Polymers, resin additives, resin compositions, and molded articles

Abstract

This invention provides a polymer that, when mixed with a thermoplastic resin to form a molded article, exhibits good Charpy impact strength and surface impact strength, as well as a resin composition using the same. [Solution] A polymer containing polymer A and polymer B, wherein polymer A is a constituent unit derived from a vinyl monomer containing a group represented by the following formula (1), A polymer containing a structural unit derived from an alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms, wherein polymer portion B contains a structural unit derived from a vinyl monomer different from the vinyl monomer, and the Tg is 0°C or lower. -(C m H 2m O) n X ···(1)

Description

[Technical Field]

[0001] The present invention relates to polymers, resin additives, resin compositions, and molded articles. [Background technology]

[0002] Rubber-containing core-shell polymers are produced by graft polymerization of vinyl monomers onto a rubbery polymer. These polymers are manufactured by emulsion polymerization and can be dispersed in a wide variety of resins while maintaining a predetermined rubber particle size and rubber structure. Therefore, they are suitable for use in resins where impact strength is required.

[0003] To improve the impact strength of a resin, it is generally considered beneficial to uniformly disperse rubber within the resin. However, rubber itself has low compatibility with general thermoplastic resins, making it difficult to uniformly disperse rubber within a resin using rubber alone.

[0004] To improve the dispersibility of rubber in resins, graft polymerization of rubbery polymers with vinyl monomers is known. Methyl methacrylate is preferably used as this vinyl monomer. This is because methyl methacrylate has high compatibility with a wide range of thermoplastic resins, such as polycarbonate, styrene resins, and vinyl chloride resins.

[0005] Furthermore, thermoplastic resins are used in a variety of applications, including home appliances, office equipment, and automotive parts. In particular, in automotive parts, there is a growing trend to replace metal in order to reduce the weight of the vehicle body, and resins require sufficient impact strength (Charpy impact strength and surface impact strength).

[0006] In automotive parts applications, thermoplastic resins with added graft rubber are used from the perspective of impact strength. However, while adding graft rubber to thermoplastic resins improves Charpy impact strength, it can sometimes decrease surface impact strength. To ensure higher safety in automotive parts applications, there is a need to achieve both high Charpy impact strength and high surface impact strength. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 05-070733 [Patent Document 2] Japanese Patent Publication No. 2013-166895 [Overview of the project] [Problems that the invention aims to solve]

[0008] However, when a molded article is obtained by mixing polymer microparticles that are three-dimensionally internally crosslinked, as described in Patent Document 1, or microparticles obtained by polymerizing a polymerizable unsaturated monomer containing an alkyl (meth)acrylate ester into a rubbery polymer, as described in Patent Document 2, with a thermoplastic resin, the Charpy impact strength and surface impact strength of the molded article were insufficient.

[0009] The present invention has been made in view of the above circumstances, and aims to provide a polymer that exhibits good Charpy impact strength and surface impact strength when mixed with a thermoplastic resin to form a molded article, and a resin composition using the same. [Means for solving the problem]

[0010] In order to achieve the above objectives, the present invention researchers have diligently studied the matter and found that the above problems can be solved by having a polymer possess structural units derived from specific monomers, thus completing the present invention. In other words, the gist of the present invention is as follows.

[0011] [1] A polymer comprising polymer A and polymer B, wherein polymer A comprises a constituent unit derived from a vinyl monomer containing a group represented by the following formula (1) and a constituent unit derived from an alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms, and polymer B comprises a constituent unit derived from a vinyl monomer different from the vinyl monomer, and the polymer has a Tg of 0°C or less. -(C m H 2m O) n X ···(1) (In the formula, m is an integer greater than or equal to 1, when n=1, X is a methyl group, and when n is an integer greater than or equal to 2, X is a hydrogen atom or an alkyl group.) [2] The polymer according to [1], wherein m = 2 to 5 and n = 1 to 23 in formula (1). [3] The polymer according to [1] or [2], wherein in a total of 100 parts by mass of the vinyl monomer containing the group represented by formula (1) used in the polymer A portion and the alkyl (meth)acrylate monomer having an alkyl group having 1 to 10 carbon atoms, the content of the vinyl monomer containing the group represented by formula (1) is 1 to 30 parts by mass, and the content of the alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms is 70 to 99 parts by mass. [4] The polymer according to any one of [1] to [3], wherein when the total of polymer A portion and polymer B portion is 100 parts by mass, the proportion of polymer A portion is 10 to 50 parts by mass and the proportion of polymer B portion is 50 to 90 parts by mass. [5] The polymer according to any one of [1] to [4], wherein the polymer is a core-shell polymer. [6] A polymer according to any of [1] to [5], wherein the average primary particle size is 100 to 500 nm. [7] A polymer obtained by polymerizing a rubber latex obtained by polymerizing a vinyl monomer in the presence of an emulsifier with a vinyl monomer containing a group represented by the following formula (1) and an alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms. -(C m H 2m O) n X ···(1) (In the formula, m is an integer greater than or equal to 1, when n=1, X is a methyl group, and when n is an integer greater than or equal to 2, X is a hydrogen atom or an alkyl group.) [8] In a total of 100 parts by mass of the vinyl monomer and the alkyl (meth)acrylate monomer having an alkyl group with 1 to 10 carbon atoms, the content of the vinyl monomer is 1 to 30 parts by mass, and the content of the alkyl (meth)acrylate having an alkyl group with 1 to 10 carbon atoms is 70 to 99 parts by mass. The polymer according to [7]. [9] A resin additive containing the polymer according to any one of [1] to [8].

[10] A resin composition containing the polymer according to any one of [1] to [8] and a thermoplastic resin.

[11] In 100 parts by mass of the resin composition, the ratio of the content of the polymer to the thermoplastic resin (polymer / thermoplastic resin) is 1 / 99 to 20 / 80 (parts by mass). The resin composition according to

[10] .

[12] The resin composition according to

[10] or

[11] , wherein the thermoplastic resin is a polycarbonate resin.

[13] The resin composition according to

[12] , wherein the polycarbonate resin is a polycarbonate resin having an isosorbide skeleton.

[14] A molded body made of the resin composition according to any one of

[10] to

[13] .

Effects of the Invention

[0012] According to the present invention, by having a structural unit derived from a specific monomer in the polymer, it is possible to provide a polymer in which both the Charpy impact strength and the surface impact strength of the molded body are good, and a resin composition using the same.

Modes for Carrying Out the Invention

[0013] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments without departing from the object. In this specification, "~" includes the lower limit and the upper limit. Also, for each preferred range, the upper limit and the lower limit can be arbitrarily combined and used.

[0014] The polymer according to one embodiment of the present invention contains a polymer A part and a polymer B part. The polymer A part contains a structural unit derived from a vinyl monomer containing a group represented by the following formula (1) and a structural unit derived from an alkyl (meth)acrylate having an alkyl group with 1 to 10 carbon atoms. The polymer B part contains a structural unit derived from a vinyl monomer different from the above vinyl monomer and has a Tg of 0°C or lower. -(C m H 2m O) n X ···(1) (In the formula, m is an integer of 1 or more. When n = 1, X is a methyl group. When n is an integer of 2 or more, X is a hydrogen atom or an alkyl group.)

[0015] <Polymer A part> As described above, the polymer A part according to this embodiment contains a structural unit derived from a vinyl monomer containing the group represented by the above formula (1) and a structural unit derived from an alkyl (meth)acrylate having an alkyl group with 1 to 10 carbon atoms.

[0016] Examples of the vinyl monomer containing the group represented by the above formula (1) include (meth)acrylates such as polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate, and vinyl ethers such as ethylene glycol vinyl ether and tri(ethylene glycol) divinyl ether. These may be used alone or in combination of two or more. By including the group represented by the above formula (1) in the vinyl monomer, the Charpy impact strength and surface impact strength of the molded body are improved. More preferably, in the above formula (1), m = 2 to 5 and n = 1 to 23, and even more preferably, m = 2 to 3 and n = 1 to 15. The alkyl group of X is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

[0017] The polymer A portion according to this embodiment further contains constituent units derived from alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms. Examples of alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms include alkyl acrylate monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, and n-octyl acrylate, and alkyl methacrylate monomers such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate. These may be used individually or in combination of two or more.

[0018] In the 100 parts by mass of the total of a vinyl monomer containing the group represented by formula (1) and an alkyl (meth)acrylate monomer having an alkyl group having 1 to 10 carbon atoms used in polymer A, the content of the vinyl monomer is preferably 1 to 30 parts by mass, and the content of the alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms is preferably 70 to 99 parts by mass. With these content levels, molecular-level entanglement between the polycarbonate resin having an isosorbide skeleton and polymer A is promoted, resulting in good Charpy impact strength and surface impact strength of the molded article. Furthermore, the content of the vinyl monomer is more preferably 1 to 20 parts by mass, and even more preferably 5 to 15 parts by mass. On the other hand, the content of the alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms is more preferably 80 to 99 parts by mass, and even more preferably 85 to 95 parts by mass.

[0019] The polymer A portion may contain a vinyl monomer containing the group represented by formula (1) above, and a vinyl monomer other than an alkyl (meth)acrylate monomer having an alkyl group with 1 to 10 carbon atoms. Examples of such vinyl monomers include aromatic vinyls such as styrene and α-methylstyrene, (meth)acrylate compounds such as (meth)acrylic acid and phenyl (meth)acrylate, unsaturated nitriles such as acrylonitrile and methacrylonitrile, vinyl ethers such as methyl vinyl ether and butyl vinyl ether, vinyl halides such as vinyl chloride and vinyl bromide, vinylidenes such as vinylidene chloride and vinylidene bromide, vinyl monomers having a glycidyl group such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and ethylene glycol glycidyl ether. Furthermore, crosslinkable monomers such as aromatic polyfunctional vinyl compounds like divinylbenzene and divinyltoluene, polyhydric alcohols like ethylene glycol dimethacrylate and 1,3-butanediol diacrylate, allyl carboxylates like trimethacrylate, triacrylic acid, allyl acrylate, and allyl methacrylate, and di and trialyl compounds like diallyl phthalate, diallyl sebacate, and triallyl triazine can also be used in combination. One or more of the vinyl monomers and crosslinkable monomers can be used. In addition, chain transfer agents such as t-dodecyl mercaptan, n-octyl mercaptan, and α-methylstyrene can be used as needed during polymerization.

[0020] The polymer according to this embodiment contains polymer portion B which includes a constituent unit derived from a vinyl monomer different from the vinyl monomer containing the group represented by formula (1) above. When the total amount of polymer A portion and polymer B portion is 100 parts by mass, it is preferable that the proportion of polymer A portion is 10 to 50 parts by mass and the proportion of polymer B portion is 50 to 90 parts by mass. When the proportions of polymer A portion and polymer B portion are within the above range, the dispersibility in the resin composition described later is improved, and the impact resistance is good. The proportion of polymer A portion is preferably 10 to 40 parts by mass, more preferably 10 to 35 parts by mass. On the other hand, the proportion of polymer B portion is preferably 60 to 90 parts by mass, more preferably 65 to 90 parts by mass.

[0021] One method for incorporating polymer B into polymer A is, for example, graft polymerization of polymer B into polymer A. Known methods can be used for graft polymerization, but for example, it can be produced by emulsion polymerization.

[0022] <Polymer B part> The polymer B portion that can be used in the present invention has a glass transition temperature (Tg) of 0°C or lower. If the glass transition temperature of polymer B portion is 0°C or lower, the Charpy impact strength and surface impact strength of the molded article obtained from the resin composition containing the polymer of the present invention tend to be better. The glass transition temperature of polymer portion B is preferably -20°C or lower, and more preferably -40°C or lower. The lower limit of the glass transition temperature is not particularly limited, but from the viewpoint of polymer recovery, it is preferably -150°C or higher, more preferably -120°C or higher, and even more preferably -100°C or higher. The glass transition temperature (Tg) can be calculated from the Tg and composition ratio of the monomer homopolymer using the FOX formula below, and can be controlled by selecting the monomers and their composition ratios. 1 / Tg = Σ(Wn / Tgn) / 100 (Wn is the ratio (mass%) of monomer n in the target polymer, and Tgn is the Tg (K: absolute temperature) of the monomer n homopolymer.)

[0023] The polymer B portion is preferably a rubbery polymer, and specifically includes butadiene rubber, styrene-butadiene copolymer rubber, silicone rubber, silicone-acrylic composite rubber (obtained by polymerizing one or more vinyl monomers containing acrylate in the presence of a polymer obtained from monomers mainly composed of dimethylsiloxane), acrylonitrile-butadiene copolymer rubber, acrylic rubbers such as butyl polyacrylate, block copolymers such as polyisoprene, polychloroprene, ethylene-propylene rubber, ethylene-propylene-diene ternary copolymer rubber, styrene-butadiene block copolymer rubber, and styrene-isoprene block copolymer rubber, as well as hydrogenated versions thereof.

[0024] In cold regions, improved impact strength of molded articles at lower temperatures (below -20°C) is required, therefore, butadiene rubber, styrene-butadiene copolymer rubber, acrylic-butadiene copolymer rubber, and silicone-acrylic composite rubber with a glass transition temperature of -20°C or lower are preferred.

[0025] Polymer B portion has constituent units derived from a vinyl monomer different from the vinyl monomer containing the group represented by formula (1). Polymer B portion does not have constituent units derived from the vinyl monomer containing the group represented by formula (1). Examples of vinyl monomers other than those containing the group represented by formula (1) include conjugated diene compounds such as butadiene and isoprene, aromatic vinyls such as styrene and α-methylstyrene, alkyl (meth)acrylates such as butyl acrylate and 2-ethylhexyl acrylate, unsaturated nitriles such as acrylonitrile and methacrylonitrile, vinyl ethers such as methyl vinyl ether and butyl vinyl ether, vinyl halides such as vinyl chloride and vinyl bromide, vinylidenes such as vinylidene chloride and vinylidene bromide, vinyl monomers having a glycidyl group such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and ethylene glycol glycidyl ether. Furthermore, crosslinkable monomers such as aromatic polyfunctional vinyl compounds like divinylbenzene and divinyltoluene, polyhydric alcohols like ethylene glycol dimethacrylate and 1,3-butanediol diacrylate, allyl carboxylates like trimethacrylate, triacrylic acid, allyl acrylate, and allyl methacrylate, and di and trialyl compounds like diallyl phthalate, diallyl sebacate, and triallyl triazine can also be used in combination. One or more of the vinyl monomers and crosslinkable monomers can be used. In addition, chain transfer agents such as t-dodecyl mercaptan, n-octyl mercaptan, and α-methylstyrene can be used as needed during polymerization.

[0026] The polymer of the present invention is preferably a core-shell polymer, and from the viewpoint of impact resistance, it is preferable that polymer A constitutes the shell and polymer B constitutes the core. With the above core-shell structure, the core-shell structure can be easily dispersed in the molded article, resulting in good impact resistance of the molded article, and the polymer can be easily handled as a powder. Examples of methods for producing the core-shell polymer include emulsion polymerization.

[0027] The average primary particle size of the polymer of the present invention is preferably 100 to 500 nm. When the primary particle size is within this range, scattering can be suppressed during compounding and when introducing the resin composition into the mixing apparatus, reducing the possibility of problems such as dust explosions, and furthermore, the powder has good flow characteristics, making it less likely to cause problems such as clogging of pipes in the manufacturing process. The average primary particle size of the polymer is more preferably 100 to 400 nm, and even more preferably 100 to 350 nm. The average primary particle size of the polymer can be adjusted by the amount of emulsifier in the production of a core-shell polymer by emulsion polymerization.

[0028] The average primary particle size of a polymer can be measured using a particle size analyzer employing dynamic light scattering or a capillary particle size analyzer employing CHDF (Capillary HydroDynamic Fractionation). It is preferable to measure the average primary particle size of a polymer using dynamic light scattering.

[0029] Another embodiment of the present invention is a polymer obtained by polymerizing a rubber latex obtained by polymerizing a vinyl monomer in the presence of an emulsifier with a vinyl monomer containing a group represented by the following formula (1) and an alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms. -(C m H 2m O) n X ···(1) (In the formula, m is an integer greater than or equal to 1, when n=1, X is a methyl group, and when n is an integer greater than or equal to 2, X is a hydrogen atom or an alkyl group.) As the vinyl monomer used in the rubber latex, a vinyl monomer similar to that exemplified in the <polymer B portion> above, which contains a group represented by formula (1), can be used. Furthermore, as the vinyl monomer containing the group represented by formula (1) and the alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms, the same as those exemplified in the <polymer A portion> above can be used.

[0030] In a total of 100 parts by mass of the vinyl monomer containing the group represented by formula (1) and the alkyl (meth)acrylate monomer having an alkyl group having 1 to 10 carbon atoms, it is preferable that the content of the vinyl monomer containing the group represented by formula (1) is 1 to 30 parts by mass, and the content of the alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms is 70 to 99 parts by mass. When the vinyl monomer containing the group represented by formula (1) is in the above amounts, molecular-level entanglement between the polycarbonate resin having an isosorbide skeleton and polymer A is promoted, resulting in good Charpy impact strength and surface impact strength of the molded article. Furthermore, the content of the vinyl monomer containing the group represented by formula (1) is more preferably 1 to 20 parts by mass, and even more preferably 5 to 15 parts by mass. On the other hand, the content of the alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms is more preferably 80 to 99 parts by mass, and even more preferably 85 to 95 parts by mass.

[0031] The latex-like polymer obtained by emulsion polymerization in the present invention can be obtained as a powder by coagulation, washing, and drying, or by spray recovery.

[0032] <Emulsifier> The emulsifier used in the production of the polymer is not particularly limited, but may include, for example, anionic surfactants such as fatty acid salts, alkyl sulfate salts, alkylbenzene sulfonates, alkyl phosphate salts, and dialkyl sulfosuccinates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, and glycerin fatty acid esters; and cationic surfactants such as alkylamine salts. These emulsifiers may also be used alone or in combination.

[0033] <Resin additives> The polymer of the present invention can be used as a resin additive. The resin additive may be the polymer as is, or it may contain any auxiliary agents. Examples of known auxiliary agents include stabilizers, flame retardants, flame retardant additives, hydrolysis inhibitors, antistatic agents, foaming agents, dyes, pigments, and the like.

[0034] <Resin composition> The resin composition of the present invention comprises the polymer of the present invention and a thermoplastic resin. Many thermoplastic resins, including polyester, aromatic polycarbonate, styrene resins, vinyl chloride resins, polyethylene and other olefin resins, frequently use resin modifiers with methyl methacrylate as the main component, making the polymer of the present invention suitable for use. Therefore, the thermoplastic resin is not particularly limited and can be a wide variety of resins, such as engineering plastics, styrene resins, polyesters, olefin resins, thermoplastic elastomers, biodegradable polymers, halogenated polymers, and acrylic resins. These can be used individually or in combination of two or more.

[0035] As for engineering plastics, there are no particular limitations as long as they are various known thermoplastic engineering plastics. Examples include polyester polymers such as polyphenylene ether, polycarbonate, polyethylene terephthalate, and polybutylene terephthalate; nylon polymers such as syndiotactic polystyrene, 6-nylon, and 6,6-nylon; polyarylate, polyphenylene sulfide, polyether ketone, polyether ether ketone, polysulfone, polyethersulfone, polyamide-imide, polyether-imide, and polyacetal.

[0036] Furthermore, special styrene-based resins such as heat-resistant ABS and heat-resistant acrylic resins, which require excellent heat resistance and melt-fluidity, can also be exemplified as engineering plastics in this invention.

[0037] Examples of olefin resins include high-density polyethylene, medium-density polyethylene, low-density polyethylene, copolymers of ethylene and other α-olefins; polypropylene, copolymers of propylene and other α-olefins; polybutene, poly-4-methyl-1-pentene, and the like.

[0038] Examples of thermoplastic elastomers include styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), styrene-ethylene-butene copolymer (SEB), styrene-ethylene-propylene copolymer (SEP), styrene-ethylene-butene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS), and styrene-butadiene-butylene-styrene copolymer (styrene-butadiene-styrene copolymer). Styrene-based elastomers such as partially hydrogenated butadiene-styrene copolymers (SBBS), partially hydrogenated styrene-isoprene-styrene copolymers, and partially hydrogenated styrene-isoprene-butadiene-styrene copolymers; polymeric diols (polyester diols, polyether diols, polyester ether diols, polycarbonate diols, polyester polycarbonate diols, etc.), and organic diisocyanates (organic diisocyanates include 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, and p-phenylenedi). Examples include socianates, xylylene diisocyanates, naphthalene diisocyanates, hydrogenated 4,4'-diphenylmethane diisocyanate (4,4'-dicyclohexylmethane diisocyanate), isophorone diisocyanates, hexamethylene diisocyanates, etc., and among these organic diisocyanates, 4,4'-diphenylmethane diisocyanate is preferred) and chain extenders (ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, 1 Urethane elastomers produced by reacting ,6-hexanediol, neopentyl glycol, 1,9-nonanediol, cyclohexanediol, 1,4-bis(β-hydroxyethoxy)benzene, etc.; Polyolefin elastomers such as ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer, butyl rubber, butadiene rubber, propylene-butene copolymer, and ethylene-acrylic acid ester copolymer; Polyamide elastomers; Fluorine elastomers; Chlorinated PE elastomers;Examples include acrylic elastomers.

[0039] Examples of styrene-based resins include polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene-α-methylstyrene copolymer, acrylonitrile-methyl methacrylate-styrene-α-methylstyrene copolymer, ABS resin, AS resin, MABS resin, MBS resin, AAS resin, AES resin, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, acrylonitrile-methyl methacrylate-butadiene-styrene-α-methylstyrene copolymer, styrene-maleic anhydride copolymer, styrene-maleimide copolymer, styrene-N-substituted maleimide copolymer, acrylonitrile-styrene-N-substituted maleimide copolymer, acrylonitrile-butadiene-styrene-β-isopropenylnaphthalene copolymer, and acrylonitrile-methyl methacrylate-butadiene-styrene-α-methylstyrene-maleimide copolymer. These may be contained individually or in combination of two or more.

[0040] Polyester is a polymer composed of a polybasic acid and a polyhydric alcohol, and is not particularly limited, provided that it is thermoplastic. Examples of polybasic acids include terephthalic acid, naphthaldicarboxylic acid, cyclohexyldicarboxylic acid, or their esters. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, octanediol, decanediol, cyclohexanedimethanol, hydroquinone, bisphenol A, 2,2-bis(4-hydroxyethoxyphenyl)propane, 1,4-dimethyloltetrabromobenzene, TBA-EO, etc. The polyester resin may be a homopolymer, copolymer, or a blend of two or more of these. In addition, Eastman Chemical's trade name "PETG" is also suitably used.

[0041] Examples of biodegradable polymers include microbial polymers such as biopolyesters (e.g., PHB / V), bacterial cellulose, and microbial polysaccharides (e.g., pullulan, curdlan); chemically synthesized polymers such as aliphatic polyesters (e.g., polycaprolactone, polybutylene succinate, polyethylene succinate, polyglycolic acid, polylactic acid); polyvinyl alcohol; and natural polymers such as chitosan / cellulose, starch, and cellulose acetate.

[0042] Examples of halogenated polymers include vinyl chloride homopolymers, copolymers containing 80% or more by mass of vinyl chloride, and highly chlorinated polyvinyl chloride. In addition to vinyl chloride, components of the copolymer include monovinyl compounds such as ethylene, vinyl acetate, methyl methacrylate, and butyl acrylate. These monovinyl compounds may be contained in a total amount of 20% or less by mass per 100% by mass of the copolymer. The above homopolymers and copolymers may be contained individually or in combination of two or more. Other examples include fluorinated polymers, brominated polymers, and iodized polymers.

[0043] Examples of acrylic resins include copolymers obtained by polymerizing vinyl monomers copolymerizable with methyl methacrylate. Examples of vinyl monomers copolymerizable with methyl methacrylate include alkyl acrylates such as methyl acrylate, ethyl acrylate, i-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, alkyl methacrylates such as ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate, and aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene.

[0044] Polymer alloys of the above-mentioned thermoplastic resins with engineering plastics such as polyphenylene ether, polycarbonate, polyethylene terephthalate and polybutylene terephthalate, polyamide resins such as syndiotactic polystyrene, 6-nylon and 6,6-nylon, polyarylate, polyphenylene sulfide, polyether ketone, polyether ether ketone, polysulfone, polyethersulfone, polyamide-imide, polyether-imide, and polyacetal are also included in the scope of the present invention.

[0045] Among these, polycarbonate resins that require impact resistance and transparency are preferred. The polycarbonate resin is not particularly limited as long as it is a polymer compound having a carbonate ester bond (-OC(O)-O-) in its main chain, but examples include aromatic polycarbonates such as bisphenol A-based polycarbonates and aliphatic polycarbonates. Among these, polycarbonates having an isosorbide skeleton derived from carbon-neutral plant monomers are even more preferred, as they offer an excellent balance of impact resistance, transparency, heat resistance, and hardness.

[0046] The polycarbonate resin having an isosorbide skeleton is preferably a polycarbonate resin containing a constituent unit derived from a dihydroxy compound represented by the following formula (2) (referred to as constituent unit (c)). The polycarbonate resin may be a homopolycarbonate of constituent unit (c), or a polycarbonate resin copolymerized with constituent units other than constituent unit (c). From the viewpoint of excellent impact resistance, a copolymerized polycarbonate resin is preferred.

[0047] [ka]

[0048] Examples of dihydroxy compounds represented by formula (2) above include isosorbide, isomannide, and isoidette, which are stereoisomers of each other. These may be used individually or in combination of two or more.

[0049] Among the dihydroxy compounds represented by formula (2) above, isosorbide obtained by dehydrating and condensing sorbitol produced from various starches that are abundant and readily available as plant-derived resources is most preferred in terms of ease of availability and production, weather resistance, optical properties, moldability, heat resistance, and carbon neutrality.

[0050] Furthermore, the polycarbonate resin is preferably a copolymerized polycarbonate resin containing a constituent unit (c) derived from a dihydroxy compound represented by formula (2) above, and a constituent unit (referred to as "constituent unit (d)" as appropriate) derived from one or more dihydroxy compounds selected from the group consisting of aliphatic hydrocarbon dihydroxy compounds, alicyclic hydrocarbon dihydroxy compounds, and ether-containing dihydroxy compounds. Since these dihydroxy compounds have a flexible molecular structure, the toughness of the resulting polycarbonate resin can be improved by using these dihydroxy compounds as raw materials. Among these dihydroxy compounds, it is preferable to use aliphatic hydrocarbon dihydroxy compounds and alicyclic hydrocarbon dihydroxy compounds, which have a greater effect in improving toughness, and it is most preferable to use alicyclic hydrocarbon dihydroxy compounds. Specific examples of aliphatic hydrocarbon dihydroxy compounds, alicyclic hydrocarbon dihydroxy compounds, and ether-containing dihydroxy compounds are as follows.

[0051] Examples of aliphatic hydrocarbon dihydroxy compounds include linear aliphatic dihydroxy compounds such as ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol; and branched aliphatic dihydroxy compounds such as 1,3-butanediol, 1,2-butanediol, neopentyl glycol, and hexylene glycol.

[0052] Examples of dihydroxy compounds of alicyclic hydrocarbons include primary alcohols of alicyclic hydrocarbons, such as dihydroxy compounds derived from terpene compounds like 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, 2,6-decalindimethanol, 1,5-decalindimethanol, 2,3-decalindimethanol, 2,3-norbornanedimethanol, 2,5-norbornanedimethanol, 1,3-adamantanedimethanol, and limonene; and secondary or tertiary alcohols of alicyclic hydrocarbons, such as dihydroxy compounds derived from terpene compounds like 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantanediol, hydrogenated bisphenol A, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

[0053] Examples of ether-containing dihydroxy compounds include oxyalkylene glycols and dihydroxy compounds containing an acetal ring. Examples of oxyalkylene glycols include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and polypropylene glycol.

[0054] In the polycarbonate resin, the content of constituent unit (c) relative to 100 mol% of all constituent units derived from dihydroxy compounds is preferably 30 mol% or more, more preferably 40 mol% to 95 mol%, even more preferably 45 mol% to 90 mol%, and particularly preferably 60 mol% to 85 mol%. In these cases, the content of biogenic materials can be increased, and heat resistance can be further improved. The content of constituent unit (c) in the polycarbonate resin may be 100 mol%, but from the viewpoint of increasing the molecular weight and further improving impact resistance, it is preferable that constituent units other than constituent unit (c) are copolymerized.

[0055] Furthermore, the polycarbonate resin may further contain structural units other than structural unit (c) and structural unit (d). Examples of such structural units (other dihydroxy compounds) include dihydroxy compounds containing aromatic groups. However, if the polycarbonate resin contains a large amount of structural units derived from dihydroxy compounds containing aromatic groups, a polycarbonate resin with a high molecular weight may not be obtained for the reasons mentioned above, and the effect of improving impact resistance may decrease. Therefore, from the viewpoint of further improving impact resistance, the content ratio of structural units derived from dihydroxy compounds containing aromatic groups is preferably 10 mol% or less, and more preferably 5 mol% or less, relative to 100 mol% of structural units derived from total dihydroxy compounds.

[0056] The glass transition temperature of polycarbonate resin is preferably 90°C or higher. In this case, the heat resistance of the resin composition and the content of bio-derived materials can be improved in a balanced manner. From a similar viewpoint, the glass transition temperature of polycarbonate resin is more preferably 100°C or higher, even more preferably 110°C or higher, and particularly preferably 120°C or higher. On the other hand, the glass transition temperature of polycarbonate resin is preferably 170°C or lower. In this case, the melt viscosity can be reduced by melt polymerization, and a polymer with a sufficient molecular weight can be obtained. Furthermore, if the molecular weight is increased by raising the polymerization temperature and lowering the melt viscosity, the heat resistance of the constituent unit (c) may not be sufficient, making it prone to discoloration. From the viewpoint of improving molecular weight and preventing discoloration in a more balanced manner, the glass transition temperature of polycarbonate resin is more preferably 165°C or lower, even more preferably 160°C or lower, and particularly preferably 150°C or lower.

[0057] The molecular weight of polycarbonate resin can be expressed by its reduced viscosity, with higher reduced viscosity indicating a larger molecular weight. The reduced viscosity is typically 0.30 dL / g or higher, preferably 0.33 dL / g or higher. In this case, the mechanical strength of the molded article can be further improved. On the other hand, the reduced viscosity is typically 1.20 dL / g or lower, more preferably 1.00 dL / g or lower, and even more preferably 0.80 dL / g or lower. In these cases, the fluidity during molding can be improved, further enhancing productivity and moldability. The reduced viscosity of polycarbonate resin is measured using a Ubbelohde viscous tube at a temperature of 20.0°C ± 0.1°C, with a solution precisely adjusted to a polycarbonate resin concentration of 0.6 g / dL using methylene chloride as the solvent.

[0058] The melt viscosity of the polycarbonate resin is preferably 400 Pa·s to 3000 Pa·s. In this case, it is possible to prevent the molded article of the resin composition from becoming brittle and to further improve its mechanical properties. Furthermore, in this case, it is possible to improve the fluidity during molding and prevent damage to the appearance of the molded article and deterioration of dimensional accuracy. Furthermore, in this case, discoloration and foaming caused by the rise in resin temperature due to shear heating can be further prevented. From a similar viewpoint, the melt viscosity of the polycarbonate resin is more preferably 600 Pa·s to 2500 Pa·s, and even more preferably 800 Pa·s to 2000 Pa·s. In this specification, melt viscosity refers to the melt viscosity measured using a capillary rheometer [manufactured by Toyo Seiki Co., Ltd.] at a temperature of 240°C and a shear rate of 91.2 sec-1.

[0059] The ratio of the polymer to the thermoplastic resin in 100 parts by mass of the resin composition (polymer / thermoplastic resin) is preferably 1 / 99 to 20 / 80 (parts by mass). When the ratio of the content is within this range, it is possible to achieve both Charpy impact strength and surface impact strength. The ratio of the content is more preferably 1 / 99 to 15 / 85 (parts by mass), and even more preferably 5 / 95 to 15 / 85 (parts by mass).

[0060] The methods for blending the materials when preparing the resin composition of the present invention include, but are not particularly limited to, known blending methods. For example, methods of mixing and kneading using a tumbler, V-type blender, super mixer, Nauter mixer, Banbury mixer, kneading roll, extruder, etc.

[0061] <Molded body> The resin composition of the present invention encompasses a molded article made from the resin composition (hereinafter also referred to as "the molded article"). The molded article can be manufactured by methods commonly used for molding thermoplastic resin compositions, such as injection molding, extrusion molding, blow molding, and calendering.

[0062] This molded product can be widely used industrially as a material in various fields such as automotive, office automation equipment, home appliances, electrical and electronic equipment, construction, lifestyle and cosmetics, and medical supplies. More specific applications of the molded product include automotive interior and exterior parts, office equipment, home appliances, and building materials. In particular, the resin composition of the present invention is suitable for automotive interior and exterior parts because it exhibits excellent Charpy impact strength and surface impact strength.

[0063] Automotive exterior parts include, for example, fenders, bumpers, fascias, door panels, side garnishes, pillars, radiator grilles, side protectors, side moldings, rear protectors, rear moldings, various spoilers, hoods, roof panels, trunk lids, detachable tops, wind reflectors, mirror housings, and outer door handles. Automotive interior parts include, for example, instrument panels, center console panels, meter components, various switches, car navigation components, car audio-visual components, and auto mobile computer components. [Examples]

[0064] The present invention will be described in further detail below with reference to manufacturing examples and embodiments. However, the present invention is not limited in any way by the following embodiments. In the following embodiments, "parts" means "parts by mass" and "%" means "mass%".

[0065] [Manufacturing of polybutadiene rubber latex (R-1)] In a pressure-resistant autoclave, 100 parts of 1,3-butadiene (Bd), 0.3 parts of tert-dodecyl mercaptan, 0.28 parts of diisopropylbenzene hydroperoxide, 0.3 parts of tetrasodium pyrophosphate, 0.0036 parts of ferrous sulfate, 0.39 parts of sodium sulfate, 0.24 parts of glucose, 1.25 parts of potassium rosinate, 1.25 parts of potassium tallowate, and 200 parts of deionized water were charged and reacted at 53°C for 12 hours with stirring to obtain polybutadiene rubber latex (R-1).

[0066] [Manufacturing of polybutadiene rubber latex (R-2)] In a pressure-resistant autoclave, 95 parts of 1,3-butadiene (Bd), 5 parts of styrene (St), 0.30 parts of tert-dodecyl mercaptan, 0.50 parts of diisopropylbenzene hydroperoxide, 0.15 parts of tetrasodium pyrophosphate, 0.0024 parts of ferrous sulfate, 0.20 parts of sodium sulfate, 0.001 parts of sodium hydroxide, 0.34 parts of sodium hydroxymethanesulfinate, 1.36 parts of potassium rosinate, 0.64 parts of potassium tallowate, and 150 parts of deionized water were charged and reacted at 56°C for 12 hours with stirring to obtain polybutadiene rubber latex (R-2).

[0067] [Manufacturing of polybutadiene / acrylic copolymer rubber latex (R-3)] In a pressure-resistant autoclave, 45 parts of 1,3-butadiene (Bd), 55 parts of butyl acrylate (BA), 1.32 parts of potassium tallowate, 0.55 parts of sodium lauroyl sarcosinate, 0.20 parts of diisopropylbenzene hydroperoxide, 0.20 parts of glucose, 0.05 parts of sodium hydroxymethanesulfinate, 0.0003 parts of disodium ethylenediaminetetraacetate, 0.003 parts of ferrous sulfate, 0.30 parts of sodium tetrasodium pyrophosphate, and 180 parts of deionized water were charged and reacted at 60°C for 12 hours with stirring to obtain polybutadiene rubber latex (R-3).

[0068] [Production of acid group-containing copolymer latex (K-1)] In a glass reactor equipped with a reflux condenser, 1.67 parts potassium tallowate, 2.5 parts sodium dioctyl sulfosuccinate, 0.3 parts sodium formaldehyde sulfoxylate, 0.003 parts ferrous sulfate, 0.009 parts disodium ethylenediaminetetraacetate, and 196 parts deionized water were charged, and the temperature inside the glass reactor was raised while stirring until it reached 60°C. Next, a mixture consisting of 85 parts n-butyl acrylate, 15 parts methacrylic acid, and 0.5 parts cumene hydroperoxide was continuously added to the mixture of raw materials over 2 hours, and then polymerized by holding for another 2 hours to obtain an acid group-containing copolymer latex (K-1).

[0069] [Manufacturing Example 1] Manufacturing of core-shell polymer (A-1) 222 parts of polybutadiene rubber latex (R-1) (70 parts as the starting monomer component) were placed in a glass reaction vessel (separable flask) equipped with a stirrer and reflux condenser. The atmosphere inside the separable flask was replaced with nitrogen by passing a stream of nitrogen gas through it. 4.24 parts of acid group-containing copolymer latex (K-1) were added, and the liquid temperature was raised to 40°C and held for 10 minutes. Next, an aqueous solution consisting of 0.94 parts of dipotassium alkenylsuccinate and 27 parts of deionized water was added, and the liquid temperature was raised to 80°C. Furthermore, an aqueous solution consisting of 0.09 parts of sodium formaldehyde sulfoxylate dihydrate and 3.8 parts of deionized water was added. Subsequently, a mixture consisting of 27 parts methyl methacrylate (MMA), 3 parts polyethylene glycol monomethacrylate, and 0.11 parts tert-butyl hydroperoxide was added dropwise to the reaction vessel over 60 minutes, and heating and stirring were continued for 120 minutes. In this way, vinyl monomers were graft polymerized onto the rubbery polymer to obtain core-shell polymer latex (A-1). Furthermore, the following products were used: dipotassium alkenylsuccinate (product name "Latemul ASK, manufactured by Kao Corporation"), tert-butyl hydroperoxide (product name "Perbutyl H, manufactured by NOF Corporation"), and polyethylene glycol monomethacrylate (product name "Bremmer PE-90, manufactured by NOF Corporation").

[0070] 288.18 parts of the obtained core-shell polymer latex (A-1) were mixed with 2.2 parts of a stabilizer emulsion. Then, an aqueous solution of 5 parts calcium acetate and 173 parts deionized water was heated to 90°C, and the core-shell polymer latex (A-1) containing the stabilizer emulsion was added to the aqueous solution to form a slurry. The slurry was agglomerated by raising the liquid temperature to 95°C and holding it for 5 minutes. The aggregate was collected, immersed in 1500 parts of deionized water, and the dewatering process was repeated twice. Finally, it was dried at 60°C for 12 hours to obtain core-shell polymer (A-1) powder.

[0071] [Manufacturing Examples 2-7, 10-12] Manufacturing of core-shell polymers (A-2)-(A-7), (B-1)-(B-3) Powders of core-shell polymers (A-2) to (A-7) and (B-1) to (B-3) were obtained in the same manner as in Production Example 1, except that the composition of the graft was changed to the components shown in Table 2. Note that PE-90 (Bremmer PE-90, polyethylene glycol monomethacrylate), PE-350 (Bremmer PE-350, polyethylene glycol monomethacrylate), PP-1000 (Bremmer PP-1000, polypropylene glycol monomethacrylate), and PP-800 (Bremmer PP-800, polypropylene glycol monomethacrylate) are trade names of NOF Corporation, MEMA is 2-methoxyethyl methacrylate, HEMA is 2-hydroxyethyl methacrylate, and HPMA is 2-hydroxypropyl methacrylate. The relationship with formula (1) above is shown in Table 1.

[0072] [Table 1]

[0073] [Manufacturing Example 8] Manufacturing of core-shell polymer (A-8) 176 parts of polybutadiene rubber latex (R-2) (70 parts as the starting monomer component) and 45 parts of deionized water were charged into a glass reaction vessel (separable flask) equipped with a stirrer and reflux condenser. The atmosphere inside the separable flask was replaced with nitrogen by passing a stream of nitrogen gas through it. 4.24 parts of acid group-containing copolymer latex (K-1) were added, and the liquid temperature was raised to 40°C and held for 10 minutes. Next, an aqueous solution consisting of 0.94 parts of dipotassium alkenylsuccinate and 27 parts of deionized water was added, and the liquid temperature was raised to 80°C. Furthermore, an aqueous solution consisting of 0.09 parts of sodium formaldehyde sulfoxylate dihydrate and 3.8 parts of deionized water was added. Subsequently, a mixture consisting of 27 parts methyl methacrylate (MMA), 3 parts polyethylene glycol monomethacrylate, and 0.11 parts cumene hydroperoxide was added dropwise to the reaction vessel over 60 minutes, and heating and stirring were continued for 120 minutes. In this way, vinyl monomers were graft polymerized onto the rubbery polymer to obtain core-shell polymer latex (A-8). For reference, the following products were used: dipotassium alkenylsuccinate (product name "Latemul ASK, manufactured by Kao Corporation"), tert-butyl hydroperoxide (product name "Perbutyl H, manufactured by NOF Corporation"), and polyethylene glycol monomethacrylate (product name "Bremmer PE-350, manufactured by NOF Corporation").

[0074] 286.18 parts of the obtained core-shell polymer latex (A-8) were mixed with 2.2 parts of a stabilizer emulsion. Then, an aqueous solution of 5 parts calcium acetate and 173 parts deionized water was heated to 90°C, and the core-shell polymer latex (A-8) containing the stabilizer emulsion was added to this aqueous solution to form a slurry. The slurry was agglomerated by raising the liquid temperature to 95°C and holding it for 5 minutes. The aggregate was collected, immersed in 1500 parts of deionized water, and the dewatering process was repeated twice. Finally, it was dried at 60°C for 12 hours to obtain core-shell polymer (A-8) powder.

[0075] [Manufacturing Example 9] Manufacturing of core-shell polymer (A-9) 219 parts of polybutadiene rubber latex (R-3) (70 parts as the starting monomer component) were placed in a glass reaction vessel (separable flask) equipped with a stirrer and reflux condenser. The atmosphere inside the separable flask was replaced with nitrogen by passing a stream of nitrogen gas through it. 4.24 parts of acid group-containing copolymer latex (K-1) were added, and the liquid temperature was raised to 40°C and held for 10 minutes. Next, an aqueous solution consisting of 0.94 parts of dipotassium alkenylsuccinate and 27 parts of deionized water was added, and the liquid temperature was raised to 80°C. Furthermore, an aqueous solution consisting of 0.09 parts of sodium formaldehyde sulfoxylate dihydrate and 3.8 parts of deionized water was added. Subsequently, a mixture consisting of 27 parts methyl methacrylate (MMA), 3 parts polyethylene glycol monomethacrylate, and 0.11 parts tert-butyl hydroperoxide was added dropwise to the reaction vessel over 60 minutes, and heating and stirring were continued for 120 minutes. In this way, vinyl monomers were graft polymerized onto the rubbery polymer to obtain core-shell polymer latex (A-9). For reference, the following products were used: dipotassium alkenylsuccinate (product name "Latemul ASK, manufactured by Kao Corporation"), tert-butyl hydroperoxide (product name "Perbutyl H, manufactured by NOF Corporation"), and polyethylene glycol monomethacrylate (product name "Bremmer PE-350, manufactured by NOF Corporation").

[0076] 285.18 parts of the obtained core-shell polymer latex (A-9) were mixed with 2.2 parts of a stabilizer emulsion. Then, an aqueous solution of 5 parts calcium acetate and 173 parts deionized water was heated to 90°C, and the core-shell polymer latex (A-9) containing the stabilizer emulsion was added to this aqueous solution to form a slurry. The liquid temperature was raised to 95°C and held for 5 minutes to cause the slurry to coagulate. The coagulated material was collected, immersed in 1500 parts of deionized water, and the dewatering process was repeated twice. Finally, it was dried at 60°C for 12 hours to obtain core-shell polymer (A-9) powder.

[0077] [Manufacturing Example 13] Manufacturing of core-shell polymer (B-4) 89 parts of deionized water were placed in a glass reaction vessel (separable flask) equipped with a stirrer and reflux condenser. The atmosphere inside the separable flask was replaced with nitrogen by passing a stream of nitrogen gas through it. 0.052 parts of sodium dioctyl sulfosuccinate were added, the temperature was raised to 80°C, and an aqueous solution consisting of 0.05 parts of potassium persulfate and 5 parts of deionized water was added. Subsequently, an emulsion consisting of 40 parts of methyl methacrylate (MMA), 29.55 parts of butyl acrylate (BA), 0.45 parts of allyl methacrylate (AMA), 0.7 parts of sodium dioctyl sulfosuccinate, and 70 parts of deionized water was added dropwise to the reaction vessel over 180 minutes, and heating and stirring were continued for another 60 minutes. Subsequently, an emulsion consisting of 27 parts methyl methacrylate (MMA), 3 parts polyethylene glycol monomethacrylate, 0.3 parts sodium dioctyl sulfosuccinate, and 22.5 parts deionized water was added dropwise to the reaction vessel over 60 minutes. Heating and stirring were then continued for 120 minutes to graft polymerization of vinyl monomers onto the rubbery polymer, yielding core-shell polymer latex (B-4). For the sodium dioctyl sulfosuccinate, we used the trade name "Perex OT-P, manufactured by Kao Corporation"; for cumene hydroperoxide, we used the trade name "Permil H, manufactured by NOF Corporation"; and for polyethylene glycol monomethacrylate, we used the trade name "Bremmer PE-350, manufactured by NOF Corporation."

[0078] An aqueous solution was prepared by mixing 287.6 parts of the obtained core-shell polymer latex (B-4) with 5 parts of calcium acetate and 173 parts of deionized water. This solution was heated to 90°C, and the core-shell polymer latex (B-4) was added to the aqueous solution to form a slurry. The slurry was agglomerated by raising the liquid temperature to 95°C and holding it for 5 minutes. The aggregate was collected, immersed in 1500 parts of deionized water, and the dewatering process was repeated twice. The mixture was then dried at 60°C for 12 hours to obtain core-shell polymer (B-4) powder.

[0079] [Measurement of particle size] Measurements were taken using the concentrated particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).

[0080] Table 2 shows the composition for each production example, the glass transition temperature (Tg) of the polymer B portion calculated using the FOX equation for the obtained core-shell polymer, and the average primary particle size.

[0081] [Table 2]

[0082] [Example 1] The obtained core-shell polymer (A-1) and the polycarbonate resin "DURABIO D7340R" (manufactured by Mitsubishi Chemical Corporation) having an isosorbide skeleton were blended and mixed in the composition shown in Table 3 to obtain a mixture. This mixture was supplied to a devolatile twin-screw extruder (manufactured by Ikegai Iron Works Co., Ltd., PCM-30) heated to a barrel temperature of 240°C and kneaded to produce pellets of the resin composition of Example 1 containing 10% by mass of the core-shell polymer.

[0083] [Examples 2-9, Comparative Examples 1-5] Resin pellets were obtained in the same manner as in Example 1, except that the formulation was changed as shown in Table 3.

[0084] [Charpy impact test] Each pellet was supplied separately to a Sumitomo injection molding machine SE100DU (manufactured by Sumitomo Heavy Industries, Ltd.), and molded bodies (test pieces) measuring 80 mm in length, 10 mm in width, and 4 mm in thickness were obtained at a cylinder temperature of 240°C and a mold temperature of 60°C. The Charpy impact test was conducted in accordance with ISO-179-1, using a TYPE A notch in accordance with ISO-2818, and measured at a temperature of 23°C. In the Charpy impact test, the Charpy strength was 20 kJ / m 2 The above items are marked with "〇", 20kJ / m³ 2 Values ​​less than a certain amount were marked with "×".

[0085] [Surface impact test] Each pellet was supplied separately to a Sumitomo injection molding machine SE100DU (manufactured by Sumitomo Heavy Industries, Ltd.), and molded bodies (test pieces) measuring 100 mm in length, 50 mm in width, and 2 mm in thickness were obtained at a cylinder temperature of 240°C and a mold temperature of 60°C. The surface impact test was conducted using a DuPont H-100 impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), employing a striker with a hemispherical tip and a specimen support stand with an inner diameter of 10 inches. After cooling the specimen to the measurement temperature, the tip of the striker was brought into horizontal contact with the specimen, and then a 5 kg weight was dropped vertically from a position of 1500 mm. The fracture mode was visually observed. Measurements were taken at 23°C and 0°C. The fracture mode was determined using the classification described in ISO-6603-2, and specimens exhibiting mechanical behavior of YD, YS, or YU were classified as ductile fracture, with their proportions being measured. In the 0°C surface impact test, samples with a ductile fracture rate of 40% or higher were marked with "○", and those with a rate of less than 40% were marked with "×".

[0086] [Table 3]

[0087] The polymers of the present invention, as seen in Examples 1 to 9, exhibited excellent Charpy impact strength and surface impact strength in molded articles. On the other hand, Comparative Example 1 did not contain a polymer and therefore exhibited inferior Charpy impact strength. Furthermore, Comparative Examples 2 to 4 used polymers that did not contain constituent units derived from vinyl monomers containing the group represented by formula (1) above, and therefore exhibited inferior surface impact strength. In Comparative Example 5, the Tg of polymer portion B exceeded 0°C, resulting in inferior Charpy impact strength and surface impact strength.

Claims

1. A polymer comprising polymer A and polymer B, wherein polymer A contains a constituent unit derived from a vinyl monomer containing a group represented by the following formula (1) and a constituent unit derived from an alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms, and polymer B contains a constituent unit derived from a vinyl monomer different from the vinyl monomer, and the polymer has a Tg of 0°C or less. -(C ｍ H ２ｍ O) ｎ X ・・・(1) (In the formula, m is an integer greater than or equal to 1, when n = 1, X is a methyl group, and when n is an integer greater than or equal to 2, X is a hydrogen atom or an alkyl group.)

2. The polymer according to claim 1, wherein in formula (1), m = 2 to 5 and n = 1 to 23.

3. The polymer according to claim 1, wherein in a total of 100 parts by mass of the vinyl monomer containing the group represented by formula (1) used in the polymer A portion and the alkyl (meth)acrylate monomer having an alkyl group having 1 to 10 carbon atoms, the content of the vinyl monomer containing the group represented by formula (1) is 1 to 30 parts by mass, and the content of the alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms is 70 to 99 parts by mass.

4. The polymer according to claim 1, wherein when the total of polymer portion A and polymer portion B is 100 parts by mass, the proportion of polymer portion A is 10 to 50 parts by mass and the proportion of polymer portion B is 50 to 90 parts by mass.

5. The polymer according to claim 1, wherein the polymer is a core-shell polymer.

6. The polymer according to claim 1, wherein the average primary particle diameter is 100 to 500 nm.

7. A polymer obtained by polymerizing a rubber latex, which is obtained by polymerizing a vinyl monomer in the presence of an emulsifier, with a vinyl monomer containing a group represented by the following formula (1) and an alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms. -(C ｍ H ２ｍ O) ｎ X ・・・(1) (In the formula, m is an integer greater than or equal to 1, when n = 1, X is a methyl group, and when n is an integer greater than or equal to 2, X is a hydrogen atom or an alkyl group.)

8. The polymer according to claim 7, wherein in a total of 100 parts by mass of the vinyl monomer and the alkyl (meth)acrylate monomer having an alkyl group having 1 to 10 carbon atoms, the content of the vinyl monomer is 1 to 30 parts by mass, and the content of the alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms is 70 to 99 parts by mass.

9. A resin additive comprising the polymer according to any one of claims 1 to 8.

10. A resin composition comprising a polymer according to any one of claims 1 to 8 and a thermoplastic resin.

11. The resin composition according to claim 10, wherein the ratio of the content of the polymer to the thermoplastic resin in 100 parts by mass of the resin composition (polymer / thermoplastic resin) is 1 / 99 to 20 / 80 (parts by mass).

12. The resin composition according to claim 10, wherein the thermoplastic resin is a polycarbonate resin.

13. The resin composition according to claim 12, wherein the polycarbonate resin is a polycarbonate resin having an isosorbide skeleton.

14. A molded article comprising the resin composition described in claim 10.

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