JP2005264050A - Compatibilizer for flexible material, method for producing the same, and thermoplastic resin composition - Google Patents
Compatibilizer for flexible material, method for producing the same, and thermoplastic resin composition Download PDFInfo
- Publication number
- JP2005264050A JP2005264050A JP2004080673A JP2004080673A JP2005264050A JP 2005264050 A JP2005264050 A JP 2005264050A JP 2004080673 A JP2004080673 A JP 2004080673A JP 2004080673 A JP2004080673 A JP 2004080673A JP 2005264050 A JP2005264050 A JP 2005264050A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- mass
- compatibilizer
- uncrosslinked
- graft copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 43
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 239000000463 material Substances 0.000 title abstract description 3
- 239000000178 monomer Substances 0.000 claims abstract description 117
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 52
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 14
- 150000001993 dienes Chemical class 0.000 claims abstract description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 108
- 229920005989 resin Polymers 0.000 claims description 46
- 239000011347 resin Substances 0.000 claims description 46
- 239000004816 latex Substances 0.000 claims description 36
- 229920000126 latex Polymers 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 30
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 23
- 239000007779 soft material Substances 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 14
- 238000000465 moulding Methods 0.000 abstract description 13
- 238000005299 abrasion Methods 0.000 abstract description 5
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 abstract description 3
- 229920002943 EPDM rubber Polymers 0.000 description 93
- 229920001971 elastomer Polymers 0.000 description 19
- -1 for example Polymers 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 239000005060 rubber Substances 0.000 description 14
- 239000003995 emulsifying agent Substances 0.000 description 13
- 235000019645 odor Nutrition 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 10
- 239000003505 polymerization initiator Substances 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 7
- 239000008121 dextrose Substances 0.000 description 7
- 239000011790 ferrous sulphate Substances 0.000 description 7
- 235000003891 ferrous sulphate Nutrition 0.000 description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 6
- 229940048086 sodium pyrophosphate Drugs 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 6
- 229920001890 Novodur Polymers 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 3
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 description 3
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 3
- VTCSNDCDIZADBA-UHFFFAOYSA-N 2,5-dichloro-5-ethenylcyclohexa-1,3-diene Chemical compound ClC1=CCC(Cl)(C=C)C=C1 VTCSNDCDIZADBA-UHFFFAOYSA-N 0.000 description 3
- UUVOWFWRTLPGBP-UHFFFAOYSA-N 5,6-dichloro-5-ethenylcyclohexa-1,3-diene Chemical compound ClC1C=CC=CC1(Cl)C=C UUVOWFWRTLPGBP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KCFXNGDHQPMIAQ-UHFFFAOYSA-N 1-(4-methylphenyl)pyrrole-2,5-dione Chemical compound C1=CC(C)=CC=C1N1C(=O)C=CC1=O KCFXNGDHQPMIAQ-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 2
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
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- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
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- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 2
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- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 2
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Landscapes
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Abstract
Description
本発明は、耐衝撃性、流動性、耐薬品性、光沢、成形性、表面外観及び成形収縮率、耐熱性、耐摩耗性に優れ、臭気を感じさせず、ポリオレフィン系樹脂に溶着可能な軟質性の熱可塑性樹脂組成物を可能ならしめる相溶化剤に関する。 The present invention is excellent in impact resistance, fluidity, chemical resistance, gloss, moldability, surface appearance and molding shrinkage ratio, heat resistance, wear resistance, softness that can be welded to polyolefin resin without feeling odor. The present invention relates to a compatibilizing agent that enables a heat-resistant thermoplastic resin composition.
スチレン系樹脂、例えばジエン系ゴムに芳香族ビニル、（メタ）アクリル酸エステル系単量体、シアン化ビニル、共重合可能な他の単量体をグラフト重合してなるＡＢＳ樹脂は、成形性、耐衝撃性、剛性、塗装性に優れているため、電気製品、自動車部品、建材、雑貨等の用途に用いられてきている。しかし、有機溶剤に対しては脆弱で、成形品の表面に塗布すると表面が侵食されるなどの現象が発生し、用途が制約されているという問題がある。
一方、ポリオレフィン系樹脂、例えばポリプロピレン樹脂は、透明性、延展伸性、剛性に優れ、また耐水性、耐薬品性、耐加水分解性、ヒンジ特性、表面硬度や光沢、耐熱性、絶縁性及び流動性が良好な樹脂であり、これらの特性からフィルム、電気部品、家庭日用品、雑貨、自動車部品などの用途に幅広く使用されている汎用樹脂である。しかし、耐衝撃性、低温特性が不十分である。
それぞれの樹脂の欠点を補い、特性を生かした高分子複合材料を開発する目的で、スチレン系樹脂とポリオレフィン系樹脂をポリマーアロイ化することが過去に検討されている。しかし、スチレン系樹脂とポリオレフィン系樹脂は非相溶性であるので、混合すると、層状剥離が発生して物性はむしろ悪化し、また、界面の強度も乏しいので、他の樹脂に溶着させることすらできない。また、スチレン系樹脂とポリオレフィン系樹脂を混合して成形する場合、スチレン系樹脂、ポリオレフィン系樹脂の収縮率の差が大きいことにより、内部応力を生じて耐衝撃性が低下する。
Styrenic resin, for example, ABS resin formed by graft polymerization of aromatic vinyl, (meth) acrylic acid ester monomer, vinyl cyanide, and other copolymerizable monomers on diene rubber, moldability, Because of its excellent impact resistance, rigidity, and paintability, it has been used in applications such as electrical products, automobile parts, building materials, and miscellaneous goods. However, it is fragile to organic solvents, and when applied to the surface of a molded product, there is a problem that the surface is eroded and the use is restricted.
On the other hand, polyolefin resins, such as polypropylene resins, are excellent in transparency, stretchability, rigidity, water resistance, chemical resistance, hydrolysis resistance, hinge characteristics, surface hardness, gloss, heat resistance, insulation and fluidity. It is a general-purpose resin widely used in applications such as films, electrical parts, household goods, sundries, and automobile parts. However, impact resistance and low temperature characteristics are insufficient.
In the past, it has been studied to polymerize a styrene resin and a polyolefin resin for the purpose of compensating for the defects of each resin and developing a polymer composite material utilizing the characteristics. However, since the styrene resin and the polyolefin resin are incompatible with each other, when they are mixed, delamination occurs, the physical properties are rather deteriorated, and the strength at the interface is poor, so it cannot even be welded to other resins. . Further, when molding by mixing a styrene resin and a polyolefin resin, an internal stress is generated due to a large difference in shrinkage between the styrene resin and the polyolefin resin, and impact resistance is lowered.
そこで、スチレン系樹脂とポリオレフィン系樹脂を用いて上記の問題のないポリマーアロイを作製する目的で、従来、種々の化学反応変性技術や相溶化剤の開発が試みられている。
例えば、化学反応変性技術として、無水カルボン酸変性やエポキシ変性を用いて各相の界面の強度を高める方法がある。
相溶化剤として、ＡＢＳ樹脂とポリプロピレン樹脂を相溶化する目的で、エチレン−酢酸ビニル共重合体を添加することにより耐薬品性を改良したポリマーアロイや、芳香族ビニル−共役ジエンブロック共重合体により耐薬品性を改良した熱可塑性樹脂組成物が開示されている（例えば、特許文献１、２参照。）
また、相溶化剤としてＡＥＳ樹脂を含有する、スチレン系樹脂組成物が開示されている（例えば、特許文献３参照。）。特許文献３に記載のスチレン系樹脂組成物は、エチレン−プロピレン系ゴム質重合体であるＡＥＳを用いることにより、同じポリオレフィン系樹脂であるポリプロピレン樹脂との相溶性を高め、また、固化する際の、スチレン系樹脂とポリオレフィン系樹脂の収縮率の差を緩和したものである。
For example, as a chemical reaction modification technique, there is a method of increasing the interface strength of each phase using carboxylic anhydride modification or epoxy modification.
As a compatibilizing agent, for the purpose of compatibilizing ABS resin and polypropylene resin, a polymer alloy improved in chemical resistance by adding an ethylene-vinyl acetate copolymer or an aromatic vinyl-conjugated diene block copolymer. A thermoplastic resin composition having improved chemical resistance is disclosed (for example, see Patent Documents 1 and 2).
Moreover, the styrene resin composition containing AES resin as a compatibilizing agent is disclosed (for example, refer patent document 3). The styrenic resin composition described in Patent Document 3 uses AES, which is an ethylene-propylene rubbery polymer, to improve compatibility with polypropylene resin, which is the same polyolefin resin, and to solidify. The difference in shrinkage between the styrene resin and the polyolefin resin is alleviated.
しかしながら、化学反応変性技術を用いた場合、固化する際の根本的な問題である、スチレン系樹脂とポリオレフィン系樹脂の収縮率の差は解決されておらず、したがって、現在のところ実用上充分な技術は確立されていない。加えて、化学反応による悪臭が製品に残存する。
特許文献１、２に記載の発明では、耐熱性の不足や、層状剥離の発生などの問題が存在する。
また、特許文献３に記載の製造方法では、検討の結果、単純にＡＥＳを混合するだけでは、得られる樹脂組成物の面衝撃性や光沢が、実用上は不足することが判明した。
However, when the chemical reaction modification technique is used, the difference in shrinkage between the styrene resin and the polyolefin resin, which is a fundamental problem when solidifying, has not been solved. Technology has not been established. In addition, a bad odor due to a chemical reaction remains in the product.
In the inventions described in Patent Documents 1 and 2, there are problems such as insufficient heat resistance and occurrence of delamination.
Further, in the production method described in Patent Document 3, as a result of investigation, it has been found that the surface impact properties and gloss of the obtained resin composition are insufficient in practice by simply mixing AES.
本発明は前記課題を解決するためになされたもので、流動性、耐衝撃性、耐薬品性、光沢、成形性、表面外観、耐熱性、耐摩耗性に優れ、臭気を感じさせず、成形収縮率が小さく、ポリオレフィン系樹脂に充分な溶着性がある軟質性の熱可塑性樹脂組成物を可能ならしめる相溶化剤を提供することを目的とする。 The present invention has been made to solve the above problems, and is excellent in fluidity, impact resistance, chemical resistance, gloss, moldability, surface appearance, heat resistance, and wear resistance, and does not feel odor and is molded. An object of the present invention is to provide a compatibilizing agent that enables a soft thermoplastic resin composition having a small shrinkage ratio and sufficient weldability to a polyolefin resin.
本発明の軟質材用相溶化剤は、芳香族ビニル系単量体もしくは（メタ）アクリル酸エステル系単量体またはこれらの混合物を含む単量体成分が、未架橋エチレン−プロピレン−非共役ジエン系ゴム質重合体にグラフト重合した未架橋エチレン−プロピレン−非共役ジエン系グラフト共重合体を含有することを特徴とする。
前記単量体成分は、該単量体成分の全質量に対し０〜６０質量％のシアン化ビニル系単量体をさらに含有することが好ましい。
前記未架橋エチレン−プロピレン−非共役ジエン系ゴム質重合体は、エチレン成分の含有率が５０〜９０質量％であることが好ましい
本発明の軟質材用相溶化剤の製造方法は、未架橋エチレン−プロピレン非共役ジエン系ゴム質重合体ラテックス６０〜９０質量部の存在下に、芳香族ビニル系単量体もしくは（メタ）アクリル酸エステル系単量体またはこれらの混合物からなる単量体成分４０〜１０質量部を重合して未架橋エチレン−プロピレン−非共役ジエン系グラフト共重合体を合成する重合工程を有することを特徴とする。
The compatibilizer for a soft material of the present invention comprises an aromatic vinyl monomer, a (meth) acrylic acid ester monomer, or a monomer component containing a mixture of these, an uncrosslinked ethylene-propylene-nonconjugated diene It contains an uncrosslinked ethylene-propylene-nonconjugated diene graft copolymer graft-polymerized to a rubber-based polymer.
The monomer component preferably further contains 0 to 60% by mass of a vinyl cyanide monomer based on the total mass of the monomer component.
The uncrosslinked ethylene-propylene-nonconjugated diene rubber polymer preferably has an ethylene component content of 50 to 90% by mass. The method for producing a compatibilizer for a soft material of the present invention comprises uncrosslinked ethylene. A monomer component 40 comprising an aromatic vinyl monomer, a (meth) acrylic acid ester monomer, or a mixture thereof in the presence of 60 to 90 parts by mass of a propylene non-conjugated diene rubber polymer latex. It has the superposition | polymerization process of superposing | polymerizing 10 mass parts and synthesize | combining an unbridged ethylene-propylene-nonconjugated diene type graft copolymer.
本発明の熱可塑性樹脂組成物は、本発明の軟質材用相溶化剤と、スチレン系単量体混合物を重合してなるスチレン系樹脂（ａ）と、ポリオレフィン系樹脂（ｂ）とを含有することを特徴とする。
本発明の熱可塑性樹脂組成物において、電子顕微鏡観察により認められる形態は、層状構造であることが好ましい。
The thermoplastic resin composition of the present invention contains the softener compatibilizer of the present invention, a styrene resin (a) obtained by polymerizing a styrene monomer mixture, and a polyolefin resin (b). It is characterized by that.
In the thermoplastic resin composition of the present invention, the form recognized by observation with an electron microscope is preferably a layered structure.
本発明の軟質材用相溶化剤によれば、流動性、耐衝撃性、耐薬品性、光沢、成形性、表面外観、耐熱性、耐摩耗性に優れ、臭気を感じさせず、ポリオレフィン系樹脂に充分な溶着性がある軟質性の熱可塑性樹脂組成物を提供することができる。 According to the softener compatibilizer of the present invention, the polyolefin resin is excellent in fluidity, impact resistance, chemical resistance, gloss, moldability, surface appearance, heat resistance, and wear resistance, and does not feel odor. It is possible to provide a soft thermoplastic resin composition having sufficient weldability.
以下、本発明を詳細に説明する。
本発明の軟質材用相溶化剤は、芳香族ビニル系単量体もしくは（メタ）アクリル酸エステル系単量体またはこれらの混合物を含む単量体成分が、未架橋エチレン−プロピレン−非共役ジエン系ゴム質重合体にグラフト重合された未架橋エチレン−プロピレン−非共役ジエン系グラフト共重合体を含有する。
Hereinafter, the present invention will be described in detail.
The compatibilizer for a soft material of the present invention comprises an aromatic vinyl monomer, a (meth) acrylic acid ester monomer, or a monomer component containing a mixture of these, an uncrosslinked ethylene-propylene-nonconjugated diene It contains an uncrosslinked ethylene-propylene-nonconjugated diene graft copolymer graft-polymerized to a rubber-based polymer.
前記単量体成分は、芳香族ビニル系単量体もしくは（メタ）アクリル酸エステル系単量体またはこれらの混合物を含有する。
芳香族ビニル系単量体としては、例えば、スチレン、α−メチルスチレン、ビニルトルエン、ｏ−エチルスチレン及びｏ−ジクロロスチレン、ｐ−ジクロロスチレン等が挙げられ、これらのうちスチレンやα‐メチルスチレンが好ましく用いられる。これらの単量体は、単独で用いても２種以上を併用してもよい。
（メタ）アクリル酸エステル系単量体としては、メチルアクリレート、エチルアクリレート、プロピルアクリレート、ブチルアクリレート、アミルアクリレート、ヘキシルアクリレート、オクチルアクリレート、２−エチルヘキシルアクリレート、シクロヘキシルアクリレート、ドデシルアクリレート、オクタデシルアクリレート、フェニルアクリレート及びベンジルアクリレート等のアクリル酸エステル；メチルメタクリレート、エチルメタクリレート、プロピルメタクリレート、ブチルメタクリレート、アミルメタクリレート、ヘキシルメタクリレート、オクチルメタクリレート、２‐エチルヘキシルメタクリレート、シクロヘキシルメタクリレート、ドデシルメタクリレート、オクタデシルメタクリレート、フェニルメタクリレート及びベンジルメタクリレート等のメタクリル酸エステルが挙げられ、これらのうちメチルアクリレート、エチルアクリレート、メチルメタクリレート、エチルメタクリレートが好ましく用いられる。また、これらの単量体は、単独で用いても２種以上を併用してもかまわない。
The monomer component contains an aromatic vinyl monomer, a (meth) acrylic acid ester monomer, or a mixture thereof.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, o-dichlorostyrene, and p-dichlorostyrene. Among these, styrene and α-methylstyrene are used. Is preferably used. These monomers may be used alone or in combination of two or more.
As (meth) acrylic acid ester monomers, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate And acrylic esters such as benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and the like Include methacrylic acid esters such as benzyl methacrylate, among them methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate are preferably used. Moreover, these monomers may be used independently or may use 2 or more types together.
前記単量体成分は、該単量体成分の全質量に対し０〜６０質量％のシアン化ビニル系単量体をさらに含有することが好ましい。
シアン化ビニル系単量体としては、アクリロニトリル、メタクリロニトリル等が好ましく用いられる。またこれらの単量体は、単独で用いても２種以上を併用してもよい。
The monomer component preferably further contains 0 to 60% by mass of a vinyl cyanide monomer based on the total mass of the monomer component.
As the vinyl cyanide monomer, acrylonitrile, methacrylonitrile and the like are preferably used. Moreover, these monomers may be used independently or may use 2 or more types together.
前記単量体成分は、共重合可能な他の単量体をさらに含有してもよい。共重合可能な他の単量体としては、例えばα‐又はβ‐不飽和ジカルボン酸のイミド化合物、不飽和カルボン酸アミド化合物などがあげられる。
α‐又はβ‐不飽和ジカルボン酸のイミド化合物としては、マレイミド、Ｎ‐メチルマレイミド、Ｎ‐ブチルマレイミド、Ｎ‐（ｐ‐メチルフェニル）マレイミド、Ｎ‐フェニルマレイミド、Ｎ‐シクロヘキシルマレイミド等が挙げられる。不飽和カルボン酸アミド化合物としては、アクリルアミドやメタクリルアミド等が挙げられる。これらの単量体は、単独で用いても２種以上を併用してもかまわない。
後述の未架橋エチレン―プロピレン―非共役ジエン系ゴム質重合体（以下、未架橋ＥＰＤＭと称する）にグラフト重合される単量体成分が０〜６０質量％のシアン化ビニル系単量体を含有することにより、本発明の軟質材用相溶化剤を含有させた熱可塑性樹脂組成物の耐衝撃性、外観を向上させることができる。シアン化ビニル系単量体の含有率が６０％を超えると、得られる未架橋ＥＰＤＭグラフト共重合体と、例えばポリオレフィン系樹脂との相溶性が低下し、層状剥離や光沢の低下をおこすため、好ましくない。
The monomer component may further contain another copolymerizable monomer. Examples of other copolymerizable monomers include imide compounds of α- or β-unsaturated dicarboxylic acids, unsaturated carboxylic acid amide compounds, and the like.
Examples of the imide compound of α- or β-unsaturated dicarboxylic acid include maleimide, N-methylmaleimide, N-butylmaleimide, N- (p-methylphenyl) maleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like. . Examples of unsaturated carboxylic acid amide compounds include acrylamide and methacrylamide. These monomers may be used alone or in combination of two or more.
The monomer component to be graft-polymerized to an uncrosslinked ethylene-propylene-nonconjugated diene rubber polymer (hereinafter referred to as uncrosslinked EPDM), which will be described later, contains 0-60 mass% vinyl cyanide monomer. By doing so, the impact resistance and appearance of the thermoplastic resin composition containing the compatibilizer for soft materials of the present invention can be improved. If the content of the vinyl cyanide monomer exceeds 60%, the compatibility of the resulting uncrosslinked EPDM graft copolymer with, for example, a polyolefin resin is reduced, causing delamination and gloss reduction. It is not preferable.
本発明に用いられる未架橋エチレン―プロピレン―非共役ジエン系ゴム質重合体（未架橋ＥＰＤＭ）は、エチレン成分の含有率が、５０〜９０質量％であることが好ましい。
５０質量％未満の場合、本発明の軟質材用相溶化剤を含有させた熱可塑性樹脂組成物において、目的とする摺動性が得られにくく、また、電子顕微鏡にて観察した構造がＩＰＮ（Ｉｎｔｅｒｐｅｎｅｔｒａｔｉｎｇ ｐｏｌｙｍｅｒ ｎｅｔｗｏｒｋ；相互貫入高分子網目）様の層状構造ではなく、したがって耐衝撃性を発現させることができない。なお、ＩＰＮとは、異種の高分子網目が、単なるブレンドでなく互いにからみあった構造をいい、このような構造をとる複合材料は、耐衝撃性のうち特に面衝撃強度に優れるといわれている。
９０質量％を超える場合、本発明の軟質材用相溶化剤を含有させた熱可塑性樹脂組成物において衝撃強度の低下を招く場合がある。
The uncrosslinked ethylene-propylene-nonconjugated diene rubbery polymer (uncrosslinked EPDM) used in the present invention preferably has an ethylene component content of 50 to 90% by mass.
When the amount is less than 50% by mass, the thermoplastic resin composition containing the softener compatibilizer of the present invention is difficult to obtain the desired slidability, and the structure observed with an electron microscope is IPN ( It is not a layered structure like an interpenetrating polymer network (interpenetrating polymer network), and therefore cannot exhibit impact resistance. Note that IPN refers to a structure in which different types of polymer networks are tangled with each other, not just a blend, and a composite material having such a structure is said to be particularly excellent in surface impact strength among impact resistances.
When exceeding 90 mass%, the impact strength may be reduced in the thermoplastic resin composition containing the compatibilizer for soft material of the present invention.
未架橋ＥＰＤＭの非共役ジエン成分は、１，４−ヘキサジエン、５−エチリデン−２−ノルボルネン、５−ビニルノルボルネン及びシクロペンタジエン等が好ましく用いられる。
未架橋ＥＰＤＭの、ＭＬ１＋４、１２５℃におけるムーニー粘度は、１０〜４０であることが好ましい。１０未満の場合、引張強度が低下することがあり、４０を超える場合、成形時における流動性が低下することがあるため好ましくない。
As the non-conjugated diene component of the uncrosslinked EPDM, 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinylnorbornene, cyclopentadiene and the like are preferably used.
The Mooney viscosity of uncrosslinked EPDM at ML 1 + 4 at 125 ° C. is preferably 10-40. If it is less than 10, the tensile strength may decrease, and if it exceeds 40, the fluidity during molding may decrease, which is not preferable.
本発明に用いられる未架橋エチレン−プロピレン−非共役ジエン系グラフト共重合体（以下、未架橋ＥＰＤＭグラフト共重合体と称する）は、グラフト率が１５〜９０％であることが好ましい。この範囲であることにより、例えば本発明の軟質材用相溶化剤に、ポリオレフィン系樹脂と協同してポリオレフィンマトリクスを形成させることができる。また、この範囲より大きくても小さくても、成形外観や耐衝撃性が悪くなる。グラフト率は、２０〜６０％であることがさらに好ましい。
未架橋ＥＰＤＭグラフト共重合体のアセトン可溶重合体の質量平均分子量は、１００００〜８００００であることが好ましい。１００００未満の場合、本発明の軟質材用相溶化剤とスチレン系樹脂との相溶性が低下するため、本発明の軟質材用相溶化剤を含有させた熱可塑性樹脂組成物の耐衝撃性が損なわれることがあり、８００００を超える場合、熱可塑性樹脂組成物の流動性が低下することがある。
The graft ratio of the uncrosslinked ethylene-propylene-nonconjugated diene graft copolymer (hereinafter referred to as uncrosslinked EPDM graft copolymer) used in the present invention is preferably 15 to 90%. By being in this range, for example, the compatibilizer for soft material of the present invention can form a polyolefin matrix in cooperation with the polyolefin resin. In addition, if it is larger or smaller than this range, the molding appearance and impact resistance deteriorate. The graft rate is more preferably 20 to 60%.
The mass average molecular weight of the acetone-soluble polymer of the uncrosslinked EPDM graft copolymer is preferably 10,000 to 80,000. If it is less than 10,000, the compatibility between the compatibilizer for soft materials of the present invention and the styrene resin is lowered, so the impact resistance of the thermoplastic resin composition containing the compatibilizer for soft materials of the present invention is low. When it exceeds 80,000, the fluidity of the thermoplastic resin composition may be lowered.
未架橋ＥＰＤＭグラフト共重合体において、未架橋エチレン−プロピレン−非共役ジエン系ゴム質重合体を使用することにより、後述する（ｂ）成分のポリオレフィン系樹脂との相溶性を飛躍的に向上させ、軟質性やさらに他のポリオレフィン系樹脂との熱溶着性などの機能を付加させる軟質材用相溶化剤を提供することができる。 In the uncrosslinked EPDM graft copolymer, by using an uncrosslinked ethylene-propylene-nonconjugated diene-based rubbery polymer, the compatibility with the polyolefin-based resin of the component (b) described later is dramatically improved, It is possible to provide a compatibilizer for a soft material that adds functions such as softness and heat-weldability with other polyolefin resins.
本発明の軟質材用相溶化剤の製造方法は、未架橋エチレン―プロピレン非共役ジエン系ゴム質重合体ラテックス６０〜９０質量部（固形分として）の存在下に、芳香族ビニル系単量体もしくは（メタ）アクリル酸エステル系単量体またはこれらの混合物からなる単量体成分４０〜１０質量部を重合して未架橋エチレン―プロピレン―非共役ジエン系グラフト共重合体を合成する重合工程を有する。 The method for producing a compatibilizer for a soft material according to the present invention comprises an aromatic vinyl monomer in the presence of 60 to 90 parts by mass (as a solid content) of an uncrosslinked ethylene-propylene non-conjugated diene rubber polymer latex. Alternatively, a polymerization step of synthesizing an uncrosslinked ethylene-propylene-nonconjugated diene graft copolymer by polymerizing 40 to 10 parts by mass of a monomer component comprising a (meth) acrylic acid ester monomer or a mixture thereof. Have.
本発明の製造方法における未架橋エチレン―プロピレン―非共役ジエン系ゴム質重合体ラテックス（以下、未架橋ＥＰＤＭラテックスと称する）とは、エチレン−プロピレン−非共役ジエン系ゴム質重合体（以下、ＥＰＤＭと称する）を主に水に分散したラテックスであって、クメンハイドロパーオキサイド等の開始剤およびシビニルベンゼン等の架橋剤の存在下に架橋反応を行う工程が適用されていないものである。
未架橋ＥＰＤＭラテックスは、例えば、ＥＰＤＭに乳化剤を添加して乳化し、 さらに多価アルコールを添加することにより調製することができる。
ＥＰＤＭの所定量を適当な溶媒に溶解して、これに乳化剤を添加して乳化させ多価アルコールを添加する。溶媒としては、ｎ−ヘキサンやシクロヘキサン等の脂肪族又は脂環式炭化水素溶媒を用いることができる。
乳化剤としては特に制限はないが、例えば、オレイン酸カリウム及び不均化ロジン酸カリウム等の界面活性剤が用いられる。更に、多価アルコールとしては、エチレングリコール、テトラメチレングリコール又はグリセリン等を用いることができる。
乳化剤の添加量は、ＥＰＤＭ１００質量部に対して、１〜１０質量部とするのが好ましい。なお、乳化剤は、オレイン酸をＥＰＤＭに混合しておき、これに水酸化カリウム水溶液を添加してオレイン酸カリウムを生成させることにより添加することもできる。多価アルコールの添加量は、ＥＰＤＭ１００質量部に対して０．１〜１質量部が好適である。
The uncrosslinked ethylene-propylene-nonconjugated diene rubber polymer latex (hereinafter referred to as uncrosslinked EPDM latex) in the production method of the present invention is an ethylene-propylene-nonconjugated diene rubber polymer (hereinafter referred to as EPDM). In the presence of an initiator such as cumene hydroperoxide and a cross-linking agent such as civinylbenzene.
Uncrosslinked EPDM latex can be prepared, for example, by adding an emulsifier to EPDM and emulsifying, and further adding a polyhydric alcohol.
A predetermined amount of EPDM is dissolved in a suitable solvent, and an emulsifier is added thereto to emulsify, and a polyhydric alcohol is added. As the solvent, an aliphatic or alicyclic hydrocarbon solvent such as n-hexane or cyclohexane can be used.
Although there is no restriction | limiting in particular as an emulsifier, Surfactants, such as potassium oleate and disproportionated potassium rosinate, are used, for example. Furthermore, as the polyhydric alcohol, ethylene glycol, tetramethylene glycol, glycerin, or the like can be used.
The addition amount of the emulsifier is preferably 1 to 10 parts by mass with respect to 100 parts by mass of EPDM. In addition, an emulsifier can also be added by mixing oleic acid with EPDM and adding potassium hydroxide aqueous solution to this to produce potassium oleate. The addition amount of the polyhydric alcohol is preferably 0.1 to 1 part by mass with respect to 100 parts by mass of EPDM.
本発明の軟質材用相溶化剤の製造方法において、未架橋ＥＰＤＭラテックスは、平均粒子径が０．２〜１．０μｍであることが好ましい。このことにより、本発明の製造方法により製造した軟質材用相溶化剤は、スチレン系樹脂とポリオレフィン系樹脂を相溶化することができる。粒子径が０．２μｍ未満のときには、本発明の製造方法で得られた軟質材用相溶化剤と、例えばスチレン系樹脂とポリオレフィン系樹脂とを含有した熱可塑性樹脂組成物が充分な柔軟性を示さず、１．０μｍを超えるときには、上記のような熱可塑性樹脂組成物においてスチレン系樹脂とポリオレフィン系樹脂が充分な相溶性を示さず、耐衝撃性が悪化することがある。 In the method for producing a softener compatibilizer of the present invention, the uncrosslinked EPDM latex preferably has an average particle size of 0.2 to 1.0 μm. Thereby, the compatibilizer for soft material manufactured by the manufacturing method of the present invention can compatibilize styrene resin and polyolefin resin. When the particle size is less than 0.2 μm, the thermoplastic resin composition containing the compatibilizer for soft material obtained by the production method of the present invention and, for example, a styrene resin and a polyolefin resin has sufficient flexibility. When not exceeding 1.0 μm, the styrene resin and the polyolefin resin do not exhibit sufficient compatibility in the thermoplastic resin composition as described above, and the impact resistance may deteriorate.
未架橋ＥＰＤＭラテックスのゲル含有率は０〜１０質量％であることが好ましい。ゲル含有率が１０質量％より多いときは、本発明の軟質材用相溶化剤を含有させた熱可塑性樹脂組成物の耐衝撃性が著しく悪化することがある。
なお、未架橋ＥＰＤＭラテックスのゲル含有率は、このラテックスを希硫酸で水洗、乾燥後、１ｇ採取し２００ｍｌのトルエン中に４０時間浸漬し、次いで２００メッシュのステンレス金網にて濾過し、残渣を乾燥することによって求めることができる。
The gel content of the uncrosslinked EPDM latex is preferably 0 to 10% by mass. When the gel content is more than 10% by mass, the impact resistance of the thermoplastic resin composition containing the softener compatibilizer of the present invention may be remarkably deteriorated.
The gel content of the uncrosslinked EPDM latex is determined by washing the latex with dilute sulfuric acid and drying, collecting 1 g, immersing in 200 ml of toluene for 40 hours, and then filtering through a 200-mesh stainless wire mesh to dry the residue. You can ask for it.
前記重合工程において、未架橋ＥＰＤＭグラフト共重合体は、前記未架橋ＥＰＤＭラテックス６０〜９０質量部の存在下に、前記単量体成分４０〜１０質量部を重合させることにより合成される。
未架橋ＥＰＤＭラテックスが６０質量部未満で単量体成分が４０質量部を超える場合は、最終の熱可塑性樹脂組成物の耐摩耗性は改善されにくく、また未架橋ＥＰＤＭラテックスが９０質量部を超え、単量体成分が１０質量部未満である場合は、熱可塑性樹脂組成物の光沢、表面外観が悪化することがある。
単量体成分と未架橋ＥＰＤＭラテックスの配合量をこの範囲とすることにより、すなわち未架橋ＥＰＤＭグラフト共重合体を高ゴム分率に調製することにより、スチレン系樹脂あるいは本発明の相溶化剤自体と、ポリオレフィン系樹脂との相溶化作用に貢献するＥＰＤＭが、前記単量体成分に含まれる単量体に由来する重合体で覆われることなく、グラフト重合体を製造することができる。
In the polymerization step, the uncrosslinked EPDM graft copolymer is synthesized by polymerizing 40 to 10 parts by mass of the monomer component in the presence of 60 to 90 parts by mass of the uncrosslinked EPDM latex.
When the uncrosslinked EPDM latex is less than 60 parts by mass and the monomer component exceeds 40 parts by mass, the abrasion resistance of the final thermoplastic resin composition is hardly improved, and the uncrosslinked EPDM latex exceeds 90 parts by mass. When the monomer component is less than 10 parts by mass, the gloss and surface appearance of the thermoplastic resin composition may be deteriorated.
By setting the blending amount of the monomer component and the uncrosslinked EPDM latex within this range, that is, by adjusting the uncrosslinked EPDM graft copolymer to a high rubber fraction, the styrenic resin or the compatibilizer of the present invention itself. A graft polymer can be produced without EPDM contributing to the compatibilizing action with the polyolefin resin being covered with the polymer derived from the monomer contained in the monomer component.
得られた未架橋ＥＰＤＭラテックスを前記単量体成分と混合し、公知の方法でグラフト重合させることにより、未架橋ＥＰＤＭグラフト共重合体を得ることができる。
重合方法としては特に限定されないが、例えば、乳化重合、塊状重合、懸濁重合、溶液重合、またこれらの組み合わせ等の方法を用いることができる。
The resulting uncrosslinked EPDM latex is mixed with the monomer component and graft polymerized by a known method to obtain an uncrosslinked EPDM graft copolymer.
Although it does not specifically limit as a polymerization method, For example, methods, such as emulsion polymerization, block polymerization, suspension polymerization, solution polymerization, these combinations, can be used.
乳化重合の場合、例えば、前記未架橋ＥＰＤＭラテックス及び前記単量体成分を合計で１００質量部となるように混合し、重合開始剤としてレドックス系開始剤の存在下、６０〜９５℃の温度にて反応させることにより重合反応を行うことができる。
レドックス系開始剤としては、過酸化物が用いられ、通常の場合、硫酸第一鉄−キレート剤−還元剤と組み合わせて使用される。本発明において、過酸化物としては、油溶性の有機過酸化物が好ましい。
油溶性の有機過酸化物としては、クメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、ターシャリーブチルハイドロパーオキサイド等が好ましい。さらに、クメンハイドロパーオキサイドを、硫酸第一鉄、ピロリン酸ナトリウム及びデキストローズと組み合わせて用いることが好ましい。
In the case of emulsion polymerization, for example, the uncrosslinked EPDM latex and the monomer component are mixed so as to be 100 parts by mass in total, and the temperature is set to 60 to 95 ° C. in the presence of a redox initiator as a polymerization initiator. The polymerization reaction can be carried out by reacting them.
As the redox initiator, a peroxide is used, and is usually used in combination with a ferrous sulfate-chelating agent-reducing agent. In the present invention, the peroxide is preferably an oil-soluble organic peroxide.
As the oil-soluble organic peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, tertiary butyl hydroperoxide and the like are preferable. Furthermore, it is preferable to use cumene hydroperoxide in combination with ferrous sulfate, sodium pyrophosphate and dextrose.
以下、本発明の前記重合工程において好適な方法を例示する。
前記未架橋ＥＰＤＭラテックスに、硫酸第一鉄と、ピロリン酸ナトリウムと、デキストローズの一部、好ましくはこれらの全量として配合量１００質量部のうち０．３〜０．８質量部を加える。その後、重合反応を開始し、反応開始時から少なくとも１時間の添加時間にわたって、前記単量体成分及びクメンハイドロパーオキサイドを連続的に未架橋ＥＰＤＭラテックスに加える。このとき、硫酸第一鉄と、ピロリン酸ナトリウムと、デキストローズの残部及び乳化剤を、単量体成分及びクメンハイドロパーオキサイドの添加時間よりも３０分以上長い時間にわたって連続的に未架橋ＥＰＤＭラテックスに加えるのが好ましい。
前記単量体成分及びクメンハイドロパーオキサイドの添加時間が１時間未満の場合、ラテックス安定性が悪化することにより、重合収率が低下する。
このように、重合開始剤、単量体成分及び乳化剤の添加量や、ラテックスへの添加時期、添加時間等を調整し、更に、所定の反応温度にて反応させることによって、乳化剤の使用量を従来の約１／３程度に低減して、単量体の添加率が高く、かつ、重合安定性を格段に高めて、目的とする優れた性質、例えば優れた表面外観を有し、臭気の限りなく低減された未架橋ＥＰＤＭグラフト共重合体を得ることができる。
Hereafter, a suitable method in the said polymerization process of this invention is illustrated.
To the uncrosslinked EPDM latex is added ferrous sulfate, sodium pyrophosphate, a part of dextrose, and preferably 0.3 to 0.8 parts by mass out of 100 parts by mass as the total amount thereof. Thereafter, the polymerization reaction is started, and the monomer component and cumene hydroperoxide are continuously added to the uncrosslinked EPDM latex over an addition time of at least 1 hour from the start of the reaction. At this time, ferrous sulfate, sodium pyrophosphate, the remainder of dextrose and the emulsifier are continuously converted into uncrosslinked EPDM latex over a period of 30 minutes or longer than the addition time of the monomer component and cumene hydroperoxide. It is preferable to add.
When the addition time of the monomer component and cumene hydroperoxide is less than 1 hour, the latex stability deteriorates, resulting in a decrease in polymerization yield.
Thus, by adjusting the addition amount of the polymerization initiator, the monomer component and the emulsifier, the addition time to the latex, the addition time, etc., and further reacting at a predetermined reaction temperature, the use amount of the emulsifier can be reduced. It is reduced to about 1/3 of the conventional one, the addition rate of the monomer is high, the polymerization stability is remarkably increased, and it has the desired excellent properties, for example, excellent surface appearance, Unreduced uncrosslinked EPDM graft copolymer can be obtained as much as possible.
本発明の製造方法において、重合工程により得られた未架橋ＥＰＤＭグラフト共重合体には、必要に応じて酸化防止剤を添加することができる。次いで、得られた未架橋ＥＰＤＭグラフト共重合体から樹脂固形分を析出させる。この場合、析出剤としては、例えば、硫酸、酢酸、塩化カルシウム、硫酸マグネシウム等の水溶液を単独、又は併用して用いることができる。析出物を分離し、これを水洗、脱水、乾燥することにより、未架橋ＥＰＤＭグラフト共重合体を粉体として回収することができる。 In the production method of the present invention, an antioxidant can be added to the uncrosslinked EPDM graft copolymer obtained by the polymerization step, if necessary. Subsequently, resin solid content is precipitated from the obtained uncrosslinked EPDM graft copolymer. In this case, as the precipitating agent, for example, an aqueous solution of sulfuric acid, acetic acid, calcium chloride, magnesium sulfate or the like can be used alone or in combination. By separating the precipitate and washing it with water, dehydrating and drying, the uncrosslinked EPDM graft copolymer can be recovered as a powder.
本発明の熱可塑性樹脂組成物は、未架橋ＥＰＤＭグラフト共重合体を含む前記軟質材用相溶化剤と、スチレン系単量体混合物を重合してなるスチレン系樹脂（ａ）と、ポリオレフィン系樹脂（ｂ）とを含有する。 The thermoplastic resin composition of the present invention includes a softener compatibilizer containing an uncrosslinked EPDM graft copolymer, a styrene resin (a) obtained by polymerizing a styrene monomer mixture, and a polyolefin resin. (B).
前記スチレン系単量体混合物は、スチレン系単量体を含むものであればよく、スチレン系単量体のみからなってもよいし、スチレン系単量体と重合可能な他の単量体をさらに含んでもよい。
前記スチレン系単量体混合物は、（メタ）アクリル酸エステル系単量体、シアン化ビニル系単量体およびこれらと共重合可能な他の単量体からなる群から選択される１種以上の単量体をさらに含有することが好ましい。
前記スチレン系単量体混合物に用いられるスチレン系単量体としては、スチレン、α‐メチルスチレン、ビニルトルエン、ｏ‐エチルスチレン、ｏ‐ジクロロスチレン、ｐ‐ジクロロスチレン等が挙げられる。これらの単量体は、単独で用いても２種以上を併用してもよい。
The styrenic monomer mixture only needs to contain a styrenic monomer, and may consist of only a styrenic monomer, or may contain other monomers polymerizable with the styrenic monomer. Further, it may be included.
The styrene monomer mixture is one or more selected from the group consisting of (meth) acrylic acid ester monomers, vinyl cyanide monomers and other monomers copolymerizable therewith. It is preferable to further contain a monomer.
Examples of the styrene monomer used in the styrene monomer mixture include styrene, α-methyl styrene, vinyl toluene, o-ethyl styrene, o-dichlorostyrene, and p-dichlorostyrene. These monomers may be used alone or in combination of two or more.
前記スチレン系単量体混合物に用いられる、芳香族ビニル系単量体と重合可能な他の単量体としては、（メタ）アクリル酸エステル系単量体、シアン化ビニル系単量体、α‐またはβ‐不飽和ジカルボン酸のイミド化合物、不飽和カルボン酸アミド化合物等が挙げられる。
（メタ）アクリル酸エステル系単量体、シアン化ビニル系単量体としては、前記の未架橋ＥＰＤＭグラフト共重合体に用いられる単量体と同様のものが挙げられる。これらの単量体は、単独で用いても２種以上を併用してもよい。
α‐またはβ‐不飽和ジカルボン酸のイミド化合物としても、前記の未架橋ＥＰＤＭグラフト共重合体に用いられる単量体と同様のものを挙げることができる。これらの単量体は、単独で用いても２種以上を併用してもよい。
Other monomers that can be polymerized with the aromatic vinyl monomer used in the styrene monomer mixture include (meth) acrylic acid ester monomers, vinyl cyanide monomers, α Examples thereof include an imide compound of-or β-unsaturated dicarboxylic acid, and an unsaturated carboxylic acid amide compound.
Examples of the (meth) acrylic acid ester monomer and the vinyl cyanide monomer include the same monomers as those used in the uncrosslinked EPDM graft copolymer. These monomers may be used alone or in combination of two or more.
Examples of the imide compound of α- or β-unsaturated dicarboxylic acid may include the same monomers as those used in the uncrosslinked EPDM graft copolymer. These monomers may be used alone or in combination of two or more.
本発明におけるスチレン系樹脂（ａ）の具体例としては、ポリスチレン、ポリメチルメタクリレート、スチレン−アクリロニトリル共重合体、スチレン−α−メチルスチレン−アクリロニトリル三元共重合体、スチレン−アクリロニトリル−メチルメタククリレート三元共重合体、スチレン−アクリロニトリル−Ｎ−フェニルマレイミド三元共重合体、スチレン−α−メチルスチレン−アクリロニトリル−Ｎ−フェニルマレイミド四元共重合体等が挙げられる。これらの重合体または共重合体は、単独でも用いても、２種以上を併用してもよい。 Specific examples of the styrene resin (a) in the present invention include polystyrene, polymethyl methacrylate, styrene-acrylonitrile copolymer, styrene-α-methylstyrene-acrylonitrile terpolymer, styrene-acrylonitrile-methyl methacrylate. Examples thereof include terpolymers, styrene-acrylonitrile-N-phenylmaleimide terpolymers, and styrene-α-methylstyrene-acrylonitrile-N-phenylmaleimide quaternary copolymers. These polymers or copolymers may be used alone or in combination of two or more.
なお、スチレン系樹脂（ａ）は、スチレン系樹脂（ａ）と混合可能なゴム強化樹脂や、その他の樹脂をさらに含有してもよい。 The styrene resin (a) may further contain a rubber-reinforced resin that can be mixed with the styrene resin (a) or other resins.
ここで、ゴム強化樹脂とは、ゴム質重合体に、芳香族ビニル系単量体、（メタ）アクリル酸エステル系単量体、シアン化ビニル系単量体、これらと共重合可能な他の単量体からなる群から選択された１種以上の単量体からなる混合物が重合してなるグラフト共重合体を含有するものを示す。
ゴム質重合体としては、公知のいかなるものも使用でき、例えば、ブタジエン、イソプレン、ジメチルブタジエン、クロロプレン、及びシクロペンタジエン等の共役ジエンゴム、ブタジエン−スチレンゴム、ブタジエン−アクリロニトリルゴム、アクリレート系ゴム、シリコン系ゴムが好ましい。また、これらのゴム質重合体は、単独で用いても２種以上を併用してもよい。
Here, the rubber reinforced resin is a rubbery polymer, an aromatic vinyl monomer, a (meth) acrylic acid ester monomer, a vinyl cyanide monomer, or other copolymerizable with these. The one containing a graft copolymer formed by polymerizing a mixture of one or more monomers selected from the group consisting of monomers is shown.
As the rubbery polymer, any known polymer can be used, for example, conjugated diene rubber such as butadiene, isoprene, dimethylbutadiene, chloroprene, and cyclopentadiene, butadiene-styrene rubber, butadiene-acrylonitrile rubber, acrylate rubber, silicon series Rubber is preferred. These rubbery polymers may be used alone or in combination of two or more.
前記ゴム強化樹脂に含有されるグラフト共重合体に用いられる芳香族ビニル系単量体としては、スチレン、α‐メチルスチレン、ビニルトルエン、ｏ‐エチルスチレン及びｏ‐ジクロロスチレン、ｐ‐ジクロロスチレン等が挙げられ、剛性、耐衝撃性等の物性の面からスチレン及びα−メチルスチレンが好ましい。またこれらの単量体は、単独で用いても２種以上を併用してもかまわない。
また、（メタ）アクリル酸エステル系単量体として、メチルアクリレート、エチルアクリレート、プロピルアクリレート、ブチルアクリレート、アミルアクリレート、ヘキシルアクリレート、オクチルアクリレート、２−エチルヘキシルアクリレート、シクロヘキシルアクリレート、ドデシルアクリレート、オクタデシルアクリレート、フェニルアクリレート及びベンジルアクリレート等のアクリル酸エステル；メチルメタクリレート、エチルメタクリレート、プロピルメタクリレート、ブチルメタクリレート、アミルメタクリレート、ヘキシルメタクリレート、オクチルメタクリレート、２‐エチルヘキシルメタクリレート、シクロヘキシルメタクリレート、ドデシルメタクリレート、オクタデシルメタクリレート、フェニルメタクリレート及びベンジルメタクリレート等のメタクリル酸エステルが挙げられ、耐衝撃性、耐熱性などの物性の面からメチルメタクリレート、エチルメタクリレート、メチルアクリレート、エチルアクリレートが好ましい。これらの単量体は、単独で用いても２種以上を併用してもかまわない。
シアン化ビニル系単量体としては、アクリロニトリル及びメタクリロニトリル等が挙げられる。またこれらの単量体は、単独で用いても２種以上を併用してもかまわない。
上記の単量体と共重合可能なその他の単量体としては、マレイミド、Ｎ‐メチルマレイミド、Ｎ‐ブチルマレイミド、Ｎ‐（ｐ‐メチルフェニル）マレイミド、Ｎ‐フェニルマレイミド、Ｎ‐シクロヘキシルマレイミド等のα‐又はβ‐不飽和ジカルボン酸のイミド化合物；アクリルアミド、メタクリルアミド等の不飽和カルボン酸アミド化合物が挙げられる。また、これらの単量体は、単独で用いても２種以上を併用してもかまわない。
Examples of aromatic vinyl monomers used in the graft copolymer contained in the rubber-reinforced resin include styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, o-dichlorostyrene, and p-dichlorostyrene. Styrene and α-methylstyrene are preferable from the viewpoint of physical properties such as rigidity and impact resistance. These monomers may be used alone or in combination of two or more.
As (meth) acrylic acid ester monomers, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl Acrylic esters such as acrylate and benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate And methacrylic acid esters such as benzyl methacrylate and the like, impact resistance, methyl methacrylate from the viewpoint of physical properties such as heat resistance, ethyl methacrylate, methyl acrylate, ethyl acrylate preferred. These monomers may be used alone or in combination of two or more.
Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile. These monomers may be used alone or in combination of two or more.
Other monomers copolymerizable with the above monomers include maleimide, N-methylmaleimide, N-butylmaleimide, N- (p-methylphenyl) maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, etc. An imide compound of α- or β-unsaturated dicarboxylic acid; unsaturated carboxylic acid amide compounds such as acrylamide and methacrylamide; Moreover, these monomers may be used independently or may use 2 or more types together.
前記ゴム強化樹脂のグラフト率は、通常のスチレン系樹脂の範疇でよく、例えば、３０〜１５０質量％である。なお、グラフト率は、下記の式で求められる。
（グラフト率）＝（ゴム質重合体にグラフトしている単量体成分の総質量／ゴム質重合体の総質量）×１００ [質量％]
The graft ratio of the rubber-reinforced resin may be in the range of a normal styrene resin, for example, 30 to 150% by mass. In addition, a graft rate is calculated | required by the following formula.
(Graft ratio) = (total mass of monomer components grafted on rubber polymer / total mass of rubber polymer) × 100 [mass%]
本発明の熱可塑性樹脂組成物に用いられるポリオレフィン系樹脂（ｂ）としては、例えば、プロピレンの単独重合体ならびにプロピレンとエチレンやブテン−１、ペンテン−１等のα−オレフィンの１種又は２種以上よりなるランダムもしくはブロック共重合体や、カルボン酸、無水マレイン酸等により変性した変性ポリプロピレン、また低密度ポリエチレン、直鎖状低密度ポリエチレン、高密度ポリエチレン、エチレン−ブチレン共重合体または非晶質ポリオレフィン系樹脂等を用いることができる。 Examples of the polyolefin resin (b) used in the thermoplastic resin composition of the present invention include one or two propylene homopolymers and propylene and α-olefins such as ethylene, butene-1, and pentene-1. Random or block copolymers comprising the above, modified polypropylene modified with carboxylic acid, maleic anhydride, etc., low density polyethylene, linear low density polyethylene, high density polyethylene, ethylene-butylene copolymer or amorphous A polyolefin resin or the like can be used.
本発明の熱可塑性樹脂組成物は、未架橋ＥＰＤＭグラフト共重合体とスチレン系樹脂（ａ）とポリオレフィン系樹脂（ｂ）の合計を１００質量部としたときに、未架橋ＥＰＤＭグラフト共重合体３０質量部以上を含有することが好ましい。このことにより、熱可塑性樹脂組成物中で、ポリオレフィン系樹脂が単に分散相やマトリクス相を形成するのではなく、ＩＰＮ様の層状構造をとることができ、その結果、特に面衝撃強度を高度に発現することができる。なお、このような層状構造は、電子顕微鏡による観察で確認できる。
未架橋ＥＰＤＭグラフト共重合体が３０質量部未満であると、得られる熱可塑性樹脂組成物の耐衝撃性が劣り、この熱可塑性樹脂組成物のスチレン系樹脂に対する熱溶着性とポリオレフィン系樹脂に対する熱溶着性がいずれも劣り、また伸びが劣りやすくなるため好ましくない。
The thermoplastic resin composition of the present invention has an uncrosslinked EPDM graft copolymer 30 when the total of the uncrosslinked EPDM graft copolymer, the styrene resin (a), and the polyolefin resin (b) is 100 parts by mass. It is preferable to contain at least part by mass. Thus, in the thermoplastic resin composition, the polyolefin resin does not simply form a dispersed phase or a matrix phase, but can take an IPN-like layered structure. As a result, the surface impact strength is particularly high. Can be expressed. Such a layered structure can be confirmed by observation with an electron microscope.
When the uncrosslinked EPDM graft copolymer is less than 30 parts by mass, the resulting thermoplastic resin composition has inferior impact resistance. The thermoplastic resin composition has a heat weldability to a styrene resin and a heat to a polyolefin resin. Since the weldability is inferior and the elongation tends to be inferior, it is not preferable.
本発明の熱可塑性樹脂組成物には、さらに所望に応じ公知の着色剤、熱安定剤、造核剤、滑剤、離型剤、難燃剤、紫外線吸収剤、静電防止剤等の添加剤を添加してもよい。また、ガラス繊維、カーボン繊維、タルク、炭酸カルシウム等を添加して補強することもできる。また、要求される性能に応じて、他の重合体、例えば、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリカーボネート、エチレン−酢酸スチレン系樹脂等の樹脂や、他の熱可塑性エラストマー（ＴＰＥ）、例えば、ＴＰＯ、ＴＰＥＥ、ＴＰＵ、ＴＰＳ、ＲＢなどのエラストマーを適宜加えることができる。 The thermoplastic resin composition of the present invention may further contain additives such as known colorants, heat stabilizers, nucleating agents, lubricants, mold release agents, flame retardants, ultraviolet absorbers and antistatic agents, as desired. It may be added. Further, glass fiber, carbon fiber, talc, calcium carbonate or the like can be added for reinforcement. Depending on the required performance, other polymers such as polybutylene terephthalate, polyethylene terephthalate, polycarbonate, ethylene-styrene acetate resin, and other thermoplastic elastomers (TPE) such as TPO, Elastomers such as TPEE, TPU, TPS, and RB can be added as appropriate.
本発明の熱可塑性組成物は、前記未架橋ＥＰＤＭグラフト共重合体、スチレン系樹脂（ａ）、スチレン系樹脂（ａ）に混合されるゴム強化樹脂、ポリオレフィン系樹脂（ｂ）、および上記のような添加剤を、ヘンシェルミキサー、Ｖ型ブレンダー、又はタンブラー等の混合装置で混合し、一軸押出機、二軸押出機、バンバリーミキサー、コニーダー、ロール等の溶融混練装置を用いて溶融混練することにより得ることができるが、何らこのような製造方法に限定されるものではない。 The thermoplastic composition of the present invention includes the uncrosslinked EPDM graft copolymer, the styrene resin (a), the rubber reinforced resin mixed with the styrene resin (a), the polyolefin resin (b), and the above-described composition. By mixing with a mixing device such as a Henschel mixer, V-type blender, or tumbler, and then melt-kneading using a melt-kneading device such as a single-screw extruder, twin-screw extruder, Banbury mixer, kneader, or roll. Although it can obtain, it is not limited to such a manufacturing method at all.
このようにして得られた熱可塑性樹脂組成物は、通常の成形方法、例えば、射出成形、押出成形、ブロー成形、シート成形、真空成形、二色成形等により、所望の形状に成形して用いることができる。 The thermoplastic resin composition thus obtained is used after being molded into a desired shape by an ordinary molding method such as injection molding, extrusion molding, blow molding, sheet molding, vacuum molding, two-color molding and the like. be able to.
本発明の軟質材用相溶化剤は、ポリオレフィン系樹脂とスチレン系樹脂の相溶性を飛躍的に向上させることができ、スチレン系樹脂に対して、軟質性や、ポリオレフィン系樹脂との熱溶着性などの機能を付加させることができる。
本発明の熱可塑性樹脂組成物は、良好な流動性、耐衝撃性、耐薬品性、光沢、成形性、表面外観及び成形収縮率、耐熱性、耐摩耗性を示し、軟質材特有の臭気を生じない。さらに、ポリオレフィン系樹脂に溶着可能であることから、本発明の熱可塑性樹脂組成物とポリオレフィン系樹脂との二層シートの成形を行うことができる。
The compatibilizer for a soft material of the present invention can dramatically improve the compatibility between a polyolefin resin and a styrene resin, and is soft to the styrene resin and heat weldable with the polyolefin resin. Etc. can be added.
The thermoplastic resin composition of the present invention exhibits good fluidity, impact resistance, chemical resistance, gloss, moldability, surface appearance and molding shrinkage, heat resistance, wear resistance, and has a odor peculiar to soft materials. Does not occur. Furthermore, since it can be welded to the polyolefin resin, a two-layer sheet of the thermoplastic resin composition of the present invention and the polyolefin resin can be molded.
本発明の熱可塑性樹脂の成形品は、単独での使用はもちろん、ポリオレフィン系樹脂に溶着可能であることから、それらの材料の接合部にも使用できる。例えば、家庭電化製品のバンパー、コネクターキャップ、冷蔵庫のガスケット、風呂蓋つなぎ、吸着盤、シール材などに用いられ、優れた柔軟性、表面光沢、衝撃強度、耐候性、耐薬品性を保持することができる。 The molded article of the thermoplastic resin according to the present invention can be used not only for use alone but also for a joint portion of these materials because it can be welded to a polyolefin resin. For example, it is used for bumpers, connector caps, refrigerator gaskets, bath lids, suction cups, sealing materials, etc. for home appliances, and retains excellent flexibility, surface gloss, impact strength, weather resistance, and chemical resistance. Can do.
以上説明したように、本発明の軟質材用相溶化剤によれば、流動性、耐衝撃性、耐薬品性、光沢、成形性、表面外観及び成形収縮率、耐熱性、耐摩耗性に優れ、臭気を感じさせず、ポリオレフィン系樹脂に充分な溶着性がある軟質性の熱可塑性樹脂組成物を提供することができる。
さらに、単量体成分に０〜６０％のシアン化ビニル系単量体を含むことによって、これを用いた熱可塑性樹脂組成物の耐衝撃性、外観を向上させることができる。
未架橋ＥＰＤＭのエチレン成分の含有率が５０〜９０質量％であれば、熱可塑性樹脂組成物に耐摩耗性を付与することができ、良好な耐衝撃性を発現させることができる。
また、未架橋ＥＰＤＭのＭＬ１＋４、１２５℃におけるムーニー粘度が１０〜４０であれば、さらに良好な耐衝撃性を発現することができる。
さらに、未架橋ＥＰＤＭグラフト共重合体のグラフト率が１５〜９０％であれば、オレフィン系樹脂にポリオレフィンマトリクスを形成させることができる。また、アセトン可溶重合体の質量平均分子量が１００００〜８００００であれば、これを用いた未架橋ＥＰＤＭグラフト共重合体を含有させた熱可塑性樹脂組成物にさらに良好な耐衝撃性と流動性を保持させることができる。
さらに、未架橋ＥＰＤＭグラフト共重合体のゴム分率が高いと、熱可塑性樹脂組成物において、さらに良好な柔軟性、面衝撃性を発現させることができる。
As described above, according to the softener compatibilizer of the present invention, the fluidity, impact resistance, chemical resistance, gloss, moldability, surface appearance and mold shrinkage, heat resistance, and wear resistance are excellent. It is possible to provide a soft thermoplastic resin composition that does not feel odor and has sufficient weldability to the polyolefin resin.
Furthermore, by including 0 to 60% vinyl cyanide monomer in the monomer component, impact resistance and appearance of a thermoplastic resin composition using the monomer can be improved.
When the content of the ethylene component of the uncrosslinked EPDM is 50 to 90% by mass, the thermoplastic resin composition can be provided with wear resistance, and good impact resistance can be exhibited.
Moreover, if the Mooney viscosity at 125 ° C. of ML 1 + 4 of uncrosslinked EPDM is 10 to 40, even better impact resistance can be exhibited.
Furthermore, when the graft ratio of the uncrosslinked EPDM graft copolymer is 15 to 90%, a polyolefin matrix can be formed on the olefin resin. Further, if the mass average molecular weight of the acetone-soluble polymer is 10,000 to 80,000, the thermoplastic resin composition containing the uncrosslinked EPDM graft copolymer using the acetone-soluble polymer has better impact resistance and fluidity. Can be retained.
Furthermore, when the rubber fraction of the uncrosslinked EPDM graft copolymer is high, even better flexibility and surface impact can be expressed in the thermoplastic resin composition.
以下に、具体的な実施例を挙げて本発明を更に詳細に説明するが、本発明はこれら実施例に限定されるものではない。
＜製造例１ 未架橋ＥＰＤＭグラフト共重合体の製造＞
「未架橋エチレン−プロピレン−非共役ジエン系ゴム質重合体ラテックス（未架橋ＥＰＤＭラテックス）の製造」
ＥＰＤＭ（商品名：ＥＰＴ３０１２Ｐ、三井化学製、エチレン含有率：７０質量％、ムーニー粘度（ＭＬ１＋４、１２５℃）：１１）１００質量部をｎ−ヘキサン５５６質量部に溶解した後、オレイン酸４．５質量部を加え溶解し、重合体溶液とした。別に、水７００質量部に水酸化カリウム０．９質量部を溶解した水溶液に、エチレングリコール０．５質量部を加え６０℃に保ち、これに先に調製した重合体溶液を徐々に加えて乳化した後、ホモミキサーで攪拌した。次いで溶剤と水の一部を留去して、未架橋ＥＰＤＭラテックスを得た。未架橋ＥＰＤＭラテックスのゲル含有率は０質量％、粒子径は０．４〜０．６μｍであった。
なお、未架橋ＥＰＤＭラテックスのゲル含有率は、ラテックスを希硫酸で水洗、乾燥後、１ｇ採取し２００ｍｌのトルエン中に４０時間浸漬し、次いで２００メッシュのステンレス金網にて濾過し、残渣を乾燥することによって求めた。
ＥＰＤＭのエチレン含有率は、公知の熱分解ガスクロマトグラフィー法を用いて確認した。また、ＥＰＤＭのムーニー粘度は、ＪＩＳ−Ｋ６３００に従い株式会社島津製作所製のムーニー粘度計（ＳＭＶ２００）を使用して１２５℃で１分間予熱した後、１２５℃で４分間測定し、ＥＰＤＭのムーニー粘度（ＭＬ１＋４、１２５℃）として表示した。
Hereinafter, the present invention will be described in more detail with specific examples, but the present invention is not limited to these examples.
<Production Example 1 Production of Uncrosslinked EPDM Graft Copolymer>
"Production of uncrosslinked ethylene-propylene-nonconjugated diene rubber polymer latex (uncrosslinked EPDM latex)"
After dissolving 100 parts by mass of EPDM (trade name: EPT3012P, manufactured by Mitsui Chemicals, ethylene content: 70 mass%, Mooney viscosity (ML 1 + 4 , 125 ° C.): 11) in 556 parts by mass of n-hexane, oleic acid 4. 5 parts by mass was added and dissolved to obtain a polymer solution. Separately, 0.5 parts by mass of ethylene glycol was added to an aqueous solution in which 0.9 parts by mass of potassium hydroxide was dissolved in 700 parts by mass of water and maintained at 60 ° C., and the previously prepared polymer solution was gradually added to emulsify. Then, the mixture was stirred with a homomixer. Next, a part of the solvent and water was distilled off to obtain an uncrosslinked EPDM latex. The gel content of the uncrosslinked EPDM latex was 0% by mass, and the particle size was 0.4 to 0.6 μm.
The gel content of the uncrosslinked EPDM latex was determined by washing the latex with dilute sulfuric acid and drying, collecting 1 g, immersing it in 200 ml of toluene for 40 hours, then filtering through a 200 mesh stainless steel wire mesh and drying the residue. Was determined by
The ethylene content of EPDM was confirmed using a known pyrolysis gas chromatography method. The Mooney viscosity of EPDM was preheated at 125 ° C. for 1 minute using a Mooney viscometer (SMV200) manufactured by Shimadzu Corporation according to JIS-K6300, and then measured at 125 ° C. for 4 minutes. ML 1 + 4 , 125 ° C.).
「未架橋ＥＰＤＭグラフト共重合体−１の製造」
攪拌機付きステンレス重合槽に、上記で製造した未架橋ＥＰＤＭラテックス７０質量部（固形分）、水１７０質量部（ラテックス中の水分も含む）、水酸化ナトリウム０．０１質量部、硫酸第一鉄０．０１質量部、デキストローズ０．５７質量部を仕込み、８０℃に加温した後、単量体成分としてアクリロニトリル１０質量部からなるシアン化ビニル系単量体およびスチレン２０質量部からなる芳香族ビニル系単量体と、重合開始剤としてクメンハイドロパーオキサイド１．０質量部とからなる溶液を１５０分間で添加した。さらに、ピロリン酸ナトリウム０．４５質量部、硫酸第一鉄０．０１質量部、デキストローズ０．５６質量部、オレイン酸ナトリウム１．０質量部及び水からなる触媒溶液を１８０分間添加して重合反応を行い、未架橋ＥＰＤＭグラフト共重合体−１の分散液を得た。単量体転化率は９２質量％であった。
未架橋ＥＰＤＭグラフト共重合体−１の分散液に、硫酸３質量部が水１００質量部に溶解した凝固剤を添加し、９０℃で凝固させた。その後、脱水、乾燥して、未架橋ＥＰＤＭグラフト共重合体−１の粉末を得た。なお、凝固析出物は０．３０質量％であった。
なお、単量体転化率は、ラテックスの一部を採取してガスクロマトグラフィーを用いて求めた残存単量体の質量から算出した。
“Production of Uncrosslinked EPDM Graft Copolymer-1”
In a stainless polymerization tank equipped with a stirrer, 70 parts by mass (solid content) of the uncrosslinked EPDM latex produced above, 170 parts by mass of water (including water in the latex), 0.01 parts by mass of sodium hydroxide, and ferrous sulfate 0 .01 parts by mass, 0.57 parts by mass of dextrose, and after heating to 80 ° C., as a monomer component, a vinyl cyanide monomer consisting of 10 parts by mass of acrylonitrile and an aromatic consisting of 20 parts by mass of styrene A solution comprising a vinyl monomer and 1.0 part by mass of cumene hydroperoxide as a polymerization initiator was added over 150 minutes. Furthermore, a catalyst solution consisting of 0.45 parts by mass of sodium pyrophosphate, 0.01 parts by mass of ferrous sulfate, 0.56 parts by mass of dextrose, 1.0 part by mass of sodium oleate and water was added for 180 minutes for polymerization. Reaction was performed to obtain a dispersion of uncrosslinked EPDM graft copolymer-1. The monomer conversion was 92% by mass.
A coagulant in which 3 parts by mass of sulfuric acid was dissolved in 100 parts by mass of water was added to the dispersion of uncrosslinked EPDM graft copolymer-1, and coagulated at 90 ° C. Then, it dehydrated and dried to obtain a powder of uncrosslinked EPDM graft copolymer-1. The solidified precipitate was 0.30% by mass.
The monomer conversion rate was calculated from the mass of the residual monomer obtained by sampling a part of the latex and using gas chromatography.
「未架橋ＥＰＤＭグラフト共重合体−２の製造」
単量体成分としてメチルメタクリレート３０質量部からなる（メタ）アクリル酸エステル系単量体を用いた以外は、未架橋ＥＰＤＭグラフト共重合体−１と同様の方法で重合し、凝固、脱水、乾燥の工程を行って、粉末状の未架橋ＥＰＤＭグラフト共重合体−２を得た。単量体転化率は９３質量％であった。また、凝固析出物は０．２８質量％であった。
“Production of Uncrosslinked EPDM Graft Copolymer-2”
Polymerized in the same manner as uncrosslinked EPDM graft copolymer-1, except that a (meth) acrylic acid ester monomer consisting of 30 parts by mass of methyl methacrylate was used as the monomer component, and then coagulated, dehydrated and dried. The powder of uncrosslinked EPDM graft copolymer-2 was obtained by performing the above process. The monomer conversion was 93% by mass. The solidified precipitate was 0.28% by mass.
「未架橋ＥＰＤＭグラフト共重合体−３の製造」
単量体成分としてスチレン３０質量部からなる芳香族ビニル系単量体を用いた以外は、未架橋ＥＰＤＭグラフト共重合体−１と同様の方法で重合し、凝固、脱水、乾燥の工程を行って、粉末状の未架橋ＥＰＤＭグラフト共重合体−３を得た。単量体転化率は９４質量％であった。また、凝固析出物は０．２７質量％であった。
“Production of Uncrosslinked EPDM Graft Copolymer-3”
Polymerization is carried out in the same manner as uncrosslinked EPDM graft copolymer-1, except that an aromatic vinyl monomer composed of 30 parts by mass of styrene is used as the monomer component, and the steps of coagulation, dehydration and drying are performed. Thus, powdery uncrosslinked EPDM graft copolymer-3 was obtained. The monomer conversion was 94% by mass. The solidified precipitate was 0.27% by mass.
＜製造例２ 架橋ＥＰＤＭグラフト共重合体の製造＞
「架橋ＥＰＤＭラテックスの製造」
製造例１と同様の方法で得た未架橋ＥＰＤＭラテックスに、ゴム成分であるＥＰＤＭ１００質量部に対して、ジビニルベンゼン１．５質量部、ジーｔ−ブチルパーオキシトリメチルシクロヘキサン１．０質量部を添加して、１２０℃で１時間反応させることにより架橋ＥＰＤＭラテックスを製造した。架橋ＥＰＤＭラテックスのゲル含有率は４８質量％で、粒径は０．５７μｍであった。
<Production Example 2 Production of Crosslinked EPDM Graft Copolymer>
"Production of crosslinked EPDM latex"
To uncrosslinked EPDM latex obtained in the same manner as in Production Example 1, 1.5 parts by weight of divinylbenzene and 1.0 part by weight of di-t-butylperoxytrimethylcyclohexane are added to 100 parts by weight of EPDM which is a rubber component. Then, a cross-linked EPDM latex was produced by reacting at 120 ° C. for 1 hour. The gel content of the crosslinked EPDM latex was 48% by mass, and the particle size was 0.57 μm.
「架橋ＥＰＤＭグラフト共重合体の製造」
攪拌機付きステンレス重合槽に、上記で製造した架橋ＥＰＤＭラテックス６０質量部（固形分）、水１７０質量部（ラテックス中の水分も含む）、水酸化ナトリウム０．０１質量部、ピロリン酸ナトリウム０．４５質量部、硫酸第一鉄０．０１質量部、デキストローズ０．５７質量部を８０℃に加温した後、アクリロニトリル１２質量部、スチレン２８質量部からなる単量体成分と、重合開始剤としてクメンハイドロパーオキサイド１．０質量部とからなる溶液を１５０分間で添加した。また、ピロリン酸ナトリウム０．４５質量部、硫酸第一鉄０．０１質量部、デキストローズ０．５６質量部オレイン酸ナトリウム１．０質量部及び水からなる触媒溶液を１８０分間添加し、重合反応を行って、架橋ＥＰＤＭグラフト共重合体の分散液を得た。この分散液に対して、上記未架橋ＥＰＤＭグラフト共重合体−１と同様の方法で凝固、脱水、乾燥の工程を行って、架橋ＥＰＤＭグラフト共重合体の粉末を得た。単量体転化率は９３質量％であった。また、凝固析出物は０．２８質量％であった。
“Production of Crosslinked EPDM Graft Copolymer”
In a stainless polymerization tank equipped with a stirrer, 60 parts by mass (solid content) of the crosslinked EPDM latex produced above, 170 parts by mass of water (including water in the latex), 0.01 parts by mass of sodium hydroxide, 0.45 sodium pyrophosphate As a polymerization initiator, a monomer component consisting of 12 parts by mass of acrylonitrile and 28 parts by mass of styrene, after heating part by mass, 0.01 parts by mass of ferrous sulfate, 0.57 parts by mass of dextrose to 80 ° C. A solution consisting of 1.0 part by mass of cumene hydroperoxide was added over 150 minutes. Also, a catalyst solution consisting of 0.45 parts by mass of sodium pyrophosphate, 0.01 parts by mass of ferrous sulfate, 0.56 parts by mass of dextrose, 1.0 part by mass of sodium oleate and water is added for 180 minutes, and the polymerization reaction To obtain a dispersion of a crosslinked EPDM graft copolymer. The dispersion was subjected to coagulation, dehydration and drying steps in the same manner as for the uncrosslinked EPDM graft copolymer-1 to obtain a crosslinked EPDM graft copolymer powder. The monomer conversion was 93% by mass. The solidified precipitate was 0.28% by mass.
＜グラフト率の測定＞
製造例１、２で得られた未架橋ＥＰＤＭグラフト共重合体および架橋ＥＰＤＭグラフト共重合体のグラフト率を、以下の方法で測定した。
グラフト重合体の一定質量（ｘ）をアセトン中に投入し、浸とう機で２時間浸とうして遊離の共重合体を溶解させ、遠心分離機を用いてこの溶液を１５０００ｒｐｍで３０分間にわたって遠心分離して不溶分を得た。次に、乾燥機で充分に揮発分を除いて、乾燥した不溶分の質量（ｙ）を得た。下記式によりグラフト率を算出した。
グラフト率＝[｛（ｙ）−（ｘ）×グラフト共重合体のゴム分率｝／｛（ｘ）×グラフト共重合体のゴム分率｝]×１００ ［質量％］
その結果、未架橋ＥＰＤＭグラフト共重合体−１、２、３のグラフト率は、それぞれ２４．３％、２５．１％、２７．１％であった。また、上記の架橋ＥＰＤＭグラフト共重合体のグラフト率は、３５．１％であった。
＜アセトン可溶成分の質量平均分子量の測定＞
未架橋ＥＰＤＭグラフト共重合体−１、２、３のアセトン可溶成分の質量平均分子量Ｍｗを、ゲル・パーミネーション・クロマトグラフィー（東ソー製、ＨＬＣ８０２０）にて、ＴＨＦを溶剤として用いてスチレン換算分子量として測定した。
その結果、アセトン可溶成分の質量平均分子量Ｍｗは、未架橋ＥＰＤＭグラフト共重合体−１、２、３および架橋ＥＰＤＭグラフト共重合体について、それぞれ３３０００、５４０００、２３０００、２２０００であった。
<Measurement of graft ratio>
The graft ratios of the uncrosslinked EPDM graft copolymer and the crosslinked EPDM graft copolymer obtained in Production Examples 1 and 2 were measured by the following method.
A constant mass (x) of the graft polymer is put into acetone, and the free copolymer is dissolved by immersing in an immersion machine for 2 hours, and this solution is centrifuged at 15000 rpm for 30 minutes using a centrifuge. Separation gave insolubles. Next, the volatile matter was sufficiently removed with a dryer, and the mass (y) of the dried insoluble matter was obtained. The graft ratio was calculated by the following formula.
Graft ratio = [{(y)-(x) × Rubber fraction of graft copolymer} / {(x) × Rubber fraction of graft copolymer}] × 100 [mass%]
As a result, the graft ratios of uncrosslinked EPDM graft copolymers-1, 2, and 3 were 24.3%, 25.1%, and 27.1%, respectively. The graft ratio of the crosslinked EPDM graft copolymer was 35.1%.
<Measurement of mass average molecular weight of acetone-soluble component>
The weight average molecular weight Mw of the acetone-soluble component of the uncrosslinked EPDM graft copolymers-1, 2, and 3 was determined by gel permeation chromatography (manufactured by Tosoh Corporation, HLC8020) using THF as a solvent and styrene equivalent molecular weight. As measured.
As a result, the mass average molecular weight Mw of the acetone-soluble component was 33,000, 54000, 23000, and 22000 for the uncrosslinked EPDM graft copolymers-1, 2, 3 and the crosslinked EPDM graft copolymer, respectively.
＜製造例３ スチレン系樹脂（ａ）の製造＞
スチレン系樹脂（ａ）として、下記のスチレン系樹脂１〜３を製造した。
（スチレン系樹脂−１の製造）
脂肪酸塩を乳化剤とし、ラウリルパーオキサイドを重合開始剤とし、ドデシルメルカプタンを連鎖移動剤として用いて、水中にて、スチレン７２．０部、アクリロニトリルからなるシアン化ビニル系単量体２８．０部を乳化重合させて、スチレン系樹脂−１（ＰＳＡＮ）を得た。この共重合体の質量平均分子量Ｍｗは６７０００、数平均分子量Ｍｎは３２０００、分子量分布Ｍｗ／Ｍｎは２．１であった。数平均分子量及び質量平均分子量は、ゲル・パーミネーション・クロマトグラフィーによる。
（スチレン系樹脂−２の製造）
脂肪族塩を乳化剤とし、ラウリルパーオキサイドを重合開始剤とし、ドデシルメルカプタンを連鎖移動剤として用いて、水中にてスチレン７０部、メチルメタクリレートからなる（メタ）アクリル酸エステル系単量体３０部を乳化重合させて、スチレン系樹脂−２（ＭＳ系）を得た。
（スチレン系樹脂−３の製造）
脂肪族塩を乳化剤とし、ラウリルパーオキサイドを重合開始剤とし、ドデシルメルカプタンを連鎖移動剤として用いて、水中にてスチレン１８部、α−メチルスチレン４６．６部、アクリロニトリルからなるシアン化ビニル系単量体２８．６部及びＮ−フェニルマレイミドからなるα‐不飽和ジカルボン酸のイミド化合物６．８部を乳化重合させて、スチレン系樹脂−３（ＰＭＩ系）を得た。
<Production Example 3 Production of Styrenic Resin (a)>
The following styrene resins 1 to 3 were produced as the styrene resin (a).
(Production of styrene resin-1)
Using a fatty acid salt as an emulsifier, lauryl peroxide as a polymerization initiator, and dodecyl mercaptan as a chain transfer agent, 72.0 parts of styrene and 28.0 parts of a vinyl cyanide monomer composed of acrylonitrile are added in water. Emulsion polymerization was performed to obtain a styrene resin-1 (PSAN). The weight average molecular weight Mw of this copolymer was 67,000, the number average molecular weight Mn was 32000, and the molecular weight distribution Mw / Mn was 2.1. The number average molecular weight and the mass average molecular weight are determined by gel permeation chromatography.
(Production of styrene resin-2)
Using an aliphatic salt as an emulsifier, lauryl peroxide as a polymerization initiator, and dodecyl mercaptan as a chain transfer agent, 70 parts of styrene monomer in water and 30 parts of a (meth) acrylate monomer based on methyl methacrylate Emulsion polymerization was performed to obtain a styrene resin-2 (MS system).
(Production of styrene resin-3)
A vinyl cyanide monomer composed of 18 parts of styrene, 46.6 parts of α-methylstyrene, and acrylonitrile in water using an aliphatic salt as an emulsifier, lauryl peroxide as a polymerization initiator, and dodecyl mercaptan as a chain transfer agent. 28.6 parts of a monomer and 6.8 parts of an imide compound of α-unsaturated dicarboxylic acid composed of N-phenylmaleimide were emulsion polymerized to obtain styrene resin-3 (PMI system).
スチレン系樹脂（ａ）に混合するゴム強化樹脂として、下記のグラフト共重合体１、２を製造した。
（グラフト共重合体−１の製造）
乳化剤の存在下に水中にてポリブタジエン５０部にスチレン３５部とアクリロニトリル１５部を、クメンハイドロパーオキサイドを含むレドックス重合開始剤を用いて常法にしたがって乳化重合させ、グラフト共重合体−１を得た。
（グラフト共重合体−２の製造）
乳化剤の存在下に水中にてポリブタジエン５０部にスチレン５０部を、クメンハイドロパーオキサイドを含むレドックス系重合開始剤を用いて常法にしたがって乳化重合させ、グラフト共重合体−２を得た。
The following graft copolymers 1 and 2 were produced as rubber-reinforced resins to be mixed with the styrene resin (a).
(Production of graft copolymer-1)
In the presence of an emulsifier, 50 parts of polybutadiene in water and 35 parts of styrene and 15 parts of acrylonitrile are emulsion-polymerized according to a conventional method using a redox polymerization initiator containing cumene hydroperoxide to obtain graft copolymer-1. It was.
(Production of graft copolymer-2)
Graft copolymer-2 was obtained by subjecting 50 parts of polybutadiene to 50 parts of styrene in water in the presence of an emulsifier and emulsion polymerization using a redox polymerization initiator containing cumene hydroperoxide according to a conventional method.
＜ポリオレフィン系樹脂（ｂ）＞
ポリオレフィン系樹脂（ｂ）としては、ポリオレフィン系樹脂１、２としてグランドポリマー製のＪ７０９Ｗ、Ｊ２２６Ｅを用いた。また、ポリオレフィン系樹脂３、４としては、三井化学製の２２０８Ｊ、Ａ２２０Ｊを用いた。
<Polyolefin resin (b)>
As the polyolefin resin (b), J709W and J226E manufactured by Grand Polymer were used as the polyolefin resins 1 and 2. As the polyolefin resins 3 and 4, 2208J and A220J manufactured by Mitsui Chemicals were used.
＜実施例１〜７、比較例１〜３＞
上記製造例で得られた未架橋ＥＰＤＭグラフト共重合体または架橋ＥＰＤＭグラフト共重合体と、スチレン系樹脂（ａ）と、グラフト共重合体と、ポリオレフィン系樹脂（ｂ）を表１に示す割合でＶ型ブレンダーによって均一に混合し、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を４４ｍｍ径の二軸押出機でバレル温度１８０℃にて溶融混練し、ダイスから吐出されるストランドを切断して成型用ペレットを得た。このペレットを、型締圧力７５ｔ（トン）の射出成形機（東芝製）に試験片金型を取り付けてシリンダー温度２２０℃、金型温度５０℃、射出圧力５０ｋｇ／ｃｍ２冷却時間３０秒間の成形条件で成形して試験片を作製した。
<Examples 1-7, Comparative Examples 1-3>
Table 1 shows the ratio of uncrosslinked EPDM graft copolymer or crosslinked EPDM graft copolymer obtained in the above production example, styrene resin (a), graft copolymer, and polyolefin resin (b). The mixture was uniformly mixed with a V-type blender to obtain a thermoplastic resin composition. The obtained thermoplastic resin composition was melt-kneaded at a barrel temperature of 180 ° C. with a 44 mm diameter twin-screw extruder, and the strand discharged from the die was cut to obtain a molding pellet. The pellets were molded into an injection molding machine (manufactured by Toshiba) with a clamping pressure of 75 t (tons), and a cylinder temperature was 220 ° C., a mold temperature was 50 ° C., an injection pressure was 50 kg / cm 2 and a cooling time was 30 seconds. The test piece was produced by molding under conditions.
得られた試験片について、各種特性の評価を行った。結果を表１に示す。
物性評価は、それぞれ下記の方法および装置にて測定した。
耐衝撃性：アイゾット衝撃強度、試験片厚み３．２ｍｍ、ＡＳＴＭ Ｄ２５６
耐熱性：熱変形温度、試験片厚み６．４ｍｍ、ＡＳＴＭ Ｄ６４８（曲げ応力：１．８ＭＰａ）
低温特性：面衝撃試験、試験片厚み２．５ｍｍ、ＩＳＯ ６６０３−２（試料温度：−３０℃）
硬度：ショアＤ、ＡＳＴＭ Ｄ２２４０
引張強度：引張降伏強さ、試験片厚み３．２ｍｍ、ＡＳＴＭ Ｄ６３８
成形収縮率：ＡＳＴＭ Ｄ９５５−７３、ＩＳＯ ２５５７に準拠
光沢：スガ試験機製デジタル変角光度計（ＵＧＶ−５Ｄ、入射角６０°、反射角６０°）
表面外観：５０×５０×３．２ｍｍの平板状成形体にて目視評価した。○はフォギング（ガス付着）なし、×はフォギングありを示す。
耐摩耗性：大栄科学精器製作所製平面摩耗試験機Ｍ４０３−８３Ｂ法、テーブル往復回転６０回／分±２回、ストローク１４０ｍｍ、荷重４．９Ｎで、摩擦子にガーゼを取り付け、サンプルを１０回摩擦後、レーザー顕微鏡により、線粗さ（Ｒａ）を測定した。表１において、○は表面に傷が確認されなかったことを、×は表面に傷が確認されたことを示す。
耐薬品性：溶媒浸漬法を用いた。なお、メチルエチルケトン（ＭＥＫ）に２４時間浸漬の後、目視で表面を観察した。○はクラックなし、かつ膨張なしを示し、×はクラック又は膨張が発生したことを示す。
流動性：溶出速度（ＭＦＲ）を、ＡＳＴＭ Ｄ１２３８（２３０℃、２．１６ｋｇ）にて評価した。
熱溶着試験：７６ｍｍ×２５ｍｍ×３．２ｍｍの試験片を、同じ形状の試験片に成形したポリオレフィン系樹脂と熱板溶着装置により溶着し、冷却後、ＡＳＴＭ Ｄ６３８により引張強度を測定した。
電子顕微鏡観察：日本電子（株）製の電子顕微鏡ＪＥＭ−１００ＣＸ２を用い、酸化ルテニウムと酸化オスミウムで染色してモルホロジーの観察を行った。
臭気：３人の被験者にて官能試験法を行った。５段階評価とし、５：無臭、４：ごくわずかに臭気を感じる、３：やや臭気を感じる、２：明らかに臭気を感じる、１：強い臭気として評価を行った。
なお、熱可塑樹脂組成物における未架橋ＥＰＤＭ、スチレン系樹脂（ａ）の含有量を、フィルムを用い、ＦＴ赤外分光光度計（ＮＩＣＯＬＥＴ製、ＮＥＸＵＳ６７０）により測定し、また、未架橋ＥＰＤＭの含有量を、熱分解ガスクロマトグラフィー装置（島津ＧＣ−１４型、日本分光工業ＪＨＰ３Ｓ熱分解装置）でも測定した。
About the obtained test piece, various characteristics were evaluated. The results are shown in Table 1.
The physical properties were measured by the following methods and apparatuses, respectively.
Impact resistance: Izod impact strength, specimen thickness 3.2 mm, ASTM D256
Heat resistance: heat distortion temperature, specimen thickness 6.4 mm, ASTM D648 (bending stress: 1.8 MPa)
Low temperature characteristics: surface impact test, specimen thickness 2.5 mm, ISO 6603-2 (sample temperature: −30 ° C.)
Hardness: Shore D, ASTM D2240
Tensile strength: tensile yield strength, specimen thickness 3.2 mm, ASTM D638
Mold shrinkage: ASTM D955-73, conforming to ISO 2557 Gloss: Suga Test Instruments digital variable angle photometer (UGV-5D, incident angle 60 °, reflection angle 60 °)
Surface appearance: Visual evaluation was performed with a flat molded body of 50 × 50 × 3.2 mm. ○ indicates no fogging (gas adhesion), and × indicates fogging.
Abrasion resistance: Plane abrasion tester M403-83B method manufactured by Daiei Kagaku Seisaku Seisakusho, table reciprocating rotation 60 times / min ± 2 times, stroke 140 mm, load 4.9 N, gauze attached to friction element, sample 10 times After rubbing, the line roughness (Ra) was measured with a laser microscope. In Table 1, “◯” indicates that no scratch was observed on the surface, and “X” indicates that the scratch was confirmed on the surface.
Chemical resistance: Solvent immersion method was used. The surface was visually observed after immersion in methyl ethyl ketone (MEK) for 24 hours. ○ indicates no crack and no expansion, and x indicates that a crack or expansion occurred.
Fluidity: Elution rate (MFR) was evaluated by ASTM D1238 (230 ° C., 2.16 kg).
Thermal welding test: A test piece of 76 mm × 25 mm × 3.2 mm was welded with a polyolefin resin molded into a test piece of the same shape and a hot plate welding apparatus, and after cooling, the tensile strength was measured by ASTM D638.
Electron microscope observation: Using an electron microscope JEM-100CX2 manufactured by JEOL Ltd., morphology was observed by staining with ruthenium oxide and osmium oxide.
Odor: A sensory test was performed on three subjects. Evaluation was made on a 5-grade scale, 5: no odor, 4: very slightly odor, 3: slightly odor, 2: clearly odor, 1: strong odor.
The content of uncrosslinked EPDM and styrene resin (a) in the thermoplastic resin composition was measured with a film using a FT infrared spectrophotometer (manufactured by NICOLET, NEXUS670), and the content of uncrosslinked EPDM. The amount was also measured by a pyrolysis gas chromatography apparatus (Shimadzu GC-14 type, JASCO JHP3S pyrolysis apparatus).
表１より、実施例１〜７においては、得られた熱可塑性樹脂組成物の、電子顕微鏡にて観察した構造が層状であり、アイゾット衝撃強度、耐熱性、低温特性、硬度、引張強度、成形収縮率、光沢、表面外観、耐摩耗性、耐薬品性、ＭＦＲ、ポリプロピレンへの溶着性がいずれも極めて良好であり、しかも臭気を感じさせないものとなっていた。
しかし、未架橋ＥＰＤＭグラフト共重合体を含有しない比較例１、未架橋ＥＰＤＭグラフト共重合体をスチレン系樹脂（ａ）のみと混合した比較例２、未架橋ＥＰＤＭグラフト共重合体を含有せず、架橋ＥＰＤＭグラフト共重合体をスチレン系樹脂（ａ）およびポリオレフィン系樹脂（ｂ）と混合した比較例３では、いずれも上記の物性を同時に満たすことはできなかった。
From Table 1, in Examples 1-7, the structure observed with the electron microscope of the obtained thermoplastic resin composition is layered, Izod impact strength, heat resistance, low temperature characteristics, hardness, tensile strength, molding The shrinkage rate, gloss, surface appearance, abrasion resistance, chemical resistance, MFR, and weldability to polypropylene were all very good and did not make odors felt.
However, Comparative Example 1 containing no uncrosslinked EPDM graft copolymer, Comparative Example 2 in which the uncrosslinked EPDM graft copolymer was mixed only with the styrenic resin (a), and containing no uncrosslinked EPDM graft copolymer, In Comparative Example 3 in which the crosslinked EPDM graft copolymer was mixed with the styrene resin (a) and the polyolefin resin (b), none of the above physical properties could be satisfied at the same time.
本発明の軟質材用相溶化剤を用いた熱可塑性樹脂組成物は、電気製品、自動車部品、建材、フィルム、家庭日用品、各種スイッチボタン等の、人が手に触れ、柔軟性が求められる用途、携帯電話の電源コネクターカバーなどのカバー類等の用途に好適に用いられる。
The thermoplastic resin composition using the compatibilizer for soft materials of the present invention is used for applications such as electrical products, automobile parts, building materials, films, household goods, various switch buttons, etc. where human touch is required and flexibility is required. It is preferably used for applications such as covers such as a power connector cover of a mobile phone.
Claims (6)
The thermoplastic resin composition according to claim 5, wherein the form recognized by observation with an electron microscope is a layered structure.
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| JP2022015082A (en) * | 2020-07-08 | 2022-01-21 | 三井化学株式会社 | Graft copolymer and method for producing the same |
| JP2022015083A (en) * | 2020-07-08 | 2022-01-21 | 三井化学株式会社 | Graft copolymer and method for producing the same |
| CN117209947A (en) * | 2023-09-26 | 2023-12-12 | 广州美村橡胶科技股份有限公司 | Composite modified ethylene propylene diene monomer rubber material for sealing water pipe and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2022015082A (en) * | 2020-07-08 | 2022-01-21 | 三井化学株式会社 | Graft copolymer and method for producing the same |
| JP2022015083A (en) * | 2020-07-08 | 2022-01-21 | 三井化学株式会社 | Graft copolymer and method for producing the same |
| JP7546392B2 (en) | 2020-07-08 | 2024-09-06 | 三井化学株式会社 | Graft copolymer and method for producing same |
| JP7546391B2 (en) | 2020-07-08 | 2024-09-06 | 三井化学株式会社 | Graft copolymer and method for producing same |
| CN117209947A (en) * | 2023-09-26 | 2023-12-12 | 广州美村橡胶科技股份有限公司 | Composite modified ethylene propylene diene monomer rubber material for sealing water pipe and preparation method thereof |
| CN117209947B (en) * | 2023-09-26 | 2024-03-15 | 广州美村橡胶科技股份有限公司 | Composite modified ethylene propylene diene monomer rubber material for sealing water pipe and preparation method thereof |
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