polymerization and obtain a composite rubber latex.

While maintaining the liquid temperature of this latex at 50 ° C., 16.1 parts of methyl methacrylate (MMA), 0.9 parts of n-butyl acrylate (nBA), 3.0 parts of glycidyl methacrylate (GMA), and t-butyl hydro A mixed solution of 0.05 part of peroxide (t-BH) was dropped into this latex at a rate of 0.5 part/minute to carry out a graft polymerization reaction. After completion of dropping, the temperature was maintained at 50° C. for 1 hour and then cooled to 25° C. to obtain a latex of polyorganosiloxane-containing graft copolymer (B-1).

The latex had a solid content of 32% by mass and a polymerization rate of 99.9% or more.
The number average particle diameter (Dn) measured by a capillary particle size distribution meter was 102 nm, the mass average particle diameter (Dw) was 107 nm, and Dw/Dn was 1.05.

Next, 630 parts of an aqueous solution having a calcium acetate concentration of 0.8% by mass was heated to 50° C., and the resulting graft copolymer latex was gradually added dropwise to the aqueous solution with stirring to solidify. The resulting graft copolymer was filtered, washed, dehydrated, and dried to obtain a powder of graft copolymer (B-1) containing epoxy groups.

The graft copolymer (B-1) has a polyorganosiloxane-derived Tg of −118° C., a poly(meth)acrylate polymer-derived Tg of −27° C., and a vinyl monomer component (b). It had a polymer-derived Tg of 111°C.

<Production Example 2-2> (Production of rubber-containing graft polymer (B-2))
Except for changing the polyorganosiloxane latex to be used to the polyorganosiloxane latex (β-1-2) obtained in Production Example 1-2, the above Production Example 2-1 (rubber-containing graft polymer (B-1) Production) to obtain a latex of a polyorganosiloxane-containing graft copolymer (B-2).

The latex had a solid content of 32% by mass and a polymerization rate of 99.9% or more.
The number average particle diameter (Dn) measured by a capillary particle size distribution meter was 306 nm, the mass average particle diameter (Dw) was 521 nm, and Dw/Dn was 1.70.

Next, 630 parts of an aqueous solution having a calcium acetate concentration of 0.8% by mass was heated to 60° C., and while stirring, the obtained graft copolymer latex was gradually added dropwise to the aqueous solution to solidify it. The resulting graft copolymer was filtered, washed, dehydrated, and dried to obtain a powder of graft copolymer (B-2) containing epoxy groups.

The graft copolymer (B-2) has a polyorganosiloxane-derived Tg of −118° C., a poly(meth)acrylate polymer-derived Tg of −27° C., and a vinyl monomer component (b). It had a polymer-derived Tg of 112°C.

<Production Example 2-3> (Production of rubber-containing graft polymer (B-3))
In the same manner as in Production Example 2-1 (Production of rubber-containing graft polymer (B-1)), except that the ratio of the vinyl monomer component (b) used for graft polymerization was as shown in Table 1, A latex of polyorganosiloxane-containing graft copolymer (B-3) was obtained.

The latex had a solid content of 32% by mass and a polymerization rate of 99.9% or more.
The number average particle diameter (Dn) measured by a capillary particle size distribution meter was 103 nm, the mass average particle diameter (Dw) was 107 nm, and Dw/Dn was 1.04.

Next, 630 parts of an aqueous solution having a calcium acetate concentration of 0.8% by mass was heated to 50° C., and while stirring, the obtained graft copolymer latex was gradually added dropwise to the aqueous solution to solidify it. The resulting graft copolymer was filtered, washed, dehydrated, and dried to obtain a powder of graft copolymer (B-3) containing epoxy groups.

The graft copolymer (B-3) has a polyorganosiloxane-derived Tg of −115° C., a poly(meth)acrylate polymer-derived Tg of −26° C., and a vinyl monomer component (b). It had a polymer-derived Tg of 114°C.

<Production Example 2-4> (Production of rubber-containing graft polymer (B-4))
In the same manner as in Production Example 2-1 (Production of rubber-containing graft polymer (B-1)), except that the ratio of the vinyl monomer component (b) used for graft polymerization was as shown in Table 1, A latex of polyorganosiloxane-containing graft copolymer (B-4) was obtained.

The latex had a solid content of 32% by mass and a polymerization rate of 99.9% or more.
The number average particle diameter (Dn) measured by a capillary particle size distribution meter was 101 nm, the mass average particle diameter (Dw) was 107 nm, and Dw/Dn was 1.06.

Next, 630 parts of an aqueous solution having a calcium acetate concentration of 0.8% by mass was heated to 55° C., and while stirring, the obtained graft copolymer latex was gradually added dropwise to the aqueous solution to solidify it. The resulting graft copolymer was filtered, washed, dehydrated, and dried to obtain a powder of graft copolymer (B-4). The graft copolymer (B-4) does not contain epoxy groups.

The graft copolymer (B-4) has a polyorganosiloxane-derived Tg of −118° C., a poly(meth)acrylate polymer-derived Tg of −27° C., and a vinyl monomer component (b). It had a polymer-derived Tg of 116°C.

<Examples 1 to 12, Comparative Examples 1 to 11>
Rubber-containing graft polymer (B) and polymer (C) were added in the amounts shown in Tables 2 and 3 to 100 parts by mass of polyamide resin PA6 to obtain a mixture. This mixture was supplied to a devolatilizing twin-screw extruder (manufactured by Ikegai Co., Ltd., PCM-30 (trade name)) heated to a barrel temperature of 250° C. and kneaded to prepare pellets of each resin composition.

Each obtained resin composition pellet was dried at 80° C. for 10 hours and then injection molded under the following conditions to prepare a test piece for evaluation.
Injection molding machine: SE100DU (product name) manufactured by Sumitomo Heavy Industries, Ltd.
Cylinder temperature: 250°C, mold temperature: 80°C
Specification of test piece: length 80 mm x width 10 mm x thickness 4 mm

[Impact resistance evaluation]
Notches of TYPE A conforming to ISO 179-1 were cut into the obtained test piece, and Charpy impact strength was measured at 23°C and -40°C. The results obtained are shown in Tables 2 and 3. In addition, it can be said that impact resistance is so favorable that a numerical value is high, and it is preferable. Also, in the table, N.I. B. indicates that the test piece did not break completely in the Charpy impact test, and it can be said that the impact resistance is superior to the case with numerical values, which is preferable.

[Heat deterioration resistance evaluation]
Each resin composition pellet obtained by kneading with the twin-screw extruder is placed in an unsaturated type ultra-accelerated life test device (PC-422R7, manufactured by Hirayama Seisakusho Co., Ltd.) set at a temperature of 110 ° C. and a humidity of 100% RH. It was left to stand still for 60 hours and subjected to wet heat treatment.

Each resin composition pellet obtained by kneading with the twin-screw extruder and each resin composition pellet after the wet heat treatment were dried at 80 ° C. for 10 hours, respectively, and then melt indexer (Tateyama Kagaku Kogyo Co., Ltd. L227-42 (L220 type)) was used to measure the melt mass flow rate (MFR) value in accordance with JIS K 7210 under conditions of a measurement temperature of 250° C. and a load of 2.16 kg. The results obtained are shown in Tables 2 and 3.
Incidentally, it can be said that the smaller the difference in the MFR values before and after the wet heat treatment, the better the resistance to heat deterioration, which is preferable.

A comparison of Examples 1 to 12 with Comparative Examples 1 to 11 reveals that the epoxy group-containing rubber-containing graft polymer (B) and the polymer (C) containing a carboxy group or a derivative thereof are added to the polyamide resin (A). It can be seen that the Charpy impact strength and heat deterioration resistance are excellent only when both are included.

<Example 13, Comparative Examples 12 to 14>
To 100 parts by mass of polyamide resin PA66, the rubber-containing graft polymer (B) and polymer (C) were added in the amounts shown in Table 4 to obtain a mixture. This mixture was supplied to a devolatilizing twin-screw extruder (manufactured by Ikegai Co., Ltd., PCM-30 (trade name)) heated to a barrel temperature of 285° C. and kneaded to prepare pellets of each resin composition.

Each obtained resin composition pellet was dried at 80° C. for 10 hours and then injection molded under the following conditions to prepare a test piece for evaluation.
Injection molding machine: SE100DU (product name) manufactured by Sumitomo Heavy Industries, Ltd.
Cylinder temperature: 285°C, mold temperature: 80°C
Specification of test piece: length 80 mm x width 10 mm x thickness 4 mm

[Impact resistance evaluation]
Notches of TYPE A conforming to ISO 179-1 were cut into the obtained test piece, and Charpy impact strength was measured at 23°C and -40°C. Table 4 shows the results obtained. In addition, it can be said that impact resistance is so favorable that a numerical value is high, and it is preferable.

[Heat deterioration resistance evaluation]
Each resin composition pellet obtained by kneading with the twin-screw extruder is placed in an unsaturated type ultra-accelerated life test device (PC-422R7, manufactured by Hirayama Seisakusho Co., Ltd.) set at a temperature of 110 ° C. and a humidity of 100% RH. It was left to stand still for 60 hours and subjected to wet heat treatment.

Each resin composition pellet obtained by kneading with the twin-screw extruder and each resin composition pellet after the wet heat treatment were dried at 80 ° C. for 10 hours, respectively, and then melt indexer (Tateyama Kagaku Kogyo Co., Ltd. L227-42 (L220 type)) was used to measure the melt mass flow rate (MFR) value in accordance with JIS K 7210 under conditions of a measurement temperature of 285°C and a load of 2.16 kg. Table 4 shows the results obtained.
Incidentally, it can be said that the smaller the difference in the MFR values before and after the wet heat treatment, the better the resistance to heat deterioration, which is preferable.

Comparing Example 13 with Comparative Examples 12 to 14, it was found that the epoxy group-containing rubber-containing graft polymer (B) and the polymer (C) containing a carboxy group and/or a derivative thereof were added to the polyamide resin (A). It can be seen that the Charpy impact strength and heat deterioration resistance are excellent only when both are included.

<Example 14, Comparative Examples 15 to 17>
Polyamide resin PA66, glass fiber-containing polyamide resin PA66+GF, rubber-containing graft polymer (B) and polymer (C) were added in the amounts shown in Table 5 to obtain a mixture. In any mixture, the polyamide resin content was 100 parts by mass and the GF content ratio was 20 wt%.
This mixture was supplied to a devolatilizing twin-screw extruder (manufactured by Ikegai Co., Ltd., PCM-30 (trade name)) heated to a barrel temperature of 285° C. and kneaded to prepare pellets of each resin composition.

Each obtained resin composition pellet was dried at 80° C. for 10 hours and then injection molded under the following conditions to prepare a test piece for evaluation.
Injection molding machine: SE100DU (product name) manufactured by Sumitomo Heavy Industries, Ltd.
Cylinder temperature: 285°C, mold temperature: 80°C
Specification of test piece: length 80 mm x width 10 mm x thickness 4 mm

[Impact resistance evaluation]
Notches of TYPE A conforming to ISO 179-1 were cut into the obtained test piece, and Charpy impact strength was measured at 23°C and -40°C. Table 5 shows the results obtained. In addition, it can be said that impact resistance is so favorable that a numerical value is high, and it is preferable.

[Heat deterioration resistance evaluation]
Each resin composition pellet obtained by kneading with the twin-screw extruder is placed in an unsaturated type ultra-accelerated life test device (PC-422R7, manufactured by Hirayama Seisakusho Co., Ltd.) set at a temperature of 110 ° C. and a humidity of 100% RH. It was left to stand still for 60 hours and subjected to wet heat treatment.

Each resin composition pellet obtained by kneading with the twin-screw extruder and each resin composition pellet after the wet heat treatment were dried at 80 ° C. for 10 hours, respectively, and then melt indexer (Tateyama Kagaku Kogyo Co., Ltd. Manufactured by L227-42 (L220 type)), in accordance with JIS K 7210, at a measurement temperature of 285 ° C. and a load of 2.16 kg, the melt mass flow rate (MFR) value was measured. shown in
Incidentally, it can be said that the smaller the difference in the MFR values before and after the wet heat treatment, the better the resistance to heat deterioration, which is preferable.

Comparing Example 14 with Comparative Examples 15 to 17, it was found that the epoxy group-containing rubber-containing graft polymer (B) and the polymer (C) containing a carboxy group and/or a derivative thereof were added to the polyamide resin (A). It can be seen that the Charpy impact strength and heat deterioration resistance are excellent only when both are included.

Claims (8)

A resin composition comprising a polyamide resin (A), a rubber-containing graft polymer (B) having an epoxy group, and a polymer (C) containing a carboxy group and/or a derivative thereof. The ratio of the rubber-containing graft polymer (B) to 100 parts by weight of the polyamide resin (A) is 0.1 to 30 parts by weight, and the ratio of the polymer (C) is 0.1 to 10 parts by weight. , The resin composition of claim 1. 3. The resin composition according to claim 1, wherein the rubber-containing graft polymer (B) contains at least one of polyorganosiloxane and polyalkyl(meth)acrylate as a rubber component. The resin composition according to any one of claims 1 to 3, wherein the polymer (C) contains a dicarboxylic anhydride group. The resin composition according to any one of claims 1 to 4, wherein the polymer (C) has an acid value of 1 to 2500 mgKOH/g. The resin composition according to any one of claims 1 to 5, wherein the polymer (C) has an acid value of 20 to 200 mgKOH/g. The polyamide resin composition according to any one of claims 1 to 6, wherein the polymer (C) contains an α-olefin having 10 to 80 carbon atoms as a copolymer component. A molded article containing the resin composition according to any one of claims 1 to 7.