JP3913061B2 - Printed resin film for decorative plate lamination, decorative plate laminated with the resin film, unit bath using the decorative plate, refrigerator door - Google Patents
Printed resin film for decorative plate lamination, decorative plate laminated with the resin film, unit bath using the decorative plate, refrigerator door Download PDFInfo
- Publication number
- JP3913061B2 JP3913061B2 JP2001539677A JP2001539677A JP3913061B2 JP 3913061 B2 JP3913061 B2 JP 3913061B2 JP 2001539677 A JP2001539677 A JP 2001539677A JP 2001539677 A JP2001539677 A JP 2001539677A JP 3913061 B2 JP3913061 B2 JP 3913061B2
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- printing
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- Expired - Lifetime
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- 229920005989 resin Polymers 0.000 title claims description 431
- 239000011347 resin Substances 0.000 title claims description 431
- 238000003475 lamination Methods 0.000 title claims description 37
- 239000010410 layer Substances 0.000 claims description 275
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 114
- -1 polybutylene terephthalate Polymers 0.000 claims description 106
- 229920001225 polyester resin Polymers 0.000 claims description 58
- 239000004645 polyester resin Substances 0.000 claims description 58
- 238000010030 laminating Methods 0.000 claims description 43
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 42
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 42
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 25
- 238000002844 melting Methods 0.000 claims description 21
- 230000008018 melting Effects 0.000 claims description 21
- 239000004840 adhesive resin Substances 0.000 claims description 20
- 229920006223 adhesive resin Polymers 0.000 claims description 20
- 239000000049 pigment Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- 238000004049 embossing Methods 0.000 claims description 16
- 239000012790 adhesive layer Substances 0.000 claims description 15
- 229920000554 ionomer Polymers 0.000 claims description 14
- 238000009998 heat setting Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229920000515 polycarbonate Polymers 0.000 claims description 8
- 239000004417 polycarbonate Substances 0.000 claims description 8
- 229920006290 polyethylene naphthalate film Polymers 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 2
- 238000009824 pressure lamination Methods 0.000 claims 2
- 239000000976 ink Substances 0.000 description 31
- 238000002156 mixing Methods 0.000 description 26
- 238000001125 extrusion Methods 0.000 description 25
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 19
- 229910000831 Steel Inorganic materials 0.000 description 17
- 239000010959 steel Substances 0.000 description 17
- 229920000915 polyvinyl chloride Polymers 0.000 description 12
- 239000004800 polyvinyl chloride Substances 0.000 description 12
- 239000006071 cream Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229920000180 alkyd Polymers 0.000 description 9
- 238000013461 design Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000008602 contraction Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000011112 polyethylene naphthalate Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000002341 toxic gas Substances 0.000 description 3
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- MKYQRMFHQALHNR-UHFFFAOYSA-N 6,11-dioxatricyclo[11.3.1.14,16]octadeca-1(16),2,4(18),13(17),14-pentaene-5,12-dione Chemical compound C1=C(C=C2)C(=O)OCCCCOC(=O)C3=CC=C1C2=C3 MKYQRMFHQALHNR-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- MFPOUZMIWRBOON-UHFFFAOYSA-N [Mo].[Co].[Zn] Chemical compound [Mo].[Co].[Zn] MFPOUZMIWRBOON-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-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
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 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
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- PJFPFKALGCPVLG-UHFFFAOYSA-N cyclohexane;3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound C1CCCCC1.O=C1OCCOC(=O)C2=CC=C1C=C2 PJFPFKALGCPVLG-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/10—Applying flat materials, e.g. leaflets, pieces of fabrics
- B44C1/105—Applying flat materials, e.g. leaflets, pieces of fabrics comprising an adhesive layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/10—Applying flat materials, e.g. leaflets, pieces of fabrics
- B44C1/14—Metallic leaves or foils, e.g. gold leaf
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C5/00—Processes for producing special ornamental bodies
- B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
- B44C5/0446—Ornamental plaques, e.g. decorative panels, decorative veneers bearing graphical information
Landscapes
- Laminated Bodies (AREA)
Description
【技術分野】
【０００１】
本発明は、化粧板積層用印刷樹脂フィルム、その樹脂フィルムを積層した化粧板、及びその化粧板を用いたユニットバス、冷蔵庫、冷蔵庫のドア、カーテンレール、洗面ユニット、洗濯機、システムキッチン、間仕切り、壁パネル、室内ドア、室内収納庫、蛍光灯の反射板、オーディオビジュアル機器の外板、電子レンジの外板、オーブンの外板、ファンヒーターの外板、ストーブの外板、エアコンディショナー等の各種機器の外板に関する。また、家具、エレベータ、建築物等の内装品に適用される、特に印刷模様を要求される用途に適した化粧板積層用樹脂フィルムおよびその樹脂フィルムを積層した化粧板に関する。
【背景技術】
【０００２】
従来、各種家具類や建築内装材等に使用される化粧板としては、
（１）基材となる樹脂層に通常の方法を用いて印刷を施し、印刷層の表面保護のために、アクリル系樹脂、ポリエステル系樹脂等のコート層を設けた化粧フィルム、
（２）基材となる樹脂層に印刷を施した後、透明な二軸延伸ポリエステルフィルムを接着剤層を介して積層した化粧フィルム、
（３）ポリ塩化ビニルフィルムの上に通常の方法を用いて印刷を施した後、透明なポリ塩化ビニルフィルムや二軸延伸ポリエステルフィルムを積層した化粧フィルム、
などの化粧フィルムを、接着剤を介して亜鉛めっき鋼板などの基板に積層したものが知られている。
【発明が解決しようとする課題】
【０００３】
しかしながら、上記（１）の化粧フィルムを積層した化粧板は、化粧フィルムの強度が不十分であるため、折り曲げ加工などを施す場合、加工時に化粧フィルムが割れたり、折り曲げ部のインキが剥離し易いという問題があり、折り曲げ加工などを施す用途には適していない。また、上記（２）の化粧フィルムを積層した化粧板は、耐汚染性、耐溶剤性などの表面物性には優れているが、表面フィルムの柔軟性に乏しく、軟化温度が高いためエンボス加工を施した場合、エンボスが入り難い。
さらに、上記（３）の化粧フィルムを積層した化粧板は、ポリ塩化ビニルフィルムが用いられているため、耐汚染性、耐溶剤性などの表面物性が劣り、また焼却して廃棄処理する際に、塩化水素ガスのような有毒ガスおよびそれに起因する有害物質が発生して環境を汚染したり、焼却する際に焼却炉を傷めたりするおそれがあるなどの問題を抱えている。
また、上記（２）や（３）の化粧フィルムのように、二軸延伸ポリエステルフィルムを表層に積層した化粧フィルムは、鋼板に熱圧着により積層する際に、基材樹脂層の融点近傍の熱履歴を受けるために熱収縮が生じたり、融着が生じたりする問題点がある。
本発明は、従来のポリ塩化ビニル樹脂フィルムやポリオレフィン樹脂フィルムを用いた高鮮映性化粧シートの表面樹脂層に用いられている二軸延伸ポリエステル樹脂フィルムの加工性を確保した化粧板積層用印刷樹脂フィルムを提供することを目的とする。
また、本発明は、従来のポリ塩化ビニル樹脂フィルムやポリオレフィン樹脂フィルムを用いた化粧シートと同等以上の印刷鮮映性を有する意匠性に優れた絵柄模様を有する化粧板積層用印刷樹脂フィルムを提供することを目的とする。
さらに、本発明は、環境適性に優れ、耐汚染性、耐溶剤性などの表面物性、さらには、加工性にも優れた化粧板積層用印刷樹脂フィルムおよびその樹脂フィルムを積層した化粧板を提供することを目的とする。
【発明の開示】
【０００４】
本発明の請求項１の化粧板積層用印刷樹脂フィルムは、
最表層が透明な二軸延伸ポリエステル樹脂フィルムであり、その下層に印刷層、基材樹脂層、接着樹脂層を順次積層してなる樹脂フィルムであって、
ポリブチレンテレフタレート、ポリトリメチレンテレフタレート、又は変性ポリブチレンテレフタレートからなる基材樹脂層と接着樹脂層と、を積層し、
前記基材樹脂層の上面に印刷層を設け、
前記印刷層が二軸延伸ポリエステル樹脂フィルムと接するようにして重ね合わせ、
熱ロール間に通して圧着積層してなることを特徴とする。
請求項２の化粧板積層用印刷樹脂フィルムは、
最表層が透明な二軸延伸ポリエステル樹脂フィルムであり、その下層に基材樹脂層、印刷層、着色樹脂層、接着樹脂層を順次積層してなる樹脂フィルムであって、
着色樹脂層の上に印刷層を設け、
その上にポリブチレンテレフタレート、ポリトリメチレンテレフタレート、又は変性ポリブチレンテレフタレートからなる基材樹脂層を重ね合わせて、
熱ロール間に通して圧着積層して予備積層フィルムとし、
さらにその上に直接または接着剤層を介して二軸延伸ポリエステル樹脂フィルムを重ね合わせて、熱ロール間に通して圧着積層してなることを特徴とする。
請求項３の化粧板積層用印刷樹脂フィルムは、
最表層が透明な二軸延伸ポリエステル樹脂フィルムであり、その下層に印刷層、基材樹脂層を順次積層してなる樹脂フィルムであって、
ポリブチレンテレフタレート、ポリトリメチレンテレフタレート、又は変性ポリブチレンテレフタレートからなる基材樹脂層の上面に、二軸延伸ポリエステル樹脂フィルムの下面に設けた印刷層を重ね合わせ、熱ロールに通して圧着積層してなることを特徴とする。
請求項４の化粧板積層用印刷樹脂フィルムは、
最表層が透明な二軸延伸ポリエステル樹脂フィルムであり、その下層に基材樹脂層、印刷層、着色樹脂層、接着樹脂層を順次積層してなる樹脂フィルムであって、
着色樹脂層の上に印刷層を施し、その上にポリブチレンテレフタレート、ポリトリメチレンテレフタレート、又は変性ポリブチレンテレフタレートからなる基材樹脂層を重ね合わせ、熱ロールに通して圧着積層して予備積層フィルムとし、
さらにその上に直接または接着剤層を介して二軸延伸ポリエステル樹脂フィルムを重ね合わせて、熱ロール間に通して圧着積層してなることを特徴とする。
請求項５の化粧板積層用印刷樹脂フィルムは、請求項１〜４のいずれかにおいて、前記印刷層が、絵柄印刷層である上層と、前記基材樹脂層全面を隠蔽し、かつ前記絵柄印刷層の印刷下地色を付与するベタ印刷層である下層とからなることを特徴とする。
請求項６の化粧板積層用印刷樹脂フィルムは、請求項１〜４のいずれかにおいて、
前記印刷層が絵柄印刷層またはベタ印刷層からなることを特徴とする。
請求項７の化粧板積層用印刷樹脂フィルムは、請求項１〜４のいずれかにおいて、
前記基材樹脂層がエンボス加工を施され、該エンボス加工により形成されたエンボス凹部にインキが充填されてなる印刷層を有することを特徴とする。
請求項８の化粧板積層用印刷樹脂フィルムは、請求項１〜４のいずれかにおいて、
前記二軸延伸ポリエステル樹脂フィルムの熱固定温度Ｔｈｓ（℃）、融点Ｔｍ１（℃）、および前記基材樹脂の融点Ｔｍ２（℃）が、下記の関係式、 Ｔｍ２−３５≦Ｔｈｓ≦Ｔｍ２＋１５≦Ｔｍ１を満足することを特徴とする。
請求項９の化粧板積層用印刷樹脂フィルムは、請求項１〜４、又は８のいずれかにおいて、前記二軸延伸ポリエステル樹脂フィルムが、二軸延伸ポリエチレンテレフタレートフィルム、二軸延伸ポリエチレンナフタレートフィルム、又は変性ポリエチレンテレフタレートの二軸延伸フィルムであることを特徴とする。
請求項１０の化粧板積層用印刷樹脂フィルムは、請求項２又は４において、
前記着色樹脂層が着色顔料を混練したポリエステル樹脂からなることを特徴とする。
請求項１１の化粧板積層用印刷樹脂フィルムは、請求項１において、
前記基材樹脂層が、ポリブチレンテレフタレート、ポリトリメチレンテレフタレート、 又は変性ポリブチレンテレフタレートからなる基材樹脂層に変えて、変性ポリブチレンテレフタレートとポリブチレンテレフタレートの２層樹脂からなることを特徴とする。
請求項１２の化粧板積層用印刷樹脂フィルムは、請求項１又は１０において、
前記基材樹脂層が、ポリブチレンテレフタレート、ポリトリメチレンテレフタレート、又は変性ポリブチレンテレフタレートからなる基材樹脂層に変えて、ポリブチレンテレフタレートと変性ポリブチレンテレフタレートのブレンド樹脂であるか、ポリブチレンテレフタレートと変性ポリエチレンテレフタレートのブレンド樹脂であるか、ポリブチレンテレフタレートとポリエチレンテレフタレートのブレンド樹脂であるか、ポリブチレンテレフタレートとポリカーボネートのブレンド樹脂であるか、又は、ポリブチレンテレフタレートとポリトリメチレンテレフタレートのブレンド樹脂であるか、を特徴とする。
請求項１３の化粧板積層用印刷樹脂フィルムは、請求項１〜４、９のいずれかにおいて、
前記二軸延伸ポリエステル樹脂フィルムにエンボス加工が施されていることを特徴とする。
請求項１４の化粧板積層用印刷樹脂フィルムは、請求項１〜１３のいずれかにおいて、
前記二軸延伸ポリエステル樹脂フィルムの上にさらに艶調整層を設けたことを特徴とする。
請求項１５の化粧板積層用印刷樹脂フィルムは、請求項１または２において、
前記接着樹脂層が変性ポリエチレンテレフタレートからなることを特徴とする。
請求項１６の化粧板積層用印刷樹脂フィルムは、請求項１または２において、
前記接着樹脂層が、樹脂成分中にアイオノマーを含有した樹脂からなることを特徴とする。
請求項１７の化粧板積層用印刷樹脂フィルムは、請求項１〜４のいずれかにおいて、
前記基材樹脂層が、樹脂成分中にアイオノマーを含有した樹脂からなることを特徴とする。
請求項１８の化粧板積層用印刷樹脂フィルムは、請求項２または４において、
前記着色樹脂層が、樹脂成分中にアイオノマーを含有した樹脂からなることを特徴とする。
請求項１９の化粧板は、樹脂フィルムを積層する基板の少なくとも片面に、請求項１〜１８のいずれかに記載の化粧板積層用印刷樹脂フィルムを積層したことを特徴とする。
請求項２０の化粧板は、請求項１９において、前記基板と前記化粧板積層用印刷樹脂フィルムの間に接着剤層を介して積層したことを特徴とする。
請求項２１の化粧板は、請求項１９又は２０において、前記基板が金属板であることを特徴とする。
請求項２２のユニットバス又は冷蔵庫ドアは、請求項１９〜２１のいずれかに記載の化粧板を用いてなることを特徴とする。
【発明を実施するための最良の形態】
【０００５】
本発明の発明者等は、化粧板に用いられる複数の樹脂層からなる化粧板積層用印刷樹脂フィルムにおいて、鮮映性を高めるために用いられてきた最表面の樹脂層として用いる二軸延伸ポリエステル樹脂フィルムの加工性を向上させるために鋭意検討した。その結果、二軸延伸ポリエステル樹脂フィルムの熱固定温度Ｔｈｓ（℃）と、そのフィルムを構成するポリエステル樹脂の融点Ｔｍ１（℃）と、その下部に設けられた基材樹脂層の樹脂の融点Ｔｍ２（℃）が下記の関係式 Ｔｍ２−３５≦Ｔｈｓ≦Ｔｍ２＋１５≦Ｔｍ１を満足し、さらに好ましくは二軸延伸ポリエステル樹脂フィルムと基材樹脂層の厚み比を１：１０〜６：１０の範囲とすることにより、二軸延伸ポリエステル樹脂フィルム積層板の加工性を向上させることができることを見出した。
【０００６】
さらに、焼却時に有毒ガスおよびそれに起因する有害物質が発生して環境を汚染するおそれがあるポリ塩化ビニル樹脂フィルムに替わる、高鮮映性および意匠性に優れた絵柄模様を有し、かつ耐汚染性、耐溶剤性などの表面物性に優れた化粧板に積層する印刷可能な樹脂フィルムについて鋭意検討した。
【０００７】
その結果、接着樹脂層として共重合ポリエステル樹脂フィルムを用い、選択的に積層される着色樹脂層ならびに印刷下地となる基材樹脂層として、樹脂の固有粘度が１．０〜２．０のポリブチレンテレフタレートフィルム、ポリトリメチレンテレフタレートフィルム、変性ポリブチレンテレフタレートフィルム、もしくはそれらの２層フィルムやブレンド樹脂フィルムを用いると好ましいことを見出した。そして、それらのフィルムに絵柄印刷層またはベタ印刷層、もしくは絵柄印刷層とベタ印刷層を形成し、さらに透明な二軸延伸ポリエステル樹脂フィルムを最表層として用い、上記フィルムを下から順次積層することにより、前述の要求特性を満足する化粧板に積層する樹脂フィルムが得られることを見出した。
【０００８】
また、基材樹脂層にエンボス加工を施してエンボス凹部を形成した後、ワイピング法を用いてエンボス凹部にインキを充填してなるワイピング印刷層を設けてもよい。
さらに、上記の樹脂フィルムを金属板に積層した化粧板は、樹脂フィルムの上記の優れたフィルム物性に加えて、意匠性にも優れていることを見出した。
以下に本発明についてその内容を説明する。図２〜図４に本発明の化粧板積層用印刷樹脂フィルムの一実施例を断面図で示す。図５及び図６に本発明の化粧板の一実施例を断面図で示す。図中の各符号はそれぞれ次のものを指す。
【０００９】
本発明の化粧板積層用印刷樹脂フィルム１は、図２（ｃ）および（ｄ）に示すように、二軸延伸ポリエステル樹脂フィルム１０の裏面全面に絵柄印刷層６ａとベタ印刷層６ｂが設けられ、その下面に基材樹脂層７が積層されており（図２（ｃ））、さらに基材樹脂層７の下面に選択的に接着樹脂層４が積層されている（図２（ｄ））。
【００１０】
また、本発明の化粧板積層用印刷樹脂フィルム１は、図３（ｅ）および（ｆ）に示すように、二軸延伸ポリエステル樹脂フィルム１０の下面に選択的に直接（図３（ｅ）、（ｆ））、または接着剤層を介して（図示せず）、その上面にエンボス加工により形成されたエンボス凹部８に、ワイピングインキが充填されたワイピング印刷層９が設けられた基材樹脂層７が積層され、その下面に絵柄印刷層６ａが施された着色樹脂層５が積層されており（図３（ｅ））、さらに着色樹脂層５の下面に選択的に接着樹脂層４が積層されている（図３（ｆ））。
さらに、本発明の化粧板積層用印刷樹脂フィルム１は、図４に示すように、図３R>３（ｅ）または（ｆ）の化粧板積層用印刷樹脂フィルム１の着色樹脂層５に、絵柄印刷層６ａとベタ印刷層６ｂの両方が設けられていてもよい。
図５は、図３（ｆ）に示した化粧板積層用印刷樹脂フィルム１を、接着剤層３を介して基板２に積層した化粧板１１を示す。
図６は、図４に示した化粧板積層用印刷樹脂フィルム１を、接着剤層３を介して基板２に積層した化粧板１１を示す。
さらに、本発明の化粧板積層用印刷樹脂フィルム１は、上面に凹凸を付与するために表面をエンボス加工されたエンボスロールを用いてエンボス加工を施したり、鏡面仕上げとするために、鏡面ロールを用いてロールプレスしてもよい。
【００１１】
本発明の基材樹脂層７および着色樹脂層５に用いる樹脂としては、ポリブチレンテレフタレート（ＰＢＴ）、特に１．０〜２．０の固有粘度（ＩＶ値）を有するＰＢＴ、ポリトリメチレンテレフタレート（ＰＴＴ）、酸成分であるテレフタル酸の好ましくは２〜２０モル％をイソフタル酸で置換してなる変性ポリブチレンテレフタレート（変性ＰＢＴ）、ＰＢＴと変性ＰＢＴを好ましい混合比ＰＢＴ／変性ＰＢＴ（重量％）が９５／５〜４０／６０でブレンドしてなるブレンド樹脂、ＰＢＴとポリエチレンテレフタレート（ＰＥＴ）を好ましい混合比ＰＢＴ／ＰＥＴ（重量％）が９８／２〜５０／５０でブレンドしてなるブレンド樹脂、ＰＢＴとポリカーボネート（ＰＣ）を好ましい混合比ＰＢＴ／ＰＣ（重量％）が９５／５〜３０／７０でブレンドしてなるブレンド樹脂、ＰＢＴとＰＴＴを好ましい混合比ＰＢＴ／ＰＴＴ（重量％）が９５／５〜４０／６０でブレンドしてなるブレンド樹脂が好ましい。
【００１２】
これらの樹脂の固有粘度は、製膜性の面から１．５以下、耐水経時性（耐水劣化性）の面から１．２以上であることが好ましい。
また、着色樹脂層５は上記の樹脂に押出機を用いて製膜する際に着色顔料を混練することにより得られるが、着色樹脂層５と同様に、基材樹脂層７も押出機を用いて製膜する際に、樹脂中に着色顔料を混練して着色基材樹脂層としてもよい。
【００１３】
絵柄印刷層６ａは、例えば、木目、石目、天然皮革の表面柄、布目、抽象柄などの模様を表現した印刷層であり、ベタ印刷層６ｂは基材樹脂層７または着色樹脂層５の全面を隠蔽し絵柄印刷層６ａの印刷下地色を与える印刷層であると共に、基材樹脂層７と二軸延伸ポリエステル樹脂フィルム１０との熱接着性を付与する層でもある。印刷層６ａおよび６ｂを形成するインキのビヒクルとしては、例えばニトロセルロース、酢酸セルロースなどのセルロース誘導体、ポリエステルウレタン樹脂などの公知のものが使用できるが、なかでも密着性及び熱接着性の両観点からニトロセルロース−アルキッド樹脂系インキが好ましい。
【００１４】
また、基材樹脂層７に選択的にエンボス加工を施してエンボス凹部８を形成した後、ワイピング印刷法を用いてエンボス凹部８にインキを充填してなるワイピング印刷層９を設ける場合、エンボス凹部８に充填されるワイピングインキとしては、塗料もしくはインキが用いられる。
【００１５】
例えば、天然樹脂またはその変成樹脂類、セルロース誘導体類、ポリエステル系樹脂、アクリル系樹脂、ポリウレタン系樹脂等の合成樹脂類をビヒクルの構成材料とし、ビヒクル中に着色顔料、体質顔料等を添加して成る塗料もしくはインキが用いられる。使用されるビヒクルとしてはウレタン２液硬化型のものが好適に用いられる。ワイピング印刷法としては、ドクターブレード法、ロールコート法など、従来から使用されているワイピング印刷法のいずれによっても良い。
【００１６】
二軸延伸ポリエステル樹脂フィルム１０としては、可塑剤及びハロゲン属元素等を含まないポリエステル樹脂からなることを特徴とし、特に透明なポリエチレンテレフタレート、またはポリエチレンナフタレート、もしくは酸性分であるテレフタル酸の一部をイソフタル酸で置換してなる変性ポリエチレンテレフタレートの二軸延伸フィルムであることが好ましい。さらに本発明に用いる二軸延伸ポリエステル樹脂フィルムは、樹脂フィルムの熱固定温度Ｔｈｓ（℃）と、樹脂の融点Ｔｍ１（℃）と、前記基材樹脂の融点Ｔｍ２（℃）との下記の関係式、 Ｔｍ２−３５≦Ｔｈｓ≦Ｔｍ２＋１５≦Ｔｍ１を満足することが好ましく、さらに、二軸延伸ポリエステル樹脂フィルムと基材樹脂層の厚み比を１：１０〜６：１０の範囲とすることが好ましい。
【００１７】
これらの熱固定温度や融点の測定方法については後述するが、熱固定温度が（Ｔｍ２−３５）℃未満では、基板への積層時に表面樹脂フィルムの収縮が著しく大きくなり、一方、（Ｔｍ２＋１５）℃を超えると基板への積層時にフィルムの配向度の低下がほとんどなく、積層板上フィルムの加工性が低下して好ましくない。
【００１８】
また、二軸延伸ポリエステル樹脂フィルムと基材樹脂層の厚み比が１：１０未満では、印刷柄の深みがなくなる上にフィルムの積層時にしわが入りやすいなどの問題が生じ、一方、６：１０を超えると基板への積層時に二軸延伸ポリエステル樹脂フィルムの収縮応力が大きくなり、好ましくない。
【００１９】
また、この最表層となる二軸延伸ポリエステル樹脂フィルムの表面にもエンボス加工を施してエンボス凹部を形成して、化粧板積層用印刷樹脂フィルム全体に立体感を付与したり、または鏡面ロールを用いてロールプレスし、鏡面仕上げとしたりすることができる。さらに、二軸延伸ポリエステル樹脂フィルムの上にさらに艶調整層を設けることにより、美麗な光沢を付与することもできる。
【００２０】
さらに、最表層となる二軸延伸ポリエステル樹脂フィルムの表面に艶調整層を設けることにより、意匠性をさらに向上させた化粧板積層用印刷樹脂フィルムとすることも可能である。この艷調整層は無色透明であっても、艶消しの透明であってもよく、化粧板積層用印刷樹脂フィルムの表面の光沢度を調整するとともに、表面保護層としても機能する。艶調整層は適宜のビヒクルを用いた塗料を塗布することにより、形成させることができる。ビヒクルとしては、フェノール樹脂、不飽和ポリエステル樹脂、エポキシ樹脂、ポリウレタン樹脂などの熱硬化性樹脂の１種、または２種以上の混合樹脂を用いることができる。艶調整層を形成する塗料には、通常適量の艶消し剤を分散させて所望の光沢度を付与する。艶消し剤としては、マイカ、シリカ、アルミナ、炭酸カルシウム、珪藻土、珪砂、シラスバルーンなどが用いられる。上記の塗料の塗布方法としては、グラビアコート、ロールコート、エアナイフコートなど、公知の塗布方法を用いることができる。
【００２１】
接着剤層４に用いられる樹脂としては、エチレンテレフタレート／イソフタレート共重合体などの共重合ポリエステル樹脂を用いることが好ましい。
この共重合ポリエステル樹脂を構成する材料の例としては、上記の他に、以下の組成を有する共重合ポリエステル樹脂などが好適に用いられる。すなわち、樹脂を形成するソフトセグメントとして、ポリエチレングリコール、ポリテトラメチレングリコールなどのポリオキシアルキレングリコール、あるいはポリε−カプロラクトン、アゼライン酸、セバシン酸、ドデカンジオン酸、ダイマー酸などのＨＯＯＣ−［ＣＨ２］ｎ−ＣＯＯＨの分子構造を有する脂肪族ジカルボン酸と、脂肪族および／または脂環族ジオールからなる脂肪族ポリエステルなどが好適に用いられる。
【００２２】
また、樹脂を構成するハードセグメントとしては、エチレンテレフタレート、ブチレンテレフタレート、シクロヘキサンジメチレンテレフタレート、シクロヘキサンジメチレンシクロヘキサンジカルボキシレート、ブチレン２，６ナフタレンジカルボキシレートなどの芳香族および／または脂環族エステルユニットから選ばれた少なくとも１つから構成されていることが好ましい。
【００２３】
さらに、アルコール成分として、１，４ブタンジオール残基を含有していることが耐溶剤性の点で好ましく、共重合ポリエステルを形成する全アルコール成分に占める１，４ブタンジオール残部が４０モル％以上、６５モル％以下であることが好ましい。
化粧板積層用印刷樹脂フィルム１と基板２とのより強い密着力が要求される場合には、請求項１〜４のいずれかに記載した樹脂層の構成に応じて、接着樹脂層４、基材樹脂層７、着色樹脂層５のいずれかの、基板２と接触する樹脂層の樹脂成分の一部をアイオノマーで置換させることが好ましい。この場合、アイオノマーは樹脂中に１〜５０重量％含有させることが好ましい。
【００２４】
本発明の化粧板積層用印刷樹脂フィルム１の最表層として用いる二軸延伸ポリエステル樹脂フィルム１０において、重要な要因である二軸延伸フィルムの熱固定温度および融点、ならびに基材樹脂層７に用いる樹脂の融点は、それぞれ以下のようにして測定する。
測定器としてパーキンエルマー社製の示差走査熱量計ＤＳＣ−７を使用し、二軸延伸ポリエステル樹脂フィルム１０の試料約５ｍｇをセミミクロン天秤で精秤し、窒素ガスを流しつつ、２０℃／分の昇温速度で昇温させていき、図１（ａ）に示す昇温曲線を描き、昇温曲線における吸熱ピークから熱固定温度Ｔｈｓと融点Ｔｍ１を求める。同様にして、基材樹脂層７に用いる樹脂の試料約５ｍｇをセミミクロン天秤で精秤し、窒素ガスを流しつつ、２０℃／分の昇温速度で昇温させていき、図１（ｂ）に示す昇温曲線を描き、昇温曲線における吸熱ピークから融点Ｔｍ２を求める。
【００２５】
図２（ｃ）に示す本発明の化粧板積層用印刷樹脂フィルム１は、次のようにして作成することができる。すなわち、単層フィルムとして製膜した基材樹脂層７の上面に、二軸延伸ポリエステル樹脂フィルム１０の下面に設けた絵柄印刷層６ａとベタ印刷層６ｂからなる印刷層６を重ね合わせ、基材樹脂層７と二軸延伸ポリエステル樹脂フィルム１０を重ね合せたまま１対の熱ロール間に通して挟み付けて加熱圧着して積層し、一枚の積層フィルムを製造する。加熱しながら加圧することにより、二軸延伸ポリエステル樹脂フィルム１０のベタ印刷層６ｂの面を基材樹脂層７に融着して一枚の化粧板積層用印刷樹脂フィルム１を作るものである。
【００２６】
また、図２（ｄ）に示すように、化粧板積層用印刷樹脂フィルム１は、共押出しにより２層フィルムとして製膜した接着樹脂層４と基材樹脂層７の積層フィルムの基材樹脂層７側の上面に、絵柄印刷層６ａとベタ印刷層６ｂからなる印刷層６を設け、図２（ｃ）に示したのと同様にして、接着樹脂層４と基材樹脂層７の共押出し積層フィルムの印刷層６が二軸延伸ポリエステル樹脂フィルム１０と接するようにして重ね合せ、１対の熱ロール間に通して挟み付けて加熱圧着して積層し、一枚の積層フィルムを製造したものであってもよい。
【００２７】
また、樹脂に顔料を混練した着色樹脂層５を押出しにより単層フィルムとして製膜し、この着色樹脂層５の上に絵柄印刷層６ａを施し、その上に基材樹脂層７を重ね合せたまま１対の熱ロール間に通して挟み付けて加熱圧着して積層し、１枚の予備積層フィルムを製造する。なお、その際、前記の熱ロールとしてエンボスロールを使用することにより、積層と基材樹脂層７のエンボス加工を同時に実施することが可能で、基材樹脂層７の表面にワイピング印刷用エンボス凹部８を形成し、ワイピングインキを充填してワイピング印刷層９を設けることにより、高意匠性の絵柄模様を付与することができる。さらに、予備積層フィルム上に直接または接着剤層を介して二軸延伸ポリエステル樹脂フィルム１０を重ね合せたまま１対の熱ロール間に通して挟み付けて加熱圧着して積層することによって、図３（ｅ）に示す化粧板積層用印刷樹脂フィルム１を得ることができる。
【００２８】
また、図３（ｆ）に示すように、接着樹脂層４と樹脂に顔料を混練した着色樹脂層５を共押出しにより２層フィルムとして製膜し、図３（ｅ）に示したのと同様にして、前記着色樹脂層５の上に絵柄印刷層６ａを施し、さらに、その上に基材樹脂層７を重ね合せ、１対の熱ロール間に通して挟み付けて加熱圧着して積層し、１枚の予備積層フィルムを製造してもよい。なお、これらの樹脂フィルムの作成に際して、前記の熱ロールとしてエンボスロールを使用することにより、積層と基材樹脂層７のエンボス加工を同時に実施することが可能である。基材樹脂層７の表面にワイピング印刷用エンボス凹部８を形成し、ワイピングインキを充填してワイピング印刷層９を設けることにより、高意匠性の絵柄模様を付与することができる。さらに、図３（ｆ）に示したのと同様にして、予備積層フィルム上に直接または接着剤層を介して二軸延伸ポリエステル樹脂フィルム１０を積層することによって、図３（ｆ）に示す化粧板積層用印刷樹脂フィルム１を得ることができる。そして、着色樹脂層５および基材樹脂層７が寸法安定性に優れるため、張力や熱に起因する伸縮変動を抑えることが可能となり、印刷柄とエンボス柄が同調した、高意匠性を有するエンボス化粧フィルムとすることができる。上記の積層作業やエンボス加工などの工程は、従来のポリ塩化ビニル樹脂フィルムにおけるのと同じ装置で作業することが可能である。
【００２９】
さらに、図３（ｆ）の着色樹脂層５の表面にベタ印刷層６ｂを設け、その上に絵柄印刷層６ａを設けた樹脂フィルムを用いることにより、図４に示すように、意匠性をより一層向上させた化粧板積層用印刷樹脂フィルム１とすることも可能である。
また、上記の方法によって得られた化粧板積層用印刷樹脂フィルム１を、接着剤層３を介在させてまたは介さずに基板２と貼合わせることにより、図５または図６に示すような化粧板１１が得られる。基板２としては、例えば、鋼板、アルミニウム合金板、亜鉛や亜鉛−アルミニウム合金、亜鉛−コバルト−モリブデン合金などの亜鉛合金をめっきした亜鉛めっき鋼板などの金属板が用いられる。さらに基板２として、木材単板、木材合板、パーチクルボード、ＭＤＦ等の木質板、石膏ボード、珪酸カルシウムボード、石綿スレートボードなどの無機質からなるボード、紙なども用いることもできる。
【００３０】
化粧板積層用印刷樹脂フィルム１と基板２の貼合わせに選択的に用いられる接着剤層３の接着剤としては、一般的な接着剤、例えば、酢酸ビニル樹脂系、エチレン−ビニルアセテート樹脂系、尿素樹脂系、ウレタン樹脂系などのエマルジョン型接着剤が、火気に対して安全で、臭気もなく、価格的にも安価なため好ましく用いられる。
次に実施例により本発明をさらに詳細に説明する。
【００３１】
（実施例１〜８、及び比較例１〜３）
表１と表２に示す製膜の際の熱固定温度（Ｔｈｓ）を有する、厚さ２５μｍの透明二軸延伸ポリエチレンテレフタレートフィルム（ＰＥＴ−ＢＯ、融点（Ｔｍ１）：２５７℃）、透明二軸延伸ポリエチレンナフタレートフィルム（ＰＥＮ−ＢＯ、融点：２６９℃）、または酸性分が９５モル％のテレフタル酸と５モル％のイソフタル酸からなる変性ポリエチレンテレフタレートの透明二軸延伸フィルム（変性ＰＥＴ−ＢＯ、融点：２４６℃）のいずれか片面に、ニトロセルロース−アルキド系インキを用い、絵柄印刷層および着色ベタ印刷層をグラビア輪転機によりインラインにて印刷したものと、表１に示す固有粘度を有する市販のポリブチレンテレフタレート（ＰＢＴ、融点（Ｔｍ２）：２２５℃）を用いて押出製膜機により作成した厚さ７０μｍの単層の未延伸フィルム（実施例１〜３、実施例７〜８、比較例１〜２）を基材樹脂層として、または上記のＰＢＴとイソフタル酸１２モル％を共重合した市販の変性ポリエチレンテレフタレート（変性ＰＥＴ）を用いて押出製膜機により共押し出しして作成した厚さ７０μｍ（ＰＢＴ６０μｍ、変性ＰＥＴ１０μｍ）からなる、ＰＢＴを基材樹脂層とし、変性ＰＥＴを接着樹脂層とする二層の未延伸フィルム（実施例４〜６、比較例３）を、印刷層とＰＢＴ基材樹脂層が接するように重ねて、圧着用ロールの加熱温度：１２０℃、樹脂フィルムの送り速度：２０ｍ／ｍｉｎ、圧着用ロールのニップ圧：２５ｋｇｆ／ｃｍ２ の条件で両フィルムを加熱圧着して積層し、化粧板積層用印刷樹脂フィルムを作成した。
【００３２】
次に、厚さ０．５ｍｍの電気亜鉛合金めっき鋼板にポリエステル系接着剤を５ｇ／ｍ２の塗布量で塗布し、上記の化粧板積層用印刷樹脂フィルムを電気亜鉛合金めっき鋼板に、加熱温度：２２５℃、接着圧力：１５ｋｇｆ／ｃｍ２、圧着時間：５秒の条件で加熱圧着し、化粧板を得た。
【００３３】
（実施例９）
イソフタル酸１２．５モル％を共重合した市販の変性ポリブチレンテレフタレート樹脂（変性ＰＢＴ）にクリーム色顔料２０重量％を混練した着色樹脂を押出製膜機により作成した厚さ３０μｍの未延伸着色フィルムの片面に、ニトロセルロース−アルキド系インキを用い、絵柄印刷層をグラビア輪転機によりインラインにて印刷したものと、基材樹脂層として市販のポリトリメチレンテレフタレート（ＰＴＴ）を押出製膜機により作成した厚さ４０μｍの未延伸フィルムと、製膜の際の熱固定温度を２１０℃とした、厚さ２５μｍの透明のＰＥＴ−ＢＯ（融点：２５７℃）とを、基材樹脂層のＰＴＴフィルムが着色フィルムの印刷面および透明のＰＥＴ−ＢＯと接するように重ねて、圧着用ロールの加熱温度：１２０℃、樹脂フィルムの送り速度：２０ｍ／ｍｉｎ、圧着用ロールのニップ圧：２５ｋｇｆ／ｃｍ２ の条件で加熱圧着して積層し、化粧板積層用印刷樹脂フィルムを作成した。
【００３４】
次に、実施例１と同一の電気亜鉛合金めっき鋼板に、実施例１と同一の条件で前記の化粧板積層用印刷樹脂フィルムを加熱圧着し、化粧板を得た。
（実施例１０）
クリーム色顔料２０重量％を混練して着色したＰＢＴと、実施例４と同一の変性ＰＥＴを押出製膜機により共押し出しして、厚さ７０μｍ（着色ＰＢＴ６０μｍ、変性ＰＥＴ１０μｍ）からなる二層の未延伸フィルムを作成し、着色フィルム面に実施例９と同一の絵柄印刷層を実施例９と同一の条件で印刷した。顔料を含有しない、実施例９と同一の変性ＰＢＴを基材樹脂層とし、実施例９と同一の透明のＰＥＴ−ＢＯを用い、基材樹脂層の変性ＰＢＴフィルムが二層の未延伸フィルムの着色フィルム側の印刷面および透明のＰＥＴ−ＢＯと接するように重ねて、実施例９と同一の条件で加熱圧着して積層し、化粧板積層用印刷樹脂フィルムを作成した。
次に、実施例１と同一の電気亜鉛合金めっき鋼板に、実施例１と同一の条件で前記の化粧板積層用印刷樹脂フィルムを加熱圧着し、化粧板を得た。
【００３５】
（実施例１１）
市販のＰＴＴにクリーム色顔料２０重量％を混練した着色樹脂を押出製膜機により作成した厚さ３０μｍの未延伸着色フィルムの片面に、ニトロセルロース−アルキド系インキを用い、着色ベタ印刷層をグラビア輪転機によりインラインにて印刷した。また、基材樹脂層として、市販のＰＢＴと市販のポリエチレンテレフタレート（ＰＥＴ）を７０／３０の混合比（重量）で混合し押出製膜機により溶融させ、エンボス加工を施したキャスティングロール上に押し出して作成した厚さ４０μｍの未延伸フィルムのキャスティングロールと接触した面に、２液硬化型ウレタン系着色インキをロールコート法によって塗工した後、ドクターブレードでエンボス凹部以外の部分に付着している着色インキを除去し、未延伸フィルムの表面に形成されているエンボス凹部内に着色インキを充填、固化させ、片面に印刷を施した基材樹脂フィルムを作成した。次いで実施例１０と同一の透明のＰＥＴ−ＢＯを準備し、着色フィルムの印刷面が基材樹脂フィルムの非印刷面側に接し、基材樹脂フィルムの印刷面が透明のＰＥＴ−ＢＯと接するように重ねて、実施例１の加熱圧着による積層条件と同条件にて加熱圧着して積層し、化粧板積層用印刷樹脂フィルムを作成した。
次に、実施例１と同一の電気亜鉛合金めっき鋼板に、実施例１と同一の条件で前記の化粧板積層用印刷樹脂フィルムを加熱圧着し、化粧板を得た。
【００３６】
（実施例１２）
市販のＰＢＴと市販のＰＥＴを７０／３０の混合比（重量）で混合してなるブレンド樹脂にクリーム色顔料２０重量％を混練した着色樹脂を押出製膜機により作成した厚さ３０μｍの未延伸着色フィルムの片面に、ニトロセルロース−アルキド系インキを用い、着色ベタ印刷層をグラビア輪転機によりインラインにて印刷した。また、実施例９と同一の変性ＰＢＴと市販のＰＢＴを７０／３０の混合比（重量）でブレンドした樹脂を押出製膜機により厚さ４０μｍの基材樹脂フィルムとして作成した。次いで、実施例１１と同一のＰＥＴ−ＢＯを準備し、着色樹脂フィルムの印刷面とＰＥＴ−ＢＯがそれぞれ基材樹脂フィルムと接するように重ね合わせ、実施例１の加熱圧着による積層条件と同条件にてＰＥＴ−ＢＯ面をエンボスロール側として、エンボスロールとシリコンゴムロールからなる圧着用ロールの間に通して圧着することにより、ＰＥＴ−ＢＯ表面にエンボス凹部を有する３層化粧フィルムを作成した。
次に、実施例１と同一の電気亜鉛合金めっき鋼板に、実施例１と同一の条件で前記の化粧板積層用印刷樹脂フィルムを加熱圧着し、化粧板を得た。
【００３７】
（実施例１３）
実施例９と同一の変性ＰＢＴと市販のＰＢＴを７０／３０の混合比（重量）でブレンドした樹脂にクリーム色顔料２０重量％を混練して着色した樹脂と、実施例４と同一の変性ＰＥＴを押出製膜機により共押し出しして、厚さ７０（着色ブレンド樹脂６０μｍ、変性ＰＥＴ１０μｍ）からなる二層の未延伸フィルムを作成し、着色フィルム面に実施例９と同一の絵柄印刷層を実施例９と同一の条件で印刷した。基材樹脂層として、市販のポリカーボネート（ＰＣ）と市販のＰＢＴを６０／４０の混合比（重量）で混合してなるブレンド樹脂を、押出製膜機により厚さ４０μｍの未延伸フィルムを作成した。次いで実施例１０と同一の透明のＰＥＴ−ＢＯを準備し、着色フィルムの印刷面と透明のＰＥＴ−ＢＯの片面が基材樹脂フィルムのそれぞれ面に接するように重ねて、実施例１の加熱圧着による積層条件と同条件にて加熱圧着して積層し、化粧板積層用印刷樹脂フィルムを作製した。
さらに、このようにして作成した化粧板積層用印刷樹脂フィルムの表面に、２液硬化型ポリウレタン系艶調整用塗料（昭和インク製）をグラビアロールコートした。
次に、実施例１と同一の電気亜鉛合金めっき鋼板に、実施例１と同一の条件で前記の化粧板積層用印刷樹脂フィルムを加熱圧着し、化粧板を得た。
【００３８】
（実施例１４）
実施例９と同一の変性ＰＢＴと市販のＰＢＴを７０／３０の混合比（重量）でブレンドした樹脂にクリーム色顔料２０重量％を混練して着色した樹脂と、実施例４と同一の変性ＰＥＴを押出製膜機により共押し出しして、厚さ７０（着色ブレンド樹脂６０μｍ、変性ＰＥＴ１０μｍ）からなる二層の未延伸フィルムを作成し、着色フィルム面に実施例９と同一の絵柄印刷層を実施例９と同一の条件で印刷した。基材樹脂層として、実施例９と同一の変性ＰＢＴと市販のＰＢＴを１０μｍ／３０μｍの厚さ比率となるように、押出製膜機により全厚さ４０μｍの未延伸フィルムを作成した。次いで実施例１０と同一の透明のＰＥＴ−ＢＯを準備し、着色フィルムの印刷面が基材樹脂フィルムの変性ＰＢＴ層と、透明のＰＥＴ−ＢＯの片面が基材樹脂フィルムのＰＢＴ層とそれぞれ接するように重ねて、実施例１の加熱圧着による積層条件と同条件にて加熱圧着して積層し、化粧板積層用印刷樹脂フィルムを作製した。
さらに、このようにして作成した化粧板積層用印刷樹脂フィルムの表面に、２液硬化型ポリウレタン系艷調整用塗料（昭和インク製）をグラビアロールコートした。
次に、実施例１と同一の電気亜鉛合金めっき鋼板に、実施例１と同一の条件で前記の化粧板積層用印刷樹脂フィルムを加熱圧着し、化粧板を得た。
【００３９】
（実施例１５）
実施例１３と同一のＰＣとＰＢＴからなるブレンド樹脂にクリーム色顔料２０重量％を混練して着色した樹脂を押出製膜機により押し出し、厚さ７０μｍの未延伸フィルムを作成し、その片面に、ニトロセルロース−アルキッド系インキを用い、絵柄印刷層および着色ベタ印刷層をグラビア輪転機によりインラインにて印刷した。基材樹脂層として、実施例４と同一の変性ＰＥＴと市販のＰＢＴを４０／６０の混合比（重量）で混合してなるブレンド樹脂を、押出製膜機により厚さ４０μｍの未延伸フィルムを作成した。次いで実施例１０と同一の透明のＰＥＴ−ＢＯを準備し、着色フィルムの印刷面と透明のＰＥＴ−ＢＯの片面が基材樹脂フィルムのそれぞれ面に接するように重ねて、実施例１の加熱圧着による積層条件と同条件にて加熱圧着して積層し、化粧板積層用印刷樹脂フィルムを作製した。
次に、実施例１と同一の電気亜鉛合金めっき鋼板に、実施例１と同一の条件で前記の化粧板積層用印刷樹脂フィルムを加熱圧着し、化粧板を得た。
【００４０】
（実施例１６）
実施例１５と同一の変性ＰＥＴとＰＢＴからなるブレンド樹脂にクリーム色顔料２０重量％を混練して着色した樹脂を押出製膜機により押し出し、厚さ７０μｍの未延伸フィルムを作成し、その片面に、ニトロセルロース−アルキド系インキを用い、絵柄印刷層および着色ベタ印刷層をグラビア輪転機によりインラインにて印刷した。基材樹脂層として、実施例９と同一のＰＴＴと市販のＰＢＴを５０／５０の混合比（重量）で混合してなるブレンド樹脂を、押出製膜機により厚さ４０μｍの未延伸フィルムを作成した。次いで実施例１０と同一の透明のＰＥＴ−ＢＯを準備し、着色フィルムの印刷面と透明のＰＥＴ−ＢＯの片面が基材樹脂フィルムのそれぞれの面に接するように重ねて、実施例１の加熱圧着による積層条件と同条件にて加熱圧着して積層し、化粧板積層用印刷樹脂フィルムを作製した。
次に、実施例１と同一の電気亜鉛合金めっき鋼板に、実施例１と同一の条件で前記の化粧板積層用印刷樹脂フィルムを加熱圧着し、化粧板を得た。
【００４１】
（実施例１７）
実施例１６と同一のＰＴＴとＰＢＴからなるブレンド樹脂にクリーム色顔料２０重量％を混練して着色した樹脂を押出製膜機により押し出し、厚さ７０μｍの未延伸フィルムを作成し、その片面に、ニトロセルロース−アルキド系インキを用い、絵柄印刷層および着色ベタ印刷層をグラビア輪転機によりインラインにて印刷した。基材樹脂層として、市販のＰＢＴと市販のアイオノマーを９０／１０の混合比（重量）でブレンドした樹脂を、押出製膜機により厚さ４０μｍの未延伸フィルムを作成した。次いで実施例１０と同一の透明のＰＥＴ−ＢＯを準備し、着色フィルムの印刷面と透明のＰＥＴ−ＢＯの片面が基材樹脂フィルムのそれぞれの面に接するように重ねて、実施例１の加熱圧着による積層条件と同条件にて加熱圧着して積層し、化粧板積層用印刷樹脂フィルムを作製した。
次に、実施例１と同一の電気亜鉛合金めっき鋼板に、実施例１と同一の条件で前記の化粧板積層用印刷樹脂フィルムを加熱圧着し、化粧板を得た。
【００４２】
（実施例１８）
実施例１７と同一のＰＢＴとアイオノマーからなるブレンド樹脂にクリーム色顔料２０重量％を混練して着色した樹脂を押出製膜機により押し出し、厚さ７０μｍの未延伸フィルムを作成し、その片面に、ニトロセルロース−アルキド系インキを用い、絵柄印刷層および着色ベタ印刷層をグラビア輪転機によりインラインにて印刷した。基材樹脂層として、実施例１と同一のＰＢＴを押出製膜機により厚さ４０μｍの未延伸フィルムを作成した。次いで実施例１０と同一の透明のＰＥＴ−ＢＯを準備し、着色フィルムの印刷面と透明のＰＥＴ−ＢＯの片面が基材樹脂フィルムのそれぞれの面に接するように重ねて、実施例１の加熱圧着による積層条件と同条件にて加熱圧着して積層し、化粧板積層用印刷樹脂フィルムを作製した。
次に、実施例１と同一の電気亜鉛合金めっき鋼板に、実施例１と同一の条件で前記の化粧板積層用印刷樹脂フィルムを加熱圧着し、化粧板を得た。
【００４３】
（実施例１９）
実施例９と同一の変性ＰＢＴと市販のＰＢＴを７０／３０の混合比（重量）でブレンドした樹脂にクリーム色顔料２０重量％を混練して着色した樹脂と、実施例１７と同一のＰＢＴとアイオノマーからなるブレンド樹脂を押出製膜機により共押し出しして、厚さ７０（着色ブレンド樹脂６０μｍ、ＰＢＴ／アイオノマーブレンド樹脂１０μｍ）からなる二層の未延伸フィルムを作成し、着色フィルム面に実施例９と同一の絵柄印刷層を実施例９と同一の条件で印刷した。基材樹脂層として、ＰＢＴを押出製膜機により厚さ４０μｍの未延伸フィルムを作成した。次いで実施例１０と同一の透明のＰＥＴ−ＢＯを準備し、着色フィルムの印刷面と透明のＰＥＴ−ＢＯの片面が基材樹脂フィルムのそれぞれの面に接するように重ねて、実施例１の加熱圧着による積層条件と同条件にて加熱圧着して積層し、化粧板積層用印刷樹脂フィルムを作製した。
次に、実施例１と同一の電気亜鉛合金めっき鋼板に、実施例１と同一の条件で前記の化粧板積層用印刷樹脂フィルムを加熱圧着し、化粧板を得た。
【００４４】
（樹脂フィルムの特性評価）
実施例１〜１９及び比較例１〜３で作成した化粧板を、下記の特性について評価した。
（基板への積層時の表面フィルムの熱収縮）
本発明の化粧板積層用印刷樹脂フィルムの表面フィルムの熱収縮の良否は、実施例１〜１９及び比較例１〜３で作成した、化粧フィルムを金属板に積層した化粧金属板の表面フィルム両端部の熱収縮幅を測定し、下記の３段階の基準で評価した。
○：両端部の収縮幅が２ｍｍ以下。
△：両端部の収縮幅が２ｍｍ〜１０ｍｍ。
×：両端部の収縮幅が１０ｍｍ以上。
上記の評点において、○および△は使用上の問題はない。なお、この試験は１０枚の試験片について実施した。
【００４５】
（樹脂フィルムの加工性）
本発明の化粧板積層用印刷樹脂フィルムの加工性の良否は、実施例１〜１９及び比較例１〜３で作成した、化粧フィルムを金属板に積層した化粧金属板に、ＪＩＳ Ｚ ２２４８（金属材料曲げ試験方法）に準拠して、０Ｔ曲げ加工を施し、曲げ加工部のフィルムの表面を肉眼観察し、下記の４段階の基準で評価した。
◎：折り曲げ部に割れは全く認められない。
○：折り曲げ部の先端にかすかな白色化が認められる。
△：折り曲げ部全体に白色化が認められる。
×：折り曲げ部にかなりの程度の割れが認められる。
上記の評点において、◎および○は使用上の問題はない。なお、この試験は１０枚の試験片について実施した。
【００４６】
（ワイピング印刷用エンボス加工性）
本発明の化粧板積層用印刷樹脂フィルムのワイピング印刷用エンボス加工性の良否は、エンボス加工を施した樹脂フィルムの基材樹脂層の表面の粗さの程度によって判断される。本発明においては、平均表面粗さ（Ｒａ）：１１μｍの凹凸が付与された砂目の彫刻ロールを用いてエンボス加工を施した樹脂フィルムの基材樹脂層の表面を肉眼観察し、エンボス加工性の良否を下記の３段階の基準で評価した。
○：良好、
△：やや不良、
×：不良
なお、上記の評価基準は、ポリ塩化ビニル樹脂フィルムの表面粗さ（Ｒａ：μｍ）を東京精密社製ＳＵＲＦＣＯＭ表面粗さ計を用いてＪＩＳ Ｂ０６０１に準拠して測定し、平均表面粗さが４μｍである場合をエンボス加工性の合格基準とし、平均表面粗さが４μｍのポリ塩化ビニル樹脂フィルムの表面と同等以上の外観を有するものを良好（○）とし、ポリ塩化ビニル樹脂フィルムの表面と比べてやや劣るが実用上問題ない外観を有するものをやや不良（△）とし、エンボス加工が入らないものを不良（×）として、判定した。
【００４７】
（耐汚染性）
実施例１〜１９及び比較例１〜３で作成した化粧板の最表層の樹脂フィルム面に、黒色の油性マジックインキで描画し２４時間放置した後、エタノールを含浸させた布で清拭し、樹脂フィルム面に残存するマジックインキの程度を肉眼観察し、下記の基準で評価した。
◎：マジックインキは全く認められない。
○：実用上問題ない程度の極くわずかなマジックインキの残存が認められる。
△：実用上問題となる程度のわずかなマジックインキの残存が認められる。
×：かなりの程度にマジックインキの残存が認められる。
【００４８】
（耐溶剤性）
実施例１〜１９及び比較例１〜３で作成した化粧板の最表層の樹脂フィルム面に、メチルエチルケトンを含浸させたスポンジを載せ、２４時間放置した後、フィルム表面の変色および膨れの発生の程度を肉眼観察し、下記の基準で評価した。
◎：変色および膨れの発生は全く認められない。
○：実用上問題ない程度の極くわずかな変色または膨れの発生が認められる。
△：実用上問題となる程度のわずかな変色または膨れの発生が認められる。
×：かなりの程度に変色および膨れが認められる。
【００４９】
（耐水劣化性）
本発明の化粧板を高温多湿の状態で長時間経時させた場合（例えばユニットバスの内装材として用いた場合など）を想定し、長時間水と接した場合の樹脂フィルムの耐水劣化性をデュポン衝撃試験法で評価した。
実施例１〜１９及び比較例１〜３で作成した化粧板積層用印刷樹脂フィルムを、厚さ０．５ｍｍの電気亜鉛合金めっき鋼板に積層し試験片とした。この試験片を６０ｍｍ×６０ｍｍの大きさに切り出し、３８±２℃の温度に保持された脱塩水中に１カ月間浸漬した後室温で乾燥し、デュポン衝撃試験機を用い、ＪＩＳ Ｋ ５４００に準拠した条件（衝撃部の大きさ１／２ｉｎｃｈφ、重さ１ｋｇ、落下高さ５０ｃｍ）で衝撃を負荷した。衝撃を負荷した後の樹脂フィルムの状態を肉眼観察し、下記の５段階で評価した。
◎：樹脂フィルムに割れが認められない。
○：樹脂フィルムの一部に細かい割れが認められる。
△：樹脂フィルムの加工部全体に細かい割れが認められる。
×：樹脂フィルムの加工部全体に大きな割れが認められる。
××：樹脂フィルム全体に割れが著しい。
上記の評点において、◎および○は使用上の問題はない。なお、この試験は１０枚の試験片について実施した。
【００５０】
（鮮映性）
実施例１〜１９及び比較例１〜３で作成した化粧板積層用印刷樹脂フィルムを、厚さ０．５ｍｍの電気亜鉛合金めっき鋼板に積層し試験片とした。この試験片表面の鮮映度を、財団法人日本色彩研究所製の携帯用鮮明度光沢計ＰＧＤ−４型により測定した。なお、本発明でいう鮮映性とは、写像鮮映性すなわち化粧面に写した正反射像の鮮明さを意味し、高鮮映とは前記の鮮映度が０．８以上の場合をさす。
これらの樹脂フィルムの特性評価を表３と表４に示す。なお、表１〜４において、ＰＥＴ−ＢＯは透明二軸延伸ポリエチレンテレフタレートを、変性ＰＥＴ−ＢＯは変性ポリエチレンテレフタレートの透明二軸延伸フィルムを、ＰＥＮ−ＢＯは透明二軸延伸ポリエチレンナフタレートを、ＰＥＴはポリエチレンテレフタレートをＰＢＴはポリブチレンテレフタレートを、ＰＴＴはポリトリメチレンテレフタレートを、ＰＥＮはポリエチレンナフタレートを、変性ＰＥＴはイソフタル酸共重合ポリエチレンテレフタレートを、変性ＰＢＴはイソフタル酸共重合ポリブチレンテレフタレートを、変性ＰＢＴ／／ＰＢＴはイソフタル酸共重合ポリブチレンテレフタレートとポリブチレンテレフタレートの２層樹脂を、変性ＰＢＴ／ＰＢＴはイソフタル酸共重合ポリブチレンテレフタレートとポリブチレンテレフタレートのブレンド樹脂を、変性ＰＥＴ／ＰＢＴはイソフタル酸共重合ポリエチレンテレフタレートとポリブチレンテレフタレートのブレンド樹脂を、ＰＢＴ／ＰＥＴはポリブチレンテレフタレートとポリエチレンテレフタレートのブレンド樹脂を、ＰＣ／ＰＢＴはポリカーボネートとポリブチレンテレフタレートのブレンド樹脂を、ＰＴＴ／ＰＢＴはポリトリメチレンテレフタレートとポリブチレンテレフタレートのブレンド樹脂を、ＰＢＴ／アイオノマーはポリブチレンテレフタレートとアイオノマーのブレンド樹脂をそれぞれ示す。
【００５１】
表３と表４に示すように、本発明の化粧板積層用印刷樹脂フィルムは、積層時の表面フィルムの熱収縮、加工性、エンボス性、耐汚染性、耐溶剤性、耐水劣化性、鮮映性のいずれにおいても優れた特性を示す。
【００５２】
【表１】
【００５３】
【表２】
【００５４】
【表３】
【００５５】
【表４】
【産業上の利用可能性】
【００５６】
本発明の化粧板積層用印刷樹脂フィルムは上記のように構成されており、従来のポリ塩化ビニル樹脂フィルムやオレフィン樹脂フィルムを用いた化粧シートの表面樹脂層にも用いられている二軸延伸ポリエステル樹脂フィルムの熱固定温度Ｔｈｓが該樹脂の融点Ｔｍ１と前記基材樹脂の融点Ｔｍ２を用いた関係、Ｔｍ２−３５≦Ｔｈｓ≦Ｔｍ２＋１５≦Ｔｍ１の範囲に、さらに、該樹脂層と前記基材樹脂層の厚み比が１：１０〜６：１０の範囲に規定することにより、基板への積層時に熱収縮が小さく、安定した加工性を有する化粧板用印刷フィルムを得ることができる。
さらに、ポリブチレンテレフタレートフィルムからなる基材樹脂層および着色樹脂層が熱や張力に対する伸縮変動が少なく、優れた寸法安定性を有しているため、印刷見当精度の良い印刷物を得ることができる。
また、従来のポリ塩化ビニル樹脂フィルムと同様の製造方法および製造条件で化粧フィルムが得られるために、新規設備の増設や設備の改造などの設備投資を必要とせず、従来のポリ塩化ビニル樹脂フィルムと同様の、印刷柄とエンボス柄が同調した意匠性に優れた絵柄模様を表現することができる。
そのうえ、基材樹脂層や表面樹脂層を構成する樹脂中に可塑剤を含有していないために、可塑剤のブリードによる表面汚染などの問題が生じることなく、耐汚染性、耐溶剤性、耐水性などの表面物性に優れている。
またさらに、焼却廃棄する際に、塩化水素ガスのような有毒ガスの発生がないため、環境を汚染する心配もなく環境保全においても優れており、ユニットバス、冷蔵庫、冷蔵庫ドアの外装用板、カーテンレール、洗面ユニット、洗濯機、システムキッチン、間仕切り、壁パネル、室内ドア、室内収納庫、蛍光灯の反射板、オーディオビジュアル機器の外板、電子レンジの外板、オーブンの外板、ファンヒーターの外板、ストーブの外板、エアコンディショナーの外板などに好適に適用できる。
【図面の簡単な説明】
【００５７】
図１の（ａ）は本発明の二軸延伸ポリエステル樹脂フィルムの、示差走査熱量計による昇温曲線であり、（ｂ）は本発明の基材樹脂層の樹脂フィルムの示差走査熱量計による昇温曲線である。図２の（ｃ）は本発明の化粧板積層用印刷樹脂フィルムの一例を示す断面図であり、（ｄ）は本発明の化粧板積層用印刷樹脂フィルムの他の一例を示す断面図である。図３の（ｅ）は本発明の化粧板積層用印刷樹脂フィルムの他の一例を示す断面図であり、（ｆ）は本発明の化粧板積層用印刷樹脂フィルムの他の一例を示す断面図である。図４は本発明の化粧板積層用印刷樹脂フィルムの他の一例を示す断面図である。図５は本発明の化粧板の一例を示す断面図である。図６は本発明の化粧板の他の一例を示す断面図である。【Technical field】
[0001]
The present invention relates to a printing resin film for laminating decorative plates, a decorative plate laminated with the resin film, and a unit bath, refrigerator, refrigerator door, curtain rail, wash unit, washing machine, system kitchen, partition using the decorative plate , Wall panels, indoor doors, indoor storage, fluorescent light reflectors, audio visual equipment skins, microwave oven skins, oven skins, fan heater skins, stove skins, air conditioners, etc. It relates to the outer panel of various devices. In addition, the present invention relates to a resin film for laminating a decorative plate, which is applied to interior products such as furniture, elevators, and buildings, and particularly suitable for uses requiring a printed pattern, and a decorative plate laminated with the resin film.
[Background]
[0002]
Conventionally, as a decorative board used for various furniture and building interior materials,
(1) A decorative film in which a resin layer serving as a base material is printed using a normal method, and a coating layer such as an acrylic resin or a polyester resin is provided to protect the surface of the printed layer,
(2) A decorative film in which a transparent biaxially stretched polyester film is laminated via an adhesive layer after printing on a resin layer serving as a substrate;
(3) A decorative film in which a transparent polyvinyl chloride film or a biaxially stretched polyester film is laminated after printing on a polyvinyl chloride film using a normal method,
Such a film is laminated on a substrate such as a galvanized steel sheet via an adhesive.
[Problems to be solved by the invention]
[0003]
However, since the decorative plate laminated with the decorative film of (1) has insufficient strength of the decorative film, the decorative film is easily cracked during processing, or the ink in the bent portion is easily peeled off. This is not suitable for applications such as bending. In addition, the decorative board laminated with the decorative film of (2) above is excellent in surface properties such as stain resistance and solvent resistance, but the surface film is poor in flexibility and has a high softening temperature so that it can be embossed. When applied, embossing is difficult to enter.
Furthermore, since the decorative board laminated with the decorative film of (3) above uses a polyvinyl chloride film, surface properties such as contamination resistance and solvent resistance are inferior, and when incinerated and discarded. In addition, toxic gas such as hydrogen chloride gas and harmful substances resulting from it are contaminated in the environment, and there is a risk of damaging the incinerator during incineration.
In addition, the decorative film in which the biaxially stretched polyester film is laminated on the surface layer, like the decorative film of (2) or (3) above, is heated near the melting point of the base resin layer when laminated on the steel sheet by thermocompression bonding. There is a problem that heat shrinkage occurs due to the history and fusion occurs.
The present invention is a decorative board laminate printing that ensures the workability of a biaxially stretched polyester resin film used for the surface resin layer of a high-definition decorative sheet using a conventional polyvinyl chloride resin film or polyolefin resin film. It aims at providing a resin film.
In addition, the present invention provides a printed resin film for laminating decorative plates having a design pattern having a print quality equivalent to or better than a decorative sheet using a conventional polyvinyl chloride resin film or polyolefin resin film and having an excellent design. The purpose is to do.
Furthermore, the present invention provides a printed resin film for laminating a decorative plate and a decorative plate laminated with the resin film, which are excellent in environmental suitability, surface properties such as contamination resistance and solvent resistance, and excellent in workability. The purpose is to do.
DISCLOSURE OF THE INVENTION
[0004]
The decorative resin laminated printing resin film according to claim 1 of the present invention,
The outermost layer is a transparent biaxially stretched polyester resin film, and a resin film formed by sequentially laminating a printing layer, a base resin layer, and an adhesive resin layer on the lower layer,
Laminating a base resin layer and an adhesive resin layer made of polybutylene terephthalate, polytrimethylene terephthalate, or modified polybutylene terephthalate,
A printing layer is provided on the upper surface of the base resin layer,
The printed layer is overlapped so as to be in contact with the biaxially stretched polyester resin film,
It is characterized by being formed by pressure-bonding through hot rolls.
The printed resin film for laminating decorative plates according to claim 2
The outermost layer is a transparent biaxially stretched polyester resin film, and a resin film formed by sequentially laminating a base resin layer, a printing layer, a colored resin layer, and an adhesive resin layer on the lower layer,
A printing layer is provided on the colored resin layer,
A base resin layer made of polybutylene terephthalate, polytrimethylene terephthalate, or modified polybutylene terephthalate is overlaid thereon,
Passing between the hot rolls and pressure laminating to make a pre-laminated film,
Furthermore, it is characterized in that a biaxially stretched polyester resin film is superposed directly or via an adhesive layer, and is pressed and laminated between hot rolls.
The printed resin film for laminating decorative plates according to claim 3 is:
The outermost layer is a transparent biaxially stretched polyester resin film, and a resin film formed by sequentially laminating a printing layer and a base resin layer on the lower layer,
A printed layer provided on the lower surface of the biaxially stretched polyester resin film is overlaid on the upper surface of the base resin layer made of polybutylene terephthalate, polytrimethylene terephthalate, or modified polybutylene terephthalate, and is pressure-bonded and laminated through a heat roll. It is characterized by becoming.
The printed resin film for laminate of claim 4 is
The outermost layer is a transparent biaxially stretched polyester resin film, and a resin film formed by sequentially laminating a base resin layer, a printing layer, a colored resin layer, and an adhesive resin layer on the lower layer,
A printed layer is applied on the colored resin layer, and a base resin layer made of polybutylene terephthalate, polytrimethylene terephthalate, or modified polybutylene terephthalate is overlaid on the colored resin layer. age,
Furthermore, it is characterized in that a biaxially stretched polyester resin film is superposed directly or via an adhesive layer, and is pressed and laminated between hot rolls.
A printed resin film for laminating a decorative board according to claim 5 is the printed resin film according to any one of claims 1 to 4, wherein the printed layer conceals the entire upper surface which is a pattern printed layer and the entire surface of the base resin layer, and the pattern printing. It consists of the lower layer which is a solid printing layer which gives the printing base color of a layer.
The printed resin film for decorative laminate of claim 6 is any one of claims 1 to 4,
The printing layer may be a pattern printing layer or a solid printing layer.
The printed resin film for decorative laminate of claim 7 is any one of claims 1 to 4,
The base resin layer is embossed and has a printed layer in which ink is filled in an embossed recess formed by the embossing.
The printed resin film for laminating decorative sheets according to claim 8 is any one of claims 1 to 4,
The heat setting temperature Ths (° C), the melting point Tm1 (° C) of the biaxially stretched polyester resin film, and the melting point Tm2 (° C) of the base resin are expressed by the following relational expression: Tm2-35 ≦ Ths ≦ Tm2 + 15 ≦ Tm1 is satisfied.
The decorative resin laminate printing resin film according to claim 9 is any one of claims 1 to 4 or 8, wherein the biaxially stretched polyester resin film is a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, Alternatively, it is a biaxially stretched film of modified polyethylene terephthalate.
A printed resin film for laminating a decorative board according to claim 10 is characterized in that in claim 2 or 4,
The colored resin layer is made of a polyester resin kneaded with a color pigment.
The printed resin film for laminating a decorative board according to claim 11 is characterized in that in claim 1,
The base resin layer is polybutylene terephthalate, polytrimethylene terephthalate, Or it changes to the base-material resin layer which consists of a modified polybutylene terephthalate, It consists of two-layer resin of a modified polybutylene terephthalate and a polybutylene terephthalate, It is characterized by the above-mentioned.
The printed resin film for laminating a decorative sheet according to claim 12 is according to claim 1 or 10,
The base resin layer is a blend resin of polybutylene terephthalate and modified polybutylene terephthalate instead of a base resin layer made of polybutylene terephthalate, polytrimethylene terephthalate, or modified polybutylene terephthalate, or polybutylene terephthalate and It is a blended resin of modified polyethylene terephthalate, a blend resin of polybutylene terephthalate and polyethylene terephthalate, a blend resin of polybutylene terephthalate and polycarbonate, or a blend resin of polybutylene terephthalate and polytrimethylene terephthalate It is characterized by.
The decorative resin laminated printing resin film according to claim 13 is any one of claims 1 to 4 and 9,
The biaxially stretched polyester resin film is embossed.
The printed resin film for decorative laminate of claim 14 is any one of claims 1 to 13,
A gloss adjusting layer is further provided on the biaxially stretched polyester resin film.
The printing resin film for decorative laminate of claim 15 is the claim 1 or 2,
The adhesive resin layer is made of modified polyethylene terephthalate.
The decorative resin laminated printing resin film according to claim 16 is the claim 1 or 2,
The adhesive resin layer is made of a resin containing an ionomer in a resin component.
The printed resin film for decorative laminate of claim 17 is any one of claims 1 to 4,
The base resin layer is made of a resin containing an ionomer in a resin component.
The decorative resin laminated printing resin film according to claim 18, according to claim 2 or 4,
The colored resin layer is made of a resin containing an ionomer in a resin component.
The decorative board according to claim 19 is characterized in that the printed resin film for laminating decorative board according to any one of claims 1 to 18 is laminated on at least one surface of a substrate on which the resin film is laminated.
A decorative board according to a twentieth aspect is characterized in that, in the nineteenth aspect, the decorative board is laminated between the substrate and the printed resin film for laminating the decorative board via an adhesive layer.
The decorative board according to claim 21 is characterized in that, in claim 19 or 20, the substrate is a metal plate.
A unit bath or a refrigerator door according to a twenty-second aspect is characterized by using the decorative board according to any one of the nineteenth to twenty-first aspects.
BEST MODE FOR CARRYING OUT THE INVENTION
[0005]
The inventors of the present invention have developed a biaxially stretched polyester used as the outermost resin layer that has been used to enhance the sharpness in a printed resin film for laminating a decorative plate comprising a plurality of resin layers used for a decorative plate. In order to improve the workability of the resin film, intensive studies were conducted. As a result, the heat setting temperature Ths (° C.) of the biaxially stretched polyester resin film, the melting point Tm1 (° C.) of the polyester resin constituting the film, and the melting point Tm2 of the resin of the base resin layer provided therebelow ( ° C) satisfies the following relational expression Tm2-35 ≦ Ths ≦ Tm2 + 15 ≦ Tm1, and more preferably, the thickness ratio of the biaxially stretched polyester resin film and the base resin layer is in the range of 1:10 to 6:10. Thus, it was found that the workability of the biaxially stretched polyester resin film laminate can be improved.
[0006]
In addition, it has a design pattern with high definition and design that replaces the polyvinyl chloride resin film, which may pollute the environment due to the generation of toxic gases and harmful substances during incineration. The resin film that can be laminated on a decorative board having excellent surface properties such as property and solvent resistance has been intensively studied.
[0007]
As a result, a copolyester resin film is used as the adhesive resin layer, and a polybutylene having an intrinsic viscosity of 1.0 to 2.0 as a colored resin layer to be selectively laminated and a base resin layer serving as a printing base It has been found that it is preferable to use a terephthalate film, a polytrimethylene terephthalate film, a modified polybutylene terephthalate film, or a two-layer film or a blend resin film thereof. Then, a pattern printing layer or a solid printing layer, or a pattern printing layer and a solid printing layer are formed on those films, and a transparent biaxially stretched polyester resin film is used as the outermost layer, and the above films are sequentially laminated from the bottom. Thus, it was found that a resin film to be laminated on a decorative board satisfying the above-mentioned required characteristics can be obtained.
[0008]
Moreover, after embossing is performed on the base resin layer to form an embossed recess, a wiping print layer in which ink is filled into the embossed recess using a wiping method may be provided.
Furthermore, it discovered that the decorative board which laminated | stacked said resin film on the metal plate was excellent also in the design property in addition to the said outstanding film physical property of a resin film.
The contents of the present invention will be described below. FIG. 2 to FIG. 4 are sectional views showing one embodiment of the printing resin film for laminating decorative plates of the present invention. 5 and 6 are sectional views showing an embodiment of the decorative board of the present invention. Each symbol in the figure indicates the following.
[0009]
As shown in FIGS. 2 (c) and 2 (d), the decorative resin laminate printing resin film 1 of the present invention is provided with a pattern printing layer 6 a and a solid printing layer 6 b on the entire back surface of the biaxially stretched polyester resin film 10. The base resin layer 7 is laminated on the lower surface (FIG. 2C), and the adhesive resin layer 4 is selectively laminated on the lower surface of the base resin layer 7 (FIG. 2D). .
[0010]
Further, the decorative resin laminate printing resin film 1 of the present invention is selectively directly on the lower surface of the biaxially stretched polyester resin film 10 as shown in FIGS. 3 (e) and 3 (f) (FIG. 3 (e), (F)) or a base resin layer provided with a wiping printing layer 9 filled with wiping ink in an embossed recess 8 formed by embossing on its upper surface via an adhesive layer (not shown) 7 is laminated, and a colored resin layer 5 with a pattern printing layer 6a is laminated on the lower surface thereof (FIG. 3E), and an adhesive resin layer 4 is selectively laminated on the lower surface of the colored resin layer 5. (FIG. 3 (f)).
Further, as shown in FIG. 4, the decorative resin laminate printing resin film 1 of the present invention has a pattern on the colored resin layer 5 of the decorative resin laminate printing resin film 1 shown in FIG. 3R> 3 (e) or (f). Both the print layer 6a and the solid print layer 6b may be provided.
FIG. 5 shows a decorative board 11 in which the decorative resin laminate printing resin film 1 shown in FIG. 3 (f) is laminated on the substrate 2 via the adhesive layer 3.
FIG. 6 shows a decorative board 11 in which the decorative resin laminate printing resin film 1 shown in FIG. 4 is laminated on the substrate 2 via the adhesive layer 3.
Further, the decorative resin laminated printing resin film 1 of the present invention is provided with a mirror surface roll for embossing using a embossed roll whose surface is embossed in order to give unevenness to the upper surface, You may use and roll press.
[0011]
As a resin used for the base resin layer 7 and the colored resin layer 5 of the present invention, polybutylene terephthalate (PBT), particularly PBT having an intrinsic viscosity (IV value) of 1.0 to 2.0, polytrimethylene terephthalate ( PTT), modified polybutylene terephthalate (modified PBT) obtained by substituting preferably 2 to 20 mol% of terephthalic acid which is an acid component with isophthalic acid, a preferred mixing ratio PBT / modified PBT (wt%) A blend resin obtained by blending at 95/5 to 40/60, a blend resin obtained by blending PBT and polyethylene terephthalate (PET) at a preferred mixing ratio PBT / PET (wt%) of 98/2 to 50/50, PBT / polycarbonate (PC) with a preferred mixing ratio PBT / PC (wt%) of 95/5 to 30/70 Rend to become blended resin, preferably the mixing ratio of PBT and PTT PBT / PTT (wt%) is preferably blended resin obtained by blending at 95 / 5-40 / 60.
[0012]
The intrinsic viscosity of these resins is preferably 1.5 or less from the viewpoint of film forming properties and 1.2 or more from the viewpoint of water aging resistance (water deterioration resistance).
Further, the colored resin layer 5 is obtained by kneading a colored pigment when forming a film on the above resin using an extruder. Similarly to the colored resin layer 5, the base resin layer 7 is also used by an extruder. When forming a film, a colored pigment may be mixed in the resin to form a colored base resin layer.
[0013]
The pattern print layer 6 a is a print layer expressing a pattern such as a grain pattern, a stone pattern, a surface pattern of natural leather, a fabric pattern, an abstract pattern, and the solid print layer 6 b is a base resin layer 7 or a colored resin layer 5. In addition to being a printing layer that conceals the entire surface and gives the printing base color of the pattern printing layer 6 a, it is also a layer that imparts thermal adhesiveness between the base resin layer 7 and the biaxially stretched polyester resin film 10. As the ink vehicle for forming the printing layers 6a and 6b, known ones such as cellulose derivatives such as nitrocellulose and cellulose acetate and polyester urethane resins can be used, and in particular, from both the viewpoints of adhesion and thermal adhesiveness. Nitrocellulose-alkyd resin-based inks are preferred.
[0014]
In addition, when embossing is selectively performed on the base resin layer 7 to form the embossed recess 8, and then the embossed recess 8 is filled with ink using the wiping printing method, the embossed recess is provided. As the wiping ink filled in 8, paint or ink is used.
[0015]
For example, natural resins or their modified resins, cellulose derivatives, polyester resins, acrylic resins, polyurethane resins, and other synthetic resins are used as vehicle constituent materials, and colored pigments, extender pigments, etc. are added to the vehicle. A paint or ink is used. As the vehicle used, a urethane two-component curable type is suitably used. As the wiping printing method, any conventionally used wiping printing method such as a doctor blade method or a roll coating method may be used.
[0016]
The biaxially stretched polyester resin film 10 is made of a polyester resin that does not contain a plasticizer and a halogen element, and is particularly transparent polyethylene terephthalate, polyethylene naphthalate, or a part of terephthalic acid that is an acidic component. Is preferably a biaxially stretched film of modified polyethylene terephthalate obtained by substituting with isophthalic acid. Furthermore, the biaxially stretched polyester resin film used in the present invention has the following relational expression among the heat setting temperature Ths (° C.) of the resin film, the melting point Tm 1 (° C.) of the resin, and the melting point Tm 2 (° C.) of the base resin. Tm2-35 ≦ Ths ≦ Tm2 + 15 ≦ Tm1 is preferably satisfied, and the thickness ratio of the biaxially stretched polyester resin film and the base resin layer is preferably in the range of 1:10 to 6:10.
[0017]
Methods for measuring these heat setting temperatures and melting points will be described later. When the heat setting temperature is less than (Tm2-35) ° C., the shrinkage of the surface resin film becomes extremely large during lamination to the substrate, while (Tm2 + 15) ° C. Exceeding this is undesirable because there is almost no decrease in the degree of orientation of the film during lamination on the substrate, and the workability of the film on the laminate is reduced.
[0018]
On the other hand, when the thickness ratio between the biaxially stretched polyester resin film and the base resin layer is less than 1:10, there is a problem that the depth of the printed pattern is lost and wrinkles easily occur when the films are laminated. If it exceeds 1, the shrinkage stress of the biaxially stretched polyester resin film becomes large during lamination to the substrate, which is not preferable.
[0019]
In addition, the surface of the biaxially stretched polyester resin film, which is the outermost layer, is also embossed to form embossed recesses, giving a three-dimensional effect to the entire decorative resin laminate printing resin film, or using a mirror roll Can be roll-pressed to give a mirror finish. Furthermore, a beautiful gloss can be imparted by further providing a gloss adjusting layer on the biaxially stretched polyester resin film.
[0020]
Furthermore, by providing a gloss adjusting layer on the surface of the biaxially stretched polyester resin film as the outermost layer, it is possible to obtain a printed resin film for laminating a decorative plate with further improved design. This wrinkle adjusting layer may be colorless and transparent, or may be matte transparent, and adjusts the glossiness of the surface of the decorative resin laminated printing resin film and also functions as a surface protective layer. The gloss adjusting layer can be formed by applying a paint using an appropriate vehicle. As the vehicle, one kind of thermosetting resin such as phenol resin, unsaturated polyester resin, epoxy resin, polyurethane resin, or a mixed resin of two or more kinds can be used. The paint for forming the gloss adjusting layer is usually imparted with a desired glossiness by dispersing an appropriate amount of matting agent. As the matting agent, mica, silica, alumina, calcium carbonate, diatomaceous earth, silica sand, shirasu balloon and the like are used. As the coating method of the coating material, known coating methods such as gravure coating, roll coating, and air knife coating can be used.
[0021]
As the resin used for the adhesive layer 4, it is preferable to use a copolymer polyester resin such as an ethylene terephthalate / isophthalate copolymer.
As an example of the material constituting the copolymer polyester resin, in addition to the above, a copolymer polyester resin having the following composition is preferably used. That is, as a soft segment forming a resin, polyoxyalkylene glycol such as polyethylene glycol and polytetramethylene glycol, or HOOC- [CH2] n such as polyε-caprolactone, azelaic acid, sebacic acid, dodecanedioic acid, and dimer acid An aliphatic polyester composed of an aliphatic dicarboxylic acid having a molecular structure of —COOH and an aliphatic and / or alicyclic diol is preferably used.
[0022]
The hard segment constituting the resin includes aromatic and / or alicyclic ester units such as ethylene terephthalate, butylene terephthalate, cyclohexane dimethylene terephthalate, cyclohexane dimethylene cyclohexane dicarboxylate, butylene 2,6 naphthalene dicarboxylate, etc. It is preferable that it is composed of at least one selected from.
[0023]
Furthermore, it is preferable that the alcohol component contains 1,4 butanediol residue from the viewpoint of solvent resistance, and the remainder of 1,4 butanediol in the total alcohol component forming the copolymer polyester is 40 mol% or more. , 65 mol% or less is preferable.
In the case where stronger adhesion between the decorative resin laminated printed resin film 1 and the substrate 2 is required, the adhesive resin layer 4 and the substrate are formed according to the structure of the resin layer according to any one of claims 1 to 4. It is preferable to replace a part of the resin component of the resin layer in contact with the substrate 2 of either the material resin layer 7 or the colored resin layer 5 with an ionomer. In this case, the ionomer is preferably contained in the resin in an amount of 1 to 50% by weight.
[0024]
In the biaxially stretched polyester resin film 10 used as the outermost layer of the printed resin film 1 for decorative board lamination of the present invention, the heat setting temperature and melting point of the biaxially stretched film, which are important factors, and the resin used for the base resin layer 7 The melting point of is measured as follows.
Using a differential scanning calorimeter DSC-7 manufactured by Perkin Elmer as a measuring device, about 5 mg of a sample of the biaxially stretched polyester resin film 10 is precisely weighed with a semi-micron balance, and nitrogen gas is allowed to flow, at 20 ° C./min. The temperature is raised at a rate of temperature rise, a temperature rise curve shown in FIG. 1A is drawn, and a heat fixing temperature Ths and a melting point Tm1 are obtained from an endothermic peak in the temperature rise curve. Similarly, about 5 mg of a resin sample used for the base resin layer 7 is precisely weighed with a semi-micron balance, and the temperature is increased at a rate of temperature increase of 20 ° C./min while flowing nitrogen gas. The melting point Tm2 is obtained from the endothermic peak in the rising temperature curve.
[0025]
The decorative resin laminate printing resin film 1 of the present invention shown in FIG. 2 (c) can be prepared as follows. That is, the print layer 6 composed of the pattern print layer 6a and the solid print layer 6b provided on the lower surface of the biaxially stretched polyester resin film 10 is superposed on the upper surface of the base resin layer 7 formed as a single layer film. While the resin layer 7 and the biaxially stretched polyester resin film 10 are superposed, the resin layer 7 is passed between a pair of hot rolls and sandwiched by thermocompression bonding to produce a single laminated film. By applying pressure while heating, the surface of the solid print layer 6b of the biaxially stretched polyester resin film 10 is fused to the base resin layer 7 to make a single printed resin film 1 for decorative plate lamination.
[0026]
Moreover, as shown in FIG.2 (d), the printing resin film 1 for decorative board lamination is the base resin layer of the laminated film of the adhesive resin layer 4 and the base resin layer 7 which were formed into a two-layer film by coextrusion. A printing layer 6 comprising a pattern printing layer 6a and a solid printing layer 6b is provided on the upper surface on the 7 side, and the adhesive resin layer 4 and the base resin layer 7 are co-extruded in the same manner as shown in FIG. The laminated film printed layer 6 is laminated so that it is in contact with the biaxially stretched polyester resin film 10, and is sandwiched between a pair of hot rolls and laminated by thermocompression bonding to produce a laminated film. It may be.
[0027]
Further, a colored resin layer 5 in which a pigment is kneaded with a resin is formed into a single-layer film by extrusion, a pattern printing layer 6a is applied on the colored resin layer 5, and a base resin layer 7 is overlaid thereon. As it is, it is passed between a pair of heat rolls and sandwiched by thermocompression bonding to produce one pre-laminated film. At that time, by using an embossing roll as the heat roll, it is possible to carry out lamination and embossing of the base resin layer 7 at the same time. By forming No. 8 and filling the wiping ink and providing the wiping printing layer 9, a highly designable pattern can be imparted. Further, the biaxially stretched polyester resin film 10 is placed on the pre-laminated film directly or via an adhesive layer while being overlapped and sandwiched between a pair of hot rolls and laminated by thermocompression bonding. The decorative resin laminated printed resin film 1 shown in (e) can be obtained.
[0028]
Further, as shown in FIG. 3 (f), the adhesive resin layer 4 and the colored resin layer 5 in which the resin is kneaded with the pigment are co-extruded to form a two-layer film, which is the same as shown in FIG. 3 (e). Then, a pattern printing layer 6a is applied on the colored resin layer 5, and further, a base resin layer 7 is overlaid on the colored resin layer 5, sandwiched between a pair of hot rolls, and thermocompression bonded. One pre-laminated film may be produced. In addition, when producing these resin films, it is possible to simultaneously perform lamination and embossing of the base resin layer 7 by using an embossing roll as the heat roll. By forming the embossed concave portion 8 for wiping printing on the surface of the base resin layer 7 and filling the wiping ink to provide the wiping printing layer 9, it is possible to give a high design pattern. Further, in the same manner as shown in FIG. 3 (f), the biaxially stretched polyester resin film 10 is laminated on the pre-laminated film directly or via an adhesive layer, thereby making the makeup shown in FIG. 3 (f). The printed resin film 1 for board lamination can be obtained. Since the colored resin layer 5 and the base resin layer 7 are excellent in dimensional stability, it is possible to suppress fluctuations in expansion and contraction caused by tension and heat, and embossing having high design characteristics in which the printed pattern and the embossed pattern are synchronized. It can be set as a decorative film. Steps such as the above laminating operation and embossing can be performed with the same apparatus as in a conventional polyvinyl chloride resin film.
[0029]
Furthermore, by providing a solid print layer 6b on the surface of the colored resin layer 5 in FIG. 3 (f) and using a resin film provided with a pattern print layer 6a thereon, as shown in FIG. It is also possible to make the printing resin film 1 for decorative plate lamination further improved.
Moreover, the decorative board as shown in FIG. 5 or FIG. 6 is obtained by laminating the printed resin film 1 for laminating the decorative board obtained by the above method with the substrate 2 with or without the adhesive layer 3 interposed therebetween. 11 is obtained. As the board | substrate 2, metal plates, such as a galvanized steel plate which plated zinc alloys, such as a steel plate, an aluminum alloy plate, zinc, a zinc-aluminum alloy, a zinc-cobalt-molybdenum alloy, are used, for example. Further, as the substrate 2, a board made of an inorganic material such as a wood veneer, a wood plywood, a particle board, an MDF, a plaster board, a calcium silicate board, an asbestos slate board, or the like can also be used.
[0030]
As an adhesive of the adhesive layer 3 that is selectively used for laminating the printed resin film 1 for decorative plate lamination and the substrate 2, general adhesives such as vinyl acetate resin, ethylene-vinyl acetate resin, Emulsion adhesives such as urea resin and urethane resin are preferably used because they are safe against fire, have no odor, and are inexpensive.
Next, the present invention will be described in more detail with reference to examples.
[0031]
(Examples 1-8 and Comparative Examples 1-3)
A transparent biaxially stretched polyethylene terephthalate film (PET-BO, melting point (Tm1): 257 ° C.) having a thickness of 25 μm, having a heat setting temperature (Ths) during film formation shown in Table 1 and Table 2, transparent biaxial stretching Polyethylene naphthalate film (PEN-BO, melting point: 269 ° C.) or a transparent biaxially stretched film of modified polyethylene terephthalate composed of 95 mol% terephthalic acid and 5 mol% isophthalic acid (modified PET-BO, melting point) : 246 [deg.] C.) on one side using a nitrocellulose-alkyd ink, a pattern printing layer and a colored solid printing layer printed in-line with a gravure rotary press, and commercially available ones having the intrinsic viscosities shown in Table 1 Thickness created by an extrusion film-forming machine using polybutylene terephthalate (PBT, melting point (Tm2): 225 ° C.) A 70 μm single-layer unstretched film (Examples 1 to 3, Examples 7 to 8, Comparative Examples 1 to 2) was used as a base resin layer, or a commercially available PBT copolymerized with 12 mol% of isophthalic acid. Two layers of PBT composed of 70 μm thick (PBT 60 μm, modified PET 10 μm) prepared by co-extrusion using a modified polyethylene terephthalate (modified PET) with an extrusion film forming machine and a modified PET as an adhesive resin layer Layer unstretched films (Examples 4 to 6 and Comparative Example 3) are stacked so that the printed layer and the PBT base resin layer are in contact with each other, the heating temperature of the pressure-bonding roll is 120 ° C., and the feeding speed of the resin film is 20 m. / Min, nip pressure of pressure-bonding roll: 25 kgf / cm2The two films were laminated by thermocompression bonding under the conditions described above to prepare a decorative resin laminated printed resin film.
[0032]
Next, a polyester-based adhesive is applied to an electrogalvanized steel sheet having a thickness of 0.5 mm at an application amount of 5 g / m2, and the decorative resin laminate printing resin film is applied to the electrogalvanized steel sheet at a heating temperature: 225 ° C., adhesion pressure: 15 kgf / cm2Crimping time: Heat-bonded under conditions of 5 seconds to obtain a decorative board.
[0033]
Example 9
An unstretched colored film having a thickness of 30 μm prepared by an extrusion film forming machine using a colored resin obtained by kneading 20% by weight of a cream color pigment with a commercially available modified polybutylene terephthalate resin (modified PBT) copolymerized with 12.5 mol% of isophthalic acid. Using a nitrocellulose-alkyd ink on one side, a pattern printing layer printed inline with a gravure rotary press, and a commercially available polytrimethylene terephthalate (PTT) as a base resin layer made by an extrusion film forming machine The unstretched film having a thickness of 40 μm and the transparent PET-BO having a thickness of 25 μm (melting point: 257 ° C.) having a heat setting temperature of 210 ° C. during film formation are used as the PTT film of the base resin layer. The heating surface of the pressure-bonding roll is 120 ° C., the resin film is fed so as to be in contact with the printed surface of the colored film and the transparent PET-BO. Degrees: 20m / min, nip pressure of crimping roll: 25kgf / cm2The laminate was formed by thermocompression bonding under the above conditions to prepare a decorative resin laminated printed resin film.
[0034]
Next, the decorative resin laminate printing resin film was thermocompression bonded to the same electrogalvanized steel sheet as in Example 1 under the same conditions as in Example 1 to obtain a decorative sheet.
(Example 10)
A PBT colored by kneading 20% by weight of a cream pigment and the same modified PET as in Example 4 were co-extruded by an extrusion film forming machine, and a two-layer uncoated film having a thickness of 70 μm (colored PBT 60 μm, modified PET 10 μm). A stretched film was prepared, and the same pattern printing layer as in Example 9 was printed on the colored film surface under the same conditions as in Example 9. The same modified PBT as in Example 9 containing no pigment was used as the base resin layer, the same transparent PET-BO as in Example 9 was used, and the modified PBT film of the base resin layer was a two-layer unstretched film. The laminate was laminated so as to be in contact with the printed surface on the colored film side and the transparent PET-BO, and was laminated under heat and pressure under the same conditions as in Example 9 to prepare a printed resin film for decorative plate lamination.
Next, the decorative resin laminate printing resin film was thermocompression bonded to the same electrogalvanized steel sheet as in Example 1 under the same conditions as in Example 1 to obtain a decorative sheet.
[0035]
(Example 11)
Using a nitrocellulose-alkyd ink on one side of an unstretched colored film of 30 μm in thickness, which was prepared by extrusion film forming using a colored resin in which 20% by weight of cream color pigment was kneaded with commercially available PTT, Printed inline on a rotary press. Also, as a base resin layer, commercially available PBT and commercially available polyethylene terephthalate (PET) are mixed at a mixing ratio (weight) of 70/30, melted by an extrusion film forming machine, and extruded onto an embossed casting roll. After the two-component curable urethane-based colored ink is applied by a roll coating method to the surface of the 40 μm thick unstretched film that is in contact with the casting roll, it adheres to a portion other than the embossed concave portion with a doctor blade. The colored ink was removed, the embossed recess formed on the surface of the unstretched film was filled with the colored ink and solidified, and a base resin film was printed on one side. Next, the same transparent PET-BO as in Example 10 was prepared, so that the printed surface of the colored film was in contact with the non-printed surface side of the base resin film, and the printed surface of the base resin film was in contact with the transparent PET-BO. Then, the laminated laminate was formed by thermocompression bonding under the same conditions as the lamination conditions by thermocompression bonding of Example 1 to produce a decorative resin laminate printing resin film.
Next, the decorative resin laminate printing resin film was thermocompression bonded to the same electrogalvanized steel sheet as in Example 1 under the same conditions as in Example 1 to obtain a decorative sheet.
[0036]
(Example 12)
Unstretched 30μm thick made by extrusion film-forming machine made of colored resin kneaded with 20% by weight of cream color pigment in blend resin made by mixing commercially available PBT and commercially available PET in 70/30 mixing ratio (weight) On one side of the colored film, a nitrocellulose-alkyd ink was used, and a colored solid printing layer was printed inline by a gravure rotary press. Further, a resin obtained by blending the same modified PBT as in Example 9 and a commercially available PBT at a mixing ratio (weight) of 70/30 was prepared as a base resin film having a thickness of 40 μm by an extrusion film forming machine. Next, the same PET-BO as in Example 11 was prepared, and the printed surface of the colored resin film and the PET-BO were overlapped so as to be in contact with the base resin film, respectively. With the PET-BO surface as the embossing roll side, a three-layer decorative film having an embossed recess on the PET-BO surface was prepared by passing through a pressure-bonding roll consisting of an embossing roll and a silicon rubber roll.
Next, the decorative resin laminate printing resin film was thermocompression bonded to the same electrogalvanized steel sheet as in Example 1 under the same conditions as in Example 1 to obtain a decorative sheet.
[0037]
(Example 13)
A resin obtained by kneading 20% by weight of a cream pigment into a resin obtained by blending the same modified PBT as in Example 9 and a commercially available PBT at a mixing ratio (weight) of 70/30, and the same modified PET as in Example 4. Were coextruded by an extrusion film forming machine to create a two-layer unstretched film having a thickness of 70 (colored blend resin 60 μm, modified PET 10 μm), and the same pattern printing layer as in Example 9 was applied to the colored film surface. Printing was performed under the same conditions as in Example 9. As a base resin layer, an unstretched film having a thickness of 40 μm was prepared by an extrusion film forming machine using a blend resin obtained by mixing a commercially available polycarbonate (PC) and a commercially available PBT at a mixing ratio (weight) of 60/40. . Next, the same transparent PET-BO as in Example 10 is prepared, and the printed surface of the colored film and the transparent PET-BO are overlapped so that one side of the substrate is in contact with the surface of the base resin film. The laminate was laminated under pressure and pressure bonding under the same conditions as in the above, to produce a decorative resin laminated printed resin film.
Further, the surface of the decorative resin laminated printing resin film thus prepared was gravure roll coated with a two-component curable polyurethane gloss adjusting paint (Showa Ink).
Next, the decorative resin laminate printing resin film was thermocompression bonded to the same electrogalvanized steel sheet as in Example 1 under the same conditions as in Example 1 to obtain a decorative sheet.
[0038]
(Example 14)
A resin obtained by kneading 20% by weight of a cream pigment into a resin obtained by blending the same modified PBT as in Example 9 and a commercially available PBT at a mixing ratio (weight) of 70/30, and the same modified PET as in Example 4. Were coextruded by an extrusion film forming machine to create a two-layer unstretched film having a thickness of 70 (colored blend resin 60 μm, modified PET 10 μm), and the same pattern printing layer as in Example 9 was applied to the colored film surface. Printing was performed under the same conditions as in Example 9. As the base resin layer, an unstretched film having a total thickness of 40 μm was prepared by an extrusion film forming machine so that the same modified PBT as in Example 9 and commercially available PBT had a thickness ratio of 10 μm / 30 μm. Next, the same transparent PET-BO as in Example 10 was prepared, and the printed surface of the colored film was in contact with the modified PBT layer of the base resin film, and one side of the transparent PET-BO was in contact with the PBT layer of the base resin film. In this manner, the laminates were laminated by thermocompression bonding under the same conditions as those for thermocompression bonding in Example 1 to produce a decorative resin laminate printing resin film.
Further, the surface of the decorative resin laminated printing resin film thus prepared was gravure roll coated with a two-component curable polyurethane-based wrinkle-adjusting paint (Showa Ink).
Next, the decorative resin laminate printing resin film was thermocompression bonded to the same electrogalvanized steel sheet as in Example 1 under the same conditions as in Example 1 to obtain a decorative sheet.
[0039]
(Example 15)
The resin blended with the same blend resin consisting of PC and PBT as in Example 13 with 20% by weight of cream color pigment was extruded by an extrusion film forming machine to create an unstretched film having a thickness of 70 μm. Using a nitrocellulose-alkyd ink, the pattern printing layer and the colored solid printing layer were printed inline by a gravure rotary press. As the base resin layer, blend resin formed by mixing the same modified PET as in Example 4 and commercially available PBT at a mixing ratio (weight) of 40/60, an unstretched film having a thickness of 40 μm was obtained by an extrusion film forming machine. Created. Next, the same transparent PET-BO as in Example 10 is prepared, and the printed surface of the colored film and the transparent PET-BO are overlapped so that one side of the substrate is in contact with the surface of the base resin film. The laminate was laminated under pressure and pressure bonding under the same conditions as in the above, to produce a decorative resin laminated printed resin film.
Next, the decorative resin laminate printing resin film was thermocompression bonded to the same electrogalvanized steel sheet as in Example 1 under the same conditions as in Example 1 to obtain a decorative sheet.
[0040]
(Example 16)
A blended resin composed of the same modified PET and PBT as in Example 15 was kneaded with 20% by weight of a cream pigment and colored resin was extruded by an extrusion film forming machine to produce an unstretched film having a thickness of 70 μm. Using a nitrocellulose-alkyd ink, the pattern printing layer and the colored solid printing layer were printed inline by a gravure rotary press. As a base resin layer, an unstretched film having a thickness of 40 μm is prepared by an extrusion film forming machine using a blend resin obtained by mixing the same PTT as in Example 9 and a commercially available PBT at a mixing ratio (weight) of 50/50. did. Next, the same transparent PET-BO as in Example 10 is prepared, and the printed surface of the colored film and the transparent PET-BO are overlapped so that one side of the substrate is in contact with each surface of the base resin film. Lamination was performed under the same conditions as the lamination conditions by pressure bonding to produce a decorative resin laminated printed resin film.
Next, the decorative resin laminate printing resin film was thermocompression bonded to the same electrogalvanized steel sheet as in Example 1 under the same conditions as in Example 1 to obtain a decorative sheet.
[0041]
(Example 17)
A blended resin composed of the same PTT and PBT as in Example 16 was mixed with 20% by weight of a cream color pigment and extruded with an extrusion film forming machine to create an unstretched film with a thickness of 70 μm. Using a nitrocellulose-alkyd ink, a pattern printing layer and a colored solid printing layer were printed in-line with a gravure rotary press. As a base resin layer, an unstretched film having a thickness of 40 μm was prepared by an extrusion film forming machine using a resin obtained by blending commercially available PBT and a commercially available ionomer at a mixing ratio (weight) of 90/10. Next, the same transparent PET-BO as in Example 10 is prepared, and the printed surface of the colored film and the transparent PET-BO are overlapped so that one side of the substrate is in contact with each surface of the base resin film. Lamination was performed under the same conditions as the lamination conditions by pressure bonding to produce a decorative resin laminated printed resin film.
Next, the decorative resin laminate printing resin film was thermocompression bonded to the same electrogalvanized steel sheet as in Example 1 under the same conditions as in Example 1 to obtain a decorative sheet.
[0042]
(Example 18)
A blended resin composed of the same PBT and ionomer as in Example 17 was kneaded with 20% by weight of a cream color pigment and extruded with an extrusion film forming machine to create an unstretched film having a thickness of 70 μm. Using a nitrocellulose-alkyd ink, a pattern printing layer and a colored solid printing layer were printed in-line with a gravure rotary press. As the base resin layer, an unstretched film having a thickness of 40 μm was prepared by an extrusion film forming machine using the same PBT as in Example 1. Next, the same transparent PET-BO as in Example 10 is prepared, and the printed surface of the colored film and the transparent PET-BO are overlapped so that one side of the substrate is in contact with each surface of the base resin film. Lamination was performed under the same conditions as the lamination conditions by pressure bonding to produce a decorative resin laminated printed resin film.
Next, the decorative resin laminate printing resin film was thermocompression bonded to the same electrogalvanized steel sheet as in Example 1 under the same conditions as in Example 1 to obtain a decorative sheet.
[0043]
(Example 19)
A resin obtained by kneading 20% by weight of a cream color pigment into a resin obtained by blending the same modified PBT as in Example 9 and a commercially available PBT at a mixing ratio (weight) of 70/30, and the same PBT as in Example 17 A blend resin made of an ionomer is coextruded by an extrusion film forming machine to prepare a two-layer unstretched film having a thickness of 70 (colored blend resin 60 μm, PBT / ionomer blend resin 10 μm). 9 was printed under the same conditions as in Example 9. As a base resin layer, an unstretched film having a thickness of 40 μm was prepared using an extrusion film forming machine for PBT. Next, the same transparent PET-BO as in Example 10 is prepared, and the printed surface of the colored film and the transparent PET-BO are overlapped so that one side of the substrate is in contact with each surface of the base resin film. Lamination was performed under the same conditions as the lamination conditions by pressure bonding to produce a decorative resin laminated printed resin film.
Next, the decorative resin laminate printing resin film was thermocompression bonded to the same electrogalvanized steel sheet as in Example 1 under the same conditions as in Example 1 to obtain a decorative sheet.
[0044]
(Characteristic evaluation of resin film)
The decorative board created in Examples 1-19 and Comparative Examples 1-3 was evaluated about the following characteristic.
(Thermal shrinkage of the surface film when laminated on the substrate)
The heat shrinkage of the surface film of the decorative resin laminated printing resin film of the present invention is determined by the examples of the surface film both ends of the decorative metal plate prepared in Examples 1 to 19 and Comparative Examples 1 to 3 and laminated the decorative film on the metal plate. The heat shrinkage width of each part was measured and evaluated according to the following three criteria.
○: Shrinkage width at both ends is 2 mm or less.
(Triangle | delta): The shrinkage | contraction width | variety of both ends is 2-10 mm.
X: The shrinkage | contraction width | variety of both ends is 10 mm or more.
In the above scores, ○ and Δ are not problematic in use. In addition, this test was implemented about ten test pieces.
[0045]
(Processability of resin film)
The quality of the processability of the printed resin film for laminating laminated sheets of the present invention was determined according to JIS Z 2248 (metal) on the decorative metal sheet prepared in Examples 1 to 19 and Comparative Examples 1 to 3 and laminated the decorative film on the metal sheet. In accordance with the material bending test method), 0T bending was performed, the film surface of the bent portion was visually observed, and evaluated according to the following four criteria.
(Double-circle): A crack is not recognized at all in a bending part.
○: Slight whitening is observed at the end of the bent portion.
(Triangle | delta): Whitening is recognized by the whole bending part.
X: A considerable degree of cracking is observed in the bent portion.
In the above ratings, ◎ and ○ are not problematic in use. In addition, this test was implemented about ten test pieces.
[0046]
(Embossability for wiping printing)
The embossability for wiping printing of the decorative resin laminate printing resin film of the present invention is determined by the degree of roughness of the surface of the base resin layer of the embossed resin film. In the present invention, the surface of the base resin layer of the resin film embossed using a grained engraving roll having an average surface roughness (Ra): 11 μm of irregularities is visually observed, and embossability is obtained. Was evaluated according to the following three criteria.
○: Good,
Δ: Somewhat bad,
×: Defect
In addition, said evaluation criteria measured the surface roughness (Ra: micrometer) of a polyvinyl chloride resin film based on JIS B0601 using the SURFCOM surface roughness meter by Tokyo Seimitsu Co., Ltd., and average surface roughness was 4 micrometers. Is the acceptable standard for embossability, and the one with an average surface roughness equal to or better than the surface of the polyvinyl chloride resin film with a thickness of 4 μm is considered good (◯), compared with the surface of the polyvinyl chloride resin film. A product having an appearance that was slightly inferior but practically acceptable was judged as slightly defective (Δ), and a product not embossed was judged as defective (x).
[0047]
(Contamination resistance)
On the resin film surface of the outermost layer of the decorative board created in Examples 1 to 19 and Comparative Examples 1 to 3, after drawing with black oil-based magic ink and leaving it for 24 hours, it was wiped with a cloth impregnated with ethanol, The degree of magic ink remaining on the resin film surface was visually observed and evaluated according to the following criteria.
(Double-circle): Magic ink is not recognized at all.
○: A very slight amount of magic ink remained to the extent that there is no practical problem.
(Triangle | delta): Remaining slight magic ink which is a problem in practical use is recognized.
X: Remaining magic ink is recognized to a considerable extent.
[0048]
(Solvent resistance)
A sponge impregnated with methyl ethyl ketone was placed on the outermost resin film surface of the decorative board prepared in Examples 1 to 19 and Comparative Examples 1 to 3, and after standing for 24 hours, the degree of discoloration and swelling of the film surface Were visually observed and evaluated according to the following criteria.
A: No discoloration or swelling is observed.
◯: Generation of slight discoloration or swelling that is not problematic for practical use is recognized.
(Triangle | delta): Generation | occurrence | production of slight discoloration or swelling of the grade which is a problem practically is recognized.
X: Discoloration and swelling are recognized to a considerable extent.
[0049]
(Water degradation resistance)
Assuming that the decorative board of the present invention is aged for a long time in a hot and humid state (for example, when used as an interior material of a unit bath), the water deterioration resistance of the resin film when in contact with water for a long time is determined by DuPont The impact test method evaluated.
The printed resin films for laminating decorative plates prepared in Examples 1 to 19 and Comparative Examples 1 to 3 were laminated on an electrogalvanized steel sheet having a thickness of 0.5 mm to obtain test pieces. This test piece was cut into a size of 60 mm × 60 mm, immersed in demineralized water maintained at a temperature of 38 ± 2 ° C. for 1 month, dried at room temperature, and in compliance with JIS K 5400 using a DuPont impact tester. The impact was applied under the conditions (impact part size 1/2 inch φ, weight 1 kg, drop height 50 cm). The state of the resin film after the impact was loaded was observed with the naked eye and evaluated in the following five stages.
(Double-circle): A crack is not recognized by the resin film.
○: Fine cracks are observed in a part of the resin film.
(Triangle | delta): A fine crack is recognized in the whole process part of a resin film.
X: A big crack is recognized by the whole process part of a resin film.
XX: The crack is remarkable in the whole resin film.
In the above ratings, ◎ and ○ are not problematic in use. In addition, this test was implemented about ten test pieces.
[0050]
(Vividness)
The printed resin films for laminating decorative plates prepared in Examples 1 to 19 and Comparative Examples 1 to 3 were laminated on an electrogalvanized steel sheet having a thickness of 0.5 mm to obtain test pieces. The sharpness of the surface of the test piece was measured with a portable sharpness gloss meter PGD-4 manufactured by Japan Color Research Institute. The sharpness in the present invention means the sharpness of the image, that is, the sharpness of the specular image reflected on the makeup surface, and the high-definition means that the sharpness is 0.8 or more. Sure.
Table 3 and Table 4 show the characteristic evaluation of these resin films. In Tables 1 to 4, PET-BO is transparent biaxially stretched polyethylene terephthalate, modified PET-BO is a transparent biaxially stretched polyethylene terephthalate film, PEN-BO is transparent biaxially stretched polyethylene naphthalate, PET Is polyethylene terephthalate, PBT is polybutylene terephthalate, PTT is polytrimethylene terephthalate, PEN is polyethylene naphthalate, modified PET is isophthalic acid copolymerized polyethylene terephthalate, modified PBT is isophthalic acid copolymerized polybutylene terephthalate, modified PBT // PBT is a two-layer resin of isophthalic acid copolymerized polybutylene terephthalate and polybutylene terephthalate, and modified PBT / PBT is an isophthalic acid copolymerized polybutylene terephthalate and polybutylene. Blend resin for phthalate, modified PET / PBT for isophthalic acid copolymer polyethylene terephthalate and polybutylene terephthalate, PBT / PET for polybutylene terephthalate and polyethylene terephthalate, PC / PBT for polycarbonate and polybutylene terephthalate PTT / PBT represents a blend resin of polytrimethylene terephthalate and polybutylene terephthalate, and PBT / ionomer represents a blend resin of polybutylene terephthalate and ionomer.
[0051]
As shown in Tables 3 and 4, the printing resin film for laminating decorative sheets of the present invention is a heat shrink, processability, embossing property, contamination resistance, solvent resistance, water deterioration resistance, freshness of the surface film during lamination. It shows excellent characteristics in all of the film quality.
[0052]
[Table 1]
[0053]
[Table 2]
[0054]
[Table 3]
[0055]
[Table 4]
[Industrial applicability]
[0056]
The decorative resin laminated printing resin film of the present invention is configured as described above, and is also used for the surface resin layer of a decorative sheet using a conventional polyvinyl chloride resin film or olefin resin film. The relationship between the resin film heat setting temperature Ths using the melting point Tm1 of the resin and the melting point Tm2 of the base resin, and the range of Tm2-35 ≦ Ths ≦ Tm2 + 15 ≦ Tm1, and further, the resin layer and the base resin layer By defining the thickness ratio in the range of 1:10 to 6:10, it is possible to obtain a printed film for decorative plates having a small heat shrinkage when laminated on a substrate and having stable processability.
Furthermore, since the base resin layer and the colored resin layer made of a polybutylene terephthalate film have little variation in expansion and contraction with respect to heat and tension and have excellent dimensional stability, a printed matter with high printing registration accuracy can be obtained.
In addition, since a decorative film can be obtained with the same manufacturing method and manufacturing conditions as conventional polyvinyl chloride resin films, there is no need for capital investment such as expansion of new facilities or modification of existing facilities. Similar to the above, it is possible to express a pattern having excellent design properties in which the printed pattern and the embossed pattern are synchronized.
In addition, since the resin constituting the base resin layer and the surface resin layer does not contain a plasticizer, it does not cause problems such as surface contamination due to bleed of plasticizer, and is resistant to contamination, solvent resistance, and water resistance. Excellent surface properties such as properties.
Furthermore, since no toxic gas such as hydrogen chloride gas is generated during incineration, it is excellent in environmental protection without worrying about polluting the environment. Unit bath, refrigerator, exterior plate for refrigerator door, Curtain rail, wash unit, washing machine, system kitchen, partition, wall panel, indoor door, indoor storage, fluorescent light reflector, audiovisual equipment skin, microwave oven skin, oven skin, fan heater The present invention can be suitably applied to an outer panel of a heater, an outer panel of a stove, an outer panel of an air conditioner and the like.
[Brief description of the drawings]
[0057]
(A) of FIG. 1 is a temperature rise curve of the biaxially stretched polyester resin film of the present invention by a differential scanning calorimeter, and (b) is a rise of the resin film of the base resin layer of the present invention by a differential scanning calorimeter. It is a temperature curve. (C) of FIG. 2 is sectional drawing which shows an example of the printing resin film for lamination | stacking of decorative board of this invention, (d) is sectional drawing which shows another example of the printing resin film for lamination | stacking of decorative board of this invention. . (E) of FIG. 3 is sectional drawing which shows another example of the printing resin film for lamination | stacking of decorative board of this invention, (f) is sectional drawing which shows another example of the printing resin film for lamination | stacking of decorative board of this invention. It is. FIG. 4 is a cross-sectional view showing another example of the printing resin film for laminating decorative sheets according to the present invention. FIG. 5 is a sectional view showing an example of the decorative board of the present invention. FIG. 6 is a cross-sectional view showing another example of the decorative board of the present invention.
Claims (22)
ポリブチレンテレフタレート、ポリトリメチレンテレフタレート、又は変性ポリブチレンテレフタレートからなる基材樹脂層と接着樹脂層と、を積層し、
前記基材樹脂層の上面に印刷層を設け、
前記印刷層が二軸延伸ポリエステル樹脂フィルムと接するようにして重ね合わせ、
熱ロール間に通して圧着積層してなる化粧板積層用印刷樹脂フィルム。The outermost layer is a transparent biaxially stretched polyester resin film, and a resin film formed by sequentially laminating a printing layer, a base resin layer, and an adhesive resin layer on the lower layer ,
Laminating a base resin layer and an adhesive resin layer made of polybutylene terephthalate, polytrimethylene terephthalate, or modified polybutylene terephthalate,
A printing layer is provided on the upper surface of the base resin layer,
The printed layer is overlapped so as to be in contact with the biaxially stretched polyester resin film,
A printed resin film for laminating decorative sheets, which is laminated by pressing between hot rolls .
着色樹脂層の上に印刷層を設け、
その上にポリブチレンテレフタレート、ポリトリメチレンテレフタレート、又は変性ポリブチレンテレフタレートからなる基材樹脂層を重ね合わせて、
熱ロール間に通して圧着積層して予備積層フィルムとし、
さらにその上に直接または接着剤層を介して二軸延伸ポリエステル樹脂フィルムを重ね合わせて、熱ロール間に通して圧着積層してなる化粧板積層用印刷樹脂フィルム。The outermost layer is a transparent biaxially stretched polyester resin film, and a resin film formed by sequentially laminating a base resin layer, a printing layer, a colored resin layer, and an adhesive resin layer on the lower layer ,
A printing layer is provided on the colored resin layer,
A base resin layer made of polybutylene terephthalate, polytrimethylene terephthalate, or modified polybutylene terephthalate is overlaid thereon,
Passing between the hot rolls and pressure laminating to make a pre-laminated film,
Furthermore, the printing resin film for lamination | stacking of a decorative board laminated | stacked on a biaxially-stretched polyester resin film on it directly or through an adhesive layer, and carrying out pressure | pressure lamination | stacking through a hot roll .
ポリブチレンテレフタレート、ポリトリメチレンテレフタレート、又は変性ポリブチレンテレフタレートからなる基材樹脂層の上面に、二軸延伸ポリエステル樹脂フィルムの下面に設けた印刷層を重ね合わせ、熱ロールに通して圧着積層してなる化粧板積層用印刷樹脂フィルム。The outermost layer is a transparent biaxially stretched polyester resin film, and a resin film formed by sequentially laminating a printing layer and a base resin layer on the lower layer ,
A printed layer provided on the lower surface of the biaxially stretched polyester resin film is overlaid on the upper surface of the base resin layer made of polybutylene terephthalate, polytrimethylene terephthalate, or modified polybutylene terephthalate, and then pressure-bonded and laminated through a heat roll. A printed resin film for decorative board lamination.
着色樹脂層の上に印刷層を施し、その上にポリブチレンテレフタレート、ポリトリメチレンテレフタレート、又は変性ポリブチレンテレフタレートからなる基材樹脂層を重ね合わせ、熱ロールに通して圧着積層して予備積層フィルムとし、
さらにその上に直接または接着剤層を介して二軸延伸ポリエステル樹脂フィルムを重ね合わせて、熱ロール間に通して圧着積層してなる化粧板積層用印刷樹脂フィルム。The outermost layer is a transparent biaxially stretched polyester resin film, and a resin film formed by sequentially laminating a base resin layer, a printing layer, a colored resin layer, and an adhesive resin layer on the lower layer ,
A printed layer is applied on the colored resin layer, and a base resin layer made of polybutylene terephthalate, polytrimethylene terephthalate, or modified polybutylene terephthalate is overlaid on the colored resin layer. age,
Furthermore, the printing resin film for lamination | stacking of a decorative board laminated | stacked on a biaxially-stretched polyester resin film on it directly or through an adhesive layer, and carrying out pressure | pressure lamination | stacking through a hot roll .
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33052199 | 1999-11-19 | ||
| PCT/JP2000/008132 WO2001038090A1 (en) | 1999-11-19 | 2000-11-17 | Printing resin film for laminated decorative sheet, decorative sheet having the resin film laminated, and unit bath and door of refrigerator using the decorative sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP3913061B2 true JP3913061B2 (en) | 2007-05-09 |
Family
ID=18233571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001539677A Expired - Lifetime JP3913061B2 (en) | 1999-11-19 | 2000-11-17 | Printed resin film for decorative plate lamination, decorative plate laminated with the resin film, unit bath using the decorative plate, refrigerator door |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP3913061B2 (en) |
| AU (1) | AU1416001A (en) |
| MY (1) | MY128498A (en) |
| TW (1) | TW572824B (en) |
| WO (1) | WO2001038090A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4947479B2 (en) * | 2001-07-06 | 2012-06-06 | 大日本印刷株式会社 | Polyolefin decorative sheet for decorative steel sheet and decorative steel sheet |
| DE10309917A1 (en) * | 2003-03-07 | 2004-09-16 | Klöckner Pentaplast B.V., SM Weert | Plastic film for furniture or furniture parts |
| JP6370709B2 (en) * | 2012-10-26 | 2018-08-08 | 東洋鋼鈑株式会社 | Resin film and resin film laminated decorative board |
| JP6653988B2 (en) * | 2014-08-06 | 2020-02-26 | リケンテクノス株式会社 | Multilayer resin sheet for front panel construction |
| JP2020131586A (en) * | 2019-02-21 | 2020-08-31 | 宇部エクシモ株式会社 | Hollow structural sheet |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0872190A (en) * | 1994-09-02 | 1996-03-19 | Dainippon Printing Co Ltd | Decorative sheet |
| JPH0976445A (en) * | 1995-09-20 | 1997-03-25 | Dainippon Printing Co Ltd | Vivid decorative sheet and manufacture of decorative plate |
-
2000
- 2000-11-17 TW TW89124355A patent/TW572824B/en not_active IP Right Cessation
- 2000-11-17 MY MYPI20005404 patent/MY128498A/en unknown
- 2000-11-17 JP JP2001539677A patent/JP3913061B2/en not_active Expired - Lifetime
- 2000-11-17 WO PCT/JP2000/008132 patent/WO2001038090A1/en active Application Filing
- 2000-11-17 AU AU14160/01A patent/AU1416001A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001038090A1 (en) | 2001-05-31 |
| MY128498A (en) | 2007-02-28 |
| AU1416001A (en) | 2001-06-04 |
| TW572824B (en) | 2004-01-21 |
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