JP5369575B2 - Decorative sheet - Google Patents
Decorative sheet Download PDFInfo
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- JP5369575B2 JP5369575B2 JP2008243121A JP2008243121A JP5369575B2 JP 5369575 B2 JP5369575 B2 JP 5369575B2 JP 2008243121 A JP2008243121 A JP 2008243121A JP 2008243121 A JP2008243121 A JP 2008243121A JP 5369575 B2 JP5369575 B2 JP 5369575B2
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- layer
- inorganic compound
- gloss
- resin
- decorative sheet
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- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 30
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 17
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 17
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 11
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 8
- 239000012798 spherical particle Substances 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 46
- 239000011241 protective layer Substances 0.000 claims description 18
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 3
- 239000002075 main ingredient Substances 0.000 abstract description 5
- 238000010186 staining Methods 0.000 abstract description 2
- -1 acrylic polyol Chemical class 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229940116351 sebacate Drugs 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 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 2
- 239000002023 wood Substances 0.000 description 2
- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 1
- WXHVQMGINBSVAY-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 WXHVQMGINBSVAY-UHFFFAOYSA-N 0.000 description 1
- PSMYELRXRQIDAX-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(2-hydroxy-3-tridecoxypropoxy)phenol Chemical compound OC1=CC(OCC(O)COCCCCCCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 PSMYELRXRQIDAX-UHFFFAOYSA-N 0.000 description 1
- SITYOOWCYAYOKL-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(3-dodecoxy-2-hydroxypropoxy)phenol Chemical compound OC1=CC(OCC(O)COCCCCCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 SITYOOWCYAYOKL-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- FLPKSBDJMLUTEX-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)(CCCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FLPKSBDJMLUTEX-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011229 interlayer Substances 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
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 229950002083 octabenzone Drugs 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
本発明は建築材の内外装に用いる化粧シートに関するものであり、特にはテーブル、食卓、キッチン等の水平面用途であって、グロス/マット調のツヤ調整による意匠性を有し、かつ表面の各種耐性に優れた化粧シートに関する。 The present invention relates to a decorative sheet used for the interior and exterior of building materials, particularly for horizontal surfaces such as tables, dining tables, kitchens, etc., having a design by gloss / matte gloss adjustment, and various surfaces The present invention relates to a decorative sheet having excellent resistance.
前記用途の化粧シートの構造としては、下地となる着色樹脂上に絵柄模様層を設け、各種耐性を付与するための透明樹脂層、表面保護層を設けたものが知られている。着色樹脂層や透明樹脂層としては、近年の環境問題を重視する傾向から塩化ビニル系樹脂ではなく複合オレフィン系樹脂フィルムなどが好適に用いられている。絵柄模様層としては木目等の意匠をグラビア印刷によりインキ層として設けたものが多いが、抽象柄といわれる幾何学模様を表現したものもある。 As a structure of the decorative sheet for the above-mentioned use, there is known a structure in which a pattern layer is provided on a colored resin as a base, and a transparent resin layer and a surface protective layer for imparting various resistances are provided. As the colored resin layer and the transparent resin layer, a composite olefin resin film or the like is preferably used instead of the vinyl chloride resin because of recent tendency to place importance on environmental problems. As the pattern layer, many designs such as grain are provided as an ink layer by gravure printing, but there are also those expressing a geometric pattern called an abstract pattern.
このような化粧シートにグロス調/マット調となるツヤを調整するためのツヤ調整層を適宜設けることが可能である。このようやツヤ調整層としては、絵柄模様層の上に設けて、適量の添加剤を添加した樹脂を、塗布厚を調整して塗布することで絵柄模様層を視認できる程度に化粧シートのツヤを調整することが可能となる。 Such a decorative sheet can be appropriately provided with a gloss adjusting layer for adjusting gloss that is glossy / matte. In this way, the gloss adjusting layer is provided on the pattern layer and coated with a resin to which an appropriate amount of additive has been added so that the pattern layer can be visually recognized by adjusting the coating thickness. Can be adjusted.
しかし、このようなツヤ調整層が表面側に設けられると、表面に添加剤が浮き出る影響で化粧シート表面の対汚染性、対傷付き性などに問題あるものとなってしまう。 However, when such a gloss adjusting layer is provided on the surface side, there is a problem in the antifouling property and the scratch resistance of the decorative sheet surface due to the influence of the additive floating on the surface.
本発明はこのような問題点を解決するためになされたものであり、すなわちその課題とするところは、優れたツヤ調整による意匠を有しつつも、表面の対汚染性、対傷付き性など各種耐性を有する化粧シートを提供することにある。 The present invention has been made in order to solve such problems, that is, the problem is that the surface has anti-staining properties, scratch resistance, etc. while having a design with excellent gloss adjustment. The object is to provide a decorative sheet having various resistances.
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、着色樹脂層上に絵柄模様層、透明樹脂層、ツヤ調整層、表面保護層を少なくともこの順に設けてなる化粧シートにおいて、前記ツヤ調整層がウレタン系樹脂を主剤として不定形無機化合物粒子を含有してなるものであり、前記不定形無機化合物粒子は無機酸化物で粒子形状が球状粒子で無く、前記不定形無機化合物粒子の外形の最大直径部分と最小直径部分の平均としてみた平均粒径が3〜10μmであり、前記表面保護層がシリコーンを含有したウレタン系樹脂を主剤として平均粒径1〜2μmの球状無機化合物粒子を1〜3重量%含有してなるものであることを特徴とする化粧シートである。 The present invention solves this problem. That is, the invention according to claim 1 is a makeup in which a pattern layer, a transparent resin layer, a gloss adjusting layer, and a surface protective layer are provided in this order on a colored resin layer. In the sheet, the gloss adjusting layer contains an amorphous inorganic compound particle containing a urethane resin as a main ingredient, and the amorphous inorganic compound particle is an inorganic oxide and the particle shape is not a spherical particle, but the amorphous shape. The average particle diameter as an average of the maximum diameter portion and the minimum diameter portion of the outer shape of the inorganic compound particles is 3 to 10 μm, and the surface protective layer is a spherical particle having an average particle diameter of 1 to 2 μm mainly composed of a urethane-based resin containing silicone. A decorative sheet comprising 1 to 3% by weight of inorganic compound particles.
本発明はその請求項1記載の発明により、ツヤ調整層と表面保護層に添加する無機化合物粒子の種類を異なるものとし、さらに表面保護層にシリコーンを添加することで、表面の対汚染性、対傷付き性など各種耐性を有するとともにツヤ調整による優れた意匠を有するものとなる。また、ツヤ調整層と表面保護層の層間強度も強く製造も容易な化粧シートを得ることが可能となる。 According to the first aspect of the present invention, the type of the inorganic compound particles added to the gloss adjusting layer and the surface protective layer is different, and by adding silicone to the surface protective layer, the surface contamination resistance is improved. It has various resistances such as scratch resistance and has an excellent design by adjusting gloss. In addition, it is possible to obtain a decorative sheet that has a high interlayer strength between the gloss adjusting layer and the surface protective layer and is easy to manufacture.
以下本発明を図面に基づき詳細に説明する。図1に本発明の化粧シートの一実施例の断面の形状を示す。着色樹脂層1の上に絵柄模様層2、透明樹脂層3、ツヤ調整層4、表面保護層5を設けてなる。 Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 shows the cross-sectional shape of one embodiment of the decorative sheet of the present invention. A pattern layer 2, a transparent resin layer 3, a gloss adjustment layer 4, and a surface protective layer 5 are provided on the colored resin layer 1.
本発明における着色樹脂層1としては、熱可塑性樹脂からなり、適宜顔料、酸化防止剤や耐候性処方を施したフィルムであるのが好適である。熱可塑性樹脂自体は、特に原材料を問わない。例えば、アクリルフィルム、オレフィン系フィルム、塩化ビニル系フィルム、ポリエステル系フィルム、エチレンビニルアセテートフィルム、ポリイミドフィルム、などが挙げられる。またフィルムによっては本発明の化粧シートを木質材料に接着することを想定し、接着性向上のために裏面にプライマー処理を施すことも必要に応じて行えばよい。厚さは、とくに限定されるものではないが、10〜300μm程度が最も汎用的に用いられる。 The colored resin layer 1 in the present invention is preferably a film made of a thermoplastic resin and appropriately applied with a pigment, an antioxidant and a weather resistance formulation. The thermoplastic resin itself is not particularly limited as a raw material. For example, an acrylic film, an olefin film, a vinyl chloride film, a polyester film, an ethylene vinyl acetate film, a polyimide film, and the like can be given. Further, depending on the film, it is assumed that the decorative sheet of the present invention is adhered to the wood material, and the primer treatment may be performed on the back surface as necessary to improve the adhesion. The thickness is not particularly limited, but about 10 to 300 μm is most commonly used.
本発明における絵柄模様層2としては、絵柄を形成するのはインキであり、顔料およびバインダーは適宜選定すればよい。フィルムとの接着性を考慮し、適宜原材料を選定すればよい。例えば、イソシアネート硬化剤と活性水素を有したバインダーを混合させた塗工液が、接着性の点では優位である。絵柄模様層を施す方法は、従来から行われているグラビア印刷が好適であるが、スクリーン印刷、オフセット印刷、グラビアオフセット印刷、フレキソ印刷などとくに印刷手法は問わない。 As the pattern layer 2 in the present invention, it is ink that forms the pattern, and the pigment and the binder may be appropriately selected. A raw material may be appropriately selected in consideration of adhesiveness with the film. For example, a coating liquid in which an isocyanate curing agent and a binder having active hydrogen are mixed is superior in terms of adhesiveness. Conventionally, the gravure printing performed conventionally is suitable for the method of applying the pattern pattern layer, but the printing method is not particularly limited, such as screen printing, offset printing, gravure offset printing, flexographic printing.
本発明における透明樹脂層3としては、熱可塑性樹脂フィルムであればとくに限定されるものではない。オレフィン系フィルムや塩化ビニル系フィルム、非晶質ポリエステルフィルムに関しては、加熱軟化による各種加工適性を有しているので好適である。厚さは限定されるものではないが、10μm〜300μmが好適である。前記絵柄模様層2を設けた着色樹脂層1と透明樹脂層3とを積層する方法はとくに限定するものではなく、選択された樹脂やインキに応じて適宜積層すればよい。例えば塩化ビニルフィルムに塩化ビニル酢酸ビニル共重合樹脂系インキで印刷された場合には、透明塩化ビニルとは熱圧で積層すればよい。また、オレフィン系フィルムにウレタン系インキにて印刷されている場合は、ウレタン系のドライラミネート接着剤で、透明印刷オレフィンフィルムと積層すればよい。 The transparent resin layer 3 in the present invention is not particularly limited as long as it is a thermoplastic resin film. Olefin-based films, vinyl chloride-based films, and amorphous polyester films are suitable because they have various processability by heat softening. Although thickness is not limited, 10 micrometers-300 micrometers are suitable. The method of laminating the colored resin layer 1 provided with the pattern layer 2 and the transparent resin layer 3 is not particularly limited, and may be appropriately laminated according to the selected resin or ink. For example, when a vinyl chloride film is printed with a vinyl chloride vinyl acetate copolymer resin ink, the transparent vinyl chloride may be laminated with heat pressure. Moreover, what is necessary is just to laminate | stack with a transparent printing olefin film with a urethane-type dry laminate adhesive, when printing on the olefin-type film with urethane-type ink.
本発明におけるツヤ調整層4としては、ウレタン系樹脂を主剤として、不定形無機化合物粒子を含有している。ウレタン系樹脂としては、不定形無機化合物粒子の脱落を防ぎ塗膜中に保持できる様な、適度の柔軟性が要求されるアクリルポリオールとイソシアネート化合物との反応生成物で、アクリルウレタン樹脂を使用することが望ましい。 The gloss adjusting layer 4 in the present invention contains an amorphous inorganic compound particle with a urethane resin as a main ingredient. The urethane resin is a reaction product of an acrylic polyol and an isocyanate compound that requires moderate flexibility so that the amorphous inorganic compound particles can be prevented from falling off and retained in the coating film, and an acrylic urethane resin is used. It is desirable.
前記アクリルポリオールとしては、例えば(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチル等の(メタ)アクリレートモノマーに、ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート等の水酸基含有(メタ)アクリレートモノマーと、必要に応じてこれらと共重合可能な、例えば(メタ)アクリロニトリル、(メタ)アクリル酸、スチレン、α−メチルスチレン、ビニルトルエン等の重合性モノマーとを共重合させてなる、アクリル骨格を主鎖とし、側鎖に水酸基を有するポリマーである。 Examples of the acrylic polyol include (meth) acrylate monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like. A hydroxyl group-containing (meth) acrylate monomer and a copolymerizable monomer such as (meth) acrylonitrile, (meth) acrylic acid, styrene, α-methylstyrene, vinyltoluene, etc. This polymer is a polymer having an acrylic skeleton as the main chain and a hydroxyl group in the side chain.
前記イソシアネート化合物としては、たとえはトリレンジイソシアネート(TDI)、ジフェニルメタンジイソシアネート(MDI)、キシリレンジイソシアネート(XDI)、ヘキサメチレンジイソシアネート(HDI)、イソホロンジイソシアネート(IPDI)等が用いられ、適宜選定すればよい。 Examples of the isocyanate compound include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and the like. .
前記不定形無機化合物粒子としては、シリカやアルミナなどの無機酸化物が好適に用いられ、粒子形状としては球状粒子で無ければよく、鱗片状、多角形状など適宜使用可能であるが、特に限定されるものではない。球状粒子であるとツヤ調整の効果が十分に発現できず、また添加量が好適な範囲でのツヤ調整が困難なものとなる。平均粒径は、不定形であると測定が困難であるが、おおよそ外形の最大直径部分と最小直径部分の平均として考えればよく、粒子全体としての平均が3〜10μmのものが用いられる。これより外れると添加量が好適な範囲でのツヤ調整が困難なものとなる。 As the amorphous inorganic compound particles, inorganic oxides such as silica and alumina are preferably used, and the particle shape is not limited to spherical particles, and can be used as appropriate, such as scaly and polygonal shapes, but is not particularly limited. It is not something. If it is a spherical particle, the effect of adjusting the gloss cannot be sufficiently exhibited, and it becomes difficult to adjust the gloss within a suitable amount of addition. The average particle diameter is difficult to measure if it is indefinite, but it can be considered as an average of the maximum diameter portion and the minimum diameter portion of the outer shape, and the average particle size is 3 to 10 μm. If it deviates from this, it will become difficult to adjust the gloss within a suitable amount of addition.
本発明における表面保護層5としては、前記シリコーンを含有したウレタン系樹脂を主剤として平均粒径1〜2μmの球状無機化合物粒子を1〜3重量%含有してなるものが用いられる。 As the surface protective layer 5 in the present invention, one containing 1 to 3% by weight of spherical inorganic compound particles having an average particle diameter of 1 to 2 [mu] m with the urethane-based resin containing silicone as a main ingredient is used.
前記シリコーンを添加したウレタン系樹脂としては、シリコーン成分を表層に出ていればよく、方法は特に問わないが、例えば、前記ウレタン系樹脂にシリコーンオイルを添加して、表面上にブリードさせることで、耐汚染性を有する表面保護層を作成することができる。また、前記ウレタン樹脂を成形する際に用いる、アクリルポリオールの側鎖にオルガノポリシロキサン基が導入し、ポリイソシアネート化合物と架橋させることで、シリコーン変性アクリルウレタン層を作成することでも、耐汚染性を有する表面保護層を作成することができる。 The urethane resin to which the silicone is added is not particularly limited as long as the silicone component is exposed on the surface layer. For example, by adding silicone oil to the urethane resin and bleed on the surface. A surface protective layer having stain resistance can be produced. Also, when the urethane resin is molded, an organopolysiloxane group is introduced into the side chain of the acrylic polyol and crosslinked with the polyisocyanate compound, thereby creating a silicone-modified acrylic urethane layer. The surface protective layer which has can be created.
前記平均粒径1〜2μmの球状無機化合物粒子としては、珪素化合物であることが望ましく、水和性があればシリコーン変性樹脂との相性が低下しやすい。添加量は1〜3重量%の範囲が好適であり、表面保護層の厚みはこれら粒径と添加量とにより調整すればよい。 The spherical inorganic compound particles having an average particle diameter of 1 to 2 μm are preferably silicon compounds, and if they have hydration properties, the compatibility with the silicone-modified resin tends to decrease. The addition amount is preferably in the range of 1 to 3% by weight, and the thickness of the surface protective layer may be adjusted by the particle size and the addition amount.
また、ツヤ調整層4及び表面保護層5にはそのほかに、耐候性の処方を行うため、紫外線吸収剤(ベンゾトリアゾール系、トリアジン系、ベンゾフェノン系など)やヒンダードアミン系光安定剤を適宜添加する。添加部数は所望の耐候性に応じて添加すればよいが、樹脂固形分に対して0.1%〜50%、好ましくは1%〜30%である。 In addition to the gloss adjusting layer 4 and the surface protective layer 5, an ultraviolet absorber (benzotriazole, triazine, benzophenone, etc.) or a hindered amine light stabilizer is appropriately added in order to perform weather resistance prescription. The added part may be added according to the desired weather resistance, but is 0.1% to 50%, preferably 1% to 30%, based on the resin solid content.
ベンゾトリアゾール系紫外線吸収剤としては、2−(2−ヒドロキシ−5−t−ブチルフェニル)−2H−ベンゾトリアゾール、2−(5−メチル−2−ヒドロキシフェニル)ベンゾトリアゾール、2−[2−ヒドロキシ−3,5−ビス(α,α−ジメチルベンジル)フェニル]−2H−ベンゾトリアゾール,2−(3,5−ジ−t−ブチル−2−ヒドロキシフェニル)ベンゾトリアゾール、2−(3−t−ブチル−5−メチル−2−ヒドロキシフェニル)−5−クロロベンゾトリアゾール、2−(3,5−ジ−t−ブチル−2−ヒドロキシフェニル)−5−クロロベンゾトリアゾール、2−(3,5−ジ−t−アミル−2−ヒドロキシフェニル)ベンゾトリアゾール,2−(2’−ヒドロキシ−5’−t−オクチルフェニル)ベンゾトリアゾールなどやこれらの混合物、変性物、重合物、誘導体が挙げられる。 Examples of the benzotriazole ultraviolet absorber include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy −3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t- Butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5- Di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazo And the like, mixtures thereof, modified products, polymers, and derivatives.
また、トリアジン系紫外線吸収剤としては、2−(4,6−ジフェニル−1,3,5−トリアジン−2−イル)−5−[(ヘキシル)オキシ]−フェノール、2−[4−[(2−ヒドロキシ−3−ドデシルオキシプロピル)オキシ]−2−ヒドロキシフェニル]−4,6−ビス(2,4−ジメチルフェニル)−1,3,5−トリアジン、2−[4−[(2−ヒドロキシ−3−トリデシルオキシプロピル)オキシ]−2−ヒドロキシフェニル]−4,6−ビス(2,4ジメチルフェニル)−1,3,5−トリアジン、2,4−ビス(2,4−ジメチルフェニル)−6−(2−ヒドロキシ−4−イソ−オクチルオキシフェニル)−s−トリアジンなどやこれらの混合物、変性物、重合物、誘導体が挙げられる。 Examples of triazine ultraviolet absorbers include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4-[( 2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2- Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4dimethylphenyl) -1,3,5-triazine, 2,4-bis (2,4-dimethyl) Phenyl) -6- (2-hydroxy-4-iso-octyloxyphenyl) -s-triazine and the like, and mixtures, modified products, polymers, and derivatives thereof.
また、ベンゾフェノン系紫外線吸収剤としては、オクタベンゾンや変性物、重合物、誘導体が挙げられる。またイソシアネート添加による架橋によって、樹脂成分と結合を望めるため、紫外線吸収剤は水酸基を有したものが適している。 Examples of the benzophenone-based ultraviolet absorber include octabenzone, modified products, polymers, and derivatives. In addition, since a bond with a resin component can be expected by crosslinking by addition of an isocyanate, a UV absorber having a hydroxyl group is suitable.
また、樹脂自体の光・熱・水などによる劣化を防止するため、ヒンダードアミン系光安定剤を適宜添加する。添加部数は所望の耐候性に応じて添加すればよいが、樹脂固形分に対して0.1〜50重量%、好ましくは1〜30重量%である。具体的には、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)[[3,5−ビス(1,1−ジメチルエチル)−4−ヒドリキシフェニル]メチル]ブチルマロネート、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジニル)セバケート、メチル(1,2,2,6,6−ペンタメチル−4−ポペリジニル)セバケート、デカン二酸ビス(2,2,6,6−テトラメチル−1(オクチルオキシ)−4−ピペリジニル)エステルなどやこれらの混合物、変性物、重合物、誘導体などが挙げられる。 In addition, a hindered amine light stabilizer is appropriately added in order to prevent the resin itself from being deteriorated by light, heat, water or the like. The added part may be added according to the desired weather resistance, but is 0.1 to 50% by weight, preferably 1 to 30% by weight, based on the resin solid content. Specifically, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate Bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-popperidinyl) sebacate, bis (2,2, decanedioic acid) 6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester and the like, mixtures thereof, modified products, polymers, derivatives and the like.
着色樹脂層として、厚さ70μmの着色ポリオレフィン系フィルムの上に、2液硬化型ウレタン樹脂系グラビアインキで木目柄の絵柄模様層と、2液硬化型ポリエステルウレタン系接着剤介して、透明樹脂層としての厚さ80μmの透明ポリオレフィン系樹脂を共押出しにより積層し、押出しと同時に表面に導管柄のエンボスを施した。 As a colored resin layer, a transparent resin layer is formed on a colored polyolefin film having a thickness of 70 μm with a two-component curable urethane resin gravure ink and a wood pattern patterned layer and a two-component curable polyester urethane adhesive. A transparent polyolefin resin having a thickness of 80 μm was laminated by co-extrusion, and at the same time as extrusion, the surface was embossed with a conduit handle.
前記透明樹脂層の上に、ツヤ調整層として、アクリルポリオール100重量部、イソシアネート硬化剤5重量部、艶消し剤として不定形シリカ2.5重量部を配合した塗工液をグラビアコートにて乾燥後の塗布量が3.0g/m2となるように塗工した。 A coating liquid containing 100 parts by weight of an acrylic polyol, 5 parts by weight of an isocyanate curing agent, and 2.5 parts by weight of amorphous silica as a matting agent is dried with a gravure coat on the transparent resin layer. The coating was performed so that the subsequent coating amount was 3.0 g / m 2 .
前記ツヤ調整層の上に、保護層としてアクリルポリオール100重量部、イソシアネート硬化剤5重量部、シリコーンオイル3重量部、平均粒径2μmの球状シリカ2重量部を配合した塗工液をグラビアコートにて乾燥後の塗布量が3.0g/m2となるように塗工して化粧シートを得た。 A gravure coating is a coating liquid in which 100 parts by weight of an acrylic polyol, 5 parts by weight of an isocyanate curing agent, 3 parts by weight of silicone oil, and 2 parts by weight of spherical silica having an average particle diameter of 2 μm are blended as a protective layer on the gloss adjusting layer. Then, coating was performed such that the coating amount after drying was 3.0 g / m 2 to obtain a decorative sheet.
<比較例1>
前記実施例1において、保護層に無機化合物のシリカを添加しなかった以外は実施例1と同様にして化粧シートを得た。
<Comparative Example 1>
In Example 1, a decorative sheet was obtained in the same manner as Example 1 except that the inorganic compound silica was not added to the protective layer.
<比較例2>
前記実施例1において、保護層に添加する球状シリカの平均粒経を6μmのものを用いた以外は実施例1と同様にして化粧シートを得た。
<Comparative example 2>
A decorative sheet was obtained in the same manner as in Example 1 except that the average particle size of spherical silica added to the protective layer in Example 1 was 6 μm.
<化粧板作成>
厚み2.7mmのMDF(中密度繊維板)の表面に、接着剤として2液水性エマルジョン接着剤(中央理化工業(株)製「リカボンド」(「BA−10L」と「BA−11B」を100重量部:5重量部で混合)をウエット状態で70g/m2に塗工したあと、ラミネータにて前記化粧シート実施例1、比較例1、比較例2と貼り合わせ、化粧板を得た。
<Making a decorative board>
On the surface of a 2.7 mm thick MDF (medium density fiberboard), a two-component aqueous emulsion adhesive (“Rikabond” (“BA-10L” and “BA-11B” manufactured by Chuo Rika Kogyo Co., Ltd.) is used as an adhesive. (Parts by weight: mixed at 5 parts by weight) was applied in a wet state to 70 g / m 2 , and then bonded to the decorative sheet Example 1, Comparative Example 1, and Comparative Example 2 with a laminator to obtain a decorative board.
<性能評価方法>
性能評価は、各実施例及び比較例で得た化粧版について、マジックインキ拭き取り、耐スチールウール性にて評価した。
<Performance evaluation method>
Performance evaluation evaluated the decorative plate obtained in each Example and the comparative example by wiping off magic ink and resistance to steel wool.
<マジックインキ拭き取り>
化粧板の表面に黒色速乾性インキ(速乾性筆記具<JIS S 6037(1964)に定めたもの>)で幅10mmの線を引き、1分間放置した後、ティッシュペーパーで空拭きした。その工程を5回行った後、目視にてマジックの拭き取り具合を確認した。○:マジック残り無し、×:マジック残りありで評価
<Magic ink wiping>
A line having a width of 10 mm was drawn on the surface of the decorative board with a black quick-drying ink (fast-drying writing instrument <specified in JIS S 6037 (1964)>), left for 1 minute, and then wiped with tissue paper. After the process was performed five times, the wiping condition of the magic was visually confirmed. ○: No magic remaining, ×: Evaluation with magic remaining
<耐スチールウール試験>
化粧板の表面に50g荷重のスチールウール(#0000)にて20往復させる。その後、目視にて傷の付き具合を確認する。○:傷無し、×:傷有りで評価。
以上の結果を表1にまとめる。
<Steel wool resistance test>
It is made to reciprocate 20 times with the steel wool (# 0000) of a 50-g load on the surface of a decorative board. Then, visually check the degree of damage. ○: No scratch, ×: Scratched.
The results are summarized in Table 1.
本発明の化粧シートは、特にテーブル、食卓、キッチン等の水平面用途に利用可能である。 The decorative sheet of the present invention can be used particularly for horizontal surfaces such as tables, dining tables, and kitchens.
1…着色樹脂層
2…絵柄模様層
3…透明樹脂層
4…ツヤ調整層
5…表面保護層
DESCRIPTION OF SYMBOLS 1 ... Colored resin layer 2 ... Pattern pattern layer 3 ... Transparent resin layer 4 ... Gloss adjustment layer 5 ... Surface protective layer
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JPH0924577A (en) * | 1995-07-10 | 1997-01-28 | Nkk Corp | Precoating metal plate with excellent stain resistance, flaw resistance and durability |
JP3951533B2 (en) * | 2000-01-11 | 2007-08-01 | 凸版印刷株式会社 | Veneer |
JP4578756B2 (en) * | 2002-01-16 | 2010-11-10 | 凸版印刷株式会社 | Cosmetic material |
JP2006016528A (en) * | 2004-07-02 | 2006-01-19 | Dainippon Ink & Chem Inc | Coating composition for decorative sheet and decorative sheet |
JP4978226B2 (en) * | 2006-02-28 | 2012-07-18 | 大日本印刷株式会社 | Decorative sheet |
JP4961964B2 (en) * | 2006-11-15 | 2012-06-27 | 凸版印刷株式会社 | Decorative sheet and method for producing the same |
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