JPWO2017159732A1 - Resin composition for coating - Google Patents
Resin composition for coating Download PDFInfo
- Publication number
- JPWO2017159732A1 JPWO2017159732A1 JP2018505977A JP2018505977A JPWO2017159732A1 JP WO2017159732 A1 JPWO2017159732 A1 JP WO2017159732A1 JP 2018505977 A JP2018505977 A JP 2018505977A JP 2018505977 A JP2018505977 A JP 2018505977A JP WO2017159732 A1 JPWO2017159732 A1 JP WO2017159732A1
- Authority
- JP
- Japan
- Prior art keywords
- coating
- resin
- resin composition
- component
- acid
- 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
- 238000000576 coating method Methods 0.000 title claims abstract description 82
- 239000011248 coating agent Substances 0.000 title claims abstract description 73
- 239000011342 resin composition Substances 0.000 title claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 14
- 150000003944 halohydrins Chemical group 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 229920003180 amino resin Polymers 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229920000877 Melamine resin Polymers 0.000 claims description 10
- 239000004640 Melamine resin Substances 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 238000001035 drying Methods 0.000 abstract description 19
- 239000000126 substance Substances 0.000 abstract description 13
- 238000003860 storage Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- -1 amine compound Chemical class 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000600 sorbitol Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- ATCRIUVQKHMXSH-UHFFFAOYSA-N 2,4-dichlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1Cl ATCRIUVQKHMXSH-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-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
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JEBWAOITKHXCBF-BEAPMJEYSA-N (3s,3ar,6r,6ar)-3,6-bis(oxiran-2-ylmethoxy)-2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan Chemical compound O([C@@H]1[C@H]2OC[C@H]([C@H]2OC1)OCC1OC1)CC1CO1 JEBWAOITKHXCBF-BEAPMJEYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- LHJGJYXLEPZJPM-UHFFFAOYSA-N 2,4,5-trichlorophenol Chemical compound OC1=CC(Cl)=C(Cl)C=C1Cl LHJGJYXLEPZJPM-UHFFFAOYSA-N 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical class NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
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- 239000002270 dispersing agent Substances 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
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- 238000001879 gelation Methods 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 238000007759 kiss coating Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical group N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 229960004319 trichloroacetic acid Drugs 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
製造ラインでの使用に耐えうる貯蔵安定性及び速乾性を有し、かつ、塗膜の密着性及び耐薬品性等の塗膜物性に優れるコーティング用樹脂組成物を提供する。本発明は、樹脂基材に塗布するための組成物であって、(A)1分子中にエポキシ基及び/又はハロヒドリン基を2〜15個有する多官能反応性化合物、及び、(B)数平均分子量250〜10,000のアミノ樹脂を含むことを特徴とするコーティング用樹脂組成物に関する。Disclosed is a coating resin composition that has storage stability and quick-drying properties that can withstand use in a production line, and is excellent in coating film properties such as adhesion and chemical resistance of the coating film. The present invention is a composition for application to a resin substrate, (A) a polyfunctional reactive compound having 2 to 15 epoxy groups and / or halohydrin groups in one molecule, and (B) number The present invention relates to a coating resin composition comprising an amino resin having an average molecular weight of 250 to 10,000.
Description
本発明は、コーティング用樹脂組成物に関する。 The present invention relates to a coating resin composition.
従来、樹脂基材を用いた工業製品は、例えばパソコンの筺体や各種フィルム等の形状の違いはあるが広く普及している。これらの製造方法に共通することとして、製造ラインで塗装から乾燥までを一貫して行うという点が挙げられる。上記の様に製造ラインで塗装から乾燥までを一貫して行う際には、その工程に要する時間が生産性へと直結する。そのため、生産性を向上させるために上記工程を短時間で完了させる必要がある。 2. Description of the Related Art Conventionally, industrial products using a resin base material have been widely used, although there are differences in the shapes of personal computer housings and various films, for example. Common to these production methods is that the production line is consistently performed from painting to drying. As described above, when the production line is consistently performed from painting to drying, the time required for the process is directly linked to productivity. Therefore, in order to improve productivity, it is necessary to complete the said process in a short time.
短時間での乾燥を行う方法としては、例えば一液型のアクリル樹脂系塗料を用いる方法が挙げられる。しかし、基本的な技術情報として既に認知されている様に、一液型塗料は比較的短時間での乾燥が可能であるものの、密着性や耐薬品性等の塗膜物性が必ずしも十分ではない。この点を改善する方法としては、例えばアクリル樹脂とイソシアネート樹脂とを反応させる二液型塗料が知られているが、この場合、塗膜物性は良好であるものの、乾燥時にアクリル樹脂とイソシアネート樹脂とを反応させる必要があるために比較的乾燥時間が長く、また、塗料を調製して塗装するまでの間にも反応が進行するためにゲル化等が起こるといった貯蔵安定性の問題があるため、実際の使用は限られたものであった。 As a method for drying in a short time, for example, a method using a one-pack type acrylic resin-based paint can be mentioned. However, as already recognized as basic technical information, one-component paints can be dried in a relatively short time, but their coating properties such as adhesion and chemical resistance are not always sufficient. . As a method for improving this point, for example, a two-component paint is known in which an acrylic resin and an isocyanate resin are reacted. In this case, although the coating film properties are good, the acrylic resin and the isocyanate resin are not dried. Since there is a problem of storage stability such that gelation occurs because the reaction progresses before the paint is prepared and applied, since the drying time is relatively long. Actual use was limited.
二液型塗料を短時間で乾燥させる方法としては、乾燥温度を高温にする方法や比較的反応性の高い樹脂同士を組み合わせる方法がある。しかし、樹脂基材はその耐熱性の問題から、樹脂基材の材質や乾燥時間による違いはあるものの、一般的には高温での処理は困難である。そのため、現実的には塗料に用いる樹脂種の選択による解決が行われる。樹脂種としては、例えばエポキシ樹脂とアミン化合物等の硬化剤との組み合わせが広く知られているが、速乾性と貯蔵安定性とはトレードオフの関係にあり、これらの両立は一般的に困難である。この課題を解決する方法として、例えば硬化剤の表面を微粒子で覆うことで貯蔵安定性を向上させる方法(例えば、特許文献1、2)が報告されているが、この方法では微粒子が塗膜中に残留する問題が有り、その使用範囲は制限されるものである。その他の方法としては、硬化剤としてアミノトリアジン環構造を持つ化合物でノボラック樹脂を変性する方法(例えば、特許文献3)が報告されているが、硬化剤の構造が複雑で相溶する溶剤やエポキシ樹脂種が限られるため、その使用範囲は制限されるものである。 As a method of drying the two-component paint in a short time, there are a method of increasing the drying temperature and a method of combining resins having relatively high reactivity. However, due to the heat resistance problem of resin base materials, processing at high temperatures is generally difficult, although there are differences depending on the material of the resin base material and the drying time. Therefore, in reality, a solution is made by selecting a resin type used for the paint. As a resin type, for example, a combination of an epoxy resin and a curing agent such as an amine compound is widely known, but quick drying and storage stability are in a trade-off relationship, and it is generally difficult to achieve both of them. is there. As a method for solving this problem, for example, a method for improving the storage stability by covering the surface of the curing agent with fine particles (for example, Patent Documents 1 and 2) has been reported. However, the range of use is limited. As another method, a method of modifying a novolak resin with a compound having an aminotriazine ring structure as a curing agent has been reported (for example, Patent Document 3). However, the curing agent has a complicated structure and a compatible solvent or epoxy. Since the resin types are limited, the range of use is limited.
本発明は、製造ラインでの使用に耐えうる貯蔵安定性及び速乾性を有し、かつ、塗膜の密着性及び耐薬品性等の塗膜物性に優れるコーティング用樹脂組成物を提供することを目的とする。 The present invention provides a coating resin composition that has storage stability and quick drying properties that can withstand use in a production line, and that is excellent in coating film properties such as adhesion and chemical resistance of the coating film. Objective.
本発明者は、上記課題を解決するために鋭意検討した結果、特定数のエポキシ基及び/又はハロヒドリン基を有する多官能反応性化合物と、特定の数平均分子量を有するアミノ樹脂とを必須成分として含む二液型のエポキシ樹脂組成物が、貯蔵安定性及び速乾性に優れ、かつ、二液型塗料の特徴である塗膜の密着性及び耐薬品性等の塗膜物性に優れ、樹脂基材に塗布するためのコーティング用組成物として好適に用いられることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventor has, as essential components, a polyfunctional reactive compound having a specific number of epoxy groups and / or halohydrin groups and an amino resin having a specific number average molecular weight. The two-part epoxy resin composition contains excellent storage stability and quick-drying, and is excellent in coating film properties such as adhesion and chemical resistance, which are the characteristics of the two-part paint. The present invention has been completed by finding that it can be suitably used as a coating composition for application to a coating.
すなわち、本発明のコーティング用樹脂組成物は、樹脂基材に塗布するための組成物であって、
(A)1分子中にエポキシ基及び/又はハロヒドリン基を2〜15個有する多官能反応性化合物、及び、
(B)数平均分子量250〜10,000のアミノ樹脂
を含むことを特徴とする。That is, the coating resin composition of the present invention is a composition for applying to a resin substrate,
(A) a polyfunctional reactive compound having 2 to 15 epoxy groups and / or halohydrin groups in one molecule, and
(B) An amino resin having a number average molecular weight of 250 to 10,000 is included.
本発明のコーティング用樹脂組成物において、(B)アミノ樹脂がメラミン樹脂であることが好ましい。 In the coating resin composition of the present invention, the (B) amino resin is preferably a melamine resin.
本発明のコーティング用樹脂組成物において、(B)成分の含有量が(A)成分100重量部に対して10〜10,000重量部であることが好ましい。 In the coating resin composition of the present invention, the content of the component (B) is preferably 10 to 10,000 parts by weight with respect to 100 parts by weight of the component (A).
本発明のコーティング用樹脂組成物において、(A)多官能反応性化合物が1分子中にエポキシ基及び/又はハロヒドリン基を2〜10個有することが好ましい。 In the coating resin composition of the present invention, it is preferable that the (A) polyfunctional reactive compound has 2 to 10 epoxy groups and / or halohydrin groups in one molecule.
本発明の部材は、樹脂基材と、本発明のコーティング用樹脂組成物を用いて樹脂基材上に形成された塗膜とを有することを特徴とする。 The member of this invention has a resin base material and the coating film formed on the resin base material using the resin composition for coating of this invention, It is characterized by the above-mentioned.
本発明の部材において、樹脂基材の材質がポリエステルであることが好ましい。 In the member of the present invention, the resin base material is preferably polyester.
本発明の部材の製造方法は、本発明の部材を製造するための方法であって、
本発明のコーティング用樹脂組成物を樹脂基材の少なくとも一つの面に塗布する工程(1)、及び、
工程(1)で塗布したコーティング用樹脂組成物を60〜250℃で5〜300秒間加熱して硬化させる工程(2)
を含むことを特徴とする。The member manufacturing method of the present invention is a method for manufacturing the member of the present invention,
A step (1) of applying the coating resin composition of the present invention to at least one surface of a resin substrate; and
Step (2) for curing the coating resin composition applied in step (1) by heating at 60 to 250 ° C. for 5 to 300 seconds.
It is characterized by including.
本発明のコーティング用樹脂組成物は、特定数のエポキシ基及び/又はハロヒドリン基を有する多官能反応性化合物と、特定の数平均分子量を有するアミノ樹脂とを含むため、貯蔵安定性及び速乾性に優れるとともに、塗膜の密着性及び耐薬品性に優れ、樹脂基材に塗布するためのコーティング用組成物として好適に用いられる。 Since the coating resin composition of the present invention contains a polyfunctional reactive compound having a specific number of epoxy groups and / or halohydrin groups and an amino resin having a specific number average molecular weight, the storage stability and quick drying properties are improved. While being excellent, it is excellent in the adhesiveness and chemical resistance of a coating film, and is suitably used as a coating composition for coating on a resin substrate.
<<コーティング用樹脂組成物>>
本発明のコーティング用樹脂組成物は、樹脂基材に塗布するための組成物であって、
(A)1分子中にエポキシ基及び/又はハロヒドリン基を2〜15個有する多官能反応性化合物、及び、
(B)数平均分子量250〜10,000のアミノ樹脂
を含むことを特徴とする。<< Resin composition for coating >>
The coating resin composition of the present invention is a composition for applying to a resin substrate,
(A) a polyfunctional reactive compound having 2 to 15 epoxy groups and / or halohydrin groups in one molecule, and
(B) An amino resin having a number average molecular weight of 250 to 10,000 is included.
<(A)多官能反応性化合物>
(A)多官能反応性化合物(以下、単に(A)成分ともいう)としては、1分子中にエポキシ基及び/又はハロヒドリン基を2〜15個有する限り特に限定されず、エポキシ基を有する化合物として例えば、ソルビトールポリグリシジルエーテル、ビスフェノールAジグリシジルエーテル、グリセリンポリグリシジルエーテル、ポリグリセリンポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、レゾルシノールジグリシジルエーテル、イソソルビドジグリシジルエーテル、イソマンニドジグリシジルエーテル、イソイディットジグリシジルエーテル、水添ビスフェノールAジグリシジルエーテル、クレゾールノボラックポリグリシジルエーテル等が挙げられる。ハロヒドリン化合物としては、例えば、ハロゲンと水を、二重結合をもつ化合物に反応させて得られる化合物や、エピハロヒドリン類とアルコール化合物とをルイス酸触媒存在下で反応させて得られる化合物(ハロヒドリンエーテル化合物)を挙げることができる。例えば、ソルビトールポリハロヒドリン、グリセリンポリハロヒドリン、ジグリセリンポリクロロヒドリン、エチレングリコールジハロヒドリン、プロピレングリコールジクロロヒドリンなどが挙げられる。これらは単独で用いても良いし、2種以上を併用しても良い。<(A) polyfunctional reactive compound>
The (A) polyfunctional reactive compound (hereinafter also simply referred to as the component (A)) is not particularly limited as long as it has 2 to 15 epoxy groups and / or halohydrin groups in one molecule, and a compound having an epoxy group For example, sorbitol polyglycidyl ether, bisphenol A diglycidyl ether, glycerin polyglycidyl ether, polyglycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, resorcinol diglycidyl ether, isosorbide diglycidyl ether, isomanni Examples include dodiglycidyl ether, isoidid diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and cresol novolac polyglycidyl ether. Examples of the halohydrin compound include compounds obtained by reacting halogen and water with a compound having a double bond, and compounds obtained by reacting epihalohydrins and alcohol compounds in the presence of a Lewis acid catalyst (halohydrin). Ether compounds). Examples include sorbitol polyhalohydrin, glycerin polyhalohydrin, diglycerin polychlorohydrin, ethylene glycol dihalohydrin, propylene glycol dichlorohydrin. These may be used alone or in combination of two or more.
(A)成分が1分子中に有するエポキシ基及び/又はハロヒドリン基の数は、2〜15個である限り特に限定されないが、2〜10個であることが好ましく、2〜6個であることがより好ましく、2〜4個であることがさらに好ましい。(A)成分が1分子中に有するエポキシ基及び/又はハロヒドリン基の数が2個未満であると、樹脂組成物を硬化させて塗膜を形成するために必要な架橋反応が不可能であり、15個を超えると、貯蔵安定性が低下することがある。 The number of epoxy groups and / or halohydrin groups that component (A) has in one molecule is not particularly limited as long as it is 2 to 15, but is preferably 2 to 10, and preferably 2 to 6 Is more preferable, and 2 to 4 is more preferable. If the number of epoxy groups and / or halohydrin groups in the molecule (A) is less than 2, the crosslinking reaction required to cure the resin composition and form a coating film is impossible. If it exceeds 15, the storage stability may be lowered.
(A)成分がエポキシ化合物の場合、エポキシ当量は、特に限定されないが、100〜1000であることが好ましく、120〜700であることがより好ましい。エポキシ当量が100未満であると、硬化不良となることがあり、1000を超えると、貯蔵安定性が悪くなることがある。(A)成分がハロヒドリン基を有する化合物の場合、加水分解性塩素は特に限定されないが、通常10%〜30%である。 When the component (A) is an epoxy compound, the epoxy equivalent is not particularly limited, but is preferably 100 to 1000, and more preferably 120 to 700. When the epoxy equivalent is less than 100, curing may be poor, and when it exceeds 1000, the storage stability may be deteriorated. In the case where the component (A) is a compound having a halohydrin group, hydrolyzable chlorine is not particularly limited, but is usually 10% to 30%.
本発明のコーティング用樹脂組成物において、(A)成分の含有量は、特に限定されないが、1〜90重量%であることが好ましく、1〜50重量%であることがより好ましい。含有量が1重量%未満であると、(A)成分が不足することで十分に架橋反応が進まずに硬化不良となることがあり、90重量%を超えると、(B)成分が不足することで十分に架橋反応が進まずに硬化不良となることがある。 In the coating resin composition of the present invention, the content of the component (A) is not particularly limited, but is preferably 1 to 90% by weight, and more preferably 1 to 50% by weight. If the content is less than 1% by weight, the component (A) may be insufficient and the crosslinking reaction may not sufficiently proceed, resulting in curing failure. If the content exceeds 90% by weight, the component (B) is insufficient. In some cases, the crosslinking reaction does not proceed sufficiently, resulting in poor curing.
<(B)アミノ樹脂>
(B)アミノ樹脂(以下、単に(B)成分ともいう)は、本発明のコーティング用樹脂組成物において(A)成分の硬化剤として配合される。(B)成分を用いることで貯蔵安定性が向上する理由としては、(B)成分の数平均分子量が比較的大きく、(A)成分との反応に関与するアミノ基が常温では(B)成分の立体構造の内側にあるため、(A)成分との反応が起こりにくいことが考えられる。また、(B)成分を用いることで加熱により硬化させる際の速乾性が向上する理由としては、アミノ基はそもそも(A)成分との反応性が高く、加熱により(B)成分の立体構造が変化しアミノ基が表面に現れると即座に(A)成分との反応が進行するためと考えられる。<(B) Amino resin>
(B) Amino resin (hereinafter also simply referred to as component (B)) is blended as a curing agent for component (A) in the coating resin composition of the present invention. The reason why the storage stability is improved by using the component (B) is that the number average molecular weight of the component (B) is relatively large, and the amino group involved in the reaction with the component (A) is the component (B) at room temperature. It is considered that the reaction with the component (A) hardly occurs because it is inside the three-dimensional structure. In addition, the reason why the quick drying property when cured by heating is improved by using the component (B) is that the amino group is highly reactive with the component (A) in the first place, and the three-dimensional structure of the component (B) is increased by heating. This is probably because the reaction with the component (A) proceeds immediately when the amino group changes and the amino group appears on the surface.
(B)成分としては、数平均分子量が250〜10,000である限り特に限定されず、例えば、ベンゾグアナミン樹脂を含むメラミン樹脂、尿素樹脂、グリオキザール樹脂等が挙げられる。これらは単独で用いても良いし、2種以上を併用しても良い。これらの中では、塗膜の強度や密着性の観点からメラミン樹脂が好ましい。メラミン樹脂とは、メラミン又はその誘導体とアルデヒド化合物の重縮合物であり、メラミン樹脂を構成するモノマーとしては、例えばメラミン又はその誘導体としてメチロールメラミン、ベンゾグアナミン等を用いることができ、アルデヒド化合物としてホルムアルデヒド等を用いることができる。これらメラミン又はその誘導体とアルデヒド化合物の各モノマーは、単独で用いても良いし、2種類以上を併用しても良い。 The component (B) is not particularly limited as long as the number average molecular weight is 250 to 10,000, and examples thereof include melamine resins including benzoguanamine resins, urea resins, and glyoxal resins. These may be used alone or in combination of two or more. In these, a melamine resin is preferable from a viewpoint of the intensity | strength of a coating film, or adhesiveness. The melamine resin is a polycondensate of melamine or a derivative thereof and an aldehyde compound. As a monomer constituting the melamine resin, for example, methylolmelamine, benzoguanamine or the like can be used as the melamine or derivative thereof, and formaldehyde or the like can be used as the aldehyde compound. Can be used. These monomers of melamine or a derivative thereof and an aldehyde compound may be used alone or in combination of two or more.
(B)成分の数平均分子量は、250〜10,000である限り特に限定されないが、500〜2,000であることが好ましく、700〜1,300であることがより好ましい。数平均分子量が250未満であると、速乾性が不十分となることがあり、10,000を超えると、(A)成分との相溶性が不十分となることがある。 Although the number average molecular weight of (B) component is not specifically limited as long as it is 250-10,000, it is preferable that it is 500-2,000, and it is more preferable that it is 700-1,300. When the number average molecular weight is less than 250, quick drying may be insufficient, and when it exceeds 10,000, compatibility with the component (A) may be insufficient.
本発明のコーティング用樹脂組成物において、(B)成分の含有量は、特に限定されないが、(A)成分100重量部に対して10〜10,000重量部であることが好ましく、10〜500重量部であることがより好ましい。(B)成分の含有量が10重量部未満の場合や10,000重量部を超える場合には、速乾性が不十分となることがある。 In the coating resin composition of the present invention, the content of the component (B) is not particularly limited, but is preferably 10 to 10,000 parts by weight with respect to 100 parts by weight of the component (A). More preferred are parts by weight. When the content of the component (B) is less than 10 parts by weight or more than 10,000 parts by weight, the quick drying property may be insufficient.
本発明のコーティング用樹脂組成物は、(A)成分及び(B)成分に加えて、本発明の目的を損なわない範囲内で、任意に他の成分を含有していても良い。他の成分としては、特に限定されないが、例えば、溶剤、硬化促進剤、消泡剤、レベリング剤、有機増粘剤、酸化防止剤、光安定剤、接着性向上剤、離型剤、補強材、軟化剤、着色剤、難燃剤、帯電防止剤、湿潤分散剤等が挙げられる。 In addition to the component (A) and the component (B), the coating resin composition of the present invention may optionally contain other components as long as the object of the present invention is not impaired. Examples of other components include, but are not limited to, solvents, curing accelerators, antifoaming agents, leveling agents, organic thickeners, antioxidants, light stabilizers, adhesion improvers, mold release agents, and reinforcing materials. , Softeners, colorants, flame retardants, antistatic agents, wetting and dispersing agents, and the like.
<溶剤>
溶剤としては、特に限定はなく、水系又は有機溶剤系の何れも好適に使用できるが、例えば、トルエン、エチルベンゼン、トリメチルベンゼン、キシレン等の芳香族炭化水素系溶剤、ペンタン、ヘキサン、シクロヘキサン等の脂肪族炭化水素系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤、メタノール、エタノール、イソプロパノール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール等のアルコール系溶剤、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルジグリコール、エチルジグリコール、ブチルジグリコール、プロピレングリコールモノメチルエーテル等のグリコールエーテル系溶剤、酢酸エチル、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート等のエステル系溶剤、水等が挙げられる。また、芳香族炭化水素系溶剤として使用できる市販品としては、ソルベッソ100、ソルベッソ150、ソルベッソ200等が挙げられる。これらは単独で用いても良いし、2種以上を併用しても良い。<Solvent>
The solvent is not particularly limited, and any of water-based and organic solvent-based solvents can be suitably used. For example, aromatic hydrocarbon solvents such as toluene, ethylbenzene, trimethylbenzene, and xylene, and fats such as pentane, hexane, and cyclohexane. Aromatic hydrocarbon solvents, acetone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, methyl cellosolve, ethyl cellosolve, Glycol ether solvents such as butyl cellosolve, methyl diglycol, ethyl diglycol, butyl diglycol, propylene glycol monomethyl ether, ethyl acetate, butyl acetate Ester solvents such as propylene glycol monomethyl ether acetate, water and the like. Examples of commercially available products that can be used as the aromatic hydrocarbon solvent include Solvesso 100, Solvesso 150, Solvesso 200, and the like. These may be used alone or in combination of two or more.
本発明のコーティング用樹脂組成物が溶剤を含有する場合、その含有量は、塗布方法、所望する硬化塗膜の膜厚によって選択すればよく、特に限定されないが、(A)成分100重量部に対して10〜5000重量部であることが好ましく、20〜2000重量部であることがより好ましい。含有量が10重量部未満であると、粘度が高くなり、均一に塗工できないことがあり、5000重量部を超えると、十分な膜厚の塗膜が得られないことがある他、経済性やVOC削減の観点から好ましくない。 When the coating resin composition of the present invention contains a solvent, the content may be selected depending on the coating method and the desired thickness of the cured coating film, and is not particularly limited. It is preferable that it is 10-5000 weight part with respect to it, and it is more preferable that it is 20-2000 weight part. When the content is less than 10 parts by weight, the viscosity becomes high and uniform coating may not be possible. When the content exceeds 5000 parts by weight, a coating film having a sufficient film thickness may not be obtained. And not preferable from the viewpoint of VOC reduction.
<硬化促進剤>
硬化促進剤としては、特に限定されないが、例えば、ギ酸、酢酸、乳酸、グリコール酸、酪酸、イソ酪酸、プロピオン酸、カプロン酸、オクタン酸、ヘプタン酸、クロロ酢酸、ジクロロ酢酸、トリクロロ酢酸及びチオグリコール酸等の脂肪族カルボン酸類、リンゴ酸、シュウ酸、コハク酸、マロン酸、フマル酸、マレイン酸、酒石酸及びクエン酸等のポリカルボン酸類、安息香酸、p−トルイル酸、p−アミノ安息香酸、p−クロロ安息香酸、2, 4−ジクロロ安息香酸等の安息香酸誘導体、フタル酸、イソフタル酸及びテレフタル酸等のフタル酸誘導体及びサリチル酸等の芳香族カルボン酸類、フェノール、m−クレゾール、p−クロロフェノール、p−ニトロフェノール、2,4−ジクロロフェノール、o−アミノフェノール、p−アミノフェノール及び2,4,5−トリクロロフェノール等のフェノール類、レゾルシノール、ハイドロキノン、カテコール及びフロログルシノール等のポリフェノール類、ノボラック等のフェノール樹脂類、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブチルアルコール、tert−ブチルアルコール等の脂肪族アルコール類、エチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール等のグリコール類、グリセリン、ポリグリセリン等のグリセロール類、トルエンスルホン酸、メタンスルホン酸等のスルホン酸類等が挙げられる。これらは単独で用いても良いし、2種以上を併用しても良い。<Curing accelerator>
The curing accelerator is not particularly limited. For example, formic acid, acetic acid, lactic acid, glycolic acid, butyric acid, isobutyric acid, propionic acid, caproic acid, octanoic acid, heptanoic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid and thioglycol Aliphatic carboxylic acids such as acids, polycarboxylic acids such as malic acid, oxalic acid, succinic acid, malonic acid, fumaric acid, maleic acid, tartaric acid and citric acid, benzoic acid, p-toluic acid, p-aminobenzoic acid, p-chlorobenzoic acid, benzoic acid derivatives such as 2,4-dichlorobenzoic acid, phthalic acid derivatives such as phthalic acid, isophthalic acid and terephthalic acid, and aromatic carboxylic acids such as salicylic acid, phenol, m-cresol, p-chloro Phenol, p-nitrophenol, 2,4-dichlorophenol, o-aminophenol, p-amino Phenols such as phenol and 2,4,5-trichlorophenol, polyphenols such as resorcinol, hydroquinone, catechol and phloroglucinol, phenol resins such as novolac, methanol, ethanol, propanol, isopropanol, butanol, isobutyl alcohol, tert -Aliphatic alcohols such as butyl alcohol, glycols such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol, glycerols such as glycerin and polyglycerin, and sulfonic acids such as toluenesulfonic acid and methanesulfonic acid . These may be used alone or in combination of two or more.
本発明のコーティング用樹脂組成物が硬化促進剤を含有する場合、その含有量は、特に限定されないが、(A)成分100重量部に対して0.01〜2000重量部であることが好ましく、0.1〜2000重量部であることがより好ましい。含有量が0.01重量部未満であると、硬化促進剤を添加する効果が十分に得られないことがあり、2000重量部を超えると、塗膜外観が損なわれることがあり、経済性の観点からも好ましくないことがある。 When the coating resin composition of the present invention contains a curing accelerator, its content is not particularly limited, but is preferably 0.01 to 2000 parts by weight with respect to 100 parts by weight of component (A), More preferably, it is 0.1 to 2000 parts by weight. When the content is less than 0.01 parts by weight, the effect of adding a curing accelerator may not be sufficiently obtained. When the content exceeds 2000 parts by weight, the appearance of the coating film may be impaired. It may not be preferable also from a viewpoint.
<<部材>>
本発明の部材は、樹脂基材と、本発明のコーティング用樹脂組成物を用いて樹脂基材上に形成された塗膜とを有することを特徴とする。<< Member >>
The member of this invention has a resin base material and the coating film formed on the resin base material using the resin composition for coating of this invention, It is characterized by the above-mentioned.
<樹脂基材>
樹脂基材の材質は、特に限定されないが、ポリエチレンテレフタラート、ポリエチレンナフタレート等のポリエステル、ポリエチレン、ポリプロピレン、ポリメチルペンテン等のポリオレフィン、ナイロン6、ナイロン66等のポリアミド、ポリカーボネート、ポリ酢酸ビニル、ポリイミド、ABS樹脂等が挙げられる。これらの中では、経済性、加工容易性の観点からポリエステルが好ましい。<Resin substrate>
The material of the resin base material is not particularly limited. Polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene, polypropylene, and polymethylpentene, polyamides such as nylon 6 and nylon 66, polycarbonate, polyvinyl acetate, polyimide , ABS resin and the like. Among these, polyester is preferable from the viewpoints of economy and processability.
樹脂基材の厚みは、特に限定されず、フィルム、シート、板、積層体等、成形加工等により製造される様々な成形品に成形されたものを樹脂基材として用いることができる。 The thickness of the resin base material is not particularly limited, and a resin base material that is formed into various molded products such as a film, a sheet, a plate, a laminate, and the like manufactured by a molding process can be used.
<塗膜>
塗膜は、本発明のコーティング用樹脂組成物を用いて樹脂基材上に形成される。本発明のコーティング用樹脂組成物を用いて樹脂基材上に塗膜を形成する方法としては、特に限定されないが、本発明のコーティング用樹脂組成物を樹脂基材の少なくとも一つの面に塗布した後、加熱して硬化させる方法等が挙げられる。本発明のコーティング用樹脂組成物を塗布する方法、及び、加熱して硬化させる方法については、後述する。<Coating film>
The coating film is formed on the resin substrate using the coating resin composition of the present invention. A method for forming a coating film on a resin substrate using the coating resin composition of the present invention is not particularly limited, but the coating resin composition of the present invention was applied to at least one surface of the resin substrate. Thereafter, a method of heating and curing can be used. The method for applying the coating resin composition of the present invention and the method for curing by heating will be described later.
塗膜の厚みは、特に限定されないが、0.1〜30μmであることが好ましく、0.3〜20μmであることがより好ましい。厚みが0.1μm未満であると、塗膜の平滑性が不十分となることがあり、30μmを超えると、内部応力の増加により密着性が不十分となることがある。 Although the thickness of a coating film is not specifically limited, It is preferable that it is 0.1-30 micrometers, and it is more preferable that it is 0.3-20 micrometers. When the thickness is less than 0.1 μm, the smoothness of the coating film may be insufficient, and when it exceeds 30 μm, the adhesion may be insufficient due to an increase in internal stress.
<<部材の製造方法>>
本発明の部材の製造方法は、本発明の部材を製造するための方法であって、
本発明のコーティング用樹脂組成物を樹脂基材の少なくとも一つの面に塗布する工程(1)、及び、
工程(1)で塗布したコーティング用樹脂組成物を60〜250℃で5〜300秒間加熱して硬化させる工程(2)
を含むことを特徴とする。<< Member manufacturing method >>
The member manufacturing method of the present invention is a method for manufacturing the member of the present invention,
A step (1) of applying the coating resin composition of the present invention to at least one surface of a resin substrate; and
Step (2) for curing the coating resin composition applied in step (1) by heating at 60 to 250 ° C. for 5 to 300 seconds.
It is characterized by including.
<工程(1)>
本工程では、本発明のコーティング用樹脂組成物を樹脂基材の少なくとも一つの面に塗布する。本発明のコーティング用樹脂組成物を塗布する方法としては、特に限定されないが、例えば、バーコート法、スピンコート法、スプレーコート法、ディップコート法、ノズルコート法、グラビアコート法、リバースロールコート法、ダイコート法、エアドクターコート法、ブレードコート法、ロッドコート法、カーテンコート法、ナイフコート法、トランスファロールコート法、スクイズコート法、含浸コート法、キスコート法、カレンダコート法、押出コート法等が挙げられる。<Step (1)>
In this step, the coating resin composition of the present invention is applied to at least one surface of the resin substrate. The method for applying the coating resin composition of the present invention is not particularly limited. For example, a bar coating method, a spin coating method, a spray coating method, a dip coating method, a nozzle coating method, a gravure coating method, a reverse roll coating method. , Die coating method, air doctor coating method, blade coating method, rod coating method, curtain coating method, knife coating method, transfer roll coating method, squeeze coating method, impregnation coating method, kiss coating method, calendar coating method, extrusion coating method, etc. Can be mentioned.
<工程(2)>
本工程では、工程(1)で塗布したコーティング用樹脂組成物を加熱して硬化させる。<Step (2)>
In this step, the coating resin composition applied in step (1) is heated and cured.
工程(2)において、加熱温度は特に限定されないが、60〜250℃であることが好ましく、60〜150℃であることがより好ましい。加熱温度が60℃未満であると、硬化不良となることがあり、250℃を超えると、樹脂基材の材質によっては基材の形状が損なわれることがある。また、加熱時間は、5〜300秒間である限り特に限定されないが、20〜120秒間であることが好ましい。加熱時間が5秒間未満であると、硬化不良となることがあり、300秒間を超えると、樹脂基材の材質によっては基材の形状が損なわれることがあり、また、工程に要する時間が長くなるため生産性の観点からも好ましくない。 In the step (2), the heating temperature is not particularly limited, but is preferably 60 to 250 ° C, and more preferably 60 to 150 ° C. When the heating temperature is less than 60 ° C., curing may be poor, and when it exceeds 250 ° C., the shape of the substrate may be impaired depending on the material of the resin substrate. The heating time is not particularly limited as long as it is 5 to 300 seconds, but is preferably 20 to 120 seconds. When the heating time is less than 5 seconds, curing may be poor, and when it exceeds 300 seconds, the shape of the substrate may be damaged depending on the material of the resin substrate, and the time required for the process is long. Therefore, it is not preferable from the viewpoint of productivity.
以下、実施例を挙げて本発明を説明するが、本発明は以下の実施例に限定されない。以下、「部」又は「%」は特記ない限り、それぞれ「重量部」又は「重量%」を意味する。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to a following example. Hereinafter, “part” or “%” means “part by weight” or “% by weight”, respectively, unless otherwise specified.
(合成例1)
ソルビトール50gをトルエン20gに分散させ、四塩化すず0.18gを添加し、撹拌しながら、95℃以上100℃以下の温度範囲にて、エピクロルヒドリン62gを2時間かけて添加し、反応させた。エピクロルヒドリンの消失をJIS K 7236に記載された滴定法により確認し、溶剤として使用したトルエンを減圧濃縮で除去した。得られた濃縮物を水100gに溶解させ、ソルビトールポリクロルヒドリン化合物の水溶液(全固形分濃度52.5%)を得た。(Synthesis Example 1)
50 g of sorbitol was dispersed in 20 g of toluene, 0.18 g of tin tetrachloride was added, and 62 g of epichlorohydrin was added over 2 hours in the temperature range of 95 ° C. or more and 100 ° C. or less while stirring. The disappearance of epichlorohydrin was confirmed by a titration method described in JIS K 7236, and toluene used as a solvent was removed by concentration under reduced pressure. The obtained concentrate was dissolved in 100 g of water to obtain an aqueous solution of sorbitol polychlorohydrin compound (total solid content concentration 52.5%).
(使用材料)
下記の実施例及び比較例においては、以下の材料を使用した。
・(A)多官能反応性化合物
ソルビトールポリグリシジルエーテル(ナガセケムテックス株式会社製、デナコールEX−614B、エポキシ当量:173、1分子あたりのエポキシ基の数:3〜4個)
ビスフェノールAジグリシジルエーテル(三菱化学株式会社製、828、エポキシ当量:188、1分子あたりのエポキシ基の数:2個)
ソルビトールポリクロロヒドリン(合成例1、1分子あたりのハロヒドリン基の数:2〜4個)
・(B)アミノ樹脂
メラミン樹脂(DIC株式会社製、スーパーベッカミンL−145−60、数平均分子量:1073、固形分濃度:55%)
・アミン化合物
トリエチレンテトラミン(東京化成工業株式会社製、分子量:146)
・硬化促進剤
トルエンスルホン酸
・溶剤
トルエン(和光純薬工業株式会社製)
・樹脂基材
ポリエステル(PET)フィルム(東レ株式会社製、ルミラー、膜厚50μm)(Materials used)
In the following examples and comparative examples, the following materials were used.
(A) Polyfunctional reactive compound sorbitol polyglycidyl ether (manufactured by Nagase ChemteX Corporation, Denacol EX-614B, epoxy equivalent: 173, number of epoxy groups per molecule: 3 to 4)
Bisphenol A diglycidyl ether (Mitsubishi Chemical Corporation, 828, epoxy equivalent: 188, number of epoxy groups per molecule: 2)
Sorbitol polychlorohydrin (Synthesis Example 1, number of halohydrin groups per molecule: 2 to 4)
(B) Amino resin melamine resin (manufactured by DIC Corporation, Super Becamine L-145-60, number average molecular weight: 1073, solid content concentration: 55%)
・ Amine compound triethylenetetramine (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 146)
・ Hardening accelerator Toluenesulfonic acid ・ Solvent toluene (Wako Pure Chemical Industries, Ltd.)
-Resin-based polyester (PET) film (manufactured by Toray Industries, Inc., Lumirror, film thickness 50 μm)
(実施例1〜3、比較例1〜4)
下記表1に示す重量比で各成分を混合し、コーティング用樹脂組成物を得た。得られたコーティング用樹脂組成物を用いて後述する方法により貯蔵安定性の評価を行った。また、得られたコーティング用樹脂組成物を、バーコーター(No.2)を用いて樹脂基材上に塗布し、熱風乾燥機を用いて130℃で60秒間加熱することにより硬化させて塗膜を形成し、部材を得た。部材を室温まで冷却させたものを試験片として用いて、後述する方法により速乾性、密着性及び耐薬品性の評価を行った。これらの結果を表1に示す。(Examples 1-3, Comparative Examples 1-4)
Each component was mixed by the weight ratio shown in following Table 1, and the resin composition for coating was obtained. The storage stability was evaluated by the method described later using the obtained resin composition for coating. Further, the obtained coating resin composition is applied onto a resin substrate using a bar coater (No. 2), and cured by heating at 130 ° C. for 60 seconds using a hot air dryer to form a coating film. To obtain a member. Using the sample cooled to room temperature as a test piece, quick drying, adhesion and chemical resistance were evaluated by the methods described below. These results are shown in Table 1.
(評価方法)
・貯蔵安定性
コーティング用樹脂組成物を23 ℃条件下で静置して、濁りが発生するまでの時間を確認した。確認は最長で12時間までとした。
・速乾性
作製直後の試験片の塗膜を指で触りタックの有無を確認し、下記の基準により2段階で評価した。
○:タック無し
×:タック有り
・密着性
作製直後の試験片の塗膜を指で10回擦り、塗膜の剥離の有無を確認し、下記の基準により2段階で評価した。
○:剥離無し
×:剥離有り
・耐薬品性
作製直後の試験片を用いて耐薬品性試験を行った。具体的には、ラビングテスターを用いてメチルエチルケトンを染み込ませたガーゼを荷重300gの条件で試験片の塗膜表面に押し当てた状態で30回往復させてラビング試験を行い、塗膜の剥離の有無を確認し、下記の基準により2段階で評価した。
○:剥離無し
×:剥離有り(Evaluation method)
-The resin composition for storage-stable coating was allowed to stand at 23 ° C, and the time until turbidity was confirmed was confirmed. Confirmation was up to 12 hours.
-The coating film of the test piece immediately after preparation of quick-drying was touched with a finger to confirm the presence or absence of tack, and evaluated in two stages according to the following criteria.
○: No tack x: Tacked / Adhesiveness The coating film of the test piece immediately after preparation of the specimen was rubbed 10 times with a finger to confirm the presence or absence of peeling of the coating film, and evaluated in two stages according to the following criteria.
○: No peeling ×: Peeling / chemical resistance A chemical resistance test was performed using a test piece immediately after preparation. Specifically, using a rubbing tester, the gauze impregnated with methyl ethyl ketone was reciprocated 30 times in a state where it was pressed against the coating surface of the test piece under the condition of a load of 300 g. And was evaluated in two stages according to the following criteria.
○: No peeling ×: With peeling
本発明のコーティング用樹脂組成物は130℃、60秒という低温、短時間の乾燥条件であっても十分に乾燥させることが可能であり、その塗膜の密着性、耐薬品性も良好であった。一方、従来技術である比較例1〜4では低温、短時間の乾燥条件では十分に乾燥させることができず、その結果として密着性、耐薬品性も不十分であった。 The coating resin composition of the present invention can be sufficiently dried even under low temperature and short drying conditions of 130 ° C. and 60 seconds, and the coating film has good adhesion and chemical resistance. It was. On the other hand, Comparative Examples 1 to 4 which are conventional techniques cannot be sufficiently dried under low temperature and short time drying conditions, and as a result, adhesion and chemical resistance are insufficient.
Claims (7)
(A)1分子中にエポキシ基及び/又はハロヒドリン基を2〜15個有する多官能反応性化合物、及び、
(B)数平均分子量250〜10,000のアミノ樹脂
を含むことを特徴とするコーティング用樹脂組成物。A composition for application to a resin substrate,
(A) a polyfunctional reactive compound having 2 to 15 epoxy groups and / or halohydrin groups in one molecule, and
(B) A coating resin composition comprising an amino resin having a number average molecular weight of 250 to 10,000.
請求項1〜4のいずれか1項に記載のコーティング用樹脂組成物を樹脂基材の少なくとも一つの面に塗布する工程(1)、及び、
工程(1)で塗布したコーティング用樹脂組成物を60〜250℃で5〜300秒間加熱して硬化させる工程(2)
を含むことを特徴とする部材の製造方法。
A method for producing the member according to claim 5 or 6, comprising:
A step (1) of applying the coating resin composition according to any one of claims 1 to 4 to at least one surface of a resin substrate; and
Step (2) for curing the coating resin composition applied in step (1) by heating at 60 to 250 ° C. for 5 to 300 seconds.
The manufacturing method of the member characterized by including.
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JP2001271026A (en) * | 2000-03-28 | 2001-10-02 | Kawakami Paint Mfg Co Ltd | Coating resin composition |
JP2002001874A (en) * | 2000-06-20 | 2002-01-08 | Kansai Paint Co Ltd | Overcoat composition for laminated film of packing material |
JP2003206362A (en) * | 2002-01-11 | 2003-07-22 | Toyo Ink Mfg Co Ltd | Resin composition for overcoat for plastic film and its use |
JP2012162636A (en) * | 2011-02-07 | 2012-08-30 | Kansai Paint Co Ltd | Water dispersion, and aqueous coating composition |
WO2013077307A1 (en) * | 2011-11-22 | 2013-05-30 | 日本ペイント株式会社 | Hard coating composition |
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JP2001026749A (en) * | 1999-03-03 | 2001-01-30 | Kansai Paint Co Ltd | Overcoating composition and laminated film for adhesion |
JP3938020B2 (en) * | 2002-11-25 | 2007-06-27 | 東洋インキ製造株式会社 | Exterior coating composition for drawn cans excellent in high-speed paintability and use of the composition |
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KR20120068624A (en) * | 2010-12-17 | 2012-06-27 | 아크조노벨코팅스인터내셔널비.브이. | Organic-inorganic hybrid paint composition |
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JP2001271026A (en) * | 2000-03-28 | 2001-10-02 | Kawakami Paint Mfg Co Ltd | Coating resin composition |
JP2002001874A (en) * | 2000-06-20 | 2002-01-08 | Kansai Paint Co Ltd | Overcoat composition for laminated film of packing material |
JP2003206362A (en) * | 2002-01-11 | 2003-07-22 | Toyo Ink Mfg Co Ltd | Resin composition for overcoat for plastic film and its use |
JP2012162636A (en) * | 2011-02-07 | 2012-08-30 | Kansai Paint Co Ltd | Water dispersion, and aqueous coating composition |
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