KR100286213B1 - A cure type coating composition for ultraviolet rays - Google Patents
A cure type coating composition for ultraviolet rays Download PDFInfo
- Publication number
- KR100286213B1 KR100286213B1 KR1019990007554A KR19990007554A KR100286213B1 KR 100286213 B1 KR100286213 B1 KR 100286213B1 KR 1019990007554 A KR1019990007554 A KR 1019990007554A KR 19990007554 A KR19990007554 A KR 19990007554A KR 100286213 B1 KR100286213 B1 KR 100286213B1
- Authority
- KR
- South Korea
- Prior art keywords
- formula
- silicone
- curable coating
- represented
- group
- Prior art date
Links
- 239000008199 coating composition Substances 0.000 title claims description 17
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 34
- 238000000576 coating method Methods 0.000 claims abstract description 34
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 20
- -1 polysiloxane Polymers 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 14
- 239000012948 isocyanate Substances 0.000 claims abstract description 11
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000003277 amino group Chemical group 0.000 claims abstract description 7
- 229910000077 silane Inorganic materials 0.000 claims abstract description 7
- 238000004804 winding Methods 0.000 claims abstract description 7
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 5
- 238000007259 addition reaction Methods 0.000 claims abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- SKDKWDVYZOKBPL-UHFFFAOYSA-N benzyl(dimethyl)silicon Chemical compound C[Si](C)CC1=CC=CC=C1 SKDKWDVYZOKBPL-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- GDDVTIGTERZVBW-UHFFFAOYSA-N [dimethyl(trimethylsilyloxy)silyl]oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)(C)O[Si](C)(C)C GDDVTIGTERZVBW-UHFFFAOYSA-N 0.000 claims description 2
- HEFKLCDJYBXBAF-UHFFFAOYSA-N diethoxy(2-methylpropyl)silane Chemical compound CCO[SiH](CC(C)C)OCC HEFKLCDJYBXBAF-UHFFFAOYSA-N 0.000 claims description 2
- JQZUMFHYRULBEN-UHFFFAOYSA-N diethyl(methyl)silicon Chemical compound CC[Si](C)CC JQZUMFHYRULBEN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims description 2
- 150000004756 silanes Chemical group 0.000 claims 2
- OIKHZBFJHONJJB-UHFFFAOYSA-N dimethyl(phenyl)silicon Chemical compound C[Si](C)C1=CC=CC=C1 OIKHZBFJHONJJB-UHFFFAOYSA-N 0.000 claims 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 claims 1
- OGMDYZVGIYQLCM-UHFFFAOYSA-N hexyl(dimethoxy)silane Chemical compound CCCCCC[SiH](OC)OC OGMDYZVGIYQLCM-UHFFFAOYSA-N 0.000 claims 1
- 229940094989 trimethylsilane Drugs 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 28
- 238000011109 contamination Methods 0.000 abstract description 13
- 239000000123 paper Substances 0.000 abstract description 12
- 230000000704 physical effect Effects 0.000 abstract description 9
- 235000014347 soups Nutrition 0.000 abstract description 8
- 239000000356 contaminant Substances 0.000 abstract description 5
- 239000002023 wood Substances 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- 229920003002 synthetic resin Polymers 0.000 abstract description 4
- 239000000057 synthetic resin Substances 0.000 abstract description 4
- 239000004744 fabric Substances 0.000 abstract description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 20
- 235000021109 kimchi Nutrition 0.000 description 6
- 230000002688 persistence Effects 0.000 description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000006224 matting agent Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 150000003673 urethanes Chemical class 0.000 description 3
- NOTSENYEYVSAHZ-UHFFFAOYSA-N 2-ethyl-3-methylbenzene-1,4-diol Chemical compound CCC1=C(C)C(O)=CC=C1O NOTSENYEYVSAHZ-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- HXLVDKGPVGFXTH-UHFFFAOYSA-N butyl(dimethyl)silane Chemical compound CCCC[SiH](C)C HXLVDKGPVGFXTH-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- CFENKJQKDBNQRS-UHFFFAOYSA-N 1,18-diisocyanatooctadecane Chemical compound O=C=NCCCCCCCCCCCCCCCCCCN=C=O CFENKJQKDBNQRS-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- UKDKWYQGLUUPBF-UHFFFAOYSA-N 1-ethenoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOC=C UKDKWYQGLUUPBF-UHFFFAOYSA-N 0.000 description 1
- QJJDJWUCRAPCOL-UHFFFAOYSA-N 1-ethenoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOC=C QJJDJWUCRAPCOL-UHFFFAOYSA-N 0.000 description 1
- ZXKHOVDDJMJXQP-UHFFFAOYSA-N 1-ethenylcyclohexan-1-ol Chemical compound C=CC1(O)CCCCC1 ZXKHOVDDJMJXQP-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- YGTVWCBFJAVSMS-UHFFFAOYSA-N 5-hydroxypentyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCO YGTVWCBFJAVSMS-UHFFFAOYSA-N 0.000 description 1
- XFOFBPRPOAWWPA-UHFFFAOYSA-N 6-hydroxyhexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCO XFOFBPRPOAWWPA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 108010067035 Pancrelipase Proteins 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- ZNAAXKXXDQLJIX-UHFFFAOYSA-N bis(2-cyclohexyl-3-hydroxyphenyl)methanone Chemical compound C1CCCCC1C=1C(O)=CC=CC=1C(=O)C1=CC=CC(O)=C1C1CCCCC1 ZNAAXKXXDQLJIX-UHFFFAOYSA-N 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940124579 cold medicine Drugs 0.000 description 1
- 229940092125 creon Drugs 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- OIKTYAIWDCKBDE-UHFFFAOYSA-N ethoxy(hexyl)silane Chemical compound CCCCCC[SiH2]OCC OIKTYAIWDCKBDE-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 description 1
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43L—ARTICLES FOR WRITING OR DRAWING UPON; WRITING OR DRAWING AIDS; ACCESSORIES FOR WRITING OR DRAWING
- B43L1/00—Repeatedly-usable boards or tablets for writing or drawing
- B43L1/04—Blackboards
- B43L1/10—Writing surfaces thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
본 발명은 자외선 경화형 도막 조성물에 관한 것으로서, 더욱 상세하게는 이소시아네이트 올리고머에 다음 화학식 3으로 표시되는 3급 실란을 하이드로실릴레이션하고, 다음 화학식 4로 표시되는 말단 히드록실기를 2개 이상 가진 실리콘 중간체와 다음 화학식 5로 표시되는 히드록실기 함유 아크릴레이트 모노머를 부가 반응시켜 제조된 다음 화학식 1로 표시되는 실리콘 변성 우레탄 아크릴레이트 올리고머와, 아민기를 함유한 유기 폴리실록산 및 다음 화학식 2로 표시되는 글리시딜 아크릴계 화합물을 반응시킨 실리콘 아크릴레이트를 함유시킴으로써 내오염성, 내약품성, 내구성 부족 등의 단점을 완전히 보완하여 이물질과의 마찰시 흠집이 적고, 매직 등의 오염물질 접촉후에도 휴지나 마른걸레 등으로 닦기만 해도 쉽게 오염 자국이 지워지며, 김칫국물 등에도 오염되지 않는 등 비오염성이 뛰어나고 내약품성, 내구성 및 물리적 성질 또한 우수하여 기존 염화 비닐장판용 외에 종이, 합성수지, 목재, 철재, 통상의 권취형 칠판용 및 보드용에 적용 가능한 자외선 경화형 도막 조성물에 관한 것이다.The present invention relates to an ultraviolet curable coating film composition, and more particularly, to a silicone intermediate having two or more terminal hydroxyl groups represented by the following formula (4) by hydrosilylation of a tertiary silane represented by the following formula (3) to an isocyanate oligomer And a silicone-modified urethane acrylate oligomer represented by the following formula (1), an organic polysiloxane containing an amine group, and glycidyl represented by the following formula (2) prepared by addition reaction of a hydroxyl group-containing acrylate monomer represented by the following formula (5): By containing silicone acrylate reacted with acrylic compound, it completely compensates for the disadvantages of contamination resistance, chemical resistance, and lack of durability, so it is less scratched when rubbed with foreign substances, and only wipes with tissue paper or dry cloth after contact with contaminants such as magic. Even if the stain is easily removed, It is excellent in non-pollution such as not contaminated with soups, and also has excellent chemical resistance, durability and physical properties.It is an ultraviolet curable coating film applicable to paper, synthetic resin, wood, iron, ordinary winding board and board as well as existing vinyl chloride board. It relates to a composition.
상기 화학식 1에서 R1은 수소원자 또는 메틸기이고, R2는 (CH2)ℓ이고 여기서 ℓ은 1 ∼ 10의 정수이다. R3는 탄소수 4 ∼ 20의 선형 지방족, 고리형 지방족, 방향족 화합물 또는 이들 화합물의 올리고머이고, R4는 수소원자, 탄소수 1 ∼ 4의 알킬기 또는 벤질기이고, n은 1 ∼ 20의 정수이고, Y는 말단에 이중결합을 2개 이상 가지고 있는 실리콘 중간체이다.In Formula 1, R 1 is a hydrogen atom or a methyl group, R 2 is (CH 2 ) L and L is an integer of 1 to 10. R 3 is a linear aliphatic, cyclic aliphatic, aromatic compound having 4 to 20 carbon atoms or an oligomer of these compounds, R 4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a benzyl group, n is an integer of 1 to 20, Y is a silicon intermediate having two or more double bonds at its terminals.
상기 화학식 2에서 X는 수소원자 또는 메틸기이다.In Formula 2, X is a hydrogen atom or a methyl group.
상기 화학식 3에서 R4는 상기 화학식 1에서 정의한 바와 같다.R 4 in Formula 3 is as defined in Formula 1.
상기 화학식 4에서 R5는 -C3H6OC2H4OH이고, m은 1 ∼ 10의 정수이다.In Formula 4, R 5 is -C 3 H 6 OC 2 H 4 OH, and m is an integer of 1 to 10.
상기 화학식 5에서 X는 수소원자 또는 메틸기이고, ℓ은 1 ∼ 10의 정수이다.In Formula 5, X is a hydrogen atom or a methyl group, and l is an integer of 1 to 10.
Description
본 발명은 자외선 경화형 도막 조성물에 관한 것으로서, 더욱 상세하게는 이소시아네이트 올리고머에 다음 화학식 3으로 표시되는 3급 실란을 하이드로실릴레이션하고, 다음 화학식 4로 표시되는 말단 히드록실기를 2개 이상 가진 실리콘 중간체와 다음 화학식 5로 표시되는 히드록실기 함유 아크릴레이트 모노머를 부가 반응시켜 제조된 다음 화학식 1로 표시되는 실리콘 변성 우레탄 아크릴레이트 올리고머와, 아민기를 함유한 유기 폴리실록산 및 다음 화학식 2로 표시되는 글리시딜 아크릴계 화합물을 반응시킨 실리콘 아크릴레이트를 함유시킴으로써 내오염성, 내약품성, 내구성 부족 등의 단점을 완전히 보완하여 이물질과의 마찰시 흠집이 적고, 매직 등의 오염물질 접촉후에도 휴지나 마른걸레 등으로 닦기만 해도 쉽게 오염 자국이 지워지며, 김칫국물 등에도 오염되지 않는 등 비오염성이 뛰어나고 내약품성, 내구성 및 물리적 성질 또한 우수하여 기존 염화 비닐장판용 외에 종이, 합성수지, 목재, 철재, 통상의 권취형 칠판용 및 보드용에 적용 가능한 자외선 경화형 도막 조성물에 관한 것이다.The present invention relates to an ultraviolet curable coating film composition, and more particularly, to a silicone intermediate having two or more terminal hydroxyl groups represented by the following formula (4) by hydrosilylation of a tertiary silane represented by the following formula (3) to an isocyanate oligomer And a silicone-modified urethane acrylate oligomer represented by the following formula (1), an organic polysiloxane containing an amine group, and glycidyl represented by the following formula (2) prepared by addition reaction of a hydroxyl group-containing acrylate monomer represented by the following formula (5): By containing silicone acrylate reacted with acrylic compound, it completely compensates for the disadvantages of contamination resistance, chemical resistance, and lack of durability, so it is less scratched when rubbed with foreign substances, and only wipes with tissue paper or dry cloth after contact with contaminants such as magic. Even if the stain is easily removed, It is excellent in non-pollution such as not contaminated with soups, and also has excellent chemical resistance, durability and physical properties.It is an ultraviolet curable coating film applicable to paper, synthetic resin, wood, iron, ordinary winding board and board as well as existing vinyl chloride board. It relates to a composition.
화학식 1Formula 1
상기 화학식 1에서 R1은 수소원자 또는 메틸기이고, R2는 (CH2)ℓ이고 여기서 ℓ은 1 ∼ 10의 정수이다. R3는 탄소수 4 ∼ 20의 선형 지방족, 고리형 지방족, 방향족 화합물 또는 이들 화합물의 올리고머이고, R4는 수소원자, 탄소수 1 ∼ 4의 알킬기 또는 벤질기이고, n은 1 ∼ 20의 정수이고, Y는 말단에 이중결합을 2개 이상 가지고 있는 실리콘 중간체이다.In Formula 1, R 1 is a hydrogen atom or a methyl group, R 2 is (CH 2 ) L and L is an integer of 1 to 10. R 3 is a linear aliphatic, cyclic aliphatic, aromatic compound having 4 to 20 carbon atoms or an oligomer of these compounds, R 4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a benzyl group, n is an integer of 1 to 20, Y is a silicon intermediate having two or more double bonds at its terminals.
화학식 2Formula 2
상기 화학식 2에서 X는 수소원자 또는 메틸기이다.In Formula 2, X is a hydrogen atom or a methyl group.
화학식 3Formula 3
상기 화학식 3에서 R4는 상기 화학식 1에서 정의한 바와 같다.R 4 in Formula 3 is as defined in Formula 1.
화학식 4Formula 4
상기 화학식 4에서 R5는 -C3H6OC2H4OH이고, m은 1 ∼ 10의 정수이다.In Formula 4, R 5 is -C 3 H 6 OC 2 H 4 OH, and m is an integer of 1 to 10.
화학식 5Formula 5
상기 화학식 5에서 X는 수소원자 또는 메틸기이고, ℓ은 1 ∼ 10의 정수이다.In Formula 5, X is a hydrogen atom or a methyl group, and l is an integer of 1 to 10.
염화비닐 바닥재는 용도별로 보면 중보행용과 경보행용으로 나누어지는데, 중보행의 경우에는 사무실, 백화점, 일반 점포, 체육관 등에 사용되는 것으로서 내마모성, 내구성, 내오염성, 내약품성 등을 높이기 위해 일찍부터 자외선 경화형 바니쉬를 코팅하여 사용하여 왔으며, 아파트 및 일반 주택의 거실, 주방, 침실 등에 사용하는 경보행용 바닥재에도 자외선 경화형 바니쉬를 코팅함으로써 염화비닐 장판 고유의 외관 내마모성, 내구성, 내오염성, 내약품성 등을 향상시켰으나, 소비자의 욕구를 완전히 충족시킬 수 있는 수준은 아니었고, 특히 내오염성이 불량하여 오염물질(크레온, 매질, 김칫국물, 구두약 등)이 묻은 후, 잘 지워지지 않으며, 내약품성이 불량하여 옥도정기, 감기약, 음료수 등에 의한 변색이 진행되거나 기타 물리적, 기계적 성질이 현저히 떨어지는 문제점이 있었다.Vinyl chloride flooring is divided into heavy walking and warning walking by use.In the case of heavy walking, it is used in offices, department stores, general stores, gymnasiums, etc., and it is UV-curable at an early stage to increase abrasion resistance, durability, pollution resistance, and chemical resistance. The varnish has been coated and used, and UV curable varnish is also applied to floors for alarms used in living rooms, kitchens and bedrooms in apartments and general houses, thereby improving the wear resistance, durability, stain resistance and chemical resistance. It was not a level that could fully satisfy the consumer's desires. Especially, since it was poor in contamination resistance, it could not be erased well after staining pollutants (creon, medium, kimchi soup, bitumen, etc.), and inferior chemical resistance due to poor chemical resistance, Discoloration due to cold medicine, drinks, or other physical or mechanical properties There was a significant drop.
이러한 종래의 자외선 경화형 도막 조성물은 미국특허 제3,782,961호, 제3,829,531호, 제3,850,770호, 제3,874,906호, 제3,864,113호, 제3,891,523호, 제3,895,171호, 제3,899,611호, 제3,907,574호, 제3,912,516호, 제3,932,356호 및 제4,301,209호에 개시되어 있다. 그러나, 상기 특허들에 공지된 자외선 경화형 도막 조성물은 내마모성, 내오염성, 내구성 등이 부족한 단점이 있었다.Such conventional UV curable coating composition is U.S. Pat. 3,932,356 and 4,301,209. However, the ultraviolet curable coating composition known in the above patents has a disadvantage in that the wear resistance, contamination resistance, durability and the like are insufficient.
이에 본 발명자들은 상기의 문제점들을 해결하기 위하여 광범위한 연구를 수행한 결과, 자외선 경화형 도막 조성물에 이소시아네이트 올리고머와 상기 화학식 3, 4 및 5로 표시되는 화합물을 반응시켜 제조된 상기 화학식 1로 표시되는 실리콘 변성 우레탄 아크릴레이트 올리고머와 실리콘 아크릴레이트를 함유시킴으로써 내오염성, 내약품성, 내구성 부족 등의 단점을 완전히 보완하여 이물질과의 마찰시 흠집이 적고, 매직 등의 오염물질 접촉후에도 휴지나 마른걸레 등으로 닦기만 해도 쉽게 오염 자국이 지워지며, 김칫국물 등에도 오염되지 않는 등 비오염성이 뛰어나고 내약품성, 내구성 및 물리적 성질 또한 우수한 자외선 경화형 도막 조성물을 완성하게 되었다.Accordingly, the present inventors conducted extensive research to solve the above problems, and as a result, the silicone-modified compound represented by Chemical Formula 1 prepared by reacting an isocyanate oligomer with a compound represented by Chemical Formulas 3, 4, and 5 in an ultraviolet curable coating film composition By containing urethane acrylate oligomer and silicone acrylate, it completely compensates for the disadvantages of contamination resistance, chemical resistance and lack of durability, so it is less scratched when rubbed with foreign substances, and only wipes with tissue or dry cloth after contact with contaminants such as magic. Even if the stain marks are easily erased, they are not contaminated with kimchi soup, etc., resulting in excellent UV resistance and excellent UV resistance, chemical resistance, durability, and physical properties.
따라서, 본 발명에서는 매우 우수한 비오염성 및 내구성을 가지며, 코팅 표면을 보호해주어 기존 염화 비닐장판용 외에 일반적인 칠판용 응용 제품 중에 연질 시트(PVC, 종이) 등을 기재로 한 메모판, 영상 스크린, 벽걸이 칠판 등의 권취형과 경질재료(합성수지, 목재, 철재 등)를 기재로 한 판상 화이트 보드, 즉 행사계획표, 벽걸이 화이트 보드, 이동식 화이트 보드, 작전지시 및 교육용 화이트 보드 등의 보드용에 적용 가능한 자외선 경화형 도막 조성물을 제공하는 데 그 목적이 있다.Therefore, the present invention has a very excellent non-pollution and durability, and protects the coating surface, memo boards, video screens, wall boards based on soft sheets (PVC, paper), etc. in general blackboard applications in addition to the existing vinyl chloride sheet UV curable type for board-like white boards based on winding type and hard materials (synthetic resin, wood, steel, etc.), ie event schedules, wall-mounted whiteboards, mobile whiteboards, operational whiteboards and training whiteboards The purpose is to provide a coating film composition.
상술한 목적을 달성하기 위한 본 발명은 다음 화학식 1로 표시되는 실리콘 변성 우레탄 아크릴레이트 올리고머 10 ∼ 70 중량%, 반응성 모노머 10 ∼ 70 중량%, 광개시제 1 ∼ 10 중량% 및 레벨링제 1 ∼ 10 중량%를 함유하는 자외선 경화형 도막 조성물을 그 특징으로 한다.The present invention for achieving the above object is 10 to 70% by weight of silicone-modified urethane acrylate oligomer represented by the following formula (1), 10 to 70% by weight reactive monomer, 1 to 10% by weight photoinitiator and 1 to 10% by weight leveling agent It is characterized by an ultraviolet curable coating film composition containing a.
화학식 1Formula 1
상기 화학식 1에서 R1은 수소원자 또는 메틸기이고, R2는 (CH2)ℓ이고 여기서 ℓ은 1 ∼ 10의 정수이다. R3는 탄소수 4 ∼ 20의 선형 지방족, 고리형 지방족, 방향족 화합물 또는 이들 화합물의 올리고머이고, R4는 수소원자, 탄소수 1 ∼ 4의 알킬기 또는 벤질기이고, n은 1 ∼ 20의 정수이고, Y는 말단에 이중결합을 2개 이상 가지고 있는 실리콘 중간체이다.In Formula 1, R 1 is a hydrogen atom or a methyl group, R 2 is (CH 2 ) L and L is an integer of 1 to 10. R 3 is a linear aliphatic, cyclic aliphatic, aromatic compound having 4 to 20 carbon atoms or an oligomer of these compounds, R 4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a benzyl group, n is an integer of 1 to 20, Y is a silicon intermediate having two or more double bonds at its terminals.
또한, 본 발명에 따른 상기 자외선 경화형 도막 조성물에는 비오염성의 지속성을 향상시키기 위하여 아민기를 함유한 유기 폴리실록산과 다음 화학식 2로 표시되는 글리시딜 아크릴계 화합물을 반응시켜 제조된 실리콘 아크릴레이트 0.5 ∼ 10 중량%가 함유되는 것을 특징으로 한다.In addition, in the ultraviolet curable coating composition according to the present invention, 0.5 to 10 weight of silicone acrylate prepared by reacting an organic polysiloxane containing an amine group with a glycidyl acrylic compound represented by the following Formula 2 in order to improve non-pollution persistence. % Is contained.
화학식 2Formula 2
상기 화학식 2에서 X는 수소원자 또는 메틸기이다.In Formula 2, X is a hydrogen atom or a methyl group.
또한, 본 발명에서는 자외선 경화형 도막 조성물에 함유되는 상기 화학식 1로 표시되는 실리콘 변성 우레탄 아크릴레이트 올리고머의 제조방법을 포함하는 바, 이소시아네이트 올리고머와 다음 화학식 3으로 표시되는 3급 실란을 하이드로실릴레이션하고, 다음 화학식 4로 표시되는 말단에 히드록실기를 갖는 실리콘 중간체를 반응시킨 후, 다음 화학식 5로 표시되는 히드록실기 함유 아크릴레이트 모노머를 부가 반응시키는 실리콘 변성 우레탄 아크릴레이트 올리고머의 제조방법을 또다른 특징으로 한다.In addition, the present invention includes a method for producing a silicone-modified urethane acrylate oligomer represented by the formula (1) contained in the ultraviolet curable coating film composition, hydrosilylation of an isocyanate oligomer and a tertiary silane represented by the following formula (3), Next, a method of preparing a silicone-modified urethane acrylate oligomer by reacting a silicon intermediate having a hydroxyl group at the terminal represented by the following Chemical Formula 4, followed by addition reaction of a hydroxyl group-containing acrylate monomer represented by the following Chemical Formula 5 It is done.
화학식 3Formula 3
상기 화학식 3에서 R4는 상기 화학식 1에서 정의한 바와 같다.R 4 in Formula 3 is as defined in Formula 1.
화학식 4Formula 4
상기 화학식 4에서 R5는 -C3H6OC2H4OH이고, m은 1 ∼ 10의 정수이다.In Formula 4, R 5 is -C 3 H 6 OC 2 H 4 OH, and m is an integer of 1 to 10.
화학식 5Formula 5
상기 화학식 5에서 X는 수소원자 또는 메틸기이고, ℓ은 1 ∼ 10의 정수이다.In Formula 5, X is a hydrogen atom or a methyl group, and l is an integer of 1 to 10.
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명에 따른 자외선 경화형 도막 조성물에는 상기 화학식 1로 표시되는 실리콘 변성 우레탄 아크릴레이트 올리고머와 실리콘 아크릴레이트가 함유되고, 여기에 광개시제, 레벨링제 등이 포함됨으로써 내오염성, 내약품성, 내구성 부족 등의 단점을 완전히 보완하여 이물질과의 마찰시 흠집이 적고, 매직 등의 오염물질 접촉후에도 휴지나 마른걸레 등으로 닦기만 해도 쉽게 오염 자국이 지워지며, 김칫국물 등에도 오염되지 않는 등 비오염성이 뛰어나고 내약품성, 내구성 및 물리적 성질 또한 우수한 효과를 얻을 수 있다.UV-curable coating composition according to the present invention contains a silicone-modified urethane acrylate oligomer and silicone acrylate represented by the formula (1), including a photoinitiator, a leveling agent, etc. disadvantages such as contamination resistance, chemical resistance, lack of durability It completely compensates for the friction with foreign substances, and after the contact with pollutants such as magic, it can be easily removed by wiping with tissue paper or dry rag, and it is not polluted by kimchi soup. Durability and physical properties can also be achieved.
이러한 본 발명에 따른 자외선 경화형 도막 조성물에 함유되는 상기 화학식 1로 표시되는 실리콘 변성 우레탄 아크릴레이트 올리고머에는 이소시아네이트 올리고머, 3급 실란, 말단 히드록실기를 갖는 실리콘 중간체 및 히드록실기 함유 아크릴레이트 모노머가 1:0.1:0.1:2.3 ∼ 1:0.2:0.5:3의 몰비로 함유되도록 하고, 바람직하기로는 최종 제품의 경화성 및 기타 경화물성을 감안할 때 1:0.1:0.3:2.3 ∼ 1:0.2:0.4:2.5의 몰비를 갖도록 하는 것이 좋다. 만일 각 성분의 함량이 상기 몰비 범위를 벗어나게 되면 경화성이 느려지고 경화후 제품외관이 불량한 문제가 있다.The silicone-modified urethane acrylate oligomer represented by Formula 1 contained in the ultraviolet curable coating film composition according to the present invention includes an isocyanate oligomer, a tertiary silane, a silicone intermediate having a terminal hydroxyl group, and a hydroxyl group-containing acrylate monomer. It should be included in a molar ratio of: 0.1: 0.1: 2.3 to 1: 0.2: 0.5: 3, and preferably 1: 0.1: 0.3: 2.3 to 1: 0.2: 0.4: 2.5 in view of the curability and other cured product properties of the final product. It is good to have a molar ratio of. If the content of each component is out of the molar ratio range, there is a problem that the curability is slow and the appearance of the product after curing is poor.
상기 실리콘 변성 우레탄 아크릴레이트 올리고머의 구성성분중 이소시아네이트 올리고머로는 이소포론 디이소시아네이트, 4,4-디시클로헥실 메틸 디이소시아네이트, 트리메틸 헥사메틸렌 디이소시아네이트, 1,6-헥사메틸렌 디이소시아네이트, 2,4,4-트리메틸-1,6-헥사메틸렌 디이소시아네이트, 옥타데실렌 디이소시아네이트, 2,6-톨루엔 디이소시아네이트, 1,6-헥사메틸렌 이소시아네이트 올리고머인 비우렛 또는 이소시아누레이트, 2,4,4-톨루엔 디이소시아네이트 등의 이소시아네이트기가 2 ∼ 20개인 이소시아네이트 올리고머이면 어느 것이나 사용 가능하고, 바람직하기로는 도막의 응용물성면을 고려할 때 이소포론 디이소시아네이트 또는 이소시아누레이트를 사용하는 것이 좋다.Isocyanate oligomers in the components of the silicone-modified urethane acrylate oligomer include isophorone diisocyanate, 4,4-dicyclohexyl methyl diisocyanate, trimethyl hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,4, Biuret or isocyanurate, 4-trimethyl-1,6-hexamethylene diisocyanate, octadecylene diisocyanate, 2,6-toluene diisocyanate, 1,6-hexamethylene isocyanate oligomer, 2,4,4- Any isocyanate oligomer having 2 to 20 isocyanate groups such as toluene diisocyanate can be used, and preferably isophorone diisocyanate or isocyanurate is used in consideration of application properties of the coating film.
또한, 본 발명의 실리콘 변성 우레탄 아크릴레이트 올리고머 제조에 사용되는 상기 화학식 3으로 표시되는 3급 실란으로는 벤질 디메틸 실란, 부틸 디메틸 실란, 디에틸 메틸 실란, 1,1,1,3,3,5,5-헵타메틸 트리실록산, 이소부틸 디에톡시실란, 헥실 에톡시실란, 트리메틸실란 등을 사용할 수 있다.In addition, the tertiary silane represented by the formula (3) used in the preparation of the silicone-modified urethane acrylate oligomer of the present invention is benzyl dimethyl silane, butyl dimethyl silane, diethyl methyl silane, 1,1,1,3,3,5 , 5-heptamethyl trisiloxane, isobutyl diethoxysilane, hexyl ethoxysilane, trimethylsilane and the like can be used.
이러한 이소시아네이트 올리고머와 상기 화학식 3으로 표시되는 3급 실란을 0.1 ∼ 0.9 기압으로 감압하에 헥사클로로플라트닉산을 촉매로 80 ∼ 130℃에서 반응시키는 하이드로실릴레이션을 수행한다.The hydrosilylation of the isocyanate oligomer and the tertiary silane represented by Chemical Formula 3 is carried out by reacting hexachloroplatonic acid with a catalyst at 80 to 130 ° C. under reduced pressure at a pressure of 0.1 to 0.9 atm.
그런 다음 상기 화학식 4로 표시되는 말단에 히드록실기를 갖는 실리콘 중간체를 투입하여 반응시킨다. 말단에 히드록실기를 갖는 실리콘 중간체로는 디메틸 실록산, 3-히드록시 프로필-말단기와 디메틸, 메틸(프로필렌 옥사이드)실록산 등을 사용할 수 있다. 이러한 말단에 히드록실기를 갖는 실리콘 중간체에 필요에 따라서는 불포화 카르본산을 1:0.95 ∼ 1:0.7의 몰비로 축합반응시킬 수 있고, 바람직하기로는 경화성을 고려할 때 1:0.95 ∼ 1:0.85로 축합반응시키는 것이 좋다.Then, a silicon intermediate having a hydroxyl group is added to the terminal represented by Chemical Formula 4 and reacted. Dimethyl siloxane, 3-hydroxy propyl-terminal group, dimethyl, methyl (propylene oxide) siloxane, etc. can be used as a silicone intermediate which has a hydroxyl group at the terminal. If necessary, a condensation reaction of an unsaturated carboxylic acid in a molar ratio of 1: 0.95 to 1: 0.7 can be carried out to the silicone intermediate having a hydroxyl group at the terminal, and preferably 1: 0.95 to 1: 0.85 in consideration of curability. Condensation reaction is good.
한편, 상기 화학식 4로 표시되는 말단에 히드록실기를 갖는 실리콘 중간체를 40 ∼ 55℃에서 30분 ∼ 2시간동안 드롭핑하는 방법으로 반응시킨 다음, 상기 화학식 5로 표시되는 히드록실기 함유 아크릴레이트 모노머를 투입하고 발열에 주의하면서 65 ∼ 90℃로 승온하는 방법으로 부가 반응시킴으로써 상기 화학식 1로 표시되는 실리콘 변성 우레탄 아크릴레이트 올리고머를 제조한다. 이러한 말단에 이중결합과 히드록실기를 가진 아크릴레이트 모노머로는 히드록시 에틸 아크릴레이트, 히드록시 에틸 메타크릴레이트, 히드록시 프로필 아크릴레이트, 히드록시 프로필 메타크릴레이트, 히드록시 부틸 메타크릴레이트, 히드록시 펜틸 아크릴레이트, 히드록시 펜틸 메타크릴레이트, 히드록시 헥실 아크릴레이트, 히드록시 헥실 메타크릴레이트 등을 사용할 수 있다.On the other hand, the silicon intermediate having a hydroxyl group at the terminal represented by the formula (4) was reacted by dropping for 30 minutes to 2 hours at 40 to 55 ℃, and then the hydroxyl group-containing acrylate represented by the formula (5) A silicone-modified urethane acrylate oligomer represented by the formula (1) is prepared by adding a monomer and adding reaction by heating to 65 to 90 ° C while paying attention to heat generation. As the acrylate monomer having a double bond and a hydroxyl group at such a terminal, hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl acrylate, hydroxy propyl methacrylate, hydroxy butyl methacrylate, and hydroxy Hydroxy pentyl acrylate, hydroxy pentyl methacrylate, hydroxy hexyl acrylate, hydroxy hexyl methacrylate and the like can be used.
상기와 같은 과정을 통하여 제조된 상기 화학식 1로 표시되는 실리콘 변성 우레탄 아크릴레이트 올리고머는 중량평균분자량이 1,200 ∼ 40,000의 범위를 갖는 것이 비오염성의 지속성 및 외관(레벨링)을 향상시키는 면에서 좋다. 이러한 실리콘 변성 우레탄 아크릴레이트 올리고머를 포함하는 본 발명의 자외선 경화형 도막 조성물에는 반응성 모노머, 광개시제, 레벨링제, 실리콘 아크릴레이트, 소광제 및 기타 첨가제가 포함됨으로써 25℃에서 400 ∼ 500 cps의 점도를 갖는다.The silicone-modified urethane acrylate oligomer represented by Chemical Formula 1 prepared through the above process has a weight average molecular weight in the range of 1,200 to 40,000, in terms of improving non-pollution persistence and appearance (leveling). The ultraviolet curable coating film composition of the present invention containing such a silicone-modified urethane acrylate oligomer includes a reactive monomer, a photoinitiator, a leveling agent, a silicone acrylate, a quencher, and other additives, and thus has a viscosity of 400 to 500 cps at 25 ° C.
상기 화학식 1로 표시되는 실리콘 변성 우레탄 아크릴레이트 올리고머는 도막 조성물 중에 10 ∼ 70 중량% 함유되도록 하고, 바람직하기로는 도막의 물성과 바니쉬의 점도를 고려하여 25 ∼ 60 중량%를 사용하는 것이 좋다. 만일, 함량이 10 중량% 미만이면 비오염성, 부착성 및 외관이 저하되며, 70 중량%를 초과하면 점도가 높아 작업성이 불량하고 도막이 강해진다.The silicone-modified urethane acrylate oligomer represented by the formula (1) is to be contained in 10 to 70% by weight in the coating film composition, preferably 25 to 60% by weight in consideration of the physical properties of the coating film and the viscosity of the varnish. If the content is less than 10% by weight, the non-pollution, adhesion and appearance is lowered, if it exceeds 70% by weight, the viscosity is high, workability is poor and the coating film is strong.
또한, 본 발명의 도막 조성물에 함유되는 반응성 모노머는 실리콘 변성 우레탄 아크릴레이트 올리고머와 함께 중합되어 도막의 물성에 영향을 주는 것으로서 하나 또는 그 이상의 모노머를 사용할 수 있는데, 주로 사용되는 것은 아크릴산 에스테르 모노머 또는 단관능 비닐기를 갖는 모노머이고, 이는 도막 조성물 중에 10 ∼ 70 중량% 함유되도록 한다.In addition, the reactive monomer contained in the coating composition of the present invention may be polymerized together with the silicone-modified urethane acrylate oligomer to affect the physical properties of the coating film, and one or more monomers may be used. It is a monomer which has a functional vinyl group, and it is made to contain 10 to 70 weight% in a coating film composition.
이러한 반응성 모노머 중에서 아크릴산 에스테르는 알코올과 불포화 카르본산을 에스테르 반응시켜 제조한 것으로서 이러한 아크릴산 에스테르로는 1,4-부탄디올 디아크릴레이트, 1,6-헥산디올 디아크릴레이트, 네오펜틸글리콜 디아크릴레이트, 펜타에리스리톨 트리메타크릴레이트, 트리메틸올프로판 트리아크릴레이트, 에틸헥실 아크릴레이트, 에틸헥실 메타크릴레이트, 펜틸 아크릴레이트, 헥실 아크릴레이트, 시클로헥실 메타크릴레이트, 트리프로필렌글리콜 디아크릴레이트, 폴리에틸렌글리콜 디아크릴레이트 등이 있다. 반응성 모노머로 상기 아크릴산 에스테르를 사용하는 경우 실리콘 변성 우레탄 아크릴레이트 올리고머와 1:8 ∼ 8:1의 중량비로 사용하는 것이 바람직하다.Among these reactive monomers, the acrylic acid ester is prepared by esterifying an alcohol with an unsaturated carboxylic acid. Examples of the acrylic acid ester include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentylglycol diacrylate, Pentaerythritol trimethacrylate, trimethylolpropane triacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, pentyl acrylate, hexyl acrylate, cyclohexyl methacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate Rate and the like. When using the said acrylic acid ester as a reactive monomer, it is preferable to use it by the weight ratio of silicone modified urethane acrylate oligomer and 1: 8-8: 1.
또다른 반응성 모노머인 상기 단관능 비닐기를 갖는 모노머로는 N-비닐-2-피롤리돈, 비닐 아세테이트, 비닐 부티레이트, 비닐 이소부티레이트, 비닐 카프레이트, 비닐 카프로에이트, 비닐 카프틸레이트, 비닐 세틸에테르, 비닐 시클로헥산올, 비닐-N-데카노에이트, 비닐 옥타데실에테르 등이 있는데, 바니쉬의 코팅 작업을 용이하게 하기 위해 점도를 맞추고, 경화속도를 증가시키기 위해서는 N-비닐-2-피롤리돈이 유용하게 사용되며, 이러한 단관능 비닐기를 갖는 모노머를 반응성 모노머로 사용하는 경우 실리콘 변성 우레탄 아크릴레이트 올리고머와 1:7 ∼ 7:1의 중량비로 사용하며, 바람직하기로는 1:3 ∼ 3:1의 중량비로 사용하는 것이 좋다.The monomer having the above monofunctional vinyl group which is another reactive monomer is N-vinyl-2-pyrrolidone, vinyl acetate, vinyl butyrate, vinyl isobutyrate, vinyl caprate, vinyl caproate, vinyl captylate, vinyl cetyl ether , Vinyl cyclohexanol, vinyl-N-decanoate, vinyl octadecyl ether, etc., to adjust the viscosity to facilitate coating of varnish, and to increase the curing rate, N-vinyl-2-pyrrolidone When the monomer having such a monofunctional vinyl group is used as the reactive monomer, it is used in a weight ratio of silicone modified urethane acrylate oligomer and 1: 7 to 7: 1, and preferably 1: 3 to 3: 1. It is recommended to use in the weight ratio of.
이러한 반응성 모노머는 바니쉬의 점도, 도막의 유연성, 경도, 부착성 등과 밀접한 관계가 있으므로 적당한 비율로 혼용하는 것이 좋다.Such reactive monomers are closely related to the viscosity of the varnish, the flexibility of the coating film, the hardness, and the adhesion.
광개시제는 자외선에 의해 활성을 띠는 통상의 중합개시제를 사용하며, 특히 벤조페논계, 벤질디메탈계, 아세토페논계, 안트라퀴논계, 티옥산톤계 중합개시제를 사용하고, 도막 조성물 중에 1 ∼ 10 중량% 함유되도록 한다. 이러한 광개시제로는 히드록시 시클로헥실 페닐케톤, 2,2-디메톡시-2-페닐, 아세토페논, 벤조페논, 페닐-2-히드록시-2-페닐 케톤 등을 주로 사용한다.The photoinitiator uses a conventional polymerization initiator activated by ultraviolet rays, and in particular, a benzophenone-based, benzyldimetal-based, acetophenone-based, anthraquinone-based, and thioxanthone-based polymerization initiator are used in the coating film composition. Percent by weight. As such photoinitiators, hydroxy cyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyl, acetophenone, benzophenone, phenyl-2-hydroxy-2-phenyl ketone and the like are mainly used.
레벨링제로는 실리콘계 또는 실리콘 폴리아크릴계 화합물을 사용하고, 도막 조성물 중에 0.1 ∼ 10 중량%로 사용한다. 그리고, 도막 조성물에 반광이나 무광이 요구될 때에는 소광제를 사용할 수 있는데, 실리카계 소광제는 요구되는 광택에 따라 도막 조성물 중에 1 ∼ 10 중량%로 사용할 수 있다.As a leveling agent, a silicone type or silicone polyacrylic compound is used, and 0.1 to 10 weight% is used in a coating film composition. When semi-gloss or matte is required for the coating film composition, a matting agent may be used, but the silica-based matting agent may be used in an amount of 1 to 10% by weight in the coating composition.
한편, 본 발명에 따른 실리콘 아크릴레이트는 아민기를 함유한 유기 폴리실록산과 상기 화학식 2로 표시되는 글리시딜 아크릴계 화합물을 반응시켜 제조한 것을 사용하는데, 아민기를 함유한 유기 폴리실록산과 글리시딜 아크릴계 화합물은 0.8:1.05 ∼ 1:2의 몰비로 사용하고, 경화 도막의 비오염성 지속성 향상을 위해서는 1:1.05 ∼ 1:1.1의 몰비로 사용하는 것이 바람직하다. 이러한 실리콘 아크릴레이트는 전체 조성물의 0.5 ∼ 10 중량% 사용할 때 양호한 비오염성의 지속성 향상을 기대할 수 있다. 만일 함량이 0.5 중량% 미만이면 지속성의 향상을 기대하기 어렵고, 10 중량%를 초과하면 외관이 불량해진다.Meanwhile, the silicone acrylate according to the present invention may be prepared by reacting an organic polysiloxane containing an amine group with a glycidyl acrylic compound represented by Formula 2, and the organic polysiloxane containing an amine group and a glycidyl acrylic compound may be used. It is preferable to use it in the molar ratio of 0.8: 1.05-1: 2, and to use it in the molar ratio of 1: 1.05-1: 1.1 in order to improve the non-pollution sustainability of a cured coating film. Such silicone acrylates can expect good non-contamination persistence improvement when used with 0.5-10% by weight of the total composition. If the content is less than 0.5% by weight, it is difficult to expect improvement in the persistence, and when the content is more than 10% by weight, the appearance becomes poor.
기타의 첨가제는 공지의 화합물을 제반 요구에 의해 첨가량을 변화시켜 사용할 수 있다.Other additives can use a well-known compound by changing the addition amount according to various requirements.
상기와 같은 화학식 1로 표시되는 실리콘 변성 우레탄 아크릴레이트 올리고머를 함유하는 자외선 경화형 도막 조성물은 내오염성, 내약품성, 내구성 부족 등의 단점을 완전히 보완하여 이물질과의 마찰시 흠집이 적고, 매직 등의 오염물질 접촉후에도 휴지나 마른걸레 등으로 닦기만 해도 쉽게 오염 자국이 지워지며, 김칫국물 등에도 오염되지 않는 등 비오염성이 뛰어나고 내약품성, 내구성 및 물리적 성질 또한 우수하여 기존 염화 비닐장판용 외에 종이, 합성수지, 목재, 철재, 통상의 권취형 칠판용 및 보드용에 적용 가능하다.The ultraviolet curable coating film composition containing the silicone-modified urethane acrylate oligomer represented by Formula 1 completely compensates for the disadvantages such as contamination resistance, chemical resistance, and lack of durability, and thus has fewer scratches when friction with foreign substances, and contamination such as magic. Even after contact with materials, the stain marks can be easily removed by wiping with tissue paper or dry rag.It is not contaminated with kimchi soup, etc., and has excellent non-pollution properties and excellent chemical resistance, durability and physical properties. Applicable to wood, steel, common winding boards and boards.
이와 같은 본 발명을 실시예에 의거하여 상세하게 설명하겠는 바, 본 발명이 실시예에 한정되는 것은 아니다.Although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example.
제조예 1 : 실리콘 변성 우레탄 아크릴레이트 올리고머의 제조Preparation Example 1 Preparation of Silicone-Modified Urethane Acrylate Oligomer
4구 라운드 플라스크에 이소시아누레이트 올리고머 564.4g을 투입하고, 헥사클로로 플라트닉산 0.56g을 투입한 다음, 콘덴서, 온도계 및 교반기를 장착하였다. 그런 다음 내용물을 100℃까지 가온시키고 벤질 디메틸 실란 43.5g을 서서히 투입하여 4시간 동안 반응시켰다. 이때, 반응종료 확인은 적외선 분석기를 이용하였다. 그런 다음 내용물의 온도를 45℃로 유지시켜 디메틸실록산, 3-히드록시 프로필-말단 123g을 첨가하고 1시간동안 반응시킨 후, 히드록시 프로필 아크릴레이트 268.8g을 30분간 천천히 적가하면서 반응을 진행시켰다. 이때, 무촉매 반응을 진행시 반응온도를 70℃ 이내로 하여 실리콘 변성 우레탄 아크릴레이트 올리고머를 제조하였다.564.4 g of isocyanurate oligomer was added to a four-necked round flask, 0.56 g of hexachloro platonic acid was added thereto, and then a condenser, a thermometer, and a stirrer were mounted. Then, the contents were warmed up to 100 ° C., and 43.5 g of benzyl dimethyl silane was slowly added thereto and reacted for 4 hours. At this time, the reaction termination was confirmed using an infrared analyzer. Thereafter, the temperature of the contents was maintained at 45 ° C., and 123 g of dimethylsiloxane and 3-hydroxy propyl-terminus were added and reacted for 1 hour. At this time, the silicon-modified urethane acrylate oligomer was prepared at a reaction temperature of 70 ° C. or less during the progress of the non-catalytic reaction.
제조예 2 : 실리콘 변성 우레탄 아크릴레이트 올리고머의 제조Preparation Example 2 Preparation of Silicone-Modified Urethane Acrylate Oligomer
이소시아누레이트 569.9g, 3급 부틸 디메틸 실란 34.0g, 디메틸 실록산, 3-히드록시 프로필-말단 124.2g, 히드록시 에틸 아크릴레이트 271.2g을 사용하여 상기 제조예 1과 동일한 방법으로 실리콘 변성 우레탄 아크릴레이트 올리고머를 제조하였다.Silicone-modified urethane acrylic in the same manner as in Preparation Example 1, using 569.9 g of isocyanurate, 34.0 g of tertiary butyl dimethyl silane, dimethyl siloxane, 124.2 g of 3-hydroxypropyl-terminus, and 271.2 g of hydroxyethyl acrylate. Rate oligomers were prepared.
제조예 3 : 실리콘 변성 우레탄 아크릴레이트 올리고머의 제조Preparation Example 3 Preparation of Silicone-Modified Urethane Acrylate Oligomer
이소시아누레이트 556.6g, 벤질 디메틸 실란 34.0g, 디메틸 실록산, 3-히드록시 프로필-말단 121.3g, 히드록시 에틸 아크릴레이트 264.9g을 사용하여 상기 제조예 1과 동일한 방법으로 실리콘 변성 우레탄 아크릴레이트 올리고머를 제조하였다.Silicone-modified urethane acrylate oligomer in the same manner as in Preparation Example 1 using 556.6 g of isocyanurate, 34.0 g of benzyl dimethyl silane, dimethyl siloxane, 121.3 g of 3-hydroxy propyl-terminus, and 264.9 g of hydroxy ethyl acrylate Was prepared.
제조예 4 : 실리콘 아크릴레이트의 제조Preparation Example 4 Preparation of Silicone Acrylate
4구 라운드 플라스크에 말단에 히드록실기를 가진 폴리디메틸 실록산 257g을 투입하고 온도계, 콘덴서, 교반기를 장착한 다음, 3-에틸렌디아미노 프로필메틸디메톡시 실란 242g을 30분간 적가한 후(이때, 물중탕을 사용하여 발열을 제어함), 10℃에서 2시간동안 반응시켜 아민기를 가진 유기 폴리실록산을 제조하였다.Into a four-necked round flask, 257 g of polydimethyl siloxane having a hydroxyl group at the end was added, a thermometer, a condenser and a stirrer were added, and 242 g of 3-ethylenediamino propylmethyldimethoxy silane was added dropwise for 30 minutes (at this time, water An exotherm was used to control the exotherm), followed by reaction at 10 ° C. for 2 hours to prepare an organic polysiloxane having an amine group.
교반하면서 이후 중합금지제인 메틸에틸하이드로퀴논(MEHQ) 1g을 투입하고 글리시딜 아크릴레이트 500g을 10분간 적가하면서 반응온도를 60 ∼ 70℃로 승온하여 8시간동안 반응시켜 실리콘 아크릴레이트를 제조하였다. 이때, 반응의 진행 사항은 적외선 분석기를 사용하여 측정하였다.After stirring, 1 g of methyl ethyl hydroquinone (MEHQ), which is a polymerization inhibitor, was added thereto, and 500 g of glycidyl acrylate was added dropwise for 10 minutes to raise the reaction temperature to 60 to 70 ° C. to react for 8 hours to prepare silicone acrylate. At this time, the progress of the reaction was measured using an infrared analyzer.
실시예 1Example 1
상기 제조예 1에서 제조한 실리콘 변성 우레탄 아크릴레이트 올리고머 222 중량부, 우레탄 아크릴레이트(UCB사, 에버크릴 1290) 222 중량부, 1,6-헥산디올 디아크릴레이트 200 중량부, 트리프로필렌글리콜 디아크릴레이트 66 중량부, 네오펜틸글리콜 디아크릴레이트 240 중량부, 광개시제로 2-히드록시-2-메틸페닐프로판-1-온(시바가이기사, 다로큐어 1173) 40 중량부, 레벨링제로 실리콘 디아크릴레이트(UCB사, 에버크릴 350) 10 중량부를 40℃에서 교반하여 25℃에서 점도가 800 cps인 실리콘 변성 우레탄 아크릴레이트 올리고머를 함유한 자외선 경화형 도막 조성물을 얻었다.222 parts by weight of the silicone-modified urethane acrylate oligomer prepared in Preparation Example 1, 222 parts by weight of urethane acrylate (UCB, Evercryl 1290), 200 parts by weight of 1,6-hexanediol diacrylate, tripropylene glycol diacryl 66 parts by weight, neopentylglycol diacrylate 240 parts by weight, 40 parts by weight of 2-hydroxy-2-methylphenylpropan-1-one (Shibagai Corporation, Tarocure 1173) as a photoinitiator, silicone diacrylate as a leveling agent ( UCB, Evercryl 350) 10 weight part was stirred at 40 degreeC, and the ultraviolet curable coating film composition containing the silicone modified urethane acrylate oligomer whose viscosity is 800 cps at 25 degreeC was obtained.
실시예 2Example 2
상기 제조예 2에서 제조한 실리콘 변성 우레탄 아크릴레이트 올리고머를 사용한 것 이외에는 상기 실시예 1과 동일한 방법으로 실리콘 변성 우레탄 아크릴레이트 올리고머를 함유한 자외선 경화형 도막 조성물을 얻었다.A UV curable coating film composition containing a silicone-modified urethane acrylate oligomer was obtained in the same manner as in Example 1 except that the silicone-modified urethane acrylate oligomer prepared in Preparation Example 2 was used.
실시예 3Example 3
상기 제조예 3에서 제조한 실리콘 변성 우레탄 아크릴레이트 올리고머를 사용한 것 이외에는 상기 실시예 1과 동일한 방법으로 실리콘 변성 우레탄 아크릴레이트 올리고머를 함유한 자외선 경화형 도막 조성물을 얻었다.A UV curable coating film composition containing a silicone-modified urethane acrylate oligomer was obtained in the same manner as in Example 1 except that the silicone-modified urethane acrylate oligomer prepared in Preparation Example 3 was used.
실시예 4Example 4
상기 제조예 1에서 제조한 실리콘 변성 우레탄 아크릴레이트 올리고머를 사용하고 상기 실시예 1에서 사용한 레벨링제 대신에 제조예 4에서 제조한 실리콘 아크릴레이트를 사용한 것 이외에는 상기 실시예 1과 동일한 방법으로 실리콘 변성 우레탄 아크릴레이트 올리고머를 함유한 자외선 경화형 도막 조성물을 얻었다.The silicone-modified urethane was prepared in the same manner as in Example 1, except that the silicone-modified urethane acrylate oligomer prepared in Preparation Example 1 was used and the silicone acrylate prepared in Preparation Example 4 was used instead of the leveling agent used in Example 1. The ultraviolet curable coating film composition containing the acrylate oligomer was obtained.
실시예 5Example 5
상기 제조예 2에서 제조한 실리콘 변성 우레탄 아크릴레이트 올리고머를 사용하고 상기 실시예 1에서 사용한 레벨링제 대신에 제조예 4에서 제조한 실리콘 아크릴레이트를 사용한 것 이외에는 상기 실시예 1과 동일한 방법으로 실리콘 변성 우레탄 아크릴레이트 올리고머를 함유한 자외선 경화형 도막 조성물을 얻었다.The silicone-modified urethane was prepared in the same manner as in Example 1, except that the silicone-modified urethane acrylate oligomer prepared in Preparation Example 2 was used and the silicone acrylate prepared in Preparation Example 4 was used instead of the leveling agent used in Example 1. The ultraviolet curable coating film composition containing the acrylate oligomer was obtained.
실시예 6Example 6
상기 제조예 3에서 제조한 실리콘 변성 우레탄 아크릴레이트 올리고머를 사용하고 상기 실시예 1에서 사용한 레벨링제 대신에 제조예 4에서 제조한 실리콘 아크릴레이트를 사용한 것 이외에는 상기 실시예 1과 동일한 방법으로 실리콘 변성 우레탄 아크릴레이트 올리고머를 함유한 자외선 경화형 도막 조성물을 얻었다.The silicone-modified urethane was prepared in the same manner as in Example 1, except that the silicone-modified urethane acrylate oligomer prepared in Preparation Example 3 was used and the silicone acrylate prepared in Preparation Example 4 was used instead of the leveling agent used in Example 1. The ultraviolet curable coating film composition containing the acrylate oligomer was obtained.
비교예Comparative example
상기 실시예 1의 실리콘 변성 우레탄 아크릴레이트 올리고머 222 중량부와 우레탄 아크릴레이트(UCB사, 에버크릴 1290) 222 중량부 대신에 우레탄 아크릴레이트(UCB사, 에버크릴 1290) 444 중량부를 사용한 것 이외에는 상기 실시예 1과 동일한 방법으로 자외선 경화형 도막 조성물을 제조하였다.The above-described embodiment except that 222 parts by weight of the silicone-modified urethane acrylate oligomer of Example 1 and 444 parts by weight of urethane acrylate (UCB, Evercryl 1290) were used instead of 222 parts by weight of urethane acrylate (UCB, Evercryl 1290). An ultraviolet curable coating film composition was manufactured in the same manner as in Example 1.
실험예Experimental Example
상기 실시예 1 ∼ 6 및 비교예에서 제조한 자외선 경화형 도막 조성물에 대하여 비오염성을 측정하고, 그 결과를 다음 표 1에 나타내었고, 경화물성을 측정한 다음 그 결과를 다음 표 2에 나타내었다.Non-pollution properties of the UV curable coating compositions prepared in Examples 1 to 6 and Comparative Examples were measured, and the results are shown in Table 1 below, and the cured physical properties were measured, and the results are shown in Table 2 below.
비오염성은 유성매직(검정, 빨강, 파랑)으로 오염 후, 24시간 경과후 화장지로 닦아내어 그 흔적을 관찰한 것이며, 내마모성은 텔레다인 테이버사 모델 505를 사용하여 250, 500, 1000 rpm으로 회전시킨후 손실된 ㎎수를 표시한 것이고, 슬립성은 코팅된 건조 표면에서 ASTM D 4518에 의하여 측정한 것이다.Non-contamination is oily magic (black, red, blue) after staining, wiped with toilet paper after 24 hours and observed the traces, wear resistance is rotated at 250, 500, 1000 rpm using Teledyne Taber Model 505 The number of mg lost after the test is shown, and the slip property is measured by ASTM D 4518 on the coated dry surface.
상기 표 1 및 표 2에 나타낸 바와 같이, 본 발명의 실리콘 변성 우레탄 아크릴레이트 올리고머를 함유하는 자외선 경화형 도막 조성물이 종래의 도막 조성물에 비교하여 우수함을 알 수 있고, 특히 비오염성이 우수하며, 염화비닐 장판, 종이, 권취형 및 보드용 응용 제품 등에 적용하여 사용할 수 있다.As shown in Table 1 and Table 2, it can be seen that the ultraviolet curable coating film composition containing the silicone-modified urethane acrylate oligomer of the present invention is superior to the conventional coating film composition, in particular, excellent in non-pollution property, vinyl chloride It can be applied to slate plate, paper, winding type and board application products.
상술한 바와 같이, 본 발명의 자외선 경화형 도막 조성물은 내오염성, 내약품성, 내구성 부족 등의 단점을 완전히 보완하여 이물질과의 마찰시 흠집이 적고, 매직 등의 오염물질 접촉후에도 휴지나 마른걸레 등으로 닦기만 해도 쉽게 오염 자국이 지워지며, 김칫국물 등에도 오염되지 않는 등 비오염성이 뛰어나고 내약품성, 내구성 및 물리적 성질 또한 우수하여 기존 염화 비닐장판용 외에 종이, 합성수지, 목재, 철재, 통상의 권취형 칠판용 및 보드용에 적용 가능함을 알 수 있다.As described above, the UV-curable coating composition of the present invention completely compensates for the disadvantages such as contamination resistance, chemical resistance, and lack of durability, so that there are few scratches when friction with foreign substances, even after contact with contaminants such as magic, such as toilet paper or dry mop. It is easy to wipe off stain marks easily, and it is not contaminated with Kimchi soup, etc., and has excellent non-pollution properties, and also has excellent chemical resistance, durability and physical properties.It can be used for paper, synthetic resin, wood, steel, ordinary winding type It can be seen that it is applicable to blackboards and boards.
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| KR1019990007554A KR100286213B1 (en) | 1999-03-08 | 1999-03-08 | A cure type coating composition for ultraviolet rays |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101030692B1 (en) * | 2004-12-31 | 2011-04-26 | 주식회사 케이씨씨 | Preparing method for urethane acrylate oligomer and UV-curable composition for decosheet |
| KR101332969B1 (en) * | 2010-12-31 | 2013-11-25 | 동국대학교 산학협력단 | Non-Solvent Type Pressure Sensitive Adhesive Resin Composition and Pressure Sensitive Adhesive Film Containing Thereof |
| WO2014025104A1 (en) * | 2012-08-07 | 2014-02-13 | (주)엘지하우시스 | Interior sheet for vehicles and method for manufacturing same |
| KR101426140B1 (en) | 2012-08-27 | 2014-08-05 | 조광페인트주식회사 | Matt paint composition and manufacturing method of sheet for matt paint composition |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010058978A (en) * | 1999-12-30 | 2001-07-06 | 김충세 | A cure type coating composition for UV |
| KR101018955B1 (en) * | 2003-12-31 | 2011-03-02 | 주식회사 케이씨씨 | Preparing method for water dispersable silicon-acryl-urethane resin and aqueous coating composition for automobile containing said water dispersable silicon-acryl-urethane resin |
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1999
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101030692B1 (en) * | 2004-12-31 | 2011-04-26 | 주식회사 케이씨씨 | Preparing method for urethane acrylate oligomer and UV-curable composition for decosheet |
| KR101332969B1 (en) * | 2010-12-31 | 2013-11-25 | 동국대학교 산학협력단 | Non-Solvent Type Pressure Sensitive Adhesive Resin Composition and Pressure Sensitive Adhesive Film Containing Thereof |
| WO2014025104A1 (en) * | 2012-08-07 | 2014-02-13 | (주)엘지하우시스 | Interior sheet for vehicles and method for manufacturing same |
| KR101481865B1 (en) * | 2012-08-07 | 2015-01-12 | (주)엘지하우시스 | Interior sheet for motor vehicle and method for preparing the same |
| CN104520143A (en) * | 2012-08-07 | 2015-04-15 | 乐金华奥斯有限公司 | Interior sheet for vehicles and method for manufacturing same |
| US9487673B2 (en) | 2012-08-07 | 2016-11-08 | Lg Hausys, Ltd. | Interior sheet for vehicles and method for manufacturing same |
| CN104520143B (en) * | 2012-08-07 | 2017-07-28 | 乐金华奥斯有限公司 | Automobile cosmetic sheet and preparation method thereof |
| KR101426140B1 (en) | 2012-08-27 | 2014-08-05 | 조광페인트주식회사 | Matt paint composition and manufacturing method of sheet for matt paint composition |
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