JP4359771B2 - Decorative sheet - Google Patents
Decorative sheet Download PDFInfo
- Publication number
- JP4359771B2 JP4359771B2 JP2004097685A JP2004097685A JP4359771B2 JP 4359771 B2 JP4359771 B2 JP 4359771B2 JP 2004097685 A JP2004097685 A JP 2004097685A JP 2004097685 A JP2004097685 A JP 2004097685A JP 4359771 B2 JP4359771 B2 JP 4359771B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- decorative sheet
- resin
- sebacate
- plasticizer
- 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.)
- Expired - Fee Related
Links
- 239000010410 layer Substances 0.000 claims description 108
- 229920005989 resin Polymers 0.000 claims description 94
- 239000011347 resin Substances 0.000 claims description 94
- 239000004014 plasticizer Substances 0.000 claims description 53
- -1 sebacic acid diester Chemical class 0.000 claims description 41
- 239000003973 paint Substances 0.000 claims description 39
- 239000003960 organic solvent Substances 0.000 claims description 26
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 23
- 239000002344 surface layer Substances 0.000 claims description 20
- 239000011241 protective layer Substances 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000012790 adhesive layer Substances 0.000 claims description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 12
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 12
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 10
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 9
- ALOUNLDAKADEEB-UHFFFAOYSA-N dimethyl sebacate Chemical compound COC(=O)CCCCCCCCC(=O)OC ALOUNLDAKADEEB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000002537 cosmetic Substances 0.000 claims description 4
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940014772 dimethyl sebacate Drugs 0.000 claims description 3
- VNTXONBESJNLBI-UHFFFAOYSA-N dinonyl decanedioate Chemical compound CCCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCCC VNTXONBESJNLBI-UHFFFAOYSA-N 0.000 claims description 3
- DNWILILLQPIREP-UHFFFAOYSA-N ditridecyl decanedioate Chemical compound CCCCCCCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCCCCCCC DNWILILLQPIREP-UHFFFAOYSA-N 0.000 claims description 3
- KSCKTBJJRVPGKM-UHFFFAOYSA-N octan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-] KSCKTBJJRVPGKM-UHFFFAOYSA-N 0.000 claims description 3
- 229940116351 sebacate Drugs 0.000 claims description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 23
- 239000002585 base Substances 0.000 description 22
- 229920001971 elastomer Polymers 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 229920001577 copolymer Polymers 0.000 description 16
- 229920005672 polyolefin resin Polymers 0.000 description 14
- 238000007639 printing Methods 0.000 description 14
- 239000012855 volatile organic compound Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000004743 Polypropylene Substances 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 229920001155 polypropylene Polymers 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000003086 colorant Substances 0.000 description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 9
- 239000000806 elastomer Substances 0.000 description 9
- 239000004925 Acrylic resin Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000005060 rubber Substances 0.000 description 8
- 229920000178 Acrylic resin Polymers 0.000 description 7
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- 238000010030 laminating Methods 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229920003244 diene elastomer Polymers 0.000 description 5
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000005865 ionizing radiation Effects 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000306 polymethylpentene Polymers 0.000 description 3
- 239000011116 polymethylpentene Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- FCKXGFANXSHGAW-DTXPUJKBSA-N (2s)-n,n'-bis[(2s)-1-(2-chloro-4-nitroanilino)-1-oxo-3-phenylpropan-2-yl]-2-hydroxybutanediamide Chemical compound C([C@H](NC(=O)C[C@H](O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(=O)NC=1C(=CC(=CC=1)[N+]([O-])=O)Cl)C(=O)NC=1C(=CC(=CC=1)[N+]([O-])=O)Cl)C1=CC=CC=C1 FCKXGFANXSHGAW-DTXPUJKBSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229940097275 indigo Drugs 0.000 description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 2
- 238000003905 indoor air pollution Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- JLEXUIVKURIPFI-UHFFFAOYSA-N tris phosphate Chemical compound OP(O)(O)=O.OCC(N)(CO)CO JLEXUIVKURIPFI-UHFFFAOYSA-N 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- UBWFWCYQLDDVFQ-ARJAWSKDSA-N (z)-4-oxo-4-prop-2-enoyloxybut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OC(=O)C=C UBWFWCYQLDDVFQ-ARJAWSKDSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 description 1
- VQMHSKWEJGIXGA-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-6-dodecyl-4-methylphenol Chemical compound CCCCCCCCCCCCC1=CC(C)=CC(N2N=C3C=CC=CC3=N2)=C1O VQMHSKWEJGIXGA-UHFFFAOYSA-N 0.000 description 1
- CJWOWMAVPAZGBG-UHFFFAOYSA-N 2-[2-[3-[2-(2H-benzotriazol-4-yl)phenyl]-5-(2-phenylpropan-2-yl)phenyl]propan-2-yl]phenol Chemical compound OC1=C(C(C)(C)C=2C=C(C=C(C2)C2=C(C=CC=C2)C2=CC=CC=3NN=NC32)C(C)(C)C3=CC=CC=C3)C=CC=C1 CJWOWMAVPAZGBG-UHFFFAOYSA-N 0.000 description 1
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- PZBLUWVMZMXIKZ-UHFFFAOYSA-N 2-o-(2-ethoxy-2-oxoethyl) 1-o-ethyl benzene-1,2-dicarboxylate Chemical compound CCOC(=O)COC(=O)C1=CC=CC=C1C(=O)OCC PZBLUWVMZMXIKZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- WZSFTHVIIGGDOI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3-[2-methyl-3-[(4,5,6,7-tetrachloro-3-oxoisoindol-1-yl)amino]anilino]isoindol-1-one Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C2=C1C(NC1=CC=CC(NC=3C4=C(C(=C(Cl)C(Cl)=C4Cl)Cl)C(=O)N=3)=C1C)=NC2=O WZSFTHVIIGGDOI-UHFFFAOYSA-N 0.000 description 1
- DBOSBRHMHBENLP-UHFFFAOYSA-N 4-tert-Butylphenyl Salicylate Chemical compound C1=CC(C(C)(C)C)=CC=C1OC(=O)C1=CC=CC=C1O DBOSBRHMHBENLP-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical compound C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- RDOFJDLLWVCMRU-UHFFFAOYSA-N Diisobutyl adipate Chemical compound CC(C)COC(=O)CCCCC(=O)OCC(C)C RDOFJDLLWVCMRU-UHFFFAOYSA-N 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 description 1
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Description
本発明は、揮発性有機化合物（ＶＯＣ）による室内空気汚染が低減又は解消された化粧シートに関する。 The present invention relates to a decorative sheet in which indoor air pollution due to a volatile organic compound (VOC) is reduced or eliminated.
化粧シートは、種々の対象物品の表面を被覆し、美観を付与するために用いられる。その対象物品の種類は多く、とりわけ建築物の内外装、家具、家庭電機製品、厨房家具等に広く用いられている。 The decorative sheet is used for covering the surface of various target articles and imparting an aesthetic appearance. There are many types of target articles, and in particular, they are widely used for interior / exterior of buildings, furniture, household electrical appliances, kitchen furniture, and the like.
このような化粧シートとしては、例えば、特許文献１にポリオレフィン系樹脂からなる基材シート上に設けた化粧柄の面に少なくとも紫外線硬化型樹脂からなる接着剤層、溶融押出しコーティングによる透明ポリオレフィン系樹脂よりなり、且つ、当該透明ポリオレフィン系樹脂層の表面が凹凸模様であることを特徴とする化粧シートが開示されている。 Examples of such a decorative sheet include, for example, an adhesive layer made of at least a UV curable resin on the surface of a decorative pattern provided on a base sheet made of a polyolefin resin in Patent Document 1, and a transparent polyolefin resin made by melt extrusion coating. And a decorative sheet characterized in that the surface of the transparent polyolefin-based resin layer has an uneven pattern.
また、例えば、特許文献２にポリオレフィン系樹脂等の基材シートが不透明着色シートであり、当該基材シートの表側とする面に絵柄層が水性インキを用いて形成され、さらにその上に、接着層を介して、透明オーバーレイ層が形成されてなる化粧シートが開示されている。 In addition, for example, in Patent Document 2, a base material sheet such as a polyolefin resin is an opaque colored sheet, and a pattern layer is formed using a water-based ink on the surface to be the front side of the base material sheet. A decorative sheet in which a transparent overlay layer is formed via a layer is disclosed.
これらの化粧シートには、化粧シートを保護するための最表面層として、いわゆるＯＰ層（オーバープリント層）が形成される。そして、耐候性を高めるためにＯＰ層に紫外線吸収剤を添加する場合がある。 In these decorative sheets, a so-called OP layer (overprint layer) is formed as an outermost surface layer for protecting the decorative sheet. And in order to improve a weather resistance, an ultraviolet absorber may be added to OP layer.
しかしながら、ＯＰ層を水系塗工剤で形成する場合、紫外線吸収剤を所定量含ませることが困難であるため、所望の耐候性を付与することが困難である。他方、紫外線吸収剤を含有させるために従来のように有機溶剤を使用することが考えられるが、当然ながらＶＯＣの問題が発生する。しかも、ＯＰ層は最表面層（仕上げ層）であるため、乾燥処理に供される時間、回数等が他の層に比べて少ない場合が多く、残存ＶＯＣ量が多くなり易い傾向がある。従って、特に残存ＶＯＣ量低減の観点から、従来の化粧シートにはさらなる改善の余地がある。
本発明は、揮発性有機化合物（ＶＯＣ）による室内空気汚染の問題を軽減又は解消できる化粧シートを提供することを主な目的とする。 The main object of the present invention is to provide a decorative sheet that can reduce or eliminate the problem of indoor air pollution caused by volatile organic compounds (VOC).
本発明者は、上記目的を達成すべく鋭意研究を重ねた結果、化粧シートの少なくとも最表面層を、特定材料を含む塗料により形成する場合に、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 to achieve the above object, the present inventors have found that the above object can be achieved when at least the outermost surface layer of the decorative sheet is formed of a paint containing a specific material, and the present invention has been completed. It came to do.
即ち、本発明は、下記の化粧シートに係る。
１．基材シート上に、有機溶剤を含む塗料から形成される層を少なくとも一層有する化粧シートであって、少なくとも最表面層が炭素数５以下の有機溶剤と可塑剤とを含む塗料により形成されていることを特徴とする化粧シート。
２．可塑剤が、セバシン酸ジエステルである上記項１記載の化粧シート。
３．可塑剤が、セバシン酸ジブチル、セバシン酸ジオクチル、セバシン酸ジエチル、セバシン酸ジノニル、セバシン酸ジメチル、セバシン酸ジカプリル及びセバシン酸ジトリデシルからなる群から選択される少なくとも１種である上記項１記載の化粧シート。
４．可塑剤が、セバシン酸ジオクチルである上記項１記載の化粧シート。
５．基材シート上に絵柄層、透明性接着剤層、透明性樹脂層及び最表面層として透明性保護層を有する上記項１〜４のいずれかに記載の化粧シート。
６．上記項１〜５のいずれかに記載の化粧シートの基材シート側を被着材に貼着してなる化粧材。
以下、本発明の化粧シートについて詳細に説明する。
That is, the present invention relates to the following decorative sheet.
1. A decorative sheet having at least one layer formed from a paint containing an organic solvent on a base sheet, wherein at least the outermost surface layer is formed of a paint containing an organic solvent having 5 or less carbon atoms and a plasticizer. A decorative sheet characterized by that.
2. Item 2. The decorative sheet according to Item 1, wherein the plasticizer is sebacic acid diester.
3. The cosmetic sheet according to item 1, wherein the plasticizer is at least one selected from the group consisting of dibutyl sebacate, dioctyl sebacate, diethyl sebacate, dinonyl sebacate, dimethyl sebacate, dicapryl sebacate and ditridecyl sebacate. .
4). Item 2. The decorative sheet according to Item 1, wherein the plasticizer is dioctyl sebacate.
5. Item 5. The decorative sheet according to any one of Items 1 to 4, further comprising a transparent protective layer as a pattern layer, a transparent adhesive layer, a transparent resin layer, and an outermost surface layer on the base sheet.
6). A cosmetic material obtained by adhering the base sheet side of the decorative sheet according to any one of Items 1 to 5 to an adherend.
Hereinafter, the decorative sheet of the present invention will be described in detail.
本発明の化粧シートは、基材シート上に、有機溶剤を含む塗料から形成される層を少なくとも一層有し、少なくとも最表面層が炭素数５以下の有機溶剤と可塑剤とを含む塗料（以下「本発明塗料」とも言う）により形成されていることを特徴とする。 The decorative sheet of the present invention has at least one layer formed from a paint containing an organic solvent on a base material sheet, and at least the outermost layer is a paint containing an organic solvent having 5 or less carbon atoms and a plasticizer (below) It is also called “the paint of the present invention”).
このように、少なくとも最表面層が炭素数５以下の有機溶剤と可塑剤とを含む塗料により形成されていることにより、理由の詳細は不明であるが、化粧シート中の残存ＶＯＣ量を低減することができる。 Thus, at least the outermost surface layer is formed of a paint containing an organic solvent having a carbon number of 5 or less and a plasticizer, but the details of the reason are unknown, but the amount of VOC remaining in the decorative sheet is reduced. be able to.
この理由としては、例えば、塗料中に含まれる可塑剤の作用により、該塗料から形成された層の乾燥時における表面硬化膜の形成速度が遅延し、炭素数５以下の有機溶剤が十分に揮発する時間を確保できるためと考えられる。また、塗料中に含まれる可塑剤の作用により、該塗料から形成される層が柔軟な構造（該溶剤の揮発経路を層中に確保する構造）を形成することも理由の一つと考えられる。 This is because, for example, the action of the plasticizer contained in the paint delays the formation rate of the surface cured film when the layer formed from the paint is dried, and the organic solvent having 5 or less carbon atoms is sufficiently volatilized. It is thought that it is possible to secure time to do. Further, it is considered that one of the reasons is that a layer formed from the paint forms a flexible structure (a structure that secures a volatilization route of the solvent in the layer) by the action of the plasticizer contained in the paint.
本発明塗料は、炭素数５以下の有機溶剤を含む。炭素数５以下の有機溶剤（以下「本発明溶剤」又は「弱溶剤」とも言う）としては、例えば、メタノール、エタノール、イソプロパノール（ＩＰＡ）、イソブタノール、ペンタノール等のアルコール類（特に、脂肪族アルコール類）；アセトン、メチルエチルケトン、ジエチルケトン等のケトン類；酢酸メチル、酢酸エチル、酢酸イソプロピルのカルボン酸エステル類等が挙げられる。これらの有機溶剤は、１種又は２種以上で用いることができる。 The paint of the present invention contains an organic solvent having 5 or less carbon atoms. Examples of the organic solvent having 5 or less carbon atoms (hereinafter also referred to as “the solvent of the present invention” or “weak solvent”) include alcohols such as methanol, ethanol, isopropanol (IPA), isobutanol and pentanol (particularly aliphatic Alcohols); ketones such as acetone, methyl ethyl ketone, and diethyl ketone; and carboxylic acid esters of methyl acetate, ethyl acetate, and isopropyl acetate. These organic solvents can be used alone or in combination of two or more.
本発明塗料中の本発明溶剤の含有割合は特に限定されないが、通常１０〜８５重量％の中から設定できる。本発明塗料には、通常、樹脂成分も含まれるが、特に樹脂成分としてアクリル系樹脂、ウレタン系樹脂、アクリル−ウレタン系樹脂等の２液硬化型樹脂を用いる場合には、溶剤含有割合は５０〜８５重量％が好ましい。また、電離放射線硬化型樹脂を用いる場合には、溶剤含有割合は１０〜３５重量％が好ましい。 Although the content rate of this invention solvent in this invention coating material is not specifically limited, Usually, it can set from 10 to 85 weight%. The paint of the present invention usually contains a resin component, but particularly when a two-component curable resin such as an acrylic resin, a urethane resin, or an acrylic-urethane resin is used as the resin component, the solvent content is 50. ~ 85 wt% is preferred. Moreover, when using ionizing radiation-curable resin, the solvent content is preferably 10 to 35% by weight.
本発明溶剤の中でも、塗料中に紫外線吸収剤も添加する場合には、紫外線吸収剤の溶解性、さらには耐候性の観点から、イソプロパノール、メチルエチルケトン及び酢酸エチルの少なくとも１種が特に好ましい。例えば、メチルエチルケトン及びイソプロパノールの混合溶剤、酢酸エチル及びイソプロパノールの混合溶剤等が好適である。 Among the solvents of the present invention, when an ultraviolet absorber is also added to the paint, at least one of isopropanol, methyl ethyl ketone and ethyl acetate is particularly preferable from the viewpoints of solubility of the ultraviolet absorber and further weather resistance. For example, a mixed solvent of methyl ethyl ketone and isopropanol, a mixed solvent of ethyl acetate and isopropanol, and the like are suitable.
本発明塗料には、炭素数６以上の有機溶剤は、本発明の効果を妨げない範囲で含まれていてもよいが、なるべく含まれていないことが望ましい。即ち、本発明では、炭素数６以上の有機溶剤を含まない塗料を用いることが好ましい。 The paint of the present invention may contain an organic solvent having 6 or more carbon atoms as long as the effects of the present invention are not hindered, but it is desirable that the paint is not contained as much as possible. That is, in the present invention, it is preferable to use a paint that does not contain an organic solvent having 6 or more carbon atoms.
また、本発明では、本発明溶剤とともに、水を併用することもできる。即ち、本発明では、水を含まない溶剤のほか、水を含む溶剤も使用することができる。この場合、本発明溶剤と水との割合は特に限定されず、用いる有機溶剤の種類等に応じて適宜決定できるが、一般的には重量比で本発明溶剤：水＝１：１〜５０程度とすればよい。 Moreover, in this invention, water can also be used together with this invention solvent. That is, in the present invention, a solvent containing water can be used in addition to a solvent containing no water. In this case, the ratio of the solvent of the present invention to water is not particularly limited and can be appropriately determined according to the type of the organic solvent to be used. Generally, the solvent of the present invention: water is about 1: 1 to 50 by weight ratio. And it is sufficient.
本発明塗料は、可塑剤を含む。可塑剤としては特に限定されないが、該塗料から形成された層の乾燥時における表面硬化膜の形成速度を遅延させることのできる可塑剤、及び該塗料から形成される層が柔軟な構造（該溶剤の揮発経路を層中に確保する構造）を形成できる可塑剤を用いるのが好ましい。 The paint of the present invention contains a plasticizer. Although it does not specifically limit as a plasticizer, The plasticizer which can delay the formation rate of the surface hardening film at the time of drying of the layer formed from this coating material, and the layer formed from this coating material have a flexible structure (this solvent It is preferable to use a plasticizer capable of forming a structure that secures a volatilization path in the layer.
このような可塑剤としては、一般に樹脂用可塑剤として公知のもの又は市販品から適宜選択すればよいが、例えば；
１）フタル酸ジメチル、フタル酸ジエチル、フタル酸ジブチル、フタル酸ジ−２−エチルヘキシル、フタル酸ジノルマルオクチル、フタル酸ジイソノニル、フタル酸ジノニル、フタル酸ジイソデシル、フタル酸混基エステル（Ｃ6〜Ｃ11）、フタル酸ブチルベンジル、エチルフタリルエチルグリコレート等のフタル酸エステル系可塑剤、
２）アジピン酸ジメチル、アジピン酸ジブチル、アジピン酸ジイソブチル、アジピン酸ビス（２−エチルヘキシル）、アジピン酸ジイソデシル、アジピン酸ビス（ブチルジグリコール）、アジピン酸ジオクチル、アジピン酸ジイソノニル、アジピン酸ジノルマルアルキル（Ｃ6,8,10）、アジピン酸ジアルキル（Ｃ7,9）等のアジピン酸エステル系可塑剤、
３）リン酸トリメチル、リン酸トリエチル、リン酸トリメチル、リン酸トリフェニル、リン酸トリクレシル、リン酸トリキシレニル、リン酸クレジルジフェニル、リン酸−２−エチルジフェニル、リン酸トリス（２−ブトキシエチル）、リン酸トリス（２−エチルヘキシル）、リン酸トリス（ブトキシエチル）等のリン酸エステル系可塑剤、
４）トリメリット酸トリオクチル等のトリメリット酸エステル系可塑剤、
５）アセチルクエン酸トリブチル等のクエン酸エステル系可塑剤、
６）エポキシ化大豆油等のエポキシ系可塑剤、
７）セバシン酸；セバシン酸モノエステル；セバシン酸ジエステル（セバシン酸ジブチル、セバシン酸ジオクチル、セバシン酸ジエチル、セバシン酸ジノニル、セバシン酸ジメチル、セバシン酸ジカプリル、セバシン酸ジトリデシル等）；セバシン酸ポリエステルポリオールなどのセバシン酸系可塑剤、
８）アゼライン酸ジオクチル、アゼライン酸ビス（２−エチルヘキシル）等のアゼライン酸エステル系可塑剤、
９）リシノール酸メチルアセチル等のリシノール酸エステル系可塑剤、
１０）Ｎ−メチルベンゼンスルホンアミド等のスルホンアミド系可塑剤、
１１）トリアセチン、オクチルアセテート等の酢酸エステル系可塑剤、
１２）ポリ（１，３−ブタンジオールアジペート）等のポリエステル系可塑剤、
１３）その他、塩素化パラフィン系可塑剤、サクシン酸エステル系可塑剤、
などが挙げられる。
Such a plasticizer may be appropriately selected from known or commercially available plasticizers for resins, for example;
1) dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, phthalic acid di-n-octyl, diisononyl phthalate, dinonyl phthalate, diisodecyl phthalate,混基ester (C 6 -C 11 ), phthalate plasticizers such as butylbenzyl phthalate and ethylphthalylethyl glycolate,
2) Dimethyl adipate, dibutyl adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisodecyl adipate, bis (butyl diglycol) adipate, dioctyl adipate, diisononyl adipate, dinormal alkyl adipate ( C 6 , 8 , 10 ), adipic acid ester plasticizers such as dialkyl adipate (C 7 , 9 ),
3) Trimethyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethyldiphenyl phosphate, tris (2-butoxyethyl) phosphate , Phosphate ester plasticizers such as tris phosphate (2-ethylhexyl), tris phosphate (butoxyethyl),
4) trimellitic acid ester plasticizer such as trioctyl trimellitic acid,
5) Citrate plasticizers such as tributyl acetylcitrate,
6) Epoxy plasticizers such as epoxidized soybean oil,
7) sebacic acid; sebacic acid monoester; sebacic acid diester (dibutyl sebacate, dioctyl sebacate, diethyl sebacate, dinonyl sebacate, dimethyl sebacate, dicapryl sebacate, ditridecyl sebacate, etc.); sebacic acid polyester polyol, etc. Sebacic acid plasticizer,
8) Azelaic acid ester plasticizers such as dioctyl azelate and bis (2-ethylhexyl) azelate
9) Ricinoleic acid ester plasticizers such as methylacetyl ricinoleate,
10) Sulfonamide plasticizers such as N-methylbenzenesulfonamide,
11) Acetate plasticizers such as triacetin and octyl acetate,
12) Polyester plasticizers such as poly (1,3-butanediol adipate),
13) Other, chlorinated paraffin plasticizer, succinate ester plasticizer,
Etc.
これらの可塑剤の中でも、セバシン酸ジエステルが好ましく、特にセバシン酸ジオクチル（ＤＯＳ）が好ましい。 Among these plasticizers, sebacic acid diester is preferable, and dioctyl sebacate (DOS) is particularly preferable.
これらの可塑剤は、１種又は２種以上を混合して使用できる。本発明塗料中の可塑剤の含有割合は、可塑剤の種類により異なるが、通常０．１〜２０重量％、好ましくは０．５〜５重量％程度である。 These plasticizers can be used alone or in combination of two or more. The content of the plasticizer in the paint of the present invention varies depending on the type of plasticizer, but is usually 0.1 to 20% by weight, preferably about 0.5 to 5% by weight.
本発明塗料は、上記した炭素数５以下の有機溶剤（弱溶剤）と可塑剤とを含んでいればよく、例えば、弱溶剤（水を含んでもよい）、可塑剤及び樹脂から構成できる。この場合の各成分の配合割合は、樹脂、弱溶剤等の種類に応じて適宜設定できるが、例えば、樹脂成分がアクリル系樹脂、ウレタン系樹脂、アクリル−ウレタン系樹脂等の２液硬化型樹脂の場合には、弱溶剤５０〜８５重量％、可塑剤０．１〜２０重量％及び樹脂１０〜４０重量％の範囲内が好ましい。また、樹脂成分が電離放射線硬化型樹脂の場合には、弱溶剤１０〜３５重量％、可塑剤０．１〜２０重量％及び樹脂６０〜８５重量％の範囲内が好ましい。但し、具体的な各成分の種類により最適割合は異なるため、必ずしも上記範囲に限定されない。 The coating composition of the present invention only needs to contain the organic solvent (weak solvent) having 5 or less carbon atoms and a plasticizer, and can be composed of, for example, a weak solvent (may contain water), a plasticizer, and a resin. The mixing ratio of each component in this case can be set as appropriate according to the type of resin, weak solvent, etc., but for example, the resin component is a two-component curable resin such as an acrylic resin, a urethane resin, or an acrylic-urethane resin. In this case, it is preferable that the weak solvent is 50 to 85% by weight, the plasticizer is 0.1 to 20% by weight, and the resin is 10 to 40% by weight. Further, when the resin component is an ionizing radiation curable resin, it is preferably within a range of 10 to 35% by weight of a weak solvent, 0.1 to 20% by weight of a plasticizer, and 60 to 85% by weight of a resin. However, since the optimum ratio varies depending on the specific type of each component, it is not necessarily limited to the above range.
本発明塗料には、必要に応じて、紫外線吸収剤、酸化防止剤、着色剤、熱安定剤、界面活性剤、光安定剤、帯電防止剤等の公知の添加剤がさらに含まれていてもよい。 The coating composition of the present invention may further contain known additives such as an ultraviolet absorber, an antioxidant, a colorant, a heat stabilizer, a surfactant, a light stabilizer, and an antistatic agent as necessary. Good.
添加剤の中でも、特に紫外線吸収剤としては、例えば、下記（１）〜（５）のようなものを好適に使用することができる。
（１）ベンゾフェノン系：２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシ−ベンゾフェノン、２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノン、２−ヒドロキシ−４−メトキシ−ベンゾフェノン−５−スルホン酸等、
（２）ベンゾトリアゾール系：２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’−ｔ−ブチル−５’−メチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジクミルフェニル）フェニルベンゾトリアゾール、２−（２’−ヒドロキシ−３’−ドデシル−５’−メチルフェニル）ベンゾトリアゾール、２，２’−メチレンビス［４−（１，１，３，３−テトラメチルブチル）−６−（２Ｈ−ベンゾトリアゾール−２−イル）フェノール］等、
（３）アクリレート系：エチル−２−シアノ−３，３’−ジフェニルアクリレート、２−エチルヘキシル−２−シアノ−３，３’−ジフェニルアクリレート等、
（４）サリシレート系：フェニルサリシレート、４−ｔ−ブチルフェニルサリシレート等、
（５）オキザニリド系：２−エトキシ−２’−エチルオキザリックアシドビスアニリド、２−エトキシン−５−ｔ−ブチル−２’−エチルオキザリックアシドビスアニリド等、
（６）トリアジン系：２―（４，６−ジフェニル−１，３，５―トリアジン−２−イル）−５−［（ヘキシル）オキシ］フェノール、１，３，５―トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン、１，３，５−トリ［［３，５−ビスー（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］等。
Among the additives, particularly as the ultraviolet absorber, for example, the following (1) to (5) can be suitably used.
(1) Benzophenone series: 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid, etc. ,
(2) Benzotriazole series: 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzo Triazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) phenylbenzo Triazole, 2- (2′-hydroxy-3′-dodecyl-5′-methylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- ( 2H-benzotriazol-2-yl) phenol], etc.
(3) Acrylate series: ethyl-2-cyano-3,3′-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, etc.
(4) Salicylate type: phenyl salicylate, 4-t-butylphenyl salicylate, etc.
(5) Oxanilide type: 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxyn-5-t-butyl-2′-ethyloxalic acid bisanilide, etc.
(6) Triazine series: 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 1,3,5-triazine-2,4 6 (1H, 3H, 5H) -trione, 1,3,5-tri [[3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] and the like.
これらの紫外線吸収剤は、１種又は２種以上で用いることができる。本発明では、特にベンゾトリアゾール系紫外線吸収剤が好ましい。 These ultraviolet absorbers can be used alone or in combination of two or more. In the present invention, a benzotriazole-based ultraviolet absorber is particularly preferable.
紫外線吸収剤の含有量は、用いる紫外線吸収剤の種類等によって異なるが、本発明塗料１００重量部に対して０．５重量部以上、特に０．８〜３重量部程度、さらに０．８〜２．５重量部とすることが望ましい。 The content of the ultraviolet absorber varies depending on the type of the ultraviolet absorber used and the like, but is 0.5 parts by weight or more, particularly about 0.8 to 3 parts by weight, more preferably 0.8 to 100 parts by weight with respect to 100 parts by weight of the paint of the present invention. 2.5 parts by weight is desirable.
本発明の化粧シートは、前記の通り、少なくとも最表面層が本発明塗料により形成されていればよいが、最表面層以外の層であって基材シート以外の層も本発明塗料により形成されていることが好ましい。これにより、化粧シート中の残存ＶＯＣ量をより低減することができる。 As described above, at least the outermost surface layer of the decorative sheet of the present invention should be formed by the paint of the present invention. However, the layer other than the outermost surface layer and the layer other than the base sheet is also formed of the present paint. It is preferable. Thereby, the residual VOC amount in the decorative sheet can be further reduced.
この場合、最表面層に含まれる有機溶剤及び可塑剤と、当該他の層に含まれる有機溶剤及び可塑剤とは、同じものであってもよいし、互いに異なっていてよい。 In this case, the organic solvent and plasticizer contained in the outermost layer and the organic solvent and plasticizer contained in the other layer may be the same or different from each other.
本発明の化粧シートは、前記の通り、少なくとも最表面層が、本発明塗料により形成されていればよい。従って、それ以外の層構成は基本的には従来の化粧シートと同様とすることができる。例えば、基材シート上に絵柄層、透明性接着剤層、透明性樹脂層及び最表面層として透明性保護層を有する化粧シートを採用することができる。以下、この層構成を有する化粧シートを具体例に挙げて説明する。 As described above, at least the outermost surface layer of the decorative sheet of the present invention only needs to be formed by the paint of the present invention. Accordingly, the other layer configuration can be basically the same as that of the conventional decorative sheet. For example, a decorative sheet having a transparent protective layer as a pattern layer, a transparent adhesive layer, a transparent resin layer, and an outermost surface layer can be employed on the base sheet. Hereinafter, a decorative sheet having this layer structure will be described as a specific example.
図１は、上記構成を有する化粧シートの積層構造（断面図）の模式図である。 FIG. 1 is a schematic diagram of a laminated structure (cross-sectional view) of a decorative sheet having the above configuration.
図１の態様では、図中の下面側より、プライマー層２／基材シート３／絵柄層４／透明性接着剤層５／透明性樹脂層６／及び透明性保護層７（最表面層）が順に積層されて化粧シート１が構成されている。勿論、絵柄層の形成態様を変更して、絵柄層を基材シート３と透明性樹脂層６との間であって、透明性樹脂層６に接触する態様（バックプリント）で形成してもよい。両者の形態はいずれも本発明の化粧シートに含まれる。 In the aspect of FIG. 1, primer layer 2 / base sheet 3 / pattern layer 4 / transparent adhesive layer 5 / transparent resin layer 6 / and transparent protective layer 7 (outermost surface layer) from the lower surface side in the figure. Are laminated in order to form the decorative sheet 1. Of course, the pattern layer may be formed in a mode (backprint) between the base sheet 3 and the transparent resin layer 6 and in contact with the transparent resin layer 6 by changing the pattern layer formation mode. Good. Both forms are included in the decorative sheet of the present invention.
図１の最下面のプライマー層２（裏面プライマー層）は、化粧シート１と被着材との接着性を向上させるためのものであり、本発明では任意的な層である。また、所望により、最上面から必要な層まで及ぶエンボス加工による凹凸を有していてもよい。 The primer layer 2 (back surface primer layer) at the bottom of FIG. 1 is for improving the adhesion between the decorative sheet 1 and the adherend, and is an optional layer in the present invention. Moreover, you may have the unevenness | corrugation by embossing ranging from the uppermost surface to a required layer depending on necessity.
次に、本発明の化粧シート１を構成する各層について、図１に従って順に説明する。 Next, each layer which comprises the decorative sheet 1 of this invention is demonstrated in order according to FIG.
プライマー層
最下面のプライマー層２は、化粧シート１と被着材（木質材、金属板等の基材）との接着性を向上させるために、必要に応じて設けることができる。プライマー層は、どの段階で形成してもよい。例えば、１）何も積層されていない状態の基材シート３にプライマー層２を積層する、２）基材シート３上に透明性樹脂層６までを含む各層を積層した後にプライマー層２を積層する、３）基材シート３上に透明性保護層７までを含む各層を積層した後にプライマー層２を積層することができる。また、これら以外の順序・方法で積層することもできる。
The primer layer 2 on the lowermost surface of the primer layer can be provided as necessary in order to improve the adhesion between the decorative sheet 1 and the adherend (a base material such as a wood material or a metal plate). The primer layer may be formed at any stage. For example, 1) the primer layer 2 is laminated on the base material sheet 3 in a state where nothing is laminated, and 2) the primer layer 2 is laminated after laminating each layer including the transparent resin layer 6 on the base material sheet 3. 3) After each layer including the transparent protective layer 7 is laminated on the base material sheet 3, the primer layer 2 can be laminated. Moreover, it can also laminate | stack by the order and method other than these.
プライマー層２は、例えば、ポリエステル樹脂、ポリウレタン樹脂、アクリル樹脂、ポリカーボネート樹脂、塩化ビニル／酢酸ビニル共重合体、ポリビニルブチラール樹脂、ニトロセルロース樹脂等の各種樹脂を１種又は２種以上用いて形成することができる。 The primer layer 2 is formed using, for example, one or more of various resins such as polyester resin, polyurethane resin, acrylic resin, polycarbonate resin, vinyl chloride / vinyl acetate copolymer, polyvinyl butyral resin, and nitrocellulose resin. be able to.
プライマー層の形成は、これらの樹脂成分を適当な溶媒に溶解又は分散して得られる塗料組成物を用い、これを公知の塗布手段又は印刷手段によって実施することができる。 The primer layer can be formed by using a coating composition obtained by dissolving or dispersing these resin components in a suitable solvent, and using a known coating means or printing means.
上記塗料組成物としては、特に水性組成物を用いることが望ましい。より具体的には、樹脂成分（バインダー）が水又は水系溶媒に溶解又は分散してなる樹脂溶液又は樹脂分散液（樹脂エマルション）を好適に用いることができる。上記の水系溶媒としては、水と水溶性有機溶剤との混合溶媒を使用することができる。水溶性有機溶剤は特に限定されず、例えば、エタノール、イソプロピルアルコール等のアルコール類のほか、グリコール類、グリコールエーテル類等を挙げることができる。混合溶媒の水と水溶性有機溶剤との割合も樹脂成分の種類等に応じて適宜設定することができる。本発明において、水性組成物を用いることにより、室内空気汚染の防止に効果的に寄与することができる。なお、これらの水性組成物は、公知のもの又は市販品を使用することもできる。 As the coating composition, it is particularly desirable to use an aqueous composition. More specifically, a resin solution or resin dispersion (resin emulsion) in which a resin component (binder) is dissolved or dispersed in water or an aqueous solvent can be suitably used. As the aqueous solvent, a mixed solvent of water and a water-soluble organic solvent can be used. The water-soluble organic solvent is not particularly limited, and examples thereof include alcohols such as ethanol and isopropyl alcohol, glycols, glycol ethers, and the like. The ratio of the water of the mixed solvent and the water-soluble organic solvent can be appropriately set according to the type of the resin component. In the present invention, the use of the aqueous composition can effectively contribute to prevention of indoor air contamination. In addition, a well-known thing or a commercial item can also be used for these aqueous compositions.
特に、水性組成物に適した樹脂成分として、後記の絵柄層の形成で使用される水性組成物の樹脂成分と同様のものを使用することができる。 In particular, as the resin component suitable for the aqueous composition, the same resin component as that of the aqueous composition used in the formation of the pattern layer described later can be used.
基材シート
基材シート３は、公知の化粧シートに用いられる素材であればいずれも使用可能である。例えば、各種の紙類、プラスチックス、金属又は合金、これらの複合材料等が挙げられる。これらの材料をシート、箔等の形態で使用すればよい。この中でも、印刷又は塗装による美観の付与が容易であり、化粧シートの製造時の加工性あるいは化粧シートを対象物品の表面に適用するときの加工性（例えば、折り曲げ、成形等）に優れているという点でプラスチックスが好ましい。
Substrate sheet base sheet 3 and either can be used as long as the material used in the known decorative sheet. Examples thereof include various papers, plastics, metals or alloys, and composite materials thereof. What is necessary is just to use these materials with forms, such as a sheet | seat and foil. Among these, it is easy to impart aesthetics by printing or painting, and it is excellent in processability when manufacturing a decorative sheet or processability (for example, bending, molding, etc.) when applying the decorative sheet to the surface of a target article. In this respect, plastics are preferable.
プラスチックスとしては、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、ポリ塩化ビニル樹脂、ポリ塩化ビニリデン樹脂、ポリビニルアルコール樹脂、塩化ビニル−酢酸ビニル共重合樹脂、エチレン−酢酸ビニル共重合樹脂、エチレン−ビニルアルコール共重合樹脂、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンナフタレート−イソフタレート共重合樹脂、ポリメタクリル酸メチル樹脂、ポリメタクリル酸エチル樹脂、ポリアクリル酸ブチル樹脂、ナイロン６もしくはナイロン６６等で代表されるポリアミド樹脂、三酢酸セルロース樹脂、セロファン、ポリスチレン樹脂、ポリカーボネート樹脂、ポリアリレート樹脂、ポリイミド樹脂等を使用できる。 Examples of plastics include polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer. Polyamides represented by resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polyethylene naphthalate-isophthalate copolymer resins, polymethyl methacrylate resins, polyethyl methacrylate resins, polybutyl acrylate resins, nylon 6 or nylon 66 Resin, cellulose triacetate resin, cellophane, polystyrene resin, polycarbonate resin, polyarylate resin, polyimide resin and the like can be used.
上記のような素材からなるプラスチックスのうちでも、有害物質を生じるおそれのないポリオレフィン系樹脂を用いることが望ましい。 Among the plastics made of the above materials, it is desirable to use a polyolefin resin that does not cause harmful substances.
このようなポリオレフィン系樹脂としては、非エラストマーであるポリオレフィン系樹脂と、ポリオレフィン系熱可塑性エラストマーの２つのタイプがある。 As such a polyolefin resin, there are two types, a polyolefin resin which is a non-elastomer and a polyolefin thermoplastic elastomer.
前者の非エラストマーとしては、具体的には、ポリエチレン（低密度、中密度又は高密度）、ポリプロピレン（アイソタクチック型、シンジオタクチック型、これらの混合型）、ポリメチルペンテン、ポリブテン、エチレン／プロピレン共重合体、プロピレン／ブテン共重合体等の高結晶質のものが例示される。 Specific examples of the non-elastomer include polyethylene (low density, medium density or high density), polypropylene (isotactic type, syndiotactic type, mixed type thereof), polymethylpentene, polybutene, ethylene / Examples thereof include highly crystalline ones such as a propylene copolymer and a propylene / butene copolymer.
後者のエラストマーとしては、次に示す（１）〜（８）のようなものが例示される。
（１）主原料がハードセグメントである高結晶質の高密度ポリエチレン、又はアイソタクチックポリプロピレン等からなり、更に、ソフトセグメントとしてのエラストマー及び、必要に応じて無機充填剤を添加したもの。
Examples of the latter elastomer include the following (1) to (8).
(1) Made of high crystalline high-density polyethylene whose main raw material is a hard segment, isotactic polypropylene, or the like, and further added with an elastomer as a soft segment and, if necessary, an inorganic filler.
ここで、エラストマーとしては、ジエン系ゴム、水素添加ジエン系ゴム、オレフィンエラストマー等が用いられる。ジエン系ゴムとしては、イソプレンゴム、ブタジエンゴム、ブチルゴム、プロピレン／ブタジエンゴム、アクリロニトリル／ブタジエンゴム、アクリロニトリル／イソプレンゴム、スチレン／ブタジエンゴム等がある。水素添加ジエンゴムは、上記のジエン系ゴム分子の二重結合の少なくとも一部分に水素原子を付加させてなり、ポリオレフィン系樹脂（例えば、高密度ポリエチレン又はポリプロピレン）の結晶化を抑えて柔軟性を向上させたものである。オレフィンエラストマーとしては、２種類又は３種類以上のオレフィンと共重合し得るポリエンを少なくとも１種加えた弾性共重合体であり、オレフィンとしてはエチレン、プロピレン、α−オレフィン等が使用され、ポリエンとしては１，４−ヘキサジエン、環状ジエン、ノルボルネン等が使用される。好ましいオレフィン系共重合体ゴムとしては、例えば、エチレン／プロピレン共重合体ゴム等のオレフィンを主成分とする弾性共重合体が挙げられる。これらのエラストマーは、必要に応じて、有機過酸化物、硫黄等の架橋剤を用いて適量架橋させてもよい。
（２）ハードセグメントがアイソタクチックポリプロピレン、ソフトセグメントがアタクチックポリプロピレンであるもので、好ましくは、後者の割合が５重量％未満のもの（特公平６−２３２７８号公報記載）。
（３）エチレン／プロピレン／ブテンの共重合体で、ブテンとして、１−ブテン、２−ブテン、又はイソブチレンの３種の構造異性体の１種を含むもの。具体的には、例えば、次の（３ａ）〜（３ｃ）が代表的である。
（３ａ）エチレン／プロピレン／ブテンの３元のランダム共重合体であり、モノマー中のプロピレンが、好ましくは９０重量％であるもの（特開平９−１１１０５５号公報記載）。
（３ｂ）プロピレン成分含有率が５０重量％以上である、エチレン／プロピレン／ブテンの３元の共重合体からなる非晶質と、結晶質ポリプロピレンからなるもの（特開平５−７７３７１号公報記載）。
（３ｃ）プロピレン及び／又は１−ブテンの含有量が５０重量％以上の低結晶質と、アイソタクチックポリプロピレン等の結晶性ポリオレフィンを含むものに、更に、油ゲル化剤を０．５重量％添加したもの（特開平７−３１６３５８号公報記載のもの）。
（４）ハードセグメントがポリエチレン、ポリプロピレン又はポリメチルペンテン等の結晶質であり、ソフトセグメントが部分架橋したエチレン／プロピレン非共役ジエン３元共重合体ゴム等のモノオレフィン共重合体ゴムであるもの（特公昭５３−２１０２１号公報記載のもの）。
（５）ハードセグメントとしてのオレフィン系共重合体（結晶質）とソフトセグメントとしての未架橋モノオレフィン共重合体ゴムとを加熱しつつ剪断応力を加え、部分架橋させてあるもの（特公昭５３−３４２１０号公報記載のもの）。
（６）過酸化物と混合・加熱すると分子量が減って流動性が増す過酸化物分解型オレフィン重合体、例えば、アイソタクチックポリプロピレン、プロピレン／エチレン共重合体、又はプロピレン／ブテン−１共重合体をハードセグメントとし、同様な操作で流動性が減る過酸化物架橋型モノオレフィン重合体、例えば、エチレン／プロピレン共重合体ゴム、エチレン／プロピレン／非共役ジエン３元共重合体ゴム等をソフトセグメントとし、更には、同様な操作で架橋せず、流動性も変わらない過酸化物非架橋型炭化水素ゴム、等を過酸化物の存在下で混合・加熱して得られるもの（特公昭５６−１５７４１号公報記載のもの）。
（７）エチレン／スチレン／ブタジエン共重合体（特開平２−１３９２３２号公報記載のもの）。
（８）水酸基又はカルボキシル基を持たせた上記（１）〜（７）のオレフィン系エラストマー。
Here, as the elastomer, diene rubber, hydrogenated diene rubber, olefin elastomer or the like is used. Examples of the diene rubber include isoprene rubber, butadiene rubber, butyl rubber, propylene / butadiene rubber, acrylonitrile / butadiene rubber, acrylonitrile / isoprene rubber, and styrene / butadiene rubber. Hydrogenated diene rubber is made by adding a hydrogen atom to at least a part of the double bond of the above diene rubber molecule, and suppresses crystallization of polyolefin resin (for example, high density polyethylene or polypropylene) to improve flexibility. It is a thing. The olefin elastomer is an elastic copolymer to which at least one polyene copolymerizable with two or three or more olefins is added. Ethylene, propylene, α-olefin, etc. are used as the olefin, 1,4-hexadiene, cyclic diene, norbornene and the like are used. Preferable olefin copolymer rubber includes, for example, an elastic copolymer containing olefin as a main component such as ethylene / propylene copolymer rubber. These elastomers may be crosslinked in an appropriate amount using a crosslinking agent such as an organic peroxide or sulfur as required.
(2) The hard segment is isotactic polypropylene and the soft segment is atactic polypropylene, and preferably the latter proportion is less than 5% by weight (described in JP-B-6-23278).
(3) A copolymer of ethylene / propylene / butene containing as a butene one of three structural isomers of 1-butene, 2-butene, or isobutylene. Specifically, for example, the following (3a) to (3c) are representative.
(3a) A ternary random copolymer of ethylene / propylene / butene, wherein propylene in the monomer is preferably 90% by weight (described in JP-A-9-1111055).
(3b) A propylene component content of 50% by weight or more, consisting of an amorphous copolymer of ethylene / propylene / butene and a crystalline polypropylene (described in JP-A-5-77371) .
(3c) In addition to a low crystalline material having a propylene and / or 1-butene content of 50% by weight or more and a crystalline polyolefin such as isotactic polypropylene, an oil gelling agent is further added by 0.5% by weight. Added (described in JP-A-7-316358).
(4) The hard segment is a crystalline material such as polyethylene, polypropylene or polymethylpentene, and the soft segment is a monoolefin copolymer rubber such as a partially crosslinked ethylene / propylene non-conjugated diene terpolymer rubber ( Japanese Patent Publication No. 53-21021).
(5) An olefin copolymer (crystalline) as a hard segment and an uncrosslinked monoolefin copolymer rubber as a soft segment are partially crosslinked by applying shear stress while heating (Japanese Patent Publication No. 53- 34210).
(6) Peroxide-decomposable olefin polymer, whose molecular weight decreases and fluidity increases when mixed and heated with a peroxide, such as isotactic polypropylene, propylene / ethylene copolymer, or propylene / butene-1 copolymer Peroxide-crosslinked monoolefin polymers, such as ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated diene terpolymer rubber, etc., which have a polymer as a hard segment and whose fluidity is reduced by the same operation, are soft. A segment obtained by mixing and heating a peroxide non-crosslinked hydrocarbon rubber that does not crosslink by the same operation and does not change fluidity in the presence of peroxide (Japanese Examined Patent Publication 56) -15741).
(7) An ethylene / styrene / butadiene copolymer (as described in JP-A-2-139232).
(8) The olefin elastomer according to the above (1) to (7) having a hydroxyl group or a carboxyl group.
上記のポリオレフィン系樹脂は、紫外線吸収剤及び光安定剤の少なくとも１種を添加したものを使用することができる。これらの紫外線吸収剤及び光安定剤は、公知又は市販のものを使用すればよい。 As the polyolefin-based resin, one added with at least one of an ultraviolet absorber and a light stabilizer can be used. These ultraviolet absorbers and light stabilizers may be known or commercially available.
基材シートは、対象物品に貼り付けたときの隠蔽性を向上させる目的、化粧シートに付与する模様の外観を向上させる目的等で公知の着色剤により着色することもできる。 The base sheet can also be colored with a known colorant for the purpose of improving the concealing property when attached to the target article, the purpose of improving the appearance of the pattern to be applied to the decorative sheet, and the like.
着色剤としては、例えば、カーボンブラック、弁柄、黄鉛、群青、チタン白等の無機顔料；キナクリドンレッド、イソインドリノンイエロー、フタロシアニンブルー等の有機顔料；アルミニウム、真鍮、二酸化チタン被覆雲母等の鱗片状箔片からなる光輝性顔料等が使用できる。また、インジゴ（藍）等で代表される天然染料、アゾ染料、インジゴイド染料、硫化染料、ニトロ染料、ニトロソ染料等の合成染料の各種の染料を使用することもできる。これら着色剤は、１種又は２種以上で用いることができる。 Examples of the colorant include inorganic pigments such as carbon black, petal, yellow lead, ultramarine blue, and titanium white; organic pigments such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; aluminum, brass, titanium dioxide-coated mica, and the like. A bright pigment made of a scale-like foil piece can be used. Various dyes such as natural dyes typified by indigo (indigo), synthetic dyes such as azo dyes, indigoid dyes, sulfur dyes, nitro dyes and nitroso dyes can also be used. These colorants can be used alone or in combination of two or more.
また、充填剤を配合することもできる。例えば、炭酸カルシウム、硫酸バリウム、水酸化アルミニウム、水酸化マグネシウム、滑石、カオリナイト等が挙げられる。これらは、１種又は２種以上で用いることができる。 Moreover, a filler can also be mix | blended. Examples thereof include calcium carbonate, barium sulfate, aluminum hydroxide, magnesium hydroxide, talc, and kaolinite. These can be used alone or in combination of two or more.
基材シートの厚みは、一般的には２０μｍ〜１５０μｍ程度であるが、化粧シートの用途等によっては上記範囲を超えてもよい。 The thickness of the base sheet is generally about 20 μm to 150 μm, but may exceed the above range depending on the use of the decorative sheet.
透明性樹脂層
透明性樹脂層６は、透明性を有するものであれば特に限定されない。例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリアミド、ポリエチレン、ポリプロピレン、エチレン・酢酸ビニル共重合体、エチレン・アクリル酸共重合体、エチレン・アクリル酸エステル共重合体、アイオノマー、ポリメチルペンテン、アクリル酸エステル、メタアクリル酸エステル、ポリカーボネート、セルローストリアセテート等を挙げることができる。好ましくは、基材シート３と同様の理由で、ポリプロピレン樹脂を代表とするポリオレフィン系樹脂を使用する。従って、透明性樹脂層６としてポリオレフィン系樹脂を使用する場合は、基材シート３を構成するものとして挙げた各種のポリオレフィン系樹脂を使用することができる。
Transparent resin layer The transparent resin layer 6 is not particularly limited as long as it has transparency. For example, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, ionomer, polymethylpentene, acrylic acid ester, Examples thereof include methacrylic acid ester, polycarbonate, and cellulose triacetate. Preferably, for the same reason as the base sheet 3, a polyolefin resin typified by a polypropylene resin is used. Therefore, when a polyolefin resin is used as the transparent resin layer 6, various polyolefin resins listed as constituting the base sheet 3 can be used.
なお、透明性樹脂層は、透明性を有する限り、着色されていてもよいが、特に着色剤を配合しない方が望ましい。 The transparent resin layer may be colored as long as it has transparency, but it is particularly desirable not to add a colorant.
透明性樹脂層の形成方法は限定的でなく、例えば予め形成されたシート又はフィルムを隣接する層に積層する方法、透明性樹脂層を形成し得る樹脂組成物を溶融押出することにより隣接する層上に塗工する方法、隣接する層と一緒にラミネートする方法等のいずれも採用することができる。本発明では、特に溶融押出により透明性樹脂層を形成することが好ましい。とりわけ、透明性樹脂層は、ポリオレフィン系樹脂を溶融押出によって塗工することが望ましい。具体的には、絵柄層上に予め接着剤層を形成し、当該接着剤層上にポリプロピレン系熱可塑性エラストマーを溶融押出して塗工することにより透明性樹脂層を好適に形成することができる。溶融押出の方法は、例えばＴダイ等を用いる公知の方法に従って実施すればよい。 The forming method of the transparent resin layer is not limited, for example, a method of laminating a preformed sheet or film on an adjacent layer, an adjacent layer by melt-extruding a resin composition capable of forming a transparent resin layer Any of a method of coating on top and a method of laminating together with an adjacent layer can be employed. In the present invention, it is particularly preferable to form the transparent resin layer by melt extrusion. In particular, the transparent resin layer is preferably applied by melt extrusion of a polyolefin resin. Specifically, the transparent resin layer can be suitably formed by forming an adhesive layer on the pattern layer in advance, and melt-extruding and applying a polypropylene-based thermoplastic elastomer onto the adhesive layer. What is necessary is just to implement the method of melt extrusion, for example according to the well-known method using a T die.
透明性樹脂層６の厚みは、基材シート３と同様、通常は２０μｍ〜１５０μｍ程度であるが、化粧シートの用途等に応じて上記範囲を超えてもよい。 The thickness of the transparent resin layer 6 is usually about 20 μm to 150 μm, similarly to the base sheet 3, but may exceed the above range depending on the use of the decorative sheet and the like.
絵柄層
絵柄層４は、化粧シートに、意匠的な外観を付与するためのものである。絵柄層４の形成は基材シート３側でもよいし、透明性樹脂層６側（バックプリント）でもよい。
The pattern layer The pattern layer 4 is for imparting a design appearance to the decorative sheet. The pattern layer 4 may be formed on the base sheet 3 side or on the transparent resin layer 6 side (back print).
絵柄層４は、絵、文字、図等の任意のものでよく、用途に合わせて適宜組み合わせることができる
絵柄層の形成方法は限定されないが、一般的には印刷インキを用いる印刷法により好適に形成できる。印刷法としては、バインダーの選択範囲が広いという点でグラビア印刷法が適しているが、これ以外の印刷法でもよい。また、印刷法のほかに、電子写真法、インキジェット法等も適用できる。
The pattern layer 4 may be an arbitrary one such as a picture, a character, a figure, and the like, and can be appropriately combined depending on the application. The formation method of the pattern layer is not limited, but is generally more suitable for a printing method using printing ink. Can be formed. As the printing method, the gravure printing method is suitable in that the selection range of the binder is wide, but other printing methods may be used. In addition to the printing method, an electrophotographic method, an ink jet method, or the like can also be applied.
絵柄層は、染料、顔料等の着色剤と樹脂成分（バインダー）とを含む組成物により形成することができる。絵柄層４が印刷法により形成されるときは、上記組成物を印刷インキとして使用すればよい。これらは、公知又は市販の塗料（印刷インキ）を使用することもできる。 The pattern layer can be formed of a composition containing a colorant such as a dye or a pigment and a resin component (binder). When the pattern layer 4 is formed by a printing method, the above composition may be used as a printing ink. These can also use a well-known or commercially available coating material (printing ink).
本発明では、着色剤を含む水性組成物により形成されることが望ましい。この水性組成物としては、プライマー層の形成に使用される水性組成物と同様のものを用いることができる。上記のような水性組成物を絵柄層の形成に用いることによって、印刷時において印刷用版からプラスチックシートにインキが移るまでの間に乾燥することがない。しかも、有機溶剤と異なり、乾燥までの間に揮発して室内空気が汚染される問題も解消される。 In this invention, it is desirable to form with the aqueous composition containing a coloring agent. As this aqueous composition, the thing similar to the aqueous composition used for formation of a primer layer can be used. By using the aqueous composition as described above for the formation of the pattern layer, it does not dry during printing until the ink is transferred from the printing plate to the plastic sheet. In addition, unlike organic solvents, the problem of volatilization before drying and contamination of room air is also eliminated.
水性組成物に適した樹脂成分としては、例えばアルカリ溶液可溶性（メタ）アクリル系共重合体を用いることができる。この共重合体は、例えば（メタ）アクリル酸エステル、ヒドロキシエチル（メタ）アクリレート、ヒドロキシエチルメタクリレート等の（メタ）アクリル系モノマー；（メタ）アクリロニトリル等のニトリル系モノマー；（メタ）アクリルアミド等のアミド系モノマー又はそのようなアミド系モノマーのＮ−アルコキシ置換体又は同Ｎ−メチロール置換体；スチレン、ビニルトルエン、α−メチルスチレン、ジビニルベンゼン等のスチレン系モノマー；ジアリルフタレート、アリルグリジジルエーテル、トリアリルイソシアヌレート等のアリル系モノマー；酢酸ビニル、Ｎ−ビニルピロリドン等の重合性二重結合を有するモノマー等の１種又は２種以上と、カルボキシル基を有する（メタ）アクリル酸マレイン酸、無水マレイン酸、フマール酸、イタコン酸等の不飽和カルボン酸の１種又は２種以上との共重合体からなるものを挙げることができる。 As a resin component suitable for the aqueous composition, for example, an alkali solution-soluble (meth) acrylic copolymer can be used. This copolymer includes, for example, (meth) acrylic monomers such as (meth) acrylic acid ester, hydroxyethyl (meth) acrylate, and hydroxyethyl methacrylate; nitrile monomers such as (meth) acrylonitrile; amides such as (meth) acrylamide N-alkoxy substituted or N-methylol substituted monomers of such amide monomers; styrene monomers such as styrene, vinyltoluene, α-methylstyrene, divinylbenzene; diallyl phthalate, allyl glycidyl ether, tri Allyl monomers such as allyl isocyanurate; one or more monomers having a polymerizable double bond such as vinyl acetate and N-vinylpyrrolidone, and (meth) acrylic maleic anhydride and maleic anhydride having a carboxyl group Acid, fumar , There may be mentioned those consisting of a copolymer of one or more unsaturated carboxylic acids such as itaconic acid.
また、例えばポリアルリルアミド系樹脂、ポリ（メタ）アクリル酸系樹脂、ポリエチレンオキシド系樹脂、ポリＮ−ビニルピロリドン系樹脂、水溶性ポリウレタン系樹脂（２液硬化型ポリウレタン系樹脂）、水溶性ポリエステル系樹脂、水溶性ポリアミド系樹脂、水溶性アミノ系樹脂、水溶性フェノール系樹脂等の水溶性合成樹脂、ポリヌクレオチド、ポリペプチド、もしくは多糖類等の水溶性天然高分子等も使用することができる。 In addition, for example, polyarrylamide resin, poly (meth) acrylic acid resin, polyethylene oxide resin, poly N-vinylpyrrolidone resin, water-soluble polyurethane resin (two-component curable polyurethane resin), water-soluble polyester Water-soluble synthetic resins such as water-based resins, water-soluble polyamide-based resins, water-soluble amino-based resins, water-soluble phenol-based resins, water-soluble natural polymers such as polynucleotides, polypeptides, or polysaccharides can also be used. .
さらに、例えば天然ゴム、合成ゴム、ポリ酢酸ビニル系樹脂、（メタ）アクリル系樹脂、ポリウレタン系樹脂を使用することができる。 Furthermore, for example, natural rubber, synthetic rubber, polyvinyl acetate resin, (meth) acrylic resin, and polyurethane resin can be used.
また、アクリル変性ウレタン樹脂、ポリエステル変性ウレタン樹脂、塩化ビニル−酢酸ビニル共重合体変性ウレタン樹脂等のウレタン系樹脂、ポリオール系樹脂、もしくは塩化
ビニル−酢酸ビニル共重合体とアクリル系樹脂との混合樹脂等も用いることができる。
Also, urethane-based resins such as acrylic-modified urethane resins, polyester-modified urethane resins, vinyl chloride-vinyl acetate copolymer-modified urethane resins, polyol resins, or mixed resins of vinyl chloride-vinyl acetate copolymers and acrylic resins. Etc. can also be used.
これらの樹脂成分を含む水性組成物は、公知のもの又は市販品を使用することもできる。 As the aqueous composition containing these resin components, known products or commercially available products can be used.
また、水性組成物に配合される着色剤は、基材シートで使用される着色剤として挙げた顔料又は染料と同様のものを使用することができる。 Moreover, the thing similar to the pigment or dye mentioned as a coloring agent used with a base material sheet can be used for the coloring agent mix | blended with an aqueous composition.
透明性接着剤層
接着剤層５は、化粧シート１を構成する基材シート３と透明性樹脂層６を、絵柄層４を介して積層するために形成される。
The transparent adhesive layer adhesive layer 5 is formed for laminating the base sheet 3 and the transparent resin layer 6 constituting the decorative sheet 1 via the pattern layer 4.
接着剤層５は、公知の接着剤を用いて形成することができる。例えば、ポリエステル、ポリウレタン、アクリル樹脂等の汎用されている樹脂あるいはその２液硬化物等を使用することができる。 The adhesive layer 5 can be formed using a known adhesive. For example, a widely used resin such as polyester, polyurethane, acrylic resin, or a two-component cured product thereof can be used.
本発明では、接着剤層は、ＶＯＣ低減等の効果がより高められるという点で、水性組成物により形成されることが望ましい。水性組成物としては、前記の絵柄層等の形成で使用される水性組成物として掲げたものと同様のものを使用することができる。なお、水性組成物は、絵柄層等で使用される水性組成物と同一組成であってもよいし、互いに異なっていてもよい。 In the present invention, the adhesive layer is desirably formed of an aqueous composition in that the effect of reducing VOC and the like is further enhanced. As an aqueous composition, the thing similar to what was hung up as an aqueous composition used by formation of the said pattern layer etc. can be used. The aqueous composition may be the same composition as the aqueous composition used in the pattern layer or the like, or may be different from each other.
透明性保護層（最表面層）
透明性保護層７は、化粧シート１の透明性樹脂層６上、即ち最表面に積層されるものである。
Transparency protective layer (outermost layer)
The transparent protective layer 7 is laminated on the transparent resin layer 6 of the decorative sheet 1, that is, on the outermost surface.
透明性保護層７の形成は、前記のとおり、本発明塗料を用いて行う。即ち、可塑剤及び炭素数５以下の有機溶剤（弱溶剤）を含む塗料により形成する。より具体的には、可塑剤、弱溶剤、樹脂等を含む塗料により透明性保護層を形成できる。 The transparent protective layer 7 is formed using the paint of the present invention as described above. That is, it is formed by a paint containing a plasticizer and an organic solvent (weak solvent) having 5 or less carbon atoms. More specifically, the transparent protective layer can be formed by a paint containing a plasticizer, a weak solvent, a resin, and the like.
樹脂としては特に限定されず、公知の樹脂成分を採用することができる。例えば、アクリル系樹脂、ウレタン系樹脂、アクリル−ウレタン系樹脂等の２液硬化型樹脂を挙げることができる。また、樹脂成分として電離放射性硬化型樹脂を使用してもよい。本発明では、樹脂成分として、公知の水系塗工剤等で使用されている樹脂成分（樹脂エマルション）も使用してもよい。 It does not specifically limit as resin, A well-known resin component is employable. Examples thereof include two-component curable resins such as acrylic resins, urethane resins, and acrylic-urethane resins. Moreover, you may use ionizing radiation curable resin as a resin component. In the present invention, a resin component (resin emulsion) used in a known aqueous coating agent or the like may be used as the resin component.
本発明塗料は、着色剤を配合せずに使用することが望ましい。また、必要に応じて、形成後の透明性保護層７の艶調整、表面の耐久性向上等の目的で、無機系充填剤等を配合することもできる。 The paint of the present invention is desirably used without blending a colorant. Moreover, an inorganic filler etc. can also be mix | blended for the objectives, such as gloss adjustment of the transparent protective layer 7 after formation, and surface durability improvement as needed.
透明性保護層７を形成するに際し、透明性樹脂層６上に本発明塗料を塗布し、乾燥させることにより透明性保護層を形成することができる。電離放射性硬化型樹脂を用いる場合には、電子線を照射して硬化させることにより行えばよい。 When the transparent protective layer 7 is formed, the transparent protective layer can be formed by applying the paint of the present invention on the transparent resin layer 6 and drying it. In the case of using an ionizing radiation curable resin, it may be performed by irradiating and curing an electron beam.
本発明の化粧シートでは、最表面層（透明性保護層）の厚みが０．１〜２５μｍ程度となるよう形成することが好ましい。この範囲に設定すれば、優れた保護効果に加えてＶＯＣ低減効果が得られる。 In the decorative sheet of the present invention, the outermost surface layer (transparent protective layer) is preferably formed so that the thickness is about 0.1 to 25 μm. If set in this range, a VOC reduction effect can be obtained in addition to an excellent protection effect.
透明性保護層７は、基材シート３上に透明性樹脂層６までを含む各層を積層した後に積層することが好ましい。透明性保護層７の積層の際には、プライマー層２を伴っていても伴っていなくてもよい。また、予め溶融押出しにより製造された透明シート６を用いる場合には、透明性保護層７を予め透明性樹脂層６上に積層してもよいし、透明性樹脂層１を下層と積層した後に透明性保護層７を積層してもよい。 The transparent protective layer 7 is preferably laminated after laminating each layer including the transparent resin layer 6 on the base sheet 3. When the transparent protective layer 7 is laminated, the primer layer 2 may or may not be accompanied. Moreover, when using the transparent sheet 6 manufactured by melt extrusion previously, you may laminate | stack the transparent protective layer 7 on the transparent resin layer 6 previously, or after laminating | stacking the transparent resin layer 1 with a lower layer. A transparent protective layer 7 may be laminated.
本発明の化粧シート１の製造手順（積層工程）は特に限定されない。例えば、基材シート３及び透明性樹脂層６のいずれもがポリオレフィン系樹脂シートである場合は、基材シート３への印刷による絵柄層４の形成、絵柄層４上への接着剤層５の塗布形成、接着剤層５上への溶融押出しによる透明性樹脂層６の積層及びコーティングによる透明性保護層７の積層を行えばよい。 The manufacturing procedure (lamination process) of the decorative sheet 1 of the present invention is not particularly limited. For example, when both the base sheet 3 and the transparent resin layer 6 are polyolefin-based resin sheets, the formation of the pattern layer 4 by printing on the base sheet 3 and the formation of the adhesive layer 5 on the pattern layer 4 are performed. The transparent resin layer 6 may be laminated by coating formation, melt extrusion onto the adhesive layer 5, and the transparent protective layer 7 may be laminated by coating.
本発明の化粧シートは、少なくとも最表面層が炭素数５以下の有機溶剤と可塑剤とを含む塗料により形成されているため、理由の詳細は不明であるが、化粧シート中の残存ＶＯＣ量を低減することができる。理由としては、例えば、塗料中に含まれる可塑剤の作用により、該塗料から形成された層の乾燥時における表面硬化膜の形成速度が遅延し、炭素数５以下の有機溶剤が揮発する時間を十分に確保できるためと考えられる。また、塗料中に含まれる可塑剤の作用により、該塗料から形成される層が柔軟な構造（該溶剤の揮発経路を層中に確保する構造）を形成することも理由の一つと考えられる。 In the decorative sheet of the present invention, at least the outermost surface layer is formed of a paint containing an organic solvent having a carbon number of 5 or less and a plasticizer. Therefore, the details of the reason are unknown, but the amount of VOC remaining in the decorative sheet is determined. Can be reduced. The reason is that, for example, due to the action of the plasticizer contained in the paint, the formation rate of the surface cured film is delayed when the layer formed from the paint is dried, and the time for the organic solvent having 5 or less carbon atoms to volatilize is reduced. This is considered to be sufficient. Further, it is considered that one of the reasons is that a layer formed from the paint forms a flexible structure (a structure that secures a volatilization route of the solvent in the layer) by the action of the plasticizer contained in the paint.
以下に実施例及び比較例を示し、本発明をより具体的に説明する。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１〜３及び比較例１〜３
下記表１に示す炭素数５以下の有機溶剤（弱溶剤）及び可塑剤、並びに２液硬化型アクリル−ウレタン系樹脂からなる塗料を用いて基材シート上に最表面層（厚み：２μｍ）を形成し、２層構造からなる化粧シートを作製した。ＤＯＳは、セバシン酸ジオクチルを示す。
Examples 1-3 and Comparative Examples 1-3
The outermost surface layer (thickness: 2 μm) is formed on the base material sheet using a paint composed of an organic solvent (weak solvent) having 5 or less carbon atoms and a plasticizer and a two-component curable acrylic-urethane resin shown in Table 1 below. A decorative sheet having a two-layer structure was formed. DOS indicates dioctyl sebacate.
基材シートとしては、溶剤系印刷ラミシート（イソプロパノール（ＩＰＡ）を０．５ｍｇ／ｍ2、酢酸エチルを２．６２５ｍｇ／ｍ2含む厚さ１５０μｍの基材シート）を用いた。 As the substrate sheet, using the solvent based printing Ramishito (isopropanol (IPA) and 0.5 mg / m 2, the base sheet having a thickness of 150μm containing ethyl acetate 2.625mg / m 2).
実施例４〜６及び比較例４〜６
下記表３に示す炭素数５以下の有機溶剤（弱溶剤）及び可塑剤、並びに２液硬化型アクリル−ウレタン系樹脂からなる塗料を用いて基材シート上に最表面層（厚み：２μｍ）を形成し、２層構造からなる化粧シートを作製した。基材シートとしては、溶剤を含有しない二軸延伸ポリプロピレンフィルム（厚み：５０μｍ）を用いた。
Examples 4-6 and Comparative Examples 4-6
The outermost surface layer (thickness: 2 μm) is formed on the base sheet using a paint composed of an organic solvent (weak solvent) having 5 or less carbon atoms and a plasticizer and a two-component curable acrylic-urethane resin shown in Table 3 below. A decorative sheet having a two-layer structure was formed. As the base sheet, a biaxially stretched polypropylene film (thickness: 50 μm) containing no solvent was used.
１ 化粧シート
２ 裏面プライマー層
３ 基材シート
４ 絵柄層
５ 透明性接着剤層
６ 透明性樹脂層
７ 透明性保護層（最表面層）
DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Back surface primer layer 3 Base material sheet 4 Picture layer 5 Transparent adhesive layer 6 Transparent resin layer 7 Transparent protective layer (outermost surface layer)
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| JP2004097685A JP4359771B2 (en) | 2004-03-30 | 2004-03-30 | Decorative sheet |
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