JP2018080229A - Curable resin composition - Google Patents
Curable resin composition Download PDFInfo
- Publication number
- JP2018080229A JP2018080229A JP2016221995A JP2016221995A JP2018080229A JP 2018080229 A JP2018080229 A JP 2018080229A JP 2016221995 A JP2016221995 A JP 2016221995A JP 2016221995 A JP2016221995 A JP 2016221995A JP 2018080229 A JP2018080229 A JP 2018080229A
- Authority
- JP
- Japan
- Prior art keywords
- curable resin
- resin composition
- compound
- mass
- meth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 11
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 9
- 239000003822 epoxy resin Substances 0.000 claims description 28
- 229920000647 polyepoxide Polymers 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- 150000001412 amines Chemical class 0.000 claims description 25
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 abstract description 13
- 238000000576 coating method Methods 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 7
- 229920000768 polyamine Polymers 0.000 abstract description 6
- 239000004566 building material Substances 0.000 abstract description 3
- 230000032258 transport Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- -1 amine compound Chemical class 0.000 description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000004848 polyfunctional curative Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- IMYZQPCYWPFTAG-UHFFFAOYSA-N Mecamylamine Chemical compound C1CC2C(C)(C)C(NC)(C)C1C2 IMYZQPCYWPFTAG-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000004843 novolac epoxy resin Substances 0.000 description 3
- 238000004382 potting Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000011187 glycerol Nutrition 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229920000962 poly(amidoamine) Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- YQMXOIAIYXXXEE-UHFFFAOYSA-N 1-benzylpyrrolidin-3-ol Chemical compound C1C(O)CCN1CC1=CC=CC=C1 YQMXOIAIYXXXEE-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- SNGZGCFWZHOVOS-UHFFFAOYSA-N 2-(2-methyloctoxymethyl)oxirane Chemical compound CCCCCCC(C)COCC1CO1 SNGZGCFWZHOVOS-UHFFFAOYSA-N 0.000 description 1
- AQKDMKKMCVJJTC-UHFFFAOYSA-N 2-(2-methylpropoxymethyl)oxirane Chemical compound CC(C)COCC1CO1 AQKDMKKMCVJJTC-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- NPKKFQUHBHQTSH-UHFFFAOYSA-N 2-(decoxymethyl)oxirane Chemical compound CCCCCCCCCCOCC1CO1 NPKKFQUHBHQTSH-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- ZXJBWUAALADCRI-UHFFFAOYSA-N 2-(octadecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCCCCCCCOCC1CO1 ZXJBWUAALADCRI-UHFFFAOYSA-N 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- NXIFLHKNGSUALF-UHFFFAOYSA-N 2-[(2,3-dibromo-4-methylphenoxy)methyl]oxirane Chemical compound BrC1=C(Br)C(C)=CC=C1OCC1OC1 NXIFLHKNGSUALF-UHFFFAOYSA-N 0.000 description 1
- WAPRZVXVTPSWEB-UHFFFAOYSA-N 2-[(2-butan-2-ylphenoxy)methyl]oxirane Chemical compound CCC(C)C1=CC=CC=C1OCC1OC1 WAPRZVXVTPSWEB-UHFFFAOYSA-N 0.000 description 1
- HJEORQYOUWYAMR-UHFFFAOYSA-N 2-[(2-butylphenoxy)methyl]oxirane Chemical compound CCCCC1=CC=CC=C1OCC1OC1 HJEORQYOUWYAMR-UHFFFAOYSA-N 0.000 description 1
- DNVXWIINBUTFEP-UHFFFAOYSA-N 2-[(2-phenylphenoxy)methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1C1=CC=CC=C1 DNVXWIINBUTFEP-UHFFFAOYSA-N 0.000 description 1
- CUFXMPWHOWYNSO-UHFFFAOYSA-N 2-[(4-methylphenoxy)methyl]oxirane Chemical compound C1=CC(C)=CC=C1OCC1OC1 CUFXMPWHOWYNSO-UHFFFAOYSA-N 0.000 description 1
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 1
- WUIQPLSONDMSBW-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(CC)COCC1CO1 WUIQPLSONDMSBW-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- RQZUWSJHFBOFPI-UHFFFAOYSA-N 2-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COCC1CO1 RQZUWSJHFBOFPI-UHFFFAOYSA-N 0.000 description 1
- FVCHRIQAIOHAIC-UHFFFAOYSA-N 2-[1-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COC(C)COCC1CO1 FVCHRIQAIOHAIC-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- PKLOCHBLBMUEFT-UHFFFAOYSA-N 2-[3-(oxiran-2-ylmethoxy)butan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)C(C)OCC1CO1 PKLOCHBLBMUEFT-UHFFFAOYSA-N 0.000 description 1
- JROOCDXTPKCUIO-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)CCOCC1CO1 JROOCDXTPKCUIO-UHFFFAOYSA-N 0.000 description 1
- CAYJDIDYXCENIR-UHFFFAOYSA-N 2-[5-(oxiran-2-ylmethoxy)pentoxymethyl]oxirane Chemical compound C1OC1COCCCCCOCC1CO1 CAYJDIDYXCENIR-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- AGXAFZNONAXBOS-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=CC(CC2OC2)=CC=1CC1CO1 AGXAFZNONAXBOS-UHFFFAOYSA-N 0.000 description 1
- SNZYOYGFWBZAQY-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-methyloxirane Chemical compound CC1CO1.CCC(CO)(CO)CO SNZYOYGFWBZAQY-UHFFFAOYSA-N 0.000 description 1
- RSROEZYGRKHVMN-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;oxirane Chemical compound C1CO1.CCC(CO)(CO)CO RSROEZYGRKHVMN-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
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- RDIGYBZNNOGMHU-UHFFFAOYSA-N 3-amino-2,4,5-tris(oxiran-2-ylmethyl)phenol Chemical compound OC1=CC(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 RDIGYBZNNOGMHU-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- UHUUGQDYCYKQTC-UHFFFAOYSA-N 4-[2,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1CC(C=1C=CC(O)=CC=1)(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UHUUGQDYCYKQTC-UHFFFAOYSA-N 0.000 description 1
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 description 1
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 description 1
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- UMILHIMHKXVDGH-UHFFFAOYSA-N Triethylene glycol diglycidyl ether Chemical compound C1OC1COCCOCCOCCOCC1CO1 UMILHIMHKXVDGH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229960005237 etoglucid Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940105570 ornex Drugs 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical class NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ADXGNEYLLLSOAR-UHFFFAOYSA-N tasosartan Chemical compound C12=NC(C)=NC(C)=C2CCC(=O)N1CC(C=C1)=CC=C1C1=CC=CC=C1C=1N=NNN=1 ADXGNEYLLLSOAR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Abstract
Description
本発明は優れた低温硬化性を有する硬化性樹脂組成物に関するもので、詳細には５℃のような低温でも迅速に硬化することができる、低温硬化可能なエポキシ樹脂組成物に関する。 The present invention relates to a curable resin composition having excellent low-temperature curability, and particularly relates to a low-temperature curable epoxy resin composition that can be rapidly cured even at a low temperature of 5 ° C.
従来、建材や輸送機のコーティングのような、雰囲気条件が一定でない環境における硬化性樹脂組成物の施工では、例えば冬場の屋外のような低温環境でも問題なく硬化する材料を用いる必要があった。このような材料として例えば、特許文献１〜３にはエポキシ樹脂にアクリル官能性基を３つ以上有する化合物とアミン化合物を組み合わせた、低温での反応性を向上させた硬化性樹脂組成物が提案されている。 Conventionally, in the construction of a curable resin composition in an environment where the atmospheric conditions are not constant, such as coatings for building materials and transportation equipment, it has been necessary to use a material that cures without problems even in a low-temperature environment such as outdoors in winter. As such a material, for example, Patent Documents 1 to 3 propose a curable resin composition having improved reactivity at low temperature, which is a combination of an epoxy compound and a compound having three or more acrylic functional groups in an epoxy resin. Has been.
しかしながら、これらの材料は低温での硬化自体は可能であるものの、完全に硬化しきるまでには十分な時間が必要であり、低温速硬化の観点からは必ずしも十分な性能を示すものでは無かった。 However, although these materials can be cured at a low temperature per se, a sufficient time is required until they are completely cured. From the viewpoint of low-temperature rapid curing, these materials do not always exhibit sufficient performance.
本発明では、前記の課題を解決するべく鋭意検討を行った結果、硬化剤として特定構造のアミン化合物、及び特定構造のアクリル官能性化合物を含む、エポキシ系の硬化性樹脂組成物を用いることにより、これを実現するに至った。すなわち、本発明の第一の実施態様は、以下（Ａ）〜（Ｃ）を含んでなる、硬化性樹脂組成物である。
（Ａ）分子中にエポキシ基を１つ以上有する化合物 １００質量部に対し
（Ｂ）分子中に（メタ）アクリロイル基を３つ以上有する化合物 ２〜２５質量部
（Ｃ）マンニッヒ変性アミン化合物 ３０〜７５質量部
In the present invention, as a result of intensive studies to solve the above problems, by using an epoxy curable resin composition containing an amine compound having a specific structure and an acrylic functional compound having a specific structure as a curing agent. This has been achieved. That is, the first embodiment of the present invention is a curable resin composition comprising the following (A) to (C).
(A) Compound having at least one epoxy group in the molecule 100 parts by mass (B) Compound having at least three (meth) acryloyl groups in the molecule 2 to 25 parts by mass (C) Mannich modified amine compound 30 to 75 parts by mass
また本発明は、以下の実施態様も含んだものである。
第二の実施態様は、前記（Ｃ）の２５℃における粘度が、５０〜１０００ｍＰａ・ｓである、前記第一の実施態様に記載の硬化性樹脂組成物である。
The present invention also includes the following embodiments.
2nd embodiment is a curable resin composition as described in said 1st embodiment whose viscosity in 25 degreeC of said (C) is 50-1000 mPa * s.
第三の実施態様は、前記（Ａ）がビスフェノール型エポキシ樹脂を含むものである、前記第一または第二の実施態様に記載の硬化性樹脂組成物である。 A third embodiment is the curable resin composition according to the first or second embodiment, wherein (A) includes a bisphenol-type epoxy resin.
第四の実施態様は、前記（Ａ）及び（Ｂ）を含む組成と前記（Ｃ）を含む組成を別梱包とし、使用する際に混合して用いる二液混合タイプの、前記第一乃至第三の実施態様に記載の硬化性樹脂組成物である。 In the fourth embodiment, the composition containing (A) and (B) and the composition containing (C) are packaged separately, and the two-component mixed type used by mixing them when they are used. It is a curable resin composition as described in a 3rd embodiment.
第五の実施態様は、前記硬化性樹脂組成物が、建造物、自動車車輌、船舶、航空機、鉄道車輌、道路、橋梁の床面、壁面または天井面に敷設して用いるものである、前記第一乃至第四の実施態様に記載の硬化性樹脂組成物である。 In a fifth embodiment, the curable resin composition is used by being laid on a floor surface, wall surface or ceiling surface of a building, automobile vehicle, ship, aircraft, railway vehicle, road, bridge, and the like. The curable resin composition according to any one of the first to fourth embodiments.
第六の実施態様は、前記第一乃至第五の実施態様に記載の硬化性樹脂組成物を硬化することにより得られた硬化物である。 The sixth embodiment is a cured product obtained by curing the curable resin composition described in the first to fifth embodiments.
本発明では、一般にある程度の温度がないと完全硬化し難いエポキシ樹脂を主成分とする硬化性樹脂組成物においても、前記組み合わせの組成物を用いることで、１０℃未満の低温でも２４時間以内に硬化できる、低温硬化性に優れた硬化性樹脂組成物を提供することが可能となった。すなわち本発明は、低温での塗工作業が想定される環境条件においても、エポキシ樹脂組成物が備える特性を有した、接着、シール、コーティング、ポッティング等の用途に利用できることを見出し、完成するに至ったものである。 In the present invention, even in the case of a curable resin composition mainly composed of an epoxy resin that is difficult to be completely cured unless there is a certain temperature, the composition of the combination is used within 24 hours even at a low temperature of less than 10 ° C. It has become possible to provide a curable resin composition that can be cured and has excellent low-temperature curability. That is, the present invention finds that it can be used for applications such as adhesion, sealing, coating, potting, etc., which have the characteristics of the epoxy resin composition even in environmental conditions where low temperature coating work is assumed. It has come.
以下より本発明について詳説する。
本発明に使用される（Ａ）は、分子中にエポキシ基を１つ以上有する化合物である。当該（Ａ）は、本発明の硬化性樹脂組成物において、硬化塗膜を形成する主要な成分であって、分子中にエポキシ基を１つ以上有する化合物であれば、その構造については特段の限定無く用いることができる。エポキシ基を１つ有する単官能エポキシ化合物の具体例としては、メチルグリシジルエーテル、エチルグリシジルエーテル、ブチルグリシジルエーテル、イソブチルグリシジルエーテル、フェニルグリシジルエーテル、２−エチルヘキシルグリシジルエーテル、デシルグリシジルエーテル、ステアリルグリシジルエーテル、アリルグリシジルエーテル、２−メチルオクチルグリシジルエーテル、メトキシポリエチレングリコールモノグリシジルエーテル、エトキシポリエチレングリコールモノグリシジルエーテル、ブトキシポリエチレングリコールモノグリシジルエーテル、フェノキシポリエチレングリコールモノグリシジルエーテル、ｐ−ターシャリーブチルフェニルグリシジルエーテル、ｓｅｃ−ブチルフェニルグリシジルエーテル、ｎ−ブチルフェニルグリシジルエーテル、フェニルフェノールグリシジルエーテル、クレジルグリシジルエーテル、ジブロモクレジルグリシジルエーテル等の化合物を挙げることができる。
The present invention will be described in detail below.
(A) used in the present invention is a compound having one or more epoxy groups in the molecule. The (A) is a major component for forming a cured coating film in the curable resin composition of the present invention, and if it is a compound having one or more epoxy groups in the molecule, its structure is special. It can be used without limitation. Specific examples of the monofunctional epoxy compound having one epoxy group include methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, Allyl glycidyl ether, 2-methyloctyl glycidyl ether, methoxy polyethylene glycol monoglycidyl ether, ethoxy polyethylene glycol monoglycidyl ether, butoxy polyethylene glycol monoglycidyl ether, phenoxy polyethylene glycol monoglycidyl ether, p-tertiary butyl phenyl glycidyl ether, sec- Butyl phenyl glycidyl ether, n Butylphenyl glycidyl ether, phenylphenol glycidyl ether, cresyl glycidyl ether, and compounds such as dibromo cresyl glycidyl ether.
エポキシ基を２つ有する二官能エポキシ化合物の具体例としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＡＳ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、テトラブロモビスフェノールＡ型エポキシ樹脂などのビスフェノール型エポキシ樹脂、およびこれらを水添したものである水添ビスフェノール型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂と２官能イソシアネートを反応させて得られるオキサゾリドン型エポキシ樹脂、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、１，２−ブタンジオールジグリシジルエーテル、１，３−ブタンジオールジグリシジルエーテル、１，４−ブタンジオールジグリシジルエーテル、２，３−ブタンジオールジグリシジルエーテル、１，５−ペンタンジオールジグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，４−シクロヘキサンジメタノールジグリシジルエーテルなどのアルキレングリコール型エポキシ樹脂、ジエチレングリコールジグリシジルエーテル、ジプロピレングリコールジグリシジルエーテル、トリエチレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、などのアルキレンオキサイドジオール型エポキシ樹脂、レゾルシンジグリシジルエーテル、ヒドロキノンジグリシジルエーテル、４,４'−ジヒドロキシ−３,３',５,５'−テトラメチルビフェニルジグリシジルエーテル、１,６−ジヒドロキシナフタレンのジグリシジルエーテル、９,９−ビス（４−ヒドロキシフェニル）フルオレンのジグリシジルエーテル、ジグリシジルアニリン、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂等を挙げることができる。 Specific examples of the bifunctional epoxy compound having two epoxy groups include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AS type epoxy resin, bisphenol AD type epoxy resin, and tetrabromobisphenol A. Bisphenol epoxy resin such as epoxy resin, hydrogenated bisphenol epoxy resin obtained by hydrogenation of these, oxazolidone epoxy resin obtained by reacting bisphenol A epoxy resin with bifunctional isocyanate, ethylene glycol diglycidyl Ether, propylene glycol diglycidyl ether, 1,2-butanediol diglycidyl ether, 1,3-butanediol diglycidyl ether, 1,4-butanediol jig Sidyl ether, 2,3-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether Alkylene glycol type epoxy resin such as diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc. Diol type epoxy resin, resorcin diglycidyl ether, hydroquinone diglycidyl Of 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylbiphenyl diglycidyl ether, 1,6-dihydroxynaphthalene diglycidyl ether, 9,9-bis (4-hydroxyphenyl) fluorene Examples thereof include diglycidyl ether, diglycidyl aniline, biphenyl type epoxy resin, and naphthalene type epoxy resin.
エポキシ基を３つ以上有する多官能エポキシ化合物の具体例としては、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂などのノボラック型エポキシ樹脂、トリス(ｐ−ヒドロキシフェニル）メタンのトリグリシジルエーテル、テトラキス(ｐ−ヒドロキシフェニル）エタンのテトラグリシジルエーテル、トリグリシジルイソシアヌレート、グリセリンのトリグリシジルエーテル、ペンタエリスリトールのテトラグリシジルエーテルや、またテトラグリシジルジアミノジフェニルメタン、テトラグリシジル−ｍ−キシリレンジアミン、トリグリシジル−ｍ−アミノフェノール、トリグリシジル−ｐ−アミノフェノール等のグリシジルアミン化合物などを挙げることができる。これらの化合物は、それぞれ単独で用いてもよく、また２種類以上を混合して用いてもよい。本発明においては、得られる硬化物の耐熱性、機械的特性の観点から、分子内にエポキシ基を２個以上含む化合物を使用するのが好ましく、より好適にはビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂から選ばれるビスフェノール型エポキシ樹脂を含むことが望ましい。また必要に応じて、作業性や硬化物の機械特性を調整する目的で前記ビスフェノール型エポキシ樹脂に単官能エポキシ化合物を含ませても良い。 Specific examples of polyfunctional epoxy compounds having three or more epoxy groups include novolak epoxy resins such as phenol novolac epoxy resins, cresol novolac epoxy resins, naphthol novolac epoxy resins, and tris (p-hydroxyphenyl) methane. Triglycidyl ether, tetrakisyl ether of tetrakis (p-hydroxyphenyl) ethane, triglycidyl isocyanurate, triglycidyl ether of glycerin, tetraglycidyl ether of pentaerythritol, tetraglycidyl diaminodiphenylmethane, tetraglycidyl-m-xylylenediamine And glycidylamine compounds such as triglycidyl-m-aminophenol and triglycidyl-p-aminophenol. These compounds may be used alone or in combination of two or more. In the present invention, from the viewpoint of heat resistance and mechanical properties of the resulting cured product, it is preferable to use a compound containing two or more epoxy groups in the molecule, more preferably bisphenol A type epoxy resin, bisphenol F. It is desirable to include a bisphenol type epoxy resin selected from epoxy type epoxy resins. If necessary, a monofunctional epoxy compound may be included in the bisphenol-type epoxy resin for the purpose of adjusting workability and mechanical properties of the cured product.
公知の（Ａ）の市販品としては、例えば三菱化学株式会社製のｊＥＲ８２８、１００１、８０１、８０６、８０７、１５２、６０４、６３０、８７１、ＹＸ８０００、ＹＸ８０３４、ＹＸ４０００、大日本インキ工業株式会社製のエピクロン８３０、８５０、８３０ＬＶＰ、８５０ＣＲＰ、８３５ＬＶ、ＨＰ４０３２Ｄ、７０３、７２０、７２６、８２０、旭電化工業株式会社製のＥＰ４１００、ＥＰ４０００、ＥＰ４０８０，ＥＰ４０８５、ＥＰ４０８８、ＥＰＵ６、ＥＰＵ７Ｎ、ＥＰＲ４０２３、ＥＰＲ１３０９、ＥＰ４９２０、日産化学工業株式会社製のＴＥＰＩＣ、信越化学工業株式会社製のＫＦ−１０１、ＫＦ−１００１、ＫＦ−１０５、Ｘ−２２−１６３Ｂ、Ｘ−２２−９００２、ナガセケムテックス株式会社製デナコールＥＸ４１１、３１４、２０１、２１２、２５２、ダウケミカル社製品のＤＥＲ−３３１、３３２、３３４、５４２等が挙げられるがこれらに限定されるものではない。これらの化合物は、それぞれ単独で用いてもよく、また２種類以上を混合して用いてもよい。 As a known commercial product of (A), for example, jER828, 1001, 801, 806, 807, 152, 604, 630, 871, manufactured by Mitsubishi Chemical Corporation, YX8000, YX8034, YX4000, manufactured by Dainippon Ink Industries, Ltd. Epicron 830, 850, 830LVP, 850CRP, 835LV, HP4032D, 703, 720, 726, 820, EP4100, EP4000, EP4080, EP4085, EP4088, EPU6, EPU7N, EPR4023, EPR1309, EP4920, Nissan Chemical Co., Ltd. TEPIC manufactured by Kogyo Co., Ltd., KF-101, KF-1001, KF-105, X-22-163B, X-22-9002, manufactured by Shin-Etsu Chemical Co., Ltd., Denacor EX manufactured by Nagase ChemteX Corporation 11,314,201,212,252, but DER-331,332,334,542 like Dow Chemical Company products include but are not limited thereto. These compounds may be used alone or in combination of two or more.
本発明に使用される（Ｂ）は、分子中に（メタ）アクリロイル基を３つ以上有する化合物である。本発明では、アクリルとメタクリルを合わせて（メタ）アクリロイル、（メタ）アクリル等と表記する。当該（Ｂ）は、本発明の硬化性樹脂組成物において、反応性希釈剤として作用すると共に、硬化性樹脂組成物の低温硬化性を高める目的で用いられる。すなわち当該化合物は、エポキシ樹脂組成物の硬化剤に用いられるアミン化合物と比較的低温でも付加反応を行うことが知られているものである。本発明においては、低温環境下では後述の（Ｃ）マンニッヒ変性ポリアミン化合物が（Ａ）のエポキシ基を１つ以上有する化合物と反応するより先に当該化合物と反応が進み、硬化塗膜の形成に寄与するものと考えられる。 (B) used in the present invention is a compound having three or more (meth) acryloyl groups in the molecule. In the present invention, acrylic and methacryl are collectively referred to as (meth) acryloyl, (meth) acryl and the like. The (B) is used for the purpose of enhancing the low temperature curability of the curable resin composition while acting as a reactive diluent in the curable resin composition of the present invention. That is, this compound is known to undergo an addition reaction with an amine compound used as a curing agent for an epoxy resin composition even at a relatively low temperature. In the present invention, under a low temperature environment, the reaction with the compound proceeds before the (C) Mannich-modified polyamine compound (C) described later reacts with a compound having one or more epoxy groups of (A) to form a cured coating film. It is thought to contribute.
（メタ）アクリロイル基を３つ以上有する化合物の具体例としては、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンエチレンオキシド変性トリ（メタ）アクリレート、トリメチロールプロパンプロピレンオキシド変性トリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリス（２−（メタ）アクリロイルオキシエチル）イソシアヌレート、ペンタエリスリトールトリ（メタ）アクリレートとトリレンジイソシアネートの２：１付加物、ペンタエリスリトールトリ（メタ）アクリレートとヘキサメチレンジイソシアネートの２：１付加物、ノボラックのグリシジルエーテルのような３官能以上のエポキシ化合物に（メタ）アクリル酸を付加させたエポキシ（メタ）アクリレート化合物などを挙げることができる。これらの化合物は、それぞれ単独で用いてもよく、また２種類以上を混合して用いてもよい。 Specific examples of the compound having three or more (meth) acryloyl groups include trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, glycerin. Tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate and tolylene diisocyanate 2: Adduct, 2: 1 adduct of pentaerythritol tri (meth) acrylate and hexamethylene diisocyanate, and epoxy (meth) acrylate compound in which (meth) acrylic acid is added to a trifunctional or higher functional epoxy compound such as glycidyl ether of novolak And so on. These compounds may be used alone or in combination of two or more.
本発明においては、得られる硬化物の機械的特性や入手容易性の観点から、当該（Ｂ）としては分子内に（メタ）アクリロイル基を３個含む化合物を使用するのが好ましく、より好適にはトリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートであり、特に好適にはトリメチロールプロパントリ（メタ）アクリレートを用いることにより、とりわけ少量で効果的に低温硬化性を発現することができるようになる。 In the present invention, it is preferable to use a compound containing three (meth) acryloyl groups in the molecule as the (B) from the viewpoint of mechanical properties and availability of the obtained cured product, and more preferably Is trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and particularly preferably uses trimethylolpropane tri (meth) acrylate to exhibit low-temperature curability effectively even in small amounts Will be able to.
本発明における当該（Ｂ）の組成量としては、前記（Ａ）１００質量部に対して２〜２５質量部、より好適には３〜２０質量部、特に好適には５〜１８質量部である。前記下限値以上であることにより、本発明の硬化性樹脂組成物に対する低温硬化性が付与されることとなり、前記上限値以下であることにより、硬化物の硬度や柔軟性といった機械特性に問題を生じることなく、さらに硬化性樹脂組成物の貯蔵安定性にも悪影響を生じない。 The composition amount of (B) in the present invention is 2 to 25 parts by mass, more preferably 3 to 20 parts by mass, and particularly preferably 5 to 18 parts by mass with respect to 100 parts by mass of (A). . By being above the lower limit value, low temperature curability for the curable resin composition of the present invention will be imparted, and by being below the upper limit value, there is a problem with mechanical properties such as hardness and flexibility of the cured product. It does not occur and does not adversely affect the storage stability of the curable resin composition.
本発明に使用される（Ｃ）は、マンニッヒ変性アミン化合物である。マンニッヒ変性ポリアミン化合物とは一般に、アミン化合物と、フェノール類と、アルデヒド類とを縮合させてなる化合物であり、本発明においては前記（Ｂ）と組み合わせることで特に良好な低温硬化性を発現するための成分である。当該（Ｃ）は、機構は不明であるが前記（Ｂ）と特異的に反応することにより、エポキシ樹脂組成物に対して特に優れた低温硬化性をもたらすものであり、当該化合物以外の組合せではこのような格段の作用を発現することができない。本発明において当該（Ｃ）は、２５℃における粘度が５０〜１０００ｍＰａ・ｓの範囲にあるものが特に好ましいが、特段の制限を設けるものではない。 (C) used in the present invention is a Mannich-modified amine compound. The Mannich-modified polyamine compound is generally a compound obtained by condensing an amine compound, a phenol, and an aldehyde. In the present invention, particularly good low-temperature curability is exhibited by combining with (B). It is a component. The mechanism of (C) is unclear, but by reacting specifically with the (B), the epoxy resin composition exhibits particularly excellent low-temperature curability. In combinations other than the compound, Such a remarkable effect cannot be expressed. In the present invention, the (C) having a viscosity at 25 ° C. in the range of 50 to 1000 mPa · s is particularly preferable, but does not provide any particular limitation.
公知の（Ｃ）の市販品としては、例えばＡｉｒ Ｐｒｏｄｕｃｔｓ社製品のアンカミン２４３２（アミン価３８７）、アンカミン２０８９Ｍ（アミン価３６８）、アンカミン１６３７、アンカミン１８５６、ＢＡＳＦ社製品のバーサミンＦ−２０（アミン価４００〜４８０）、バーサミンＩ−３６８（アミン価３７０〜４００）、バーサミンＭ−１（アミン価３７５〜４２５）、Ｈｅｘｉｏｎ社製品のエピキュアー３５４９、エピキュアー３３７８、エピキュアー３０１２、Ｗｉｔｃｏ社製品のＴＬ０７１２（アミン価７０５）、株式会社ＡＤＥＫＡ製品のアデカハードナーＥＨ−３４２Ｍ（アミン価３０７）、アデカハードナーＥＨ−３４２Ｍ１７（アミン価３８６）、アデカハードナーＥＨ−３５０（アミン価３８５）、アデカハードナーＥＨ−３５１（アミン価３０６）、アデカハードナーＥＨ−４５１Ｎ、アデカハードナーＥＨ−２３０、株式会社Ｔ＆Ｋ ＴＯＫＡ製品のフジキュアー５４１０、三和化学工業株式会社製品のサンマイドＷ−３０００（アミン価３４０）、サンマイドＷ−１０００（アミン価３４０）、サンマイドＷ−５００（アミン価２８０）、サンマイドＣＸ−１０２（アミン価２８８）、サンマイドＸ−９６３、大都産業株式会社製品のダイトクラールＳＫ−９００ＦＢ（アミン価３８５）、ダイトクラールＸ−９５１８、ダイトクラールＸ−９５５３（アミン価４４０）、ＰＴＩジャパン株式会社製品のハードナーＫＡ−９３５（アミン価３４０）、大日本インキ化学工業株式会社製品のラッカマイドＶ６−２２１（アミン価４２０）、ペトロケミカルス株式会社製品のレジコンＰＨ−０３６等が挙げられるがこれらに限定されるものではない。これら市販品は、それぞれ単独で用いてもよく、また２種類以上を混合して用いてもよい。またこれらの市販品は、ＪＩＳ−Ｋ−７２３７等で規定されるアミン価が３００〜５００の範囲にあるものを好適に用いることができるが、特段の制限を設けるものでは無い。 Known commercial products of (C) include, for example, Ancamine 2432 (amine number 387), ancamine 2089M (amine number 368), Ancamine 1637, Ancamine 1856, manufactured by Air Products, Versamine F-20 (amine value) manufactured by BASF 400-480), Versamine I-368 (amine number 370-400), Versamine M-1 (amine number 375-425), Hexion's EpiCure 3549, EpiCure 3378, EpiCure 3012, Witco's TL0712 (Amine number) 705), Adeka Hardener EH-342M (Amine Number 307), Adeka Hardener EH-342M17 (Amine Number 386), Adeka Hardener EH-350 (Amine Number 385), Adeka Hardener EH-351 (amine number 306), Adeka Hardener EH-451N, Adeka Hardner EH-230, Fujicure 5410 of T & K TOKA Co., Ltd., Sanmide W-3000 (amine number 340) of Sanwa Chemical Industry Co., Ltd., Sunmide W -1000 (amine number 340), sunmide W-500 (amine number 280), sunmide CX-102 (amine number 288), sunmide X-963, Daito Sangyo Co., Ltd. product Ditocraal SK-900FB (amine number 385), Daitokural X-9518, Daitokural X-9553 (amine number 440), Hardener KA-935 (amine number 340) manufactured by PTI Japan Co., Ltd., Rakkamide V6-221 (amine number 420) manufactured by Dainippon Ink & Chemicals, Inc. ), Petrochemica Although registration control PH-036 or the like, Inc. products and the like but is not limited to these. These commercially available products may be used alone or in combination of two or more. In addition, these commercially available products can suitably use those having an amine value defined in JIS-K-7237 and the like in the range of 300 to 500, but are not particularly limited.
本発明における当該（Ｃ）の組成量としては、前記（Ａ）１００質量部に対して３０〜７５質量部、より好適には３３〜７２質量部、特に好適には３６〜６９質量部である。前記下限値以上であることにより、本発明の硬化性樹脂組成物が十分に硬化することができ、前記上限以下であることにより、貯蔵安定性に問題のない硬化性樹脂組成物を提供することができる。 The composition amount of (C) in the present invention is 30 to 75 parts by mass, more preferably 33 to 72 parts by mass, and particularly preferably 36 to 69 parts by mass with respect to 100 parts by mass of (A). . By being at least the lower limit, the curable resin composition of the present invention can be sufficiently cured, and by being below the upper limit, a curable resin composition having no problem in storage stability is provided. Can do.
また本発明においては、硬化性樹脂組成物の特性を損なわない範囲において任意の添加成分をさらに含ませることができる。当該成分としては例えば、可塑剤、溶剤、希釈剤、シランカップリング剤等の接着性向上成分、分散剤、レベリング剤、湿潤剤、消泡剤等の界面活性剤、帯電防止剤、表面潤滑剤、防錆剤、防腐剤、粘弾性調整剤、レオロジー調整剤、着色剤、紫外線吸収剤等の老化防止剤、有機または無機粉体からなる充填剤等を挙げることができる。さらに本発明の硬化性樹脂組成物には、粘弾性の調整等を目的としてとして、ポリエステル樹脂、ポリカーボネート樹脂、ポリアクリル樹脂、ポリウレタン樹脂、ポリビニル樹脂等の高分子材料を含有させてもよい。 Moreover, in this invention, arbitrary addition components can be further included in the range which does not impair the characteristic of curable resin composition. Examples of the components include adhesive improvement components such as plasticizers, solvents, diluents, silane coupling agents, surfactants such as dispersants, leveling agents, wetting agents, antifoaming agents, antistatic agents, and surface lubricants. And rust inhibitors, preservatives, viscoelasticity modifiers, rheology modifiers, colorants, anti-aging agents such as UV absorbers, and fillers made of organic or inorganic powders. Furthermore, the curable resin composition of the present invention may contain a polymer material such as polyester resin, polycarbonate resin, polyacrylic resin, polyurethane resin, and polyvinyl resin for the purpose of adjusting viscoelasticity.
本発明の好ましい梱包形態としては、前記（Ａ）と（Ｂ）を含む組成を１つの梱包とし、前記（Ｃ）を別梱包として、使用時にこれらを混合して用いる、所謂二液混合タイプとして用いるものである。当該別梱包とすることにより、貯蔵中に（Ａ）、（Ｂ）と（Ｃ）が接触することが無いため、貯蔵安定性が更に向上した硬化性樹脂組成物を提供することができる。またこれら別梱包の二液を混合する際には、従来知られている方法で混合することができ、例えばスタティックミキサー、回転式ミキサー（ダイナミックミキサー）等を用途に応じ適宜選択することができる。 As a preferred packing form of the present invention, the composition containing the (A) and (B) is a single package, the (C) is a separate package, and these are used as a so-called two-component mixed type used by mixing them at the time of use. It is what is used. By using the separate packaging, (A), (B), and (C) do not come into contact with each other during storage, so that a curable resin composition with further improved storage stability can be provided. Moreover, when mixing these two separately packed liquids, they can be mixed by a conventionally known method. For example, a static mixer, a rotary mixer (dynamic mixer), or the like can be appropriately selected according to the application.
本発明の硬化性樹脂組成物は、接着剤、シール剤、コーティング剤、ポッティング剤等、従来エポキシ系の硬化性樹脂組成物が用いられている用途に適用することができるが、特に優れた低温硬化性を有することから、建材や輸送機のコーティングなど、冬場の屋外のような低温環境下で施工するような用途、具体的には建造物、自動車車輌、船舶、航空機、鉄道車輌、道路、橋梁の床面や壁面、天井面の防錆、防水、防汚、表面保護、美観向上等を目的としたコーティング、シール、また骨材等と混合して敷設する樹脂モルタルとして用いることができる。なお本発明では、前記の硬化性樹脂組成物を硬化することにより得られた硬化物も技術範囲に含むものである。 The curable resin composition of the present invention can be applied to applications in which an epoxy-based curable resin composition is conventionally used, such as an adhesive, a sealing agent, a coating agent, and a potting agent, but has an excellent low temperature. Because it has curability, it can be used for construction in low-temperature environments such as outdoors in winter, such as coatings for building materials and transportation equipment, specifically buildings, automobiles, ships, aircraft, railway vehicles, roads, It can be used as a resin mortar to be laid and mixed with coatings, seals, aggregates and the like for the purpose of rust prevention, waterproofing, antifouling, surface protection, aesthetics improvement, etc. on the floor surface, wall surface and ceiling surface of the bridge. In addition, in this invention, the hardened | cured material obtained by hardening | curing the said curable resin composition is also contained in a technical range.
以下、実施例により本発明の効果を詳説するが、これら実施例は本発明の態様の限定を意図するものでは無い。 Hereinafter, the effects of the present invention will be described in detail by way of examples. However, these examples are not intended to limit the embodiments of the present invention.
本発明の硬化性樹脂組成物の特性は、以下方法による実施例にて評価検討を行った。本発明の硬化性樹脂組成物及び比較に用いた硬化性樹脂組成物（合わせて単に「組成物」ともいう）に含まれる構成成分は、以下に示す材料を用いた。また各組成物は、表１に記載した組成比に従い調製した。なお表中に記載の数値は、各成分の組成質量比である。 The characteristics of the curable resin composition of the present invention were evaluated and examined in the following examples. The constituents contained in the curable resin composition of the present invention and the curable resin composition used for comparison (also simply referred to as “composition”) used the following materials. Moreover, each composition was prepared according to the composition ratio described in Table 1. In addition, the numerical value described in a table | surface is a composition mass ratio of each component.
（Ａ）分子中にエポキシ基を１つ以上有する化合物
・ｊＥＲ８２８：ビスフェノールＡ型エポキシ樹脂、エポキシ当量約１８８、三菱化学株式会社製品
・ＳＲ−ＮＰＧ：ネオペンチルグリコールジグリシジルエーテル、エポキシ当量１４５、坂本薬品工業株式会社製品
（Ｂ）分子中にアクリロイル基を３つ以上有する化合物
・ＴＭＰＴＡ：トリメチロールプロパントリアクリレート、ダイセル・オルネクス株式会社製品
（Ｂ）の比較成分（分子中にアクリロイル基を２つ有する化合物）
・Ａ−ＤＣＰ：トリシクロデカンジメタノールジアクリレート、新中村化学工業株式会社製品
（Ｃ）マンニッヒ変性アミン化合物（粘度はＢＬ型粘度計、ローター＃２または３、６０ｒｐｍで３０秒回転後の測定値より算出した値）
・ダイトクラールＸ−９５５３：大都産業株式会社製品、アミン価４４０のマンニッヒ変性アミン化合物、２５℃での粘度２９０ｍＰａ・ｓ
・ハードナーＫＡ−９３５：ＰＴＩジャパン株式会社製品、アミン価３４０のマンニッヒ変性アミン化合物、２５℃での粘度７００ｍＰａ・ｓ
・アデカハードナーＥＨ−４５１Ｎ：株式会社ＡＤＥＫＡ製品、アミン価４２０のマンニッヒ変性アミン化合物、２５℃での粘度４００ｍＰａ・ｓ
・アデカハードナーＥＨ−６０１９：株式会社ＡＤＥＫＡ製品、アミン価４３０のマンニッヒ変性アミン化合物、２５℃での粘度１，２００ｍＰａ・ｓ
（Ｃ）の比較成分
・ＰＨ−８９９：アイカ工業株式会社製品、脂肪族ポリアミン化合物、２５℃での粘度８５ｍＰａ・ｓ
・アンカミン２５９６：製品、脂環式ポリアミン化合物 、２５℃での粘度６５００ｍＰａ・ｓ
・アンカミド２５８９：Ａｉｒ Ｐｒｏｄｕｃｔｓ社製品、ポリアミドアミン化合物、２５℃での粘度２，０００ｍＰａ・ｓ
・アデカハードナーＥＨ−２３００：株式会社ＡＤＥＫＡ製品、変性脂肪族ポリアミン化合物、２５℃での粘度３，０００ｍＰａ・ｓ
・トーマイドＴＸＳ−４３５：株式会社Ｔ＆Ｋ ＴＯＫＡ製品、変性ポリアミドアミン化合物、２５℃での粘度１２，０００ｍＰａ・ｓ
(A) Compound having one or more epoxy groups in the molecule jER828: Bisphenol A type epoxy resin, epoxy equivalent of about 188, Mitsubishi Chemical Corporation product SR-NPG: Neopentyl glycol diglycidyl ether, epoxy equivalent 145, Sakamoto Yakuhin Kogyo Co., Ltd. product (B) Compound having 3 or more acryloyl groups in its molecule ・ TMPTA: Trimethylolpropane triacrylate, Daicel Ornex Co., Ltd. product (B) comparative component (having two acryloyl groups in the molecule) Compound)
A-DCP: Tricyclodecane dimethanol diacrylate, Shin-Nakamura Chemical Co., Ltd. product (C) Mannich modified amine compound (viscosity measured after rotating for 30 seconds at 60 rpm with BL type viscometer, rotor # 2 or 3, Calculated value)
Daitokural X-9553: product of Daito Sangyo Co., Ltd., Mannich modified amine compound having an amine value of 440, viscosity at 25 ° C. 290 mPa · s
・ Hardener KA-935: PTI Japan Co., Ltd. product, Mannich modified amine compound having an amine value of 340, viscosity at 25 ° C. 700 mPa · s
Adeka Hardener EH-451N: ADEKA product, Mannich-modified amine compound having an amine value of 420, viscosity at 25 ° C. of 400 mPa · s
Adeka Hardener EH-6019: ADEKA product, Mannich-modified amine compound having an amine value of 430, viscosity at 25 ° C. of 1,200 mPa · s
Comparative component of (C) PH-899: Aika Industry Co., Ltd. product, aliphatic polyamine compound, viscosity at 25 ° C. 85 mPa · s
Ancamine 2596: product, alicyclic polyamine compound, viscosity at 25 ° C. 6500 mPa · s
Ancamide 2589: Air Products product, polyamidoamine compound, viscosity at 25 ° C. 2,000 mPa · s
Adeka Hardener EH-2300: ADEKA product, modified aliphatic polyamine compound, viscosity at 25 ° C. 3,000 mPa · s
・ Tomide TXS-435: T & K TOKA Co., Ltd., modified polyamidoamine compound, viscosity at 25 ° C. 12,000 mPa · s
上記（Ａ）は、（Ｂ）又はその比較成分と均一に混合したものを本剤として予め用意した。評価を行う際に当該本剤は、所定量の（Ｃ）又はその比較成分と均一に混合攪拌したものを調整し、混合後の経過時間が３分未満のものを評価用の組成物として本実施例での評価に供した。 The above (A) was prepared in advance as this agent by mixing uniformly with (B) or its comparative component. When performing the evaluation, the agent is prepared by uniformly mixing and stirring with a predetermined amount of (C) or a comparative component thereof, and a composition having an elapsed time after mixing of less than 3 minutes is used as an evaluation composition. It used for the evaluation in an Example.
上記手順により調製した評価用の組成物は、以下の条件により特性評価を行った。その結果は表１に併せて示した。
［低温硬化性］
前記評価用の組成物を５℃環境下で２００ｍｌのポリカップ容器にて当該容器の半分の高さが埋まる量を目安として調整し、同環境下で１６時間静置した。然る後、アルコールで洗浄した指先でその表面を軽く触れた時の触覚、並びに組成物が入ったポリカップを逆さに置いたときの流出状態の目視確認により低温硬化性を評価した。評価基準は、指先にべとつきを感じず、全量が流出するまで２４時間以上を要するものを◎、べとつきを感じるが、全量が流出するまで２４時間以上を要するものを○、べとつきを感じ、全量が流出するまで２時間以上２４時間未満であるものを△、べとつきを感じ、全量が流出するまで２時間未満であるものを×とした。
［硬化速度］
前記低温硬化性評価を行った組成物と同じ要領で組成物を調整し、調製後直ちにポリカップの中央にポリプロピレン製攪拌棒（直径約５ｍｍ、長さ約１５ｃｍ）を垂直に立ててこれをクランプで固定した。然る後前記クランプを外し、前記攪拌棒が倒れずに自立した状態となるまでの時間を測定することにより硬化速度を評価した。当該測定は組成物の調製後は１０分単位で測定を行い、自立状態となるまでの時間を表記した。測定時間が６０分を経過してからは１２０，３６０，７２０，１４４０分経過時に測定を行い、１４４０分経過しても自立しない状態のものはその時点で測定を終了して、結果を×として表記した。
The composition for evaluation prepared by the above procedure was evaluated for characteristics under the following conditions. The results are also shown in Table 1.
[Low temperature curability]
The composition for evaluation was adjusted in a 200 ml polycup container under a 5 ° C. environment, using the amount of half the height of the container as a guide, and allowed to stand in the same environment for 16 hours. Thereafter, the low temperature curability was evaluated by tactile sensation when the surface was lightly touched with a fingertip washed with alcohol, and visual check of the outflow state when the polycup containing the composition was placed upside down. The evaluation criteria are ◎ for those that do not feel sticky to the fingertips and require 24 hours or more until the total amount flows out, ◎, those that feel sticky, but those that require more than 24 hours until the total amount flows out, feel sticky, the total amount is The case where it was 2 hours or more and less than 24 hours until flowing out was evaluated as Δ, the stickiness was felt, and the case where it was less than 2 hours until the whole amount flowed out was evaluated as x.
[Curing speed]
The composition was adjusted in the same manner as the composition for which the low-temperature curability evaluation was performed, and immediately after the preparation, a polypropylene stirring rod (diameter: about 5 mm, length: about 15 cm) was vertically set at the center of the polycup, and this was clamped. Fixed. Thereafter, the clamp was removed, and the curing rate was evaluated by measuring the time until the stirring rod became self-supporting without falling down. The measurement was performed in units of 10 minutes after the preparation of the composition, and the time until the self-sustaining state was expressed. Measurements are taken when 120, 360, 720, and 1440 minutes have elapsed after the measurement time has passed 60 minutes. If the measurement time is not self-supporting even after 1440 minutes, the measurement is terminated at that point, and the result is x. Indicated.
実施例１〜５の結果より、本発明の硬化性樹脂組成物は所定の組成比で各成分を含有することにより、低温での優れた硬化特性を有していることが確認できた。（Ｃ）として比較的粘度が高い材料を用いた実施例５では、若干低温硬化性が低下していることが確認できる。他方で、硬化剤として本発明の（Ｃ）に含まれない化合物を用いた比較例１〜５では、いずれも硬化特性が不十分なものとなることが確認された。また本発明で特定した範囲から外れる組成比で（Ｃ）を含む比較例６では、硬化速度が大幅に低下することが認められた。さらに（Ｂ）として、本発明の範囲に含まれない化合物を用いた比較例７では、極めて硬化速度が低下することが認められた。 From the results of Examples 1 to 5, it was confirmed that the curable resin composition of the present invention had excellent curing characteristics at low temperatures by containing each component at a predetermined composition ratio. In Example 5 using a material having a relatively high viscosity as (C), it can be confirmed that the low-temperature curability is slightly lowered. On the other hand, it was confirmed that in Comparative Examples 1 to 5 using a compound not included in (C) of the present invention as a curing agent, the curing characteristics were insufficient. Moreover, in the comparative example 6 containing (C) with the composition ratio which remove | deviates from the range specified by this invention, it was recognized that a cure rate falls significantly. Further, as (B), in Comparative Example 7 using a compound not included in the scope of the present invention, it was recognized that the curing rate was extremely reduced.
本発明による硬化性樹脂組成物は、優れた物性を備えたエポキシ樹脂において、非常に良好な低温硬化性を備えるものであって、冬場の屋外のような低温環境においても施工が可能な接着剤、シール剤、コーティング剤、ポッティング剤等を提供できる、極めて有用なものである。 The curable resin composition according to the present invention is an epoxy resin having excellent physical properties, and has a very good low-temperature curability, and can be applied even in a low-temperature environment such as outdoors in winter. It is extremely useful to provide a sealing agent, a coating agent, a potting agent and the like.
Claims (6)
（Ａ）分子中にエポキシ基を１つ以上有する化合物 １００質量部に対し
（Ｂ）分子中に（メタ）アクリロイル基を３つ以上有する化合物 ２〜２５質量部
（Ｃ）マンニッヒ変性アミン化合物 ３０〜７５質量部 A curable resin composition comprising (A) to (C) below.
(A) Compound having at least one epoxy group in the molecule 100 parts by mass (B) Compound having at least three (meth) acryloyl groups in the molecule 2 to 25 parts by mass (C) Mannich modified amine compound 30 to 75 parts by mass
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| JP2000044653A (en) * | 1998-07-31 | 2000-02-15 | Mitsubishi Chemicals Corp | Resin composition for floor material |
| JP2010024408A (en) * | 2008-07-24 | 2010-02-04 | Nippon Paint Marine Kk | Anticorrosive coating material composition, double-layered coating film formed by using the same and vessel and marine structure equipped with double-layered coating film |
| JP2014148639A (en) * | 2013-02-04 | 2014-08-21 | Chugoku Marine Paints Ltd | Two component type primer, primer coated film, laminate antifouling coated film and antifouling method of base material |
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| JP2000044653A (en) * | 1998-07-31 | 2000-02-15 | Mitsubishi Chemicals Corp | Resin composition for floor material |
| JP2010024408A (en) * | 2008-07-24 | 2010-02-04 | Nippon Paint Marine Kk | Anticorrosive coating material composition, double-layered coating film formed by using the same and vessel and marine structure equipped with double-layered coating film |
| JP2014148639A (en) * | 2013-02-04 | 2014-08-21 | Chugoku Marine Paints Ltd | Two component type primer, primer coated film, laminate antifouling coated film and antifouling method of base material |
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