JPS63113086A - Water-based paint composition - Google Patents
Water-based paint compositionInfo
- Publication number
- JPS63113086A JPS63113086A JP25855586A JP25855586A JPS63113086A JP S63113086 A JPS63113086 A JP S63113086A JP 25855586 A JP25855586 A JP 25855586A JP 25855586 A JP25855586 A JP 25855586A JP S63113086 A JPS63113086 A JP S63113086A
- Authority
- JP
- Japan
- Prior art keywords
- water
- parts
- acrylate
- paint
- resin
- 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
- 239000003973 paint Substances 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 50
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 18
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 hydroxyalkyl acrylate Chemical compound 0.000 claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 5
- IWLBIFVMPLUHLK-UHFFFAOYSA-N azane;formaldehyde Chemical compound N.O=C IWLBIFVMPLUHLK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- 229920003180 amino resin Polymers 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001412 amines Chemical class 0.000 abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 abstract description 3
- 229910021529 ammonia Inorganic materials 0.000 abstract description 2
- 239000007859 condensation product Substances 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 22
- 239000011248 coating agent Substances 0.000 description 21
- 229920000178 Acrylic resin Polymers 0.000 description 15
- 239000004925 Acrylic resin Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000008199 coating composition Substances 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- XGJZQNMUVTZITK-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexamethoxy-1,3,5-triazine-2,4,6-triamine Chemical compound CON(OC)C1=NC(N(OC)OC)=NC(N(OC)OC)=N1 XGJZQNMUVTZITK-UHFFFAOYSA-N 0.000 description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 235000013361 beverage Nutrition 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-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
- 229920000877 Melamine resin Polymers 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- GJIDOLBZYSCZRX-UHFFFAOYSA-N hydroxymethyl prop-2-enoate Chemical compound OCOC(=O)C=C GJIDOLBZYSCZRX-UHFFFAOYSA-N 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010998 test method 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
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- MIYFFZILCMZNRY-UHFFFAOYSA-N 1-hydroxypentyl prop-2-enoate Chemical compound CCCCC(O)OC(=O)C=C MIYFFZILCMZNRY-UHFFFAOYSA-N 0.000 description 1
- QBDAFARLDLCWAT-UHFFFAOYSA-N 2,3-dihydropyran-6-one Chemical compound O=C1OCCC=C1 QBDAFARLDLCWAT-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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- OHCUUVLMXARGTH-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxypropoxy)propoxy]propoxy]propyl prop-2-enoate Chemical compound C=CC(=O)OCC(C)OCC(C)OCC(C)OCC(C)OC(=O)C=C OHCUUVLMXARGTH-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- VNGLVZLEUDIDQH-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;2-methyloxirane Chemical class CC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 VNGLVZLEUDIDQH-UHFFFAOYSA-N 0.000 description 1
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920003270 Cymel® Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- NBZANZVJRKXVBH-GYDPHNCVSA-N alpha-Cryptoxanthin Natural products O[C@H]1CC(C)(C)C(/C=C/C(=C\C=C\C(=C/C=C/C=C(\C=C\C=C(/C=C/[C@H]2C(C)=CCCC2(C)C)\C)/C)\C)/C)=C(C)C1 NBZANZVJRKXVBH-GYDPHNCVSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- HSOOVEKLGOIEFF-UHFFFAOYSA-N ethenyl nitrate Chemical compound [O-][N+](=O)OC=C HSOOVEKLGOIEFF-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 239000000314 lubricant 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
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
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)
Abstract
Description
【発明の詳細な説明】
〔発明の目的〕
（産業上の利用分野）
本発明は、水酸基含有アルキル（メタ）アクリレートと
、グリコールもしくはポリオキシアルキレングリコール
のジ（メタ）アクリレートと、α・βモ等で水性化せし
めた水性樹脂に、水性のアミノブラスト樹脂を配合した
塗料組成物に関し、特に耐水性。Detailed Description of the Invention [Objective of the Invention] (Industrial Field of Application) The present invention relates to a hydroxyl group-containing alkyl (meth)acrylate, a di(meth)acrylate of glycol or polyoxyalkylene glycol, and an α/β moiety. Regarding coating compositions in which water-based aminoblast resin is blended with water-based resin made water-based by etc., especially water resistance.
グロスに優れ溶剤の含有量を低減させることができる水
性塗料組成物に関する。The present invention relates to an aqueous coating composition that has excellent gloss and can reduce the content of solvent.
（従来の技術）
清涼飲料水等を収容する飲料缶及び食品を包装する食缶
の外面は１缶材の腐食を防止し、美的商品価値を高め、
かつ食品殺菌処理時の熱処理工程に耐えうる塗膜により
被覆形成されている。従来これらの塗料は、エポキシ／
アミノ系樹脂、アクリル／アミノ系樹脂、ポリエステル
／アミノ系樹脂等の有機溶剤溶液をロールコータ−にて
塗装し、ガスオーブンにて焼付硬化する方法が行なわれ
ている。しかしこれらの塗料は、焼付時に多量の溶剤揮
散をもたらし１大気汚染の原因となり、省資源の点から
も好ましくない。そこで、これらの問題点を解決可能な
水性塗料の出現が望まれている。(Prior art) The outer surface of beverage cans for storing soft drinks, etc. and food cans for packaging food products prevents corrosion of the can material, increases the aesthetic value of the product,
Moreover, it is coated with a coating film that can withstand the heat treatment process during food sterilization. Traditionally, these paints are epoxy/
A method is used in which an organic solvent solution of amino resin, acrylic/amino resin, polyester/amino resin, etc. is applied using a roll coater, and then baked and hardened in a gas oven. However, these paints cause a large amount of solvent to volatilize during baking, causing air pollution, and are also unfavorable from the point of view of resource conservation. Therefore, the emergence of a water-based paint that can solve these problems is desired.
公知の水性塗料は水分散性と水溶性の２タイプがあり、
水分散性樹脂は通常、界面活性剤を用いて浮化重合法で
合成されるものが多く、使用する界面活性剤が塗膜形成
後も塗膜中に残存し、耐水性を低下させる欠点があった
。一方、界面活性剤を使用しないで有機溶剤系で合成し
酸分くカルボキシル基）を含む樹脂を合成し、揮発性塩
基で中和し分散体ないは水溶性とする方法もあるが、こ
れらの水性塗料は。There are two types of known water-based paints: water-dispersible and water-soluble.
Water-dispersible resins are usually synthesized using a floatation polymerization method using surfactants, but the disadvantage is that the surfactants used remain in the coating film even after it is formed, reducing water resistance. there were. On the other hand, there is a method of synthesizing a resin containing acidic and carboxyl groups in an organic solvent system without using a surfactant, and then neutralizing it with a volatile base to make it a dispersion or water-soluble. water-based paint.
基本となる樹脂構造中に酸価２０以上の酸分が必要であ
り、耐水性、ｉｔアルカリ性等の性能が劣り、塗膜とし
ての基本性能に欠けるという欠点があった。It requires an acid component with an acid value of 20 or more in the basic resin structure, has poor performance such as water resistance and alkalinity, and has the drawback of lacking basic performance as a coating film.
−さらに上記の如き欠点を回避すべくポリエチレングリ
コールのモノ （メタ）アクリレートのようなグリコー
ルのモノアクリルエステルを使用することによりα・β
モノエチレン性不飽和カルボン酸の使用量を３〜１０％
に低下させた水性塗料の提案がされた（特公昭５２−１
７３５号公報）。この水性塗料は耐水性が向上し、耐ア
ルカリ性、防錆力にも優れるという利点を有しているが
、飲料缶９食缶等の食品殺菌処理における湧水、１１７
℃〜１２５℃のレトルト等の厳しい熱処理による塗膜の
軟化、ブリスター発生、グロスの低下等の塗膜物性に劣
るという欠点があった。更に飲料缶９食缶等の外面は缶
材の美的商品価値を高めるためにグロスの優れた塗膜を
被覆形成する必要があるが、上記塗料はこのようなグロ
スを満足させるレベルまでには至っていない。-Furthermore, in order to avoid the above-mentioned drawbacks, α and β
The amount of monoethylenically unsaturated carboxylic acid used is 3-10%.
A proposal was made for a water-based paint with a lower level of
Publication No. 735). This water-based paint has the advantage of improved water resistance, alkali resistance, and rust prevention.
There have been disadvantages in that the physical properties of the coating film are poor, such as softening of the coating film, generation of blisters, and reduction in gloss due to severe heat treatment such as retorting at temperatures between 125°C and 125°C. Furthermore, the outer surfaces of beverage cans, food cans, etc. need to be coated with a coating film with excellent gloss in order to enhance the aesthetic and commercial value of the can material, but the above-mentioned coatings have not reached a level that satisfies such gloss. not present.
また従来の水溶性塗料は、塗料の貯蔵安定性及び塗膜形
成におけるレベリング性向上のために有機溶剤を１０重
量％以上含んでおり、焼付時における溶剤揮散による大
気汚染及び省資源の点でまだ不充分であった。Furthermore, conventional water-soluble paints contain 10% by weight or more of organic solvents to improve the storage stability of the paint and the leveling properties during coating film formation. It was insufficient.
（発明が解決しようとする問題点） 本発明は、上記現状に鑑みてなされたものであり。(Problem that the invention attempts to solve) The present invention has been made in view of the above-mentioned current situation.
その目的とするところは、飲料缶１食缶等の食品殺菌処
理時の熱処理工程にも耐えうる耐水性を有し。The purpose is to have water resistance that can withstand the heat treatment process during food sterilization such as single-serve beverage cans.
缶材の美的商品価値を高めるグロスの優れた塗膜を被覆
形成し、かつ有機溶剤含有量が低い水性塗料組成物を提
供するものである。The present invention provides an aqueous coating composition that forms a coating film with excellent gloss that enhances the aesthetic commercial value of can stock, and has a low organic solvent content.
（問題点を解決するための手段）
すなわち本発明は、水可溶成分であるポリオキシアルキ
レングリコールもしくはアルキレングリコールのジアク
リレートもしくはジメタクリレートを前架橋成分とし、
親水成分である炭素数が１〜５のヒドロキシアルキルア
クリレートまたはメタクリレートを硬化架橋成分とし、
水可溶化のためのα・βモノエチレン性不飽和カルボン
酸成分を低減したアクリル共重合体を作成し水性樹脂と
した上で、水性アミノプラスト樹脂を混合することによ
り、耐水性。(Means for Solving the Problems) That is, the present invention uses polyoxyalkylene glycol or alkylene glycol diacrylate or dimethacrylate as a pre-crosslinking component, which is a water-soluble component,
Hydrophilic component hydroxyalkyl acrylate or methacrylate having 1 to 5 carbon atoms is used as a curing crosslinking component,
Water resistance is achieved by creating an acrylic copolymer with reduced α/β monoethylenically unsaturated carboxylic acid components for water solubilization, making it a water-based resin, and then mixing it with a water-based aminoplast resin.
グロスが優れ、有機溶剤の低減化が可能であることを見
い出し９本発明を完成するに至った。The present invention was completed after discovering that the gloss is excellent and the amount of organic solvent can be reduced.
本発明に従えば。According to the invention.
（ａ）炭素数が１〜５のヒドロキシアルキルアクリレー
トもしくはメタクリレート
５〜６５ｆｉ量％
（ｂ）アルキレングリコールもしくはポリオキシアルキ
レングリコールのジアクリレートもしくはジメタクリレ
ート ５〜５（１１％（ｃ）α・βモノエ
チレン性不飽和カルボン酸２〜２０重量％
（ｄ）上記（ａ）ないし（ｃ）と共重合可能なビルルモ
ノマーの１種または２種以上
２０〜８８重量％
よりなる共重合体を揮発性塩基で中和せしめた水性樹脂
と、水性アミンホルムアルデヒド縮金物とを樹脂成分と
することを特徴とする水性塗料組成物である。(a) Hydroxyalkyl acrylate or methacrylate having 1 to 5 carbon atoms 5 to 65 fi amount% (b) Alkylene glycol or polyoxyalkylene glycol diacrylate or dimethacrylate 5 to 5 (11%) (c) α/β monoethylene (d) A copolymer consisting of 20 to 88% by weight of one or more types of viruloid monomers that can be copolymerized with (a) to (c) above in a volatile base. This is an aqueous coating composition characterized in that the resin components are a blended aqueous resin and an aqueous amine-formaldehyde condensate.
以下１本発明の組成物についてさらに詳細に説明する。The composition of the present invention will be explained in more detail below.
本発明における炭素数が１〜５のヒドロキシアルキルア
クリレートまたはメタクリレート（ａ）は、ヒドロキシ
メチルアクリレート、ヒドロキシエチルアクリレート、
ヒドロキシプロピルアクリレート、ヒドロキシアミルア
クリレート、ヒドロキシへキシルアクリレート及び相当
するメタクリレートがこれに該当する。好ましくは炭素
数が１〜２のヒドロキシメチルアクリレート、ヒドロキ
シエチルアクリレート及び相当するメタクリレートがよ
い。The hydroxyalkyl acrylate or methacrylate (a) having 1 to 5 carbon atoms in the present invention includes hydroxymethyl acrylate, hydroxyethyl acrylate,
These include hydroxypropyl acrylate, hydroxyamyl acrylate, hydroxyhexyl acrylate and the corresponding methacrylates. Hydroxymethyl acrylate, hydroxyethyl acrylate and corresponding methacrylates having 1 to 2 carbon atoms are preferred.
アルキレングリコールもしくはポリオキシアルキレング
リコールのジアクリレートもしくはジメタクリレート（
′ｂ）は次の一般式で示される。Diacrylate or dimethacrylate of alkylene glycol or polyoxyalkylene glycol (
'b) is represented by the following general formula.
（式中、Ｒ，、Ｒ２，Ｒうは、ＨまたはＣＲ５であり。(In the formula, R,, R2, and R are H or CR5.
ｎは１〜５０の整数を表す。）
より具体的には上記式においてｎが１〜４で表されるエ
チレングリコールジアクリレート、ジエチレングリコー
ルジアクリレート、プロピレングリコールジアクリレー
ト、ジプロピレングリコールジアクリレート、トリプロ
ピレングリコールジアクリレート、テトラプロピレング
リコールジアクリレート及び相当するメタクリレートが
好ましい。n represents an integer from 1 to 50. ) More specifically, ethylene glycol diacrylate, diethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, and Preference is given to the corresponding methacrylates.
α・βモノエチレン性不飽和カルボン酸（ｃ）はアクリ
ル酸、メタクリル酸、クロトン酸、マレイン酸。α/β monoethylenically unsaturated carboxylic acids (c) are acrylic acid, methacrylic acid, crotonic acid, and maleic acid.
フマル酸、イタコン酸などがあり、特にアクリル酸。These include fumaric acid, itaconic acid, and especially acrylic acid.
メタクリル酸が好ましい。 ・上記（ａ）ない
し（ｃ）と共重合可能なビニルモノマー（ｄ）は９例え
ばアクリル酸エチル、アクリル酸ブチル。Methacrylic acid is preferred. - The vinyl monomer (d) copolymerizable with the above (a) to (c) is 9, for example, ethyl acrylate or butyl acrylate.
アクリル酸−２エチルヘキシル、アクリル酸シクロヘキ
シル、メタクリル酸エチル、メタクリル酸ブチル、メタ
クリル酸ステアリル、メタクリル酸シクロヘキシルなど
のアクリル酸またはメタクリル酸のアルキルエステル、
またはスチレン、ビニルトルエン。Alkyl esters of acrylic acid or methacrylic acid, such as 2-ethylhexyl acrylate, cyclohexyl acrylate, ethyl methacrylate, butyl methacrylate, stearyl methacrylate, and cyclohexyl methacrylate;
or styrene, vinyltoluene.
ａ−メチルスチレンなどの芳香族ビニル化合物及び酢酸
ビニル、ビニルエチルエーテルなどがある。Examples include aromatic vinyl compounds such as a-methylstyrene, vinyl acetate, and vinyl ethyl ether.
本発明において（ａ）成分は共重合体樹脂中５〜６５重
量％であり、５重量％以下になると架橋点が少なくなる
結果、塗膜の耐水性が劣り、また親水性基が少ないこと
から塗料安定性に欠け、逆に６５重量％以上になると架
橋点が多すぎる結果、塗膜の可とう性が劣る。In the present invention, the amount of component (a) in the copolymer resin is 5 to 65% by weight, and if it is less than 5% by weight, the number of crosslinking points will decrease, resulting in poor water resistance of the coating film and less hydrophilic groups. The coating lacks stability, and conversely, when it exceeds 65% by weight, there are too many crosslinking points, resulting in poor flexibility of the coating film.
（ｂ）成分は共重合体成分中５〜５０重量％で用いられ
、５重量％以下では前架橋効果より耐水性向上が劣り、
５０ｆｆｉ量％以上では可とう性に欠けるので。Component (b) is used in an amount of 5 to 50% by weight in the copolymer component, and if it is less than 5% by weight, the water resistance improvement is inferior to the pre-crosslinking effect,
If the amount is more than 50ffi, it will lack flexibility.
５〜５０重量％が耐水性向上と可とう性のバランスがと
れる最適の範囲である。The optimum range is 5 to 50% by weight, which provides a good balance between improved water resistance and flexibility.
（ｃ）成分は、水性化可能な限り少ない方が耐水性が良
好であり、２重量％以上でこの目的を達成するが。The water resistance of component (c) is better when the amount is as small as possible, and this objective is achieved when the amount of component (c) is 2% by weight or more.
２０重量％以上をこえると、耐水性の向上があっても十
分でなくなる。また、（ｄ）成分は２０〜８８重量％の
範囲の配合により組成物の塗膜硬度および可とう性を調
節出来る。If it exceeds 20% by weight, even if there is an improvement in water resistance, it will not be sufficient. Furthermore, the coating film hardness and flexibility of the composition can be adjusted by incorporating component (d) in a range of 20 to 88% by weight.
本発明の共重合は上記（ａ）ないしくｄｌの七ツマ−を
有機溶剤中で過酸化物またはアゾ化合物を触媒とし共重
合させ、前架橋したゲル化されていない共重合体として
得られる０重合条件は９０〜１２０℃の温度で５０重量
％以下の比較的低い重合固体含有量で実施することによ
り、ゲル化せずに合成可能となる。The copolymerization of the present invention involves copolymerizing the above (a) or dl in an organic solvent using a peroxide or an azo compound as a catalyst to obtain a pre-crosslinked, non-gelled copolymer. By carrying out the polymerization at a temperature of 90 to 120° C. and a relatively low polymerization solid content of 50% by weight or less, synthesis is possible without gelation.
これは得られた共重合体溶液の紫外線吸収強度を合成前
のものと比較すると、その吸収がほとんどなくなってい
ることからも、仕込ビニルモノマー全てが共重合してい
ることを示すものであり、前架橋しゼル化しないことは
驚くべきことである。This shows that all of the charged vinyl monomers have been copolymerized, as when comparing the ultraviolet absorption intensity of the obtained copolymer solution with that before synthesis, the absorption has almost disappeared. It is surprising that it does not pre-crosslink and gel.
以上の４成分よりなる共重合体を水性化するには。To make the copolymer consisting of the above four components water-based.
アンモニアまたは有機アミン等の揮発性塩基例えばモノ
エタノールアミン、ジメチルアミン、ジエチルアミン、
トリエチルアミン、トリエタノールアミン。Volatile bases such as ammonia or organic amines such as monoethanolamine, dimethylamine, diethylamine,
Triethylamine, triethanolamine.
ジエチルエタノールアミン等を使用する。Use diethylethanolamine, etc.
水性化後、または水性アミンプラスト樹脂を混合した後
溶液中の有機溶剤を減圧下６０〜８０℃の範囲内で留去
すると、水溶性あるいは水分散性樹脂溶液が水可溶化力
の差にともない得られる。When the organic solvent in the solution is distilled off under reduced pressure within the range of 60 to 80°C after making it water-soluble or after mixing the water-based amineplast resin, a water-soluble or water-dispersible resin solution is formed due to the difference in water solubilizing power. can get.
このため合成時の有機溶剤は後工程の留去を考慮すると
、沸点が１５０℃以下が好ましく３合成時の温度及び合
成共重合体の有機溶剤への溶解力を考慮に入れると、沸
点が８０〜１５０℃の範囲内のイソプロピルアルコール
、ｎ−ブタノール、イソブチルアルコール、ｎ−アミル
アルコール、イソアミルアルコール等のアルコール系溶
剤及び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
モノイソプロピルエーテル等のエステル系溶剤が好まし
い。Therefore, in consideration of distillation in the subsequent step, the organic solvent used during synthesis preferably has a boiling point of 150°C or lower.3 Considering the temperature during synthesis and the solubility of the synthesized copolymer in the organic solvent, the boiling point is 80°C or less. Alcohol-based solvents such as isopropyl alcohol, n-butanol, isobutyl alcohol, n-amyl alcohol, and isoamyl alcohol within the range of ~150°C, and ester-based solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monoisopropyl ether. Solvents are preferred.
本発明の水性アミンホルムアルデヒド縮合物は。The aqueous amine formaldehyde condensate of the present invention is.
アルキルエーテル化メラミン樹脂、アルキルエーテル化
尿素樹脂、フェニレン核に２個のトリアジン環の結合し
たジグアナミンのアルキルエーテル化樹脂、 ′アルキ
ルエーテル化グリコール樹脂等を単独または２種以上を
混合して用いる。好ましくは、完全にエーテル化された
ヘキサメトキシメラミンがよい。Alkyl etherified melamine resins, alkyl etherified urea resins, alkyl etherified diguanamine resins in which two triazine rings are bonded to a phenylene nucleus, and alkyl etherified glycol resins are used alone or in combination of two or more. Preferably, fully etherified hexamethoxymelamine is used.
水性化処理により水溶化あるいは水分散体化した水性樹
脂は、水性アミノプラスト樹脂と混合し、更に必要に応
じて硬化助剤としてアミンでブロックした酸触触例えば
ｐ−トルエンベンゼンスルホン酸。The aqueous resin that has been made water-solubilized or water-dispersed by the aqueous treatment is mixed with an aqueous aminoplast resin, and if necessary, an acid catalyst blocked with an amine as a curing aid, such as p-toluenebenzenesulfonic acid.
ドデシルベンゼンスルホン酸、ジノニルナフタレンジス
ルホン酸等を樹脂固型分１００部に対し０．１〜１．０
部を添加して塗料化する。また水性塗料用樹脂として一
般的に用いられている水溶性樹脂、水分散性樹脂例えば
、水溶性ポリエステル樹脂、マレイン化脂肪酸、水溶性
あるいは水分散性エポキシ樹脂及びビスフェノールＡプ
ロピレンオキサイド付加物。0.1 to 1.0 of dodecylbenzenesulfonic acid, dinonylnaphthalenedisulfonic acid, etc. per 100 parts of resin solid content.
% to form a paint. Also, water-soluble resins and water-dispersible resins commonly used as resins for water-based paints, such as water-soluble polyester resins, maleated fatty acids, water-soluble or water-dispersible epoxy resins, and bisphenol A propylene oxide adducts.
エチレンオキサイド付加物等のポリオールなどを混合す
ることも可能である。また同様にレベリング剤。It is also possible to mix polyols such as ethylene oxide adducts. Also a leveling agent.
消泡剤、潤湧剤を・添加することもできる。また顔料を
前記の脱溶剤した共重合樹脂溶液と練肉し顔料ペースト
を作成し、前述と同様の方法で塗料化することができる
。Antifoaming agents and lubricating agents can also be added. Alternatively, the pigment can be kneaded with the solvent-free copolymer resin solution to prepare a pigment paste, which can be made into a paint in the same manner as described above.
本発明の水性塗料組成物はロールコート、スプレー、は
け塗り等の公知の手段により塗装することができる。The aqueous coating composition of the present invention can be applied by known means such as roll coating, spraying, and brushing.
以下９本発明を実施例にて具体的に説明する。例中「部
」、「％」とあるのは「重量部」、「重量％」を示す。The present invention will be specifically explained below with reference to nine examples. In the examples, "parts" and "%" indicate "parts by weight" and "% by weight."
（実施例）
製造例Ａｌ （アクリル樹脂溶液の製造例）温度計、
攪拌機、還流冷却器５滴下槽、窒素ガス吹込管を備えた
四ツ目フラスコにｎ−ブタノール１００部を仕込み、窒
素ガスを導入しつつかきまぜながら温度を１００℃に保
ち１滴下槽から２−ヒドロキシエチルアクリレート１５
部、テトラエチレングリコールジアクリレート２０部、
アクリル酸２部。(Example) Production example Al (Production example of acrylic resin solution) Thermometer,
100 parts of n-butanol was charged into a four-eye flask equipped with a stirrer, a reflux condenser, 5 dropping tanks, and a nitrogen gas blowing tube, and while stirring while introducing nitrogen gas, the temperature was maintained at 100°C, and 2-hydroxy was added from the 1 dropping tank. Ethyl acrylate 15
parts, 20 parts of tetraethylene glycol diacrylate,
2 parts acrylic acid.
エチルアクリレート６３部、過酸化ベンゾイル２部の混
合物を３時間に亘って滴下した。その後１００℃に保ち
２時間反応し、過酸化ベンゾイル０．３部を添加し、１
時間反応させ終了した。４０℃以下に冷却しトリエチル
アミン３部および水２００部を添加し、６０％個型分、
残留ｎ−ブクノール１０％の透明で粘稠な樹脂溶液が得
られた。A mixture of 63 parts of ethyl acrylate and 2 parts of benzoyl peroxide was added dropwise over 3 hours. After that, it was kept at 100℃ and reacted for 2 hours, and 0.3 parts of benzoyl peroxide was added, and 1
The reaction was completed for a period of time. Cool to below 40°C, add 3 parts of triethylamine and 200 parts of water, and add 60% solids,
A clear, viscous resin solution with 10% residual n-buknol was obtained.
製造例Ａ２〜Ａ６
製造例Ａ１と同様の方法に従い、フラスコにあらかじめ
仕込んでおく溶剤組成１滴下するビニル七ツマー組成、
触媒量、追添加する触媒量９反応温度を表−１のように
変えて合成し、更に有機アミン量を表−１のように変え
て中和した。また製造例Ａ１と同様の方法に従い水を添
加し、減圧下８０℃にて合成溶剤を水とともに留去し、
６０％個型分、残留ｎ−ブタノール１０％の透明で粘稠
の樹脂溶液が得られた。Production Examples A2 to A6 Following the same method as Production Example A1, add one drop of a solvent composition prepared in advance into a flask, and add a vinyl nitrate composition;
The amount of catalyst and the amount of catalyst to be added were synthesized by changing the reaction temperature as shown in Table 1, and the amount of organic amine was further changed as shown in Table 1 for neutralization. Further, water was added according to the same method as in Production Example A1, and the synthesis solvent was distilled off together with the water at 80°C under reduced pressure.
A clear and viscous resin solution containing 60% solids and 10% residual n-butanol was obtained.
製造例Ｂｌ（ｆｉ料分散ペーストの製造例）アクリル樹
脂溶液Ａ１ ４０部、ルチル型チタン白４０部および水
１０部を混合しアトライターで分散させ、顔料分散ペー
ストが得られた。Production Example B1 (Production Example of Pigment Dispersion Paste) 40 parts of acrylic resin solution A1, 40 parts of rutile titanium white, and 10 parts of water were mixed and dispersed with an attritor to obtain a pigment dispersion paste.
製造例Ｂ２
アクリル樹脂溶液Ａ２ ４０部、ルチル型チタン白４０
部および水１０部を混合しアトライターで分散させ、顔
料分散ペーストが得られた。Production example B2 Acrylic resin solution A2 40 parts, rutile type titanium white 40
1 part and 10 parts of water were mixed and dispersed with an attritor to obtain a pigment dispersion paste.
実施例１
製造例Ａ１のアクリル樹脂溶液４７部、ヘキサメトキシ
メラミン（三井東圧化学株式会社製、サイメル３０３；
以下の例も同じ） １２部、アミンブロックしたパラト
ルエンスルホン酸（楠本化成株式会社製 ＮＡＣＵＲＥ
２５００Ｘ ｉ以下の例も同じ＞ ０゜４部及び水４０
．６部を混合し、塗料化した。Example 1 47 parts of the acrylic resin solution of Production Example A1, hexamethoxymelamine (manufactured by Mitsui Toatsu Chemical Co., Ltd., Cymel 303;
The same applies to the following examples) 12 parts, amine-blocked para-toluenesulfonic acid (NACURE manufactured by Kusumoto Kasei Co., Ltd.)
The same applies to the examples below 2500X > 0° 4 parts and water 40
．． 6 parts were mixed and made into a paint.
実施例２〜８ 実施例１と同様の方法に従い、アクリル樹脂溶液。Examples 2-8 Acrylic resin solution according to the same method as in Example 1.
水性アミノプラスト樹脂を表−２のように変えて塗料化
した。Paints were made using different water-based aminoplast resins as shown in Table 2.
実施例９
製造例Ａ１のアクリル樹脂溶液６．３部、製造例Ｂ１の
顔料分散ペースト６２．５部、ヘキサメトキシメラミン
６．３部、アミンブロックしたパラトルエンスルホン酸
０．２部及び水２４．７部を混合し塗料化した。Example 9 6.3 parts of the acrylic resin solution of Production Example A1, 62.5 parts of the pigment dispersion paste of Production Example B1, 6.3 parts of hexamethoxymelamine, 0.2 parts of amine-blocked para-toluenesulfonic acid, and 24 parts of water. 7 parts were mixed to form a paint.
実施例１０
製造例Ａ２のアクリル樹脂溶液６．３部、製造例Ｂ２の
顔料分散ペースト６２．５部、ヘキサメトキシメラミン
６．３部、アミンブロックしたパラトルエンスルホン酸
０．２部及び水２４．７部を混合し塗料化した。Example 10 6.3 parts of the acrylic resin solution of Production Example A2, 62.5 parts of the pigment dispersion paste of Production Example B2, 6.3 parts of hexamethoxymelamine, 0.2 parts of amine-blocked para-toluenesulfonic acid, and 24 parts of water. 7 parts were mixed to form a paint.
公知の水溶性アクリル樹脂と水溶性アミノプラスト樹脂
より構成される塗料及び顔料分散ペーストを分散した白
色塗料について比較例１．２として以下記す。A paint composed of a known water-soluble acrylic resin and a water-soluble aminoplast resin and a white paint in which a pigment dispersion paste is dispersed will be described below as Comparative Example 1.2.
比較例１
四ツ目フラスコにブチルセロソルブ４０部を仕込み、窒
素ガスを導入しつつ、かきまぜながら温度を１１５℃に
保ち１滴下槽からアクリル酸２０部、エチルアクリレー
ト５０部、メチルメタアクリレート２５部、ヒドロキシ
エチルアクリレート５部、過酸化ベンゾイル１部の混合
物を３時間に亘って滴下した。その後１１５℃に保ち２
時間反応し、過酸化べンゾイル０．１部を添加し１時間
反応させ終了した。Comparative Example 1 40 parts of butyl cellosolve was charged in a four-eye flask, and while stirring while introducing nitrogen gas, the temperature was maintained at 115°C, and 20 parts of acrylic acid, 50 parts of ethyl acrylate, 25 parts of methyl methacrylate, and hydroxyl were added from a drop tank. A mixture of 5 parts of ethyl acrylate and 1 part of benzoyl peroxide was added dropwise over 3 hours. Then keep it at 115℃ 2
The reaction was continued for an hour, 0.1 part of benzoyl peroxide was added, and the reaction was completed for 1 hour.
７０℃に冷却しイソプロピルアルコール６０部で希釈し
、更にトリエチルアミン２５部及び水３０部で希釈しア
クリル樹脂溶液を得た。The mixture was cooled to 70°C, diluted with 60 parts of isopropyl alcohol, and further diluted with 25 parts of triethylamine and 30 parts of water to obtain an acrylic resin solution.
上記アクリル樹脂溶液にヘキサメトキシメラミンを４２
．９部、アミンブロックしたパラトルエンスルホン酸及
び水１６４部を混合し塗料化した。Add 42% hexamethoxymelamine to the above acrylic resin solution.
．． 9 parts of amine-blocked paratoluenesulfonic acid and 164 parts of water were mixed to form a paint.
比較例２
比較例１で得られたアクリル樹脂溶液５５部、ルチル型
チタン白４０部及び水５部を混合しアトライターで分散
させた後、更に同アクリル樹脂溶液１２゜５部とへキサ
メトキシメラミン１０部、アミンブロックしたパラトル
エンスルホン酸０．４部及び水３７゜１部を混合し塗料
化した。Comparative Example 2 55 parts of the acrylic resin solution obtained in Comparative Example 1, 40 parts of rutile titanium white, and 5 parts of water were mixed and dispersed with an attritor, and then 12.5 parts of the same acrylic resin solution and 5 parts of hexamethoxy were mixed. 10 parts of melamine, 0.4 part of amine-blocked paratoluenesulfonic acid, and 37°1 part of water were mixed to form a paint.
比較例３
特公昭５２−１７３５号公報の実施例１に記載されたア
クリル樹脂溶液２用いて、アミノプラスト樹脂と触媒は
実施例１と同様にしてクリヤー系塗料を得た。Comparative Example 3 A clear paint was obtained using the acrylic resin solution 2 described in Example 1 of Japanese Patent Publication No. Sho 52-1735, using the aminoplast resin and catalyst in the same manner as in Example 1.
比較例４
比較例３のアクリル樹脂を用いて製造例Ｂｌと同様にし
てａ製したチタン顔料分散ペーストを用い。Comparative Example 4 A titanium pigment dispersion paste manufactured using the acrylic resin of Comparative Example 3 in the same manner as in Production Example B1 was used.
ついで実施例９と同様にして白色塗料をを得た。Then, a white paint was obtained in the same manner as in Example 9.
実施例１〜１０および比較例１〜４で得られた塗料の塗
料試験、塗装焼付硬化後の塗膜物性試験及びフロー塗装
性試験を行った。結果を表−３に記す。The paints obtained in Examples 1 to 10 and Comparative Examples 1 to 4 were subjected to a paint test, a paint film physical property test after baking and curing, and a flow paintability test. The results are shown in Table-3.
各試験方法は下記のとおりである。Each test method is as follows.
塗料試験
Ｏ塗料安定性試験；
各塗料を２ケ月間常温で保存した後、樹脂のゲル化９分
離の状態を観察した。Paint Test O Paint Stability Test: After each paint was stored at room temperature for two months, the state of gelation and separation of the resin was observed.
○塗料中の有機溶割合有量試験；
塗料をメチルエチルケトンで希釈し、そのままガスクロ
マトグラフィーにて定量した。○ Test for organic solubility in paint: The paint was diluted with methyl ethyl ketone and directly quantified by gas chromatography.
塗膜物性試験
板厚０．２３ｍの電気メツキブリキにロールコート塗装
により乾燥後塗膜厚７μになるように塗装し。Coating film physical property test An electroplated tin plate with a thickness of 0.23 m was coated by roll coating so that the film thickness after drying was 7 μm.
ガスオープンにて雰囲気温度１９０℃において１０分間
焼付塗装パネルを作成した。A baked painted panel was prepared at an ambient temperature of 190° C. for 10 minutes with a gas open.
○耐水性試験；
塗装パネルを水中に浸漬し、１００℃−３０分間の熱処
理を行った後、塗膜の白化状態を評価した。○Water resistance test; After the painted panel was immersed in water and heat treated at 100°C for 30 minutes, the whitening state of the paint film was evaluated.
Ｏ鉛筆硬度試験；
ＪＩＳ規格にのっとった鉛筆硬度試験法により評価した
。O Pencil hardness test: Evaluation was performed using a pencil hardness test method in accordance with JIS standards.
○密着性試験； ゴバン目剥離試験を行った。○Adhesion test; A cross-cut peel test was conducted.
○耐衝撃性； デュポン式！／２インチ、５００ｇ荷重で試験した。○Impact resistance; DuPont style! /2 inch and 500g load.
○グロス；
６０＆ｊｉ面反射率を測定した。なお、クリヤー系塗料
については実施例９の白色塗料の焼付塗膜板上に塗装し
た後測定した。○Gloss; 60&ji surface reflectance was measured. The clear paint was measured after being coated with the white paint of Example 9 on the baked coating board.
Ｏ耐錆性；
塗膜面に素地に達するクロスカットを行った試験板を用
い塩水噴霧試験７２時間おこない、カット部をセロハン
粘着テープで剥離し、その剥離面積で評価した。O Rust resistance: A salt water spray test was conducted for 72 hours using a test plate in which a cross cut was made on the coated surface to reach the substrate, and the cut portion was peeled off with cellophane adhesive tape, and the peeled area was evaluated.
塗装性試験
○フロー；
ロールコータ−にて塗装後直ちにガスオーブンにて焼付
け、フロー状態を評価した。Paintability Test - Flow; Immediately after coating with a roll coater, it was baked in a gas oven to evaluate the flow state.
本発明の水性塗料組成物は、飲料缶１食缶等の食品殺菌
処理時の熱処理工程にも耐えうる耐水性を有しており２
缶材の美的商品価値を高めるグロスの優れた塗膜を被覆
形成し、かつ有機溶剤含有率が塗料中の５％以下であっ
ても優れた塗料安定性及びフロー塗装適性を有している
。The water-based coating composition of the present invention has water resistance that can withstand the heat treatment process during food sterilization treatment for beverage cans and single-serve cans.
It forms a coating film with excellent gloss that enhances the aesthetic and commercial value of can stock, and has excellent coating stability and flow coating suitability even when the organic solvent content is 5% or less in the coating material.
（以下余白）(Margin below)
Claims (1)
レートもしくはメタクリレート ５〜６５重量％ （ｂ）アルキレングリコールもしくはポリオキシアルキ
レングリコールのジアクリレートもしくはジメタクリレ
ート５〜５０重量％ （ｃ）α・βモノエチレン性不飽和カルボン酸２〜２０
重量％ （ｄ）上記（ａ）ないし（ｃ）と共重合可能なビルルモ
ノマーの１種または２種以上 ２０〜８８重量 ％よりなる共重合体を揮発性塩基で中和せしめた水性樹
脂と、水性アミンホルムアルデヒド縮合物とを樹脂成分
とすることを特徴とする水性塗料組成物。[Claims] 1. (a) 5 to 65% by weight of hydroxyalkyl acrylate or methacrylate having 1 to 5 carbon atoms (b) 5 to 50% by weight of diacrylate or dimethacrylate of alkylene glycol or polyoxyalkylene glycol ( c) α/β monoethylenically unsaturated carboxylic acid 2-20
(d) an aqueous resin prepared by neutralizing with a volatile base a copolymer consisting of 20 to 88 wt % of one or more viruloid monomers copolymerizable with (a) to (c) above; 1. An aqueous paint composition comprising an amine formaldehyde condensate as a resin component.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61258555A JPH0788492B2 (en) | 1986-10-31 | 1986-10-31 | Aqueous coating composition |
| GB8809797A GB2217721B (en) | 1986-10-31 | 1988-04-26 | Aqueous coating compostion and process for the production thereof |
| DE3814665A DE3814665C2 (en) | 1986-10-31 | 1988-04-29 | Aqueous coating agent and process for its production |
| CA000565478A CA1336630C (en) | 1986-10-31 | 1988-04-29 | Aqueous coating composition, process for the production thereof and aqueous coating |
| US07/680,778 US5077348A (en) | 1986-10-31 | 1991-04-20 | Aqueous coating composition, process for the production thereof and aqueous coating |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61258555A JPH0788492B2 (en) | 1986-10-31 | 1986-10-31 | Aqueous coating composition |
| CA000565478A CA1336630C (en) | 1986-10-31 | 1988-04-29 | Aqueous coating composition, process for the production thereof and aqueous coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63113086A true JPS63113086A (en) | 1988-05-18 |
| JPH0788492B2 JPH0788492B2 (en) | 1995-09-27 |
Family
ID=25671870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61258555A Expired - Lifetime JPH0788492B2 (en) | 1986-10-31 | 1986-10-31 | Aqueous coating composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPH0788492B2 (en) |
| CA (1) | CA1336630C (en) |
| DE (1) | DE3814665C2 (en) |
| GB (1) | GB2217721B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5594931B2 (en) | 2006-11-02 | 2014-09-24 | 関西ペイント株式会社 | Water-based paint composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS521735A (en) * | 1975-06-20 | 1977-01-07 | Ibu Emiiru Puribasu | Radiation heating element |
| JPS5485231A (en) * | 1977-12-21 | 1979-07-06 | Nippon Oil & Fats Co Ltd | Thermosetting coating composition |
| JPS553488A (en) * | 1977-01-07 | 1980-01-11 | Vianova Kunstharz Ag | Waterrdilutable thermoosetting coating composition |
| JPS61203179A (en) * | 1985-02-27 | 1986-09-09 | ヴィアノヴァ クンストハルツ アクチェンゲゼルシャフト | Undercoating water-dilutable paint for wet-on-wet painting of transparent coating on undercoating |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4062823A (en) * | 1976-09-20 | 1977-12-13 | Ford Motor Company | Hybrid water-based enamels with partially crosslinked latexes |
-
1986
- 1986-10-31 JP JP61258555A patent/JPH0788492B2/en not_active Expired - Lifetime
-
1988
- 1988-04-26 GB GB8809797A patent/GB2217721B/en not_active Expired - Lifetime
- 1988-04-29 DE DE3814665A patent/DE3814665C2/en not_active Expired - Fee Related
- 1988-04-29 CA CA000565478A patent/CA1336630C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS521735A (en) * | 1975-06-20 | 1977-01-07 | Ibu Emiiru Puribasu | Radiation heating element |
| JPS553488A (en) * | 1977-01-07 | 1980-01-11 | Vianova Kunstharz Ag | Waterrdilutable thermoosetting coating composition |
| JPS5485231A (en) * | 1977-12-21 | 1979-07-06 | Nippon Oil & Fats Co Ltd | Thermosetting coating composition |
| JPS61203179A (en) * | 1985-02-27 | 1986-09-09 | ヴィアノヴァ クンストハルツ アクチェンゲゼルシャフト | Undercoating water-dilutable paint for wet-on-wet painting of transparent coating on undercoating |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2217721B (en) | 1991-09-04 |
| JPH0788492B2 (en) | 1995-09-27 |
| DE3814665C2 (en) | 1995-09-07 |
| CA1336630C (en) | 1995-08-08 |
| GB8809797D0 (en) | 1988-06-02 |
| DE3814665A1 (en) | 1989-11-09 |
| GB2217721A (en) | 1989-11-01 |
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