JP7421878B2 - Film formation method - Google Patents
Film formation method Download PDFInfo
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- JP7421878B2 JP7421878B2 JP2019132219A JP2019132219A JP7421878B2 JP 7421878 B2 JP7421878 B2 JP 7421878B2 JP 2019132219 A JP2019132219 A JP 2019132219A JP 2019132219 A JP2019132219 A JP 2019132219A JP 7421878 B2 JP7421878 B2 JP 7421878B2
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- 238000000034 method Methods 0.000 title claims description 35
- 230000015572 biosynthetic process Effects 0.000 title 1
- 239000000463 material Substances 0.000 claims description 292
- 239000011248 coating agent Substances 0.000 claims description 280
- 238000000576 coating method Methods 0.000 claims description 277
- 229920005989 resin Polymers 0.000 claims description 61
- 239000011347 resin Substances 0.000 claims description 61
- 239000000178 monomer Substances 0.000 claims description 60
- 238000002834 transmittance Methods 0.000 claims description 45
- 239000011230 binding agent Substances 0.000 claims description 40
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 238000012360 testing method Methods 0.000 description 95
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 55
- -1 alkoxysilanes Substances 0.000 description 33
- 150000001875 compounds Chemical class 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 18
- 239000002518 antifoaming agent Substances 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 17
- 239000000470 constituent Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 17
- 239000002131 composite material Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
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- 239000002562 thickening agent Substances 0.000 description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 14
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- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 14
- 239000004908 Emulsion polymer Substances 0.000 description 13
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- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 12
- 239000006096 absorbing agent Substances 0.000 description 12
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 5
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
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- 230000008901 benefit Effects 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
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- ARVUDIQYNJVQIW-UHFFFAOYSA-N (4-dodecoxy-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 ARVUDIQYNJVQIW-UHFFFAOYSA-N 0.000 description 2
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
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- 239000004606 Fillers/Extenders Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
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- 230000001133 acceleration Effects 0.000 description 2
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- 125000003368 amide group Chemical group 0.000 description 2
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- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004587 polysulfide sealant Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 2
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
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- POLSVAXEEHDBMJ-UHFFFAOYSA-N (2-hydroxy-4-octadecoxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 POLSVAXEEHDBMJ-UHFFFAOYSA-N 0.000 description 1
- SXJSETSRWNDWPP-UHFFFAOYSA-N (2-hydroxy-4-phenylmethoxyphenyl)-phenylmethanone Chemical compound C=1C=C(C(=O)C=2C=CC=CC=2)C(O)=CC=1OCC1=CC=CC=C1 SXJSETSRWNDWPP-UHFFFAOYSA-N 0.000 description 1
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- KTJFJTQEJVXTHT-UHFFFAOYSA-N 1-ethenoxypropan-2-yl(dimethoxy)silane Chemical compound C(=C)OCC([SiH](OC)OC)C KTJFJTQEJVXTHT-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
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- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- JJZYPAHZQPAADA-UHFFFAOYSA-N 2-(2,5-dioxooxolan-3-yl)-4-triethoxysilylbutanoic acid Chemical group CCO[Si](OCC)(OCC)CCC(C(O)=O)C1CC(=O)OC1=O JJZYPAHZQPAADA-UHFFFAOYSA-N 0.000 description 1
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- 239000003242 anti bacterial agent Substances 0.000 description 1
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- 239000003429 antifungal agent Substances 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
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- 229910052918 calcium silicate Inorganic materials 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
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- 239000010408 film Substances 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 238000009472 formulation Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
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- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
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- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
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- 239000004570 mortar (masonry) Substances 0.000 description 1
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- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- 239000004588 polyurethane sealant Substances 0.000 description 1
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- 230000008439 repair process Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000004589 rubber sealant Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OQTSOKXAWXRIAC-UHFFFAOYSA-N tetrabutan-2-yl silicate Chemical compound CCC(C)O[Si](OC(C)CC)(OC(C)CC)OC(C)CC OQTSOKXAWXRIAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ADLSSRLDGACTEX-UHFFFAOYSA-N tetraphenyl silicate Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(OC=1C=CC=CC=1)OC1=CC=CC=C1 ADLSSRLDGACTEX-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
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- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- GIHPVQDFBJMUAO-UHFFFAOYSA-N tributoxy(ethyl)silane Chemical compound CCCCO[Si](CC)(OCCCC)OCCCC GIHPVQDFBJMUAO-UHFFFAOYSA-N 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- INUOIYMEJLOQFN-UHFFFAOYSA-N tributoxy(phenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C1=CC=CC=C1 INUOIYMEJLOQFN-UHFFFAOYSA-N 0.000 description 1
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- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
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- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- VUWVDNLZJXLQPT-UHFFFAOYSA-N tripropoxy(propyl)silane Chemical compound CCCO[Si](CCC)(OCCC)OCCC VUWVDNLZJXLQPT-UHFFFAOYSA-N 0.000 description 1
- 239000004591 urethane sealant Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
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Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Description
本発明は、新規な被膜形成方法に関するものである。 The present invention relates to a novel film forming method.
従来、建築物や土木構造物の外装等においては、種々の基材に対し、その基材の保護、色彩付与等の目的で、各種被覆材によって被膜が形成されている。このような被膜面は、美観性等の観点から、凹凸模様や多色模様が付与されていることがある。但し、このような被膜面は、屋外において長期にわたり曝露されると、太陽光、降雨等の影響によって劣化する傾向がある。具体的には、変色、ひび割れ等が引き起こされるおそれがある。そのため、このような劣化が生じた被膜面（既存被膜面）については、塗り替えを行う必要が生じてくる。 Conventionally, in the exterior of buildings and civil engineering structures, coatings have been formed on various base materials using various coating materials for the purpose of protecting the base materials, imparting color to the base materials, and the like. Such a coating surface may be provided with an uneven pattern or a multicolored pattern from the viewpoint of aesthetics and the like. However, when such a coated surface is exposed outdoors for a long period of time, it tends to deteriorate due to the effects of sunlight, rain, etc. Specifically, discoloration, cracking, etc. may occur. Therefore, it becomes necessary to repaint the coating surface (existing coating surface) where such deterioration has occurred.
これに対し、近年では、既存被膜面の塗り替えを行い、美観性の向上化、基材の長寿命化等を図ろうとする動きがある。例えば、特許文献１には、窯業外壁材塗装層表面の劣化部分を研磨した後、透明コーティング剤を塗付して、元の色調を復元させる方法が記載されている。 On the other hand, in recent years, there has been a movement to repaint the existing coated surface in order to improve the aesthetic appearance and extend the life of the base material. For example, Patent Document 1 describes a method for restoring the original color tone by polishing the degraded portion of the surface of the paint layer of a ceramic exterior wall material and then applying a transparent coating agent.
ところで、上述のような既存被膜面のうち、凹凸模様を有するものについては、凹凸形状等に応じて、太陽光の当たり方、水の流れ方や滞留の程度等が、部分的に異なることとなる。そのため、太陽光や水による負荷が大きな部分では、劣化が進行しやすくなり、局所的に変色、ひび割れ等が引き起こされるおそれがある。また、多色模様を有する被膜面では、色調によって耐久性に差異にある場合、相対的に耐久性が不十分な色調の領域において、同様の劣化が生じるおそれがある。 By the way, among the existing coated surfaces mentioned above, for those with an uneven pattern, the way sunlight hits, the way water flows, the degree of retention, etc. may differ depending on the uneven shape etc. Become. Therefore, in areas where the load from sunlight or water is large, deterioration tends to progress more easily, and local discoloration, cracking, etc. may occur. Furthermore, in the case where the coating surface has a multicolored pattern and there is a difference in durability depending on the color tone, similar deterioration may occur in the region of the color tone where the durability is relatively insufficient.
このような既存被膜面に対しては、上記特許文献に記載されるような方法で塗り替えを行っても、既存被膜面の劣化の進行を十分に抑制することができず、塗り替えの効果が得られ難い場合がある。 Even if such an existing coated surface is recoated using the method described in the above patent document, the progress of deterioration of the existing coated surface cannot be sufficiently suppressed, and the effect of recoating cannot be obtained. It may be difficult to do so.
本発明はこのような問題点に鑑みなされたもので、既存被膜の凹凸模様や多色模様を活かしつつ、既存被膜に起因する変色、ひび割れ等の劣化の進行を抑制し、長期にわたり美観性を保持することができる被膜形成方法を提供することを目的とする。 The present invention was created in view of these problems, and makes use of the uneven patterns and multicolored patterns of the existing coating, suppresses the progress of deterioration such as discoloration and cracking caused by the existing coating, and maintains the aesthetic appearance for a long time. It is an object of the present invention to provide a method for forming a film that can maintain the properties of the film.
このような課題を解決するため、本発明者は鋭意検討の結果、凹凸模様及び／または多色模様を有する既存被膜面に対し、特定の被覆材を塗付して被膜を形成する被膜形成方法に想到し、本発明を完成させるに至った。 In order to solve these problems, the present inventor has conducted intensive studies and developed a coating forming method in which a specific coating material is applied to an existing coating surface having an uneven pattern and/or a multicolored pattern to form a coating. They came up with this idea and completed the present invention.
すなわち、本発明は、以下の特徴を有するものである。
１．基材上に設けられた既存被膜面に対し、第１被覆材及び第２被覆材を塗付して新設被膜を形成する被膜形成方法であって、
上記既存被膜面は、凹凸模様及び／または多色模様を有するものであり、
上記第１被覆材及び第２被覆材は、それぞれ、
結合材として、炭素数３以上のアルキル基を有する（メタ）アクリル酸アルキルエステル（Ａ）を、樹脂構成成分中に２０重量％以上含む樹脂成分を含有し、
上記炭素数３以上のアルキル基を有する（メタ）アクリル酸アルキルエステル（Ａ）として、２－エチルヘキシルアクリレート（ａ１）を含むものであり、
上記結合材は、無機分を含有するものであり、
上記第１被覆材及び第２被覆材は、それぞれ、可視光透過性を有し、紫外線透過率が３０％以下である被膜を形成するものである、
ことを特徴とする被膜形成方法。
２．上記第１被覆材及び第２被覆材の結合材は、それぞれ、
上記炭素数３以上のアルキル基を有する（メタ）アクリル酸アルキルエステル（Ａ）として、２－エチルヘキシルアクリレート（ａ１）を含むものであり、
上記（Ａ）成分中に占める上記（ａ１）成分の重量比をｒとすると、
第１被覆材の結合材におけるｒ（ｒ１）は、第２被覆材の結合材におけるｒ（ｒ２）よりも大である
ことを特徴とする１．記載の被膜形成方法。
３．上記結合材の不揮発分に占める無機分の重量比率をｓとすると、
第１被覆材の結合材におけるｓ（ｓ１）は、第２被覆材の結合材におけるｓ（ｓ２）よりも大であることを特徴とする１．または２．に記載の被膜形成方法。
なお、ｓは、下記式にて算出される値である。
［式］ｓ（重量％）＝｛結合材に含まれる無機分の重量｝／｛結合材の不揮発分の重量｝×１００
（「結合材の不揮発分の重量」、及び「結合材に含まれる無機分の重量」は、ＪＩＳ Ｋ ５６０１－１－２「加熱残分」の方法に準じて測定することができる。「結合材の不揮発分の重量」は、加熱温度１３５℃、加熱時間６０分の条件にて測定したときの値であり、「結合材に含まれる無機分の重量」は、加熱温度５５０℃、加熱時間１８０分の条件にて測定したときの値である。）
４．上記第１被覆材の結合材は、樹脂構成成分中に、エポキシ基含有モノマーを含むものであることを特徴とする１．～３．のいずれかに記載の被膜形成方法。
５．上記新設被膜の膜厚が３０μｍ以上であることを特徴とする１．～４．のいずれかに記載の被膜形成方法。
That is, the present invention has the following features.
1. A film forming method in which a first coating material and a second coating material are applied to an existing coating surface provided on a base material to form a new coating, the method comprising:
The existing coating surface has an uneven pattern and/or a multicolored pattern,
The first covering material and the second covering material are each
Contains a resin component containing 20% by weight or more of a (meth)acrylic acid alkyl ester (A) having an alkyl group having 3 or more carbon atoms as a binder in the resin component,
The (meth)acrylic acid alkyl ester (A) having an alkyl group having 3 or more carbon atoms includes 2-ethylhexyl acrylate (a1),
The above-mentioned binding material contains an inorganic component,
The first coating material and the second coating material each form a coating that is transparent to visible light and has an ultraviolet transmittance of 30% or less.
A film forming method characterized by:
2. The binding materials of the first covering material and the second covering material are each:
The (meth)acrylic acid alkyl ester (A) having an alkyl group having 3 or more carbon atoms includes 2-ethylhexyl acrylate (a1),
If the weight ratio of the component (a1) in the component (A) is r,
1. r(r 1 ) in the binding material of the first covering material is larger than r(r 2 ) in the binding material of the second covering material. The film forming method described.
3. If the weight ratio of the inorganic content to the nonvolatile content of the binder is s, then
s (s 1 ) in the binding material of the first covering material is larger than s (s 2 ) in the binding material of the second covering material 1. or 2. The film forming method described in .
Note that s is a value calculated using the following formula.
[Formula] s (weight %) = {Weight of inorganic components contained in the binder} / {Weight of non-volatile components of the binder} x 100
(The "weight of non-volatile content of the binder" and the "weight of inorganic content contained in the binder" can be measured according to the method of JIS K 5601-1-2 "Heating residue". "Weight of non-volatile matter in the material" is the value measured at a heating temperature of 135°C and a heating time of 60 minutes. "Weight of inorganic content contained in the binder" is a value measured at a heating temperature of 550°C and a heating time of 60 minutes. (Values measured under 180 minute conditions.)
4. 1. The binder of the first coating material contains an epoxy group-containing monomer in the resin constituent components. ~3. The method for forming a film according to any one of the above.
5. 1. The thickness of the newly installed coating is 30 μm or more. ~4. The method for forming a film according to any one of the above.
本発明の被膜形成方法によれば、既存被膜の凹凸模様や多色模様を活かしつつ、既存被膜に起因する変色、ひび割れ等の劣化の進行を抑制し、長期にわたり美観性を保持することができる。 According to the film forming method of the present invention, it is possible to take advantage of the uneven pattern and multicolored pattern of the existing film, suppress the progress of deterioration such as discoloration and cracking caused by the existing film, and maintain the aesthetic appearance for a long period of time. .
以下、本発明を実施するための形態について説明する。 EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated.
本発明は、基材上に設けられた既存被膜面（凹凸模様及び／または多色模様を有する既存被膜面）に対し、特定の被覆材を塗付して新設被膜を形成する被膜形成方法である。 The present invention is a film forming method in which a specific coating material is applied to an existing film surface (an existing film surface having an uneven pattern and/or a multicolored pattern) provided on a base material to form a new film. be.
このような既存被膜面に対し、従来の透明コーティング剤によって塗り替えを行っても、元来劣化しやすい部分では、変色、ひび割れ等の進行を抑制することは困難であり、ひび割れについては、既存被膜面に生じていた微細なひび割れが経時的に進行してしまうおそれもある。このようなひび割れは、塗り替え後の被膜にも波及しやすく、そうすると新設被膜による美観性、遮水性等が損われ、基材の長寿命化等の点においても十分な効果が得られ難くなる。 Even if such existing coating surfaces are repainted with conventional transparent coating agents, it is difficult to suppress the progress of discoloration and cracking in areas that are naturally prone to deterioration. There is also a risk that fine cracks that have formed on the surface will progress over time. Such cracks tend to spread to the coating after repainting, which impairs the aesthetics, water-blocking properties, etc. of the newly installed coating, and makes it difficult to obtain sufficient effects in terms of extending the life of the base material.
これに対し、本発明では、既存被膜面の凹凸模様や多色模様を活かしつつ、既存被膜面に起因する変色、ひび割れ等の劣化の進行を抑制し、長期にわたり美観性を保持することができ、基材の長寿命化等を図ることも可能となる。このような効果は、本発明の特定新設被膜によって、太陽光や水への耐性が十分に付与されること等によって奏されるものと考えられる。 In contrast, the present invention makes it possible to maintain the aesthetic appearance for a long period of time by suppressing the progress of deterioration such as discoloration and cracking caused by the existing coating surface while making use of the uneven pattern and multicolored pattern of the existing coating surface. , it is also possible to extend the life of the base material. It is thought that such an effect is produced by the specific new coating of the present invention imparting sufficient resistance to sunlight and water.
本発明では、基材上に設けられた既存被膜面を塗装対象とする。このような既存被膜面としては、例えば、建築物、土木構造物等の基材表面に形成されたものが挙げられ、特に、太陽光や水等の影響を受けやすい外装面（外壁、屋根等）に形成されたものが好適である。基材としては、例えば、コンクリート、モルタル、板状基材等が挙げられる。このうち、板状基材としては、例えば、セメントボード、押出成形板、スレート板、ＰＣ板、ＡＬＣ板、繊維強化セメント板、金属系サイディングボード、窯業系サイディングボード、セラミック板、珪酸カルシウム板、プラスチックボード、硬質木片セメント板、塩ビ押出サイディングボード、合板等が挙げられる。本発明は、基材が板状基材である場合に、特に有用である。 In the present invention, the existing coating surface provided on the base material is to be painted. Examples of such existing coated surfaces include those formed on the base material surfaces of buildings, civil engineering structures, etc., and are particularly applicable to exterior surfaces that are easily affected by sunlight and water (external walls, roofs, etc.). ) is suitable. Examples of the base material include concrete, mortar, and plate-shaped base materials. Among these, examples of plate-like base materials include cement boards, extruded boards, slate boards, PC boards, ALC boards, fiber-reinforced cement boards, metal siding boards, ceramic siding boards, ceramic boards, calcium silicate boards, Examples include plastic board, hard wood cement board, PVC extrusion siding board, and plywood. The present invention is particularly useful when the base material is a plate-like base material.
既存被膜面が複数の板状基材で構成される場合、板状基材どうしの継ぎ目は、シーリング材、乾式目地材等の目地材等が充填されたものであってもよい。このうちシーリング材としては、例えば、シリコーン系シーリング材、変性シリコーン系シーリング材、ポリサルファイド系シーリング材、変性ポリサルファイド系シーリング材、アクリルウレタン系シーリング材、ポリウレタン系シーリング材、ＳＢＲ系シーリング材、ブチルゴム系シーリング材等が挙げられる。 When the existing coating surface is composed of a plurality of plate-shaped base materials, the joints between the plate-shaped base materials may be filled with a joint material such as a sealant or a dry joint material. Among these, examples of sealants include silicone sealants, modified silicone sealants, polysulfide sealants, modified polysulfide sealants, acrylic urethane sealants, polyurethane sealants, SBR sealants, and butyl rubber sealants. Examples include wood.
既存被膜面は、凹凸模様及び／または多色模様を有するものである。このような既存被膜は、１種または２種以上のコーティング剤によって形成されたものである。コーティング剤としては、着色ないし無着色、あるいは不透明ないし透明等の種々のものが使用でき、例えば、酢酸ビニル樹脂、ポリエステル樹脂、アルキド樹脂、エポキシ樹脂、アクリル樹脂、ウレタン樹脂等の有機質結合材、あるいはシリコン樹脂、アルコキシシラン、コロイダルシリカ、ケイ酸塩等の無機質結合材、アクリルシリコン樹脂等の有機無機複合結合材等が挙げられる。既存被膜面は、１層または２層以上の被膜であり、例えば、着色被膜層、透明被膜層等が積層されたものであってもよい。 The existing coating surface has an uneven pattern and/or a multicolored pattern. Such existing coatings are formed using one or more coating agents. Various coating agents can be used, such as colored or uncolored, opaque or transparent, such as organic binders such as vinyl acetate resin, polyester resin, alkyd resin, epoxy resin, acrylic resin, urethane resin, etc. Examples include inorganic binders such as silicone resins, alkoxysilanes, colloidal silica, and silicates, and organic-inorganic composite binders such as acrylic silicone resins. The existing coating surface is a coating of one layer or two or more layers, and may be a layered layer of colored coating layers, transparent coating layers, etc., for example.
凹凸模様としては、種々のものが挙げられ、例えばタイル調模様、レンガ調模様、石目調模様、岩石調模様、木目調模様、幾何学的模様、縞模様、格子模様、水玉模様、砂壁模様、ゆず肌模様、さざ波模様等の他、動植物等をデザイン化した図形模様等が挙げられる。具体的に、凹凸模様を正面から見たときの凸部の形状としては、例えば正方形、長方形、円形、楕円形、三角形、菱形、多角形、不定形等の形状が挙げられる。また、凹凸模様における凸部の断面形状としては、例えば台形、正方形、長方形、半円形、波形、階段形、三角形、山形、不定形等が挙げられる。凹凸模様における凹部は、平坦で目地を形成するもの等であってもよい。凹部と凸部との高低差は、各々の部位で一定であっても相違していてもよいが、好ましくは２０ｍｍ以下、より好ましくは１～１５ｍｍ程度である。このような凹凸模様は、基材、既存被膜のいずれか一方または両方に付されたものであればよい。 There are various types of uneven patterns, such as tile-like patterns, brick-like patterns, stone-like patterns, rock-like patterns, wood-like patterns, geometric patterns, striped patterns, lattice patterns, polka dot patterns, and sand wall patterns. , yuzu skin pattern, ripple pattern, etc., as well as graphic patterns with designs of animals and plants. Specifically, the shape of the convex portion when the concave-convex pattern is viewed from the front includes, for example, a square, a rectangle, a circle, an ellipse, a triangle, a rhombus, a polygon, an irregular shape, and the like. Further, the cross-sectional shape of the convex portions in the uneven pattern includes, for example, trapezoid, square, rectangle, semicircle, wave, step, triangle, chevron, irregular shape, and the like. The recesses in the uneven pattern may be flat and form joints. The height difference between the concave portion and the convex portion may be constant or different in each region, but is preferably 20 mm or less, and more preferably about 1 to 15 mm. Such an uneven pattern may be provided on either or both of the base material and the existing coating.
多色模様は、少なくとも２色以上の色彩が視認可能な状態で混在する模様であり、例えば、２色以上の斑点が混在する模様、背景色上に斑点（１色または２色以上）が散在する模様、２色以上に塗り分けられた模様（例えば、島状模様、線状模様、タイル調模様、レンガ調模様、石目調模様、岩石調模様、木目調模様、幾何学的模様、縞模様、格子模様、ランダム模様等）等が挙げられる。このような多色模様は、例えば、各種印刷手法（インクジェット印刷等）で形成されたものであってもよいし、石材調仕上塗材、多彩模様塗料等の装飾性コーティング剤によって形成されたものであってもよい。 A multicolor pattern is a pattern in which at least two or more colors are visibly mixed, such as a pattern in which spots of two or more colors are mixed, or spots (one or more colors) scattered on a background color. patterns, patterns painted in two or more colors (for example, island patterns, linear patterns, tile-like patterns, brick-like patterns, stone-like patterns, rock-like patterns, wood-like patterns, geometric patterns, stripes) pattern, lattice pattern, random pattern, etc.). Such a multicolored pattern may be formed, for example, by various printing methods (inkjet printing, etc.), or may be formed using a decorative coating agent such as a stone finish coating material or a multicolored pattern paint. It may be.
既存被膜は、このようなコーティング剤が、現場塗装、あるいは工場塗装（ライン塗装）等により、基材上に既に塗装されている種々の被膜である。このようなコーティング剤は、例えば、常温乾燥型、常温硬化型、焼付け硬化型、紫外線（ＵＶ）硬化型、電子線硬化型等のいずれのものであってもよい。 Existing coatings are various coatings in which such a coating agent has already been applied onto a substrate by on-site coating, factory coating (line coating), or the like. Such a coating agent may be, for example, a room temperature drying type, a room temperature curing type, a baking curing type, an ultraviolet (UV) curing type, an electron beam curing type, or the like.
本発明は、特に、最表面の既存被膜が、無機質被膜（上記無機質結合材を含む被膜）、有機無機複合被膜（上記有機無機複合結合材を含む被膜）、フッ素樹脂被膜（上記フッ素樹脂を含む被膜）等から選ばれる１種以上である場合に好適であり、さらには、これらの透明被膜に好適に適用できる。 In particular, the present invention provides that the existing coating on the outermost surface is an inorganic coating (a coating containing the above-mentioned inorganic binder), an organic-inorganic composite coating (a coating containing the above-mentioned organic-inorganic composite binder), or a fluororesin coating (a coating containing the above-mentioned fluororesin). It is preferable to use one or more types selected from the following, and furthermore, it can be suitably applied to these transparent films.
本発明は、上述のような既存被膜面が経年劣化した際の塗り替え方法（改装方法）として、好ましく適用できる。経年劣化の程度は、特に限定されるものではないが、壁面として概ね５年以上（さらには８年以上）使用されたものは、本発明の対象として好適である。新設被膜の形成前には、必要に応じ、既存被膜面の洗浄や部分補修等を行うことができる。既存被膜面がシーリング材等の目地材を有する場合、既存の目地材をそのまま残しておいてもよいが、新設被膜の形成前に新たな目地材を打設することもできるし、既存の目地材の表面に塗装等の処理を施すこともできる。 The present invention can be preferably applied as a repainting method (renovation method) when an existing coating surface as described above has deteriorated over time. The degree of deterioration over time is not particularly limited, but walls that have been used for approximately 5 years or more (even 8 years or more) are suitable as objects of the present invention. Before forming a new coating, cleaning or partial repair of the existing coating surface can be performed as necessary. If the existing coating surface has a joint material such as a sealant, the existing joint material may be left as is, but a new joint material may be placed before the new coating is formed, or the existing joint material may be left in place. It is also possible to apply treatments such as painting to the surface of the material.
本発明では、上述のような既存被膜面に対し、第１被覆材と第２被覆材を塗付して新設被膜を形成する。本発明における第１被覆材及び第２被覆材は、いずれも、結合材として、炭素数３以上のアルキル基を有する（メタ）アクリル酸アルキルエステル（Ａ）（以下「（Ａ）成分」ともいう）を、樹脂構成成分中に２０重量％以上含む樹脂成分を含有し、さらに当該結合材は無機分を含有する。そして、第１被覆材及び第２被覆材は、いずれも、可視光透過性を有し、紫外線透過率が３０％以下である被膜を形成するものである。このような第１被覆材及び第２被覆材（以下、両方を総称して単に「被覆材」ともいう）の共通事項について、まず説明する。 In the present invention, a new coating is formed by applying a first coating material and a second coating material to the existing coating surface as described above. In both the first coating material and the second coating material in the present invention, a (meth)acrylic acid alkyl ester (A) having an alkyl group having 3 or more carbon atoms (hereinafter also referred to as "component (A)") is used as a binding material. ) in the resin constituent components in an amount of 20% by weight or more, and the binder further contains an inorganic component. The first coating material and the second coating material both form a coating that is transparent to visible light and has an ultraviolet transmittance of 30% or less. First, common features of the first covering material and the second covering material (hereinafter, both may be collectively referred to simply as "covering material") will be described.
本発明における被覆材は、結合材として樹脂成分を含有し、当該樹脂成分は、樹脂構成成分として、炭素数３以上のアルキル基を有する（メタ）アクリル酸アルキルエステル（Ａ）を含む。このような樹脂成分は、（Ａ）成分によって、主に水への耐性を付与することができる。なお、本発明では、アクリル酸アルキルエステルとメタクリル酸アルキルエステルとを併せて（メタ）アクリル酸アルキルエステルと表記している。 The coating material in the present invention contains a resin component as a binding material, and the resin component contains (meth)acrylic acid alkyl ester (A) having an alkyl group having 3 or more carbon atoms as a resin constituent component. Such a resin component can mainly be provided with resistance to water by the component (A). In the present invention, acrylic acid alkyl ester and methacrylic acid alkyl ester are collectively referred to as (meth)acrylic acid alkyl ester.
（Ａ）成分におけるアルキル基の形態としては、例えば、直鎖状、分岐状、環状等が挙げられる。（Ａ）成分としては、例えば、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ｎ－ペンチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸ネオペンチル、（メタ）アクリル酸ｔ－ペンチル、（メタ）アクリル酸１－エチルプロピル、（メタ）アクリル酸２－メチルブチル、（メタ）アクリル酸３－メチルブチル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２－エチルブチル、（メタ）アクリル酸２－メチルペンチル、（メタ）アクリル酸４－メチルペンチル、（メタ）アクリル酸ｎ－ヘプチル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ｎ－ノニル、（メタ）アクリル酸ｎ－デシル、（メタ）アクリル酸ｎ－ウンデシル、（メタ）アクリル酸ｎ－ラウリル等が挙げられる。これらは、１種または２種以上で使用できる。これらの中でも、（Ａ）成分としては、炭素数４以上（より好ましくは４～１０、さらに好ましくは６～８）のアルキル基を有するものが好適である。 Examples of the form of the alkyl group in component (A) include linear, branched, and cyclic. Component (A) includes, for example, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, t-pentyl (meth)acrylate, 1-ethylpropyl (meth)acrylate, 2-methylbutyl (meth)acrylate , 3-methylbutyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, 2-methylpentyl (meth)acrylate, (meth)acrylic acid 4-Methylpentyl, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, (meth)acrylate ) n-decyl acrylate, n-undecyl (meth)acrylate, n-lauryl (meth)acrylate, and the like. These can be used alone or in combination of two or more. Among these, those having an alkyl group having 4 or more carbon atoms (more preferably 4 to 10, still more preferably 6 to 8) are suitable as component (A).
樹脂構成成分中の（Ａ）成分の比率は２０重量％以上、好ましくは２５～９９重量％、より好ましくは３０～９８重量％である。（Ａ）成分が上記比率であれば、水に対する耐性等を高めることができ、変色、ひび割れ等の劣化抑制、美観性保持等の効果を得ることが可能となる。なお、本発明において、「α～β」は「α以上β以下」と同義である。 The proportion of component (A) in the resin constituent components is 20% by weight or more, preferably 25 to 99% by weight, more preferably 30 to 98% by weight. When the component (A) is in the above ratio, resistance to water, etc. can be improved, and effects such as suppressing deterioration such as discoloration and cracking, and maintaining aesthetic appearance can be obtained. In the present invention, "α to β" is synonymous with "above α and below β".
本発明の被覆材では、樹脂構成成分中の（Ａ）成分として、炭素数３以上のアルキル主鎖を有する（メタ）アクリル酸アルキルエステル（ａ１）（以下「（ａ１）成分」ともいう）を含むことが好ましい。このような（ａ１）成分としては、そのアルキル部分が、直鎖状または分枝状のアルキル基（環状を除く）であって、主鎖（最も長い炭素直鎖）の炭素数が３以上であるものが使用できる。樹脂成分が（ａ１）成分を含むものであれば、水に対する耐性に加え、ひび割れ防止性をいっそう高めることができ、遮水性、美観性保持、基材長寿命化等の点でより好適である。 In the coating material of the present invention, (meth)acrylic acid alkyl ester (a1) having an alkyl main chain having 3 or more carbon atoms (hereinafter also referred to as "component (a1)") is used as component (A) in the resin constituent components. It is preferable to include. In such a component (a1), the alkyl moiety is a linear or branched alkyl group (excluding cyclic ones), and the main chain (longest straight carbon chain) has 3 or more carbon atoms. Something can be used. If the resin component contains component (a1), in addition to water resistance, crack prevention properties can be further improved, and it is more suitable in terms of water-blocking properties, maintaining aesthetic appearance, extending the life of the base material, etc. .
（ａ１）成分は、アルキル部分に炭素数３以上のアルキル主鎖を有する。（ａ１）成分のアルキル部分は、このようなアルキル主鎖を有する限り、種々の側鎖（例えば、アルキル主鎖よりも少ない炭素数のアルキル基等）を有するものであってもよい。（ａ１）成分としては、上述の（Ａ）成分のうち、このような条件を満たすものが使用でき、例えば、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸１－エチルプロピル、（メタ）アクリル酸ｔ－ペンチル、（メタ）アクリル酸ネオペンチル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸２－メチルブチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸３－メチルブチル、（メタ）アクリル酸２－エチルブチル、（メタ）アクリル酸ｎ－ペンチル、（メタ）アクリル酸２－メチルペンチル、（メタ）アクリル酸４－メチルペンチル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ｎ－ヘプチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸ｎ－ノニル、（メタ）アクリル酸ｎ－デシル、（メタ）アクリル酸ｎ－ウンデシル、（メタ）アクリル酸ｎ－ラウリル等が挙げられる。これらは、１種または２種以上で使用できる。これらの中でも、（ａ１）成分としては、アルキル部分に炭素数４以上（より好ましくは４～１０、さらに好ましくは６～８）のアルキル主鎖を有するものが好適である。 Component (a1) has an alkyl main chain having 3 or more carbon atoms in the alkyl moiety. The alkyl moiety of component (a1) may have various side chains (for example, an alkyl group having fewer carbon atoms than the alkyl main chain) as long as it has such an alkyl main chain. As component (a1), among the above-mentioned components (A), those satisfying such conditions can be used, such as n-propyl (meth)acrylate, isobutyl (meth)acrylate, and (meth)acrylate. 1-ethylpropyl, t-pentyl (meth)acrylate, neopentyl (meth)acrylate, n-butyl (meth)acrylate, 2-methylbutyl (meth)acrylate, isopentyl (meth)acrylate, (meth)acrylate 3-methylbutyl acid, 2-ethylbutyl (meth)acrylate, n-pentyl (meth)acrylate, 2-methylpentyl (meth)acrylate, 4-methylpentyl (meth)acrylate, n-(meth)acrylate hexyl, 2-ethylhexyl (meth)acrylate, n-heptyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, (meth)acrylic acid Examples include n-decyl, n-undecyl (meth)acrylate, and n-lauryl (meth)acrylate. These can be used alone or in combination of two or more. Among these, as component (a1), those having an alkyl main chain having 4 or more carbon atoms (more preferably 4 to 10, still more preferably 6 to 8) in the alkyl moiety are suitable.
（ａ１）以外の（Ａ）成分（以下「（ａ２）成分」ともいう）としては、例えば、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸シクロヘキシル等が挙げられる。これらは、１種または２種以上で使用できる。 Examples of component (A) other than (a1) (hereinafter also referred to as "component (a2)") include isopropyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, etc. It will be done. These can be used alone or in combination of two or more.
（Ａ）成分中に占める（ａ１）成分の重量比は「ｒ」として表すことができる。この「ｒ」は、下記式にて算出される値である。
［式］ ｒ＝｛樹脂構成成分中の（ａ１）成分の重量｝／｛樹脂構成成分中の（Ａ）成分の重量｝
The weight ratio of component (a1) in component (A) can be expressed as "r". This "r" is a value calculated using the following formula.
[Formula] r = {weight of component (a1) in resin component}/{weight of component (A) in resin component}
樹脂構成成分としては、上記（Ａ）成分に加え、上記（Ａ）成分を除くその他のモノマー（以下「（Ｂ）成分」ともいう）を含むことができる。（Ｂ）成分としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、あるいは、カルボキシル基含有モノマー、アミノ基含有モノマー、ピリジン系モノマー、水酸基含有モノマー、ニトリル基含有モノマー、アミド基含有モノマー、エポキシ基含有モノマー、カルボニル基含有モノマー、スルホン酸基含有モノマー、アルコキシシリル基含有モノマー、フッ素含有モノマー、芳香族モノマー、ポリオキシアルキレン鎖含有モノマー、ジビニル系モノマー、トリビニル系モノマー、紫外線吸収性基含有モノマー、光安定性基含有モノマー等が挙げられる。これらは、１種または２種以上で使用できる。（Ｂ）成分の構成比率は、樹脂構成成分中に｛（Ａ）成分と（Ｂ）成分の総量中に｝、好ましくは８０重量％以下（より好ましくは１～７５重量％、より好ましくは２～７０重量％）である。なお、本発明において、モノマーとは、重合性不飽和二重結合を有する化合物である。 In addition to the above-mentioned (A) component, the resin constituent components can include other monomers (hereinafter also referred to as "(B) component") other than the above-mentioned (A) component. Component (B) is, for example, methyl (meth)acrylate, ethyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, or a carboxyl group-containing monomer, an amino group-containing monomer, or a pyridine monomer. , hydroxyl group-containing monomer, nitrile group-containing monomer, amide group-containing monomer, epoxy group-containing monomer, carbonyl group-containing monomer, sulfonic acid group-containing monomer, alkoxysilyl group-containing monomer, fluorine-containing monomer, aromatic monomer, polyoxyalkylene chain-containing monomer Examples include monomers, divinyl monomers, trivinyl monomers, ultraviolet absorbing group-containing monomers, photostable group-containing monomers, and the like. These can be used alone or in combination of two or more. The composition ratio of component (B) is preferably 80% by weight or less (more preferably 1 to 75% by weight, more preferably 2% by weight) in the resin components {in the total amount of components (A) and (B)}. ~70% by weight). In addition, in this invention, a monomer is a compound which has a polymerizable unsaturated double bond.
本発明において、上記（Ｂ）成分として、紫外線吸収性基含有モノマー、及び／または光安定性基含有モノマーを含む態様は、本発明の効果向上の点で好ましいものである。紫外線吸収性基含有モノマーは、紫外線吸収性基と重合性不飽和二重結合を有する化合物であり、紫外線吸収性基としては、例えば、ベンゾフェノン系紫外線吸収性基、ベンゾトリアゾール系紫外線吸収性基、トリアジン系紫外線吸収性基、サリチレート系紫外線吸収性基等が挙げられる。光安定性基含有モノマーは、光安定性基と重合性不飽和二重結合を有する化合物であり、光安定性基としては、例えば、ピペリジル基等が挙げられる。 In the present invention, an embodiment containing a monomer containing an ultraviolet absorbing group and/or a monomer containing a photostable group as the component (B) is preferable in terms of improving the effects of the present invention. The ultraviolet absorbing group-containing monomer is a compound having an ultraviolet absorbing group and a polymerizable unsaturated double bond, and examples of the ultraviolet absorbing group include a benzophenone ultraviolet absorbing group, a benzotriazole ultraviolet absorbing group, Examples include triazine-based ultraviolet absorbing groups and salicylate-based ultraviolet absorbing groups. The photostable group-containing monomer is a compound having a photostable group and a polymerizable unsaturated double bond, and examples of the photostable group include a piperidyl group.
このような樹脂成分は、例えば、（Ａ）成分（好ましくは（ａ１）成分を含む）と、必要に応じ（Ｂ）成分を含むモノマー群を重合すること等によって製造できる。樹脂成分の形態としては、例えば、水溶性樹脂、水分散性樹脂、溶剤可溶形樹脂、無溶剤形樹脂、非水分散形樹脂等、あるいはこれらを複合したもの等が挙げられる。このうち水分散性樹脂（樹脂エマルション）は、１段ないし多段（２段、または３段以上）の乳化重合法等によって製造することができる。これらは架橋反応性を有するものであってもよく、また１液型、２液型等のいずれであってもよい。 Such a resin component can be produced, for example, by polymerizing component (A) (preferably containing component (a1)) and, if necessary, a monomer group containing component (B). Examples of the form of the resin component include water-soluble resins, water-dispersible resins, solvent-soluble resins, solvent-free resins, non-aqueous dispersible resins, and composites thereof. Among these, the water-dispersible resin (resin emulsion) can be produced by a one-stage to multi-stage (two-stage, three-stage or more) emulsion polymerization method. These may have crosslinking reactivity, and may be either one-part type, two-part type, etc.
第１被覆材及び第２被覆材における結合材は、いずれも、無機分を含むものである。このような無機分は、結合材を構成する無機質化合物に由来するものであり、既存被膜に起因する劣化の進行抑制、既存被膜面への密着性向上等に寄与し、本発明の効果を高めるものである。 The binder in the first coating material and the second coating material both contain an inorganic component. Such an inorganic component is derived from the inorganic compound that constitutes the binder, and contributes to suppressing the progress of deterioration caused by the existing coating, improving adhesion to the existing coating surface, etc., and enhancing the effects of the present invention. It is something.
このような無機質化合物としては、例えば、ケイ素化合物、アルミニウム化合物、チタン化合物、ジルコニウム化合物等が挙げられる。これらは、１種または２種以上で使用できる。本発明では、無機質化合物として、ケイ素化合物を含むことが望ましい。 Examples of such inorganic compounds include silicon compounds, aluminum compounds, titanium compounds, and zirconium compounds. These can be used alone or in combination of two or more. In the present invention, it is desirable to include a silicon compound as the inorganic compound.
ケイ素化合物としては、例えば、反応性シリル基含有モノマー、反応性シリル基含有メルカプト化合物、シランカップリング剤、アルコキシシラン化合物（４官能アルコキシシラン化合物、３官能アルコキシシラン化合物、２官能アルコキシシラン化合物等）、シロキサン化合物等、あるいはこれらの重縮合物等が挙げられる。これらは１種または２種以上で使用できる。反応性シリル基は、例えば、アルコキシル基、フェノキシ基、水酸基、メルカプト基、アミノ基、アセトキシ基、オキシム基、アミド基、ハロゲン基等から選ばれる１種以上の官能基がケイ素原子に結合したものである。このような反応性シリル基としては、特に、アルコキシル基、水酸基から選ばれる１種以上の官能基がケイ素原子に結合したものが好適である。 Examples of silicon compounds include reactive silyl group-containing monomers, reactive silyl group-containing mercapto compounds, silane coupling agents, alkoxysilane compounds (tetrafunctional alkoxysilane compounds, trifunctional alkoxysilane compounds, bifunctional alkoxysilane compounds, etc.) , siloxane compounds, or polycondensates thereof. These can be used alone or in combination of two or more. The reactive silyl group is one in which one or more functional groups selected from, for example, an alkoxyl group, a phenoxy group, a hydroxyl group, a mercapto group, an amino group, an acetoxy group, an oxime group, an amide group, a halogen group, etc. are bonded to a silicon atom. It is. As such a reactive silyl group, one in which one or more functional groups selected from an alkoxyl group and a hydroxyl group are bonded to a silicon atom is particularly suitable.
反応性シリル基含有モノマーは、反応性シリル基とエチレン性不飽和二重結合とを有する化合物であり、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリ－ｎ－ブトキシシラン、ビニルトリス（β－メトキシエトキシ）シラン、アリルトリメトキシシラン、トリメトキシシリルエチルビニルエーテル、トリエトキシシリルエチルビニルエーテル、トリメトキシシリルプロピルビニルエーテル、トリエトキシシリルプロピルビニルエーテル、γ－（メタ）アクリロイルオキシプロピルトリメトキシシラン、γ－（メタ）アクリロイルオキシプロピルトリエトキシシラン、γ－（メタ）アクリロイルオキシプロピルメチルジメトキシシラン、ビニルメチルジメトキシシラン、メチルジメトキシシリルエチルビニルエーテル、メチルジメトキシシリルプロピルビニルエーテル等が挙げられる。 The reactive silyl group-containing monomer is a compound having a reactive silyl group and an ethylenically unsaturated double bond, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-butoxysilane, vinyltris(β- methoxyethoxy)silane, allyltrimethoxysilane, trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, triethoxysilylpropyl vinyl ether, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltrimethoxysilane, ) Acryloyloxypropyltriethoxysilane, γ-(meth)acryloyloxypropylmethyldimethoxysilane, vinylmethyldimethoxysilane, methyldimethoxysilylethyl vinyl ether, methyldimethoxysilylpropyl vinyl ether, and the like.
反応性シリル基含有メルカプト化合物は、反応性シリル基とメルカプト基とを有する化合物であり、例えば、３－メルカプトプロピルトリメトキシシラン、３－メルカプトプロピルトリエトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルメチルジエトキシシラン、３－メルカプトプロピルジメチルメトキシシラン、３－メルカプトプロピルジメチルエトキシシラン、３－メルカプトプロピルトリアセトキシシラン、３－メルカプトプロピルメチルジアセトキシシラン、３－メルカプトプロピルジメチルアセトキシシラン、３－メルカプトプロピルトリオキシムシラン等が挙げられる。 The reactive silyl group-containing mercapto compound is a compound having a reactive silyl group and a mercapto group, such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, -Mercaptopropylmethyldiethoxysilane, 3-mercaptopropyldimethylmethoxysilane, 3-mercaptopropyldimethylethoxysilane, 3-mercaptopropyltriacetoxysilane, 3-mercaptopropylmethyldiacetoxysilane, 3-mercaptopropyldimethylacetoxysilane, 3 -Mercaptopropyltrioxime silane and the like.
シランカップリング剤は、例えば、一分子中に、少なくとも１個以上の反応性シリル基とその他の官能基を有する化合物であり、例えば、３－イソシアネートプロピルトリメトキシシラン、３－イソシアネートプロピルトリエトキシシラン等のイソシアネート基含有シラン化合物；トリス－（トリメトキシシリルプロピル）イソシアヌレート等のイソシアヌレート基含有シラン化合物；２－(３,４－エポキシシクロヘキシル)エチルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、ポリマー型多官能エポキシシラン等のエポキシ基含有シラン化合物；３－トリエトキシシリルプロピルコハク酸無水物、３－トリメトキシシリルプロピルコハク酸無水物、３－メチルジメトキシシリルプロピルコハク酸無水物、メチルジエトキシシリルプロピルコハク酸無水物、１－カルボキシ－３－トリエトキシシリルプロピルコハク酸無水物等の酸無水物基（カルボキシル基）含有シラン化合物；Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－アミノプロピルメチルジメトキシシラン等のアミノ基含有シラン化合物；３－トリエトキシシリル－Ｎ－（１、３－ジメチル－ブチリデン）プロピルアミン、３－トリメトキシシリル－Ｎ－（１、３－ジメチル－ブチリデン）プロピルアミン等のケトイミノ基含有シラン化合物；等が挙げられる。 The silane coupling agent is, for example, a compound having at least one reactive silyl group and other functional group in one molecule, such as 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane. Isocyanate group-containing silane compounds such as tris-(trimethoxysilylpropyl)isocyanurate; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxy Epoxy group-containing silane compounds such as silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, polymer-type polyfunctional epoxysilane; 3-triethoxysilylpropylsuccinic anhydride, 3-triethoxysilane Acid anhydride groups such as methoxysilylpropylsuccinic anhydride, 3-methyldimethoxysilylpropylsuccinic anhydride, methyldiethoxysilylpropylsuccinic anhydride, 1-carboxy-3-triethoxysilylpropylsuccinic anhydride ( carboxyl group)-containing silane compound; N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3 - Amino group-containing silane compounds such as aminopropyltriethoxysilane and 3-aminopropylmethyldimethoxysilane; 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, 3-trimethoxysilyl-N- Ketoimino group-containing silane compounds such as (1,3-dimethyl-butylidene)propylamine; and the like.
アルコキシシラン化合物としては、例えば、テトラエトキシシラン、テトラメトキシシラン、テトラｎ－プロポキシシラン、テトライソプロポキシシラン、テトライソブトキシシラン、テトラｓｅｃ－ブトキシシラン、テトラｔ－ブトキシシラン、テトラフェノキシシラン等の４官能アルコキシシラン化合物；メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリプロポキシシラン、エチルトリブトキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、プロピルトリプロポキシシラン、プロピルトリブトキシシラン、ブチルトリメトキシシラン、ブチルトリエトキシシラン、ブチルトリプロポキシシラン、ブチルトリブトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、デシルトリメトキシシラン、トリフルオロプロピルトリメトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、フェニルトリブトキシシラン等の３官能アルコキシシラン化合物；ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジメチルジブトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジエチルジブトキシシラン、ジエチルジプロポキシシラン、ジプロピルジメトキシシラン、ジプロピルジエトキシシラン、ジブチルジメトキシシラン、ジブチルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、ジフェニルジブトキシシラン、ジメトキシメチルフェニルシラン、メチルフェニルジエトキシシラン等の２官能アルコキシシラン化合物；等が挙げられる。 Examples of alkoxysilane compounds include tetraethoxysilane, tetramethoxysilane, tetran-propoxysilane, tetraisopropoxysilane, tetraisobutoxysilane, tetrasec-butoxysilane, tetrat-butoxysilane, and tetraphenoxysilane. Functional alkoxysilane compounds; methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, Propyltriethoxysilane, propyltripropoxysilane, propyltributoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, butyltributoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, Trifunctional alkoxysilane compounds such as trifluoropropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxy Silane, diethyldibutoxysilane, diethyldipropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, dimethoxymethylphenylsilane , bifunctional alkoxysilane compounds such as methylphenyldiethoxysilane; and the like.
シロキサン化合物としては、例えば、環状シロキサン化合物、直鎖状シロキサン化合物、分岐状シロキサン化合物等が挙げられる。このうち、環状シロキサン化合物としては、例えば、ヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン等が挙げられる。 Examples of the siloxane compound include cyclic siloxane compounds, linear siloxane compounds, and branched siloxane compounds. Among these, examples of the cyclic siloxane compound include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like.
このような無機質化合物は、塗付時の被覆材に含まれていればよく、例えば、樹脂成分の重合時ないし重合後、被覆材の製造時、被覆材の調合時等に導入することができる。具体的に、ケイ素化合物については、例えば、樹脂成分の重合時に、上記（Ｂ）成分として反応性シリル基含有モノマーを使用することができ、また、樹脂成分の重合時に、連鎖移動剤として反応性シリル基含有メルカプト化合物を使用することができる。また、シランカップリング剤、４官能アルコキシシラン化合物、３官能アルコキシシラン化合物、２官能アルコキシシラン化合物、シロキサン化合物等、あるいはこれらの重縮合物は、例えば、樹脂成分の重合時に使用したり、重合後の樹脂成分に混合したり、被覆材の製造時に混合したり、被覆材の調合時に混合したりすることができる。 Such an inorganic compound only needs to be included in the coating material at the time of application; for example, it can be introduced during or after the polymerization of the resin component, during the production of the coating material, during the formulation of the coating material, etc. . Specifically, for silicon compounds, for example, a reactive silyl group-containing monomer can be used as the component (B) during the polymerization of the resin component, and a reactive silyl group-containing monomer can be used as a chain transfer agent during the polymerization of the resin component. Mercapto compounds containing silyl groups can be used. In addition, silane coupling agents, tetrafunctional alkoxysilane compounds, trifunctional alkoxysilane compounds, bifunctional alkoxysilane compounds, siloxane compounds, etc., or polycondensates thereof, may be used, for example, during polymerization of resin components or after polymerization. It can be mixed with the resin component of , mixed at the time of manufacturing the covering material, or mixed at the time of preparing the covering material.
結合材の不揮発分に占める無機分の重量比率は、「ｓ」として表すことができる。この「ｓ」は、下記式にて算出される値である。
［式］ ｓ（重量％）＝｛結合材に含まれる無機分の重量｝／｛結合材の不揮発分の重量｝×１００
The weight ratio of the inorganic content to the nonvolatile content of the binder can be expressed as "s". This "s" is a value calculated using the following formula.
[Formula] s (weight %) = {Weight of inorganic components contained in the binder} / {Weight of non-volatile components of the binder} x 100
ここで、「結合材の不揮発分の重量」、及び「結合材に含まれる無機分の重量」は、ＪＩＳ Ｋ５６０１－１－２「加熱残分」の方法に準じて測定することができる。「結合材の不揮発分の重量」は、加熱温度１３５℃、加熱時間６０分の条件にて測定したときの値であり、「結合材に含まれる無機分の重量」は、加熱温度５５０℃、加熱時間１８０分の条件にて測定したときの値である。 Here, the "weight of non-volatile content of the binder" and the "weight of inorganic content contained in the binder" can be measured according to the method of JIS K5601-1-2 "Heating residue". "Weight of non-volatile components of the binder" is a value measured at a heating temperature of 135°C and a heating time of 60 minutes. "Weight of inorganic components contained in the binder" is a value measured at a heating temperature of 550°C and a heating time of 60 minutes. This value was measured under the condition of heating time of 180 minutes.
本発明における被覆材は、可視光透過性を有する被膜を形成するものである。これにより、透明性を有する被膜を形成することができ、既存被膜面の色調（多色模様等）を活かした仕上りを得ることが可能となる。この可視光透過性は、既存被膜面が視認できる程度であればよく、被膜は無色透明、着色透明のいずれであってもよく、また艶有り、艶消し（７分艶、５分艶、３分艶等を含む）のいずれであってもよい。着色透明の被膜は、例えば、着色顔料、染料等を含む被覆材によって形成できる。艶消しの被膜は、例えば、体質顔料、艶消し剤等を含む被覆材によって形成できる。 The coating material in the present invention forms a film that transmits visible light. As a result, it is possible to form a transparent film, and it is possible to obtain a finish that takes advantage of the color tone (multicolored pattern, etc.) of the existing film surface. This visible light transmittance only needs to be such that the surface of the existing coating can be visually recognized. (including gloss, etc.). A colored transparent film can be formed using a coating material containing a colored pigment, dye, etc., for example. The matte film can be formed by, for example, a coating material containing an extender pigment, a matte agent, and the like.
可視光透過性の程度は、可視光透過率で示すことができる。可視光透過率は、好ましくは３０％以上、より好ましくは３５～１００％、さらに好ましくは４０～９５％である。なお、可視光透過率は、膜厚３０μｍの被膜について、波長５８０ｎｍの光の透過率を、分光光度計を用いて測定した値（被膜なし（空気）の場合を透過率１００％とする）である。 The degree of visible light transmittance can be indicated by visible light transmittance. The visible light transmittance is preferably 30% or more, more preferably 35 to 100%, and even more preferably 40 to 95%. In addition, the visible light transmittance is the value measured using a spectrophotometer for the transmittance of light at a wavelength of 580 nm for a film with a thickness of 30 μm (transmittance is 100% in the case of no film (air)). be.
このような可視光透過性を得るには、例えば、被覆材中の着色顔料比率を低く設定すればよい。被覆材中の着色顔料比率は、好ましくは１０重量％以下、より好ましくは５重量％以下、さらに好ましくは０～３重量％である。被覆材が着色顔料を含まない態様も好適である。 In order to obtain such visible light transmittance, for example, the proportion of colored pigment in the coating material may be set low. The proportion of colored pigment in the coating material is preferably 10% by weight or less, more preferably 5% by weight or less, even more preferably 0 to 3% by weight. Embodiments in which the coating material does not contain colored pigments are also suitable.
本発明における被覆材は、紫外線透過率が３０％以下、好ましくは２０％以下、より好ましくは０～１５％である被膜を形成するものである。本発明では、紫外線透過率が上記範囲内であることにより、太陽光に対する耐性等を高めることができ、変色、ひび割れ等の劣化抑制、美観性保持等の効果を得ることが可能となる。なお、紫外線透過率は、膜厚３０μｍの被膜について、波長３５０ｎｍの光の透過率を、分光光度計を用いて測定した値（被膜なし（空気）の場合を透過率１００％とする）である。 The coating material of the present invention forms a film having an ultraviolet transmittance of 30% or less, preferably 20% or less, and more preferably 0 to 15%. In the present invention, when the ultraviolet transmittance is within the above range, resistance to sunlight can be increased, and effects such as suppressing deterioration such as discoloration and cracking and maintaining aesthetic appearance can be obtained. In addition, the ultraviolet transmittance is the value measured by using a spectrophotometer to measure the transmittance of light at a wavelength of 350 nm for a film with a thickness of 30 μm (transmittance is 100% in the case of no film (air)). .
このような紫外線透過率を得る手段としては、例えば、
（１）紫外線吸収性基を有する樹脂成分を含有する被覆材を使用する。
（２）紫外線吸収剤を含有する被覆材を使用する。
（３）紫外線遮蔽性粉体を含む被覆材を使用する。
等が挙げられる。これらの手段は、単独で採用してもよいし、組み合わせて採用してもよい。
As means for obtaining such ultraviolet transmittance, for example,
(1) A coating material containing a resin component having an ultraviolet absorbing group is used.
(2) Use a coating material containing an ultraviolet absorber.
(3) Use a coating material containing ultraviolet-shielding powder.
etc. These means may be employed singly or in combination.
上記（１）では、例えば、（Ｂ）成分として紫外線吸収性基含有モノマーを含む樹脂成分を使用すればよい。樹脂構成成分中における紫外線吸収性基含有モノマーの比率は、好ましくは０．０５～１０重量％、より好ましくは０．１～５重量％である。 In the above (1), for example, a resin component containing an ultraviolet absorbing group-containing monomer may be used as the component (B). The proportion of the ultraviolet absorbing group-containing monomer in the resin component is preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight.
上記（２）における紫外線吸収剤（重合性不飽和二重結合を有する化合物を除く）としては、例えば、ベンゾフェノン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤、トリアジン系紫外線吸収剤、サリチレート系紫外線吸収剤、シアノアクリレート系紫外線吸収剤、ベンゾエート系紫外線吸収剤、マロン酸エステル系紫外線吸収剤、シュウ酸アニリド系紫外線吸収剤等が挙げられる。このうち、ベンゾフェノン系紫外線吸収剤としては、例えば、２，４－ジヒドロキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン－５－スルホン酸、２－ヒドロキシ－４－ｎ－オクトキシベンゾフェノン、２－ヒドロキシ－４－ｎ－ドデシルオキシベンゾフェノン、２－ヒドロキシ－４－ベンジルオキシベンゾフェノン、ビス（５－ベンゾイル－４－ヒドロキシ－２－メトキシフェニル）メタン、２，２’－ジヒドロキシ－４－メトキシベンゾフェノン、２，２’－ジヒドロキシ－４，４’ジメトキシベンゾフェノン、２，２’，４，４’－テトラヒドロキシベンゾフェノン、４－ドデシルオキシ－２－ヒドロキシベンゾフェノン、２－ヒドロキシ－４－メトキシ－２’－カルボキシベンゾフェノン、２－ヒドロキシ－４－ステアリルオキシベンゾフェノン等が挙げられる。ベンゾトリアゾール系紫外線吸収剤としては、例えば、２－（２－ヒドロキシ－５－ｔ－ブチルフェニル）－２Ｈ－ベンゾトリアゾール、３－（２Ｈ－ベンゾトリアゾール－２－イル）－５－（１，１－ジメチルエチル）－４－ヒドロキシアルキルエステル、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ビス（１－メチル－１－フェニルエチル）フェノール、２－（２Ｈ－ベンゾトリアゾール－２－イル）－６－（１－メチル－１－フェニルエチル）－４－（１，１，３，３－テトラメチルブチル）フェノール、メチル３－（３－（２Ｈ－ベンゾトリアゾール－２－イル）－５－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネートとポリエチレングリコールの反応生成物等が挙げられる。トリアジン系紫外線吸収剤としては、例えば、２－（４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン－２－イル）－５－ヒドロキシフェニル誘導体、２－（２，４－ジヒドロキシフェニル）－４，６－ビス－（２，４－ジメチルフェニル）－１，３，５－トリアジンと（２－エチルヘキシル）－グリシド酸エステルの反応生成物、２，４－ビス「２－ヒドロキシ－４－ブトキシフェニル］－６－（２，４－ジブトキシフェニル）－１，３－５－トリアジン等が挙げられる。これらは、１種または２種以上で使用できる。紫外線吸収剤の混合比率は、樹脂成分１００重量部に対し、好ましくは０．０５～１０重量部、より好ましくは０．１～５重量部である。 Examples of the ultraviolet absorber in (2) above (excluding compounds having a polymerizable unsaturated double bond) include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, and salicylate ultraviolet absorbers. UV absorbers, cyanoacrylate-based UV absorbers, benzoate-based UV absorbers, malonic acid ester-based UV absorbers, oxalic acid anilide-based UV absorbers, and the like. Among these, examples of benzophenone ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and 2-hydroxy-4-n -Octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2'-dihydroxy -4-methoxybenzophenone, 2,2'-dihydroxy-4,4'dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4- Examples include methoxy-2'-carboxybenzophenone and 2-hydroxy-4-stearyloxybenzophenone. Examples of benzotriazole ultraviolet absorbers include 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 3-(2H-benzotriazol-2-yl)-5-(1,1 -dimethylethyl)-4-hydroxyalkyl ester, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl) -yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol-2-yl) Examples include reaction products of -5-t-butyl-4-hydroxyphenyl)propionate and polyethylene glycol. Examples of triazine-based ultraviolet absorbers include 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hydroxyphenyl derivatives, 2-(2 ,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester reaction product, 2,4-bis' Examples include 2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3-5-triazine.These can be used alone or in combination of two or more.Ultraviolet absorber The mixing ratio is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the resin component.
上記（３）における紫外線遮蔽性粉体としては、紫外線を吸収及び／または反射する性能を有するものが使用でき、例えば、アルミナ、酸化ジルコニウム、硫酸バリウム、沈降性硫酸バリウム、炭酸カルシウム、炭酸マグネシウム、水酸化アルミニウム、水酸化マグネシウム、酸化チタン、酸化マグネシウム、酸化亜鉛、窒化ホウ素、オキシ塩化ビスマス、リン酸亜鉛、雲母、寒水石、タルク、珪藻土、白土、カオリン、クレー、陶土、バライト粉、珪砂、珪石粉、ホワイトカーボン、金属粉、有機樹脂粉体等が挙げられる。これらは、１種または２種以上で使用できる。紫外線遮蔽性粉体の平均粒子径は、好ましくは１～２００ｎｍである。上記（３）においては、可視光透過性が確保できる範囲内で、紫外線遮蔽性粉体の混合比率を設定することが望ましい。 As the ultraviolet shielding powder in (3) above, those having the ability to absorb and/or reflect ultraviolet rays can be used, such as alumina, zirconium oxide, barium sulfate, precipitated barium sulfate, calcium carbonate, magnesium carbonate, Aluminum hydroxide, magnesium hydroxide, titanium oxide, magnesium oxide, zinc oxide, boron nitride, bismuth oxychloride, zinc phosphate, mica, agarite, talc, diatomaceous earth, white clay, kaolin, clay, china clay, barite powder, silica sand, Examples include silica powder, white carbon, metal powder, and organic resin powder. These can be used alone or in combination of two or more. The average particle diameter of the ultraviolet shielding powder is preferably 1 to 200 nm. In (3) above, it is desirable to set the mixing ratio of the ultraviolet shielding powder within a range that can ensure visible light transparency.
本発明における被覆材は、上記成分以外に、本発明の効果を著しく阻害しない範囲内において、必要に応じ、公知の添加剤、例えば、骨材、色粒、着色顔料、体質顔料、染料、艶消し剤、増粘剤、湿潤剤、凍結防止剤、造膜助剤、防腐剤、防黴剤、防藻剤、抗菌剤、分散剤、消泡剤、光安定剤、酸化防止剤、密着性付与剤、低汚染化剤、親水化剤、撥水剤、架橋剤、硬化促進剤、触媒等を含むものであってもよい。被覆材の形態としては、例えば、１液型、２液型（主剤と硬化剤からなる形態）、３液以上の多液型等が挙げられる。２液型や多液型の被覆材においては、被覆材の塗付時（塗付直前）に主剤と硬化剤等を調合することができる。 In addition to the above-mentioned components, the coating material of the present invention may contain known additives, such as aggregate, colored grains, colored pigments, extender pigments, dyes, and gloss, if necessary, within a range that does not significantly impede the effects of the present invention. Eraser, thickener, wetting agent, antifreeze agent, film forming aid, preservative, antifungal agent, antialgae agent, antibacterial agent, dispersant, antifoaming agent, light stabilizer, antioxidant, adhesion It may contain a imparting agent, a stain-reducing agent, a hydrophilic agent, a water repellent, a crosslinking agent, a curing accelerator, a catalyst, and the like. Examples of the form of the coating material include a one-component type, a two-component type (form consisting of a base agent and a curing agent), a multi-component type containing three or more components, and the like. In two-component or multi-component coating materials, the base agent, curing agent, etc. can be mixed at the time of applying the coating material (immediately before application).
本発明では、既存被膜面に対し、このような被覆材（第１被覆材及び第２被覆材）を塗付（塗装）することにより、新設被膜を形成する。すなわち、既存被膜面に対し、第１被覆材と第２被覆材を順に塗付して新設被膜を形成する。このような新設被膜は可視光透過性を有する。本発明では、第１被覆材を塗付し、その被膜を乾燥させた後に、第２被覆材を塗付することが望ましい。 In the present invention, a new coating is formed by applying (painting) such coating materials (first coating material and second coating material) to an existing coating surface. That is, the first coating material and the second coating material are sequentially applied to the existing coating surface to form a new coating. Such a newly installed coating is transparent to visible light. In the present invention, it is desirable to apply the first coating material, dry the film, and then apply the second coating material.
本発明では、第１被覆材、第２被覆材として、（Ａ）成分に対する（ａ１）成分の比ｒが異なる結合材を使用することができる。この場合、第１被覆材の結合材におけるｒ（以下「ｒ１」ともいう）は、第２被覆材の結合材におけるｒ（以下「ｒ２」ともいう）よりも大であることが望ましい。すなわち、ｒ１－ｒ２＞０を満たすことが望ましい。このような態様の結合材を含む第１被覆材と第２被覆材を使用することにより、既存被膜面に起因する変色、ひび割れ等の劣化の進行を十分に抑制することができ、既存被膜面への密着性等も向上する。さらに、美観性保持、基材長寿命化等の効果を高めることもできる。なお、ｒ１、ｒ２は、それぞれ下記式１、下記式２にて算出される値である。
［式１］ ｒ１＝｛第１被覆材における樹脂構成成分中の（ａ１）成分の重量｝／｛第１被覆材における樹脂構成成分中の（Ａ）成分の重量｝
［式２］ ｒ２＝｛第２被覆材における樹脂構成成分中の（ａ１）成分の重量｝／｛第２被覆材における樹脂構成成分中の（Ａ）成分の重量｝
In the present invention, bonding materials having different ratios r of component (a1) to component (A) can be used as the first coating material and the second coating material. In this case, it is desirable that r in the binding material of the first covering material (hereinafter also referred to as "r 1 ") is larger than r in the binding material of the second covering material (hereinafter also referred to as "r 2 "). That is, it is desirable to satisfy r 1 −r 2 >0. By using the first coating material and the second coating material containing the binder in this manner, it is possible to sufficiently suppress the progress of deterioration such as discoloration and cracking caused by the existing coating surface, and the existing coating surface It also improves adhesion to the surface. Furthermore, effects such as maintaining aesthetic appearance and extending the life of the base material can be enhanced. Note that r 1 and r 2 are values calculated by the following formula 1 and the following formula 2, respectively.
[Formula 1] r 1 = {weight of component (a1) in the resin components in the first coating material}/{weight of component (A) in the resin components in the first coating material}
[Formula 2] r 2 = {weight of component (a1) in the resin components in the second coating material}/{weight of component (A) in the resin components in the second coating material}
上記式で表わされるｒ１は、好ましくは０．１～１．０、より好ましくは０．２～０．９、さらに好ましくは０．３～０．８５、特に好ましくは０．４～０．８であり、ｒ２は、好ましくは０．０５～０．８、より好ましくは０．１～０．６、さらに好ましくは０．１５～０．５５、特に好ましくは０．２～０．５である。ｒ１とｒ２との差（ｒ１－ｒ２）は、好ましくは０．０１以上、より好ましくは０．０５～０．９、さらに好ましくは０．０８～０．８、特に好ましくは０．１～０．７である。このような場合、上述の効果を十分に得ることが可能となる。 r 1 represented by the above formula is preferably 0.1 to 1.0, more preferably 0.2 to 0.9, even more preferably 0.3 to 0.85, particularly preferably 0.4 to 0. 8, and r 2 is preferably 0.05 to 0.8, more preferably 0.1 to 0.6, even more preferably 0.15 to 0.55, particularly preferably 0.2 to 0.5. It is. The difference between r 1 and r 2 (r 1 - r 2 ) is preferably 0.01 or more, more preferably 0.05 to 0.9, even more preferably 0.08 to 0.8, particularly preferably 0. .1 to 0.7. In such a case, it becomes possible to fully obtain the above-mentioned effects.
本発明において、第１被覆材と、第２被覆材とでは、結合材の不揮発分に占める無機分の重量比率ｓが異なる結合材を使用することができる。この場合、第１被覆材の結合材におけるｓ（以下「ｓ１」ともいう）は、第２被覆材の結合材におけるｓ（以下「ｓ２」ともいう）よりも大であることが望ましい。すなわち、ｓ１－ｓ２＞０を満たすことが望ましい。このような態様の結合材を含む第１被覆材と第２被覆材を使用することにより、既存被膜面に起因する変色、ひび割れ等の劣化の進行を十分に抑制することができ、既存被膜面への密着性等も向上する。さらに、美観性保持、基材長寿命化等の効果を高めることもできる。なお、ｓ１、ｓ２は、それぞれ下記式３、下記式４にて算出される値である。
［式３］ ｓ１（重量％）＝｛第１被覆材における結合材に含まれる無機分の重量｝／｛第１被覆材における結合材の不揮発分の重量｝×１００
［式４］ ｓ２（重量％）＝｛第２被覆材における結合材に含まれる無機分の重量｝／｛第２被覆材における結合材の不揮発分の重量｝×１００
In the present invention, the first coating material and the second coating material can use binders having different weight ratios of inorganic components to nonvolatile components of the binder. In this case, it is desirable that s (hereinafter also referred to as "s 1 ") in the binding material of the first covering material be larger than s (hereinafter also referred to as "s 2 ") in the binding material of the second covering material. That is, it is desirable to satisfy s 1 −s 2 >0. By using the first coating material and the second coating material containing the binder in this manner, it is possible to sufficiently suppress the progress of deterioration such as discoloration and cracking caused by the existing coating surface, and the existing coating surface It also improves adhesion to the surface. Furthermore, effects such as maintaining aesthetic appearance and extending the life of the base material can be enhanced. Note that s 1 and s 2 are values calculated using Equation 3 below and Equation 4 below, respectively.
[Formula 3] s 1 (wt%) = {Weight of inorganic components contained in the binder in the first coating material}/{Weight of non-volatile components of the binder in the first coating material}×100
[Formula 4] s 2 (weight %) = {weight of inorganic components contained in the binder in the second coating material} / {weight of non-volatile components of the binder in the second coating material}×100
上記式で表わされるｓ１は、好ましくは０．１～２０重量％、より好ましくは１～１５重量％、さらに好ましくは２～１０重量％であり、ｓ２は、好ましくは０．０１～１０重量％、より好ましくは０．０３～３重量％、さらに好ましくは０．０５～２重量％である。ｓ１とｓ２との差（ｓ１－ｓ２）は、好ましくは０．１～２０重量％、より好ましくは１～１５重量％である。このような場合、上述の効果を十分に得ることが可能となる。 s 1 represented by the above formula is preferably 0.1 to 20% by weight, more preferably 1 to 15% by weight, even more preferably 2 to 10% by weight, and s 2 is preferably 0.01 to 10% by weight. % by weight, more preferably 0.03 to 3% by weight, even more preferably 0.05 to 2% by weight. The difference between s 1 and s 2 (s 1 −s 2 ) is preferably 0.1 to 20% by weight, more preferably 1 to 15% by weight. In such a case, it becomes possible to fully obtain the above-mentioned effects.
本発明において、第１被覆材の結合材としては、樹脂構成成分中に、（Ａ）成分、及び（Ｂ）成分としてエポキシ基含有モノマーを含むものを使用することができる。第１被覆材において、このような樹脂成分を使用することにより、既存被膜面への密着性が高まり、本発明の効果向上を図ることができる。 In the present invention, as the binder of the first coating material, a resin component containing an epoxy group-containing monomer as the component (A) and the component (B) can be used. By using such a resin component in the first coating material, the adhesion to the existing coating surface is increased, and the effects of the present invention can be improved.
エポキシ基含有モノマーとしては、例えば、グリシジル（メタ）アクリレート、ジグリシジルフマレート、３，４－エポキシシクロヘキシル（メタ）アクリレート、３，４－エポキシビニルシクロヘキサン、アリルグリシジルエーテル、ε－カプロラクトン変性グリシジル（メタ）アクリレート、β－メチルグリシジル（メタ）アクリレート等が挙げられる。これらは、１種または２種以上を組み合わせて使用することができる。 Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, diglycidyl fumarate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxyvinylcyclohexane, allyl glycidyl ether, and ε-caprolactone-modified glycidyl (meth)acrylate. ) acrylate, β-methylglycidyl (meth)acrylate, and the like. These can be used alone or in combination of two or more.
樹脂構成成分中のエポキシ基含有モノマーの比率は、好ましくは０．１～２０重量％（より好ましくは０．５～１５重量％）である。このような範囲内であれば、密着性向上効果を十分に得ることができ、本発明の効果向上を図ることができる。 The proportion of the epoxy group-containing monomer in the resin constituents is preferably 0.1 to 20% by weight (more preferably 0.5 to 15% by weight). Within this range, a sufficient effect of improving adhesion can be obtained, and the effects of the present invention can be improved.
このような第１被覆材及び第２被覆材の積層によって形成される新設被膜の膜厚は、好ましくは３０μｍ以上、より好ましくは５０μｍ以上、さらに好ましくは６０μｍ以上、特に好ましくは６５μｍ超、最も好ましくは７０μｍ以上である。膜厚の下限が上記範囲内であることにより、新設被膜に、太陽光や水への耐性が十分に付与され、既存被膜面に起因する変色、ひび割れ等の劣化抑制、長期にわたる美観性保持等の点で好適である。新設被膜の膜厚の上限は特に限定されないが、好ましくは３００μｍ以下、より好ましくは２５０μｍ以下、さらに好ましくは２００μｍ以下である。膜厚の上限が上記範囲内であれば、既存被膜面の凹凸模様等を活かした仕上りを得ることができる。なお、本発明における膜厚は、乾燥膜厚のことである。 The thickness of the new coating formed by laminating the first coating material and the second coating material is preferably 30 μm or more, more preferably 50 μm or more, even more preferably 60 μm or more, particularly preferably more than 65 μm, and most preferably is 70 μm or more. By keeping the lower limit of the film thickness within the above range, the newly installed film will have sufficient resistance to sunlight and water, suppress deterioration such as discoloration and cracking caused by the existing film surface, and maintain its aesthetic appearance over a long period of time. It is suitable in this respect. The upper limit of the thickness of the newly installed coating is not particularly limited, but is preferably 300 μm or less, more preferably 250 μm or less, and still more preferably 200 μm or less. If the upper limit of the film thickness is within the above range, it is possible to obtain a finish that takes advantage of the uneven pattern of the existing film surface. Note that the film thickness in the present invention is a dry film thickness.
第１被覆材の被膜と第２被覆材の被膜との膜厚比｛（第１被覆材の被膜の膜厚）：（第２被覆材の被膜の膜厚）｝は、好ましくは８０：２０～２０：８０、より好ましくは７０：３０～３０：７０、さらに好ましくは６５：３５～３５：６５である。このような態様であることにより、既存被膜面に起因する変色、ひび割れ等の抑制、既存被膜面への密着性向上化、長期にわたる美観性保持等の点において、十分な効果を得ることができる。 The film thickness ratio between the film of the first coating material and the film of the second coating material {(thickness of the film of the first coating material):(film thickness of the film of the second coating material)} is preferably 80:20. ~20:80, more preferably 70:30~30:70, even more preferably 65:35~35:65. With this aspect, sufficient effects can be obtained in terms of suppressing discoloration, cracking, etc. caused by the existing coating surface, improving adhesion to the existing coating surface, maintaining aesthetic appearance over a long period of time, etc. .
第１被覆材、第２被覆材は、それぞれ複数回塗り重ねることができる。また、第１被覆材に該当する被覆材を２種以上塗り重ねたり、第２被覆材に該当する被覆材を２種以上塗り重ねたりすることも可能である。例えば、無色透明型、着色透明型、艶有り型、艶消し型等、色や艶の程度が異なる２種以上を塗り重ねることができる。塗り重ねを行う際には、適宜インターバルを設け、被膜を乾燥させることもできる。このような場合、塗り重ね後の膜厚が上記条件を満たすことが望ましい。なお、第１被覆材を２種以上塗り重ねる場合は、第１被覆材のうち、少なくとも最下層（既存被膜面側）の被膜が上記ｒ１及び／またはｓ１を満たすことが望ましい。第２被覆材を２種以上塗り重ねる場合は、第２被覆材のうち、少なくとも最上層（表面側）の被膜が上記ｒ２及び／またはｓ２を満たすことが望ましい。 The first coating material and the second coating material can each be coated multiple times. It is also possible to overcoat two or more types of coating material corresponding to the first coating material, or to overcoat two or more types of coating material corresponding to the second coating material. For example, two or more types with different colors and degrees of gloss, such as a colorless transparent type, a colored transparent type, a glossy type, and a matte type, can be coated over each other. When recoating, appropriate intervals may be provided to allow the film to dry. In such a case, it is desirable that the film thickness after recoating satisfies the above conditions. In addition, when two or more kinds of first coating materials are coated over each other, it is desirable that at least the bottom layer (on the existing coating surface side) of the first coating materials satisfies r 1 and/or s 1 above. When two or more types of second coating materials are coated, it is desirable that at least the uppermost layer (surface side) of the second coating materials satisfies r 2 and/or s 2 above.
各被覆材の塗付においては、公知の塗装器具を用いることができる。塗装器具としては、例えば、スプレー、ローラー、刷毛等を使用することができる。各被覆材の塗付け量、塗り重ね数等は、最終的な膜厚が上記範囲内となるように設定することが望ましい。第１被覆材、第２被覆材の塗付け量は、それぞれ、好ましくは０．０５～０．４ｋｇ／ｍ２、より好ましくは０．０８～０．３ｋｇ／ｍ２である。各被覆材の塗り重ね数は、好ましくは１～３回である。塗装時には、各被覆材を必要に応じ適宜希釈することもできる。各被覆材塗付後の乾燥は、常温（好ましくは０～５０℃、より好ましくは５～４５℃）で行えばよく、必要に応じ加熱することもできる。 In applying each coating material, known painting equipment can be used. As the painting tool, for example, a spray, a roller, a brush, etc. can be used. It is desirable that the amount of each coating material applied, the number of coats, etc. be set so that the final film thickness is within the above range. The coating amounts of the first coating material and the second coating material are preferably 0.05 to 0.4 kg/m 2 , more preferably 0.08 to 0.3 kg/m 2 . The number of coats of each coating material is preferably 1 to 3 times. At the time of painting, each coating material can be diluted as necessary. Drying after application of each coating material may be carried out at room temperature (preferably 0 to 50°C, more preferably 5 to 45°C), and may be heated if necessary.
以下に実施例を示し、本発明の特徴をより明確にする。 Examples are shown below to clarify the features of the present invention.
被覆材として、以下のものを用意した。 The following materials were prepared as covering materials.
・被覆材１：結合材１｛シクロヘキシルメタクリレート・２－エチルヘキシルアクリレート・メチルメタクリレート・紫外線吸収性基含有モノマー・光安定性基含有モノマー・アクリル酸・γ－メタクリロイルオキシプロピルトリメトキシシラン（重量比２０：５２：２３：２：１：１：１）の乳化重合体とアルコキシシラン化合物との複合物、樹脂構成成分中（Ａ）成分７２重量％、ｒ＝０．７２、ｓ＝０．５重量％｝、増粘剤、造膜助剤、消泡剤、及び水の混合物。可視光透過率６２％、紫外線透過率５％。 ・Coating material 1: Binding material 1 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 20: Composite of emulsion polymer (52:23:2:1:1:1) and alkoxysilane compound, component (A) 72% by weight in the resin constituents, r = 0.72, s = 0.5% by weight }, a mixture of a thickener, a coalescing agent, an antifoaming agent, and water. Visible light transmittance 62%, UV transmittance 5%.
・被覆材２：結合材２｛シクロヘキシルメタクリレート・２－エチルヘキシルアクリレート・メチルメタクリレート・紫外線吸収性基含有モノマー・光安定性基含有モノマー・アクリル酸・γ－メタクリロイルオキシプロピルトリメトキシシラン（重量比２５：４０：３０：２：１：１：１）の乳化重合体とアルコキシシラン化合物との複合物、樹脂構成成分中（Ａ）成分６５重量％、ｒ＝０．６２、ｓ＝０．５重量％｝、増粘剤、造膜助剤、消泡剤、及び水の混合物。可視光透過率６３％、紫外線透過率４％。 ・Coating material 2: Binding material 2 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 25: Composite of emulsion polymer (40:30:2:1:1:1) and alkoxysilane compound, component (A) 65% by weight in the resin constituents, r = 0.62, s = 0.5% by weight }, a mixture of a thickener, a coalescing agent, an antifoaming agent, and water. Visible light transmittance 63%, UV transmittance 4%.
・被覆材３：結合材３｛シクロヘキシルメタクリレート・２－エチルヘキシルアクリレート・メチルメタクリレート・紫外線吸収性基含有モノマー・光安定性基含有モノマー・アクリル酸・γ－メタクリロイルオキシプロピルトリメトキシシラン（重量比２５：３０：４０：２：１：１：１）の乳化重合体とアルコキシシラン化合物との複合物、樹脂構成成分中（Ａ）成分５５重量％、ｒ＝０．５５、ｓ＝０．５重量％｝、増粘剤、造膜助剤、消泡剤、及び水の混合物。可視光透過率６３％、紫外線透過率５％。 ・Coating material 3: Binding material 3 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 25: Composite of emulsion polymer (30:40:2:1:1:1) and alkoxysilane compound, component (A) 55% by weight in the resin constituents, r = 0.55, s = 0.5% by weight }, a mixture of a thickener, a coalescing agent, an antifoaming agent, and water. Visible light transmittance 63%, UV transmittance 5%.
・被覆材４：結合材４｛シクロヘキシルメタクリレート・２－エチルヘキシルアクリレート・メチルメタクリレート・紫外線吸収性基含有モノマー・光安定性基含有モノマー・アクリル酸・γ－メタクリロイルオキシプロピルトリメトキシシラン（重量比３２：１８：４５：２：１：１：１）の乳化重合体とアルコキシシラン化合物との複合物、樹脂構成成分中（Ａ）成分５０重量％、ｒ＝０．３６、ｓ＝０．５重量％｝、増粘剤、造膜助剤、消泡剤、及び水の混合物。可視光透過率６２％、紫外線透過率４％。 ・Coating material 4: Binding material 4 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 32: Composite of emulsion polymer (18:45:2:1:1:1) and alkoxysilane compound, component (A) 50% by weight in the resin constituents, r = 0.36, s = 0.5% by weight }, a mixture of a thickener, a coalescing agent, an antifoaming agent, and water. Visible light transmittance 62%, UV transmittance 4%.
・被覆材５：結合材５｛シクロヘキシルメタクリレート・２－エチルヘキシルアクリレート・メチルメタクリレート・紫外線吸収性基含有モノマー・光安定性基含有モノマー・アクリル酸・γ－メタクリロイルオキシプロピルトリメトキシシラン（重量比２８：１２：５５：２：１：１：１）の乳化重合体とアルコキシシラン化合物との複合物、樹脂構成成分中（Ａ）成分４０重量％、ｒ＝０．３０、ｓ＝０．５重量％｝、増粘剤、造膜助剤、消泡剤、及び水の混合物。可視光透過率６２％、紫外線透過率４％。 ・Coating material 5: Binding material 5 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 28: 12:55:2:1:1:1) composite of emulsion polymer and alkoxysilane compound, component (A) 40% by weight in the resin constituents, r = 0.30, s = 0.5% by weight }, a mixture of a thickener, a coalescing agent, an antifoaming agent, and water. Visible light transmittance 62%, UV transmittance 4%.
・被覆材６：結合材６｛シクロヘキシルメタクリレート・２－エチルヘキシルアクリレート・メチルメタクリレート・紫外線吸収性基含有モノマー・光安定性基含有モノマー・アクリル酸・γ－メタクリロイルオキシプロピルトリメトキシシラン（重量比４６：４：４５：２：１：１：１）の乳化重合体とアルコキシシラン化合物との複合物、樹脂構成成分中（Ａ）成分５０重量％、ｒ＝０．０８、ｓ＝０．５重量％｝、増粘剤、造膜助剤、消泡剤、及び水の混合物。可視光透過率６１％、紫外線透過率６％。 ・Coating material 6: Binding material 6 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 46: Composite of emulsion polymer (4:45:2:1:1:1) and alkoxysilane compound, component (A) 50% by weight in the resin constituents, r = 0.08, s = 0.5% by weight }, a mixture of a thickener, a coalescing agent, an antifoaming agent, and water. Visible light transmittance 61%, UV transmittance 6%.
・被覆材７：結合材７｛シクロヘキシルメタクリレート・２－エチルヘキシルアクリレート・メチルメタクリレート・光安定性基含有モノマー・アクリル酸・γ－メタクリロイルオキシプロピルトリメトキシシラン（重量比２５：３０：４２：１：１：１）の乳化重合体とアルコキシシラン化合物との複合物、樹脂構成成分中（Ａ）成分５５重量％、ｒ＝０．５５、ｓ＝０．５重量％｝、増粘剤、造膜助剤、消泡剤、水、及びトリアジン系紫外線吸収剤（樹脂成分１００重量部に対し０．３重量部）の混合物。可視光透過率６１％、紫外線透過率２４％。 ・Coating material 7: Binding material 7 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 25:30:42:1:1) : Composite of emulsion polymer of 1) and alkoxysilane compound, component (A) in the resin constituents 55% by weight, r=0.55, s=0.5% by weight}, thickener, film forming aid A mixture of an antifoaming agent, an antifoaming agent, water, and a triazine ultraviolet absorber (0.3 parts by weight per 100 parts by weight of the resin component). Visible light transmittance 61%, UV transmittance 24%.
・被覆材８：結合材８｛シクロヘキシルメタクリレート・２－エチルヘキシルアクリレート・メチルメタクリレート・光安定性基含有モノマー・アクリル酸・γ－メタクリロイルオキシプロピルトリメトキシシラン（重量比３２：１８：４７：１：１：１）の乳化重合体とアルコキシシラン化合物との複合物、樹脂構成成分中（Ａ）成分５０重量％、ｒ＝０．３６、ｓ＝０．５重量％｝、増粘剤、造膜助剤、消泡剤、水、及びトリアジン系紫外線吸収剤（樹脂成分１００重量部に対し０．３重量部）の混合物。可視光透過率６０％、紫外線透過率２６％。 ・Coating material 8: Binding material 8 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, monomer containing a photostable group, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 32:18:47:1:1) : Composite of emulsion polymer of 1) and alkoxysilane compound, (50% by weight of component (A) in the resin constituents, r = 0.36, s = 0.5% by weight}, thickener, film forming aid) A mixture of an antifoaming agent, an antifoaming agent, water, and a triazine ultraviolet absorber (0.3 parts by weight per 100 parts by weight of the resin component). Visible light transmittance 60%, UV transmittance 26%.
・被覆材９：結合材９｛シクロヘキシルメタクリレート・２－エチルヘキシルアクリレート・メチルメタクリレート・紫外線吸収性基含有モノマー・光安定性基含有モノマー・アクリル酸・γ－メタクリロイルオキシプロピルトリメトキシシラン（重量比２５：３０：３９：２：１：１：２）の乳化重合体とアルコキシシラン化合物との複合物、樹脂構成成分中（Ａ）成分５５重量％、ｒ＝０．５５、ｓ＝３．０重量％｝、増粘剤、造膜助剤、消泡剤、及び水の混合物。可視光透過率６２％、紫外線透過率４％。 ・Coating material 9: Binding material 9 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 25: 30:39:2:1:1:2) composite of emulsion polymer and alkoxysilane compound, component (A) 55% by weight in the resin constituents, r = 0.55, s = 3.0% by weight }, a mixture of a thickener, a coalescing agent, an antifoaming agent, and water. Visible light transmittance 62%, UV transmittance 4%.
・被覆材１０：結合材１０｛シクロヘキシルメタクリレート・２－エチルヘキシルアクリレート・メチルメタクリレート・紫外線吸収性基含有モノマー・光安定性基含有モノマー・アクリル酸・γ－メタクリロイルオキシプロピルトリメトキシシラン（重量比２５：３０：３９：２：１：１：２）の乳化重合体とアルコキシシラン化合物との複合物、樹脂構成成分中（Ａ）成分５５重量％、ｒ＝０．５５、ｓ＝４．５重量％｝、増粘剤、造膜助剤、消泡剤、及び水の混合物。可視光透過率６１％、紫外線透過率４％。 ・Coating material 10: Binding material 10 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 25: Composite of emulsion polymer (30:39:2:1:1:2) and alkoxysilane compound, component (A) 55% by weight in the resin constituents, r = 0.55, s = 4.5% by weight }, a mixture of a thickener, a coalescing agent, an antifoaming agent, and water. Visible light transmittance 61%, UV transmittance 4%.
・被覆材１１：結合材１１｛シクロヘキシルメタクリレート・２－エチルヘキシルアクリレート・メチルメタクリレート・紫外線吸収性基含有モノマー・光安定性基含有モノマー・アクリル酸・γ－メタクリロイルオキシプロピルトリメトキシシラン・グリシジルメタクリレート（重量比２４：３０：３９：２：１：１：２：１）の乳化重合体とアルコキシシラン化合物との複合物、樹脂構成成分中（Ａ）成分５４重量％、ｒ＝０．５６、ｓ＝４．５重量％｝、増粘剤、造膜助剤、消泡剤、及び水の混合物。可視光透過率６１％、紫外線透過率４％。 ・Coating material 11: Binding material 11 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane, glycidyl methacrylate (weight A composite of an emulsion polymer and an alkoxysilane compound with a ratio of 24:30:39:2:1:1:2:1), component (A) in the resin component 54% by weight, r = 0.56, s = 4.5% by weight}, a mixture of thickener, coalescent, antifoaming agent, and water. Visible light transmittance 61%, UV transmittance 4%.
・被覆材１２：結合材１２｛シクロヘキシルメタクリレート・２－エチルヘキシルアクリレート・メチルメタクリレート・紫外線吸収性基含有モノマー・光安定性基含有モノマー・アクリル酸・γ－メタクリロイルオキシプロピルトリメトキシシラン・グリシジルメタクリレート（重量比２４：４０：２９：２：１：１：２：１）の乳化重合体とアルコキシシラン化合物との複合物、樹脂構成成分中（Ａ）成分６４重量％、ｒ＝０．６３、ｓ＝４．５重量％｝、増粘剤、造膜助剤、消泡剤、及び水の混合物。可視光透過率６１％、紫外線透過率５％。 ・Coating material 12: Binding material 12 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane, glycidyl methacrylate (weight A composite of an emulsion polymer and an alkoxysilane compound with a ratio of 24:40:29:2:1:1:2:1), component (A) 64% by weight in the resin components, r = 0.63, s = 4.5% by weight}, a mixture of thickener, coalescent, antifoaming agent, and water. Visible light transmittance 61%, UV transmittance 5%.
・被覆材１３：結合材１３｛シクロヘキシルメタクリレート・２－エチルヘキシルアクリレート・メチルメタクリレート・紫外線吸収性基含有モノマー・光安定性基含有モノマー・アクリル酸（重量比１０：８：７８：２：１：１）の乳化重合体、樹脂構成成分中（Ａ）成分１８重量％、ｒ＝０．４４、ｓ＝０重量％｝、増粘剤、造膜助剤、消泡剤、及び水の混合物。可視光透過率６０％、紫外線透過率５％。 ・Coating material 13: Binding material 13 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid (weight ratio 10:8:78:2:1:1) ), a mixture of component (A) in the resin components: 18% by weight, r=0.44, s=0% by weight}, a thickener, a film-forming aid, an antifoaming agent, and water. Visible light transmittance 60%, UV transmittance 5%.
・被覆材１４：結合材１４｛シクロヘキシルメタクリレート・２－エチルヘキシルアクリレート・メチルメタクリレート・アクリル酸（重量比１０：８：８１：１）の乳化重合体、樹脂構成成分中（Ａ）成分１８重量％、ｒ＝０．４４、ｓ＝０重量％｝、増粘剤、造膜助剤、消泡剤、及び水の混合物。可視光透過率５９％、紫外線透過率５５％。 ・Coating material 14: Binding material 14 {emulsion polymer of cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, and acrylic acid (weight ratio 10:8:81:1), component (A) 18% by weight among the resin components, r=0.44, s=0% by weight}, a mixture of a thickener, a coalescing agent, an antifoaming agent, and water. Visible light transmittance 59%, UV transmittance 55%.
（実施例１）
既存被膜面として、屋外曝露により劣化した窯業系サイディングボート（表面にタイル調の凹凸模様を有し、凹部には黒色のアクリル系樹脂被膜、凸部には褐色のアクリル系樹脂被膜、全体にアクリルシリコン系樹脂透明被膜を有するもの）を用意した。この既存被膜面の全面に対し、第１被覆材として被覆材１を乾燥膜厚（表１では「膜厚」と表記。以下同様。）が３８μｍとなるようにスプレー塗装し、３時間乾燥後、第２被覆材として被覆材２を乾燥膜厚が３８μｍとなるようにスプレー塗装し、７日間乾燥養生することにより、試験体を作製した。なお、塗装ないし養生の工程は、すべて標準状態（気温２３℃、相対湿度５０％）下で行った。
(Example 1)
The existing coating surface is a ceramic siding boat that has deteriorated due to outdoor exposure (the surface has a tile-like uneven pattern, a black acrylic resin coating is applied to the concave areas, a brown acrylic resin coating is applied to the convex areas, and the entire surface is acrylic). (having a transparent silicone resin coating) was prepared. Coating material 1 was spray-painted as the first coating material over the entire surface of this existing coating surface so that the dry film thickness (denoted as "film thickness" in Table 1. The same applies hereinafter) was 38 μm, and after drying for 3 hours. A test specimen was prepared by spray-coating coating material 2 as a second coating material so that the dry film thickness was 38 μm, and drying and curing for 7 days. The painting and curing steps were all performed under standard conditions (temperature 23° C., relative humidity 50%).
［試験Ｉ］
上記方法で得られた試験体について、ＪＩＳ Ｋ５６００－５－６に準じた碁盤目テープ法にて密着性を評価した。評価基準は、「Ａ：欠損部面積が１０％未満」、「Ｂ：欠損部面積が１０％以上３０％未満」、「Ｃ：欠損部面積が３０％以上５０％未満」、「Ｄ：欠損部面積が５０％以上」とした。試験結果を表１に示す。
[Test I]
The adhesion of the test specimens obtained by the above method was evaluated using a checkerboard tape method according to JIS K5600-5-6. The evaluation criteria are "A: Defect area is less than 10%,""B: Defect area is 10% or more and less than 30%,""C: Defect area is 30% or more and less than 50%," and "D: Defect area is 30% or more and less than 50%." 50% or more of the area. The test results are shown in Table 1.
［試験ＩＩ］
上記方法で得られた試験体について、促進耐候性試験機としてアイスーパーＵＶテスター（岩崎電気株式会社製）を用い、光照射６時間・結露２時間（計８時間）を１サイクルとして６０サイクルまで促進試験を行った。この際、２０サイクル終了時点、４０サイクル終了時点、及び６０サイクル終了時点での試験体表面の外観変化（ひび割れの状態）を観察するとともに、促進前後の色差を測定した。外観変化については、「Ａ：変化なし」、「Ｄ：ひび割れが進行」とする４段階（優；Ａ＞Ｂ＞Ｃ＞Ｄ；劣）にて評価した。また、色差については、「Ａ：色差１未満」、「Ｂ：色差１以上３未満」、「Ｃ：色差３以上１０未満」、「Ｄ：色差１０以上」として評価した。試験結果を表１に示す。
[Test II]
For the test specimens obtained by the above method, an iSuper UV tester (manufactured by Iwasaki Electric Co., Ltd.) was used as an accelerated weathering tester, and one cycle consisted of 6 hours of light irradiation and 2 hours of dew condensation (8 hours in total), up to 60 cycles. An accelerated test was conducted. At this time, changes in appearance (crack state) on the surface of the specimen were observed at the end of the 20th cycle, at the end of the 40th cycle, and at the end of the 60th cycle, and the color difference before and after acceleration was measured. Appearance changes were evaluated on a four-level scale (Excellent; A>B>C>D; Poor): "A: No change" and "D: Cracking progressed." The color difference was evaluated as "A: Color difference less than 1,""B: Color difference 1 or more and less than 3,""C: Color difference 3 or more and less than 10," and "D: Color difference 10 or more." The test results are shown in Table 1.
（実施例２）
第１被覆材及び第２被覆材として、それぞれ被覆材２を使用した以外は、実施例１と同様の方法で試験体を作製し、同様の試験を行った。試験結果を表１に示す。
(Example 2)
A test body was prepared in the same manner as in Example 1, except that Coating Material 2 was used as the first coating material and the second coating material, and the same test was conducted. The test results are shown in Table 1.
（実施例３）
第１被覆材として被覆材１、第２被覆材として被覆材３を使用した以外は、実施例１と同様の方法で試験体を作製し、同様の試験を行った。試験結果を表１に示す。
(Example 3)
A test body was prepared in the same manner as in Example 1, except that Coating Material 1 was used as the first coating material and Coating Material 3 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.
（実施例４）
第１被覆材として被覆材２、第２被覆材として被覆材４を使用した以外は、実施例１と同様の方法で試験体を作製し、同様の試験を行った。試験結果を表１に示す。
(Example 4)
A test body was prepared in the same manner as in Example 1, except that coating material 2 was used as the first coating material and coating material 4 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.
（実施例５）
第１被覆材として被覆材３、第２被覆材として被覆材４を使用した以外は、実施例１と同様の方法で試験体を作製し、同様の試験を行った。試験結果を表１に示す。
(Example 5)
A test body was prepared in the same manner as in Example 1, except that coating material 3 was used as the first coating material and coating material 4 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.
（実施例６）
第１被覆材として被覆材３、第２被覆材として被覆材５を使用した以外は、実施例１と同様の方法で試験体を作製し、同様の試験を行った。試験結果を表１に示す。
(Example 6)
A test body was prepared in the same manner as in Example 1, except that coating material 3 was used as the first coating material and coating material 5 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.
（実施例７）
第１被覆材及び第２被覆材として、それぞれ被覆材４を使用した以外は、実施例１と同様の方法で試験体を作製し、同様の試験を行った。試験結果を表１に示す。
(Example 7)
A test body was prepared in the same manner as in Example 1, except that Coating Material 4 was used as the first coating material and the second coating material, and the same test was conducted. The test results are shown in Table 1.
（実施例８）
第１被覆材として被覆材４、第２被覆材として被覆材３を使用した以外は、実施例１と同様の方法で試験体を作製し、同様の試験を行った。試験結果を表１に示す。
(Example 8)
A test body was prepared in the same manner as in Example 1, except that coating material 4 was used as the first coating material and coating material 3 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.
（実施例９）
第１被覆材として被覆材４、第２被覆材として被覆材６を使用した以外は、実施例１と同様の方法で試験体を作製し、同様の試験を行った。試験結果を表１に示す。
(Example 9)
A test body was prepared in the same manner as in Example 1, except that coating material 4 was used as the first coating material and coating material 6 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.
（実施例１０）
第１被覆材として被覆材７、第２被覆材として被覆材８を使用した以外は、実施例１と同様の方法で試験体を作製し、同様の試験を行った。試験結果を表１に示す。
(Example 10)
A test body was prepared in the same manner as in Example 1, except that coating material 7 was used as the first coating material and coating material 8 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.
（実施例１１）
第１被覆材及び第２被覆材の乾燥膜厚がそれぞれ１２μｍとなるように塗装した以外は、実施例３と同様の方法で試験体を作製し、同様の試験を行った。試験結果を表１に示す。
(Example 11)
A test body was prepared in the same manner as in Example 3, except that the first coating material and the second coating material were coated so that each had a dry film thickness of 12 μm, and the same tests were conducted. The test results are shown in Table 1.
（実施例１２）
第１被覆材として被覆材９、第２被覆材として被覆材４を使用した以外は、実施例１と同様の方法で試験体を作製し、同様の試験を行った。試験結果を表１に示す。
(Example 12)
A test body was prepared in the same manner as in Example 1, except that coating material 9 was used as the first coating material and coating material 4 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.
（実施例１３）
第１被覆材として被覆材１０、第２被覆材として被覆材４を使用した以外は、実施例１と同様の方法で試験体を作製し、同様の試験を行った。試験結果を表１に示す。
(Example 13)
A test body was prepared in the same manner as in Example 1, except that coating material 10 was used as the first coating material and coating material 4 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.
（実施例１４）
第１被覆材として被覆材１１、第２被覆材として被覆材４を使用した以外は、実施例１と同様の方法で試験体を作製し、同様の試験を行った。試験結果を表１に示す。
(Example 14)
A test body was prepared in the same manner as in Example 1, except that coating material 11 was used as the first coating material and coating material 4 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.
（実施例１５）
第１被覆材として被覆材１２、第２被覆材として被覆材４を使用した以外は、実施例１と同様の方法で試験体を作製し、同様の試験を行った。試験結果を表１に示す。
(Example 15)
A test body was prepared in the same manner as in Example 1, except that coating material 12 was used as the first coating material and coating material 4 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.
（比較例１）
第１被覆材及び第２被覆材として、それぞれ被覆材１３を使用した以外は、実施例１と同様の方法で試験体を作製し、同様の試験を行った。試験結果を表１に示す。
(Comparative example 1)
A test body was prepared in the same manner as in Example 1, except that coating material 13 was used as the first coating material and the second coating material, and the same test was conducted. The test results are shown in Table 1.
（比較例２）
第１被覆材及び第２被覆材として、それぞれ被覆材１４を使用した以外は、実施例１と同様の方法で試験体を作製し、同様の試験を行った。試験結果を表１に示す。
(Comparative example 2)
A test body was prepared in the same manner as in Example 1, except that the coating material 14 was used as the first coating material and the second coating material, and the same test was conducted. The test results are shown in Table 1.
［試験ＩＩＩ］
実施例１～１５の試験体について６か月間屋外曝露を行い、試験体表面の汚れ等による外観変化を観察し、汚れの程度が軽微であったものを「Ａ」とする４段階（優；Ａ＞Ｂ＞Ｃ＞Ｄ；劣）で評価した。試験結果を表１に示す。
[Test III]
The test specimens of Examples 1 to 15 were exposed outdoors for 6 months, and changes in appearance due to dirt, etc. on the surface of the test specimens were observed. Those with a slight degree of dirt were rated "A" (4 grades: excellent; A>B>C>D; poor). The test results are shown in Table 1.
（実施例１６）
既存被膜面として、屋外曝露により劣化した窯業系サイディングボート｛表面にタイル目地調の凸部と凹部（目地）、凸部にはさらに不定形の凹凸模様を有し、最表層塗膜として無機質クリヤー被膜を有するもの｝を用意した。この既存被膜面の全面に対し、第１被覆材として被覆材２を乾燥膜厚が３８μｍとなるようにスプレー塗装し、３時間乾燥後、第２被覆材として被覆材４を乾燥膜厚が３８μｍとなるようにスプレー塗装し、７日間乾燥養生することにより、試験体を作製した。なお、塗装ないし養生の工程は、すべて標準状態下で行った。この試験体では、上記実施例４と同様の被覆材を用いている。
(Example 16)
The existing coating surface is a ceramic siding boat that has deteriorated due to outdoor exposure.The surface has protrusions and depressions (joints) similar to tile joints, and the protrusions have an irregular pattern of irregularities, and an inorganic clear coating is used as the top layer coating. one with a coating} was prepared. Coating material 2 was spray-coated as the first coating material to a dry film thickness of 38 μm over the entire surface of the existing coating surface, and after drying for 3 hours, coating material 4 was applied as the second coating material to a dry film thickness of 38 μm. A test specimen was prepared by spray painting and drying and curing for 7 days. All painting and curing processes were performed under standard conditions. This test specimen uses the same covering material as in Example 4 above.
［試験ＩＶ］
上記方法で得られた試験体について、ＪＩＳ Ｋ５６００－５－６に準じた碁盤目テープ法にて密着性を評価した。評価基準は、上記［試験Ｉ］と同様である。試験結果を表２に示す。
[Test IV]
The adhesion of the test specimens obtained by the above method was evaluated using a checkerboard tape method according to JIS K5600-5-6. The evaluation criteria are the same as in [Test I] above. The test results are shown in Table 2.
［試験Ｖ］
上記方法で得られた試験体について、促進耐候性試験機としてアイスーパーＵＶテスター（岩崎電気株式会社製）を用い、光照射６時間・結露２時間（計８時間）を１サイクルとして６０サイクルまで促進試験を行った。この際、２０サイクル終了時点、４０サイクル終了時点、及び６０サイクル終了時点での試験体表面の外観変化（ひび割れの状態）を観察するとともに、促進前後の色差を測定した。評価基準は、上記［試験ＩＩ］と同様である。試験結果を表２に示す。
[Test V]
For the test specimens obtained by the above method, an iSuper UV tester (manufactured by Iwasaki Electric Co., Ltd.) was used as an accelerated weathering tester, and one cycle consisted of 6 hours of light irradiation and 2 hours of dew condensation (8 hours in total), up to 60 cycles. An accelerated test was conducted. At this time, changes in appearance (crack state) on the surface of the specimen were observed at the end of the 20th cycle, at the end of the 40th cycle, and at the end of the 60th cycle, and the color difference before and after acceleration was measured. The evaluation criteria are the same as in [Test II] above. The test results are shown in Table 2.
（実施例１７）
第１被覆材として被覆材３、第２被覆材として被覆材４を使用した以外は、実施例１６と同様の方法で試験体を作製し、同様の試験を行った。この試験体では、上記実施例５と同様の被覆材を用いている。試験結果を表２に示す。
(Example 17)
A test body was prepared in the same manner as in Example 16, except that coating material 3 was used as the first coating material and coating material 4 was used as the second coating material, and the same test was conducted. This test specimen uses the same covering material as in Example 5 above. The test results are shown in Table 2.
（実施例１８）
第１被覆材として被覆材３、第２被覆材として被覆材５を使用した以外は、実施例１６と同様の方法で試験体を作製し、同様の試験を行った。この試験体では、上記実施例６と同様の被覆材を用いている。試験結果を表２に示す。
(Example 18)
A test body was prepared in the same manner as in Example 16, except that coating material 3 was used as the first coating material and coating material 5 was used as the second coating material, and the same test was conducted. This test specimen uses the same covering material as in Example 6 above. The test results are shown in Table 2.
（実施例１９）
第１被覆材として被覆材９、第２被覆材として被覆材４を使用した以外は、実施例１６と同様の方法で試験体を作製し、同様の試験を行った。この試験体では、上記実施例１２と同様の被覆材を用いている。試験結果を表２に示す。
(Example 19)
A test body was prepared in the same manner as in Example 16, except that coating material 9 was used as the first coating material and coating material 4 was used as the second coating material, and the same test was conducted. This test specimen uses the same covering material as in Example 12 above. The test results are shown in Table 2.
（実施例２０）
第１被覆材として被覆材１０、第２被覆材として被覆材４を使用した以外は、実施例１６と同様の方法で試験体を作製し、同様の試験を行った。この試験体では、上記実施例１３と同様の被覆材を用いている。試験結果を表２に示す。
(Example 20)
A test body was prepared in the same manner as in Example 16, except that coating material 10 was used as the first coating material and coating material 4 was used as the second coating material, and the same test was conducted. This test specimen uses the same covering material as in Example 13 above. The test results are shown in Table 2.
（実施例２１）
第１被覆材として被覆材１１、第２被覆材として被覆材４を使用した以外は、実施例１６と同様の方法で試験体を作製し、同様の試験を行った。この試験体では、上記実施例１４と同様の被覆材を用いている。試験結果を表２に示す。
(Example 21)
A test body was prepared in the same manner as in Example 16, except that coating material 11 was used as the first coating material and coating material 4 was used as the second coating material, and the same test was conducted. This test specimen uses the same covering material as in Example 14 above. The test results are shown in Table 2.
（実施例２２）
第１被覆材として被覆材１２、第２被覆材として被覆材４を使用した以外は、実施例１６と同様の方法で試験体を作製し、同様の試験を行った。この試験体では、上記実施例１５と同様の被覆材を用いている。試験結果を表２に示す。
(Example 22)
A test body was prepared in the same manner as in Example 16, except that coating material 12 was used as the first coating material and coating material 4 was used as the second coating material, and the same test was conducted. This test specimen uses the same covering material as in Example 15 above. The test results are shown in Table 2.
Claims (5)
上記既存被膜面は、凹凸模様及び／または多色模様を有するものであり、
上記第１被覆材及び第２被覆材は、それぞれ、
結合材として、炭素数３以上のアルキル基を有する（メタ）アクリル酸アルキルエステル（Ａ）を、樹脂構成成分中に２０重量％以上含む樹脂成分を含有し、
上記炭素数３以上のアルキル基を有する（メタ）アクリル酸アルキルエステル（Ａ）として、２－エチルヘキシルアクリレート（ａ１）を含むものであり、
上記結合材は、無機分を含有するものであり、
上記第１被覆材及び第２被覆材は、それぞれ、可視光透過性を有し、紫外線透過率が３０％以下である被膜を形成するものである、
ことを特徴とする被膜形成方法。 A film forming method in which a first coating material and a second coating material are applied to an existing coating surface provided on a base material to form a new coating, the method comprising:
The existing coating surface has an uneven pattern and/or a multicolored pattern,
The first covering material and the second covering material are each
Contains a resin component containing 20% by weight or more of a (meth)acrylic acid alkyl ester (A) having an alkyl group having 3 or more carbon atoms as a binder in the resin component,
The (meth)acrylic acid alkyl ester (A) having an alkyl group having 3 or more carbon atoms includes 2-ethylhexyl acrylate (a1),
The above-mentioned binding material contains an inorganic component,
The first coating material and the second coating material each form a coating that is transparent to visible light and has an ultraviolet transmittance of 30% or less.
A film forming method characterized by:
上記炭素数３以上のアルキル基を有する（メタ）アクリル酸アルキルエステル（Ａ）として、２－エチルヘキシルアクリレート（ａ１）を含むものであり、
上記（Ａ）成分中に占める上記（ａ１）成分の重量比をｒとすると、
第１被覆材の結合材におけるｒ（ｒ１）は、第２被覆材の結合材におけるｒ（ｒ２）よりも大である
ことを特徴とする請求項１記載の被膜形成方法。 The binding materials of the first covering material and the second covering material are each:
The (meth)acrylic acid alkyl ester (A) having an alkyl group having 3 or more carbon atoms includes 2-ethylhexyl acrylate (a1),
If the weight ratio of the component (a1) in the component (A) is r,
2. The film forming method according to claim 1, wherein r( r1 ) in the binding material of the first coating material is larger than r( r2 ) in the binding material of the second coating material.
第１被覆材の結合材におけるｓ（ｓ１）は、第２被覆材の結合材におけるｓ（ｓ２）よりも大であることを特徴とする請求項１または２に記載の被膜形成方法。
なお、ｓは、下記式にて算出される値である。
［式］ｓ（重量％）＝｛結合材に含まれる無機分の重量｝／｛結合材の不揮発分の重量｝×１００
（「結合材の不揮発分の重量」、及び「結合材に含まれる無機分の重量」は、ＪＩＳ Ｋ ５６０１－１－２「加熱残分」の方法に準じて測定することができる。「結合材の不揮発分の重量」は、加熱温度１３５℃、加熱時間６０分の条件にて測定したときの値であり、「結合材に含まれる無機分の重量」は、加熱温度５５０℃、加熱時間１８０分の条件にて測定したときの値である。） If the weight ratio of the inorganic content to the nonvolatile content of the binder is s, then
3. The film forming method according to claim 1, wherein s( s1 ) in the binding material of the first coating material is larger than s( s2 ) in the binding material of the second coating material.
Note that s is a value calculated using the following formula.
[Formula] s (weight %) = {Weight of inorganic components contained in the binder} / {Weight of non-volatile components of the binder} x 100
(The "weight of non-volatile content of the binder" and the "weight of inorganic content contained in the binder" can be measured according to the method of JIS K 5601-1-2 "Heating residue". "Weight of non-volatile matter in the material" is the value measured at a heating temperature of 135°C and a heating time of 60 minutes. "Weight of inorganic content contained in the binder" is a value measured at a heating temperature of 550°C and a heating time of 60 minutes. (Values measured under 180 minute conditions.)
5. The film forming method according to claim 1, wherein the newly formed film has a thickness of 30 μm or more.
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