JP4093774B2 - RESIN COMPOSITION FOR CALENDAR SHEET AND CALENDAR SHEET MOLDED ARTICLE - Google Patents
RESIN COMPOSITION FOR CALENDAR SHEET AND CALENDAR SHEET MOLDED ARTICLE Download PDFInfo
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- JP4093774B2 JP4093774B2 JP2002064834A JP2002064834A JP4093774B2 JP 4093774 B2 JP4093774 B2 JP 4093774B2 JP 2002064834 A JP2002064834 A JP 2002064834A JP 2002064834 A JP2002064834 A JP 2002064834A JP 4093774 B2 JP4093774 B2 JP 4093774B2
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- 239000011342 resin composition Substances 0.000 title claims description 18
- -1 aromatic vinyl compound Chemical class 0.000 claims description 52
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 40
- 239000000178 monomer Substances 0.000 claims description 17
- 229920002554 vinyl polymer Polymers 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 15
- 230000000379 polymerizing effect Effects 0.000 claims description 12
- 229920000578 graft copolymer Polymers 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N methyl cyanide Natural products CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims 1
- 238000002845 discoloration Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920000126 latex Polymers 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 238000003490 calendering Methods 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 229920001890 Novodur Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-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
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- MDNFYIAABKQDML-UHFFFAOYSA-N heptyl 2-methylprop-2-enoate Chemical compound CCCCCCCOC(=O)C(C)=C MDNFYIAABKQDML-UHFFFAOYSA-N 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、発色性、暗所変色性にすぐれたカレンダーシート用樹脂組成物および該樹脂組成物を成形してなるカレンダーシート成形体に関するものである。
【０００２】
【従来の技術】
カレンダー成形はシートあるいはフィルム製品を作るために有用な成形法であり、壁紙や表皮材などの成形に応用されている。 カレンダー成形後は、製品を長期的に保管することが多く、特に倉庫などの暗所で保管した場合に黄色に変色する暗所変色の問題がある。
このような問題を解決するため、特開２０００−３１９４９５号公報においては難燃剤と安定剤の組み合わせにより改良する方法が提案されているが、難燃ＰＣ／ＡＢＳ系アアロイに限られるため、汎用的な暗所変色に優れたカレンダーシート成形体を得る事は困難であった。
また、同時に意匠性、製品設計の観点から、着色時の発色性に優れ、同時に耐衝撃強度が高いことが求められている。
【０００３】
【発明が解決しようとする課題】
本発明は、発色性、暗所変色性にすぐれたカレンダーシート用樹脂組成物および該樹脂組成物を成形してなるカレンダーシート成形体を提供することを目的とするものである。
【０００４】
【課題を解決するための手段】
即ち、本発明は、
（１）ゴム状重合体と、芳香族ビニル化合物および不飽和カルボン酸アルキルエステル化合物さらに必要に応じてシアン化ビニル化合物からなる少なくとも不飽和カルボン酸アルキルエステル化合物を２０重量％含有してなるゴム強化スチレン系樹脂（Ａ）１００重量部に対してフェノール系安定剤（Ｂ）としてパラクレゾールジサイクロペンタジエンブチール化合物０．０１〜１重量部を添加してなるカレンダーシート用樹脂組成物、
（２）ゴム強化スチレン系樹脂（Ａ）が、ゴム状重合体の存在下に芳香ビニル化合物２０〜５０重量％、不飽和カルボン酸アルキルエステル化合物５０〜８０重量％およびシアン化ビニル化合物０〜３０重量％からなる単量体を重合してなるグラフト重合体（ａ−１）１０〜９０重量部、および芳香ビニル化合物２０〜８０重量％、不飽和カルボン酸アルキルエステル化合物２０〜８０重量％およびシアン化ビニル化合物０〜３０重量％からなる単量体を重合してなる共重合体（ａ−２）からなる（１）記載のカレンダーシート用樹脂組成物、
（３）ゴム強化スチレン系樹脂（Ａ）が、ゴム状重合体の存在下に芳香ビニル化合物６０〜８０重量％、シアン化ビニル化合物２０〜４０重量％および不飽和カルボン酸アルキルエステル化合物０〜２０重量％からなる単量体を重合してなるグラフト重合体（ａ−１）１０〜９０重量部、および芳香ビニル化合物２０〜５０重量％、不飽和カルボン酸アルキルエステル化合物５０〜８０重量％およびシアン化ビニル化合物０〜３０重量％からなる単量体を重合してなる共重合体（ａ−２）９０〜１０重量部からなる（１）記載のカレンダーシート用樹脂組成物、
（４）（１）〜（３）記載の樹脂組成物をカレンダー成形してなるカレンダーシート成形体を提供するものである。
【０００５】
【発明の実施の形態】
以下、本発明につき詳細に説明する。
本発明におけるゴム強化スチレン系樹脂（Ａ）は、ゴム状重合体と、芳香族ビニル化合物および不飽和カルボン酸アルキルエステル化合物さらに必要に応じてシアン化ビニル化合物からなる少なくとも不飽和カルボン酸アルキルエステル化合物を２０重量％含有してなるゴム強化スチレン系樹脂である。特に、該ゴム強化スチレン系樹脂（Ａ）が、ゴム状重合体の存在下に芳香ビニル化合物２０〜５０重量％、不飽和カルボン酸アルキルエステル化合物５０〜８０重量％およびシアン化ビニル化合物０〜３０重量％からなる単量体を重合してなるグラフト重合体（ａ−１）１０〜９０重量部、および芳香ビニル化合物２０〜８０重量％、不飽和カルボン酸アルキルエステル化合物２０〜８０重量％およびシアン化ビニル化合物０〜３０重量％からなる単量体を重合してなる共重合体（ａ−２）からなるもの、または、ゴム状重合体の存在下に芳香ビニル化合物６０〜８０重量％、シアン化ビニル化合物２０〜４０重量％および不飽和カルボン酸アルキルエステル化合物０〜２０重量％からなる単量体を重合してなるグラフト重合体（ａ−１）１０〜９０重量部、および芳香ビニル化合物２０〜５０重量％、不飽和カルボン酸アルキルエステル化合物５０〜８０重量％およびシアン化ビニル化合物０〜３０重量％からなる単量体を重合してなる共重合体（ａ−２）９０〜１０重量部からなるものが好ましい。
【０００６】
上記のとおり、本発明におけるゴム強化スチレン系樹脂（Ａ）は少なくとも不飽和カルボン酸アルキルエステル化合物を２０重量％含有することが必要であり、該含有量が２０重量％未満ではカレンダーシート成形体の発色性、暗所変色性が悪くなるため好ましくない。なお、該不飽和カルボン酸アルキルエステル化合物含有量の上限には特に制限はないが、ゴム強化スチレン系樹脂としての特性を考慮しその上限は９０重量％程度である。
【０００７】
ゴム強化スチレン系樹脂（Ａ）で使用されるゴム状重合体は、ポリブタジエン、ブタジエン−スチレン共重合体（ＳＢＲ）、ブタジエン−アクリロニトリル共重合体（ＮＢＲ）、ブタジエン−アクリル酸エステル共重合体などのジエン系ゴム、エチレン−プロピレン共重合体（ＥＰＲ）、エチレン−プロピレン−非共役ジエン共重合体（ＥＰＤＭ）などのオレフィン系ゴム、ポリブチルアクリレート、ポリ２−エチルヘキシルアクリレートなどのアクリル系ゴム、シリコンゴム、シリコン−アクリル複合ゴムなどのシリコーン系ゴムなどが挙げられる。特に好ましくはポリブタジエンまたはエチレン−プロピレン−非共役ジエン共重合体である。
【０００８】
芳香族ビニル化合物としては、スチレン、α−メチルスチレン、ο−メチルスチレン、ｐ−メチルスチレン、ο−エチルスチレン、ｐ−エチルスチレンなどが例示され、単独または２種以上混合して使用することができる。これらのうち、特にスチレンが好ましい。
【０００９】
不飽和カルボン酸アルキルエステル化合物としては、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチル、アクリル酸ペンチル、メタクリル酸ペンチル、アクリル酸ヘキシル、メタクリル酸ヘキシル、アクリル酸ヘプチル、メタクリル酸ヘプチル、アクリル酸２−エチルヘキシル、メタクリル酸２−エチルヘキシル、アクリル酸オクチル、メタクリル酸オクチル、アクリル酸ｎ−ノニル、アクリル酸イソノニルなどを例示することができ、単独または２種以上混合して使用することができる。特にメタクリル酸メチルが好ましい。
【００１０】
シアン化ビニル化合物としては、アクリロニトリル、メタクリロニトリル、クロロアクリロニトリルが例示され、単独または２種以上混合して使用することができる。これらのうち、特にアクリロニトリルが好ましい。
【００１１】
本発明で使用されるフェノール系安定剤（Ｂ）〔パラクレゾールジサイクロペンタジエンブチール化合物〕は、立体障害構造（ヒンダード）で、かつ平均分子量５００以上が好ましく、例えばｐ−クレゾールとジシクロペンタジエンのブチル化反応物（商品名：Ｇｏｏｄ Ｙｅａｒ社製 商品名：Ｗｉｎｇｓｔａｙ Ｌ）が例示される。
【００１２】
本発明におけるフェノール系安定剤（Ｂ）〔パラクレゾールジサイクロペンタジエンブチール化合物〕の添加量は、上記ゴム強化スチレン系樹脂（Ａ）１００重量部に対して０．０１〜１重量部である。該添加量が０．０１重量部未満ではカレンダーシート成形体の発色性、暗所変色性に劣り、また１重量部を超えて添加量を増やしてもそれ以上の効果は上がらず、経済性の観点で好ましくない。
【００１３】
上記ゴム強化スチレン系樹脂（Ａ）の製造方法については特に限定されず、乳化重合法、懸濁重合法、塊状重合法、溶液重合法等が適用でき、その際に使用する重合助剤についても適宜使用することができる。 また、上記フェノール系安定剤（Ｂ）の添加方法にも特に制限はなく、溶融混練時に添加する方法や、公知の乳化剤により乳化液を作成した後、乳化重合法により作成したゴム強化スチレン系樹脂（Ａ）とラテックスブレンドすることにより添加することも可能である。
【００１４】
また、本発明における樹脂組成物には、必要に応じて、滑剤、酸化防止剤、タルク、アルカリ金属の水酸化物または炭酸塩、さらには顔料、可塑剤、紫外線吸収剤、光安定剤などの公知の添加剤を１種または２種以上混合してもよい。さらに、他の熱可塑性樹脂、例えばポリカーボネート、ポリアミド、ポリブチレンテレフタレート等の１種または２種以上と組み合わせて用いてもよい。
【００１５】
上記にて得られた本発明における樹脂組成物は、カレンダーシート用の樹脂組成物として使用される。ここでカレンダー成形方法としては、通常の２本ロール、３本ロールあるいは４本ロールによる方法が採用でき、カレンダーシート成形体として好適に使用することができる。
【００１６】
【実施例】
−ゴム強化スチレン系樹脂（Ａ）−
グラフト共重合体（a−１−１〜３）：窒素置換した反応器にブタジエン１００部、ロジン酸カリウム（乳化剤）２．５部、過硫酸カリウム（開始剤）０．３部、ノルマルドデシルメルカプタン（分子量調整剤）０．３部および脱イオン水１００部を仕込み、６０℃で重合を行った。重合完了後、真空下６００ｍｍＨｇで残留モノマーを回収し、ポリブタジエンゴムラテックス（重量平均粒子径０．３５μｍ、固形分５０％）を得た。得られたポリブタジエンゴムラテックス、スチレンおよびメタクリル酸メチルを表１に示したモノマー組成で公知の乳化重合法に基づきグラフト重合した。その後、得られたグラフト共重合体ラテックスを塩析、脱水、乾燥を経てグラフト共重合体（ａ−１−１）を得た。また、表１に示すモノマー組成に変更した以外は同様にしてグラフト共重合体（ａ−１−２、３）を得た。
【００１７】
共重合体（ａ−２−１〜３）：窒素置換した反応器に、表２に示したモノマー組成でスチレン、メタクリル酸メチル、ベンゾイルパーオキサイド（開始剤）０．３部、ノルマルルドデシルメルカプタン（分子量調整剤）０．３部を仕込み、７０℃で公知の塊状重合法により共重合体（ａ−２−１）を得た。また、表２に示すモノマー組成に変更した以外は同様にして共重合体（ａ−２−２〜４）を得た。
【００１８】
フェノール系安定剤（Ｂ−１）：パラクレゾールジサイクロペンタジエンブチール化合物〔Ｇｏｏｄ Ｙｅａｒ社製 商品名：Ｗｉｎｇｓｔａｙ Ｌ〕
【００１９】
フェノール系安定剤（Ｂ−ｉ）：Ｎ−オクタデシル−３−（３，５−ジターシャリーブチル−４−ヒドロキシフェニル）プロピオネ-ト〔共同薬品（株）製 商品名：スミライザーＢＰ−７６〕
【００２０】
［実施例１〜４および比較例１〜３］
上記にて得られたゴム強化スチレン系樹脂（Ａ）（グラフト共重合体（ａ−１）、共重合体（ａ−２）、フェノール系安定剤（Ｂ）を表３に示す配合比率（表中の単位は重量部）で混合したのち、押出機で溶融混練し、各種樹脂組成物を得た。得られた樹脂組成物を、２３０℃に設定した４本ロールを備えたカレンダーシート成形機で２ｍｍ厚のカレンダーシートを成形した。さらに得られたシートにつき下記の評価を行った。結果を表３に示す。
【００２１】
（１）暗所変色性の評価
上記のカレンダーシートから平板試験片（５０ｍｍ×５０ｍｍ×２ｍｍ（厚み））を切り出し、６３℃、雨ありの条件で２４時間、サンシャインウェザーメーターで照射を行い、さらに４５℃、湿度９５％の暗所中で３６時間放置してシート成形体の試験前後の黄変度（ΔＹＩ）を色差計（スガ試験機製）により測定した。ΔＹＩが小さいほど暗所変色性が良好である。
（２）発色性の評価
上記（１）の平板試験片のＬ＊を、色差計の試験片の押さえを白色と黒色のプレートに替えることにより、Ｌ＊の差 ΔＬ＊（＝Ｌ＊（白）−Ｌ＊（黒））を測定し、発色性を評価した。ΔＬ＊が大きいほど発色性が良好である。
【００２２】
【表１】
【表２】
【表３】
【発明の効果】
以上のとおり、本発明におけるカレンダーシート用樹脂組成物を使用して得られたカレンダーシート成形体は発色性、暗所変色性に優れるものであり、このような性能が要求される用途に好適に使用することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a calender sheet resin composition having excellent color developability and dark discoloration, and a calender sheet molded article formed by molding the resin composition.
[0002]
[Prior art]
Calendar molding is a molding method useful for making sheets or film products, and is applied to molding wallpaper and skin materials. After calendering, products are often stored for a long period of time, and there is a problem of dark place discoloration that changes to yellow when stored in a dark place such as a warehouse.
In order to solve such problems, Japanese Patent Application Laid-Open No. 2000-319495 proposes a method of improving by combining a flame retardant and a stabilizer, but is limited to a flame retardant PC / ABS alloy, and is therefore versatile. It was difficult to obtain a calender sheet molding excellent in discoloration in the dark place.
At the same time, from the viewpoints of design and product design, it is required to have excellent color developability during coloring and at the same time high impact strength.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a resin composition for a calender sheet excellent in color developability and dark discoloration, and a calender sheet molding formed by molding the resin composition.
[0004]
[Means for Solving the Problems]
That is, the present invention
(1) Rubber reinforcement comprising a rubber-like polymer, an aromatic vinyl compound and an unsaturated carboxylic acid alkyl ester compound and, if necessary, at least 20% by weight of an unsaturated carboxylic acid alkyl ester compound comprising a vinyl cyanide compound. A resin composition for a calendar sheet obtained by adding 0.01 to 1 part by weight of a paracresol dicyclopentadiene butyle compound as a phenol-based stabilizer (B) to 100 parts by weight of a styrene resin (A),
(2) The rubber-reinforced styrene resin (A) is 20 to 50% by weight of an aromatic vinyl compound, 50 to 80% by weight of an unsaturated carboxylic acid alkyl ester compound and 0 to 30 of a vinyl cyanide compound in the presence of a rubbery polymer. 10 to 90 parts by weight of a graft polymer (a-1) obtained by polymerizing a monomer consisting of 10% by weight, 20 to 80% by weight of an aromatic vinyl compound, 20 to 80% by weight of an unsaturated carboxylic acid alkyl ester compound and cyan A resin composition for a calendar sheet according to (1), comprising a copolymer (a-2) obtained by polymerizing a monomer comprising 0 to 30% by weight of a vinyl fluoride compound;
(3) The rubber-reinforced styrene-based resin (A) is 60 to 80% by weight of an aromatic vinyl compound, 20 to 40% by weight of a vinyl cyanide compound, and an unsaturated carboxylic acid alkyl ester compound 0 to 20 in the presence of a rubber-like polymer. 10 to 90 parts by weight of a graft polymer (a-1) obtained by polymerizing a monomer consisting of 10% by weight, 20 to 50% by weight of an aromatic vinyl compound, 50 to 80% by weight of an unsaturated carboxylic acid alkyl ester compound, and cyan A resin composition for a calendar sheet according to (1), comprising 90 to 10 parts by weight of a copolymer (a-2) obtained by polymerizing a monomer comprising 0 to 30% by weight of a vinyl chloride compound;
(4) A calendar sheet molded body obtained by calendar molding of the resin composition described in (1) to (3) is provided.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The rubber-reinforced styrene resin (A) in the present invention comprises at least an unsaturated carboxylic acid alkyl ester compound comprising a rubber-like polymer, an aromatic vinyl compound and an unsaturated carboxylic acid alkyl ester compound, and optionally a vinyl cyanide compound. Is a rubber-reinforced styrene resin containing 20% by weight. In particular, the rubber-reinforced styrenic resin (A) contains 20 to 50% by weight of an aromatic vinyl compound, 50 to 80% by weight of an unsaturated carboxylic acid alkyl ester compound, and a vinyl cyanide compound 0 to 30 in the presence of a rubbery polymer. 10 to 90 parts by weight of a graft polymer (a-1) obtained by polymerizing a monomer consisting of 10% by weight, 20 to 80% by weight of an aromatic vinyl compound, 20 to 80% by weight of an unsaturated carboxylic acid alkyl ester compound and cyan A copolymer (a-2) formed by polymerizing a monomer comprising 0 to 30% by weight of a vinyl fluoride compound, or 60 to 80% by weight of an aromatic vinyl compound in the presence of a rubbery polymer, cyanide Graft polymer (a-1) 1 obtained by polymerizing a monomer comprising 20 to 40% by weight of a vinyl fluoride compound and 0 to 20% by weight of an unsaturated carboxylic acid alkyl ester compound -90 parts by weight, and a copolymer obtained by polymerizing a monomer comprising 20 to 50% by weight of an aromatic vinyl compound, 50 to 80% by weight of an unsaturated carboxylic acid alkyl ester compound and 0 to 30% by weight of a vinyl cyanide compound (A-2) What consists of 90-10 weight part is preferable.
[0006]
As described above, the rubber-reinforced styrene-based resin (A) in the present invention needs to contain at least 20% by weight of an unsaturated carboxylic acid alkyl ester compound, and if the content is less than 20% by weight, This is not preferable because the color developability and dark discoloration deteriorate. The upper limit of the unsaturated carboxylic acid alkyl ester compound content is not particularly limited, but the upper limit is about 90% by weight in consideration of characteristics as a rubber-reinforced styrene resin.
[0007]
Rubber-like polymers used in the rubber-reinforced styrene resin (A) are polybutadiene, butadiene-styrene copolymer (SBR), butadiene-acrylonitrile copolymer (NBR), butadiene-acrylic acid ester copolymer, and the like. Olefin rubber such as diene rubber, ethylene-propylene copolymer (EPR), ethylene-propylene-nonconjugated diene copolymer (EPDM), acrylic rubber such as polybutyl acrylate and poly 2-ethylhexyl acrylate, silicone rubber And silicone rubber such as silicon-acrylic composite rubber. Particularly preferred is polybutadiene or ethylene-propylene-nonconjugated diene copolymer.
[0008]
Examples of the aromatic vinyl compound include styrene, α-methyl styrene, ο-methyl styrene, p-methyl styrene, ο-ethyl styrene, p-ethyl styrene and the like, and these may be used alone or in combination of two or more. it can. Of these, styrene is particularly preferable.
[0009]
Examples of unsaturated carboxylic acid alkyl ester compounds include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl acrylate, Pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, n-nonyl acrylate, isononyl acrylate, etc. And can be used alone or in combination of two or more. In particular, methyl methacrylate is preferred.
[0010]
Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, and chloroacrylonitrile, which can be used alone or in combination of two or more. Of these, acrylonitrile is particularly preferred.
[0011]
The phenol-based stabilizer (B) [paracresol dicyclopentadiene butyrate compound] used in the present invention has a steric hindrance structure (hindered) and preferably has an average molecular weight of 500 or more, for example, p-cresol and dicyclopentadiene. A butylated reaction product (trade name: Good Year, product name: Wingstay L) is exemplified.
[0012]
The addition amount of the phenol-based stabilizer (B) [paracresol dicyclopentadiene butyrate compound] in the present invention is 0.01 to 1 part by weight with respect to 100 parts by weight of the rubber-reinforced styrene resin (A). When the addition amount is less than 0.01 parts by weight, the color development property and darkness discoloration of the calendered sheet are inferior, and even if the addition amount is increased beyond 1 part by weight, no further effect is obtained, and economical efficiency is improved. It is not preferable from the viewpoint.
[0013]
The method for producing the rubber-reinforced styrene resin (A) is not particularly limited, and an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution polymerization method, and the like can be applied. It can be used as appropriate. Further, the method for adding the phenol stabilizer (B) is not particularly limited, and is a method of adding at the time of melt kneading or a rubber-reinforced styrene resin prepared by an emulsion polymerization method after preparing an emulsion with a known emulsifier. It is also possible to add it by latex blending with (A).
[0014]
Further, the resin composition in the present invention includes, as necessary, a lubricant, an antioxidant, talc, an alkali metal hydroxide or carbonate, a pigment, a plasticizer, an ultraviolet absorber, a light stabilizer and the like. One or more known additives may be mixed. Furthermore, you may use in combination with 1 type (s) or 2 or more types, such as another thermoplastic resin, for example, a polycarbonate, polyamide, polybutylene terephthalate.
[0015]
The resin composition in the present invention obtained above is used as a resin composition for a calendar sheet. Here, as a calendering method, a method using a normal two-roll, three-roll or four-roll can be adopted, and it can be suitably used as a calender sheet molding.
[0016]
【Example】
-Rubber reinforced styrene resin (A)-
Graft copolymer (a-1-1-3): 100 parts of butadiene, 2.5 parts of potassium rosinate (emulsifier), 0.3 parts of potassium persulfate (initiator), normal dodecyl mercaptan in a nitrogen-substituted reactor (Molecular weight adjusting agent) 0.3 part and 100 parts of deionized water were charged, and polymerization was carried out at 60 ° C. After completion of the polymerization, the residual monomer was recovered under vacuum at 600 mmHg to obtain a polybutadiene rubber latex (weight average particle size 0.35 μm, solid content 50%). The obtained polybutadiene rubber latex, styrene and methyl methacrylate were graft-polymerized with the monomer composition shown in Table 1 based on a known emulsion polymerization method. Thereafter, the obtained graft copolymer latex was salted out, dehydrated and dried to obtain a graft copolymer (a-1-1). Moreover, except having changed into the monomer composition shown in Table 1, the graft copolymer (a-1-2, 3) was obtained similarly.
[0017]
Copolymer (a-2-1-3): Styrene, methyl methacrylate, 0.3 parts of benzoyl peroxide (initiator), normal-dodecyl mercaptan with the monomer composition shown in Table 2 in a nitrogen-substituted reactor (Molecular weight adjusting agent) 0.3 part was charged, and a copolymer (a-2-1) was obtained by a known bulk polymerization method at 70 ° C. Moreover, the copolymer (a-2-2-4) was obtained similarly except having changed into the monomer composition shown in Table 2.
[0018]
Phenol-based stabilizer (B-1): paracresol dicyclopentadiene butyle compound [trade name: Wingstay L, manufactured by Good Year)
[0019]
Phenol-based stabilizer (Bi): N-octadecyl-3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate [trade name: Sumilyzer BP-76, manufactured by Kyodo Yakuhin Co., Ltd.]
[0020]
[Examples 1-4 and Comparative Examples 1-3]
The rubber-reinforced styrenic resin (A) obtained above (graft copolymer (a-1), copolymer (a-2), phenolic stabilizer (B) is shown in Table 3 in the mixing ratio (Table The resin was melt kneaded with an extruder to obtain various resin compositions, and a calendar sheet molding machine provided with four rolls set at 230 ° C. A 2 mm-thick calender sheet was molded, and the following evaluation was performed on the obtained sheet, and the results are shown in Table 3.
[0021]
(1) Evaluation of discoloration in the dark place A flat test piece (50 mm × 50 mm × 2 mm (thickness)) was cut out from the above calendar sheet, irradiated with a sunshine weather meter at 63 ° C. for 24 hours under rain, The sheet was left in a dark place at 45 ° C. and 95% humidity for 36 hours, and the yellowing degree (ΔYI) before and after the test of the sheet molded product was measured with a color difference meter (manufactured by Suga Test Instruments). The smaller the ΔYI, the better the dark place discoloration.
(2) Evaluation of color developability L * of the flat plate test piece in (1) above is changed by changing the press of the test piece of the color difference meter to a white and black plate, and the difference of L * ΔL * (= L * (white ) -L * (black)) was measured to evaluate the color developability. The larger ΔL *, the better the color developability.
[0022]
[Table 1]
[Table 2]
[Table 3]
【The invention's effect】
As described above, the calendar sheet molded body obtained using the calendar sheet resin composition of the present invention is excellent in color developability and dark discoloration, and is suitable for applications that require such performance. Can be used.
Claims (4)
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| JP2002064834A JP4093774B2 (en) | 2002-03-11 | 2002-03-11 | RESIN COMPOSITION FOR CALENDAR SHEET AND CALENDAR SHEET MOLDED ARTICLE |
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