WO2023190796A1 - Coating material, coating film layer, and laminate - Google Patents
Coating material, coating film layer, and laminate Download PDFInfo
- Publication number
- WO2023190796A1 WO2023190796A1 PCT/JP2023/013034 JP2023013034W WO2023190796A1 WO 2023190796 A1 WO2023190796 A1 WO 2023190796A1 JP 2023013034 W JP2023013034 W JP 2023013034W WO 2023190796 A1 WO2023190796 A1 WO 2023190796A1
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- amount
- paint
- mol
- resin
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000000576 coating method Methods 0.000 title claims abstract description 35
- 239000011248 coating agent Substances 0.000 title claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 49
- 239000011347 resin Substances 0.000 claims abstract description 49
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 28
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 27
- 239000003973 paint Substances 0.000 claims description 75
- 239000011247 coating layer Substances 0.000 claims description 61
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229920006122 polyamide resin Polymers 0.000 claims description 7
- 229920001225 polyester resin Polymers 0.000 claims description 7
- 239000004645 polyester resin Substances 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 claims description 5
- 125000004185 ester group Chemical group 0.000 claims description 5
- 125000001033 ether group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 5
- 229920005668 polycarbonate resin Polymers 0.000 claims description 4
- 239000004431 polycarbonate resin Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 description 49
- 239000003795 chemical substances by application Substances 0.000 description 21
- 229920002050 silicone resin Polymers 0.000 description 18
- -1 fluororesins Polymers 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 229920001296 polysiloxane Polymers 0.000 description 11
- 229920004482 WACKER® Polymers 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 229920002545 silicone oil Polymers 0.000 description 9
- 230000002265 prevention Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000002390 adhesive tape Substances 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000010422 painting Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920006310 Asahi-Kasei Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 239000013464 silicone adhesive Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 238000007592 spray painting technique Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- UZUNCLSDTUBVCN-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-6-(2-phenylpropan-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound C=1C(C(C)(C)CC(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C(O)C=1C(C)(C)C1=CC=CC=C1 UZUNCLSDTUBVCN-UHFFFAOYSA-N 0.000 description 1
- SITYOOWCYAYOKL-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(3-dodecoxy-2-hydroxypropoxy)phenol Chemical compound OC1=CC(OCC(O)COCCCCCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 SITYOOWCYAYOKL-UHFFFAOYSA-N 0.000 description 1
- ZADOWCXTUZWAKL-UHFFFAOYSA-N 3-(3-trimethoxysilylpropyl)oxolane-2,5-dione Chemical compound CO[Si](OC)(OC)CCCC1CC(=O)OC1=O ZADOWCXTUZWAKL-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000533950 Leucojum Species 0.000 description 1
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004954 Polyphthalamide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FLPKSBDJMLUTEX-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)(CCCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FLPKSBDJMLUTEX-UHFFFAOYSA-N 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- UJRDRFZCRQNLJM-UHFFFAOYSA-N methyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OC)=CC(N2N=C3C=CC=CC3=N2)=C1O UJRDRFZCRQNLJM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical class C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006375 polyphtalamide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000004590 silicone sealant Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Definitions
- the present invention relates to paints, coating layers, and laminates, and specifically relates to objects such as solar panels, aircraft, railways, automobiles, wind power generators, houses, traffic lights, signboards, tunnels, snow eaves prevention boards, bridges, and road signs.
- This invention relates to paints, coating layers, and laminates used to prevent snow and ice from adhering to surfaces.
- oil-containing paints and coating layers have been developed in various industrial fields as a measure to prevent snow and ice from accreting on the surfaces of objects.
- Patent Document 1 discloses an anti-icing and snow coating composition containing chemically reactive silicone rubber and silicone oil.
- the present invention has been made in view of the above-mentioned conventional circumstances, and is capable of forming a coating layer that has excellent adhesion to a base material, etc., and has an excellent function of preventing icing and/or snowing.
- the problem to be solved is to provide paint.
- [1] Contains a resin component having a hydrosilyl group and a vinyl group, and an oil component, The amount of excess hydrosilyl group represented by the following formula exceeds 0.0015 mol/100 g, Paints containing silane coupling agents.
- [Amount of surplus hydrosilyl group (mol/100g)] [Amount of hydrosilyl groups in the paint (mol/100g)] - [Amount of vinyl groups in the paint (mol/100g)]
- the hydrophilic group is at least one selected from the group consisting of a carbinol group, a hydroxy group, a carboxy group, a carboxylic anhydride group, an amino group, a sulfo group, an ether group, an epoxy group, a mercapto group, a thiol group, and an ester group.
- [4] A coating layer formed from the paint according to any one of [1] to [3].
- [5] A laminate in which the coating layer described in [4] is laminated on a base material.
- the laminate according to [5], wherein the base material includes any one selected from polyester resin, polyamide resin, polycarbonate resin, and metal.
- the paint of the present invention it is possible to form a coating layer that has excellent adhesion to substrates and the like and has an excellent function of preventing icing and/or snowing.
- FIG. 1 is a cross-sectional view showing a coating layer formed using the paint of the present invention together with a base material.
- FIG. 2 is a sectional view showing an example of a layer structure including a coating layer formed from the paint of the present invention together with a base material.
- the coating material of the present invention contains a resin component having a hydrosilyl group and a vinyl group, and an oil component, has an amount of surplus hydrosilyl groups represented by the following formula exceeding 0.0015 mol/100 g, and contains a silane coupling agent.
- Amount of surplus hydrosilyl group (mol/100g)] [Amount of hydrosilyl groups in the paint (mol/100g)] - [Amount of vinyl groups in the paint (mol/100g)]
- the coating material of the present invention contains at least one resin component.
- the resin component has a hydrosilyl group and a vinyl group.
- examples of the resin component include a resin component containing only a resin, a resin component containing a resin and a curing agent, and the like.
- the resin may be any of a moisture-curable resin that is cured by moisture, an ultraviolet-curable resin that is cured by ultraviolet irradiation, and a thermosetting resin that is cured by heating. Further, the resin may be a resin or a thermoplastic resin that is cured by adding a curing agent that crosslinks with the resin.
- resins include, but are not limited to, silicone resins, polyurethane resins, polyurethane acrylic resins, vinyl chloride resins, polyester resins, elastomers, fluororesins, polyamide resins, polyolefin resins (polyethylene, polypropylene, etc.), acrylic resins, and EPDM.
- silicone resins polyurethane resins, polyurethane acrylic resins, vinyl chloride resins, polyester resins, elastomers, fluororesins, polyamide resins, polyolefin resins (polyethylene, polypropylene, etc.), acrylic resins, and EPDM.
- silicone resins silicone resins
- polyurethane resins polyurethane acrylic resins
- vinyl chloride resins polyester resins
- elastomers elastomers
- fluororesins polyamide resins
- polyolefin resins polyethylene, polypropylene, etc.
- acrylic resins and EPDM.
- EPDM ethylene propylene dien
- any suitable silicone resin may be employed as long as the effects of the present invention are not impaired.
- the number of silicone resins may be one, or two or more.
- Such silicone resin may be a condensation type silicone resin or an addition type silicone resin.
- such silicone resin may be a one-component silicone resin that is dried alone (for example, a one-component room temperature curable (RTV) resin), or a two-component silicone resin (for example, a one-component room temperature curable (RTV) resin). , two-component room temperature curable (RTV) resin).
- silicone resins examples include silicone resins having hydrosilyl groups and vinyl groups, silicone resins having vinyl groups, and the like. It is also possible to include as a resin a silicone resin having neither a hydrosilyl group nor a vinyl group.
- silicone resin examples include one-component RTV rubber manufactured by Shin-Etsu Chemical Co., Ltd. (for example, KE-3423, KE-347, KE-3475, KE-3495, KE-4895, KE-4896, KE-1830, KE-1884, KE-3479, KE-348, KE-4897, KE-4898, KE-1820, KE-1825, KE-1831, KE-1833, KE-1885, KE-1056, KE-1151, KE- 1842, KE-1886, KE-3424G, KE-3494, KE-3490, KE-40RTV, KE-4890, KE-3497, KE-3498, KE-3493, KE-3466, KE-3467, KE-1862, KE-1867, KE-3491, KE-3492, KE-3417, KE-3418, KE-3427, KE-3428, KE-
- KE-1800T-A/B, KE-66, KE-1031-A/B, KE-200, KE-118) , KE-103, KE-108, KE-119, KE-109E-A/B, KE-1051J-A/B, KE-1012-A/B, KE-106, KE-1282-A/B, KE -1283-A/B, KE-1800-A/B/C, KE-1801-A/B/C, KE-1802-A/B/C, KE-1281-A/B, KE-1204-A /B, KE-1204-AL/BL, KE-1280-A/B, KE-513-A/B, KE-521-A/B, KE-1285-A/B, KE-1861-A/B , KE-12, KE-14, KE-17, KE-113, KE-24, KE-26, KE-1414, KE-1415, KE-1416,
- KEG-2000-40A/B KEG-2000-50A/B, KEG-2000-60A/B, KEG-2000-70A/B, KEG-2001-40A/B, KEG-2001-50A/B, KE-1950-10A/B, KE-1950-20A/B, KE-1950-30A/B, KE-1950-35A/B, KE- 1950-40A/B, KE-1950-50A/B, KE-1950-60A/B, KE-1950-70A/B, KE-1935A/B, KE-1987A/B, KE-1988A/B, KE- 2019-40A/B, KE-2019-50A/B, KE-2019-60A/B, KE-2017-30A/B, KE-2017-40A/B, KE-2017-50A/B, KE-2090- 40A/B, KE-2090-50A/B, KE-2090-60A/B, KE-2090-70A/B, KE-2096-40A
- the content of the resin in the coating material of the present invention is preferably 15% by mass or more, more preferably 25% by mass or more, and even more preferably 35% by mass or more. Further, the resin content in the coating material of the present invention is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less.
- the curing agent examples include those whose main chain is a repeating unit of diorganosiloxane and whose terminal end is a triorganosiloxane structure, and may have a branched or cyclic structure.
- the organo group bonded to silicon at the terminal or in the repeating unit include methyl group, ethyl group, octyl group, phenyl group, etc.
- a curing agent in which two or more of these groups are substituted with hydrogen is preferred. That is, the curing agent preferably has a hydrosilyl group. Specific examples include hydrogen silicone and the like.
- Specific curing agents include, for example, cat-1310s, KF-99, and KF-9901 manufactured by Shin-Etsu Chemical Co., Ltd., and HMS-151, HMS-301, and HMS-501 manufactured by Gelest.
- Examples of embodiments in which a curing agent is used include an embodiment in which an additional curing agent independent of the resin is added.
- the curing agent can be used, for example, to adjust the amount of hydrosilyl groups and the amount of excess hydrosilyl groups in the paint.
- KE-2098-60A/B is a mixture of KE-2098-60A, a silicone polymer having a vinyl group, and KE-2098-60B, a silicone polymer having a hydrosilyl group, at a mass ratio of 1:1.
- a resin containing a set of a polymer having a vinyl group and a polymer having a hydrosilyl group is used, a desired amount of excess hydrosilyl groups may be obtained without adding an additional curing agent.
- an additional curing agent independent of this may be further added.
- the coating material of the present invention contains at least one oil component.
- oil component for example, silicone oil, fluorine oil, hydrocarbon oil, polyether oil, ester oil, phosphorus compound oil, mineral oil, alcohol, etc. can be used.
- silicone oil examples include silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. (for example, KF96L series, KF96 series, KF69 series, KF99 series, KF50 series, KF54 series, KF410 series, KF412 series, KF414 series, FL series, KF -56A, KF-6000, KF-6001, KF-6002, KF-6003, etc.), silicone oil manufactured by Momentive Corporation (e.g. Element14*PDMS series, TSF404 series, TSF410 series, TSF4300 series, TSF431 series, TSF433 series) , TSF437 series, TSF4420 series, TSF4421 series, etc.), silicone oil manufactured by Dow Corning Toray Co., Ltd.
- silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. for example, KF96L series, KF96 series, KF69 series, KF99 series, KF50 series, KF54 series, KF410 series, KF412 series, K
- WACKER registered trademark
- SILICONE FLUID AK series WACKER (registered trademark) SILICONE FLUID AP series
- WACKER registered trademark
- SILICONE FLUID AR series WACKER (registered trademark) SILICONE FLUID AR series
- WACKER registered trademark
- SILICONE FLUID AS series WACKER (registered trademark)
- WACKER registered trademark
- TN series WACKER (registered trademark) TN series
- WACKER registered trademark) L series
- WA CKER registered trademark Liquid paraffin such as AF series
- the oil component has a hydrophilic group.
- the hydrophilic group include carbinol group, hydroxy group, carboxy group, carboxylic anhydride group, amino group, sulfo group, ether group, epoxy group, mercapto group, thiol group, ester group, etc. At least one group selected from the group consisting of a hydroxy group, a carboxy group, a carboxylic anhydride group, an amino group, a sulfo group, an ether group, an epoxy group, a mercapto group, a thiol group, and an ester group is preferred.
- carbinol groups are more preferred from the viewpoint of exhibiting excellent icing and/or snow accretion prevention functions.
- oil component only one type of oil component may be used, or two or more types of oil components may be used.
- the coating material of the present invention contains at least one silane coupling agent.
- the silane coupling agent include those having as a functional group at least one group selected from the group consisting of isocyanate groups, vinyl groups, epoxy groups, amino groups, and mercapto groups, acid anhydrides, and the like. .
- silane coupling agent examples include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyldimethoxymethylsilane, 3-isocyanatepropyltriethoxysilane, isocyanatemethyltrimethoxysilane, isocyanatemethyltriethoxysilane, and isocyanatemethyldimethoxymethylsilane. etc.
- silane coupling agent examples include vinyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, -aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, and the like.
- the adhesion of the formed coating layer to the substrate improves when the paint contains a silane coupling agent, but in addition to the hydrosilyl group, the functional groups of the silane coupling agent improve the adhesion to the substrate. It is presumed that the adhesion is improved due to reaction and/or interaction with the functional groups of In addition, since the silane coupling agent reacts with the hydrosilyl group of the resin component, the hydrosilyl group of the resin component and the hydrophilic group of the oil component, etc., can prevent the oil component from seeping out from the coating layer under low temperature conditions. It is thought that this reaction can be suppressed. As a result, it is considered possible to provide a paint that can form a coating layer that has excellent adhesion to substrates and has excellent anti-icing and/or snow accretion functions.
- a resin containing the silane coupling agent in advance may be used, or an additional silane coupling agent independent of the resin may be added.
- resins that contain a silane coupling agent in advance include KE-2098-60A/B.
- an additional silane coupling agent may be added independently from this resin.
- the content of the silane coupling agent in the coating material of the present invention is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, and still more preferably 0.15% by mass or more. Further, the content of the silane coupling agent in the coating material of the present invention is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 6% by mass or less. In addition, only one type of silane coupling agent may be used, or two or more types may be used.
- a coating layer formed from a paint that does not contain a silane coupling agent may not have the ability to prevent icing and/or snow accumulation.
- the paint of the present invention can contain a solvent.
- solvents include aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, hydrocarbon solvents such as hexane, octane, decane, and isoparaffin, and ketone solvents such as acetone and methyl ethyl ketone. Examples include solvents.
- the coating material of the present invention can further contain a curing catalyst.
- a curing catalyst for example, platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, hexachloride platinum (IV) acid, chlorotris (triphenylphosphine) rhodium (I) Examples include metal catalysts such as.
- the paint of the present invention can further contain fillers such as silica, talc, calcium carbonate, titanium oxide, clay, and pigments.
- silica for example, silica manufactured by Nippon Aerosil Co., Ltd. (for example, AEROSIL50, 130, 200, 300, R972, R974, R976, RX50, RX200, RX300, RY50, RY300, R7200, R8200, R9200), etc. may be used. I can do it.
- the coating material of the present invention may contain any other appropriate additives as long as the effects of the present invention are not impaired.
- examples of such other additives include weathering agents, ultraviolet absorbers, and light stabilizers. Ultraviolet absorbers and light stabilizers are highly effective when used together.
- ultraviolet absorbers include ADEKA LA-24, LA-29, LA-31, LA-31RG, LA-31G, LA-32, LA-36, LA-46, LA-F70, 1413, BASF TinuvinPS, Tinuvin99-2, Tinuvin326, Tinuvin384-2, Tinuvin900, Tinuvin928, Tinuvin970, Tinuvin1130, Tinuvin400, Tinuvin405, Ti Examples include nuvin460, Tinuvin477, Tinuvin479, UVA-903KT, UVA-935LH, and the like.
- light stabilizers include LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, and LA- manufactured by ADEKA. 87, LA-402AF, LA-40MP, LA-40Si, BASF Tinuvin111, Tinuvin123, Tinuvin144, Tinuvin152, Tinuvin249, Tinuvin292, Tinuvin770DF, Tinuvin5 100, etc.
- reaction control agent The coating material of the present invention may further contain a reaction control agent so that a coating film can be stably produced.
- reaction control agents include reaction control agents manufactured by Shin-Etsu Chemical Co., Ltd. (product number: NO. 6-10) and reaction control agents manufactured by Dow Toray Industries, Inc. (product numbers: SILASTICTMRD-9, SILASTICTM RD-201). , a reaction control agent manufactured by Momentive (product number: ME75), a reaction control agent manufactured by Gelest (product numbers: VMS-005, VMS-T11), and the like.
- the coating material of the present invention can be obtained by mixing and/or stirring the above-mentioned components by a known method.
- the amount of hydrosilyl groups in the paint and the amount of vinyl groups in the paint can be determined, for example, by compositional analysis of the paint by NMR (nuclear magnetic resonance) measurement. Then, the amount of excess hydrosilyl groups can be determined from the amount of hydrosilyl groups in the paint and the amount of vinyl groups in the paint.
- the amount of surplus hydrosilyl groups in the present invention exceeds 0.0015 mol/100 g, preferably exceeds 0.0030 mol/100 g, more preferably exceeds 0.0045 mol/100 g, and even more preferably exceeds 0.0060 mol/100 g.
- the amount of surplus hydrosilyl groups in the present invention is preferably 0.1 mol/100 g or less, more preferably 0.075 mol/100 g or less, and still more preferably 0.05 mol/100 g or less.
- the amount of surplus hydrosilyl groups is 0.0015 mol/100 g or less, the adhesion of the coating layer formed from the paint to the substrate etc. may be poor.
- the present invention relates to a coating layer formed from the above-mentioned coating material.
- the present invention also relates to a laminate in which the coating layer is laminated on a base material.
- the coating layer of the present invention preferably has a surface oil amount of 40 ⁇ g/cm 2 or more as measured by the method described below. It is preferable that the surface oil amount is 40 ⁇ g/cm 2 or more because the oil component is oozed out from the coating layer under low temperature conditions and the icing and/or snow accretion prevention function is improved.
- the coating layer is left at -20°C for 16 hours, and the oil component that bleeds onto the surface of the coating layer is collected using a cell scraper in an environment of -20°C.
- the collected oil component is absorbed using oil-absorbing paper until no change in the mass of the oil-absorbing paper is observed.
- Oil collection with a cell scraper and blotting with oil-blotting paper are repeated 7 times per minute.
- the difference in mass between the oil-blotting paper before and after oil-blotting is defined as the amount of surface oil.
- the amount of surface oil is measured three times and the average value is used.
- PDT adhesion Evaluation of adhesion (adhesion) was carried out with reference to JIS K-5600-5-6 (mechanical properties of coating film, adhesion). Specifically, the cross-cut test cutter guide (product name "Super Cutter Guide”, manufactured by Taiyu Kizai Co., Ltd.), cutter, polyimide adhesive tape (NO. 360UL, thickness 0.06 mm x width 50 mm, manufactured by Nitto Denko Co., Ltd.) prepared. Polyimide adhesive tape uses silicone adhesive and was selected because it has high adhesion to the silicone layer.
- a transparent adhesive tape cut to a length of about 75 mm was pasted on the grid-cut area, and firmly rubbed with fingers to stick it. More specifically, the tape was rubbed flat with a finger at the area where it covered the grid and at least over a length exceeding 20 mm. Whether the tape was in proper contact with the paint film was determined by the color of the paint film seen through the tape.
- Adhesion was evaluated in accordance with JIS K5600-5-6 in six grades from 0 to 5.
- the coating layer of the present invention preferably has an icing force of 0.7 N/cm 2 or less as measured by the method below.
- the coating layer was attached to a stainless steel flat plate so that the coating layer was on the surface, and the plate was left standing in a -20°C environment for 16 hours.
- a cylindrical block of ice having a weight of 6 g and an adhesion area of 4.9 cm 2 is prepared, and the bottom surface of the block of ice is brought into contact with a surface kept at a constant temperature of 10° C. for 10 seconds to adhere to the coating layer.
- the environmental temperature was set to -20°C, and 3 hours after the ice block was attached, the ice block was pushed at a speed of 0.1 mm/sec with a load cell from a direction parallel to the floor surface in an environment of -20°C.
- the load applied during 40 seconds is measured with a force gauge.
- the value obtained by dividing the measured maximum load by the adhesion area of 4.9 cm 2 is defined as the icing force.
- the icing force was measured three times and the average value was used.
- 10° C. constant temperature surface refers to the surface of a device whose temperature can be changed using, for example, a Peltier element, and is used to partially melt the bottom of the ice block.
- the icing force is 0.7 N/cm 2 or less, excellent icing and/or snow accretion prevention function can be exhibited.
- the icing force is more preferably 0.6 N/cm 2 or less, still more preferably 0.5 N/cm 2 or less. Further, the icing force is preferably as small as possible, but may be, for example, 0.2 N/cm 2 or more, or 0.4 N/cm 2 or more.
- Another embodiment of the coating layer of the present invention is a coating layer formed of a coating material containing a resin component and an oil component, and the PET adhesion of the coating layer measured by the above method is: Of the six grades of evaluation according to JIS K5600-5-6, a rating of 0 to 1 is preferable.
- a first coating layer 11 can be obtained by coating a base material 10 with the paint of the present invention. That is, a laminate including the base material 10 and the first coating layer 11 can be obtained.
- a method for applying the paint of the present invention general methods such as brush painting, spray painting, and various types of coater painting can be used. Painting is usually done once or twice.
- a primer is applied to the base material 10, and the paint of the present invention is applied over the primer. You may also apply paint.
- the thickness of the first coating layer 11 is not particularly limited, but from the viewpoint of the quality of the coating film after drying, it is preferably 2000 ⁇ m or less, and from the viewpoint of strength, it is preferably 50 ⁇ m or more.
- Examples of the base material 10 used in the present invention include polyurethane resins, polyurethane acrylic resins, rubber resins, vinyl chloride resins, polyester resins such as polyethylene terephthalate (PET) resins, polycarbonate (PC) resins, silicone resins, elastomers, Base materials such as fluororesin, polyamide resin, polyolefin resin (polyethylene, polypropylene, etc.), metal plate or metal foil (aluminum, copper, silver, iron, nickel, tin, stainless steel, etc.), concrete, ceramics, etc. can be used.
- PET polyethylene terephthalate
- PC polycarbonate
- silicone resins silicone resins
- Base materials such as fluororesin, polyamide resin, polyolefin resin (polyethylene, polypropylene, etc.), metal plate or metal foil (aluminum, copper, silver, iron, nickel, tin, stainless steel, etc.), concrete, ceramics, etc. can be used.
- the base material 10 is preferably a base material containing any one selected from polyester resin, polyamide resin, polycarbonate resin, and metal.
- the polyester resin include polyethylene terephthalate and polybutylene terephthalate
- the polyamide resin include nylon 6, nylon 66, and polyphthalamide.
- the metal include stainless steel, aluminum, and iron.
- the base material 10 may be in the form of a film or a sheet.
- the paint of the present invention After the paint of the present invention is applied to the substrate 10, the paint can be cured or dried by allowing it to stand, for example, for 3 minutes to 3 hours in an environment of 20 to 180°C.
- a top coat can be applied as necessary on the first coating layer 11 obtained from the paint of the present invention to form a second coating layer 12. . That is, a laminate including the base material 10, the first coating layer 11, and the second coating layer 12 can be obtained.
- the top coat does not need to contain an oil component.
- top coat As a method for applying the top coat, general methods such as brush painting, spray painting, and various coater coatings can be used. Painting is usually done once or twice.
- the thickness of the second coating layer 12 is not particularly limited, but should be such that the oil component can easily permeate to the surface of the coating layer, in other words, ensuring oil permeability to the second coating layer 12. Therefore, it is preferably 500 ⁇ m or less, and from the viewpoint of strength, it is preferably 50 ⁇ m or more.
- the curing or drying temperature and curing or drying time when applying the top coat to the first coating layer 11 are the same as the curing or drying temperature and curing or drying time when applying the coating of the present invention to the base material 10. The same is true.
- the curing or drying of the paint of the present invention and the curing or drying of the top coat may be performed simultaneously or separately.
- ⁇ 1> Contains a resin component having a hydrosilyl group and a vinyl group, and an oil component, The amount of excess hydrosilyl group represented by the following formula exceeds 0.0015 mol/100 g, Paints containing silane coupling agents.
- [Amount of surplus hydrosilyl group (mol/100g)] [Amount of hydrosilyl groups in the paint (mol/100g)] - [Amount of vinyl groups in the paint (mol/100g)] ⁇ 2>
- the hydrophilic group is at least one selected from the group consisting of a carbinol group, a hydroxy group, a carboxy group, a carboxylic anhydride group, an amino group, a sulfo group, an ether group, an epoxy group, a mercapto group, a thiol group, and an ester group.
- the paint according to ⁇ 2> which is a seed group.
- ⁇ 4> A coating layer formed from the paint according to any one of ⁇ 1> to ⁇ 3>.
- ⁇ 5> A laminate in which the coating layer described in ⁇ 4> is laminated on a base material.
- the base material includes any one selected from polyester resin, polyamide resin, polycarbonate resin, and metal.
- Example 1 ⁇ Preparation of paint> As paint components, resin: KE-2098-60 and first oil component (incompatible oil): KF-6003 were prepared. In the examples, the component with the highest content among the oil components is referred to as the first oil component, and the component with the second highest content is referred to as the second oil component.
- the resin component KE-2098-60 is a mixture of KE-2098-60A and KE-2098-60B at a mass ratio of 1:1.
- ⁇ KF-6003 Carbinol-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.
- the resin (42 parts by mass) and the first oil component (58 parts by mass) were mixed under conditions of 25° C. and 101 kPa.
- the resulting mixed solution was stirred for 60 seconds with a spatula, and further stirred for 120 seconds and defoamed for 300 seconds using a rotation/revolution mixer (CONDITIONING MIXER AR-250, manufactured by Shinky Co., Ltd.) to obtain a paint.
- the obtained coating material was applied onto a PET film (Lumirror #75S10 manufactured by Toray Industries, Inc.) and cured by heating in a 150° C. environment for 10 minutes to form a coating layer with a thickness of about 250 ⁇ m.
- Examples 2 to 4 Comparative Examples 1 to 3
- a paint and a coating layer were obtained according to the method described in Example 1, except that the paint components and their contents were as shown in Table 1.
- the resin component KE-1950-50 is a mixture of KE-1950-50A and KE-1950-50B at a mass ratio of 1:1.
- ⁇ KF-96 (50cs): Dimethylsiloxane oil, Shin-Etsu Chemical Co., Ltd. ⁇ 3-Isocyanatepropyltriethoxysilane: Silane coupling agent, Shin-Etsu Manufactured by Kagaku Kogyo Co., Ltd.
- the amount of surplus hydrosilyl groups (mol/100g) is the amount obtained by subtracting the amount of vinyl groups in the paint (mol/100g) from the amount of hydrosilyl groups in the paint (mol/100g).
- the composition of the paint was analyzed by NMR under the following measurement conditions, the amount of hydrosilyl groups in the paint (mol/100g) and the amount of vinyl groups in the paint (mol/100g) were determined, and the amount of excess hydrosilyl groups (mol/100g) was determined. 100g) was calculated using the following formula. The results are shown in Table 1.
- Measurement conditions equipment Bruker Biospin, AVANCEIII-600 with Cryo Probe observation frequency: 600MHz (1H), 79MHz (29Si) Measurement solvent: CDCl3 Measurement temperature: 300K Chemical shift standard: Measurement solvent [7.25ppm (1H)] Internal standard (TMS) [0.00ppm (29Si)]
- the object of measurement is the amount of oil bled onto the surface of the coating layer at -20°C.
- the amount of surface oil was measured using the following method.
- the paint layer cut into a size of 10 cm x 2 cm near the center was left at -20°C for 16 hours, and the oil that had bled onto the surface of the paint layer was removed using a cell scraper (manufactured by Kennis Co., Ltd.) under a temperature environment of -20°C. , CSS-10).
- the oil was absorbed until no change in the mass (oil absorption amount) of the oil-absorbing paper was observed.
- Collecting oil with a cell scraper and blotting it with oil-blotting paper was repeated 7 times per minute.
- the difference in mass of the oil-blotting paper before and after oil-blotting was taken as the amount of surface oil.
- the amount of surface oil was measured three times, and the average value was calculated.
- the evaluation criteria are as follows. ⁇ (Good)...40 ⁇ g/ cm2 or more ⁇ (Poor)...40 ⁇ g/ cm2 or more
- PDT adhesion Evaluation of adhesion (adhesion) was carried out with reference to JIS K-5600-5-6 (mechanical properties of coating film, adhesion). Specifically, the cross-cut test cutter guide (product name "Super Cutter Guide”, manufactured by Taiyu Kizai Co., Ltd.), cutter, polyimide adhesive tape (NO. 360UL, thickness 0.06 mm x width 50 mm, manufactured by Nitto Denko Co., Ltd.) prepared. Polyimide adhesive tape uses silicone adhesive and was selected because it has high adhesion to the silicone layer.
- a transparent adhesive tape cut to a length of about 75 mm was pasted on the grid-cut area, and firmly rubbed with fingers to stick it. More specifically, the tape was rubbed flat with a finger at the area where it covered the grid and at least over a length exceeding 20 mm. Whether the tape was in proper contact with the paint film was judged by the color of the paint film seen through the tape.
- Adhesion was evaluated in accordance with JIS K5600-5-6 in six grades from 0 to 5.
- the evaluation criteria are as follows. ⁇ (Good)...Out of 6 stages of evaluation, it is classified as 0-1 ⁇ (Poor)...Out of 6 stages of evaluation, it is classified as 2-5
- the object of measurement is the force required to move ice blocks attached to the coating layer in an environment of -20°C, and for convenience, in this specification, the magnitude of this force is defined as "icing force”. did.
- the icing force was measured using the following method. First, a cylindrical block of ice was created. To make ice cubes, place a stainless steel ring (inner diameter 25 mm) on the bottom of a styrene square case type 16 (manufactured by As One), pour 6 g of pure water into it, freeze it at -20°C for more than 16 hours, and then remove the stainless steel ring after freezing. It was made by removing.
- the coating layer was attached to a stainless steel flat plate so that the coating layer was on the surface, and the plate was left standing in a -20°C environment for 16 hours.
- a cylindrical block of ice having a weight of 6 g and an adhering area of 4.9 cm 2 was prepared, and the bottom surface of the block of ice was brought into contact with a surface kept at a constant temperature of 10° C. for 10 seconds to adhere to the coating layer.
- the environmental temperature was set to -20°C, and 3 hours after the ice cubes were attached, the ice cubes were placed on a load cell (DPU-50 manufactured by Imada Co., Ltd., with attachment treatment) in a -20°C environment from a direction parallel to the floor surface.
- a type A-4 was pressed at a speed of 0.1 mm/sec, and the load applied during 40 seconds was measured with a force gauge (ZTS-50N manufactured by Imada Co., Ltd.). The value obtained by dividing the measured maximum load by the adhesion area of 4.9 cm 2 was recorded as the icing force.
- the test was conducted three times and the average value was determined.
- the paint of the present invention provides a coating layer that has excellent adhesion to substrates, etc., and has an excellent ability to prevent icing and/or snow accretion.
- the paint of the present invention has excellent adhesion to substrates, etc., and can form a coating layer with excellent icing and/or snow accretion prevention functions. It can be used to prevent snow and ice from adhering to the surfaces of objects such as wind power generators, houses, traffic lights, signboards, tunnels, snow eaves prevention boards, bridges, and road signs.
Abstract
The present invention addresses the problem of providing a coating material that has excellent adhesion to a base material and the like, and is capable of forming a coating film layer having an excellent function in preventing ice accretion and/or snow accretion. The present invention pertains to a coating material which contains an oil component and a resin component having a hydrosilyl group and a vinyl group, in which an excess hydrosilyl group amount represented by the formula below exceeds 0.0015 mol/100 g, and which contains a silane coupling agent. [Excess hydrosilyl group amount (mol/100 g)] = [amount of hydrosilyl groups in coating material (mol/100 g)] - [amount of vinyl groups in coating material (mol/100 g)]
Description
本発明は、塗料、塗膜層及び積層体に関し、詳しくは、太陽光パネル、航空機、鉄道、自動車、風力発電機、住宅、信号機、看板、トンネル、雪庇防止板、橋梁、道路標識等の物体表面への雪や氷の付着を防止するために用いられる塗料、塗膜層及び積層体に関する。
The present invention relates to paints, coating layers, and laminates, and specifically relates to objects such as solar panels, aircraft, railways, automobiles, wind power generators, houses, traffic lights, signboards, tunnels, snow eaves prevention boards, bridges, and road signs. This invention relates to paints, coating layers, and laminates used to prevent snow and ice from adhering to surfaces.
物体表面への氷の付着（着氷）や降雪による雪片の付着（着雪）は、様々な分野において多くの被害や障害をもたらす原因となっている。例えば、航空機翼への着氷、機関車下部への着雪及び凍結、自動車のヘッドライトへの着雪、太陽光パネルや風力発電機のブレードへの着氷、信号機の灯器への着雪及び凍結等は、これらの運行、運転、安全性に対する障害となり得る。
また、住宅屋根や看板等への着雪及び凍結は、これらの構築物の損傷や落雪による人への被害の原因となり得る。 The adhesion of ice to the surface of objects (icing) and the adhesion of snowflakes due to snowfall (snow accretion) are causes of much damage and trouble in various fields. For example, ice on aircraft wings, snow and ice on the bottom of locomotives, snow on car headlights, ice on solar panels and wind turbine blades, and snow on traffic light equipment. and freezing, etc., can pose obstacles to their operation, operation, and safety.
Furthermore, snow accretion and freezing on residential roofs, signboards, etc. can cause damage to these structures and damage to people due to falling snow.
また、住宅屋根や看板等への着雪及び凍結は、これらの構築物の損傷や落雪による人への被害の原因となり得る。 The adhesion of ice to the surface of objects (icing) and the adhesion of snowflakes due to snowfall (snow accretion) are causes of much damage and trouble in various fields. For example, ice on aircraft wings, snow and ice on the bottom of locomotives, snow on car headlights, ice on solar panels and wind turbine blades, and snow on traffic light equipment. and freezing, etc., can pose obstacles to their operation, operation, and safety.
Furthermore, snow accretion and freezing on residential roofs, signboards, etc. can cause damage to these structures and damage to people due to falling snow.
従来、各産業分野において、このような物体表面への着雪や着氷を防止するための対策として、オイルを含有する塗料や塗膜層が開発されている。
Conventionally, oil-containing paints and coating layers have been developed in various industrial fields as a measure to prevent snow and ice from accreting on the surfaces of objects.
例えば、特許文献１では、化学反応形シリコーンゴムとシリコーンオイルを含有する着氷雪防止塗料組成物が開示されている。
For example, Patent Document 1 discloses an anti-icing and snow coating composition containing chemically reactive silicone rubber and silicone oil.
しかしながら、本発明者の検討によると、特許文献１に開示されているような従来の塗料から得られる塗膜層においては、基材等への密着性、並びに、着氷及び／又は着雪防止機能が必ずしも十分ではなかった。
However, according to the studies of the present inventors, in the coating layer obtained from the conventional paint as disclosed in Patent Document 1, the adhesion to the base material etc. and the prevention of icing and/or snow accretion are insufficient. Functionality was not always sufficient.
本発明は、上記従来の実情に鑑みてなされたものであって、基材等への密着性に優れ、優れた着氷及び／又は着雪防止機能を有する塗膜層を形成することができる塗料を提供することを解決すべき課題としている。
The present invention has been made in view of the above-mentioned conventional circumstances, and is capable of forming a coating layer that has excellent adhesion to a base material, etc., and has an excellent function of preventing icing and/or snowing. The problem to be solved is to provide paint.
本発明者は鋭意検討を重ねた結果、以下の塗料によって上記課題を解決できることを見出し、本発明を完成するに至った。
As a result of extensive studies, the inventors of the present invention have found that the above-mentioned problems can be solved with the following coating material, and have completed the present invention.
［１］
ヒドロシリル基及びビニル基を有する樹脂成分と、オイル成分とを含み、
下記式で表される余剰ヒドロシリル基量が０．００１５ｍｏｌ／１００ｇを超え、
シランカップリング剤を含む、塗料。
［余剰ヒドロシリル基量（ｍｏｌ／１００ｇ）］
＝［塗料中のヒドロシリル基の量（ｍｏｌ／１００ｇ）］－［塗料中のビニル基の量（ｍｏｌ／１００ｇ）］
［２］
前記オイル成分が親水性基を有する、［１］に記載の塗料。
［３］
前記親水性基が、カルビノール基、ヒドロキシ基、カルボキシ基、無水カルボン酸基、アミノ基、スルホ基、エーテル基、エポキシ基、メルカプト基、チオール基及びエステル基からなる群から選択される少なくとも１種の基である、［２］に記載の塗料。
［４］
［１］～［３］のいずれか１つに記載の塗料により形成された、塗膜層。
［５］
基材上に［４］に記載の塗膜層が積層されてなる、積層体。
［６］
前記基材が、ポリエステル樹脂、ポリアミド樹脂、ポリカーボネート樹脂及び金属から選択されるいずれか１種を含む、［５］に記載の積層体。 [1]
Contains a resin component having a hydrosilyl group and a vinyl group, and an oil component,
The amount of excess hydrosilyl group represented by the following formula exceeds 0.0015 mol/100 g,
Paints containing silane coupling agents.
[Amount of surplus hydrosilyl group (mol/100g)]
= [Amount of hydrosilyl groups in the paint (mol/100g)] - [Amount of vinyl groups in the paint (mol/100g)]
[2]
The paint according to [1], wherein the oil component has a hydrophilic group.
[3]
The hydrophilic group is at least one selected from the group consisting of a carbinol group, a hydroxy group, a carboxy group, a carboxylic anhydride group, an amino group, a sulfo group, an ether group, an epoxy group, a mercapto group, a thiol group, and an ester group. The paint according to [2], which is a seed base.
[4]
A coating layer formed from the paint according to any one of [1] to [3].
[5]
A laminate in which the coating layer described in [4] is laminated on a base material.
[6]
The laminate according to [5], wherein the base material includes any one selected from polyester resin, polyamide resin, polycarbonate resin, and metal.
ヒドロシリル基及びビニル基を有する樹脂成分と、オイル成分とを含み、
下記式で表される余剰ヒドロシリル基量が０．００１５ｍｏｌ／１００ｇを超え、
シランカップリング剤を含む、塗料。
［余剰ヒドロシリル基量（ｍｏｌ／１００ｇ）］
＝［塗料中のヒドロシリル基の量（ｍｏｌ／１００ｇ）］－［塗料中のビニル基の量（ｍｏｌ／１００ｇ）］
［２］
前記オイル成分が親水性基を有する、［１］に記載の塗料。
［３］
前記親水性基が、カルビノール基、ヒドロキシ基、カルボキシ基、無水カルボン酸基、アミノ基、スルホ基、エーテル基、エポキシ基、メルカプト基、チオール基及びエステル基からなる群から選択される少なくとも１種の基である、［２］に記載の塗料。
［４］
［１］～［３］のいずれか１つに記載の塗料により形成された、塗膜層。
［５］
基材上に［４］に記載の塗膜層が積層されてなる、積層体。
［６］
前記基材が、ポリエステル樹脂、ポリアミド樹脂、ポリカーボネート樹脂及び金属から選択されるいずれか１種を含む、［５］に記載の積層体。 [1]
Contains a resin component having a hydrosilyl group and a vinyl group, and an oil component,
The amount of excess hydrosilyl group represented by the following formula exceeds 0.0015 mol/100 g,
Paints containing silane coupling agents.
[Amount of surplus hydrosilyl group (mol/100g)]
= [Amount of hydrosilyl groups in the paint (mol/100g)] - [Amount of vinyl groups in the paint (mol/100g)]
[2]
The paint according to [1], wherein the oil component has a hydrophilic group.
[3]
The hydrophilic group is at least one selected from the group consisting of a carbinol group, a hydroxy group, a carboxy group, a carboxylic anhydride group, an amino group, a sulfo group, an ether group, an epoxy group, a mercapto group, a thiol group, and an ester group. The paint according to [2], which is a seed base.
[4]
A coating layer formed from the paint according to any one of [1] to [3].
[5]
A laminate in which the coating layer described in [4] is laminated on a base material.
[6]
The laminate according to [5], wherein the base material includes any one selected from polyester resin, polyamide resin, polycarbonate resin, and metal.
本発明の塗料により、基材等への密着性に優れ、優れた着氷及び／又は着雪防止機能を有する塗膜層を形成することができる。
With the paint of the present invention, it is possible to form a coating layer that has excellent adhesion to substrates and the like and has an excellent function of preventing icing and/or snowing.
以下、本発明の実施形態をさらに詳しく説明するが、本発明は下記実施形態に何ら制限されるものではない。
Hereinafter, embodiments of the present invention will be described in more detail, but the present invention is not limited to the following embodiments.
＜塗料＞
本発明の塗料は、ヒドロシリル基及びビニル基を有する樹脂成分と、オイル成分とを含み、下記式で表される余剰ヒドロシリル基量が０．００１５ｍｏｌ／１００ｇを超え、シランカップリング剤を含む。
［余剰ヒドロシリル基量（ｍｏｌ／１００ｇ）］
＝［塗料中のヒドロシリル基の量（ｍｏｌ／１００ｇ）］－［塗料中のビニル基の量（ｍｏｌ／１００ｇ）］ <Paint>
The coating material of the present invention contains a resin component having a hydrosilyl group and a vinyl group, and an oil component, has an amount of surplus hydrosilyl groups represented by the following formula exceeding 0.0015 mol/100 g, and contains a silane coupling agent.
[Amount of surplus hydrosilyl group (mol/100g)]
= [Amount of hydrosilyl groups in the paint (mol/100g)] - [Amount of vinyl groups in the paint (mol/100g)]
本発明の塗料は、ヒドロシリル基及びビニル基を有する樹脂成分と、オイル成分とを含み、下記式で表される余剰ヒドロシリル基量が０．００１５ｍｏｌ／１００ｇを超え、シランカップリング剤を含む。
［余剰ヒドロシリル基量（ｍｏｌ／１００ｇ）］
＝［塗料中のヒドロシリル基の量（ｍｏｌ／１００ｇ）］－［塗料中のビニル基の量（ｍｏｌ／１００ｇ）］ <Paint>
The coating material of the present invention contains a resin component having a hydrosilyl group and a vinyl group, and an oil component, has an amount of surplus hydrosilyl groups represented by the following formula exceeding 0.0015 mol/100 g, and contains a silane coupling agent.
[Amount of surplus hydrosilyl group (mol/100g)]
= [Amount of hydrosilyl groups in the paint (mol/100g)] - [Amount of vinyl groups in the paint (mol/100g)]
［樹脂成分］
本発明の塗料は、少なくとも１種の樹脂成分を含有する。樹脂成分は、ヒドロシリル基及びビニル基を有する。
樹脂成分としては、例えば、樹脂のみを含む樹脂成分、樹脂と硬化剤とを含む樹脂成分等を挙げることができる。 [Resin component]
The coating material of the present invention contains at least one resin component. The resin component has a hydrosilyl group and a vinyl group.
Examples of the resin component include a resin component containing only a resin, a resin component containing a resin and a curing agent, and the like.
本発明の塗料は、少なくとも１種の樹脂成分を含有する。樹脂成分は、ヒドロシリル基及びビニル基を有する。
樹脂成分としては、例えば、樹脂のみを含む樹脂成分、樹脂と硬化剤とを含む樹脂成分等を挙げることができる。 [Resin component]
The coating material of the present invention contains at least one resin component. The resin component has a hydrosilyl group and a vinyl group.
Examples of the resin component include a resin component containing only a resin, a resin component containing a resin and a curing agent, and the like.
（樹脂）
樹脂は、湿分により硬化する湿分硬化型樹脂、紫外線照射により硬化する紫外線硬化型樹脂、加熱により硬化する熱硬化型樹脂のいずれであってもよい。また、樹脂は、樹脂と架橋反応する硬化剤を添加することによって硬化する樹脂や熱可塑性樹脂であってもよい。 (resin)
The resin may be any of a moisture-curable resin that is cured by moisture, an ultraviolet-curable resin that is cured by ultraviolet irradiation, and a thermosetting resin that is cured by heating. Further, the resin may be a resin or a thermoplastic resin that is cured by adding a curing agent that crosslinks with the resin.
樹脂は、湿分により硬化する湿分硬化型樹脂、紫外線照射により硬化する紫外線硬化型樹脂、加熱により硬化する熱硬化型樹脂のいずれであってもよい。また、樹脂は、樹脂と架橋反応する硬化剤を添加することによって硬化する樹脂や熱可塑性樹脂であってもよい。 (resin)
The resin may be any of a moisture-curable resin that is cured by moisture, an ultraviolet-curable resin that is cured by ultraviolet irradiation, and a thermosetting resin that is cured by heating. Further, the resin may be a resin or a thermoplastic resin that is cured by adding a curing agent that crosslinks with the resin.
樹脂としては、特に限定されないが、例えば、シリコーン樹脂、ポリウレタン樹脂、ポリウレタンアクリル樹脂、塩化ビニル樹脂、ポリエステル樹脂、エラストマー類、フッ素樹脂、ポリアミド樹脂、ポリオレフィン樹脂（ポリエチレン、ポリプロピレン等）、アクリル樹脂、ＥＰＤＭ（エチレンプロピレンジエンゴム）、ＳＥＢＳ（スチレン系熱可塑エラストマー）、ＳＢＲ（スチレンブタジエンゴム）等が挙げられる。
Examples of resins include, but are not limited to, silicone resins, polyurethane resins, polyurethane acrylic resins, vinyl chloride resins, polyester resins, elastomers, fluororesins, polyamide resins, polyolefin resins (polyethylene, polypropylene, etc.), acrylic resins, and EPDM. (ethylene propylene diene rubber), SEBS (styrene thermoplastic elastomer), SBR (styrene butadiene rubber), and the like.
シリコーン樹脂としては、本発明の効果を損なわない範囲で、任意の適切なシリコーン樹脂を採用し得る。シリコーン樹脂は、１種のみであってもよいし、２種以上であってもよい。このようなシリコーン樹脂としては、縮合型のシリコーン樹脂であってもよいし、付加型のシリコーン樹脂であってもよい。また、このようなシリコーン樹脂としては、単独で乾燥させる１液型のシリコーン樹脂（例えば、１液型の室温硬化性（ＲＴＶ）樹脂）であってもよいし、２液型のシリコーン樹脂（例えば、２液型の室温硬化性（ＲＴＶ）樹脂）であってもよい。
As the silicone resin, any suitable silicone resin may be employed as long as the effects of the present invention are not impaired. The number of silicone resins may be one, or two or more. Such silicone resin may be a condensation type silicone resin or an addition type silicone resin. Further, such silicone resin may be a one-component silicone resin that is dried alone (for example, a one-component room temperature curable (RTV) resin), or a two-component silicone resin (for example, a one-component room temperature curable (RTV) resin). , two-component room temperature curable (RTV) resin).
シリコーン樹脂の例としては、ヒドロシリル基及びビニル基を有するシリコーン樹脂、ビニル基を有するシリコーン樹脂等を挙げることができる。また、ヒドロシリル基もビニル基も有しないシリコーン樹脂を、樹脂として含むことも可能である。
Examples of silicone resins include silicone resins having hydrosilyl groups and vinyl groups, silicone resins having vinyl groups, and the like. It is also possible to include as a resin a silicone resin having neither a hydrosilyl group nor a vinyl group.
シリコーン樹脂としては、例えば、信越化学工業株式会社製の１液型ＲＴＶゴム（例えば、ＫＥ－３４２３、ＫＥ－３４７、ＫＥ－３４７５、ＫＥ－３４９５、ＫＥ－４８９５、ＫＥ－４８９６、ＫＥ－１８３０、ＫＥ－１８８４、ＫＥ－３４７９、ＫＥ－３４８、ＫＥ－４８９７、ＫＥ－４８９８、ＫＥ－１８２０、ＫＥ－１８２５、ＫＥ－１８３１、ＫＥ－１８３３、ＫＥ－１８８５、ＫＥ－１０５６、ＫＥ－１１５１、ＫＥ－１８４２、ＫＥ－１８８６、ＫＥ－３４２４Ｇ、ＫＥ－３４９４、ＫＥ－３４９０、ＫＥ－４０ＲＴＶ、ＫＥ－４８９０、ＫＥ－３４９７、ＫＥ－３４９８、ＫＥ－３４９３、ＫＥ－３４６６、ＫＥ－３４６７、ＫＥ－１８６２、ＫＥ－１８６７、ＫＥ－３４９１、ＫＥ－３４９２、ＫＥ－３４１７、ＫＥ－３４１８、ＫＥ－３４２７、ＫＥ－３４２８、ＫＥ－４１、ＫＥ－４２、ＫＥ－４４、ＫＥ－４５、ＫＥ－４４１、ＫＥ－４４５、ＫＥ－４５Ｓ等）、信越化学工業株式会社製の２液型ＲＴＶゴム（例えば、ＫＥ－１８００Ｔ－Ａ／Ｂ、ＫＥ－６６、ＫＥ－１０３１－Ａ／Ｂ、ＫＥ－２００、ＫＥ－１１８、ＫＥ－１０３、ＫＥ－１０８、ＫＥ－１１９、ＫＥ－１０９Ｅ－Ａ／Ｂ、ＫＥ－１０５１Ｊ－Ａ／Ｂ、ＫＥ－１０１２－Ａ／Ｂ、ＫＥ－１０６、ＫＥ－１２８２－Ａ／Ｂ、ＫＥ－１２８３－Ａ／Ｂ、ＫＥ－１８００－Ａ／Ｂ／Ｃ、ＫＥ－１８０１－Ａ／Ｂ／Ｃ、ＫＥ－１８０２－Ａ／Ｂ／Ｃ、ＫＥ－１２８１－Ａ／Ｂ、ＫＥ－１２０４－Ａ／Ｂ、ＫＥ－１２０４－ＡＬ／ＢＬ、ＫＥ－１２８０－Ａ／Ｂ、ＫＥ－５１３－Ａ／Ｂ、ＫＥ－５２１－Ａ／Ｂ、ＫＥ－１２８５－Ａ／Ｂ、ＫＥ－１８６１－Ａ／Ｂ、ＫＥ－１２、ＫＥ－１４、ＫＥ－１７、ＫＥ－１１３、ＫＥ－２４、ＫＥ－２６、ＫＥ－１４１４、ＫＥ－１４１５、ＫＥ－１４１６、ＫＥ－１４１７、ＫＥ－１３００Ｔ、ＫＥ－１３１０ＳＴ、ＫＥ－１３１４－２、ＫＥ－１３１６、ＫＥ－１６００、ＫＥ－１１７６０３－Ａ／Ｂ、ＫＥ－１６０６、ＫＥ－１２２２－Ａ／Ｂ、ＫＥ－１２４１等）、信越化学工業株式会社製のシリコーンシーラント（例えば、ＫＥ－４２ＡＳ、ＫＥ－４２０、ＫＥ－４５０等）、信越化学工業株式会社製のゴムコンパウンド（例えば、ＫＥ－６５５－Ｕ、ＫＥ－６７５－Ｕ、ＫＥ－９３１－Ｕ、ＫＥ－９４１－Ｕ、ＫＥ－９５１－Ｕ、ＫＥ－９６１－Ｕ、ＫＥ－９７１－Ｕ、ＫＥ－９８１－Ｕ、ＫＥ－９６１Ｔ－Ｕ、ＫＥ－９７１Ｔ－Ｕ、ＫＥ－８７１Ｃ－Ｕ、ＫＥ－９４１０－Ｕ、ＫＥ－９５１０－Ｕ、ＫＥ－９６１０－Ｕ、ＫＥ－９７１０－Ｕ、ＫＥ－７４２－Ｕ、ＫＥ－７５２－Ｕ、ＫＥ－７６２－Ｕ、ＫＥ－７７２－Ｕ、ＫＥ－７８２－Ｕ、ＫＥ－８５０－Ｕ、ＫＥ－８７０－Ｕ、ＫＥ－８８０－Ｕ、ＫＥ－８９０－Ｕ、ＫＥ－９５９０－Ｕ、ＫＥ－５５９０－Ｕ、ＫＥ－５５２－Ｕ、ＫＥ－５８２－Ｕ、ＫＥ－５５２Ｂ－Ｕ、ＫＥ－５５５－Ｕ、ＫＥ－５７５－Ｕ、ＫＥ－５４１－Ｕ、ＫＥ－５５１－Ｕ、ＫＥ－５６１－Ｕ、ＫＥ－５７１－Ｕ、ＫＥ－５８１－Ｕ、ＫＥ－５２０－Ｕ、ＫＥ－５３０Ｂ－２－Ｕ、ＫＥ－５４０Ｂ－２－Ｕ、ＫＥ－１５５１－Ｕ、ＫＥ－１５７１－Ｕ、ＫＥ－１５２－Ｕ、ＫＥ－１７４－Ｕ、ＫＥ－３６０１ＳＢ－Ｕ、ＫＥ－３７１１－Ｕ、ＫＥ－３８０１Ｍ－Ｕ、ＫＥ－５６１２Ｇ－Ｕ、ＫＥ－５６２０ＢＬ－Ｕ、ＫＥ－５６２０Ｗ－Ｕ、ＫＥ－５６３４－Ｕ、ＫＥ－７５１１－Ｕ、ＫＥ－７６１１－Ｕ、ＫＥ－７６５－Ｕ、ＫＥ－７８５－Ｕ、ＫＥ－７００８－Ｕ、ＫＥ－７００５－Ｕ、ＫＥ－５０３－Ｕ、ＫＥ－５０４２－Ｕ、ＫＥ－５０５－Ｕ、ＫＥ－６８０１－Ｕ、ＫＥ－１３６Ｙ－Ｕ等）、信越化学工業株式会社製のＬＩＭＳ（液状シリコーンゴム射出成形システム）（例えば、ＫＥＧ－２０００－４０Ａ／Ｂ、ＫＥＧ－２０００－５０Ａ／Ｂ、ＫＥＧ－２０００－６０Ａ／Ｂ、ＫＥＧ－２０００－７０Ａ／Ｂ、ＫＥＧ－２００１－４０Ａ／Ｂ、ＫＥＧ－２００１－５０Ａ／Ｂ、ＫＥ－１９５０－１０Ａ／Ｂ、ＫＥ－１９５０－２０Ａ／Ｂ、ＫＥ－１９５０－３０Ａ／Ｂ、ＫＥ－１９５０－３５Ａ／Ｂ、ＫＥ－１９５０－４０Ａ／Ｂ、ＫＥ－１９５０－５０Ａ／Ｂ、ＫＥ－１９５０－６０Ａ／Ｂ、ＫＥ－１９５０－７０Ａ／Ｂ、ＫＥ－１９３５Ａ／Ｂ、ＫＥ－１９８７Ａ／Ｂ、ＫＥ－１９８８Ａ／Ｂ、ＫＥ－２０１９－４０Ａ／Ｂ、ＫＥ－２０１９－５０Ａ／Ｂ、ＫＥ－２０１９－６０Ａ／Ｂ、ＫＥ－２０１７－３０Ａ／Ｂ、ＫＥ－２０１７－４０Ａ／Ｂ、ＫＥ－２０１７－５０Ａ／Ｂ、ＫＥ－２０９０－４０Ａ／Ｂ、ＫＥ－２０９０－５０Ａ／Ｂ、ＫＥ－２０９０－６０Ａ／Ｂ、ＫＥ－２０９０－７０Ａ／Ｂ、ＫＥ－２０９６－４０Ａ／Ｂ、ＫＥ－２０９６－５０Ａ／Ｂ、ＫＥ－２０９６－６ＯＡ／Ｂ等）、ＫＥ－２０９８－４０Ａ／Ｂ、ＫＥ－２０９８－５０Ａ／Ｂ、ＫＥ－２０９８－６０Ａ／Ｂ、信越化学工業株式会社製のジメチコノール（例えば、Ｘ－２１－５８４７、Ｘ－２１－５８４９）、旭化成ワッカーシリコーン株式会社製のＬＲ７６６５シリーズ、旭化成ワッカーシリコーン株式会社製のＬＲ３０３３シリーズ、モメンティブ株式会社製のＴＳＥ３０３２シリーズ等、東レダウコーニング製のシルガード１８４等を用いることができる。
Examples of the silicone resin include one-component RTV rubber manufactured by Shin-Etsu Chemical Co., Ltd. (for example, KE-3423, KE-347, KE-3475, KE-3495, KE-4895, KE-4896, KE-1830, KE-1884, KE-3479, KE-348, KE-4897, KE-4898, KE-1820, KE-1825, KE-1831, KE-1833, KE-1885, KE-1056, KE-1151, KE- 1842, KE-1886, KE-3424G, KE-3494, KE-3490, KE-40RTV, KE-4890, KE-3497, KE-3498, KE-3493, KE-3466, KE-3467, KE-1862, KE-1867, KE-3491, KE-3492, KE-3417, KE-3418, KE-3427, KE-3428, KE-41, KE-42, KE-44, KE-45, KE-441, KE- 445, KE-45S, etc.), two-component RTV rubber manufactured by Shin-Etsu Chemical Co., Ltd. (for example, KE-1800T-A/B, KE-66, KE-1031-A/B, KE-200, KE-118) , KE-103, KE-108, KE-119, KE-109E-A/B, KE-1051J-A/B, KE-1012-A/B, KE-106, KE-1282-A/B, KE -1283-A/B, KE-1800-A/B/C, KE-1801-A/B/C, KE-1802-A/B/C, KE-1281-A/B, KE-1204-A /B, KE-1204-AL/BL, KE-1280-A/B, KE-513-A/B, KE-521-A/B, KE-1285-A/B, KE-1861-A/B , KE-12, KE-14, KE-17, KE-113, KE-24, KE-26, KE-1414, KE-1415, KE-1416, KE-1417, KE-1300T, KE-1310ST, KE -1314-2, KE-1316, KE-1600, KE-117603-A/B, KE-1606, KE-1222-A/B, KE-1241, etc.), silicone sealants manufactured by Shin-Etsu Chemical Co., Ltd. (e.g. , KE-42AS, KE-420, KE-450, etc.), rubber compounds manufactured by Shin-Etsu Chemical Co., Ltd. (for example, KE-655-U, KE-675-U, KE-931-U, KE-941-U) , KE-951-U, KE-961-U, KE-971-U, KE-981-U, KE-961T-U, KE-971T-U, KE-871C-U, KE-9410-U, KE -9510-U, KE-9610-U, KE-9710-U, KE-742-U, KE-752-U, KE-762-U, KE-772-U, KE-782-U, KE-850 -U, KE-870-U, KE-880-U, KE-890-U, KE-9590-U, KE-5590-U, KE-552-U, KE-582-U, KE-552B-U , KE-555-U, KE-575-U, KE-541-U, KE-551-U, KE-561-U, KE-571-U, KE-581-U, KE-520-U, KE -530B-2-U, KE-540B-2-U, KE-1551-U, KE-1571-U, KE-152-U, KE-174-U, KE-3601SB-U, KE-3711-U , KE-3801M-U, KE-5612G-U, KE-5620BL-U, KE-5620W-U, KE-5634-U, KE-7511-U, KE-7611-U, KE-765-U, KE -785-U, KE-7008-U, KE-7005-U, KE-503-U, KE-5042-U, KE-505-U, KE-6801-U, KE-136Y-U, etc.), Shin-Etsu LIMS (liquid silicone rubber injection molding system) manufactured by Kagaku Kogyo Co., Ltd. (for example, KEG-2000-40A/B, KEG-2000-50A/B, KEG-2000-60A/B, KEG-2000-70A/B, KEG-2001-40A/B, KEG-2001-50A/B, KE-1950-10A/B, KE-1950-20A/B, KE-1950-30A/B, KE-1950-35A/B, KE- 1950-40A/B, KE-1950-50A/B, KE-1950-60A/B, KE-1950-70A/B, KE-1935A/B, KE-1987A/B, KE-1988A/B, KE- 2019-40A/B, KE-2019-50A/B, KE-2019-60A/B, KE-2017-30A/B, KE-2017-40A/B, KE-2017-50A/B, KE-2090- 40A/B, KE-2090-50A/B, KE-2090-60A/B, KE-2090-70A/B, KE-2096-40A/B, KE-2096-50A/B, KE-2096-6OA/ B, etc.), KE-2098-40A/B, KE-2098-50A/B, KE-2098-60A/B, dimethiconol manufactured by Shin-Etsu Chemical Co., Ltd. (e.g., X-21-5847, X-21-5849) ), Asahi Kasei Wacker Silicone Co., Ltd.'s LR7665 series, Asahi Kasei Wacker Silicone Co., Ltd.'s LR3033 series, Momentive Co., Ltd.'s TSE3032 series, Toray Dow Corning's Sylgard 184, etc. can be used.
本発明の塗料における樹脂の含有量は、好ましくは１５質量％以上、より好ましくは２５質量％以上、さらに好ましくは３５質量％以上である。また、本発明の塗料における樹脂の含有量は、好ましくは９０質量％以下、より好ましくは８０質量％以下、さらに好ましくは７０質量％以下である。
The content of the resin in the coating material of the present invention is preferably 15% by mass or more, more preferably 25% by mass or more, and even more preferably 35% by mass or more. Further, the resin content in the coating material of the present invention is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less.
（硬化剤）
硬化剤としては、例えば主鎖がジオルガノシロキサンの繰返し単位であり、末端がトリオルガノシロキサン構造であるものが例示され、分岐や環状構造を有するものであってもよい。末端や繰返し単位中のケイ素に結合するオルガノ基としては、メチル基、エチル基、オクチル基、フェニル基などが例示され、これらの２個以上が水素に置換された硬化剤が好ましい。すなわち、硬化剤は、ヒドロシリル基を有するものが好ましい。具体例としては、ハイドロジェンシリコーン等が挙げられる。具体的な硬化剤としては、例えば、信越化学工業株式会社製のｃａｔ－１３１０ｓ、ＫＦ－９９、ＫＦ－９９０１、Ｇｅｌｅｓｔ社製のＨＭＳ－１５１、ＨＭＳ－３０１、ＨＭＳ－５０１等が挙げられる。 (hardening agent)
Examples of the curing agent include those whose main chain is a repeating unit of diorganosiloxane and whose terminal end is a triorganosiloxane structure, and may have a branched or cyclic structure. Examples of the organo group bonded to silicon at the terminal or in the repeating unit include methyl group, ethyl group, octyl group, phenyl group, etc. A curing agent in which two or more of these groups are substituted with hydrogen is preferred. That is, the curing agent preferably has a hydrosilyl group. Specific examples include hydrogen silicone and the like. Specific curing agents include, for example, cat-1310s, KF-99, and KF-9901 manufactured by Shin-Etsu Chemical Co., Ltd., and HMS-151, HMS-301, and HMS-501 manufactured by Gelest.
硬化剤としては、例えば主鎖がジオルガノシロキサンの繰返し単位であり、末端がトリオルガノシロキサン構造であるものが例示され、分岐や環状構造を有するものであってもよい。末端や繰返し単位中のケイ素に結合するオルガノ基としては、メチル基、エチル基、オクチル基、フェニル基などが例示され、これらの２個以上が水素に置換された硬化剤が好ましい。すなわち、硬化剤は、ヒドロシリル基を有するものが好ましい。具体例としては、ハイドロジェンシリコーン等が挙げられる。具体的な硬化剤としては、例えば、信越化学工業株式会社製のｃａｔ－１３１０ｓ、ＫＦ－９９、ＫＦ－９９０１、Ｇｅｌｅｓｔ社製のＨＭＳ－１５１、ＨＭＳ－３０１、ＨＭＳ－５０１等が挙げられる。 (hardening agent)
Examples of the curing agent include those whose main chain is a repeating unit of diorganosiloxane and whose terminal end is a triorganosiloxane structure, and may have a branched or cyclic structure. Examples of the organo group bonded to silicon at the terminal or in the repeating unit include methyl group, ethyl group, octyl group, phenyl group, etc. A curing agent in which two or more of these groups are substituted with hydrogen is preferred. That is, the curing agent preferably has a hydrosilyl group. Specific examples include hydrogen silicone and the like. Specific curing agents include, for example, cat-1310s, KF-99, and KF-9901 manufactured by Shin-Etsu Chemical Co., Ltd., and HMS-151, HMS-301, and HMS-501 manufactured by Gelest.
硬化剤を用いる態様として、例えば、樹脂とは独立した追加の硬化剤を添加する態様が挙げられる。硬化剤は、例えば、塗料中のヒドロシリル基の量及び余剰ヒドロシリル基量を調節するために用いることができる。
Examples of embodiments in which a curing agent is used include an embodiment in which an additional curing agent independent of the resin is added. The curing agent can be used, for example, to adjust the amount of hydrosilyl groups and the amount of excess hydrosilyl groups in the paint.
ビニル基を有するポリマーとヒドロシリル基を有するポリマーとがセットとなっている樹脂を用いる場合には、硬化剤を添加しなくともよい場合がある。例えば、ビニル基を有するシリコーンポリマーであるＫＥ－２０９８－６０Ａとヒドロシリル基を有するシリコーンポリマーであるＫＥ－２０９８－６０Ｂとを質量比１：１で混合させるＫＥ－２０９８－６０Ａ／Ｂのように、ビニル基を有するポリマーとヒドロシリル基を有するポリマーとがセットとなっている樹脂を用いた場合には、追加の硬化剤を添加しなくとも所望の余剰ヒドロシリル基量が得られる場合がある。ビニル基を有するポリマーとヒドロシリル基を有するポリマーとがセットとなっている樹脂を使用する場合であっても、これとは独立した追加の硬化剤をさらに添加してもよい。
When using a resin containing a set of a polymer having a vinyl group and a polymer having a hydrosilyl group, it may not be necessary to add a curing agent. For example, KE-2098-60A/B is a mixture of KE-2098-60A, a silicone polymer having a vinyl group, and KE-2098-60B, a silicone polymer having a hydrosilyl group, at a mass ratio of 1:1. When a resin containing a set of a polymer having a vinyl group and a polymer having a hydrosilyl group is used, a desired amount of excess hydrosilyl groups may be obtained without adding an additional curing agent. Even when a resin containing a set of a polymer having a vinyl group and a polymer having a hydrosilyl group is used, an additional curing agent independent of this may be further added.
［オイル成分］
本発明の塗料は、少なくとも１種のオイル成分を含有する。 [Oil component]
The coating material of the present invention contains at least one oil component.
本発明の塗料は、少なくとも１種のオイル成分を含有する。 [Oil component]
The coating material of the present invention contains at least one oil component.
オイル成分として、例えば、シリコーンオイル、フッ素オイル、炭化水素系オイル、ポリエーテル系オイル、エステル系オイル、リン化合物系オイル、鉱油系オイル、アルコール等を用いることができる。
As the oil component, for example, silicone oil, fluorine oil, hydrocarbon oil, polyether oil, ester oil, phosphorus compound oil, mineral oil, alcohol, etc. can be used.
シリコーンオイルとしては、例えば、信越化学工業株式会社製のシリコーンオイル（例えば、ＫＦ９６Ｌシリーズ、ＫＦ９６シリーズ、ＫＦ６９シリーズ、ＫＦ９９シリーズ、ＫＦ５０シリーズ、ＫＦ５４シリーズ、ＫＦ４１０シリーズ、ＫＦ４１２シリーズ、ＫＦ４１４シリーズ、ＦＬシリーズ、ＫＦ－５６Ａ、ＫＦ－６０００、ＫＦ－６００１、ＫＦ－６００２、ＫＦ－６００３等）、モメンティブ株式会社製のシリコーンオイル（例えば、Ｅｌｅｍｅｎｔ１４＊ＰＤＭＳシリーズ、ＴＳＦ４０４シリーズ、ＴＳＦ４１０シリーズ、ＴＳＦ４３００シリーズ、ＴＳＦ４３１シリーズ、ＴＳＦ４３３シリーズ、ＴＳＦ４３７シリーズ、ＴＳＦ４４２０シリーズ、ＴＳＦ４４２１シリーズ等）、東レダウコーニング株式会社製のシリコーンオイル（例えば、ＢＹ１６－８４６シリーズ、ＳＦ８４１６シリーズ、ＳＦ８４２７シリーズ、ＳＦ－８４２８シリーズ、ＳＨ２００シリーズ、ＳＨ２０３シリーズ、ＳＨ２３０シリーズ、ＳＦ８４１９シリーズ、ＦＳ１２６５シリーズ、ＳＨ５１０シリーズ、ＳＨ５５０シリーズ、ＳＨ７１０シリーズ、ＦＺ－２１１０シリーズ、ＦＺ－２２０３シリーズ、ＢＹ１６－２０１等）、旭化成ワッカーシリコーン社製のシリコーンオイル（ＷＡＣＫＥＲ（登録商標）ＳＩＬＩＣＯＮＥ ＦＬＵＩＤ ＡＫシリーズ、ＷＡＣＫＥＲ（登録商標）ＳＩＬＩＣＯＮＥ ＦＬＵＩＤ ＡＰシリーズ、ＷＡＣＫＥＲ（登録商標）ＳＩＬＩＣＯＮＥ ＦＬＵＩＤ ＡＲシリーズ、ＷＡＣＫＥＲ（登録商標）ＳＩＬＩＣＯＮＥ ＦＬＵＩＤ ＡＳシリーズ、ＷＡＣＫＥＲ（登録商標）ＴＮシリーズ、ＷＡＣＫＥＲ（登録商標）Ｌシリーズ、ＷＡＣＫＥＲ（登録商標）ＡＦシリーズ等）等、流動パラフィンを用いることができる。
Examples of silicone oil include silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. (for example, KF96L series, KF96 series, KF69 series, KF99 series, KF50 series, KF54 series, KF410 series, KF412 series, KF414 series, FL series, KF -56A, KF-6000, KF-6001, KF-6002, KF-6003, etc.), silicone oil manufactured by Momentive Corporation (e.g. Element14*PDMS series, TSF404 series, TSF410 series, TSF4300 series, TSF431 series, TSF433 series) , TSF437 series, TSF4420 series, TSF4421 series, etc.), silicone oil manufactured by Dow Corning Toray Co., Ltd. (for example, BY16-846 series, SF8416 series, SF8427 series, SF-8428 series, SH200 series, SH203 series, SH230 series, SF8419) series, FS1265 series, SH510 series, SH550 series, SH710 series, FZ-2110 series, FZ-2203 series, BY16-201, etc.), silicone oil manufactured by Asahi Kasei Wacker Silicone Co., Ltd. (WACKER (registered trademark) SILICONE FLUID AK series, WACKER (registered trademark) SILICONE FLUID AP series, WACKER (registered trademark) SILICONE FLUID AR series, WACKER (registered trademark) SILICONE FLUID AS series, WACKER (registered trademark) TN series, WACKER (registered trademark) L series, WA CKER (registered trademark) Liquid paraffin such as AF series) can be used.
また、オイル成分は親水性基を有することが好ましい。親水性基としては、例えば、カルビノール基、ヒドロキシ基、カルボキシ基、無水カルボン酸基、アミノ基、スルホ基、エーテル基、エポキシ基、メルカプト基、チオール基、エステル基等が挙げられ、カルビノール基、ヒドロキシ基、カルボキシ基、無水カルボン酸基、アミノ基、スルホ基、エーテル基、エポキシ基、メルカプト基、チオール基及びエステル基からなる群から選択される少なくとも１種の基が好ましい。これらの中でも、優れた着氷及び／又は着雪防止機能を発揮する観点から、カルビノール基がより好ましい。
Moreover, it is preferable that the oil component has a hydrophilic group. Examples of the hydrophilic group include carbinol group, hydroxy group, carboxy group, carboxylic anhydride group, amino group, sulfo group, ether group, epoxy group, mercapto group, thiol group, ester group, etc. At least one group selected from the group consisting of a hydroxy group, a carboxy group, a carboxylic anhydride group, an amino group, a sulfo group, an ether group, an epoxy group, a mercapto group, a thiol group, and an ester group is preferred. Among these, carbinol groups are more preferred from the viewpoint of exhibiting excellent icing and/or snow accretion prevention functions.
なお、オイル成分は１種類のみ用いてもよいし、２種類以上用いてもよい。
Note that only one type of oil component may be used, or two or more types of oil components may be used.
［シランカップリング剤］
本発明の塗料は、少なくとも１種のシランカップリング剤を含有する。シランカップリング剤としては、例えば、イソシアネート基、ビニル基、エポキシ基、アミノ基及びメルカプト基からなる群から選択される少なくとも１種の基を官能基として有するものや、酸無水物等が挙げられる。 [Silane coupling agent]
The coating material of the present invention contains at least one silane coupling agent. Examples of the silane coupling agent include those having as a functional group at least one group selected from the group consisting of isocyanate groups, vinyl groups, epoxy groups, amino groups, and mercapto groups, acid anhydrides, and the like. .
本発明の塗料は、少なくとも１種のシランカップリング剤を含有する。シランカップリング剤としては、例えば、イソシアネート基、ビニル基、エポキシ基、アミノ基及びメルカプト基からなる群から選択される少なくとも１種の基を官能基として有するものや、酸無水物等が挙げられる。 [Silane coupling agent]
The coating material of the present invention contains at least one silane coupling agent. Examples of the silane coupling agent include those having as a functional group at least one group selected from the group consisting of isocyanate groups, vinyl groups, epoxy groups, amino groups, and mercapto groups, acid anhydrides, and the like. .
シランカップリング剤としては、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ジメトキシメチルシラン、３－イソシアネートプロピルトリエトキシシラン、イソシアネートメチルトリメトキシシラン、イソシアネートメチルトリエトキシシラン、イソシアネートメチルジメトキシメチルシラン等が挙げられる。
Examples of the silane coupling agent include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyldimethoxymethylsilane, 3-isocyanatepropyltriethoxysilane, isocyanatemethyltrimethoxysilane, isocyanatemethyltriethoxysilane, and isocyanatemethyldimethoxymethylsilane. etc.
シランカップリング剤としては、例えばビニルトリエトキシシラン、３－グリシドキシプロピルトリエトキシシラン、ｐ－スチリルトリメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－アクリロキシ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－メルカプトプロピルトリメトキシシラン、３－トリメトキシシリルプロピルコハク酸無水物等が挙げられる。
Examples of the silane coupling agent include vinyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, -aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, and the like.
塗料がシランカップリング剤を含むことにより、形成される塗膜層の基材への密着性が向上する理由は定かではないが、ヒドロシリル基に加えてシランカップリング剤が有する官能基が基材の官能基と反応および／または相互作用するために、密着性が向上するのではないかと推測される。また、シランカップリング剤は樹脂成分が有するヒドロシリル基と反応するため、低温条件下における塗膜層からのオイル成分の滲出の妨げとなる、樹脂成分のヒドロシリル基とオイル成分の親水性基等との反応を抑制することができると考えられる。その結果として、基材等への密着性に優れ、優れた着氷及び／又は着雪防止機能を持つ塗膜層を形成することができる塗料を提供することができると考えられる。
It is not clear why the adhesion of the formed coating layer to the substrate improves when the paint contains a silane coupling agent, but in addition to the hydrosilyl group, the functional groups of the silane coupling agent improve the adhesion to the substrate. It is presumed that the adhesion is improved due to reaction and/or interaction with the functional groups of In addition, since the silane coupling agent reacts with the hydrosilyl group of the resin component, the hydrosilyl group of the resin component and the hydrophilic group of the oil component, etc., can prevent the oil component from seeping out from the coating layer under low temperature conditions. It is thought that this reaction can be suppressed. As a result, it is considered possible to provide a paint that can form a coating layer that has excellent adhesion to substrates and has excellent anti-icing and/or snow accretion functions.
シランカップリング剤を用いる場合には、あらかじめシランカップリング剤が含まれている樹脂を使用してもよく、樹脂とは独立した追加のシランカップリング剤を添加してもよい。あらかじめシランカップリング剤が含まれている樹脂の具体例としては、ＫＥ－２０９８－６０Ａ／Ｂ等が挙げられる。また、あらかじめシランカップリング剤が含まれている樹脂を使用する場合は、これとは独立した追加のシランカップリング剤をさらに添加してもよい。
When using a silane coupling agent, a resin containing the silane coupling agent in advance may be used, or an additional silane coupling agent independent of the resin may be added. Specific examples of resins that contain a silane coupling agent in advance include KE-2098-60A/B. Furthermore, when using a resin that contains a silane coupling agent in advance, an additional silane coupling agent may be added independently from this resin.
本発明の塗料におけるシランカップリング剤の含有量は、好ましくは０．０５質量％以上、より好ましくは０．１０質量％以上、さらに好ましくは０．１５質量％以上である。また、本発明の塗料におけるシランカップリング剤の含有量は、好ましくは１０質量％以下、より好ましくは８質量％以下、さらに好ましくは６質量％以下である。
なお、シランカップリング剤は１種類のみ用いてもよいし、２種類以上用いてもよい。 The content of the silane coupling agent in the coating material of the present invention is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, and still more preferably 0.15% by mass or more. Further, the content of the silane coupling agent in the coating material of the present invention is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 6% by mass or less.
In addition, only one type of silane coupling agent may be used, or two or more types may be used.
なお、シランカップリング剤は１種類のみ用いてもよいし、２種類以上用いてもよい。 The content of the silane coupling agent in the coating material of the present invention is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, and still more preferably 0.15% by mass or more. Further, the content of the silane coupling agent in the coating material of the present invention is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 6% by mass or less.
In addition, only one type of silane coupling agent may be used, or two or more types may be used.
シランカップリング剤を含まない塗料により形成された塗膜層は、着氷及び／又は着雪防止機能が得られない恐れがある。
A coating layer formed from a paint that does not contain a silane coupling agent may not have the ability to prevent icing and/or snow accumulation.
［溶剤］
本発明の塗料は、溶剤を含有することできる。
溶剤としては、例えば、トルエン、キシレン等の芳香族炭化水素系溶剤、酢酸エチル、酢酸ブチル等のエステル系溶剤、ヘキサン、オクタン、デカン、イソパラフィン等の炭化水素系溶剤、アセトン、メチルエチルケトン等のケトン系溶剤等を挙げることができる。 [solvent]
The paint of the present invention can contain a solvent.
Examples of solvents include aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, hydrocarbon solvents such as hexane, octane, decane, and isoparaffin, and ketone solvents such as acetone and methyl ethyl ketone. Examples include solvents.
本発明の塗料は、溶剤を含有することできる。
溶剤としては、例えば、トルエン、キシレン等の芳香族炭化水素系溶剤、酢酸エチル、酢酸ブチル等のエステル系溶剤、ヘキサン、オクタン、デカン、イソパラフィン等の炭化水素系溶剤、アセトン、メチルエチルケトン等のケトン系溶剤等を挙げることができる。 [solvent]
The paint of the present invention can contain a solvent.
Examples of solvents include aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, hydrocarbon solvents such as hexane, octane, decane, and isoparaffin, and ketone solvents such as acetone and methyl ethyl ketone. Examples include solvents.
［硬化触媒］
本発明の塗料は、さらに硬化触媒を含有することができる。
硬化触媒としては、例えば、白金（０）－１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体、ヘキサクロリド白金（ＩＶ）酸、クロロトリス（トリフェニルホスフィン）ロジウム（Ｉ）等の金属触媒等を挙げることができる。 [Curing catalyst]
The coating material of the present invention can further contain a curing catalyst.
As a curing catalyst, for example, platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, hexachloride platinum (IV) acid, chlorotris (triphenylphosphine) rhodium (I) Examples include metal catalysts such as.
本発明の塗料は、さらに硬化触媒を含有することができる。
硬化触媒としては、例えば、白金（０）－１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体、ヘキサクロリド白金（ＩＶ）酸、クロロトリス（トリフェニルホスフィン）ロジウム（Ｉ）等の金属触媒等を挙げることができる。 [Curing catalyst]
The coating material of the present invention can further contain a curing catalyst.
As a curing catalyst, for example, platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, hexachloride platinum (IV) acid, chlorotris (triphenylphosphine) rhodium (I) Examples include metal catalysts such as.
［その他の成分］
本発明の塗料は、さらにシリカ、タルク、炭酸カルシウム、酸化チタン、クレー、顔料などのフィラーを含有することができる。
シリカとしては、例えば、日本アエロジル株式会社製のシリカ（例えば、ＡＥＲＯＳＩＬ５０、１３０、２００、３００、Ｒ９７２、Ｒ９７４、Ｒ９７６、ＲＸ５０、ＲＸ２００、ＲＸ３００、ＲＹ５０、ＲＹ３００、Ｒ７２００、Ｒ８２００、Ｒ９２００）等を用いることができる。 [Other ingredients]
The paint of the present invention can further contain fillers such as silica, talc, calcium carbonate, titanium oxide, clay, and pigments.
As the silica, for example, silica manufactured by Nippon Aerosil Co., Ltd. (for example, AEROSIL50, 130, 200, 300, R972, R974, R976, RX50, RX200, RX300, RY50, RY300, R7200, R8200, R9200), etc. may be used. I can do it.
本発明の塗料は、さらにシリカ、タルク、炭酸カルシウム、酸化チタン、クレー、顔料などのフィラーを含有することができる。
シリカとしては、例えば、日本アエロジル株式会社製のシリカ（例えば、ＡＥＲＯＳＩＬ５０、１３０、２００、３００、Ｒ９７２、Ｒ９７４、Ｒ９７６、ＲＸ５０、ＲＸ２００、ＲＸ３００、ＲＹ５０、ＲＹ３００、Ｒ７２００、Ｒ８２００、Ｒ９２００）等を用いることができる。 [Other ingredients]
The paint of the present invention can further contain fillers such as silica, talc, calcium carbonate, titanium oxide, clay, and pigments.
As the silica, for example, silica manufactured by Nippon Aerosil Co., Ltd. (for example, AEROSIL50, 130, 200, 300, R972, R974, R976, RX50, RX200, RX300, RY50, RY300, R7200, R8200, R9200), etc. may be used. I can do it.
本発明の塗料は、本発明の効果を損なわない範囲で、任意の適切な他の添加剤を含んでいてもよい。このような他の添加剤としては、例えば、耐候剤として紫外線吸収剤、光安定剤が挙げられる。紫外線吸収剤と光安定剤は併用すると効果が高い。
The coating material of the present invention may contain any other appropriate additives as long as the effects of the present invention are not impaired. Examples of such other additives include weathering agents, ultraviolet absorbers, and light stabilizers. Ultraviolet absorbers and light stabilizers are highly effective when used together.
紫外線吸収剤の具体例としては、ＡＤＥＫＡ製のＬＡ－２４，ＬＡ－２９、ＬＡ－３１、ＬＡ－３１ＲＧ、ＬＡ－３１Ｇ、ＬＡ－３２、ＬＡ－３６、ＬＡ－４６、ＬＡ－Ｆ７０、１４１３、ＢＡＳＦ製のＴｉｎｕｖｉｎＰＳ、Ｔｉｎｕｖｉｎ９９－２、Ｔｉｎｕｖｉｎ３２６、Ｔｉｎｕｖｉｎ３８４－２、Ｔｉｎｕｖｉｎ９００、Ｔｉｎｕｖｉｎ９２８、Ｔｉｎｕｖｉｎ９７０、Ｔｉｎｕｖｉｎ１１３０、Ｔｉｎｕｖｉｎ４００、Ｔｉｎｕｖｉｎ４０５、Ｔｉｎｕｖｉｎ４６０、Ｔｉｎｕｖｉｎ４７７、Ｔｉｎｕｖｉｎ４７９、ＵＶＡ－９０３ＫＴ、ＵＶＡ－９３５ＬＨなどが挙げられる。
Specific examples of ultraviolet absorbers include ADEKA LA-24, LA-29, LA-31, LA-31RG, LA-31G, LA-32, LA-36, LA-46, LA-F70, 1413, BASF TinuvinPS, Tinuvin99-2, Tinuvin326, Tinuvin384-2, Tinuvin900, Tinuvin928, Tinuvin970, Tinuvin1130, Tinuvin400, Tinuvin405, Ti Examples include nuvin460, Tinuvin477, Tinuvin479, UVA-903KT, UVA-935LH, and the like.
光安定剤の具体例としては、ＡＤＥＫＡ製のＬＡ－５２、ＬＡ－５７、ＬＡ－６３Ｐ、ＬＡ－６８、ＬＡ－７２、ＬＡ－７７Ｙ、ＬＡ－７７Ｇ、ＬＡ－８１、ＬＡ－８２、ＬＡ－８７、ＬＡ－４０２ＡＦ、ＬＡ－４０ＭＰ、ＬＡ－４０Ｓｉ、ＢＡＳＦ製のＴｉｎｕｖｉｎ１１１、Ｔｉｎｕｖｉｎ１２３、Ｔｉｎｕｖｉｎ１４４、Ｔｉｎｕｖｉｎ１５２、Ｔｉｎｕｖｉｎ２４９、Ｔｉｎｕｖｉｎ２９２、Ｔｉｎｕｖｉｎ７７０ＤＦ、Ｔｉｎｕｖｉｎ５１００などが挙げられる。
Specific examples of light stabilizers include LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, and LA- manufactured by ADEKA. 87, LA-402AF, LA-40MP, LA-40Si, BASF Tinuvin111, Tinuvin123, Tinuvin144, Tinuvin152, Tinuvin249, Tinuvin292, Tinuvin770DF, Tinuvin5 100, etc.
（反応制御剤）
本発明の塗料は、塗膜を安定的に作製できるように、さらに反応制御剤を含有することができる。反応制御剤としては、例えば、信越化学工業株式会社製の反応制御剤（品番：ＮＯ．６－１０）、ダウ・東レ株式会社製の反応制御剤（品番：ＳＩＬＡＳＴＩＣＴＭＲＤ－９、ＳＩＬＡＳＴＩＣＴＭ ＲＤ－２０１）、モメンティブ社製の反応制御剤（品番：ＭＥ７５）、Ｇｅｌｅｓｔ社製の反応制御剤（品番：ＶＭＳ－００５、ＶＭＳ－Ｔ１１）等を挙げることができる。 (Reaction control agent)
The coating material of the present invention may further contain a reaction control agent so that a coating film can be stably produced. Examples of reaction control agents include reaction control agents manufactured by Shin-Etsu Chemical Co., Ltd. (product number: NO. 6-10) and reaction control agents manufactured by Dow Toray Industries, Inc. (product numbers: SILASTICTMRD-9, SILASTICTM RD-201). , a reaction control agent manufactured by Momentive (product number: ME75), a reaction control agent manufactured by Gelest (product numbers: VMS-005, VMS-T11), and the like.
本発明の塗料は、塗膜を安定的に作製できるように、さらに反応制御剤を含有することができる。反応制御剤としては、例えば、信越化学工業株式会社製の反応制御剤（品番：ＮＯ．６－１０）、ダウ・東レ株式会社製の反応制御剤（品番：ＳＩＬＡＳＴＩＣＴＭＲＤ－９、ＳＩＬＡＳＴＩＣＴＭ ＲＤ－２０１）、モメンティブ社製の反応制御剤（品番：ＭＥ７５）、Ｇｅｌｅｓｔ社製の反応制御剤（品番：ＶＭＳ－００５、ＶＭＳ－Ｔ１１）等を挙げることができる。 (Reaction control agent)
The coating material of the present invention may further contain a reaction control agent so that a coating film can be stably produced. Examples of reaction control agents include reaction control agents manufactured by Shin-Etsu Chemical Co., Ltd. (product number: NO. 6-10) and reaction control agents manufactured by Dow Toray Industries, Inc. (product numbers: SILASTICTMRD-9, SILASTICTM RD-201). , a reaction control agent manufactured by Momentive (product number: ME75), a reaction control agent manufactured by Gelest (product numbers: VMS-005, VMS-T11), and the like.
［塗料の製造方法］
本発明の塗料は、上述の各成分を、公知の方法によって混合及び／又は撹拌して得ることができる。 [Paint manufacturing method]
The coating material of the present invention can be obtained by mixing and/or stirring the above-mentioned components by a known method.
本発明の塗料は、上述の各成分を、公知の方法によって混合及び／又は撹拌して得ることができる。 [Paint manufacturing method]
The coating material of the present invention can be obtained by mixing and/or stirring the above-mentioned components by a known method.
［塗料の特徴］
（余剰ヒドロシリル基量）
本発明の塗料は、下記式で表される余剰ヒドロシリル基量が０．００１５ｍｏｌ／１００ｇを超える。
［余剰ヒドロシリル基量（ｍｏｌ／１００ｇ）］
＝［塗料中のヒドロシリル基の量（ｍｏｌ／１００ｇ）］－［塗料中のビニル基の量（ｍｏｌ／１００ｇ）］ [Characteristics of paint]
(Excess hydrosilyl group amount)
In the coating material of the present invention, the amount of surplus hydrosilyl groups represented by the following formula exceeds 0.0015 mol/100 g.
[Amount of surplus hydrosilyl group (mol/100g)]
= [Amount of hydrosilyl groups in the paint (mol/100g)] - [Amount of vinyl groups in the paint (mol/100g)]
（余剰ヒドロシリル基量）
本発明の塗料は、下記式で表される余剰ヒドロシリル基量が０．００１５ｍｏｌ／１００ｇを超える。
［余剰ヒドロシリル基量（ｍｏｌ／１００ｇ）］
＝［塗料中のヒドロシリル基の量（ｍｏｌ／１００ｇ）］－［塗料中のビニル基の量（ｍｏｌ／１００ｇ）］ [Characteristics of paint]
(Excess hydrosilyl group amount)
In the coating material of the present invention, the amount of surplus hydrosilyl groups represented by the following formula exceeds 0.0015 mol/100 g.
[Amount of surplus hydrosilyl group (mol/100g)]
= [Amount of hydrosilyl groups in the paint (mol/100g)] - [Amount of vinyl groups in the paint (mol/100g)]
（余剰ヒドロシリル基量の測定方法）
上記式における、塗料中のヒドロシリル基の量及び塗料中のビニル基の量は、例えば、ＮＭＲ（核磁気共鳴）測定による塗料の組成分析によって求めることができる。そして、塗料中のヒドロシリル基の量及び塗料中のビニル基の量から、余剰ヒドロシリル基量を求めることができる。 (Method for measuring excess hydrosilyl group amount)
In the above formula, the amount of hydrosilyl groups in the paint and the amount of vinyl groups in the paint can be determined, for example, by compositional analysis of the paint by NMR (nuclear magnetic resonance) measurement. Then, the amount of excess hydrosilyl groups can be determined from the amount of hydrosilyl groups in the paint and the amount of vinyl groups in the paint.
上記式における、塗料中のヒドロシリル基の量及び塗料中のビニル基の量は、例えば、ＮＭＲ（核磁気共鳴）測定による塗料の組成分析によって求めることができる。そして、塗料中のヒドロシリル基の量及び塗料中のビニル基の量から、余剰ヒドロシリル基量を求めることができる。 (Method for measuring excess hydrosilyl group amount)
In the above formula, the amount of hydrosilyl groups in the paint and the amount of vinyl groups in the paint can be determined, for example, by compositional analysis of the paint by NMR (nuclear magnetic resonance) measurement. Then, the amount of excess hydrosilyl groups can be determined from the amount of hydrosilyl groups in the paint and the amount of vinyl groups in the paint.
本発明における余剰ヒドロシリル基量は０．００１５ｍｏｌ／１００ｇを超え、好ましくは０．００３０ｍｏｌ／１００ｇを超え、より好ましくは０．００４５ｍｏｌ／１００ｇを超え、さらに好ましくは０．００６０ｍｏｌ／１００ｇを超える。また、本発明における余剰ヒドロシリル基量は、好ましくは０．１ｍｏｌ／１００ｇ以下であり、より好ましくは０．０７５ｍｏｌ／１００ｇ以下であり、さらに好ましくは０．０５ｍｏｌ／１００ｇ以下である。
The amount of surplus hydrosilyl groups in the present invention exceeds 0.0015 mol/100 g, preferably exceeds 0.0030 mol/100 g, more preferably exceeds 0.0045 mol/100 g, and even more preferably exceeds 0.0060 mol/100 g. Moreover, the amount of surplus hydrosilyl groups in the present invention is preferably 0.1 mol/100 g or less, more preferably 0.075 mol/100 g or less, and still more preferably 0.05 mol/100 g or less.
余剰ヒドロシリル基量が０．００１５ｍｏｌ／１００ｇ以下である場合には、塗料により形成された塗膜層の、基材等への密着性に劣る恐れがある。
If the amount of surplus hydrosilyl groups is 0.0015 mol/100 g or less, the adhesion of the coating layer formed from the paint to the substrate etc. may be poor.
＜塗膜層、積層体＞
本発明は、上記の塗料により形成された塗膜層に関する。また、本発明は、基材上に前記塗膜層が積層されてなる積層体にも関する。 <Coating film layer, laminate>
The present invention relates to a coating layer formed from the above-mentioned coating material. The present invention also relates to a laminate in which the coating layer is laminated on a base material.
本発明は、上記の塗料により形成された塗膜層に関する。また、本発明は、基材上に前記塗膜層が積層されてなる積層体にも関する。 <Coating film layer, laminate>
The present invention relates to a coating layer formed from the above-mentioned coating material. The present invention also relates to a laminate in which the coating layer is laminated on a base material.
［塗膜層の特徴］
（表面オイル量）
本発明の塗膜層は、下記の方法によって測定される表面オイル量は４０μｇ／ｃｍ２以上であることが好ましい。表面オイル量が４０μｇ／ｃｍ２以上であることにより、低温条件下において塗膜層からオイル成分が滲出され、着氷及び／又は着雪防止機能が向上するため好ましい。 [Characteristics of coating layer]
(Surface oil amount)
The coating layer of the present invention preferably has a surface oil amount of 40 μg/cm 2 or more as measured by the method described below. It is preferable that the surface oil amount is 40 μg/cm 2 or more because the oil component is oozed out from the coating layer under low temperature conditions and the icing and/or snow accretion prevention function is improved.
（表面オイル量）
本発明の塗膜層は、下記の方法によって測定される表面オイル量は４０μｇ／ｃｍ２以上であることが好ましい。表面オイル量が４０μｇ／ｃｍ２以上であることにより、低温条件下において塗膜層からオイル成分が滲出され、着氷及び／又は着雪防止機能が向上するため好ましい。 [Characteristics of coating layer]
(Surface oil amount)
The coating layer of the present invention preferably has a surface oil amount of 40 μg/cm 2 or more as measured by the method described below. It is preferable that the surface oil amount is 40 μg/cm 2 or more because the oil component is oozed out from the coating layer under low temperature conditions and the icing and/or snow accretion prevention function is improved.
（表面オイル量の測定方法）
前記塗膜層を－２０℃で１６時間放置し、前記塗膜層の表面にブリードしたオイル成分を、－２０℃の環境下においてセルスクレーパーで採取する。採取したオイル成分を油取り紙によって、油取り紙の質量変化が見られなくなるまで吸い取る。
セルスクレーパーによるオイル採取と油取り紙による吸い取りは、１分間に７回繰り返す。オイル吸い取り前後の油取り紙の質量差を表面オイル量とする。表面オイル量の測定は３回行い、その平均値を採用する。 (Method of measuring surface oil amount)
The coating layer is left at -20°C for 16 hours, and the oil component that bleeds onto the surface of the coating layer is collected using a cell scraper in an environment of -20°C. The collected oil component is absorbed using oil-absorbing paper until no change in the mass of the oil-absorbing paper is observed.
Oil collection with a cell scraper and blotting with oil-blotting paper are repeated 7 times per minute. The difference in mass between the oil-blotting paper before and after oil-blotting is defined as the amount of surface oil. The amount of surface oil is measured three times and the average value is used.
前記塗膜層を－２０℃で１６時間放置し、前記塗膜層の表面にブリードしたオイル成分を、－２０℃の環境下においてセルスクレーパーで採取する。採取したオイル成分を油取り紙によって、油取り紙の質量変化が見られなくなるまで吸い取る。
セルスクレーパーによるオイル採取と油取り紙による吸い取りは、１分間に７回繰り返す。オイル吸い取り前後の油取り紙の質量差を表面オイル量とする。表面オイル量の測定は３回行い、その平均値を採用する。 (Method of measuring surface oil amount)
The coating layer is left at -20°C for 16 hours, and the oil component that bleeds onto the surface of the coating layer is collected using a cell scraper in an environment of -20°C. The collected oil component is absorbed using oil-absorbing paper until no change in the mass of the oil-absorbing paper is observed.
Oil collection with a cell scraper and blotting with oil-blotting paper are repeated 7 times per minute. The difference in mass between the oil-blotting paper before and after oil-blotting is defined as the amount of surface oil. The amount of surface oil is measured three times and the average value is used.
（ＰＥＴ密着性）
密着（付着）性の評価は、ＪＩＳ Ｋ－５６００－５－６（塗膜の機械的特性 付着性）を参考に実施した。
具体的には、クロスカット試験カッターガイド（商品名「スーパーカッターガイド」、太佑機材株式会社製）、カッター、ポリイミド粘着テープ（ＮＯ．３６０ＵＬ、厚み０．０６ｍｍ×幅５０ｍｍ、日東電工株式会社製）を準備した。ポリイミド粘着テープにはシリコーン粘着剤が使用されており、シリコーン層と密着性が高いため選択した。 (PET adhesion)
Evaluation of adhesion (adhesion) was carried out with reference to JIS K-5600-5-6 (mechanical properties of coating film, adhesion).
Specifically, the cross-cut test cutter guide (product name "Super Cutter Guide", manufactured by Taiyu Kizai Co., Ltd.), cutter, polyimide adhesive tape (NO. 360UL, thickness 0.06 mm x width 50 mm, manufactured by Nitto Denko Co., Ltd.) prepared. Polyimide adhesive tape uses silicone adhesive and was selected because it has high adhesion to the silicone layer.
密着（付着）性の評価は、ＪＩＳ Ｋ－５６００－５－６（塗膜の機械的特性 付着性）を参考に実施した。
具体的には、クロスカット試験カッターガイド（商品名「スーパーカッターガイド」、太佑機材株式会社製）、カッター、ポリイミド粘着テープ（ＮＯ．３６０ＵＬ、厚み０．０６ｍｍ×幅５０ｍｍ、日東電工株式会社製）を準備した。ポリイミド粘着テープにはシリコーン粘着剤が使用されており、シリコーン層と密着性が高いため選択した。 (PET adhesion)
Evaluation of adhesion (adhesion) was carried out with reference to JIS K-5600-5-6 (mechanical properties of coating film, adhesion).
Specifically, the cross-cut test cutter guide (product name "Super Cutter Guide", manufactured by Taiyu Kizai Co., Ltd.), cutter, polyimide adhesive tape (NO. 360UL, thickness 0.06 mm x width 50 mm, manufactured by Nitto Denko Co., Ltd.) prepared. Polyimide adhesive tape uses silicone adhesive and was selected because it has high adhesion to the silicone layer.
得られた積層体をクロスカット試験カッターガイドを用いて、積層体のみに塗膜に対して垂直にカッターで４ｍｍ間隔で６本切込みを入れた。その後、方向を９０°変えて先ほどの切込みに直行するように６本切込みを入れた（計２５マス）。
Using a cross-cut test cutter guide for the obtained laminate, six cuts were made perpendicular to the coating film only in the laminate with a cutter at 4 mm intervals. After that, the direction was changed by 90 degrees and six cuts were made perpendicular to the previous cuts (total of 25 squares).
長さ約７５ｍｍにカットした透明付着テープを格子にカットした部分に張り付け、指でしっかりこすりつけ張り付けた。より詳細には、格子の部分にかかった個所と最低２０ｍｍを超える長さで、指でテープを平らになるようにこすった。テープが塗膜に正しく接触しているかを、テープを通してみられる塗膜の色で判断した。
A transparent adhesive tape cut to a length of about 75 mm was pasted on the grid-cut area, and firmly rubbed with fingers to stick it. More specifically, the tape was rubbed flat with a finger at the area where it covered the grid and at least over a length exceeding 20 mm. Whether the tape was in proper contact with the paint film was determined by the color of the paint film seen through the tape.
テープを付着させてから５分以内にテープの端をつかみ、６０°に近い角度で０．５～１秒で確実に引き離した。密着性評価は、ＪＩＳ Ｋ５６００－５－６に従い、０～５分類の６段階で評価を行った。
Within 5 minutes of applying the tape, I grabbed the edge of the tape and pulled it off securely in 0.5-1 seconds at an angle close to 60°. Adhesion was evaluated in accordance with JIS K5600-5-6 in six grades from 0 to 5.
（着氷力）
本発明の塗膜層の下記の方法によって測定される着氷力は０．７Ｎ／ｃｍ２以下であることが好ましい。 (Icing power)
The coating layer of the present invention preferably has an icing force of 0.7 N/cm 2 or less as measured by the method below.
本発明の塗膜層の下記の方法によって測定される着氷力は０．７Ｎ／ｃｍ２以下であることが好ましい。 (Icing power)
The coating layer of the present invention preferably has an icing force of 0.7 N/cm 2 or less as measured by the method below.
（着氷力の測定方法）
ステンレス平板に、前記塗膜層が表面となるように前記塗膜層を貼着し、－２０℃環境に１６時間静置する。重さ６ｇ、付着面積４．９ｃｍ２とした円柱状の氷塊を準備し、氷塊の底面を１０℃恒温の表面に１０秒間接触させ、前記塗膜層上に付着させる。
環境温度－２０℃に設定し、氷塊を付着させてから３時間後に、－２０℃の環境下において、床面に対して平行な方向から氷塊をロードセルで、速度０．１ｍｍ／秒で押し、４０秒の間に加わった荷重をフォースゲージで測定する。測定された最大荷重を付着面積４．９ｃｍ２で除算した値を着氷力とする。着氷力の測定は３回行い、その平均値を採用する。 (Measurement method of icing force)
The coating layer was attached to a stainless steel flat plate so that the coating layer was on the surface, and the plate was left standing in a -20°C environment for 16 hours. A cylindrical block of ice having a weight of 6 g and an adhesion area of 4.9 cm 2 is prepared, and the bottom surface of the block of ice is brought into contact with a surface kept at a constant temperature of 10° C. for 10 seconds to adhere to the coating layer.
The environmental temperature was set to -20°C, and 3 hours after the ice block was attached, the ice block was pushed at a speed of 0.1 mm/sec with a load cell from a direction parallel to the floor surface in an environment of -20°C. The load applied during 40 seconds is measured with a force gauge. The value obtained by dividing the measured maximum load by the adhesion area of 4.9 cm 2 is defined as the icing force. The icing force was measured three times and the average value was used.
ステンレス平板に、前記塗膜層が表面となるように前記塗膜層を貼着し、－２０℃環境に１６時間静置する。重さ６ｇ、付着面積４．９ｃｍ２とした円柱状の氷塊を準備し、氷塊の底面を１０℃恒温の表面に１０秒間接触させ、前記塗膜層上に付着させる。
環境温度－２０℃に設定し、氷塊を付着させてから３時間後に、－２０℃の環境下において、床面に対して平行な方向から氷塊をロードセルで、速度０．１ｍｍ／秒で押し、４０秒の間に加わった荷重をフォースゲージで測定する。測定された最大荷重を付着面積４．９ｃｍ２で除算した値を着氷力とする。着氷力の測定は３回行い、その平均値を採用する。 (Measurement method of icing force)
The coating layer was attached to a stainless steel flat plate so that the coating layer was on the surface, and the plate was left standing in a -20°C environment for 16 hours. A cylindrical block of ice having a weight of 6 g and an adhesion area of 4.9 cm 2 is prepared, and the bottom surface of the block of ice is brought into contact with a surface kept at a constant temperature of 10° C. for 10 seconds to adhere to the coating layer.
The environmental temperature was set to -20°C, and 3 hours after the ice block was attached, the ice block was pushed at a speed of 0.1 mm/sec with a load cell from a direction parallel to the floor surface in an environment of -20°C. The load applied during 40 seconds is measured with a force gauge. The value obtained by dividing the measured maximum load by the adhesion area of 4.9 cm 2 is defined as the icing force. The icing force was measured three times and the average value was used.
なお、上述の「１０℃恒温の表面」とは、例えばペルチェ素子で温度変化できる装置の表面のことであり、氷塊の底面を一部融解させるために用いられる。
Note that the above-mentioned "10° C. constant temperature surface" refers to the surface of a device whose temperature can be changed using, for example, a Peltier element, and is used to partially melt the bottom of the ice block.
当該着氷力が０．７Ｎ／ｃｍ２以下であれば、優れた着氷及び／又は着雪防止機能を発揮できる。当該着氷力は、より好ましくは０．６Ｎ／ｃｍ２以下、さらに好ましくは０．５Ｎ／ｃｍ２以下である。また、当該着氷力は小さいほど好ましいが、例えば、０．２Ｎ／ｃｍ２以上であってもよく、０．４Ｎ／ｃｍ２以上であってもよい。
If the icing force is 0.7 N/cm 2 or less, excellent icing and/or snow accretion prevention function can be exhibited. The icing force is more preferably 0.6 N/cm 2 or less, still more preferably 0.5 N/cm 2 or less. Further, the icing force is preferably as small as possible, but may be, for example, 0.2 N/cm 2 or more, or 0.4 N/cm 2 or more.
（塗膜層の好ましい特徴）
また、本発明の塗膜層の別の実施形態は、樹脂成分及びオイル成分を含有する塗料により形成された塗膜層であって、塗膜層の上記方法によって測定されるＰＥＴ密着性は、ＪＩＳ Ｋ５６００－５－６に従う６段階の評価のうち、０～１分類であることが好ましい。 (Preferred characteristics of coating layer)
Another embodiment of the coating layer of the present invention is a coating layer formed of a coating material containing a resin component and an oil component, and the PET adhesion of the coating layer measured by the above method is: Of the six grades of evaluation according to JIS K5600-5-6, a rating of 0 to 1 is preferable.
また、本発明の塗膜層の別の実施形態は、樹脂成分及びオイル成分を含有する塗料により形成された塗膜層であって、塗膜層の上記方法によって測定されるＰＥＴ密着性は、ＪＩＳ Ｋ５６００－５－６に従う６段階の評価のうち、０～１分類であることが好ましい。 (Preferred characteristics of coating layer)
Another embodiment of the coating layer of the present invention is a coating layer formed of a coating material containing a resin component and an oil component, and the PET adhesion of the coating layer measured by the above method is: Of the six grades of evaluation according to JIS K5600-5-6, a rating of 0 to 1 is preferable.
［塗膜層及び積層体の製造方法］
塗膜層を得るには、例えば図１に示すように、本発明の塗料を基材１０に塗装することによって第１塗膜層１１を得ることができる。すなわち、基材１０と第１塗膜層１１とを含む積層体を得ることができる。
本発明の塗料の塗装方法としては、ハケ塗り、スプレー塗装、各種コーター塗装などの一般的な方法を用いることができる。塗装は、通常１～２回行われる。また、本発明の塗料により形成された塗膜層の基材１０への接着力向上や基材１０の錆び止めなどのために、基材１０にプライマーを塗装し、プライマーの上から本発明の塗料を塗装してもよい。 [Method for manufacturing coating layer and laminate]
To obtain the coating layer, for example, as shown in FIG. 1, afirst coating layer 11 can be obtained by coating a base material 10 with the paint of the present invention. That is, a laminate including the base material 10 and the first coating layer 11 can be obtained.
As a method for applying the paint of the present invention, general methods such as brush painting, spray painting, and various types of coater painting can be used. Painting is usually done once or twice. Further, in order to improve the adhesion of the coating layer formed by the paint of the present invention to thebase material 10 and to prevent the base material 10 from rusting, a primer is applied to the base material 10, and the paint of the present invention is applied over the primer. You may also apply paint.
塗膜層を得るには、例えば図１に示すように、本発明の塗料を基材１０に塗装することによって第１塗膜層１１を得ることができる。すなわち、基材１０と第１塗膜層１１とを含む積層体を得ることができる。
本発明の塗料の塗装方法としては、ハケ塗り、スプレー塗装、各種コーター塗装などの一般的な方法を用いることができる。塗装は、通常１～２回行われる。また、本発明の塗料により形成された塗膜層の基材１０への接着力向上や基材１０の錆び止めなどのために、基材１０にプライマーを塗装し、プライマーの上から本発明の塗料を塗装してもよい。 [Method for manufacturing coating layer and laminate]
To obtain the coating layer, for example, as shown in FIG. 1, a
As a method for applying the paint of the present invention, general methods such as brush painting, spray painting, and various types of coater painting can be used. Painting is usually done once or twice. Further, in order to improve the adhesion of the coating layer formed by the paint of the present invention to the
第１塗膜層１１の厚みは、特に限定されないが、乾燥後の塗膜の品質の観点から、２０００μｍ以下が好ましく、また、強度の点から、５０μｍ以上が好ましい。
The thickness of the first coating layer 11 is not particularly limited, but from the viewpoint of the quality of the coating film after drying, it is preferably 2000 μm or less, and from the viewpoint of strength, it is preferably 50 μm or more.
本発明で用いる基材１０としては、例えば、ポリウレタン樹脂、ポリウレタンアクリル樹脂、ゴム系樹脂、塩化ビニル樹脂、ポリエチレンテレフタレート（ＰＥＴ）樹脂等のポリエステル樹脂、ポリカーボネート（ＰＣ）樹脂、シリコーン樹脂、エラストマー類、フッ素樹脂、ポリアミド樹脂、ポリオレフィン樹脂（ポリエチレン、ポリプロピレン等）、金属板若しくは金属箔（アルミニウム、銅、銀、鉄、ニッケル、スズ、ステンレス等）、コンクリート、セラミックス等の基材を用いることができる。これらのうち、原料費または耐久性の観点から、基材１０が、ポリエステル樹脂、ポリアミド樹脂、ポリカーボネート樹脂及び金属から選択されるいずれか１種を含む基材であることが好ましい。前記ポリエステル樹脂としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリアミド樹脂としてナイロン６、ナイロン６６、ポリフタルアミドなどが挙げられる。前記金属としては、ステンレス、アルミニウム、鉄などが挙げられる。
また、基材１０はフィルム状やシート状でもよい。 Examples of thebase material 10 used in the present invention include polyurethane resins, polyurethane acrylic resins, rubber resins, vinyl chloride resins, polyester resins such as polyethylene terephthalate (PET) resins, polycarbonate (PC) resins, silicone resins, elastomers, Base materials such as fluororesin, polyamide resin, polyolefin resin (polyethylene, polypropylene, etc.), metal plate or metal foil (aluminum, copper, silver, iron, nickel, tin, stainless steel, etc.), concrete, ceramics, etc. can be used. Among these, from the viewpoint of raw material cost or durability, the base material 10 is preferably a base material containing any one selected from polyester resin, polyamide resin, polycarbonate resin, and metal. Examples of the polyester resin include polyethylene terephthalate and polybutylene terephthalate, and examples of the polyamide resin include nylon 6, nylon 66, and polyphthalamide. Examples of the metal include stainless steel, aluminum, and iron.
Further, thebase material 10 may be in the form of a film or a sheet.
また、基材１０はフィルム状やシート状でもよい。 Examples of the
Further, the
本発明の塗料を基材１０に塗装した後は、例えば２０～１８０℃の環境下で、例えば３分～３時間静置することによって、塗料を硬化又は乾燥させることができる。
After the paint of the present invention is applied to the substrate 10, the paint can be cured or dried by allowing it to stand, for example, for 3 minutes to 3 hours in an environment of 20 to 180°C.
なお、例えば図２に示すように、本発明の塗料から得られる第１塗膜層１１の上に、必要に応じて上塗塗料を塗装して、第２塗膜層１２を形成することができる。すなわち、基材１０と第１塗膜層１１と第２塗膜層１２とを含む積層体を得ることができる。
上塗塗料としては、特に制限はなく、例えば、本発明の塗料と同様のものを使用することができるが、上塗塗料はオイル成分を含有しなくてもよい。 For example, as shown in FIG. 2, a top coat can be applied as necessary on thefirst coating layer 11 obtained from the paint of the present invention to form a second coating layer 12. . That is, a laminate including the base material 10, the first coating layer 11, and the second coating layer 12 can be obtained.
There are no particular limitations on the top coat, and for example, the same paint as the paint of the present invention can be used, but the top coat does not need to contain an oil component.
上塗塗料としては、特に制限はなく、例えば、本発明の塗料と同様のものを使用することができるが、上塗塗料はオイル成分を含有しなくてもよい。 For example, as shown in FIG. 2, a top coat can be applied as necessary on the
There are no particular limitations on the top coat, and for example, the same paint as the paint of the present invention can be used, but the top coat does not need to contain an oil component.
上塗塗料の塗装方法としては、ハケ塗り、スプレー塗装、各種コーター塗装などの一般的な方法を用いることができる。塗装は、通常１～２回行われる。
As a method for applying the top coat, general methods such as brush painting, spray painting, and various coater coatings can be used. Painting is usually done once or twice.
第２塗膜層１２の厚みは、特に限定されないが、オイル成分が塗膜層の表面まで容易に透過することができるように、言い換えれば、第２塗膜層１２に対するオイル透過性を担保するため、５００μｍ以下が好ましく、また、強度の点から、５０μｍ以上が好ましい。
The thickness of the second coating layer 12 is not particularly limited, but should be such that the oil component can easily permeate to the surface of the coating layer, in other words, ensuring oil permeability to the second coating layer 12. Therefore, it is preferably 500 μm or less, and from the viewpoint of strength, it is preferably 50 μm or more.
上塗塗料を、第１塗膜層１１に塗装する際の硬化又は乾燥温度及び硬化又は乾燥時間は、本発明の塗料を、基材１０に塗装する際の硬化又は乾燥温度及び硬化又は乾燥時間と同様である。
なお、本発明の塗料の硬化又は乾燥と上塗塗料の硬化又は乾燥は、同時に行ってもよいし、別々に行ってもよい。 The curing or drying temperature and curing or drying time when applying the top coat to thefirst coating layer 11 are the same as the curing or drying temperature and curing or drying time when applying the coating of the present invention to the base material 10. The same is true.
The curing or drying of the paint of the present invention and the curing or drying of the top coat may be performed simultaneously or separately.
なお、本発明の塗料の硬化又は乾燥と上塗塗料の硬化又は乾燥は、同時に行ってもよいし、別々に行ってもよい。 The curing or drying temperature and curing or drying time when applying the top coat to the
The curing or drying of the paint of the present invention and the curing or drying of the top coat may be performed simultaneously or separately.
以上説明したように、本明細書には次の事項が開示されている。
＜１＞
ヒドロシリル基及びビニル基を有する樹脂成分と、オイル成分とを含み、
下記式で表される余剰ヒドロシリル基量が０．００１５ｍｏｌ／１００ｇを超え、
シランカップリング剤を含む、塗料。
［余剰ヒドロシリル基量（ｍｏｌ／１００ｇ）］
＝［塗料中のヒドロシリル基の量（ｍｏｌ／１００ｇ）］－［塗料中のビニル基の量（ｍｏｌ／１００ｇ）］
＜２＞
前記オイル成分が親水性基を有する、＜１＞に記載の塗料。
＜３＞
前記親水性基が、カルビノール基、ヒドロキシ基、カルボキシ基、無水カルボン酸基、アミノ基、スルホ基、エーテル基、エポキシ基、メルカプト基、チオール基及びエステル基からなる群から選択される少なくとも１種の基である、＜２＞に記載の塗料。
＜４＞
＜１＞～＜３＞のいずれか１つに記載の塗料により形成された、塗膜層。
＜５＞
基材上に＜４＞に記載の塗膜層が積層されてなる、積層体。
＜６＞
前記基材が、ポリエステル樹脂、ポリアミド樹脂、ポリカーボネート樹脂及び金属から選択されるいずれか１種を含む、＜５＞に記載の積層体。 As explained above, the following matters are disclosed in this specification.
<1>
Contains a resin component having a hydrosilyl group and a vinyl group, and an oil component,
The amount of excess hydrosilyl group represented by the following formula exceeds 0.0015 mol/100 g,
Paints containing silane coupling agents.
[Amount of surplus hydrosilyl group (mol/100g)]
= [Amount of hydrosilyl groups in the paint (mol/100g)] - [Amount of vinyl groups in the paint (mol/100g)]
<2>
The paint according to <1>, wherein the oil component has a hydrophilic group.
<3>
The hydrophilic group is at least one selected from the group consisting of a carbinol group, a hydroxy group, a carboxy group, a carboxylic anhydride group, an amino group, a sulfo group, an ether group, an epoxy group, a mercapto group, a thiol group, and an ester group. The paint according to <2>, which is a seed group.
<4>
A coating layer formed from the paint according to any one of <1> to <3>.
<5>
A laminate in which the coating layer described in <4> is laminated on a base material.
<6>
The laminate according to <5>, wherein the base material includes any one selected from polyester resin, polyamide resin, polycarbonate resin, and metal.
＜１＞
ヒドロシリル基及びビニル基を有する樹脂成分と、オイル成分とを含み、
下記式で表される余剰ヒドロシリル基量が０．００１５ｍｏｌ／１００ｇを超え、
シランカップリング剤を含む、塗料。
［余剰ヒドロシリル基量（ｍｏｌ／１００ｇ）］
＝［塗料中のヒドロシリル基の量（ｍｏｌ／１００ｇ）］－［塗料中のビニル基の量（ｍｏｌ／１００ｇ）］
＜２＞
前記オイル成分が親水性基を有する、＜１＞に記載の塗料。
＜３＞
前記親水性基が、カルビノール基、ヒドロキシ基、カルボキシ基、無水カルボン酸基、アミノ基、スルホ基、エーテル基、エポキシ基、メルカプト基、チオール基及びエステル基からなる群から選択される少なくとも１種の基である、＜２＞に記載の塗料。
＜４＞
＜１＞～＜３＞のいずれか１つに記載の塗料により形成された、塗膜層。
＜５＞
基材上に＜４＞に記載の塗膜層が積層されてなる、積層体。
＜６＞
前記基材が、ポリエステル樹脂、ポリアミド樹脂、ポリカーボネート樹脂及び金属から選択されるいずれか１種を含む、＜５＞に記載の積層体。 As explained above, the following matters are disclosed in this specification.
<1>
Contains a resin component having a hydrosilyl group and a vinyl group, and an oil component,
The amount of excess hydrosilyl group represented by the following formula exceeds 0.0015 mol/100 g,
Paints containing silane coupling agents.
[Amount of surplus hydrosilyl group (mol/100g)]
= [Amount of hydrosilyl groups in the paint (mol/100g)] - [Amount of vinyl groups in the paint (mol/100g)]
<2>
The paint according to <1>, wherein the oil component has a hydrophilic group.
<3>
The hydrophilic group is at least one selected from the group consisting of a carbinol group, a hydroxy group, a carboxy group, a carboxylic anhydride group, an amino group, a sulfo group, an ether group, an epoxy group, a mercapto group, a thiol group, and an ester group. The paint according to <2>, which is a seed group.
<4>
A coating layer formed from the paint according to any one of <1> to <3>.
<5>
A laminate in which the coating layer described in <4> is laminated on a base material.
<6>
The laminate according to <5>, wherein the base material includes any one selected from polyester resin, polyamide resin, polycarbonate resin, and metal.
以下、実施例等を挙げて本発明をより具体的に説明するが、本発明は以下の実施例に何ら限定されるものではない。
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
［実施例１］
＜塗料の作製＞
塗料成分として、樹脂：ＫＥ－２０９８－６０、第１オイル成分（非相溶オイル）：ＫＦ－６００３を用意した。なお、実施例において、オイル成分のうち最も含有量が多い成分を第１オイル成分、次に多い成分を第２オイル成分とする。樹脂成分ＫＥ－２０９８－６０は、ＫＥ－２０９８－６０ＡとＫＥ－２０９８－６０Ｂを質量比１：１で混合したものである。 [Example 1]
<Preparation of paint>
As paint components, resin: KE-2098-60 and first oil component (incompatible oil): KF-6003 were prepared. In the examples, the component with the highest content among the oil components is referred to as the first oil component, and the component with the second highest content is referred to as the second oil component. The resin component KE-2098-60 is a mixture of KE-2098-60A and KE-2098-60B at a mass ratio of 1:1.
＜塗料の作製＞
塗料成分として、樹脂：ＫＥ－２０９８－６０、第１オイル成分（非相溶オイル）：ＫＦ－６００３を用意した。なお、実施例において、オイル成分のうち最も含有量が多い成分を第１オイル成分、次に多い成分を第２オイル成分とする。樹脂成分ＫＥ－２０９８－６０は、ＫＥ－２０９８－６０ＡとＫＥ－２０９８－６０Ｂを質量比１：１で混合したものである。 [Example 1]
<Preparation of paint>
As paint components, resin: KE-2098-60 and first oil component (incompatible oil): KF-6003 were prepared. In the examples, the component with the highest content among the oil components is referred to as the first oil component, and the component with the second highest content is referred to as the second oil component. The resin component KE-2098-60 is a mixture of KE-2098-60A and KE-2098-60B at a mass ratio of 1:1.
各成分の詳細は、下記のとおりである。
・ＫＥ－２０９８－６０：シリコーン樹脂、信越化学工業株式会社製；１００質量％のＫＥ－２０９８－６０中、シランカップリング剤（３－イソシアネートプロピルトリエトキシシラン）を０．５質量％含む；余剰ヒドロシリル基量＝０．０１７４ｍоｌ／１００ｇ、ビニル基の量＝０．００８９ｍоｌ／１００ｇ、ヒドロシリル基の量＝０．０２６３ｍоｌ／１００ｇ
・ＫＦ－６００３：カルビノール変性シリコーンオイル、信越化学工業株式会社製 Details of each component are as follows.
・KE-2098-60: Silicone resin, manufactured by Shin-Etsu Chemical Co., Ltd.; Contains 0.5% by mass of a silane coupling agent (3-isocyanatepropyltriethoxysilane) in 100% by mass of KE-2098-60; surplus Amount of hydrosilyl group = 0.0174mol/100g, amount of vinyl group = 0.0089mol/100g, amount of hydrosilyl group = 0.0263mol/100g
・KF-6003: Carbinol-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.
・ＫＥ－２０９８－６０：シリコーン樹脂、信越化学工業株式会社製；１００質量％のＫＥ－２０９８－６０中、シランカップリング剤（３－イソシアネートプロピルトリエトキシシラン）を０．５質量％含む；余剰ヒドロシリル基量＝０．０１７４ｍоｌ／１００ｇ、ビニル基の量＝０．００８９ｍоｌ／１００ｇ、ヒドロシリル基の量＝０．０２６３ｍоｌ／１００ｇ
・ＫＦ－６００３：カルビノール変性シリコーンオイル、信越化学工業株式会社製 Details of each component are as follows.
・KE-2098-60: Silicone resin, manufactured by Shin-Etsu Chemical Co., Ltd.; Contains 0.5% by mass of a silane coupling agent (3-isocyanatepropyltriethoxysilane) in 100% by mass of KE-2098-60; surplus Amount of hydrosilyl group = 0.0174mol/100g, amount of vinyl group = 0.0089mol/100g, amount of hydrosilyl group = 0.0263mol/100g
・KF-6003: Carbinol-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.
樹脂（４２質量部）、第１オイル成分（５８質量部）を、２５℃、１０１ｋＰａの条件下で混合した。得られた混合液をスパチュラで６０秒間撹拌し、自転・公転ミキサー（シンキー社製、ＣＯＮＤＩＴＩＯＮＩＮＧ ＭＩＸＥＲ ＡＲ－２５０）でさらに１２０秒間の撹拌と３００秒間の脱泡をし、塗料を得た。
The resin (42 parts by mass) and the first oil component (58 parts by mass) were mixed under conditions of 25° C. and 101 kPa. The resulting mixed solution was stirred for 60 seconds with a spatula, and further stirred for 120 seconds and defoamed for 300 seconds using a rotation/revolution mixer (CONDITIONING MIXER AR-250, manufactured by Shinky Co., Ltd.) to obtain a paint.
＜塗膜層の形成＞
得られた塗料を、ＰＥＴフィルム（東レ株式会社製 ルミラー＃７５Ｓ１０）上に塗布し、１５０℃環境下において１０分、加熱硬化させることによって厚さ約２５０μｍの塗膜層を形成した。 <Formation of coating layer>
The obtained coating material was applied onto a PET film (Lumirror #75S10 manufactured by Toray Industries, Inc.) and cured by heating in a 150° C. environment for 10 minutes to form a coating layer with a thickness of about 250 μm.
得られた塗料を、ＰＥＴフィルム（東レ株式会社製 ルミラー＃７５Ｓ１０）上に塗布し、１５０℃環境下において１０分、加熱硬化させることによって厚さ約２５０μｍの塗膜層を形成した。 <Formation of coating layer>
The obtained coating material was applied onto a PET film (Lumirror #75S10 manufactured by Toray Industries, Inc.) and cured by heating in a 150° C. environment for 10 minutes to form a coating layer with a thickness of about 250 μm.
［実施例２～４、比較例１～３］
塗料成分及びその含有量を表１に記載のとおりとした以外は、実施例１に記載の方法に準じて、塗料及び塗膜層を得た。 [Examples 2 to 4, Comparative Examples 1 to 3]
A paint and a coating layer were obtained according to the method described in Example 1, except that the paint components and their contents were as shown in Table 1.
塗料成分及びその含有量を表１に記載のとおりとした以外は、実施例１に記載の方法に準じて、塗料及び塗膜層を得た。 [Examples 2 to 4, Comparative Examples 1 to 3]
A paint and a coating layer were obtained according to the method described in Example 1, except that the paint components and their contents were as shown in Table 1.
表１に記載の各成分の詳細は、下記のとおりである。樹脂成分ＫＥ－１９５０－５０は、ＫＥ－１９５０－５０ＡとＫＥ－１９５０－５０Ｂを質量比１：１で混合したものである。
・ＫＥ－１９５０－５０：シリコーン樹脂、信越化学工業株式会社製；シランカップリング剤なし；余剰ヒドロシリル基量＝０．００２１ｍоｌ／１００ｇ、ビニル基の量＝０．００８３ｍоｌ／１００ｇ、ヒドロシリル基の量＝０．０１０４ｍоｌ／１００ｇ
・ＫＦ－９９０１：ハイドロジェンシリコーン、信越化学工業株式会社製；シランカップリング剤なし；余剰ヒドロシリル基量＝０．７１４３ｍоｌ／１００ｇ、ビニル基の量＝０ｍоｌ／１００ｇ、ヒドロシリル基の量＝０．７１４３ｍоｌ／１００ｇ
・ＢＹ１６－２０１：カルビノール変性シリコーンオイル、東レダウコーニング株式会社製
・ＫＦ－９６（５０ｃｓ）：ジメチルシロキサンオイル、信越化学工業株式会社製
・３－イソシアネートプロピルトリエトキシシラン：シランカップリング剤、信越化学工業株式会社製 Details of each component listed in Table 1 are as follows. The resin component KE-1950-50 is a mixture of KE-1950-50A and KE-1950-50B at a mass ratio of 1:1.
・KE-1950-50: silicone resin, manufactured by Shin-Etsu Chemical Co., Ltd.; no silane coupling agent; amount of surplus hydrosilyl groups = 0.0021 mol/100 g, amount of vinyl groups = 0.0083 mol/100 g, amount of hydrosilyl groups = 0.0104mol/100g
・KF-9901: Hydrogen silicone, manufactured by Shin-Etsu Chemical Co., Ltd.; No silane coupling agent; Excess hydrosilyl group amount = 0.7143 mol/100 g, vinyl group amount = 0 mol/100 g, hydrosilyl group amount = 0.7143 mol /100g
・BY16-201: Carbinol-modified silicone oil, Dow Corning Toray Co., Ltd. ・KF-96 (50cs): Dimethylsiloxane oil, Shin-Etsu Chemical Co., Ltd. ・3-Isocyanatepropyltriethoxysilane: Silane coupling agent, Shin-Etsu Manufactured by Kagaku Kogyo Co., Ltd.
・ＫＥ－１９５０－５０：シリコーン樹脂、信越化学工業株式会社製；シランカップリング剤なし；余剰ヒドロシリル基量＝０．００２１ｍоｌ／１００ｇ、ビニル基の量＝０．００８３ｍоｌ／１００ｇ、ヒドロシリル基の量＝０．０１０４ｍоｌ／１００ｇ
・ＫＦ－９９０１：ハイドロジェンシリコーン、信越化学工業株式会社製；シランカップリング剤なし；余剰ヒドロシリル基量＝０．７１４３ｍоｌ／１００ｇ、ビニル基の量＝０ｍоｌ／１００ｇ、ヒドロシリル基の量＝０．７１４３ｍоｌ／１００ｇ
・ＢＹ１６－２０１：カルビノール変性シリコーンオイル、東レダウコーニング株式会社製
・ＫＦ－９６（５０ｃｓ）：ジメチルシロキサンオイル、信越化学工業株式会社製
・３－イソシアネートプロピルトリエトキシシラン：シランカップリング剤、信越化学工業株式会社製 Details of each component listed in Table 1 are as follows. The resin component KE-1950-50 is a mixture of KE-1950-50A and KE-1950-50B at a mass ratio of 1:1.
・KE-1950-50: silicone resin, manufactured by Shin-Etsu Chemical Co., Ltd.; no silane coupling agent; amount of surplus hydrosilyl groups = 0.0021 mol/100 g, amount of vinyl groups = 0.0083 mol/100 g, amount of hydrosilyl groups = 0.0104mol/100g
・KF-9901: Hydrogen silicone, manufactured by Shin-Etsu Chemical Co., Ltd.; No silane coupling agent; Excess hydrosilyl group amount = 0.7143 mol/100 g, vinyl group amount = 0 mol/100 g, hydrosilyl group amount = 0.7143 mol /100g
・BY16-201: Carbinol-modified silicone oil, Dow Corning Toray Co., Ltd. ・KF-96 (50cs): Dimethylsiloxane oil, Shin-Etsu Chemical Co., Ltd. ・3-Isocyanatepropyltriethoxysilane: Silane coupling agent, Shin-Etsu Manufactured by Kagaku Kogyo Co., Ltd.
＜測定＞
（余剰ヒドロシリル基量）
余剰ヒドロシリル基量（ｍｏｌ／１００ｇ）とは、塗料中のヒドロシリル基の量（ｍｏｌ／１００ｇ）から塗料中のビニル基の量（ｍｏｌ／１００ｇ）を差し引いた量のことである。下記測定条件のＮＭＲにて塗料の組成分析を行い、塗料中のヒドロシリル基の量（ｍｏｌ／１００ｇ）と塗料中のビニル基の量（ｍｏｌ／１００ｇ）を定量し、余剰ヒドロシリル基量（ｍｏｌ／１００ｇ）を下記式にて算出した。結果を表１に示す。 <Measurement>
(Excess hydrosilyl group amount)
The amount of surplus hydrosilyl groups (mol/100g) is the amount obtained by subtracting the amount of vinyl groups in the paint (mol/100g) from the amount of hydrosilyl groups in the paint (mol/100g). The composition of the paint was analyzed by NMR under the following measurement conditions, the amount of hydrosilyl groups in the paint (mol/100g) and the amount of vinyl groups in the paint (mol/100g) were determined, and the amount of excess hydrosilyl groups (mol/100g) was determined. 100g) was calculated using the following formula. The results are shown in Table 1.
（余剰ヒドロシリル基量）
余剰ヒドロシリル基量（ｍｏｌ／１００ｇ）とは、塗料中のヒドロシリル基の量（ｍｏｌ／１００ｇ）から塗料中のビニル基の量（ｍｏｌ／１００ｇ）を差し引いた量のことである。下記測定条件のＮＭＲにて塗料の組成分析を行い、塗料中のヒドロシリル基の量（ｍｏｌ／１００ｇ）と塗料中のビニル基の量（ｍｏｌ／１００ｇ）を定量し、余剰ヒドロシリル基量（ｍｏｌ／１００ｇ）を下記式にて算出した。結果を表１に示す。 <Measurement>
(Excess hydrosilyl group amount)
The amount of surplus hydrosilyl groups (mol/100g) is the amount obtained by subtracting the amount of vinyl groups in the paint (mol/100g) from the amount of hydrosilyl groups in the paint (mol/100g). The composition of the paint was analyzed by NMR under the following measurement conditions, the amount of hydrosilyl groups in the paint (mol/100g) and the amount of vinyl groups in the paint (mol/100g) were determined, and the amount of excess hydrosilyl groups (mol/100g) was determined. 100g) was calculated using the following formula. The results are shown in Table 1.
［余剰ヒドロシリル基量（ｍｏｌ／１００ｇ）］
＝［塗料中のヒドロシリル基の量（ｍｏｌ／１００ｇ）］－［塗料中のビニル基の量（ｍｏｌ／１００ｇ）］ [Amount of surplus hydrosilyl group (mol/100g)]
= [Amount of hydrosilyl groups in the paint (mol/100g)] - [Amount of vinyl groups in the paint (mol/100g)]
＝［塗料中のヒドロシリル基の量（ｍｏｌ／１００ｇ）］－［塗料中のビニル基の量（ｍｏｌ／１００ｇ）］ [Amount of surplus hydrosilyl group (mol/100g)]
= [Amount of hydrosilyl groups in the paint (mol/100g)] - [Amount of vinyl groups in the paint (mol/100g)]
測定条件
装置：Bruker Biospin,AVANCEIII-600 with Cryo
Ｐｒｏｂｅ観測周波数：６００ＭＨｚ（１Ｈ）、７９ＭＨｚ（２９Ｓｉ）
測定溶媒：ＣＤＣｌ３
測定温度：３００Ｋ
化学シフト基準：測定溶媒［７．２５ｐｐｍ（１Ｈ）］
内部標準（ＴＭＳ）［０．００ｐｐｍ（２９Ｓｉ）］ Measurement conditions equipment: Bruker Biospin, AVANCEIII-600 with Cryo
Probe observation frequency: 600MHz (1H), 79MHz (29Si)
Measurement solvent: CDCl3
Measurement temperature: 300K
Chemical shift standard: Measurement solvent [7.25ppm (1H)]
Internal standard (TMS) [0.00ppm (29Si)]
装置：Bruker Biospin,AVANCEIII-600 with Cryo
Ｐｒｏｂｅ観測周波数：６００ＭＨｚ（１Ｈ）、７９ＭＨｚ（２９Ｓｉ）
測定溶媒：ＣＤＣｌ３
測定温度：３００Ｋ
化学シフト基準：測定溶媒［７．２５ｐｐｍ（１Ｈ）］
内部標準（ＴＭＳ）［０．００ｐｐｍ（２９Ｓｉ）］ Measurement conditions equipment: Bruker Biospin, AVANCEIII-600 with Cryo
Probe observation frequency: 600MHz (1H), 79MHz (29Si)
Measurement solvent: CDCl3
Measurement temperature: 300K
Chemical shift standard: Measurement solvent [7.25ppm (1H)]
Internal standard (TMS) [0.00ppm (29Si)]
＜評価＞
得られた塗膜層を用いて、下記の評価を行った。結果を表１に示す。 <Evaluation>
The following evaluations were performed using the obtained coating layer. The results are shown in Table 1.
得られた塗膜層を用いて、下記の評価を行った。結果を表１に示す。 <Evaluation>
The following evaluations were performed using the obtained coating layer. The results are shown in Table 1.
（－２０℃表面オイル量）
測定対象は、－２０℃における、塗膜層の表面にブリードしたオイル量である。表面オイル量の測定は、以下の方法で行った。 (-20℃ surface oil amount)
The object of measurement is the amount of oil bled onto the surface of the coating layer at -20°C. The amount of surface oil was measured using the following method.
測定対象は、－２０℃における、塗膜層の表面にブリードしたオイル量である。表面オイル量の測定は、以下の方法で行った。 (-20℃ surface oil amount)
The object of measurement is the amount of oil bled onto the surface of the coating layer at -20°C. The amount of surface oil was measured using the following method.
中心付近において１０ｃｍ×２ｃｍのサイズにカットした塗膜層を、－２０℃で１６時間放置し、塗膜層の表面にブリードしたオイルを、－２０℃の温度環境下においてセルスクレーパー（ケニス社製、ＣＳＳ－１０）で採取した。そのオイルを油取り紙の質量（吸油量）変化が見られなくなるまで吸い取った。
The paint layer cut into a size of 10 cm x 2 cm near the center was left at -20°C for 16 hours, and the oil that had bled onto the surface of the paint layer was removed using a cell scraper (manufactured by Kennis Co., Ltd.) under a temperature environment of -20°C. , CSS-10). The oil was absorbed until no change in the mass (oil absorption amount) of the oil-absorbing paper was observed.
セルスクレーパーによるオイル採取と油取り紙の吸い取りは、１分間に７回繰り返した。オイル吸い取り前後の油取り紙の質量差を表面オイル量とした。表面オイル量の測定は３回行い、その平均値を算出した。
Collecting oil with a cell scraper and blotting it with oil-blotting paper was repeated 7 times per minute. The difference in mass of the oil-blotting paper before and after oil-blotting was taken as the amount of surface oil. The amount of surface oil was measured three times, and the average value was calculated.
評価基準は以下のとおりである。
○（良好）・・・４０μｇ／ｃｍ２以上
×（不良）・・・４０μｇ／ｃｍ２未満 The evaluation criteria are as follows.
○(Good)...40μg/ cm2 or more ×(Poor)...40μg/ cm2 or more
○（良好）・・・４０μｇ／ｃｍ２以上
×（不良）・・・４０μｇ／ｃｍ２未満 The evaluation criteria are as follows.
○(Good)...40μg/ cm2 or more ×(Poor)...40μg/ cm2 or more
（ＰＥＴ密着性）
密着（付着）性の評価は、ＪＩＳ Ｋ－５６００－５－６（塗膜の機械的特性 付着性）を参考に実施した。
具体的には、クロスカット試験カッターガイド（商品名「スーパーカッターガイド」、太佑機材株式会社製）、カッター、ポリイミド粘着テープ（ＮＯ．３６０ＵＬ、厚み０．０６ｍｍ×幅５０ｍｍ、日東電工株式会社製）を準備した。ポリイミド粘着テープにはシリコーン粘着剤が使用されており、シリコーン層と密着性が高いため選択した。 (PET adhesion)
Evaluation of adhesion (adhesion) was carried out with reference to JIS K-5600-5-6 (mechanical properties of coating film, adhesion).
Specifically, the cross-cut test cutter guide (product name "Super Cutter Guide", manufactured by Taiyu Kizai Co., Ltd.), cutter, polyimide adhesive tape (NO. 360UL, thickness 0.06 mm x width 50 mm, manufactured by Nitto Denko Co., Ltd.) prepared. Polyimide adhesive tape uses silicone adhesive and was selected because it has high adhesion to the silicone layer.
密着（付着）性の評価は、ＪＩＳ Ｋ－５６００－５－６（塗膜の機械的特性 付着性）を参考に実施した。
具体的には、クロスカット試験カッターガイド（商品名「スーパーカッターガイド」、太佑機材株式会社製）、カッター、ポリイミド粘着テープ（ＮＯ．３６０ＵＬ、厚み０．０６ｍｍ×幅５０ｍｍ、日東電工株式会社製）を準備した。ポリイミド粘着テープにはシリコーン粘着剤が使用されており、シリコーン層と密着性が高いため選択した。 (PET adhesion)
Evaluation of adhesion (adhesion) was carried out with reference to JIS K-5600-5-6 (mechanical properties of coating film, adhesion).
Specifically, the cross-cut test cutter guide (product name "Super Cutter Guide", manufactured by Taiyu Kizai Co., Ltd.), cutter, polyimide adhesive tape (NO. 360UL, thickness 0.06 mm x width 50 mm, manufactured by Nitto Denko Co., Ltd.) prepared. Polyimide adhesive tape uses silicone adhesive and was selected because it has high adhesion to the silicone layer.
クロスカット試験カッターガイドを用いて、塗膜に対して垂直となるように、得られた積層体に対してカッターで４ｍｍ間隔の切込みを６本入れた。その後、方向を９０°変えて先ほどの切込みに直行するように６本切込みを入れた（計２５マス）。
Cross-cut test Using a cutter guide, six cuts were made with a cutter at 4 mm intervals in the resulting laminate, perpendicular to the coating film. After that, the direction was changed by 90 degrees and six cuts were made perpendicular to the previous cuts (total of 25 squares).
長さ約７５ｍｍにカットした透明付着テープを格子にカットした部分に張り付け、指でしっかりこすりつけ張り付けた。より詳細には、格子の部分にかかった個所と最低２０ｍｍを超える長さで、指でテープを平らになるようにこすった。テープが塗膜に正しく接触しているかテープを通してみられる塗膜の色で判断した。
A transparent adhesive tape cut to a length of about 75 mm was pasted on the grid-cut area, and firmly rubbed with fingers to stick it. More specifically, the tape was rubbed flat with a finger at the area where it covered the grid and at least over a length exceeding 20 mm. Whether the tape was in proper contact with the paint film was judged by the color of the paint film seen through the tape.
テープを付着させてから５分以内にテープの端をつかみ、６０°に近い角度で０．５～１秒で確実に引き離した。密着性評価は、ＪＩＳ Ｋ５６００－５－６に従い、０～５分類の６段階で評価を行った。
Within 5 minutes of applying the tape, I grabbed the edge of the tape and pulled it off securely in 0.5-1 seconds at an angle close to 60°. Adhesion was evaluated in accordance with JIS K5600-5-6 in six grades from 0 to 5.
評価基準は以下のとおりである。
〇（良好）・・・６段階の評価中、０～１分類である
×（不良）・・・６段階の評価中、２～５分類である The evaluation criteria are as follows.
〇 (Good)...Out of 6 stages of evaluation, it is classified as 0-1 ×(Poor)...Out of 6 stages of evaluation, it is classified as 2-5
〇（良好）・・・６段階の評価中、０～１分類である
×（不良）・・・６段階の評価中、２～５分類である The evaluation criteria are as follows.
〇 (Good)...Out of 6 stages of evaluation, it is classified as 0-1 ×(Poor)...Out of 6 stages of evaluation, it is classified as 2-5
（着氷力）
測定対象は、－２０℃の環境下において、塗膜層に付着した氷塊を移動させるために要する力であって、便宜上、本明細書では、この力の大きさを「着氷力」と定義した。 (Icing power)
The object of measurement is the force required to move ice blocks attached to the coating layer in an environment of -20°C, and for convenience, in this specification, the magnitude of this force is defined as "icing force". did.
測定対象は、－２０℃の環境下において、塗膜層に付着した氷塊を移動させるために要する力であって、便宜上、本明細書では、この力の大きさを「着氷力」と定義した。 (Icing power)
The object of measurement is the force required to move ice blocks attached to the coating layer in an environment of -20°C, and for convenience, in this specification, the magnitude of this force is defined as "icing force". did.
着氷力の測定は、以下の方法で行った。
まず、円柱状の氷塊を作製した。氷塊は、スチロール角型ケース１６型（アズワン社製）の底面にステンレスリング（内径２５ｍｍ）を置き、そこに６ｇの純水を注ぎ込んで－２０℃で１６時間以上凍結させ、凍結後にステンレスリングを除去することによって作製した。 The icing force was measured using the following method.
First, a cylindrical block of ice was created. To make ice cubes, place a stainless steel ring (inner diameter 25 mm) on the bottom of a styrene square case type 16 (manufactured by As One), pour 6 g of pure water into it, freeze it at -20°C for more than 16 hours, and then remove the stainless steel ring after freezing. It was made by removing.
まず、円柱状の氷塊を作製した。氷塊は、スチロール角型ケース１６型（アズワン社製）の底面にステンレスリング（内径２５ｍｍ）を置き、そこに６ｇの純水を注ぎ込んで－２０℃で１６時間以上凍結させ、凍結後にステンレスリングを除去することによって作製した。 The icing force was measured using the following method.
First, a cylindrical block of ice was created. To make ice cubes, place a stainless steel ring (inner diameter 25 mm) on the bottom of a styrene square case type 16 (manufactured by As One), pour 6 g of pure water into it, freeze it at -20°C for more than 16 hours, and then remove the stainless steel ring after freezing. It was made by removing.
次いで、ステンレス平板に、塗膜層が表面となるように塗膜層を貼着し、－２０℃環境に１６時間静置した。重さ６ｇ、付着面積４．９ｃｍ２とした円柱状の氷塊を準備し、氷塊の底面を１０℃恒温の表面に１０秒間接触させ、塗膜層上に付着させた。
Next, the coating layer was attached to a stainless steel flat plate so that the coating layer was on the surface, and the plate was left standing in a -20°C environment for 16 hours. A cylindrical block of ice having a weight of 6 g and an adhering area of 4.9 cm 2 was prepared, and the bottom surface of the block of ice was brought into contact with a surface kept at a constant temperature of 10° C. for 10 seconds to adhere to the coating layer.
環境温度－２０℃に設定し、氷塊を付着させてから３時間後に、－２０℃の環境下において、床面に対して平行な方向から氷塊をロードセル（株式会社イマダ製 ＤＰＵ－５０、アタッチメント治具 Ａ型Ａ－４）で、速度０．１ｍｍ／秒で押し、４０秒の間に加わった荷重をフォースゲージ（株式会社イマダ製 ＺＴＳ－５０Ｎ）で測定した。測定された最大荷重を付着面積４．９ｃｍ２で除算した値を着氷力として記録した。試験は３回行い、その平均値を求めた。
The environmental temperature was set to -20℃, and 3 hours after the ice cubes were attached, the ice cubes were placed on a load cell (DPU-50 manufactured by Imada Co., Ltd., with attachment treatment) in a -20℃ environment from a direction parallel to the floor surface. A type A-4) was pressed at a speed of 0.1 mm/sec, and the load applied during 40 seconds was measured with a force gauge (ZTS-50N manufactured by Imada Co., Ltd.). The value obtained by dividing the measured maximum load by the adhesion area of 4.9 cm 2 was recorded as the icing force. The test was conducted three times and the average value was determined.
尚、この測定方法は、「着雪氷防止技術に関する研究（第１報）、北海道立工業試験場報告Ｎｏ．２９２（１９９３）」を参考にして決定したものである。着氷力は、少なくとも－２０℃においては、表面オイル量の増加に応答して略比例的に減少する。
This measurement method was determined with reference to "Research on snow and ice prevention technology (first report), Hokkaido Industrial Research Institute Report No. 292 (1993)." The icing force decreases approximately proportionally in response to an increase in the amount of surface oil, at least at -20°C.
表１の結果より、本発明の塗料から、基材等への密着性に優れ、優れた着氷及び／又は着雪防止機能を有する塗膜層が得られることがわかった。
From the results in Table 1, it was found that the paint of the present invention provides a coating layer that has excellent adhesion to substrates, etc., and has an excellent ability to prevent icing and/or snow accretion.
以上、図面を参照しながら各種の実施の形態について説明したが、本発明はかかる例に限定されないことは言うまでもない。当業者であれば、特許請求の範囲に記載された範疇内において、各種の変更例又は修正例に想到し得ることは明らかであり、それらについても当然に本発明の技術的範囲に属するものと了解される。また、発明の趣旨を逸脱しない範囲において、上記実施の形態における各構成要素を任意に組み合わせてもよい。
Although various embodiments have been described above with reference to the drawings, it goes without saying that the present invention is not limited to such examples. It is clear that those skilled in the art can come up with various changes or modifications within the scope of the claims, and these naturally fall within the technical scope of the present invention. Understood. Further, each of the constituent elements in the above embodiments may be arbitrarily combined without departing from the spirit of the invention.
なお、本出願は、２０２２年３月３１日出願の日本特許出願（特願２０２２－０５９６４７）及び２０２２年９月２９日出願の日本特許出願（特願２０２２－１５６７５２）に基づくものであり、その内容は本出願の中に参照として援用される。
This application is based on the Japanese patent application filed on March 31, 2022 (Japanese patent application No. 2022-059647) and the Japanese patent application filed on September 29, 2022 (Japanese patent application No. 2022-156752). The contents are incorporated by reference into this application.
本発明の塗料は、基材等への密着性に優れ、優れた着氷及び／又は着雪防止機能を有する塗膜層を形成することができることから、太陽光パネル、航空機、鉄道、自動車、風力発電機、住宅、信号機、看板、トンネル、雪庇防止板、橋梁、道路標識等の物体表面への雪や氷の付着を防止するために利用することができる。
The paint of the present invention has excellent adhesion to substrates, etc., and can form a coating layer with excellent icing and/or snow accretion prevention functions. It can be used to prevent snow and ice from adhering to the surfaces of objects such as wind power generators, houses, traffic lights, signboards, tunnels, snow eaves prevention boards, bridges, and road signs.
１０ 基材
１１ 第１塗膜層
１２ 第２塗膜層 10Base material 11 First coating layer 12 Second coating layer
１１ 第１塗膜層
１２ 第２塗膜層 10
Claims (6)
- ヒドロシリル基及びビニル基を有する樹脂成分と、オイル成分とを含み、
下記式で表される余剰ヒドロシリル基量が０．００１５ｍｏｌ／１００ｇを超え、
シランカップリング剤を含む、塗料。
［余剰ヒドロシリル基量（ｍｏｌ／１００ｇ）］
＝［塗料中のヒドロシリル基の量（ｍｏｌ／１００ｇ）］－［塗料中のビニル基の量（ｍｏｌ／１００ｇ）］ Contains a resin component having a hydrosilyl group and a vinyl group, and an oil component,
The amount of excess hydrosilyl group represented by the following formula exceeds 0.0015 mol/100 g,
Paints containing silane coupling agents.
[Amount of surplus hydrosilyl group (mol/100g)]
= [Amount of hydrosilyl groups in the paint (mol/100g)] - [Amount of vinyl groups in the paint (mol/100g)] - 前記オイル成分が親水性基を有する、請求項１に記載の塗料。 The paint according to claim 1, wherein the oil component has a hydrophilic group.
- 前記親水性基が、カルビノール基、ヒドロキシ基、カルボキシ基、無水カルボン酸基、アミノ基、スルホ基、エーテル基、エポキシ基、メルカプト基、チオール基及びエステル基からなる群から選択される少なくとも１種の基である、請求項２に記載の塗料。 The hydrophilic group is at least one selected from the group consisting of a carbinol group, a hydroxy group, a carboxy group, a carboxylic anhydride group, an amino group, a sulfo group, an ether group, an epoxy group, a mercapto group, a thiol group, and an ester group. 3. A paint according to claim 2, which is seed based.
- 請求項１～３のいずれか１項に記載の塗料により形成された、塗膜層。 A coating layer formed from the coating material according to any one of claims 1 to 3.
- 基材上に請求項４に記載の塗膜層が積層されてなる、積層体。 A laminate comprising the coating layer according to claim 4 laminated on a base material.
- 前記基材が、ポリエステル樹脂、ポリアミド樹脂、ポリカーボネート樹脂及び金属から選択されるいずれか１種を含む、請求項５に記載の積層体。 The laminate according to claim 5, wherein the base material includes any one selected from polyester resin, polyamide resin, polycarbonate resin, and metal.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022-059647 | 2022-03-31 | ||
| JP2022059647 | 2022-03-31 | ||
| JP2022156752 | 2022-09-29 | ||
| JP2022-156752 | 2022-09-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2023190796A1 true WO2023190796A1 (en) | 2023-10-05 |
Family
ID=88202674
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2023/013034 WO2023190796A1 (en) | 2022-03-31 | 2023-03-29 | Coating material, coating film layer, and laminate |
| PCT/JP2023/013033 WO2023190795A1 (en) | 2022-03-31 | 2023-03-29 | Coating film layer |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2023/013033 WO2023190795A1 (en) | 2022-03-31 | 2023-03-29 | Coating film layer |
Country Status (1)
| Country | Link |
|---|---|
| WO (2) | WO2023190796A1 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04288381A (en) * | 1991-01-23 | 1992-10-13 | Showa Electric Wire & Cable Co Ltd | Heat-resistant coating material |
| JPH07258606A (en) * | 1994-03-23 | 1995-10-09 | Shin Etsu Chem Co Ltd | Silicone composition for releasing paper |
| JP2003515650A (en) * | 1999-11-29 | 2003-05-07 | アーベーベー・リサーチ・リミテッド | Additional crosslinkable silicone rubber mixture |
| JP2005512796A (en) * | 2001-12-21 | 2005-05-12 | ロディア・シミ | Crosslinker for crosslinkable silicone compositions based on hydrogenated silicone oils containing Si-H units in the chain ends and chains and having a low platinum content |
| JP2016108415A (en) * | 2014-12-04 | 2016-06-20 | 日東電工株式会社 | Adhesive tape for preventing deposition of aquatic organisms |
| WO2019235497A1 (en) * | 2018-06-04 | 2019-12-12 | 東亞合成株式会社 | Water repellent oil repellent film composition and use of same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2768056C1 (en) * | 2018-11-09 | 2022-03-23 | Нитто Денко Корпорейшн | Sheet body |
| CA3118554A1 (en) * | 2018-11-09 | 2020-05-14 | Nitto Denko Corporation | Coating material and film |
| WO2021193973A1 (en) * | 2020-03-27 | 2021-09-30 | 日東電工株式会社 | Coating material and multilayer body |
-
2023
- 2023-03-29 WO PCT/JP2023/013034 patent/WO2023190796A1/en unknown
- 2023-03-29 WO PCT/JP2023/013033 patent/WO2023190795A1/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04288381A (en) * | 1991-01-23 | 1992-10-13 | Showa Electric Wire & Cable Co Ltd | Heat-resistant coating material |
| JPH07258606A (en) * | 1994-03-23 | 1995-10-09 | Shin Etsu Chem Co Ltd | Silicone composition for releasing paper |
| JP2003515650A (en) * | 1999-11-29 | 2003-05-07 | アーベーベー・リサーチ・リミテッド | Additional crosslinkable silicone rubber mixture |
| JP2005512796A (en) * | 2001-12-21 | 2005-05-12 | ロディア・シミ | Crosslinker for crosslinkable silicone compositions based on hydrogenated silicone oils containing Si-H units in the chain ends and chains and having a low platinum content |
| JP2016108415A (en) * | 2014-12-04 | 2016-06-20 | 日東電工株式会社 | Adhesive tape for preventing deposition of aquatic organisms |
| WO2019235497A1 (en) * | 2018-06-04 | 2019-12-12 | 東亞合成株式会社 | Water repellent oil repellent film composition and use of same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023190795A1 (en) | 2023-10-05 |
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