JPH11227116A - Decorative material - Google Patents
Decorative materialInfo
- Publication number
- JPH11227116A JPH11227116A JP5440998A JP5440998A JPH11227116A JP H11227116 A JPH11227116 A JP H11227116A JP 5440998 A JP5440998 A JP 5440998A JP 5440998 A JP5440998 A JP 5440998A JP H11227116 A JPH11227116 A JP H11227116A
- Authority
- JP
- Japan
- Prior art keywords
- protective layer
- surface protective
- ionizing radiation
- curable resin
- layer
- 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
- 239000000463 material Substances 0.000 title claims description 30
- 229920005989 resin Polymers 0.000 claims description 56
- 239000011347 resin Substances 0.000 claims description 56
- 239000010410 layer Substances 0.000 claims description 36
- 239000011241 protective layer Substances 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 23
- 239000011146 organic particle Substances 0.000 claims description 20
- 239000012798 spherical particle Substances 0.000 claims description 20
- 230000005865 ionizing radiation Effects 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 8
- 239000002537 cosmetic Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 description 31
- 239000011248 coating agent Substances 0.000 description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- -1 polyethylene Polymers 0.000 description 16
- 239000000178 monomer Substances 0.000 description 15
- 239000000123 paper Substances 0.000 description 15
- 239000011342 resin composition Substances 0.000 description 14
- 238000010894 electron beam technology Methods 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 11
- 238000005299 abrasion Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000007639 printing Methods 0.000 description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000001023 inorganic pigment Substances 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 239000010954 inorganic particle Substances 0.000 description 5
- 239000012860 organic pigment Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000001055 blue pigment Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920006295 polythiol Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- JZLWSRCQCPAUDP-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;urea Chemical compound NC(N)=O.NC1=NC(N)=NC(N)=N1 JZLWSRCQCPAUDP-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- GKZPEYIPJQHPNC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GKZPEYIPJQHPNC-UHFFFAOYSA-N 0.000 description 1
- KAJBSGLXSREIHP-UHFFFAOYSA-N 2,2-bis[(2-sulfanylacetyl)oxymethyl]butyl 2-sulfanylacetate Chemical compound SCC(=O)OCC(CC)(COC(=O)CS)COC(=O)CS KAJBSGLXSREIHP-UHFFFAOYSA-N 0.000 description 1
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-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
- PTJDGKYFJYEAOK-UHFFFAOYSA-N 2-butoxyethyl prop-2-enoate Chemical compound CCCCOCCOC(=O)C=C PTJDGKYFJYEAOK-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- NIAGUSHJWAMKBZ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical compound CC(=C)C(O)=O.NC1=NC(N)=NC(N)=N1 NIAGUSHJWAMKBZ-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 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
- 239000004641 Diallyl-phthalate Substances 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
- 229920000896 Ethulose Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001756 Polyvinyl chloride acetate Polymers 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 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
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000010425 asbestos 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
- 239000011324 bead Substances 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- WMAFNLQQGPUKCM-UHFFFAOYSA-N ethoxymethyl 2-methylprop-2-enoate Chemical compound CCOCOC(=O)C(C)=C WMAFNLQQGPUKCM-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- HRKWOOHVRHBXHJ-UHFFFAOYSA-N hexan-2-yl prop-2-enoate Chemical compound CCCCC(C)OC(=O)C=C HRKWOOHVRHBXHJ-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 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
- 239000002655 kraft paper Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000007644 letterpress printing Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000011088 parchment paper Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- QCTJRYGLPAFRMS-UHFFFAOYSA-N prop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical compound OC(=O)C=C.NC1=NC(N)=NC(N)=N1 QCTJRYGLPAFRMS-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は化粧材に関する。特
に、耐摩耗性を有する化粧材の意匠性向上に関する。[0001] The present invention relates to a decorative material. In particular, it relates to improving the design of a wear-resistant decorative material.
【0002】[0002]
【従来の技術】従来の表面保護層を有する化粧紙におい
て、表面保護層にヌープ硬度が1300kg/cm2 以
上の球状粒子のみを含有するものは知られている。 2. Description of the Related Art A conventional decorative paper having a surface protective layer is known in which the surface protective layer contains only spherical particles having a Knoop hardness of 1300 kg / cm 2 or more.
【0003】[0003]
【発明が解決しようとする課題】しかしながら、上記従
来の化粧紙は、表面保護層の表面がフラットで凹凸がな
いため意匠性に乏しいものであった。However, the above-mentioned conventional decorative paper is poor in design because the surface of the surface protective layer is flat and has no irregularities.
【0004】本発明は如上の問題に鑑み、上記従来の欠
点を解消するためになされたものであり、意匠性に優れ
た、耐摩耗性を有する化粧材を提供することを目的とす
る。[0004] In view of the above problems, the present invention has been made to solve the above-mentioned conventional disadvantages, and an object of the present invention is to provide a decorative material having excellent design and abrasion resistance.
【0005】[0005]
【課題を解決するための手段】本発明は、(1)基材の
少なくとも片面にベタ層、絵柄層、表面保護層が基材側
からこの順に設けられており、上記表面保護層は該層の
膜厚の1.2〜2.0倍となるような粒径の有機粒子を
含有する電離放射線硬化性樹脂からなることを特徴とす
る化粧材、(2)表面保護層を構成する電離放射線硬化
性樹脂が架橋間平均分子量が150〜1000である電
離放射線硬化性樹脂であり、表面保護層を構成する電離
放射線硬化性樹脂に更にヌープ硬度が1300kg/c
m2 以上の球状粒子を含有する上記(1)記載の化粧材
を要旨とする。According to the present invention, (1) a solid layer, a picture layer, and a surface protective layer are provided on at least one side of a substrate in this order from the substrate side. A decorative material comprising an ionizing radiation-curable resin containing organic particles having a particle size of 1.2 to 2.0 times the film thickness of (2) ionizing radiation constituting a surface protective layer The curable resin is an ionizing radiation curable resin having an average molecular weight between crosslinks of 150 to 1000, and the ionizing radiation curable resin constituting the surface protective layer further has a Knoop hardness of 1300 kg / c.
containing m 2 or more spherical particles summarized as decorative material as described in (1) above.
【0006】[0006]
【発明の実施の形態】以下、本発明を図面に基づき詳細
に説明する。図1は本発明の化粧材の一例を示す縦断面
図である。本発明において、化粧材は、基材1の表面に
ベタ層2、絵柄層3、表面保護層4が基材1側からこの
順に設けられて構成されている。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a longitudinal sectional view showing an example of the decorative material of the present invention. In the present invention, the decorative material is configured such that a solid layer 2, a pattern layer 3, and a surface protective layer 4 are provided on a surface of a substrate 1 in this order from the substrate 1 side.
【0007】基材1としては、薄葉紙、クラフト紙、チ
タン紙、リンター紙、板紙、石膏ボード紙、紙にポリ塩
化ビニルをゾル塗工又はドライラミネートしたいわゆる
ビニル壁紙原反、或いは上質紙、コート紙、アート紙、
硫酸紙、グラシン紙、パーチメント紙、パラフィン紙等
の紙、硝子繊維,石綿,チタン酸カリウム繊維,アルミ
ナ繊維,シリカ繊維,炭素繊維等の無機質繊維からなる
シート又はフィルム、ポリエステルやビニロン等の有機
樹脂等を用いた織布又は不織布、ポリエチレン,ポリプ
ロピレン等のポリオレフィン樹脂,ポリ塩化ビニル,ポ
リ塩化ビニリデン,ポリビニルアルコール,エチレン−
酢酸ビニル共重合体,エチレン−ビニルアルコール共重
合体等のビニル系樹脂,ポリエチレンテレフタレート,
ポリブチレンテレフタレート等のポリエステル樹脂,ポ
リメタクリル酸メチル,ポリアクリル酸メチル,ポリメ
タクリル酸エチル等のアクリル樹脂,ポリスチレン、ア
クリロニトリル・ブタジエン−スチレン共重合体(AB
S),三酢酸セルロース,セロハン,ポリカーボネート
等の樹脂からなるシート又はフィルム、アルミニウム,
鉄,ステンレス鋼,銅等の金属箔等を用いることができ
る。基材1の厚みは任意である。As the substrate 1, thin paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, a so-called vinyl wallpaper raw material obtained by sol-coating or dry-laminating polyvinyl chloride on paper, or high-quality paper, coated paper Paper, art paper,
Paper or paper such as sulfuric acid paper, glassine paper, parchment paper, paraffin paper, sheet or film made of inorganic fiber such as glass fiber, asbestos, potassium titanate fiber, alumina fiber, silica fiber, carbon fiber, and organic resin such as polyester or vinylon Woven or non-woven fabric, such as polyethylene, polypropylene or other polyolefin resin, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene
Vinyl resins such as vinyl acetate copolymer and ethylene-vinyl alcohol copolymer, polyethylene terephthalate,
Polyester resin such as polybutylene terephthalate, acrylic resin such as polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, polystyrene, acrylonitrile-butadiene-styrene copolymer (AB
S), a sheet or film made of a resin such as cellulose triacetate, cellophane, and polycarbonate;
Metal foil such as iron, stainless steel, and copper can be used. The thickness of the substrate 1 is arbitrary.
【0008】ベタ層2としては、ベヒクルに必要に応じ
て、顔料、染料等の着色剤、体質顔料、溶剤、安定剤、
可塑剤、触媒、硬化剤等を適宜混合してなるインキ組成
物等を用いることができる。[0008] The solid layer 2 includes a coloring agent such as a pigment and a dye, an extender pigment, a solvent, a stabilizer,
An ink composition obtained by appropriately mixing a plasticizer, a catalyst, a curing agent, and the like can be used.
【0009】上記ベヒクルとしては熱可塑性樹脂、熱硬
化性樹脂、電離放射線硬化性樹脂等の中から用途、必要
な物性、印刷適性等に応じて適宜選択する。熱可塑性樹
脂としては例えば、エチルセルロース,硝酸セルロー
ス,酢酸セルロース,エチルヒドロキシエチルセルロー
ス,セルロースアセテートプロピオネート等のセルロー
ス誘導体、ポリスチレン,ポリα−メチルスチレン等の
スチレン樹脂又はスチレン共重合体、ポリメタクリル酸
メチル,ポリメタクリル酸エチル,ポリアクリル酸エチ
ル,ポリアクリル酸ブチル等のアクリル樹脂、ポリ塩化
ビニル,ポリ酢酸ビニル,塩化ビニル−酢酸ビニル共重
合体,ポリビニルブチラール等のビニル共重合体、ロジ
ン,ロジン変性マレイン酸樹脂,ロジン変性フェノール
樹脂,重合ロジン等のロジンエステル樹脂、クマロン樹
脂、ビニルトルエン樹脂、ポリアミド樹脂等の天然又は
合成樹脂が挙げられる。The above-mentioned vehicle is appropriately selected from a thermoplastic resin, a thermosetting resin, an ionizing radiation-curable resin and the like according to the use, required physical properties, printability and the like. Examples of the thermoplastic resin include cellulose derivatives such as ethyl cellulose, cellulose nitrate, cellulose acetate, ethyl hydroxyethyl cellulose, cellulose acetate propionate, styrene resins such as polystyrene and poly α-methylstyrene, styrene copolymers, and polymethyl methacrylate. Acrylic resin such as styrene, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, polyvinyl copolymer such as polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, rosin, rosin modified Rosin ester resins such as maleic acid resin, rosin-modified phenol resin, and polymerized rosin, and natural or synthetic resins such as coumarone resin, vinyl toluene resin, and polyamide resin.
【0010】また、熱硬化性樹脂としては、フェノール
樹脂、尿素樹脂、ジアリルフタレート樹脂、メラミン樹
脂、グアナミン樹脂、不飽和ポリエステル系樹脂、ポリ
ウレタン系樹脂、エポキシ樹脂、アミノアルキッド樹
脂、メラミン−尿素共縮合樹脂、珪素樹脂、ポリヒロキ
サン樹脂等があり、これらに必要に応じて架橋剤、重合
開始剤等の硬化剤、重合促進剤、溶剤、粘度調整剤、体
質顔料等を添加する。硬化剤としては通常、イソシアネ
ートが不飽和ポリエステル系樹脂,ポリウレタン系樹脂
に、アミンがエポキシ樹脂に、メチルエチルケトンパー
オキサイド等の過酸化物,アゾビスイソブチロニトリル
等のラジカル開始剤が不飽和ポリエステル系樹脂に、そ
れぞれよく使用される。イソシアネートとしては、2価
以上の脂肪族又は芳香族イソシアネートを使用できる
が、熱変色防止、耐候性の点から脂肪族イソシアネート
が望ましい。具体例としてはトリレンジイソシアネー
ト、キシレンジイソシアネート、4,4−ジフェニルメ
タンジイソシアネート、ヘキサメチレンジイソシアネー
ト、リジンジイソシアネート等が挙げられる。また、硬
化反応を促進するために、必要に応じて塗工後加熱して
もよい。例えばイソシアネート硬化ウレタン硬化型不飽
和ポリエステル系樹脂又はポリウレタン系樹脂の場合は
通常40〜60℃で1〜5日程度、またポリシロキサン
樹脂の場合は通常80〜150℃で1〜300分程度で
ある。As the thermosetting resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, amino alkyd resin, melamine-urea cocondensation There are resins, silicon resins, polyhydroxy resins and the like, and a crosslinking agent, a curing agent such as a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, an extender, and the like are added as necessary. As the curing agent, isocyanate is usually used for unsaturated polyester resin and polyurethane resin, amine is used for epoxy resin, peroxide such as methyl ethyl ketone peroxide, and radical initiator such as azobisisobutyronitrile are used for unsaturated polyester resin. Often used for resins. As the isocyanate, a divalent or higher aliphatic or aromatic isocyanate can be used, but an aliphatic isocyanate is preferable from the viewpoint of preventing thermal discoloration and weather resistance. Specific examples include tolylene diisocyanate, xylene diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, and the like. Further, in order to accelerate the curing reaction, if necessary, heating may be performed after coating. For example, in the case of an isocyanate-cured urethane-curable unsaturated polyester-based resin or a polyurethane-based resin, it is usually about 1 to 5 days at 40 to 60 ° C, and in the case of a polysiloxane resin, it is usually about 1 to 300 minutes at 80 to 150 ° C. .
【0011】また、電離放射線樹脂としては、後述する
表面保護層4に用いられるものと同様のものを用いるこ
とができる。As the ionizing radiation resin, the same resin as that used for the surface protective layer 4 described later can be used.
【0012】インキ組成物に含有させることができる上
記顔料としては、通常使用される有機又は無機系の顔料
が挙げられる。黄色顔料としては、モノアゾ、ジスア
ゾ、ポリアゾ等のアゾ系顔料、イソインドリノン等の有
機顔料、黄鉛、黄色酸化鉄、カドミウムイエロー、チタ
ンイエロー、アンチモン黄等の無機顔料が使用できる。
赤色顔料としては、モノアゾ、ジスアゾ、ポリアゾ等の
アゾ系顔料、キナクリドン等の有機顔料、弁柄、朱、カ
ドミウムレッド、クロムバーミリオン等の無機顔料が使
用できる。青色顔料としては、フタロシアニンブルー、
インダスレンブルー等の有機顔料、紺青、群青、コバル
トブルー等の無機顔料が使用できる。黒色顔料として
は、アニリンブラック等の有機顔料、カーボンブラック
等の無機顔料が使用できる。白色顔料としては、二酸化
チタン、亜鉛華、三酸化アンチモン等の無機顔料が挙げ
られる。The above-mentioned pigment which can be contained in the ink composition includes commonly used organic or inorganic pigments. As the yellow pigment, azo pigments such as monoazo, disazo and polyazo, organic pigments such as isoindolinone, and inorganic pigments such as graphite, yellow iron oxide, cadmium yellow, titanium yellow and antimony yellow can be used.
As the red pigment, azo pigments such as monoazo, disazo and polyazo, organic pigments such as quinacridone, and inorganic pigments such as red iron oxide, vermilion, cadmium red, and chromium vermilion can be used. As the blue pigment, phthalocyanine blue,
Organic pigments such as induslen blue and inorganic pigments such as navy blue, ultramarine blue and cobalt blue can be used. Organic pigments such as aniline black and inorganic pigments such as carbon black can be used as the black pigment. Examples of the white pigment include inorganic pigments such as titanium dioxide, zinc white, and antimony trioxide.
【0013】ベタ層2を形成するには、スクリーンベタ
印刷を用いたり、公知の各種塗工方法、例えばロールコ
ート、カーテンフローコート、ワイヤーバーコート、リ
バースコート、グラビアコート、グラビアリバースコー
ト、エアーナイフコート、キスコート、ブレードコー
ト、スムーズコート、コンマコート、スプレーコート、
かけ流しコート、刷毛塗り等の方法を用い、乾燥時で通
常、1.0〜10.0μm程度の膜厚に形成する。The solid layer 2 is formed by screen solid printing or by various known coating methods such as roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, and air knife. Coat, kiss coat, blade coat, smooth coat, comma coat, spray coat,
The film is usually formed to a thickness of about 1.0 to 10.0 μm by drying using a method such as pouring coating or brush coating.
【0014】絵柄層3は、インキにより線や面やそれら
の組み合わせからなる、絵柄や図形、文字等やそれらの
組み合わせ等からなる模様を形成した層であり、層厚方
向任意断面において該層は平面方向に必ずしも連続して
いない層である。絵柄層3としては前記ベタ層2に用い
たのと同様のインキ組成を用いることができる。絵柄層
3は、該層3を構成するインキを塗工或いは印刷等によ
って設けた後、乾燥硬化させて形成する。絵柄層3を設
ける方法としては、クラビア,活版,フレキソ等の凸版
印刷、平版オフセット,ダイリソ印刷等の平版印刷、シ
ルクスクリーン等の孔版印刷、静電印刷、インキジェッ
トプリント等の公知の各種方法を用いることができる。The pattern layer 3 is a layer in which a pattern composed of a pattern, a figure, a character, etc., or a combination thereof, etc., formed of lines, surfaces, or a combination thereof with ink is formed. The layer is not necessarily continuous in the plane direction. The same ink composition as that used for the solid layer 2 can be used for the picture layer 3. The picture layer 3 is formed by applying or printing the ink constituting the layer 3 and then drying and curing the ink. As a method of providing the picture layer 3, various known methods such as letterpress printing such as gravure, letterpress, and flexo, lithographic printing such as lithographic offset and dilithographic printing, stencil printing such as silk screen, electrostatic printing, and ink jet printing can be used. Can be used.
【0015】表面保護層4は、後述する電離放射線硬化
性樹脂組成物を硬化せしめてなるものである。表面保護
層4の膜厚は通常、15〜35g/m2 程度とする。該
表面保護層4は、該層4の膜厚Tの1.2〜2.0倍と
なるような粒径の有機粒子5を含有した電離放線硬化性
樹脂6から構成されている。即ち、電離放射線硬化性樹
脂6に有機粒子5を含有せしめてなる電離放射性硬化性
組成物を、絵柄層3まで設けたものの絵柄層3側に塗工
して硬化せしめて表面保護層4とした時、該表面保護層
4の膜厚の1.2〜2.0倍となって表面保護層4の表
面上に一部が突出し得るような有機粒子5を含有した電
離放射線硬化性樹脂6によって、表面保護層4が構成さ
れている。The surface protective layer 4 is formed by curing an ionizing radiation curable resin composition described later. The film thickness of the surface protective layer 4 is usually about 15 to 35 g / m 2 . The surface protective layer 4 is made of an ionizing radiation-curable resin 6 containing organic particles 5 having a particle size of 1.2 to 2.0 times the thickness T of the layer 4. That is, the ionizing radiation-curable composition obtained by adding the organic particles 5 to the ionizing radiation-curable resin 6 was applied to the pattern layer 3 side of the one provided with the pattern layer 3 and cured to form the surface protective layer 4. At this time, the ionizing radiation-curable resin 6 containing the organic particles 5 having a thickness of 1.2 to 2.0 times the thickness of the surface protective layer 4 and protruding partially on the surface of the surface protective layer 4 is used. , A surface protection layer 4.
【0016】表面保護層4の膜厚Tは任意であるが、通
常15〜35μmであり、25μm程度が一般的であ
る。The thickness T of the surface protective layer 4 is arbitrary, but is usually 15 to 35 μm, and is generally about 25 μm.
【0017】有機粒子5としては、合成高分子化合物か
らなるプラスチックビーズが挙げられる。その種類とし
ては、アクリル、ポリカーボネート、ウレタン、メラミ
ン、スチレン、ふっ素樹脂等の樹脂が挙げられる。これ
らのうち、コーティング適性、インキの安定性が良好で
あることから、アクリル及びウレタン樹脂製の有機粒子
が好ましい。有機粒子の粒径は、5〜100μmが好ま
しく、10〜50μmがさらに好ましい。有機粒子の粒
径が、5μm未満であると、十分な効果が得られず、1
00μmを超えるとコーティング適性が低下する虞れが
ある。Examples of the organic particles 5 include plastic beads made of a synthetic polymer compound. Examples of the type include resins such as acrylic, polycarbonate, urethane, melamine, styrene, and fluororesin. Among these, organic particles made of acrylic and urethane resins are preferred because of their good coating suitability and good ink stability. The particle size of the organic particles is preferably from 5 to 100 μm, more preferably from 10 to 50 μm. If the particle size of the organic particles is less than 5 μm, a sufficient effect cannot be obtained and 1
If it exceeds 00 μm, the coating aptitude may be reduced.
【0018】また、有機粒子5には表面保護層4の膜厚
が1.2〜2.0倍となるような粒径のものを用いる
が、表面保護層4の膜厚が1.2未満であると表面凹凸
が乏しくなるという欠点がある。また2.0倍を超える
と表面スクラッチ性が弱くなるという欠点がある。有機
粒子を含有せしめることによって、無機粒子を含有せし
めた場合と比較して滑らかな表面性が得られるという効
果がある。有機粒子5は透明性を有するのが好ましく、
その透明性が高いほど好ましい。The organic particles 5 have a particle size such that the thickness of the surface protective layer 4 is 1.2 to 2.0 times, but the thickness of the surface protective layer 4 is less than 1.2. In this case, there is a disadvantage that surface irregularities are poor. On the other hand, if it exceeds 2.0 times, there is a disadvantage that the surface scratching property is weakened. By incorporating organic particles, there is an effect that smooth surface properties can be obtained as compared with the case of incorporating inorganic particles. The organic particles 5 preferably have transparency,
The higher the transparency, the better.
【0019】有機粒子5の含有量としては5〜20重量
%が好ましい。この範囲であると凹凸感を有する化粧シ
ートができる。尚、上記範囲を外れると表面凹凸が乏し
くなるという虞れがある。The content of the organic particles 5 is preferably 5 to 20% by weight. When it is in this range, a decorative sheet having a feeling of unevenness can be obtained. In addition, if it is out of the above range, there is a possibility that surface irregularities become poor.
【0020】本発明においては、上記表面保護層4を構
成する電離放射線硬化性樹脂6が架橋間平均分子量が1
50〜1000である電離放射線硬化性樹脂であり、且
つ表面保護層4を構成する電離放射線硬化性樹脂6が、
更にヌープ硬度が1300kg/cm2 以上の球状粒子
7を含有したものであるのが好ましい。このように構成
されていると更に耐摩耗性が良好である。In the present invention, the ionizing radiation-curable resin 6 constituting the surface protective layer 4 has an average molecular weight between crosslinks of 1
50-1000 ionizing radiation-curable resin, and the ionizing radiation-curable resin 6 constituting the surface protection layer 4 is:
Further, it preferably contains spherical particles 7 having a Knoop hardness of 1300 kg / cm 2 or more. With this configuration, the wear resistance is further improved.
【0021】ここで言うヌープ硬度とは、ヌープ圧子を
用いて測定される微小押し込み硬さで、試験前に菱形の
圧痕をつけた時の荷重を、永久凹みの長い方の対角線の
長さより求めた凹みの投影面積で除した商で表される値
である。この試験方法は、ASTM C−849に記載
されている。The Knoop hardness referred to here is a minute indentation hardness measured using a Knoop indenter, and the load when a diamond-shaped indentation is formed before the test is obtained from the length of the longer diagonal line of the permanent dent. It is a value represented by the quotient divided by the projected area of the dent. This test method is described in ASTM C-849.
【0022】球状粒子7の材質は、具体的に、α−アル
ミナ、シリカ、酸化クロム、酸化鉄、ダイヤモンド、黒
鉛等の無機粒子が挙げられる。又、上記α−アルミナと
しては、溶融アルミナ、バイヤー法アルミナ等があり、
又上記以外の無機粒子としては、ジルコニア、チタニ
ア、或いはこれらや溶融アルミナ、バイヤー法アルミナ
等との共融混合物が挙げられる。これらの無機粒子の形
状を球形にする方法としたは、粉砕した不定形の上記無
機化合物を融点以上の高温炉中に投入し溶融させ、表面
張力を利用して球状にする方法や、上記無機物を融点以
上の高温で溶融したものを霧状に吹き出して球状にする
方法等が挙げられる。Specific examples of the material of the spherical particles 7 include inorganic particles such as α-alumina, silica, chromium oxide, iron oxide, diamond, and graphite. Further, as the α-alumina, there are fused alumina, Bayer alumina and the like,
Examples of the inorganic particles other than those described above include zirconia, titania, and a eutectic mixture of these materials, fused alumina, and Bayer alumina. The method of forming the shape of these inorganic particles into a sphere is as follows: a method in which a pulverized amorphous inorganic compound is put into a high-temperature furnace having a melting point or higher and melted to be spherical by using surface tension; Melted at a high temperature equal to or higher than the melting point, and blown out into a mist to form a sphere.
【0023】特に好ましい球状粒子7は、非常に硬度が
高く耐摩耗性に対する効果が大きいことと球形状のもの
が比較的容易に得やすい等の理由から、球形のα−アル
ミナを挙げることができる。球形のα−アルミナは、特
開平2−55269号公報に記載されているように、ア
ルミナ水和物等の鉱化剤或いは結晶剤を、電融アルミ
ナ、焼結アルミナ等の粉砕品に少量添加し、1400°
C以上の温度で2時間以上熱処理することで、アルミナ
中のカッティングエッジが減少し同時に形状が球形化し
たものが得られる。このような球形状のアルミナは、昭
和電工(株)より「球状アルミナAS−10、AS−2
0、AS−30、AS−40、AS−50」として各種
市販されている。Particularly preferred spherical particles 7 include spherical α-alumina because they have a very high hardness and a large effect on abrasion resistance, and spherical particles are relatively easily obtained. . As described in JP-A-2-55269, a small amount of a spherical α-alumina is added to a pulverized product such as fused alumina or sintered alumina by adding a mineralizer or crystallization agent such as alumina hydrate. And 1400 °
By performing the heat treatment at a temperature equal to or higher than C for 2 hours or longer, a cutting edge in alumina is reduced and a shape having a spherical shape is obtained at the same time. Such spherical alumina is available from Showa Denko KK as "Spherical alumina AS-10, AS-2".
0, AS-30, AS-40, and AS-50 ".
【0024】また球状粒子7は、その粒子表面を処理す
ることができる。例えばステアリン酸等の脂肪酸で処理
すると分散性が向上する。又、表面をシランカップリン
グ剤で処理することで、バインダーとして使用する架橋
性樹脂との間の密着性や塗工組成物中での粒子の分散性
が向上する。シランカップリング剤としては、分子中に
ラジカル重合性不飽和結合を有するアルコキシラン等が
挙げられる。The spherical particles 7 can be treated on the surface of the particles. For example, treatment with a fatty acid such as stearic acid improves dispersibility. In addition, by treating the surface with a silane coupling agent, the adhesion to the crosslinkable resin used as a binder and the dispersibility of the particles in the coating composition are improved. Examples of the silane coupling agent include an alkoxylan having a radical polymerizable unsaturated bond in a molecule.
【0025】電離放射線硬化性樹脂6が、架橋間平均分
子量が上記範囲内であると耐スクラッチ性、耐汚染性、
耐溶剤性、耐水性に優れるという効果が得られる。ま
た、ヌープ硬度が1300kg/cm2 以上の球状粒子
7を含有させると、耐摩耗性を付与することができると
いう効果がある。球状粒子7は有機粒子でもよいが、イ
ンキ沈降安定性が良好であるという理由のため無機粒子
の方が好ましい。球状粒子7は透明性を有するのが好ま
しく、透明性が高いほど好ましい。When the ionizing radiation-curable resin 6 has an average molecular weight between crosslinks within the above range, scratch resistance, stain resistance,
The effect of being excellent in solvent resistance and water resistance is obtained. When spherical particles 7 having a Knoop hardness of 1300 kg / cm 2 or more are contained, there is an effect that abrasion resistance can be imparted. The spherical particles 7 may be organic particles, but inorganic particles are preferred because ink sedimentation stability is good. The spherical particles 7 preferably have transparency, and the higher the transparency, the more preferable.
【0026】球状粒子7は、真球状、或いは球を偏平に
した楕円球状並びに真球状や楕円球状に近い形状等のよ
うに、表面が滑らかな曲面で囲まれていれば良い。特に
粒子表面に突起や角のない、いわゆるカッティングエッ
ジのない球状が好ましい。球状粒子7は、同じ材質の不
定形の粒子と比較して、表面樹脂層それ自身の耐摩耗性
を大きく向上させると共に、塗工装置を摩耗させず、塗
膜の硬化後もこれと接する他の物を摩耗させず、更に塗
膜の透明度も高くなるという特徴があり、カッティング
エッジのない場合、特にその効果が大きい。The spherical particles 7 may have a smooth curved surface such as a true sphere, an ellipsoidal sphere obtained by flattening a sphere, and a shape close to a true sphere or an ellipsoidal sphere. In particular, a spherical shape having no projections or corners on the particle surface and having no so-called cutting edge is preferable. The spherical particles 7 greatly improve the abrasion resistance of the surface resin layer itself as compared with amorphous particles of the same material, do not wear the coating device, and come into contact with the coating film after the coating film is cured. It is characterized in that it does not wear the object and the transparency of the coating film is also increased. In the case where there is no cutting edge, the effect is particularly large.
【0027】上記において球状粒子7の粒径は均一な凹
凸感を表現させるという理由のため、有機粒子5の粒径
の1/2〜2/3倍であるのが好ましく、表面保護層4
の膜厚の0.5〜1.0倍であるのが好ましい。球状粒
子7の含有量としては15〜25重量%が好ましい。In the above description, the particle size of the spherical particles 7 is preferably 1/2 to 2/3 times the particle size of the organic particles 5 for the reason that a uniform unevenness can be expressed.
Is preferably 0.5 to 1.0 times the thickness of the film. The content of the spherical particles 7 is preferably 15 to 25% by weight.
【0028】表面保護層4に用いられる電離放射線硬化
性樹脂としては、電磁波又は荷電粒子線のうち分子を重
合、架橋し得るエネルギー量子を有する、紫外線、電子
線等の電離放射線により硬化し得る透明樹脂であって、
分子中に重合性不飽和結合又はエポキシ基を有するプレ
ポリマー、オリゴマー、及び/又は単量体を適宜混合し
た組成物が用いられる。これらの組成物としては、ウレ
タンアクリレート、ポリエステルアクリレート、エポキ
シアクリレート等のアクリレート、シロキサン等の珪素
樹脂、ポリエステル、エポキシ等が挙げられる。The ionizing radiation-curable resin used for the surface protective layer 4 is a transparent resin which has an energy quantum capable of polymerizing and crosslinking molecules among electromagnetic waves or charged particle beams and which can be cured by ionizing radiation such as ultraviolet rays and electron beams. Resin,
A composition in which a prepolymer, an oligomer, and / or a monomer having a polymerizable unsaturated bond or an epoxy group in a molecule is appropriately mixed is used. Examples of these compositions include acrylates such as urethane acrylate, polyester acrylate, and epoxy acrylate, silicon resins such as siloxane, polyester, and epoxy.
【0029】前記プレポリマー、オリゴマーの例として
は不飽和ジカルボン酸と多価アルコールの縮合物等の不
飽和ポリエステル類、ポリエステルメタクリレート、ポ
リエーテルメタクリレート、ポリオールメタクリレー
ト、メラミンメタクリレート等のメタクリレート類、ポ
リエステルアクリレート、エポキシアクリレート、ウレ
タンアクリレート、ポリエーテルアクリレート、ポリオ
ールアクリレート、メラミンアクリレート等のアクリレ
ート類等が挙げられる。Examples of the prepolymers and oligomers include unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols, methacrylates such as polyester methacrylate, polyether methacrylate, polyol methacrylate and melamine methacrylate, polyester acrylates, and the like. Examples include acrylates such as epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate.
【0030】また、前記単量体の例としては、スチレ
ン、α−メチルスチレン等のスチレン系単量体、アクリ
ル酸メチル、アクリル酸−2−エチルヘキシル、アクリ
ル酸メトキシエチル、アクリル酸ブトキシエチル、アク
リル酸ブチル、アクリル酸メトキシブチル、アクリル酸
フェニル等のアクリル酸エステル類、メタクリル酸メチ
ル、メタクリル酸エチル、メタクリル酸プロピル、メタ
クリル酸メトキシエチル、メタクリル酸エトキシメチ
ル、メタクリル酸フェニル、メタクリル酸ラウリル等の
メタクリル酸エステル類、アクリル酸−2−(N、N−
ジエチルアミノ)エチル、メタクリル酸−2−(N、N
−ジメチルアミノ)エチル、アクリル酸−2−(N、N
−ジベンジルアミノ)エチル、メタクリル酸−2−
(N、N−ジメチルアミノ)メチル、アクリル酸−2−
(N、N−ジエチルアミノ)プロピル等の不飽和酸の置
換アミノアルコースエステル類、アクリルアミド、メタ
クリルアミド等の不飽和カルボン酸アミド、エチレング
リコールジアクリレート、プロピレングリコールジアク
リレート、ネオペンチルグリコールジアクリレート、
1,6−ヘキサンジオールジアクリレート、ジエチレン
グリコールジアクリレート、トリエチレングリコールジ
アクリレート等の化合物、ジプロピレングリコールジア
クリレート、エチレングリコールアクリレート、プロピ
レングリコールジメタクリレート、ジエチレングリコー
ルジメタクリレート等の多官能性化合物、及び/又は、
分子中に2個以上のチオール基を有するポリチオール化
合物、例えば、トリメチロールプロパントリチオグリコ
レート、トリメチロールプロパントリチオプロピレー
ト、ペンタエリスリトールテトラチオグリコール等が挙
げられる。Examples of the above monomers include styrene monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, acrylic Acrylates such as butyl acrylate, methoxy butyl acrylate and phenyl acrylate, methacryl such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate and lauryl methacrylate Acid esters, acrylic acid-2- (N, N-
Diethylamino) ethyl, methacrylic acid-2- (N, N
-Dimethylamino) ethyl, acrylic acid-2- (N, N
-Dibenzylamino) ethyl, methacrylic acid-2-
(N, N-dimethylamino) methyl, acrylic acid-2-
Substituted aminoalkose esters of unsaturated acids such as (N, N-diethylamino) propyl, unsaturated carboxylic acid amides such as acrylamide and methacrylamide, ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate;
Compounds such as 1,6-hexanediol diacrylate, diethylene glycol diacrylate, and triethylene glycol diacrylate; polyfunctional compounds such as dipropylene glycol diacrylate, ethylene glycol acrylate, propylene glycol dimethacrylate, and diethylene glycol dimethacrylate; and / or ,
Polythiol compounds having two or more thiol groups in the molecule, such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, and pentaerythritol tetrathioglycol.
【0031】以上の化合物を必要に応じ1種もしくは2
種以上混合して用いるが、樹脂組成物に通常の塗工適性
を付与するために、前記プレポリマー又はオリゴマーを
5重量%以上、前記単量体及び/又はポリチオールを9
5重量%以下とすることが好ましい。If necessary, one or two of the above compounds may be used.
The prepolymer or oligomer is used in an amount of 5% by weight or more and the monomer and / or polythiol is used in an amount of 9% or more in order to impart ordinary coating suitability to the resin composition.
It is preferable that the content be 5% by weight or less.
【0032】単量体の選定に際しては、硬化物の可撓性
が要求される場合には塗工適性上支障のない範囲で単量
体の量を少なめにしたり、1官能又は2官能アクリレー
ト系単量体を用い比較的低架橋密度の構造とする。ま
た、硬化物の耐熱性、硬度、耐溶剤性等を要求される場
合には塗工適性上支障のない範囲で単量体の量を多めに
したり、3官能以上のアクリレート系単量体を用い高架
橋密度の構造とするのが好ましい。1、2官能単量体と
3官能以上の単量体を混合し塗工適性と硬化物の物性と
を調整することもできる。以上のような1官能アクリレ
ート系単量体としては、2−ヒドロキシアクリレート、
2−ヘキシルアクリレート、フェノキシエチルアクリレ
ート等が挙げられる。また、2官能アクリレート系単量
体としては、エチレングリコールジアクリレート、1,
6−ヘキサンジオールアクリレート等が、3官能以上の
アクリレート系単量体としてはトリメチロールプロパン
トリアクリレート、ペンタエリスリトールヘキサアクリ
レート、ジペンタエリスリトールヘキサアクリレート等
が挙げられる。In selecting a monomer, when the flexibility of the cured product is required, the amount of the monomer may be reduced within a range that does not impair coating suitability, or a monofunctional or bifunctional acrylate-based compound may be used. A structure having a relatively low crosslink density is formed by using a monomer. When the heat resistance, hardness, solvent resistance, etc. of the cured product are required, increase the amount of the monomer within a range that does not hinder coating suitability, or use a trifunctional or higher functional acrylate monomer. It is preferable to use a structure having a high crosslinking density. It is also possible to adjust the coating suitability and the physical properties of the cured product by mixing mono- and difunctional monomers and tri- or higher functional monomers. As the monofunctional acrylate monomer as described above, 2-hydroxyacrylate,
Examples include 2-hexyl acrylate and phenoxyethyl acrylate. As the bifunctional acrylate monomer, ethylene glycol diacrylate, 1,1,
Examples of acrylate monomers having 6-hexanediol acrylate and the like having three or more functional groups include trimethylolpropane triacrylate, pentaerythritol hexaacrylate, and dipentaerythritol hexaacrylate.
【0033】また、硬化物の可撓性、表面硬度等の物性
を調節するために前記プレポリマー、オリゴマー、単量
体の少なくとも1種に対して、以下のような電離放射線
非硬化性樹脂を1〜70重量%、好ましくは5〜50重
量%、混合して用いることができる。電離放射線非硬化
性樹脂としては、ウレタン系、繊維素系、ポリエステル
系、アクリル系、ブチラール、ポリ塩化ビニル、ポリ酢
酸ビニル等の熱可塑性樹脂を用いることができ、特に可
撓性の点から繊維素系、ウレタン系、ブチラールが好ま
しい。In order to adjust physical properties such as flexibility and surface hardness of the cured product, at least one of the above prepolymers, oligomers and monomers is used with the following ionizing radiation non-curable resin. 1 to 70% by weight, preferably 5 to 50% by weight can be used as a mixture. Examples of the non-ionizing radiation non-curable resin include thermoplastic resins such as urethane, cellulose, polyester, acrylic, butyral, polyvinyl chloride, and polyvinyl acetate. Elementary, urethane and butyral are preferred.
【0034】上述した如き電離放射線硬化性樹脂組成物
を、特に紫外線で硬化させる場合には、該電離放射線硬
化性樹脂組成物に光重合開始剤として、アセトフェノン
類、ベンゾフェノン類、ミヒラーベンゾイルベンゾエー
ト、α−アミロキシムエステル、テトラメチルチウラム
モノサルファイド、チオキサントン類、及び/又は光増
感剤としてn−ブチルアミン、トリエチルアミン、トリ
−n−ブチルホスフィン等を混合して用いることもでき
る。When the ionizing radiation-curable resin composition as described above is cured particularly with ultraviolet rays, acetophenones, benzophenones, Michler's benzoyl benzoate, as photopolymerization initiators are added to the ionizing radiation-curable resin composition. α-Amiloxime esters, tetramethylthiuram monosulfide, thioxanthones, and / or n-butylamine, triethylamine, tri-n-butylphosphine, and the like as a photosensitizer may be mixed and used.
【0035】本発明においては、表面保護層4に有機粒
子5や球状粒子7を含有させているので、該粒子5、7
を上記した電離放射線硬化性樹脂組成物に混合して分散
させる。In the present invention, since the surface protective layer 4 contains the organic particles 5 and the spherical particles 7, the particles 5, 7
Is mixed and dispersed in the ionizing radiation-curable resin composition described above.
【0036】表面保護層4は、以上の如き電離放射線硬
化性樹脂組成物を塗工等によって設けた後、電離放射線
を照射して硬化させて形成する。電離放射線硬化性組成
物は、前記したベタ層2の形成用インキ組成物を塗工す
る場合の方法と同じ方法を用いることができ、乾燥時で
通常、0.1〜100μm程度の膜厚に塗工する。The surface protective layer 4 is formed by applying the ionizing radiation-curable resin composition as described above by coating or the like, and then irradiating with ionizing radiation to cure the composition. For the ionizing radiation-curable composition, the same method as the method for applying the above-described ink composition for forming the solid layer 2 can be used, and when dried, the film thickness is usually about 0.1 to 100 μm. Apply.
【0037】前記電離放射線のうちの紫外線の発生源と
しては超高圧水銀燈、高圧水銀燈、低圧水銀燈、カーボ
ンアーク、ブラックライトランプ、メタルハライドラン
プ等を用いることができる。また、電子線源としてはコ
ックロフトワルトン型、バンデグラフ型、共振変圧器
型、絶縁コア変圧器型、或いは直線型、ダイナミトロン
型、高周波等の各種電子線加速器を用い、100〜10
00keV、好ましくは100〜300keVのエネル
ギーを持つ電子を照射する。電子線の照射線量としては
通常、0.5〜30Mrad程度である。Ultraviolet lamps, high-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, black light lamps, metal halide lamps, and the like can be used as the source of the ultraviolet rays of the ionizing radiation. As the electron beam source, various electron beam accelerators such as Cockloft-Walton type, Bande graph type, Resonant transformer type, Insulated core transformer type, or linear type, Dynamitron type and high frequency are used.
Irradiation with electrons having an energy of 00 keV, preferably 100 to 300 keV is performed. The irradiation dose of the electron beam is usually about 0.5 to 30 Mrad.
【0038】本発明の化粧材は、寝具、壁面などの表面
保護性能が必要で高意匠を必要とする部材等に好適に使
用できる。The decorative material of the present invention can be suitably used for members requiring surface protection performance such as bedding and wall surfaces and requiring a high design.
【0039】[0039]
【実施例】次に、具体的実施例を挙げて本発明を更に詳
細に説明する。 実施例1 基材に含浸紙〔(株)興人製GF−601、坪量60g
/m2 )を用い、その上にグラビア印刷によりベタ印刷
と木目柄をザ・インクテック(株)製商品名「HAT」
を用いて印刷して絵柄層を形成し、次いで該絵柄層の上
に下記組成の塗工用樹脂組成物をロールコートにてコー
ティングし、電子線照射装置を用いて加速電圧175K
eV、照射線量5Mradになるように電子線を照射
し、樹脂を完全に硬化させ膜厚15μm(粒子を含まな
い部分の膜厚を指す。以下同様とする。)の表面保護層
を形成した。得られた化粧材は、表面が意匠的に優位性
の高い化粧材であった。 塗工用樹脂組成物の組成 電子線硬化性樹脂(エポキシアクリレートを主成分とする)100重量部 球状ウレタン粒子(平均粒径25μm) 10重量部 シリコーンアクリレート 2重量部Next, the present invention will be described in more detail with reference to specific examples. Example 1 A base material impregnated paper [GF-601 manufactured by Kojin Co., Ltd., basis weight 60 g
/ M 2 ), and solid printing and wood grain pattern by gravure printing on top of it. The product name “HAT” manufactured by The Inktech Co., Ltd.
To form a pattern layer, then coat the pattern layer with a coating resin composition having the following composition by roll coating, and use an electron beam irradiation device to accelerate the voltage to 175K.
The resin was completely cured by irradiating an electron beam at an eV and an irradiation dose of 5 Mrad to form a surface protective layer having a thickness of 15 μm (refer to the thickness of a portion not containing particles; the same applies hereinafter). The obtained decorative material was a decorative material whose surface was highly superior in design. Composition of coating resin composition 100 parts by weight of electron beam curable resin (mainly composed of epoxy acrylate) 10 parts by weight of spherical urethane particles (average particle size 25 μm) 2 parts by weight of silicone acrylate
【0040】比較例1 実施例1と同じ基材とインクを用い、実施例1と同様に
絵柄層を形成し、次いで該絵柄層の上に下記組成の塗工
用樹脂組成物をロールコートにてコーティングし、実施
例1と同様の条件にて電子線を照射し、樹脂を完全に硬
化させ膜厚15μmの表面保護層を形成した。 塗工用樹脂組成物の組成 電子線硬化性樹脂(エポキシアクリレートを主成分とする)100重量部 球状ウレタン粒子(平均粒径5μm) 10重量部 シリコーンアクリレート 2重量部Comparative Example 1 Using the same base material and ink as in Example 1, a pattern layer was formed in the same manner as in Example 1, and a coating resin composition having the following composition was roll-coated on the pattern layer. Then, an electron beam was irradiated under the same conditions as in Example 1, and the resin was completely cured to form a 15 μm-thick surface protective layer. Composition of resin composition for coating 100 parts by weight of electron beam curable resin (mainly composed of epoxy acrylate) 10 parts by weight of spherical urethane particles (average particle size 5 μm) 2 parts by weight of silicone acrylate
【0041】実施例2 実施例1と同じ基材とインクを用い、実施例1と同様に
絵柄層を形成し、次いで該絵柄層の上に下記のように有
機粒子及び球状粒子を含む塗工用樹脂組成物をロールコ
ートにてコーティングし、実施例1と同様の条件にて電
子線を照射し、樹脂を完全に硬化させ膜厚25μmの表
面保護層を形成した。得られた化粧材は、耐摩耗性に優
れ、また表面が意匠的に優位性の高い化粧材であった。 塗工用樹脂組成物の組成 電子線硬化性樹脂(ポリエーテル系ウレタンアクリレートを主成分とし、架 橋間分子量が500) 100重量部 球状ウレタン粒子(平均粒径50μm) 10重量部 球状アルミナ(平均粒径25μm・ヌープ硬度1350kg/cm2 ) 20重量部 シリコーンアクリレート 2重量部Example 2 Using the same base material and ink as in Example 1, a pattern layer was formed in the same manner as in Example 1, and then a coating containing organic particles and spherical particles was formed on the pattern layer as described below. The resin composition for coating was coated with a roll coat, and irradiated with an electron beam under the same conditions as in Example 1 to completely cure the resin to form a surface protective layer having a thickness of 25 μm. The obtained decorative material was excellent in abrasion resistance, and the surface was a decorative material having high design advantage. Composition of coating resin composition Electron beam curable resin (mainly composed of polyether-based urethane acrylate, molecular weight between bridges is 500) 100 parts by weight Spherical urethane particles (average particle size 50 μm) 10 parts by weight Spherical alumina (average particle size) Diameter 25 μm, Knoop hardness 1350 kg / cm 2 ) 20 parts by weight Silicone acrylate 2 parts by weight
【0042】比較例2 実施例1と同じ基材とインクを用い、実施例1と同様に
絵柄層を形成し、次いで該絵柄層の上に下記のように球
状粒子を含む塗工用樹脂組成物をロールコートにてコー
ティングし、実施例1と同様の条件にて電子線を照射
し、樹脂を完全に硬化させ膜厚25μmの表面保護層を
形成した。 塗工用樹脂組成物の組成 電子線硬化性樹脂(ポリエーテル系ウレタンアクリレートを主成分とし、架 橋間分子量が500) 100重量部 球状アルミナ(平均粒径25μm・ヌープ硬度1350kg/cm2 ) 20重量部 シリコーンアクリレート 2重量部Comparative Example 2 Using the same base material and ink as in Example 1, a pattern layer was formed in the same manner as in Example 1, and then a coating resin composition containing spherical particles as described below was formed on the pattern layer. The material was coated with a roll coat, and irradiated with an electron beam under the same conditions as in Example 1 to completely cure the resin and form a 25 μm-thick surface protective layer. Composition of coating resin composition Electron beam curable resin (polyether-based urethane acrylate as a main component, molecular weight between bridges is 500) 100 parts by weight Spherical alumina (average particle size 25 μm, Knoop hardness 1350 kg / cm 2 ) 20 parts by weight Parts Silicone acrylate 2 parts by weight
【0043】〔耐摩耗性の評価〕上記実施例及び比較例
で得られた化粧材について、耐摩耗性をJISK−69
02に準ずる方法により、S−42、500g荷重の下
で測定した。その結果を表1に示す。[Evaluation of Abrasion Resistance] The decorative materials obtained in the above Examples and Comparative Examples were evaluated for abrasion resistance according to JIS K-69.
S-42 was measured under a load of 500 g by a method according to Example No. 02. Table 1 shows the results.
【0044】[0044]
【表1】 [Table 1]
【0045】[0045]
【発明の効果】本発明の化粧材は、上述したように表面
保護層が、特定の膜厚になるような粒径の有機粒子を含
み、かつ電離放射線硬化性樹脂により構成されているた
めに、鮮明な凹凸が得られ、極めて優れた意匠性が得ら
れるという効果を有する。As described above, in the decorative material of the present invention, since the surface protective layer contains organic particles having a specific thickness so as to have a specific thickness and is made of an ionizing radiation-curable resin. This has the effect of obtaining clear irregularities and obtaining extremely excellent design properties.
【0046】また、本発明の化粧材は、表面保護層に特
定の架橋間平均分子量を有する電離放射線硬化性樹脂を
用い、かつ上記の有機粒子に特定の硬度を有する球状粒
子を併用することにより、さらに耐摩耗性に優れ、同時
に意匠的に優位性の高い表面を持った化粧材が得られる
という効果を有する。Further, the decorative material of the present invention is obtained by using an ionizing radiation-curable resin having a specific average molecular weight between crosslinks for the surface protective layer and using the above organic particles in combination with spherical particles having a specific hardness. In addition, there is an effect that a cosmetic material having a surface having excellent abrasion resistance and a high design superiority can be obtained.
【図1】本発明の化粧材の一例を示す縦断面図である。FIG. 1 is a longitudinal sectional view showing an example of a decorative material of the present invention.
【図2】本発明の化粧材の別の例を示す縦断面図であ
る。FIG. 2 is a longitudinal sectional view showing another example of the decorative material of the present invention.
1 基材 2 ベタ層 3 絵柄層 4 表面保護層 5 有機粒子 6 電離放射線硬化性樹脂層 7 球状粒子 Reference Signs List 1 base material 2 solid layer 3 picture layer 4 surface protection layer 5 organic particles 6 ionizing radiation curable resin layer 7 spherical particles
Claims (2)
層、表面保護層が基材側からこの順に設けられており、
上記表面保護層は該層の膜厚の1.2〜2.0倍となる
ような粒径の有機粒子を含有する電離放射線硬化性樹脂
からなることを特徴とする化粧材。1. A solid layer, a picture layer, and a surface protective layer are provided on at least one surface of a substrate in this order from the substrate side.
A decorative material, wherein the surface protective layer comprises an ionizing radiation-curable resin containing organic particles having a particle size of 1.2 to 2.0 times the thickness of the layer.
樹脂が架橋間平均分子量が150〜1000である電離
放射線硬化性樹脂であり、表面保護層を構成する電離放
射線硬化性樹脂に更にヌープ硬度が1300kg/cm
2 以上の球状粒子を含有する請求項1記載の化粧材。2. The ionizing radiation-curable resin constituting the surface protective layer is an ionizing radiation-curable resin having an average molecular weight between crosslinks of 150 to 1,000, and the ionizing radiation curable resin constituting the surface protective layer is further provided with a Knoop hardness. Is 1300kg / cm
The cosmetic material according to claim 1, comprising two or more spherical particles.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5440998A JP4003990B2 (en) | 1998-02-19 | 1998-02-19 | Cosmetic material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5440998A JP4003990B2 (en) | 1998-02-19 | 1998-02-19 | Cosmetic material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH11227116A true JPH11227116A (en) | 1999-08-24 |
JP4003990B2 JP4003990B2 (en) | 2007-11-07 |
Family
ID=12969914
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5440998A Expired - Lifetime JP4003990B2 (en) | 1998-02-19 | 1998-02-19 | Cosmetic material |
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Country | Link |
---|---|
JP (1) | JP4003990B2 (en) |
Cited By (11)
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JP2008238602A (en) * | 2007-03-27 | 2008-10-09 | Dainippon Printing Co Ltd | Decorative sheet |
JP2008238601A (en) * | 2007-03-27 | 2008-10-09 | Dainippon Printing Co Ltd | Decorative sheet |
JP2009096179A (en) * | 2007-09-27 | 2009-05-07 | Dainippon Printing Co Ltd | Decorative sheet |
JP2011516299A (en) * | 2008-03-31 | 2011-05-26 | スリーエム イノベイティブ プロパティズ カンパニー | Decorative sheet |
WO2014119510A1 (en) * | 2013-01-29 | 2014-08-07 | 東洋紡株式会社 | Film for surface decoration |
JP2017141665A (en) * | 2017-03-09 | 2017-08-17 | 大日本印刷株式会社 | Floor decoration sheet and its manufacturing method |
WO2019138397A1 (en) * | 2018-01-15 | 2019-07-18 | 3M Innovative Properties Company | Scratch resistant film and surface coating composition |
WO2022209516A1 (en) * | 2021-03-31 | 2022-10-06 | 大日本印刷株式会社 | Decorative sheet and decorative material |
JP2022158947A (en) * | 2021-03-31 | 2022-10-17 | 大日本印刷株式会社 | Decorative sheet and decorative material |
US20230041625A1 (en) * | 2020-01-22 | 2023-02-09 | Toppan Inc. | Decorative sheet, decorative plate, and method for producing decorative sheet |
WO2023176981A1 (en) * | 2022-03-17 | 2023-09-21 | 大日本印刷株式会社 | Decorative sheet and decorative material |
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