JP5858090B2 - Decorative sheet - Google Patents
Decorative sheet Download PDFInfo
- Publication number
- JP5858090B2 JP5858090B2 JP2014103248A JP2014103248A JP5858090B2 JP 5858090 B2 JP5858090 B2 JP 5858090B2 JP 2014103248 A JP2014103248 A JP 2014103248A JP 2014103248 A JP2014103248 A JP 2014103248A JP 5858090 B2 JP5858090 B2 JP 5858090B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- styrene
- resin
- film
- decorative sheet
- 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.)
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 193
- 229920005989 resin Polymers 0.000 claims description 101
- 239000011347 resin Substances 0.000 claims description 101
- 229920001971 elastomer Polymers 0.000 claims description 84
- 239000005060 rubber Substances 0.000 claims description 74
- 229920000578 graft copolymer Polymers 0.000 claims description 51
- -1 aromatic vinyl compound Chemical class 0.000 claims description 45
- 229920002554 vinyl polymer Polymers 0.000 claims description 43
- 239000000178 monomer Substances 0.000 claims description 37
- 229920001577 copolymer Polymers 0.000 claims description 34
- 239000010410 layer Substances 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 26
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- 238000013461 design Methods 0.000 claims description 17
- 239000012790 adhesive layer Substances 0.000 claims description 16
- 229920003244 diene elastomer Polymers 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 150000001993 dienes Chemical class 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 description 40
- 238000000034 method Methods 0.000 description 29
- 238000004519 manufacturing process Methods 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 19
- 229920000126 latex Polymers 0.000 description 19
- 239000004816 latex Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 18
- 230000007547 defect Effects 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 229920000178 Acrylic resin Polymers 0.000 description 14
- 239000004925 Acrylic resin Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000000465 moulding Methods 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 239000003505 polymerization initiator Substances 0.000 description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 11
- 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 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 11
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
- 239000003086 colorant Substances 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 238000007639 printing Methods 0.000 description 9
- 239000005062 Polybutadiene Substances 0.000 description 8
- 229920002857 polybutadiene Polymers 0.000 description 8
- 239000004711 α-olefin Substances 0.000 description 8
- 229920000800 acrylic rubber Polymers 0.000 description 7
- 229920000058 polyacrylate Polymers 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 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 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000008103 glucose Substances 0.000 description 5
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 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 5
- 229940048086 sodium pyrophosphate Drugs 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 5
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 4
- 150000008360 acrylonitriles Chemical class 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 229920005672 polyolefin resin Polymers 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 4
- 239000011115 styrene butadiene Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000002348 vinylic group Chemical group 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-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
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000012461 cellulose resin Substances 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920006249 styrenic copolymer Polymers 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- JVPKLOPETWVKQD-UHFFFAOYSA-N 1,2,2-tribromoethenylbenzene Chemical compound BrC(Br)=C(Br)C1=CC=CC=C1 JVPKLOPETWVKQD-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- LNOKVKHZEYOLIQ-UHFFFAOYSA-N 1-(2,6-diethylphenyl)pyrrole-2,5-dione Chemical compound CCC1=CC=CC(CC)=C1N1C(=O)C=CC1=O LNOKVKHZEYOLIQ-UHFFFAOYSA-N 0.000 description 1
- VMDQUQBEIFMAIC-UHFFFAOYSA-N 1-(2,6-dimethylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC(C)=C1N1C(=O)C=CC1=O VMDQUQBEIFMAIC-UHFFFAOYSA-N 0.000 description 1
- LJDGDRYFCIHDPX-UHFFFAOYSA-N 1-(2-methoxyphenyl)pyrrole-2,5-dione Chemical compound COC1=CC=CC=C1N1C(=O)C=CC1=O LJDGDRYFCIHDPX-UHFFFAOYSA-N 0.000 description 1
- QYOJZFBQEAZNEW-UHFFFAOYSA-N 1-(2-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC=C1N1C(=O)C=CC1=O QYOJZFBQEAZNEW-UHFFFAOYSA-N 0.000 description 1
- BLLFPKZTBLMEFG-UHFFFAOYSA-N 1-(4-hydroxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(O)=CC=C1N1C(=O)C=CC1=O BLLFPKZTBLMEFG-UHFFFAOYSA-N 0.000 description 1
- MKRBAPNEJMFMHU-UHFFFAOYSA-N 1-benzylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1=CC=CC=C1 MKRBAPNEJMFMHU-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- BAWHYOHVWHQWFQ-UHFFFAOYSA-N 1-naphthalen-1-ylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC2=CC=CC=C12 BAWHYOHVWHQWFQ-UHFFFAOYSA-N 0.000 description 1
- NQDOCLXQTQYUDH-UHFFFAOYSA-N 1-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)N1C(=O)C=CC1=O NQDOCLXQTQYUDH-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- LQZDDWKUQKQXGC-UHFFFAOYSA-N 2-(2-methylprop-2-enoxymethyl)oxirane Chemical compound CC(=C)COCC1CO1 LQZDDWKUQKQXGC-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
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- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
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- 239000004797 high-impact polystyrene Substances 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
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- 238000007561 laser diffraction method Methods 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
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- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
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- 150000007524 organic acids Chemical class 0.000 description 1
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- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 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
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- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
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- JZFHXRUVMKEOFG-UHFFFAOYSA-N tert-butyl dodecaneperoxoate Chemical compound CCCCCCCCCCCC(=O)OOC(C)(C)C JZFHXRUVMKEOFG-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Laminated Bodies (AREA)
Description
本発明は、加飾シートに関し、詳しくは、樹脂成形物などの表面加飾に用いられるインサート成形用の加飾シートに関する。 The present invention relates to a decorative sheet, and more particularly, to a decorative sheet for insert molding used for surface decoration such as a resin molded product.
従来、樹脂成形物の表面を加飾した加飾成形品は、加飾シートを射出成形の金型内に配置した後、アクリル系樹脂、ポリカーボネート樹脂、ＡＢＳ樹脂などの溶融樹脂をキャビティ内に射出充填して固化させることにより、樹脂成形物の成形と同時にその表面に加飾シートを接着積層して一体化する方法で製造されている。 Conventionally, a decorative molded product that decorated the surface of a resin molded product, after placing a decorative sheet in an injection mold, inject a molten resin such as acrylic resin, polycarbonate resin, ABS resin into the cavity By filling and solidifying, a decorative sheet is bonded and laminated on the surface at the same time as molding of the resin molded product, and the method is integrated.
通常、加飾シートの裏面（樹脂成形物と密着する面）側には、射出成形する樹脂との密着性や成形性などの点より、同様の樹脂が用いられ、表面側には、意匠性などの点より、アクリル樹脂などの透明性樹脂が用いられ、絵柄意匠も表現するため、表面層と裏面層の間には図柄層が用いられることが多い。 Usually, the same resin is used on the back side (surface that is in close contact with the resin molded product) of the decorative sheet from the viewpoint of adhesion to the resin to be injection-molded and moldability, and the design side is on the front side. In view of the above, a transparent resin such as an acrylic resin is used, and a design is also expressed, so that a design layer is often used between the front surface layer and the back surface layer.
こうした加飾シートとしては、例えば、アクリルフィルム上に図柄が設けられ、その上にアクリロニトリルブタジエンスチレンフィルム（基材フィルム）が積層された絵付インサートフィルムが提案され、そして、上記フィルムのブタジエン含有比率は２０〜５０重量％が好ましいとされている（特許文献１）。 As such a decorative sheet, for example, a picture insert film in which a pattern is provided on an acrylic film and an acrylonitrile butadiene styrene film (base film) is laminated thereon is proposed, and the butadiene content ratio of the film is It is said that 20 to 50 weight% is preferable (patent document 1).
また、透明アクリル樹脂から成る表面シートの裏面に、バインダー樹脂がアクリル樹脂と塩化ビニル−酢酸ビニル共重合体との混合物から成る絵柄インキ層、アクリル樹脂と塩化ビニル−酢酸ビニル共重合体との混合物から成る接着剤層、及び、ブタジエン成分の比率が２０質量％未満のアクリロニトリル−ブタジエン−スチレン共重合体樹脂から成る基材シートを、この順に積層して成る、射出成形同時加飾用シートが提案されている（特許文献２）。 Also, on the back side of the front sheet made of transparent acrylic resin, the binder ink is a pattern ink layer made of a mixture of acrylic resin and vinyl chloride-vinyl acetate copolymer, and a mixture of acrylic resin and vinyl chloride-vinyl acetate copolymer. A sheet for simultaneous injection molding is proposed, in which a base material sheet made of an acrylonitrile-butadiene-styrene copolymer resin having a butadiene component ratio of less than 20% by mass is laminated in this order. (Patent Document 2).
しかしながら、上記のような加飾シートは、加熱した際に基材フィルム（基材シート）に凸状のブツ等が生じるという欠点（加熱欠点）がある。斯かる加熱欠点は、加飾シートを樹脂成形物に積層して加飾成形品とした際、加飾成形品における図柄にゆがみ等の不備をもたらす原因となる。 However, the decorative sheet as described above has a defect (heating defect) in that a convex film or the like is generated on the base film (base sheet) when heated. Such a heating defect causes a defect such as distortion in the design of the decorative molded product when the decorative sheet is laminated on the resin molded product to obtain a decorative molded product.
本発明は、上記実情に鑑みなされたものであり、その目的は、基材フィルムとして、加熱欠点がなく、しかも、樹脂成形物との密着性にも優れ、更には、それ自体の製膜性にも優れる、特定のフィルムを用いた加飾シートを提供することにある。 The present invention has been made in view of the above circumstances, and its purpose is not to have a heating defect as a base film, and is excellent in adhesion to a resin molded product, and further, has its own film forming property. Another object of the present invention is to provide a decorative sheet using a specific film.
すなわち、本発明の要旨は、透明性樹脂フィルムの裏面に図柄層を印刷した印刷フィルムの印刷面に基材フィルムを積層して成る加飾シート、または、透明性樹脂フィルムの裏面に図柄層を印刷した後に更に図柄層の上に接着層を形成した印刷フィルムの接着層面に基材フィルムを積層して成る加飾シートであって、基材フィルムが以下に記載のゴム強化スチレン系樹脂にて構成されていることを特徴とする加飾シートに存する。 That is, the gist of the present invention is that a decorative sheet formed by laminating a base film on the printing surface of a printed film on which the pattern layer is printed on the back surface of the transparent resin film , or a pattern layer on the back surface of the transparent resin film. It is a decorative sheet formed by laminating a base film on the adhesive layer surface of a printed film in which an adhesive layer is further formed on the design layer after printing, and the base film is made of the rubber-reinforced styrene resin described below. It exists in the decoration sheet | seat characterized by being comprised.
［ゴム強化スチレン系樹脂］
グラフト率が５０〜２００％であり且つゴム含有率が５〜５５質量％であるゴム含有スチレン系グラフト重合体（Ｉ）を含有し、ゴム含有率が５〜４０質量％であり且つアセトンに可溶な成分の極限粘度が０．０５〜０．８０ｄｌ／ｇである樹脂。
[Rubber reinforced styrene resin]
Contains a rubber-containing styrene-based graft polymer (I) having a graft ratio of 50 to 200% and a rubber content of 5 to 55% by mass, a rubber content of 5 to 40% by mass and acceptable for acetone. Resin whose intrinsic viscosity of a soluble component is 0.05-0.80 dl / g.
本発明によれば前記の課題が達成される。 According to the present invention, the above-described problems are achieved.
以下、添付図面を参照し本発明を詳細に説明する。本発明の加飾シートは、図１に例示するように、透明性樹脂フィルム（１）と基材フィルム（４）との間に図柄層（２）が配置された構成とされる。また、所望により、図２に例示するように、基材フィルム（４）と図柄層（２）との間に接着剤層（３）を配置することが出来る。 Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. As illustrated in FIG. 1, the decorative sheet of the present invention has a configuration in which a design layer (2) is disposed between a transparent resin film (1) and a base film (4). If desired, an adhesive layer (3) can be disposed between the base film (4) and the design layer (2) as illustrated in FIG.
本発明の好ましい態様においては、基材フィルムは着色フィルムとされる。これにより、インサートフィルムの被着体である樹脂成形物の色を隠蔽したり、図柄層による意匠表現の基調色を表すことが出来る利点がある。 In a preferred embodiment of the present invention, the base film is a colored film. Thereby, there exists an advantage which can conceal the color of the resin molding which is a to-be-adhered body of an insert film, or can represent the base color of the design expression by a design layer.
〔透明性樹脂フィルム〕
透明性樹脂フィルムの透明性はヘイズで表すことが出来る。本発明で用いる透明性樹脂フィルムのヘイズは、通常２０％以下、好ましくは１５％以下、更に好ましくは１０％以下である。透明性樹脂フィルムの厚みは、通常２０〜５００μｍ、好ましくは３０〜４００μｍであり、更に好ましくは４０〜３００μｍである。透明性樹脂フィルムが薄すぎると図柄層の印刷等が困難になりやすく、厚すぎると巻きロールとして製品化するのが困難になりやすい。透明性樹脂フィルムは、通常、無着色であるが、必要に応じ、着色透明にすることも出来る。
[Transparent resin film]
The transparency of the transparent resin film can be represented by haze. The haze of the transparent resin film used in the present invention is usually 20% or less, preferably 15% or less, more preferably 10% or less. The thickness of the transparent resin film is usually 20 to 500 μm, preferably 30 to 400 μm, and more preferably 40 to 300 μm. If the transparent resin film is too thin, it is difficult to print the pattern layer, and if it is too thick, it is difficult to produce a wound roll. The transparent resin film is usually uncolored, but can be colored and transparent as required.
透明性樹脂としては、アクリル樹脂、ポリエステル樹脂、ポリカーボネート樹脂、スチレン系樹脂、ポリオレフィン樹脂などが挙げられ、好ましくはアクリル樹脂である。アクリル樹脂としては、例えば、ポリメチル（メタ）アクリレート、ポリエチル（メタ）アクリレート、ポリブチル（メタ）アクリレート、メチル（メタ）アクリレート−ブチル（メタ）アクリレート共重合体、エチル（メタ）アクリレート−ブチル（メタ）アクリレート共重合体、メチル（メタ）アクリレート−スチレン共重合体などのアクリル樹脂などが挙げられる。これらは２種以上の混合物として用いることも出来る。なお、上記の「（メタ）アクリレート」とはアクリレート又はメタクリレートを意味する。 Examples of the transparent resin include an acrylic resin, a polyester resin, a polycarbonate resin, a styrene resin, and a polyolefin resin, and an acrylic resin is preferable. Examples of the acrylic resin include polymethyl (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, ethyl (meth) acrylate-butyl (meth). Examples thereof include acrylic resins such as acrylate copolymers and methyl (meth) acrylate-styrene copolymers. These can also be used as a mixture of two or more. In addition, said "(meth) acrylate" means an acrylate or a methacrylate.
透明性樹脂フィルムには、透明性を損なわない限り、必要に応じ、滑剤、充填剤、紫外線吸収剤、光安定剤、酸化防止剤、老化防止剤、可塑剤、蛍光増白剤、耐候剤、帯電防止剤、難燃剤、防曇剤、抗菌剤、防かび剤、防汚剤、粘着付与剤などの各種添加剤が配合されていてもよい。 In the transparent resin film, as long as the transparency is not impaired, a lubricant, a filler, an ultraviolet absorber, a light stabilizer, an antioxidant, an anti-aging agent, a plasticizer, a fluorescent whitening agent, a weathering agent, Various additives such as an antistatic agent, a flame retardant, an antifogging agent, an antibacterial agent, an antifungal agent, an antifouling agent, and a tackifier may be blended.
〔図柄層〕
図柄層は、図柄や絵柄などを表現するために印刷などによって形成される。図柄層の材
料は、主に着色剤と樹脂バインダーから成り、必要に応じ、分散剤やワックスが添加される。
[Design layer]
The symbol layer is formed by printing or the like in order to express a symbol or a pattern. The material of the pattern layer is mainly composed of a colorant and a resin binder, and a dispersant and a wax are added as necessary.
着色材としては、カーボンブラック、酸化鉄、モノアゾイエロー等の着色顔料；アルミニウム、亜鉛、銀、銅などの金属粉からなるメタリック顔料；キナクリドンレッド、イソインドリノン、フタロシアニンブルー等の着色剤が挙げられる。 Examples of the colorant include color pigments such as carbon black, iron oxide, and monoazo yellow; metallic pigments made of metal powder such as aluminum, zinc, silver, and copper; and colorants such as quinacridone red, isoindolinone, and phthalocyanine blue. .
樹脂バインダーとしては、アクリル系樹脂、ビニル系樹脂、オレフィン系樹脂、セルロース系樹脂、ウレタン系樹脂、メラミン系樹脂、エポキシ系樹脂、スチレン樹脂、ポリアミド系樹脂などが挙げられる。 Examples of the resin binder include acrylic resins, vinyl resins, olefin resins, cellulose resins, urethane resins, melamine resins, epoxy resins, styrene resins, and polyamide resins.
図柄層の形成方法としては、透明性樹脂フィルムに印刷する方法や塗工する方法などが挙げられる。印刷方法としては、グラビア印刷、シルク印刷、オフセット印刷などが挙げられ、塗工方法としては、リップコーター、リバースコーター、グラビアコーター等が挙げられる。 Examples of the method for forming the pattern layer include a method for printing on a transparent resin film and a method for coating. Examples of the printing method include gravure printing, silk printing, and offset printing. Examples of the coating method include lip coater, reverse coater, and gravure coater.
図柄層の厚さは、通常０．２〜５０μｍ、好ましくは０．３〜３０μｍ、更に好ましくは０．５〜２０μｍである。図柄層厚さが薄すぎると所望の色相に印刷形成し難く、厚すぎると乾燥などに時間が掛かりやすい。また、図柄層は必要に応じて部分的に形成することも出来る。 The thickness of the pattern layer is usually 0.2 to 50 μm, preferably 0.3 to 30 μm, and more preferably 0.5 to 20 μm. If the pattern layer thickness is too thin, it is difficult to form a print with a desired hue, and if it is too thick, it takes time to dry. Moreover, a design layer can also be formed partially as needed.
〔接着剤層〕
接着剤層を構成する樹脂としては、アクリル系樹脂、ビニル系樹脂、オレフィン系樹脂、セルロース系樹脂、ウレタン系樹脂、メラミン系樹脂、エポキシ系樹脂、スチレン樹脂、ポリアミド系樹脂などが挙げられる。
[Adhesive layer]
Examples of the resin constituting the adhesive layer include acrylic resins, vinyl resins, olefin resins, cellulose resins, urethane resins, melamine resins, epoxy resins, styrene resins, and polyamide resins.
接着剤層の厚さは、通常０．１〜３０μｍ、好ましくは０．２〜２０μｍ、更に好ましくは０．５〜１０μｍである。接着剤層の厚さが薄すぎると接着性が得にくく、厚すぎると乾燥などに時間が掛かりやすい。また、生産性が低下する。接着剤層は必要に応じて部分的に形成することも出来る。 The thickness of the adhesive layer is usually 0.1 to 30 μm, preferably 0.2 to 20 μm, more preferably 0.5 to 10 μm. If the thickness of the adhesive layer is too thin, it is difficult to obtain adhesiveness, and if it is too thick, it takes time to dry. In addition, productivity is reduced. The adhesive layer can be partially formed as necessary.
〔基材フィルム〕
本発明の加飾シートは、基材フィルムが特定のゴム強化スチレン系樹脂にて構成されている点に特徴がある。すなわち、基材フィルムは、グラフト率が５０〜２００％であり且つゴム含有率が５〜５５質量％であるゴム含有スチレン系グラフト重合体（Ｉ）、及び、所望により、スチレン系（共）重合体（II）を含有し、ゴム含有率が５〜４０質量％であり且つアセトンに可溶な成分の極限粘度が０．０５〜０．８０ｄｌ／ｇである樹脂にて構成される。上記のゴム強化スチレン系樹脂については、その製造法を含め、後述する、
[Base film]
The decorative sheet of the present invention is characterized in that the base film is composed of a specific rubber-reinforced styrene resin. That is, the base film has a rubber-containing styrene-based graft polymer (I) having a graft ratio of 50 to 200% and a rubber content of 5 to 55% by mass, and, if desired, a styrene-based (co) weight. It is composed of a resin containing the coalescence (II), having a rubber content of 5 to 40% by mass, and an intrinsic viscosity of a component soluble in acetone of 0.05 to 0.80 dl / g. About the rubber-reinforced styrene-based resin, including its production method, described later,
基材フィルムが着色フィルムの場合に用いられる着色剤としては、例えば、黒色顔料や白色顔料が挙げられる。黒色顔料としては、例えば、カーボンブラック、鉄黒などが挙げられ、白色顔料としては、例えば、チタン白、亜鉛華、三酸化二アンチモン等が挙げられる。また、必要に応じ、図柄層の絵柄の基調色となる着色剤を添加することも出来る。この着色剤としては、前記図柄層で述べた公知の各種顔料や染料などを用いることも出来る。 Examples of the colorant used when the base film is a colored film include black pigments and white pigments. Examples of the black pigment include carbon black and iron black. Examples of the white pigment include titanium white, zinc white, and antimony trioxide. Further, if necessary, a colorant that becomes the base color of the design of the design layer can be added. As this colorant, various known pigments and dyes described in the design layer can be used.
カーボンブラック等の着色剤には、例えば、着色剤の分散安定性を高めるため、湿潤・分散剤を少量添加することが出来る。湿潤・分散剤としては、脂肪酸塩、硫酸塩、スルホン酸塩、燐酸塩などのアニオン性化合物、脂肪族アミン塩などのカチオン性化合物、非イオン系化合物、高分子化合物、両性化合物、フッ素系化合物などが挙げられる。 For example, a small amount of a wetting / dispersing agent can be added to the colorant such as carbon black in order to enhance the dispersion stability of the colorant. Wetting / dispersing agents include anionic compounds such as fatty acid salts, sulfates, sulfonates, and phosphates, cationic compounds such as aliphatic amine salts, nonionic compounds, polymer compounds, amphoteric compounds, and fluorine compounds. Etc.
基材フィルムには、前述の透明性樹脂フィルムの場合と同様、必要に応じ、滑剤、充填剤、難燃剤、酸化防止剤、安定剤、帯電防止剤、可塑剤、老化防止剤などの公知の各種添加剤を配合することが出来る。 For the base film, as in the case of the transparent resin film described above, known lubricants, fillers, flame retardants, antioxidants, stabilizers, antistatic agents, plasticizers, anti-aging agents, and the like as necessary. Various additives can be blended.
基材フィルムが着色フィルムの場合、その原料組成物の製造方法としては、ゴム含有スチレン系グラフト重合体（Ｉ）又スチレン系（共）重合体（II）に、着色剤、及び必要に応じて上記添加剤を配合し、溶融混練装置により溶融混練する方法が挙げられる。溶融混練に用いる装置としては、一軸押出機、二軸押出機、バンバリーミキサー、ニーダー、連続ニーダー等が挙げられる。溶融混練の温度は、通常１９０〜２６０℃程度である。基材フィルムを得るための押出成形の温度は、通常１９０〜２６０℃程度である。 When the base film is a colored film, the raw material composition can be produced by using a rubber-containing styrene-based graft polymer (I) or styrene-based (co) polymer (II), a colorant, and if necessary. The method of mix | blending the said additive and melt-kneading with a melt-kneading apparatus is mentioned. Examples of the apparatus used for melt kneading include a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, and a continuous kneader. The temperature of melt kneading is usually about 190 to 260 ° C. The temperature of extrusion molding for obtaining the base film is usually about 190 to 260 ° C.
基材フィルムの厚みは、成形性などの点より、通常２０〜１０００μｍ、好ましくは３０〜８００μｍ、更に好ましくは５０〜６００μｍである。基材フィルムの表面や裏面などの他層と接する面には、他層との密着性を向上させるため、コロナ放電処理、プラズマ処理、プライマー塗工などの易接着処理を施すことが出来る。 The thickness of the base film is usually 20 to 1000 μm, preferably 30 to 800 μm, and more preferably 50 to 600 μm from the viewpoint of moldability. In order to improve the adhesion with the other layer, the surface of the base film such as the front surface and the back surface can be subjected to easy adhesion treatment such as corona discharge treatment, plasma treatment, and primer coating.
〔ゴム強化スチレン系樹脂〕
本発明では、前述の通り、グラフト率が５０〜２００％であり且つゴム含有率が５〜５５質量％であるゴム含有スチレン系グラフト重合体（Ｉ）、及び、所望により、スチレン系（共）重合体（II）を含有し、ゴム含有率が５〜４０質量％であり且つアセトンに可溶な成分の極限粘度が０．０５〜０．８０ｄｌ／ｇである樹脂を用いる。
[Rubber reinforced styrene resin]
In the present invention, as described above, the rubber-containing styrene-based graft polymer (I) having a graft ratio of 50 to 200% and a rubber content of 5 to 55% by mass, and, if desired, a styrene-based (co) A resin containing the polymer (II), having a rubber content of 5 to 40% by mass, and having an intrinsic viscosity of a component soluble in acetone of 0.05 to 0.80 dl / g is used.
ゴム強化スチレン系樹脂としては、ゴム質重合体（ａ）の存在下に芳香族ビニル化合物を含むビニル系単量体（ｂ１）を重合させてなるゴム含有スチレン系グラフト重合体、並びに、ゴム含有スチレン系グラフト重合体及び芳香族ビニル化合物を含むビニル系単量体（ｂ２）を重合させてなるスチレン系（共）重合体の混合物が挙げられる。 Examples of the rubber-reinforced styrene resin include a rubber-containing styrene-based graft polymer obtained by polymerizing a vinyl monomer (b1) containing an aromatic vinyl compound in the presence of the rubber-like polymer (a), and a rubber-containing polymer. Examples thereof include a mixture of a styrene-based (co) polymer obtained by polymerizing a styrene-based graft polymer and a vinyl monomer (b2) containing an aromatic vinyl compound.
ゴム含有スチレン系グラフト重合体（Ｉ）には、通常、芳香族ビニル化合物を含むビニル系単量体（ｂ１）がゴム質重合体（ａ）にグラフト共重合したグラフト共重合体と、ゴム質重合体（ａ）にグラフトしていない未グラフト成分、すなわち、残部のビニル系単量体（ｂ１）による（共）重合体とが含まれる。ゴム含有スチレン系グラフト重合体（Ｉ）は２種以上を組み合わせて用いることも出来る。 The rubber-containing styrene-based graft polymer (I) usually includes a graft copolymer in which a vinyl monomer (b1) containing an aromatic vinyl compound is graft-copolymerized with the rubber-like polymer (a), and rubber The ungrafted component which is not grafted to the polymer (a), that is, the (co) polymer by the remaining vinyl monomer (b1) is included. Two or more rubber-containing styrene-based graft polymers (I) can be used in combination.
ゴム強化スチレン系樹脂ゴム含有率は、加熱欠点の発生防止、密着性、機械的物性などの点より、５〜４０質量％、好ましくは８〜３８質量％、更に好ましくは１５〜３６質量％、特に好ましくは２１〜３５質量％である。ゴム強化スチレン系樹脂が、ゴム含有スチレン系グラフト重合体からなる場合、並びに、ゴム含有スチレン系グラフト重合体及びスチレン系（共）重合体の混合物からなる場合、の何れにおいても、ゴム強化スチレン系樹脂（Ｉ）のゴム含有率は、ゴム含有スチレン系グラフト重合体（Ｉ）の重合処方の条件や重合転化率から算出し、更に、ゴム含有スチレン系グラフト重合体（Ｉ）とスチレン系（共）重合体（II）との配合比率から求める法、熱分解ガスクロマトグラフィー（ＰｙＧＣ）により求める方法、赤外線吸収スペクトル（ＩＲ）により求める方法等により得ることが出来る。 The rubber-reinforced styrene-based resin rubber content is 5 to 40% by mass, preferably 8 to 38% by mass, more preferably 15 to 36% by mass, from the viewpoints of prevention of heating defects, adhesion, mechanical properties, and the like. Most preferably, it is 21-35 mass%. In both cases where the rubber-reinforced styrene resin is made of a rubber-containing styrene-based graft polymer and a mixture of a rubber-containing styrene-based graft polymer and a styrene-based (co) polymer, the rubber-reinforced styrene-based resin is used. The rubber content of the resin (I) is calculated from the polymerization prescription conditions and the polymerization conversion rate of the rubber-containing styrene-based graft polymer (I). Further, the rubber-containing styrene-based graft polymer (I) and the styrene-based (co-polymer) ) Obtained from the blending ratio with the polymer (II), obtained by pyrolysis gas chromatography (PyGC), obtained by infrared absorption spectrum (IR), and the like.
ゴム強化スチレン系樹脂のアセトンに可溶な成分の極限粘度［η］（メチルエチルケトン中３０℃で測定）は、押出性、成形加工性、密着性などの点より、０．０５〜０．８０ｄｌ／ｇ、好ましくは０．０７〜０．７０ｄｌ／ｇ、更に好ましくは０．０９〜０．６０ｄｌ／ｇ、特に好ましくは０．１２〜０．５５ｄｌ／ｇである。 The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the rubber-reinforced styrene resin-soluble component is 0.05 to 0.80 dl / from the viewpoint of extrudability, molding processability, adhesion and the like. g, preferably 0.07 to 0.70 dl / g, more preferably 0.09 to 0.60 dl / g, and particularly preferably 0.12 to 0.55 dl / g.
極限粘度［η］は、以下の要領で求めることが出来る。ゴム強化スチレン系樹脂が、ゴム含有スチレン系グラフト重合体からなる場合、並びに、ゴム含有スチレン系グラフト重合体及びスチレン系（共）重合体の混合物からなる場合、の何れにおいても、ゴム強化スチレン系樹脂をアセトンに溶解し、遠心分離後に回収されたアセトン可溶分をメチルエチルケトンに溶解させ、濃度の異なるものを５点調製し、ウベローデ粘度管のより、３０℃で各濃度の還元粘度を測定し、極限粘度［η］を求める。 The intrinsic viscosity [η] can be determined in the following manner. In both cases where the rubber-reinforced styrene resin is made of a rubber-containing styrene-based graft polymer and a mixture of a rubber-containing styrene-based graft polymer and a styrene-based (co) polymer, the rubber-reinforced styrene-based resin is used. Dissolve the resin in acetone, dissolve the acetone-soluble matter recovered after centrifugation in methyl ethyl ketone, prepare 5 samples with different concentrations, and measure the reduced viscosity at each concentration at 30 ° C from the Ubbelohde viscosity tube. Determine the intrinsic viscosity [η].
ゴム強化スチレン系樹脂のアセトンに可溶な成分の極限粘度［η］は、グラフト共重合体及びスチレン系（共）重合体を製造する際に用いる、重合開始剤、連鎖移動剤、乳化剤、溶剤などの種類や量、更には、重合時間、重合温度などを調節することにより、制御することが出来る。ゴム強化スチレン系樹脂の極限粘度［η］は、極限粘度［η］が互いに異なるゴム含有スチレン系グラフト重合体及びスチレン系（共）重合体を適宜に選択することにより調節することも出来る。 The intrinsic viscosity [η] of the rubber-reinforced styrene resin-soluble component is the polymerization initiator, chain transfer agent, emulsifier, solvent used in the production of the graft copolymer and styrene (co) polymer. It is possible to control by adjusting the kind and amount of the above, and the polymerization time and polymerization temperature. The intrinsic viscosity [η] of the rubber-reinforced styrene resin can be adjusted by appropriately selecting rubber-containing styrene graft polymers and styrene (co) polymers having different intrinsic viscosities [η].
ゴム含有スチレン系グラフト重合体（Ｉ）のゴム含有量は、加熱欠点の発生防止や機械的物性の点より、５〜５５質量％、好ましくは７〜５３質量％、更に好ましくは９〜５１質量％である。ゴム含有スチレン系グラフト重合体（Ｉ）のゴム含有率は、重合処方及び重合転化率から算出する方法、熱分解ガスクロマトクラフィー（ＰｙＧＣ）、赤外線吸収スペクトル（ＩＲ）により求める方法などにより得ることが出来る。 The rubber content of the rubber-containing styrene-based graft polymer (I) is 5 to 55% by mass, preferably 7 to 53% by mass, and more preferably 9 to 51% by mass from the viewpoint of preventing the occurrence of heating defects and mechanical properties. %. The rubber content of the rubber-containing styrene-based graft polymer (I) can be obtained by a method of calculating from a polymerization prescription and a polymerization conversion rate, a method of obtaining by pyrolysis gas chromatography (PyGC), infrared absorption spectrum (IR), and the like. I can do it.
ゴム含有スチレン系グラフト重合体（Ｉ）の形成に用いられるゴム質重合体（ａ）は、室温でゴム質であれば、特に限定されず、単独重合体及び共重合体の何れでもよい。また、このゴム質重合体（ａ）は架橋重合体及び非架橋重合体の何れでもよい。 The rubbery polymer (a) used for forming the rubber-containing styrene-based graft polymer (I) is not particularly limited as long as it is rubbery at room temperature, and may be either a homopolymer or a copolymer. The rubbery polymer (a) may be a crosslinked polymer or a non-crosslinked polymer.
ゴム質重合体（ａ）としては、例えば、共役ジエン系ゴム、水添共役ジエン系ゴム、エチレン・α−オレフィン系共重合体ゴム、アクリル系ゴム、シリコーンゴム、シリコーン・アクリル複合ゴム等が挙げられる。これらは２種以上を組み合わせて用いることも出来る。耐衝撃性の観点からは、共役ジエン系ゴムが好ましく、耐候性の観点からは、アクリル系ゴム、シリコーンゴム、シリコーン・アクリル複合ゴム、エチレン・α−オレフィン系共重合体ゴム及び水添共役ジエン系ゴムが好ましい。 Examples of the rubbery polymer (a) include conjugated diene rubber, hydrogenated conjugated diene rubber, ethylene / α-olefin copolymer rubber, acrylic rubber, silicone rubber, and silicone / acrylic composite rubber. It is done. These may be used in combination of two or more. From the viewpoint of impact resistance, conjugated diene rubbers are preferred, and from the viewpoint of weather resistance, acrylic rubber, silicone rubber, silicone / acrylic composite rubber, ethylene / α-olefin copolymer rubber and hydrogenated conjugated diene are used. System rubber is preferred.
ゴム質重合体（ａ）の形状は、例えば、粒子状（球状、略球状）、直線状、曲線状などとすることが出来る。粒子状である場合、その体積平均粒子径は、機械的物性や加工性の点より、通常５〜２，０００ｎｍ、好ましくは１０〜１，５００ｎｍ、更に好ましくは５０〜１，２００ｎｍである。上記体積平均粒子径は、電子顕微鏡写真を用いた画像解析、レーザー回折法、光散乱法などにより測定することが出来る。 The shape of the rubber polymer (a) can be, for example, particulate (spherical or substantially spherical), linear, curved or the like. When it is in the form of particles, the volume average particle diameter is usually 5 to 2,000 nm, preferably 10 to 1,500 nm, more preferably 50 to 1,200 nm, from the viewpoint of mechanical properties and processability. The volume average particle diameter can be measured by image analysis using an electron micrograph, a laser diffraction method, a light scattering method, or the like.
ゴム質重合体（ａ）の体積平均粒子径は、例えば、１００〜４００ｎｍ程度の比較的小粒子径のゴム質重合体と４００〜１２００ｎｍ程度の比較的大粒子径のゴム質重合体とを併用することにより調節することも出来る。併用する場合、比較的小粒子径のゴム質重合体と比較的大粒子径のゴム質重合体との配合割合は、通常６０〜９９／４０〜１、好ましくは７０〜９５／３０〜５である。 The volume average particle size of the rubber polymer (a) is, for example, a combination of a rubber polymer having a relatively small particle size of about 100 to 400 nm and a rubber polymer having a relatively large particle size of about 400 to 1200 nm. You can also adjust it. When used in combination, the blending ratio of the rubber polymer having a relatively small particle diameter and the rubber polymer having a relatively large particle diameter is usually 60 to 99/40 to 1, preferably 70 to 95/30 to 5. is there.
共役ジエン系ゴムとしては、ポリブタジエン、ブタジエン・スチレンランダム共重合体、ブタジエン・スチレンブロック共重合体、ブタジエン・アクリロニトリル共重合体などが挙げられる。これらは２種以上を組み合わせて用いることが出来る。共役ジエン系ゴムのガラス転移温度は、可撓性、低温衝撃性などの観点から、通常−２０℃以下である。 Examples of the conjugated diene rubber include polybutadiene, butadiene / styrene random copolymer, butadiene / styrene block copolymer, butadiene / acrylonitrile copolymer, and the like. These can be used in combination of two or more. The glass transition temperature of the conjugated diene rubber is usually −20 ° C. or less from the viewpoints of flexibility, low temperature impact property and the like.
水添共役ジエン系ゴムとしては、共役ジエン系化合物に由来する構造単位を含む（共）重合体を水素添加してなる（共）重合体であれば、特に限定されず、例えば、水添ポリブ
タジエン、水添スチレン・ブタジエンゴム、スチレン・エチレンブチレン・オレフィン結晶ブロックポリマー、オレフィン結晶・エチレンブチレン・オレフィン結晶ブロックポリマー、スチレン・エチレンブチレン・スチレンブロックポリマー、ブタジエン・アクリロニトリル共重合体の水素添加物などが挙げられる。
The hydrogenated conjugated diene rubber is not particularly limited as long as it is a (co) polymer obtained by hydrogenating a (co) polymer containing a structural unit derived from a conjugated diene compound, for example, hydrogenated polybutadiene. Hydrogenated styrene / butadiene rubber, styrene / ethylene butylene / olefin crystal block polymer, olefin crystal / ethylene butylene / olefin crystal block polymer, styrene / ethylene butylene / styrene block polymer, hydrogenated butadiene / acrylonitrile copolymer, etc. Can be mentioned.
アクリル系ゴムとしては、アルキル基の炭素数が２〜８のアクリル酸アルキルエステルに由来する構造単位の割合が上記アクリル系ゴムを構成する構造単位の全量に対して８０質量％以上である（共）重合体が好ましい。 As an acrylic rubber, the proportion of structural units derived from an alkyl acrylate ester having 2 to 8 carbon atoms in the alkyl group is 80% by mass or more based on the total amount of structural units constituting the acrylic rubber (both ) A polymer is preferred.
アルキル基の炭素数が２〜８のアクリル酸アルキルエステルとしては、アクリル酸エチル、アクリル酸プロピル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸ヘキシル、アクリル酸ｎ−オクチル、アクリル酸２−エチルヘキシル等が挙げられ、好ましくは、アクリル酸ｎ−ブチル、アクリル酸イソブチル及びアクリル酸２−エチルヘキシルである。これらは２種以上を組み合わせて用いることも出来る。 Examples of the alkyl acrylate having 2 to 8 carbon atoms in the alkyl group include ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, n-octyl acrylate, and 2-ethylhexyl acrylate. Preferred are n-butyl acrylate, isobutyl acrylate and 2-ethylhexyl acrylate. These may be used in combination of two or more.
アクリル系ゴムが他の単量体に由来する構造単位を含む場合、他の単量体としては、アクリロニトリル、ビニルエステル、メタクリル酸アルキルエステル、（メタ）アクリル酸、スチレン等の単官能性単量体；エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート等のモノ又はポリエチレングリコールジ（メタ）アクリレート、ジビニルベンゼン、ジアリルフタレート、ジアリルマレエート、ジアリルサクシネート、トリアリルトリアジン等のジ又はトリアリル化合物などの架橋性単量体などが挙げられる。架橋性単量体に由来する構造単位の含有量は、構造単位の全量に対し、通常０．０１〜１０質量％程度である。アクリル系ゴムの好ましい製造方法は乳化重合法である。 When the acrylic rubber contains a structural unit derived from another monomer, the other monomer may be a monofunctional unit such as acrylonitrile, vinyl ester, methacrylic acid alkyl ester, (meth) acrylic acid, styrene, etc. Body: Mono- or polyethylene glycol di (meth) acrylate such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, divinylbenzene, diallyl Examples thereof include crosslinkable monomers such as di- or triallyl compounds such as phthalate, diallyl maleate, diallyl succinate and triallyl triazine. Content of the structural unit derived from a crosslinkable monomer is about 0.01-10 mass% normally with respect to the whole quantity of a structural unit. A preferred method for producing the acrylic rubber is an emulsion polymerization method.
シリコーンゴムはラテックス状のゴムが好ましく、その一例としては、米国特許第２，８９１，９２０号明細書、米国特許第３，２９４，７２５号明細書などに記載された方法により製造されたポリオルガノシロキサン系ゴムが挙げられる。 The silicone rubber is preferably a latex rubber, and examples thereof include polyorgano produced by the methods described in US Pat. No. 2,891,920, US Pat. No. 3,294,725, and the like. A siloxane rubber is mentioned.
シリコーン・アクリル複合ゴムは、ポリオルガノシロキサンゴムとポリアルキル（メタ）アクリレート系ゴムを含有するゴム質重合体である。好ましいシリコーン・アクリル複合ゴムは、ポリオルガノシロキサンゴム及びポリアルキル（メタ）アクリレート系ゴムが分離できないように相互に絡み合った構造を有する複合ゴムである。 Silicone / acrylic composite rubber is a rubbery polymer containing polyorganosiloxane rubber and polyalkyl (meth) acrylate rubber. A preferable silicone-acrylic composite rubber is a composite rubber having a structure in which polyorganosiloxane rubber and polyalkyl (meth) acrylate rubber are intertwined with each other so that they cannot be separated.
シリコーン・アクリル複合ゴムは、例えば、特開平４−２３９０１０号公報、特開平４−１００８１２号公報などに記載された方法で製造することが出来る。 Silicone / acrylic composite rubber can be produced, for example, by the methods described in JP-A-4-239010, JP-A-4-100812, and the like.
エチレン・α−オレフィン系共重合体ゴムは、エチレン単位と、炭素数３以上のα−オレフィンからなる単位を含む共重合体であり、エチレン・α−オレフィン共重合体、エチレン・α−オレフィン・非共役ジエン共重合体などが挙げられる。 The ethylene / α-olefin copolymer rubber is a copolymer including an ethylene unit and a unit composed of an α-olefin having 3 or more carbon atoms, and includes an ethylene / α-olefin copolymer, an ethylene / α-olefin copolymer, Non-conjugated diene copolymers are exemplified.
エチレン・α−オレフィン共重合体としては、エチレン・プロピレン共重合体、エチレン・ブテン−１共重合体などが挙げられる。また、エチレン・α−オレフィン・非共役ジエン共重合体としては、エチレン・プロピレン・非共役ジエン共重合体、エチレン・ブテン−１・非共役ジエン共重合体などが挙げられる。 Examples of the ethylene / α-olefin copolymer include an ethylene / propylene copolymer and an ethylene / butene-1 copolymer. Examples of the ethylene / α-olefin / non-conjugated diene copolymer include an ethylene / propylene / non-conjugated diene copolymer and an ethylene / butene-1 / non-conjugated diene copolymer.
ゴム含有スチレン系グラフト重合体（Ｉ）の製造に用いられるビニル系単量体（ｂ１）は芳香族ビニル化合物を含む。すなわち、このビニル系単量体（ｂ１）は、芳香族ビニル化合物のみからなるものであってよいし、芳香族ビニル化合物及びこの化合物と共重合可
能な他の単量体からなるものであってもよい。他の単量体としては、シアン化ビニル化合物、（メタ）アクリル酸エステル化合物、マレイミド系化合物、不飽和酸無水物、カルボキシル基含有不飽和化合物、ヒドロキシル基含有不飽和化合物、エポキシ基含有不飽和化合物、オキサゾリン基含有不飽和化合物などが挙げられる。これらは２種以上を組み合わせて用いることも出来る。
The vinyl monomer (b1) used for the production of the rubber-containing styrene graft polymer (I) contains an aromatic vinyl compound. That is, the vinyl monomer (b1) may be composed only of an aromatic vinyl compound, or composed of an aromatic vinyl compound and another monomer copolymerizable with this compound. Also good. Other monomers include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, and epoxy group-containing unsaturated compounds. Compounds, oxazoline group-containing unsaturated compounds, and the like. These may be used in combination of two or more.
芳香族ビニル化合物は、少なくとも１つのビニル結合と、少なくとも１つの芳香族環とを有する化合物であれば、特に限定されない。その例としては、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｐ−メチルスチレン、β−メチルスチレン、エチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、ビニルトルエン、ビニルキシレン、ビニルナフタレン、モノクロロスチレン、ジクロロスチレン、モノブロモスチレン、ジブロモスチレン、トリブロモスチレン、フルオロスチレン等が挙げられる。これらは２種以上を組み合わせて用いることも出来る。また、これらの中では、スチレン及びα−メチルスチレンが好ましく、特にスチレンが好ましい。 The aromatic vinyl compound is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. Examples thereof include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene, monochlorostyrene, dichloromethane. Examples thereof include styrene, monobromostyrene, dibromostyrene, tribromostyrene, and fluorostyrene. These may be used in combination of two or more. Of these, styrene and α-methylstyrene are preferable, and styrene is particularly preferable.
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、エタクリロニトリル、α−エチルアクリロニトリル、α−イソプロピルアクリロニトリル、α−クロロアクリロニトリル、α−フルオロアクリロニトリル等が挙げられる。これらは２種以上を組み合わせて用いことも出来る。これらの中ではアクリロニトリルが好ましい。 Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile and the like. These can also be used in combination of two or more. Of these, acrylonitrile is preferred.
（メタ）アクリル酸エステル化合物としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓｅｃ−ブチル、（メタ）アクリル酸ｔｅｒｔ−ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ｎ−オクチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸フェニル、（メタ）アクリル酸ベンジル等が挙げられる。これらは２種以上を組み合わせて用いることも出来る。 Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( (Meth) acrylic acid isobutyl, (meth) acrylic acid sec-butyl, (meth) acrylic acid tert-butyl, (meth) acrylic acid hexyl, (meth) acrylic acid n-octyl, (meth) acrylic acid 2-ethylhexyl, ( Examples thereof include cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and the like. These may be used in combination of two or more.
マレイミド系化合物としては、マレイミド、Ｎ−メチルマレイミド、Ｎ−イソプロピルマレイミド、Ｎ−ブチルマレイミド、Ｎ−ドデシルマレイミド、Ｎ−フェニルマレイミド、Ｎ−（２−メチルフェニル）マレイミド、Ｎ−（４−メチルフェニル）マレイミド、Ｎ−（２、６−ジメチルフェニル）マレイミド、Ｎ−（２、６−ジエチルフェニル）マレイミド、Ｎ−（２−メトキシフェニル）マレイミド、Ｎ−ベンジルマレイミド、Ｎ−（４−ヒドロキシフェニル）マレイミド、Ｎ−ナフチルマレイミド、Ｎ−シクロヘキシルマレイミド等が挙げられる。これらは２種以上を組み合わせて用いることも出来る。これらの中ではＮ−フェニルマレイミドが好ましい。 As maleimide compounds, maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) ) Maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) Maleimide, N-naphthylmaleimide, N-cyclohexylmaleimide and the like can be mentioned. These may be used in combination of two or more. Of these, N-phenylmaleimide is preferred.
なお、上記のゴム強化芳香族ビニル系樹脂に、マレイミド系化合物に由来する構造単位を導入する他の方法としては、例えば、無水マレイン酸の不飽和ジカルボン酸無水物を共重合した後にイミド化する方法でもよい。 In addition, as another method for introducing a structural unit derived from a maleimide compound into the rubber-reinforced aromatic vinyl resin, for example, an unsaturated dicarboxylic anhydride of maleic anhydride is copolymerized and then imidized. The method may be used.
不飽和酸無水物としては、無水マレイン酸、無水イタコン酸、無水シトラコン酸などが挙げられる。これらは２種以上を組み合わせて用いることも出来る。 Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These may be used in combination of two or more.
カルボキシル基含有不飽和化合物としては、（メタ）アクリル酸、エタクリル酸、マレイン酸、フマル酸、イタコン酸、クロトン酸、桂皮酸などが挙げられる。これらは２種以上を組み合わせて用いることも出来る。 Examples of the carboxyl group-containing unsaturated compound include (meth) acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. These may be used in combination of two or more.
ヒドロキシル基含有不飽和化合物としては、（メタ）アクリル酸２−ヒドロキシメチル、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、；ｏ−ヒドロキシスチレン、ｍ−ヒドロキシスチレン、ｐ−ヒドロキシスチレン等が挙げられる。これらは２種以上を組み合わせて用いることも出来る。 Examples of the hydroxyl group-containing unsaturated compound include 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene etc. are mentioned. These may be used in combination of two or more.
エポキシ基含有不飽和化合物としては、（メタ）アクリル酸グリシジル、（メタ）アクリル酸３，４−オキシシクロヘキシル、ビニルグリシジルエーテル、アリルグリシジルエーテル、メタリルグリシジルエーテル等が挙げられる。これらは２種以上を組み合わせて用いることも出来る。 Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, 3,4-oxycyclohexyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether, and methallyl glycidyl ether. These may be used in combination of two or more.
オキサゾリン基含有不飽和化合物としてはビニルオキサゾリン等が挙げられる。 Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline.
本発明において、上記ビニル系単量体（ｂ１）は、芳香族ビニル化合物及びシアン化ビニル化合物を含むことが好ましく、その合計使用量は、成形加工性、耐薬品性、耐加水分解性、寸法安定性、成形外観性などの観点から、ビニル系単量体（ｂ１）全量に対し、通常７０〜１００質量％、好ましくは８０〜１００質量％である。また、芳香族ビニル化合物及びシアン化ビニル化合物の使用比率は、成形加工性、耐薬品性、耐加水分解性、寸法安定性、成形外観性などの観点から、これらの合計を１００質量％とした場合、それぞれ、通常５〜９５質量％及び５〜９５質量％、好ましくは５０〜９５質量％及び５〜５０質量％、更に好ましくは６０〜９５質量％及び５〜４０質量％である。 In the present invention, the vinyl monomer (b1) preferably contains an aromatic vinyl compound and a vinyl cyanide compound, and the total amount used thereof is molding processability, chemical resistance, hydrolysis resistance, dimensions. From the viewpoint of stability, molded appearance, etc., the content is usually 70 to 100% by mass, preferably 80 to 100% by mass, based on the total amount of the vinyl monomer (b1). In addition, the use ratio of the aromatic vinyl compound and the vinyl cyanide compound was 100% by mass in total from the viewpoint of molding processability, chemical resistance, hydrolysis resistance, dimensional stability, molding appearance, and the like. In this case, it is usually 5 to 95% by mass and 5 to 95% by mass, preferably 50 to 95% by mass and 5 to 50% by mass, and more preferably 60 to 95% by mass and 5 to 40% by mass, respectively.
ゴム含有スチレン系グラフト重合体（Ｉ）として、好ましいのは、ゴム質重合体（ａ）の存在下に、芳香族ビニル化合物及びシアン化ビニル化合物を含むビニル系単量体（ｂ１）を重合して得られたグラフト共重合体である。 As the rubber-containing styrene-based graft polymer (I), a vinyl monomer (b1) containing an aromatic vinyl compound and a vinyl cyanide compound is preferably polymerized in the presence of the rubber-like polymer (a). The graft copolymer obtained in this way.
ゴム含有スチレン系グラフト重合体（Ｉ）の重合方法としては、乳化重合、懸濁重合、溶液重合、塊状重合、又は、これらを組み合わせた重合法が挙げられる。ゴム含有スチレン系グラフト重合体（Ｉ）の製造の際、ゴム質重合体（ａ）及び上記ビニル系単量体（ｂ１）は、反応系において、上記ゴム質重合体（ａ）全量の存在下に上記ビニル系単量体（ｂ１）を一括添加して重合を開始してよいし、分割して又は連続的に添加しながら重合を行ってもよい。また、上記ゴム質重合体（ａ）の一部存在下、又は、非存在下に、上記ビニル系単量体（ｂ１）を一括添加して重合を開始してよいし、分割して又は連続的に添加してもよい。この際、上記ゴム質重合体（ａ）の残部は、反応の途中で、一括して、分割して又は連続的に添加してもよい。 Examples of the polymerization method of the rubber-containing styrene-based graft polymer (I) include emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a polymerization method combining these. In the production of the rubber-containing styrene-based graft polymer (I), the rubber-like polymer (a) and the vinyl-type monomer (b1) are present in the reaction system in the presence of the total amount of the rubber-like polymer (a). The vinyl monomer (b1) may be added all at once to initiate the polymerization, or the polymerization may be carried out while being divided or continuously added. Further, in the presence or absence of part of the rubber polymer (a), the vinyl monomer (b1) may be added all at once to initiate polymerization, or may be divided or continuously. May be added. Under the present circumstances, you may add the remainder of the said rubber-like polymer (a) collectively, divided | segmented or continuously in the middle of reaction.
乳化重合によりゴム含有スチレン系グラフト重合体を製造する場合には、重合開始剤、連鎖移動剤（分子量調節剤）、乳化剤、水などが用いられる。 When producing a rubber-containing styrene-based graft polymer by emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water, and the like are used.
重合開始剤としては、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、パラメンタンハイドロパーオキサイド等の有機過酸化物と、含糖ピロリン酸処方、スルホキシレート処方等の還元剤とを組み合わせたレドックス系開始剤；過硫酸カリウム等の過硫酸塩；ベンゾイルパーオキサイド（ＢＰＯ）、ラウロイルパーオキサイド、ｔｅｒｔ−ブチルパーオキシラウレイト、ｔｅｒｔ−ブチルパーオキシモノカーボネート等の過酸化物などが挙げられる。これらは２種以上を組み合わせて用いることも出来る。また、上記重合開始剤の使用量は、上記ビニル系単量体（ｂ１１）全量に対し、通常０．１〜１．５質量％である。重合開始剤は、反応系に一括して、又は、連続的に添加することが出来る。 As a polymerization initiator, a redox system in which an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, etc. is combined with a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation. Initiators; persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, tert-butyl peroxylaurate, and tert-butyl peroxymonocarbonate. These may be used in combination of two or more. Moreover, the usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinylic monomer (b11) whole quantity. The polymerization initiator can be added to the reaction system all at once or continuously.
連鎖移動剤としては、オクチルメルカプタン、ｎ−ドデシルメルカプタン、ｔｅｒｔ−ドデシルメルカプタン、ｎ−ヘキシルメルカプタン、ｎ−ヘキサデシルメルカプタン、ｎ−テトラデシルメルカプタン、ｔｅｒｔ−テトラデシルメルカプタン等のメルカプタン類；ターピノーレン類、α−メチルスチレンのダイマー等が挙げられる。これらは２種以上
を組み合わせて用いることも出来る。連鎖移動剤の使用量は、上記ビニル系単量体（ｂ１）全量に対し、通常０．０５〜２．０質量％である。連鎖移動剤は、反応系に一括して、又は、連続的に添加することが出来る。
Examples of chain transfer agents include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan; terpinolenes, α -A dimer of methylstyrene or the like. These may be used in combination of two or more. The usage-amount of a chain transfer agent is 0.05-2.0 mass% normally with respect to the said vinylic monomer (b1) whole quantity. The chain transfer agent can be added to the reaction system all at once or continuously.
乳化剤としては、アニオン系界面活性剤及びノニオン系界面活性剤が挙げられる。アニオン系界面活性剤としては、高級アルコールの硫酸エステル；ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩；ラウリル硫酸ナトリウム等の脂肪族スルホン酸塩；高級脂肪族カルボン酸塩、脂肪族リン酸塩などが挙げられる。また、ノニオン系界面活性剤としては、ポリエチレングリコールのアルキルエステル型化合物、アルキルエーテル型化合物などが挙げられる。これらは２種以上を組み合わせて用いることも出来る。乳化剤の使用量は、上記ビニル系単量体（ｂ１１）全量に対し、通常０．３〜５．０質量％である。 Examples of the emulsifier include anionic surfactants and nonionic surfactants. Anionic surfactants include higher alcohol sulfates; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylates and aliphatic phosphates. Is mentioned. Examples of nonionic surfactants include polyethylene glycol alkyl ester compounds and alkyl ether compounds. These may be used in combination of two or more. The usage-amount of an emulsifier is 0.3-5.0 mass% normally with respect to the said vinylic monomer (b11) whole quantity.
乳化重合は、ビニル系単量体（ｂ１）、重合開始剤などの種類に応じ、公知の条件で行うことが出来る。この乳化重合により得られたラテックスは、通常、凝固剤により凝固させ、重合体成分を粉末状とし、その後、これを水洗、乾燥することによって精製される。この際に用いる凝固剤としては、塩化カルシウム、硫酸マグネシウム、塩化マグネシウム、塩化ナトリウム等の無機塩；硫酸、塩酸等の無機酸；酢酸、乳酸などの有機酸等が挙げられる。 Emulsion polymerization can be carried out under known conditions depending on the type of vinyl monomer (b1), polymerization initiator, and the like. The latex obtained by this emulsion polymerization is usually purified by coagulation with a coagulant to form a polymer component in powder form, and then washing and drying the polymer component. Examples of the coagulant used at this time include inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid.
ゴム強化スチレン系樹脂に、ゴム含有スチレン系グラフト重合体を２種以上含有させる場合には、各ラテックスから樹脂を単離した後、混合してもよいが、他の方法として、各樹脂をそれぞれ含むラテックスの混合物を凝固する等の方法がある。溶液重合、塊状重合及び塊状−懸濁重合によるゴム含有スチレン系グラフト重合体の製造方法は、公知の方法を適用することが出来る。 When two or more kinds of rubber-containing styrene-based graft polymers are contained in the rubber-reinforced styrene-based resin, the resins may be mixed after being isolated from each latex. There are methods such as coagulating a latex mixture. A known method can be applied to the method for producing a rubber-containing styrene-based graft polymer by solution polymerization, bulk polymerization, and bulk-suspension polymerization.
ゴム含有スチレン系グラフト重合体（Ｉ）のグラフト率は、加熱欠点の発生防止と押出性の点より、５０〜２００％、好ましくは５１〜１９０％であり、更に好ましくは５２〜１８０％である。 The graft ratio of the rubber-containing styrene-based graft polymer (I) is 50 to 200%, preferably 51 to 190%, more preferably 52 to 180%, from the viewpoint of preventing the occurrence of heating defects and extrudability. .
グラフト率は、下記式により求めることが出来る。
［数１］
グラフト率（％）＝｛（Ｓ−Ｔ）／Ｔ｝×１００
The graft ratio can be determined by the following formula.
[Equation 1]
Graft rate (%) = {(S−T) / T} × 100
上記式中、Ｓはゴム含有スチレン系グラフト重合体（Ｉ）１グラムをアセトン（ゴム質重合体（ａ）がアクリル系ゴムの場合はアセトニトリル）２０ｍｌに投入し、２５℃の温度条件下で振とう機により２時間振とうした後、５℃の温度条件下、遠心分離機（回転数；２３，０００ｒｐｍ）で６０分間遠心分離し、不溶分と可溶分とを分離して得られる不溶分の質量（ｇ）であり、Ｔはゴム含有スチレン系グラフト重合体（Ｉ）１グラムに含まれるゴム質重合体（ａ）の質量（ｇ）である。このゴム質重合体（ａ）の質量は、重合処方及び重合転化率から算出する方法、赤外線吸収スペクトル（ＩＲ）により求める方法などにより得ることが出来る。 In the above formula, S represents 1 gram of rubber-containing styrene-based graft polymer (I) in 20 ml of acetone (acetonitrile when the rubbery polymer (a) is an acrylic rubber) and shaken at 25 ° C. Insoluble matter obtained by shaking for 2 hours with a shaker and then centrifuging for 60 minutes in a centrifuge (rotation speed: 23,000 rpm) under a temperature condition of 5 ° C. to separate insolubles and solubles. T is the mass (g) of the rubbery polymer (a) contained in 1 gram of the rubber-containing styrene-based graft polymer (I). The mass of the rubbery polymer (a) can be obtained by a method of calculating from a polymerization prescription and a polymerization conversion rate, a method of obtaining from an infrared absorption spectrum (IR), and the like.
ゴム強化スチレン系樹脂がゴム含有スチレン系グラフト重合体（Ｉ）及びスチレン系（共）重合体（II）の混合物である場合、スチレン系（共）重合体（II）は単独重合体及び共重合体の何れでもよく又これらの組合せでもよい。 When the rubber-reinforced styrene resin is a mixture of the rubber-containing styrene graft polymer (I) and the styrene (co) polymer (II), the styrene (co) polymer (II) is a homopolymer and a copolymer. Any of these may be combined, or a combination thereof may be used.
ゴム含有スチレン系グラフト重合体（Ｉ）のグラフト率は、ゴム含有スチレン系グラフト重合体（Ｉ）を製造する際に用いる、重合開始剤、連鎖移動剤、乳化剤などの種類や量、更には、仕込時期、仕込時間、重合温度、重合時間などを調節することにより、制御す
ことが出来る。
The graft ratio of the rubber-containing styrene-based graft polymer (I) is determined based on the type and amount of a polymerization initiator, a chain transfer agent, an emulsifier, etc. used when the rubber-containing styrene-based graft polymer (I) is produced. It can be controlled by adjusting the charging time, charging time, polymerization temperature, polymerization time and the like.
スチレン系（共）重合体（II）の重合に用いられるビニル系単量体（ｂ２）としては、芳香族ビニル化合物のみであってよいし、この芳香族ビニル化合物と他の単量体との組合せであってもよい。他の単量体としては、シアン化ビニル化合物、（メタ）アクリル酸エステル化合物、マレイミド系化合物、不飽和酸無水物、カルボキシル基含有不飽和化合物、ヒドロキシル基含有不飽和化合物、エポキシ基含有不飽和化合物、オキサゾリン基含有不飽和化合物などが挙げられる。これらは２種以上を組み合わせて用いることも出来る。上記の各化合物としては、ビニル系単量体（ｂ１）において例示した化合物が適用される。 The vinyl monomer (b2) used for the polymerization of the styrene (co) polymer (II) may be only an aromatic vinyl compound, or the aromatic vinyl compound and other monomers. It may be a combination. Other monomers include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, and epoxy group-containing unsaturated compounds. Compounds, oxazoline group-containing unsaturated compounds, and the like. These may be used in combination of two or more. As each of the above compounds, the compounds exemplified in the vinyl monomer (b1) are applied.
スチレン系（共）重合体（II）は好ましくは共重合体であり、そして、ビニル系単量体（ｂ２）は芳香族ビニル化合物と他の単量体とから成ることが好ましい。他の単量体としては、好ましくはシアン化ビニル化合物及びマレイミド系化合物であり、更に好ましくはシアン化ビニル化合物である。 The styrenic (co) polymer (II) is preferably a copolymer, and the vinyl monomer (b2) is preferably composed of an aromatic vinyl compound and another monomer. Other monomers are preferably vinyl cyanide compounds and maleimide compounds, and more preferably vinyl cyanide compounds.
ビニル系単量体（ｂ２）が芳香族ビニル化合物及びシアン化ビニル化合物を含む場合、これらの合計量は、上記ビニル系単量体（ｂ２）全体に対し、通常４０〜１００質量％、好ましくは５０〜１００質量％である。また、芳香族ビニル化合物及びシアン化ビニル化合物の使用比率は、成形加工性、耐薬品性、成形外観性などの観点から、これらの合計を１００質量％とした場合、それぞれ、通常５〜９５質量％及び５〜９５質量％、好ましくは４０〜９５質量％及び５〜６０質量％、更に好ましくは５０〜９０質量％及び１０〜５０質量％である。 When the vinyl monomer (b2) contains an aromatic vinyl compound and a vinyl cyanide compound, the total amount thereof is usually 40 to 100% by mass, preferably with respect to the whole vinyl monomer (b2). It is 50-100 mass%. In addition, the use ratio of the aromatic vinyl compound and the vinyl cyanide compound is usually 5 to 95 masses each when the total is 100 mass% from the viewpoint of molding processability, chemical resistance, and molding appearance. % And 5 to 95% by mass, preferably 40 to 95% by mass and 5 to 60% by mass, more preferably 50 to 90% by mass and 10 to 50% by mass.
スチレン系（共）重合体（II）は、重合開始剤の存在下または非存在下に芳香族ビニル化合物を含むビニル系単量体（ｂ２）を重合することにより製造することが出来る。重合方法は、重合開始剤を用いる場合は、溶液重合、塊状重合、乳化重合、懸濁重合などが好適であり、これらの重合方法を組み合わせた方法でもよい。また、重合開始剤を用いない場合は熱重合を採用することが出来る。 The styrene (co) polymer (II) can be produced by polymerizing the vinyl monomer (b2) containing an aromatic vinyl compound in the presence or absence of a polymerization initiator. When a polymerization initiator is used as the polymerization method, solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like are suitable, and a method combining these polymerization methods may be used. In the case where no polymerization initiator is used, thermal polymerization can be employed.
重合開始剤としては、ゴム含有スチレン系グラフト重合体（Ｉ）の製造方法の説明にて例示した化合物の１種または２種以上を用いることが出来る。重合開始剤の使用量は、ビニル系単量体（ｂ２）全量に対し、通常０．１〜１．５質量％である。なお、必要に応じ、ゴム含有スチレン系グラフト重合体の製造時に使用可能な連鎖移動剤や乳化剤を用いることが出来る。 As a polymerization initiator, the 1 type (s) or 2 or more types of the compound illustrated by description of the manufacturing method of rubber-containing styrene-type graft polymer (I) can be used. The usage-amount of a polymerization initiator is 0.1-1.5 mass% normally with respect to vinyl-type monomer (b2) whole quantity. If necessary, a chain transfer agent or an emulsifier that can be used when producing the rubber-containing styrene-based graft polymer can be used.
スチレン系（共）重合体（II）の製造の際、ビニル系単量体（ｂ２）の全量を反応系に収容した状態で重合を開始してよいし、任意に選択した単量体成分を分割添加または連続添加して重合を行ってもよい。更に、上記の重合開始剤を用いる場合は、反応系に一括して又は連続的に添加することが出来る。スチレン系（共）重合体（II）は２種以上を組み合わせて用いることも出来る。 In the production of the styrene-based (co) polymer (II), the polymerization may be started in a state where the total amount of the vinyl-based monomer (b2) is accommodated in the reaction system, and an arbitrarily selected monomer component is added. Polymerization may be carried out by divided addition or continuous addition. Furthermore, when using said polymerization initiator, it can add to a reaction system collectively or continuously. Styrenic (co) polymers (II) can be used in combination of two or more.
〔加飾シートの製法〕
加飾シートを得る方法としては、例えば、図１に示すような層構成の場合は、透明性樹脂フィルム（１）の裏面に図柄層（２）を印刷した印刷フィルムを用意し、この印刷フィルムの印刷面とゴム強化スチレン系樹脂からなる着色または非着色の基材フィルム（４）とを積層する方法が挙げられる。また、例えば、図２に示すような層構成の場合は、透明性樹脂フィルム（１）の裏面に図柄層（２）を印刷し、更に続いて接着剤層（３）を塗工又は印刷して形成した印刷フィルムを用意し、この印刷フィルムの接着剤層（３）の熱融着により、ゴム強化スチレン系樹脂からなる着色または非着色の基材フィルム（４）を接
着積層する方法が挙げられる。
[Production method of decorative sheet]
As a method for obtaining a decorative sheet, for example, in the case of a layer structure as shown in FIG. 1, a printing film having a pattern layer (2) printed on the back surface of a transparent resin film (1) is prepared. And a method of laminating a printed surface and a colored or non-colored base film (4) made of a rubber-reinforced styrene resin. Also, for example, in the case of a layer structure as shown in FIG. 2, the design layer (2) is printed on the back surface of the transparent resin film (1), and then the adhesive layer (3) is applied or printed. And a method of laminating a colored or non-colored base film (4) made of a rubber-reinforced styrene resin by heat-sealing the adhesive layer (3) of the printed film. It is done.
本発明の加飾シート（５）の厚みは、成形性や作業性の点より、通常５０〜１５００μｍ、好ましくは８０〜１２００μｍ、更に好ましくは１００〜１０００μｍである。 The thickness of the decorative sheet (5) of the present invention is usually from 50 to 1500 μm, preferably from 80 to 1200 μm, more preferably from 100 to 1000 μm, from the viewpoint of moldability and workability.
〔加飾成形品〕
図３に例示するように、加飾成形品（７）は樹脂成形物（６）の表面に加飾シート（５）が積層された構成を有し、加飾シート（５）はその基材フィルム（４）側が積層される。
[Decorative products]
As illustrated in FIG. 3, the decorative molded product (7) has a configuration in which a decorative sheet (5) is laminated on the surface of a resin molded product (6), and the decorative sheet (5) is a base material thereof. The film (4) side is laminated.
加飾成形品（７）は、加飾シート（５）をインサート射出成形方法に適用し、被着体である樹脂成形物（６）に積層することにより得ることが出来る。樹脂成形物（６）の形状は、少なくともその加飾面が加飾シート（５）の成形性を活かせるような形状が好適であるが、全体形状としては、加飾シート（５）をその加飾面に積層できる形状であればよく、板状（平板、曲面板）、柱状、三次元立体物などとすることが出来る。 The decorative molded product (7) can be obtained by applying the decorative sheet (5) to an insert injection molding method and laminating the resin molded product (6) as an adherend. The shape of the resin molded product (6) is preferably such that at least the decorative surface can make use of the moldability of the decorative sheet (5), but the overall shape is the decorative sheet (5). The shape may be any shape that can be laminated on the decorative surface, and may be a plate shape (flat plate, curved plate), a column shape, a three-dimensional solid object, or the like.
樹脂成形物（６）に用いられる熱可塑性樹脂としては、スチレン系樹脂（ポリスチレン、ハイインパクトポリスチレン、ＡＳ樹脂、ＡＢＳ樹脂、ＭＢＳ樹脂、ＡＥＳ樹脂、ＡＡＳ樹脂など）；ポリエステル系樹脂（ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリナフタレンテレフタレート等）；オレフィン系樹脂（ポリエチレン、ポリプロピレン等）；ポリカーボネート樹脂；ポリアミド系樹脂；ポリアリレート樹脂；ポリアセタール樹脂；ポリ塩化ビニル等の塩化ビニル系樹脂；ポリメタクリル酸メチル（ＰＭＭＡ）等の（メタ）アクリル酸エステルの１種以上を用いた（共）重合体などのアクリル系樹脂；ポリフェニレンエーテル；ポリフェニレンサルファイド；イミド系樹脂；ポリエーテルケトン、ポリエーテルエーテルケトン等のケトン系樹脂；ポリスルホン、ポリエーテルスルホン等のスルホン系樹脂；生分解性プラスチック等が挙げられる。これらは２種以上を組み合わせて用いることも出来る。 Examples of the thermoplastic resin used for the resin molded product (6) include styrene resins (polystyrene, high impact polystyrene, AS resin, ABS resin, MBS resin, AES resin, AAS resin, etc.); polyester resins (polyethylene terephthalate, poly Butylene terephthalate, polynaphthalene terephthalate, etc.); Olefin resins (polyethylene, polypropylene, etc.); Polycarbonate resins; Polyamide resins; Polyarylate resins; Polyacetal resins; Vinyl chloride resins such as polyvinyl chloride; Acrylic resins such as (co) polymers using one or more of (meth) acrylic acid esters such as: polyphenylene ether; polyphenylene sulfide; imide resin; polyether ketone, polyether ether Ketone resins such as Teruketon; polysulfone, sulfonated resins polyether sulfone; biodegradable plastic and the like. These may be used in combination of two or more.
前記のインサート成形方法は、射出成形の雌雄両型間にインサートフィルム（加飾シート）を配置した後、型内に溶融状態の樹脂を射出充填し、樹脂成形物の成形と同時にその表面にインサートフィルムを積層する方法である。インサート成形の際、加飾シートの予備成形は行っても行わなくもよい。また、加飾シートの予熱は、行っても行わなくてもよいが、行うことが好ましい。 In the above-mentioned insert molding method, an insert film (decorative sheet) is placed between both male and female molds for injection molding, and then a molten resin is injected and filled into the mold. This is a method of laminating films. During insert molding, the decorative sheet may be preformed or not. Further, the preheating of the decorative sheet may or may not be performed, but is preferably performed.
加飾成形品は、例えば、自動車などの車両の内装材または外装材、幅木、回縁などの造作部材、窓枠、扉枠などの建具、壁、床、天井などの建築物の内装材、テレビ受像機、空調機などの家電製品の筐体、容器などに用いられる。 A decorative molded product is, for example, an interior or exterior material of a vehicle such as an automobile, a construction material such as a baseboard or a rim, a fitting such as a window frame or a door frame, an interior material of a building such as a wall, floor, or ceiling. It is used for housings and containers of household electrical appliances such as television receivers and air conditioners.
以下、実施例により本発明を更に詳細に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。なお、以下において「部」及び「％」は特に断らない限り質量基準である。また、以下の諸例で採用した評価方法は次の通りである。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. In the following, “part” and “%” are based on mass unless otherwise specified. The evaluation methods employed in the following examples are as follows.
（１）評価方法 (1) Evaluation method
（１−１）着色基材フィルムの加熱欠点数：
着色基材フィルムを３００ｍｍ（ＭＤ）×２１０ｍｍ（ＴＤ）の試験片に切り出し、小型真空製形機（成光産業株式会社製「３００Ｘ」）に取付固定した。着色基材フィルム表面から４０ｍｍ離れ、予め４５０℃に加熱したヒーターを用い、着色基材フィルムを１０秒間加熱し、フィルムをドローダウンさせた。ドローダウンさせた着色基材フィルムの中
央部１００ｍｍ×１００ｍｍ片の範囲の存在する０．２ｍｍ×０．２ｍｍ以上の大きさのブツ等の欠点数をきょう雑物測定図表を用いて計測した。
(1-1) Number of heating defects of the colored base film:
The colored substrate film was cut into a 300 mm (MD) × 210 mm (TD) test piece and attached and fixed to a small vacuum molding machine (“300X” manufactured by Seiko Sangyo Co., Ltd.). The colored base film was heated for 10 seconds using a heater that was 40 mm away from the colored base film surface and heated to 450 ° C. in advance, and the film was drawn down. The number of defects such as blisters having a size of 0.2 mm × 0.2 mm or more in the range of the central portion of the colored base film that was drawn down, which was 100 mm × 100 mm, was measured using a contaminant measurement chart.
（１−２）製膜性の評価：
着色基材フィルムの肉厚は、シックネスゲージ（ミツトヨ社製「ＩＤ−Ｃ１１１２Ｃ」）を用い、着色基材フィルム製造開始から１時間経過後の着色基材フィルムを切り取り、着色基材フィルムの幅方向の中心及び中心より両端に向けて１０ｍｍ間隔で測定し、その平均値を採用した。なお、着色基材フィルムの端部から２０ｍｍの範囲にある測定点の値は、上記平均値の計算から除去した。そして、着色基材フィルムの厚み高低差が２０μｍ未満である場合は製膜性を◎とし、２０μｍ以上３０μｍ未満である場合は製膜性を○とし、３０μｍ以上４０μｍ未満である場合は製膜性を△とし、４０μｍ以上である場合は製膜性を×とした。
(1-2) Evaluation of film forming property:
The thickness of the colored base film is measured by using a thickness gauge (“ID-C1112C” manufactured by Mitutoyo Corporation), cutting the colored base film one hour after the start of the production of the colored base film, and the width direction of the colored base film. Measured at 10 mm intervals from the center and both ends from the center, and the average value was adopted. In addition, the value of the measurement point in the range of 20 mm from the edge part of the colored base film was removed from the calculation of the average value. And, when the thickness difference of the colored substrate film is less than 20 μm, the film forming property is ◎, when it is 20 μm or more and less than 30 μm, the film forming property is ◯, and when it is 30 μm or more and less than 40 μm, the film forming property is Is Δ, and when it is 40 μm or more, the film forming property is x.
（１−３）樹脂成形物との密着性：
着色基材フィルムを７００ｍｍ（ＭＤ）×４００ｍｍ（ＴＤ）の試験片に切り出し、射出成形機の金型内に固定し、その後、金型を閉じ、耐熱ＡＢＳ樹脂（テクノポリマー社製「テクノＭＵＨ Ｅ１５００」）を射出し成形した。着色基材フィルムと樹脂成形物との一体成形品を金型から取り出し、温度２３℃、湿度５０％で２４時間状態調節後、着色基材フィルムと樹脂成形物との密着性を評価した。そして、着色基材フィルムが樹脂成形物と剥がれずフィルムが破断する場合を○とし、着色基材フィルムが樹脂成形物と密着面で僅かに剥離するが途中でフィルムが破断する場合を△とし、着色基材フィルムが樹脂成形物と密着面で剥離しフィルムが破断しない場合を×とした。
(1-3) Adhesiveness with resin molding:
The colored base film is cut into a 700 mm (MD) × 400 mm (TD) test piece, fixed in a mold of an injection molding machine, and then the mold is closed, and a heat-resistant ABS resin (“Techno MUH E1500, manufactured by Techno Polymer Co., Ltd.) is used. ]) Was injected and molded. An integrally molded product of the colored substrate film and the resin molded product was taken out from the mold, and after adjusting the state at a temperature of 23 ° C. and a humidity of 50% for 24 hours, the adhesion between the colored substrate film and the resin molded product was evaluated. And, when the colored base film is not peeled off from the resin molded product and the film is broken, ◯, and when the colored base film is slightly peeled from the resin molded product and the adhesion surface, the film is broken halfway, and Δ The case where the colored base film peeled off from the resin molded product at the contact surface and the film did not break was marked as x.
（１−４）加飾シートの加熱欠点数：
加飾シートを３００ｍｍ（ＭＤ）×２１０ｍｍ（ＴＤ）の試験片に切り出し、小型真空製形機（成光産業株式会社製「３００Ｘ」）に印刷フィルム側を下側として取付固定した。加飾シート表面から４０ｍｍ離れ、予め４５０℃に加熱したヒーターを用い、加飾シートを１０秒間加熱し、加飾シートをドローダウンさせた。ドローダウンさせた加飾シートの中央部１００ｍｍ×１００ｍｍ片の範囲の印刷フィルム側に存在する０．２ｍｍ×０．２ｍｍ以上の大きさのブツ等の欠点数をきょう雑物測定図表を用いて計測した。
(1-4) The number of heating defects of the decorative sheet:
The decorative sheet was cut into a test piece of 300 mm (MD) × 210 mm (TD), and attached and fixed to a small vacuum molding machine (“300X” manufactured by Seiko Sangyo Co., Ltd.) with the printing film side as the lower side. Using a heater that was 40 mm away from the surface of the decorative sheet and heated to 450 ° C. in advance, the decorative sheet was heated for 10 seconds to draw down the decorative sheet. Measure the number of defects, such as looseness of 0.2 mm x 0.2 mm or more, present on the printed film side in the range of 100 mm x 100 mm pieces in the center of the decorative sheet that has been drawn down, using a measurement table for impurities. did.
（２）製造方法 (2) Manufacturing method
（２−１）ゴム含有スチレン系グラフト重合体の製造 (2-1) Production of rubber-containing styrene-based graft polymer
（２−１−１）グラフト重合体（Ｇ１）の製造：
攪拌機を備えたガラス製反応器に、イオン交換水７５部、ロジン酸カリウム０．５部、ｔ−ドデシルメルカプタン０．３部、ポリブタジエンラテックス（平均粒子径：３００ｎｍ、ゲル含有率８０％）８部（固形分換算）及びスチレン・ブタジエンラテックス（スチレン／ブタジエン＝３０／７０、平均粒子径６００ｎｍ、ゲル含有率０％）２部（固形分換算）、スチレン２１．５部及びアクリロニトリル８．５部を入れ、窒素気流中で攪拌しながら昇温した。内温が４５℃に達した時点でピロリン酸ナトリウム０．２部、硫酸第一鉄７水和物０．０１及びブドウ糖０．２部をイオン交換水２０部に溶解した溶液を加えた。その後、クメンハイドロパーオキサイド０．０７部を加えて重合を開始し、１時間重合させた。次いで、イオン交換水５０部、ロジン酸カリウム０．７部、スチレン４３部、アクリロニトリル１７部、ｔ−ドデシルメルカプタン０．３部、クメンハイドロパーオキサイド０．２部を５時間かけて連続的に添加した。１時間重合させた後、２，２´−メチレン−ビス（４−エチレン−６−ｔ−ブチルフェノール）０．２部を添加し重合を完結させた。このラテックスに硫酸マグネシウムを添加し、樹脂成分を凝固させた。その後、水洗、更に乾燥することによりグラフト重合体（Ｇ１）を得た。グラフト率は１５０％、アセ
トン可溶分の極限粘度は０．１０であった。
(2-1-1) Production of graft polymer (G1):
In a glass reactor equipped with a stirrer, 75 parts of ion exchange water, 0.5 part of potassium rosinate, 0.3 part of t-dodecyl mercaptan, 8 parts of polybutadiene latex (average particle size: 300 nm, gel content 80%) (In terms of solid content) and styrene / butadiene latex (styrene / butadiene = 30/70, average particle size 600 nm, gel content 0%) 2 parts (in terms of solid content), 21.5 parts of styrene and 8.5 parts of acrylonitrile. The mixture was heated while stirring in a nitrogen stream. When the internal temperature reached 45 ° C., a solution prepared by dissolving 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.2 parts of glucose in 20 parts of ion-exchanged water was added. Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization, and polymerization was carried out for 1 hour. Next, 50 parts of ion-exchanged water, 0.7 part of potassium rosinate, 43 parts of styrene, 17 parts of acrylonitrile, 0.3 part of t-dodecyl mercaptan, 0.2 part of cumene hydroperoxide are continuously added over 5 hours. did. After polymerization for 1 hour, 0.2 part of 2,2′-methylene-bis (4-ethylene-6-t-butylphenol) was added to complete the polymerization. Magnesium sulfate was added to this latex to coagulate the resin component. Then, the graft polymer (G1) was obtained by washing with water and further drying. The graft ratio was 150%, and the intrinsic viscosity of the acetone-soluble component was 0.10.
（２−１−２）グラフト重合体（Ｇ２）の製造：
攪拌機を備えたガラス製反応器に、イオン交換水７５部、ロジン酸カリウム０．３５部、ｔ−ドデシルメルカプタン０．２部、ゴム質重合体としてポリブタジエンラテックス（平均粒子径：３００ｎｍ、ゲル含有率８０％）３２部（固形分換算）及びスチレン・ブタジエンラテックス（スチレン／ブタジエン＝３０／７０、平均粒子径６００ｎｍ、ゲル含有率０％）８部（固形分換算）、スチレン１４部及びアクリロニトリル６部を入れ、窒素気流中で攪拌しながら昇温した。内温が４５℃に達した時点でピロリン酸ナトリウム０．２部、硫酸第一鉄７水和物０．０１及びブドウ糖０．２部をイオン交換水２０部に溶解した溶液を加えた。その後、クメンハイドロパーオキサイド０．０７部を加えて重合を開始し、１時間重合させた。次いで、イオン交換水５０部、ロジン酸カリウム０．７部、スチレン２９部、アクリロニトリル１１部、ｔ−ドデシルメルカプタン０．１５部、クメンハイドロパーオキサイド０．１１部を３時間かけて連続的に添加した。１時間重合させた後、２，２´−メチレン−ビス（４−エチレン−６−ｔ−ブチルフェノール）０．２部を添加し重合を完結させた。このラテックスに硫酸マグネシウムを添加し、樹脂成分を凝固させた。その後、水洗、更に乾燥することによりグラフト重合体（Ｇ２）を得た。グラフト率は５５％、アセトン可溶分の極限粘度は０．３９であった。
(2-1-2) Production of graft polymer (G2):
In a glass reactor equipped with a stirrer, 75 parts of ion exchange water, 0.35 part of potassium rosinate, 0.2 part of t-dodecyl mercaptan, polybutadiene latex (average particle size: 300 nm, gel content) as a rubbery polymer 80%) 32 parts (solid content conversion) and styrene-butadiene latex (styrene / butadiene = 30/70, average particle diameter 600 nm, gel content 0%) 8 parts (solid content conversion), styrene 14 parts and
（２−１−３）グラフト重合体（Ｇ３）の製造：
攪拌機を備えたガラス製反応器に、イオン交換水７５部、ロジン酸カリウム０．２部、ｔ−ドデシルメルカプタン０．１２部、ゴム質重合体としてポリブタジエンラテックス（平均粒子径：３００ｎｍ、ゲル含有率８０％）４０部（固形分換算）及びスチレン・ブタジエンラテックス（スチレン／ブタジエン＝３０／７０、平均粒子径６００ｎｍ、ゲル含有率０％）１０部（固形分換算）、スチレン１２部及びアクリロニトリル５部を入れ、窒素気流中で攪拌しながら昇温した。内温が４５℃に達した時点でピロリン酸ナトリウム０．２部、硫酸第一鉄７水和物０．０１及びブドウ糖０．２部をイオン交換水２０部に溶解した溶液を加えた。その後、クメンハイドロパーオキサイド０．０７部を加えて重合を開始し、１時間重合させた。次いで、イオン交換水５０部、ロジン酸カリウム０．５部、スチレン２４部、アクリロニトリル９部、ｔ−ドデシルメルカプタン０．４部、クメンハイドロパーオキサイド０．１７部を４時間かけて連続的に添加した。１時間重合させた後、２，２´−メチレン−ビス（４−エチレン−６−ｔ−ブチルフェノール）０．２部を添加し重合を完結させた。このラテックスに硫酸マグネシウムを添加し、樹脂成分を凝固させた。その後、水洗、更に乾燥することによりグラフト重合体（Ｇ３）を得た。グラフト率は５８％、アセトン可溶分の極限粘度は０．３０であった。
(2-1-3) Production of graft polymer (G3):
In a glass reactor equipped with a stirrer, 75 parts of ion exchange water, 0.2 part of potassium rosinate, 0.12 part of t-dodecyl mercaptan, polybutadiene latex (average particle size: 300 nm, gel content) as a rubbery polymer 80%) 40 parts (in terms of solid content) and 10 parts of styrene-butadiene latex (styrene / butadiene = 30/70, average particle size 600 nm, gel content 0%) (in terms of solid content), 12 parts of styrene and 5 parts of acrylonitrile The mixture was heated with stirring in a nitrogen stream. When the internal temperature reached 45 ° C., a solution prepared by dissolving 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.2 parts of glucose in 20 parts of ion-exchanged water was added. Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization, and polymerization was carried out for 1 hour. Subsequently, 50 parts of ion-exchanged water, 0.5 part of potassium rosinate, 24 parts of styrene, 9 parts of acrylonitrile, 0.4 part of t-dodecyl mercaptan, and 0.17 part of cumene hydroperoxide are continuously added over 4 hours. did. After polymerization for 1 hour, 0.2 part of 2,2′-methylene-bis (4-ethylene-6-t-butylphenol) was added to complete the polymerization. Magnesium sulfate was added to this latex to coagulate the resin component. Then, the graft polymer (G3) was obtained by washing with water and further drying. The graft ratio was 58%, and the intrinsic viscosity of the acetone-soluble component was 0.30.
（２−１−４）グラフト重合体（Ｇ４）の製造：
攪拌機を備えたガラス製反応器に、イオン交換水７５部、ｔ−ドデシルメルカプタン０．１部、ゴム質重合体としてポリブタジエンラテックス（平均粒子径：３００ｎｍ、ゲル含有率８０％）４８部（固形分換算）及びスチレン・ブタジエンラテックス（スチレン／ブタジエン＝３０／７０、平均粒子径６００ｎｍ、ゲル含有率０％）１２部（固形分換算）、スチレン９．５部及びアクリロニトリル４部を入れ、窒素気流中で攪拌しながら昇温した。内温が４５℃に達した時点でピロリン酸ナトリウム０．２部、硫酸第一鉄７水和物０．０１及びブドウ糖０．２部をイオン交換水２０部に溶解した溶液を加えた。その後、クメンハイドロパーオキサイド０．０７部を加えて重合を開始し、１時間重合させた。次いで、イオン交換水５０部、ロジン酸カリウム０．２部、スチレン１９部、アクリロニトリル７．５部、ｔ−ドデシルメルカプタン０．２５部、クメンハイドロパーオキサイド０．２部を２時間かけて連続的に添加した。１時間重合させた後、２，２´−メチレン−ビス（４−エチレン−６−ｔ−ブチルフェノール）０．２部を添加し重合を完結させた。このラテックスに硫酸マグネシウムを添加し、樹脂成分を凝固させた。その後、水洗、更に
乾燥することによりグラフト重合体（Ｇ４）を得た。グラフト率は５７％、アセトン可溶分の極限粘度は０．３５であった。
(2-1-4) Production of graft polymer (G4):
In a glass reactor equipped with a stirrer, 75 parts of ion-exchanged water, 0.1 part of t-dodecyl mercaptan, 48 parts of polybutadiene latex (average particle size: 300 nm, gel content 80%) as a rubber polymer (solid content) Conversion) and 12 parts of styrene-butadiene latex (styrene / butadiene = 30/70, average particle size 600 nm, gel content 0%) (converted to solid content), 9.5 parts of styrene and 4 parts of acrylonitrile, in a nitrogen stream The temperature was raised with stirring. When the internal temperature reached 45 ° C., a solution prepared by dissolving 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.2 parts of glucose in 20 parts of ion-exchanged water was added. Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization, and polymerization was carried out for 1 hour. Subsequently, 50 parts of ion-exchanged water, 0.2 part of potassium rosinate, 19 parts of styrene, 7.5 parts of acrylonitrile, 0.25 part of t-dodecyl mercaptan, and 0.2 part of cumene hydroperoxide are continuously added over 2 hours. Added to. After polymerization for 1 hour, 0.2 part of 2,2′-methylene-bis (4-ethylene-6-t-butylphenol) was added to complete the polymerization. Magnesium sulfate was added to this latex to coagulate the resin component. Then, the graft polymer (G4) was obtained by washing with water and further drying. The graft ratio was 57%, and the intrinsic viscosity of the acetone-soluble component was 0.35.
（２−１−５）グラフト重合体（Ｇ５）の製造：
攪拌機を備えたガラス製反応器に、イオン交換水７５部、ロジン酸カリウム０．３５部、ｔ−ドデシルメルカプタン０．２４部、ゴム質重合体としてポリブタジエンラテックス（平均粒子径：３００ｎｍ、ゲル含有率８０％）３２部（固形分換算）及びスチレン・ブタジエンラテックス（スチレン／ブタジエン＝３０／７０、平均粒子径６００ｎｍ、ゲル含有率０％）８部（固形分換算）、スチレン１４部及びアクリロニトリル６部を入れ、窒素気流中で攪拌しながら昇温した。内温が４５℃に達した時点でピロリン酸ナトリウム０．２部、硫酸第一鉄７水和物０．０１及びブドウ糖０．２部をイオン交換水２０部に溶解した溶液を加えた。その後、クメンハイドロパーオキサイド０．０７部を加えて重合を開始し、１時間重合させた。次いで、イオン交換水５０部、ロジン酸カリウム０．７部、スチレン２９部、アクリロニトリル１１部、ｔ−ドデシルメルカプタン０．２部、クメンハイドロパーオキサイド０．１１部を１時間３０分かけて連続的に添加した。１時間重合させた後、２，２´−メチレン−ビス（４−エチレン−６−ｔ−ブチルフェノール）０．２部を添加し重合を完結させた。このラテックスに硫酸マグネシウムを添加し、樹脂成分を凝固させた。その後、水洗、更に乾燥することによりグラフト重合体（Ｇ５）を得た。グラフト率は４５％、アセトン可溶分の極限粘度は０．３９であった。
(2-1-5) Production of graft polymer (G5):
In a glass reactor equipped with a stirrer, 75 parts of ion exchange water, 0.35 part of potassium rosinate, 0.24 part of t-dodecyl mercaptan, polybutadiene latex (average particle size: 300 nm, gel content) as a rubbery polymer 80%) 32 parts (solid content conversion) and styrene-butadiene latex (styrene / butadiene = 30/70, average particle diameter 600 nm, gel content 0%) 8 parts (solid content conversion), styrene 14 parts and
（２−２）スチレン系（共）重合体：
スチレン系（共）重合体として、以下に記載のスチレン・アクリロニトリル樹脂（ＡＳ樹脂）を用いた。
(2-2) Styrene (co) polymer:
The styrene-acrylonitrile resin (AS resin) described below was used as the styrene-based (co) polymer.
ＡＳ１：アクリロニトリル含有率２４％、極限粘度０．１０
ＡＳ２：アクリロニトリル含有率２９％、極限粘度０．１３
ＡＳ３：アクリロニトリル含有率２８％、極限粘度０．１５
ＡＳ４：アクリロニトリル含有率２７％、極限粘度０．２０
ＡＳ５：アクリロニトリル含有率２７％、極限粘度０．３９
ＡＳ６：アクリロニトリル含有率２７％、極限粘度１．２０
AS1: 24% acrylonitrile content, intrinsic viscosity 0.10
AS2: Acrylonitrile content 29%, intrinsic viscosity 0.13
AS3: Acrylonitrile content 28%, intrinsic viscosity 0.15
AS4: Acrylonitrile content 27%, intrinsic viscosity 0.20
AS5: 27% acrylonitrile content, intrinsic viscosity 0.39
AS6: 27% acrylonitrile content, intrinsic viscosity 1.20
（２−３）ゴム強化スチレン系樹脂の製造：
表１に示すグラフト重合体とＡＳ樹脂との合計１００質量部にカーボンブラック（三菱化学製「汎用カラーＲＣＦ＃４５」）０．１５質量部、熱安定剤（チバスペシャルティーケミカルズ社製「ＩＲＧＡＮＯＸ１０１０」）０．４質量部および滑剤としてステアリン酸カルシウム（日東化成工業社製）０．２質量部を配合し、高速混合機により均一混合した後、φ５８ｍｍベント式二軸押出機（Ｌ／Ｄ＝３２）を用いて混練し、ストランドカット法によりペレット化し表１に示す着色樹脂のペレットを得た。
(2-3) Production of rubber-reinforced styrene resin:
Carbon black ("general-purpose color RCF # 45" manufactured by Mitsubishi Chemical Corporation) 0.15 parts by mass and heat stabilizer ("IRGANOX 1010" manufactured by Ciba Specialty Chemicals) in a total of 100 parts by mass of the graft polymer and AS resin shown in Table 1 ) After blending 0.4 parts by mass and 0.2 parts by mass of calcium stearate (manufactured by Nitto Kasei Kogyo Co., Ltd.) as a lubricant and uniformly mixing with a high-speed mixer, a φ58 mm vented twin screw extruder (L / D = 32) Were kneaded and pelletized by a strand cut method to obtain colored resin pellets shown in Table 1.
（２−４）着色基材フィルムの製造：
製造例１〜１１：
Ｔダイ（ダイ幅；１６００ｍｍ、リップ間隔１ｍｍ）を備え、スクリュー径１１５ｍｍの押出機を備えたフィルム成形機を用い、押出機に表１に示す着色樹脂のペレットを供給してＴダイから溶融温度２３０℃で樹脂を吐出させ、フィルムとした。その後、このフィルムをエアーナイフによりキャストロール（ロール表面温度７０℃）に面密着させ、冷却固化し、押出機及びキャストロールの運転条件を調節することにより、表１に記載した厚みの着色基材フィルムを製造し、製膜性、加熱欠点数および樹脂成形品との密着性を評価した。
(2-4) Production of colored base film:
Production Examples 1 to 11:
Using a film forming machine equipped with a T die (die width: 1600 mm,
（２−５）加飾シートの製造：
実施例１：
ポリメチルメタクリレート（ＰＭＭＡ）を主成分とする厚さ１００μで無色透明のアクリル樹脂フィルム（ヘイズ：１０％以下）を透明性樹脂フィルムとし、このフィルムの裏側の面に、バインダーの樹脂にアクリル樹脂と塩化ビニル−酢酸ビニル共重合体との６対４質量比の混合樹脂を用い、着色剤にキナクリドンレッド、イソインドリノン、フタロシアニンブルー、及びカーボンブラックを用いた着色インキで、木目柄の図柄層をグラビア印刷法で形成し、更にその上にアクリル樹脂と塩化ビニル−酢酸ビニル共重合体と６対４質量比の混合物を用いた塗液をグラビアロールコート法で全面に厚さ５μｍの接着剤層を形成し、印刷フィルムを得た。次に、製造例１で製造した着色基材フィルムを印刷フィルムの接着剤層側と重ね、輪転式熱プレス機により、両フィルムを熱溶着により積層して加飾シートを得、加熱欠点数を評価した。結果を表２に示す。
(2-5) Production of decorative sheet:
Example 1:
A colorless and transparent acrylic resin film (haze: 10% or less) having a thickness of 100 μm, which is mainly composed of polymethyl methacrylate (PMMA), is used as a transparent resin film. Using a mixed resin of 6 to 4 mass ratio of vinyl chloride-vinyl acetate copolymer and coloring ink using quinacridone red, isoindolinone, phthalocyanine blue, and carbon black as a colorant, An adhesive layer having a thickness of 5 μm is formed on the entire surface by a gravure roll coating method, which is formed by a gravure printing method, and further a coating liquid using a mixture of acrylic resin, vinyl chloride-vinyl acetate copolymer and 6 to 4 mass ratio is formed thereon. And a printed film was obtained. Next, the colored base film produced in Production Example 1 is overlapped with the adhesive layer side of the printing film, and both films are laminated by thermal welding with a rotary heat press to obtain a decorative sheet, and the number of heating defects is determined. evaluated. The results are shown in Table 2.
実施例２：
着色基材フィルムとして、製造例１で製造した着色基材フィルムの代わりに、製造例２で製造した着色基材フィルムを用いる以外は、実施例１と同様にして、加飾シートを得、加熱欠点数を評価した。結果を表２に示す。
Example 2:
As a colored substrate film, a decorative sheet is obtained and heated in the same manner as in Example 1 except that the colored substrate film produced in Production Example 2 is used instead of the colored substrate film produced in Production Example 1. The number of defects was evaluated. The results are shown in Table 2.
比較例１：
着色基材フィルムとして、製造例１で製造した着色基材フィルムの代わりに、製造例８で製造した着色基材フィルムを用いる以外は、実施例１と同様にして、加飾シートを得、
加熱欠点数を評価した。結果を表２に示す。
Comparative Example 1:
As a colored substrate film, a decorative sheet is obtained in the same manner as in Example 1 except that the colored substrate film produced in Production Example 8 is used instead of the colored substrate film produced in Production Example 1.
The number of heating defects was evaluated. The results are shown in Table 2.
比較例２：
着色基材フィルムとして、製造例１で製造した着色基材フィルムの代わりに、製造例９で製造した着色基材フィルムを用いる以外は、実施例１と同様にして、加飾シートを得、加熱欠点数を評価した。結果を表２に示す。
Comparative Example 2:
As a colored substrate film, a decorative sheet is obtained in the same manner as in Example 1 except that the colored substrate film produced in Production Example 9 is used instead of the colored substrate film produced in Production Example 1. The number of defects was evaluated. The results are shown in Table 2.
１：透明樹脂フィルム
２：図柄層
３：接着剤層
４：基材フィルム
５：樹脂成形物
６：加飾シート
７：加飾成形品
1: transparent resin film 2: design layer 3: adhesive layer 4: substrate film 5: resin molded product 6: decorative sheet 7: decorative molded product
Claims (5)
［ゴム強化スチレン系樹脂］
グラフト率が５０〜２００％であり且つゴム含有率が５〜５５質量％である共役ジエン系ゴム含有スチレン系グラフト重合体（Ｉ）を含有し、ゴム含有率が５〜４０質量％であり且つアセトンに可溶な成分の極限粘度が０．０５〜０．８０ｄｌ／ｇである樹脂。 A decorative sheet made by laminating a base film on the printed surface of a printed film with a pattern layer printed on the back side of the transparent resin film, or after the pattern layer is printed on the back side of the transparent resin film, It is a decorative sheet formed by laminating a base film on the adhesive layer surface of a printed film having an adhesive layer formed thereon, and the base film is composed of the conjugated diene rubber reinforced styrene resin described below. Decorative sheet characterized by.
[Rubber reinforced styrene resin]
Containing a conjugated diene rubber-containing styrene-based graft polymer (I) having a graft ratio of 50 to 200% and a rubber content of 5 to 55% by mass, a rubber content of 5 to 40% by mass and Resin whose intrinsic viscosity of components soluble in acetone is 0.05 to 0.80 dl / g.
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