JP6349914B2 - Multilayer glossy decorative sheet - Google Patents
Multilayer glossy decorative sheet Download PDFInfo
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- JP6349914B2 JP6349914B2 JP2014090040A JP2014090040A JP6349914B2 JP 6349914 B2 JP6349914 B2 JP 6349914B2 JP 2014090040 A JP2014090040 A JP 2014090040A JP 2014090040 A JP2014090040 A JP 2014090040A JP 6349914 B2 JP6349914 B2 JP 6349914B2
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- decorative sheet
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- 229920005989 resin Polymers 0.000 claims description 58
- 239000011347 resin Substances 0.000 claims description 58
- 230000005865 ionizing radiation Effects 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 25
- 238000009501 film coating Methods 0.000 claims description 10
- 239000010409 thin film Substances 0.000 claims description 10
- 239000001023 inorganic pigment Substances 0.000 claims description 9
- 229920002050 silicone resin Polymers 0.000 claims description 7
- 230000001360 synchronised effect Effects 0.000 claims description 6
- 239000002932 luster Substances 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 56
- 239000010410 layer Substances 0.000 description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- -1 polyethylene terephthalate Polymers 0.000 description 16
- 238000011109 contamination Methods 0.000 description 11
- 238000007639 printing Methods 0.000 description 10
- 238000013461 design Methods 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 8
- 229920005862 polyol Polymers 0.000 description 8
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 8
- 150000003077 polyols Chemical class 0.000 description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 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 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229920003180 amino resin Polymers 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
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 238000005510 radiation hardening Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- CZZVAVMGKRNEAT-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)CO.OCC(C)(C)C(O)=O CZZVAVMGKRNEAT-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- XJELOQYISYPGDX-UHFFFAOYSA-N ethenyl 2-chloroacetate Chemical compound ClCC(=O)OC=C XJELOQYISYPGDX-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 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
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920006352 transparent thermoplastic Polymers 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Description
本発明は建築物の内装，外装，家具，建具、車両の内装等の表面に用い、表面に凹凸の手触り感を与える多層光沢化粧シートに関し、特には表面の耐汚染性など各種耐性に優れ、かつ絵柄と同調した凹凸を表面に有する意匠性に優れた多層光沢化粧シートに関する。 The present invention relates to a multi-layer glossy decorative sheet that is used on the interior and exterior of buildings, exteriors, furniture, fittings, interiors of vehicles, etc., and gives a rough feel to the surface, in particular excellent in various resistances such as surface contamination resistance, In addition, the present invention relates to a multi-layer glossy decorative sheet having irregularities synchronized with a pattern on the surface and excellent in design.
凹凸の手触り感のある多層光沢化粧シートとしては、まず、表面の層にエンボスにより凹部を設けたものや、盛上げ印刷により凸部を設けたものなど、物理的に凹凸を設けたものがある。
一方、印刷などにより凹凸の手触り感のある絵柄模様を設けたあと、さらに凹凸があるように見せる為に、絵柄模様の表面側に、絵柄模様に同調させた光沢差をつけた艶調整層を設け、立体感のある多層光沢化粧シートとするものもあった。
As the multi-layer glossy decorative sheet having an uneven feel, first, there are those having a physical unevenness such as a surface layer provided with a concave portion by embossing or a surface layer provided with a convex portion.
On the other hand, a gloss adjustment layer with a gloss difference synchronized with the pattern on the surface side of the pattern is provided on the surface side of the pattern to make it appear as if the pattern is more uneven after printing. Some were provided as multi-layer glossy decorative sheets with a three-dimensional effect.
しかしながら、エンボスによる方法では凹部の深さに限界があり、盛上げ印刷では表面の耐汚染性など各種耐性に劣るものとなり、艶調整層を設ける方法では十分な立体感をえることは出来なかった。 However, the embossing method has a limit on the depth of the concave portion, and the print-up printing is inferior to various resistances such as surface contamination resistance, and the method of providing the gloss adjusting layer cannot provide a sufficient three-dimensional effect.
本発明はこのような問題点を解決する為になされたものであり、その課題とするところは、十分な立体感を有し、かつ表面の耐汚染性など各種耐性にすぐれた多層光沢化粧シートを得ることにある。 The present invention has been made to solve such problems, and the object of the present invention is to provide a multi-layer glossy decorative sheet having a sufficient three-dimensional effect and having various resistances such as surface contamination resistance. There is in getting.
本発明はこの課題を解決したものであり、すなわちその請求項１記載の発明は、少なくとも絵柄模様層と、透明艶調整層と、表面に前記絵柄模様と同調した電離放射線硬化型樹脂からなる凸部とを有し、前記凸部の高さが３０〜１００μｍである多層光沢化粧シートであって、前記透明艶調整層と前記絵柄模様と同調した電離放射線硬化型樹脂からなる凸部の間に絵柄模様層と同調した耐汚染薄膜コーティング樹脂グロスマット層を設けてなり、前記透明艶調整層には粒径が２〜３μｍの無機系顔料及び粒径が３〜４μｍの無機系顔料が添加されており、前記電離放射線硬化型樹脂からなる凸部には、粒径が１０〜１５μｍの無機系顔料が添加されていることを特徴とする多層光沢化粧シートである。
The present invention solves this problem, that is, the invention according to claim 1 is a convex made of at least a pattern layer, a transparent gloss adjusting layer, and an ionizing radiation curable resin synchronized with the pattern on the surface. A multi-layer glossy decorative sheet having a height of 30-100 μm, wherein the convex portion is made of an ionizing radiation curable resin synchronized with the transparent gloss adjusting layer and the pattern. A stain resistant thin film coating resin gloss matte layer is provided in synchronization with the pattern layer, and an inorganic pigment having a particle size of 2 to 3 μm and an inorganic pigment having a particle size of 3 to 4 μm are added to the transparent gloss adjusting layer. The multilayer glossy decorative sheet is characterized in that an inorganic pigment having a particle size of 10 to 15 μm is added to the convex portion made of the ionizing radiation curable resin .
またその請求項２記載の発明は、前記電離放射線硬化型樹脂からなる凸部に反応型シリコーン樹脂を１０〜５０重量％含有することを特徴とする請求項１記載の多層光沢化粧シートである。 The invention according to claim 2 is the multilayer glossy decorative sheet according to claim 1 , characterized in that 10 to 50% by weight of a reactive silicone resin is contained in the convex portion made of the ionizing radiation curable resin.
本発明はその請求項１記載の発明により、視覚的及び触感的に優れた立体感と手触り感を有し、かつ表面の耐汚染性など各種耐性にすぐれた多層光沢化粧シートとすることが可能となる。 According to the invention of the first aspect of the present invention, it is possible to provide a multilayer glossy decorative sheet having excellent three-dimensional appearance and touch feeling in terms of visual and tactile sensation and excellent in various resistances such as surface contamination resistance. It becomes.
またその請求項２記載の発明により、電離放射線硬化型樹脂からなる凸部に粒径と割合を限定した粒状粒子を含有することで、表面の耐汚染性が良く、光沢差が増すことにより、本物の木材に近い照り感を再現することができる。 Further, according to the invention of claim 2, by containing granular particles with a limited particle size and ratio in the convex portion made of ionizing radiation curable resin, surface contamination resistance is good and gloss difference is increased. It can reproduce the feeling of shine close to real wood.
またその請求項３記載の発明により、電離放射線硬化型樹脂からなる凸部にさらに反応型シリコーン樹脂を１０〜５０重量％含有することで、表面の耐汚染性をさらに良いものとすることが可能となる。 Further, according to the invention described in claim 3, it is possible to further improve the surface contamination resistance by further containing 10 to 50% by weight of a reactive silicone resin in the convex portion made of ionizing radiation curable resin. It becomes.
以下本発明を図面に基づき詳細に説明する。図１に本発明の多層光沢化粧シート１の一実施例の断面の構造を示す。基材２０の一方の面にプライマー層１０を設け、更に基材２０のもう一方の面の上に適宜の第一の絵柄模様層３０、第二の絵柄模様層４０、透明艶調整層５０、耐汚染薄膜コーティング樹脂グロスマット層６０、電離放射線硬化型樹脂からなる凸部７０を設けてなる。 Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 shows a cross-sectional structure of an embodiment of the multi-layer glossy decorative sheet 1 of the present invention. The primer layer 10 is provided on one surface of the base material 20, and an appropriate first design pattern layer 30, second design pattern layer 40, transparent gloss adjustment layer 50, on the other surface of the base material 20, A contamination-resistant thin film coating resin gloss mat layer 60 and a convex portion 70 made of an ionizing radiation curable resin are provided.
本発明におけるプライマー層１０としては、板状基材等と積層する場合、接着剤の種類に応じてもうけることができる。ＰＵＲ（湿気硬化型ポリウレタンホットメルト）接着剤や一液や二液硬化型ウレタン樹脂にシリカ等を配合プライマー層１０を設けることができる。 The primer layer 10 in the present invention can be provided according to the type of adhesive when it is laminated with a plate-like substrate or the like. The primer layer 10 can be provided by blending silica or the like into a PUR (moisture curable polyurethane hot melt) adhesive or a one-component or two-component curable urethane resin.
本発明における基材２０としては、後述する第一及び第二の絵柄模様層３０、４０を印刷等により設けることが可能であり、多層光沢化粧シートとしての加工適性を有するものであれば従来公知のものが使用可能であるが、塩化ビニルを使用しないものとしてポリエチレンテレフタレート樹脂やポリブチレンテレフタレート樹脂等のポリエステル系樹脂シート、ポリエチレン樹脂やポリプロピレン樹脂等のポリオレフィン系樹脂シートなどが好ましい。基材２０には、必要に応じ、従来公知の充填剤、発泡剤、難燃剤、滑剤、酸化防止剤、紫外線吸収剤、光安定剤などの各種の添加剤を常法に従って添加することができる。基材２０の厚みは、用途などによるが、５０〜１００μｍ程度が好ましい。特に、不燃申請を行う場合は、樹脂系や厚み、発熱量等を考慮する。 As the substrate 20 in the present invention, first and second pattern layers 30 and 40 to be described later can be provided by printing or the like, and conventionally known as long as it has processing suitability as a multilayer glossy decorative sheet. Although those using no vinyl chloride are preferable, polyester resin sheets such as polyethylene terephthalate resin and polybutylene terephthalate resin, polyolefin resin sheets such as polyethylene resin and polypropylene resin, and the like are preferable. Various additives such as conventionally known fillers, foaming agents, flame retardants, lubricants, antioxidants, ultraviolet absorbers, light stabilizers and the like can be added to the base material 20 according to conventional methods as necessary. . The thickness of the substrate 20 is preferably about 50 to 100 μm, although it depends on the application. In particular, when applying for non-combustibility, the resin system, thickness, calorific value, etc. are considered.
本発明における第一及び第二の絵柄模様層３０、４０としては、本発明の多層光沢化粧シート１に絵柄による意匠性を付与するために設けられるものである。第一の絵柄模様層３０は、着色ベタインキや光輝性顔料インキからなるベタ層を設けてもよい。また、第二の絵柄層４０は染料または顔料等の着色剤を適当なバインダー樹脂と共に適当な希釈溶媒中に溶解または分散してなる印刷インキまたは塗料等を使用して、例えばグラビア印刷法またはオフセット印刷法等の各種印刷法や、グラビアコート法またはロールコート法等の各種塗工法などによって形成されるのが一般的である。バインダー樹脂としては、例えばウレタン系樹脂、アクリル系樹脂、塩化酢酸ビニル系樹脂、ポリイミド系樹脂、硝化綿等またはそれらの混合物等がよく使用されるが、勿論これらに限定されるものではない。絵柄の種類は、例えば木目柄、石目柄、布目柄、抽象柄、幾何学模様、文字または記号、それらの組み合わせ等、所望により任意であり、単色無地であっても良い。また、多層光沢化粧シートの隠蔽性を向上するために、第一の絵柄模様層３０の裏面側に、二酸化チタンや酸化鉄等の不透明顔料を多く含む不透明な印刷インキまたは塗料による隠蔽層が併設される場合もある。 The first and second design pattern layers 30 and 40 in the present invention are provided for imparting design properties to the multilayer glossy decorative sheet 1 of the present invention. The first pattern layer 30 may be provided with a solid layer made of colored solid ink or glitter pigment ink. The second picture layer 40 is formed by using a printing ink or paint obtained by dissolving or dispersing a colorant such as a dye or pigment in a suitable diluent solvent together with a suitable binder resin, for example, gravure printing or offset. It is generally formed by various printing methods such as a printing method and various coating methods such as a gravure coating method or a roll coating method. As the binder resin, for example, urethane resin, acrylic resin, vinyl chloroacetate resin, polyimide resin, nitrified cotton, or a mixture thereof is often used, but it is not limited thereto. The type of the pattern is arbitrary as desired, for example, a wood grain pattern, a stone pattern, a cloth pattern, an abstract pattern, a geometric pattern, a character or a symbol, a combination thereof, etc., and may be a solid color. In addition, in order to improve the concealability of the multi-layer glossy decorative sheet, a concealing layer made of an opaque printing ink or paint containing a large amount of an opaque pigment such as titanium dioxide or iron oxide is provided on the back side of the first pattern layer 30. Sometimes it is done.
本発明における透明艶調整層５０としては、表面の光沢を調整するためのものであり、各種の透明熱可塑性樹脂層との接着の汎用性、多層光沢化粧シートを導管溝内へ彎曲させる際の変形追従性、及び耐擦傷性の点から、その樹脂成分（バインダー樹脂）として２液硬化型ウレタン樹脂を選択し、これに、所望の艶に応じて艶調整剤（マット剤或いは艶消剤とも呼称される）を添加或いは無添加とした組成物を塗工して得られる。表面を高光沢とする場合には、艶調整剤を無添加とする。また、低光沢とする場合には、添加する。艶調整剤としてはシリカ、アルミナ（α−アルミナ等）、炭酸カルシウム、硫酸バリウム、カオリナイト、アルミノシリケート等の無機物、或いはポリカーボネート、ナイロン、ウレタン樹脂等の有機物（樹脂）の微粒子が挙げられる。艶調整剤の平均粒径は、１〜１０μｍ程度が好ましく、添加量は所望の光沢に応じて適宜選択するが、通常は最大で３０質量％程度である。２液硬化型ウレタン樹脂としては、ポリオールを主体とし、イソシアネートを架橋剤（硬化剤）とするウレタン樹脂である。ポリオールとしては、分子中に２個以上の水酸基を有するもので、例えばポリエチレングリコール、ポリプロピレングリコール、アクリルポリオール、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール、ポリウレタンポリオール等が用いられる。また、イソシアネートとしては、分子中に２個以上のイソシアネート基を有する多価イソシアネートが用いられる。 The transparent gloss adjusting layer 50 according to the present invention is for adjusting the gloss of the surface. The versatility of adhesion with various transparent thermoplastic resin layers, when the multilayer glossy decorative sheet is bent into the conduit groove, From the viewpoint of deformation followability and scratch resistance, a two-component curable urethane resin is selected as the resin component (binder resin), and a gloss adjusting agent (matting agent or matting agent) is selected depending on the desired gloss. It is obtained by coating a composition with or without addition). When making the surface highly glossy, no gloss adjusting agent is added. Moreover, when making it low glossiness, it adds. Examples of the gloss adjusting agent include inorganic substances such as silica, alumina (α-alumina, etc.), calcium carbonate, barium sulfate, kaolinite, aluminosilicate, and organic (resin) fine particles such as polycarbonate, nylon, and urethane resin. The average particle size of the gloss adjusting agent is preferably about 1 to 10 μm, and the addition amount is appropriately selected according to the desired gloss, but is usually about 30% by mass at maximum. The two-component curable urethane resin is a urethane resin mainly composed of polyol and isocyanate as a crosslinking agent (curing agent). As the polyol, one having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol and the like are used. As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule is used.
例えば、２，４−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等の芳香族イソシアネート、或いは、１，６−ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、水素添加トリレンジイソシアネート、水素添加ジフェニルメタンジイソシアネート等の脂肪族（乃至は脂環式）イソシアネートが用いられる。或いはまた、上記各種イソシアネートの付加体又は多量体を用いることができる。例えば、トリレンジイソシアネートの付加体、トリレンジイソシアネート３量体（ｔｒｉｍｅｒ）等がある。尚、上記イソシアネートに於いて脂肪族（乃至は脂環式）イソシアネートは耐候性、耐熱黄変性も良好に出来る点で好ましく、具体的には例えば１，６−ヘキサメチレンジイソシアネートなどが使用できる。前記透明艶調整層５０の無機系顔料の粒径が２〜３μｍの粒径と３〜４μｍの粒径、且つ凸部７０の無機系顔料の粒径が１０〜１５μｍからなるとよりリアル感がでる。
前記各艶調整剤を添加して、マット部分の艶は反射光沢係数値で３から５程度とするのが意匠的に好ましい。
For example, aromatic isocyanate such as 2,4-tolylene diisocyanate, xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Aliphatic (or alicyclic) isocyanates are used. Alternatively, adducts or multimers of the above various isocyanates can be used. For example, there are tolylene diisocyanate adducts, tolylene diisocyanate trimers, and the like. Of the above-mentioned isocyanates, aliphatic (or alicyclic) isocyanates are preferred in that they can be well weathered and heat-resistant yellowed. Specifically, for example, 1,6-hexamethylene diisocyanate can be used. When the particle size of the inorganic pigment of the transparent gloss adjusting layer 50 is 2 to 3 μm and 3 to 4 μm, and the particle size of the inorganic pigment of the convex portion 70 is 10 to 15 μm, a more realistic feeling can be obtained. .
It is preferable in terms of design that each gloss adjusting agent is added so that the gloss of the mat portion is about 3 to 5 in terms of reflection gloss coefficient.
本発明における耐汚染薄膜コーティング樹脂グロスマット層６０と電離放射線硬化型樹脂からなる凸部７０としては同様の樹脂が使える。高さが３０〜１００μｍであって、前記凸部の電離放射線硬化型樹脂１００重量％に対して粒径１０〜１５μｍのシリカ等の粒状粒子を適宜組み合わせて５〜２０重量％含有したものが用いられる。
電離放射線硬化型樹脂としては、電磁波又は荷電粒子線の中で分子を架橋、重合させ得るエネルギー量子を有するもの、すなわち、紫外線又は電子線などを照射することにより、架橋、硬化する樹脂組成物を指す。具体的には、従来又は電離放射線もしくは紫外線硬化性樹脂組成物として慣用されている重合性モノマー及び重合性オリゴマーないしはプレポリマーの中から適宜選択して用いることができる。
The same resin can be used as the convex portion 70 made of the contamination resistant thin film coating resin gloss mat layer 60 and the ionizing radiation curable resin in the present invention. A material having a height of 30 to 100 μm and containing 5 to 20% by weight of particle particles such as silica having a particle size of 10 to 15 μm with respect to 100% by weight of the ionizing radiation curable resin of the convex portion is used. It is done.
Ionizing radiation curable resins include those having energy quanta capable of crosslinking and polymerizing molecules in electromagnetic waves or charged particle beams, that is, resin compositions that are crosslinked and cured by irradiation with ultraviolet rays or electron beams. Point to. Specifically, it can be appropriately selected from polymerizable monomers and polymerizable oligomers or prepolymers conventionally used as ionizing radiation or ultraviolet curable resin compositions.
代表的には、重合性モノマーとして、分子中にラジカル重合性不飽和基を持つ（メタ）アクリレート系モノマーが好適であり、中でも多官能性（メタ）アクリレートが好ましい。なお、ここで「（メタ）アクリレート」とは「アクリレート又はメタクリレート」を意味する。多官能性（メタ）アクリレートとしては、分子内にエチレン性不飽和結合を２個以上有する（メタ）アクリレートであればよく、特に制限はない。具体的にはエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、カプロラクトン変性ジシクロペンテニルジ（メタ）アクリレート、エチレンオキシド変性リン酸ジ（メタ）アクリレート、アリル化シクロヘキシルジ（メタ）アクリレート、イソシアヌレートジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、エチレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、プロピオン酸変性ジペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、プロピレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、トリス（アクリロキシエチル）イソシアヌレート、プロピオン酸変性ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、エチレンオキシド変性ジペンタエリスリトールヘキサ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレートなどが挙げられる。これらの多官能性（メタ）アクリレートは１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Typically, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is suitable as the polymerizable monomer, and among them, a polyfunctional (meth) acrylate is preferable. Here, “(meth) acrylate” means “acrylate or methacrylate”. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified diphosphate ( (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylo Propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris ( Acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Is mentioned. These polyfunctional (meth) acrylates may be used singly or in combination of two or more.
本発明においては、前記多官能性（メタ）アクリレートとともに、その粘度を低下させるなどの目的で、単官能性（メタ）アクリレートを、本発明の目的を損なわない範囲で適宜併用することができる。単官能性（メタ）アクリレートとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレートなどが挙げられる。これらの単官能性（メタ）アクリレートは１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 In the present invention, a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate as long as the object of the present invention is not impaired, for the purpose of lowering the viscosity. Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. These monofunctional (meth) acrylates may be used alone or in combination of two or more.
次に、重合性オリゴマーとしては、分子中にラジカル重合性不飽和基を持つオリゴマー、例えばエポキシ（メタ）アクリレート系、ウレタン（メタ）アクリレート系、ポリエステル（メタ）アクリレート系、ポリエーテル（メタ）アクリレート系などが挙げられる。ここで、エポキシ（メタ）アクリレート系オリゴマーは、例えば、比較的低分子量のビスフェノール型エポキシ樹脂やノボラック型エポキシ樹脂のオキシラン環に、（メタ）アクリル酸を反応しエステル化することにより得ることができる。また、このエポキシ（メタ）アクリレート系オリゴマーを部分的に二塩基性カルボン酸無水物で変性したカルボキシル変性型のエポキシ（メタ）アクリレートオリゴマーも用いることができる。ウレタン（メタ）アクリレート系オリゴマーは、例えば、ポリエーテルポリオールやポリエステルポリオールとポリイソシアネートの反応によって得られるポリウレタンオリゴマーを、（メタ）アクリル酸でエステル化することにより得ることができる。ポリエステル（メタ）アクリレート系オリゴマーとしては、例えば多価カルボン酸と多価アルコールの縮合によって得られる両末端に水酸基を有するポリエステルオリゴマーの水酸基を（メタ）アクリル酸でエステル化することにより、あるいは、多価カルボン酸にアルキレンオキシドを付加して得られるオリゴマーの末端の水酸基を（メタ）アクリル酸でエステル化することにより得ることができる。ポリエーテル（メタ）アクリレート系オリゴマーは、ポリエーテルポリオールの水酸基を（メタ）アクリル酸でエステル化することにより得ることができる。 Next, as the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate The system etc. are mentioned. Here, the epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. . Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Examples of polyester (meth) acrylate oligomers include esterification of hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.
さらに、重合性オリゴマーとしては、他にポリブタジエンオリゴマーの側鎖に（メタ）アクリレート基をもつ疎水性の高いポリブタジエン（メタ）アクリレート系オリゴマー、主鎖にポリシロキサン結合をもつシリコーン（メタ）アクリレート系オリゴマー、小さな分子内に多くの反応性基をもつアミノプラスト樹脂を変性したアミノプラスト樹脂（メタ）アクリレート系オリゴマー、あるいはノボラック型エポキシ樹脂、ビスフェノール型エポキシ樹脂、脂肪族ビニルエーテル、芳香族ビニルエーテル等の分子中にカチオン重合性官能基を有するオリゴマーなどがある。 Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.
本発明における電離放射線硬化型樹脂１００重量％に対して２０〜３０重量％含有する粒径３〜１５μｍの粒状粒子としては、樹脂などの有機系、ガラスやシリカなどの無機系などがあり特に限定はしないが、特には手触り感と耐汚染性の点から真球状のアクリルビーズが好適である。含有量として２０重量％より少ないと、手触り感があまり感じられないものとなり、３０重量％より多いと耐汚染性が悪くなる傾向となる。そして、粒径が３μｍより小さいと、手触り感があまり感じられないものとなり、１６μｍより大きいと耐汚染性が悪くなる傾向となる。 The granular particles having a particle diameter of 3 to 15 μm contained in an amount of 20 to 30% by weight with respect to 100% by weight of the ionizing radiation curable resin in the present invention include organic systems such as resins and inorganic systems such as glass and silica. Although not, true spherical acrylic beads are particularly preferred from the viewpoints of touch and stain resistance. When the content is less than 20% by weight, the feeling of touch is not felt so much, and when the content is more than 30% by weight, the stain resistance tends to deteriorate. When the particle size is smaller than 3 μm, the feeling of touch is not felt so much, and when it is larger than 16 μm, the contamination resistance tends to be deteriorated.
また本発明における電離放射線硬化型樹脂からなる凸部７０には、所望物性に応じて、各種添加剤を配合することができる。この添加剤としては、例えば耐候性改善剤、耐摩耗性向上剤、重合禁止剤、架橋剤、赤外線吸収剤、帯電防止剤、接着性向上剤、レベリング剤、チクソ性付与剤、カップリング剤、可塑剤、消泡剤、充填剤、溶剤、着色剤などが挙げられる。 Moreover, various additives can be mix | blended with the convex part 70 which consists of ionizing radiation hardening type resin in this invention according to a desired physical property. Examples of this additive include a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, a coupling agent, A plasticizer, an antifoamer, a filler, a solvent, a coloring agent, etc. are mentioned.
また本発明における電離放射線硬化型樹脂からなる凸部７０の形状は、特に限定されず、丸、四角形、六角形の規則的に並んだような定形の形状でも、不定型な絵柄であってもよく、不定型な絵柄であると触感、マット感、光沢感及び意匠性に優れることから好ましい。また電離放射線硬化型樹脂からなる凸部７０を第一の絵柄模様層３０、第二の絵柄層４０と、更に耐汚染薄膜コーティング樹脂グロスマット層６０と同調させることによりリアル感が得られる。 Further, the shape of the convex portion 70 made of the ionizing radiation curable resin in the present invention is not particularly limited, and may be a regular shape such as a regular array of circles, squares, hexagons, or an irregular pattern. Often, an irregular pattern is preferable because it is excellent in touch, matte, gloss and design. Further, a realistic feeling can be obtained by synchronizing the convex portion 70 made of ionizing radiation curable resin with the first pattern layer 30, the second pattern layer 40, and the stain resistant thin film coating resin gloss mat layer 60.
本発明では、耐汚染薄膜コーティング樹脂グロスマット層６０、電離放射線硬化型樹脂からなる凸部７０に反応型シリコーン樹脂を１０〜５０重量％含有することが好ましい。反応型シリコーン樹脂としては、主鎖にシリコーン骨格をもった材料、剥型剤等に使用されるシリコーンオイル、などが挙げられるが、特には耐汚染性の点から側鎖にシリコーン骨格をもった紫外線効果型アクリレート樹脂が好適である。反応型シリコーン樹脂の含有量が１０重量％より少ないと、耐汚染性が悪くなる傾向であり、５０重量％より多いとシリコーンのブリードアウトによる基材との接着不良等の不具合が起こる可能性がある。あるいは後述する耐汚染薄膜コーティング樹脂グロスマット層６０に用いる樹脂と同様ものであれば表面が同様の樹脂からなり、好ましいものとなる。 In this invention, it is preferable to contain 10-50 weight% of reactive silicone resin in the convex part 70 which consists of an antifouling thin film coating resin gloss mat layer 60 and ionizing radiation hardening type resin. Examples of the reactive silicone resin include materials having a silicone skeleton in the main chain, silicone oil used for a release agent, and the like, and in particular, have a silicone skeleton in the side chain from the viewpoint of stain resistance. UV effect acrylate resins are preferred. If the content of the reactive silicone resin is less than 10% by weight, the stain resistance tends to deteriorate, and if it exceeds 50% by weight, problems such as poor adhesion to the substrate due to silicone bleed out may occur. is there. Or if it is the same as resin used for the antifouling thin film coating resin gloss mat layer 60 mentioned later, the surface will consist of the same resin, and will become preferable.
本発明において透明艶調整層５０の表面に適宜設ける層厚０．５〜１．５μｍの耐汚染薄膜コーティング樹脂グロスマット層６０に用いる樹脂としては、特に図に示さないが、ブロックイソシアネート硬化型ウレタン系樹脂が好適に用いられる。層厚が０．５μｍより薄いと十分な耐汚染の効果が得られず、層厚が１．５μｍより厚いと立体感と意匠性を損なうものとなる。 In the present invention, the resin used for the stain-resistant thin film coating resin gloss mat layer 60 having a layer thickness of 0.5 to 1.5 μm appropriately provided on the surface of the transparent gloss adjusting layer 50 is not particularly shown in the drawing, but is a blocked isocyanate curable urethane. System resins are preferably used. If the layer thickness is less than 0.5 μm, a sufficient anti-contamination effect cannot be obtained, and if the layer thickness is more than 1.5 μm, the three-dimensional effect and the design are impaired.
基材２０として厚さ６０μｍの７６．２ｇ／ｍ２の無機顔料ポリブチレンテレフタレート樹脂９２．７重量部のフィルムを用い、第一の絵柄模様層３０として光輝性顔料（パール顔料）２９重量部、ウレタン樹脂７１重量部からなるインキを乾燥重量０．７ｇ／ｍ２全面ベタ印刷した。これに第二の絵柄模様層４０として木目調の絵柄をウレタン樹脂系インキにより乾燥重量１．８ｇ／ｍ２グラビア印刷した。
乾燥後、この表面に透明艶調整層５０としての粒径が２〜３μｍの粒径と３〜４μｍの粒径シリカ粉末を２０．９重量部添加して艶を低く調整し、反応型シリコーン樹脂を２３．４重量部と適量の紫外線開始剤を添加した紫外線硬化型樹脂を乾燥後の塗布量９．０ｇ／ｍ２となるように塗工した。反射光沢係数は４であった。
透明艶調整層５０の架橋硬化後、前記第二の絵柄模様層４０の絵柄と同調する印刷版で、耐汚染薄膜コーティング樹脂グロスマット層６０として粒径が２〜３μｍの粒径シリカ粉末を１０．７重量部添加して艶を低く調整した。次に、反応型シリコーン樹脂を５１．３重量部と適量の紫外線開始剤を添加した紫外線硬化型樹脂を乾燥後の塗布量７．４ｇ／ｍ２となるように塗工した。反射光沢係数は４であった。
乾燥後、電離放射線硬化型樹脂からなる凸部７０として、前記第二の絵柄模様層４０の絵柄と同調する印刷版で、凸部の高さが３０μｍ、凸部同士の間隔が１ｍｍとなるように紫外線硬化型樹脂（各種添加剤含む）８８．８重量部に粒径１４μｍのシリカを１１．６重量部、反応型シリコーン添加剤を７．６重量部添加したインキを用いて盛上げ印刷により８．０ｇ／ｍ２設け、本発明の多層光沢化粧シート１を得た。
Using a film of 92.7 parts by weight of a 76.2 g / m 2 inorganic pigment polybutylene terephthalate resin having a thickness of 60 μm as the substrate 20, 29 parts by weight of a glitter pigment (pearl pigment) as the first pattern layer 30, An ink composed of 71 parts by weight of urethane resin was solid-printed on the entire surface with a dry weight of 0.7 g / m 2 . A wood grain-like pattern was printed as a second pattern pattern layer 40 with a urethane resin-based ink at a dry weight of 1.8 g / m 2 gravure.
After drying, 20.9 parts by weight of silica powder having a particle size of 2 to 3 μm and a particle size of 3 to 4 μm as a transparent gloss adjusting layer 50 is added to the surface to adjust the gloss to a low level. Was coated with an ultraviolet curable resin to which 23.4 parts by weight and an appropriate amount of an ultraviolet initiator were added so that the coating amount after drying was 9.0 g / m 2 . The reflection gloss coefficient was 4.
After the cross-linking and curing of the transparent gloss adjusting layer 50, 10 μg of silica powder having a particle size of 2 to 3 μm is used as the stain-resistant thin film coating resin gloss mat layer 60 on the printing plate synchronized with the pattern of the second pattern layer 40. The gloss was adjusted low by adding 7 parts by weight. Next, 51.3 parts by weight of a reactive silicone resin and an ultraviolet curable resin added with an appropriate amount of an ultraviolet initiator were applied so that the coating amount after drying was 7.4 g / m 2 . The reflection gloss coefficient was 4.
After drying, the projection 70 made of ionizing radiation curable resin is a printing plate that synchronizes with the pattern of the second pattern layer 40 so that the height of the projection is 30 μm and the interval between the projections is 1 mm. And 88.8 parts by weight of an ultraviolet curable resin (including various additives), 81.6 parts by weight of silica having a particle size of 14 μm and 7.6 parts by weight of a reactive silicone additive, and 8 by weight-printing. The multilayer glossy decorative sheet 1 of the present invention was obtained by providing 0.0 g / m 2 .
電離放射線硬化型樹脂からなる凸部７０への粒径１０μｍのシリカとした以外は実施例１と同様にして多層光沢化粧シートを得た。 A multilayer glossy decorative sheet was obtained in the same manner as in Example 1 except that silica having a particle size of 10 μm on the convex portion 70 made of an ionizing radiation curable resin was used.
＜比較例１＞
電離放射線硬化型樹脂からなる凸部７０への粒径５μｍのウレタンビーズとした以外は実施例１と同様にして多層光沢化粧シートを得た。
<Comparative Example 1>
A multilayer glossy decorative sheet was obtained in the same manner as in Example 1 except that urethane beads having a particle diameter of 5 μm were formed on the convex portion 70 made of an ionizing radiation curable resin.
＜比較例２＞
電離放射線硬化型樹脂からなる凸部７０への粒径２０μｍのウレタンビーズとした以外は実施例１と同様にして多層光沢化粧シートを得た。
<Comparative example 2>
A multilayer glossy decorative sheet was obtained in the same manner as in Example 1 except that urethane beads having a particle diameter of 20 μm were formed on the convex portion 70 made of an ionizing radiation curable resin.
＜性能評価＞
手触り感を評価する為にブラインド評価を行った。比較としてシリカ、ウレタンビーズを含有していない以外は実施例１と同様の多層光沢化粧シートを用い、見えない状態で手触り感に違いが感じられるかどうかを○×で評価した。
見た目のリアル感を評価する為に目視評価をおこなった。リアル感がある場合を○、リアル感がない場合を×として評価した。
耐汚染性を評価する為に油性マーカー黒のティッシュペーパでの拭き取り試験を行った。簡単に拭き取れる場合を○、拭き残しが発生する場合を×として評価した。
<Performance evaluation>
Blind evaluation was performed to evaluate the feeling of touch. As a comparison, a multilayer glossy decorative sheet similar to Example 1 was used except that silica and urethane beads were not contained, and whether or not a difference in touch feeling was felt in an invisible state was evaluated as ◯.
Visual evaluation was performed to evaluate the real feeling of appearance. The case where there was a real feeling was evaluated as ◯, and the case where there was no real feeling was evaluated as x.
In order to evaluate the stain resistance, a wiping test was conducted with a tissue paper of black oil marker. The case where it was easy to wipe off was evaluated as ◯, and the case where unwiping occurred was evaluated as x.
以上の結果を表１で示す。実施例１と実施例２は手触り感、見た目のリアル感及び、耐汚染性の全ての評価にて良好な結果が得られたが、比較例１と比較例２は同様な結果は得られなかった。 The results are shown in Table 1. In Examples 1 and 2, good results were obtained in all evaluations of touch, appearance, and stain resistance, but Comparative Examples 1 and 2 did not give similar results. It was.
本発明の多層光沢化粧シートはこれまで木目意匠に拘るユーザーにも工業製品である木目印刷シートの拡販に結びつく。このことから木材資源の節約にもつながり、又、一方、耐汚染性にも優れる事から耐久消費財としての省資源化にもつながる。 The multilayer glossy decorative sheet of the present invention will lead to the expansion of sales of the wood grain printed sheet, which is an industrial product, to users who have been involved in wood grain designs. This leads to savings in wood resources, and on the other hand, it also leads to resource saving as durable consumer goods because of its excellent contamination resistance.
１…多層光沢化粧シート
１０…プライマー層
２０…基材
３０…第一の絵柄模様層
４０…第二の絵柄模様層
５０…透明艶調整層
６０…耐汚染薄膜コーティング樹脂グロスマット層
７０…電離放射線硬化型樹脂からなる凸部
DESCRIPTION OF SYMBOLS 1 ... Multilayer glossy decorative sheet 10 ... Primer layer 20 ... Base material 30 ... 1st pattern pattern layer 40 ... 2nd pattern pattern layer 50 ... Transparent gloss adjustment layer 60 ... Antifouling thin film coating resin gloss mat layer 70 ... Ionizing radiation Convex part made of curable resin
Claims (2)
前記透明艶調整層と前記絵柄模様と同調した電離放射線硬化型樹脂からなる凸部の間に絵柄模様層と同調した耐汚染薄膜コーティング樹脂グロスマット層を設けてなり、前記透明艶調整層には粒径が２〜３μｍの無機系顔料及び粒径が３〜４μｍの無機系顔料が添加されており、前記電離放射線硬化型樹脂からなる凸部には、粒径が１０〜１５μｍの無機系顔料が添加されていることを特徴とする多層光沢化粧シート。 A multilayer glossy decorative sheet having at least a pattern layer, a transparent gloss adjusting layer, and a convex portion made of an ionizing radiation curable resin synchronized with the pattern on the surface, wherein the height of the convex portion is 30 to 100 μm. Because
It is provided stain thin film coating resin gloss matte layer tuned with the picture pattern layer between the convex portion made of an ionizing radiation curable resin tuned to the picture pattern and the transparent luster control layer, the transparent luster control layer An inorganic pigment having a particle diameter of 2 to 3 μm and an inorganic pigment having a particle diameter of 3 to 4 μm are added, and an inorganic pigment having a particle diameter of 10 to 15 μm is formed on the convex portion made of the ionizing radiation curable resin. A multilayer glossy decorative sheet characterized in that is added .
The multilayer glossy decorative sheet according to claim 1, wherein the convex part made of the ionizing radiation curable resin contains 10 to 50% by weight of a reactive silicone resin.
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| JP6763150B2 (en) * | 2016-02-04 | 2020-09-30 | 凸版印刷株式会社 | Decorative sheet and decorative board |
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| JP6922332B2 (en) * | 2017-03-29 | 2021-08-18 | 大日本印刷株式会社 | Cosmetic sheet |
| JP7375417B2 (en) * | 2019-09-26 | 2023-11-08 | 大日本印刷株式会社 | Decorative sheets and decorative resin molded products |
| JP7040656B2 (en) * | 2020-02-21 | 2022-03-23 | 大日本印刷株式会社 | Manufacturing method of decorative material, laminate and decorative material |
| JP2022014765A (en) * | 2020-07-07 | 2022-01-20 | スリーエム イノベイティブ プロパティズ カンパニー | Film and method for manufacturing the same |
| JP2022138674A (en) * | 2021-03-10 | 2022-09-26 | 聚紡股▲ふん▼有限公司 | Film material having special tactile structure and method for producing the same |
| JP7287415B2 (en) * | 2021-03-31 | 2023-06-06 | 大日本印刷株式会社 | decorative material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS61202839A (en) * | 1985-03-06 | 1986-09-08 | 大日本印刷株式会社 | "uzukuri"-like grain decorative wood |
| JP2008087158A (en) * | 2006-09-29 | 2008-04-17 | Dainippon Printing Co Ltd | Decorative sheet |
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