WO2022202557A1 - Thermoplastic resin composition and manufacturing method therefor - Google Patents
Thermoplastic resin composition and manufacturing method therefor Download PDFInfo
- Publication number
- WO2022202557A1 WO2022202557A1 PCT/JP2022/011971 JP2022011971W WO2022202557A1 WO 2022202557 A1 WO2022202557 A1 WO 2022202557A1 JP 2022011971 W JP2022011971 W JP 2022011971W WO 2022202557 A1 WO2022202557 A1 WO 2022202557A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mass
- acid ester
- methacrylic acid
- monomer unit
- resin composition
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 73
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000178 monomer Substances 0.000 claims abstract description 203
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 63
- 150000001993 dienes Chemical class 0.000 claims abstract description 62
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims abstract description 60
- 239000002245 particle Substances 0.000 claims abstract description 45
- 229920001577 copolymer Polymers 0.000 claims abstract description 34
- 125000005396 acrylic acid ester group Chemical group 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims description 58
- 229920001971 elastomer Polymers 0.000 claims description 55
- 239000000806 elastomer Substances 0.000 claims description 47
- 229920000578 graft copolymer Polymers 0.000 claims description 46
- 229920001400 block copolymer Polymers 0.000 claims description 37
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 33
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 17
- 238000004898 kneading Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 32
- 239000004014 plasticizer Substances 0.000 abstract description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 19
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 16
- -1 acrylic ester Chemical class 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000005060 rubber Substances 0.000 description 8
- 238000001746 injection moulding Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000013013 elastic material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- MUZDXNQOSGWMJJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O MUZDXNQOSGWMJJ-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 229920000359 diblock copolymer Polymers 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- 238000010556 emulsion polymerization method Methods 0.000 description 4
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 4
- 239000012285 osmium tetroxide Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 238000010558 suspension polymerization method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
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- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010550 living polymerization reaction Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920003066 styrene-(meth)acrylic acid ester copolymer Polymers 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- HEXDQNXIVJEYLG-UHFFFAOYSA-N (2-methylphenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1C HEXDQNXIVJEYLG-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- SRXJYTZCORKVNA-UHFFFAOYSA-N 1-bromoethenylbenzene Chemical compound BrC(=C)C1=CC=CC=C1 SRXJYTZCORKVNA-UHFFFAOYSA-N 0.000 description 1
- XKMDZVINHIFHLY-UHFFFAOYSA-N 1-ethenyl-3,5-dimethylbenzene Chemical compound CC1=CC(C)=CC(C=C)=C1 XKMDZVINHIFHLY-UHFFFAOYSA-N 0.000 description 1
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- OMNYXCUDBQKCMU-UHFFFAOYSA-N 2,4-dichloro-1-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C(Cl)=C1 OMNYXCUDBQKCMU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- BQARUDWASOOSRH-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-yl hydrogen carbonate Chemical compound CC(C)(C)OOC(C)(C)OC(O)=O BQARUDWASOOSRH-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 229920005510 ACRYPET® VH5 Polymers 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- 102100035474 DNA polymerase kappa Human genes 0.000 description 1
- 101710108091 DNA polymerase kappa Proteins 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
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- 240000007594 Oryza sativa Species 0.000 description 1
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- 238000003917 TEM image Methods 0.000 description 1
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- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
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- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
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- 229940096992 potassium oleate Drugs 0.000 description 1
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
Definitions
- the present invention relates to a thermoplastic resin composition, a molded product thereof, and a chemical-resistant transparent molded product using the molded product.
- ABS resins Rubber-modified thermoplastic resins
- OA equipment OA equipment
- pachinko parts etc.
- Transparent ABS resin is used for applications that require transparency particularly in terms of functionality.
- organic solvents such as alcohol and plasticizers, and fat emulsions. Needs improvement.
- Patent Documents 1 and 2 propose a resin composition comprising a styrene-acrylonitrile-methyl methacrylate copolymer and a graft copolymer.
- Patent Document 3 proposes a resin composition comprising a copolymer of alkyl acrylate having 1 to 4 carbon atoms and methyl methacrylate, a styrene-acrylonitrile copolymer, and a graft copolymer.
- Patent Document 4 a styrene-methyl methacrylate-based resin, a copolymer of vinyl cyanide and an aromatic vinyl, and a rubber-like elastic body containing a styrene-based monomer, a methacrylic acid ester-based monomer, and a vinyl cyanide-based A resin composition comprising a graft copolymer obtained by copolymerizing with a monomer has been proposed.
- JP-A-2002-179873 Japanese Patent Application Laid-Open No. 2002-212369 JP-A-2-274747 International Publication No. 2010/082613
- the present inventors have made intensive studies to solve the above problems, and found that a phase containing an aromatic vinyl-based monomer unit, a methacrylic acid ester-based monomer unit, and an acrylic acid ester monomer unit containing a graft copolymer having a diene rubber-like elastomer, the acrylic acid ester monomer unit contained in 100% by mass of the phase is 1 to 15% by mass, and the thermoplastic resin composition Among the particles contained in the thermoplastic resin composition, the average value of the short diameter of the particles that do not contain a diene rubber-like elastomer is 50 nm or less. rice field.
- the present invention is as follows. Graft containing a phase containing an aromatic vinyl-based monomer unit (a), a methacrylic acid ester-based monomer unit (b), and an acrylic acid ester-based monomer unit (c), and having a diene-based rubbery elastomer system copolymer, the acrylic ester monomer unit (c) contained in 100% by mass of the phase is 1 to 15% by mass, and among the particles contained in the thermoplastic resin composition, the diene-based A thermoplastic resin composition in which particles containing no rubber-like elastic material have an average short diameter of 50 nm or less.
- the aromatic vinyl-based monomer unit (a) contained in 100% by mass of the phase is 20 to 50% by mass, and the methacrylic acid ester-based monomer unit (b) is 30 to 75% by mass. %, and a haze value of a 2 mm-thick molded article obtained from the thermoplastic resin composition is 10% or less.
- the total mass of the polymer (A), the graft copolymer (B), and the methacrylic acid ester-acrylic acid ester block copolymer (C) component is set to 100% by mass.
- the polymer (A) is 20 to 60% by mass
- the graft copolymer (B) is 10 to 45% by mass
- the methacrylic acid ester-acrylic acid ester block copolymer (C) is 1 to 15% by mass
- the polymer (A) is an aromatic vinyl when the total mass of the aromatic vinyl monomer unit and the methacrylic acid ester monomer unit is 100% by mass.
- the graft copolymer (B) contains 0 to 40% by mass of the monomer unit and 60 to 100% by mass of the methacrylic acid ester monomer unit, and the graft copolymer (B) is a diene rubber-like elastomer.
- the methacrylate-acrylate block copolymer (C) comprises a methacrylate polymer block and acrylic acid When the total mass of the ester-based polymer blocks is 100%, the heat containing 25 to 75% by mass of the methacrylic acid ester-based polymer block and 25 to 75% by mass of the acrylic acid ester-based polymer block It is a plastic resin composition.
- the aromatic vinyl-based monomer unit when the total mass of the aromatic vinyl-based monomer unit and the vinyl cyanide-based monomer unit is 100% by mass, the aromatic vinyl-based monomer unit is 75 to 90% by mass.
- a thermoplastic resin composition containing 1 to 50% by mass of a copolymer (D) containing 10 to 25% by mass of vinyl cyanide-based monomer units.
- the graft copolymer (B) comprises a diene rubber-like elastomer, an aromatic vinyl monomer, a methacrylic acid ester monomer, and a vinyl cyanide monomer. It is a thermoplastic resin composition which is a graft copolymer obtained by copolymerizing with.
- the total mass of the polymer (A), the graft copolymer (B), and the methacrylic acid ester-acrylic acid ester block copolymer (C) component is 100% by mass
- 20 to 60% by mass of the polymer (A), 10 to 45% by mass of the graft copolymer (B), and 1 to 15% of the methacrylic acid ester-acrylic acid ester block copolymer (C) A method for producing a thermoplastic resin composition comprising a step of blending within a mass% range and melt-kneading, wherein the polymer (A) is an aromatic vinyl monomer unit and a methacrylic acid ester monomer
- the aromatic vinyl monomer unit is 0 to 40% by mass
- the methacrylic acid ester monomer unit is in the range of 60 to 100% by mass.
- the graft copolymer (B) is a graft copolymer obtained by copolymerizing a diene rubber-like elastomer with at least an aromatic vinyl monomer, and the methacrylic acid ester-acrylic acid ester block copolymer
- the polymer (C) contains 25 to 75% by mass of a methacrylic acid ester polymer block, an acrylic ester A method for producing a thermoplastic resin composition containing 25 to 75% by mass of a system polymer block.
- thermoplastic resin composition of the present invention is excellent in transparency and chemical resistance, it is used in applications such as medical instruments, home appliances, communication-related equipment, and general merchandise that require chemical resistance, such as coming into contact with plastics containing plasticizers. It can be used in a wide range of application fields.
- FIG. 1 is a photograph obtained by TEM observation after dyeing the thermoplastic resin composition obtained in Example 2.
- FIG. 4 is a photograph obtained by TEM observation after dyeing the thermoplastic resin composition obtained in Example 3.
- FIG. 4 is a photograph obtained by TEM observation after dyeing the thermoplastic resin composition obtained in Comparative Example 3.
- FIG. 1 is a photograph obtained by TEM observation after dyeing the thermoplastic resin composition obtained in Example 2.
- FIG. 4 is a photograph obtained by TEM observation after dyeing the thermoplastic resin composition obtained in Example 3.
- FIG. 4 is a photograph obtained by TEM observation after dyeing the thermoplastic resin composition obtained in Comparative Example 3.
- the phases contained in the thermoplastic resin composition of the present embodiment include aromatic vinyl-based monomer units (a), methacrylic acid ester-based monomer units (b), and acrylic acid ester monomer units (c ).
- the phase includes a vinyl cyanide-based monomer unit (d), maleic anhydride, N-phenylmaleimide, N-methylmaleimide, and other N-substituted maleimide-based monomer units within a range that does not impair the effects of the present invention. , and glycidyl group-containing monomers such as glycidyl methacrylate.
- the phase substantially contains only aromatic vinyl-based monomer units (a), methacrylic acid ester-based monomer units (b), and acrylic acid ester monomer units (c), good too.
- the thermoplastic resin composition of the present embodiment contains aromatic vinyl-based monomer units (a), methacrylic acid ester-based monomer units (b), and acrylic acid ester monomer units (c). It may further contain a phase other than the phase to be formed.
- the phase contained in the thermoplastic resin composition of the present embodiment contains aromatic vinyl-based monomer units (a).
- the aromatic vinyl monomer is not particularly limited, substituted styrenes having substituents such as styrene, ⁇ -methylstyrene, p-methylstyrene, 3,5-dimethylstyrene, 4-methoxystyrene, and 2-hydroxystyrene, ⁇ -bromostyrene, Halogenated styrenes such as 2,4-dichlorostyrene, 1-vinylnaphthalene and the like can be mentioned.
- the aromatic vinyl-based monomer unit (a) is preferably styrene or ⁇ -methylstyrene from the viewpoint of availability, polymerizability, and the like.
- the phase contained in the thermoplastic resin composition of the present embodiment contains methacrylic acid ester-based monomer units (b).
- the methacrylic acid ester-based monomer unit include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate. From the viewpoint of imparting heat resistance to the resin, it is preferable to use methyl methacrylate.
- These methacrylic acid ester-based monomer units may be used alone, or two or more of them may be used in combination. These methacrylic acid ester-based monomer units can be produced, for example, using raw materials consisting of or containing the corresponding monomers.
- the phase contained in the thermoplastic resin composition of the present embodiment contains acrylic acid ester monomer units (c).
- monomers that induce acrylate units include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, glycidyl acrylate, and cyclohexyl acrylate. , phenyl acrylate, and benzyl acrylate.
- the acrylate ester monomer unit (c) is preferably butyl acrylate from the viewpoint of chemical resistance.
- the average short diameter of particles not containing a diene rubber-like elastomer is 50 nm or less.
- Particles not containing a diene rubber-like elastomer are particles derived from an acrylic block copolymer. In one aspect, particles that do not contain a diene-based rubbery elastomer may not be identified.
- particles not containing a diene-based rubber-like elastomer cannot be confirmed means that, for example, when TEM observation is performed under the conditions shown below, particles other than particles dyed with osmium tetroxide (OsO 4 ) It refers to a state in which a portion clearly different in brightness from other portions is not observed.
- the components that can constitute the particles that do not contain the diene rubbery elastomer may be nano-dispersed, and the chemical resistance can be exhibited without impairing the transparency.
- the average minor axis exceeds 50 nm, the transparency deteriorates, which is not preferable.
- the average short diameter of the particles that do not contain a diene rubbery elastomer is preferably 40 nm or less, more preferably 30 nm or less.
- the shape of the particles that do not contain a diene-based rubbery elastic material is not particularly limited, and may be spherical, rod-like, or the like.
- the short diameter means the minimum diameter of the diameters connecting the diagonal lines in the particles constituting the bright phase portion.
- a photograph was taken using a transmission electron microscope (H-7500, manufactured by Hitachi High-Tech Co., Ltd.). Note that the photographing is appropriately set within the range of 6000 to 20,000 times. 1 to 3 of the present invention are enlarged at a magnification of 20,000 times (accelerating voltage of 80 kv).
- the average value of the short diameters of the particles that do not contain a diene rubbery elastomer can be calculated, for example, as follows.
- a substance capable of selectively dyeing a diene-based rubber-like elastomer e.g., osmium tetroxide (OsO 4 )
- osmium tetroxide OsO 4
- ruthenium tetroxide that dyes an amorphous part of a saturated hydrocarbon
- the method for making the average short diameter of the particles that do not contain a diene rubber-like elastomer to be 50 nm or less is not particularly limited.
- a method of melt-kneading the acid ester-acrylic acid ester block copolymer (C) with another resin is simple and preferable.
- the monomers that induce the methacrylic acid ester units (b) and the acrylic acid ester units (c) in the methacrylic acid ester-acrylic acid ester block copolymer (C) include the monomers described above.
- the methacrylic acid ester polymer block is a polymer block mainly composed of a methacrylic acid ester polymer block, and the methacrylic acid ester-acrylic acid ester block copolymer It preferably contains 25 to 75% by mass, more preferably 35 to 65% by mass, and still more preferably 45 to 55% by mass of methacrylate units in 100% by mass of the polymer. Specifically, for example, it is 25, 35, 45, 55, 65, or 75% by mass, and may be within a range between any two of the numerical values exemplified here.
- the acrylic acid ester polymer block is a polymer block mainly composed of an acrylic acid ester polymer block, and the methacrylic acid ester-acrylic acid ester block copolymer It preferably contains 25 to 75% by mass, more preferably 35 to 65% by mass, and still more preferably 45 to 55% by mass of acrylate units in 100% by mass of the polymer. If the acrylate-based polymer block exceeds 75% by mass, the dispersion will be insufficient and the transparency will be lowered. Specifically, for example, it is 25, 35, 45, 55, 65, or 75% by mass, and may be within a range between any two of the numerical values exemplified here.
- the content of the aromatic vinyl monomer unit (a) contained in 100% by mass of the phase contained in the thermoplastic resin composition is preferably 20 to 50% by mass, and is 20 to 30% by mass. is more preferred. Specifically, for example, it is 20, 22, 24, 26, 28, 30, 35, 40, 45, or 50% by mass, and may be within a range between any two of the numerical values exemplified here. . If the content of the aromatic vinyl-based monomer unit (a) exceeds 50% by mass, the thermoplastic resin composition will have reduced transparency and chemical resistance. If the content of the aromatic vinyl-based monomer unit (a) is less than 20% by mass, mechanical properties such as moldability and rigidity are deteriorated.
- the content of the methacrylic acid ester-based monomer unit (b) contained in 100% by mass of the phase contained in the thermoplastic resin composition is preferably 30 to 80% by mass, and is 50 to 75% by mass. is more preferred. Specifically, it is, for example, 30, 40, 50, 55, 60, 65, 70, 75, or 80% by mass, and may be within a range between any two of the numerical values exemplified here. If the content of the methacrylic acid ester-based monomer unit (b) exceeds 80% by mass, the impact strength of the thermoplastic resin composition is lowered. Moreover, when the content of the methacrylic acid ester-based monomer unit (b) is less than 30% by mass, the transparency is lowered.
- the content of the acrylic ester monomer unit (c) contained in 100% by mass of the phase contained in the thermoplastic resin composition is 1 to 15% by mass from the viewpoint of chemical resistance, transparency, and heat resistance. and preferably 4 to 10% by mass. Specifically, for example, it is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 15% by mass, and is within a range between any two of the numerical values exemplified here. good too.
- Aromatic vinyl monomer aromatic vinyl monomer unit (a), methacrylic acid ester monomer unit (b), and Components other than the acrylic acid ester monomer unit (c) are preferably less than 20% by mass, more preferably less than 15% by mass, from the viewpoint of maintaining the chemical resistance, transparency, and strength of the present invention. . Specifically, it is less than 20, 18, 16, or 15% by mass, for example.
- the phases contained in the thermoplastic resin composition are substantially aromatic vinyl-based monomer units (a), methacrylic acid ester-based monomer units (b), and acrylic acid ester monomer units (c).
- each monomer unit contained in the phase contained in the thermoplastic resin composition can be calculated from the blending amount by analyzing the composition of the raw material to be blended by IR, NMR, etc., or the thermoplastic resin composition. It can be obtained by measuring pyrolysis GC / MS, NMR, etc. for the MEK soluble content of.
- the thermoplastic resin composition of the present embodiment may contain a polymer (A) containing methacrylic acid ester-based monomer units.
- This structure is not particularly limited, and a copolymer having any structure containing aromatic vinyl-based monomer units and methacrylic acid ester-based monomer units can be used. That is, it may be a copolymer having any structure of block copolymers such as random copolymers, alternating copolymers, periodic copolymers, and graft copolymers.
- the content of the polymer (A) contained in 100% by mass of the thermoplastic resin composition of the present embodiment is 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass, from the viewpoint of transparency. % by mass or more. From the viewpoint of chemical resistance and strength, the content is 60% by mass or less, preferably 55% by mass or less, and more preferably 50% by mass or less.
- Examples of the methacrylic acid ester-based monomer units possessed by the polymer (A) include monomer units derived from methacrylic acid esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate. From the viewpoint of imparting, it is preferable to have a monomer unit derived from methyl methacrylate.
- the polymer (A) may have these methacrylic acid ester-based monomer units alone, or may have two or more of them. These methacrylic acid ester-based monomer units can be produced, for example, using a raw material consisting of one or more of the corresponding monomers, or containing them.
- the above polymer (A) is a copolymer containing monomer units derived from copolymerizable monomers in addition to aromatic vinyl-based monomer units and methacrylic acid ester-based monomer units.
- copolymerizable monomers include, but are not limited to, ⁇ , ⁇ -unsaturated carboxylic acid alkyl esters, ⁇ , ⁇ -unsaturated carboxylic acids, aromatic vinyls, cyanides, Examples include vinyl, N-substituted maleimides, maleic anhydride, and the like.
- the polymer (A) is When the aromatic vinyl-based monomer unit is contained within the range of 0 to 40% by mass and the methacrylic acid ester-based monomer unit is contained within the range of 60 to 100% by mass, the monomer unit composition of the phase is within the above range. It is preferable because it is easy to adjust.
- the aromatic vinyl-based monomer unit is contained in the range of 0 to 30% by mass and the methacrylic acid ester-based monomer unit is contained in the range of 70 to 100% by mass, and the aromatic vinyl-based monomer It is more preferable that the body unit is 0 to 25% by mass, the methacrylic acid ester monomer unit is contained in the range of 75 to 100% by mass, and the aromatic vinyl monomer unit is 0 to 20% by mass. , the methacrylic acid ester-based monomer unit is even more preferably contained within the range of 80 to 100% by mass.
- the polymer (A) has Other copolymerizable monomers are preferably contained in an amount of less than 5% by mass, preferably less than 3% by mass, in order to maintain transparency and strength.
- the thermoplastic resin composition of this embodiment contains a graft copolymer (B).
- the content of the graft copolymer (B) contained in 100% by mass of the thermoplastic resin composition of the present embodiment is 10% by mass or more, preferably 17% by mass or more, from the viewpoint of impact resistance. Preferably, it is 20% by mass or more. From the viewpoint of fluidity, the content is 45% by mass or less, preferably 42% by mass or less, and more preferably 40% by mass or less.
- the diene rubber-like elastic material constituting the graft copolymer (B) is not particularly limited, but includes, for example, a diene rubber-like elastic material having a glass transition temperature (Tg) of 0°C or lower.
- diene-based rubber-like elastomers include, but are not limited to, polybutadiene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, polyisoprene, polychloroprene, styrene-butadiene block copolymer rubber, and styrene-isoprene. conjugated diene rubbers such as block copolymer rubbers; These diene rubber-like elastomers can be used singly or in combination of two or more.
- the diene rubber-like elastomer is preferably a conjugated diene rubber, such as polybutadiene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber. Rubber is more preferred.
- the diene rubber-like elastomer contained in the graft copolymer (B) is preferably in the form of particles from the viewpoint of impact resistance and chemical resistance under strain.
- the mass average particle diameter of the particles is preferably 100 nm or more and less than 500 nm.
- it is 100 nm or more, the effect of improving chemical resistance and impact resistance is increased, and when it is less than 500 nm, appearance such as gloss tends to be maintained in addition to impact resistance.
- the monomer to be grafted onto the diene rubber-like elastomer includes at least an aromatic vinyl monomer.
- Examples of the monomer corresponding to the aromatic vinyl structure include those exemplified as specific examples of the aromatic vinyl monomer in the polymer (A).
- monomers to be grafted onto the diene rubber-like elastomer are not particularly limited, but vinyl cyanide monomers and methacrylic acid ester monomers are more preferable.
- methacrylic acid ester-based monomer include those exemplified for the polymer (A).
- vinyl cyanide monomers used as monomers of the graft copolymer include, but are not limited to, acrylonitrile, methacrylonitrile, and ethacrylonitrile.
- One of these vinyl cyanide monomers may be used alone, or two or more thereof may be used in combination.
- the method for producing the diene rubber-like elastomer constituting the graft copolymer (B) is not particularly limited, and examples thereof include bulk polymerization, solution polymerization, suspension polymerization, bulk suspension polymerization, and An emulsion polymerization method is mentioned. Among these, the emulsion polymerization method, the suspension polymerization method, or the bulk suspension polymerization method is preferable from the viewpoint that a particulate rubber component can be obtained and the particle size can be easily controlled.
- the diene rubber-like elastomer constituting the graft copolymer (B) When a polymer having a plurality of Tg's is used as the diene rubber-like elastomer constituting the graft copolymer (B), different monomer compositions are polymerized in multiple steps. That is, by obtaining a plurality of types of polymers each having a different Tg, which are polymerized with different monomer compositions, and making a mixture of these, the diene rubber-like elastomer as described above can be produced. . In this case, it is preferable to manufacture by multi-stage polymerization using an emulsion polymerization method.
- the diene rubbery elastomer when a polymer having a composition gradient is used as the diene rubbery elastomer, the diene rubbery elastomer can be produced by polymerizing while continuously changing the monomer composition.
- a block copolymer of an aromatic vinyl monomer and a conjugated diene monomer for example, a styrene-butadiene block copolymer
- living anionic polymerization is performed in a solution. By doing so, the diene rubber-like elastic body as described above can be produced.
- the method of producing the graft copolymer (B), for example, the method of graft-copolymerizing the monomer mixture onto the diene rubber-like elastomer is not particularly limited. method, suspension polymerization method, bulk suspension polymerization method, and emulsion polymerization method. After the production of the particulate diene rubber-like elastomer, the graft copolymerization may be continuously carried out in the same reactor. Copolymerization may be carried out.
- the graft-based copolymer (B) is a graft-based copolymer having a diene-based rubber-like elastic body and having the above-described monomer units graft-copolymerized thereto.
- the graft copolymer (B) has a rubbery elastomer as a main component, and the ratio of the diene rubbery elastomer to 100% by mass of the graft copolymer (B) is 30% by mass or more. Preferably, it is 35% by mass or more.
- the proportion of the methacrylic acid ester-based monomer unit is 5 to 50 mass% with respect to 100 mass% of the total mass of the graft-copolymerized monomer units and the diene rubber-like elastomer. %, more preferably 10 to 45% by mass, even more preferably 15 to 40% by mass. Specifically, for example, it is 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% by mass, and may be within a range between any two of the numerical values exemplified here. . It is preferable from the viewpoint of transparency that the ratio of the graft-copolymerized methacrylic acid ester-based monomer units is 5% by mass or more.
- the proportion of the methacrylic acid ester-based monomer unit is 50% by mass or less.
- a monomer to be grafted onto the diene rubber-like elastomer which is the aromatic vinyl monomer, the methacrylic acid ester monomer, or the vinyl cyanide monomer
- the amount of monomers other than the above is less than 5% by mass in 100% by mass of the graft copolymer (B).
- the monomers to be grafted onto the diene rubbery elastomer are substantially only aromatic vinyl monomers, methacrylic acid ester monomers, and vinyl cyanide monomers. may be
- the thermoplastic resin composition of the present embodiment may contain a methacrylic acid ester-acrylic acid ester block copolymer (C).
- the methacrylic acid ester-acrylic acid ester block copolymer (C) contained in 100% by mass of the thermoplastic resin composition of the present embodiment is in the range of 1 to 15% by mass, preferably 3 to 13% by mass. 5 to 11% by mass is more preferable. If it is less than 1% by mass, the chemical resistance is poor, and if it exceeds 15% by mass, the heat resistance is lowered.
- the methacrylic acid ester-acrylic acid ester block copolymer (C) preferably has a refractive index of 1.472 to 1.485. By having a refractive index within the above range, it is possible to maintain the transparency of the resin composition.
- the binding form of the block copolymer is not particularly limited, and diblock copolymers, triblock copolymers, multiblock copolymers having 4 or more polymer blocks, and star block copolymers can be used. , diblock copolymers and triblock copolymers are preferred from the standpoint of ease of production.
- the method for producing the block copolymer (C) is not particularly limited, but for example, a method of living polymerization of monomers constituting each polymer block is used.
- Methods of such living polymerization include, for example, a method of anionic polymerization in the presence of a mineral acid salt such as an alkali metal or alkaline earth metal salt using an organic alkali metal compound as a polymerization initiator, and a method of polymerizing an organic alkali metal compound.
- a method of anionic polymerization in the presence of an organoaluminum compound as an initiator can be used.
- the block copolymer (C) contains a monomer unit different from a monomer mainly composed of an acrylic acid ester or a monomer mainly composed of methyl methacrylate within a range that does not impair the effects of the present invention. may have.
- Examples of the different monomers include unsaturated carboxylic acids, olefins, conjugated dienes, aromatic vinyls, acrylamides, methacrylamides, acrylonitrile, methacrylonitrile, vinyl acetate, vinylpyridine, vinylketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, ⁇ -caprolactone, valerolactone and the like.
- the content of such different monomers includes monomers mainly composed of acrylic acid esters constituting the block copolymer (C), monomers mainly composed of methyl methacrylate, and monomers different from these.
- the total content of the monomer units is 100% by mass, it is preferably less than 5% by mass, more preferably less than 3% by mass, in order to maintain transparency and chemical resistance.
- thermoplastic resin composition of the present embodiment preferably contains a copolymer (D) containing vinyl cyanide monomer units and aromatic vinyl monomer units as structural units.
- Examples of the vinyl cyanide monomer constituting the copolymer (D) include, but are not limited to, acrylonitrile, methacrylonitrile, and ethacrylonitrile. is preferred. One of these vinyl cyanide monomers may be used alone, or two or more thereof may be used in combination.
- aromatic vinyl-based monomers contained in the polymer (A) are illustrated as aromatic vinyl-based monomers corresponding to the aromatic vinyl-based monomer units constituting the copolymer (D). The following are listed.
- the copolymer (D) may contain monomer units corresponding to other monomers copolymerizable with the vinyl cyanide monomer and the aromatic vinyl monomer.
- Other monomers include acrylate monomers.
- acrylic acid ester monomers include, but are not limited to, alkyl methacrylates such as methyl methacrylate, cyclohexyl methacrylate, methylphenyl methacrylate, and isopropyl methacrylate; methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl Examples include alkyl acrylates such as acrylates.
- Other monomers include N-substituted maleimide monomers such as maleic anhydride, N-phenylmaleimide and N-methylmaleimide, and glycidyl group-containing monomers such as glycidyl methacrylate. These may be used individually by 1 type, and may use 2 or more types together.
- the content of such a vinyl cyanide monomer and other monomers copolymerizable with the aromatic vinyl monomer is determined by the vinyl cyanide monomer unit constituting the copolymer (D), the aromatic
- the total content of the group vinyl-based monomer units, other copolymerizable monomers, and other monomers is 100% by mass, it is preferably less than 10% by mass, more preferably 5% by mass. % in order to maintain chemical resistance and transparency.
- the proportion of the vinyl cyanide monomer unit is 10 to 25% by mass with respect to the total mass (100% by mass) of the vinyl cyanide monomer unit and the aromatic vinyl monomer unit constituting the copolymer (D). is preferably 15 to 25% by mass, and more preferably 17 to 22% by mass. It is preferable from the viewpoint of chemical resistance that the proportion of vinyl cyanide monomer units is 10% by mass or more. Moreover, it is preferable from the viewpoint of transparency that the proportion of vinyl cyanide monomer units is 25% by mass or less.
- the ratio of the aromatic vinyl monomer units to the total mass (100% by mass) of the vinyl cyanide monomer units and the aromatic vinyl monomer units constituting the copolymer (D) was 75. It is preferably up to 90% by mass, more preferably 75 to 85% by mass, and more preferably 78 to 83% by mass. A ratio of the aromatic vinyl-based monomer units of 75% by mass or more is preferable from the viewpoint of transparency, and a ratio of 90% by mass or less is preferable from the viewpoint of chemical resistance.
- the copolymer (D) is 1 to 50% by mass, preferably 5 to 45% by mass, in 100% by mass of the thermoplastic resin composition of the present embodiment. It is preferably 10 to 40% by mass, more preferably.
- thermoplastic resin composition of the present embodiment there are no particular restrictions on melt extrusion, and known methods can be employed.
- the polymer (A), the graft copolymer (B), the methacrylic acid ester-acrylic acid ester block copolymer (C) and the copolymer (D) are mixed in a known mixture such as a Henschel mixer or a tumbler mixer.
- a known mixture such as a Henschel mixer or a tumbler mixer.
- the mixture is preliminarily mixed in an apparatus, fed to a single-screw extruder, a twin-screw extruder, or the like, melt-kneaded, and then prepared into pellets.
- the thermoplastic resin composition of the present embodiment includes a polymer (A), a graft copolymer (B), a methacrylic acid ester-acrylic acid ester block copolymer (C), and a copolymer other than (D).
- any known additive can be blended within a range that does not impair the effects of the present invention.
- plasticizers such as higher fatty acids, acid esters, acid amides, and higher alcohols, lubricants, silicone oils, and the like can be blended.
- Phosphite-based, hindered phenol-based, benzotriazole-based, benzophenone-based, benzoate-based, and cyanoacrylate-based antioxidants and UV absorbers can also be blended in order to impart weather resistance.
- an antistatic agent, a coloring agent, a pigment, a dye, a lubricant, an antiblocking agent, a foaming agent, a foaming aid, a cross-linking agent, a cross-linking aid, and the like can be blended.
- the molded article of the present embodiment is not particularly limited as long as it is a molded article of the thermoplastic resin composition of the present embodiment, and can be produced by a known molding method.
- the molding method is not limited to the following, and examples include press molding, injection molding, gas-assisted injection molding, welding molding, extrusion molding, blow molding, film molding, blow molding, and multiphase molding. method, and foam molding method. Among these, the injection molding method and the gas-assisted injection molding method are preferable from the viewpoint of productivity.
- the cylinder set temperature is preferably 220 to 290°C.
- the temperature is preferably 220°C or higher, more preferably 225°C or higher, and even more preferably 230°C or higher.
- the temperature is preferably 290°C or lower, more preferably 280°C or lower, and even more preferably 270°C or lower.
- insert molding with metal, outsert molding, gas assist molding, etc. may be used in combination.
- the mold to be used is also not particularly limited, and the gate shape may be any type of pin gate, tab gate, film gate, submarine gate, fan gate, ring gate, direct gate, and disc gate.
- the mold temperature is preferably 30 to 90°C, more preferably 50 to 70°C.
- the temperature is 30°C or higher, the surface smoothness of the molded product is enhanced.
- the temperature is 90° C. or lower, the cooling rate increases, and productivity improves.
- a complete mixing type continuous reactor with a volume of about 20 L equipped with a stirring blade, a column plug flow type continuous reactor with a volume of about 11 L, and a flash type devolatilization tank with a preheater were connected in series.
- 0.0073 parts by mass of t-butylperoxyisopropyl monocarbonate and 0.32 parts by mass of n-dodecyl mercaptan are mixed with a solution composed of 70% by mass of methyl methacrylate, 18% by mass of styrene, and 12% by mass of ethylbenzene to prepare raw materials. solution.
- This raw material solution was fed at a rate of 3.9 kg/h to a complete mixing type continuous reactor maintained at a temperature of 125° C. and polymerized.
- the conversion rate at the exit of the fully mixed continuous reactor was controlled at 55-58%.
- this polymerization solution was supplied to a tower-type plug-flow continuous reactor adjusted to have a gradient from 125° C. to 144° C. in the direction of flow for polymerization.
- the conversion rate at the tower plug flow type continuous reactor outlet was controlled at 75-78%.
- this polymerization solution While heating this polymerization solution to 230°C with a preheater, it was introduced into a flash-type devolatilization tank whose pressure was reduced to 1.3 kPa, and unreacted monomers were removed at a temperature of 235°C in the tank.
- the resin at 232° C. was extracted with a gear pump, extruded and cut into strands to obtain a pellet-shaped styrene-methacrylic acid ester copolymer (A-2).
- a pellet-shaped styrene-methacrylic acid ester copolymer (A-3) was obtained in the same manner as (A-2) except that the methyl methacrylate was 63% by mass and the styrene was 25% by mass.
- This raw material solution was supplied to a complete mixing type continuous reactor controlled at a rate of 6.0 kg/h at a temperature of 130° C. and polymerized.
- the stirring speed of the complete mixing reactor was 180 rpm.
- the reaction liquid was continuously withdrawn from the complete mixing reactor and supplied to a tower-type plug flow continuous reactor adjusted to have a temperature gradient from 130° C. to 160° C. in the direction of flow for polymerization. While heating this polymerization solution to 230°C with a preheater, it was introduced into a flash-type devolatilization tank whose pressure was reduced to 1.0 kPa, and unreacted monomers were removed at a temperature of 235°C in the tank. This resin was extruded and cut into strands to obtain a pellet-shaped copolymer (D-1).
- a copolymer (D-2) was obtained in the same manner as (D-1) except that styrene was 75 parts by mass, acrylonitrile was 25 parts by mass, and n-dodecylmercaptan was 0.025 parts by mass.
- a copolymer (D-3) was obtained in the same manner as (D-1) except that 88 parts by mass of styrene and 12 parts by mass of acrylonitrile were used.
- ⁇ Evaluation method> Total light transmittance/HAZE According to ASTM D-1003, a plate with a thickness of 2 mm is measured using a HAZE meter (NDH-2000) manufactured by Nippon Denshoku Industries Co., Ltd., and the total light transmittance and HAZE are measured. rate was taken as transparency.
- DOP dioctyl phthalate
- DINP dipropyl phthalate
- ethanol for disinfection manufactured by Kenei Pharmaceutical Co., Ltd.
- ⁇ bt/2a 2 ⁇ 1 ⁇ X 2 (a 2 ⁇ b 2 )/a 4 ⁇ ⁇ 3/2 ⁇ 100
- ⁇ Critical strain (%)
- ⁇ a: Long axis of jig ( 250 mm)
- ⁇ b: Short axis of jig ( 150 mm)
- X Distance (mm) from the crack occurrence position.
- thermoplastic resin composition The composition of the phase contained in the thermoplastic resin composition and the average short diameter of the particles not containing the diene rubber-like elastomer of the obtained thermoplastic resin composition were calculated by the method described above. The pellets were then injection molded to obtain a molded body. Transparency and chemical resistance of the resulting moldings were evaluated and shown in Tables 1 and 2.
- Figure 1 TEM observation after the diene rubber-like elastomer of the thermoplastic resin composition obtained in Example 2 was double-stained with osmium tetroxide (OsO 4 ) and ruthenium tetroxide (RuO 4 ) by a conventional method. This is a photograph obtained by Diene-based rubbery elastomer-free particles (particles contained in the thermoplastic resin composition that do not contain a diene-based rubbery elastomer) are observed as a bright phase portion.
- OsO 4 osmium tetroxide
- RuO 4 ruthenium tetroxide
- the average minor diameter of the diene-based rubber-like elastomer-free particles (among the particles contained in the thermoplastic resin composition, the average minor diameter of the particles that do not contain the diene-based rubber-like elastomer) is 50 nm or less. be.
- FIG. 2 A photograph obtained by TEM observation after the thermoplastic resin composition obtained in Example 3 was double-stained in the same manner as in Example 2.
- FIG. Diene-based rubber-like elastomer-free particles are observed as linear bright phase portions.
- the average short diameter of the diene rubber-like elastomer-free particles is 50 nm or less.
- Example 3 A photograph obtained by TEM observation after the thermoplastic resin composition obtained in Comparative Example 3 was double dyed in the same manner as in Example 2. Particles not containing a diene rubber-like elastomer are observed as a bright phase portion. The average short diameter of the diene rubber-like elastomer-free particles exceeds 50 nm.
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Abstract
The present invention provides a resin composition having excellent transparency and chemical resistance to a plasticizer or the like. Provided is a thermoplastic resin composition containing a phase that includes an aromatic vinyl monomer unit (a), a methacrylic acid ester monomer unit (b), and an acrylic acid ester monomer unit (c). The thermoplastic resin composition also includes a graft-based copolymer having a diene-based rubber-like elastic body. The acrylic acid ester monomer unit (c) included in 100 mass% of the abovementioned phase accounts for 1-15 mass% thereof. From among the particles included in the thermoplastic resin composition, the average short diameter value of particles not included in the diene-based rubber-like elastic body is 50 nm or less.
Description
本発明は熱可塑性樹脂組成物、その成形体及びその成形体を用いた耐薬品性透明成形物に関する。
The present invention relates to a thermoplastic resin composition, a molded product thereof, and a chemical-resistant transparent molded product using the molded product.
一般に、ＡＢＳ樹脂のようなゴム変性熱可塑性樹脂は、耐衝撃性、機械物性、成形加工性に優れているため、家電製品、電気・電子機器部品、ＯＡ機器、パチンコ部品等に幅広く使用されており、特に機能面等で透明性を必要とされる用途には、透明ＡＢＳ樹脂が使用される。しかしながら、このような透明樹脂は、アルコールや可塑剤などの有機溶剤や脂肪乳剤などに対する耐性が十分ではなく、用途や使用環境によっては割れやクラックが発生するという問題点があり、耐薬品性の改善を求められている。
In general, rubber-modified thermoplastic resins such as ABS resins have excellent impact resistance, mechanical properties, and molding processability, so they are widely used for home appliances, electrical and electronic equipment parts, OA equipment, pachinko parts, etc. Transparent ABS resin is used for applications that require transparency particularly in terms of functionality. However, such transparent resins are not sufficiently resistant to organic solvents such as alcohol and plasticizers, and fat emulsions. Needs improvement.
これら透明ＡＢＳ樹脂の耐薬品性を向上させる手段としては、シアン化ビニルの含有割合を高めることが一般的に知られており、いわゆる高ニトリル含有熱可塑性樹脂組成物が種々提案されている。
As a means of improving the chemical resistance of these transparent ABS resins, it is generally known to increase the content of vinyl cyanide, and various so-called nitrile-containing thermoplastic resin compositions have been proposed.
例えば、特許文献１～２では、スチレン－アクリロニトリル－メタクリル酸メチルの共重合体とグラフト系共重合体からなる樹脂組成物が提案されている。また、特許文献３では、炭素数１～４のアルキルアクリレートとメチルメタクリレートとの共重合体、スチレン－アクリロニトリル共重合体及びグラフト系共重合体からなる樹脂組成物が提案されている。さらに、特許文献４では、スチレン－メタクリル酸メチル系樹脂、シアン化ビニルと芳香族ビニルの共重合体、ゴム状弾性体にスチレン系単量体とメタクリル酸エステル系単量体とシアン化ビニル系単量体とを共重合してなるグラフト系共重合体からなる樹脂組成物が提案されている。
For example, Patent Documents 1 and 2 propose a resin composition comprising a styrene-acrylonitrile-methyl methacrylate copolymer and a graft copolymer. Patent Document 3 proposes a resin composition comprising a copolymer of alkyl acrylate having 1 to 4 carbon atoms and methyl methacrylate, a styrene-acrylonitrile copolymer, and a graft copolymer. Furthermore, in Patent Document 4, a styrene-methyl methacrylate-based resin, a copolymer of vinyl cyanide and an aromatic vinyl, and a rubber-like elastic body containing a styrene-based monomer, a methacrylic acid ester-based monomer, and a vinyl cyanide-based A resin composition comprising a graft copolymer obtained by copolymerizing with a monomer has been proposed.
しかしながら、上記文献記載の従来技術ではニトリル系官能基を有する構造を多く有するため透明性が悪化するという問題を有しており、かつ洗剤に対する耐性については例示があるが、三方活栓等の塩ビチューブと接続する部材では塩ビチューブに含まれる可塑剤がブリードアウトして汚染されることで割れが発生するなど必ずしも耐薬品性が充分でない課題があった。
However, the prior art described in the above document has a problem that transparency deteriorates because it has many structures having nitrile functional groups, and there are examples of resistance to detergents, but PVC tubes such as three-way stopcocks The plasticizer contained in the PVC tube bleeds out and contaminates the member connected to the pipe, which causes cracks.
そこで本発明者らは、上記の課題を解決すべく鋭意研究を重ねた結果、芳香族ビニル系単量体単位、メタクリル酸エステル系単量体単位、アクリル酸エステル単量体単位を含む相を含有し、ジエン系ゴム状弾性体を有するグラフト系共重合体を含み、当該相１００質量％中に含まれるアクリル酸エステル単量体単位が１～１５質量％であり、前記熱可塑性樹脂組成物に含まれる粒子のうち、ジエン系ゴム状弾性体を含まない粒子の短径の平均値が５０ｎｍ以下である熱可塑性樹脂組成物が可塑剤等への耐薬品性、透明性に優れることを見出した。
Therefore, the present inventors have made intensive studies to solve the above problems, and found that a phase containing an aromatic vinyl-based monomer unit, a methacrylic acid ester-based monomer unit, and an acrylic acid ester monomer unit containing a graft copolymer having a diene rubber-like elastomer, the acrylic acid ester monomer unit contained in 100% by mass of the phase is 1 to 15% by mass, and the thermoplastic resin composition Among the particles contained in the thermoplastic resin composition, the average value of the short diameter of the particles that do not contain a diene rubber-like elastomer is 50 nm or less. rice field.
すなわち、本発明は以下のとおりである。芳香族ビニル系単量体単位（ａ）、メタクリル酸エステル系単量体単位（ｂ）、アクリル酸エステル単量体単位（ｃ）を含む相を含有し、ジエン系ゴム状弾性体を有するグラフト系共重合体を含み、前記相１００質量％中に含まれるアクリル酸エステル単量体単位（ｃ）が１～１５質量％であり、前記熱可塑性樹脂組成物に含まれる粒子のうち、ジエン系ゴム状弾性体を含まない粒子の短径の平均値が５０ｎｍ以下である、熱可塑性樹脂組成物。
That is, the present invention is as follows. Graft containing a phase containing an aromatic vinyl-based monomer unit (a), a methacrylic acid ester-based monomer unit (b), and an acrylic acid ester-based monomer unit (c), and having a diene-based rubbery elastomer system copolymer, the acrylic ester monomer unit (c) contained in 100% by mass of the phase is 1 to 15% by mass, and among the particles contained in the thermoplastic resin composition, the diene-based A thermoplastic resin composition in which particles containing no rubber-like elastic material have an average short diameter of 50 nm or less.
本発明は一側面において、前記相１００質量％中に含まれる芳香族ビニル系単量体単位（ａ）が２０～５０質量％、メタクリル酸エステル系単量体単位（ｂ）が３０～７５質量％であり、熱可塑性樹脂組成物から得られる２ｍｍ厚の成形品のＨａｚｅ値が１０％以下である、熱可塑性樹脂組成物である。
In one aspect of the present invention, the aromatic vinyl-based monomer unit (a) contained in 100% by mass of the phase is 20 to 50% by mass, and the methacrylic acid ester-based monomer unit (b) is 30 to 75% by mass. %, and a haze value of a 2 mm-thick molded article obtained from the thermoplastic resin composition is 10% or less.
また、本発明は一側面において、重合体（Ａ）、グラフト系共重合体（Ｂ）、及びメタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）成分の合計質量を１００質量％とした場合に、前記重合体（Ａ）を２０～６０質量％、前記グラフト系共重合体（Ｂ）を１０～４５質量％、前記メタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）を１～１５質量％の範囲内で含み、前記重合体（Ａ）は、芳香族ビニル系単量体単位及びメタクリル酸エステル系単量体単位の合計質量を１００質量％とした場合に、芳香族ビニル系単量体単位を０～４０質量％、メタクリル酸エステル系単量体単位を６０～１００質量％の範囲内で含み、前記グラフト系共重合体（Ｂ）は、ジエン系ゴム状弾性体に少なくとも芳香族ビニル系単量体を共重合してなるグラフト系共重合体を含み、前記メタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）は、メタクリル酸エステル系重合体ブロック及びアクリル酸エステル系重合体ブロックの合計質量を１００％とした場合に、メタクリル酸エステル系重合体ブロックを２５～７５質量％、アクリル酸エステル系重合体ブロックを２５～７５質量％の範囲内で含む、熱可塑性樹脂組成物である。
In one aspect of the present invention, the total mass of the polymer (A), the graft copolymer (B), and the methacrylic acid ester-acrylic acid ester block copolymer (C) component is set to 100% by mass. In the case, the polymer (A) is 20 to 60% by mass, the graft copolymer (B) is 10 to 45% by mass, and the methacrylic acid ester-acrylic acid ester block copolymer (C) is 1 to 15% by mass, and the polymer (A) is an aromatic vinyl when the total mass of the aromatic vinyl monomer unit and the methacrylic acid ester monomer unit is 100% by mass. The graft copolymer (B) contains 0 to 40% by mass of the monomer unit and 60 to 100% by mass of the methacrylic acid ester monomer unit, and the graft copolymer (B) is a diene rubber-like elastomer. The methacrylate-acrylate block copolymer (C) comprises a methacrylate polymer block and acrylic acid When the total mass of the ester-based polymer blocks is 100%, the heat containing 25 to 75% by mass of the methacrylic acid ester-based polymer block and 25 to 75% by mass of the acrylic acid ester-based polymer block It is a plastic resin composition.
本発明は一側面において、芳香族ビニル系単量体単位、シアン化ビニル系単量体単位の合計質量を１００質量％とした場合に、芳香族ビニル系単量体単位が７５～９０質量％、シアン化ビニル系単量体単位が１０～２５質量％である共重合体（Ｄ）を１～５０質量％含む、熱可塑性樹脂組成物である。
In one aspect of the present invention, when the total mass of the aromatic vinyl-based monomer unit and the vinyl cyanide-based monomer unit is 100% by mass, the aromatic vinyl-based monomer unit is 75 to 90% by mass. , a thermoplastic resin composition containing 1 to 50% by mass of a copolymer (D) containing 10 to 25% by mass of vinyl cyanide-based monomer units.
また、本発明は一側面において、グラフト系共重合体（Ｂ）がジエン系ゴム状弾性体に芳香族ビニル系単量体と、メタクリル酸エステル系単量体と、シアン化ビニル系単量体とを共重合してなるグラフト系共重合体である、熱可塑性樹脂組成物である。
In one aspect of the present invention, the graft copolymer (B) comprises a diene rubber-like elastomer, an aromatic vinyl monomer, a methacrylic acid ester monomer, and a vinyl cyanide monomer. It is a thermoplastic resin composition which is a graft copolymer obtained by copolymerizing with.
本発明は一側面において、重合体（Ａ）、グラフト系共重合体（Ｂ）、及びメタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）成分の合計質量を１００質量％とした場合に、前記重合体（Ａ）を２０～６０質量％、前記グラフト系共重合体（Ｂ）を１０～４５質量％、前記メタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）を１～１５質量％の範囲内で配合し、溶融混練する工程を含む熱可塑性樹脂組成物の製造方法であって、前記重合体（Ａ）は、芳香族ビニル系単量体単位及びメタクリル酸エステル系単量体単位の合計質量を１００質量％とした場合に、芳香族ビニル系単量体単位を０～４０質量％、メタクリル酸エステル系単量体単位を６０～１００質量％の範囲内で含み、前記グラフト系共重合体（Ｂ）は、ジエン系ゴム状弾性体に少なくとも芳香族ビニル系単量体を共重合してなるグラフト系共重合体であり、前記メタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）は、メタクリル酸エステル系重合体ブロック及びアクリル酸エステル系重合体ブロックの合計質量を１００％とした場合に、メタクリル酸エステル系重合体ブロックを２５～７５質量％、アクリル酸エステル系重合体ブロックを２５～７５質量％の範囲内で含む、熱可塑性樹脂組成物の製造方法である。
In one aspect of the present invention, when the total mass of the polymer (A), the graft copolymer (B), and the methacrylic acid ester-acrylic acid ester block copolymer (C) component is 100% by mass, , 20 to 60% by mass of the polymer (A), 10 to 45% by mass of the graft copolymer (B), and 1 to 15% of the methacrylic acid ester-acrylic acid ester block copolymer (C) A method for producing a thermoplastic resin composition comprising a step of blending within a mass% range and melt-kneading, wherein the polymer (A) is an aromatic vinyl monomer unit and a methacrylic acid ester monomer When the total mass of the body units is 100% by mass, the aromatic vinyl monomer unit is 0 to 40% by mass, and the methacrylic acid ester monomer unit is in the range of 60 to 100% by mass. The graft copolymer (B) is a graft copolymer obtained by copolymerizing a diene rubber-like elastomer with at least an aromatic vinyl monomer, and the methacrylic acid ester-acrylic acid ester block copolymer The polymer (C) contains 25 to 75% by mass of a methacrylic acid ester polymer block, an acrylic ester A method for producing a thermoplastic resin composition containing 25 to 75% by mass of a system polymer block.
本発明の熱可塑性樹脂組成物は透明性、耐薬品性に優れるため可塑剤を含むプラスチックと接触する等、耐薬品性が要求される医療用器具や家電製品、通信関連機器及び一般雑貨などの用途分野で幅広く利用することができる。
Since the thermoplastic resin composition of the present invention is excellent in transparency and chemical resistance, it is used in applications such as medical instruments, home appliances, communication-related equipment, and general merchandise that require chemical resistance, such as coming into contact with plastics containing plasticizers. It can be used in a wide range of application fields.
＜用語の説明＞
本願明細書において、例えば、「Ａ～Ｂ」なる記載は、Ａ以上でありＢ以下であることを意味する。 <Description of terms>
In the specification of the present application, for example, the description “A to B” means A or more and B or less.
本願明細書において、例えば、「Ａ～Ｂ」なる記載は、Ａ以上でありＢ以下であることを意味する。 <Description of terms>
In the specification of the present application, for example, the description “A to B” means A or more and B or less.
以下、本発明の実施形態について、詳細に説明する。以下に示す実施形態は互いに組み合わせ可能である。
Hereinafter, embodiments of the present invention will be described in detail. The embodiments shown below can be combined with each other.
＜熱可塑性樹脂組成物に含有される相＞
本実施形態の熱可塑性樹脂組成物に含有される相は、芳香族ビニル系単量体単位（ａ）、メタクリル酸エステル系単量体単位（ｂ）、及びアクリル酸エステル単量体単位（ｃ）を含有する。当該相は、本発明の効果を損なわない範囲で、シアン化ビニル系単量体単位（ｄ）、無水マレイン酸、Ｎ－フェニルマレイミド、Ｎ－メチルマレイミド等のＮ－置換マレイミド系単量体単位、及びグリシジルメタクリレート等のグリシジル基含有単量体を含有してもよい。当該相は、実質的に芳香族ビニル系単量体単位（ａ）、メタクリル酸エステル系単量体単位（ｂ）、及びアクリル酸エステル単量体単位（ｃ）のみを含有するものであってもよい。
また、本実施形態の熱可塑性樹脂組成物は、芳香族ビニル系単量体単位（ａ）、メタクリル酸エステル系単量体単位（ｂ）、及びアクリル酸エステル単量体単位（ｃ）を含有する相以外の相をさらに含有してもよい。 <Phase contained in the thermoplastic resin composition>
The phases contained in the thermoplastic resin composition of the present embodiment include aromatic vinyl-based monomer units (a), methacrylic acid ester-based monomer units (b), and acrylic acid ester monomer units (c ). The phase includes a vinyl cyanide-based monomer unit (d), maleic anhydride, N-phenylmaleimide, N-methylmaleimide, and other N-substituted maleimide-based monomer units within a range that does not impair the effects of the present invention. , and glycidyl group-containing monomers such as glycidyl methacrylate. The phase substantially contains only aromatic vinyl-based monomer units (a), methacrylic acid ester-based monomer units (b), and acrylic acid ester monomer units (c), good too.
In addition, the thermoplastic resin composition of the present embodiment contains aromatic vinyl-based monomer units (a), methacrylic acid ester-based monomer units (b), and acrylic acid ester monomer units (c). It may further contain a phase other than the phase to be formed.
本実施形態の熱可塑性樹脂組成物に含有される相は、芳香族ビニル系単量体単位（ａ）、メタクリル酸エステル系単量体単位（ｂ）、及びアクリル酸エステル単量体単位（ｃ）を含有する。当該相は、本発明の効果を損なわない範囲で、シアン化ビニル系単量体単位（ｄ）、無水マレイン酸、Ｎ－フェニルマレイミド、Ｎ－メチルマレイミド等のＮ－置換マレイミド系単量体単位、及びグリシジルメタクリレート等のグリシジル基含有単量体を含有してもよい。当該相は、実質的に芳香族ビニル系単量体単位（ａ）、メタクリル酸エステル系単量体単位（ｂ）、及びアクリル酸エステル単量体単位（ｃ）のみを含有するものであってもよい。
また、本実施形態の熱可塑性樹脂組成物は、芳香族ビニル系単量体単位（ａ）、メタクリル酸エステル系単量体単位（ｂ）、及びアクリル酸エステル単量体単位（ｃ）を含有する相以外の相をさらに含有してもよい。 <Phase contained in the thermoplastic resin composition>
The phases contained in the thermoplastic resin composition of the present embodiment include aromatic vinyl-based monomer units (a), methacrylic acid ester-based monomer units (b), and acrylic acid ester monomer units (c ). The phase includes a vinyl cyanide-based monomer unit (d), maleic anhydride, N-phenylmaleimide, N-methylmaleimide, and other N-substituted maleimide-based monomer units within a range that does not impair the effects of the present invention. , and glycidyl group-containing monomers such as glycidyl methacrylate. The phase substantially contains only aromatic vinyl-based monomer units (a), methacrylic acid ester-based monomer units (b), and acrylic acid ester monomer units (c), good too.
In addition, the thermoplastic resin composition of the present embodiment contains aromatic vinyl-based monomer units (a), methacrylic acid ester-based monomer units (b), and acrylic acid ester monomer units (c). It may further contain a phase other than the phase to be formed.
本実施形態の熱可塑性樹脂組成物に含有される相は、芳香族ビニル系単量体単位（ａ）を含有する。芳香族ビニル系単量体としては特に限定されないが、スチレン、αーメチルスチレン、ｐーメチルスチレン、３、５ージメチルスチレン、４ーメトキシスチレン、２ーヒドロキシスチレンなどの置換基を有する置換スチレン、αーブロムスチレン、２、４ージクロロスチレンなどのハロゲン化スチレン、１ービニルナフタレンなどが挙げられる。芳香族ビニル系単量体単位（ａ）は、入手の容易性や重合性等の観点から、スチレンまたはαーメチルスチレンが好ましい。
The phase contained in the thermoplastic resin composition of the present embodiment contains aromatic vinyl-based monomer units (a). Although the aromatic vinyl monomer is not particularly limited, substituted styrenes having substituents such as styrene, α-methylstyrene, p-methylstyrene, 3,5-dimethylstyrene, 4-methoxystyrene, and 2-hydroxystyrene, α-bromostyrene, Halogenated styrenes such as 2,4-dichlorostyrene, 1-vinylnaphthalene and the like can be mentioned. The aromatic vinyl-based monomer unit (a) is preferably styrene or α-methylstyrene from the viewpoint of availability, polymerizability, and the like.
本実施形態の熱可塑性樹脂組成物に含有される相は、メタクリル酸エステル系単量体単位（ｂ）を含有する。メタクリル酸エステル系単量体単位としては、メチルメタクリレート、エチルメタクリレート、ブチルメタクリレート等のメタクリル酸エステルがあげられるが、樹脂への耐熱性付与の観点からは、メチルメタクリレートを用いることが好ましい。これらのメタクリル酸エステル系単量体単位は単独で用いてもよいが二種類以上を併用してもよい。これらのメタクリル酸エステル系単量体単位については、例えば、対応する単量体からなる、あるいは含んでなる原料を用いて製造することができる。
The phase contained in the thermoplastic resin composition of the present embodiment contains methacrylic acid ester-based monomer units (b). Examples of the methacrylic acid ester-based monomer unit include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate. From the viewpoint of imparting heat resistance to the resin, it is preferable to use methyl methacrylate. These methacrylic acid ester-based monomer units may be used alone, or two or more of them may be used in combination. These methacrylic acid ester-based monomer units can be produced, for example, using raw materials consisting of or containing the corresponding monomers.
本実施形態の熱可塑性樹脂組成物に含有される相は、アクリル酸エステル単量体単位（ｃ）を含有する。アクリル酸エステル単位を誘導する単量体としては、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸－２－エチルヘキシル、アクリル酸ヒドロキシエチル、アクリル酸グリシジル、アクリル酸シクロヘキシル、アクリル酸フェニル、アクリル酸ベンジル等が挙げられる。アクリル酸エステル単量体単位（ｃ）は、耐薬品性の観点から、アクリル酸ブチルが好ましい。
The phase contained in the thermoplastic resin composition of the present embodiment contains acrylic acid ester monomer units (c). Examples of monomers that induce acrylate units include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, glycidyl acrylate, and cyclohexyl acrylate. , phenyl acrylate, and benzyl acrylate. The acrylate ester monomer unit (c) is preferably butyl acrylate from the viewpoint of chemical resistance.
本実施形態の熱可塑性樹脂組成物中に含まれる粒子のうち、ジエン系ゴム状弾性体を含まない粒子の短径の平均値は、５０ｎｍ以下である。ジエン系ゴム状弾性体を含まない粒子とは、アクリル系ブロック共重合体に由来する粒子である。
一態様においては、ジエン系ゴム状弾性体を含まない粒子が確認できなくてもよい。ここでいう「ジエン系ゴム状弾性体を含まない粒子が確認できない」とは、例えば、以下に示す条件においてＴＥＭ観察を行った場合に、四酸化オスミウム（ＯｓＯ４）により染色された粒子以外に他の部分と明確に明度が異なる部分が観測されない状態となることをいう。このような場合には、当該ジエン系ゴム状弾性体を含まない粒子を構成しうる成分がナノ分散している場合があり、透明性を損なわず耐薬品性を発揮できる。一方で、短径の平均値が５０ｎｍを超えると、透明性が悪化するため好ましくない。ジエン系ゴム状弾性体を含まない粒子の短径の平均値が４０ｎｍ以下であると好ましく、３０ｎｍ以下であると更に好ましい。ジエン系ゴム状弾性体を含まない粒子の形状については特に限定されず、球状、ロッド状などであってもよい。
また、短径とは、明相部を構成する粒子中の対角線を結んだ径の最小径をいう。
＜ＴＥＭ観察条件＞
ＴＥＭ観察は以下の通り行った。樹脂組成物のペレットから超薄切片を切り出し、四酸化オスミウム蒸気中で３０分間染色し、更に四酸化ルテニウム蒸気中で３０分間染色した。透過型電子顕微鏡（株式会社日立ハイテク製、Ｈ－７５００）を用いて、写真を撮影した。なお、撮影は、６０００～２０，０００倍の範囲で適宜設定する。なお、本発明の図１～３は拡大倍率を２０，０００倍（加速電圧８０ｋｖ）とした。 Among the particles contained in the thermoplastic resin composition of the present embodiment, the average short diameter of particles not containing a diene rubber-like elastomer is 50 nm or less. Particles not containing a diene rubber-like elastomer are particles derived from an acrylic block copolymer.
In one aspect, particles that do not contain a diene-based rubbery elastomer may not be identified. Here, "particles not containing a diene-based rubber-like elastomer cannot be confirmed" means that, for example, when TEM observation is performed under the conditions shown below, particles other than particles dyed with osmium tetroxide (OsO 4 ) It refers to a state in which a portion clearly different in brightness from other portions is not observed. In such a case, the components that can constitute the particles that do not contain the diene rubbery elastomer may be nano-dispersed, and the chemical resistance can be exhibited without impairing the transparency. On the other hand, if the average minor axis exceeds 50 nm, the transparency deteriorates, which is not preferable. The average short diameter of the particles that do not contain a diene rubbery elastomer is preferably 40 nm or less, more preferably 30 nm or less. The shape of the particles that do not contain a diene-based rubbery elastic material is not particularly limited, and may be spherical, rod-like, or the like.
Moreover, the short diameter means the minimum diameter of the diameters connecting the diagonal lines in the particles constituting the bright phase portion.
<TEM Observation Conditions>
TEM observation was performed as follows. Ultra-thin sections were cut from the resin composition pellets, stained in osmium tetroxide vapor for 30 minutes, and further stained in ruthenium tetroxide vapor for 30 minutes. A photograph was taken using a transmission electron microscope (H-7500, manufactured by Hitachi High-Tech Co., Ltd.). Note that the photographing is appropriately set within the range of 6000 to 20,000 times. 1 to 3 of the present invention are enlarged at a magnification of 20,000 times (accelerating voltage of 80 kv).
一態様においては、ジエン系ゴム状弾性体を含まない粒子が確認できなくてもよい。ここでいう「ジエン系ゴム状弾性体を含まない粒子が確認できない」とは、例えば、以下に示す条件においてＴＥＭ観察を行った場合に、四酸化オスミウム（ＯｓＯ４）により染色された粒子以外に他の部分と明確に明度が異なる部分が観測されない状態となることをいう。このような場合には、当該ジエン系ゴム状弾性体を含まない粒子を構成しうる成分がナノ分散している場合があり、透明性を損なわず耐薬品性を発揮できる。一方で、短径の平均値が５０ｎｍを超えると、透明性が悪化するため好ましくない。ジエン系ゴム状弾性体を含まない粒子の短径の平均値が４０ｎｍ以下であると好ましく、３０ｎｍ以下であると更に好ましい。ジエン系ゴム状弾性体を含まない粒子の形状については特に限定されず、球状、ロッド状などであってもよい。
また、短径とは、明相部を構成する粒子中の対角線を結んだ径の最小径をいう。
＜ＴＥＭ観察条件＞
ＴＥＭ観察は以下の通り行った。樹脂組成物のペレットから超薄切片を切り出し、四酸化オスミウム蒸気中で３０分間染色し、更に四酸化ルテニウム蒸気中で３０分間染色した。透過型電子顕微鏡（株式会社日立ハイテク製、Ｈ－７５００）を用いて、写真を撮影した。なお、撮影は、６０００～２０，０００倍の範囲で適宜設定する。なお、本発明の図１～３は拡大倍率を２０，０００倍（加速電圧８０ｋｖ）とした。 Among the particles contained in the thermoplastic resin composition of the present embodiment, the average short diameter of particles not containing a diene rubber-like elastomer is 50 nm or less. Particles not containing a diene rubber-like elastomer are particles derived from an acrylic block copolymer.
In one aspect, particles that do not contain a diene-based rubbery elastomer may not be identified. Here, "particles not containing a diene-based rubber-like elastomer cannot be confirmed" means that, for example, when TEM observation is performed under the conditions shown below, particles other than particles dyed with osmium tetroxide (OsO 4 ) It refers to a state in which a portion clearly different in brightness from other portions is not observed. In such a case, the components that can constitute the particles that do not contain the diene rubbery elastomer may be nano-dispersed, and the chemical resistance can be exhibited without impairing the transparency. On the other hand, if the average minor axis exceeds 50 nm, the transparency deteriorates, which is not preferable. The average short diameter of the particles that do not contain a diene rubbery elastomer is preferably 40 nm or less, more preferably 30 nm or less. The shape of the particles that do not contain a diene-based rubbery elastic material is not particularly limited, and may be spherical, rod-like, or the like.
Moreover, the short diameter means the minimum diameter of the diameters connecting the diagonal lines in the particles constituting the bright phase portion.
<TEM Observation Conditions>
TEM observation was performed as follows. Ultra-thin sections were cut from the resin composition pellets, stained in osmium tetroxide vapor for 30 minutes, and further stained in ruthenium tetroxide vapor for 30 minutes. A photograph was taken using a transmission electron microscope (H-7500, manufactured by Hitachi High-Tech Co., Ltd.). Note that the photographing is appropriately set within the range of 6000 to 20,000 times. 1 to 3 of the present invention are enlarged at a magnification of 20,000 times (accelerating voltage of 80 kv).
熱可塑性樹脂組成物に含まれる粒子のうち、ジエン系ゴム状弾性体を含まない粒子の短径の平均値は、例えば、以下のようにして算出できる。
（１）ジエン系ゴム状弾性体を選択的に染色可能な物質（例えば四酸化オスミウム（ＯｓＯ４））により樹脂を染色し、さらに飽和系炭化水素の非晶部を染色する物質（四酸化ルテニウム（ＲｕＯ４））で染色して、ＴＥＭ観察を行う。（図１～図３）
（２）観察したＴＥＭ画像の３μｍ四方の領域において観測される粒子のうち、ジエン系ゴム状弾性体以外の粒子として染色されていない粒子を３０個選択し、その短径を測定し、その数の算術平均を求める。
また、ＴＥＭ－ＩＲや、ナノＩＲイメージング等によっても、熱可塑性樹脂組成物に含まれる粒子の組成を特定可能である。このような手法によりジエン系ゴム状弾性体以外の粒子を特定し、上述のようにしてその短径の平均値を算出することも可能である。 Among the particles contained in the thermoplastic resin composition, the average value of the short diameters of the particles that do not contain a diene rubbery elastomer can be calculated, for example, as follows.
(1) A substance capable of selectively dyeing a diene-based rubber-like elastomer (e.g., osmium tetroxide (OsO 4 )) dyes a resin, and a substance (ruthenium tetroxide) that dyes an amorphous part of a saturated hydrocarbon (RuO 4 )) and observed with TEM. (Figures 1 to 3)
(2) Among the particles observed in the 3 μm square area of the observed TEM image, select 30 particles that are not dyed as particles other than the diene-based rubber-like elastomer, measure the short diameter, and measure the number of particles. Find the arithmetic mean of
The composition of the particles contained in the thermoplastic resin composition can also be identified by TEM-IR, nano-IR imaging, or the like. It is also possible to specify particles other than the diene-based rubber-like elastic material by such a method, and to calculate the average value of the short diameters thereof as described above.
（１）ジエン系ゴム状弾性体を選択的に染色可能な物質（例えば四酸化オスミウム（ＯｓＯ４））により樹脂を染色し、さらに飽和系炭化水素の非晶部を染色する物質（四酸化ルテニウム（ＲｕＯ４））で染色して、ＴＥＭ観察を行う。（図１～図３）
（２）観察したＴＥＭ画像の３μｍ四方の領域において観測される粒子のうち、ジエン系ゴム状弾性体以外の粒子として染色されていない粒子を３０個選択し、その短径を測定し、その数の算術平均を求める。
また、ＴＥＭ－ＩＲや、ナノＩＲイメージング等によっても、熱可塑性樹脂組成物に含まれる粒子の組成を特定可能である。このような手法によりジエン系ゴム状弾性体以外の粒子を特定し、上述のようにしてその短径の平均値を算出することも可能である。 Among the particles contained in the thermoplastic resin composition, the average value of the short diameters of the particles that do not contain a diene rubbery elastomer can be calculated, for example, as follows.
(1) A substance capable of selectively dyeing a diene-based rubber-like elastomer (e.g., osmium tetroxide (OsO 4 )) dyes a resin, and a substance (ruthenium tetroxide) that dyes an amorphous part of a saturated hydrocarbon (RuO 4 )) and observed with TEM. (Figures 1 to 3)
(2) Among the particles observed in the 3 μm square area of the observed TEM image, select 30 particles that are not dyed as particles other than the diene-based rubber-like elastomer, measure the short diameter, and measure the number of particles. Find the arithmetic mean of
The composition of the particles contained in the thermoplastic resin composition can also be identified by TEM-IR, nano-IR imaging, or the like. It is also possible to specify particles other than the diene-based rubber-like elastic material by such a method, and to calculate the average value of the short diameters thereof as described above.
本実施形態の熱可塑性樹脂組成物に含まれる粒子のうち、ジエン系ゴム状弾性体を含まない粒子の短径の平均値を５０ｎｍ以下とする方法は特に限定されないが、特定の組成をもつメタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）を他の樹脂と溶融混錬する方法が簡便で好ましい。メタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）中のメタクリル酸エステル単位（ｂ）、アクリル酸エステル単位(ｃ)を誘導する単量体としては前述した単量体が挙げられる。
Among the particles contained in the thermoplastic resin composition of the present embodiment, the method for making the average short diameter of the particles that do not contain a diene rubber-like elastomer to be 50 nm or less is not particularly limited. A method of melt-kneading the acid ester-acrylic acid ester block copolymer (C) with another resin is simple and preferable. Examples of the monomers that induce the methacrylic acid ester units (b) and the acrylic acid ester units (c) in the methacrylic acid ester-acrylic acid ester block copolymer (C) include the monomers described above.
メタクリル酸エステル－アクリル酸エステル系ブロック共重合体のうちメタクリル酸エステル系重合体ブロックは、メタクリル酸エステル系重合体ブロックを主体とする重合体ブロックであり、メタクリル酸エステル－アクリル酸エステル系ブロック共重合体１００質量％中にメタクリル酸エステル単位を２５～７５質量％含むことが好ましく、より好ましくは３５～６５質量％、さらに好ましくは４５～５５質量％含む。具体的には例えば、２５、３５、４５、５５、６５、又は、７５質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
Among methacrylic acid ester-acrylic acid ester block copolymers, the methacrylic acid ester polymer block is a polymer block mainly composed of a methacrylic acid ester polymer block, and the methacrylic acid ester-acrylic acid ester block copolymer It preferably contains 25 to 75% by mass, more preferably 35 to 65% by mass, and still more preferably 45 to 55% by mass of methacrylate units in 100% by mass of the polymer. Specifically, for example, it is 25, 35, 45, 55, 65, or 75% by mass, and may be within a range between any two of the numerical values exemplified here.
メタクリル酸エステル－アクリル酸エステル系ブロック共重合体のうちアクリル酸エステル系重合体ブロックは、アクリル酸エステル系重合体ブロックを主体とする重合体ブロックであり、メタクリル酸エステル－アクリル酸エステル系ブロック共重合体１００質量％中にアクリル酸エステル単位を２５～７５質量％含むことが好ましく、より好ましくは３５～６５質量％、さらに好ましくは４５～５５質量％含む。アクリル酸エステル系重合体ブロックが７５質量％を超える場合は分散が不充分となり、透明性が低下する。具体的には例えば、２５、３５、４５、５５、６５、又は、７５質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
Of the methacrylic acid ester-acrylic acid ester block copolymers, the acrylic acid ester polymer block is a polymer block mainly composed of an acrylic acid ester polymer block, and the methacrylic acid ester-acrylic acid ester block copolymer It preferably contains 25 to 75% by mass, more preferably 35 to 65% by mass, and still more preferably 45 to 55% by mass of acrylate units in 100% by mass of the polymer. If the acrylate-based polymer block exceeds 75% by mass, the dispersion will be insufficient and the transparency will be lowered. Specifically, for example, it is 25, 35, 45, 55, 65, or 75% by mass, and may be within a range between any two of the numerical values exemplified here.
熱可塑性樹脂組成物に含有される相１００質量％中に含まれる芳香族ビニル系単量体単位（ａ）の含有量は２０～５０質量％であることが好ましく、２０～３０質量％であることがさらに好ましい。具体的には例えば、２０、２２、２４、２６、２８、３０、３５、４０、４５、又は５０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。芳香族ビニル系単量体単位（ａ）の含有量が５０質量％を超えると熱可塑性樹脂組成物の透明性が低下したり耐薬品性が低下する。芳香族ビニル系単量体単位（ａ）の含有量が２０質量％未満であると、成形性や剛性などの機械物性が低下する。
The content of the aromatic vinyl monomer unit (a) contained in 100% by mass of the phase contained in the thermoplastic resin composition is preferably 20 to 50% by mass, and is 20 to 30% by mass. is more preferred. Specifically, for example, it is 20, 22, 24, 26, 28, 30, 35, 40, 45, or 50% by mass, and may be within a range between any two of the numerical values exemplified here. . If the content of the aromatic vinyl-based monomer unit (a) exceeds 50% by mass, the thermoplastic resin composition will have reduced transparency and chemical resistance. If the content of the aromatic vinyl-based monomer unit (a) is less than 20% by mass, mechanical properties such as moldability and rigidity are deteriorated.
熱可塑性樹脂組成物に含有される相１００質量％中に含まれるメタクリル酸エステル系単量体単位（ｂ）の含有量は３０～８０質量％であることが好ましく、５０～７５質量％であることがさらに好ましい。具体的には例えば、３０、４０、５０、５５、６０、６５、７０、７５、又は８０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。メタクリル酸エステル系単量体単位（ｂ）の含有量が８０質量％を超えると熱可塑性樹脂組成物の衝撃強度が低下する。また、メタクリル酸エステル系単量体単位（ｂ）の含有量が３０質量％未満であると、透明性が低下する。
The content of the methacrylic acid ester-based monomer unit (b) contained in 100% by mass of the phase contained in the thermoplastic resin composition is preferably 30 to 80% by mass, and is 50 to 75% by mass. is more preferred. Specifically, it is, for example, 30, 40, 50, 55, 60, 65, 70, 75, or 80% by mass, and may be within a range between any two of the numerical values exemplified here. If the content of the methacrylic acid ester-based monomer unit (b) exceeds 80% by mass, the impact strength of the thermoplastic resin composition is lowered. Moreover, when the content of the methacrylic acid ester-based monomer unit (b) is less than 30% by mass, the transparency is lowered.
熱可塑性樹脂組成物に含有される相１００質量％中に含まれるアクリル酸エステル単量体単位（ｃ）の含有量は、耐薬品性や透明性、耐熱性の観点から、１～１５質量％であり、４～１０質量％であることが好ましい。具体的には例えば、１、２、３、４、５、６、７、８、９、１０、又は１５質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
The content of the acrylic ester monomer unit (c) contained in 100% by mass of the phase contained in the thermoplastic resin composition is 1 to 15% by mass from the viewpoint of chemical resistance, transparency, and heat resistance. and preferably 4 to 10% by mass. Specifically, for example, it is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 15% by mass, and is within a range between any two of the numerical values exemplified here. good too.
熱可塑性樹脂組成物に含有される相１００質量％中に含まれる、芳香族ビニル系単量体芳香族ビニル系単量体単位（ａ）、メタクリル酸エステル系単量体単位（ｂ）、及びアクリル酸エステル単量体単位（ｃ）以外の成分は、本発明の耐薬品性や透明性、強度を保つ観点から、２０質量％未満であることが好ましく、より好ましくは１５質量％未満である。具体的には例えば、２０、１８、１６、または１５質量％未満である。熱可塑性樹脂組成物に含有される相は、実質的に芳香族ビニル系単量体単位（ａ）、メタクリル酸エステル系単量体単位（ｂ）、及びアクリル酸エステル単量体単位（ｃ）のみを含有するものであってもよい。
熱可塑性樹脂組成物に含有される相に含まれる各単量体単位の含有量は、配合する原料の組成をＩＲやＮＭＲ等で分析して配合量から算出する方法や、熱可塑性樹脂組成物のＭＥＫ可溶分について熱分解ＧＣ／ＭＳやＮＭＲ等を測定することで求められる。 Aromatic vinyl monomer aromatic vinyl monomer unit (a), methacrylic acid ester monomer unit (b), and Components other than the acrylic acid ester monomer unit (c) are preferably less than 20% by mass, more preferably less than 15% by mass, from the viewpoint of maintaining the chemical resistance, transparency, and strength of the present invention. . Specifically, it is less than 20, 18, 16, or 15% by mass, for example. The phases contained in the thermoplastic resin composition are substantially aromatic vinyl-based monomer units (a), methacrylic acid ester-based monomer units (b), and acrylic acid ester monomer units (c). It may contain only
The content of each monomer unit contained in the phase contained in the thermoplastic resin composition can be calculated from the blending amount by analyzing the composition of the raw material to be blended by IR, NMR, etc., or the thermoplastic resin composition. It can be obtained by measuring pyrolysis GC / MS, NMR, etc. for the MEK soluble content of.
熱可塑性樹脂組成物に含有される相に含まれる各単量体単位の含有量は、配合する原料の組成をＩＲやＮＭＲ等で分析して配合量から算出する方法や、熱可塑性樹脂組成物のＭＥＫ可溶分について熱分解ＧＣ／ＭＳやＮＭＲ等を測定することで求められる。 Aromatic vinyl monomer aromatic vinyl monomer unit (a), methacrylic acid ester monomer unit (b), and Components other than the acrylic acid ester monomer unit (c) are preferably less than 20% by mass, more preferably less than 15% by mass, from the viewpoint of maintaining the chemical resistance, transparency, and strength of the present invention. . Specifically, it is less than 20, 18, 16, or 15% by mass, for example. The phases contained in the thermoplastic resin composition are substantially aromatic vinyl-based monomer units (a), methacrylic acid ester-based monomer units (b), and acrylic acid ester monomer units (c). It may contain only
The content of each monomer unit contained in the phase contained in the thermoplastic resin composition can be calculated from the blending amount by analyzing the composition of the raw material to be blended by IR, NMR, etc., or the thermoplastic resin composition. It can be obtained by measuring pyrolysis GC / MS, NMR, etc. for the MEK soluble content of.
＜メタクリル酸エステル系単量体単位を含む重合体（Ａ）＞
本実施形態の熱可塑性樹脂組成物はメタクリル酸エステル系単量体単位を含む重合体（Ａ）を含有してもよい。この構造は、特に限定されず、芳香族ビニル系単量体単位及びメタクリル酸エステル系単量体単位を含む任意の構造の共重合体を用いることができる。すなわち、ランダム共重合体、交互共重合体、周期的共重合体、グラフト系共重合体等のブロック共重合体のいずれの構造の共重合体であってもよい。
本実施形態の熱可塑性樹脂組成物１００質量％に含まれる重合体（Ａ）の含有量は、透明性の観点から２０質量％以上であり、好ましくは２５質量％以上であり、より好ましくは３０質量％以上である。また、耐薬品性、強度の観点から６０質量％以下であり、好ましくは５５質量％以下であり、より好ましくは５０質量％以下である。 <Polymer (A) containing a methacrylic acid ester-based monomer unit>
The thermoplastic resin composition of the present embodiment may contain a polymer (A) containing methacrylic acid ester-based monomer units. This structure is not particularly limited, and a copolymer having any structure containing aromatic vinyl-based monomer units and methacrylic acid ester-based monomer units can be used. That is, it may be a copolymer having any structure of block copolymers such as random copolymers, alternating copolymers, periodic copolymers, and graft copolymers.
The content of the polymer (A) contained in 100% by mass of the thermoplastic resin composition of the present embodiment is 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass, from the viewpoint of transparency. % by mass or more. From the viewpoint of chemical resistance and strength, the content is 60% by mass or less, preferably 55% by mass or less, and more preferably 50% by mass or less.
本実施形態の熱可塑性樹脂組成物はメタクリル酸エステル系単量体単位を含む重合体（Ａ）を含有してもよい。この構造は、特に限定されず、芳香族ビニル系単量体単位及びメタクリル酸エステル系単量体単位を含む任意の構造の共重合体を用いることができる。すなわち、ランダム共重合体、交互共重合体、周期的共重合体、グラフト系共重合体等のブロック共重合体のいずれの構造の共重合体であってもよい。
本実施形態の熱可塑性樹脂組成物１００質量％に含まれる重合体（Ａ）の含有量は、透明性の観点から２０質量％以上であり、好ましくは２５質量％以上であり、より好ましくは３０質量％以上である。また、耐薬品性、強度の観点から６０質量％以下であり、好ましくは５５質量％以下であり、より好ましくは５０質量％以下である。 <Polymer (A) containing a methacrylic acid ester-based monomer unit>
The thermoplastic resin composition of the present embodiment may contain a polymer (A) containing methacrylic acid ester-based monomer units. This structure is not particularly limited, and a copolymer having any structure containing aromatic vinyl-based monomer units and methacrylic acid ester-based monomer units can be used. That is, it may be a copolymer having any structure of block copolymers such as random copolymers, alternating copolymers, periodic copolymers, and graft copolymers.
The content of the polymer (A) contained in 100% by mass of the thermoplastic resin composition of the present embodiment is 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass, from the viewpoint of transparency. % by mass or more. From the viewpoint of chemical resistance and strength, the content is 60% by mass or less, preferably 55% by mass or less, and more preferably 50% by mass or less.
上記の重合体（Ａ）が有するメタクリル酸エステル系単量体単位としては、メチルメタクリレート、エチルメタクリレート、ブチルメタクリレート等のメタクリル酸エステルに由来する単量体単位があげられるが、樹脂への耐熱性付与の観点からは、メチルメタクリレートに由来する単量体単位を有することが好ましい。重合体（Ａ）は、これらのメタクリル酸エステル系単量体単位を単独で有していてもよいが二種類以上を有してもよい。これらのメタクリル酸エステル系単量体単位については、例えば、対応する単量体の１種又は２種以上からなる、あるいはそれらを含んでなる原料を用いて製造することができる。
Examples of the methacrylic acid ester-based monomer units possessed by the polymer (A) include monomer units derived from methacrylic acid esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate. From the viewpoint of imparting, it is preferable to have a monomer unit derived from methyl methacrylate. The polymer (A) may have these methacrylic acid ester-based monomer units alone, or may have two or more of them. These methacrylic acid ester-based monomer units can be produced, for example, using a raw material consisting of one or more of the corresponding monomers, or containing them.
上記の重合体（Ａ）は、芳香族ビニル系単量体単位とメタクリル酸エステル系単量体単位の他に共重合可能な単量体に由来する単量体単位を含む共重合体であってもよい。その他の共重合可能な単量体としては、以下に限定されるものではないが、例えば、α，β－不飽和カルボン酸アルキルエステル、α，β－不飽和カルボン酸、芳香族ビニル、シアン化ビニル、Ｎ－置換マレイミド類、無水マレイン酸等が挙げられる。
The above polymer (A) is a copolymer containing monomer units derived from copolymerizable monomers in addition to aromatic vinyl-based monomer units and methacrylic acid ester-based monomer units. may Other copolymerizable monomers include, but are not limited to, α,β-unsaturated carboxylic acid alkyl esters, α,β-unsaturated carboxylic acids, aromatic vinyls, cyanides, Examples include vinyl, N-substituted maleimides, maleic anhydride, and the like.
なお、この重合体（Ａ）は、芳香族ビニル系単量体単位、メタクリル酸エステル系単量体単位、及びその他の共重合可能な単量体の合計質量を１００質量％とした場合に、芳香族ビニル系単量体単位が０～４０質量％、メタクリル酸エステル系単量体単位が６０～１００質量％の範囲内で含まれていると、相の単量体単位組成を前記範囲に調整しやすいため好ましい。また、芳香族ビニル系単量体単位が０～３０質量％、メタクリル酸エステル系単量体単位が７０～１００質量％の範囲内で含まれていることがより好ましく、芳香族ビニル系単量体単位が０～２５質量％、メタクリル酸エステル系単量体単位が７５～１００質量％の範囲内で含まれていることが更に好ましく、芳香族ビニル系単量体単位が０～２０質量％、メタクリル酸エステル系単量体単位が８０～１００質量％の範囲内で含まれていることが更により好ましい。
また、この重合体（Ａ）は、芳香族ビニル系単量体単位、メタクリル酸エステル系単量体単位、及びその他の共重合可能な単量体の合計質量を１００質量％とした場合に、その他の共重合可能な単量体が５質量％未満、好ましくは３質量％未満含まれていることが透明性や強度を保てるため好ましい。 In addition, when the total mass of the aromatic vinyl-based monomer unit, the methacrylic acid ester-based monomer unit, and other copolymerizable monomers is 100% by mass, the polymer (A) is When the aromatic vinyl-based monomer unit is contained within the range of 0 to 40% by mass and the methacrylic acid ester-based monomer unit is contained within the range of 60 to 100% by mass, the monomer unit composition of the phase is within the above range. It is preferable because it is easy to adjust. In addition, it is more preferable that the aromatic vinyl-based monomer unit is contained in the range of 0 to 30% by mass and the methacrylic acid ester-based monomer unit is contained in the range of 70 to 100% by mass, and the aromatic vinyl-based monomer It is more preferable that the body unit is 0 to 25% by mass, the methacrylic acid ester monomer unit is contained in the range of 75 to 100% by mass, and the aromatic vinyl monomer unit is 0 to 20% by mass. , the methacrylic acid ester-based monomer unit is even more preferably contained within the range of 80 to 100% by mass.
In addition, when the total mass of the aromatic vinyl-based monomer unit, the methacrylic acid ester-based monomer unit, and other copolymerizable monomers is 100% by mass, the polymer (A) has Other copolymerizable monomers are preferably contained in an amount of less than 5% by mass, preferably less than 3% by mass, in order to maintain transparency and strength.
また、この重合体（Ａ）は、芳香族ビニル系単量体単位、メタクリル酸エステル系単量体単位、及びその他の共重合可能な単量体の合計質量を１００質量％とした場合に、その他の共重合可能な単量体が５質量％未満、好ましくは３質量％未満含まれていることが透明性や強度を保てるため好ましい。 In addition, when the total mass of the aromatic vinyl-based monomer unit, the methacrylic acid ester-based monomer unit, and other copolymerizable monomers is 100% by mass, the polymer (A) is When the aromatic vinyl-based monomer unit is contained within the range of 0 to 40% by mass and the methacrylic acid ester-based monomer unit is contained within the range of 60 to 100% by mass, the monomer unit composition of the phase is within the above range. It is preferable because it is easy to adjust. In addition, it is more preferable that the aromatic vinyl-based monomer unit is contained in the range of 0 to 30% by mass and the methacrylic acid ester-based monomer unit is contained in the range of 70 to 100% by mass, and the aromatic vinyl-based monomer It is more preferable that the body unit is 0 to 25% by mass, the methacrylic acid ester monomer unit is contained in the range of 75 to 100% by mass, and the aromatic vinyl monomer unit is 0 to 20% by mass. , the methacrylic acid ester-based monomer unit is even more preferably contained within the range of 80 to 100% by mass.
In addition, when the total mass of the aromatic vinyl-based monomer unit, the methacrylic acid ester-based monomer unit, and other copolymerizable monomers is 100% by mass, the polymer (A) has Other copolymerizable monomers are preferably contained in an amount of less than 5% by mass, preferably less than 3% by mass, in order to maintain transparency and strength.
＜グラフト系共重合体（Ｂ）＞
本実施形態の熱可塑性樹脂組成物はグラフト系共重合体（Ｂ）を含有する。
本実施形態の熱可塑性樹脂組成物１００質量％に含まれるグラフト共重合体（Ｂ）の含有量は、耐衝撃性の観点から１０質量％以上であり、好ましくは１７質量％以上であり、より好ましくは２０質量％以上である。また、流動性の観点から４５質量％以下であり、好ましくは４２質量％以下であり、より好ましくは４０質量％以下である。 <Graft copolymer (B)>
The thermoplastic resin composition of this embodiment contains a graft copolymer (B).
The content of the graft copolymer (B) contained in 100% by mass of the thermoplastic resin composition of the present embodiment is 10% by mass or more, preferably 17% by mass or more, from the viewpoint of impact resistance. Preferably, it is 20% by mass or more. From the viewpoint of fluidity, the content is 45% by mass or less, preferably 42% by mass or less, and more preferably 40% by mass or less.
本実施形態の熱可塑性樹脂組成物はグラフト系共重合体（Ｂ）を含有する。
本実施形態の熱可塑性樹脂組成物１００質量％に含まれるグラフト共重合体（Ｂ）の含有量は、耐衝撃性の観点から１０質量％以上であり、好ましくは１７質量％以上であり、より好ましくは２０質量％以上である。また、流動性の観点から４５質量％以下であり、好ましくは４２質量％以下であり、より好ましくは４０質量％以下である。 <Graft copolymer (B)>
The thermoplastic resin composition of this embodiment contains a graft copolymer (B).
The content of the graft copolymer (B) contained in 100% by mass of the thermoplastic resin composition of the present embodiment is 10% by mass or more, preferably 17% by mass or more, from the viewpoint of impact resistance. Preferably, it is 20% by mass or more. From the viewpoint of fluidity, the content is 45% by mass or less, preferably 42% by mass or less, and more preferably 40% by mass or less.
グラフト系共重合体（Ｂ）を構成するジエン系ゴム状弾性体としては、特に限定されないが、例えば、ガラス転移温度（Ｔｇ）が０℃以下のジエン系ゴム状弾性体が挙げられる。ジエン系ゴム状弾性体としては、以下に限定されないが、例えば、ポリブタジエン、スチレン－ブタジエン共重合ゴム、アクリロニトリル－ブタジエン共重合ゴム、ポリイソプレン、ポリクロロプレン、スチレン－ブタジエンブロック共重合ゴム、スチレン－イソプレンブロック共重合ゴム等の共役ジエン系ゴム、が挙げられる。これらのジエン系ゴム状弾性体は、１種を単独で、又は２種以上を組み合わせて用いることができる。
The diene rubber-like elastic material constituting the graft copolymer (B) is not particularly limited, but includes, for example, a diene rubber-like elastic material having a glass transition temperature (Tg) of 0°C or lower. Examples of diene-based rubber-like elastomers include, but are not limited to, polybutadiene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, polyisoprene, polychloroprene, styrene-butadiene block copolymer rubber, and styrene-isoprene. conjugated diene rubbers such as block copolymer rubbers; These diene rubber-like elastomers can be used singly or in combination of two or more.
これらの中でも、耐衝撃性や歪み下の耐薬品性の観点から、ジエン系ゴム状弾性体は、共役ジエン系ゴムであることが好ましく、ポリブタジエン、スチレン－ブタジエン共重合ゴム、アクリロニトリル－ブタジエン共重合ゴムであることがより好ましい。
Among these, from the viewpoint of impact resistance and chemical resistance under strain, the diene rubber-like elastomer is preferably a conjugated diene rubber, such as polybutadiene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber. Rubber is more preferred.
また、グラフト系共重合体（Ｂ）に含まれるジエン系ゴム状弾性体は、耐衝撃性や歪み下の耐薬品性の観点から、粒子状の形態であることが好ましい。ジエン系ゴム状弾性体が粒子状であるとき、当該粒子の質量平均粒子径は、１００ｎｍ以上５００ｎｍ未満が好ましい。１００ｎｍ以上であると、耐薬品性や耐衝撃性の改良効果が大きくなり、５００ｎｍ未満であれば、耐衝撃性に加えて光沢等の外観を保持する傾向にある。
In addition, the diene rubber-like elastomer contained in the graft copolymer (B) is preferably in the form of particles from the viewpoint of impact resistance and chemical resistance under strain. When the diene-based rubbery elastomer is particulate, the mass average particle diameter of the particles is preferably 100 nm or more and less than 500 nm. When it is 100 nm or more, the effect of improving chemical resistance and impact resistance is increased, and when it is less than 500 nm, appearance such as gloss tends to be maintained in addition to impact resistance.
ジエン系ゴム状弾性体にグラフトさせる単量体としては、少なくとも芳香族ビニル系単量体を含む。芳香族ビニル構造に対応する単量体としては重合体（A）で芳香族ビニル単量体の具体例として例示したものが挙げられる。
The monomer to be grafted onto the diene rubber-like elastomer includes at least an aromatic vinyl monomer. Examples of the monomer corresponding to the aromatic vinyl structure include those exemplified as specific examples of the aromatic vinyl monomer in the polymer (A).
その他にジエン系ゴム状弾性体にグラフトさせる単量体として、特に限定されるものではないが、シアン化ビニル単量体、メタクリル酸エステル系単量体を含むことがさらに好ましい。メタクリル酸エステル系単量体としては重合体（A）で具体例として例示したものが挙げられる。
In addition, monomers to be grafted onto the diene rubber-like elastomer are not particularly limited, but vinyl cyanide monomers and methacrylic acid ester monomers are more preferable. Specific examples of the methacrylic acid ester-based monomer include those exemplified for the polymer (A).
上記グラフト共重合体の単量体として使用されるシアン化ビニル単量体としては、以下に限定されるものではないが、例えば、アクリロニトリル、メタクリロニトリル、及びエタクリロニトリルが挙げられる。これらのシアン化ビニル単量体は、１種を単独で用いてもよく、又は２種以上を組み合わせて用いてもよい。
Examples of vinyl cyanide monomers used as monomers of the graft copolymer include, but are not limited to, acrylonitrile, methacrylonitrile, and ethacrylonitrile. One of these vinyl cyanide monomers may be used alone, or two or more thereof may be used in combination.
グラフト系共重合体（Ｂ）を構成するジエン系ゴム状弾性体の製造方法としては、特に限定されず、例えば、塊状重合法、溶液重合法、懸濁重合法、塊状懸濁重合法、及び乳化重合法が挙げられる。これらの中でも、粒子状のゴム成分が得られ、その粒子径の制御が容易である観点から、乳化重合法、懸濁重合法、又は塊状懸濁重合法が好ましい。
The method for producing the diene rubber-like elastomer constituting the graft copolymer (B) is not particularly limited, and examples thereof include bulk polymerization, solution polymerization, suspension polymerization, bulk suspension polymerization, and An emulsion polymerization method is mentioned. Among these, the emulsion polymerization method, the suspension polymerization method, or the bulk suspension polymerization method is preferable from the viewpoint that a particulate rubber component can be obtained and the particle size can be easily controlled.
グラフト系共重合体（Ｂ）を構成するジエン系ゴム状弾性体として、複数のＴｇを有する重合体を用いる場合は、異なる単量体組成のものを、多段階に分けて重合する。すなわち、各々異なる単量体組成で重合した、各々が異なるＴｇを有する複数種類の重合体を得、これらの混合物とすることにより、上記のようなジエン系ゴム状弾性体を製造することができる。この場合、乳化重合法を用い、多段重合により製造することが好ましい。
When a polymer having a plurality of Tg's is used as the diene rubber-like elastomer constituting the graft copolymer (B), different monomer compositions are polymerized in multiple steps. That is, by obtaining a plurality of types of polymers each having a different Tg, which are polymerized with different monomer compositions, and making a mixture of these, the diene rubber-like elastomer as described above can be produced. . In this case, it is preferable to manufacture by multi-stage polymerization using an emulsion polymerization method.
また、ジエン系ゴム状弾性体として、組成勾配を有する重合体を用いる場合、単量体組成を連続的に変化させて重合することにより、当該ジエン系ゴム状弾性体を製造することができる。
Further, when a polymer having a composition gradient is used as the diene rubbery elastomer, the diene rubbery elastomer can be produced by polymerizing while continuously changing the monomer composition.
ジエン系ゴム状弾性体として、芳香族ビニル系単量体と、共役ジエン系単量体のブロック共重合体（例えば、スチレン－ブタジエンブロック共重合体）を用いる場合、溶液中でリビングアニオン重合を行うことにより、上記のようなジエン系ゴム状弾性体を製造することができる。
When a block copolymer of an aromatic vinyl monomer and a conjugated diene monomer (for example, a styrene-butadiene block copolymer) is used as the diene rubber-like elastomer, living anionic polymerization is performed in a solution. By doing so, the diene rubber-like elastic body as described above can be produced.
また、グラフト系共重合体（Ｂ）を製造する方法、例えば、ジエン系ゴム状弾性体に単量体混合物をグラフト共重合させる方法としては、特に限定されず、例えば、塊状重合法、溶液重合法、懸濁重合法、塊状懸濁重合法、乳化重合法が挙げられる。なお、粒子状のジエン系ゴム状弾性体を製造した後、同一の反応器で連続的にグラフト共重合を行ってもよく、ジエン系ゴム状弾性体粒子を一旦ラテックスとして単離した後、グラフト共重合を行ってもよい。
The method of producing the graft copolymer (B), for example, the method of graft-copolymerizing the monomer mixture onto the diene rubber-like elastomer, is not particularly limited. method, suspension polymerization method, bulk suspension polymerization method, and emulsion polymerization method. After the production of the particulate diene rubber-like elastomer, the graft copolymerization may be continuously carried out in the same reactor. Copolymerization may be carried out.
グラフト系共重合体（Ｂ）は、ジエン系ゴム状弾性体を有し、これに上述のような単量体単位がグラフト共重したグラフト系共重合体である。グラフト系共重合体（Ｂ）は、ゴム状弾性体を主成分として有し、グラフト系共重合体（Ｂ）１００質量％に対するジエン系ゴム状弾性体の割合が３０質量％以上であり、より好ましくは３５質量％以上である。
The graft-based copolymer (B) is a graft-based copolymer having a diene-based rubber-like elastic body and having the above-described monomer units graft-copolymerized thereto. The graft copolymer (B) has a rubbery elastomer as a main component, and the ratio of the diene rubbery elastomer to 100% by mass of the graft copolymer (B) is 30% by mass or more. Preferably, it is 35% by mass or more.
グラフト系共重合体（Ｂ）において、グラフト共重合している単量体単位とジエン系ゴム状弾性体の合計質量１００質量％に対する、メタクリル酸エステル系単量体単位の割合は５～５０質量％であることが好ましく、１０～４５質量％であることがより好ましく、１５～４０質量％であることがさらに好ましい。具体的には例えば、５、１０、１５、２０、２５、３０、３５、４０、４５、又は５０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。グラフト共重合しているメタクリル酸エステル系単量体単位の割合が５質量％以上であると、透明性の観点から好ましい。また、メタクリル酸エステル系単量体単位の割合が５０質量％以下であると、耐衝撃性の観点から好ましい。
グラフト系共重合体（Ｂ）において、ジエン系ゴム状弾性体にグラフトさせる単量体であって、上記の芳香族ビニル系単量体、メタクリル酸エステル系単量体、シアン化ビニル単量体以外の単量体は、グラフト系共重合体（Ｂ）１００質量％中５質量％未満であることが好ましい。グラフト系共重合体（Ｂ）において、ジエン系ゴム状弾性体にグラフトさせる単量体は、実質的に芳香族ビニル系単量体、メタクリル酸エステル系単量体、シアン化ビニル単量体のみであってもよい。 In the graft copolymer (B), the proportion of the methacrylic acid ester-based monomer unit is 5 to 50 mass% with respect to 100 mass% of the total mass of the graft-copolymerized monomer units and the diene rubber-like elastomer. %, more preferably 10 to 45% by mass, even more preferably 15 to 40% by mass. Specifically, for example, it is 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% by mass, and may be within a range between any two of the numerical values exemplified here. . It is preferable from the viewpoint of transparency that the ratio of the graft-copolymerized methacrylic acid ester-based monomer units is 5% by mass or more. Moreover, it is preferable from the viewpoint of impact resistance that the proportion of the methacrylic acid ester-based monomer unit is 50% by mass or less.
In the graft copolymer (B), a monomer to be grafted onto the diene rubber-like elastomer, which is the aromatic vinyl monomer, the methacrylic acid ester monomer, or the vinyl cyanide monomer It is preferable that the amount of monomers other than the above is less than 5% by mass in 100% by mass of the graft copolymer (B). In the graft copolymer (B), the monomers to be grafted onto the diene rubbery elastomer are substantially only aromatic vinyl monomers, methacrylic acid ester monomers, and vinyl cyanide monomers. may be
グラフト系共重合体（Ｂ）において、ジエン系ゴム状弾性体にグラフトさせる単量体であって、上記の芳香族ビニル系単量体、メタクリル酸エステル系単量体、シアン化ビニル単量体以外の単量体は、グラフト系共重合体（Ｂ）１００質量％中５質量％未満であることが好ましい。グラフト系共重合体（Ｂ）において、ジエン系ゴム状弾性体にグラフトさせる単量体は、実質的に芳香族ビニル系単量体、メタクリル酸エステル系単量体、シアン化ビニル単量体のみであってもよい。 In the graft copolymer (B), the proportion of the methacrylic acid ester-based monomer unit is 5 to 50 mass% with respect to 100 mass% of the total mass of the graft-copolymerized monomer units and the diene rubber-like elastomer. %, more preferably 10 to 45% by mass, even more preferably 15 to 40% by mass. Specifically, for example, it is 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% by mass, and may be within a range between any two of the numerical values exemplified here. . It is preferable from the viewpoint of transparency that the ratio of the graft-copolymerized methacrylic acid ester-based monomer units is 5% by mass or more. Moreover, it is preferable from the viewpoint of impact resistance that the proportion of the methacrylic acid ester-based monomer unit is 50% by mass or less.
In the graft copolymer (B), a monomer to be grafted onto the diene rubber-like elastomer, which is the aromatic vinyl monomer, the methacrylic acid ester monomer, or the vinyl cyanide monomer It is preferable that the amount of monomers other than the above is less than 5% by mass in 100% by mass of the graft copolymer (B). In the graft copolymer (B), the monomers to be grafted onto the diene rubbery elastomer are substantially only aromatic vinyl monomers, methacrylic acid ester monomers, and vinyl cyanide monomers. may be
＜メタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）＞
本実施形態の熱可塑性樹脂組成物はメタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）を含有してもよい。
本実施形態の熱可塑性樹脂組成物１００質量％に含まれるメタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）は１～１５質量％の範囲内であり、３～１３質量％が好ましく、５～１１質量％が更に好ましい。１質量％未満であると耐薬品性が劣り、１５質量％を超えると耐熱性が低下する。 <Methacrylate-acrylate block copolymer (C)>
The thermoplastic resin composition of the present embodiment may contain a methacrylic acid ester-acrylic acid ester block copolymer (C).
The methacrylic acid ester-acrylic acid ester block copolymer (C) contained in 100% by mass of the thermoplastic resin composition of the present embodiment is in the range of 1 to 15% by mass, preferably 3 to 13% by mass. 5 to 11% by mass is more preferable. If it is less than 1% by mass, the chemical resistance is poor, and if it exceeds 15% by mass, the heat resistance is lowered.
本実施形態の熱可塑性樹脂組成物はメタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）を含有してもよい。
本実施形態の熱可塑性樹脂組成物１００質量％に含まれるメタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）は１～１５質量％の範囲内であり、３～１３質量％が好ましく、５～１１質量％が更に好ましい。１質量％未満であると耐薬品性が劣り、１５質量％を超えると耐熱性が低下する。 <Methacrylate-acrylate block copolymer (C)>
The thermoplastic resin composition of the present embodiment may contain a methacrylic acid ester-acrylic acid ester block copolymer (C).
The methacrylic acid ester-acrylic acid ester block copolymer (C) contained in 100% by mass of the thermoplastic resin composition of the present embodiment is in the range of 1 to 15% by mass, preferably 3 to 13% by mass. 5 to 11% by mass is more preferable. If it is less than 1% by mass, the chemical resistance is poor, and if it exceeds 15% by mass, the heat resistance is lowered.
メタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）は屈折率が１．４７２～１．４８５であることが好ましい。上記範囲の屈折率を有することで、樹脂組成物の透明性を保持することが可能となる。
The methacrylic acid ester-acrylic acid ester block copolymer (C) preferably has a refractive index of 1.472 to 1.485. By having a refractive index within the above range, it is possible to maintain the transparency of the resin composition.
上記ブロック共重合体の結合形態に特に制限はなく、ジブロック共重合体、トリブロック共重合体、重合体ブロックを４以上有するマルチブロック共重合、スター型ブロック共重合体を用いることができるが、製造の容易さからジブロック共重合体、トリブロック共重合体が好ましい。
The binding form of the block copolymer is not particularly limited, and diblock copolymers, triblock copolymers, multiblock copolymers having 4 or more polymer blocks, and star block copolymers can be used. , diblock copolymers and triblock copolymers are preferred from the standpoint of ease of production.
上記ブロック共重合体（Ｃ）の製造方法としては特に制限はないが、例えば、各重合体ブロックを構成する単量体をリビング重合する方法が使用される。このようなリビング重合の手法としては、例えば、有機アルカリ金属化合物を重合開始剤とし、アルカリ金属またはアルカリ土類金属の塩などの鉱酸塩存在下でアニオン重合する方法、有機アルカリ金属化合物を重合開始剤とし、有機アルミニウム化合物の存在下でアニオン重合する方法などが挙げられる。
The method for producing the block copolymer (C) is not particularly limited, but for example, a method of living polymerization of monomers constituting each polymer block is used. Methods of such living polymerization include, for example, a method of anionic polymerization in the presence of a mineral acid salt such as an alkali metal or alkaline earth metal salt using an organic alkali metal compound as a polymerization initiator, and a method of polymerizing an organic alkali metal compound. A method of anionic polymerization in the presence of an organoaluminum compound as an initiator can be used.
上記ブロック共重合体（Ｃ）は、本発明の効果を損なわない範囲で、アクリル酸エステルを主体とする単量体、あるいはメタクリル酸メチルを主体とする単量体とは異なる単量体単位を有していてもよい。
The block copolymer (C) contains a monomer unit different from a monomer mainly composed of an acrylic acid ester or a monomer mainly composed of methyl methacrylate within a range that does not impair the effects of the present invention. may have.
上記異なる単量体として、不飽和カルボン酸、オレフィン、共役ジエン、芳香族ビニル、アクリルアミド、メタクリルアミド、アクリロニトリル、メタクリロニトリル、酢酸ビニル、ビニルピリジン、ビニルケトン、塩化ビニル、塩化ビニリデン、フッ化ビニリデン、ε－カプロラクトン、バレロラクトンなどが挙げられる。
このような異なる単量体の含有量は、ブロック共重合体（Ｃ）を構成するアクリル酸エステルを主体とする単量体、メタクリル酸メチルを主体とする単量体、及びこれらとは異なる単量体単位の合計含有量を１００質量％とした場合に、好ましくは５質量％未満であり、より好ましくは３質量％未満であることが透明性や耐薬品性を保つため好ましい。 Examples of the different monomers include unsaturated carboxylic acids, olefins, conjugated dienes, aromatic vinyls, acrylamides, methacrylamides, acrylonitrile, methacrylonitrile, vinyl acetate, vinylpyridine, vinylketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, ε-caprolactone, valerolactone and the like.
The content of such different monomers includes monomers mainly composed of acrylic acid esters constituting the block copolymer (C), monomers mainly composed of methyl methacrylate, and monomers different from these. When the total content of the monomer units is 100% by mass, it is preferably less than 5% by mass, more preferably less than 3% by mass, in order to maintain transparency and chemical resistance.
このような異なる単量体の含有量は、ブロック共重合体（Ｃ）を構成するアクリル酸エステルを主体とする単量体、メタクリル酸メチルを主体とする単量体、及びこれらとは異なる単量体単位の合計含有量を１００質量％とした場合に、好ましくは５質量％未満であり、より好ましくは３質量％未満であることが透明性や耐薬品性を保つため好ましい。 Examples of the different monomers include unsaturated carboxylic acids, olefins, conjugated dienes, aromatic vinyls, acrylamides, methacrylamides, acrylonitrile, methacrylonitrile, vinyl acetate, vinylpyridine, vinylketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, ε-caprolactone, valerolactone and the like.
The content of such different monomers includes monomers mainly composed of acrylic acid esters constituting the block copolymer (C), monomers mainly composed of methyl methacrylate, and monomers different from these. When the total content of the monomer units is 100% by mass, it is preferably less than 5% by mass, more preferably less than 3% by mass, in order to maintain transparency and chemical resistance.
＜共重合体（Ｄ）＞
本実施形態の熱可塑性樹脂組成物は、シアン化ビニル単量体単位と、芳香族ビニル系単量体単位とを構成単位として含む共重合体（Ｄ）を含有することが好ましい。 <Copolymer (D)>
The thermoplastic resin composition of the present embodiment preferably contains a copolymer (D) containing vinyl cyanide monomer units and aromatic vinyl monomer units as structural units.
本実施形態の熱可塑性樹脂組成物は、シアン化ビニル単量体単位と、芳香族ビニル系単量体単位とを構成単位として含む共重合体（Ｄ）を含有することが好ましい。 <Copolymer (D)>
The thermoplastic resin composition of the present embodiment preferably contains a copolymer (D) containing vinyl cyanide monomer units and aromatic vinyl monomer units as structural units.
共重合体（Ｄ）を構成するシアン化ビニル単量体としては、以下に限定されるものではないが、例えば、アクリロニトリル、メタクリロニトリル、及びエタクリロニトリルが挙げられ、重合性の観点からアクリロニトリルが好ましい。これらのシアン化ビニル単量体は、１種を単独で用いてもよく、又は２種以上を組み合わせて用いてもよい。
Examples of the vinyl cyanide monomer constituting the copolymer (D) include, but are not limited to, acrylonitrile, methacrylonitrile, and ethacrylonitrile. is preferred. One of these vinyl cyanide monomers may be used alone, or two or more thereof may be used in combination.
共重合体（Ｄ）を構成する芳香族ビニル系単量体単位に対応する芳香族ビニル系単量体としては、重合体（Ａ）に含まれる芳香族ビニル系単量体の具体例として例示したものが挙げられる。
Specific examples of the aromatic vinyl-based monomers contained in the polymer (A) are illustrated as aromatic vinyl-based monomers corresponding to the aromatic vinyl-based monomer units constituting the copolymer (D). The following are listed.
共重合体（Ｄ）は、シアン化ビニル単量体及び芳香族ビニル系単量体と共重合可能なその他の単量体に対応する単量体単位を含んでもよい。その他の単量体としては、アクリル酸エステル単量体が挙げられる。アクリル酸エステル単量体としては、以下に限定されるものではないが、例えば、メチルメタクリレート、シクロヘキシルメタクリレート、メチルフェニルメタクリレート、イソプロピルメタクリレート等のアルキルメタクリレート；メチルアクリレート、エチルアクリレート、ブチルアクリレート、２－エチルヘキシルアクリレート等のアルキルアクリレート等が挙げられる。また、その他の単量体としては、無水マレイン酸、Ｎ－フェニルマレイミド、Ｎ－メチルマレイミド等のＮ－置換マレイミド系単量体、及びグリシジルメタクリレート等のグリシジル基含有単量体も挙げられる。これらは、１種単独で使用してもよく、２種以上を併用してもよい。
このようなシアン化ビニル単量体及び芳香族ビニル系単量体と共重合可能なその他の単量体の含有量は、共重合体（Ｄ）を構成するシアン化ビニル単量体単位、芳香族ビニル系単量体単位、共重合可能なその他の単量体、及びその他の単量体の合計含有量を１００質量％とした場合に好ましくは１０質量％未満であり、より好ましくは５質量％未満であることが耐薬品性や透明性を保つため好ましい。 The copolymer (D) may contain monomer units corresponding to other monomers copolymerizable with the vinyl cyanide monomer and the aromatic vinyl monomer. Other monomers include acrylate monomers. Examples of acrylic acid ester monomers include, but are not limited to, alkyl methacrylates such as methyl methacrylate, cyclohexyl methacrylate, methylphenyl methacrylate, and isopropyl methacrylate; methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl Examples include alkyl acrylates such as acrylates. Other monomers include N-substituted maleimide monomers such as maleic anhydride, N-phenylmaleimide and N-methylmaleimide, and glycidyl group-containing monomers such as glycidyl methacrylate. These may be used individually by 1 type, and may use 2 or more types together.
The content of such a vinyl cyanide monomer and other monomers copolymerizable with the aromatic vinyl monomer is determined by the vinyl cyanide monomer unit constituting the copolymer (D), the aromatic When the total content of the group vinyl-based monomer units, other copolymerizable monomers, and other monomers is 100% by mass, it is preferably less than 10% by mass, more preferably 5% by mass. % in order to maintain chemical resistance and transparency.
このようなシアン化ビニル単量体及び芳香族ビニル系単量体と共重合可能なその他の単量体の含有量は、共重合体（Ｄ）を構成するシアン化ビニル単量体単位、芳香族ビニル系単量体単位、共重合可能なその他の単量体、及びその他の単量体の合計含有量を１００質量％とした場合に好ましくは１０質量％未満であり、より好ましくは５質量％未満であることが耐薬品性や透明性を保つため好ましい。 The copolymer (D) may contain monomer units corresponding to other monomers copolymerizable with the vinyl cyanide monomer and the aromatic vinyl monomer. Other monomers include acrylate monomers. Examples of acrylic acid ester monomers include, but are not limited to, alkyl methacrylates such as methyl methacrylate, cyclohexyl methacrylate, methylphenyl methacrylate, and isopropyl methacrylate; methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl Examples include alkyl acrylates such as acrylates. Other monomers include N-substituted maleimide monomers such as maleic anhydride, N-phenylmaleimide and N-methylmaleimide, and glycidyl group-containing monomers such as glycidyl methacrylate. These may be used individually by 1 type, and may use 2 or more types together.
The content of such a vinyl cyanide monomer and other monomers copolymerizable with the aromatic vinyl monomer is determined by the vinyl cyanide monomer unit constituting the copolymer (D), the aromatic When the total content of the group vinyl-based monomer units, other copolymerizable monomers, and other monomers is 100% by mass, it is preferably less than 10% by mass, more preferably 5% by mass. % in order to maintain chemical resistance and transparency.
共重合体（Ｄ）を構成するシアン化ビニル単量体単位及び芳香族ビニル系単量体単位の合計質量（１００質量％）に対する、シアン化ビニル単量体単位の割合は１０～２５質量％であることが好ましく、１５～２５質量％であることがさらに好ましく、１７～２２質量％であることがより好ましい。シアン化ビニル単量体単位の割合が１０質量％以上であると、耐薬品性の観点から好ましい。また、シアン化ビニル単量体単位の割合が２５質量％以下であると、透明性の観点から好ましい。
The proportion of the vinyl cyanide monomer unit is 10 to 25% by mass with respect to the total mass (100% by mass) of the vinyl cyanide monomer unit and the aromatic vinyl monomer unit constituting the copolymer (D). is preferably 15 to 25% by mass, and more preferably 17 to 22% by mass. It is preferable from the viewpoint of chemical resistance that the proportion of vinyl cyanide monomer units is 10% by mass or more. Moreover, it is preferable from the viewpoint of transparency that the proportion of vinyl cyanide monomer units is 25% by mass or less.
また、共重合体（Ｄ）を構成するシアン化ビニル単量体単位及び芳香族ビニル系単量体単位の合計質量（１００質量％）に対する、芳香族ビニル系単量体単位の割合は、７５～９０質量％であることが好ましく、７５～８５質量％であることがさらに好ましく、７８～８３質量％であることがより好ましい。芳香族ビニル系単量体単位の割合が７５質量％以上であると透明性の観点から好ましく、９０質量％以下であると、耐薬品性の観点から好ましい。
Further, the ratio of the aromatic vinyl monomer units to the total mass (100% by mass) of the vinyl cyanide monomer units and the aromatic vinyl monomer units constituting the copolymer (D) was 75. It is preferably up to 90% by mass, more preferably 75 to 85% by mass, and more preferably 78 to 83% by mass. A ratio of the aromatic vinyl-based monomer units of 75% by mass or more is preferable from the viewpoint of transparency, and a ratio of 90% by mass or less is preferable from the viewpoint of chemical resistance.
共重合体（Ｄ）は、透明性、及び耐薬品性の観点から、本実施形態の熱可塑性樹脂組成物１００質量％中、１～５０質量％であり、５～４５質量％であることが好ましく、１０～４０質量％であることがより好ましい。
From the viewpoint of transparency and chemical resistance, the copolymer (D) is 1 to 50% by mass, preferably 5 to 45% by mass, in 100% by mass of the thermoplastic resin composition of the present embodiment. It is preferably 10 to 40% by mass, more preferably.
本実施形態の熱可塑性樹脂組成物の製造において、溶融押出しについて特に制限はなく、公知の方法を採用することができる。例えば、重合体（Ａ）、グラフト系共重合体（Ｂ）、メタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）及び共重合体（Ｄ）をヘンシェルミキサーやタンブラーミキサー等の公知の混合装置にて予備混合した後、単軸押出機または二軸押出機等に供給して溶融混練した後、ペレットとして調整する方法がある。
In the production of the thermoplastic resin composition of the present embodiment, there are no particular restrictions on melt extrusion, and known methods can be employed. For example, the polymer (A), the graft copolymer (B), the methacrylic acid ester-acrylic acid ester block copolymer (C) and the copolymer (D) are mixed in a known mixture such as a Henschel mixer or a tumbler mixer. There is a method in which the mixture is preliminarily mixed in an apparatus, fed to a single-screw extruder, a twin-screw extruder, or the like, melt-kneaded, and then prepared into pellets.
本実施形態の熱可塑性樹脂組成物には、重合体（Ａ）、グラフト系共重合体（Ｂ）、メタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）及び共重合体（Ｄ）以外にも、本発明の効果を損なわない範囲で任意の公知の添加剤を配合することができる。例えば、流動性や離型性を向上させるために、高級脂肪酸、酸エステル系、及び酸アミド系、さらに高級アルコール等の可塑剤や滑剤、シリコーンオイル等を配合することができる。また、耐候性を付与するために、ホスファイト系、ヒンダードフェノール系、ベンゾトリアゾール系、ベンゾフェノン系、ベンゾエート系、及びシアノアクリレート系の酸化防止剤や紫外線吸収剤を配合することができる。その他、帯電防止剤、着色剤、顔料、染料、滑剤、ブロッキング防止剤、発泡剤、発泡助剤、架橋剤、架橋助剤などを配合することができる。
The thermoplastic resin composition of the present embodiment includes a polymer (A), a graft copolymer (B), a methacrylic acid ester-acrylic acid ester block copolymer (C), and a copolymer other than (D). Also, any known additive can be blended within a range that does not impair the effects of the present invention. For example, in order to improve fluidity and releasability, plasticizers such as higher fatty acids, acid esters, acid amides, and higher alcohols, lubricants, silicone oils, and the like can be blended. Phosphite-based, hindered phenol-based, benzotriazole-based, benzophenone-based, benzoate-based, and cyanoacrylate-based antioxidants and UV absorbers can also be blended in order to impart weather resistance. In addition, an antistatic agent, a coloring agent, a pigment, a dye, a lubricant, an antiblocking agent, a foaming agent, a foaming aid, a cross-linking agent, a cross-linking aid, and the like can be blended.
本実施形態の成形品は、本実施形態の熱可塑性樹脂組成物の成形品であれば、特に限定されるものではなく、公知の成形法により製造することができる。
成形法としては、以下に限定されず、例えば、プレス成形法、射出成形法、ガスアシスト射出成形法、溶着成形法、押出成形法、吹込成形法、フィルム成形法、中空成形法、多相成形法、及び発泡成形法が挙げられる。これらの中でも、生産性の観点から、射出成形法、ガスアシスト射出成形法が好ましい。 The molded article of the present embodiment is not particularly limited as long as it is a molded article of the thermoplastic resin composition of the present embodiment, and can be produced by a known molding method.
The molding method is not limited to the following, and examples include press molding, injection molding, gas-assisted injection molding, welding molding, extrusion molding, blow molding, film molding, blow molding, and multiphase molding. method, and foam molding method. Among these, the injection molding method and the gas-assisted injection molding method are preferable from the viewpoint of productivity.
成形法としては、以下に限定されず、例えば、プレス成形法、射出成形法、ガスアシスト射出成形法、溶着成形法、押出成形法、吹込成形法、フィルム成形法、中空成形法、多相成形法、及び発泡成形法が挙げられる。これらの中でも、生産性の観点から、射出成形法、ガスアシスト射出成形法が好ましい。 The molded article of the present embodiment is not particularly limited as long as it is a molded article of the thermoplastic resin composition of the present embodiment, and can be produced by a known molding method.
The molding method is not limited to the following, and examples include press molding, injection molding, gas-assisted injection molding, welding molding, extrusion molding, blow molding, film molding, blow molding, and multiphase molding. method, and foam molding method. Among these, the injection molding method and the gas-assisted injection molding method are preferable from the viewpoint of productivity.
射出成形法を用いる場合、シリンダー設定温度は２２０～２９０℃が好ましい。射出成形に十分な流動性を確保するために２２０℃以上が好ましく、より好ましくは２２５℃以上、さらに好ましくは２３０℃以上である。また、樹脂の熱劣化防止の観点から、２９０℃以下が好ましく、より好ましくは２８０℃以下、さらに好ましくは２７０℃以下である。また射出成形法においては、金属とのインサート成形、アウトサート成形、ガスアシスト成形等を組み合わせて使用してもよい。使用する金型についても特に限定されず、ゲート形状についてもピンゲート、タブゲート、フィルムゲート、サブマリンゲート、ファンゲート、リングゲート、ダイレクトゲート、及びディスクゲートのいずれの種類であってもよい。金型温度は、３０～９０℃が好ましく、５０～７０℃がより好ましい。３０℃以上であることにより、成形品の表面平滑性が高くなる。９０℃以下であることにより冷却速度が上がるため生産性が向上する。
When using the injection molding method, the cylinder set temperature is preferably 220 to 290°C. In order to ensure sufficient fluidity for injection molding, the temperature is preferably 220°C or higher, more preferably 225°C or higher, and even more preferably 230°C or higher. From the viewpoint of preventing thermal deterioration of the resin, the temperature is preferably 290°C or lower, more preferably 280°C or lower, and even more preferably 270°C or lower. In the injection molding method, insert molding with metal, outsert molding, gas assist molding, etc. may be used in combination. The mold to be used is also not particularly limited, and the gate shape may be any type of pin gate, tab gate, film gate, submarine gate, fan gate, ring gate, direct gate, and disc gate. The mold temperature is preferably 30 to 90°C, more preferably 50 to 70°C. When the temperature is 30°C or higher, the surface smoothness of the molded product is enhanced. When the temperature is 90° C. or lower, the cooling rate increases, and productivity improves.
以下、具体的な実施例及び比較例を挙げて本実施形態について詳細に説明する。なお、本実施形態は、以下の例に限定されるものではない。実施例及び比較例中の評価、各種測定は以下の方法で行った。また、組成及び配合は、特に記述がない限り質量単位を示す。
The present embodiment will be described in detail below with specific examples and comparative examples. In addition, this embodiment is not limited to the following examples. Evaluations and various measurements in Examples and Comparative Examples were performed by the following methods. In addition, composition and blending are in units of mass unless otherwise specified.
〔熱可塑性樹脂組成物の原料〕
（重合体（Ａ））
＜Ａ－１＞
三菱ケミカル社アクリペットＶＨ５（メタクリル酸メチル９９質量％、アクリル酸メチル１．０質量％）を重合体（Ａ－１）として用いた。 [Raw material of thermoplastic resin composition]
(Polymer (A))
<A-1>
Mitsubishi Chemical Corporation ACRYPET VH5 (99% by mass of methyl methacrylate, 1.0% by mass of methyl acrylate) was used as the polymer (A-1).
（重合体（Ａ））
＜Ａ－１＞
三菱ケミカル社アクリペットＶＨ５（メタクリル酸メチル９９質量％、アクリル酸メチル１．０質量％）を重合体（Ａ－１）として用いた。 [Raw material of thermoplastic resin composition]
(Polymer (A))
<A-1>
Mitsubishi Chemical Corporation ACRYPET VH5 (99% by mass of methyl methacrylate, 1.0% by mass of methyl acrylate) was used as the polymer (A-1).
＜Ａ－２＞
攪拌翼を備えた容積約２０Ｌの完全混合型連続反応槽、容積約１１Ｌの塔式プラグフロー型連続反応槽、予熱器を備えたフラッシュ型脱揮槽を直列に接続して構成した。メタクリル酸メチル７０質量％、スチレン１８質量％、エチルベンゼン１２質量％で構成する溶液に対し、ｔ－ブチルパーオキシイソプロピルモノカーボネート０．００７３質量部、ｎ－ドデシルメルカプタン０．３２質量部を混合し原料溶液とした。この原料溶液を毎時３．９ｋｇで温度１２５℃に保った完全混合型連続反応槽に供給し、重合した。完全混合型連続反応槽出口における転化率は５５～５８％に制御した。さらにこの重合溶液を流れの方向に向かって１２５℃から１４４℃の勾配がつくように調整した塔式プラグフロー型連続反応槽に供給し、重合した。塔式プラグフロー型連続反応槽出口における転化率を７５～７８％に制御した。この重合溶液を予熱器で２３０℃に加温しながら、１．３ｋＰａに減圧したフラッシュ型脱揮槽に導入し、槽内温度２３５℃にて未反応単量体を除去した。２３２℃の樹脂をギアポンプで抜き出し、ストランド状に押出し切断することにより、ペレット形状のスチレン－メタクリル酸エステル系共重合体（Ａ－２）を得た。 <A-2>
A complete mixing type continuous reactor with a volume of about 20 L equipped with a stirring blade, a column plug flow type continuous reactor with a volume of about 11 L, and a flash type devolatilization tank with a preheater were connected in series. 0.0073 parts by mass of t-butylperoxyisopropyl monocarbonate and 0.32 parts by mass of n-dodecyl mercaptan are mixed with a solution composed of 70% by mass of methyl methacrylate, 18% by mass of styrene, and 12% by mass of ethylbenzene to prepare raw materials. solution. This raw material solution was fed at a rate of 3.9 kg/h to a complete mixing type continuous reactor maintained at a temperature of 125° C. and polymerized. The conversion rate at the exit of the fully mixed continuous reactor was controlled at 55-58%. Further, this polymerization solution was supplied to a tower-type plug-flow continuous reactor adjusted to have a gradient from 125° C. to 144° C. in the direction of flow for polymerization. The conversion rate at the tower plug flow type continuous reactor outlet was controlled at 75-78%. While heating this polymerization solution to 230°C with a preheater, it was introduced into a flash-type devolatilization tank whose pressure was reduced to 1.3 kPa, and unreacted monomers were removed at a temperature of 235°C in the tank. The resin at 232° C. was extracted with a gear pump, extruded and cut into strands to obtain a pellet-shaped styrene-methacrylic acid ester copolymer (A-2).
攪拌翼を備えた容積約２０Ｌの完全混合型連続反応槽、容積約１１Ｌの塔式プラグフロー型連続反応槽、予熱器を備えたフラッシュ型脱揮槽を直列に接続して構成した。メタクリル酸メチル７０質量％、スチレン１８質量％、エチルベンゼン１２質量％で構成する溶液に対し、ｔ－ブチルパーオキシイソプロピルモノカーボネート０．００７３質量部、ｎ－ドデシルメルカプタン０．３２質量部を混合し原料溶液とした。この原料溶液を毎時３．９ｋｇで温度１２５℃に保った完全混合型連続反応槽に供給し、重合した。完全混合型連続反応槽出口における転化率は５５～５８％に制御した。さらにこの重合溶液を流れの方向に向かって１２５℃から１４４℃の勾配がつくように調整した塔式プラグフロー型連続反応槽に供給し、重合した。塔式プラグフロー型連続反応槽出口における転化率を７５～７８％に制御した。この重合溶液を予熱器で２３０℃に加温しながら、１．３ｋＰａに減圧したフラッシュ型脱揮槽に導入し、槽内温度２３５℃にて未反応単量体を除去した。２３２℃の樹脂をギアポンプで抜き出し、ストランド状に押出し切断することにより、ペレット形状のスチレン－メタクリル酸エステル系共重合体（Ａ－２）を得た。 <A-2>
A complete mixing type continuous reactor with a volume of about 20 L equipped with a stirring blade, a column plug flow type continuous reactor with a volume of about 11 L, and a flash type devolatilization tank with a preheater were connected in series. 0.0073 parts by mass of t-butylperoxyisopropyl monocarbonate and 0.32 parts by mass of n-dodecyl mercaptan are mixed with a solution composed of 70% by mass of methyl methacrylate, 18% by mass of styrene, and 12% by mass of ethylbenzene to prepare raw materials. solution. This raw material solution was fed at a rate of 3.9 kg/h to a complete mixing type continuous reactor maintained at a temperature of 125° C. and polymerized. The conversion rate at the exit of the fully mixed continuous reactor was controlled at 55-58%. Further, this polymerization solution was supplied to a tower-type plug-flow continuous reactor adjusted to have a gradient from 125° C. to 144° C. in the direction of flow for polymerization. The conversion rate at the tower plug flow type continuous reactor outlet was controlled at 75-78%. While heating this polymerization solution to 230°C with a preheater, it was introduced into a flash-type devolatilization tank whose pressure was reduced to 1.3 kPa, and unreacted monomers were removed at a temperature of 235°C in the tank. The resin at 232° C. was extracted with a gear pump, extruded and cut into strands to obtain a pellet-shaped styrene-methacrylic acid ester copolymer (A-2).
＜Ａ－３＞
メタクリル酸メチルを６３質量％、スチレンを２５質量％にした以外は（Ａ－２）と同様にペレット形状のスチレン－メタクリル酸エステル系共重合体（Ａ－３）を得た。 <A-3>
A pellet-shaped styrene-methacrylic acid ester copolymer (A-3) was obtained in the same manner as (A-2) except that the methyl methacrylate was 63% by mass and the styrene was 25% by mass.
メタクリル酸メチルを６３質量％、スチレンを２５質量％にした以外は（Ａ－２）と同様にペレット形状のスチレン－メタクリル酸エステル系共重合体（Ａ－３）を得た。 <A-3>
A pellet-shaped styrene-methacrylic acid ester copolymer (A-3) was obtained in the same manner as (A-2) except that the methyl methacrylate was 63% by mass and the styrene was 25% by mass.
（グラフト系共重合体（Ｂ））
＜Ｂ－１＞
体積平均粒子径０．３１μｍのジエン系ゴム状弾性体ラテックスを固形分換算で３０ｋｇ計量して容積２００Ｌのオートクレーブに移し、純水９０ｋｇを加え、撹拌しながら窒素気流下で温度５０℃に昇温した。ここに硫酸第一鉄１．５ｇ、エチレンジアミン四酢酸・四ナトリウム３ｇ、ナトリウム・ホルムアルデヒドスルホキシレート１００ｇを純水２ｋｇに溶解したものを加え、スチレン７．５ｋｇ、メチルメタクリレート２２．５ｋｇ、ｔ－ドデシルメルカプタン６０ｇからなる混合物と、ジイソプロピルベンゼンハイドロパーオキサイド６０ｇ、オレイン酸カリウム４５０ｇを純水８ｋｇに分散した溶解液とを別々に６時間かけて連続添加した。添加終了後、温度を７０℃に昇温して、さらにジイソプロピルベンゼンハイドロパーオキサイド３０ｇ添加した後２時間放置して重合を終了させた。得られた乳化液にｎ－オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート３００ｇを加え、純水で固形分を１５質量％に希釈した後に温度７０℃に昇温し、激しく撹拌しながら希硫酸を加えて塩析を行い、その後温度を９５℃に昇温して凝固させ、次に脱水、水洗、乾燥して粉末状のグラフト共重合体含有重合体（Ｂ－１）を得た。 (Graft-based copolymer (B))
<B-1>
30 kg of diene rubber-like elastomer latex with a volume average particle size of 0.31 μm was weighed in terms of solid content, transferred to an autoclave with a volume of 200 L, 90 kg of pure water was added, and the temperature was raised to 50° C. under a nitrogen stream while stirring. did. To this, 1.5 g of ferrous sulfate, 3 g of ethylenediaminetetraacetic acid/tetrasodium, and 100 g of sodium formaldehyde sulfoxylate dissolved in 2 kg of pure water were added, followed by 7.5 kg of styrene, 22.5 kg of methyl methacrylate, and t-dodecyl. A mixture of 60 g of mercaptan and a solution prepared by dispersing 60 g of diisopropylbenzene hydroperoxide and 450 g of potassium oleate in 8 kg of pure water were separately added continuously over 6 hours. After completion of the addition, the temperature was raised to 70° C., 30 g of diisopropylbenzene hydroperoxide was further added, and the mixture was allowed to stand for 2 hours to complete the polymerization. 300 g of n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added to the resulting emulsion, diluted with pure water to a solid content of 15% by mass, and then heated to 70°C. The temperature is raised, dilute sulfuric acid is added with vigorous stirring to effect salting out, then the temperature is raised to 95° C. to solidify, then dehydrated, washed with water and dried to obtain a powdery graft copolymer-containing polymer. (B-1) was obtained.
＜Ｂ－１＞
体積平均粒子径０．３１μｍのジエン系ゴム状弾性体ラテックスを固形分換算で３０ｋｇ計量して容積２００Ｌのオートクレーブに移し、純水９０ｋｇを加え、撹拌しながら窒素気流下で温度５０℃に昇温した。ここに硫酸第一鉄１．５ｇ、エチレンジアミン四酢酸・四ナトリウム３ｇ、ナトリウム・ホルムアルデヒドスルホキシレート１００ｇを純水２ｋｇに溶解したものを加え、スチレン７．５ｋｇ、メチルメタクリレート２２．５ｋｇ、ｔ－ドデシルメルカプタン６０ｇからなる混合物と、ジイソプロピルベンゼンハイドロパーオキサイド６０ｇ、オレイン酸カリウム４５０ｇを純水８ｋｇに分散した溶解液とを別々に６時間かけて連続添加した。添加終了後、温度を７０℃に昇温して、さらにジイソプロピルベンゼンハイドロパーオキサイド３０ｇ添加した後２時間放置して重合を終了させた。得られた乳化液にｎ－オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート３００ｇを加え、純水で固形分を１５質量％に希釈した後に温度７０℃に昇温し、激しく撹拌しながら希硫酸を加えて塩析を行い、その後温度を９５℃に昇温して凝固させ、次に脱水、水洗、乾燥して粉末状のグラフト共重合体含有重合体（Ｂ－１）を得た。 (Graft-based copolymer (B))
<B-1>
30 kg of diene rubber-like elastomer latex with a volume average particle size of 0.31 μm was weighed in terms of solid content, transferred to an autoclave with a volume of 200 L, 90 kg of pure water was added, and the temperature was raised to 50° C. under a nitrogen stream while stirring. did. To this, 1.5 g of ferrous sulfate, 3 g of ethylenediaminetetraacetic acid/tetrasodium, and 100 g of sodium formaldehyde sulfoxylate dissolved in 2 kg of pure water were added, followed by 7.5 kg of styrene, 22.5 kg of methyl methacrylate, and t-dodecyl. A mixture of 60 g of mercaptan and a solution prepared by dispersing 60 g of diisopropylbenzene hydroperoxide and 450 g of potassium oleate in 8 kg of pure water were separately added continuously over 6 hours. After completion of the addition, the temperature was raised to 70° C., 30 g of diisopropylbenzene hydroperoxide was further added, and the mixture was allowed to stand for 2 hours to complete the polymerization. 300 g of n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added to the resulting emulsion, diluted with pure water to a solid content of 15% by mass, and then heated to 70°C. The temperature is raised, dilute sulfuric acid is added with vigorous stirring to effect salting out, then the temperature is raised to 95° C. to solidify, then dehydrated, washed with water and dried to obtain a powdery graft copolymer-containing polymer. (B-1) was obtained.
＜Ｂ－２＞
Ｄｏｗ社製パラロイドＥＸＬ－２６７８（ブタジエン系ゴム７５質量％、メタクリル酸メチル８質量％、スチレン１７質量％のメタクリル酸メチル－ブタジエン－スチレン共重合体）をグラフト系重合体（Ｂ－２）として用いた。 <B-2>
Paraloid EXL-2678 manufactured by Dow (a methyl methacrylate-butadiene-styrene copolymer containing 75% by mass of butadiene rubber, 8% by mass of methyl methacrylate, and 17% by mass of styrene) was used as the graft polymer (B-2). board.
Ｄｏｗ社製パラロイドＥＸＬ－２６７８（ブタジエン系ゴム７５質量％、メタクリル酸メチル８質量％、スチレン１７質量％のメタクリル酸メチル－ブタジエン－スチレン共重合体）をグラフト系重合体（Ｂ－２）として用いた。 <B-2>
Paraloid EXL-2678 manufactured by Dow (a methyl methacrylate-butadiene-styrene copolymer containing 75% by mass of butadiene rubber, 8% by mass of methyl methacrylate, and 17% by mass of styrene) was used as the graft polymer (B-2). board.
＜Ｂ－３＞
三菱ケミカル社製メタブレンＣ－２２３Ａ（ブタジエン系ゴム８７質量％、アクリロニトリル７質量％、スチレン６質量％のアクリロニトリル－ブタジエン－スチレン共重合体）をグラフト系重合体（Ｂ－３）として用いた。 <B-3>
METABLEN C-223A (acrylonitrile-butadiene-styrene copolymer containing 87% by mass of butadiene rubber, 7% by mass of acrylonitrile, and 6% by mass of styrene) manufactured by Mitsubishi Chemical Corporation was used as the graft polymer (B-3).
三菱ケミカル社製メタブレンＣ－２２３Ａ（ブタジエン系ゴム８７質量％、アクリロニトリル７質量％、スチレン６質量％のアクリロニトリル－ブタジエン－スチレン共重合体）をグラフト系重合体（Ｂ－３）として用いた。 <B-3>
METABLEN C-223A (acrylonitrile-butadiene-styrene copolymer containing 87% by mass of butadiene rubber, 7% by mass of acrylonitrile, and 6% by mass of styrene) manufactured by Mitsubishi Chemical Corporation was used as the graft polymer (B-3).
＜Ｃ－１＞
クラレ社製クラリティＬＡ１８９２（アクリル酸n-ブチル５０質量％、メタクリル酸メチル５０質量％のジブロック共重合体、屈折率１．４７９）をメタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ－１）として用いた。 <C-1>
Clarity LA1892 manufactured by Kuraray Co., Ltd. (n-butyl acrylate 50% by weight, methyl methacrylate 50% by weight diblock copolymer, refractive index 1.479) was added to a methacrylate-acrylate block copolymer (C- 1).
クラレ社製クラリティＬＡ１８９２（アクリル酸n-ブチル５０質量％、メタクリル酸メチル５０質量％のジブロック共重合体、屈折率１．４７９）をメタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ－１）として用いた。 <C-1>
Clarity LA1892 manufactured by Kuraray Co., Ltd. (n-butyl acrylate 50% by weight, methyl methacrylate 50% by weight diblock copolymer, refractive index 1.479) was added to a methacrylate-acrylate block copolymer (C- 1).
＜Ｃ－２＞
クラレ社製クラリティＬＡ４２８５（アクリル酸n-ブチル５０質量％、メタクリル酸メチル５０質量％のトリブロック共重合体、屈折率１．４７９）をメタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ－２）として用いた。 <C-2>
Clarity LA4285 manufactured by Kuraray Co., Ltd. (50% by mass of n-butyl acrylate, 50% by mass of methyl methacrylate, a triblock copolymer, refractive index of 1.479) was added to a methacrylate-acrylate block copolymer (C- 2).
クラレ社製クラリティＬＡ４２８５（アクリル酸n-ブチル５０質量％、メタクリル酸メチル５０質量％のトリブロック共重合体、屈折率１．４７９）をメタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ－２）として用いた。 <C-2>
Clarity LA4285 manufactured by Kuraray Co., Ltd. (50% by mass of n-butyl acrylate, 50% by mass of methyl methacrylate, a triblock copolymer, refractive index of 1.479) was added to a methacrylate-acrylate block copolymer (C- 2).
＜Ｃ－３＞
クラレ社製クラリティＬＡ２１４０（アクリル酸n-ブチル８０質量％、メタクリル酸メチル２０質量％のジブロック共重合体、屈折率１．４６９）をメタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ－３）として用いた。 <C-3>
Clarity LA2140 manufactured by Kuraray Co., Ltd. (diblock copolymer of 80% by weight of n-butyl acrylate and 20% by weight of methyl methacrylate, refractive index of 1.469) was added to a methacrylate-acrylate block copolymer (C- 3).
クラレ社製クラリティＬＡ２１４０（アクリル酸n-ブチル８０質量％、メタクリル酸メチル２０質量％のジブロック共重合体、屈折率１．４６９）をメタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ－３）として用いた。 <C-3>
Clarity LA2140 manufactured by Kuraray Co., Ltd. (diblock copolymer of 80% by weight of n-butyl acrylate and 20% by weight of methyl methacrylate, refractive index of 1.469) was added to a methacrylate-acrylate block copolymer (C- 3).
（共重合体（Ｄ））
＜Ｄ－１＞
撹拌機を備えた容積約２０リットルの完全混合型連続反応槽、容積約４０Ｌの塔式プラグフロー型連続反応槽、予熱器を備えたフラッシュ型脱揮槽を直列に接続して構成した。スチレン８１質量部、アクリロニトリル１９質量部、エチルベンゼン１０質量部で構成する溶液に対し、ｔ－ブチルパーオキシイソプロピルモノカーボネート０．０２質量部とｎ－ドデシルメルカプタン０．０２質量部を混合し原料溶液とした。この原料溶液を毎時６．０ｋｇで温度１３０℃に制御した完全混合型連続反応槽に供給し、重合した。なお、完全混合型反応器の撹拌数は１８０ｒｐｍで実施した。さらに完全混合型反応器より反応液を連続的に抜き出し、流れの方向に向かって温度１３０℃から１６０℃の勾配がつくように調整した塔式プラグフロー型連続反応槽に供給し、重合した。この重合溶液を予熱器で２３０℃に加温しながら、１.０ｋＰａに減圧したフラッシュ型脱揮槽に導入し、槽内温度２３５℃にて未反応単量体を除去した。この樹脂をストランド状に押出し切断することによりペレット形状の共重合体（Ｄ－１）を得た。 (Copolymer (D))
<D-1>
A complete mixing type continuous reactor with a volume of about 20 liters equipped with a stirrer, a column plug flow type continuous reactor with a volume of about 40 L, and a flash type devolatilization tank with a preheater were connected in series. 0.02 parts by mass of t-butylperoxyisopropylmonocarbonate and 0.02 parts by mass of n-dodecyl mercaptan were mixed with a solution composed of 81 parts by mass of styrene, 19 parts by mass of acrylonitrile, and 10 parts by mass of ethylbenzene to form a raw material solution. did. This raw material solution was supplied to a complete mixing type continuous reactor controlled at a rate of 6.0 kg/h at a temperature of 130° C. and polymerized. The stirring speed of the complete mixing reactor was 180 rpm. Furthermore, the reaction liquid was continuously withdrawn from the complete mixing reactor and supplied to a tower-type plug flow continuous reactor adjusted to have a temperature gradient from 130° C. to 160° C. in the direction of flow for polymerization. While heating this polymerization solution to 230°C with a preheater, it was introduced into a flash-type devolatilization tank whose pressure was reduced to 1.0 kPa, and unreacted monomers were removed at a temperature of 235°C in the tank. This resin was extruded and cut into strands to obtain a pellet-shaped copolymer (D-1).
＜Ｄ－１＞
撹拌機を備えた容積約２０リットルの完全混合型連続反応槽、容積約４０Ｌの塔式プラグフロー型連続反応槽、予熱器を備えたフラッシュ型脱揮槽を直列に接続して構成した。スチレン８１質量部、アクリロニトリル１９質量部、エチルベンゼン１０質量部で構成する溶液に対し、ｔ－ブチルパーオキシイソプロピルモノカーボネート０．０２質量部とｎ－ドデシルメルカプタン０．０２質量部を混合し原料溶液とした。この原料溶液を毎時６．０ｋｇで温度１３０℃に制御した完全混合型連続反応槽に供給し、重合した。なお、完全混合型反応器の撹拌数は１８０ｒｐｍで実施した。さらに完全混合型反応器より反応液を連続的に抜き出し、流れの方向に向かって温度１３０℃から１６０℃の勾配がつくように調整した塔式プラグフロー型連続反応槽に供給し、重合した。この重合溶液を予熱器で２３０℃に加温しながら、１.０ｋＰａに減圧したフラッシュ型脱揮槽に導入し、槽内温度２３５℃にて未反応単量体を除去した。この樹脂をストランド状に押出し切断することによりペレット形状の共重合体（Ｄ－１）を得た。 (Copolymer (D))
<D-1>
A complete mixing type continuous reactor with a volume of about 20 liters equipped with a stirrer, a column plug flow type continuous reactor with a volume of about 40 L, and a flash type devolatilization tank with a preheater were connected in series. 0.02 parts by mass of t-butylperoxyisopropylmonocarbonate and 0.02 parts by mass of n-dodecyl mercaptan were mixed with a solution composed of 81 parts by mass of styrene, 19 parts by mass of acrylonitrile, and 10 parts by mass of ethylbenzene to form a raw material solution. did. This raw material solution was supplied to a complete mixing type continuous reactor controlled at a rate of 6.0 kg/h at a temperature of 130° C. and polymerized. The stirring speed of the complete mixing reactor was 180 rpm. Furthermore, the reaction liquid was continuously withdrawn from the complete mixing reactor and supplied to a tower-type plug flow continuous reactor adjusted to have a temperature gradient from 130° C. to 160° C. in the direction of flow for polymerization. While heating this polymerization solution to 230°C with a preheater, it was introduced into a flash-type devolatilization tank whose pressure was reduced to 1.0 kPa, and unreacted monomers were removed at a temperature of 235°C in the tank. This resin was extruded and cut into strands to obtain a pellet-shaped copolymer (D-1).
＜Ｄ－２＞
スチレン７５質量部、アクリロニトリル２５質量部、ｎ－ドデシルメルカプタン０．０２５質量部とした以外は、（Ｄ－１）と同様に行い、共重合体（Ｄ－２）を得た。 <D-2>
A copolymer (D-2) was obtained in the same manner as (D-1) except that styrene was 75 parts by mass, acrylonitrile was 25 parts by mass, and n-dodecylmercaptan was 0.025 parts by mass.
スチレン７５質量部、アクリロニトリル２５質量部、ｎ－ドデシルメルカプタン０．０２５質量部とした以外は、（Ｄ－１）と同様に行い、共重合体（Ｄ－２）を得た。 <D-2>
A copolymer (D-2) was obtained in the same manner as (D-1) except that styrene was 75 parts by mass, acrylonitrile was 25 parts by mass, and n-dodecylmercaptan was 0.025 parts by mass.
＜Ｄ－３＞
スチレン８８質量部、アクリロニトリル１２質量部とした以外は、（Ｄ－１）と同様に行い、共重合体（Ｄ－３）を得た。 <D-3>
A copolymer (D-3) was obtained in the same manner as (D-1) except that 88 parts by mass of styrene and 12 parts by mass of acrylonitrile were used.
スチレン８８質量部、アクリロニトリル１２質量部とした以外は、（Ｄ－１）と同様に行い、共重合体（Ｄ－３）を得た。 <D-3>
A copolymer (D-3) was obtained in the same manner as (D-1) except that 88 parts by mass of styrene and 12 parts by mass of acrylonitrile were used.
＜評価方法＞
全光線透過率・ＨＡＺＥ：ＡＳＴＭ Ｄ－１００３に準じて、厚さ２ｍｍのプレートを日本電色工業社製ＨＡＺＥメーター（ＮＤＨ－２０００）を用いて全光線透過率及びＨＡＺＥを測定し、全光線透過率を透明性とした。 <Evaluation method>
Total light transmittance/HAZE: According to ASTM D-1003, a plate with a thickness of 2 mm is measured using a HAZE meter (NDH-2000) manufactured by Nippon Denshoku Industries Co., Ltd., and the total light transmittance and HAZE are measured. rate was taken as transparency.
全光線透過率・ＨＡＺＥ：ＡＳＴＭ Ｄ－１００３に準じて、厚さ２ｍｍのプレートを日本電色工業社製ＨＡＺＥメーター（ＮＤＨ－２０００）を用いて全光線透過率及びＨＡＺＥを測定し、全光線透過率を透明性とした。 <Evaluation method>
Total light transmittance/HAZE: According to ASTM D-1003, a plate with a thickness of 2 mm is measured using a HAZE meter (NDH-2000) manufactured by Nippon Denshoku Industries Co., Ltd., and the total light transmittance and HAZE are measured. rate was taken as transparency.
耐薬品性：ベルゲン式１／４楕円治具にプレス成形した試験片（３５０×２０×２ｍｍｔ）を曲率に沿って固定し、対象薬品を均一に塗布し２３℃、湿度５５％ＲＨ下で４８時間放置後、クレーズ及びクラックの発生状況を確認し、下記式より臨界歪みε（％）を算出し、その値が０．３％未満のものを×、０．３～０．６％のものを△、０．６～０．９％のものを○、０．９％以上のものを◎とした。なお、薬品としてジオクチルフタレート（ＤＯＰ、東京化成工業株式会社製）、フタル酸ジプロピル（ＤＩＮＰ、東京化成工業株式会社製）、消毒用エタノール（健栄製薬株式会社製）を使用した。
・ε＝ｂｔ／２ａ２｛１－Ｘ２（ａ２－ｂ２）／ａ４｝－３／２×１００
・ε：臨界歪み（％）
・ａ：治具の長軸（＝２５０ｍｍ）
・ｂ：治具の短軸（＝１５０ｍｍ）
・ｔ：試験片の厚み（＝２ｍｍ）
・Ｘ：クラック発生位置からの距離（ｍｍ）。 Chemical resistance: A test piece (350 x 20 x 2mmt) press-molded on a Bergen type 1/4 elliptical jig is fixed along the curvature, and the target chemical is evenly applied and tested at 23°C and 55% RH. After standing for a period of time, the occurrence of crazes and cracks was checked, and the critical strain ε (%) was calculated from the following formula. was rated as Δ, 0.6 to 0.9% as ◯, and 0.9% or more as ⊚. As chemicals, dioctyl phthalate (DOP, manufactured by Tokyo Chemical Industry Co., Ltd.), dipropyl phthalate (DINP, manufactured by Tokyo Chemical Industry Co., Ltd.), and ethanol for disinfection (manufactured by Kenei Pharmaceutical Co., Ltd.) were used.
・ε=bt/2a 2 {1−X 2 (a 2 −b 2 )/a 4 } −3/2 ×100
・ε: Critical strain (%)
・a: Long axis of jig (=250 mm)
・b: Short axis of jig (=150 mm)
・ t: thickness of test piece (= 2 mm)
・X: Distance (mm) from the crack occurrence position.
・ε＝ｂｔ／２ａ２｛１－Ｘ２（ａ２－ｂ２）／ａ４｝－３／２×１００
・ε：臨界歪み（％）
・ａ：治具の長軸（＝２５０ｍｍ）
・ｂ：治具の短軸（＝１５０ｍｍ）
・ｔ：試験片の厚み（＝２ｍｍ）
・Ｘ：クラック発生位置からの距離（ｍｍ）。 Chemical resistance: A test piece (350 x 20 x 2mmt) press-molded on a Bergen type 1/4 elliptical jig is fixed along the curvature, and the target chemical is evenly applied and tested at 23°C and 55% RH. After standing for a period of time, the occurrence of crazes and cracks was checked, and the critical strain ε (%) was calculated from the following formula. was rated as Δ, 0.6 to 0.9% as ◯, and 0.9% or more as ⊚. As chemicals, dioctyl phthalate (DOP, manufactured by Tokyo Chemical Industry Co., Ltd.), dipropyl phthalate (DINP, manufactured by Tokyo Chemical Industry Co., Ltd.), and ethanol for disinfection (manufactured by Kenei Pharmaceutical Co., Ltd.) were used.
・ε=bt/2a 2 {1−X 2 (a 2 −b 2 )/a 4 } −3/2 ×100
・ε: Critical strain (%)
・a: Long axis of jig (=250 mm)
・b: Short axis of jig (=150 mm)
・ t: thickness of test piece (= 2 mm)
・X: Distance (mm) from the crack occurrence position.
＜実施例１～１３、比較例１～４＞
上記の方法で得られた重合体（Ａ）、グラフト系共重合体（Ｂ）、メタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）、共重合体（Ｄ）を表１及び２に示す配合割合にてヘンシェルミキサーで混合した後、二軸押出機（東芝機械社製ＴＥＭ３５Ｂ、シリンダー温度２２０℃）を用いて溶融混練してペレットを作成し熱可塑性樹脂組成物を得た。得られた熱可塑性樹脂組成物の熱可塑性樹脂組成物に含有される相の組成及びジエン系ゴム状弾性体を含まない粒子の短径の平均値は前述した方法で算出した。次いでこのペレットを射出成形し、成形体を得た。得られた成形体の透明性、耐薬品性を評価し、表１、２に示した。 <Examples 1 to 13, Comparative Examples 1 to 4>
The polymer (A), the graft copolymer (B), the methacrylic acid ester-acrylic acid ester block copolymer (C), and the copolymer (D) obtained by the above method are shown in Tables 1 and 2. After mixing with a Henschel mixer at the indicated compounding ratio, they were melt-kneaded using a twin-screw extruder (TEM35B manufactured by Toshiba Machine Co., Ltd., cylinder temperature: 220° C.) to prepare pellets to obtain a thermoplastic resin composition. The composition of the phase contained in the thermoplastic resin composition and the average short diameter of the particles not containing the diene rubber-like elastomer of the obtained thermoplastic resin composition were calculated by the method described above. The pellets were then injection molded to obtain a molded body. Transparency and chemical resistance of the resulting moldings were evaluated and shown in Tables 1 and 2.
上記の方法で得られた重合体（Ａ）、グラフト系共重合体（Ｂ）、メタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）、共重合体（Ｄ）を表１及び２に示す配合割合にてヘンシェルミキサーで混合した後、二軸押出機（東芝機械社製ＴＥＭ３５Ｂ、シリンダー温度２２０℃）を用いて溶融混練してペレットを作成し熱可塑性樹脂組成物を得た。得られた熱可塑性樹脂組成物の熱可塑性樹脂組成物に含有される相の組成及びジエン系ゴム状弾性体を含まない粒子の短径の平均値は前述した方法で算出した。次いでこのペレットを射出成形し、成形体を得た。得られた成形体の透明性、耐薬品性を評価し、表１、２に示した。 <Examples 1 to 13, Comparative Examples 1 to 4>
The polymer (A), the graft copolymer (B), the methacrylic acid ester-acrylic acid ester block copolymer (C), and the copolymer (D) obtained by the above method are shown in Tables 1 and 2. After mixing with a Henschel mixer at the indicated compounding ratio, they were melt-kneaded using a twin-screw extruder (TEM35B manufactured by Toshiba Machine Co., Ltd., cylinder temperature: 220° C.) to prepare pellets to obtain a thermoplastic resin composition. The composition of the phase contained in the thermoplastic resin composition and the average short diameter of the particles not containing the diene rubber-like elastomer of the obtained thermoplastic resin composition were calculated by the method described above. The pellets were then injection molded to obtain a molded body. Transparency and chemical resistance of the resulting moldings were evaluated and shown in Tables 1 and 2.
＜図１～３＞
図１：実施例２で得られた熱可塑性樹脂組成物のジエン系ゴム状弾性体を、四酸化オスミウム（ＯｓＯ４）及び四酸化ルテニウム（ＲｕＯ４）で常法により二重染色した後にＴＥＭ観察して得られた写真である。ジエン系ゴム状弾性体非含有粒子（熱可塑性樹脂組成物に含まれる粒子のうち、ジエン系ゴム状弾性体を含まない粒子）が明相部として観測される。ジエン系ゴム状弾性体非含有粒子の短径の平均値（熱可塑性樹脂組成物に含まれる粒子のうち、ジエン系ゴム状弾性体を含まない粒子の短径の平均値）は、５０ｎｍ以下である。
図２：実施例３で得られた熱可塑性樹脂組成物を、実施例２と同様に二重染色した後にＴＥＭ観察して得られた写真である。ジエン系ゴム状弾性体非含有粒子が線状の明相部として観測される。ジエン系ゴム状弾性体非含有粒子の短径の平均値は、５０ｎｍ以下である。
図３：比較例３で得られた熱可塑性樹脂組成物を、実施例２と同様に二重染色した後にＴＥＭ観察して得られた写真である。ジエン系ゴム状弾性体非含有粒子が明相部として観測される。ジエン系ゴム状弾性体非含有粒子の短径の平均値は、５０ｎｍを超えている。 <Figures 1 to 3>
Figure 1: TEM observation after the diene rubber-like elastomer of the thermoplastic resin composition obtained in Example 2 was double-stained with osmium tetroxide (OsO 4 ) and ruthenium tetroxide (RuO 4 ) by a conventional method. This is a photograph obtained by Diene-based rubbery elastomer-free particles (particles contained in the thermoplastic resin composition that do not contain a diene-based rubbery elastomer) are observed as a bright phase portion. The average minor diameter of the diene-based rubber-like elastomer-free particles (among the particles contained in the thermoplastic resin composition, the average minor diameter of the particles that do not contain the diene-based rubber-like elastomer) is 50 nm or less. be.
FIG. 2: A photograph obtained by TEM observation after the thermoplastic resin composition obtained in Example 3 was double-stained in the same manner as in Example 2. FIG. Diene-based rubber-like elastomer-free particles are observed as linear bright phase portions. The average short diameter of the diene rubber-like elastomer-free particles is 50 nm or less.
FIG. 3: A photograph obtained by TEM observation after the thermoplastic resin composition obtained in Comparative Example 3 was double dyed in the same manner as in Example 2. Particles not containing a diene rubber-like elastomer are observed as a bright phase portion. The average short diameter of the diene rubber-like elastomer-free particles exceeds 50 nm.
図１：実施例２で得られた熱可塑性樹脂組成物のジエン系ゴム状弾性体を、四酸化オスミウム（ＯｓＯ４）及び四酸化ルテニウム（ＲｕＯ４）で常法により二重染色した後にＴＥＭ観察して得られた写真である。ジエン系ゴム状弾性体非含有粒子（熱可塑性樹脂組成物に含まれる粒子のうち、ジエン系ゴム状弾性体を含まない粒子）が明相部として観測される。ジエン系ゴム状弾性体非含有粒子の短径の平均値（熱可塑性樹脂組成物に含まれる粒子のうち、ジエン系ゴム状弾性体を含まない粒子の短径の平均値）は、５０ｎｍ以下である。
図２：実施例３で得られた熱可塑性樹脂組成物を、実施例２と同様に二重染色した後にＴＥＭ観察して得られた写真である。ジエン系ゴム状弾性体非含有粒子が線状の明相部として観測される。ジエン系ゴム状弾性体非含有粒子の短径の平均値は、５０ｎｍ以下である。
図３：比較例３で得られた熱可塑性樹脂組成物を、実施例２と同様に二重染色した後にＴＥＭ観察して得られた写真である。ジエン系ゴム状弾性体非含有粒子が明相部として観測される。ジエン系ゴム状弾性体非含有粒子の短径の平均値は、５０ｎｍを超えている。 <Figures 1 to 3>
Figure 1: TEM observation after the diene rubber-like elastomer of the thermoplastic resin composition obtained in Example 2 was double-stained with osmium tetroxide (OsO 4 ) and ruthenium tetroxide (RuO 4 ) by a conventional method. This is a photograph obtained by Diene-based rubbery elastomer-free particles (particles contained in the thermoplastic resin composition that do not contain a diene-based rubbery elastomer) are observed as a bright phase portion. The average minor diameter of the diene-based rubber-like elastomer-free particles (among the particles contained in the thermoplastic resin composition, the average minor diameter of the particles that do not contain the diene-based rubber-like elastomer) is 50 nm or less. be.
FIG. 2: A photograph obtained by TEM observation after the thermoplastic resin composition obtained in Example 3 was double-stained in the same manner as in Example 2. FIG. Diene-based rubber-like elastomer-free particles are observed as linear bright phase portions. The average short diameter of the diene rubber-like elastomer-free particles is 50 nm or less.
FIG. 3: A photograph obtained by TEM observation after the thermoplastic resin composition obtained in Comparative Example 3 was double dyed in the same manner as in Example 2. Particles not containing a diene rubber-like elastomer are observed as a bright phase portion. The average short diameter of the diene rubber-like elastomer-free particles exceeds 50 nm.
表１の結果から、本発明にかかる実施例は、得られた成形体が優れた透明性と可塑剤等への耐薬品性を備えていることが分かる。表２の結果から、本発明の構成を満たさない比較例は、得られた成形体が透明性と可塑剤等への耐薬品性の少なくとも一方が劣っていることが分かる。
From the results in Table 1, it can be seen that the molded articles obtained in Examples according to the present invention have excellent transparency and chemical resistance to plasticizers and the like. From the results in Table 2, it can be seen that the comparative examples, which do not satisfy the constitution of the present invention, are inferior in at least one of transparency and chemical resistance to plasticizers and the like.
Claims (6)
- 熱可塑性樹脂組成物であって、
芳香族ビニル系単量体単位（ａ）、メタクリル酸エステル系単量体単位（ｂ）、アクリル酸エステル単量体単位（ｃ）を含む相を含有し、
ジエン系ゴム状弾性体を有するグラフト系共重合体を含み、
前記相１００質量％中に含まれるアクリル酸エステル単量体単位（ｃ）が１～１５質量％であり、
前記熱可塑性樹脂組成物に含まれる粒子のうち、ジエン系ゴム状弾性体を含まない粒子の短径の平均値が５０ｎｍ以下である、
熱可塑性樹脂組成物。 A thermoplastic resin composition,
A phase containing an aromatic vinyl-based monomer unit (a), a methacrylic acid ester-based monomer unit (b), and an acrylic acid ester monomer unit (c),
including a graft copolymer having a diene rubbery elastomer,
The acrylic acid ester monomer unit (c) contained in 100% by mass of the phase is 1 to 15% by mass,
Among the particles contained in the thermoplastic resin composition, the average value of the short diameter of the particles that do not contain a diene rubbery elastomer is 50 nm or less.
A thermoplastic resin composition. - 前記相１００質量％中に含まれる芳香族ビニル系単量体単位（ａ）が２０～５０質量％、メタクリル酸エステル系単量体単位（ｂ）が３０～７５質量％であり、熱可塑性樹脂組成物から得られる２ｍｍ厚の成形品のＨａｚｅ値が１０％以下である請求項１に記載の熱可塑性樹脂組成物。 The aromatic vinyl monomer unit (a) contained in 100% by mass of the phase is 20 to 50% by mass, and the methacrylic acid ester monomer unit (b) is 30 to 75% by mass, and the thermoplastic resin 2. The thermoplastic resin composition according to claim 1, wherein a molded product having a thickness of 2 mm obtained from the composition has a haze value of 10% or less.
- 重合体（Ａ）、グラフト系共重合体（Ｂ）、及びメタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）成分の合計質量を１００質量％とした場合に、前記重合体（Ａ）を２０～６０質量％、前記グラフト系共重合体（Ｂ）を１０～４５質量％、前記メタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）を１～１５質量％の範囲内で含み、
前記重合体（Ａ）は、芳香族ビニル系単量体単位及びメタクリル酸エステル系単量体単位の合計質量を１００質量％とした場合に、芳香族ビニル系単量体単位を０～４０質量％、メタクリル酸エステル系単量体単位を６０～１００質量％の範囲内で含み、
前記グラフト系共重合体（Ｂ）は、ジエン系ゴム状弾性体に少なくとも芳香族ビニル系単量体を共重合してなるグラフト系共重合体を含み、
前記メタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）は、メタクリル酸エステル系重合体ブロック及びアクリル酸エステル系重合体ブロックの合計質量を１００％とした場合に、メタクリル酸エステル系重合体ブロックを２５～７５質量％、アクリル酸エステル系重合体ブロックを２５～７５質量％の範囲内で含む、
請求項１又は２に記載の熱可塑性樹脂組成物。 When the total mass of the polymer (A), the graft copolymer (B), and the methacrylic acid ester-acrylic acid ester block copolymer (C) component is 100% by mass, the polymer (A) 20 to 60% by mass, 10 to 45% by mass of the graft copolymer (B), and 1 to 15% by mass of the methacrylic acid ester-acrylic acid ester block copolymer (C) ,
The polymer (A) contains 0 to 40 mass of the aromatic vinyl monomer unit when the total mass of the aromatic vinyl monomer unit and the methacrylic acid ester monomer unit is 100% by mass. %, containing a methacrylic acid ester-based monomer unit in the range of 60 to 100% by mass,
The graft copolymer (B) includes a graft copolymer obtained by copolymerizing a diene rubber-like elastomer with at least an aromatic vinyl monomer,
The methacrylic acid ester-acrylic acid ester-based block copolymer (C) is a methacrylic acid ester-based polymer when the total mass of the methacrylic acid ester-based polymer block and the acrylic acid ester-based polymer block is 100%. 25 to 75% by mass of blocks and 25 to 75% by mass of acrylic acid ester polymer blocks,
The thermoplastic resin composition according to claim 1 or 2. - 芳香族ビニル系単量体単位、シアン化ビニル系単量体単位の合計質量を１００質量％とした場合に、芳香族ビニル系単量体単位が７５～９０質量％、シアン化ビニル系単量体単位が１０～２５質量％である共重合体（Ｄ）を１～５０質量％含む請求項１～３のいずれか一項に記載の熱可塑性樹脂組成物。 When the total mass of the aromatic vinyl-based monomer unit and the vinyl cyanide-based monomer unit is 100% by mass, the aromatic vinyl-based monomer unit is 75 to 90% by mass, and the vinyl cyanide-based monomer is The thermoplastic resin composition according to any one of claims 1 to 3, comprising 1 to 50% by mass of the copolymer (D) having a body unit of 10 to 25% by mass.
- グラフト系共重合体（Ｂ）が、ジエン系ゴム状弾性体に芳香族ビニル系単量体と、メタクリル酸エステル系単量体と、シアン化ビニル系単量体とを共重合してなるグラフト系共重合体である請求項１～４のいずれか一項に記載の熱可塑性樹脂組成物。 The graft copolymer (B) is a graft obtained by copolymerizing an aromatic vinyl-based monomer, a methacrylic acid ester-based monomer, and a vinyl cyanide-based monomer with a diene rubber-like elastomer. The thermoplastic resin composition according to any one of claims 1 to 4, which is a system copolymer.
- 熱可塑性樹脂組成物の製造方法であって、
重合体（Ａ）、グラフト系共重合体（Ｂ）、及びメタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）成分の合計質量を１００質量％とした場合に、前記重合体（Ａ）を２０～６０質量％、前記グラフト系共重合体（Ｂ）を１０～４５質量％、前記メタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）を１～１５質量％の範囲内で配合し、溶融混練する工程を含む熱可塑性樹脂組成物の製造方法であって、
前記重合体（Ａ）は、芳香族ビニル系単量体単位及びメタクリル酸エステル系単量体単位の合計質量を１００質量％とした場合に、芳香族ビニル系単量体単位を０～４０質量％、メタクリル酸エステル系単量体単位を６０～１００質量％の範囲内で含み、
前記グラフト系共重合体（Ｂ）は、ジエン系ゴム状弾性体に少なくとも芳香族ビニル系単量体を共重合してなるグラフト系共重合体であり、
前記メタクリル酸エステル－アクリル酸エステル系ブロック共重合体（Ｃ）は、メタクリル酸エステル系重合体ブロック及びアクリル酸エステル系重合体ブロックの合計質量を１００％とした場合に、メタクリル酸エステル系重合体ブロックを２５～７５質量％、アクリル酸エステル系重合体ブロックを２５～７５質量％の範囲内で含む、
熱可塑性樹脂組成物の製造方法。 A method for producing a thermoplastic resin composition,
When the total mass of the polymer (A), the graft copolymer (B), and the methacrylic acid ester-acrylic acid ester block copolymer (C) component is 100% by mass, the polymer (A) 20 to 60% by mass, 10 to 45% by mass of the graft copolymer (B), and 1 to 15% by mass of the methacrylic acid ester-acrylic acid ester block copolymer (C). and a method for producing a thermoplastic resin composition comprising a step of melt-kneading,
The polymer (A) contains 0 to 40 mass of the aromatic vinyl monomer unit when the total mass of the aromatic vinyl monomer unit and the methacrylic acid ester monomer unit is 100% by mass. %, containing a methacrylic acid ester-based monomer unit in the range of 60 to 100% by mass,
The graft copolymer (B) is a graft copolymer obtained by copolymerizing a diene rubber-like elastomer with at least an aromatic vinyl monomer,
The methacrylic acid ester-acrylic acid ester-based block copolymer (C) is a methacrylic acid ester-based polymer when the total mass of the methacrylic acid ester-based polymer block and the acrylic acid ester-based polymer block is 100%. 25 to 75% by mass of blocks and 25 to 75% by mass of acrylic acid ester polymer blocks,
A method for producing a thermoplastic resin composition.
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| JP2013209556A (en) * | 2012-03-30 | 2013-10-10 | Asahi Kasei Chemicals Corp | Thermoplastic resin composition and its molded article |
| JP2014194005A (en) * | 2013-03-01 | 2014-10-09 | Unitika Ltd | Thermoplastic resin composition and molded article |
| JP2015042735A (en) * | 2013-07-23 | 2015-03-05 | ユニチカ株式会社 | Polylactic acid-based resin composition and molding |
| WO2016167292A1 (en) * | 2015-04-17 | 2016-10-20 | 株式会社クラレ | Methacrylic resin composition |
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| JP2013209556A (en) * | 2012-03-30 | 2013-10-10 | Asahi Kasei Chemicals Corp | Thermoplastic resin composition and its molded article |
| JP2014194005A (en) * | 2013-03-01 | 2014-10-09 | Unitika Ltd | Thermoplastic resin composition and molded article |
| JP2015042735A (en) * | 2013-07-23 | 2015-03-05 | ユニチカ株式会社 | Polylactic acid-based resin composition and molding |
| WO2016167292A1 (en) * | 2015-04-17 | 2016-10-20 | 株式会社クラレ | Methacrylic resin composition |
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