JP4741364B2 - Laminated body - Google Patents
Laminated body Download PDFInfo
- Publication number
- JP4741364B2 JP4741364B2 JP2005366628A JP2005366628A JP4741364B2 JP 4741364 B2 JP4741364 B2 JP 4741364B2 JP 2005366628 A JP2005366628 A JP 2005366628A JP 2005366628 A JP2005366628 A JP 2005366628A JP 4741364 B2 JP4741364 B2 JP 4741364B2
- Authority
- JP
- Japan
- Prior art keywords
- mass
- composition
- rubber
- resin
- heat storage
- 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.)
- Active
Links
- 229920005989 resin Polymers 0.000 claims description 68
- 239000011347 resin Substances 0.000 claims description 68
- 229920002554 vinyl polymer Polymers 0.000 claims description 57
- 238000005338 heat storage Methods 0.000 claims description 53
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 52
- 239000001023 inorganic pigment Substances 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 43
- 239000011342 resin composition Substances 0.000 claims description 43
- 229920001971 elastomer Polymers 0.000 claims description 40
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 34
- 229920005992 thermoplastic resin Polymers 0.000 claims description 26
- 238000012360 testing method Methods 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 21
- 239000005060 rubber Substances 0.000 claims description 20
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- 239000004800 polyvinyl chloride Substances 0.000 claims description 14
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 14
- 239000000314 lubricant Substances 0.000 claims description 13
- 239000000049 pigment Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 11
- 238000004898 kneading Methods 0.000 claims description 9
- 229920000800 acrylic rubber Polymers 0.000 claims description 8
- 229920003244 diene elastomer Polymers 0.000 claims description 8
- 229920000058 polyacrylate Polymers 0.000 claims description 8
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- CLNYHERYALISIR-UHFFFAOYSA-N nona-1,3-diene Chemical compound CCCCCC=CC=C CLNYHERYALISIR-UHFFFAOYSA-N 0.000 claims description 5
- 230000001143 conditioned effect Effects 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 41
- -1 acryl Chemical group 0.000 description 32
- 229910052742 iron Inorganic materials 0.000 description 32
- 239000010410 layer Substances 0.000 description 31
- 239000000178 monomer Substances 0.000 description 26
- 229910052804 chromium Inorganic materials 0.000 description 23
- 229920001577 copolymer Polymers 0.000 description 23
- 239000002023 wood Substances 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- 239000008188 pellet Substances 0.000 description 15
- 239000011572 manganese Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000975 dye Substances 0.000 description 11
- 229910052748 manganese Inorganic materials 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000003086 colorant Substances 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 9
- 239000004816 latex Substances 0.000 description 9
- 229920000126 latex Polymers 0.000 description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-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
- 239000011651 chromium Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000012860 organic pigment Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 229920005672 polyolefin resin Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 229920006395 saturated elastomer Polymers 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
- 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 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 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
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 2
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920006132 styrene block copolymer Polymers 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 229920006032 ungrafted co-polymer Polymers 0.000 description 2
- 125000002348 vinylic group Chemical group 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- 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
- 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
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910002515 CoAl Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 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 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- UGUYQBMBIJFNRM-UHFFFAOYSA-N but-2-en-2-ylbenzene Chemical compound CC=C(C)C1=CC=CC=C1 UGUYQBMBIJFNRM-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001993 dienes Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-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
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 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 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Description
本発明は、基材とそれに積層された低蓄熱性樹脂組成物からなる木目調模様を有する層とを備えてなる積層体に関する。 The present invention relates to a laminate comprising a substrate and a layer having a woodgrain pattern made of a low heat storage resin composition laminated thereon.
従来、成形時に木目調模様を発現する熱可塑性樹脂組成物としては、ポリ塩化ビニル樹脂（PVC）を主成分とするものが知られており、窓枠などの成形品として使用されている（特許文献１及び２参照）。
しかし、ポリ塩化ビニル樹脂は耐熱性が十分でないため、該樹脂製の窓枠は太陽光の照射によって温度が上昇し、変形や収縮等の寸法変化を生じ、その結果、窓枠の気密性、保温性、開閉機能等が損なわれるという欠点があった。また、ポリ塩化ビニル樹脂に着色剤を配合した場合には、その着色剤が暗色系顔料などのように太陽光照射によって発熱するものである場合、成形品の温度上昇が一層促進されるため、着色の選択肢が制限されていた。
一方、スチレン系樹脂についても、成形時に木目調の模様を発現する組成物が提案されており（参考文献３参照）、また、太陽光照射時の蓄熱が少ない組成物も提案されている（特許文献４及び５参照）。しかし、スチレン系樹脂はポリ塩化ビニル樹脂に比べて高価であり、また、耐候性が十分でないことがあった。
Conventionally, as a thermoplastic resin composition that expresses a wood grain pattern at the time of molding, a composition mainly composed of polyvinyl chloride resin (PVC) is known and used as a molded product such as a window frame (patent) Reference 1 and 2).
However, since the polyvinyl chloride resin has insufficient heat resistance, the temperature of the resin window frame rises due to the irradiation of sunlight, causing dimensional changes such as deformation and shrinkage. There was a fault that heat retention, opening and closing function, etc. were impaired. In addition, when a colorant is blended in the polyvinyl chloride resin, when the colorant is one that generates heat by irradiation with sunlight, such as a dark pigment, the temperature rise of the molded product is further promoted, Coloring options were limited.
On the other hand, for styrene-based resins, a composition that expresses a wood grain pattern at the time of molding has been proposed (see Reference 3), and a composition that has little heat storage during sunlight irradiation has also been proposed (patent) References 4 and 5). However, the styrene resin is more expensive than the polyvinyl chloride resin, and the weather resistance may not be sufficient.
本発明の目的は、太陽光の照射時においても温度上昇が抑制された、木目調模様を有する層を備えてなることにより、蓄熱性が低く、耐候性、木目着色性、耐熱性（寸法安定性）等に優れた積層体を提供することにある。 The object of the present invention is to provide a layer having a woodgrain pattern in which the temperature rise is suppressed even during the irradiation of sunlight, so that the heat storage property is low, weather resistance, wood coloring, heat resistance (dimensional stability) It is to provide a laminate having excellent properties.
本発明者等は、上記目的を達成すべく鋭意検討した結果、特定の無機顔料を配合してなる低蓄熱性樹脂組成物からなる層を基材に積層することにより、蓄熱性が低く、耐候性、木目調模様の着色性、耐熱性（寸法安定性）等に優れた木目調模様を有する積層体が提供できることを見出し、本発明を完成するに至った。
すなわち、本発明によれば、基材と、それに積層された木目調模様を有する層とを備えてなる積層体であって、前記木目調模様を有する層は熱可塑性樹脂（Ａ）を含む低蓄熱性樹脂組成物からなり、該組成物は、赤外線反射特性を有する無機顔料（Ｂ）を該組成物全体に対して０．５〜１３質量％含有し、かつ、該組成物の下記試験条件で得られる温度上昇が７３℃以下であることを特徴とする積層体が提供される。
〔試験条件〕
前記低蓄熱性樹脂組成物からなる成形品（長さ８０ｍｍ、幅５５ｍｍ、厚さ２．５ｍｍ）を、温度２５±２℃、湿度５０±５％ＲＨに調節された室で６０分間状態調節した後、高さ２００ｍｍからその表面に赤外線ランプ（出力１００Ｗ）を６０分間照射した後の成形品の表面温度を測定し、赤外線ランプ照射前の初期温度との差を温度上昇とする。
As a result of intensive investigations to achieve the above object, the present inventors have laminated a layer made of a low heat storage resin composition formed by blending a specific inorganic pigment on a base material, resulting in low heat storage and weather resistance. It has been found that a laminate having a wood grain pattern having excellent properties, colorability of wood grain pattern, heat resistance (dimensional stability), etc. can be provided, and the present invention has been completed.
That is, according to the present invention, a laminate comprising a base material and a layer having a woodgrain pattern laminated thereon, wherein the layer having a woodgrain pattern is a low-layer containing a thermoplastic resin (A). It consists of a heat storage resin composition, and the composition contains 0.5 to 13% by mass of the inorganic pigment (B) having infrared reflection characteristics with respect to the entire composition, and the following test conditions of the composition The laminated body is characterized in that the temperature rise obtained in (1) is 73 ° C. or less.
〔Test conditions〕
A molded article (length 80 mm, width 55 mm, thickness 2.5 mm) made of the low heat storage resin composition was conditioned for 60 minutes in a room adjusted to a temperature of 25 ± 2 ° C. and a humidity of 50 ± 5% RH. Thereafter, the surface temperature of the molded article after the surface is irradiated with an infrared lamp (output 100 W) for 60 minutes from a height of 200 mm is measured, and the difference from the initial temperature before irradiation with the infrared lamp is defined as a temperature rise.
本発明の積層体において、基材に積層された木目調模様を有する層は、赤外線反射特性を有する無機顔料を所定量含有することにより光照射時の温度上昇が所定温度以下に抑制された低蓄熱性樹脂組成物から形成されているため、基材に木目調模様の外観を付与できるだけでなく、基材の蓄熱を低減させ、基材の耐候性、木目調模様の着色性、耐熱性（寸法安定性）をも改善することができる。 In the laminate of the present invention, the layer having a woodgrain pattern laminated on the base material contains a predetermined amount of an inorganic pigment having infrared reflection characteristics, so that the temperature rise during light irradiation is suppressed to a predetermined temperature or less. Since it is formed from a heat storage resin composition, it can not only give the substrate a woodgrain appearance, but also reduce the heat storage of the substrate, weather resistance of the substrate, coloration of the woodgrain pattern, heat resistance ( Dimensional stability) can also be improved.
以下、本発明を詳しく説明する。尚、本明細書において、「（共）重合」とは、単独重合及び共重合を意味し、「（メタ）アクリル」とは、アクリル及び／又はメタクリルを意味し、「（メタ）アクリレート」とは、アクリレート及び／又はメタクリレートを意味する。 The present invention will be described in detail below. In the present specification, “(co) polymerization” means homopolymerization and copolymerization, “(meth) acryl” means acryl and / or methacryl, and “(meth) acrylate” Means acrylate and / or methacrylate.
以下、本発明を更に詳しく説明する。
本発明の積層体の木目調模様を有する層は、低蓄熱性樹脂組成物から形成される。この低蓄熱性樹脂組成物は、熱可塑性樹脂（Ａ）を含むものであれば特に限定されない。
熱可塑性樹脂（Ａ）としては、ゴム強化ビニル系樹脂；ポリエチレン系樹脂、ポリプロピレン系樹脂、エチレン・α−オレフィン系樹脂などのポリオレフィン系樹脂；ポリ塩化ビニル樹脂；ポリ塩化ビニリデン樹脂；ポリ酢酸ビニル樹脂；飽和ポリエステル系樹脂；（メタ）アクリル酸エステル化合物の（共）重合体等のアクリル系樹脂；フッ素樹脂；アクリロニトリル・スチレン樹脂、芳香族ビニル化合物等の（共）重合体などのスチレン系樹脂、エチレン・酢酸ビニル樹脂等が挙げられる。これらは、１種単独でまたは２種以上を組み合わせて使用することができる。これらのうち、ゴム強化ビニル系樹脂、ポリ塩化ビニル樹脂、アクリル系樹脂が好ましく、ゴム強化ビニル系樹脂が特に好ましい。
Hereinafter, the present invention will be described in more detail.
The layer having the woodgrain pattern of the laminate of the present invention is formed from a low heat storage resin composition. This low heat storage resin composition will not be specifically limited if it contains a thermoplastic resin (A).
Thermoplastic resins (A) include rubber-reinforced vinyl resins; polyethylene resins, polypropylene resins, polyolefin resins such as ethylene / α-olefin resins; polyvinyl chloride resins; polyvinylidene chloride resins; A saturated polyester resin; an acrylic resin such as a (co) polymer of a (meth) acrylic ester compound; a fluororesin; a styrene resin such as a (co) polymer such as an acrylonitrile / styrene resin or an aromatic vinyl compound; Examples thereof include ethylene / vinyl acetate resin. These can be used individually by 1 type or in combination of 2 or more types. Of these, rubber reinforced vinyl resins, polyvinyl chloride resins, and acrylic resins are preferable, and rubber reinforced vinyl resins are particularly preferable.
ゴム強化ビニル系樹脂は、ビニル系樹脂中に、その耐衝撃性等を改良するためにゴム質重合体（ａ）を含有してなるものである。
ゴム質重合体（ａ）としては、ジエン系ゴム質重合体及び非ジエン系ゴム質重合体の何れも使用できる。本明細書において、非ジエン系ゴム質重合体は、主鎖の一部に二重結合を備えても良く、許容される二重結合の量の上限はゴム質重合体の種類によって異なり一義的には決められないが、種類毎に適宜実験を行うことにより決めることができる。
ジエン系ゴム質重合体としては、ポリブタジエン、スチレン・ブタジエン共重合体、ブタジエン・アクリロニトリル共重合体、スチレン・ブタジエン・スチレンブロック共重合体、スチレン・イソプレン・スチレンブロック共重合体等が挙げられる。
非ジエン系ゴム質重合体としては、エチレン・プロピレン共重合体、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共重合体、エチレン・ブテン−１・非共役ジエン共重合体、イソブチレン・イソプレン共重合体等のエチレン・α−オレフィン共重合体、アクリル系ゴム、ポリウレタンゴム、シリコーンゴムの他、上記ジエン系ゴム質重合体の水素添加物等が挙げられる。この水素添加物には、上記ブロック共重合体の水素添加物の他に、スチレンブロックとスチレン・ブタジエンランダム共重合体の水素添加物等が含まれる。水素添加物の好ましい水素添加率は共役ジエン単位部分の９０モル％以上である。
本発明においては、これらのうち、耐候性及び木目調模様の鮮映性の点から、非ジエン系ゴム質重合体を用いることが好ましく、上記水素添加物及びアクリル系ゴムが更に好ましく、アクリル系ゴムが特に好ましい。
上記ゴム質重合体（ａ）は、１種単独でまたは２種以上を組み合わせて使用することができる。また、本発明のゴム強化ビニル系樹脂は、１種のゴム質重合体を使用して得られたゴム強化ビニル系樹脂単独からなるものであっても、異なるゴム質重合体を使用して得られた２種以上のゴム強化ビニル系樹脂を組み合わせたものであってもよい。本発明においては、ゴム強化ビニル系樹脂を乳化重合により得る場合には、ラテックス状のゴム質重合体が好ましい。
The rubber-reinforced vinyl resin contains a rubbery polymer (a) in order to improve impact resistance and the like in the vinyl resin.
As the rubber polymer (a), either a diene rubber polymer or a non-diene rubber polymer can be used. In the present specification, the non-diene rubbery polymer may have a double bond in a part of the main chain, and the upper limit of the amount of double bond allowed is unambiguous depending on the type of rubber polymer. However, it can be determined by conducting an experiment for each type as appropriate.
Examples of the diene rubbery polymer include polybutadiene, styrene / butadiene copolymer, butadiene / acrylonitrile copolymer, styrene / butadiene / styrene block copolymer, styrene / isoprene / styrene block copolymer, and the like.
Non-diene rubbery polymers include ethylene / propylene copolymers, ethylene / propylene / non-conjugated diene copolymers, ethylene / butene-1 copolymers, ethylene / butene-1 / non-conjugated diene copolymers, In addition to ethylene / α-olefin copolymers such as isobutylene / isoprene copolymers, acrylic rubbers, polyurethane rubbers, silicone rubbers, hydrogenated products of the diene rubbery polymers, and the like. The hydrogenated product includes a hydrogenated product of a styrene block and a styrene / butadiene random copolymer in addition to the hydrogenated product of the block copolymer. A preferable hydrogenation rate of the hydrogenated product is 90 mol% or more of the conjugated diene unit portion.
In the present invention, among these, it is preferable to use a non-diene rubber polymer from the viewpoint of weather resistance and wood grain pattern vividness, the hydrogenated product and acrylic rubber are more preferable, acrylic type Rubber is particularly preferred.
The said rubbery polymer (a) can be used individually by 1 type or in combination of 2 or more types. Further, the rubber-reinforced vinyl resin of the present invention can be obtained by using a different rubber polymer, even if it is composed of a rubber-reinforced vinyl resin alone obtained by using one kind of rubber polymer. A combination of two or more rubber-reinforced vinyl resins obtained may be used. In the present invention, when a rubber-reinforced vinyl resin is obtained by emulsion polymerization, a latex-like rubbery polymer is preferable.
ゴム質重合体（ａ）を乳化重合で得る場合、そのゲル含率は、好ましくは９８質量％以下であり、更に好ましくは４０〜９８質量％である。この範囲とすることにより耐衝撃性及び表面外観に優れた木目調模様の層を得ることができる。
ゲル含率は、以下に示す方法により求めることができる。
先ず、ゴム質重合体１ｇをトルエン１００ｍｌに投入し、室温で４８時間静置する。その後、１００メッシュの金網（質量をＷ１グラムとする）で濾過したトルエン不溶分と金網を、温度８０℃で６時間真空乾燥して秤量（質量Ｗ２グラムとする）する。Ｗ１及びＷ２を、下記式（１）に代入して、ゲル含率を得る。
ゲル含率＝〔{Ｗ２（ｇ）−Ｗ１（ｇ）}／１（ｇ）〕×１００ （１）
When the rubbery polymer (a) is obtained by emulsion polymerization, the gel content is preferably 98% by mass or less, and more preferably 40 to 98% by mass. By setting it within this range, it is possible to obtain a woodgrain layer having excellent impact resistance and surface appearance.
The gel content can be determined by the following method.
First, 1 g of a rubbery polymer is put into 100 ml of toluene and allowed to stand at room temperature for 48 hours. Thereafter, the toluene-insoluble matter and the wire mesh filtered through a 100-mesh wire mesh (mass is W 1 gram) are vacuum-dried at a temperature of 80 ° C. for 6 hours and weighed (mass W is 2 grams). Substituting W 1 and W 2 into the following formula (1) to obtain the gel content.
Gel content = [{W 2 (g) −W 1 (g)} / 1 (g)] × 100 (1)
尚、ゲル含率は、ゴム質重合体の製造時に、架橋性単量体の種類及びその使用量、分子量調節剤の種類及びその使用量、重合時間、重合温度、重合転化率等を適宜設定することにより調整される。 The gel content is set appropriately at the time of production of the rubbery polymer, such as the type and amount of the crosslinkable monomer, the type and amount of the molecular weight regulator, the polymerization time, the polymerization temperature and the polymerization conversion rate It is adjusted by doing.
上記ラテックスを用いる場合の、ラテックス中のゴム質重合体（ａ）の重量平均粒子径は、好ましくは５００〜８０００Åであり、更に好ましくは１０００〜５０００Å、特に好ましくは１０００〜４０００Åである。５００Å未満では成形品の耐衝撃性が劣る傾向にあり、８０００Åを超えると木目調模様の層の表面光沢が劣る場合がある。 When the latex is used, the weight average particle diameter of the rubber-like polymer (a) in the latex is preferably 500 to 8000, more preferably 1000 to 5000, and particularly preferably 1000 to 4000. If it is less than 500 mm, the impact resistance of the molded product tends to be inferior, and if it exceeds 8000 mm, the surface gloss of the woodgrain pattern layer may be inferior.
上記ゴム質重合体（ａ）を製造する方法としては、平均粒子径の調整等を考慮し、通常、乳化重合法が好ましいが、この場合、平均粒子径は乳化剤の種類・量、開始剤の種類・量、重合時間、重合温度及び攪拌条件等の製造条件を適宜選択することにより調整することができる。また、粒子径分布の他の調整方法としては、異なる粒子径の上記ゴム質重合体（ａ）の少なくとも２種類をブレンドする方法でもよい。 As a method for producing the rubber polymer (a), an emulsion polymerization method is usually preferred in consideration of adjustment of the average particle size and the like. It can be adjusted by appropriately selecting the production conditions such as type / amount, polymerization time, polymerization temperature and stirring conditions. Another method for adjusting the particle size distribution may be a method of blending at least two kinds of the rubbery polymers (a) having different particle sizes.
上記ゴム強化ビニル系樹脂のビニル系樹脂を構成するビニル系単量体成分（ｂ）としては特に限定されず、芳香族ビニル化合物、（メタ）アクリル酸エステル化合物、シアン化ビニル化合物、マレイミド系化合物、酸無水物等が挙げられる。これらは、１種単独でまたは２種以上を組み合わせて用いることができる。 The vinyl monomer component (b) constituting the vinyl resin of the rubber-reinforced vinyl resin is not particularly limited, and is an aromatic vinyl compound, a (meth) acrylic ester compound, a vinyl cyanide compound, a maleimide compound. And acid anhydrides. These can be used individually by 1 type or in combination of 2 or more types.
芳香族ビニル化合物としては、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｐ−メチルスチレン、ｔ−ブチルスチレン、ビニルトルエン、メチル−α−メチルスチレン、ジビニルベンゼン、臭素化スチレン等が挙げられる。これらのうち、スチレン、α−メチルスチレン、ｐ−メチルスチレンが好ましい。また、これらは、１種単独でまたは２種以上を組み合わせて用いることができる。 Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, t-butylstyrene, vinyltoluene, methyl-α-methylstyrene, divinylbenzene, brominated styrene and the like. Of these, styrene, α-methylstyrene, and p-methylstyrene are preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.
（メタ）アクリル酸エステル化合物としては、例えば、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル等が挙げられる。これらのうち、メタクリル酸メチルが好ましい。また、これらは、１種単独でまたは２種以上を組み合わせて用いることができる。 Examples of the (meth) acrylic acid ester compound include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. Of these, methyl methacrylate is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.
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等が挙げられ、これらのうち、アクリロニトリルが好ましい。また、これらは、１種単独でまたは２種以上を組み合わせて用いることができる。
マレイミド系化合物としては、例えば、マレイミド、Ｎ−メチルマレイミド、Ｎ−ブチルマレイミド、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−ヒドロキシフェニル）マレイミド、Ｎ−シクロヘキシルマレイミド等が挙げられる。これらのうち、Ｎ−フェニルマレイミドが好ましい。また、これらは、１種単独でまたは２種以上を組み合わせて用いることができる。尚、マレイミド系化合物を導入する他の方法としては、例えば、無水マレイン酸を共重合し、その後イミド化する方法でもよい。
Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Among these, acrylonitrile is preferable. Moreover, these can be used individually by 1 type or in combination of 2 or more types.
Examples of maleimide compounds include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide and the like. Is mentioned. Of these, N-phenylmaleimide is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types. In addition, as another method of introducing the maleimide compound, for example, a method of copolymerizing maleic anhydride and then imidizing may be used.
酸無水物としては、例えば、無水マレイン酸、無水イタコン酸、無水シトラコン酸等が挙げられる。また、これらは、１種単独でまたは２種以上を組み合わせて用いることができる。 Examples of the acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Moreover, these can be used individually by 1 type or in combination of 2 or more types.
上記ビニル系単量体成分（ｂ）は、芳香族ビニル化合物を含むことが好ましく、その場合、芳香族ビニル化合物（ｂ１）と、それ以外のビニル系単量体（ｂ２）との重合割合（成分（ｂ１）／成分（ｂ２））は、これらの合計を１００質量％とした場合、好ましくは１０〜９５／５〜９０（単位：質量％）、より好ましくは２０〜８５／１５〜８０（単位：質量％）である。芳香族ビニル化合物（ｂ１）の使用量が少なすぎると、成形加工性、成形品の美的外観性が劣る傾向にあり、多すぎると、ビニル系単量体（ｂ２）の使用による効果が十分に発揮できない傾向にある。尚、上記ビニル系単量体（ｂ２）は、好ましくは（メタ）アクリル酸エステル化合物、シアン化ビニル化合物、マレイミド化合物等から選ばれた少なくとも１種から構成される。また、本発明の組成物の木目調模様の着色性、鮮映性を向上させるために、上記ビニル系単量体成分（ｂ）は、（メタ）アクリル酸エステル化合物を含むことが好ましく、メタクリル酸メチルを含むことが特に好ましい。（メタ）アクリル酸エステル化合物の使用量は、ビニル系単量体成分（ｂ）全体１００質量％に対して、２０〜９５質量％が好ましく、４０〜９０質量％が更に好ましい。 The vinyl monomer component (b) preferably contains an aromatic vinyl compound. In that case, the polymerization ratio of the aromatic vinyl compound (b1) and the other vinyl monomer (b2) ( Component (b1) / component (b2)) is preferably 10 to 95/5 to 90 (unit: mass%), more preferably 20 to 85/15 to 80 (unit: mass%) when the total of these is 100% by mass. (Unit: mass%). If the amount of the aromatic vinyl compound (b1) used is too small, the molding processability and the aesthetic appearance of the molded product tend to be inferior. If it is too much, the effect of using the vinyl monomer (b2) is sufficient. There is a tendency not to show. The vinyl monomer (b2) is preferably composed of at least one selected from (meth) acrylic acid ester compounds, vinyl cyanide compounds, maleimide compounds and the like. The vinyl monomer component (b) preferably contains a (meth) acrylic acid ester compound in order to improve the colorability and sharpness of the woodgrain pattern of the composition of the present invention. It is particularly preferred to include methyl acid. The amount of the (meth) acrylic acid ester compound used is preferably 20 to 95 mass%, more preferably 40 to 90 mass%, based on 100 mass% of the entire vinyl monomer component (b).
また、本発明の目的を損なわない範囲で、ビニル系単量体成分（ｂ）として、更に以下の単量体化合物を使用することができる。その例としては、エポキシ基、ヒドロキシル基、アミノ基、アミド基、カルボン酸基、オキサゾリン基等の群から選ばれる少なくとも１種の官能基を含有するビニル化合物が挙げられる。その例としては、グリシジルメタクリレート、グリシジルアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシエチルアクリレート、アクリルアミド、アクリル酸、メタクリル酸、ビニルオキサゾリン等が挙げられる。 Moreover, the following monomer compounds can be further used as the vinyl monomer component (b) as long as the object of the present invention is not impaired. Examples thereof include vinyl compounds containing at least one functional group selected from the group of epoxy groups, hydroxyl groups, amino groups, amide groups, carboxylic acid groups, oxazoline groups, and the like. Examples thereof include glycidyl methacrylate, glycidyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylamide, acrylic acid, methacrylic acid, vinyl oxazoline and the like.
ゴム強化ビニル系樹脂は、通常、下記成分（Ａ１）、または成分（Ａ１）及び成分（Ａ２）とからなる。
成分（Ａ１）：ゴム質重合体（ａ）の存在下にビニル系単量体成分（ｂ）を重合して得られたゴム変性ビニル系樹脂。
成分（Ａ２）：ゴム質重合体（ａ）の非存在下にビニル系単量体成分（ｂ）を重合して得られた（共）重合体。
上記成分（Ａ１）は、通常、ビニル系単量体成分（ｂ）がゴム質重合体（ａ）にグラフト（共）重合してなるグラフト共重合体と、ゴム質重合体にグラフトしていない未グラフト共重合体（上記成分（Ａ２）と実質的に同じ）とを含む。
しかし、上記成分（Ａ２）は、上記未グラフト共重合体と同一成分から構成される必要はなく、上記成分（Ａ１）の形成に用いたビニル系単量体成分（ｂ）と全く同じ組成の成分を重合して得られる重合体であってもよいし、上記成分（Ａ１）の形成に用いたビニル系単量体成分（ｂ）と異なる組成の成分を重合して得られる重合体であってもよい。更には、上記成分（Ａ１）及び成分（Ａ２）は、それぞれ２種以上の異なる組成のものを組み合わせたものであってもよい。
The rubber-reinforced vinyl resin is usually composed of the following component (A1), or component (A1) and component (A2).
Component (A1): A rubber-modified vinyl resin obtained by polymerizing the vinyl monomer component (b) in the presence of the rubbery polymer (a).
Component (A2): A (co) polymer obtained by polymerizing the vinyl monomer component (b) in the absence of the rubbery polymer (a).
The component (A1) is usually not grafted to a rubber copolymer and a graft copolymer obtained by grafting (co) polymerizing the vinyl monomer component (b) to the rubber polymer (a). An ungrafted copolymer (substantially the same as component (A2) above).
However, the component (A2) need not be composed of the same component as the ungrafted copolymer, and has the same composition as the vinyl monomer component (b) used for forming the component (A1). It may be a polymer obtained by polymerizing the components, or a polymer obtained by polymerizing components having a composition different from that of the vinyl monomer component (b) used for the formation of the component (A1). May be. Furthermore, the component (A1) and the component (A2) may be a combination of two or more different compositions.
上記ゴム強化ビニル系樹脂が、上記成分（Ａ１）単独からなる場合、及び、上記成分（Ａ１）と上記成分（Ａ２）とからなる場合のいずれにおいても、本組成物中のゴム質重合体（ａ）の含有量は、好ましくは３〜４０質量％、より好ましくは５〜３５質量％である。ゴム質重合体（ａ）の含有量が少なすぎると、耐衝撃性が劣る傾向にあり、多すぎると、硬度、剛性が劣る傾向にある。また、上記成分（Ａ１）製造時のゴム質重合体（ａ）の使用量は、ゴム質重合体（ａ）のビニル系単量体成分（ｂ）に対する質量比（ゴム質重合体（ａ）／ビニル系単量体成分（ｂ）、両者の合計１００質量％）で、５〜８０／９５〜２０が好ましく、１０〜７５／９０〜２５が更に好ましい。 Whether the rubber-reinforced vinyl resin is composed of the component (A1) alone or the component (A1) and the component (A2), the rubbery polymer ( The content of a) is preferably 3 to 40% by mass, more preferably 5 to 35% by mass. If the content of the rubbery polymer (a) is too small, the impact resistance tends to be inferior, and if it is too much, the hardness and rigidity tend to be inferior. The amount of the rubber polymer (a) used in the production of the component (A1) is the mass ratio of the rubber polymer (a) to the vinyl monomer component (b) (rubber polymer (a). / Vinyl monomer component (b), the total of both being 100 mass%), preferably 5-80 / 95-20, more preferably 10-75 / 90-25.
上記成分（Ａ１）は、ゴム質重合体（ａ）の存在下に、ビニル系単量体成分（ｂ）を、好ましくは乳化重合、溶液重合、塊状重合による方法で製造することができる。
乳化重合により製造する場合には、重合開始剤、連鎖移動剤（分子量調節剤）、乳化剤、水等が用いられる。
尚、上記成分（Ａ１）を製造するために用いられるゴム質重合体（ａ）及びビニル系単量体成分（ｂ）は、反応系において、ゴム質重合体全量の存在下に、単量体成分を一括添加してもよいし、分割又は連続添加してもよい。また、これらを組み合わせた方法でもよい。更に、ゴム質重合体の全量又は一部を、重合途中で添加して重合してもよい。
In the presence of the rubbery polymer (a), the component (A1) can be produced from the vinyl monomer component (b), preferably by emulsion polymerization, solution polymerization, or bulk polymerization.
In the case of producing by emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water and the like are used.
The rubbery polymer (a) and the vinyl monomer component (b) used for producing the component (A1) are a monomer in the reaction system in the presence of the total amount of the rubbery polymer. The components may be added all at once, or dividedly or continuously. Moreover, the method which combined these may be used. Furthermore, you may superpose | polymerize by adding the whole quantity or one part of a rubber-like polymer in the middle of superposition | polymerization.
上記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で代表される有機ハイドロパーオキサイド類と含糖ピロリン酸処方、スルホキシレート処方等で代表される還元剤との組み合わせによるレドックス系、または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、ｔ−ブチルパーオキシラウレイト、ｔ−ブチルパーオキシモノカーボネート等の過酸化物等が挙げられ、これらは、１種単独でまたは２種以上を組み合わせて用いることができる。更に、上記重合開始剤は、反応系に一括又は連続的に添加することができる。また、上記重合開始剤の使用量は、上記ビニル系単量体成分（ｂ）全量に対し、通常、０．１〜１．５質量％、好ましくは０．２〜０．７質量％である。 As the polymerization initiator, organic hydroperoxides typified by cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide and the like, and reductions typified by sugar-containing pyrophosphate prescription, sulfoxylate prescription, etc. Redox system by combination with agents, or persulfates such as potassium persulfate, peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, t-butyl peroxylaurate, t-butyl peroxymonocarbonate, etc. These may be used alone or in combination of two or more. Furthermore, the polymerization initiator can be added to the reaction system all at once or continuously. Moreover, the usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinylic monomer component (b) whole quantity, Preferably it is 0.2-0.7 mass%. .
上記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、ｔ−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、ｔ−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、α−メチルスチレンのダイマー等が挙げられ、これらは、１種単独でまたは２種以上を組み合わせて用いることができる。上記連鎖移動剤の使用量は、上記ビニル系単量体成分（ｂ）全量に対して、通常、０．０５〜２．０質量％である。 Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, terpinolene, α -The dimer of methylstyrene etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types. The amount of the chain transfer agent used is usually 0.05 to 2.0% by mass with respect to the total amount of the vinyl monomer component (b).
乳化重合の場合に使用する乳化剤としては、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、リン酸系等のアニオン性界面活性剤、ポリエチレングリコールのアルキルエステル型、アルキルエーテル型等のノニオン系界面活性剤等が挙げられる。これらは、１種単独でまたは２種以上を組み合わせて用いることができる。上記乳化剤の使用量は、通常、上記ビニル系単量体成分（ｂ）全量に対して、０．３〜５．０質量％である。 As an emulsifier used in the case of emulsion polymerization, sulfate ester of higher alcohol, alkylbenzene sulfonate such as sodium dodecylbenzene sulfonate, aliphatic sulfonate such as sodium lauryl sulfate, higher aliphatic carboxylate, phosphoric acid And anionic surfactants such as polyethylene glycol alkyl ester type and alkyl ether type nonionic surfactants. These can be used individually by 1 type or in combination of 2 or more types. The usage-amount of the said emulsifier is 0.3-5.0 mass% normally with respect to the said vinylic monomer component (b) whole quantity.
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や、硫酸、塩酸等の無機酸、酢酸、乳酸等の有機酸等が用いられる。
溶液重合、塊状重合による製造方法は、公知の方法を採用することができる。
The latex obtained by emulsion polymerization is usually purified by coagulation with a coagulant to make the polymer component into powder, and then washing and drying. As the coagulant, 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, and the like are used.
A known method can be adopted as a production method by solution polymerization or bulk polymerization.
上記成分（Ａ１）のグラフト率は、好ましくは１０〜２００％、更に好ましくは１５〜１５０％、特に好ましくは２０〜１００％である。上記成分（Ａ１）のグラフト率が１０％未満では、本発明の低蓄熱性樹脂組成物を用いて得られる木目調模様の層の外観不良、衝撃強度の低下を招くことがある。また、２００％を超えると、加工性が劣る。
尚、グラフト率は、以下に示す方法により求めることができる。
グラフト率（質量％）＝｛（Ｔ−Ｓ）／Ｓ｝×１００…（２）
上記式（２）中、Ｔは成分（Ａ１）１ｇをアセトン（ただし、ゴム質重合体（ａ）がアクリル系ゴムを使用したものである場合、アセトニトリル）２０ｍｌに投入し、振とう機により２時間振とうした後、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、Ｓは成分（Ａ１）１ｇに含まれるゴム質重合体の質量（ｇ）である。
The graft ratio of the component (A1) is preferably 10 to 200%, more preferably 15 to 150%, and particularly preferably 20 to 100%. When the graft ratio of the component (A1) is less than 10%, the appearance of the woodgrain pattern layer obtained by using the low heat storage resin composition of the present invention may be deteriorated and the impact strength may be lowered. Moreover, when it exceeds 200%, workability is inferior.
The graft rate can be determined by the following method.
Graft ratio (mass%) = {(TS) / S} × 100 (2)
In the above formula (2), T is 1 g of component (A1) in 20 ml of acetone (but acetonitrile if the rubbery polymer (a) uses acrylic rubber), and 2 by a shaker. It is the mass (g) of insoluble matter obtained by centrifuging for 60 minutes in a centrifuge (rotation speed: 23,000 rpm) after shaking for a while to separate the insoluble matter and the soluble matter. (A1) The mass (g) of the rubbery polymer contained in 1 g.
また、上記成分（Ａ１）のアセトン可溶分（ただし、ゴム質重合体（ａ）がアクリル系ゴムを使用したものである場合、アセトニトリル可溶分）の極限粘度〔η〕（メチルエチルケトン中、３０℃で測定）は、好ましくは０．１〜１．０ｄｌ／ｇ、更に好ましくは０．２〜０．９ｄｌ／ｇ、特に好ましくは０．３〜０．７ｄｌ／ｇである。この範囲とすることにより、本発明の低蓄熱性樹脂組成物は成形加工性（流動性）に優れ、該組成物を用いて得られる木目調模様の層も耐衝撃性に優れる。
尚、上記グラフト率（％）及び極限粘度〔η〕は、上記成分（Ａ１）を重合するときの、重合開始剤、連鎖移動剤、乳化剤、溶剤等の種類や量、更には重合時間、重合温度等を変えることにより、容易に制御することができる。
Further, the intrinsic viscosity [η] of the component (A1) soluble in acetone (however, in the case where the rubbery polymer (a) uses acrylic rubber, acetonitrile soluble component) (in methyl ethyl ketone, 30 (Measured at ° C.) is preferably 0.1 to 1.0 dl / g, more preferably 0.2 to 0.9 dl / g, and particularly preferably 0.3 to 0.7 dl / g. By setting it as this range, the low heat storage resin composition of this invention is excellent in moldability (fluidity), and the grain pattern layer obtained using this composition is also excellent in impact resistance.
The graft ratio (%) and intrinsic viscosity [η] are the types and amounts of polymerization initiator, chain transfer agent, emulsifier, solvent, etc., when polymerizing the component (A1), and further the polymerization time, polymerization It can be easily controlled by changing the temperature or the like.
上記成分（Ａ２）は、ビニル系単量体成分（ｂ）をゴム質重合体（ａ）の非存在下に重合させる以外、上記成分（Ａ１）と同様の方法で得ることができ、例えば、バルク重合、溶液重合、乳化重合及び懸濁重合等により得ることができる。成分（Ａ２）の重合に用いられる好ましいビニル系単量体成分（ｂ）の種類及び組合せも、上記成分（Ａ１）について記述したものがそのまま当てはまる。
上記成分（Ａ２）の極限粘度〔η〕（メチルエチルケトン中、３０℃で測定）は、好ましくは０．１〜１．０ｄｌ／ｇ、より好ましくは０．１５〜０．９ｄｌ／ｇである。極限粘度〔η〕が上記範囲内であると、木目調模様の層の成形加工性と耐衝撃性の物性バランスに優れる。尚、極限粘度〔η〕は、上記成分（Ａ１）と同様にして制御することができる。
本発明で使用されるゴム強化ビニル系樹脂は、共重合成分として（メタ）アクリル酸エステル化合物を含有するものである場合、鮮明な木目調模様の着色性が得られ、耐候性、ポリ塩化ビニル樹脂との接着性にも優れるので好ましい。（メタ）アクリル酸エステル化合物としては、メタクリル酸メチルが好ましい。（メタ）アクリル酸エステル化合物の含有量は、本発明の低蓄熱性樹脂組成物全体に対して、好ましくは５〜６０質量％、さらに好ましくは１０〜５０質量％、特に好ましくは１０〜４０質量％である。（メタ）アクリル酸エステル化合物の含有量が少ないと、鮮明な木目調模様の着色性、耐候性、ポリ塩化ビニル樹脂との接着性等の改良効果が十分でない場合がある。（メタ）アクリル酸エステル化合物の含有量が多すぎると、耐衝撃性が劣る場合がある。共重合成分として（メタ）アクリル酸エステル化合物を含有するゴム強化ビニル系樹脂は、共重合成分として（メタ）アクリル酸エステル化合物を含有する成分（Ａ１）及び共重合成分として（メタ）アクリル酸エステル化合物を含有する成分（Ａ２）のいずれか一方又は両者を含有するものであってよい。
The component (A2) can be obtained in the same manner as the component (A1) except that the vinyl monomer component (b) is polymerized in the absence of the rubbery polymer (a). It can be obtained by bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization and the like. The types and combinations of the preferred vinyl-based monomer component (b) used for the polymerization of the component (A2) are the same as those described for the component (A1).
The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the component (A2) is preferably 0.1 to 1.0 dl / g, more preferably 0.15 to 0.9 dl / g. When the intrinsic viscosity [η] is within the above range, the wood grain pattern layer is excellent in the balance between physical properties of molding processability and impact resistance. The intrinsic viscosity [η] can be controlled in the same manner as the component (A1).
When the rubber-reinforced vinyl resin used in the present invention contains a (meth) acrylic acid ester compound as a copolymer component, a clear wood grain pattern colorability is obtained, weather resistance, polyvinyl chloride It is preferable because it is excellent in adhesiveness with resin. As the (meth) acrylic acid ester compound, methyl methacrylate is preferable. The content of the (meth) acrylic acid ester compound is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and particularly preferably 10 to 40% by mass with respect to the entire low heat storage resin composition of the present invention. %. If the content of the (meth) acrylic acid ester compound is small, there are cases where the effect of improving the colorability of clear woodgrain pattern, weather resistance, adhesiveness with polyvinyl chloride resin and the like are not sufficient. When there is too much content of a (meth) acrylic acid ester compound, impact resistance may be inferior. The rubber-reinforced vinyl resin containing a (meth) acrylic acid ester compound as a copolymerization component includes a component (A1) containing a (meth) acrylic acid ester compound as a copolymerization component and a (meth) acrylic acid ester as a copolymerization component. It may contain either one or both of the component (A2) containing the compound.
本発明に係わる赤外線反射特性を有する無機顔料（Ｂ）は、熱可塑性樹脂（Ａ）に低蓄熱特性を付与するためのみならず、熱可塑性樹脂（Ａ）に木に類似した色彩および木目調の模様を付与するために用いられる。なお、本発明において、木目調模様とは、木目模様のみならず、大理石模様なども含む概念である。
かかる無機顔料（Ｂ）としては、赤外線を吸収しにくい性質を有するものであれば特に限定されず、Ｆｅ、Ｃｒ、Ｍｎ、Ｃｕ、Ｃｏ及びＮｉから選ばれる少なくとも１種の元素を含む化合物が好ましい。特に、上記元素の酸化物、複合酸化物等が好ましく、具体的には、ＦｅＯ、ＦｅＯ（ＯＨ）、Ｆｅ２Ｏ３、ＣｒＯ、Ｃｒ２Ｏ３、Ｃｒ２Ｏ３・２Ｈ２Ｏ、ＭｎＯ、Ｍｎ２Ｏ３、ＭｎＯ２、ＣｕＯ、Ｃｕ２Ｏ、ＣｏＯ、ＣｏＯ・Ａｌ２Ｏ３、Ｆｅ（Ｆｅ，Ｃｒ）２Ｏ４、（Ｃｏ，Ｆｅ）（Ｆｅ，Ｃｒ）２Ｏ４、Ｃｕ（Ｃｒ，Ｍｎ）２Ｏ４、（Ｃｕ，Ｆｅ，Ｍｎ）（Ｆｅ，Ｃｒ，Ｍｎ）２Ｏ４、（Ｆｅ，Ｚｎ）（Ｆｅ，Ｃｒ）２Ｏ４、（Ｆｅ，Ｚｎ）Ｆｅ２Ｏ４、ＣｏＡｌ２Ｏ４、Ｃｏ（Ａｌ，Ｃｒ）２Ｏ４、Ｃｒ２Ｏ３：Ｆｅ２Ｏ３、（Ｎｉ，Ｃｏ，Ｆｅ）（Ｆｅ，Ｃｒ）２Ｏ４等が挙げられる。これらのうち、好ましくは、Ｃｒ２Ｏ３：Ｆｅ２Ｏ３、（Ｃｕ，Ｆｅ，Ｍｎ）（Ｆｅ，Ｃｒ，Ｍｎ）２Ｏ４、Ｆｅ（Ｆｅ，Ｃｒ）２Ｏ４、（Ｃｏ，Ｆｅ）（Ｆｅ，Ｃｒ）２Ｏ４、Ｃｕ（Ｃｒ，Ｍｎ）２Ｏ４、（Ｎｉ，Ｃｏ，Ｆｅ）（Ｆｅ，Ｃｒ）２Ｏ４が挙げられる。また、上記例示した酸化物及び複合酸化物は、それぞれ１種単独でまたは２種以上を組み合わせて用いることができ、所望の色に着色された成形品とすることができる。
尚、上記例示した中で、ＣｏＯは、単独で用いた場合、太陽光が当たったときに赤外線の強度等によって成形品の表面に白化が発生したり、紫外線によって揮散したりすることがあるため、ＣｏＯを用いる場合は、他の無機顔料と組み合わせて用いることが好ましい。本発明の低蓄熱性樹脂組成物においては、黒系、深緑系等の暗色系の色の層を得る場合、無機顔料（Ｂ）としてＦｅ、Ｃｒ及びＭｎから選ばれる少なくとも２種の元素を含む酸化物を用いることが好ましい。その例としては、Ｆｅ（Ｆｅ，Ｃｒ）２Ｏ４、（Ｃｏ，Ｆｅ）（Ｆｅ，Ｃｒ）２Ｏ４、Ｃｕ（Ｃｒ，Ｍｎ）２Ｏ４、（Ｃｕ，Ｆｅ，Ｍｎ）（Ｆｅ，Ｃｒ，Ｍｎ）２Ｏ４、（Ｆｅ，Ｚｎ）（Ｆｅ，Ｃｒ）２Ｏ４、Ｃｒ２Ｏ３：Ｆｅ２Ｏ３等が挙げられる。これらは、１種単独でまたは２種以上を組み合わせて用いることができる。
また、黒系、深緑系等の暗色系の色の層を得るためには、上記例示した無機顔料は、その合計が、無機顔料（Ｂ）全体に対して、好ましくは６０質量％以上、より好ましくは７０〜１００質量％、更に好ましくは８０〜１００質量％となるように含有させることが必要である。１００質量％でない場合の残部は、他の顔料（無機顔料、有機顔料、カーボンブラック等）を本発明の目的を損なわない範囲で使用することができる。また、黒系、深緑系のみならず、青系、茶系等の暗色系の色についても、所望の色に応じて、１種単独でまたは色の三原色を利用した複数種の無機顔料の組み合わせによって得ることができる。従来の着色剤は、有機顔料または染料を組み合わせるものであり、成形品が退色、変色する等耐候性に劣っていたのに対し、本発明においては、無機顔料を用いているため、成形品の退色、変色等を引き起こすことがない。そして、無機顔料に由来する色を鮮やかに呈し続ける成形品とすることができる。また、黒系、深緑系等の暗色系の色の層を得るための他の好ましい態様としては、上記無機顔料（Ｂ）としてＣｏ元素及びＮｉ元素を含む酸化物を用いることが挙げられる。その例としては、（Ｎｉ，Ｃｏ，Ｆｅ）（Ｆｅ，Ｃｒ）２Ｏ４等が挙げられる。これらは、１種単独でまたは２種以上を組み合わせて用いることができる。また、他の無機顔料と組み合わせて用いることもできる。
また、上記無機顔料（Ｂ）としてＣｏ元素及びＮｉ元素を含む酸化物を用いる場合、本組成物中のＣｏ元素及びＮｉ元素の含有量の比Ｃｏ／Ｎｉが５／９５〜９５／５であることが好ましい。より好ましくは１０／９０〜９０／１０であり、更に好ましくは１５／８５〜８５／１５である。上記範囲とすることによって、暗色系着色性及び低蓄熱性に一段と優れた熱可塑性樹脂組成物とすることができる。
黒系、深緑系等の暗色系の色の層とするためには、上記例示した無機顔料は、その合計が、無機顔料（Ｂ）全体に対して、好ましくは１５質量％以上、より好ましくは２０〜１００質量％、更に好ましくは２５〜１００質量％となるように含有させることが必要である。１００質量％でない場合の残部は、本発明の目的を損なわない範囲で、他の顔料（無機顔料、有機顔料、カーボンブラック等）とすることができる。また、黒系、深緑系のみならず、青系、茶系等の暗色系の色についても、所望の色に応じて、１種単独でまたは色の三原色を利用した複数種の無機顔料の組み合わせによって得ることができる。
尚、上記いずれの態様においても、無機顔料（Ｂ）の１つにＣｏＯを用いる場合は、無機顔料全体を１００質量％とすると、ＣｏＯの含有割合は好ましくは５０質量％以下、より好ましくは４０質量％以下、更に好ましくは３０質量％以下である。残部は、他の無機顔料であり、例えば、Ｆｅ（Ｆｅ，Ｃｒ）２Ｏ４等である。
The inorganic pigment (B) having infrared reflection characteristics according to the present invention is not only for imparting low heat storage characteristics to the thermoplastic resin (A), but also has a color and wood grain similar to wood in the thermoplastic resin (A). Used to add a pattern. In the present invention, the wood grain pattern is a concept including not only a wood grain pattern but also a marble pattern.
The inorganic pigment (B) is not particularly limited as long as it has a property of hardly absorbing infrared rays, and a compound containing at least one element selected from Fe, Cr, Mn, Cu, Co and Ni is preferable. . In particular, oxides and composite oxides of the above elements are preferable. Specifically, FeO, FeO (OH), Fe 2 O 3 , CrO, Cr 2 O 3 , Cr 2 O 3 .2H 2 O, MnO, Mn 2 O 3 , MnO 2 , CuO, Cu 2 O, CoO, CoO.Al 2 O 3 , Fe (Fe, Cr) 2 O 4 , (Co, Fe) (Fe, Cr) 2 O 4 , Cu (Cr , Mn) 2 O 4 , (Cu, Fe, Mn) (Fe, Cr, Mn) 2 O 4 , (Fe, Zn) (Fe, Cr) 2 O 4 , (Fe, Zn) Fe 2 O 4 , CoAl 2 O 4 , Co (Al, Cr) 2 O 4 , Cr 2 O 3 : Fe 2 O 3 , (Ni, Co, Fe) (Fe, Cr) 2 O 4 and the like. Of these, Cr 2 O 3 : Fe 2 O 3 , (Cu, Fe, Mn) (Fe, Cr, Mn) 2 O 4 , Fe (Fe, Cr) 2 O 4 , (Co, Fe) (Fe, Cr) 2 O 4 , Cu (Cr, Mn) 2 O 4 , (Ni, Co, Fe) (Fe, Cr) 2 O 4 may be mentioned. Moreover, the oxides and composite oxides exemplified above can be used singly or in combination of two or more, and a molded product colored in a desired color can be obtained.
In the above examples, when CoO is used alone, whitening may occur on the surface of the molded product due to the intensity of infrared rays or the like when it is exposed to sunlight, or it may be volatilized by ultraviolet rays. When CoO is used, it is preferably used in combination with other inorganic pigments. In the low heat storage resin composition of the present invention, when obtaining a dark color layer such as black or deep green, the inorganic pigment (B) contains at least two elements selected from Fe, Cr and Mn. It is preferable to use an oxide. Examples thereof include Fe (Fe, Cr) 2 O 4 , (Co, Fe) (Fe, Cr) 2 O 4 , Cu (Cr, Mn) 2 O 4 , (Cu, Fe, Mn) (Fe, Cr , Mn) 2 O 4 , (Fe, Zn) (Fe, Cr) 2 O 4 , Cr 2 O 3 : Fe 2 O 3 and the like. These can be used individually by 1 type or in combination of 2 or more types.
In addition, in order to obtain a dark color layer such as black or deep green, the total amount of the inorganic pigments exemplified above is preferably 60% by mass or more with respect to the entire inorganic pigment (B). It is necessary to make it contain so that it may become preferably 70-100 mass%, More preferably, 80-100 mass%. When the amount is not 100% by mass, other pigments (inorganic pigments, organic pigments, carbon black, etc.) can be used as long as the object of the present invention is not impaired. Also, not only black and dark green, but also dark colors such as blue and brown, depending on the desired color, a single type or a combination of multiple types of inorganic pigments using the three primary colors Can be obtained by: The conventional colorant is a combination of an organic pigment or a dye, and the molded product is inferior in weather resistance such as fading and discoloration, whereas in the present invention, since an inorganic pigment is used, Does not cause fading or discoloration. And it can be set as the molded article which continues to exhibit the color derived from an inorganic pigment vividly. Further, as another preferred embodiment for obtaining a dark color layer such as black or deep green, an oxide containing a Co element and a Ni element can be used as the inorganic pigment (B). Examples thereof include (Ni, Co, Fe) (Fe, Cr) 2 O 4 and the like. These can be used individually by 1 type or in combination of 2 or more types. It can also be used in combination with other inorganic pigments.
Moreover, when using the oxide containing Co element and Ni element as said inorganic pigment (B), ratio Co / Ni of content of Co element and Ni element in this composition is 5 / 95-95 / 5. It is preferable. More preferably, it is 10 / 90-90 / 10, More preferably, it is 15 / 85-85 / 15. By setting it as the said range, it can be set as the thermoplastic resin composition which was further excellent in dark-colored coloring property and low heat storage property.
In order to obtain a dark color layer such as black or dark green, the total of the inorganic pigments exemplified above is preferably 15% by mass or more, more preferably, based on the whole inorganic pigment (B). It is necessary to make it contain so that it may become 20-100 mass%, More preferably, it is 25-100 mass%. The balance when not 100% by mass can be other pigments (inorganic pigments, organic pigments, carbon black, etc.) as long as the object of the present invention is not impaired. Also, not only black and dark green, but also dark colors such as blue and brown, depending on the desired color, a single type or a combination of multiple types of inorganic pigments using the three primary colors Can be obtained by:
In any of the above embodiments, when CoO is used as one of the inorganic pigments (B), the content of CoO is preferably 50% by mass or less, more preferably 40%, assuming that the entire inorganic pigment is 100% by mass. It is not more than mass%, more preferably not more than 30 mass%. The balance is other inorganic pigments such as Fe (Fe, Cr) 2 O 4 .
上記無機顔料（Ｂ）は粉末であることが好ましく、更に好ましくは微粉末である。形状は特に限定されないが、粉末の最大長さは、好ましくは５ｎｍ〜４０μｍ、より好ましくは１５ｎｍ〜３０μｍである。上記範囲とすることによって、取扱い性と耐衝撃性のバランスに優れる。 The inorganic pigment (B) is preferably a powder, more preferably a fine powder. The shape is not particularly limited, but the maximum length of the powder is preferably 5 nm to 40 μm, more preferably 15 nm to 30 μm. By setting it within the above range, the balance between handleability and impact resistance is excellent.
本発明で用いる低蓄熱性樹脂組成物における上記無機顔料（Ｂ）の含有量は、無機顔料（Ｂ）の種類によって異なるが、該低蓄熱性樹脂組成物全体に対して、０．５〜１３質量％、好ましくは１．０〜１０質量％、より好ましくは１．０〜８質量％である。無機顔料（Ｂ）の含有量が少なすぎると、十分な低蓄熱性を得ることができず、着色性も劣る傾向にあり、一方、多すぎると、成形加工性、耐衝撃性が劣る傾向にある。また、本発明においては、上記無機顔料（Ｂ）を用いることで耐候性が一段と向上するという効果が得られる。 Although content of the said inorganic pigment (B) in the low heat storage resin composition used by this invention changes with kinds of inorganic pigment (B), it is 0.5-13 with respect to this low heat storage resin composition whole. The mass is preferably 1.0 to 10 mass%, more preferably 1.0 to 8 mass%. If the content of the inorganic pigment (B) is too small, sufficient low heat storage properties cannot be obtained and the colorability tends to be inferior. On the other hand, if too large, the moldability and impact resistance tend to be inferior. is there. Moreover, in this invention, the effect that a weather resistance improves further by using the said inorganic pigment (B) is acquired.
本発明で用いる低蓄熱性樹脂組成物は、下記試験条件で得られる成形品の温度上昇が７３℃以下であることを特徴とし、この試験条件によって、蓄熱性を評価することができる。この温度上昇は、好ましくは６８℃以下、更に好ましくは６５℃以下である。したがって、各無機顔料（Ｂ）の具体的な含有量は、この温度上昇の要求を満たすように決定される。
〔試験条件〕
前記低蓄熱性樹脂組成物からなる成形品（長さ８０ｍｍ、幅５５ｍｍ、厚さ２．５ｍｍ）を、温度２５±２℃、湿度５０±５％ＲＨに調節された室で６０分間状態調節した後、高さ２００ｍｍからその表面に赤外線ランプ（出力１００Ｗ）を６０分間照射した後の成形品の表面温度を測定し、赤外線ランプ照射前の初期温度との差を温度上昇とする。
The low heat storage resin composition used in the present invention is characterized in that the temperature rise of a molded product obtained under the following test conditions is 73 ° C. or less, and heat storage performance can be evaluated based on the test conditions. This temperature rise is preferably 68 ° C. or less, more preferably 65 ° C. or less. Therefore, the specific content of each inorganic pigment (B) is determined so as to satisfy this temperature increase requirement.
〔Test conditions〕
A molded article (length 80 mm, width 55 mm, thickness 2.5 mm) made of the low heat storage resin composition was conditioned for 60 minutes in a room adjusted to a temperature of 25 ± 2 ° C. and a humidity of 50 ± 5% RH. Thereafter, the surface temperature of the molded article after the surface is irradiated with an infrared lamp (output 100 W) for 60 minutes from a height of 200 mm is measured, and the difference from the initial temperature before irradiation with the infrared lamp is defined as a temperature rise.
該低蓄熱性樹脂組成物は、所望の色彩を備えるために、該組成物の温度上昇が本発明における上記範囲を逸脱しない限り、上記無機顔料（Ｂ）以外に他の顔料及び／又は染料を含有することができる。なお、本明細書において、上記無機顔料（Ｂ）及び他の顔料及び／又は染料を総称する場合、「染料及び／又は顔料（Ｂ´）」と記載する。
上記の他の顔料としては、公知の無機顔料及び有機顔料が使用できる。かかる公知の無機顔料としては、亜鉛華、チタンイエローなどの酸化亜鉛、チタン白などの酸化チタン系、焼成系、群青系、コバルトブルー系、ベンガラなどの酸化鉄系、カーボンブラック系、硫化鉄、硫化カドミウムなどの硫化物系、クロム酸鉛、クロム酸亜鉛などのクロム酸塩系、炭酸塩系、金属粉系などが挙げられ、これらの中では、酸化鉄系、カーボンブラック系、群青系などが好ましく使用できる。但し、これらの無機顔料のうち、上記無機顔料（Ｂ）に属するものは除く。有機顔料としては、ペリノン系、蛍光増白剤、フタロシアニン系、キナクリドン系、パーマネントレッド、レーキレッド、ファーストイエローなどのアゾ系、ニトロソ系、ニトロ系などが挙げられ、これらの中では、アゾ系やフタロシアニン系などが好ましく使用できる。上記の染料としては、複素環系、アンスラキノン系、アゾ系、ペリノン系、ローダミンレーキなどの塩素性染料系レーキなどが挙げられる。
In order to provide the desired color, the low heat storage resin composition may contain other pigments and / or dyes in addition to the inorganic pigment (B) as long as the temperature rise of the composition does not depart from the above range in the present invention. Can be contained. In addition, in this specification, when the said inorganic pigment (B) and another pigment and / or dye are named generically, it describes as "dye and / or pigment (B ')."
As the other pigment, known inorganic pigments and organic pigments can be used. Examples of such known inorganic pigments include zinc oxides such as zinc white and titanium yellow, titanium oxides such as titanium white, calcinations, ultramarine, cobalt blue, iron oxides such as bengara, carbon black, iron sulfide, Examples include sulfides such as cadmium sulfide, chromates such as lead chromate and zinc chromate, carbonates, and metal powders. Among these, iron oxide, carbon black, ultramarine, etc. Can be preferably used. However, among these inorganic pigments, those belonging to the inorganic pigment (B) are excluded. Examples of organic pigments include perinone, fluorescent brightener, phthalocyanine, quinacridone, permanent red, lake red, first yellow, and other azo, nitroso, and nitro. A phthalocyanine series or the like can be preferably used. Examples of the dyes include chlorinated dye-based lakes such as heterocyclic, anthraquinone, azo, perinone, and rhodamine lakes.
本発明で用いる低蓄熱性樹脂組成物は、公知の方法で成形及び加工することにより、上記無機顔料（Ｂ）及びその他の着色剤の着色に由来する木目調模様を発現させることができる。好ましくは、かかる木目調模様が成形時に容易に発現されるよう、上記染料及び／又は顔料（Ｂ´）の一部又は全てを熱可塑性樹脂（Ａ´）に予め混合したマスターバッチ（「組成物（II）」）として本発明で用いる低蓄熱性樹脂組成物に含有させる。マスターバッチに含有させる染料及び／又は顔料（Ｂ´）としては、上記無機顔料（Ｂ）を用いることが低蓄熱性を効果的に付与する観点から好ましい。この場合、染料及び／又は顔料（Ｂ´）の含有量は、マスターバッチ（「組成物（II）」）全量１００質量％に対して、１〜７０質量％とすることが好ましい。 The low heat storage resin composition used in the present invention can express a woodgrain pattern derived from the coloring of the inorganic pigment (B) and other colorants by molding and processing by a known method. Preferably, a masterbatch (“composition” in which a part or all of the dye and / or pigment (B ′) is premixed in the thermoplastic resin (A ′) so that the woodgrain pattern is easily expressed at the time of molding. (II) ”) is contained in the low heat storage resin composition used in the present invention. As the dye and / or pigment (B ′) to be contained in the master batch, it is preferable to use the inorganic pigment (B) from the viewpoint of effectively imparting low heat storage property. In this case, the content of the dye and / or pigment (B ′) is preferably 1 to 70% by mass relative to 100% by mass of the total amount of the master batch (“Composition (II)”).
かかる成分（Ｂ´）のマスターバッチを構成する熱可塑性樹脂（Ａ´）としては、公知の熱可塑性樹脂がすべて使用でき、上記ゴム強化ビニル系樹脂の他、スチレン系樹脂、ポリエチレン、ポリプロピレン、ポリブテン−１などのポリオレフィン系樹脂、ナイロン６，６、ナイロン６、ナイロン１１、ナイロン１２、ナイロン４，６などのポリアミド、ポリブチレンテレフタレート、ポリエチレンテレフタレートなどのポリエステル、全芳香族ポリエステル、ポリカーボネート樹脂、ポリオキシメチレンなどのポリエーテル樹脂、ポリフェニレンスルフィド、ポリアミドエラストマーなどが挙げられ、これらは、１種単独で、または２種以上を併用することができる。好ましい熱可塑性樹脂（Ａ´）は、上記ゴム強化ビニル系樹脂、とりわけゴム強化スチレン系樹脂、その他のスチレン系樹脂、ポリアミド、ポリエステル、ポリカーボネート樹脂であり、特に好ましい熱可塑性樹脂（Ａ´）は、上記ゴム強化ビニル系樹脂及びスチレン系樹脂であり、とりわけ、該熱可塑性樹脂（Ａ´）の全体に対して１０〜９０質量％のα―メチルスチレンを共重合成分として含むものが木目調模様の鮮映性の点から好ましい。上記成分（Ａ）がゴム強化ビニル系樹脂を含むものである場合、熱可塑性樹脂（Ａ´）を構成するゴム強化ビニル系樹脂の組成は、前者のゴム強化ビニル系樹脂の組成と同一でも異なってもよい。 As the thermoplastic resin (A ′) constituting the master batch of the component (B ′), all known thermoplastic resins can be used. In addition to the rubber-reinforced vinyl resin, styrene resin, polyethylene, polypropylene, polybutene -1 and other polyolefin resins, nylon 6,6, nylon 6, nylon 11, nylon 12, nylon 4,6 and other polyamides, polybutylene terephthalate, polyethylene terephthalate and other polyesters, wholly aromatic polyesters, polycarbonate resins, polyoxy Examples thereof include polyether resins such as methylene, polyphenylene sulfide, and polyamide elastomer. These may be used alone or in combination of two or more. Preferred thermoplastic resins (A ′) are the above rubber reinforced vinyl resins, especially rubber reinforced styrene resins, other styrene resins, polyamides, polyesters, polycarbonate resins, and particularly preferred thermoplastic resins (A ′) are The rubber-reinforced vinyl resin and the styrene resin, particularly those containing 10 to 90% by mass of α-methylstyrene as a copolymer component with respect to the whole thermoplastic resin (A ′) have a woodgrain pattern. It is preferable in terms of sharpness. When the component (A) contains a rubber reinforced vinyl resin, the composition of the rubber reinforced vinyl resin constituting the thermoplastic resin (A ′) may be the same as or different from the composition of the former rubber reinforced vinyl resin. Good.
本発明で用いる低蓄熱性樹脂組成物は、木目調模様を良好に発現するように、さらに、滑剤（Ｃ）を含有することが好ましい。滑剤（Ｃ）としては、公知の滑剤を使用することができる。具体的には、長鎖のアルキル基と官能基とを有する化合物、エチレン、プロピレンなどのα−オレフィン（共）重合体、ジメチルポリシロキサンなどのシリコン含有重合体、α−オレフィンと官能基含有不飽和化合物との共重合体、エチレン系共重合体、プロピレン系共重合体、エチレン−プロピレン共重合体、シリコン含有重合体などの重合体に官能基含有不飽和化合物を付加した重合体、ポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体などを酸化し、カルボキシル基などを付加する方法によって得られる重合体などが挙げられる。 The low heat storage resin composition used in the present invention preferably further contains a lubricant (C) so as to satisfactorily express a woodgrain pattern. A known lubricant can be used as the lubricant (C). Specifically, a compound having a long-chain alkyl group and a functional group, an α-olefin (co) polymer such as ethylene or propylene, a silicon-containing polymer such as dimethylpolysiloxane, an α-olefin and a functional group-containing non-functional group. A copolymer obtained by adding a functional group-containing unsaturated compound to a polymer such as a copolymer with a saturated compound, an ethylene copolymer, a propylene copolymer, an ethylene-propylene copolymer, or a silicon-containing polymer, polyethylene, Examples thereof include polymers obtained by a method of oxidizing polypropylene, ethylene-propylene copolymer and the like and adding a carboxyl group and the like.
ここで、上記官能基としては、カルボキシル基またはその金属塩、水酸基、オキサゾリン基、酸無水物基、エステル基、アミノ基、アミド基、エポキシ基、イソシアネート基、ウレタン基、ユリア基などが挙げられる。好ましい官能基としては、カルボキシル基またはその２価の金属塩、エステル基、アミド基である。カルボキシル基の塩としては、ナトリウム、カリウム、リチウム、カルシウム、マグネシウム、アルミニウム、亜鉛、バリウム、カドミウム、マンガン、コバルト、鉛、スズなどの金属塩が挙げられる。上記官能基含有不飽和化合物としては、上記したものがすべて使用される。好ましくは、長鎖のアルキル基と官能基とを有する化合物、エチレン系共重合体である。 Here, examples of the functional group include a carboxyl group or a metal salt thereof, a hydroxyl group, an oxazoline group, an acid anhydride group, an ester group, an amino group, an amide group, an epoxy group, an isocyanate group, a urethane group, and a urea group. . Preferred functional groups are a carboxyl group or a divalent metal salt thereof, an ester group or an amide group. Examples of the carboxyl group salt include metal salts such as sodium, potassium, lithium, calcium, magnesium, aluminum, zinc, barium, cadmium, manganese, cobalt, lead, and tin. As the functional group-containing unsaturated compound, all of the above-mentioned compounds are used. A compound having a long-chain alkyl group and a functional group, or an ethylene copolymer is preferable.
本発明で用いる低蓄熱性樹脂組成物における滑剤（Ｃ）の使用量は、該低蓄熱性樹脂組成物全体に対して１〜１２質量％、好ましくは２〜８重量％である。１重量％未満では、鮮明な木目調模様が得られない場合があり、一方、１２重量％を超えると、溶融混練り時にサージングを生じ混練りできない場合がある。滑剤（Ｃ）は、上記成分（Ａ）及び成分（Ａ´）の何れか一方に含有させてもよいし、両方に含有させもよい。 The usage-amount of the lubricant (C) in the low heat storage resin composition used by this invention is 1-12 mass% with respect to this low heat storage resin composition whole, Preferably it is 2-8 weight%. If it is less than 1% by weight, a clear wood grain pattern may not be obtained. On the other hand, if it exceeds 12% by weight, surging may occur during melt-kneading and kneading may not be possible. The lubricant (C) may be contained in any one of the component (A) and the component (A ′) or in both.
上記のように染料及び／又は顔料（Ｂ´）を熱可塑性樹脂（Ａ´）に含有させて用いる場合、本発明で使用する低蓄熱性樹脂組成物は、下記組成物(I)１００質量部と、下記組成物(II)０．１〜３０質量部とをドライブレンドしてなる組成物であり、かつ、該低蓄熱性樹脂組成物中に含まれる滑剤（Ｃ）の量が、該組成物全体に対して１〜１２質量％となるように構成することが好ましい。 When the dye and / or pigment (B ′) is contained in the thermoplastic resin (A ′) as described above, the low heat storage resin composition used in the present invention is 100 parts by mass of the following composition (I): And 0.1 to 30 parts by mass of the following composition (II), and the amount of the lubricant (C) contained in the low heat storage resin composition is It is preferable to constitute so as to be 1 to 12% by mass with respect to the entire product.
組成物(I)：熱可塑性樹脂（Ａ）としてゴム強化ビニル系樹脂７５〜９９質量％、赤外線反射特性を有する無機顔料（Ｂ）０〜１３質量％、及び、滑剤（Ｃ）０〜１２質量％を溶融混練してなる熱可塑性樹脂組成物（但し、上記成分（Ａ）、（Ｂ）及び（Ｃ）の合計は１００質量％）。
組成物(II)：熱可塑性樹脂（Ａ´）１８〜９９質量％、染料及び／又は顔料（Ｂ´）１〜７０質量％、並びに、滑剤（Ｃ）０〜１２質量％を溶融混練してなる熱可塑性樹脂組成物（但し、上記成分（Ａ´）、（Ｂ´）及び（Ｃ）の合計は１００質量％）。
なお、上記の場合でも、無機顔料（Ｂ）は、組成物(I)及び組成物(II)の合計１００質量％に対して０．５〜１３質量％の範囲で含有されていなければならない。
Composition (I): 75 to 99% by mass of rubber-reinforced vinyl resin as thermoplastic resin (A), 0 to 13% by mass of inorganic pigment (B) having infrared reflection characteristics, and 0 to 12% by mass of lubricant (C) % Of a thermoplastic resin composition obtained by melt-kneading (% of the above components (A), (B) and (C) is 100% by mass).
Composition (II): 18-99% by mass of thermoplastic resin (A ′), 1-70% by mass of dye and / or pigment (B ′), and 0-12% by mass of lubricant (C) are melt-kneaded. A thermoplastic resin composition (provided that the total of the components (A ′), (B ′) and (C) is 100% by mass).
Even in the above case, the inorganic pigment (B) must be contained in the range of 0.5 to 13% by mass with respect to the total of 100% by mass of the composition (I) and the composition (II).
本発明の低蓄熱性樹脂組成物には、必要に応じて、種々の添加剤を含有させることができる。例えば、酸化防止剤、可塑剤、着色剤、難燃剤、充填剤、滑剤、帯電防止剤等である。 The low heat storage resin composition of the present invention can contain various additives as required. For example, antioxidants, plasticizers, colorants, flame retardants, fillers, lubricants, antistatic agents and the like.
本発明の低蓄熱性樹脂組成物は、各種押出機、バンバリーミキサー、ニーダー、ロール等を用い、各成分を混練りすることによって得られる。混練りするに際しては、各成分を一括して混練りしてもよく、多段添加方式で混練りしてもよい。本発明の低蓄熱性樹脂組成物が上記組成物（Ｉ）および組成物（II）からなる場合は、各組成物を上記方法で別個に混練りして得た後、両組成物をドライブレンドすることによって得られる。 The low heat storage resin composition of the present invention can be obtained by kneading each component using various extruders, Banbury mixers, kneaders, rolls and the like. When kneading, each component may be kneaded in a lump or may be kneaded by a multistage addition method. When the low heat storage resin composition of the present invention comprises the composition (I) and the composition (II), each composition is obtained by kneading separately by the above method, and then both the compositions are dry blended. Is obtained by
このようにして得られた本発明の低蓄熱性樹脂組成物は、射出成形、シート押出、真空成形、発泡成形等によってシート、フィルム等の各種成形品を作ることができる。本発明の低蓄熱性樹脂組成物を用いて木目調模様のシート、フィルム等の成形品又は積層体を成形する方法としては公知の各種の方法を採用することができるが、上記組成物（Ｉ）および組成物（II）のドライブレンド形態の組成物をそのまま成形機に供給して成形すると、きれいな木目調模様が得られるので好ましい。かくして得られた成形品を基材に積層することによって本発明の積層体を得ることができる。積層方法としては、接着剤を用いた接着、熱接着などが挙げられるが、最も好ましくは、本発明の低蓄熱性樹脂組成物の層と基材とを同時に共押出する方法である。本発明の低蓄熱性樹脂組成物の層は、通常、積層体の日光の照射される部位に積層することが好ましい。 The low heat storage resin composition of the present invention thus obtained can produce various molded articles such as sheets and films by injection molding, sheet extrusion, vacuum molding, foam molding and the like. Various known methods can be adopted as a method of forming a molded product such as a woodgrain pattern sheet or film or a laminate using the low heat storage resin composition of the present invention. ) And the composition (II) in the form of a dry blend are preferably supplied to a molding machine as they are for molding so that a beautiful woodgrain pattern can be obtained. The laminate of the present invention can be obtained by laminating the molded product thus obtained on a substrate. Examples of the lamination method include adhesion using an adhesive, thermal adhesion, and the like. Most preferably, the layer of the low heat storage resin composition of the present invention and the substrate are coextruded at the same time. In general, the layer of the low heat storage resin composition of the present invention is preferably laminated on a portion of the laminate that is irradiated with sunlight.
基材としては、いかなる材料からなるものであっても良いが、上記共押出可能な熱可塑性樹脂からなるものが好ましい。かかる熱可塑性樹脂としては、例えば、ゴム強化ビニル系樹脂；ポリエチレン系樹脂、ポリプロピレン系樹脂、エチレン・α−オレフィン系樹脂などのポリオレフィン系樹脂；ポリ塩化ビニル樹脂；ポリ塩化ビニリデン樹脂；ポリ酢酸ビニル樹脂；飽和ポリエステル系樹脂；（メタ）アクリル酸エステル化合物の（共）重合体等のアクリル系樹脂；フッ素樹脂；アクリロニトリル・スチレン樹脂、芳香族ビニル化合物等の（共）重合体などのスチレン系樹脂、エチレン・酢酸ビニル樹脂等が挙げられる。これらの内、本発明の低蓄熱性樹脂組成物は、ポリ塩化ビニル樹脂からなる基材の表面に積層して用いるのに好適であり、かくして、ポリ塩化ビニル樹脂の成形品を本発明の低蓄熱性樹脂組成物からなる層で熱を遮断することにより、ポリ塩化ビニル樹脂の低コスト性を維持したまま、その耐熱性の不足を補完し、積層体全体としての価値を高めることができる。 The substrate may be made of any material, but is preferably made of the above-extrudable thermoplastic resin. Examples of the thermoplastic resin include rubber-reinforced vinyl resins; polyethylene resins, polypropylene resins, polyolefin resins such as ethylene / α-olefin resins; polyvinyl chloride resins; polyvinylidene chloride resins; polyvinyl acetate resins. A saturated polyester resin; an acrylic resin such as a (co) polymer of a (meth) acrylic ester compound; a fluororesin; a styrene resin such as a (co) polymer such as an acrylonitrile / styrene resin or an aromatic vinyl compound; Examples thereof include ethylene / vinyl acetate resin. Among these, the low heat storage resin composition of the present invention is suitable for use by being laminated on the surface of a base material made of polyvinyl chloride resin. By shutting off heat with the layer made of the heat storage resin composition, the lack of heat resistance can be complemented while maintaining the low cost of the polyvinyl chloride resin, and the value of the entire laminate can be increased.
本発明の低蓄熱性樹脂組成物からなる木目調模様の層の厚さは、要求される熱の遮断特性に応じて適宜選択されるが、通常、シート又はフィルムの形態で基材に積層される。該層の厚さは５０〜８００μｍの範囲とすることが好ましい。 The thickness of the woodgrain pattern layer made of the low heat storage resin composition of the present invention is appropriately selected according to the required heat shielding properties, but is usually laminated on the substrate in the form of a sheet or film. The The thickness of the layer is preferably in the range of 50 to 800 μm.
本発明で使用する低蓄熱性樹脂組成物は、成形加工性に優れ、上記成形方法によって得られる積層体は、蓄熱が防止され、寸法の変化が抑制され、耐候性及び耐衝撃性も改善されるので、窓枠等の屋内家屋の構造部材、雨どい等の屋外家屋の構造部材、自動車内装部品等に好適に使用することができる。 The low heat storage resin composition used in the present invention has excellent molding processability, and the laminate obtained by the above molding method prevents heat storage, suppresses dimensional changes, and improves weather resistance and impact resistance. Therefore, it can be suitably used for structural members of indoor houses such as window frames, structural members of outdoor houses such as rain gutters, automobile interior parts, and the like.
以下に、実施例を挙げて本発明を更に具体的に説明する。尚、実施例及び比較例において、部及び％は特に断らない限り質量基準である。
１．評価方法
本実施例において用いられる評価方法は以下の通りである。なお、試験片I及びIIの作製方法は後述のとおりであり、以下の評価において、試験片IIについては表層面を評価した。
（１）蓄熱性
温度２５±２℃、湿度５０±５％ＲＨに調節された室において、長さ８０ｍｍ、幅５５ｍｍ、厚さ２．５ｍｍの試験片I及びIIの表面に、高さ２００ｍｍから赤外線ランプ（出力１００Ｗ）を照射して、６０分後の試験片I及びIIの表面温度を、表面温度計を用いて測定した。単位は℃である。
Hereinafter, the present invention will be described more specifically with reference to examples. In Examples and Comparative Examples, parts and% are based on mass unless otherwise specified.
1. Evaluation methods
The evaluation methods used in this example are as follows. In addition, the preparation methods of the test pieces I and II are as described later. In the following evaluation, the surface layer of the test piece II was evaluated.
(1) In a chamber adjusted to a heat storage temperature of 25 ± 2 ° C. and a humidity of 50 ± 5% RH, on the surfaces of test pieces I and II having a length of 80 mm, a width of 55 mm, and a thickness of 2.5 mm, from a height of 200 mm The surface temperature of the test pieces I and II after 60 minutes was measured using a surface thermometer after irradiation with an infrared lamp (output: 100 W). The unit is ° C.
（２）耐候性
長さ８０ｍｍ、幅５５ｍｍ、厚さ２．５ｍｍの試験片IIを、サンシャインウェザーオメーター（スガ試験機社製）を用いて、降雨サイクル１８分／１２０分、ブラックパネル温度６３℃として３０００時間暴露し、暴露前後の色調変化値ΔＥを算出した。
ΔＥは、多光源分光測定計（スガ試験機社製）を用いて変色度Ｌａｂ（Ｌ；明度、ａ；赤色度、ｂ；黄色度）を測定し、次式により算出した。
ΔＥ＝√〔（Ｌ１−Ｌ２）２＋（ａ１−ａ２）２＋（ｂ１−ｂ２）２〕
（式中、Ｌ１、ａ１、ｂ１は、暴露前の値を、Ｌ２、ａ２、ｂ２は暴露後の値を示す。）
ΔＥの値は、小さい方が色の変化が小さく、色調が優れていることを示す。評価基準は以下の通りである。
○；ΔＥが５以下である。
△；ΔＥが５を超えて１０未満である。
×；ΔＥが１０以上である。
(2) Weather resistance Length 80 mm, width 55 mm, thickness 2.5 mm test piece II using a sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.), rain cycle 18 minutes / 120 minutes, black panel temperature 63 After exposure for 3000 hours, the color change value ΔE before and after exposure was calculated.
ΔE was calculated from the following equation by measuring the degree of color change Lab (L: brightness, a: redness, b: yellowness) using a multi-light source spectrometer (manufactured by Suga Test Instruments Co., Ltd.).
ΔE = √ [(L 1 −L 2 ) 2 + (a 1 −a 2 ) 2 + (b 1 −b 2 ) 2 ]
(In the formula, L 1 , a 1 , and b 1 represent values before exposure, and L 2 , a 2 , and b 2 represent values after exposure.)
The smaller the value of ΔE, the smaller the color change and the better the color tone. The evaluation criteria are as follows.
A: ΔE is 5 or less.
Δ: ΔE is more than 5 and less than 10.
X: ΔE is 10 or more.
（３）木目模様の着色性
長さ８０ｍｍ、幅５５ｍｍ、厚さ２．５ｍｍの試験片IIを目視で評価した。評価基準は以下の通りである。
○；鮮やかな木目調模様である。
△；○印に比べてやや劣る。
×；不良。
(3) Colorability of wood grain pattern Test piece II having a length of 80 mm, a width of 55 mm, and a thickness of 2.5 mm was visually evaluated. The evaluation criteria are as follows.
○: Vivid wood grain pattern.
Δ: Slightly inferior to ○ mark.
X: Defect.
（４）耐熱性
長さ８０ｍｍ、幅５５ｍｍ、厚さ２．５ｍｍの試験片IIの表面に上記蓄熱性評価と同一の条件で照射を行い、試験片IIの変形の程度を目視評価した。評価基準は以下のとおりである。
○；変形がなかった。
×；変形がみられた。
(4) The surface of the test piece II having a heat resistance length of 80 mm, a width of 55 mm, and a thickness of 2.5 mm was irradiated under the same conditions as the above heat storage evaluation, and the degree of deformation of the test piece II was visually evaluated. The evaluation criteria are as follows.
○: There was no deformation.
X: Deformation was observed.
２．熱可塑性樹脂の調製
２−１．成分（Ａ−１）
製造例１〔アクリル系ゴム強化ビニル系樹脂（Ａ−１）の製造〕
（１）アクリル系ゴム質重合体ラテックス（ａラテックス）の製造
容量５Ｌの反応器に、水１４０部、不均化ロジン酸カリウム１部、β―ナフタレンスルホン酸ホルマリン縮合物のナトリウム塩１．５部、炭酸水素ナトリウム１部を仕込み、撹拌しつつ窒素気流下で内温を６０℃まで昇温した。この時点で、アクリル酸ｎ―ブチル９部とアリルメタクリレート０．１部の混合物、過硫酸カリウム０．０２５部および水２部からなる水溶液を添加し、７５℃に昇温させ、１時間反応を行なった。次いで、高級脂肪酸ナトリウム石けん０．５部と水１２部からなる水溶液、過硫酸カリウム０．１５部と水８０部からなる水溶液を添加し、その後、７５℃に保ちながらアクリル酸ｎ―ブチル９０部とアリルメタクリレート０．９部の混合物を２時間にわたって連続的に添加し、添加後３０分間７５℃で保持し、重合反応を終了した。得られたａラテックスのアクリル系ゴム質重合体粒子の重量平均粒子径は２９０ｎｍ、ゲル含量９４％であった。
2. 2. Preparation of thermoplastic resin 2-1. Ingredient (A-1)
Production Example 1 [Production of acrylic rubber-reinforced vinyl resin (A-1)]
(1) Production of acrylic rubbery polymer latex (a latex) In a reactor having a capacity of 5 L, water 140 parts, disproportionated potassium rosinate 1 part, β-naphthalenesulfonic acid formalin condensate sodium salt 1.5 Part and sodium hydrogen carbonate 1 part were added, and the internal temperature was raised to 60 ° C. under a nitrogen stream while stirring. At this point, a mixture of 9 parts of n-butyl acrylate and 0.1 part of allyl methacrylate, 0.025 part of potassium persulfate and 2 parts of water was added, the temperature was raised to 75 ° C., and the reaction was carried out for 1 hour. I did it. Next, an aqueous solution consisting of 0.5 parts of higher fatty acid sodium soap and 12 parts of water, an aqueous solution consisting of 0.15 parts of potassium persulfate and 80 parts of water, and then 90 parts of n-butyl acrylate while maintaining at 75 ° C. A mixture of 0.9 parts of allyl methacrylate was continuously added over 2 hours and kept at 75 ° C. for 30 minutes after the addition to complete the polymerization reaction. The weight average particle diameter of acrylic rubbery polymer particles of the obtained a latex was 290 nm, and the gel content was 94%.
（２）アクリル系ゴム強化ビニル系樹脂（Ａ−１）の製造
容量５Ｌの反応器にａラテックス１００部（固形分換算）、水１８０部（但し、ラテックスの水を含む）を仕込み、撹拌しつつ窒素気流下、４０℃に昇温させた。この時点で、ブドウ糖０．３部とピロリン酸ナトリウム１．２部と硫酸第１鉄０．０１部と水２０部からなる水溶液、ｔ−ブチルハイドロパーオキサイド０．１２部、不均化ロジン酸カリウム０．７２部と水９部からなる水溶液を添加した。次いで、７５℃まで昇温させ、この時点でスチレン７３部とアクリロニトリル２７部の混合物、及び、ｔ−ブチルハイドロパーオキサイド２．８部と不均化ロジン酸カリウム１．７部と水２０部からなる水溶液の添加を開始し、７５℃に保持しながら、前者は３時間、後者は３．５時間にわたって連続的に添加した。後者の添加終了後、７５℃で６０分間保持し、重合を終了した。重合転化率は９５％であった。この共重合体ラテックスを凝固、水洗、乾燥し、粉末状のアクリル系ゴム強化ビニル系樹脂（Ａ−１）を得た。グラフト率は７９％、ゴム成分含有量は５３％であった。
(2) Production of acrylic rubber-reinforced vinyl resin (A-1) A reactor with a capacity of 5 L was charged with 100 parts of a latex (in terms of solid content) and 180 parts of water (however, including latex water) and stirred. The temperature was raised to 40 ° C. under a nitrogen stream. At this point, 0.3 part glucose, 1.2 parts sodium pyrophosphate, 0.01 parts ferrous sulfate and 20 parts water, t-butyl hydroperoxide 0.12 parts, disproportionated rosin acid An aqueous solution consisting of 0.72 parts of potassium and 9 parts of water was added. The temperature is then raised to 75 ° C., at which point from a mixture of 73 parts of styrene and 27 parts of acrylonitrile, 2.8 parts of t-butyl hydroperoxide, 1.7 parts of disproportionated potassium rosinate and 20 parts of water. The aqueous solution was added, and while maintaining the temperature at 75 ° C., the former was continuously added for 3 hours and the latter was continuously added for 3.5 hours. After completion of the latter addition, the polymerization was terminated by maintaining at 75 ° C. for 60 minutes. The polymerization conversion rate was 95%. This copolymer latex was coagulated, washed with water, and dried to obtain a powdery acrylic rubber-reinforced vinyl resin (A-1). The graft ratio was 79%, and the rubber component content was 53%.
２−２．成分（Ａ−２）
製造例２〔スチレンーアクリロニトリルーメタクリル酸メチル共重合体（Ａ−２）の製造〕
内容積３０Ｌのリボン翼を備えたジャケット付重合反応容器を２基連結し、窒素置換した後、１基目の反応容器にスチレン２３部、アクリロニトリル１８部、メタクリル酸メチル５９部、トルエン２０部を連続的に添加した。同時に、ｔｅｒｔ−ドデシルメルカプタン０．１２部とトルエン５部からなる溶液及び１，１´―アゾビス（シクロヘキサンー１−カーボニトリル）０．１部とトルエン５部からなる溶液を連続的に供給した。１基目の重合温度は１１０℃にコントロールし、平均滞留時間２時間、重合転化率５７％であった。得られた共重合体溶液は、1基目の反応器の外部に設けたポンプにより、１基目供給量と同量を連続的に取出し、２基目に供給した。２基目の反応容器の重合温度は１３０℃で行い、重合転化率は７０％であった。２基目の反応容器で得られた共重合体溶液は、２軸３段ベント付き押出機を用いて、２００〜２５０℃、真空度−６００ｍｍＨｇの条件で未反応単量体と溶剤を脱揮し、結合メタクリル酸メチル含量７２％、結合スチレン含量２１％、結合アクリロニトリル含量７％、極限粘度〔η〕０．５ｄｌ／ｇの共重合体（Ａ−２）をペレットとして得た。
2-2. Ingredient (A-2)
Production Example 2 [Production of Styrene-acrylonitrile-methyl methacrylate copolymer (A-2)]
After connecting two jacketed polymerization reaction vessels equipped with ribbon wings with an internal volume of 30 L and purging with nitrogen, 23 parts of styrene, 18 parts of acrylonitrile, 59 parts of methyl methacrylate and 20 parts of toluene were added to the first reaction vessel. Added continuously. At the same time, a solution composed of 0.12 part of tert-dodecyl mercaptan and 5 parts of toluene and a solution composed of 0.1 part of 1,1′-azobis (cyclohexane-1-carbonitrile) and 5 parts of toluene were continuously supplied. The polymerization temperature of the first group was controlled at 110 ° C., the average residence time was 2 hours, and the polymerization conversion was 57%. The obtained copolymer solution was continuously taken out in the same amount as the first supply amount by a pump provided outside the first reactor and supplied to the second reactor. The polymerization temperature of the second reaction vessel was 130 ° C., and the polymerization conversion was 70%. The copolymer solution obtained in the second reaction vessel was devolatilized from the unreacted monomer and solvent under the conditions of 200 to 250 ° C. and a vacuum degree of −600 mmHg, using an extruder with a biaxial three-stage vent. Then, a copolymer (A-2) having a bound methyl methacrylate content of 72%, a bound styrene content of 21%, a bound acrylonitrile content of 7%, and an intrinsic viscosity [η] of 0.5 dl / g was obtained as pellets.
２−３．成分（Ａ−３）
ＡＥＳ樹脂（テクノポリマー（株）製、「テクノＡＥＳ Ｗ２７０」（商品名））を用いた。
２−４．成分（Ａ−４）
α―メチルスチレンーアクリロニトリル共重合体（α―メチルスチレン単位／アクリロニトリル単位＝７３／２７（％））を用いた。極限粘度〔η〕は０．８ｄｌ／ｇであった。２−５．成分（Ａ−５）
下記成分からなる組成物を用いた。
ポリ塩化ビニル樹脂（分子量１０００）１００重量部、
安定剤（Ｃａ／Ｚｎ、ワンパック品）４．２重量部、
ＰＭＭＡ（分子量：２００万）２重量部、
強化剤（アクリル系ゴム）４重量部、
炭酸カルシウム１０重量部
2-3. Ingredient (A-3)
AES resin (manufactured by Techno Polymer Co., Ltd., “Techno AES W270” (trade name)) was used.
2-4. Ingredient (A-4)
An α-methylstyrene-acrylonitrile copolymer (α-methylstyrene unit / acrylonitrile unit = 73/27 (%)) was used. The intrinsic viscosity [η] was 0.8 dl / g. 2-5. Ingredient (A-5)
A composition comprising the following components was used.
100 parts by weight of polyvinyl chloride resin (molecular weight 1000),
Stabilizer (Ca / Zn, one pack product) 4.2 parts by weight,
2 parts by weight of PMMA (molecular weight: 2 million),
4 parts by weight of reinforcing agent (acrylic rubber),
10 parts by weight of calcium carbonate
３．無機顔料（低蓄熱付与剤）
成分（Ｂ−１）；商品名「フェローカラー４２−７０３Ａ」、日本フェロー社製、Ｆｅ及びＣｒの複合酸化物（化学組成は、Ｃｒ２Ｏ３；８８〜９１％、Ｆｅ２Ｏ３；７〜１０％であり、色は黒色である。）。
成分（Ｂ−２）；商品名「フェローカラー４２−３５０Ａ」、日本フェロー社製、Ｆｅ及びＭｎの複合酸化物で、色は黄色である。
成分（Ｂ−３）；商品名「フェローカラー４２−３０３Ｂ」、日本フェロー社製、Ｃｕ、Ｃｒ及びＭｎの複合酸化物、色は茶色である。
成分（Ｂ−４）；カーボンブラック。
3. Inorganic pigment (low heat storage agent)
Ingredient (B-1): Trade name “Fellow Color 42-703A”, manufactured by Nippon Fellow, Fe and Cr composite oxide (chemical composition is Cr 2 O 3 ; 88-91%, Fe 2 O 3 ; 7 -10% and the color is black).
Component (B-2): trade name “Fellow Color 42-350A”, manufactured by Nippon Fellow, a composite oxide of Fe and Mn, which is yellow in color.
Ingredient (B-3); trade name “Fellow Color 42-303B”, manufactured by Nippon Fellow Co., Ltd., complex oxide of Cu, Cr and Mn, the color is brown.
Component (B-4); carbon black.
４．滑剤
成分（Ｃ−１）；ステアリン酸マグネシウム。
4). Lubricant component (C-1); magnesium stearate.
５．実施例１〜３、及び比較例１〜３
５−１．試験片I（単層シート）、試験片II（２層シート）の作製
（１）ペレットIの作製
表１のペレットI欄に示す成分を、同表に示す配合割合で、ヘンシェルミキサーを用いて３分間混合し、次いで、シリンダー設定温度２００℃の５０ｍｍφ押出機を用いて溶融混練りしてペレットIを得た。
（２）ペレットIIの作製
表１のペレットII欄に示す成分を、同表に示す配合割合で、ヘンシェルミキサーを用いて３分間混合し、次いで、シリンダー設定温度２００℃の５０ｍｍφ押出機を用いて溶融混練りしてペレットIIを得た。
（３）ペレットIとペレットIIの混合ペレットの作製
表１に示す配合割合のペレットIとペレットIIとを、タンブラーを用いて３分間混合し混合ペレット得た。次いで、この混合ペレットを８０℃で１時間乾燥した。
5. Examples 1-3 and Comparative Examples 1-3
5-1. Preparation of test piece I (single-layer sheet) and test piece II (double-layer sheet) (1) Preparation of pellet I Using the Henschel mixer, the components shown in the Pellet I column of Table 1 are blended in the same table. The mixture was mixed for 3 minutes, and then melt-kneaded using a 50 mmφ extruder with a cylinder set temperature of 200 ° C. to obtain pellet I.
(2) Preparation of pellet II The components shown in the column of pellet II in Table 1 were mixed for 3 minutes using a Henschel mixer at the blending ratio shown in the table, and then using a 50 mmφ extruder with a cylinder set temperature of 200 ° C. Pellets II were obtained by melt-kneading.
(3) Preparation of mixed pellets of pellet I and pellet II Pellets I and pellets II in the mixing ratio shown in Table 1 were mixed for 3 minutes using a tumbler to obtain mixed pellets. Next, the mixed pellet was dried at 80 ° C. for 1 hour.
（４）試験片Ｉ（単層シート）の作製
Tダイを備えた４０ｍｍφ押出機を用い、そのシリンダー設定温度２００℃とし、スクリュー回転数と引取速度を適宜調節することで、上記混合ペレットから幅５５ｍｍ厚さ２．５ｍｍのシートを得た。このシートから長さ８０ｍｍ、幅５５ｍｍ、厚さ２．５ｍｍの試験片Iを得た。
（５）試験片ＩＩ（２層シート）の作製
基材層として塩化ビニル樹脂（Ａ−５）を使用し、表層として上記混合ペレットを使用し、基材層用には４０ｍｍφ押出機を用い、そのシリンダー設定温度を１７０℃とし、表層用には２０ｍｍφ押出機を用い、そのシリンダー設定温度２００℃とし、スクリュー回転数と引取速度を適宜調節することで共押出し、幅５５ｍｍ厚さ２．５ｍｍ（基材層の厚さ２．３ｍｍ、表層の厚さ０．２ｍｍ）の２層シートを得た。この２層シートから長さ８０ｍｍ、幅５５ｍｍ、厚さ２．５ｍｍの試験片IIを得た。
(4) Preparation of test piece I (single layer sheet)
Using a 40 mmφ extruder equipped with a T die, the cylinder set temperature was set to 200 ° C., and the screw rotation speed and take-up speed were appropriately adjusted to obtain a sheet having a width of 55 mm and a thickness of 2.5 mm from the mixed pellet. A test piece I having a length of 80 mm, a width of 55 mm, and a thickness of 2.5 mm was obtained from this sheet.
(5) Preparation of test piece II (two-layer sheet) Using vinyl chloride resin (A-5) as a base material layer, using the above mixed pellets as a surface layer, using a 40 mmφ extruder for the base material layer, The cylinder set temperature is set to 170 ° C., a 20 mmφ extruder is used for the surface layer, the cylinder set temperature is set to 200 ° C., and the co-extrusion is performed by appropriately adjusting the screw rotation speed and the take-up speed, and the width is 55 mm and the thickness is 2.5 mm ( A two-layer sheet having a base layer thickness of 2.3 mm and a surface layer thickness of 0.2 mm was obtained. A test piece II having a length of 80 mm, a width of 55 mm, and a thickness of 2.5 mm was obtained from the two-layer sheet.
（６）評価
得られた試験片Ｉ及びＩＩを上記記載の方法で評価した。評価結果を表２に示す。
(6) Evaluation The obtained test pieces I and II were evaluated by the method described above. The evaluation results are shown in Table 2.
実施例１〜３の場合、木目調模様を有する層が本発明の所定の範囲の量の無機顔料（Ｂ）を含有し、かつ、本発明の所定の蓄熱性を満たす樹脂組成物から形成されているため、耐候性、木目模様の着色性、耐熱性の何れにおいても優れている。
これに対し、比較例１の場合、無機顔料（Ｂ）の使用量が本発明の範囲未満であるため、耐候性、木目模様の着色性に劣る。比較例２の場合、無機顔料（Ｂ）の代わりにカーボンブラックを使用しているため、蓄熱性（温度上昇）が大きく、耐候性、木目模様の着色性、耐熱性に劣る。比較例３の場合、カーボンブラックを含有する塩化ビニル樹脂層であり、蓄熱性（温度上昇）が大きく、耐候性、木目模様の着色性、耐熱性の何れも劣る。
In the case of Examples 1 to 3, the layer having a woodgrain pattern is formed from a resin composition containing the inorganic pigment (B) in an amount within the predetermined range of the present invention and satisfying the predetermined heat storage property of the present invention. Therefore, it is excellent in all of weather resistance, wood pattern coloring, and heat resistance.
On the other hand, in the case of the comparative example 1, since the usage-amount of an inorganic pigment (B) is less than the range of this invention, it is inferior to a weather resistance and the coloring property of a grain pattern. In the case of Comparative Example 2, since carbon black is used instead of the inorganic pigment (B), the heat storage (temperature rise) is large, and the weather resistance, the coloration of the wood grain pattern, and the heat resistance are inferior. In the case of the comparative example 3, it is a vinyl chloride resin layer containing carbon black, has a large heat storage property (temperature increase), and is inferior in all of weather resistance, coloration of wood grain pattern, and heat resistance.
本発明の積層体は、木目調の外観を備え、蓄熱性が低く、耐候性、木目調模様の着色性、耐熱性等に優れているので、太陽光の照射時の温度上昇が問題となる建築材料分野、車両分野等の各種成形品に利用できる。
The laminate of the present invention has a wood grain appearance, low heat storage, excellent weather resistance, wood grain pattern coloration, heat resistance, etc., and therefore a temperature rise during sunlight irradiation becomes a problem. It can be used for various molded products in the building material field, vehicle field, and the like.
Claims (7)
〔試験条件〕
前記低蓄熱性樹脂組成物からなる成形品（長さ８０ｍｍ、幅５５ｍｍ、厚さ２．５ｍｍ）を、温度２５±２℃、湿度５０±５％ＲＨに調節された室で６０分間状態調節した後、高さ２００ｍｍからその表面に赤外線ランプ（出力１００Ｗ）を６０分間照射した後の成形品の表面温度を測定し、赤外線ランプ照射前の初期温度との差を温度上昇とする。
組成物（I）：熱可塑性樹脂（Ａ）としてゴム強化ビニル系樹脂７５〜９９質量％、赤外線反射特性を有する無機顔料（Ｂ）０〜１３質量％、及び、滑剤（Ｃ）０〜１２質量％を溶融混練してなる熱可塑性樹脂組成物（但し、上記成分（Ａ）、（Ｂ）及び（Ｃ）の合計は１００質量％）。
組成物（II）：熱可塑性樹脂（Ａ´）として該樹脂（Ａ´）の全体に対して１０〜９０質量％のα―メチルスチレンを共重合成分として含むスチレン系樹脂１８〜９９質量％、染料及び／又は顔料（Ｂ´）１〜７０質量％、並びに、滑剤（Ｃ）０〜１２質量％を溶融混練してなる熱可塑性樹脂組成物（但し、上記成分（Ａ´）、（Ｂ´）及び（Ｃ）の合計は１００質量％）。 A laminate comprising a substrate and a layer having a woodgrain pattern laminated thereon, wherein the layer having a woodgrain pattern comprises 100 parts by mass of the following composition (I) and the following composition (II ) 0.1 to 30 parts by mass of a low heat storage resin composition formed by dry blending , and the composition further contains 0% of the inorganic pigment (B) having infrared reflection characteristics with respect to the whole composition. In addition to containing 5 to 13% by mass , the lubricant (C) is contained in an amount of 1 to 12% by mass relative to the entire composition, and the temperature rise obtained under the following test conditions of the composition is 73 ° C. or less. A laminate characterized by the above.
〔Test conditions〕
A molded article (length 80 mm, width 55 mm, thickness 2.5 mm) made of the low heat storage resin composition was conditioned for 60 minutes in a room adjusted to a temperature of 25 ± 2 ° C. and a humidity of 50 ± 5% RH. Thereafter, the surface temperature of the molded article after the surface is irradiated with an infrared lamp (output 100 W) for 60 minutes from a height of 200 mm is measured, and the difference from the initial temperature before irradiation with the infrared lamp is defined as a temperature rise.
Composition (I): 75 to 99% by mass of rubber-reinforced vinyl resin as thermoplastic resin (A), 0 to 13% by mass of inorganic pigment (B) having infrared reflection characteristics, and 0 to 12% by mass of lubricant (C) % Of a thermoplastic resin composition obtained by melt-kneading (% of the above components (A), (B) and (C) is 100% by mass).
Composition (II): 18-99% by mass of a styrene-based resin containing 10-90% by mass of α-methylstyrene as a copolymerization component with respect to the whole of the resin (A ′) as a thermoplastic resin (A ′), Thermoplastic resin composition obtained by melt-kneading dye and / or pigment (B ′) 1 to 70% by mass and lubricant (C) 0 to 12% by mass (however, the above components (A ′) and (B ′ ) And (C) is 100% by mass).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005366628A JP4741364B2 (en) | 2005-12-20 | 2005-12-20 | Laminated body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005366628A JP4741364B2 (en) | 2005-12-20 | 2005-12-20 | Laminated body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007168176A JP2007168176A (en) | 2007-07-05 |
| JP4741364B2 true JP4741364B2 (en) | 2011-08-03 |
Family
ID=38295383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005366628A Active JP4741364B2 (en) | 2005-12-20 | 2005-12-20 | Laminated body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4741364B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5240492B2 (en) | 2007-06-26 | 2013-07-17 | ソニー株式会社 | Communication system and communication method |
| JP6111559B2 (en) * | 2012-08-28 | 2017-04-12 | 凸版印刷株式会社 | Thermal insulation decorative sheet |
| JP6682889B2 (en) * | 2016-02-05 | 2020-04-15 | 大日本印刷株式会社 | Interior seats, rooms, vehicles |
| JP6962108B2 (en) * | 2017-09-27 | 2021-11-05 | 大日本印刷株式会社 | Decorative sheet and decorative material using it |
| JP6962109B2 (en) * | 2017-09-27 | 2021-11-05 | 大日本印刷株式会社 | Decorative sheet and decorative material using it |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002194223A (en) * | 2000-12-27 | 2002-07-10 | Setsunan Kasei Kk | Process for producing resin molding having woodgrain pattern |
| JP2003251724A (en) * | 2002-03-01 | 2003-09-09 | Fukuvi Chem Ind Co Ltd | Thermoplastic resin molding having excellent woody feeling and its manufacturing method |
| JP2004074746A (en) * | 2002-08-22 | 2004-03-11 | Techno Polymer Co Ltd | Laminate |
| JP2004124042A (en) * | 2002-08-07 | 2004-04-22 | Techno Polymer Co Ltd | Low heat storage thermoplastic resin composition and its molded article |
| JP2004250553A (en) * | 2003-02-19 | 2004-09-09 | Techno Polymer Co Ltd | Thermoplastic resin composition with low heat storage and molded product |
| JP2004322568A (en) * | 2003-04-28 | 2004-11-18 | Toppan Printing Co Ltd | Decorative material and its manufacturing method |
| JP2005132911A (en) * | 2003-10-29 | 2005-05-26 | Mitsubishi Rayon Co Ltd | Acrylic resin film, decorated acrylic resin film and laminate comprising these |
| JP2007169384A (en) * | 2005-12-20 | 2007-07-05 | Techno Polymer Co Ltd | Low-thermal storage resin composition exhibiting woodgrain pattern |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04102683A (en) * | 1990-08-21 | 1992-04-03 | Fukuvi Chem Ind Co Ltd | Covering sheet and building material using the sheet |
-
2005
- 2005-12-20 JP JP2005366628A patent/JP4741364B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002194223A (en) * | 2000-12-27 | 2002-07-10 | Setsunan Kasei Kk | Process for producing resin molding having woodgrain pattern |
| JP2003251724A (en) * | 2002-03-01 | 2003-09-09 | Fukuvi Chem Ind Co Ltd | Thermoplastic resin molding having excellent woody feeling and its manufacturing method |
| JP2004124042A (en) * | 2002-08-07 | 2004-04-22 | Techno Polymer Co Ltd | Low heat storage thermoplastic resin composition and its molded article |
| JP2004074746A (en) * | 2002-08-22 | 2004-03-11 | Techno Polymer Co Ltd | Laminate |
| JP2004250553A (en) * | 2003-02-19 | 2004-09-09 | Techno Polymer Co Ltd | Thermoplastic resin composition with low heat storage and molded product |
| JP2004322568A (en) * | 2003-04-28 | 2004-11-18 | Toppan Printing Co Ltd | Decorative material and its manufacturing method |
| JP2005132911A (en) * | 2003-10-29 | 2005-05-26 | Mitsubishi Rayon Co Ltd | Acrylic resin film, decorated acrylic resin film and laminate comprising these |
| JP2007169384A (en) * | 2005-12-20 | 2007-07-05 | Techno Polymer Co Ltd | Low-thermal storage resin composition exhibiting woodgrain pattern |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007168176A (en) | 2007-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8367770B2 (en) | Acrylate-vinyl aromatic-unsaturated nitrile graft copolymer with excellent impact strength, colorability, and weatherability, and thermoplastic resin composition containing the same | |
| US8129469B2 (en) | Graft copolymer, method for preparing the same and thermoplastic resin composition containing the same | |
| JP2007103813A (en) | Back sheet for solar cell | |
| KR100970059B1 (en) | Low Heat Storing Thermoplastic Resin Composition and Molding Thereof | |
| JP4741364B2 (en) | Laminated body | |
| JP2005530899A (en) | Impact modified composition | |
| JP3990298B2 (en) | Low heat storage thermoplastic resin composition and molded product | |
| JP2006241283A (en) | Thermoplastic resin composition and resin molded product composed of the same | |
| JP3990294B2 (en) | Low heat storage thermoplastic resin composition and molded product | |
| JP2007169384A (en) | Low-thermal storage resin composition exhibiting woodgrain pattern | |
| JP2007169383A (en) | Low-thermal storage film | |
| JP4376524B2 (en) | Thermoplastic resin composition and molded body | |
| US5516842A (en) | Polycarbonate resin composition and molded product thereof | |
| JP5556221B2 (en) | Decorative sheet | |
| JP2006056961A (en) | Thermoplastic resin composition and resin molding composed of the same | |
| EP1559747A1 (en) | Amorphous polyester resin composition | |
| KR100668950B1 (en) | Thermoplastic resin composition and method for preparing thereof | |
| JP2012223922A (en) | Decorative resin sheet | |
| JP2003292544A (en) | Hydroxy-containing acrylic polymer, matting agent, thermoplastic resin composition, thermoplastic resin film, laminate and building material | |
| JP4375590B2 (en) | Weather and chemical resistant thermoplastic resin composition | |
| JPH05214202A (en) | Thermoplastic molding material | |
| JPH04220452A (en) | Thermoplastic resin composition | |
| JP2007126532A (en) | Thermoplastic resin composition and resin molding | |
| JP2004307841A (en) | Rubber-modified styrenic resin excellent in weather resistance and impact resistance, its production process and laminate obtained by using the resin | |
| JP5858090B2 (en) | Decorative sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080912 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20101014 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20101207 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110128 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110426 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110506 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4741364 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140513 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |