JP2011073209A - Foamed decorative sheet - Google Patents
Foamed decorative sheet Download PDFInfo
- Publication number
- JP2011073209A JP2011073209A JP2009225481A JP2009225481A JP2011073209A JP 2011073209 A JP2011073209 A JP 2011073209A JP 2009225481 A JP2009225481 A JP 2009225481A JP 2009225481 A JP2009225481 A JP 2009225481A JP 2011073209 A JP2011073209 A JP 2011073209A
- Authority
- JP
- Japan
- Prior art keywords
- foamed
- decorative sheet
- resin layer
- layer
- foaming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 claims abstract description 127
- 239000011347 resin Substances 0.000 claims abstract description 127
- 238000005187 foaming Methods 0.000 claims abstract description 32
- -1 titanic acid compound Chemical class 0.000 claims abstract description 24
- 239000011342 resin composition Substances 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims description 97
- 239000004088 foaming agent Substances 0.000 claims description 43
- 239000006260 foam Substances 0.000 claims description 12
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 11
- 238000010894 electron beam technology Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 238000004049 embossing Methods 0.000 claims description 4
- 239000002344 surface layer Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 7
- 239000004604 Blowing Agent Substances 0.000 abstract 2
- 239000011241 protective layer Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 10
- 239000005038 ethylene vinyl acetate Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 8
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 6
- 235000019399 azodicarbonamide Nutrition 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 230000005865 ionizing radiation Effects 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 239000004156 Azodicarbonamide Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229920005672 polyolefin resin Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 229920000554 ionomer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000010097 foam moulding Methods 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 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
- 239000000049 pigment Substances 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- 101710155073 2-amino-3,7-dideoxy-D-threo-hept-6-ulosonate synthase Proteins 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 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
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 239000010426 asphalt Substances 0.000 description 1
- 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 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 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
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- CEDDGDWODCGBFQ-UHFFFAOYSA-N carbamimidoylazanium;hydron;phosphate Chemical compound NC(N)=N.OP(O)(O)=O CEDDGDWODCGBFQ-UHFFFAOYSA-N 0.000 description 1
- LNEUSAPFBRDCPM-UHFFFAOYSA-N carbamimidoylazanium;sulfamate Chemical compound NC(N)=N.NS(O)(=O)=O LNEUSAPFBRDCPM-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- OBJNZHVOCNPSCS-UHFFFAOYSA-N naphtho[2,3-f]quinazoline Chemical compound C1=NC=C2C3=CC4=CC=CC=C4C=C3C=CC2=N1 OBJNZHVOCNPSCS-UHFFFAOYSA-N 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 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 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、発泡化粧シートに関する。 The present invention relates to a foam decorative sheet.
従来、発泡化粧シート(発泡壁紙)としては、基材(例えば、裏打紙)に塩化ビニル樹脂の発泡樹脂層を形成したものが知られている。近年では、環境に配慮して発泡樹脂層には、エチレン−酢酸ビニル共重合体樹脂(EVA)、アクリル樹脂、オレフィン系樹脂などの、ハロゲンを含有しない樹脂が用いられてきている(特許文献1〜3等)。 Conventionally, foamed decorative sheets (foamed wallpaper) are known in which a foamed resin layer of vinyl chloride resin is formed on a base material (for example, backing paper). In recent years, in consideration of the environment, halogen-free resins such as ethylene-vinyl acetate copolymer resin (EVA), acrylic resin, and olefin resin have been used for the foamed resin layer (Patent Document 1). ~ 3 etc.).
例えば、アクリル樹脂とエチレン−酢酸ビニル共重合体樹脂とを含むエマルションに、マイクロカプセル型発泡剤を添加した塗料を、基材に塗工・乾燥後、表面に絵柄模様を印刷し、次いで加熱発泡させ、エンボス版により凹凸模様を形成してなる発泡化粧シートが知られている。また、エチレン−酢酸ビニル共重合体樹脂に熱分解型発泡剤を添加した樹脂組成物からなる未発泡樹脂層を、Tダイ押出機を用いて基材上に形成後、表面に絵柄模様層を印刷し、次いで加熱発泡させ、エンボス版により凹凸模様を形成してなる発泡化粧シートが知られている。 For example, an emulsion containing an acrylic resin and an ethylene-vinyl acetate copolymer resin is coated with a paint containing a microcapsule-type foaming agent, dried, printed with a pattern, and then heated and foamed. A foamed decorative sheet formed by forming an uneven pattern with an embossed plate is known. In addition, after forming an unfoamed resin layer made of a resin composition obtained by adding a thermally decomposable foaming agent to an ethylene-vinyl acetate copolymer resin on a substrate using a T-die extruder, a pattern layer is formed on the surface. A foamed decorative sheet is known which is printed and then heated and foamed to form an uneven pattern with an embossed plate.
そして、上記した発泡化粧シートに対して、機械的強度、下地の隠蔽性、難燃効果、延焼防止効果、寸法安定性、吸放湿性等の機能性を新たに付与する手法として、無機フィラーをオレフィン樹脂層に含有することが提案されている(特許文献4〜6等)。 And as a technique for newly imparting functionalities such as mechanical strength, concealment of the foundation, flame retardancy effect, fire spread prevention effect, dimensional stability, moisture absorption and desorption to the foamed decorative sheet described above, an inorganic filler is used. It is proposed to contain in an olefin resin layer (patent documents 4-6 etc.).
発泡化粧シートのオレフィン樹脂層に無機フィラーが含まれる場合、上記した機能性が付与されるが、一方で発泡樹脂層の発泡セルの拡張が抑制される、又は発泡セルが破泡してしまう。そのため、表面形状が荒くなる、所望の発泡倍率とすることができない、等の問題がある。 When an inorganic filler is contained in the olefin resin layer of the foamed decorative sheet, the above-described functionality is imparted. On the other hand, expansion of the foamed cell of the foamed resin layer is suppressed, or the foamed cell is broken. Therefore, there are problems such that the surface shape becomes rough and the desired expansion ratio cannot be obtained.
従って、本発明は、これらの欠点が改善された、破泡し難く、かつ、所望の発泡倍率を有する発泡化粧シートを提供することを主な目的とする。 Therefore, the main object of the present invention is to provide a foamed decorative sheet that is improved in these disadvantages, hardly breaks up, and has a desired expansion ratio.
本発明者は、鋭意研究を重ねた結果、特定の発泡樹脂層を採用することによって上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventor has found that the above object can be achieved by employing a specific foamed resin layer, and has completed the present invention.
すなわち、本発明は、下記の発泡化粧シートに係る。
1. 基材上に少なくとも発泡樹脂層を有する発泡化粧シートであって、
(1)前記発泡樹脂層が、発泡剤含有樹脂層を発泡させることにより形成され、
(2)前記発泡剤含有樹脂層が、
(i)アクリル酸及びメタクリル酸からなる群から選ばれた少なくとも一種をモノマーとして得られる重合体、並びに
(ii)チタン酸化合物
を含む樹脂組成物によって形成された層である、
ことを特徴とする発泡化粧シート。
2. 前記樹脂組成物中、前記チタン酸化合物が、前記(i)で表される重合体100重量部に対して5重量部以上20重量部未満含有する、上記項1に記載の発泡化粧シート。
3. 前記チタン酸化合物が、チタン酸カリウムである、上記項1又は2に記載の発泡化粧シート。
4. 前記発泡剤含有樹脂層が、電子線照射により架橋されている、上記項1〜3のいずれかに記載の発泡化粧シート。
5. 基材上に、非発泡樹脂層B、前記発泡樹脂層及び非発泡樹脂層Aが順に形成されている、上記項1〜4のいずれかに記載の発泡化粧シート。
6. 発泡化粧シートの最表面層の上からエンボス加工が施されている、上記項1〜5のいずれかに記載の発泡化粧シート。
7. 上記項1〜6のいずれかに記載の発泡化粧シートからなる発泡壁紙。
That is, the present invention relates to the following foamed decorative sheet.
1. A foamed decorative sheet having at least a foamed resin layer on a substrate,
(1) The foamed resin layer is formed by foaming a foaming agent-containing resin layer,
(2) The foaming agent-containing resin layer is
(I) a layer formed by a polymer obtained by using at least one selected from the group consisting of acrylic acid and methacrylic acid as a monomer, and (ii) a resin composition containing a titanic acid compound,
A foamed decorative sheet characterized by that.
2. Item 2. The foamed decorative sheet according to Item 1, wherein the titanic acid compound is contained in the resin composition in an amount of 5 parts by weight or more and less than 20 parts by weight with respect to 100 parts by weight of the polymer represented by (i).
3. Item 3. The foamed decorative sheet according to Item 1 or 2, wherein the titanate compound is potassium titanate.
4). Item 4. The foamed decorative sheet according to any one of Items 1 to 3, wherein the foaming agent-containing resin layer is crosslinked by electron beam irradiation.
5). Item 5. The foamed decorative sheet according to any one of Items 1 to 4, wherein a non-foamed resin layer B, the foamed resin layer, and the non-foamed resin layer A are sequentially formed on a substrate.
6). Item 6. The foamed decorative sheet according to any one of Items 1 to 5, which is embossed from the top surface layer of the foamed decorative sheet.
7). The foam wallpaper which consists of a foaming decorative sheet in any one of said items 1-6.
以下、本発明の発泡化粧シートについて詳細に説明する。 Hereinafter, the foamed decorative sheet of the present invention will be described in detail.
1.発泡化粧シート
本発明の発泡化粧シートは、基材上に少なくとも発泡樹脂層を有する発泡化粧シートであって、
(1)前記発泡樹脂層が、発泡剤含有樹脂層を発泡させることにより形成され、
(2)前記発泡剤含有樹脂層が、
(i)アクリル酸及びメタクリル酸からなる群から選ばれた少なくとも一種をモノマーとして得られる重合体、並びに
(ii)チタン酸化合物
を含む樹脂組成物によって形成された層であることを特徴とする。
1. Foamed decorative sheet The foamed decorative sheet of the present invention is a foamed decorative sheet having at least a foamed resin layer on a substrate,
(1) The foamed resin layer is formed by foaming a foaming agent-containing resin layer,
(2) The foaming agent-containing resin layer is
(I) It is a layer formed by a polymer obtained by using at least one selected from the group consisting of acrylic acid and methacrylic acid as a monomer, and (ii) a resin composition containing a titanic acid compound.
上記した特徴を有する本発明の発泡化粧シートは、機械的強度、下地の隠蔽性、難燃効果、延焼防止効果、寸法安定性、吸放湿性等の機能性を有するだけでなく、破泡し難く、かつ、所望の発泡倍率とすることができる。 The foamed decorative sheet of the present invention having the above-mentioned features has not only functions such as mechanical strength, base concealment, flame retardancy, fire spread prevention, dimensional stability, moisture absorption and desorption, but also breaks bubbles. It is difficult to achieve a desired expansion ratio.
基材
基材の材質は、化粧シート基材として適した機械強度、耐熱性等を有する限り特に限定されない。例えば、繊維質シートなどが一般に使用できる。
The material of the base material is not particularly limited as long as it has mechanical strength, heat resistance and the like suitable as a decorative sheet base material. For example, a fiber sheet can be generally used.
具体的には、繊維質シートの中でも、難燃紙(パルプ主体のシートをスルファミン酸グアニジン、リン酸グアジニン等の難燃剤で処理したもの);水酸化アルミニウム、水酸化マグネシウム等の無機添加剤を含む無機質紙;上質紙;薄用紙などが挙げられる。 Specifically, among fiber sheets, flame retardant paper (pulp-based sheets treated with flame retardants such as guanidine sulfamate and guanidine phosphate); inorganic additives such as aluminum hydroxide and magnesium hydroxide Inorganic paper including; fine paper; thin paper and the like.
基材の坪量は限定的ではないが、50〜300g/m2程度が好ましく、50〜80g/m2程度がより好ましい。 Although the basis weight of the substrate is not critical, preferably about 50 to 300 g / m 2, about 50 to 80 g / m 2 is more preferable.
非発泡樹脂層B
本発明では、必要に応じて基材と発泡樹脂層との間に非発泡樹脂層(非発泡樹脂層B)が形成されていてもよい。特に、非発泡樹脂層Bが接着剤層として形成される場合は、基材と発泡樹脂層との優れた密着性が得られる。
Non-foamed resin layer B
In the present invention, a non-foamed resin layer (non-foamed resin layer B) may be formed between the substrate and the foamed resin layer as necessary. In particular, when the non-foamed resin layer B is formed as an adhesive layer, excellent adhesion between the substrate and the foamed resin layer can be obtained.
非発泡樹脂層Bとしては、例えば、低密度ポリエチレン重合体、エチレン−メタクリル酸共重合体(EMAA)、エチレン−アクリル酸共重合体(EAA)、エチレン−酢酸ビニル共重合体(EVA)、エポキシ樹脂、ウレタン樹脂等を好適に用いることができる。
非発泡樹脂層Bは樹脂成分以外に公知の添加剤を含んでもよいが、樹脂成分の含有量が70〜100重量%となるように配合することが好ましい。
Examples of the non-foamed resin layer B include a low density polyethylene polymer, an ethylene-methacrylic acid copolymer (EMAA), an ethylene-acrylic acid copolymer (EAA), an ethylene-vinyl acetate copolymer (EVA), and an epoxy. Resins, urethane resins and the like can be suitably used.
The non-foamed resin layer B may contain known additives in addition to the resin component, but is preferably blended so that the content of the resin component is 70 to 100% by weight.
非発泡樹脂層Bの厚みは限定的ではないが、10〜50μm程度が好ましく、特に10〜20μm程度がより好ましい。 The thickness of the non-foamed resin layer B is not limited, but is preferably about 10 to 50 μm, more preferably about 10 to 20 μm.
発泡樹脂層
発泡樹脂層は、発泡剤含有樹脂層が発泡することにより形成された層である。
Foamed resin layer The foamed resin layer is a layer formed by foaming the foaming agent-containing resin layer.
発泡剤含有樹脂層は、アクリル酸(CH2=CHCOOH)及びメタクリル酸(CH2=C(CH3)COOH)の少なくとも1種をモノマーとして得られる重合体を樹脂成分として含む樹脂組成物により形成された層である。 The foaming agent-containing resin layer is formed of a resin composition containing, as a resin component, a polymer obtained using at least one of acrylic acid (CH 2 ═CHCOOH) and methacrylic acid (CH 2 ═C (CH 3 ) COOH) as a monomer. Layer.
アクリル酸(CH2=CHCOOH)及びメタクリル酸(CH2=C(CH3)COOH)の少なくとも1種をモノマーとして得られる重合体(本発明重合体)としては、例えばアクリル酸及びメタクリル酸の少なくとも1種をモノマーとエチレンとの組み合わせにより得られる共重合体を好適に用いることができる。より具体的には、エチレン−メタクリル酸共重合体(EMAA)、エチレン−アクリル酸共重合体(EAA)及びアイオノマー樹脂の少なくとも1種を用いることが好ましい。 Examples of the polymer (the polymer of the present invention) obtained using at least one of acrylic acid (CH 2 ═CHCOOH) and methacrylic acid (CH 2 ═C (CH 3 ) COOH) as a monomer include, for example, at least acrylic acid and methacrylic acid. A copolymer obtained by combining one type of monomer and ethylene can be preferably used. More specifically, it is preferable to use at least one of ethylene-methacrylic acid copolymer (EMAA), ethylene-acrylic acid copolymer (EAA), and ionomer resin.
前記共重合体におけるアクリル酸又はメタクリル酸の含有量は4〜20重量%程度であることが好ましい。このような樹脂に関して、市販品を使用することもできる。 The content of acrylic acid or methacrylic acid in the copolymer is preferably about 4 to 20% by weight. A commercial item can also be used regarding such resin.
また、樹脂成分のメルトフローレート値(JIS K7210:190℃,2.16kg)は、用いる重合体の種類等によるが、通常は3〜200g/10分とすることが好ましい。 Further, the melt flow rate value (JIS K7210: 190 ° C., 2.16 kg) of the resin component depends on the type of polymer to be used, but it is usually preferably 3 to 200 g / 10 minutes.
発泡剤は、熱分解型発泡剤を用いることが好ましい。熱分解型発泡剤としてはアゾジカルボンアミド(ADCA)、アゾビスホルムアミド等のアゾ系;オキシベンゼンスルホニルヒドラジド(OBSH)、パラトルエンスルホニルヒドラジド等のビドラジド系などが挙げられる。熱分解型発泡剤の含有量は、樹脂成分100重量部に対して1〜20重量部程度が好ましい。発泡倍率は4倍以上が好ましく、5〜8倍程度がより好ましい。 The foaming agent is preferably a pyrolytic foaming agent. Examples of the thermally decomposable foaming agent include azo series such as azodicarbonamide (ADCA) and azobisformamide; bidazide series such as oxybenzenesulfonyl hydrazide (OBSH) and paratoluenesulfonyl hydrazide. The content of the pyrolytic foaming agent is preferably about 1 to 20 parts by weight with respect to 100 parts by weight of the resin component. The expansion ratio is preferably 4 times or more, and more preferably about 5 to 8 times.
なお必要に応じて、一層の発泡効果を挙げるために発泡剤の分解を促進する発泡助剤を併用することができる。その発泡助剤としては使用する発泡剤の種類により異なるが、例えば発泡剤としてアゾジカルボンアミドを用いる場合には発泡助剤としてアジピン酸ジヒドラジド、酸化亜鉛、硫酸鉛、尿素、ステアリン酸亜鉛等が用いられる。発泡助剤の含有量は、樹脂成分100重量部に対して、0.3〜10重量部程度が好ましく、1〜5重量部程度がより好ましい。 If necessary, a foaming aid that accelerates the decomposition of the foaming agent can be used in combination in order to obtain a further foaming effect. For example, when azodicarbonamide is used as the foaming agent, adipic acid dihydrazide, zinc oxide, lead sulfate, urea, zinc stearate, etc. are used as the foaming aid. It is done. The content of the foaming aid is preferably about 0.3 to 10 parts by weight and more preferably about 1 to 5 parts by weight with respect to 100 parts by weight of the resin component.
本発明の発泡剤含有樹脂層を形成する樹脂組成物には、アクリル酸及びメタクリル酸の少なくとも1種をモノマーとして得られる重合体を樹脂成分として含有し、発泡剤として熱分解型発泡剤を含有するとともに、さらにチタン酸化合物を含有する。 The resin composition for forming the foaming agent-containing resin layer of the present invention contains a polymer obtained by using at least one of acrylic acid and methacrylic acid as a monomer as a resin component, and contains a pyrolytic foaming agent as the foaming agent. In addition, it further contains a titanic acid compound.
前記チタン酸化合物は、具体的には、チタン酸金属塩化合物が好ましく、チタン酸カリウム、チタン酸バリウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸マグネシウム、チタン酸鉛、チタン酸アルミニウム、チタン酸リチウム、チタン酸ナトリウムなどを挙げることができる。上記したチタン酸化合物のなかでも、チタン酸カリウムが好ましい。 Specifically, the titanate compound is preferably a metal titanate compound, potassium titanate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, lead titanate, aluminum titanate, lithium titanate. And sodium titanate. Of the above titanate compounds, potassium titanate is preferable.
チタン酸化合物の含有量は、樹脂成分100重量部に対して、5重量部以上20重量部未満が好ましく、10〜19重量部がより好ましい。 The content of the titanic acid compound is preferably 5 parts by weight or more and less than 20 parts by weight, and more preferably 10 to 19 parts by weight with respect to 100 parts by weight of the resin component.
前記チタン酸化合物は、形状に関して、特に限定されないが、繊維状であることが好ましい。 The titanic acid compound is not particularly limited in terms of shape, but is preferably fibrous.
前記チタン酸化合物が繊維状である場合、直径及び長さに関して特に限定されないが、直径は、通常、0.01μm〜100μmのものが使用でき、0.1μm〜50μmが好ましく、0.1μm〜10μmがより好ましい。また、長さは、通常、0.1μm〜10000μmのものが使用でき、1μm〜1000μmが好ましく、1μm〜100μmがより好ましい。 When the titanic acid compound is fibrous, the diameter and length are not particularly limited. However, the diameter is usually 0.01 μm to 100 μm, preferably 0.1 μm to 50 μm, preferably 0.1 μm to 10 μm. Is more preferable. Moreover, the length of 0.1 micrometer-10000 micrometers can be used normally, 1 micrometer-1000 micrometers are preferable, and 1 micrometer-100 micrometers are more preferable.
尚、チタン酸化合物は、一種単独又は二種以上混合して用いることができる。 In addition, a titanic acid compound can be used individually by 1 type or in mixture of 2 or more types.
樹脂組成物には、各種添加剤を加えてもよい。例えば、無機充填剤、顔料などである。その他、安定剤、滑剤等も添加剤として用いることができる。 Various additives may be added to the resin composition. For example, inorganic fillers and pigments. In addition, stabilizers, lubricants, and the like can be used as additives.
無機充填剤としては、例えば、炭酸カルシウム、水酸化アルミニウム、水酸化マグネシウム、三酸化アンチモン、ホウ酸亜鉛、モリブデン化合物等が挙げられる。無機充填剤を含むことにより、目透き抑制効果、表面特性向上効果等が得られる。 Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and a molybdenum compound. By including an inorganic filler, an effect of suppressing see-through, an effect of improving surface characteristics, and the like are obtained.
顔料については、例えば二酸化チタン、亜鉛華、カーボンブラック、黒色酸化鉄、黄色酸化鉄、黄鉛、モリブデートオレンジ、カドミウムイエロー、ニッケルチタンイエロー、クロムチタンイエロー、酸化鉄(弁柄)、カドミウムレッド、群青、紺青、コバルトブルー、酸化クロム、コバルトグリーン、アルミニウム粉、ブロンズ粉、雲母チタン、硫化亜鉛等の無機顔料;例えば、アニリンブラック、ペリレンブラック、アゾ系(アゾレーキ、不溶性アゾ、縮合アゾ)、多環式(イソインドリノン、イソインドリン、キノフタロン、ペリノン、フラバントロン、アントラピリミジン、アントラキノン、キナクリドン、ペリレン、ジケトピロロピロール、ジブロムアンザントロン、ジオキサジン、チオインジゴ、フタロシアニン、インダントロン、ハロゲン化フタロシアニン)等の有機顔料が挙げられる。 As for the pigment, for example, titanium dioxide, zinc white, carbon black, black iron oxide, yellow iron oxide, yellow lead, molybdate orange, cadmium yellow, nickel titanium yellow, chrome titanium yellow, iron oxide (valve), cadmium red, Inorganic pigments such as ultramarine, bitumen, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, titanium mica, and zinc sulfide; for example, aniline black, perylene black, azo (azo lake, insoluble azo, condensed azo), many Cyclic (isoindolinone, isoindoline, quinophthalone, perinone, flavantron, anthrapyrimidine, anthraquinone, quinacridone, perylene, diketopyrrolopyrrole, dibromoanthanthrone, dioxazine, thioindigo, phthalocyanine, indanthro , And organic pigments halogenated phthalocyanine), or the like.
発泡剤含有樹脂層を発泡させる方法としては、後記の製造方法に記載された方法に従って実施すれば良い。 What is necessary is just to implement according to the method described in the manufacturing method of the postscript as a method of foaming a foaming agent containing resin layer.
非発泡樹脂層A
発泡樹脂層のおもて面には、更に非発泡樹脂層Aを形成してもよい。
Non-foamed resin layer A
A non-foamed resin layer A may be further formed on the front surface of the foamed resin layer.
非発泡樹脂層(非発泡樹脂層A)は、主として発泡樹脂層を保護するものである。例えば、本発明では、アクリル酸(CH2=CHCOOH)及びメタクリル酸(CH2=C(CH3)COOH)の少なくとも1種をモノマーとして得られる重合体、ポリプロピレン重合体、高密度ポリエチレン重合体、硬質塩化ビニル重合体、ポリカーボネート重合体等、硬質性を有する樹脂成分を含む樹脂組成物により形成された層を非発泡樹脂層とすることが好ましい。なかでも、アクリル酸及びメタクリル酸の少なくとも1種をモノマーとして得られる重合体がより好ましい。 The non-foamed resin layer (non-foamed resin layer A) mainly protects the foamed resin layer. For example, in the present invention, a polymer obtained by using at least one of acrylic acid (CH 2 ═CHCOOH) and methacrylic acid (CH 2 ═C (CH 3 ) COOH) as a monomer, a polypropylene polymer, a high-density polyethylene polymer, A layer formed of a resin composition containing a hard resin component such as a hard vinyl chloride polymer or a polycarbonate polymer is preferably a non-foamed resin layer. Especially, the polymer obtained by using at least 1 sort (s) of acrylic acid and methacrylic acid as a monomer is more preferable.
前記樹脂成分としては、例えばアクリル酸及びメタクリル酸の少なくとも1種のモノマーとエチレンとの組み合わせにより得られる共重合体を樹脂成分として好適に用いることができる。より具体的には、エチレン−メタクリル酸共重合体、エチレン−アクリル酸共重合体及びアイオノマー樹脂の少なくとも1種を用いることが望ましい。アイオノマー樹脂としては、エチレン−メタクリル酸共重合体及び/又はエチレン−アクリル酸共重合体の分子間をナトリウム、亜鉛等の金属のイオンで分子間結合した構造を有する樹脂が使用できる。このような樹脂成分を用いる場合には、特に樹脂中の水素結合等に起因する強固な層を形成することができるので、優れた耐スクラッチ性、耐摩耗性等を得ることができる。これらは、公知又は市販のものを使用することができる。 As the resin component, for example, a copolymer obtained by a combination of at least one monomer of acrylic acid and methacrylic acid and ethylene can be suitably used as the resin component. More specifically, it is desirable to use at least one of an ethylene-methacrylic acid copolymer, an ethylene-acrylic acid copolymer, and an ionomer resin. As the ionomer resin, a resin having a structure in which the molecules of ethylene-methacrylic acid copolymer and / or ethylene-acrylic acid copolymer are intermolecularly bonded with metal ions such as sodium and zinc can be used. When such a resin component is used, it is possible to form a strong layer particularly due to hydrogen bonds in the resin, so that excellent scratch resistance, abrasion resistance, and the like can be obtained. These may be known or commercially available.
前記共重合体におけるアクリル酸又はメタクリル酸の含有量は4〜15重量%程度であることが好ましい。このような樹脂も市販品を使用することができる。前記樹脂組成物には、公知の添加剤を配合することもできる。 The content of acrylic acid or methacrylic acid in the copolymer is preferably about 4 to 15% by weight. Such a resin can also use a commercial item. A known additive can also be blended in the resin composition.
非発泡樹脂層の厚みは限定的ではないが、10〜50μm程度が好ましく、特に10〜20μm程度がより好ましい。 The thickness of the non-foamed resin layer is not limited, but is preferably about 10 to 50 μm, more preferably about 10 to 20 μm.
また、樹脂組成物中の前記樹脂成分の含有量は限定的ではないが、通常70〜100重量%の範囲内で適宜設定することが好ましい。 Moreover, although content of the said resin component in a resin composition is not limited, Usually, it is preferable to set suitably in the range of 70 to 100 weight%.
本発明では、非発泡樹脂層Aのおもて面に必要に応じて絵柄模様層を有してもよい。 In this invention, you may have a pattern layer on the front surface of the non-foamed resin layer A as needed.
絵柄模様層は、発泡化粧シートに意匠性を付与する。絵柄模様としては、例えば木目模様、石目模様、砂目模様、タイル貼模様、煉瓦積模様、布目模様、皮絞模様、幾何学図形、文字、記号、抽象模様等が挙げられる。絵柄模様は、発泡化粧シートの種類に応じて選択できる。 The design pattern layer imparts design properties to the foamed decorative sheet. Examples of the pattern include a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and an abstract pattern. A design pattern can be selected according to the kind of foaming decorative sheet.
絵柄模様層は、例えば、非発泡樹脂層Aのおもて面に絵柄模様を印刷することで形成できる。なお、絵柄模様層を形成する際には、必要に応じてあらかじめプライマー層を形成しても良い。印刷手法としては、例えば、グラビア印刷、フレキソ印刷、シルクスクリーン印刷、オフセット印刷等が挙げられる。印刷インキとしては、着色剤、結着材樹脂、溶剤(又は分散媒)を含む印刷インキが使用できる。これらのインキは公知又は市販のものを使用しても良い。 The pattern pattern layer can be formed, for example, by printing a pattern pattern on the front surface of the non-foamed resin layer A. In addition, when forming a picture pattern layer, you may form a primer layer previously as needed. Examples of printing methods include gravure printing, flexographic printing, silk screen printing, and offset printing. As the printing ink, a printing ink containing a colorant, a binder resin, and a solvent (or a dispersion medium) can be used. These inks may be known or commercially available.
着色剤としては、例えば、前記の発泡剤含有樹脂層で使用されるような顔料を適宜使用することができる。 As the colorant, for example, a pigment used in the above-described foaming agent-containing resin layer can be appropriately used.
結着材樹脂は、例えば、アクリル系樹脂、スチレン系樹脂、ポリエステル系樹脂、ウレタン系樹脂、塩素化ポリオレフィン系樹脂、塩化ビニル−酢酸ビニル共重合体系樹脂、ポリビニルブチラール樹脂、アルキド系樹脂、石油系樹脂、ケトン樹脂、エポキシ系樹脂、メラミン系樹脂、フッ素系樹脂、シリコーン系樹脂、繊維素誘導体、ゴム系樹脂等が挙げられる。 The binder resin is, for example, an acrylic resin, a styrene resin, a polyester resin, a urethane resin, a chlorinated polyolefin resin, a vinyl chloride-vinyl acetate copolymer resin, a polyvinyl butyral resin, an alkyd resin, or a petroleum resin. Examples include resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fiber derivatives, rubber resins, and the like.
溶剤(又は分散媒)としては、例えば、ヘキサン、ヘプタン、オクタン、トルエン、キシレン、エチルベンゼン、シクロヘキサン、メチルシクロヘキサン等の石油系有機溶剤;酢酸エチル、酢酸ブチル、酢酸−2−メトキシエチル、酢酸−2−エトキシエチル等のエステル系有機溶剤;メチルアルコール、エチルアルコール、ノルマルプロピルアルコール、イソプロピルアルコール、イソブチルアルコール、エチレングリコール、プロピレングリコール等のアルコール系有機溶剤;アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系有機溶剤;ジエチルエーテル、ジオキサン、テトラヒドロフラン等のエーテル系有機溶剤、;ジクロロメタン、四塩化炭素、トリクロロエチレン、テトラクロロエチレン等の塩素系有機溶剤;水などが挙げられる。 Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene Chlorinated organic solvents; and water.
絵柄模様層の厚みは、絵柄模様の種類より異なるが、一般には0.1〜10μm程度とすることが好ましい。 The thickness of the design pattern layer is different from the type of design pattern, but is generally preferably about 0.1 to 10 μm.
表面保護層(オーバーコート層)
本発明では、絵柄模様層の表面に艶調整及び/又は絵柄模様層の保護を意図して表面保護層を有してもよい。表面保護層の種類は限定的ではない。艶調整を目的とする表面保護層であれば、例えば、シリカなどの既知フィラーを含む表面保護層がある。表面保護層の形成方法としては、グラビア印刷などの公知の方法が採用できる。なお、絵柄模様層と表面保護層との密着性が十分に得られない場合には、絵柄模様層の表面を易接着処理(プライマー処理)した後に表面保護層を設けることもできる。
Surface protective layer (overcoat layer)
In the present invention, a surface protective layer may be provided on the surface of the design pattern layer for the purpose of adjusting the gloss and / or protecting the design pattern layer. The kind of surface protective layer is not limited. If it is a surface protective layer aiming at gloss adjustment, there exists a surface protective layer containing known fillers, such as a silica, for example. As a method for forming the surface protective layer, a known method such as gravure printing can be employed. In addition, when the adhesiveness of a pattern pattern layer and a surface protective layer is not fully acquired, a surface protective layer can also be provided after carrying out the adhesion process (primer process) of the surface of a pattern pattern layer.
発泡化粧シートの表面強度(耐スクラッチ性など)、耐汚染性、絵柄模様層の保護等を目的として表面保護層を形成する場合には、電離放射線硬化型樹脂を樹脂成分として含有するものが好適である。電離放射線硬化型樹脂としては、電子線照射によってラジカル重合(硬化)するものが好ましい。例えば、ネオペンチルグリコールジメタクリレート、トリメチロールプロパントリメタクリレート等の多官能性モノマー、オリゴマーなどが挙げられる。またその配合は、樹脂成分100重量部に対して0〜10重量部程度とすることが好ましく、特に1〜4重量部とすることがより好ましい。 When forming a surface protective layer for the purpose of surface strength (scratch resistance, etc.), stain resistance, and protection of a pattern layer of a foamed decorative sheet, those containing an ionizing radiation curable resin as a resin component are suitable. It is. The ionizing radiation curable resin is preferably one that undergoes radical polymerization (curing) by electron beam irradiation. Examples thereof include polyfunctional monomers such as neopentyl glycol dimethacrylate and trimethylolpropane trimethacrylate, oligomers, and the like. Moreover, it is preferable to set it as about 0-10 weight part with respect to 100 weight part of resin components, and it is more preferable to set it as 1-4 weight part especially.
表面保護層の厚みは限定的ではないが、0.1〜15μm程度が好ましい。 The thickness of the surface protective layer is not limited, but is preferably about 0.1 to 15 μm.
エンボス
本発明では、適宜エンボス模様を付してもよい。この場合、発泡化粧シートの最表面層(基材と反対側)の上からエンボス加工すれば良い。エンボス加工は、エンボス版の押圧等、公知の手段により実施することができる。例えば、最表面層が表面保護層である場合は、そのおもて面を加熱軟化後、エンボス版を押圧することにより所望のエンボス模様を賦型できる。エンボス模様としては、例えば木目板導管溝、石板表面凹凸、布表面テクスチャア、梨地、砂目、ヘアライン、万線条溝等がある。
Embossing In this invention, you may attach | subject an embossing pattern suitably. In this case, what is necessary is just to emboss from the uppermost surface layer (opposite side of a base material) of a foaming decorative sheet. Embossing can be performed by known means such as pressing an embossed plate. For example, when the outermost surface layer is a surface protective layer, a desired embossed pattern can be formed by pressing the embossed plate after heat-softening the front surface. Examples of the embossed pattern include a wood grain plate conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin texture, a grain texture, a hairline, and a multiline groove.
2.発泡化粧シートの製造方法
発泡化粧シートの製造方法は特に限定されない。
2. The manufacturing method of a foaming decorative sheet The manufacturing method of a foaming decorative sheet is not specifically limited.
例えば、上記発泡剤含有樹脂層の各材料を樹脂の融点以上、発泡剤が発泡しない条件下でバンバリーミキサー、加圧ニーダー、ロール、単軸押出機、二軸押出機当の公知の混錬機で溶融混錬し、カレンダー、Tダイ等の公知のシート成形機にてシート状にした後、基材上に発泡剤含有シートをラミネートする。この際、必要に応じて発泡剤含有シートの上下、若しくは一方に非発泡層を積層してもよい。次に、発泡剤含有樹脂層又は非発泡樹脂層上に絵柄層模様層と表面保護層を形成し、その後、発泡剤含有樹脂層を加熱発泡させることにより発泡樹脂層を形成する。加熱条件は、熱分解型発泡剤の分解により発泡樹脂層が形成される条件ならば限定されない。(加熱温度は200〜220℃程度、加熱時間は30〜45秒程度である。)
なお、前記加熱処理の前に、電子線照射を行ってもよい。これにより樹脂成分を架橋できるため、発泡化粧シートの表面強度、発泡程度等を制御することができる。電子線のエネルギーは、150〜250kV程度が好ましい。照射量は、1〜7Mrad程度が好ましい。電子線源としては、公知の電子線照射装置が使用できる。
For example, each material of the foaming agent-containing resin layer is a known kneading machine such as a Banbury mixer, a pressure kneader, a roll, a single screw extruder, a twin screw extruder under the condition that the foaming agent does not foam above the melting point of the resin. After melt-kneading and forming into a sheet using a known sheet molding machine such as a calendar or T-die, a foaming agent-containing sheet is laminated on the substrate. Under the present circumstances, you may laminate | stack a non-foaming layer on the upper and lower sides or one side of a foaming agent containing sheet | seat as needed. Next, a pattern layer pattern layer and a surface protective layer are formed on the foaming agent-containing resin layer or the non-foaming resin layer, and then the foaming resin layer is formed by heating and foaming the foaming agent-containing resin layer. The heating conditions are not limited as long as the foamed resin layer is formed by the decomposition of the pyrolytic foaming agent. (The heating temperature is about 200 to 220 ° C., and the heating time is about 30 to 45 seconds.)
Note that electron beam irradiation may be performed before the heat treatment. Thereby, since a resin component can be bridge | crosslinked, the surface strength of a foaming decorative sheet, a foaming degree, etc. can be controlled. The energy of the electron beam is preferably about 150 to 250 kV. The irradiation amount is preferably about 1 to 7 Mrad. A known electron beam irradiation apparatus can be used as the electron beam source.
また、電離放射線硬化型樹脂を含有する表面保護層を形成した場合には、発泡剤含有樹脂層あるいは非発泡樹脂層の樹脂成分を電子線照射によって架橋させると同時(同処理)に表面保護層を硬化させることができる。つまり、発泡剤含有樹脂層、非発泡樹脂層、絵柄模様層及び電離放射線硬化型樹脂を含有する表面保護層を順に形成後、電子線照射を行って、発泡剤含有樹脂層および非発泡樹脂層に含まれる樹脂成分を架橋するとともに表面保護層に含まれる樹脂を硬化させることができる。 In addition, when a surface protective layer containing an ionizing radiation curable resin is formed, the surface protective layer is formed simultaneously with the crosslinking of the resin component of the foaming agent-containing resin layer or the non-foamed resin layer by electron beam irradiation (same treatment). Can be cured. That is, a foaming agent-containing resin layer, a non-foaming resin layer, a pattern layer, and a surface protective layer containing an ionizing radiation curable resin are sequentially formed, and then irradiated with an electron beam to form a foaming agent-containing resin layer and a non-foaming resin layer. The resin component contained in the resin can be cross-linked and the resin contained in the surface protective layer can be cured.
ここで、上記電離放射線硬化型樹脂は、表面保護層樹脂組成物に限らず、発泡樹脂層樹脂組成物、非発泡層樹脂組成物のいずれか、もしくはその全てに添加することができる。発泡樹脂層樹脂組成物および非発泡層樹脂組成物に電離放射線硬化型樹脂を添加することにより、その樹脂成分の架橋を促進させることが可能となる。 Here, the ionizing radiation curable resin is not limited to the surface protective layer resin composition, and can be added to any or all of the foamed resin layer resin composition and the non-foamed layer resin composition. By adding an ionizing radiation curable resin to the foamed resin layer resin composition and the non-foamed layer resin composition, crosslinking of the resin component can be promoted.
本発明の発泡化粧シートは、アクリル酸及びメタクリル酸からなる群から選ばれた少なくとも一種をモノマーとして得られる重合体、並びにチタン酸化合物を含む樹脂組成物によって形成された発泡剤含有樹脂層を発泡させることによって、発泡成型後において発泡し難く、所望の発泡倍率を有することが可能となる。 The foam decorative sheet of the present invention foams a foaming agent-containing resin layer formed by a resin composition containing a polymer obtained by using at least one selected from the group consisting of acrylic acid and methacrylic acid as a monomer, and a titanic acid compound. By making it, it becomes difficult to foam after foam molding, and it becomes possible to have a desired expansion ratio.
以下に実施例及び比較例を示して本発明をより詳しく説明する。但し、本発明は実施例に限定されない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.
実施例1
発泡剤含有樹脂組成物を、以下のような配合で110℃にて10分間混練した後、厚みが100μmとなるように製膜し、裏打紙と貼り合わせた。その後、電子線照射を行い、発泡剤含有樹脂組成物中の樹脂成分を架橋させた。最終的に、発泡剤含有樹脂層上に平板印刷機(GP−II)によりOP「AL−TOP402B、大日精化製」コートを行い、ギアオーブンにて加熱(220℃)し、発泡剤含有樹脂層に含有する発泡剤を発泡させ、発泡化粧シートを作製した。
発泡剤含有樹脂組成物:
樹脂 EMAA「ニュクレルN1560(メタクリル酸含有量=15重量%、メルトフローレート値(MFR)=60)、三井・デュポン ポリケミカル製」100重量部、
二酸化チタン「タイペーク CR−63、石原産業製」40重量部、
発泡剤 ADCA(アゾジカルボンアミド)「AZウルトラ3050I、大塚化学製」7.1重量部、
チタン酸カリウム「ティスモD(繊維状、直径0.3〜0.6μm、長さ10〜20μm)、大塚化学製」19重量部、
発泡助剤 アジピン酸ジヒドラジド「ADHS、大塚化学製」4.7重量部、
安定剤 低分子量ポリエチレン「エクセレックスDM01、三井化学製」2.5重量部。
Example 1
The foaming agent-containing resin composition was kneaded at 110 ° C. for 10 minutes with the following composition, then formed into a film having a thickness of 100 μm, and bonded to the backing paper. Then, electron beam irradiation was performed and the resin component in a foaming agent containing resin composition was bridge | crosslinked. Finally, OP “AL-TOP402B, manufactured by Dainichi Seika” is coated on the foaming agent-containing resin layer with a flat printing press (GP-II), heated in a gear oven (220 ° C.), and the foaming agent-containing resin A foaming decorative sheet was produced by foaming the foaming agent contained in the layer.
Foaming agent-containing resin composition:
Resin EMAA “Nucleel N1560 (methacrylic acid content = 15 wt%, melt flow rate value (MFR) = 60), made by Mitsui DuPont Polychemical”, 100 parts by weight,
40 parts by weight of titanium dioxide “Taipeku CR-63, manufactured by Ishihara Sangyo”
Foaming agent ADCA (azodicarbonamide) "AZ Ultra 3050I, manufactured by Otsuka Chemical" 7.1 parts by weight,
19 parts by weight of potassium titanate “Tismo D (fibrous, 0.3 to 0.6 μm in diameter, 10 to 20 μm in length), manufactured by Otsuka Chemical”
Foaming aid Adipic acid dihydrazide "ADHS, Otsuka Chemical" 4.7 parts by weight,
Stabilizer Low molecular weight polyethylene “Excellex DM01, Mitsui Chemicals” 2.5 parts by weight.
実施例2
EMAAの代わりに、EAA「レスクパールAS211S(アクリル酸含有量=8.5重量%、MFR=25)、日本ポリエチレン製」を用いる以外は、実施例1と同様にして発泡化粧シートを作製した。
Example 2
A foamed decorative sheet was prepared in the same manner as in Example 1 except that EAA “RESQUEPEARL AS211S (acrylic acid content = 8.5 wt%, MFR = 25), manufactured by Nippon Polyethylene” was used instead of EMAA.
比較例1
EMAAの代わりに、エチレン−酢酸ビニル共重合体(EVA)「エバフレックスV406(酢酸ビニル含有量=20重量%、MFR=20)、三井・デュポン ポリケミカル製」を用いる以外は、実施例1と同様にして発泡化粧シートを得た。
Comparative Example 1
Example 1 is used except that ethylene-vinyl acetate copolymer (EVA) “Evaflex V406 (vinyl acetate content = 20 wt%, MFR = 20), manufactured by Mitsui DuPont Polychemical” is used instead of EMAA. A foamed decorative sheet was obtained in the same manner.
比較例2
EMAAの代わりに、ポリエチレン樹脂(PE)「サンプルD、日本ポリエチレン製」を用いる以外は、実施例1と同様にして発泡化粧シートを得た。
Comparative Example 2
A foamed decorative sheet was obtained in the same manner as in Example 1 except that polyethylene resin (PE) “Sample D, manufactured by Nippon Polyethylene” was used instead of EMAA.
比較例3
チタン酸カリウムの代わりに、炭酸カルシウム「ホワイトンH、白石工業製」を用いる以外は、実施例1と同様にして発泡化粧シートを作製した。
Comparative Example 3
A foamed decorative sheet was produced in the same manner as in Example 1 except that calcium carbonate “Whiteon H, manufactured by Shiroishi Kogyo” was used instead of potassium titanate.
比較例4
チタン酸カリウムの代わりに、ウォラストナイト「SH−1800、キンセイマテック製」を用いる以外は、実施例1と同様にして発泡化粧シートを作製した。
Comparative Example 4
A foamed decorative sheet was produced in the same manner as in Example 1 except that wollastonite “SH-1800, manufactured by Kinsei Matec” was used instead of potassium titanate.
比較例5
チタン酸カリウムの代わりに、カオリナイト「Eckalite 1、イメリス製」を用いる以外は、実施例1と同様にして発泡化粧シートを作製した。
Comparative Example 5
A foamed decorative sheet was produced in the same manner as in Example 1 except that kaolinite “Eckalite 1, manufactured by Imeris” was used instead of potassium titanate.
比較例6
チタン酸カリウムの代わりに、マイカ「A−11、山口雲母工業所製」を用いる以外は、実施例1と同様にして発泡化粧シートを作製した。
Comparative Example 6
A foamed decorative sheet was produced in the same manner as in Example 1 except that mica “A-11, manufactured by Yamaguchi Mica Industries Co., Ltd.” was used instead of potassium titanate.
比較例7
チタン酸カリウムの代わりに、タルク「TTタルク、竹原化学工業製」を用いる以外は、実施例1と同様にして発泡化粧シートを作製した。
Comparative Example 7
A foamed decorative sheet was produced in the same manner as in Example 1 except that talc “TT talc, manufactured by Takehara Chemical Industries” was used instead of potassium titanate.
比較例8
チタン酸カリウムの代わりに、シリカ「ニップシールLP、東ソー・シリカ製」を用いる以外は、実施例1と同様にして発泡化粧シートを作製した。
Comparative Example 8
A foamed decorative sheet was produced in the same manner as in Example 1 except that silica “Nipseal LP, manufactured by Tosoh Silica” was used instead of potassium titanate.
試験例(表面外観試験)
実施例及び比較例で作製された発泡化粧シートの表面を、目視により観察した。尚、評価方法は、
○:気泡抜けが確認されない
△:僅かに気泡抜けが確認される
×:気泡抜けが確認され表面に大きく孔が空いている
とした。
Test example (surface appearance test)
The surface of the foamed decorative sheet produced in the examples and comparative examples was visually observed. The evaluation method is
○: No bubble removal was confirmed Δ: Bubble removal was slightly confirmed ×: Bubble removal was confirmed and a large hole was formed on the surface.
試験例(発泡ボリューム)
実施例及び比較例で作製された発泡化粧シートの発泡ボリュームを発泡前後の厚み比率(倍率)により測定した。尚、評価方法は、発泡前後の厚み比率(倍率)に関して、
○:5倍以上
△:4倍以上、5倍未満
×:4倍未満
とした。
Test example (foam volume)
The foam volume of the foam decorative sheet produced in the examples and comparative examples was measured by the thickness ratio (magnification) before and after foaming. In addition, the evaluation method relates to the thickness ratio (magnification) before and after foaming.
○: 5 times or more Δ: 4 times or more and less than 5 times ×: less than 4 times.
実施例及び比較例で得られたシートに関して、表面外観及び発泡ボリュームの特性について調べた。その結果を表1に示す。 With respect to the sheets obtained in the examples and comparative examples, the surface appearance and the characteristics of the foam volume were examined. The results are shown in Table 1.
以上の結果からも明らかなように、本発明の発泡化粧シートは、発泡剤含有樹脂層に特定の樹脂成分、無機フィラー及び発泡剤の組み合わせを採用することによって、発泡成型後において破泡し難く、所望の発泡倍率を有することが可能になる。 As is clear from the above results, the foamed decorative sheet of the present invention is difficult to break after foam molding by employing a combination of a specific resin component, an inorganic filler and a foaming agent in the foaming agent-containing resin layer. It becomes possible to have a desired expansion ratio.
Claims (7)
(1)前記発泡樹脂層が、発泡剤含有樹脂層を発泡させることにより形成され、
(2)前記発泡剤含有樹脂層が、
(i)アクリル酸及びメタクリル酸からなる群から選ばれた少なくとも一種をモノマーとして得られる重合体、並びに
(ii)チタン酸化合物
を含む樹脂組成物によって形成された層である、
ことを特徴とする発泡化粧シート。 A foamed decorative sheet having at least a foamed resin layer on a substrate,
(1) The foamed resin layer is formed by foaming a foaming agent-containing resin layer,
(2) The foaming agent-containing resin layer is
(I) a layer formed by a polymer obtained by using at least one selected from the group consisting of acrylic acid and methacrylic acid as a monomer, and (ii) a resin composition containing a titanic acid compound,
A foamed decorative sheet characterized by that.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009225481A JP5476893B2 (en) | 2009-09-29 | 2009-09-29 | Foam decorative sheet |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009225481A JP5476893B2 (en) | 2009-09-29 | 2009-09-29 | Foam decorative sheet |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2014024312A Division JP5673877B2 (en) | 2014-02-12 | 2014-02-12 | Method for producing foamed decorative sheet and method for producing foamed decorative sheet before foaming |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2011073209A true JP2011073209A (en) | 2011-04-14 |
JP5476893B2 JP5476893B2 (en) | 2014-04-23 |
Family
ID=44017732
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2009225481A Expired - Fee Related JP5476893B2 (en) | 2009-09-29 | 2009-09-29 | Foam decorative sheet |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5476893B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018053185A (en) * | 2016-09-30 | 2018-04-05 | 積水化学工業株式会社 | Foaming agent for resin, foamable resin composition, and manufacturing method of foamed body |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01149840A (en) * | 1987-12-04 | 1989-06-12 | Hitachi Cable Ltd | Production of foamed resin article |
JP2000006729A (en) * | 1998-06-19 | 2000-01-11 | Otsuka Chem Co Ltd | Ceiling material for automobile |
WO2005005527A1 (en) * | 2003-07-15 | 2005-01-20 | Denki Kagaku Kogyo Kabushiki Kaisha | Heat-shrinkable foam films |
JP2007085385A (en) * | 2005-09-20 | 2007-04-05 | Koatsu Gas Kogyo Co Ltd | Vibration damping material |
JP2007270387A (en) * | 2006-03-31 | 2007-10-18 | Dainippon Printing Co Ltd | Foamed wallpaper |
-
2009
- 2009-09-29 JP JP2009225481A patent/JP5476893B2/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01149840A (en) * | 1987-12-04 | 1989-06-12 | Hitachi Cable Ltd | Production of foamed resin article |
JP2000006729A (en) * | 1998-06-19 | 2000-01-11 | Otsuka Chem Co Ltd | Ceiling material for automobile |
WO2005005527A1 (en) * | 2003-07-15 | 2005-01-20 | Denki Kagaku Kogyo Kabushiki Kaisha | Heat-shrinkable foam films |
JP2007085385A (en) * | 2005-09-20 | 2007-04-05 | Koatsu Gas Kogyo Co Ltd | Vibration damping material |
JP2007270387A (en) * | 2006-03-31 | 2007-10-18 | Dainippon Printing Co Ltd | Foamed wallpaper |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018053185A (en) * | 2016-09-30 | 2018-04-05 | 積水化学工業株式会社 | Foaming agent for resin, foamable resin composition, and manufacturing method of foamed body |
Also Published As
Publication number | Publication date |
---|---|
JP5476893B2 (en) | 2014-04-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4006603B2 (en) | Method for producing foam wallpaper | |
JP4816370B2 (en) | Foam wallpaper | |
JP4905221B2 (en) | Wall decoration sheet | |
JP4816369B2 (en) | Foam wallpaper | |
JP2014144644A (en) | Sheet before foaming for foamed decorative sheet, production method of sheet before foaming for foamed decorative sheet and production method of foamed decorative sheet | |
JP4811218B2 (en) | Foam wallpaper | |
JP5672864B2 (en) | Foam decorative sheet | |
JP4765470B2 (en) | Foam wallpaper | |
JP5569290B2 (en) | Foam laminated sheet | |
JP4009873B2 (en) | Foam wallpaper | |
JP2007291599A (en) | Foamed wall paper | |
JP5476899B2 (en) | Foamed decorative sheet and method for producing resin sheet | |
JP4775213B2 (en) | Foam wallpaper | |
JP2008081887A (en) | Foamed wallpaper | |
JP5476893B2 (en) | Foam decorative sheet | |
JP5760471B2 (en) | Resin laminate and resin laminate sheet | |
JP4816368B2 (en) | Foam wallpaper | |
JP5673877B2 (en) | Method for producing foamed decorative sheet and method for producing foamed decorative sheet before foaming | |
JP5725696B2 (en) | Foam wallpaper | |
JP4765469B2 (en) | Foam wallpaper | |
JP4775073B2 (en) | Raw material for foam wallpaper and foam wallpaper | |
JP5686511B2 (en) | Foam decorative sheet | |
JP4793051B2 (en) | Wall covering decorative sheet and wall covering decorative sheet | |
JP5617820B2 (en) | Foam wallpaper | |
JP4905217B2 (en) | Foam wallpaper |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120727 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130425 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130507 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130625 |
|
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: 20140114 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140127 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5476893 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
LAPS | Cancellation because of no payment of annual fees |