JPH0218147B2 - - Google Patents
Info
- Publication number
- JPH0218147B2 JPH0218147B2 JP25160083A JP25160083A JPH0218147B2 JP H0218147 B2 JPH0218147 B2 JP H0218147B2 JP 25160083 A JP25160083 A JP 25160083A JP 25160083 A JP25160083 A JP 25160083A JP H0218147 B2 JPH0218147 B2 JP H0218147B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- resins
- aqueous
- type
- groups
- 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.)
- Expired
Links
- 229920005989 resin Polymers 0.000 claims description 82
- 239000011347 resin Substances 0.000 claims description 82
- 238000000576 coating method Methods 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 21
- 229920003180 amino resin Polymers 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 229920000180 alkyd Polymers 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 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 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 229920001225 polyester resin Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 claims 1
- 229920006122 polyamide resin Polymers 0.000 claims 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims 1
- 239000003973 paint Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 125000002843 carboxylic acid group Chemical group 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- -1 maleic anhydride Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000000466 oxiranyl group Chemical group 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- NPSJHQMIVNJLNN-UHFFFAOYSA-N 2-ethylhexyl 4-nitrobenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C([N+]([O-])=O)C=C1 NPSJHQMIVNJLNN-UHFFFAOYSA-N 0.000 description 2
- 239000004808 2-ethylhexylester Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 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 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-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
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 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
- 230000000704 physical effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 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
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-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
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- BJSBGAIKEORPFG-UHFFFAOYSA-N [[6-amino-1,2,3,4-tetramethoxy-4-(methoxyamino)-1,3,5-triazin-2-yl]-methoxyamino]methanol Chemical compound CONC1(N(C(N(C(=N1)N)OC)(N(CO)OC)OC)OC)OC BJSBGAIKEORPFG-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229940113083 morpholine Drugs 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 239000005028 tinplate Substances 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
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
Description
本発明は水性塗料を使用して複層塗膜を形成す
る方法に関する。こゝでいう複層塗膜とは、皮膜
を形成する樹脂成分組成が塗膜の上層部と下層部
との間で異なつている塗膜をいう。
このような複層構造の塗膜は、異なる樹脂成分
の塗料を塗り重ねることにより得られるが、本発
明は単一種類の水性塗料を使用してあたかも異種
塗料の2コートと同様な複層塗膜を形成すること
ができる。
複層構造の塗膜は、例えば下層は基材との密着
性にすぐれた層とし、上層は仕上がり外観にすぐ
れた層とすることができるので好ましい。従来こ
のような複層構造の塗膜を単一種類の塗料を使用
して形成する方法は、粉体塗料を使用して可能で
あることが知られている。
例えば特開昭51−122137、同52−43840、同52
−43841参照。しかしながら粉体塗料は一般に使
用する樹脂のガラス転移温度が低いとブロツキン
グの問題を生ずるので使用可能性に限界があり、
また塗膜物性の改良と焼付温度の低温化のため硬
化剤を使用するのが普通であるが、塗料製造時
(溶融状態で混合分散)に反応する硬化剤は使用
できないから焼付温度は高くならざるを得ず、そ
のため熱に弱い基材には塗装できない。
水性塗料は有機溶剤を殆ど使用せず、そのため
省資源および環境保全面において好ましく、特に
水性樹脂の溶液中に水に不溶性の粉末樹脂を分散
させたタイプの水性塗料は、従来の水性塗料の欠
点である耐水性、塗装作業性、貯蔵安定性を改善
するものとして注目されている。
本発明者らは、水不溶性粉末樹脂を水性樹脂の
溶液中に分散させたタイプの水性塗料において、
該水性樹脂と粉末樹脂とが一定の条件を満たす場
合、該塗料を塗装した時、該粉末樹脂分に富み該
水性樹脂分に乏しい層と、該粉末樹脂分が乏しく
該水性樹脂分に富む層よりなる複層塗膜が得られ
ることを見出し、本発明を完成するに至つた。
本発明は、(a)皮膜構成成分として、水性樹脂
()の少なくとも1種と、該水性樹脂()の
水性溶液中に分散している水不溶性の粉末樹脂
()の少なくとも1種とを含有し、該水性樹脂
():該粉末樹脂()の固形分重量比が90:10
ないし20:80であり、該水性樹脂()の20%樹
脂濃度における該粉末樹脂に対する接触角が40゜
以下である水性塗料を基材上に塗布することと、
(b) 樹脂固形分全体のうち粉末樹脂()の占め
る割合が塗膜厚みの20%を占める上層部分と残
余の下層部分との間で少なくとも10%の差を生
ずるように未乾燥塗膜中で前記粉末樹脂()
の部分的相分離を許容することと、
(c) 次いで該塗膜を乾燥させることを特徴とする
複層塗膜形成方法に関する。
本発明により樹脂組成の異なる複層構造の塗膜
を得るためには、前記条件において水性樹脂
()の粉末樹脂()に対する接触角が40゜以下
であることと、塗料中の水性樹脂()と粉末樹
脂()との固形分重量比が90:10ないし20:80
であることが重要である。接触角が40゜をこえる
と樹脂()と()間の親和性が乏しく、未乾
燥塗膜中での粉末樹脂粒子の自由な運動および衝
突が妨げられ、塗膜が複層化し難い。
また塗料中における粉末樹脂の濃度が過少であ
れば樹脂粒子の衝突の機会が少なく、複層化し難
く、反対に粉末樹脂濃度が過剰の場合は部分的な
相分離が起こり難く、複層化しない。
本発明で使用する水性樹脂()は、三次元架
橋構造を取り得る官能基としてカルボン酸基、ス
ルホン酸基、リン酸基、水酸基、オキシラン基、
活性メチロール基、アミノ基、反応性炭素−炭素
不飽和基、イソシアネート基ないしブロツクされ
たイソシアネート基、ハロゲン基等を有してもよ
く、且つ必要によりそれ自体水性化のための官能
基(例:カルボン酸基、スルホン酸基、水酸基、
アミノ基)を有するものであればよく、樹脂の種
類としては例えばアルキド系、ポリエステル系、
マレイン化油系、マレイン化ポリアルカジエン
系、エポキシ系、アクリル系、ウレタン系、ポリ
アミド系、ポリエチレンイミン系、アミノプラス
ト系が挙げられる。
樹脂への官能基の導入は一般的方法に従つて実
施されてよく、モノマーの選択や高分子化反応の
制御により行われてよい。
具体的には、アルキド系およびポリエステル系
にあつては、多塩基酸と多価アルコールとの反応
段階でカルボキシル基が導入されて水性樹脂とな
るものでよい。マレイン化油系にあつては、乾性
油(例:アマニ油、脱水ヒマシ油、大豆油、キリ
油)を無水マレイン酸で処理することによりカル
ボキシル基が導入されて水性樹脂となるものでよ
い。マレイン化ポリアルカジエン系にあつては、
例えばポリブタジエン(例:1,2−ポリフタジ
エン、1,4−ポリブタジエン、1,2−と1,
4−の共重合ポリブタジエン)、ポリイソプレン
またはポリシクロペンタジエンに例えばその二重
結合に不飽和カルボン酸(例:無水マレイン酸、
無水ハイミツク酸、フマール酸、イタコン酸)を
付加させることによつてカルボキシル基が導入さ
れて水性樹脂となるものでよい。エポキシ系にあ
つては、ビスフエノールAとエピクロルヒドリン
の反応によつて代表される各種エポキシ樹脂に加
えて、他のエポキシ基を有する各種化合物が使用
できる。これらは本来水溶性を有するものではそ
のまま使用でき、あるいはオキシラン基の一部ま
たは全部に塩基性基もしくは酸性基を導入されて
水溶性ないし水分散性となるものでよい。アクリ
ル系については、α,β−不飽和カルボン酸
(例:アクリル酸、メタクリル酸、桂皮酸、クロ
トン酸、フマル酸、シトラコン酸、無水マレイン
酸)とアクリル酸エステル(例:メチルエステ
ル、エチルエステル、プロピルエステル、ブチル
エステル、2−エチルヘキシルエステル、ラウリ
ルエステル)および/またはメタクリル酸エステ
ル(例:メチルエステル、エチルエステル、プロ
ピルエステル、ブチルエステル、2−エチルヘキ
シルエステル、ラウリルエステル)、必要に応じ
て他の重合性モノマーを重合させることによつて
得られる水性樹脂であればよい。ウレタン系にあ
つては、ジイソシアネート化合物(例:ヘキサメ
チレンジイソシアネート、トリレンジイソシアネ
ート、4,4′−ジフエニルメタンジイソシアネー
ト、キシリレンジイソシアネート、4,4′−メチ
レンビス(シクロヘキシルイソシアネート)、イ
ソホロンジイソシアネート)と活性水素化合物と
を骨格構造とし、水溶性基が導入された樹脂が挙
げられる。ポリアミド系にあつては、ジカルボン
酸(例:フタル酸、アジピン酸、セバチン酸、二
量体脂肪酸)とポリアミン(例:エチレンジアミ
ン、ヘキサメチレンジアミン、ジエチレントリア
ミン、トリエチレンジアミン、プロピレンジアミ
ン、ブチレンジアミン)とを縮合させて得られる
アミノ基含有高分子体が好ましく、その他にラク
タム(例:ε−カプロラクタム)を開環重合して
得られるオリゴマーを更に上記ポリアミンと縮さ
せて得られるポリアミド、または上記ポリアミン
の代わりにアルカノールアミン(例:エタノール
アミン、プロパノールアミン)を用いて得られる
ポリエステルアミドが水性樹脂として使用でき
る。
ポリエチレンイミン系とは、
The present invention relates to a method of forming multilayer coatings using water-based paints. The term "multi-layer coating film" as used herein refers to a coating film in which the composition of the resin component forming the film differs between the upper layer and the lower layer of the coating. A coating film with such a multilayer structure can be obtained by layering paints with different resin components, but the present invention uses a single type of water-based paint to create a multilayer coating that is similar to two coats of different paints. A film can be formed. A coating film having a multilayer structure is preferable because, for example, the lower layer can be a layer with excellent adhesion to the base material, and the upper layer can be a layer with excellent finished appearance. Conventionally, it has been known that a method of forming such a multilayered coating film using a single type of paint is possible using a powder paint. For example, JP-A No. 51-122137, No. 52-43840, No. 52
See −43841. However, if the glass transition temperature of the resin used in powder coatings is low, blocking may occur, so there is a limit to the usability of powder coatings.
Additionally, hardening agents are normally used to improve the physical properties of the paint film and lower the baking temperature, but hardening agents that react during paint manufacturing (mixing and dispersion in the molten state) cannot be used, so the baking temperature must be high. Therefore, it cannot be applied to heat-sensitive substrates. Water-based paints use almost no organic solvents and are therefore preferable in terms of resource conservation and environmental protection.In particular, water-based paints in which water-insoluble powder resin is dispersed in a water-based resin solution have disadvantages of conventional water-based paints. It is attracting attention as a material that improves water resistance, paint workability, and storage stability. The present inventors have discovered that in a type of water-based paint in which a water-insoluble powder resin is dispersed in an aqueous resin solution,
When the aqueous resin and powder resin meet certain conditions, when the paint is applied, a layer is rich in the powder resin and poor in the aqueous resin, and a layer is poor in the powder resin and rich in the aqueous resin. The present inventors have discovered that a multilayer coating film consisting of the following can be obtained, and have completed the present invention. The present invention comprises (a) as a film constituent component, at least one aqueous resin () and at least one water-insoluble powder resin () dispersed in an aqueous solution of the aqueous resin (). and the solid content weight ratio of the aqueous resin () to the powdered resin () is 90:10.
or 20:80 and has a contact angle of 40° or less with respect to the powdered resin at a resin concentration of 20% of the aqueous resin (); The powder resin () is added to the wet coating film in such a way that the powder resin () accounts for at least 10% difference between the upper layer portion, which accounts for 20% of the coating thickness, and the remaining lower layer portion.
and (c) then drying the coating film. In order to obtain a coating film with a multilayer structure having different resin compositions according to the present invention, it is necessary that the contact angle of the water-based resin () to the powdered resin () be 40° or less under the above conditions, and that the water-based resin () in the paint be less than 40 degrees. The solid content weight ratio of and powder resin () is 90:10 to 20:80.
It is important that If the contact angle exceeds 40°, the affinity between the resins () and () will be poor, and the free movement and collision of powdered resin particles in the wet coating film will be hindered, making it difficult for the coating film to become multilayered. In addition, if the concentration of powder resin in the paint is too low, there are fewer chances for resin particles to collide, making it difficult to form multiple layers.On the other hand, if the powder resin concentration is excessive, partial phase separation is difficult to occur, and multilayers do not form. . The aqueous resin used in the present invention has functional groups capable of forming a three-dimensional crosslinked structure such as carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, hydroxyl groups, oxirane groups,
It may contain an active methylol group, an amino group, a reactive carbon-carbon unsaturated group, an isocyanate group or a blocked isocyanate group, a halogen group, and if necessary, it itself may contain a functional group for waterification (e.g. Carboxylic acid group, sulfonic acid group, hydroxyl group,
The type of resin may include, for example, alkyd type, polyester type,
Examples include maleated oil type, maleated polyalkadiene type, epoxy type, acrylic type, urethane type, polyamide type, polyethyleneimine type, and aminoplast type. Introduction of functional groups into the resin may be carried out according to general methods, and may be carried out by selecting monomers and controlling the polymerization reaction. Specifically, in the case of alkyd-based and polyester-based resins, a carboxyl group may be introduced in the reaction step of a polybasic acid and a polyhydric alcohol to form an aqueous resin. In the case of maleated oils, carboxyl groups may be introduced by treating a drying oil (eg, linseed oil, dehydrated castor oil, soybean oil, tung oil) with maleic anhydride to form an aqueous resin. For maleated polyalkadiene systems,
For example, polybutadiene (e.g. 1,2-polyphtadiene, 1,4-polybutadiene, 1,2- and 1,
4-copolymerized polybutadiene), polyisoprene or polycyclopentadiene with an unsaturated carboxylic acid (e.g. maleic anhydride,
A carboxyl group may be introduced by adding hymic anhydride, fumaric acid, itaconic acid) to form an aqueous resin. In the case of epoxy resins, in addition to various epoxy resins typified by the reaction between bisphenol A and epichlorohydrin, various other compounds having epoxy groups can be used. These may be used as they are if they are originally water-soluble, or may be made water-soluble or water-dispersible by introducing a basic group or an acidic group into some or all of the oxirane groups. For acrylics, α,β-unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, fumaric acid, citraconic acid, maleic anhydride) and acrylic esters (e.g., methyl ester, ethyl ester) , propyl ester, butyl ester, 2-ethylhexyl ester, lauryl ester) and/or methacrylic ester (e.g., methyl ester, ethyl ester, propyl ester, butyl ester, 2-ethylhexyl ester, lauryl ester), and others as necessary. Any aqueous resin that can be obtained by polymerizing polymerizable monomers may be used. In the case of urethane, it is active with diisocyanate compounds (e.g. hexamethylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), isophorone diisocyanate). Examples include resins having a skeleton structure of a hydrogen compound and into which a water-soluble group is introduced. For polyamides, dicarboxylic acids (e.g. phthalic acid, adipic acid, sebacic acid, dimer fatty acids) and polyamines (e.g. ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenediamine, propylenediamine, butylenediamine) are used. Preferred are amino group-containing polymers obtained by condensation, and polyamides obtained by further condensing oligomers obtained by ring-opening polymerization of lactams (e.g. ε-caprolactam) with the above polyamines, or substitutes for the above polyamines. Polyesteramides obtained by using alkanolamines (e.g. ethanolamine, propanolamine) can be used as the aqueous resin. What is polyethyleneimine type?
【式】を基本繰り返し単位とす
る直鎖または分枝鎖の樹脂であり、公知技術によ
つて合成することができる。なお、場合によつて
はアイネオン型樹脂を使用することもでき、例え
ばポリアミン(好ましくはジアミン)とポリハロ
ゲン化物(好ましくはジハロゲン化物)メンシユ
トキン反応による生成ポリマーで〔−(N
(R1)
(R2)−R−)o〕×
(式中、R1とR2は同一又は異
なりC1〜C6のアルキル基、RはC1〜C12のポリア
ルキレン基、XはF、Cl、BrまたはI、mは、
3〜1000の整数である。)を基本繰り返し単位と
する樹脂であり、公知技術に従つて合成すること
ができる。アミノプラスト系にあつては、メラミ
ン樹脂、尿素樹脂等の水溶性ないし親水性として
知られているものでよい。
以上の水性樹脂にあつては、カルボキシル基の
如き酸性基を有する樹脂の水性化は常法に従いそ
の酸性基を塩基(例:モノメチルアミン、ジメチ
ルアミン、トリメチルアミン、モノエチルアミ
ン、ジエチルアミン、トリエチルアミン、モノイ
ソプロピルアミン、ジイソプロピルアミン、ジエ
チレントリアミン、トリエチレンテトラミン、モ
ノエタノールアミン、ジエタノールアミン、トリ
エタノールアミン、モノイソプロパノールアミ
ン、ジイソプロパノールアミン、ジメチルエタノ
ールアミン、モルホリン、メチルモルホリン、ピ
ペラジン、アンモニア、水酸化ナトリウム、水酸
化カリウム、水酸化リチウム)で中和すればよ
い。他方、アミノ基の如き塩基性基を有する樹脂
の水性化は常法に従いその塩基性基を酸(例:塩
酸、硫酸、硝酸、酢酸、ギ酸、乳酸)で中和すれ
ばよい。
水性樹脂()として、縮合反応、付加反応、
開環反応等により相互に反応し得る官能基を有す
る樹脂を少なくとも2種組合わせて使用してもよ
い。官能基の組合わせの好ましい例としては、具
体的には、水酸基と酸性基(特にカルボン酸基)
および/またはブロツクイソシアネート基、活性
メチロール基と水酸基および/またはカルボン酸
基、オキシラン基とアミノ基および/またはカル
ボン酸基、反応性炭素−炭素不飽和基同士等が挙
げられる。特に好ましいのは、活性メチロール基
と水酸基および/またはカルボン酸基であつて、
具体的には、メラミン樹脂とアルキド樹脂、アク
リル樹脂またはマレイン化樹脂の組合わせが挙げ
られる。なお、この際の相互に反応し得る官能基
の量比が1:10〜10:1、好ましくは1:5〜
5:1になるように組合わせることが望ましい。
かゝる水性樹脂の組合せ使用によつて、塗膜の耐
溶剤性が向上せしめられる。
本発明で使用する他の必須成分である樹脂微粉
末()としては、具体的には、アクリル系、エ
ポキシ系、飽和ポリエステル系、不飽和ポリエス
テル系、アルキド系、オイルフリーアルキド系、
フエノール系、ポリエーテル系、ポリオレフイン
系、ポリジエン系、ブロツクイソシアネート系、
ビニル樹脂系、ポリカーボネート系、繊維素樹脂
系、フツ素樹脂系、ポリアミド系、アミノプラス
ト樹脂系が挙げられ、これらを少なくとも1種使
用すればよい。
かゝる樹脂微粉末()は、その粒径が塗料化
時に分散できる程度のものであればよく、通常
500μ以下であればよい。
なお、上記樹脂微粉末()は、上記樹脂を2
種類以上、しかも樹脂の官能基が縮合反応、付加
反応、開環反応等により相互に反応し得るように
組み合わせて使用してもよい。これにより塗膜の
各種物性の向上が図れる。組合せの好ましい例と
しては、具体的には水酸基を有するポリエステル
樹脂とブロツクイソシアネート(およびアミノプ
ラスト)、カルボン酸基を有するポリエステル樹
脂とエポキシ樹脂(およびアミノプラスト)、水
酸基を有するアクリル樹脂とブロツクイソシアネ
ート(およびアミノプラスト)、カルボン酸基を
有するアクリル樹脂とエポキシ樹脂(およびアミ
ノプラスト)、オキシラン基を有するアクリル樹
脂とポリカルボン酸が挙げられる。このとき相互
に反応し得る官能基の量比が1:10〜10:1、好
ましくは1:5〜5:1になるように組合わせる
ことが望ましい。この樹脂微粉末()は常法に
従つて製造したものでよく、例えば2種類以上の
樹脂を加熱溶融混合機を用いて混合分散し、次い
で粉砕機を用いて所定の粒径まで粉砕すればよ
い。この際適当量の顔料や添加剤を添加すること
もできる。
塗料は必要に応じて少量の有機溶剤(例:エチ
レングリコールモノメチルエーテル、エチレング
リコールモノエチルエーテル、エチレングリコー
ルモノブチルエーテル、メタノール、エタノー
ル、イソプロピルアルコール、n−ブチルアルコ
ール、sec−ブチルアルコール、t−ブチルアル
コール、ジメチルホルムアミド)を使用してもよ
い。
本発明にあつては上述の必須成分に加えて、必
要に応じて各種の顔料および添加剤(例:改質
剤、分散剤、表面調整剤)を使用することができ
る。これらは水性樹脂()または樹脂微粉末
()もしくはその両者を配合してよい。
水性樹脂中への顔料の添加は、水性樹脂に対
し、顔料容積濃度で40%以下が好ましい。顔料の
量が過多な時は、粒子同士の接触を妨げ、複層化
し難い。
以下に実施例および比較例を示す。その中の
「部」および「%」は重量基準による。
実施例
水性樹脂の調製It is a linear or branched resin having [Formula] as a basic repeating unit, and can be synthesized by known techniques. Note that in some cases, it is also possible to use an Aineon type resin, for example, a polymer produced by the Menshyutkin reaction between a polyamine (preferably a diamine) and a polyhalide (preferably a dihalide) [-(N (R 1 )
(R 2 )-R-) o 〕× (wherein, R 1 and R 2 are the same or different, a C 1 to C 6 alkyl group, R is a C 1 to C 12 polyalkylene group, X is F, Cl , Br or I, m is
It is an integer between 3 and 1000. ) as a basic repeating unit, and can be synthesized according to known techniques. In the case of aminoplasts, those known to be water-soluble or hydrophilic, such as melamine resins and urea resins, may be used. In the case of the above water-based resins, water-based resins having acidic groups such as carboxyl groups can be converted into water by converting the acidic groups into bases (e.g., monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropyl). Amine, diisopropylamine, diethylenetriamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, dimethylethanolamine, morpholine, methylmorpholine, piperazine, ammonia, sodium hydroxide, potassium hydroxide, Neutralize with lithium hydroxide). On the other hand, a resin having a basic group such as an amino group can be made water-soluble by neutralizing the basic group with an acid (eg, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, lactic acid) according to a conventional method. As aqueous resin (), condensation reaction, addition reaction,
At least two types of resins having functional groups that can react with each other by ring-opening reaction or the like may be used in combination. Preferred examples of combinations of functional groups include hydroxyl groups and acidic groups (especially carboxylic acid groups).
and/or blocked isocyanate groups, active methylol groups and hydroxyl and/or carboxylic acid groups, oxirane groups and amino groups and/or carboxylic acid groups, and reactive carbon-carbon unsaturated groups. Particularly preferred are active methylol groups and hydroxyl and/or carboxylic acid groups,
Specifically, a combination of a melamine resin, an alkyd resin, an acrylic resin, or a maleated resin may be used. In addition, the quantitative ratio of functional groups that can react with each other at this time is 1:10 to 10:1, preferably 1:5 to
It is desirable to combine them in a ratio of 5:1.
By using such a combination of water-based resins, the solvent resistance of the coating film can be improved. Specifically, the fine resin powder () which is another essential component used in the present invention includes acrylic, epoxy, saturated polyester, unsaturated polyester, alkyd, oil-free alkyd,
Phenol type, polyether type, polyolefin type, polydiene type, blocked isocyanate type,
Examples include vinyl resins, polycarbonates, cellulose resins, fluororesins, polyamides, and aminoplast resins, and at least one of these may be used. The particle size of such fine resin powder () is sufficient as long as it can be dispersed when it is made into a paint.
It is sufficient if it is 500μ or less. In addition, the above resin fine powder () is the above resin 2
More than one type may be used in combination so that the functional groups of the resins can react with each other through condensation reactions, addition reactions, ring-opening reactions, etc. This makes it possible to improve various physical properties of the coating film. Preferred examples of combinations include polyester resins having hydroxyl groups and blocked isocyanates (and aminoplasts), polyester resins having carboxylic acid groups and epoxy resins (and aminoplasts), and acrylic resins having hydroxyl groups and blocked isocyanates (and aminoplasts). and aminoplasts), acrylic resins and epoxy resins having carboxylic acid groups (and aminoplasts), and acrylic resins and polycarboxylic acids having oxirane groups. At this time, it is desirable to combine the functional groups that can react with each other so that the ratio of amounts is 1:10 to 10:1, preferably 1:5 to 5:1. This resin fine powder () may be manufactured according to a conventional method, for example, by mixing and dispersing two or more types of resin using a heat-melting mixer, and then pulverizing to a predetermined particle size using a pulverizer. good. At this time, appropriate amounts of pigments and additives may also be added. Paints can be prepared using a small amount of organic solvent (e.g. ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol) as needed. , dimethylformamide) may also be used. In the present invention, in addition to the above-mentioned essential components, various pigments and additives (eg, modifiers, dispersants, surface conditioners) can be used as necessary. These may be blended with an aqueous resin (), a fine resin powder (), or both. The pigment is preferably added to the aqueous resin at a volume concentration of 40% or less based on the aqueous resin. When the amount of pigment is too large, it prevents contact between particles and makes it difficult to form multiple layers. Examples and comparative examples are shown below. "Parts" and "%" therein are based on weight. Example Preparation of aqueous resin
【表】
樹脂微粉末の調製(注2)
(1) フアインデイツクM6103/エピコート1004=
1/1
(2) フアインデイツクM6103/エピコート1004/
ルチル型酸化チタン=1/1/1
(3) アルマテイツクスPD1375/エピコート
1004/ルチル型酸化チタン=1/1/1
(4) CKM918/エピコート1004/ルチル型酸化チ
タン=1/1/1
上記配合比はいずれも重量比である。
上記配合物を、常法に従い105℃でコニーダー
で溶融混合し、冷却後105μ以下に粉砕分級する。
塗料組成物の調製
実施例 1
塗料ペーストの調製
水性樹脂(A) 300部
樹脂微粉末(1) 75部
ルチル型酸化チタン顔料 50部
上記配合物を1ステンレス容器に仕込み、ペ
イントコンデイシヨナーを用いてガラスビーズ媒
体にて60分間混合分散して白色の塗料ペーストを
得た。
上記塗料ペースト340部と、ヘキサメトキシメ
チロールメラミン樹脂(以下HMMMと略称す
る。)18部を仕込み、ラボミキサーを用いて室温
で15分間混合撹拌し、白色の塗料組成物(1)を得
た。
実施例2、3、4および比較例1〜4
下記第2表の原料を使用する以外は、実施例1
と同様な手段と方法を用いて、塗料ペーストおよ
び塗料組成物を得た。[Table] Preparation of fine resin powder (Note 2) (1) Feindik M6103/Epicoat 1004=
1/1 (2) FINDIX M6103/Epicote 1004/
Rutile titanium oxide = 1/1/1 (3) Almatix PD1375/Epicoat
1004/rutile titanium oxide = 1/1/1 (4) CKM918/Epicote 1004/rutile titanium oxide = 1/1/1 The above blending ratios are all weight ratios. The above-mentioned mixture is melt-mixed in a co-kneader at 105° C. according to a conventional method, and after cooling, it is pulverized and classified to a size of 105 μm or less. Preparation Example of Paint Composition 1 Preparation of Paint Paste Water-based resin (A) 300 parts Resin fine powder (1) 75 parts Rutile type titanium oxide pigment 50 parts The above formulation was placed in a stainless steel container and used with a paint conditioner. A white paint paste was obtained by mixing and dispersing in a glass bead medium for 60 minutes. 340 parts of the above paint paste and 18 parts of hexamethoxymethylolmelamine resin (hereinafter abbreviated as HMMM) were charged and mixed and stirred for 15 minutes at room temperature using a lab mixer to obtain a white paint composition (1). Examples 2, 3, 4 and Comparative Examples 1 to 4 Example 1 except that the raw materials in Table 2 below were used.
Paint pastes and paint compositions were obtained using similar means and methods.
【表】
複層塗膜の形成
実施例および比較例で得られた塗料組成物をブ
リキ板上に乾燥膜厚が50μになるように塗布し、
30分間セツテイング後150℃×30分間加熱乾燥に
ついて第3表に示す結果を得た。
塗装条件は脱イオン水には30″/#4FC・20℃
に希釈後、スプレー塗装した。[Table] Formation of multi-layer coating film The coating compositions obtained in the Examples and Comparative Examples were applied onto a tin plate so that the dry film thickness was 50μ.
After setting for 30 minutes, the results shown in Table 3 were obtained by heating and drying at 150° C. for 30 minutes. Painting conditions are 30″/#4FC/20℃ for deionized water.
After diluting it, it was spray painted.
Claims (1)
る水不溶性の粉末樹脂()の少なくとも1種
とを含有し、該水性樹脂():該粉末樹脂
()の固形分重量比が90:10ないし20:80で
あり、 該水性樹脂()の20%樹脂濃度における該
粉末樹脂に対する接触角が40゜以下である水性
塗料を基材上に塗布することと、 (b) 樹脂固形分全体のうち粉末樹脂()の占め
る割合が塗膜厚みの20%を占める上層部分と残
余の下層部分との間で少なくとも10%の差を生
ずるように未乾燥塗膜中で前記粉末樹脂()
の部分的相分離を許容することと、 (c) 次いで該塗膜を乾燥させることを特徴とする
複層塗膜形成方法。 2 前記水性樹脂は、アルキド樹脂、ポリエステ
ル樹脂、アクリル樹脂、エポキシ樹脂、マレイン
化油、マレイン化ポリアルカジエン樹脂、ウレタ
ン樹脂、ポリアミド樹脂、ポリエチレンイミン系
樹脂、アミノプラスト、およびそれらの混合物か
ら選ばれる第1項記載の複層塗膜形成方法。[Scope of Claims] 1 (a) As film-forming components, at least one type of aqueous resin () and at least one type of water-insoluble powder resin () dispersed in an aqueous solution of the aqueous resin (). and the solid content weight ratio of the aqueous resin () to the powdered resin () is from 90:10 to 20:80, and the contact angle of the aqueous resin () to the powdered resin at 20% resin concentration is (b) The ratio of powdered resin () to the total resin solid content is 20% of the coating thickness in the upper layer and the remaining lower layer. The powdered resin () in the undried coating so that there is a difference of at least 10% between
(c) then drying the coating film. 2. The aqueous resin is selected from alkyd resins, polyester resins, acrylic resins, epoxy resins, maleated oils, maleated polyalkadiene resins, urethane resins, polyamide resins, polyethyleneimine resins, aminoplasts, and mixtures thereof. The method for forming a multilayer coating film according to item 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25160083A JPS60139365A (en) | 1983-12-27 | 1983-12-27 | Formation of composite-layered film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25160083A JPS60139365A (en) | 1983-12-27 | 1983-12-27 | Formation of composite-layered film |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60139365A JPS60139365A (en) | 1985-07-24 |
JPH0218147B2 true JPH0218147B2 (en) | 1990-04-24 |
Family
ID=17225226
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP25160083A Granted JPS60139365A (en) | 1983-12-27 | 1983-12-27 | Formation of composite-layered film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60139365A (en) |
-
1983
- 1983-12-27 JP JP25160083A patent/JPS60139365A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS60139365A (en) | 1985-07-24 |
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