JP6563316B2 - Graft copolymer - Google Patents

Description

  The present invention relates to a graft copolymer, which is soft and has excellent adhesive strength with a styrene resin.

  Styrenic resin such as ABS resin has excellent moldability and mechanical property balance, and has excellent paintability and electrical insulation, so it can be used for interior and exterior parts of vehicles, building materials, electrical and electronic equipment, It is used in a wide range of fields such as OA equipment. In recent years, for the purpose of imparting a high-class feeling to resin products, a technique for bonding a soft resin layer to a surface molded with a styrene resin has been demanded in order to realize a feel and texture like leather. . Soft PVC resin can be mentioned as a soft resin that can be bonded to styrene resin, but it is necessary to add a large amount of plasticizer, there is a problem that the plasticizer bleeds, and there is a possibility that dioxin may be generated during incineration, etc. There are environmental problems. As a soft resin other than the soft PVC resin, for example, a resin having a segment such as isoprene and butadiene as a soft component such as a styrene elastomer has been proposed, but there is a disadvantage that the adhesive strength with the ABS resin is inferior. .

  As means for solving such problems, Patent Document 1 discloses an olefin resin composition containing an olefin resin, an olefin elastomer, a styrene elastomer, a modified olefin polymer, and a tackifier. . Further, in Patent Document 2, a thermoplastic elastomer composition excellent in thermal adhesiveness with a styrene resin or the like by blending a specific rubbery polymer with a polyester block copolymer and a molded body using the same Has been proposed.

JP 7-309980 A

JP 2008-144091 A

  However, in the above method, the adhesive strength with a base material such as a styrene resin is not always sufficient, and the Shore hardness of the thermoplastic elastomer composition is high and the flexibility is insufficient. Therefore, a material that is soft and excellent in adhesiveness with a styrene resin or the like is desired.

  An object of this invention is to provide the material which is soft and excellent in adhesive strength with a styrene resin.

  As a result of diligent studies to solve such problems, the problem can be solved by graft polymerization of specific monomers to specific olefin polymers as soft and excellent adhesive properties with styrene resins, etc. And found the present invention.

  That is, the present invention provides an aromatic vinyl monomer (b) and an aromatic vinyl monomer (30) in the presence of 30 to 80 parts by weight of an olefin polymer (a) having a Shore hardness of 30A or more and less than 95A. Obtained by graft polymerization of a total of 20 to 70 parts by weight of the other vinyl monomers (c) copolymerizable with b) (the sum of (a), (b) and (c) is 100 parts by weight) It is a graft copolymer.

  The graft copolymer of the present invention can provide a material that is soft and excellent in thermal adhesiveness with a styrene resin or the like.

Hereinafter, the graft copolymer of the present invention will be described in detail.
The graft copolymer of the present invention comprises an aromatic vinyl monomer (b) and an aromatic vinyl monomer in the presence of 30 to 80 parts by weight of an olefin polymer (a) having a Shore hardness of 30A or more and less than 95A. Graft-polymerize a total of 20 to 70 parts by weight of the other vinyl monomer (c) copolymerizable with the monomer (b) (the total of (a), (b) and (c) is 100 parts by weight). The graft copolymer obtained in this way. In other words, the graft copolymer of the present invention comprises 30 to 80 parts by weight of an olefin polymer (a) having a Shore hardness of 30 A or more and less than 95 A, an aromatic vinyl monomer (b), and an aromatic vinyl type. 20 to 70 parts by weight of the total amount of other vinyl monomers (c) copolymerizable with the monomer (b) (total of (a), (b) and (c) is 100 parts by weight) Polymerized graft copolymer.

  Examples of the olefin polymer (a) used in the graft copolymer of the present invention include an ethylene polymer, a propylene polymer, a butene polymer, a 4-methyl-1-pentene polymer, ethylene · Examples include α-olefin / non-conjugated diene copolymers, modified products thereof, saponified products, hydrogenated products, and the like, and one or more of them can be used.

  Examples of ethylene polymers include ethylene homopolymers, ethylene / α-olefin copolymers, ethylene / α-olefin / non-conjugated diene copolymers, ethylene / vinyl acetate copolymers, ethylene / acrylic acid copolymers, Ethylene-based monomer units such as ethylene / acrylic acid ester copolymers, ethylene / methacrylic acid copolymers, ethylene / methacrylic acid ester copolymers, ethylene / cyclic olefin copolymers, etc. are the main units (usually polymers) The content of the monomer units based on ethylene is 50 mol% or more, with the total monomer units constituting the polymer being 100 mol%.

  Examples of the ethylene homopolymer include polyethylene. Examples of the α-olefin of the ethylene / α-olefin copolymer include propylene, 1-butene, 1-pentene, 1-nonene, 4-methyl-1-pentene, 1-hexene, and 4-methyl-1-hexene. 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like, and one kind or two or more kinds can be used.

  Examples of the non-conjugated diene of the ethylene / α-olefin / non-conjugated diene copolymer include vinylidene norbornene, ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene, and the like, and one or more can be used.

  Examples of propylene polymers include propylene homopolymers, propylene / ethylene copolymers, propylene / α-olefin copolymers, propylene / ethylene / 1-butene copolymers, propylene / cyclic olefin copolymers, and the like. A polymer having a monomer unit based on the main unit (generally, the content of the monomer unit based on propylene is 50 mol% or more with the total monomer units constituting the polymer being 100 mol%). it can.

  Examples of the propylene homopolymer include polypropylene. Examples of the α-olefin of the propylene / α-olefin copolymer include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4 Examples include α-olefins having 4 to 20 carbon atoms such as -methyl-1-pentene and 4-methyl-1-hexene, and one or more of them can be used.

  The olefin polymer (a) preferably contains an ethylene propylene copolymer from the viewpoint of flexibility. When an ethylene propylene copolymer is included as the olefin polymer (a), the content of the ethylene propylene copolymer in the olefin polymer (a) is not particularly limited, but is preferably 50 to 100% by weight. More preferably, it is 60 to 90% by weight, and further preferably 70 to 80% by weight. The “ethylene-propylene-based copolymer” is a copolymer of ethylene and propylene and an arbitrary monomer, and a monomer unit based on ethylene and a monomer unit based on propylene are main units (usually normal). The total content of monomer units constituting the polymer is 100 mol%, and the total content of monomer units based on ethylene and monomer units based on propylene is 50 mol% or more).

  The Shore hardness of the olefin polymer (a) is 30A or more and less than 95A, preferably 35A to 90A, and more preferably 40A to 85A. In this specification, the Shore hardness A is measured using a type A durometer in accordance with JIS K7215 (1986).

  There is no restriction | limiting in the shape and size of the olefin polymer (a) used for superposition | polymerization. The olefin polymer (a) in the graft copolymer of the present invention is not particularly limited, but the number average conversion particle diameter determined by the method described below from the viewpoint of increasing the graft ratio and the adhesive strength, The thickness is preferably 500 to 4500 μm, more preferably 700 to 3500 μm, and particularly preferably 1000 to 2700 μm. The number average reduced particle diameter means that when one particle is placed in a cylinder so that the particle is inscribed so that the longest diagonal line of the particle is in the height direction, the height and diameter of the cylinder are used [ (Height + Diameter) / 2] is the value obtained by calculating the average of 10 particles. In addition, when the olefin polymer (a) is substantially cylindrical, the value obtained by [(height + diameter) / 2] using the height and diameter of the cylinder and the average of 10 particles. Can be the number average equivalent particle size. Moreover, since the number average conversion particle diameter of the olefin polymer (a) in the graft copolymer is substantially the same as the number average conversion particle diameter of the olefin polymer (a) used for the graft polymerization, The number average conversion particle diameter of the olefin polymer (a) used for the graft polymerization may be the number average conversion particle diameter of the olefin polymer (a) in the graft copolymer.

  There is no restriction | limiting in particular in the manufacturing method of the olefin polymer (a) used for this invention, It can obtain by a well-known method. Further, for example, Espren EPDM and Espolex TPE series manufactured by Sumitomo Chemical Co., Ltd. can be obtained as the olefin polymer (a).

  Mineral oil or the like can be blended with the olefin polymer (a) as necessary for the purpose of adjusting the Shore hardness. Although there is no restriction | limiting in particular in mixing methods, such as mineral oil, From a viewpoint of the softness | flexibility and adhesiveness, the compounding quantity of mineral oil etc. is 10-100 weight part with respect to 100 weight part of olefin type polymers (a). It is preferable.

Although there is no restriction | limiting in particular in the density of an olefin type polymer (a), It is preferable that it is 800 or more and less than 930 (kg / m < ³ >) from a soft viewpoint. The density is measured according to JIS K7112.

  The graft copolymer of the present invention comprises an aromatic vinyl monomer (b) and other copolymerizable with the aromatic vinyl monomer (b) in the presence of the olefin polymer (a). A graft copolymer obtained by graft polymerization of the vinyl monomer (c).

  Examples of the aromatic vinyl monomer (b) used in the graft copolymer of the present invention include styrene, α-methylstyrene, paramethylstyrene, bromostyrene, and the like. it can. In particular, styrene and α-methylstyrene are preferable.

  Examples of the other vinyl monomers (c) copolymerizable with the aromatic vinyl monomer (b) include vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, ethacrylonitrile, and fumaronitrile. , Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, 4-t-butylphenyl (meth) acrylate, Bromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, 2,4,6-tribromophenyl (meth) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate, trichlorophenyl (meth) acrylate, etc. (Meta) a Acrylic acid ester monomers, N- phenylmaleimide, N- maleimide monomer cyclohexyl maleimide and the like, etc. are exemplified, they may be used singly or two or more kinds.

  The graft copolymer of the present invention can be copolymerized with the aromatic vinyl monomer (b) and the aromatic vinyl monomer (b) in the presence of 30 to 80 parts by weight of the olefin polymer (a). It is a graft copolymer obtained by graft polymerization of a total of 20 to 70 parts by weight of other vinyl monomers (c) (the total of (a), (b) and (c) is 100 parts by weight). .

  When the olefin polymer (a) is less than 30 parts by weight, the softness is inferior, and when it exceeds 80 parts by weight, the adhesion to the styrene resin is inferior. The olefin polymer (a) is preferably 35 to 75 parts by weight, and more preferably 40 to 70 parts by weight. That is, the total of the aromatic vinyl monomer (b) and the other vinyl monomer (c) is preferably 25 to 65 parts by weight, and more preferably 30 to 60 parts by weight.

Although there is no restriction | limiting in particular in the graft rate of a graft copolymer, From a softness | flexibility and adhesive viewpoint, it is preferable that a graft rate is 10% or more, and it is more preferable that it is 15% or more. In addition, a graft ratio is calculated | required from following formula 2 using content of the below-mentioned olefin type polymer (a), and the weight ratio of the dichloromethane insoluble part calculated | required by performing the fractionation operation | work with the dichloromethane of a graft copolymer. I can do it.
Formula 2
Graft ratio (%) = (Dichloromethane insoluble part weight ratio (%) − content of olefin polymer (a) (%)) / content of olefin polymer (a) (%) × 100

  The method for producing the graft copolymer of the present invention is not particularly limited, and can be obtained by emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, or a combination of these methods. preferable.

Although content of the olefin polymer (a) in the graft copolymer of this invention is not specifically limited, 10 to 85 weight% is preferable, More preferably, it is 30 to 80 weight%, More preferably, it is 40 to 75 weight% %. The content of the olefin polymer (a) in the graft copolymer can be obtained from the following formula 1, assuming that 99% of the charged amount of the olefin polymer is contained in the graft copolymer. .
Formula 1
Content (%) of olefin polymer (a) = (Amount of olefin polymer charged (parts) × 0.99) / Weight of graft copolymer (parts) × 100

  The total content of the aromatic vinyl monomer (b) and the other vinyl monomer (c) in the graft copolymer of the present invention is not particularly limited, but is preferably 1 to 70% by weight, More preferably, it is 10 to 65 weight%, More preferably, it is 25 to 60 weight%.

  The amount of the aromatic vinyl monomer (b) used (that is, the content of monomer units based on the aromatic vinyl monomer (b) in the graft copolymer of the present invention) is not particularly limited. Is preferably 1 to 70% by weight, more preferably 5 to 50% by weight, and still more preferably 10 to 40% by weight.

  The amount of the other vinyl monomer (c) used (that is, the content of the monomer unit based on the other vinyl monomer (c) in the graft copolymer of the present invention) is not particularly limited. Is preferably 1 to 70% by weight, more preferably 2 to 50% by weight, and still more preferably 3 to 30% by weight.

  The weight ratio of the aromatic vinyl monomer (b) and the other vinyl monomer (c) is not particularly limited, but the former: the latter is preferably 1:99 to 99: 1, more preferably 30: It is 70-95: 5, More preferably, it is 50: 50-85: 15.

  The total amount (total amount) of the olefin polymer (a), the aromatic vinyl monomer (b), and the other vinyl monomer (c) in the graft copolymer of the present invention is particularly limited. However, it is preferably 50% by weight or more (for example, 50 to 100% by weight), more preferably 70% by weight or more, still more preferably 90% by weight or more, and particularly preferably 95% by weight or more.

  The Shore hardness of the graft copolymer of the present invention is not particularly limited, but is preferably 35A to 95A, more preferably 40A to 93A, and still more preferably 50A to 90A.

The graft copolymer of the present invention may be used alone or in combination with other thermoplastic resins.
Although there is no restriction | limiting in particular in the kind of other thermoplastic resin which mix | blends the graft copolymer of this invention, For example, styrene resin; Acrylic resin, such as polymethylmethacrylate resin; Polycarbonate resin; Polybutylene terephthalate resin, Polyethylene terephthalate Polyester resins such as resins; polyamide resins; biodegradable resins such as polylactic acid resins; (modified) polyphenylene ether resins, polyoxymethylene resins, polysulfone resins, polyarylate resins, polyphenylene resins, heat Engineering plastics such as a plastic polyurethane-based resin can be used, and one or more kinds can be used. Among these, it is preferable to include a styrene resin and / or a polycarbonate resin. Examples of the styrene resin include rubber reinforced styrene resin and non-rubber reinforced styrene resin.

  Specific examples of rubber reinforced styrene resins include rubber reinforced polystyrene resin (HIPS resin), acrylonitrile / butadiene rubber / styrene polymer (ABS resin), acrylonitrile / acrylic rubber / styrene polymer (AAS resin), methacrylic acid. Examples include methyl-butadiene rubber / styrene resin (MBS resin), acrylonitrile / ethylene-propylene rubber / styrene polymer (AES resin), and the like.

  Specific examples of the non-rubber reinforced styrene resin include styrene polymer (PS resin), styrene / acrylonitrile copolymer (AS resin), α-methylstyrene / acrylonitrile copolymer (αMS-ACN resin), methyl methacrylate.・ Styrene copolymer (MS resin), methyl methacrylate / acrylonitrile / styrene copolymer (MAS resin), styrene / N-phenylmaleimide copolymer (S-NPMI resin), styrene / N-phenylmaleimide / acrylonitrile A polymer (SA-NPMI resin) etc. are illustrated.

  The polycarbonate resin is a polymer obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonic ester such as diphenyl carbonate are reacted. Includes 2,2-bis (4-hydroxyphenyl) propane; polycarbonate resin produced from “bisphenol A”.

  Examples of the dihydroxydiaryl compound include bisphenol A, bis (4-hydroxydiphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3- 3-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4- Bis (hydroxyaryl) alkanes such as hydroxy-3,5-dichlorophenyl) propane, 1,1-bis 4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3 Dihydroxy diaryl ethers such as' -dimethyldiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, dihydroxy diaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4 Dihydroxy diaryl sulfoxides such as' -dihydroxydiphenyl sulfoxide, dihydroxy diaries such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Sulfone, and the like.

  These may be used alone or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4′-dihydroxydiphenyls, and the like may be mixed.

  Further, the above-mentioned dihydroxydiaryl compound and a trivalent or higher valent phenol compound as shown below may be mixed and used. Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 4,6-dimethyl-2,4,6-tri- (4-hydroxy). Phenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) benzol, 1,1,1-tri- (4-hydroxyphenyl) ethane and 2,2-bis- [4,4-bis ( 4-hydroxyphenyl) cyclohexyl] propane and the like. In producing these polycarbonate resins, the weight average molecular weight of the polycarbonate resin is usually 10,000 to 80,000, preferably 15,000 to 60,000. A molecular weight regulator, a catalyst, etc. can be used as needed. The weight average molecular weight can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

  The graft copolymer of the present invention and the other thermoplastic resin are 50 to 100 parts by weight of the graft copolymer, 0 to 50 parts by weight of the other thermoplastic resin (the total of the graft copolymer and the other thermoplastic resin is 100). Parts by weight). From the viewpoint of the balance between softness and adhesive strength with the styrene resin, the graft copolymer is preferably 50 to 99 parts by weight, more preferably 60 to 90 parts by weight, and 70 to 80 parts by weight. It is particularly preferred.

  The graft copolymer of the present invention is a pigment, dye, reinforcing agent (talc, mica, clay, glass fiber, etc.) at the time of resin mixing or molding depending on the purpose, as long as the object of the present invention is not impaired. Known additives such as ultraviolet absorbers, antioxidants, lubricants, mold release agents, plasticizers, flame retardants, antistatic agents, inorganic and organic antibacterial agents can be blended.

  The graft copolymer of the present invention can be obtained by mixing the above-mentioned components. In order to mix, well-known kneading apparatuses, such as an extruder, a roll, a Banbury mixer, a kneader, can be used, for example. There is no limitation on the mixing order.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the part and% which are shown in an Example are based on a weight.

Olefin polymer (a-1)
Product name “ESPOLEX 820” (α-olefin resin, ethylene propylene rubber mixture), manufactured by Sumitomo Chemical Co., Ltd.
Shore hardness: 78A
Density: 880 (kg / cm ³ )
Number average equivalent particle size: 3800 μm
Olefin polymer (a-2)
Made by Sumitomo Chemical Co., Ltd., trade name “ESPOLEX WT485A” (α-olefin resin, ethylene propylene rubber, mineral oil mixture)
Shore hardness: 60A
Density: 880 (kg / m ³ )
Number average equivalent particle size: 3600 μm

Production of graft copolymers
Graft copolymer (A-1)
A 100 L pressure vessel is charged with 500 parts of deionized water, 0.2 part of polyoxyethylene polyoxypropylene glycol, 1.0 part of magnesium sulfate, and 100 parts of the olefin polymer (a-1). Nitrogen replacement was performed. Then, 34 parts of styrene, 16 parts of acrylonitrile, tert-butyl peroxypivalate (B (PV) Kayaku Akzo Co., Ltd. 70% pure) 1.8 parts, tert-butyl peroxy-2-ethylhexanoate 0.15 parts, 0.04 part of 1,4-benzoquinone and 50 parts of deionized water were charged and nitrogen substitution in the tank was performed. After raising the temperature in the tank to 85 ° C., the reaction was continued for 1 hour after reaching 85 ° C. After completion of the reaction, the temperature in the tank was cooled to 40 ° C., and the graft copolymer (A-1) was obtained by performing recovery, washing and drying. Further, the content of the olefin polymer (a-1) and the graft ratio of the graft copolymer (A-1) were determined by the following method.

Measurement of Olefin Polymer Content of Graft Copolymer 136 parts of the graft copolymer (A-1) was obtained after drying. By assuming that 99% of the charged amount of the olefin polymer (a-1) is contained in the graft copolymer, the content of the olefin polymer of the graft copolymer (A-1) is represented by the following formula 1. You can ask.
Formula 1
Olefin polymer content (%) = (Feed olefin polymer amount (parts) × 0.99) / Graft copolymer weight (parts) × 100
= (100 x 0.99) / 136 x 100
= 72.8 (%)

Measurement of graft ratio The graft copolymer (A-1) was fractionated using dichloromethane, and the weight ratio of the dichloromethane-insoluble part was determined to be 84.8%. Since the olefin polymer (a-1) is present in the dichloromethane insoluble part, the graft ratio can be determined from the following formula 2.
Formula 2
Graft ratio (%) = (Dichloromethane insoluble part weight ratio (%) − olefin polymer content (%)) / olefin polymer content (%) × 100
= (84.8-72.8) /72.8×100
= 16.5 (%)

Styrene resin made by Nippon A & L Co., Ltd., trade name “Clarastic GA-501” (ABS resin)

Example 1, Comparative Examples 1-2
For each of the graft copolymer, styrene resin, and olefin polymer, a test piece with ribs was prepared by injection molding using an injection molding machine having a cylinder temperature of 230 ° C. and a hot plate mold. Adhesive strength evaluation was performed using the obtained test piece. The evaluation method is shown below.

Evaluation of softness The Shore hardness A of the graft copolymer obtained above was measured according to JIS K7215 (1986) using a type A durometer. The lower the Shore hardness A, the better the softness.

Adhesive strength After preparing a test piece of length 147 mm × width 30 mm × thickness 3 mm (rib height: styrene resin test piece 2 mm, graft copolymer and olefin polymer test piece 10 mm) by the above method, styrene resin test A graft copolymer test piece or an olefin polymer test piece is adhered to the piece. In the bonding method, each test piece is pressed against a hot plate bonding tester set at 220 ° C. for 10 seconds and melted, then separated from the heater, and the ribs are instantaneously overlapped and bonded for 10 seconds.
Next, the tensile strength of the bonded test piece was measured with a tensile tester (Shimadzu AGS-5 kNG) under conditions of a test force of 5 kN and a tensile speed of 1.0 mm / min, and this was used as the adhesive strength. In addition, the set temperature of the hot plate adhesion tester was changed to 240 ° C. and 260 ° C., and the tensile strength was similarly measured. The evaluation results are shown in Table 1.

  As shown in Table 1, Comparative Examples 1-2 were examples using an olefin polymer (a) that was not graft-polymerized, and did not adhere to the styrene resin.

  As described above, since the graft copolymer of the present invention is soft and excellent in adhesive strength with a styrene resin, it is soft and practical by forming two layers on the surface of a hard resin such as a styrene resin. Molded products with high adhesive strength, various grips used for scissors, screwdrivers, toothbrushes, shavers, mice, etc .; sealing packings used for building doors, window frames, etc .; used for household appliances, etc. Various switches and knobs; Housing feet used for household appliances, etc .; Baseboard cushioning materials; Automotive interior parts such as instrument panels, center panels, center console boxes, door trims, pillars, assist grips, handles, airbag covers, etc. Can be used for various purposes according to market needs.

Claims (6)

Copolymerizable with aromatic vinyl monomer (b) and aromatic vinyl monomer (b) in the presence of 30 to 80 parts by weight of olefin polymer (a) having a Shore hardness of 40A to 85A other vinyl monomers total 20 to 70 parts by weight of (c) ((a), (b) the total of and (c) is 100 parts by weight) Ri graft copolymer der obtained by graft polymerization of ,
The number average reduced particle diameter of the olefin polymer (a) is 500 to 4500 μm,
Including a vinyl cyanide monomer as the other vinyl monomer (c),
A graft copolymer having a graft ratio of 10% by weight or more . The graft copolymer according to claim 1, wherein the content of the monomer unit based on the vinyl cyanide monomer in the graft copolymer is 1 to 70% by weight. In the presence of 40 to 80 parts by weight of the olefin polymer (a), a total of 20 to 60 parts by weight of the aromatic vinyl monomer (b) and the other vinyl monomer (c) ((a), ( The graft copolymer according to claim 1 or 2, obtained by graft polymerization of b) and (c) in a total of 100 parts by weight). The graft copolymer according to any one of claims 1 to 3, which has a Shore hardness of 35A to 95A. The graft copolymer according to any one of claims 1 to 4 , wherein the olefin polymer (a) contains an ethylene propylene copolymer. A two-layer molded product of the graft copolymer according to any one of claims 1 to 5 and a styrene resin.