JP5721199B1 - Sealer paint composition - Google Patents
Sealer paint composition Download PDFInfo
- Publication number
- JP5721199B1 JP5721199B1 JP2014122394A JP2014122394A JP5721199B1 JP 5721199 B1 JP5721199 B1 JP 5721199B1 JP 2014122394 A JP2014122394 A JP 2014122394A JP 2014122394 A JP2014122394 A JP 2014122394A JP 5721199 B1 JP5721199 B1 JP 5721199B1
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- JP
- Japan
- Prior art keywords
- coating composition
- polyamine
- epoxy resin
- sealer
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title description 20
- 239000003973 paint Substances 0.000 title description 16
- 239000008199 coating composition Substances 0.000 claims abstract description 74
- 229920000768 polyamine Polymers 0.000 claims abstract description 60
- 239000003822 epoxy resin Substances 0.000 claims abstract description 57
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 57
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 27
- 239000000919 ceramic Substances 0.000 claims abstract description 27
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 13
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000003277 amino group Chemical group 0.000 claims abstract description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims description 45
- 239000011248 coating agent Substances 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 18
- 125000001931 aliphatic group Chemical group 0.000 claims description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 28
- 239000000463 material Substances 0.000 description 27
- 238000011156 evaluation Methods 0.000 description 19
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000000839 emulsion Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000002091 cationic group Chemical group 0.000 description 7
- 238000011109 contamination Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- -1 aliphatic aromatic amines Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 2
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 2
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 2
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 2
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 2
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- ZUBZATZOEPUUQF-UHFFFAOYSA-N isononane Chemical compound CCCCCCC(C)C ZUBZATZOEPUUQF-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- OZFSDOFRXYCNKS-UHFFFAOYSA-N 3-[diethoxy(1-phenylpropan-2-yloxy)silyl]-n-ethenylpropan-1-amine Chemical compound C=CNCCC[Si](OCC)(OCC)OC(C)CC1=CC=CC=C1 OZFSDOFRXYCNKS-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- OXKAXHPVFLEQHV-UHFFFAOYSA-N 3-tri(propan-2-yloxy)silylpropan-1-amine Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCN OXKAXHPVFLEQHV-UHFFFAOYSA-N 0.000 description 1
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 1
- GHBRMZFUMLMOKO-UHFFFAOYSA-N 5-[diethoxy(methyl)silyl]pentane-1,3-diamine Chemical compound CCO[Si](C)(OCC)CCC(N)CCN GHBRMZFUMLMOKO-UHFFFAOYSA-N 0.000 description 1
- OSSMYOQKNHMTIP-UHFFFAOYSA-N 5-[dimethoxy(methyl)silyl]pentane-1,3-diamine Chemical compound CO[Si](C)(OC)CCC(N)CCN OSSMYOQKNHMTIP-UHFFFAOYSA-N 0.000 description 1
- DGRMXVRKGHVYEQ-UHFFFAOYSA-N 5-tri(propan-2-yloxy)silylpentane-1,3-diamine Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCC(N)CCN DGRMXVRKGHVYEQ-UHFFFAOYSA-N 0.000 description 1
- ZOTKGMAKADCEDH-UHFFFAOYSA-N 5-triethoxysilylpentane-1,3-diamine Chemical compound CCO[Si](OCC)(OCC)CCC(N)CCN ZOTKGMAKADCEDH-UHFFFAOYSA-N 0.000 description 1
- KHLRJDNGHBXOSV-UHFFFAOYSA-N 5-trimethoxysilylpentane-1,3-diamine Chemical compound CO[Si](OC)(OC)CCC(N)CCN KHLRJDNGHBXOSV-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 235000005956 Cosmos caudatus Nutrition 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 244000047856 Hydrocera Species 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical group 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004447 silicone coating Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
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- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
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Abstract
【課題】親水化処理された窯業基材の表面に、親水化層との付着性が良好なシーラー層を形成することができるシーラー塗料組成物を提供すること。【解決手段】エポキシ樹脂(A)と、ポリアミン(B)と、シランカップリング剤(C)と、を含み、前記エポキシ樹脂(A)は、一分子中に平均炭素数が5以上である複数のアルキル基又はシクロアルキル基を有する弱溶剤可溶型の変性エポキシ樹脂であり且つ一分子中にエポキシ基を2個以上有しエポキシ当量が150〜1500であり、前記ポリアミン(B)は、脂肪族ポリアミン及びその変性物の少なくとも一方であり、前記シランカップリング剤(C)は、エポキシ基又はアミノ基を有するアルコキシシランであるシーラー塗料組成物。【選択図】なしThe present invention provides a sealer coating composition capable of forming a sealer layer having good adhesion to a hydrophilic layer on the surface of a ceramic substrate subjected to a hydrophilic treatment. The epoxy resin (A) includes a polyamine (B) and a silane coupling agent (C), and the epoxy resin (A) has a plurality of carbon atoms having an average carbon number of 5 or more per molecule. A weak solvent-soluble modified epoxy resin having an alkyl group or a cycloalkyl group, having two or more epoxy groups in one molecule and having an epoxy equivalent of 150 to 1500, and the polyamine (B) is a fat A sealer coating composition, which is at least one of a group polyamine and a modified product thereof, and the silane coupling agent (C) is an alkoxysilane having an epoxy group or an amino group. [Selection figure] None
Description
本発明は、シーラー塗料組成物に関する。 The present invention relates to a sealer coating composition.
従来、住宅の外壁等に用いられる窯業基材には、居住者等の好み応じた、多彩な色彩及び意匠性が求められている。また、窯業基材の外観の美粧を保持することを目的として、耐汚染性を高めることも求められている。このために、窯業基材の表面に、親水性を有する塗膜(親水化層)を形成することもある。 2. Description of the Related Art Conventionally, ceramic base materials used for housing outer walls and the like are required to have various colors and design properties according to the preferences of residents and the like. In addition, for the purpose of maintaining the cosmetic appearance of the ceramic base material, it is also required to increase the stain resistance. For this reason, a coating film (hydrophilic layer) having hydrophilicity may be formed on the surface of the ceramic base material.
ところで、長期間屋外で曝露させると、太陽光、降雨、温度、湿度等の影響により親水化層が劣化することがある。また、親水化層が劣化しなくとも、長期間の屋外暴露による退色や汚染、住宅の模様替えの要望等により、塗膜の塗り替えが必要とされる場合がある。このような場合に、親水化処理された窯業基材の表面と、塗り替え後の上塗りとの付着性を確保するために下塗り(シーラー)塗料組成物を塗装してシーラー層を形成する技術が知られている(例えば、特許文献1参照)。 By the way, when exposed outdoors for a long period of time, the hydrophilic layer may deteriorate due to the influence of sunlight, rain, temperature, humidity, and the like. Even if the hydrophilic layer is not deteriorated, it may be necessary to repaint the coating film due to discoloration or contamination due to long-term outdoor exposure, a request for redesigning a house, or the like. In such a case, a technique for forming a sealer layer by applying an undercoat (sealer) coating composition to ensure adhesion between the surface of a ceramic substrate that has been subjected to a hydrophilic treatment and the topcoat after repainting is known. (For example, refer to Patent Document 1).
しかしながら、親水化層は、その表面性状及び機能の特殊さゆえに、通常用いられるシーラー塗料組成物で形成されるシーラー層との付着性が低い。従って、親水化層とシーラー層との間で剥離が生じてしまう場合があり、親水化層が形成された塗膜の塗り替えは非常に困難であった。 However, the hydrophilic layer has low adhesion to a sealer layer formed from a commonly used sealer coating composition because of the special surface properties and functions. Therefore, peeling may occur between the hydrophilic layer and the sealer layer, and it is very difficult to repaint the coating film on which the hydrophilic layer is formed.
特許文献1に記載された技術は、親水化層とシーラー層との間の付着性を向上させた、樹脂エマルションを含有する水性のシーラー塗料組成物に関する。しかしながら、特許文献1に記載された水性のシーラー塗料組成物であっても、親水化層の種類によっては、十分に高い付着性を発現できない場合がある。このように、どのような種類の親水化層に対しても十分に高い付着性を有するシーラー層を形成することができるシーラー塗料組成物は得られていないのが現状である。 The technique described in Patent Document 1 relates to an aqueous sealer coating composition containing a resin emulsion that has improved adhesion between a hydrophilized layer and a sealer layer. However, even the water-based sealer coating composition described in Patent Document 1 may not exhibit sufficiently high adhesion depending on the type of the hydrophilic layer. Thus, the present condition is that the sealer coating composition which can form the sealer layer which has sufficiently high adhesiveness with respect to any kind of hydrophilic layer is not obtained.
本発明は、上記課題に鑑みてなされたものであり、親水化処理された窯業基材の表面に、親水化層との付着性が良好なシーラー層を形成することができるシーラー塗料組成物を提供することを目的とする。 The present invention has been made in view of the above problems, and provides a sealer coating composition that can form a sealer layer having good adhesion to a hydrophilic layer on the surface of a ceramic substrate that has been subjected to a hydrophilic treatment. The purpose is to provide.
本発明は、親水化処理された窯業基材の表面を被覆する塗膜を形成するために用いられる、シーラー塗料組成物であって、
エポキシ樹脂(A)と、ポリアミン(B)と、シランカップリング剤(C)と、を含み、
前記エポキシ樹脂(A)は、一分子中に平均炭素数が5以上である複数のアルキル基又はシクロアルキル基を有する弱溶剤可溶型の変性エポキシ樹脂であり且つ一分子中にエポキシ基を2個以上有しエポキシ当量が150〜1500であり、
前記ポリアミン(B)は、脂肪族ポリアミン及びその変性物の少なくとも一方であり、
前記シランカップリング剤(C)は、エポキシ基又はアミノ基を有するアルコキシシランであり、
前記エポキシ樹脂(A)及び前記ポリアミン(B)の合計質量に対する前記シランカップリング剤(C)の質量は、3〜10質量%であり、
前記シーラー塗料組成物の全質量における、エポキシ樹脂(A)及びポリアミン(B)の合計固形分含有量は、10〜70質量%であるシーラー塗料組成物に関する。
The present invention is a sealer coating composition used for forming a coating film covering the surface of a ceramic substrate that has been subjected to a hydrophilic treatment,
An epoxy resin (A), a polyamine (B), and a silane coupling agent (C),
The epoxy resin (A) is a weak solvent-soluble modified epoxy resin having a plurality of alkyl groups or cycloalkyl groups having an average carbon number of 5 or more per molecule, and 2 epoxy groups per molecule. Having an epoxy equivalent of 150 to 1500,
The polyamine (B) is at least one of an aliphatic polyamine and a modified product thereof,
The silane coupling agent (C) is an alkoxysilane having an epoxy group or an amino group,
The mass of the silane coupling agent (C) with respect to the total mass of the epoxy resin (A) and the polyamine (B) is 3 to 10% by mass,
The total solid content of the epoxy resin (A) and the polyamine (B) in the total mass of the sealer coating composition relates to a sealer coating composition that is 10 to 70% by mass.
また、前記ポリアミン(B)は、1級アミンであることが好ましい。 The polyamine (B) is preferably a primary amine.
また、更に弱溶剤を含むことが好ましい。 Moreover, it is preferable that a weak solvent is further included.
本発明によれば、親水化処理された窯業基材の表面に、親水化層との付着性が良好なシーラー層を形成することができるシーラー塗料組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the sealer coating composition which can form the sealer layer with favorable adhesiveness with a hydrophilization layer can be provided on the surface of the ceramic base material by which the hydrophilic treatment was carried out.
<シーラー塗料組成物>
以下、本発明の実施形態について説明する。なお、本発明は以下の実施形態に限定されない。
本実施形態に係るシーラー塗料組成物は、エポキシ樹脂(A)と、ポリアミン(B)と、シランカップリング剤(C)と、を含む。
<Sealer paint composition>
Hereinafter, embodiments of the present invention will be described. In addition, this invention is not limited to the following embodiment.
The sealer coating composition according to this embodiment includes an epoxy resin (A), a polyamine (B), and a silane coupling agent (C).
エポキシ樹脂(A)は、弱溶剤可溶型の変性エポキシ樹脂である。
具体的には、エポキシ樹脂(A)は、一分子中に平均炭素数が5以上である複数のアルキル基又はシクロアルキル基を有する。アルキル基又はシクロアルキル基の結合する原子は特に限定されず、芳香族炭化水素構造中の炭素原子であってもよいし、カルボニル炭素であってもよいし、酸素原子であってもよい。エポキシ樹脂(A)が、平均炭素数が5以上である複数のアルキル基又はシクロアルキル基を有することで、エポキシ樹脂(A)の弱溶剤への溶解性が向上する。
The epoxy resin (A) is a weak solvent soluble modified epoxy resin.
Specifically, the epoxy resin (A) has a plurality of alkyl groups or cycloalkyl groups having an average carbon number of 5 or more in one molecule . The atoms connecting the A alkyl group or a cycloalkyl group is not particularly limited, it may be a carbon atom in the aromatic hydrocarbon structure may be a carbonyl carbon or may be an oxygen atom. When the epoxy resin (A) has a plurality of alkyl groups or cycloalkyl groups having an average carbon number of 5 or more, the solubility of the epoxy resin (A) in a weak solvent is improved.
また、エポキシ樹脂(A)は、一分子中に2個以上のエポキシ基を有する。エポキシ樹脂(A)が、一分子中に2個以上のエポキシ基を有することで、シーラー塗料組成物の乾燥性と形成される塗膜の性能が向上する。
更に、エポキシ樹脂(A)は、エポキシ当量が150〜1500である。エポキシ樹脂(A)のエポキシ当量が、150未満であるとエポキシ樹脂(A)の硬化性が低下し、1500を超えると塗膜に十分な物性が発現しないおそれがる。エポキシ樹脂(A)は、エポキシ当量が600〜1200であることがより好ましい。
なお、これらのエポキシ樹脂は、末端イソシアネートプレポリマーによって内部架橋されていてもよい。エポキシ当量は、例えば、JIS K7236で規定される方法によって求めることができる。
The epoxy resin (A) has two or more epoxy groups in one molecule. When the epoxy resin (A) has two or more epoxy groups in one molecule, the drying property of the sealer coating composition and the performance of the formed coating film are improved.
Furthermore, the epoxy resin (A) has an epoxy equivalent of 150-1500. If the epoxy equivalent of the epoxy resin (A) is less than 150, the curability of the epoxy resin (A) is lowered, and if it exceeds 1500, sufficient physical properties may not be exhibited in the coating film. As for an epoxy resin (A), it is more preferable that epoxy equivalent is 600-1200.
These epoxy resins may be internally cross-linked by a terminal isocyanate prepolymer. An epoxy equivalent can be calculated | required by the method prescribed | regulated by JISK7236, for example.
このようなエポキシ樹脂(A)としては、例えば、平均炭素数が5以上である複数のアルキル基又はシクロアルキル基により置換されてなるフェノールノボラック等のエポキシ樹脂;例えば、特開平3−115318号公報、特開平8−134175号公報、特開平9−12678号公報、特開平9−227825公報に提案されているようなエポキシ樹脂を挙げることができる。エポキシ樹脂(A)の代表的な市販品としては、アデカレジンEP−9100(旭電化工業株式会社製)、ハリポールEP−450(ハリマ化成株式会社製)等が挙げられる。 As such an epoxy resin (A), for example, an epoxy resin such as phenol novolac substituted with a plurality of alkyl groups or cycloalkyl groups having an average carbon number of 5 or more; for example, JP-A-3-115318 Examples thereof include epoxy resins as proposed in JP-A-8-134175, JP-A-9-12678, and JP-A-9-227825. Representative commercial products of the epoxy resin (A) include Adeka Resin EP-9100 (manufactured by Asahi Denka Kogyo Co., Ltd.), Haripor EP-450 (manufactured by Harima Chemicals Co., Ltd.) and the like.
ポリアミン(B)は、脂肪族ポリアミン及びその変性物の少なくとも一方である。
脂肪族ポリアミンとしては、ジエチレントリアミン、トリエチレンテトラアミン等の鎖状脂肪族ポリアミン、N−アミノエチルピペラジン等の環状脂肪族ポリアミン、メタキシレンジアミン等の脂肪芳香族アミンを挙げることができる。
The polyamine (B) is at least one of an aliphatic polyamine and a modified product thereof.
Examples of the aliphatic polyamines include chain aliphatic polyamines such as diethylenetriamine and triethylenetetraamine, cyclic aliphatic polyamines such as N-aminoethylpiperazine, and aliphatic aromatic amines such as metaxylenediamine.
ポリアミン(B)としては、これらの脂肪族ポリアミンの変性物を用いることができる。脂肪族ポリアミンの変性物としては脂肪族ポリアミンのエポキシド付加変性物、アミド化変性物、マンニッヒ化変性物等が挙げられる。
脂肪族ポリアミンのエポキシド付加変性物は、脂肪族ポリアミンと、フェニルグリシジルエーテル、ブチルグリシジルエーテル、ビスフェノールA−ジグリシジルエーテル、ビスフェノールF−ジグリシジルエーテル等のグリシジルエーテル類又はカルボン酸のグリシジルエステル類等の各種エポキシ化合物と、を常法によって反応させることによって製造される。アミド化変性物は、脂肪族ポリアミンと、ダイマー酸等のカルボン酸類を常法によって反応させることによって製造される。マンニッヒ化変性物は、脂肪族ポリアミンと、ホルムアルデヒド等のアルデヒド類及びフェノール、クレゾール、キシレノール、第三ブチルフェノール、レゾルシン等の核に少なくとも一個のアルデヒド反応点を有するフェノール類とを常法によって反応させることによって製造される。
As the polyamine (B), modified products of these aliphatic polyamines can be used. Examples of modified products of aliphatic polyamines include epoxide addition modified products, amidation modified products, and Mannich modified products of aliphatic polyamines.
An epoxide addition modification product of an aliphatic polyamine includes an aliphatic polyamine and glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, or glycidyl esters of carboxylic acid. It is produced by reacting various epoxy compounds with conventional methods. The amidation-modified product is produced by reacting an aliphatic polyamine with a carboxylic acid such as dimer acid by a conventional method. Mannich modified products are obtained by reacting aliphatic polyamines with aldehydes such as formaldehyde and phenols having at least one aldehyde reaction site in the nucleus such as phenol, cresol, xylenol, tert-butylphenol and resorcin. Manufactured by.
ポリアミン(B)は、1級アミノ基を有することが好ましい。ポリアミン(B)が1級アミノ基を有することで、シーラー塗料組成物の硬化性が更に向上する。
ポリアミン(B)としては、これらの脂肪族ポリアミン及びその変性物の中でも、弱溶剤可溶型のポリアミンが用いられる。
The polyamine (B) preferably has a primary amino group. When the polyamine (B) has a primary amino group, the curability of the sealer coating composition is further improved.
As the polyamine (B), among these aliphatic polyamines and modified products thereof, weak solvent-soluble polyamines are used.
ポリアミン(B)の代表的な市販品としては、ダイトクラールX−9566(大都産業株式会社製)、ニューマイド515−70(ハリマ化成株式会社製)等を挙げることができる。 As a typical commercial item of polyamine (B), Daitokural X-9566 (made by Daito Sangyo Co., Ltd.), Newmide 515-70 (made by Harima Kasei Co., Ltd.), etc. can be mentioned.
本実施形態に係るシーラー塗料組成物の全質量における、エポキシ樹脂(A)及びポリアミン(B)の合計固形分含有量、すなわち、シーラー塗料組成物中の樹脂成分の含有量は、10〜70質量%である。この含有量が、10質量%未満であると窯業基材表面の親水化層と形成されるシーラー層との間の付着性が低下し、70質量%を超えると親水化層に対するシーラー塗料組成物の浸透性が低下するため、親水化層に対するシーラー層の付着性が低下する。シーラー塗料組成物の全質量における、エポキシ樹脂(A)及びポリアミン(B)の合計固形分含有量は、30〜60質量%であることが好ましい。 The total solid content of the epoxy resin (A) and the polyamine (B) in the total mass of the sealer coating composition according to this embodiment, that is, the content of the resin component in the sealer coating composition is 10 to 70 mass. %. When the content is less than 10% by mass, the adhesion between the hydrophilic layer on the ceramic base material surface and the formed sealer layer is lowered, and when it exceeds 70% by mass, the sealer coating composition for the hydrophilic layer is formed. Therefore, the adhesion of the sealer layer to the hydrophilic layer is reduced. The total solid content of the epoxy resin (A) and the polyamine (B) in the total mass of the sealer coating composition is preferably 30 to 60% by mass.
シランカップリング剤(C)は、エポキシ基又はアミノ基を有するアルコキシシランである。
エポキシ基を有するアルコキシシランの具体例としては、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、β−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、β−(3,4−エポキシシクロヘキシル)エチルトリエトキシシラン等が挙げられる。
The silane coupling agent (C) is an alkoxysilane having an epoxy group or an amino group.
Specific examples of the alkoxysilane having an epoxy group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxy Cyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.
アミノ基を有するアルコキシシランの具体例としては、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリイソプロポキシシラン、γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルメチルジエトキシシラン、γ−(2−アミノエチル)アミノプロピルトリメトキシシラン、γ−(2−アミノエチル)アミノプロピルメチルジメトキシシラン、γ−(2−アミノエチル)アミノプロピルトリエトキシシラン、γ−(2−アミノエチル)アミノプロピルメチルジエトキシシラン、γ−(2−アミノエチル)アミノプロピルトリイソプロポキシシラン、γ−ウレイドプロピルトリメトキシシラン、N−フェニル−γ−アミノプロピルトリメトキシシラン、N−ベンジル−γ−アミノプロピルトリメトキシシラン、N−ビニルベンジル−γ−アミノプロピルトリエトキシシラン等が挙げられる。 Specific examples of the alkoxysilane having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropylmethyl. Diethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2 -Aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl- γ-amino B pills trimethoxysilane, N- vinylbenzyl -γ- aminopropyltriethoxysilane, and the like.
シランカップリング剤(C)は、基材との付着性を向上させる観点から、ジアルコキシシラン又はトリアルコキシシランを用いることが好ましい。
シランカップリング剤(C)の代表的な市販品としては、KBM−403(3−グリシドキシプロピルトリメトキシシラン)、KBE−403(3−グリシドキシプロピルトリエトキシシラン)、KBE−903(3−アミノプロピルトリエトキシシラン)、KBM−903(3−アミノプロピルトリメトキシシラン)等(以上、全て信越化学工業株式会社製)が挙げられる。
As the silane coupling agent (C), dialkoxysilane or trialkoxysilane is preferably used from the viewpoint of improving adhesion to the substrate.
Representative commercial products of the silane coupling agent (C) include KBM-403 (3-glycidoxypropyltrimethoxysilane), KBE-403 (3-glycidoxypropyltriethoxysilane), KBE-903 ( 3-aminopropyltriethoxysilane), KBM-903 (3-aminopropyltrimethoxysilane) and the like (all are manufactured by Shin-Etsu Chemical Co., Ltd.).
エポキシ樹脂(A)及びポリアミン(B)の合計質量(樹脂成分の固形分質量)に対するシランカップリング剤(C)の含有量は、3〜10質量%である。この含有量が、3質量%未満の場合には窯業基材表面の親水化層と形成されるシーラー層との間の付着性が低下し、10質量%を超える場合には耐水性が低下する。エポキシ樹脂(A)及びポリアミン(B)の合計樹脂固形分の質量に対するシランカップリング剤(C)の質量は、4〜8質量%であることが好ましい。 Content of the silane coupling agent (C) with respect to the total mass (solid content mass of a resin component) of an epoxy resin (A) and a polyamine (B) is 3-10 mass%. When this content is less than 3% by mass, the adhesion between the hydrophilic layer on the ceramic base material surface and the sealer layer to be formed is reduced, and when it exceeds 10% by mass, the water resistance is reduced. . The mass of the silane coupling agent (C) with respect to the mass of the total resin solid content of the epoxy resin (A) and the polyamine (B) is preferably 4 to 8% by mass.
本実施形態に係るシーラー塗料組成物は、上記成分(A)〜(C)に加えて、必要に応じて添加剤等の他の成分を加えてもよい。他の成分として、例えば、顔料、粘性調整剤、表面調整剤、消泡剤、光安定剤、紫外線吸収剤、酸化防止剤等が挙げられる。 In addition to the components (A) to (C), the sealer coating composition according to this embodiment may contain other components such as additives as necessary. Examples of other components include pigments, viscosity modifiers, surface modifiers, antifoaming agents, light stabilizers, ultraviolet absorbers, and antioxidants.
また、本実施形態に係るシーラー塗料組成物は、更に弱溶剤を含むことが好ましい。
従来用いられてきた樹脂エマルションを含有する水性のシーラー塗料組成物の場合、親水化処理の種類によっては親水化層とシーラー層との付着性を向上させることができない場合がある。本実施形態に係るシーラー塗料組成物は、それ自体においても水性のシーラー塗料組成物より窯業基材への浸透性が良好であるが、弱溶剤が溶剤として用いられることで、更にどのような親水化処理がなされた窯業基材の表面であっても浸透し、親水化層とシーラー層との付着性をより向上させることができる。
弱溶剤とは、脂肪族炭化水素系溶剤であり、ターペンやミネラルスピリット等に代表されるような高引火点、高沸点、低有害性であるものをいう。混合溶剤としてはミネラルスピリット、ホワイトスピリット、ミネラルターペン、イソパラフィン、ソルベント灯油、芳香族ナフサ、VM&Pナフサ、ソルベントナフサ等がある。市販品としては、エッソ石油社製のソルベッソ100、ソルベッソ150、ソルベッソ200や、コスモ石油株式会社製のスワゾール310、スワゾール1000、スワゾール1500等が挙げられる。この他、単成分溶剤としてはn−ブタン、n−ヘキサン、n−ヘプタン、n−オクタン、イソノナン、n−デカン、n−ドデカン、シクロペンタン、シクロヘキサン、シクロブタン等の脂肪族炭化水素類等が用いられる。なお、本実施形態に係るシーラー塗料組成物には、弱溶剤以外の有機溶剤を含有する場合であっても、その質量は弱溶剤の質量以下であることが好ましい。
Moreover, it is preferable that the sealer coating composition which concerns on this embodiment contains a weak solvent further.
In the case of an aqueous sealer coating composition containing a resin emulsion that has been used conventionally, the adhesion between the hydrophilic layer and the sealer layer may not be improved depending on the type of the hydrophilic treatment. The sealer coating composition according to the present embodiment is better in permeation into the ceramic base material than the aqueous sealer coating composition by itself. Even the surface of the ceramic base material that has been subjected to the chemical treatment can penetrate and improve the adhesion between the hydrophilic layer and the sealer layer.
The weak solvent is an aliphatic hydrocarbon solvent, which has a high flash point, a high boiling point, and a low toxicity as typified by terpenes and mineral spirits. Examples of the mixed solvent include mineral spirit, white spirit, mineral turpentine, isoparaffin, solvent kerosene, aromatic naphtha, VM & P naphtha, and solvent naphtha. Examples of commercially available products include Solvesso 100, Solvesso 150, Solvesso 200 manufactured by Esso Petroleum, Swazol 310, Swazol 1000, and Swazol 1500 manufactured by Cosmo Oil. In addition, as the single component solvent, aliphatic hydrocarbons such as n-butane, n-hexane, n-heptane, n-octane, isononane, n-decane, n-dodecane, cyclopentane, cyclohexane and cyclobutane are used. It is done. In addition, even if it is a case where the sealer coating composition which concerns on this embodiment contains organic solvents other than a weak solvent, it is preferable that the mass is below the mass of a weak solvent.
シーラー塗料組成物における弱溶剤の含有量は5〜90質量%であることが好ましい。弱溶剤の含有量が5質量%未満であると、シーラー塗料組成物の塗装性が低下する傾向にある。一方、弱溶剤の含有量が90質量%を超えると、窯業基材表面の親水化層と形成されるシーラー層との間の付着性が低下する傾向にある。 It is preferable that content of the weak solvent in a sealer coating composition is 5-90 mass%. When the content of the weak solvent is less than 5% by mass, the coatability of the sealer coating composition tends to be lowered. On the other hand, when the content of the weak solvent exceeds 90% by mass, the adhesion between the hydrophilic layer on the ceramic base material surface and the formed sealer layer tends to be lowered.
本実施形態に係るシーラー塗料組成物は、エポキシ樹脂(A)を含む主剤と、ポリアミン(B)を含む硬化剤と、を含む二液混合型塗料組成物であることが好ましい。二液混合型塗料組成物であることで、塗り替えを実施する現場での作業性が向上する。
本実施形態に係るシーラー塗料組成物が、二液混合型塗料組成物である場合、シランカップリング剤(C)は、主剤と硬化剤の一方に適宜配合する。具体的には、エポキシ基を有するアルコキシシランを成分(C)として用いる場合、成分(C)は主剤に配合される。一方、アミノ基を有するアルコキシシランを成分(C)として用いる場合、成分(C)は硬化剤に配合される。
The sealer coating composition according to this embodiment is preferably a two-component mixed coating composition containing a main agent containing an epoxy resin (A) and a curing agent containing a polyamine (B). By being a two-component mixed coating composition, workability at the site of repainting is improved.
When the sealer coating composition according to the present embodiment is a two-component mixed coating composition, the silane coupling agent (C) is appropriately blended with one of the main agent and the curing agent. Specifically, when an alkoxysilane having an epoxy group is used as the component (C), the component (C) is blended with the main agent. On the other hand, when using the alkoxysilane which has an amino group as a component (C), a component (C) is mix | blended with a hardening | curing agent.
<シーラー塗料組成物の調製方法>
本実施形態に係るシーラー塗料組成物の調製方法としては、特別の方法を必要とせず、当業者において通常用いられる方法を挙げることができる。例えば、エポキシ樹脂(A)を含む主剤と、ポリアミン(B)を含む硬化剤は、各成分をディスパー等の分散機で分散することにより調製する方法を、シーラー塗料組成物の調製方法として挙げることができる。
<Method for preparing sealer coating composition>
As a method for preparing the sealer coating composition according to the present embodiment, a special method is not required, and methods commonly used by those skilled in the art can be exemplified. For example, a method of preparing a main agent containing an epoxy resin (A) and a curing agent containing a polyamine (B) by dispersing each component with a disperser such as a disperser is given as a method for preparing a sealer coating composition. Can do.
<塗膜の形成方法>
以下、本実施形態に係るシーラー塗料組成物を用いた塗膜(シーラー層)の形成方法について説明する。
本実施形態に係るシーラー塗料組成物を用いることで、親水化処理された窯業基材の補修塗装を容易に行うことが可能となる。ここで、補修とは、例えば、基材表面の塗膜が経年劣化したり、何らかの理由で部分的に塗膜の性能が低下した場合に、その塗膜全体又はその一部に対して塗り重ねすることを意味する。
<Formation method of coating film>
Hereinafter, the formation method of the coating film (sealer layer) using the sealer coating composition which concerns on this embodiment is demonstrated.
By using the sealer coating composition according to the present embodiment, it becomes possible to easily perform repair coating of the ceramic base material subjected to the hydrophilic treatment. Here, the repair is, for example, when the coating film on the surface of the base material deteriorates over time or when the performance of the coating film partially deteriorates for some reason, the entire coating film or a part thereof is applied repeatedly. It means to do.
本実施形態に係るシーラー塗料組成物は、親水化処理された窯業基材の表面を被覆する塗膜を形成するために用いられる。
本実施形態における窯業基材としては、JIS A 5422に記載された窯業系サイディングや、JIS A 5430に記載された繊維強化セメント板等を挙げることができる。
The sealer coating composition according to this embodiment is used to form a coating film that covers the surface of a ceramic base material that has been subjected to a hydrophilic treatment.
Examples of the ceramic base material in the present embodiment include a ceramic siding described in JIS A 5422, a fiber reinforced cement board described in JIS A 5430, and the like.
親水化処理された窯業基材としては、各種基材であって、上記の窯業基材の最表面に、低汚染性塗料組成物を塗装して形成された塗膜を有する基材等が挙げられる。ここで、「低汚染性塗料組成物」とは、得られる塗膜において汚れが付着し難い性質が発揮される塗料組成物を意味する。低汚染性塗料組成物としては、例えば、光触媒コーティング材(光触媒による超親水性及び有機物分解性によって低汚染性能が発揮される)、低汚染性アクリルシリコーン塗料組成物、低汚染性フッ素系樹脂塗料組成物及びシリカ微粒子の水分散体を主成分とする親水コーティング材等が挙げられる。 Examples of the hydrophilized ceramic base material include various base materials, and a base material having a coating film formed by coating a low-contamination paint composition on the outermost surface of the ceramic base material. It is done. Here, the “low-contamination paint composition” means a paint composition that exhibits the property that stains hardly adhere to the obtained coating film. Examples of low-contamination paint compositions include photocatalytic coating materials (low-contamination performance is exhibited by superhydrophilicity and organic matter decomposability by photocatalysts), low-contamination acrylic silicone paint compositions, and low-contamination fluororesin paints. Examples thereof include a hydrophilic coating material mainly composed of an aqueous dispersion of the composition and silica fine particles.
窯業基材の塗膜表面が親水化処理された窯業基材の具体例としては、ニチハ株式会社製のモエンエクセラード18、モエンエクセラード16、ケイミュー株式会社製のネオロック・光セラ16、ネオロック・親水セラ16、セラディール・親水パワーコート及びエクセレージ15 パワーコート、旭トステム外装株式会社製のAT−WALL15やまがた割肌タイル16SX、AT−WALL15ニューアルマトーレSX、並びに、東レACE株式会社製のトレステージ及びトレリード等を挙げることができる。 Specific examples of the ceramic base material with a hydrophilic coating surface of the ceramic base material include MOEN EXCELLARD 18 and MOEN EXCELLARD 16 manufactured by Nichiha Co., Ltd. Hydrocera 16, Seradeel / Hydrophilic Power Coat and Exage 15 Power Coat, manufactured by Asahi Tostem Exterior Co., Ltd. Examples include a trestage and a trelead.
本実施形態に係るシーラー塗料組成物を塗装する方法は特に限定されない。塗装方法としては、例えば、刷毛、ローラー、ロールコーター、エアースプレー、エアレススプレー等の一般に用いられている塗装方法が挙げられる。塗装方法は基材の種類・用途に応じて適宜選択することができる。 The method for applying the sealer coating composition according to this embodiment is not particularly limited. Examples of the coating method include commonly used coating methods such as brushes, rollers, roll coaters, air sprays, and airless sprays. The coating method can be appropriately selected according to the type and use of the substrate.
シーラー塗料組成物は、乾燥膜厚(シーラー層の厚み)が、好ましくは5〜100μm、より好ましくは10〜40μmとなる条件で塗装される。 The sealer coating composition is applied under the condition that the dry film thickness (the thickness of the sealer layer) is preferably 5 to 100 μm, more preferably 10 to 40 μm.
シーラー塗料組成物を塗装して得られた塗膜は、必要に応じて常温(外気温)で、好ましくは10〜30℃で、乾燥させる。シーラー塗料組成物を塗装して得られた塗膜の乾燥時間は、好ましくは6時間〜1ヶ月の間、より好ましくは1日〜1週間である。 The coating film obtained by applying the sealer coating composition is dried at room temperature (outside temperature), preferably at 10 to 30 ° C., if necessary. The drying time of the coating film obtained by applying the sealer coating composition is preferably 6 hours to 1 month, more preferably 1 day to 1 week.
本実施形態に係るシーラー塗料組成物によって形成されたシーラー層の表面には、必要に応じて上塗り塗料組成物を塗布することで上塗り層が形成される。上塗り塗料組成物は、特に限定されない。上塗り塗料組成物としては、例えば、溶剤系アクリル塗料組成物、溶剤系ウレタン塗料組成物、溶剤系シリコーン塗料組成物、溶剤系フッ素塗料組成物、弱溶剤系アクリル塗料組成物、弱溶剤系ウレタン塗料組成物、弱溶剤系シリコーン塗料組成物、弱溶剤系フッ素塗料組成物、水性アクリル塗料組成物、水性ウレタン塗料組成物、水性シリコーン塗料組成物、水性フッ素塗料組成物、無機塗料組成物等が挙げられる。 On the surface of the sealer layer formed by the sealer coating composition according to the present embodiment, a top coating layer is formed by applying a top coating composition as necessary. The top coating composition is not particularly limited. Examples of the top coating composition include a solvent-based acrylic coating composition, a solvent-based urethane coating composition, a solvent-based silicone coating composition, a solvent-based fluorine coating composition, a weak solvent-based acrylic coating composition, and a weak solvent-based urethane coating. Compositions, weak solvent-based silicone paint compositions, weak solvent-based fluorine paint compositions, aqueous acrylic paint compositions, aqueous urethane paint compositions, aqueous silicone paint compositions, aqueous fluorine paint compositions, inorganic paint compositions, etc. It is done.
上塗り塗料組成物の塗装は、乾燥膜厚(上塗り層の厚み)が、好ましくは5〜100μm、より好ましくは10〜40μmとなる条件で塗装される。上塗り塗料組成物を塗装して得られた塗膜は、必要に応じて常温(外気温)で、好ましくは10〜30℃で乾燥させる。上塗り塗料組成物を塗装して得られた塗膜の乾燥時間は、好ましくは1日〜1週間である。 The top coating composition is applied under the condition that the dry film thickness (the thickness of the top coating layer) is preferably 5 to 100 μm, more preferably 10 to 40 μm. The coating film obtained by applying the top coating composition is dried at room temperature (outside temperature), preferably at 10 to 30 ° C., if necessary. The drying time of the coating film obtained by applying the top coating composition is preferably 1 day to 1 week.
なお、本発明は上記実施形態に限定されるものではなく、本発明の目的を達成できる範囲での変形、改良等は本発明に含まれる。 It should be noted that the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within a scope that can achieve the object of the present invention are included in the present invention.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。なお、特に断りのない限り「部」及び「%」は、質量基準である。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.
[エポキシ樹脂(A−1)の合成]
温度計、攪拌装置及び冷却管を備えた水分離装置を取り付けた反応装置に、エポトートYD−128(東都化成工業株式会社製、エチレングリコールジグリシジルエーテル、エポキシ当量:184〜194)380g(1モル)、トール油脂肪酸291g(1モル、平均炭素数19)及びミネラルスピリット(最終的に得られるエポキシ樹脂(A−1)溶液の不揮発分が75質量%となる量)を仕込み、約110℃に昇温し、攪拌しながら水酸化カリウムを全樹脂量に対して0.01%添加した。次いで、反応液を、150℃まで昇温し、3時間保持した。そして、反応液の酸価が2mgKOH/g以下になったことを確認し、40℃に冷却した。40℃の反応液にトリレンジイソシアネート87g(0.5モル)を滴下し、赤外分光光度計でイソシアネート基(−NCO)の吸収が認められなくなるまで反応させることでエポキシ樹脂(A−1)(75質量%ミネラルスピリット溶液)を得た。得られたエポキシ樹脂(A−1)は、外観が透明、エポキシ当量は950であった。
[Synthesis of Epoxy Resin (A-1)]
380 g (1 mol) of Epototo YD-128 (manufactured by Toto Kasei Kogyo Co., Ltd., ethylene glycol diglycidyl ether, epoxy equivalent: 184 to 194) is attached to a reactor equipped with a water separator equipped with a thermometer, a stirrer and a cooling tube. ), Tall oil fatty acid 291 g (1 mol, average carbon number 19) and mineral spirit (the amount of which the nonvolatile content of the finally obtained epoxy resin (A-1) solution is 75% by mass) are charged to about 110 ° C. The temperature was raised and 0.01% of potassium hydroxide was added to the total resin amount with stirring. Subsequently, the reaction liquid was heated up to 150 degreeC and hold | maintained for 3 hours. And it confirmed that the acid value of the reaction liquid became 2 mgKOH / g or less, and cooled to 40 degreeC. Epoxy resin (A-1) by dropping 87 g (0.5 mol) of tolylene diisocyanate into the reaction solution at 40 ° C. and reacting until no absorption of isocyanate group (—NCO) is observed with an infrared spectrophotometer. (75 mass% mineral spirit solution) was obtained. The obtained epoxy resin (A-1) had a transparent appearance and an epoxy equivalent of 950.
[エポキシ樹脂(A−2)の合成]
温度計、攪拌装置及び冷却管を備えた水分離装置を取り付けた反応装置に、エポトートYD−128(東都化成工業株式会社製、エチレングリコールジグリシジルエーテル、エポキシ当量184〜194)380g(1モル)、ノニルフェノール110g(0.5モル)、トール油脂肪酸146g(0.5モル、平均炭素数19)及びミネラルスピリット(最終的に得られるエポキシ樹脂(A−2)溶液の不揮発分が75質量%となる量)を仕込み、約110℃に昇温し、攪拌しながら水酸化カリウムを全樹脂量に対して0.01%添加した。次いで、反応液を150℃まで昇温し、3時間保持した。そして、反応液の酸価が2mgKOH/g以下になり、且つ、遊離したノニルフェノールの存在が認められなくなったことを確認した後、40℃に冷却した。40℃の反応液にトリレンジイソシアネート87g(0.5モル)を滴下し、赤外分光光度計でイソシアネート基(−NCO)の吸収が認められなくなるまで反応させることでエポキシ樹脂(A−2)(75質量%ミネラルスピリット溶液)を得た。得られたエポキシ樹脂(A−2)は、外観が透明、エポキシ当量は1020であった。
[Synthesis of Epoxy Resin (A-2)]
380 g (1 mol) of Epototo YD-128 (manufactured by Toto Kasei Kogyo Co., Ltd., ethylene glycol diglycidyl ether, epoxy equivalents 184 to 194) attached to a reactor equipped with a water separator equipped with a thermometer, a stirring device and a cooling pipe Nonylphenol 110 g (0.5 mol), tall oil fatty acid 146 g (0.5 mol, average carbon number 19) and mineral spirit (the epoxy resin (A-2) solution finally obtained has a non-volatile content of 75% by mass) Was added, and the temperature was raised to about 110 ° C., and 0.01% of potassium hydroxide was added to the total resin amount while stirring. Next, the temperature of the reaction solution was raised to 150 ° C. and held for 3 hours. Then, after confirming that the acid value of the reaction solution became 2 mgKOH / g or less and the presence of free nonylphenol was not recognized, the reaction solution was cooled to 40 ° C. Epoxy resin (A-2) is obtained by adding 87 g (0.5 mol) of tolylene diisocyanate to the reaction solution at 40 ° C. and reacting until no absorption of isocyanate group (—NCO) is observed with an infrared spectrophotometer. (75 mass% mineral spirit solution) was obtained. The resulting epoxy resin (A-2) had a transparent appearance and an epoxy equivalent of 1020.
[カチオン性樹脂エマルションの合成]
ポリゾールAP−1350(昭和電工株式会社製、アクリル樹脂エマルション、アミン価18mgKOH/g、水酸基価0mgKOH/g、粒子径65nm)100質量部(固形分質量換算)、造膜助剤としてのテキサノール(イーストマン社製)10質量部及び脱イオン水90質量部を攪拌・混合して、比較例にて用いるカチオン性樹脂エマルションを得た。
[Synthesis of cationic resin emulsion]
Polysol AP-1350 (manufactured by Showa Denko KK, acrylic resin emulsion, amine value 18 mgKOH / g, hydroxyl value 0 mgKOH / g, particle size 65 nm) 100 parts by mass (solid content mass conversion), texanol (yeast as a film-forming aid) 10 parts by mass and 90 parts by mass of deionized water were stirred and mixed to obtain a cationic resin emulsion used in the comparative example.
[ポリアミン(B−1)の合成]
加熱装置、冷却装置、攪拌装置、滴下装置及び脱水装置を取り付けた反応装置に、メタキシリレンジアミン136g(1モル)及びカルダノール(カードライトコーポレーション社製、カードライトNX−4708、水酸基当量:300)270g(0.9モル)を仕込み、攪拌を開始し、35〜50℃に昇温した。続いて、反応容器に37質量%ホルマリン水溶液72.9g(0.9モル)を60〜120分かけて滴下した。滴下終了後、反応容器に脱水装置を装着し、反応で生成される水を留去しながら、約100℃から150℃で5時間反応を進行させた。最後に、110℃、80mmHgの減圧下において脱水反応を完結させ、最終生成物としてポリアミン(B−1)を得た。得られたポリアミン(B−1)は、外観が褐色液状、アミン価は271であった。
[Synthesis of Polyamine (B-1)]
To a reaction apparatus equipped with a heating apparatus, a cooling apparatus, a stirring apparatus, a dropping apparatus and a dehydrating apparatus, 136 g (1 mol) of metaxylylenediamine and cardanol (Cardlight NX-4708, manufactured by Cardlight Corporation, hydroxyl equivalent: 300) 270 g (0.9 mol) was charged, stirring was started, and the temperature was raised to 35-50 ° C. Subsequently, 72.9 g (0.9 mol) of a 37 mass% formalin aqueous solution was dropped into the reaction vessel over 60 to 120 minutes. After completion of the dropping, a dehydrator was attached to the reaction vessel, and the reaction was allowed to proceed at about 100 ° C. to 150 ° C. for 5 hours while distilling off the water produced by the reaction. Finally, the dehydration reaction was completed under reduced pressure at 110 ° C. and 80 mmHg to obtain polyamine (B-1) as a final product. The resulting polyamine (B-1) had a brown liquid appearance and an amine value of 271.
[ポリアミン(B−2)の合成]
加熱装置、冷却装置、攪拌装置、滴下装置及び脱水装置を取り付けた反応装置に、メタキシリレンジアミン136g(1モル)、テルペンフェノール(ヤスハラケミカル株式会社製:YP−90LL、水酸基当量:330)148.5g(0.5モル)及びカルダノール135g(0.45モル)を仕込み、攪拌開始し、35〜50℃に昇温した。続いて、反応容器に37質量%ホルマリン水溶液72.9g(0.9モル)を60〜120分かけて滴下した。滴下終了後、反応容器に脱水装置を装着し、反応で生成される水を留去しながら、約100℃から150℃で5時間反応を進行させた。最後に、110℃、80mmHgの減圧下において脱水反応を完結させ、最終生成物としてポリアミン(B−2)を得た。得られたポリアミン(B−2)は、外観が褐色液状、アミン価は266であった。
[Synthesis of Polyamine (B-2)]
To a reactor equipped with a heating device, a cooling device, a stirring device, a dropping device, and a dehydrating device, 136 g (1 mol) of metaxylylenediamine, terpene phenol (manufactured by Yashara Chemical Co., Ltd .: YP-90LL, hydroxyl equivalent: 330) 5 g (0.5 mol) and cardanol 135 g (0.45 mol) were charged, stirring was started, and the temperature was raised to 35-50 ° C. Subsequently, 72.9 g (0.9 mol) of a 37 mass% formalin aqueous solution was dropped into the reaction vessel over 60 to 120 minutes. After completion of the dropping, a dehydrator was attached to the reaction vessel, and the reaction was allowed to proceed at about 100 ° C. to 150 ° C. for 5 hours while distilling off the water produced by the reaction. Finally, the dehydration reaction was completed under reduced pressure at 110 ° C. and 80 mmHg to obtain polyamine (B-2) as a final product. The resulting polyamine (B-2) had a brown liquid appearance and an amine value of 266.
[シーラー塗料組成物]
実施例及び比較例に係るシーラー塗料組成物の組成を表1及び表2に示す。シーラー塗料組成物の主剤の含有するエポキシ樹脂(A)としては、上記のエポキシ樹脂(A−1)又はエポキシ樹脂(A−2)を用いた。また、比較例10及び11においては、特許文献1で用いられたカチオン性樹脂エマルションを主剤に用いた。シーラー塗料組成物の硬化剤の含有するポリアミン(B)としては、上記のポリアミン(B−1)又はポリアミン(B−2)を用いた。シランカップリング剤(C)としては、KBM−403、KBE−403、KBM−90又はKBE−903(以上、信越化学工業株式会社製)を用いた。また、比較例1、8及び9においては、フェニルトリメトキシシランであるZ−6124(東レ・ダウコーニング株式会社製)を用いた。
なお、エポキシ基を有するアルコキシシラン(KBM−403、KBE−403)は、主剤に含有させ、それ以外のアルコキシシラン(KBM−903、KBE−903、Z−6124)は、硬化剤に含有させた。
なお、表の数値の単位は、最終的に主剤と硬化剤を混合したシーラー塗料組成物における固形分含有量であり、単位は「質量%」である。実施例及び比較例の塗料組成物は、エポキシ樹脂(A)、ポリアミン(B)、シランカップリング剤(C)及びこれらに属さない成分(カチオン性樹脂エマルション及びフェニルトリメトキシシラン)が表1及び表2に示すような固形分含有量(単位:質量%)となるように、主剤及び硬化剤をディスパーで混合することで得た。なお、シーラー塗料組成物の固形分含有量は、必要に応じてミネラルスピリットを添加して調整した。
表2において、比較例10及び11の「塗料組成物の全質量における、エポキシ樹脂組成物(A)及びポリアミン(B)の合計固形分」の欄は、塗料組成物の全質量におけるカチオン性樹脂エマルションの固形分含有量を示す。また、表2において、比較例10及び11の「エポキシ樹脂(A)及びポリアミン(B)の合計樹脂固形分の質量に対する、シランカップリング剤(C)の質量」の欄は、カチオン性樹脂エマルション固形分の質量に対するシランカップリング剤の質量を示す。
[Sealer coating composition]
Tables 1 and 2 show the compositions of the sealer coating compositions according to Examples and Comparative Examples. As the epoxy resin (A) contained in the main component of the sealer coating composition, the above epoxy resin (A-1) or epoxy resin (A-2) was used. In Comparative Examples 10 and 11, the cationic resin emulsion used in Patent Document 1 was used as the main agent. The polyamine (B-1) or polyamine (B-2) described above was used as the polyamine (B) contained in the curing agent of the sealer coating composition. As the silane coupling agent (C), KBM-403, KBE-403, KBM-90, or KBE-903 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used. In Comparative Examples 1, 8 and 9, Z-6124 (manufactured by Toray Dow Corning Co., Ltd.) which is phenyltrimethoxysilane was used.
In addition, the alkoxysilane (KBM-403, KBE-403) which has an epoxy group was contained in the main agent, and the other alkoxysilane (KBM-903, KBE-903, Z-6124) was contained in the curing agent. .
In addition, the unit of the numerical value of a table | surface is solid content in the sealer coating composition which mixed the main ingredient and the hardening | curing agent finally, and a unit is "mass%." In the coating compositions of Examples and Comparative Examples, epoxy resin (A), polyamine (B), silane coupling agent (C) and components not belonging to them (cationic resin emulsion and phenyltrimethoxysilane) are listed in Table 1 and It obtained by mixing a main ingredient and a hardening | curing agent with a disper so that it might become solid content (unit: mass%) as shown in Table 2. The solid content of the sealer coating composition was adjusted by adding mineral spirit as necessary.
In Table 2, the column of “total solid content of epoxy resin composition (A) and polyamine (B) in the total mass of the coating composition” in Comparative Examples 10 and 11 is a cationic resin in the total mass of the coating composition. The solid content of the emulsion is shown. In Table 2, the column of “mass of silane coupling agent (C) relative to the mass of total resin solids of epoxy resin (A) and polyamine (B)” in Comparative Examples 10 and 11 is a cationic resin emulsion. The mass of the silane coupling agent relative to the mass of the solid content is shown.
[評価用試験板の作製]
得られた、実施例又は比較例の塗料組成物を、無機塗料組成物及び光触媒コーティング材を塗布して得られた複層塗膜を最表面に有する窯業基材(ネオロック・光セラ16、ケイミュー株式会社製)に、刷毛を用いて塗付量が50〜80g/m2になるように塗装した。続いて、基材を室温にて24時間乾燥させることで塗膜を形成した。その上に、ファインシリコンフレッシュ(日本ペイント株式会社製)を、刷毛を用いて塗布量が100〜120g/m2なるように塗装し、室温にて7日間乾燥することで、実施例及び比較例の評価用試験板を得た。
また、窯業基材を、フッ素系塗料及び親水コーティング材を塗布して得られた複層塗膜を最表面に有するモエンエクセラード18(ニチハ株式会社製)に対しても、上記と同様に実施例又は比較例の塗料組成物を塗装して乾燥させた。これによっても、実施例及び比較例の評価用試験板を得た。
[Preparation of test plate for evaluation]
A ceramic base material having a multilayer coating film obtained by applying an inorganic coating composition and a photocatalyst coating material on the outermost surface of the obtained coating composition of Examples or Comparative Examples (Neolock / Opteracera 16, Keimu) Co., Ltd.) was applied using a brush so that the coating amount was 50 to 80 g / m 2 . Subsequently, a coating film was formed by drying the substrate at room temperature for 24 hours. On top of that, fine silicon fresh (manufactured by Nippon Paint Co., Ltd.) was applied with a brush so that the coating amount was 100 to 120 g / m 2 and dried at room temperature for 7 days. Examples and Comparative Examples A test plate for evaluation was obtained.
In addition, the same applies to Moen Xcellade 18 (manufactured by Nichiha Co., Ltd.) having a multilayer coating film on the outermost surface obtained by applying a fluorine-based paint and a hydrophilic coating material to a ceramic base material. The coating composition of Example or Comparative Example was applied and dried. Also by this, the test plate for evaluation of an Example and a comparative example was obtained.
[耐水性試験]
実施例及び比較例の評価用試験板を、23℃の温水に7日間浸漬させ引き上げた。引き上げ直後に塗膜表面のふくれを観察した。塗膜のふくれ度合いを目視し、試験板の耐水性を下記の評価基準に従って評価した。結果を表1及び表2に示す。合格ラインは5点である。
5点:全く異常なし
4点:塗膜全体の5%以内の面積においてふくれが発生
3点;塗膜全体の5%を超え15%以内の面積においてふくれが発生
2点:塗膜全体の15%を超え35%以内の面積においてふくれが発生
1点:塗膜全体の35%以上の面積においてふくれが発生
続いて、引き上げ2時間後に付着性試験を実施した。
[Water resistance test]
The test plates for evaluation of Examples and Comparative Examples were dipped in hot water at 23 ° C. for 7 days and pulled up. Immediately after the lifting, the surface of the coating film was observed to bulge. The degree of blistering of the coating film was visually observed, and the water resistance of the test plate was evaluated according to the following evaluation criteria. The results are shown in Tables 1 and 2. The passing line is 5 points.
5 points: No abnormality at all 4 points: Swelling occurred in an area within 5% of the entire coating film 3 points; Swelling occurred in an area exceeding 5% and within 15% of the entire coating film 2 points: 15 in the entire coating film Swelling occurred in an area exceeding 35% and within 35% 1 point: Swelling continuously occurred in an area of 35% or more of the entire coating film, and an adhesion test was conducted after 2 hours of lifting.
[付着性試験]
実施例及び比較例の評価用試験板を、23℃の温水に7日間浸漬させ引き上げた。続いて、ユーティリティナイフを用いて評価用試験板の塗膜の形成された表面に格子状にクロスカットを施し、4mm×4mmのマスを25個形成した後、セロテープ(登録商標、ニチバン株式会社製)を付着させて剥離した。塗膜の剥離度合い(剥離率)を下記の基準に従って目視で評価した。結果を表1及び表2に示す。合格ラインは3点以上である。
5点:カットの縁が完全に滑らかで、どの格子の目にも剥離がない
4点:剥離率5%未満
3点;剥離率5%以上15%未満
2点:剥離率15%以上35%未満
1点:剥離率35%以上
[Adhesion test]
The test plates for evaluation of Examples and Comparative Examples were dipped in hot water at 23 ° C. for 7 days and pulled up. Subsequently, a utility knife was used to cross-cut the surface on which the coating film of the test plate for evaluation was formed to form 25 4 mm × 4 mm squares, and then cellotape (registered trademark, manufactured by Nichiban Co., Ltd.) ) Was attached and peeled off. The degree of peeling (peeling rate) of the coating film was visually evaluated according to the following criteria. The results are shown in Tables 1 and 2. The passing line is 3 points or more.
5 points: the edges of the cut are completely smooth, and there is no peeling in any grid eye 4 points: peeling point less than 5% 3 points; peeling rate 5% or more but less than 15% 2 points: peeling rate 15% or more and 35% Less than 1 point: peeling rate of 35% or more
実施例1、6、7及び8と比較例1、8及び9との比較から、比較例1、8及び9の評価用試験板よりも実施例1、6、7及び8の評価用試験板の方が付着性の評価が高いことが分かった。この結果から、エポキシ樹脂(A)と、ポリアミン(B)と、シランカップリング剤(C)と、を含むシーラー塗料組成物において、シランカップリング剤(C)としてエポキシ基又はアミノ基を有するアルコキシシランを用いる方が、他の官能基を有するアルコキシシランを用いるよりも、形成されるシーラー層と窯業基材表面の親水化層との付着性が高いことが確認された。 From the comparison between Examples 1, 6, 7 and 8 and Comparative Examples 1, 8 and 9, the evaluation test plates of Examples 1, 6, 7 and 8 are more effective than the evaluation test plates of Comparative Examples 1, 8 and 9. It was found that the evaluation of adhesion was higher. From this result, in the sealer coating composition containing the epoxy resin (A), the polyamine (B), and the silane coupling agent (C), the alkoxy having an epoxy group or amino group as the silane coupling agent (C). It was confirmed that the adhesion between the formed sealer layer and the hydrophilized layer on the ceramic substrate surface is higher when silane is used than when alkoxysilane having other functional groups is used.
実施例9と比較例5との比較から、比較例5の評価用試験板よりも実施例9の評価用試験板の方が付着性の評価が高いことが分かった。また、実施例12と比較例6との比較から、実施例12の方が比較例6より耐水性に優れていることが分かった。これらの結果から、エポキシ樹脂(A)と、ポリアミン(B)と、シランカップリング剤(C)と、を含むシーラー塗料組成物において、シランカップリング剤(C)の質量がエポキシ樹脂(A)及びポリアミン(B)の合計質量に対して3〜10質量%である場合に、付着性も耐水性も良好であることが確認された。 From the comparison between Example 9 and Comparative Example 5, it was found that the evaluation test plate of Example 9 had higher adhesion evaluation than the evaluation test plate of Comparative Example 5. Further, from comparison between Example 12 and Comparative Example 6, it was found that Example 12 was superior in water resistance to Comparative Example 6. From these results, in the sealer coating composition containing the epoxy resin (A), the polyamine (B), and the silane coupling agent (C), the mass of the silane coupling agent (C) is the epoxy resin (A). And when it was 3-10 mass% with respect to the total mass of polyamine (B), it was confirmed that both adhesiveness and water resistance are favorable.
実施例2と比較例2との比較から、比較例2の評価用試験板よりも実施例2の評価用試験板の方が付着性の評価が高いことが分かった。また、実施例5と比較例3との比較から、比較例3の評価用試験板よりも実施例5の評価用試験板の方が付着性の評価が高いことが分かった。これらの結果から、エポキシ樹脂(A)と、ポリアミン(B)と、シランカップリング剤(C)と、を含むシーラー塗料組成物において、エポキシ樹脂(A)及びポリアミン(B)の合計固形分含有量が10〜70質量%であることで、形成されるシーラー層と窯業基材表面の親水化層との付着性が高くなることが確認された。 From the comparison between Example 2 and Comparative Example 2, it was found that the evaluation test plate of Example 2 had higher adhesion evaluation than the evaluation test plate of Comparative Example 2. Further, from comparison between Example 5 and Comparative Example 3, it was found that the evaluation test plate of Example 5 had higher adhesion evaluation than the evaluation test plate of Comparative Example 3. From these results, in the sealer coating composition containing the epoxy resin (A), the polyamine (B), and the silane coupling agent (C), the total solid content of the epoxy resin (A) and the polyamine (B) is contained. It was confirmed that the adhesiveness between the formed sealer layer and the hydrophilized layer on the ceramic base material surface is increased when the amount is 10 to 70% by mass.
比較例10及び11は、特許文献1の技術に対応する比較例である。実施例1、11及び12における、エポキシ樹脂(A)及びポリアミン(B)の合計樹脂固形分の質量に対するシランカップリング剤(C)の質量の値に比べ、比較例11の、その値に対応するカチオン性樹脂エマルションの樹脂固形分の質量に対するシランカップリング剤の質量の値は100%と、はるかに多量である。しかし、比較例11で形成された塗膜は、耐水性に劣ることが確認された。更に、にエポキシ樹脂(A)及びポリアミン(B)の合計樹脂固形分の質量に対するシランカップリング剤(C)の質量の値に対応する値を、実施例1と同等にした比較例10においても、やはり形成される塗膜は窯業基材への浸透性が悪いために耐水性に劣ることが確認された。 Comparative Examples 10 and 11 are comparative examples corresponding to the technique of Patent Document 1. Compared to the value of the mass of the silane coupling agent (C) relative to the mass of the total resin solids of the epoxy resin (A) and the polyamine (B) in Examples 1, 11 and 12, it corresponds to the value of Comparative Example 11 The value of the mass of the silane coupling agent relative to the mass of the resin solid content of the cationic resin emulsion is 100%, which is much larger. However, it was confirmed that the coating film formed in Comparative Example 11 was inferior in water resistance. Further, in Comparative Example 10 in which the value corresponding to the value of the mass of the silane coupling agent (C) relative to the mass of the total resin solids of the epoxy resin (A) and the polyamine (B) is equivalent to that in Example 1. Also, it was confirmed that the formed coating film was inferior in water resistance due to poor permeability to ceramic base materials.
Claims (3)
エポキシ樹脂(A)と、ポリアミン(B)と、シランカップリング剤(C)と、を含み、
前記エポキシ樹脂(A)は、一分子中に平均炭素数が5以上である複数のアルキル基又はシクロアルキル基を有する弱溶剤可溶型の変性エポキシ樹脂であり且つ一分子中にエポキシ基を2個以上有しエポキシ当量が150〜1500であり、
前記ポリアミン(B)は、脂肪族ポリアミン及びその変性物の少なくとも一方であり、
前記シランカップリング剤(C)は、エポキシ基又はアミノ基を有するアルコキシシランであり、
前記エポキシ樹脂(A)及び前記ポリアミン(B)の合計質量に対する前記シランカップリング剤(C)の質量は、3〜10質量%であり、
前記シーラー塗料組成物の全質量における、エポキシ樹脂(A)及びポリアミン(B)の合計固形分含有量は、10〜70質量%であるシーラー塗料組成物。 A sealer coating composition used to form a coating film covering the surface of a ceramic substrate that has been subjected to a hydrophilic treatment,
An epoxy resin (A), a polyamine (B), and a silane coupling agent (C),
The epoxy resin (A) is a weak solvent-soluble modified epoxy resin having a plurality of alkyl groups or cycloalkyl groups having an average carbon number of 5 or more per molecule, and 2 epoxy groups per molecule. Having an epoxy equivalent of 150 to 1500,
The polyamine (B) is at least one of an aliphatic polyamine and a modified product thereof,
The silane coupling agent (C) is an alkoxysilane having an epoxy group or an amino group,
The mass of the silane coupling agent (C) with respect to the total mass of the epoxy resin (A) and the polyamine (B) is 3 to 10% by mass,
The sealer coating composition, wherein the total solid content of the epoxy resin (A) and the polyamine (B) in the total mass of the sealer coating composition is 10 to 70% by mass.
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