JP2005324394A - Rough surface-shaped film, its manufacturing method, resin-coated metal sheet having rough surface part formed using rough surface-shaped film and its manufacturing method - Google Patents
Rough surface-shaped film, its manufacturing method, resin-coated metal sheet having rough surface part formed using rough surface-shaped film and its manufacturing method Download PDFInfo
- Publication number
- JP2005324394A JP2005324394A JP2004143386A JP2004143386A JP2005324394A JP 2005324394 A JP2005324394 A JP 2005324394A JP 2004143386 A JP2004143386 A JP 2004143386A JP 2004143386 A JP2004143386 A JP 2004143386A JP 2005324394 A JP2005324394 A JP 2005324394A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- rough surface
- film
- particle
- coated metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 260
- 239000011347 resin Substances 0.000 title claims abstract description 260
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 92
- 239000002184 metal Substances 0.000 title claims abstract description 92
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 53
- 239000002245 particle Substances 0.000 claims abstract description 46
- 230000003746 surface roughness Effects 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 12
- -1 polyethylene terephthalate Polymers 0.000 claims description 42
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 15
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 15
- 239000004743 Polypropylene Substances 0.000 claims description 11
- 229920001155 polypropylene Polymers 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000009998 heat setting Methods 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 229920001187 thermosetting polymer Polymers 0.000 claims description 9
- 229920005672 polyolefin resin Polymers 0.000 claims description 8
- 229920001225 polyester resin Polymers 0.000 claims description 7
- 239000004645 polyester resin Substances 0.000 claims description 7
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 6
- 239000004800 polyvinyl chloride Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000007788 roughening Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 10
- 238000007639 printing Methods 0.000 abstract description 8
- 229910001335 Galvanized steel Inorganic materials 0.000 description 28
- 239000008397 galvanized steel Substances 0.000 description 28
- 239000006185 dispersion Substances 0.000 description 27
- 238000007493 shaping process Methods 0.000 description 23
- 229920001577 copolymer Polymers 0.000 description 16
- 239000000853 adhesive Substances 0.000 description 15
- 230000001070 adhesive effect Effects 0.000 description 15
- 238000004049 embossing Methods 0.000 description 13
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 238000001723 curing Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000012463 white pigment Substances 0.000 description 4
- 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 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 229920002978 Vinylon Polymers 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 3
- 239000005033 polyvinylidene chloride Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000001055 blue pigment Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000011146 organic particle Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920000306 polymethylpentene Polymers 0.000 description 2
- 239000011116 polymethylpentene Substances 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- NIDZWWNRMZPMLN-UHFFFAOYSA-N [1,4,4-tris(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCC(CO)(CO)CC1 NIDZWWNRMZPMLN-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XWENCHGJOCJZQO-UHFFFAOYSA-N ethane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C(C(O)=O)C(C(O)=O)C(O)=O XWENCHGJOCJZQO-UHFFFAOYSA-N 0.000 description 1
- RWLDAJMGAVDXSH-UHFFFAOYSA-N ethane-1,1,2-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(O)=O RWLDAJMGAVDXSH-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ROTJZTYLACIJIG-UHFFFAOYSA-N pentane-1,3,5-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CCC(O)=O ROTJZTYLACIJIG-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Images
Landscapes
- Laminated Bodies (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
Abstract
Description
本発明は、樹脂表面に粗面部を形成させるために用いる粗面賦型フィルムおよびその粗面賦型フィルムの製造方法に関し、さらにその粗面賦型フィルムを用いて樹脂表面に粗面部を形成させてなる粗面部を有する樹脂被覆金属板およびその粗面部を有する樹脂被覆金属板の製造方法に関する。 The present invention relates to a rough surface-shaped film used for forming a rough surface portion on a resin surface and a method for producing the rough surface-shaped film, and further uses the rough surface-shaped film to form a rough surface portion on a resin surface. The present invention relates to a resin-coated metal plate having a rough surface portion and a method for producing a resin-coated metal plate having the rough surface portion.
冷蔵庫、オーディオ機器などの家電製品用の扉やキャビネット、建築物の壁、天井、ドア部材などの内装材として、表面に目地模様などの凹凸部を形成させた樹脂を被覆してなる樹脂被覆金属板が用いられている。例えば、特開２００４−０５２２７０号公報には、樹脂フィルムの表面に、溝状の凹部と溝状の凹部の両側に土手状の凸部が形成された目地デザイン樹脂フィルム、およびその目地デザイン樹脂フィルムを金属板に被覆してなる目地デザイン樹脂フィルム被覆金属板が提案されている。この目地デザイン樹脂フィルムにおいては、金属製のロール表面に目地模様を刻設したエンボスロールを用いて樹脂フィルム表面を加圧して目地模様を転写している。このように、エンボスロールを用いて樹脂フィルム表面に凹凸模様を転写する場合、様々な凹凸模様を有する樹脂被覆金属板を得るにはそれぞれの凹凸模様を刻設したエンボスロールを準備しなくてはならないが、エンボスロールは高価であり、また製作に時間を要するなど、製品コストが高額化し生産性が低いという問題がある。また、金属製のエンボスロールは、樹脂フィルムに比べて熱伝導性が極めて大きく、エンボスロール表面の温度を厳密に一定範囲に制御しないと、鮮明なエンボス模様が得られない。すなわち、エンボスロール表面の温度が高すぎると樹脂フィルムが硬化しないために転写したエンボス凹部の部分が熱変形してエンボス模様のシャープさが失われる。一方、エンボスロール表面の温度が低すぎると樹脂被覆金属板の冷却速度が過大になり、金属板が破断しやすくなる。 Resin-coated metal that is coated with a resin with irregularities such as joints on the surface as interior materials such as doors and cabinets for household appliances such as refrigerators and audio equipment, building walls, ceilings, door members, etc. A board is used. For example, Japanese Patent Application Laid-Open No. 2004-052270 discloses a joint design resin film in which a groove-like recess and a bank-like projection are formed on both sides of the groove-like recess on the surface of the resin film, and the joint design resin film. A joint design resin film-coated metal plate is proposed in which a metal plate is coated. In this joint design resin film, the joint pattern is transferred by pressurizing the resin film surface using an embossing roll having a joint pattern engraved on the metal roll surface. Thus, when transferring an uneven pattern on the surface of a resin film using an emboss roll, in order to obtain a resin-coated metal plate having various uneven patterns, it is necessary to prepare an emboss roll engraved with each uneven pattern. However, the embossing roll is expensive and requires a long time to manufacture, resulting in high product costs and low productivity. Further, the metal embossing roll has extremely high thermal conductivity as compared with the resin film, and a sharp embossing pattern cannot be obtained unless the temperature of the embossing roll surface is strictly controlled within a certain range. That is, if the temperature of the embossing roll surface is too high, the resin film is not cured, so that the transferred embossed concave portion is thermally deformed and the embossed pattern becomes sharp. On the other hand, if the temperature of the embossing roll surface is too low, the cooling rate of the resin-coated metal plate becomes excessive, and the metal plate tends to break.
エンボスロールを用いずに、樹脂上に凹凸模様を転写する方法として、特開平０６−１１４９３２号公報には、粒径が０．１〜１．０μｍのフィラーを練り込んだ二軸延伸ポリエステルフィルムにプラスチックシートを重ねて両者を均一に加熱加圧した後、二軸延伸ポリエステルフィルムを剥離することにより、プラスチックシートにエンボス模様を転写するエンボス加工方法が提案されている。しかし、この方法によれば樹脂上に均一なエンボス模様を形成させることはできるが、目地デザイン模様などのような他の部分とは局部的に表面の凹凸状態が異なる部分を形成させることはできない。 As a method for transferring a concavo-convex pattern onto a resin without using an embossing roll, JP-A-06-114932 discloses a biaxially stretched polyester film kneaded with a filler having a particle size of 0.1 to 1.0 μm. An embossing method has been proposed in which an embossed pattern is transferred to a plastic sheet by peeling the biaxially stretched polyester film after the plastic sheets are stacked and heated and pressed uniformly. However, according to this method, it is possible to form a uniform embossed pattern on the resin, but it is not possible to form a part whose surface unevenness is locally different from other parts such as joint design patterns. .
樹脂などの成形体の表面に、他の部分とは局部的に表面の凹凸状態が異なる部分を形成させる技術として、特開平０５−０１６２２８号公報には、基材フィルム上に無機系フィラーとバインダー樹脂からなる樹脂組成物を塗布して全面に微細な凹凸層を形成させた後、微細な凹凸層上に部分的に樹脂を印刷して平坦層を形成させるか、または基材フィルム上に部分的に撥液性樹脂を塗布し、その上に無機系フィラーとバインダー樹脂からなる樹脂組成物を塗布することにより、微細な凹凸層と局部的な平坦層が混在したグロス−マット表面を形成してなる賦型フィルムが形成され、そしてこの賦型フィルムを用いて樹脂などの成形体の表面に賦型フィルムのグロス−マット表面を転写してスウェード調の表面とする技術が提案されている。しかし、この方法によれば、樹脂などの成形体表面の殆どの部分に微細な凹凸層が形成され、局部的に平坦層が形成されたスウェード調の表面状態が得られるが、平坦な樹脂フィルム上の一部に局部的に粗面部分を形成させたり、局部的にまたは全面に粗面化程度の異なる複数の粗面部を形成することはできない。 As a technique for forming a portion having a surface unevenness locally different from other portions on the surface of a molded body such as a resin, Japanese Patent Laid-Open No. 05-016228 discloses an inorganic filler and a binder on a base film. After applying a resin composition made of resin to form a fine concavo-convex layer on the entire surface, partially printing the resin on the fine concavo-convex layer to form a flat layer, or partially on the base film By applying a liquid repellent resin and applying a resin composition consisting of an inorganic filler and a binder resin on top of it, a gloss-matt surface in which a fine uneven layer and a local flat layer are mixed is formed. There has been proposed a technique for forming a suede-like surface by transferring the gloss-matt surface of the shaped film onto the surface of a molded body such as a resin using the shaped film. However, according to this method, a fine concavo-convex layer is formed on almost the entire surface of the molded body such as a resin, and a suede-like surface state in which a flat layer is locally formed can be obtained. A rough surface portion cannot be locally formed on a part of the upper surface, or a plurality of rough surface portions having different roughening levels cannot be formed locally or on the entire surface.
本発明に関する先行技術文献として以下のものがある。
本発明は、樹脂表面に粗面部を形成させるために用いる粗面賦型フィルムおよびその粗面部型フィルムの製造方法を提供し、さらにその粗面賦型フィルムを用いて樹脂表面に局部的に粗面部を形成させてなる粗面部を有する樹脂被覆金属板およびその粗面部を有する樹脂被覆金属板の製造方法を提供することを目的とする。 The present invention provides a rough surface-shaped film used for forming a rough surface portion on a resin surface and a method for producing the rough surface-shaped film, and further uses the rough surface-shaped film to locally rough the resin surface. It aims at providing the manufacturing method of the resin-coated metal plate which has the rough surface part formed by forming a surface part, and the rough surface part.
上記課題を解決する本発明の粗面賦型フィルムは、樹脂フィルムの表面が、該表面に耐熱性粒子を分散した粒子分散樹脂層を形成することにより、粗面化されてなる粗面賦型フィルム（請求項１）であり、
上記（請求項１）の粗面賦型フィルムにおいて、前記粒子分散樹脂層が、樹脂フィルムの表面に模様を描くように局部的にまたは全面に形成されてなること（請求項２）を特徴とし、また
上記（請求項１または２）の粗面賦型フィルムにおいて、前記粒子分散樹脂層が、表面粗さの異なる複数の粒子分散樹脂層を形成することによる、粗面化程度の異なる複数の粒子分散樹脂層であること（請求項３）を特徴とし、また
上記（請求項１〜３）の粗面賦型フィルムにおいて、前記耐熱性粒子の粒子径が０．１〜１００μｍであること（請求項４）を特徴とし、また
上記（請求項１〜４）の粗面賦型フィルムにおいて、前記樹脂フィルムが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（請求項５）を特徴とし、また
上記（請求項１〜５）の粗面賦型フィルムにおいて、前記粒子分散樹脂層の樹脂部を構成する樹脂が熱硬化性樹脂であること（請求項６）であることを特徴とする。
The rough surface-imparted film of the present invention that solves the above problems is a rough surface-molded material in which the surface of the resin film is roughened by forming a particle-dispersed resin layer in which heat-resistant particles are dispersed on the surface. A film (claim 1),
In the rough surface-shaped film according to (Claim 1), the particle-dispersed resin layer is formed locally or on the entire surface so as to draw a pattern on the surface of the resin film (Claim 2). Moreover, in the rough surface-shaped film of the above (
また、本発明の粗面部賦型フィルムの製造方法は、粒径が０．１〜１００μｍの耐熱性
粒子を熱硬化性樹脂に分散させてなる粒子分散樹脂を樹脂フィルム上に塗布し、次いで加熱して樹脂を硬化させることを特徴とする粗面賦型フィルムの製造方法（請求項７）であり、
上記（請求項７）の粗面賦型フィルムの製造方法において、前記粒子分散樹脂を、前記樹脂フィルム上に模様を描くように局部的にまたは全面に塗布すること（請求項８）を特徴とし、また
上記（請求項７または８）の粗面賦型フィルムの製造方法において、前記粒子分散樹脂層を、表面粗さの異なる複数の粒子分散樹脂層を局部的にまたは全面に塗布し、粗面化程度の異なる複数の粒子分散樹脂層を形成させること（請求項９）を特徴とする。
Moreover, the manufacturing method of the rough surface part shaping | molding film of this invention apply | coats the particle-dispersed resin formed by disperse | distributing the heat-resistant particle | grains with a particle size of 0.1-100 micrometers in a thermosetting resin on a resin film, and then heats. And a method for producing a rough surface-shaped film characterized in that the resin is cured (Claim 7).
In the method for producing a rough surface-shaped film according to (Claim 7), the particle-dispersed resin is applied locally or over the entire surface so as to draw a pattern on the resin film (Claim 8). Further, in the method for producing a rough surface-shaped film according to the above (Claim 7 or 8), the particle-dispersed resin layer is coated with a plurality of particle-dispersed resin layers having different surface roughness locally or over the entire surface. A plurality of particle-dispersed resin layers having different degree of surface formation are formed (claim 9).
また、本発明の粗面部を有する樹脂被覆金属板は、上記（請求項１〜６）の粗面賦型フィルムを用いて転写された粗面部を有する熱可塑性樹脂層を金属板上に被覆してなる粗面部を有する樹脂被覆金属板（請求項１０）であり、
上記（請求項１０）の樹脂被覆金属板において、前記熱可塑性樹脂が、上記（請求項５）の二軸延伸フィルムの熱固定温度未満の軟化温度を有するポリエステル樹脂であること（請求項１１）、またはポリ塩化ビニルであること（請求項１２）、あるいはアクリル樹脂であること（請求項１３）、もしくはポリオレフィン樹脂であること（請求項１４）を特徴とし、また
上記（請求項１４）の樹脂被覆金属板において、前記ポリオレフィン樹脂が、ポリプロピレンまたはポリプロピレンを主体としポリプロピレン以外の樹脂をブレンドしてなるブレンド樹脂であること（請求項１５）を特徴とする。
Moreover, the resin-coated metal plate having a rough surface portion of the present invention is obtained by coating a metal plate with a thermoplastic resin layer having a rough surface portion transferred using the rough surface-shaped film of the above (
In the resin-coated metal plate of (Claim 10), the thermoplastic resin is a polyester resin having a softening temperature lower than the heat setting temperature of the biaxially stretched film of (Claim 5) (Claim 11). Or a polyvinyl chloride (Claim 12), an acrylic resin (Claim 13), or a polyolefin resin (Claim 14), and the resin of the above (Claim 14) In the coated metal plate, the polyolefin resin is characterized in that polypropylene or a blend resin formed by blending a resin other than polypropylene with polypropylene as a main component (claim 15).
そして、本発明の粗面部を有する樹脂被覆金属板の製造方法は、金属板に熱可塑性樹脂を被覆してなる樹脂被覆金属板を、該熱可塑性樹脂の軟化温度以上に加熱し、軟化した該熱可塑性樹脂の表面に上記（請求項１〜６）のいずれかの粗面賦型フィルムを粗面形成面が接するようにして当接し、挟圧手段を用いて加圧することにより、該熱可塑性樹脂の表面に該粗面賦型フィルムの粗面を転写した後、該粗面賦型フィルムを剥離することを特徴とする粗面部を有する樹脂被覆金属板の製造方法（請求項１６）である。
The method for producing a resin-coated metal plate having a rough surface portion according to the present invention comprises heating the resin-coated metal plate obtained by coating a metal plate with a thermoplastic resin to a temperature equal to or higher than the softening temperature of the thermoplastic resin. The surface of the thermoplastic resin is brought into contact with the surface-roughened film according to any one of claims (
本発明においては、樹脂フィルムの表面に、粒径が０．１〜１００μｍの耐熱性粒子を分散してなる粒子分散樹脂層、または表面粗さの異なる複数の粒子分散樹脂層を印刷法などの塗布法を用いて局部的にまたは全面に形成して粗面賦型フィルムを構成し、この粗面賦型フィルムを加熱した熱可塑性樹脂被覆金属板の熱可塑性樹脂層に当接して挟圧して熱可塑性樹脂の表面に粗面賦型フィルムの粗面を転写した後、粗面賦型フィルムを剥離することを特徴としており、安価でかつ平易な方法で粗面賦型フィルムが得られる。また、熱可塑性樹脂の軟化温度まで加熱された熱可塑性樹脂被覆金属板に、室温のままの粗面賦型フィルムを当接して挟圧するので、熱可塑性樹脂被覆金属板が急速に冷却され、かつ粗面賦型フィルムと熱可塑性樹脂被覆金属板が当接している時間を、熱可塑性樹脂が軟化温度以下になるまで充分に長く採れるので、エンボスロールを用いた場合よりもより鮮明なエンボス模様を得ることができる。さらに、粗面賦型フィルムは樹脂フィルム上に局部的にまたは全面に粗面化程度の異なる複数の粗面部を容易に形成させることができるので、この粗面賦型フィルムを用いると、熱可塑性樹脂被覆金属板の熱可塑性樹脂の表面に、局部的にまたは全面に粗面化程度の異なる複数の粗面部を形成させたソフィスティケートな外観を安価にかつ平易に得ることができる。 In the present invention, a particle-dispersed resin layer in which heat-resistant particles having a particle size of 0.1 to 100 μm are dispersed on the surface of a resin film, or a plurality of particle-dispersed resin layers having different surface roughnesses are printed. Using a coating method, it is formed locally or on the entire surface to form a rough surface-shaped film, and this rough surface-shaped film is pressed against a thermoplastic resin layer of a heated thermoplastic resin-coated metal plate. The rough surface-shaped film is transferred to the surface of the thermoplastic resin, and then the rough surface-shaped film is peeled off. The rough surface-shaped film can be obtained by an inexpensive and simple method. Further, the surface-roughened film is brought into contact with and sandwiched with the thermoplastic resin-coated metal plate heated to the softening temperature of the thermoplastic resin, so that the thermoplastic resin-coated metal plate is rapidly cooled, and Since the time for which the rough surface-imparting film and the thermoplastic resin-coated metal plate are in contact with each other can be taken long enough until the thermoplastic resin falls below the softening temperature, a clearer embossed pattern than when using an embossing roll is used. Can be obtained. Furthermore, since the rough surface-shaped film can easily form a plurality of rough surface portions having different roughening levels locally or on the entire surface of the resin film, if this rough surface-shaped film is used, thermoplasticity A sophisticate appearance in which a plurality of rough surface portions having different roughening levels are formed locally or entirely on the surface of the thermoplastic resin of the resin-coated metal plate can be obtained inexpensively and easily.
以下、本発明を詳細に説明する。図１〜図３に本発明の粗面賦型フィルムの態様例を示す。図１において（１）は概略平面図、（２）は概略断面図、図２において（１）は概略平面図、（２）は概略断面図、図３において（１）は概略平面図、（２）は概略断面図
ある。図１は鏡面状の樹脂フィルム１の表面に、一種類の表面粗さのストライプ模様の粒子分散樹脂層２を局部的に設けてなる粗面賦型フィルム１０とした態様例である。この粗面賦型フィルムを用いて熱可塑性樹脂被覆金属板の樹脂層に粗面を転写すると、樹脂層の表面は平滑な面に粗面のストライプ模様が局部的に形成される。本図は樹脂フィルム１の長手方向に垂直なストライプ模様の粗面部２を設ける例であるが、ストライプ模様は樹脂フィルムの長手方向に平行に設けてもよいし、斜め方向に設けてもよい。また交差させた目地状のストライプ模様としてもよい。さらに、ストライプの幅も１種類ではなく複数の種類の幅としてもよい。また粗面部は直線状のパターン以外に円、正方形、三角形、多角形の幾何学模様やそれらを組み合わせた図形、または花や雲などの形状や抽象図形など任意の形で設けてよい。
Hereinafter, the present invention will be described in detail. The example of the aspect of the rough surface shaping film of this invention is shown in FIGS. In FIG. 1, (1) is a schematic plan view, (2) is a schematic cross-sectional view, FIG. 2 (1) is a schematic plan view, (2) is a schematic cross-sectional view, and in FIG. 2) is a schematic sectional view. FIG. 1 shows an example of a rough surface-
図２は粗面賦型フィルムの基材となる鏡面状の樹脂フィルム１の表面に、２ａ、２ｂ、２ｃの表面粗さの異なる３種類の分散樹脂層を、樹脂フィルムの長手方向に３種類の平行な分散樹脂層を並べた模様でフィルム全面に設けてなる粗面賦型フィルム１０とした態様例である。異なる表面粗さを得るには、分散樹脂層において分散粒子の粒径および樹脂中の含有量を異ならせることにより得られる。図２は樹脂フィルム１の全面に分散樹脂層を設ける例を示したが、局部的に分散樹脂層を形成させない平面部を残存させてもよい。たとえば分散樹脂層２ｃを形成させずに２ａ、および２ｂのみの分散樹脂層を設けてもよい。本図においては樹脂フィルムの長手方向に３種類の長方形の分散樹脂層を並べた模様を示したが、模様としては、上記のような任意の模様を選択できる。
FIG. 2 shows three types of dispersed
図３は鏡面状の樹脂フィルム１の表面に、局部的に長方形模様の分散樹脂層２ｅを設け、さらに分散樹脂層２ｅとは異なる表面粗さの長方形模様の分散樹脂層２ｆを分散樹脂層２ｅ上に局部的に重ねて設けてなる粗面賦型フィルム１０とした態様例である。本図においては長方形の分散樹脂層２ｆを局部的に設けた長方形模様の分散樹脂層２ｅを樹脂フィルムの長手方向に間隔を置いて並べた模様を示したが、模様としては、上記のような任意の模様を選択できる。
In FIG. 3, a rectangular resin
樹脂フィルムとしては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、エチレンテレフタレート／エチレンイソフタレート共重合体、またはこれらを２種類以上ブレンドしてなるポリエステル樹脂、ポリエチレン、ポリプロピレン、エチレン／プロピレン共重合体、ポリメチルペンテンなどのポリオレフィン樹脂、ナイロン６、ナイロン６６、ナイロン６１０などのポリアミド樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン、塩化ビニル／酢酸ビニル共重合体、エチレン／酢酸ビニル共重合体、ビニルアルコールアルコール、エチレン／ビニルアルコール共重合体、ビニロンなどのビニル樹脂、ポリメタクリル酸エチル、ポリアクリル酸ブチなどのアクリル樹脂、ポリフッ化ビニル、ポリフッ化ビニリデン、ポリ４フッ化エチレン、エチレン／４フッ化エチレン共重合体などポリフッ化エチレン系樹脂、ポリスチレン、ポリカーボネート、ポリアリレート、ポリイミドなどの合成樹脂、トリアセチルセルロース、セロファンなどのセルロース系樹脂からなるフィルム、上質紙、薄葉紙、グラフト紙、グラシン紙、硫酸紙などを用いることができる。
中でもポリエチレンテレフタレートは安価であるとともに、融解温度が高く、二軸延伸して平滑面を有するフィルムとした後に高温で熱固定することにより、熱固定温度以下の温度で殆ど変形することのないフィルムとなるので、ポリエチレンテレフタレートの二軸延伸フィルムを用いた粗面賦型フィルムを加熱した熱可塑性樹脂被覆金属板に当接して狭圧しても変形することなく、熱可塑性樹脂被覆金属板の熱可塑性樹脂に鮮明な粗面を賦与することができるので、好適に用いられる。
Examples of the resin film include polyethylene terephthalate, polybutylene terephthalate, ethylene terephthalate / ethylene isophthalate copolymer, or a polyester resin obtained by blending two or more of these, polyethylene, polypropylene, ethylene / propylene copolymer, polymethylpentene, etc. Polyolefin resin, polyamide resin such as nylon 6, nylon 66, nylon 610, polyvinyl chloride, polyvinylidene chloride, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl acetate copolymer, vinyl alcohol alcohol, ethylene / vinyl alcohol Copolymers, vinyl resins such as vinylon, acrylic resins such as polyethyl methacrylate, butyric acrylate, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene Polyethylene resin such as ethylene / 4-fluoroethylene copolymer, synthetic resin such as polystyrene, polycarbonate, polyarylate, polyimide, film made of cellulose resin such as triacetylcellulose, cellophane, fine paper, thin paper, graft Paper, glassine paper, sulfate paper, or the like can be used.
Among them, polyethylene terephthalate is inexpensive, has a high melting temperature, is biaxially stretched into a film having a smooth surface, and is heat-set at a high temperature, so that the film hardly deforms at a temperature below the heat-set temperature. Therefore, the thermoplastic resin of the thermoplastic resin-coated metal plate is not deformed even if it is brought into contact with a heated thermoplastic resin-coated metal plate and narrowed by pressing a rough surface-formed film using a biaxially stretched film of polyethylene terephthalate. Since a clear rough surface can be imparted, it is preferably used.
上記の樹脂フィルム上に形成する分散樹脂層は、加熱した熱可塑性樹脂被覆金属板に当接して狭圧する際に変形することがないようにするため、樹脂部を構成する樹脂は熱硬化性樹脂であることが好ましい。熱硬化性樹脂としては、エポキシ樹脂、フェノール樹脂、メラミン樹脂、尿素樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂などを用いることができる。これらの熱硬化性樹脂に耐熱性粒子を分散させて樹脂フィルム上に塗布した後、加熱硬化させて分散樹脂層とする。 The resin constituting the resin portion is a thermosetting resin so that the dispersion resin layer formed on the resin film does not deform when pressed against a heated thermoplastic resin-coated metal plate. It is preferable that As the thermosetting resin, epoxy resin, phenol resin, melamine resin, urea resin, unsaturated polyester resin, polyurethane resin, or the like can be used. After heat-resistant particles are dispersed in these thermosetting resins and coated on a resin film, they are cured by heating to form a dispersed resin layer.
分散樹脂層中に分散させる耐熱性粒子としては、加熱した熱可塑性樹脂被覆金属板に当接して狭圧する際に変形することがない耐熱性を有する素材からなる粒子であれば特に制限が無く、無機質粒子であっても有機質粒子であってもよい。しかし熱安定性が高く、安価であり、粒度範囲が揃ったものとして入手が容易な二酸化ケイ素、二酸化チタン、炭酸カルシウムなどの無機質粒子や、アクリルビーズなどの有機質粒子を用いることが好ましい。これらの粒子径は形成する分散樹脂層により、０．１〜１００μｍの範囲で粒子径を揃えて分散樹脂層中に含有させる。また、分散樹脂層中に含有させる量としては樹脂に対して１〜３０重量％以下であることが好ましい。１重量％未満では分散樹脂層表面が殆ど粗面化しない。３０重量％を超えると印刷などによる塗布が困難になる。また、上記の粒子径の好適範囲内で微細粒子と粗大粒子を上記の好適含有量の範囲内で一定割合で混合して含有させてもよい。 The heat-resistant particles to be dispersed in the dispersed resin layer are not particularly limited as long as the particles are made of a material having heat resistance that does not deform when pressed against a heated thermoplastic resin-coated metal plate, It may be inorganic particles or organic particles. However, it is preferable to use inorganic particles such as silicon dioxide, titanium dioxide, calcium carbonate and the like, and organic particles such as acrylic beads, which have high thermal stability, are inexpensive, and are easily available as having a uniform particle size range. These particle diameters are contained in the dispersion resin layer with the same particle diameter in the range of 0.1 to 100 μm depending on the dispersion resin layer to be formed. Moreover, it is preferable that it is 1 to 30 weight% or less with respect to resin as an amount to contain in a dispersed resin layer. If it is less than 1% by weight, the surface of the dispersed resin layer is hardly roughened. If it exceeds 30% by weight, coating by printing or the like becomes difficult. In addition, fine particles and coarse particles may be mixed and contained at a constant ratio within the above-mentioned preferable content range within the above-mentioned preferable particle diameter range.
上記のようにして熱硬化性樹脂中に耐熱性粒子を分散させて樹脂フィルム上にグラビア印刷法、凹版印刷法、スクリーン印刷法などの印刷手段を用いて塗布する。塗布を容易に行えるように、熱硬化性樹脂中に耐熱性粒子を分散させる際に粘度を調整するために溶媒を用いてもよい。塗布した分散樹脂層が見かけ上硬化した後、使用した樹脂に応じたキュア温度に加熱して樹脂を加熱硬化させる。以上のようにして本発明の粗面賦型フィルムが得られる。 As described above, the heat-resistant particles are dispersed in the thermosetting resin and applied onto the resin film using a printing means such as gravure printing, intaglio printing, or screen printing. A solvent may be used to adjust the viscosity when the heat-resistant particles are dispersed in the thermosetting resin so that the coating can be easily performed. After the applied dispersed resin layer is apparently cured, the resin is heated and cured to a curing temperature corresponding to the resin used. As described above, the rough surface-shaped film of the present invention is obtained.
このようにして得られた本発明の粗面賦型フィルムを、加熱した熱可塑性樹脂被覆金属板の樹脂層に当接して挟圧して熱可塑性樹脂の表面に粗面賦型フィルムの粗面を転写した後、粗面賦型フィルムを剥離することにより、本発明の粗面部を有する樹脂被覆金属板が得られる。熱可塑性樹脂被覆金属板としては、冷延鋼板、冷延鋼板に電解めっき法を用いて亜鉛めっきしてなる電気亜鉛めっき鋼板や、亜鉛−ニッケル、亜鉛−アルミニウムなどの亜鉛合金めっきを溶融めっき法を用いてめっきしなる溶融亜鉛めっき鋼板、冷延鋼板に電解クロム酸処理、リン酸クロメート処理、塗布型クローメート処理、各種のノンクロム処理などの化成処理を施してなる表面処理鋼板、これらの亜鉛めっき鋼板にこれらの化成処理を施してなる表面処理亜鉛めっき鋼板、ステンレス鋼板、アルミニウム合金板のいずれかに、公知の積層方法を用いて熱可塑性樹脂を積層被覆してなるものを用いる。金属板上に積層被覆する熱可塑性樹脂としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、エチレンテレフタレート／エチレンイソフタレート共重合体、またはこれらを２種類以上ブレンドしてなるポリエステル樹脂、ポリエチレン、ポリプロピレン、エチレン／プロピレン共重合体、ポリメチルペンテンなどのポリオレフィン樹脂、ナイロン６、ナイロン６６、ナイロン６１０などのポリアミド樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン、塩化ビニル／酢酸ビニル共重合体、エチレン／酢酸ビニル共重合体、ポリビニルアルコール、エチレン／ビニルアルコール共重合体、ビニロンなどのビニル樹脂、ポリメタクリル酸エチル、ポリアクリル酸ブチなどのアクリル樹脂、ポリスチレン、ポリカーボネート、ポリアリレート、ポリイミドなどを用いることができるが、粗面賦型フィルムを、加熱した熱可塑性樹脂層を軟化させた熱可塑性樹脂被覆金属板の熱可塑性樹脂層に当接して挟圧して熱可塑性樹脂の表面に粗面賦型フィルムの粗面を転写する際に、粗面賦型フィルムが軟化したり変形したりすることなく、熱可塑性樹脂被覆金属板の熱可塑性樹脂のみが変形可能となるように、粗面賦型フィルムの樹脂と熱可塑性樹脂被覆金属板の熱可塑性樹脂とを組み合わせる必要がある。 The rough surface-shaped film of the present invention thus obtained is pressed against the resin layer of the heated thermoplastic resin-coated metal plate to sandwich the rough surface of the rough surface-shaped film on the surface of the thermoplastic resin. After the transfer, the resin-coated metal plate having the rough surface portion of the present invention is obtained by peeling off the rough surface shaping film. Thermoplastic resin-coated metal sheets include cold-rolled steel sheets, electrogalvanized steel sheets obtained by galvanizing cold-rolled steel sheets using electrolytic plating, and zinc alloy plating such as zinc-nickel and zinc-aluminum. Hot-dip galvanized steel sheets that are plated using galvanized steel, surface-treated steel sheets that have been subjected to chemical treatment such as electrolytic chromic acid treatment, phosphoric acid chromate treatment, coating-type chromate treatment, and various non-chromium treatments on these cold-rolled steel plates Any one of a surface-treated galvanized steel sheet, a stainless steel sheet, and an aluminum alloy sheet obtained by subjecting these steel sheets to a chemical conversion treatment is laminated with a thermoplastic resin using a known laminating method. Thermoplastic resins that are laminated and coated on metal plates include polyethylene terephthalate, polybutylene terephthalate, ethylene terephthalate / ethylene isophthalate copolymers, or polyester resins made by blending two or more of these, polyethylene, polypropylene, ethylene / propylene Copolymer, polyolefin resin such as polymethylpentene, polyamide resin such as nylon 6, nylon 66, nylon 610, polyvinyl chloride, polyvinylidene chloride, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl acetate copolymer, Polyvinyl alcohol, ethylene / vinyl alcohol copolymer, vinyl resin such as vinylon, acrylic resin such as polyethyl methacrylate and polyacrylic acid buty, polystyrene, polycarbonate, polyaryle In this case, the rough surface-molded film is brought into contact with the thermoplastic resin layer of the thermoplastic resin-coated metal plate obtained by softening the heated thermoplastic resin layer, and is sandwiched between the thermoplastic resin layers. When transferring the rough surface of the rough surface-shaped film to the surface, only the thermoplastic resin of the thermoplastic resin-coated metal plate can be deformed without softening or deforming the rough surface-shaped film. It is necessary to combine the resin of the rough surface-molding film and the thermoplastic resin of the thermoplastic resin-coated metal plate.
すなわち、前記したように、粗面賦型フィルムの基材として好適なポリエチレンテレフタレートの二軸延伸フィルムを用いた場合は、熱可塑性樹脂被覆金属板の熱可塑性樹脂として、その熱変形温度がポリエチレンテレフタレートの二軸延伸フィルムの熱固定温度よりも低い樹脂を用いる必要がある。このような樹脂としては、酸成分として以下の多塩基酸、アルコール成分として以下の多価アルコールからなるポリエステル樹脂から、上記の条件を満たすものを選択して用いる。すなわち、酸成分としてテレフタル酸、イソフタル酸、オルソフタル酸、Ｐ−β−オキシエトキシ安息香酸、ナフタレン−２，６−ジカルボン酸、ジフェノキシエタン−４，４−ジカルボン酸、５−ナトリウムスルホイソフタル酸などの二塩基性芳香族ジカルボン酸、ヘキサヒドロテレフタル酸、シクロヘキサンジカルボン酸、などの脂環族ジカルボン酸、アジピン酸、セバシン酸、ダイマー酸などの脂肪族ジカルボン酸、トリメリット酸、ピロメリット酸、ヘミメリット酸、１，１，２，２−エタンテトラカルボン酸、１，１，２−エタントリカルボン酸、１，３，５−ペンタントリカルボン酸、１，２，３，４−シクロペンタンテトラカルボン酸、ビフェニル−３，４，３’、４’−テトラカルボン酸などの多塩基酸のいずれか１種類または２種類以上と、アルコール成分としてエチレングリコール、プロピレングリコール、１，４−ブタンジオール、ネオペンチルグリコール、１，６−ヘキシレングリコール、ジエチレングリコール、トリエチレングリコール、シクロヘキサンジメタノールなどのジオール類、ペンタエリスリトール、グリセロール、トリメチロールプロパン、１，２，６−ヘキサントリオール、ソルビトール、１，１，４，４−テトラキス（ヒドロキシメチル）シクロヘキサンなどの多価アルコールのいずれか１種類または２種類以上とを縮重合させて得られるポリエステル樹脂を用いることができるが、中でも汎用のポリブチレンテレフタレート、エチレンテレフタレート／エチレンイソフタレート共重合体、またはこれらを２種類以上ブレンドしてなるポリエステル樹脂を用いることが好ましい。ポリエステル樹脂以外の樹脂として、ポリエチレン、ポリプロピレン、エチレン／プロピレン共重合体などのポリオレフィン樹脂、中でもポリプロピレン、またはポリプロピレンを主体とし、ポリエチレンなどの他のオレフィン樹脂、アイオノマー、エラストマー、スチレンブタジエンゴムなどのポリプロピレン以外の樹脂をブレンドした樹脂、さらにポリ塩化ビニル、ポリ塩化ビニリデン、塩化ビニル／酢酸ビニル共重合体、エチレン／酢酸ビニル共重合体、ビニルアルコールアルコール、エチレン／ビニルアルコール共重合体、ビニロンなどのビニル樹脂、ポリメタクリル酸エチル、ポリアクリル酸ブチルなどのアクリル樹脂なども用いることができる。 That is, as described above, when a biaxially stretched film of polyethylene terephthalate that is suitable as a base material for a rough surface-shaped film is used, the thermal deformation temperature thereof is polyethylene terephthalate as the thermoplastic resin of the thermoplastic resin-coated metal plate. It is necessary to use a resin lower than the heat setting temperature of the biaxially stretched film. As such a resin, a resin satisfying the above conditions is selected and used from a polyester resin comprising the following polybasic acid as an acid component and the following polyhydric alcohol as an alcohol component. That is, as the acid component, terephthalic acid, isophthalic acid, orthophthalic acid, P-β-oxyethoxybenzoic acid, naphthalene-2,6-dicarboxylic acid, diphenoxyethane-4,4-dicarboxylic acid, 5-sodium sulfoisophthalic acid, etc. Dibasic aromatic dicarboxylic acids, hexahydroterephthalic acid, cyclohexanedicarboxylic acid, and other alicyclic dicarboxylic acids, adipic acid, sebacic acid, dimer acid and other aliphatic dicarboxylic acids, trimellitic acid, pyromellitic acid, hemi Merit acid, 1,1,2,2-ethanetetracarboxylic acid, 1,1,2-ethanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, Any one of polybasic acids such as biphenyl-3,4,3 ′, 4′-tetracarboxylic acid Are two or more types of alcohol components such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, cyclohexanedimethanol, and the like, pentaerythritol , Glycerol, trimethylolpropane, 1,2,6-hexanetriol, sorbitol, polyhydric alcohols such as 1,1,4,4-tetrakis (hydroxymethyl) cyclohexane, one or more polycondensation The polyester resin obtained can be used, but, among them, general-purpose polybutylene terephthalate, ethylene terephthalate / ethylene isophthalate copolymer, or a blend of two or more of these. It is preferable to use a ester resin. As resins other than polyester resin, polyolefin resin such as polyethylene, polypropylene, ethylene / propylene copolymer, etc., mainly polypropylene or polypropylene, other olefin resin such as polyethylene, other than polypropylene such as ionomer, elastomer, styrene butadiene rubber, etc. , And vinyl resins such as polyvinyl chloride, polyvinylidene chloride, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl acetate copolymer, vinyl alcohol alcohol, ethylene / vinyl alcohol copolymer, vinylon Acrylic resins such as polyethyl methacrylate and polybutyl acrylate can also be used.
次に、本発明の粗面部を有する樹脂被覆金属板の製造方法について説明する。図４は本発明の粗面部を有する樹脂被覆金属板の製造方法の一態様例の模式図である。説明を簡略にするため、粗面賦型フィルム１０として、図１に示した樹脂フィルム１の長手方向に垂直なストライプ模様の粗面部２を設けたものを用いた場合を示す。図４において、金属板３上に熱可塑性樹脂４を積層してなり、コイル状に巻き取られた長尺帯状の樹脂被覆金属板２０ａは、アンコイラーなどの巻解手段３０ａから巻解かれ矢印方向に進行し、赤外線オーブンなどの加熱手段１５により、熱可塑性樹脂４の軟化温度以上の温度に加熱される。また、樹脂フィルム１の長手方向に垂直なストライプ模様の粗面部２が設けられ、コイル状に巻き取られた長尺帯状の粗面賦型フィルム１０は、アンコイラーなどの巻解手段３０ｂから巻解かれ矢印方向に進行する。矢印方向に進行した樹脂被覆金属板２０ａと粗面賦型フィルム１０は、樹脂被覆金属板２０ａの加熱された熱可塑性樹脂４と粗面賦型フィルム１０の粗面部２が当接するようにして対の加圧ロール４０ａと４０ｂからなる挟圧手段により挟み付けられて加圧され、熱可塑性樹脂４に粗面賦型フィルム１０の粗面部２が転写される。その後、合体した樹脂被覆金属板２０ａと粗面賦型フィルム１０は矢印方向に進行し、粗面賦型フィルム１０はデフレクターロール２５で進行方向を変更（図上で下方）され、樹脂被覆金属板は樹脂表面に粗面賦型フィルム１０の粗面部２が転写された凹部２ａ’を有する粗面部を有する樹脂被覆金属板２０ｂとして粗面賦型フィルム１０から剥離され、コイラーなどの巻取手段５０ａに巻き取られる。進行方向を変更された粗面賦型フィルム１０はコイラーなどの巻取手段５０ｂに巻き取られる。また、図４においてはデフレクターロール２５で粗面賦型フィルム１０と粗面部を有する樹脂被覆金属板２０ｂを剥離する例を示したが、粗面賦型フィルム１０と粗面部を有する樹脂被覆金属板２０ｂを剥離することなく巻取手段５０ａに巻き取ってもよい。この場合、粗面賦型フィルム１０は、粗面部を有する樹脂被覆金属板２０ｂがパネルなどの最終品に成形加工まで樹脂被覆金属板２０ｂの保護フィルムとして機能する。以上のようにして、本発明の粗面部を有する樹脂被覆金属板を得ることができる。
Next, the manufacturing method of the resin coating metal plate which has a rough surface part of this invention is demonstrated. FIG. 4 is a schematic view of an embodiment of a method for producing a resin-coated metal plate having a rough surface portion according to the present invention. In order to simplify the description, a case is shown in which the rough
図４では、長尺帯状の粗面賦型フィルムを用いて長尺帯状の樹脂被覆金属板の樹脂層に連続的に粗面部を形成させる態様例を示したが、切板状の樹脂被覆金属板に切板状の粗面賦型フィルムを載せ、プレス機を用いて加圧した後粗面賦型フィルムを剥離することにより、樹脂被覆金属板の樹脂表面に粗面賦型フィルムの粗面部を転写してもよい。 In FIG. 4, although the example of an aspect which forms a rough surface part continuously in the resin layer of a long strip-shaped resin-coated metal plate using a long strip-shaped rough surface shaping film was shown, a plate-shaped resin-coated metal A rough surface portion of the rough surface-shaped film is placed on the resin surface of the resin-coated metal plate by placing a cut-plate-shaped rough surface-shaped film on the plate, pressurizing it using a press, and then peeling the rough surface-shaped film. May be transferred.
以下、実施例にて本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to examples.
（実施例１）
[粗面賦型フィルムの作成]
エポキシ樹脂に二酸化ケイ素粉（平均粒子径：６．５μｍ）を２０重量％の量で分散してなる粒子分散液を作成し、ポリエチレンテレフタレートの二軸延伸フィルム（厚さ：３０μｍ、熱固定温度：２３０℃）の片面に、フィルム長手方向に垂直に幅８ｍｍ、間隔４０ｍｍ、樹脂硬化後の厚さが０．０７ｍｍとなるように、ロータリースクリーン印刷機を用いて図１に示すようなストライプ状に印刷塗布し、エポキシ樹脂が硬化した後、１５０℃で２分間加熱キュアを行い、粗面賦型フィルムとした。
(Example 1)
[Creation of rough surface film]
A particle dispersion obtained by dispersing 20% by weight of silicon dioxide powder (average particle size: 6.5 μm) in an epoxy resin is prepared, and a biaxially stretched film of polyethylene terephthalate (thickness: 30 μm, heat setting temperature: 230 ° C) on one side in a stripe shape as shown in FIG. 1 using a rotary screen printer so that the width is 8 mm perpendicular to the film longitudinal direction, the interval is 40 mm, and the thickness after resin curing is 0.07 mm. After printing and applying and curing of the epoxy resin, heat curing was performed at 150 ° C. for 2 minutes to obtain a rough surface shaping film.
[樹脂被覆亜鉛めっき鋼板の作成]
樹脂被覆金属板として、電気亜鉛めっき鋼板（板厚：０．２ｍｍ、めっき量：２０ｇ／ｍ２ 、めっき後に電解クロム酸処理を施し、クロムとして４０ｍｇ／ｍ２ 付着させた）の片面にポリエステルウレタン系の接着剤を１．５μｍの厚さに塗布し乾燥した。次いで接着剤を塗布した電気亜鉛めっき鋼板を２２５℃に加熱し、その接着剤塗布面に白色顔料を２０重量％含有するポリブチレンテレフタレートの未延伸フィルム（厚さ：２５μｍ、軟化温度：２２０℃）を当接し、１対の加圧ロールで両者を挟み付けて加圧し、樹脂被覆亜鉛めっき鋼板とした。
[Preparation of resin-coated galvanized steel sheet]
Polyester urethane on one side of an electrogalvanized steel sheet (plate thickness: 0.2 mm, plating amount: 20 g / m 2 , subjected to electrolytic chromic acid treatment after plating, and 40 mg / m 2 deposited as chromium) as a resin-coated metal plate The system adhesive was applied to a thickness of 1.5 μm and dried. Next, the electrogalvanized steel sheet coated with the adhesive was heated to 225 ° C., and an unstretched film of polybutylene terephthalate containing 20% by weight of a white pigment on the adhesive-coated surface (thickness: 25 μm, softening temperature: 220 ° C.) Were pressed between each other with a pair of pressure rolls to obtain a resin-coated galvanized steel sheet.
[粗面部を有する樹脂被覆金属板の作成]
上記の樹脂被覆亜鉛めっき鋼板を赤外線オーブンで２２５℃に加熱し、樹脂被覆亜鉛めっき鋼板の樹脂層に上記の粗面賦型フィルムのストライプ状の粗面部が接するようにして当接し、１対の挟圧ロールで両者を挟み付けて加圧し、粗面賦型フィルムのストライプ状の粗面を樹脂被覆亜鉛めっき鋼板の樹脂層に転写した。次いで粗面賦型フィルムを剥離し、表面に平滑な平面の一部にストライプ状の粗面部分が形成された、粗面部を有する樹脂被覆金属板（電気亜鉛めっき鋼板）を得た。
[Preparation of resin-coated metal plate with rough surface]
The resin-coated galvanized steel sheet is heated to 225 ° C. in an infrared oven, and is brought into contact with the resin layer of the resin-coated galvanized steel sheet so that the striped rough surface portion of the rough surface-shaped film is in contact therewith. Both of them were sandwiched and pressed by a pinching roll, and the striped rough surface of the rough surface-forming film was transferred to the resin layer of the resin-coated galvanized steel sheet. Subsequently, the rough surface shaping film was peeled off to obtain a resin-coated metal plate (electrogalvanized steel plate) having a rough surface portion in which a striped rough surface portion was formed on a part of a smooth flat surface.
（実施例２）
[粗面賦型フィルムの作成]
エポキシ樹脂に二酸化ケイ素粉（平均粒子径：１．５μｍ）を３０重量％の量で分散してなる粒子分散液（Ａ）、エポキシ樹脂に二酸化ケイ素粉（平均粒子径：６．５μｍ）を２０重量％の量で分散してなる粒子分散液（Ｂ）、エポキシ樹脂に二酸化ケイ素粉（平均粒子径：６．５μｍ）を２５重量％と二酸化ケイ素粉（平均粒子径：２５μｍ）を５重量％の量で混合分散してなる粒子分散液（Ｃ）を作成し、ポリエチレンテレフタレートの二軸延伸フィルム（厚さ：３０μｍ、熱固定温度：２３０℃）の片面に、フィルム長手方向に対してそれぞれ斜めに、粒子分散液（Ａ）を幅２５ｍｍ、樹脂硬化後の厚さが０．０８ｍｍ、粒子分散液（Ｂ）を幅１０ｍｍ、樹脂硬化後の厚さが０．０８ｍｍ、粒子分散液（Ｃ）を幅５ｍｍ、樹脂硬化後の厚さが０．１０ｍｍとなるように、ロータリースクリーン印刷機を用いて図２に示すような、３種類の分散樹脂層が樹脂フィルムの長手方向に３種類の平行な分散樹脂層を斜めに並べた模様でフィルム全面に印刷塗布し、エポキシ樹脂が硬化した後、１５０℃で２分間加熱キュアを行い、粗面賦型フィルムとした。
(Example 2)
[Creation of rough surface film]
A particle dispersion (A) in which silicon dioxide powder (average particle size: 1.5 μm) is dispersed in an amount of 30% by weight in an epoxy resin, and silicon dioxide powder (average particle size: 6.5 μm) in an epoxy resin is 20 Particle dispersion (B) dispersed in an amount of% by weight, 25% by weight of silicon dioxide powder (average particle diameter: 6.5 μm) and 5% by weight of silicon dioxide powder (average particle diameter: 25 μm) in epoxy resin A particle dispersion liquid (C) is prepared by mixing and dispersing in the amount of 1%, and on one side of a polyethylene terephthalate biaxially stretched film (thickness: 30 μm, heat setting temperature: 230 ° C.), oblique to the longitudinal direction of the film. The particle dispersion (A) is 25 mm wide, the thickness after resin curing is 0.08 mm, the particle dispersion (B) is 10 mm wide, the thickness after resin curing is 0.08 mm, and the particle dispersion (C). Width 5mm, thickness after resin curing A pattern in which three types of dispersed resin layers are obliquely arranged in the longitudinal direction of the resin film as shown in FIG. 2 using a rotary screen printer so that the thickness becomes 0.10 mm. Then, after the epoxy resin was cured, the film was heated and cured at 150 ° C. for 2 minutes to obtain a rough surface-imparted film.
[樹脂被覆亜鉛めっき鋼板の作成]
樹脂被覆金属板として、合金亜鉛めっき（Ｚｎ−４％Ｎｉ合金）鋼板（板厚：０．２ｍｍ、めっき量：３５ｇ／ｍ２ 、めっき後にリン酸クロメート処理を施し、クロムとして５５ｍｇ／ｍ２ 付着させた）の片面にポリエステルウレタン系の接着剤を１．５μｍの厚さに塗布し乾燥した。次いで接着剤を塗布した合金亜鉛めっき鋼板を１０５℃に加熱し、その接着剤塗布面に白色顔料を１５重量％と黄色顔料を５重量％含有するアクリル樹脂の未延伸フィルム（厚さ：２５μｍ、軟化温度：１００℃）を当接し、１対の加圧ロールで両者を挟み付けて加圧し、樹脂被覆亜鉛めっき鋼板とした。
[Preparation of resin-coated galvanized steel sheet]
As a resin-coated metal plate, an alloy galvanized (Zn-4% Ni alloy) steel plate (plate thickness: 0.2 mm, plating amount: 35 g / m 2 , phosphoric acid chromate treatment is applied after plating, and 55 mg / m 2 adheres as chromium. The polyester urethane-based adhesive was applied to one side of 1.5 μm in thickness and dried. Next, the galvanized steel sheet coated with adhesive was heated to 105 ° C., and an unstretched film of acrylic resin (thickness: 25 μm, containing 15% by weight of white pigment and 5% by weight of yellow pigment on the adhesive-coated surface. Softening temperature: 100 ° C.), and a pair of pressure rolls sandwiched and pressed to form a resin-coated galvanized steel sheet.
[粗面部を有する樹脂被覆金属板の作成]
上記の樹脂被覆亜鉛めっき鋼板を赤外線オーブンで１０５℃に加熱し、樹脂被覆亜鉛めっき鋼板の樹脂層に上記の粗面賦型フィルムの３種類の斜めに設けた平行な粗面部が接するようにして当接し、１対の挟圧ロールで両者を挟み付けて加圧し、粗面賦型フィルムの粗面を樹脂被覆亜鉛めっき鋼板の樹脂層に転写した。次いで粗面賦型フィルムを剥離し、表面に３種類の斜めに設けた平行な粗面部分が形成された、粗面部を有する樹脂被覆金属板（合金亜鉛めっき鋼板）を得た。
[Preparation of resin-coated metal plate with rough surface]
The resin-coated galvanized steel sheet is heated to 105 ° C. in an infrared oven so that the three parallel rough surface portions of the surface-roughened film are in contact with the resin layer of the resin-coated galvanized steel sheet. The two were pressed against each other with a pair of pinching rolls, and the rough surface of the rough surface forming film was transferred to the resin layer of the resin-coated galvanized steel sheet. Next, the rough surface-forming film was peeled off to obtain a resin-coated metal plate (alloy galvanized steel plate) having a rough surface portion on which three types of parallel rough surface portions provided obliquely were formed.
（実施例３）
[粗面賦型フィルムの作成]
エポキシ樹脂に二酸化ケイ素粉（平均粒子径：６．５μｍ）を２５重量％の量で分散してなる粒子分散液（Ｄ）、エポキシ樹脂に二酸化ケイ素粉（平均粒子径：２０μｍ）を２５重量％の量で分散してなる粒子分散液（Ｅ）を作成し、ポリエチレンテレフタレートの二軸延伸フィルム（厚さ：３０μｍ、熱固定温度：２３０℃）の片面に、ロータリースクリーン印刷機を用いて、図３に示すように粒子分散液（Ｄ）を樹脂フィルムの長手方向に３０ｍｍの間隔を置いて長方形（長径１２０ｍｍ、短径６０ｍｍ）を並べた模様で印刷塗布し、エポキシ樹脂が硬化した後、粒子分散液（Ｄ）を塗布してなる長方形の模様内に、粒子分散液（Ｅ）を用いて小さな長方形（長径７５ｍｍ、短径３０ｍｍ）を局部的に重ねて印刷塗布し、エポキシ樹脂が硬化した後、１５０℃で２分間加熱キュアを行い、粗面賦型フィルムとした。
(Example 3)
[Creation of rough surface film]
Particle dispersion (D) in which silicon dioxide powder (average particle size: 6.5 μm) is dispersed in an amount of 25% by weight in an epoxy resin, and silicon dioxide powder (average particle size: 20 μm) in an epoxy resin is 25% by weight. A particle dispersion liquid (E) dispersed in a quantity of 1% was prepared, and a rotary screen printer was used on one side of a polyethylene terephthalate biaxially stretched film (thickness: 30 μm, heat setting temperature: 230 ° C.). As shown in FIG. 3, the particle dispersion liquid (D) is printed and applied in a pattern in which rectangles (major axis 120 mm, minor axis 60 mm) are arranged at intervals of 30 mm in the longitudinal direction of the resin film. In the rectangular pattern formed by applying the dispersion liquid (D), a small rectangle (major axis 75 mm, minor axis 30 mm) is locally printed and applied using the particle dispersion liquid (E), and the epoxy resin is hard. After, for 2 minutes heat curing at 0.99 ° C., it was Somenfu type film.
[樹脂被覆ステンレス鋼板の作成]
樹脂被覆金属板として、ステンレス鋼板（ＪＩＳ ３０４、板厚：０.２ｍｍ）の片面にポリエステルウレタン系の接着剤を１．５μｍの厚さに塗布し乾燥した。次いで接着剤を塗布したステンレス鋼板を１６５℃に加熱し、その接着剤塗布面に白色顔料を１８重量％と青色顔料を２重量％含有するポリ塩化ビニルの未延伸フィルム（厚さ：２５μｍ、軟化温度：１６０℃）を当接し、１対の加圧ロールで両者を挟み付けて加圧し、樹脂被覆ステンレス鋼板とした。
[Preparation of resin-coated stainless steel sheet]
As a resin-coated metal plate, a polyester urethane adhesive was applied to one side of a stainless steel plate (JIS 304, plate thickness: 0.2 mm) to a thickness of 1.5 μm and dried. Next, the stainless steel plate coated with the adhesive was heated to 165 ° C., and an unstretched film of polyvinyl chloride containing 18% by weight of white pigment and 2% by weight of blue pigment on the adhesive-coated surface (thickness: 25 μm, softened) (Temperature: 160 ° C.), and a pair of pressure rolls sandwiched and pressed to form a resin-coated stainless steel sheet.
[粗面部を有する樹脂被覆金属板の作成]
上記の樹脂被覆ステンレス鋼板を赤外線オーブンで１６５℃に加熱し、樹脂被覆ステンレス鋼板の樹脂層に上記の粗面賦型フィルムの大小の長方形を重ねて印刷塗布して設けた粗面部が接するようにして当接し、１対の挟圧ロールで両者を挟み付けて加圧し、粗面賦型フィルムの粗面を樹脂被覆ステンレス鋼板の樹脂層に転写した。次いで粗面賦型フィルムを剥離し、表面に大小の長方形が重なった粗面部分が形成された、粗面部を有する樹脂被覆金属板（ステンレス鋼板）を得た。
[Preparation of resin-coated metal plate with rough surface]
Heat the above-mentioned resin-coated stainless steel plate to 165 ° C. in an infrared oven so that the rough surface portion of the resin-coated stainless steel plate overlaps the large and small rectangles of the above-mentioned rough surface-shaped film and is applied by printing. They were pressed against each other with a pair of pinching rolls, and the rough surface of the rough surface-forming film was transferred to the resin layer of the resin-coated stainless steel plate. Next, the rough surface-molded film was peeled off to obtain a resin-coated metal plate (stainless steel plate) having a rough surface portion on which a rough surface portion in which large and small rectangles overlapped was formed.
（実施例４）
[粗面賦型フィルム]
粗面賦型フィルムとして、実施例１と同様の粗面賦型フィルムを用いた。
Example 4
[Rough surface film]
The same rough surface-shaped film as in Example 1 was used as the rough surface-shaped film.
[樹脂被覆亜鉛めっき鋼板の作成]
樹脂被覆金属板の金属基板として、実施例１と同様の電気亜鉛めっき鋼板を用い、その片面にポリエステルウレタン系の接着剤を１．５μｍの厚さに塗布し乾燥した。次いで接着剤を塗布した電気亜鉛めっき鋼板を１６５℃に加熱し、その接着剤塗布面に黄色顔料を２０重量％含有するポリプロピレンの未延伸フィルム（厚さ：２５μｍ、軟化温度：１６０℃）を当接し、１対の加圧ロールで両者を挟み付けて加圧し、樹脂被覆亜鉛めっき鋼板とした。
[Preparation of resin-coated galvanized steel sheet]
As the metal substrate of the resin-coated metal plate, the same electrogalvanized steel plate as in Example 1 was used, and a polyester urethane adhesive was applied on one side to a thickness of 1.5 μm and dried. Next, the electrogalvanized steel sheet coated with the adhesive was heated to 165 ° C., and an unstretched polypropylene film (thickness: 25 μm, softening temperature: 160 ° C.) containing 20% by weight of yellow pigment was applied to the adhesive-coated surface. They were in contact with each other with a pair of pressure rolls and pressed to form a resin-coated galvanized steel sheet.
[粗面部を有する樹脂被覆金属板の作成]
上記の樹脂被覆亜鉛めっき鋼板を赤外線オーブンで１６５℃に加熱し、樹脂被覆亜鉛めっき鋼板の樹脂層に上記の粗面賦型フィルムのストライプ状の粗面部が接するようにして当接し、１対の挟圧ロールで両者を挟み付けて加圧し、粗面賦型フィルムのストライプ状の粗面を樹脂被覆亜鉛めっき鋼板の樹脂層に転写した。次いで粗面賦型フィルムを剥離し、表面に平滑な平面の一部にストライプ状の粗面部分が形成された、粗面部を有する樹脂被覆金属板（電気亜鉛めっき鋼板）を得た。
[Preparation of resin-coated metal plate with rough surface]
The resin-coated galvanized steel sheet is heated to 165 ° C. in an infrared oven, and is brought into contact with the resin layer of the resin-coated galvanized steel sheet so that the striped rough surface portion of the rough surface-shaped film is in contact therewith. Both of them were sandwiched and pressed by a pinching roll, and the striped rough surface of the rough surface-forming film was transferred to the resin layer of the resin-coated galvanized steel sheet. Subsequently, the rough surface shaping film was peeled off to obtain a resin-coated metal plate (electrogalvanized steel plate) having a rough surface portion in which a striped rough surface portion was formed on a part of a smooth flat surface.
（実施例５）
[粗面賦型フィルム]
粗面賦型フィルムとして、実施例２と同様の粗面賦型フィルムを用いた。
(Example 5)
[Rough surface film]
The same rough surface-shaped film as in Example 2 was used as the rough surface-shaped film.
[樹脂被覆亜鉛めっき鋼板の作成]
樹脂被覆金属板の金属基板として、実施例２と同様の合金亜鉛めっき鋼板を用い、その片面にポリエステルウレタン系の接着剤を１．５μｍの厚さに塗布し乾燥した。次いで接着剤を塗布した合金亜鉛めっき鋼板を１６５℃に加熱し、その接着剤塗布面に、ポリプロピレン８５％とスチレンブタジエンゴム１５％をブレンドしてなる樹脂に白色顔料を１５重量％と青色顔料を５重量％含有させてなる着色樹脂（厚さ：２５μｍ、軟化温度：１６０℃）を当接し、１対の加圧ロールで両者を挟み付けて加圧し、樹脂被覆亜鉛めっき鋼板とした。
[Preparation of resin-coated galvanized steel sheet]
As the metal substrate of the resin-coated metal plate, the same alloy galvanized steel sheet as in Example 2 was used, and a polyester urethane adhesive was applied on one side to a thickness of 1.5 μm and dried. Next, the alloy galvanized steel sheet coated with an adhesive is heated to 165 ° C., and 15% by weight of a white pigment and a blue pigment are added to a resin obtained by blending 85% polypropylene and 15% styrene butadiene rubber on the adhesive coated surface. A colored resin containing 5% by weight (thickness: 25 μm, softening temperature: 160 ° C.) was brought into contact with each other and pressed between a pair of pressure rolls to obtain a resin-coated galvanized steel sheet.
[粗面部を有する樹脂被覆金属板の作成]
上記の樹脂被覆亜鉛めっき鋼板を赤外線オーブンで１６５℃に加熱し、樹脂被覆亜鉛めっき鋼板の樹脂層に上記の粗面賦型フィルムの３種類の斜めに設けた平行な粗面部が接するようにして当接し、１対の挟圧ロールで両者を挟み付けて加圧し、粗面賦型フィルムの粗面を樹脂被覆亜鉛めっき鋼板の樹脂層に転写した。次いで粗面賦型フィルムを剥離し、表面に３種類の斜めに設けた平行な粗面部分が形成された、粗面部を有する樹脂被覆金属板（合金亜鉛めっき鋼板）を得た。
[Preparation of resin-coated metal plate with rough surface]
The resin-coated galvanized steel sheet is heated to 165 ° C. in an infrared oven so that the parallel rough surface portions of the three types of the above-mentioned rough surface-shaped film are in contact with the resin layer of the resin-coated galvanized steel sheet. The two were pressed against each other with a pair of pinching rolls, and the rough surface of the rough surface forming film was transferred to the resin layer of the resin-coated galvanized steel sheet. Next, the rough surface-forming film was peeled off to obtain a resin-coated metal plate (alloy galvanized steel plate) having a rough surface portion on which three types of parallel rough surface portions provided obliquely were formed.
本発明の粗面賦型フィルムは、樹脂フィルムの表面に、樹脂中に耐熱性粒子を分散してなる分散樹脂層を印刷法などの塗布法を用いて局部的にまたは全面に形成して粗面賦型フィルムを構成したものである。このように、本発明の粗面賦型フィルムは、樹脂表面に粗面を賦与するために用いられる金属製のエンボスロールに比べて、遙かに安価で平易に製造可能な粗面賦型手段であり、本発明の粗面賦型フィルムを用いた倍、粗面部を有する樹脂被覆金属板を安価に製造することができる。また、本発明の粗面賦型フィルムは、熱伝導性が低い樹脂フィルムからなる賦型フィルムを用いるため、エンボスロールによるエンボス加工におけるような、鮮明なエンボス模様を得るための厳密な温度管理が不要であり、平易に鮮明なエンボス模様が得られる。そのため、平坦な樹脂フィルム上の一部に局部的に粗面部分を形成させた目地模様やストライプ模様、さらに、局部的にまたは全面に粗面化程度の異なる複数の粗面部を形成させたソフィスティケートな外観を安価にかつ平易に得ることができる。 The rough surface-molding film of the present invention is formed by forming a dispersed resin layer, in which heat-resistant particles are dispersed in a resin, on a surface of a resin film locally or on the entire surface using a coating method such as a printing method. This is a surface-mounted film. In this way, the rough surface shaping film of the present invention is a rough surface shaping means that can be manufactured at a much lower cost and more easily than a metal embossing roll used to impart a rough surface to the resin surface. Thus, a resin-coated metal plate having double and rough surface portions using the rough surface shaping film of the present invention can be produced at low cost. Moreover, since the rough surface shaped film of the present invention uses a shaped film made of a resin film having low thermal conductivity, strict temperature control for obtaining a clear embossed pattern as in embossing with an embossing roll is required. It is not necessary and a clear embossed pattern can be easily obtained. Therefore, joint patterns and stripe patterns with a rough surface part formed on a part of a flat resin film, and a sophisticate with a plurality of rough surface parts with different surface roughnesses formed locally or on the entire surface. A simple appearance can be obtained inexpensively and easily.
１ ：樹脂フィルム
２ ：粗面部２
２ａ ：分散樹脂層
２ａ’：凹部
２ｂ ：分散樹脂層
２ｃ ：分散樹脂層
２ｄ ：分散樹脂層
２ｅ ：分散樹脂層
２ｆ ：分散樹脂層
３ ：金属板
４ ：熱可塑性樹脂
１０ ：粗面賦型フィルム
１５ ：加熱手段
２０ａ：樹脂被覆金属板
２０ｂ：粗面部を有する樹脂被覆金属板
２５：デフレクターロール
３０ａ：巻解手段
３０ｂ：巻解手段
４０ａ：加圧ロール
４０ｂ：加圧ロール
５０ａ：巻取手段
５０ｂ：巻取手段
1: Resin film 2:
2a:
2d:
4: Thermoplastic resin 10: Rough surface shaping film 15: Heating means 20a: Resin-coated metal plate 20b: Resin-coated metal plate having a rough surface portion 25:
Claims (16)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004143386A JP4813772B2 (en) | 2004-05-13 | 2004-05-13 | Method for producing resin-coated metal plate having rough surface portion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004143386A JP4813772B2 (en) | 2004-05-13 | 2004-05-13 | Method for producing resin-coated metal plate having rough surface portion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005324394A true JP2005324394A (en) | 2005-11-24 |
| JP4813772B2 JP4813772B2 (en) | 2011-11-09 |
Family
ID=35471131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004143386A Expired - Fee Related JP4813772B2 (en) | 2004-05-13 | 2004-05-13 | Method for producing resin-coated metal plate having rough surface portion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4813772B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101138553B1 (en) | 2009-10-07 | 2012-05-11 | 김정식 | Flexible Laminate THEREON AND MANUFACTURING METHOD THEREOF |
| JP2012166475A (en) * | 2011-02-15 | 2012-09-06 | Ube Nitto Kasei Co Ltd | Method for producing molded article |
| JP2014154731A (en) * | 2013-02-08 | 2014-08-25 | Tokyo Ohka Kogyo Co Ltd | Pattern forming apparatus |
| WO2018043683A1 (en) * | 2016-09-01 | 2018-03-08 | 旭硝子株式会社 | Metal laminate, method for producing same and method for producing printed board |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04314523A (en) * | 1991-04-15 | 1992-11-05 | Dainippon Printing Co Ltd | Shaping film |
| JPH0592484A (en) * | 1991-04-15 | 1993-04-16 | Dainippon Printing Co Ltd | Molded material with gloss-matte pattern |
| JPH05139095A (en) * | 1991-11-19 | 1993-06-08 | Dainippon Printing Co Ltd | Dull-finished transfer leaf and decorative material |
| JPH0691835A (en) * | 1992-09-08 | 1994-04-05 | Dainippon Printing Co Ltd | Production of decorative metal plate |
| JP2002127688A (en) * | 2000-10-24 | 2002-05-08 | Tdk Corp | Transfer film and non-glare-treated substance |
| JP2004124064A (en) * | 2002-07-30 | 2004-04-22 | Toyo Kohan Co Ltd | Roughened surface resin film, metal plate coated therewith, method for making metal plate coated therewith, metal can with surface coated therewith and its making method |
-
2004
- 2004-05-13 JP JP2004143386A patent/JP4813772B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04314523A (en) * | 1991-04-15 | 1992-11-05 | Dainippon Printing Co Ltd | Shaping film |
| JPH0592484A (en) * | 1991-04-15 | 1993-04-16 | Dainippon Printing Co Ltd | Molded material with gloss-matte pattern |
| JPH05139095A (en) * | 1991-11-19 | 1993-06-08 | Dainippon Printing Co Ltd | Dull-finished transfer leaf and decorative material |
| JPH0691835A (en) * | 1992-09-08 | 1994-04-05 | Dainippon Printing Co Ltd | Production of decorative metal plate |
| JP2002127688A (en) * | 2000-10-24 | 2002-05-08 | Tdk Corp | Transfer film and non-glare-treated substance |
| JP2004124064A (en) * | 2002-07-30 | 2004-04-22 | Toyo Kohan Co Ltd | Roughened surface resin film, metal plate coated therewith, method for making metal plate coated therewith, metal can with surface coated therewith and its making method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101138553B1 (en) | 2009-10-07 | 2012-05-11 | 김정식 | Flexible Laminate THEREON AND MANUFACTURING METHOD THEREOF |
| JP2012166475A (en) * | 2011-02-15 | 2012-09-06 | Ube Nitto Kasei Co Ltd | Method for producing molded article |
| JP2014154731A (en) * | 2013-02-08 | 2014-08-25 | Tokyo Ohka Kogyo Co Ltd | Pattern forming apparatus |
| WO2018043683A1 (en) * | 2016-09-01 | 2018-03-08 | 旭硝子株式会社 | Metal laminate, method for producing same and method for producing printed board |
| CN109661862A (en) * | 2016-09-01 | 2019-04-19 | Ａｇｃ株式会社 | The manufacturing method of metal layer lamination and its manufacturing method and printed base plate |
| CN109661862B (en) * | 2016-09-01 | 2021-08-31 | Ａｇｃ株式会社 | Metal laminate, method for producing the same, and method for producing a printed circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4813772B2 (en) | 2011-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3969625B2 (en) | Manufacturing method of resin film for decorative plate lamination | |
| JP2007264373A (en) | Label for in-mold molding container and in-mold molding container | |
| JP2010047308A (en) | Metal can body provided with foaming ink printing pattern | |
| JPH06507124A (en) | Manufacturing method of composite sheet material | |
| JP2005324394A (en) | Rough surface-shaped film, its manufacturing method, resin-coated metal sheet having rough surface part formed using rough surface-shaped film and its manufacturing method | |
| JP2016190332A (en) | Transfer sheet and decorative resin molding using the same | |
| JP2019059142A (en) | Production method of molding sheet for simultaneously molding large uneven pattern and fine uneven pattern, and molding sheet produced by the production method | |
| CN2472920Y (en) | Metal composite decorative plate | |
| JP2002096438A (en) | Multi-layer polyester film | |
| JP4727843B2 (en) | Decorative film, laminated metal plate obtained by laminating the film, and method for producing them | |
| JP2001047582A (en) | Decorative sheet and its manufacture | |
| JP4270800B2 (en) | Manufacturing method of adhesive sheet | |
| JP2002283358A (en) | Release paper and synthetic leather manufactured using the same | |
| JPH0470339A (en) | Transfer sheet and manufacture thereof | |
| JP2013199286A (en) | Hologram film attached metallic can and method of manufacturing the same | |
| JP2000154264A (en) | Pre-colored resin film, metal plate coated with pre- colored resin and can prepared from metal plate coated with pre-colored resin | |
| JP2004052270A (en) | Joint design resin film, metallic plate covered with joint design resin film, and method of manufacturing them | |
| JP3104796B2 (en) | Suede transfer foil | |
| JPH071825A (en) | Moldable transfer foil | |
| JP3089656B2 (en) | Manufacturing method of metal decorative board | |
| JPH1199598A (en) | Laminated decorative sheet using polyolefin resin film as backing and its production | |
| JP4837196B2 (en) | Manufacturing method of wall-mounted adhesive sheet | |
| JP4574763B2 (en) | Surface decorative sheet, method for producing the same, and transfer sheet used for the production | |
| JPH0114479Y2 (en) | ||
| JPH0255126A (en) | Preparation of resin coated metal plate having high sharpness |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061122 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090528 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090623 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090812 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100810 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100929 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100930 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110823 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110825 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4813772 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140902 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R255 | Notification that request for automated payment was rejected |
Free format text: JAPANESE INTERMEDIATE CODE: R2525 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |