Polymer, resin additive, resin composition, molded body, and method for producing polymer

Abstract

Provided are: a molded body in which decrease in fluidity during processing is suppressed and impact resistance is excellent; a polymer for producing the molded body; a method for producing same; and a resin composition. The polymer according to the present invention has a first polymer part and a second polymer part. The first polymer part is a polyamide polymer. The second polymer part has a constituent unit derived from a (meth)acrylate monomer. The ratio of the second polymer part is 45% by mass or more when the total of the first polymer part and the second polymer part is taken as 100% by mass.

Description

Polymer, resin additive, resin composition, molded body, and method for producing polymer

[0001] The present invention relates to a polymer, a resin additive, a resin composition, a molded article, and a method for producing a polymer. This application claims priority based on Japanese Patent Application No. 2024-050719, filed on March 27, 2024, the contents of which are incorporated herein by reference.

[0002] Modifiers are sometimes used to improve the impact strength of resins in resin molded articles such as components for electronic devices, electrical devices, office automation equipment, automobile components, building components, etc. Patent Document 1, for example, discloses an acrylic rubber graft copolymer obtained by emulsion polymerization of a vinyl monomer such as methyl methacrylate in the presence of an acrylic rubber component.

[0003] Japanese Patent Application Publication No. 2000-319482

[0004] However, there is a concern that the resin composition containing the acrylic rubber graft copolymer described in Patent Document 1 may have reduced fluidity during molding processing, and there is room for improvement in fluidity. Furthermore, there is still room for improvement in the impact resistance of a molded article containing the acrylic rubber graft copolymer. The present invention aims to provide a molded article that exhibits excellent impact resistance and that suppresses the reduction in fluidity during processing, a polymer for producing the molded article, a method for producing the polymer, and a resin composition.

[0005] The present invention has the following aspects. [1] A polymer having a first polymer portion and a second polymer portion, wherein the first polymer portion is a polyamide polymer, and the second polymer portion has structural units derived from a (meth)acrylate monomer, and the proportion of the second polymer portion is 45% by mass or more when the total of the first polymer portion and the second polymer portion is taken as 100% by mass. [2] The polymer of [1], wherein the proportion of the second polymer portion is 95% by mass or less when the total of the first polymer portion and the second polymer portion is taken as 100% by mass. [3] The polymer of [1] or [2], wherein the proportion of the first polymer portion is 5 to 55% by mass when the total of the first polymer portion and the second polymer portion is taken as 100% by mass. [4] The polymer of any of [1] to [3], wherein the proportion of the structural units derived from a (meth)acrylate monomer is 1% by mass or more relative to the total mass of all structural units constituting the second polymer portion. [5] The polymer of any one of [1] to [4], having a core-shell structure, wherein the first polymer portion constitutes the shell portion of the core-shell structure, and the second polymer portion constitutes the core portion of the core-shell structure. [6] The polymer of any one of [1] to [5], obtained by emulsion polymerization of a monomer component constituting the second polymer portion in the presence of a polyamide polymer. [7] A resin additive comprising the polymer of any one of [1] to [6]. [8] A resin composition comprising the polymer of any one of [1] to [6] and a thermoplastic resin other than the polymer of any one of [1] to [6]. [9] The resin composition of [8], wherein the thermoplastic resin comprises a polyamide resin.

[10] The resin composition of [8] or [9], wherein the proportion of the polymer relative to 100 parts by mass of the thermoplastic resin is 30 parts by mass or less.

[11] A molded product comprising the resin composition of any one of [8] to

[10] .

[12] A method for producing a polymer having a first polymer portion and a second polymer portion, wherein the first polymer portion is a polyamide polymer, and the second polymer portion has a structural unit derived from a (meth)acrylate monomer, and the method comprises emulsion-polymerizing a monomer component constituting the second polymer portion in the presence of the polyamide polymer.

[0006] The present invention also includes the following other aspects. <1> A polymer having a first polymer portion and a second polymer portion, wherein the first polymer portion is a polyamide polymer, and the second polymer portion has structural units derived from a (meth)acrylate monomer. <2> The polymer of <1>, wherein the proportion of the first polymer portion is 3 to 90 mass% when the total of the first polymer portion and the second polymer portion is 100 mass%. <3> The polymer of <1> or <2>, wherein the proportion of the structural units derived from the (meth)acrylate monomer is 10 mass% or more relative to the total mass of all structural units constituting the second polymer portion. <4> The polymer of any of <1> to <3>, obtained by emulsion polymerization of a monomer component constituting the second polymer portion in the presence of the polyamide polymer. <5> A resin composition comprising the polymer of any of <1> to <4> and a thermoplastic resin other than the polymer. <6> The resin composition according to <5> above, wherein the thermoplastic resin comprises a polyamide resin. <7> The resin composition according to <5> or <6> above, wherein the ratio of the polymer is 30 parts by mass or less per 100 parts by mass of the thermoplastic resin. <8> A molded product comprising the resin composition of any of <5> to <7> above. <9> A method for producing a polymer having a first polymer portion and a second polymer portion, wherein the first polymer portion is a polyamide polymer, and the second polymer portion has structural units derived from a (meth)acrylate monomer, the method comprising emulsion-polymerizing a monomer component constituting the second polymer portion in the presence of the polyamide polymer.

[0007] According to the present invention, it is possible to provide a molded article in which a decrease in fluidity during processing is suppressed and which has excellent impact resistance, a polymer for producing the molded article, a method for producing the polymer, and a resin composition.

[0008] The present invention will be described in more detail below by presenting preferred embodiments of the invention. However, the following description is merely an example of an embodiment of the present invention, and the present invention is not limited to the following description as long as it does not deviate from the gist of the present invention. In this specification, the following definitions of terms are adopted. The term "structural unit" refers to a structural unit derived from a monomer, i.e., a structural unit formed by polymerizing a monomer, or a structural unit in which a portion of the structural unit is converted into a different structure by processing a polymer. The generic term for acrylate and methacrylate is "(meth)acrylate." The generic term for acrylic and methacrylic is "(meth)acrylic." A "molded product" is a molded product obtained by molding a resin composition. A numerical range expressed as "to" means a numerical range that includes the numerical values ​​before and after "to" as the lower and upper limits. The numerical ranges for the content, various physical property values, and property values ​​disclosed in this specification can be arbitrarily combined to form new numerical ranges.

[0009] [Polymer] The polymer of the first aspect of the present invention is a polymer having a first polymer portion and a second polymer portion (hereinafter also referred to as "polymer (P)"). The polymer (P) may be a polymer in which the first polymer portion and the second polymer portion are covalently bonded, or a polymer in which the first polymer portion and the second polymer portion are not covalently bonded.

[0010] Examples of polymers in which the first polymer portion and the second polymer portion are covalently bonded include block copolymers having the first polymer portion and the second polymer portion. Examples of polymers in which the first polymer portion and the second polymer portion are not covalently bonded include polymers in which the second polymer portion is encapsulated or enclosed by the first polymer portion. Specifically, examples include polymers having a core-shell structure in which the core portion contains one of the first polymer portion and the second polymer portion, and the shell portion contains the other. Note that a "core-shell structure" is a structure in which a portion called the core is encapsulated in a portion called the shell.

[0011] Among these, the polymer (P) is preferably a polymer having a core-shell structure, in which the first polymer portion constitutes the shell part of the core-shell structure and the second polymer portion constitutes the core part of the core-shell structure. Preferred embodiments of the polymer (P) having a core-shell structure will be described in detail below as representative examples.

[0012] <First polymer portion> The first polymer portion is a polymer chain (A) composed of a polyamide polymer (A1). When the first polymer portion is composed of a polyamide polymer, when the polymer (P) is mixed with a thermoplastic resin (T) described below to form a resin composition, the compatibility between the polymer (P) and the thermoplastic resin (T) is increased, and the impact resistance of a molded article containing the resin composition is improved. In particular, when the polymer (P) has a core-shell structure, the first polymer portion which is the polyamide polymer (A1) constitutes the shell portion of the core-shell structure, and the thermoplastic resin (T) contains a polyamide resin (T1), the compatibility between the polymer (P) and the thermoplastic resin (T) is further increased.

[0013] The polyamide polymer (A1) refers to a polymer having an amide bond. Examples of the polyamide polymer (A1) include polyamide polymers obtained by polycondensation of diamines and dicarboxylic acids, polyamide polymers obtained by polycondensation of ω-amino-ω'carboxylic acids, and polyamide polymers obtained by ring-opening polymerization of cyclic lactams. These polyamide polymers (A1) may be used alone or in combination of two or more.

[0014] Examples of diamines include ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, phenylenediamine, and metaxylylenediamine. Examples of dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, tetradecanedicarboxylic acid, octadecanedicarboxylic acid, fumaric acid, phthalic acid, xylylenedicarboxylic acid, and dimer acid (an unsaturated dicarboxylic acid having 36 carbon atoms synthesized from an unsaturated fatty acid primarily composed of linoleic acid or oleic acid). These diamines and dicarboxylic acids may be used alone or in combination of two or more.

[0015] Examples of ω-amino-ω'carboxylic acids include 6-aminohexanoic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. These ω-amino-ω'carboxylic acids may be used alone or in combination of two or more.

[0016] Examples of cyclic lactams include ε-caprolactam, ω-caprylolactam, ω-enantholactam, ω-lauryllactam, and undecanolactam. These cyclic lactams may be used alone or in combination of two or more.

[0017] The polycondensation or ring-opening polymerization may be carried out in the presence of a polymerization regulator. Use of the polymerization regulator makes it possible to easily produce a polyamide resin having, for example, a terminal carboxyl group to terminal amino group ratio of 60 / 40 to 100 / 0. Examples of polymerization regulators include monocarboxylic acids such as caproic acid, heptanoic acid, nonanoic acid, undecanoic acid, and dodecanoic acid; and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, tetradecanedicarboxylic acid, octadecanedicarboxylic acid, fumaric acid, phthalic acid, xylylenedicarboxylic acid, and dimer acid. These polymerization regulators may be used alone or in combination of two or more.

[0018] The polyamide polymer (A1) may be —[NH(CH ２ ) ５ CO]-,-[NH(CH ２ ) ６ NHCO(CH ２ ) ４ CO]-,-[NH(CH ２ ) ６ NHCO(CH ２ ) ８ CO]-,-[NH(CH ２ ) １０ CO]-,-[NH(CH ２ ) １１ CO]-,-[NH(CH ２ ) ２ NHCO-D-CO]- (where "D" represents an unsaturated hydrocarbon having 34 carbon atoms). The polyamide polymer (A1) is preferably an aqueous emulsion containing a polyamide resin having a self-emulsifying functional group.

[0019] As the functional group having self-emulsifying property, for example, can be mentioned hydrophilic group such as nonionic, cationic, anionic, or their mixture.As such hydrophilic group, can be mentioned hydroxyl group, polyoxyethylene group, polyoxypropylene group, carbonyl group, cyano group, nitro group, amino group, monoalkylamino group, dialkylamino group, carboxyl group, sulfonic acid group, pyridinium group, quaternary ammonium group.As the polyamide resin having the above-mentioned structural unit, can be mentioned nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, nylon 6 / 66 copolymer, nylon 6 / 610 copolymer, nylon 6 / 11 copolymer, nylon 6 / 12 copolymer, nylon 6 / 66 / 11 copolymer, nylon 6 / 66 / 12 copolymer, nylon 6 / 66 / 11 / 12 copolymer, nylon 6 / 66 / 610 / 11 / 12 copolymer, dimer acid polyamide resin. These polyamide resins or aqueous emulsions containing polyamide resins may be used alone or in combination of two or more.

[0020] <Second polymer portion> The second polymer portion is a polymer chain (B) having a structural unit derived from a (meth)acrylate monomer (hereinafter also referred to as "monomer (b1)"). That is, the second polymer portion has a structural unit different from the structural unit constituting the polyamide polymer, which is the first polymer portion. By having the structural unit derived from monomer (b1) in the second polymer portion, a decrease in fluidity during processing is suppressed, and the impact resistance of the molded body is further improved. The second polymer portion may be composed only of structural units derived from monomer (b1), or may further have, in addition to the structural unit derived from monomer (b1), a structural unit derived from a monomer other than monomer (b1) (hereinafter also referred to as "monomer (b2)"), or a polyorganosiloxane (structural unit derived from organosiloxane).

[0021] Examples of the monomer (b1) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, i-pentyl (meth)acrylate, 2-methylbutyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and dodecyl (meth)acrylate. linear or branched alkyl group-containing (meth)acrylates such as cyclohexyl (meth)acrylate, 4-t-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; alicyclic (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate; 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 1,2-dihydroxyethyl (meth)acrylate, 1,2-dihydroxypropyl (meth)acrylate, 1,2-dihydroxybutyl (meth)acrylate, 1,2-dihydroxy-5-ethylhexyl (meth)acrylate, 1,1-dihydroxyethyl (meth)acrylate, 1,1-dihydroxypropyl (meth)acrylate, 1,1-dihydroxybutyl (meth)acrylate, 1,2,3- Hydroxy group-containing (meth)acrylates such as trihydroxypropyl (meth)acrylate, 1,2,3-trihydroxybutyl (meth)acrylate, 1,1,2-trihydroxypropyl (meth)acrylate, 1,1,2-trihydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, α-ethyl glycidyl acrylate, and 3,4-epoxybutyl (meth)acrylate;Aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl (meth)acrylate; oxyethylene group-containing acrylic acid esters such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, methoxydiethylene glycol mono(meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, methoxydipropylene glycol mono(meth)acrylate, methoxypolypropylene glycol mono(meth)acrylate, ethoxydiethylene glycol mono(meth)acrylate, ethyl carbitol (meth)acrylate, and 2-ethylhexyl carbitol (meth)acrylate; dimethylaminoethyl (meth)acrylate; Amino group-containing (meth)acrylates such as acrylate and diethylaminoethyl (meth)acrylate; carboxy group-containing (meth)acrylates such as (meth)acrylic acid, succinic acid mono(2-(meth)acryloyloxyethyl), and ω-carboxy-polycaprolactone mono(meth)acrylate; polyfunctional methacrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and allyl (meth)acrylate;Examples of the siloxy group-containing (meth)acrylates include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, and δ-methacryloyloxybutyldiethoxymethylsilane. Among these, methyl(meth)acrylate, n-butyl(meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, and allyl(meth)acrylate are preferred. These monomers (b1) may be used alone or in combination of two or more.

[0022] The monomer (b2) is not particularly limited as long as it is copolymerizable with the monomer (b1), and examples thereof include aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyltoluene; diene monomers such as 1,3-butadiene and isoprene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; carboxylic acid vinyl monomers such as vinyl acetate and vinyl butyrate; olefin monomers such as ethylene, propylene, and isobutylene; halogenated vinyl monomers such as vinyl chloride and vinylidene chloride; and maleimide monomers such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and N-methylmaleimide. These monomers (b2) may be used alone or in combination of two or more.

[0023] Polyorganosiloxane is a polymer containing organosiloxane units. Polyorganosiloxane can be obtained by polymerizing an organosiloxane mixture containing organosiloxane. The organosiloxane mixture may further contain components used as needed. Examples of components used as needed include siloxane-based crosslinking agents, siloxane-based crosslinking agents, and siloxane oligomers having terminal blocking groups.

[0024] Examples of organosiloxanes include linear organosiloxanes, alkoxysilane compounds, and cyclic organosiloxanes. These can be used alone or in combination of two or more. Among these, alkoxysilane compounds and cyclic organosiloxanes are preferred, and cyclic organosiloxanes are particularly preferred because of their high polymerization stability and high polymerization rate.

[0025] The alkoxysilane compound is preferably a bifunctional alkoxysilane compound. Examples thereof include dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dipropoxydimethylsilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane. These may be used alone or in combination of two or more.

[0026] The cyclic organosiloxane is preferably a 3- to 7-membered cyclic organosiloxane. Examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane. These can be used alone or in combination of two or more. Among these, octamethylcyclotetrasiloxane is preferred because it is easy to control the particle size distribution.

[0027] As the organosiloxane, from the viewpoint of the impact resistance of the molded article, cyclic dimethylsiloxane and bifunctional dialkylalkoxysilane compounds are preferred.

[0028] Cyclic dimethylsiloxane is a cyclic siloxane having two methyl groups on a silicon atom. Examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These can be used alone or in combination of two or more.

[0029] The bifunctional dialkylalkoxysilane compound is a silane compound having two alkoxy groups and two alkyl groups on a silicon atom. Examples include dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, and dipropoxydimethylsilane. These can be used alone or in combination of two or more.

[0030] The proportion of the structural units derived from monomer (b1) relative to the total mass of all structural units constituting the second polymer portion may be 1% by mass or more, 2% by mass or more, 10% by mass or more, 50% by mass or more, 70% by mass or more, or 90% by mass or more. It may also be 100% by mass or less, 99% by mass or less, or 98% by mass or less. For example, it may be 1 to 100% by mass, 2 to 100% by mass, 10 to 100% by mass, 50 to 100% by mass, 70 to 100% by mass, 90 to 100% by mass, 50 to 99% by mass, 70 to 99% by mass, 90 to 99% by mass, or 90 to 98% by mass. When the proportion of the structural units derived from monomer (b1) is equal to or greater than the above lower limit, a decrease in fluidity during processing is suppressed, and the impact resistance of the molded product is further improved.

[0031] <Proportion> When the total of the first polymer portion and the second polymer portion is taken as 100% by mass, the proportion of the first polymer portion is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. On the other hand, the proportion of the first polymer portion is preferably 55% by mass or less, more preferably 53% by mass or less, and even more preferably 50% by mass or less. For example, it may be 5 to 55% by mass, 10 to 53% by mass, or 15 to 50% by mass. When the proportion of the first polymer portion is equal to or greater than the above-mentioned lower limit, when the polymer (P) is mixed with the thermoplastic resin (T) described below to form a resin composition, the compatibility between the polymer (P) and the thermoplastic resin (T) is further enhanced, and the impact resistance of a molded article containing the resin composition is further improved. When the proportion of the first polymer portion is equal to or less than the above-mentioned upper limit, the second polymer portion is sufficiently present in the polymer (P), and the impact resistance of the molded article is further improved.

[0032] When the total of the first polymer portion and the second polymer portion is taken as 100% by mass, the proportion of the second polymer portion is 45% by mass or more, preferably 47% by mass or more, and more preferably 50% by mass or more. On the other hand, from the viewpoint of polymerization stability, the proportion of the second polymer portion is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. For example, it may be 45 to 95% by mass, 47 to 90% by mass, or 50 to 85% by mass or more. When the proportion of the second polymer portion is equal to or greater than the above lower limit, a decrease in fluidity during processing is suppressed, and the impact resistance of the molded product is further improved.

[0033] <Method for producing polymer (P)> When the polymer (P) has a core-shell structure, the method for producing the polymer (P) is not particularly limited, and the polymer (P) can be produced by known methods such as suspension polymerization, solution polymerization, and emulsion polymerization. Among these, production by emulsion polymerization is preferred from the viewpoint of ease of production. Specifically, it is preferred to produce the polymer (P) by emulsion polymerizing the monomer component (m) constituting the second polymer portion in the presence of the polyamide polymer (A1). That is, the polymer (P) is preferably a polymer obtained by emulsion polymerizing the monomer component (m) in the presence of the polyamide polymer (A1).

[0034] The monomer component (m) contains a monomer (b1). In addition to the monomer (b1), the monomer component (m) may further contain a monomer (b2) as needed. The proportion of the monomer (b1) relative to the total mass of the monomer component (m) may be 1% by mass or more, 2% by mass or more, 10% by mass or more, 50% by mass or more, 70% by mass or more, or 90% by mass or more. Alternatively, it may be 100% by mass or less, 99% by mass or less, or 98% by mass or less. For example, it may be 1 to 100% by mass, 2 to 100% by mass, 10 to 100% by mass, 50 to 100% by mass, 70 to 100% by mass, 90 to 100% by mass, 50 to 99% by mass, 70 to 99% by mass, 90 to 99% by mass, or 90 to 98% by mass.

[0035] When the total of the polyamide polymer (A1) and the monomer component (m) is taken as 100% by mass, the proportion of the polyamide polymer (A1) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. It is also preferably 55% by mass or less, more preferably 53% by mass or less, and even more preferably 50% by mass or less. For example, it may be 5 to 55% by mass, 10 to 53% by mass, or 15 to 50% by mass.

[0036] The polymer (P) can be prepared by adding the monomer component (m) to a solution (hereinafter also referred to as "dispersion") in which the polyamide polymer (A1) is dispersed in any solvent, emulsifying the mixture using a mixer, and then adding a polymerization initiator to polymerize the mixture. When carrying out emulsion polymerization, the monomer component (m) may be added all at once to polymerize the mixture, or may be added stepwise to polymerize the mixture (e.g., dropwise polymerization).

[0037] Examples of solvents used in preparing the dispersion include water, isopropyl alcohol, ethanol, methanol, acetone, methyl ethyl ketone, and diethyl ether. Among these, water is preferred. These solvents may be used alone or in combination of two or more.

[0038] The dispersion is obtained by adding polyamide polymer (A1) to a solvent and stirring under shear. The proportion of polyamide polymer (A1) relative to the total mass of the dispersion is preferably 10 to 50% by mass. When the proportion of polyamide polymer (A1) is equal to or greater than the above lower limit, the dispersibility of polyamide polymer (A1) is excellent. When the proportion of polyamide polymer (A1) is equal to or less than the above upper limit, the handleability of the dispersion is excellent. Commercially available products may be used as the dispersion. Examples of commercially available aqueous dispersions of polyamide polymer (A1) include those manufactured by Sumitomo Seika Chemicals Co., Ltd. under the trade names "Sepolsion PA150" and "Sepolsion PA200."

[0039] When adding the monomer component (m) to the dispersion, a surfactant may be further added. Examples of surfactants include anionic surfactants, cationic surfactants, and nonionic surfactants. These surfactants may be used alone or in combination of two or more. Note that the polyamide polymer (A1) has self-emulsifying properties and therefore functions as an emulsifier. Therefore, by carrying out polymerization of the monomer component (m) in the presence of the polyamide polymer (A1), the monomer component (m) can be emulsion-polymerized without adding a surfactant.

[0040] The polymerization initiator is not particularly limited as long as it is one that is used in general radical polymerization, and examples thereof include persulfates such as potassium persulfate (potassium peroxodisulfate), sodium persulfate, and ammonium persulfate; oil-soluble azo compounds such as azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile; 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,2'-azobis{2-methyl-N-[2-(1-hydroxyethyl)]propionamide}, and 2,2'-azobis{2- water-soluble azo compounds such as 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] and salts thereof, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] and salts thereof, 2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane} and salts thereof, 2,2'-azobis(2-methylpropynamidine) and salts thereof, and 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]; and organic peroxides such as benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butylperoxy-2-ethylhexanoate, and t-butylperoxyisobutyrate. These polymerization initiators may be used alone or in combination of two or more.

[0041] Examples of radical polymerization methods include a method in which polymerization is carried out using a water-soluble polymerization initiator, and a method in which polymerization is carried out by a redox reaction using an organic peroxide and a reducing agent such as ferrous sulfate or isoascorbic acid.

[0042] The amount of the polymerization initiator used is preferably 0.05 to 1 part by mass, more preferably 0.1 to 0.3 parts by mass, per 100 parts by mass of the monomer component (m). When an organic peroxide is used as the polymerization initiator, it can be used in combination with a reducing agent as a redox polymerization initiator. The amount of the reducing agent used is preferably 0.0001 to 1 part by mass per 100 parts by mass of the monomer component (m).

[0043] When the monomer component (m) is added to the dispersion, a chain transfer agent may be further added for the purpose of adjusting the molecular weight. Examples of the chain transfer agent include n-dodecyl mercaptan, t-dodecyl mercaptan, and α-methylstyrene dimer. These chain transfer agents may be used alone or in combination of two or more.

[0044] The reaction temperature when emulsion polymerizing the monomer component (m) is not particularly limited, but is, for example, preferably 45 to 90° C., more preferably 50 to 85° C. The reaction time when emulsion polymerizing the monomer component (m) is not particularly limited, but is, for example, preferably 30 minutes to 8 hours, more preferably 1 to 6 hours.

[0045] Polymer (P) is obtained in the form of a latex by emulsion polymerization of monomer component (m) in the presence of polyamide polymer (A1). The volume average particle diameter of the latex-like polymer (P) is preferably 50 to 2,000 nm, more preferably 80 to 1,000 nm. In this specification, the volume-based particle size distribution is measured using a laser diffraction / scattering particle size distribution analyzer, and the median diameter is taken as the volume average particle diameter.

[0046] The method for recovering the polymer (P) from the latex of the polymer (P) is not particularly limited. For example, the latex of the polymer (P) can be dried by a spray drying method or a freeze drying method, or coagulated to obtain the polymer (P) as a powder. Among these, drying or coagulation by a spray drying method is preferred. If the latex of the polymer (P) is dried by a spray drying method, the dispersibility of the polymer (P) powder when added to the thermoplastic resin (T) described below is likely to be improved. If the latex of the polymer (P) is coagulated, the unreacted monomer component (m), polymerization initiator, chain transfer agent, etc. can be easily removed, making it easy to obtain a powder of the polymer (P) with high purity.

[0047] When drying by spray drying, it is preferable to spray the latex of polymer (P) in the form of fine droplets and then dry it by applying hot air to them. Examples of devices that generate droplets include rotating disk type, pressure nozzle type, and two-fluid nozzle type devices. When drying the latex of polymer (P) by applying hot air, the hot air temperature is preferably 100 to 200°C. When the hot air temperature is equal to or higher than the above lower limit, the latex can be sufficiently dried. When the hot air temperature is equal to or lower than the above upper limit, thermal decomposition of the powder can be suppressed.

[0048] When coagulation is performed, for example, the latex of polymer (P) is introduced into hot water in which a coagulant has been dissolved, and the polymer (P) is separated and purified by salting out. The coagulated, wet product is washed as necessary, and then dehydrated and dried. Examples of coagulants include inorganic salts such as aluminum chloride, aluminum sulfate, sodium sulfate, magnesium sulfate, sodium nitrate, and calcium acetate; and acids such as sulfuric acid. Among these, calcium acetate is particularly preferred. These coagulants may be used alone or in combination of two or more. When two or more coagulants are used in combination, it is preferable to select a combination that is less likely to form a water-insoluble salt. For example, when calcium acetate is used in combination with sulfuric acid or its sodium salt, a water-insoluble calcium salt is likely to be formed, and separation of this calcium salt from the powder of polymer (P) is time-consuming.

[0049] It is common technical knowledge that the polymerization mode of the first polymer portion and the second polymer portion of the polymer (P) changes depending on the production method thereof, but it is difficult to specify the polymerization mode. For example, it is considered that the polymerization mode of the polymer (P) obtained by emulsion polymerization of the monomer component (m) in the presence of the polyamide polymer (A1) may be different from that of the polymer (P) obtained by other methods, resulting in differences in structure, etc. However, it is technically impossible or practical to specify the structure, etc. in such a way that such differences are clearly apparent.

[0050] <Effects> Because the first polymer portion of the polymer (P) of the first aspect of the present invention is a polyamide polymer, when the polymer (P) is mixed with the thermoplastic resin (T) described below to form a resin composition, the compatibility between the polymer (P) and the thermoplastic resin (T) is enhanced, and the impact resistance of a molded article containing the resin composition is improved. Furthermore, when the polymer (P) of the first aspect of the present invention is mixed with the thermoplastic resin (T) described below to form a resin composition, it acts to relax intermolecular hydrogen bonds formed by the thermoplastic resin (T), thereby suppressing a decrease in the fluidity of the resin composition. Furthermore, when the polymer (P) is mixed with the thermoplastic resin (T) described below to form a resin composition, the polymer (P) and the thermoplastic resin (T) are not chemically bonded, thereby further suppressing a decrease in the fluidity of the resin composition. Therefore, the polymer (P) of this embodiment is suitable as a resin additive for producing a molded article that suppresses a decrease in fluidity during processing and has excellent impact resistance, specifically as a modifier for improving the impact strength of the thermoplastic resin (T). In addition, the polymer (P) of this embodiment has excellent heat resistance and a high thermal decomposition temperature. Therefore, it is particularly useful as a modifier for thermoplastic resins (T) that are molded at high temperatures (for example, 200° C. or higher).

[0051] [Resin Composition] The resin composition of the second aspect of the present invention contains the above-mentioned polymer (P) and a thermoplastic resin (T) other than the polymer (P). In addition to the polymer (P) and the thermoplastic resin (T), the resin composition may further contain components other than the polymer (P) and the thermoplastic resin (T) (hereinafter also referred to as "optional components") as long as the effects of the present invention are not impaired.

[0052] <Polymer (P)> The proportion of the polymer (P) in the resin composition is preferably 30 parts by mass or less, more preferably 0.1 to 30 parts by mass, even more preferably 1 to 20 parts by mass, and particularly preferably 5 to 10 parts by mass, per 100 parts by mass of the thermoplastic resin (T). When the proportion of the polymer (P) is equal to or greater than the above-mentioned lower limit, the impact resistance of the molded article is further improved. When the proportion of the polymer (P) is equal to or less than the above-mentioned upper limit, the moldability when molding the resin composition is excellent.

[0053] <Thermoplastic Resin (T)> The thermoplastic resin (T) plays the role of a matrix resin. Examples of the thermoplastic resin (T) include styrene-based resins such as polystyrene, acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS), high-impact polystyrene (HIPS), and syndiotactic polystyrene; acrylic resins such as polymethyl methacrylate; polyolefin-based resins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyamide resins (hereinafter also referred to as "polyamide resin (T1)") such as nylon 6, nylon 46, nylon 66, nylon 610, nylon 11, nylon 12, nylon 6T, nylon 9T, nylon 6I, nylon M5T, and polyphenylene terephthalamide; polycarbonate, polyarylate, polyphenylene ether, polyphenylene sulfide, polyether ketone, polyether ether ketone, polysulfone, polyether sulfone, polyamide imide, polyether imide, and polyacetal. Among these, the polyamide resin (T1) is preferred from the viewpoint of particularly excellent compatibility with the polymer (P). These thermoplastic resins (T) may be used alone or in combination of two or more.

[0054] The proportion of the thermoplastic resin (T) in the resin composition is preferably 55 to 99.9 mass% relative to the total mass of the resin composition, more preferably 60 to 99 mass%, even more preferably 63 to 95 mass%, and particularly preferably 65 to 90 mass%. When the proportion of the thermoplastic resin (T) is equal to or greater than the above-mentioned lower limit, the surface appearance of the molded article is good. When the proportion of the thermoplastic resin (T) is equal to or less than the above-mentioned upper limit, the polymer (P) can be sufficiently blended, and the impact resistance of the molded article is further improved.

[0055] <Optional Components> Examples of optional components include thermoplastic elastomers (e.g., SEBS (styrene-ethylene-butylene-styrene block copolymer), SBS (e.g., styrene-butadiene-styrene block copolymer), flame retardants (e.g., phosphorus-based flame retardants, bromine-based flame retardants, silicone-based flame retardants, organometallic salt-based flame retardants), anti-dripping agents (e.g., fluorinated polyolefin, silicone, aramid fiber), antioxidants, ultraviolet absorbers, light stabilizers (e.g., phenol-based stabilizers, sulfur-based stabilizers, phosphorus-based stabilizers, ultraviolet absorbers, amine-based light stabilizers), release agents (e.g., pentaerythritol tetrastearate), lubricants (e.g., long-chain fatty acid metal salts such as magnesium stearate), sliding agents, colorants, fluorescent brighteners, phosphorescent pigments, fluorescent dyes, antistatic agents, fillers (e.g., titanium oxide, talc, mica, kaolin, calcium carbonate, glass flakes), plasticizers, and reinforcing agents (e.g., glass fiber, carbon fiber). These optional components may be used alone or in combination of two or more. SEBS (styrene-ethylene-butylene-styrene block copolymer) may be modified, and specific examples include maleic acid-modified SEBS and amine-modified SEBS.

[0056] The proportion of the optional components in the resin composition is preferably 40% by mass or less, more preferably 35% by mass or less, based on the total mass of the resin composition.

[0057] <Method for producing resin composition> The resin composition can be produced, for example, by mixing or melt-kneading the thermoplastic resin (T), the polymer (P), and, if necessary, optional components. For mixing or melt-kneading, for example, a Henschel mixer, a Banbury mixer, a single-screw extruder, a twin-screw extruder, a two-roll mill, a kneader, a Brabender, or the like can be used.

[0058] <Effects> The resin composition of the second aspect of the present invention contains the polymer (P). Therefore, by using the resin composition of this embodiment, a decrease in fluidity during processing is suppressed, and a molded article having excellent impact resistance can be obtained.

[0059] [Molded Article] The molded article of the third aspect of the present invention contains the resin composition described above. That is, the molded article of this embodiment contains a polymer (P), a thermoplastic resin (T), and, if necessary, optional components. The molded article is obtained by molding the resin composition into a desired shape. As a method for molding the resin composition, known methods can be used, such as compression molding, transfer molding, injection molding, blow molding, vacuum molding, extrusion molding, laminate molding, and calendar molding.

[0060] The molded article of the third aspect of the present invention contains the polymer (P), and therefore has excellent impact resistance. The uses of the molded article of this embodiment are not limited, and it can be widely used industrially, for example, as various materials in the automotive, office automation equipment, home appliance, electrical and electronic, construction, lifestyle and cosmetics, medical supplies, and other fields. More specifically, it can be used as housings for electronic devices, various parts, coating materials, automotive structural members, automotive interior parts, light reflectors, building structural members, and fixtures. More specifically, it can be used as interior and exterior materials for personal computer housings, mobile phone housings, personal digital assistant housings, portable game console housings, printers, copiers, and the like, conductor coating materials, automotive interior and exterior materials, building exterior materials, resin window frame members, flooring materials, piping members, and the like.

[0061] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following descriptions.

[0062] [Measurement and Evaluation] <Measurement of Volume Average Particle Diameter of Latex Polymer> Using a laser diffraction / scattering particle size distribution analyzer, the volume-based particle size distribution of the latex polymer was measured, and the median diameter was taken as the volume average particle diameter.

[0063] <Polymerization stability> The obtained latex was filtered through a nylon mesh filter (opening 150 mesh), and the solid matter remaining on the mesh filter was collected and weighed. When the polymer component of the total latex was 100%, the case where the rate of solid matter was 40% or less was rated as "A", and the case where it was 41% or more was rated as "B".

[0064] <Evaluation of Impact Resistance> A Type A notch in accordance with ISO 179-1:2023 was cut into the test piece, and the Charpy impact strength was measured at 0°C and 23°C.

[0065] <Evaluation of fluidity (MFR, ΔMFR)> Using pellets of the obtained resin composition, MFR (melt mass flow rate) was measured using a melt indexer (L244, manufactured by Techno Seven Co., Ltd.). ΔMFR was calculated using the following formula, and a smaller ΔMFR value indicates a more suppressed decrease in fluidity. ΔMFR = (MFR of thermoplastic resin only) - (MFR of resin composition containing thermoplastic resin and polymer (P) or acrylic rubber-based graft copolymer having a core-shell structure). The measurement conditions varied depending on the thermoplastic resin used, and one of the following was selected: (1) temperature 230°C / load 2.16 kg, (2) temperature 250°C / load 2.16 kg, or (3) temperature 275°C / load 2.16 kg. The resin composition pellets were dried at 40°C for 12 hours before use.

[0066] [Production Example 1] <Production of Polymer (P1)> 400 parts by mass of deionized water was charged into a polymerization apparatus equipped with a stirring rod, a condenser, and a thermometer. After thorough replacement with nitrogen, the temperature was raised to 80°C. Next, 62.5 parts by mass of a copolymer nylon resin emulsion (manufactured by Sumitomo Seika Chemicals Co., Ltd., trade name "Sepolsion PA150", solids content 40% by mass) as an aqueous dispersion of a polymer (polyamide polymer (A1)) constituting the first polymer portion, and 99.5 parts by mass of butyl acrylate (manufactured by Mitsubishi Chemical Corporation) and 0.5 parts by mass of allyl methacrylate (manufactured by Mitsubishi Chemical Corporation) as monomer components (m) constituting the second polymer portion were added to the polymerization apparatus, followed by the addition of 0.1 parts by mass of potassium peroxodisulfate (manufactured by Nacalai Tesque, Inc.) as a polymerization initiator to initiate polymerization. Polymerization was continued at 80°C for 5 hours and then cooled to obtain a latex of polymer (P1). The volume average particle diameter of the latex polymer (P1) was 120 nm. Next, 1512 parts by mass of an aqueous solution containing calcium acetate at a concentration of 0.8% by mass was heated to 60°C, and 562.6 parts by mass of the latex of polymer (P1) was gradually added dropwise to the aqueous solution while stirring to coagulate it, followed by filtration, washing, dehydration, and drying to obtain powdery polymer (P1). The composition of polymer (P1) is shown in Table 1.

[0067] [Production Example 2] <Production of Polymer (P2)> 400 parts by mass of deionized water was placed in a polymerization apparatus equipped with a stirring rod, a condenser, and a thermometer, and the atmosphere was thoroughly purged with nitrogen, followed by heating to 80°C. Next, 62.5 parts by mass of a copolymer nylon resin emulsion (manufactured by Sumitomo Seika Chemicals Co., Ltd., trade name "Sepolsion PA150", solids content 40% by mass) as an aqueous dispersion of the polymer (polyamide polymer (A1)) constituting the first polymer portion, and 85.6 parts by mass of butyl acrylate (manufactured by Mitsubishi Chemical Corporation), 9.0 parts by mass of methoxypolyethylene glycol monomethacrylate (manufactured by NOF Corporation, trade name "Blemmer PME-400"), 5.0 parts by mass of methyl methacrylate (manufactured by Mitsubishi Chemical Corporation), and 0.4 parts by mass of allyl methacrylate (manufactured by Mitsubishi Chemical Corporation) as the monomer component (m) constituting the second polymer portion were added to the polymerization apparatus, and 0.1 parts by mass of potassium peroxodisulfate (manufactured by Nacalai Tesque, Inc.) was further added as a polymerization initiator to initiate polymerization. Polymerization was continued at 80°C for 5 hours and then cooled to obtain a latex of polymer (P2). The volume average particle diameter of the latex-like polymer (P2) was 122 nm. Next, 1512 parts by mass of an aqueous solution containing calcium acetate at a concentration of 0.8% by mass was heated to 60°C, and 562.6 parts by mass of the polymer (P2) latex was gradually added dropwise to the aqueous solution while stirring to coagulate the solution, followed by filtration, washing, dehydration, and drying to obtain a powdery polymer (P2). The composition of the polymer (P2) is shown in Table 1.

[0068] [Production Examples 3 to 7, 10 to 11] <Production of Polymers (P3 to 7, 9 to 10)> Polymers (P3 to 7, 9 to 10) were obtained in the same manner as in Production Example 1, except that the raw materials for the polymers were changed as shown in Table 1.

[0069] [Production Example 8] <Production of Emulsion of Polymer (B1)> 2 parts by mass of DSMS and 98 parts by mass of octamethylcyclotetrasiloxane (manufactured by Momentive Performance Materials Japan, LLC, trade name "TSF404") were mixed to obtain 100 parts by mass of an organosiloxane mixture. An aqueous solution of 1 part by mass of DBSNa (sodium dodecylbenzenesulfonate) dissolved in 150 parts by mass of deionized water was added to the organosiloxane mixture, and the mixture was stirred at 10,000 rpm for 5 minutes using a homomixer. The mixture was then passed through a homogenizer at a pressure of 20 MPa twice to obtain a stable premixed emulsion (α1). Next, the premixed emulsion (α1) was charged into a 5 L separable flask equipped with a cooling condenser. The premixed emulsion (α1) was heated to 80°C, and a mixture of 0.2 parts by mass of sulfuric acid and 49.8 parts by mass of distilled water was continuously added for 3 minutes. The mixture was maintained at 80°C for 7 hours to carry out a polymerization reaction, and then cooled to 25°C and maintained for 6 hours. A 5% by mass aqueous sodium hydroxide solution was added to neutralize the reaction solution to pH 7.0, yielding an emulsion (β1) of polymer (B1). The solids content of the emulsion (β1) of polymer (B1) was 40% by mass.

[0070] [Production Example 9] <Production of Polymer (P8)> 250 parts by mass of the emulsion (β1) of polymer (B1) obtained in Production Example 8 and 25 parts by mass of a copolymer nylon resin emulsion (manufactured by Sumitomo Seika Chemicals Co., Ltd., trade name "Sepolsion PA150", solids content 40% by mass) as an aqueous dispersion of the polymer constituting the first polymer portion (polyamide polymer (A1)) were stirred at 200 rpm for 2 hours at 25° C. 25 parts by mass of this mixed liquid was gradually added dropwise with stirring to 1,512 parts by mass of an aqueous solution of calcium acetate having a concentration of 0.8% by mass that had been heated to 60° C. The mixture was coagulated, filtered, washed, dehydrated, and then dried to obtain a powdery polymer (P8).

[0071]

[0072] The abbreviations in Table 1 are as follows. In addition, the "proportion of first polymer portion" in Table 1 refers to the proportion (% by mass) of the first polymer portion when the total of the first polymer portion and the second polymer portion is 100% by mass. Sepolsion PA150: copolymer nylon resin emulsion (manufactured by Sumitomo Seika Chemicals Co., Ltd., trade name "Sepolsion PA150", solid content 40% by mass). nBA: n-butyl acrylate (manufactured by Mitsubishi Chemical Corporation). PME-400: methoxypolyethylene glycol monomethacrylate (manufactured by NOF Corporation, trade name "Blemmer PME-400"). MMA: methyl methacrylate (manufactured by Mitsubishi Chemical Corporation). AMA: allyl methacrylate (manufactured by Mitsubishi Chemical Corporation). EHA: ethylhexyl acrylate (manufactured by Nacalai Tesque, Inc.). 1,3-BDMA: 1,3-butanediol dimethacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.). DSMS: 3-(methacryloyloxy)propylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-502").

[0073] Example 1 95 parts by mass of a polyamide resin (manufactured by Asahi Kasei Corporation, product name "Leona 1300S", nylon 66) as the thermoplastic resin (T) and 5 parts by mass of polymer (P1) were placed in a polyethylene bag, and the polyethylene bag was vigorously shaken by hand to hand-blend. The mixture was then melt-kneaded at 280°C using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., product name "TEM35B"), and the extruded strand was cut to obtain a pelletized resin composition. The obtained pelletized resin composition was molded using an injection molding machine (manufactured by Toshiba Machine Co., Ltd., product name "IS100EN") at a molding temperature of 280°C and a mold temperature of 80°C to obtain a molded product having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm. The flowability and impact resistance of the obtained resin composition and molded product were evaluated. The results are shown in Table 2.

[0074] Examples 2 and 3: Pellet-shaped resin compositions were produced in the same manner as in Example 1, except that polymer (P3) or (P4) was used instead of polymer (P1), and molded articles were produced using the resulting pellet-shaped resin compositions. The resulting resin compositions and molded articles were evaluated for flowability and impact resistance. The results are shown in Table 2.

[0075] Examples 4 and 5 Pellet-shaped resin compositions were produced in the same manner as in Example 1, except that 95 parts by mass of a glass fiber-reinforced polyamide resin (manufactured by Asahi Kasei Corporation, trade name "Leona 1300G", a mixture of nylon 66 (67% by mass) and glass fiber (33% by mass)) was used as the thermoplastic resin (T) and the polymer (P) shown in Table 2 was used, and molded articles were produced using the resulting pellet-shaped resin compositions. The flowability and impact resistance were evaluated using the resulting resin compositions and molded articles. The results are shown in Table 2.

[0076] Examples 6 to 14 Pellet-shaped resin compositions were produced in the same manner as in Example 1, except that nylon 6 resin (manufactured by UBE Corporation, trade name "UBE Nylon 6 1022B") was used as the thermoplastic resin (T) and the polymer (P) shown in Table 3 was used, and molded articles were produced using the resulting pellet-shaped resin compositions. The flowability and impact resistance of the resulting resin compositions and molded articles were evaluated. The results are shown in Table 3.

[0077] Example 15 A pellet-shaped resin composition was produced in the same manner as in Example 1, except that nylon 6 resin (manufactured by UBE Corporation, trade name "UBE Nylon 6 1013B") was used as the thermoplastic resin (T) and the polymer (P) shown in Table 4 was used, and a molded article was produced using the resulting pellet-shaped resin composition. The flowability and impact resistance were evaluated using the resulting resin composition and molded article. The results are shown in Table 4.

[0078] Example 16 A pellet-shaped resin composition was produced in the same manner as in Example 1, except that nylon 12 resin (manufactured by UBE Corporation, trade name "UBESTA 3024U") was used as the thermoplastic resin (T) and the polymer (P) shown in Table 4 was used, and a molded article was produced using the resulting pellet-shaped resin composition. The flowability and impact resistance of the resulting resin composition and molded article were evaluated. The results are shown in Table 4.

[0079] Example 17 A pellet-shaped resin composition was produced in the same manner as in Example 1, except that a glass fiber reinforced nylon 6 resin (manufactured by UBE Corporation, product name "UBE 1015GC6") was used as the thermoplastic resin (T) and the polymer (P) shown in Table 4 was used, and a molded article was produced using the resulting pellet-shaped resin composition. The flowability and impact resistance were evaluated using the resulting resin composition and molded article. The results are shown in Table 4.

[0080] Comparative Example 1 A pellet-shaped resin composition was produced in the same manner as in Example 1, except that the amount of polyamide resin (manufactured by Asahi Kasei Corporation, trade name "Leona 1300S", nylon 66) was 100 parts by mass and polymer (P1) was not used, and a molded article was produced using the obtained pellet-shaped resin composition. The flowability and impact resistance were evaluated using the obtained resin composition and molded article. The results are shown in Table 2.

[0081] Comparative Example 2 A pellet-shaped resin composition was produced in the same manner as in Example 1, except that 5 parts by mass of an acrylic rubber graft copolymer having a core-shell structure (manufactured by Mitsubishi Chemical Corporation, trade name "METABLEN W-600A", core part: acrylic polymer, shell part: acrylic polymer) was used instead of polymer (P1), and a molded article was produced using the resulting pellet-shaped resin composition. The flowability and impact resistance were evaluated using the resulting resin composition and molded article. The results are shown in Table 2.

[0082] Comparative Example 3 A pellet-shaped resin composition was produced in the same manner as in Example 1, except that 5 parts by mass of polymer (P10) was used instead of polymer (P1), and a molded article was produced using the resulting pellet-shaped resin composition. The flowability and impact resistance of the resulting resin composition and molded article were evaluated. The results are shown in Table 2.

[0083] Comparative Example 4 A pellet-shaped resin composition was produced in the same manner as in Example 4, except that 100 parts by mass of a glass fiber reinforced polyamide resin (manufactured by Asahi Kasei Corporation, trade name "Leona 1300G", a mixture of nylon 66 (67% by mass) and glass fiber (33% by mass)) was used as the thermoplastic resin (T) and polymer (P1) was not used, and a molded article was produced using the obtained pellet-shaped resin composition. The flowability and impact resistance were evaluated using the obtained resin composition and molded article. The results are shown in Table 2.

[0084] Comparative Example 5 A pellet-shaped resin composition was produced in the same manner as in Example 4, except that 5 parts by mass of polymer (P10) was used instead of polymer (P1), and a molded article was produced using the resulting pellet-shaped resin composition. The flowability and impact resistance of the resulting resin composition and molded article were evaluated. The results are shown in Table 2.

[0085] Comparative Examples 6 to 8 Pellet-shaped resin compositions were produced in the same manner as in Example 6, except that the polymers listed in Table 3 were used instead of polymer (P1), and molded articles were produced using the resulting pellet-shaped resin compositions. The resulting resin compositions and molded articles were evaluated for flowability and impact resistance. The results are shown in Table 3.

[0086] Comparative Examples 9 and 10 Pellet-shaped resin compositions were produced in the same manner as in Example 15, except that the polymer (P1) was replaced with the polymers shown in Table 4, and molded articles were produced using the resulting pellet-shaped resin compositions. The resulting resin compositions and molded articles were evaluated for flowability and impact resistance. The results are shown in Table 4.

[0087] Comparative Examples 11 and 12 Pellet-shaped resin compositions were produced in the same manner as in Example 16, except that the polymer (P1) was replaced with the polymers shown in Table 4, and molded articles were produced using the resulting pellet-shaped resin compositions. The resulting resin compositions and molded articles were evaluated for flowability and impact resistance. The results are shown in Table 4.

[0088] Comparative Examples 13 and 14 Pellet-shaped resin compositions were produced in the same manner as in Example 17, except that the polymer (P1) was replaced with the polymers shown in Table 4, and molded articles were produced using the resulting pellet-shaped resin compositions. The resulting resin compositions and molded articles were evaluated for flowability and impact resistance. The results are shown in Table 4.

[0089]

[0090]

[0091]

[0092] The abbreviations in Tables 2 to 4 are as follows. In Table 2, "polymer ratio" refers to the ratio (parts by mass) of polymer to 100 parts by mass of thermoplastic resin (T). Leona 1300S: Polyamide resin (manufactured by Asahi Kasei Corporation, trade name "Leona 1300S", nylon 66). Leona 1300G: Glass fiber reinforced polyamide resin (manufactured by Asahi Kasei Corporation, trade name "Leona 1300G", a mixture of nylon 66 (67% by mass) and glass fiber (33% by mass)). W-600A: Acrylic rubber graft copolymer having a core-shell structure (manufactured by Mitsubishi Chemical Corporation, trade name "METABLEN W-600A", core: acrylic polymer, shell: acrylic polymer). UBE Nylon 6 1022B: Nylon 6 resin (manufactured by UBE Corporation). UBE Nylon 6 1013B: Nylon 6 resin (manufactured by UBE Corporation). UBESTA 3024U: Nylon 12 resin (manufactured by UBE Corporation) UBE 1015GC6: Glass fiber reinforced nylon 6 resin (manufactured by UBE Corporation).

[0093] As is clear from the results shown in Table 2, the resin compositions and molded articles obtained in Examples 1 to 17 had smaller ΔMFR and suppressed the decrease in fluidity during processing compared to the resin compositions and molded articles obtained in Comparative Examples 1 to 15, and also had improved impact resistance at both temperatures of -30 ° C. and 23 ° C. The resin compositions and molded articles obtained in Comparative Examples 1, 4, 6, 9, 11, and 13 did not use polymer (P), and therefore had poor impact resistance at both temperatures of -30 ° C. and 23 ° C. Specifically, the above effects can be confirmed in a comparison between Comparative Example 1 and Examples 1 to 3, a comparison between Comparative Example 4 and Examples 4 and 5, a comparison between Comparative Example 6 and Examples 6 to 14, a comparison between Comparative Example 9 and Example 15, a comparison between Comparative Example 11 and Example 16, and a comparison between Comparative Example 13 and Example 17. In the resin compositions and molded articles obtained in Comparative Examples 2 and 8, an acrylic rubber graft copolymer was used in which both the core and shell portions were acrylic polymers, and therefore, ΔMFR was large, fluidity was reduced, and impact resistance was poor at both temperatures of -30°C and 23°C. Specifically, the above-mentioned effects can be confirmed by comparing Comparative Example 2 with Examples 1 to 3, and by comparing Comparative Example 8 with Examples 6 to 14. Furthermore, in the resin compositions and molded articles obtained in Comparative Examples 3, 5, 7, 10, 12, and 14, the proportion of the second polymer portion was less than 45% by mass when the total of the first polymer portion and the second polymer portion was taken as 100% by mass, and therefore, ΔMFR was large, fluidity was reduced, and impact resistance was poor at both temperatures of -30°C and 23°C. Specifically, the above effects can be confirmed in a comparison between Comparative Example 3 and Examples 1 to 3, a comparison between Comparative Example 5 and Examples 4 and 5, a comparison between Comparative Example 7 and Examples 6 to 14, a comparison between Comparative Example 10 and Example 15, a comparison between Comparative Example 12 and Example 16, and a comparison between Comparative Example 14 and Example 17.

Claims

1. A polymer having a first polymer portion and a second polymer portion, wherein the first polymer portion is a polyamide polymer, the second polymer portion has structural units derived from a (meth)acrylate monomer, and when the total of the first polymer portion and the second polymer portion is 100% by mass, the proportion of the second polymer portion is 45% by mass or more.

2. The polymer described in claim 1, wherein the proportion of the second polymer portion is 95% by mass or less when the total of the first polymer portion and the second polymer portion is 100% by mass.

3. The polymer according to claim 2, wherein the proportion of the first polymer portion is 5 to 55% by mass when the total of the first polymer portion and the second polymer portion is 100% by mass.

4. The polymer described in claim 1, wherein the proportion of the structural units derived from the (meth)acrylate monomer is 1 mass % or more relative to the total mass of all structural units constituting the second polymer portion.

5. The polymer of claim 1, having a core-shell structure, wherein the first polymer portion constitutes the shell portion of the core-shell structure and the second polymer portion constitutes the core portion of the core-shell structure.

6. The polymer according to claim 1, which is obtained by emulsion polymerization of the monomer components constituting said second polymer portion in the presence of a polyamide polymer.

7. A resin additive comprising the polymer according to any one of claims 1 to 6.

8. A resin composition comprising the polymer according to any one of claims 1 to 6 and a thermoplastic resin other than the polymer according to any one of claims 1 to 6.

9. The resin composition according to claim 8, wherein the thermoplastic resin comprises a polyamide resin.

10. The resin composition according to claim 8, wherein the ratio of said polymer is 30 parts by mass or less per 100 parts by mass of said thermoplastic resin.

11. A molded article comprising the resin composition according to claim 8.

12. A method for producing a polymer having a first polymer portion and a second polymer portion, wherein the first polymer portion is a polyamide polymer, and the second polymer portion has structural units derived from a (meth)acrylate monomer, and the method comprises emulsion polymerizing a monomer component constituting the second polymer portion in the presence of the polyamide polymer.

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