JPH0245642B2 - TORYOYOJUSHISOSEIBUTSU - Google Patents
TORYOYOJUSHISOSEIBUTSUInfo
- Publication number
- JPH0245642B2 JPH0245642B2 JP2923580A JP2923580A JPH0245642B2 JP H0245642 B2 JPH0245642 B2 JP H0245642B2 JP 2923580 A JP2923580 A JP 2923580A JP 2923580 A JP2923580 A JP 2923580A JP H0245642 B2 JPH0245642 B2 JP H0245642B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- methacrylate
- parts
- solvent
- 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 - Lifetime
Links
- 239000000178 monomer Substances 0.000 claims description 14
- -1 alkyl methacrylate Chemical compound 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000003973 paint Substances 0.000 claims description 5
- 239000011342 resin composition Substances 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000002904 solvent Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- 239000008096 xylene Substances 0.000 description 2
- LJWQJECMFUGUDV-UHFFFAOYSA-N (4-benzoyl-3-hydroxyphenyl) prop-2-enoate Chemical compound OC1=CC(OC(=O)C=C)=CC=C1C(=O)C1=CC=CC=C1 LJWQJECMFUGUDV-UHFFFAOYSA-N 0.000 description 1
- UTOVMEACOLCUCK-SNAWJCMRSA-N (e)-4-butoxy-4-oxobut-2-enoic acid Chemical compound CCCCOC(=O)\C=C\C(O)=O UTOVMEACOLCUCK-SNAWJCMRSA-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- VVAAYFMMXYRORI-UHFFFAOYSA-N 4-butoxy-2-methylidene-4-oxobutanoic acid Chemical compound CCCCOC(=O)CC(=C)C(O)=O VVAAYFMMXYRORI-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-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
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 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 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 description 1
- ZEFVHSWKYCYFFL-UHFFFAOYSA-N diethyl 2-methylidenebutanedioate Chemical compound CCOC(=O)CC(=C)C(=O)OCC ZEFVHSWKYCYFFL-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 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
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 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
- 238000002156 mixing Methods 0.000 description 1
- 239000000025 natural resin Chemical class 0.000 description 1
- MADOXCFISYCULS-UHFFFAOYSA-N octyl 2-sulfanylacetate Chemical compound CCCCCCCCOC(=O)CS MADOXCFISYCULS-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Chemical class 0.000 description 1
- 239000000057 synthetic resin Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は耐候性に優れ、しかも耐久性にも優れ
た塗料用樹脂組成物に関するものである。
塗料は日光等に晒されるため優れた耐候性が要
求されている。かかる耐候性を改良するためにベ
ンゾフエノン系、ベンゾトリアゾール系、サリチ
ル酸エステル系等の紫外線吸収剤が塗料に添加さ
れている。しかしながら、かかる紫外線吸収剤は
低分子量化合物であるため
(1) 水、溶剤等によりベースポリマーから抽出さ
れるとか、熱により昇華してしまうことによる
耐久性の低下、
(2) ポリマーとの相溶性の問題
(3) ポリマーの物性を低下せしめる点
等の欠点を有している。
本発明らはかかる欠点のないポリマーを得るた
めに鋭意研究を行なつた結果、本発明を完成する
に至つた。
即ち、本発明は
(A) 一般式
（式中、R1は−Ｈ又は−CH3、R2は−Ｈ又は
−OH、R3は−Ｈ、−OH、−OR4又は
The present invention relates to a resin composition for paint that has excellent weather resistance and durability. Paints are required to have excellent weather resistance because they are exposed to sunlight. In order to improve such weather resistance, ultraviolet absorbers such as benzophenone, benzotriazole, and salicylic acid esters are added to paints. However, since such UV absorbers are low molecular weight compounds, (1) they may be extracted from the base polymer by water, solvents, etc., or sublimated by heat, resulting in decreased durability; (2) incompatibility with polymers; Problem (3): It has drawbacks such as deterioration of the physical properties of the polymer. The present inventors have conducted extensive research to obtain a polymer free of such defects, and as a result, have completed the present invention. That is, the present invention relates to (A) general formula (In the formula, R 1 is -H or -CH 3 , R 2 is -H or -OH, R 3 is -H, -OH, -OR 4 or
【式】R4は炭素数１〜18のアル
キル基）
で表わされるモノマー
0.05〜10重量％（単に％と略す）
(B) スチレン、アクリロニトリルおよびメタクリ
ル酸アルキルエステルから選ばれる少なくとも
一種のモノマー 20〜99.95％
(C) その他の共重合性モノマー ０〜79.95％
から得られる共重合体を含有してなる塗料用樹脂
組成物を提供するものである。
本発明で用いられる前記一般式で表わされるモ
ノマー量は0.05〜10％、好ましくは0.1〜３％で
あるが、その量が0.05％よりも少ないと充分な耐
候性をもたらさず、又、10％を越えると塗面状
態、光沢、レベリング等に問題を生じて好ましく
ない。
かかるモノマーの代表的なものを挙げれば、
２−ヒドロキシ−４−（メタ）アクリロキシベン
ゾフエノン
２，２−ジヒドロキシ−４−（メタ）アクリロキ
シベンゾフエノン
２，2′−ジヒドロキシ−４，4′−ジ（メタ）アク
リロキシベンゾフエノン等が挙げられる。
又、上記一般式のモノマーは通常、アクリル酸
クロライド又はメタクリル酸クロライドと２，４
−ジヒドロキシベンゾフエノン又はその誘導体と
から合成される。具体的な合成例を次に示す。
水酸化ナトリウム12部（重量部）とメタノール
200部を混合して作つた溶液の中へ２，４−ジヒ
ドロキシベンゾフエノン64.2部を溶かす。次に溶
媒を真空中で留去し、残留したモノナトリウム化
合物を乾燥した後無水ベンゼン500部にこれを懸
濁する。この中へアクリル酸クロライド27部を冷
却し、かき混ぜながら滴加した後、この混合物を
室温で１時間かき混ぜ、少しの間60℃に加熱し、
生成した塩化ナトリウムを吸引濾過する。この濾
液から真空中でベンゼンを留去するとアクリル酸
エステルが油状の残留物として得られる。このア
クリル酸エステルはエタノール水溶液を加えると
結晶する。このようにして得られた結晶をエタノ
ール水溶液から２回結晶すれば２−ヒドロキシ−
４−アクリロキシベンゾフエノン
約51部（論理量の64％）が融点80℃（補正せず）
の黄色の光沢ある薄片状結晶として得られる。
本発明でのスチレン、アクリロニトリルおよび
メタクリル酸アルキルエステルから選ばれる少な
くとも一種のモノマーの量は20〜99.95％、好ま
しくは35〜99.9％であるが、その量が20％よりも
少ないと塗膜の硬度、耐溶剤性、耐汚染性等が劣
化するため好ましくない。
かかるモノマーのうちのメタクリル酸アルキル
エステルとしては好ましくはアルキル基の炭素数
が１〜４のものであり、具体的にはメタクリル酸
メチル、メタクリル酸エチル、メタクリル酸ｎ−
プロピル、メタクリル酸iso−プロピル、メタク
リル酸ｎ−ブチル、メタクリル酸iso−ブチル、
メタクリル酸sec−ブチル、メタクリル酸ter−ブ
チル等が挙げられる。
又、本発明でのその他の共重合性モノマーとし
ては例えばアクリル酸メチル、アクリル酸エチ
ル、アクリル酸プロピル、アクリル酸ブチル、ア
クリル酸２−エチルヘキシル、アクリル酸ラウリ
ル、メタクリル酸ラウリル、ビニルトルエン、α
−メチルスチレン、ジメチルスチレン、（メタ）
アクリルアミド、Ｎ−メチロール（メタ）アクリ
ルアミド、酢酸ビニル、マレイン酸ジエチル、マ
レイン酸ジブチル、フマル酸ジエチル、フマル酸
ジブチル、イタコン酸ジエチル、イタコン酸ジブ
チル、（メタ）アクリル酸２−ヒドロキシエチル、
（メタ）アクリル酸２−ヒドロキシプロピル、ポ
リエチレングリコールモノ（メタ）アクリレー
ト、エチレングリコールジ（メタ）アクリレー
ト、（メタ）アクリル酸グリシジル、（メタ）アク
リル酸メチルグリシジル、（メタ）アクリル酸エ
チルグリシジル、（メタ）アクリル酸、（無水）マ
レイン酸、フマル酸、イタコン酸、マレイン酸モ
ノブチル、フマル酸モノブチル、イタコン酸モノ
ブチル等が挙げられる。これらのモノマーは二種
以上で用いることができる。
上記の各モノマーによる共重合体は、乳化重合
法、懸濁重合法、塊状重合法等の公知の方法で容
易に得られるが、溶液重合法で製造されるのが極
めて好都合である。この場合の重合は通常トルエ
ン、キシレン、エチルベンゼンもしくはエチルシ
クロヘキサンなどの炭化水素系溶剤またはそれら
の混合物；ｎ−ブタノールなどのアルコール系溶
剤；酢酸ブチルなどのエステル系溶剤；メチルイ
ソブチルケトンなどのケトン系溶剤；あるいはセ
ロソルブなどのエーテルアルコール系溶剤などを
単独で、あるいは２種以上を組み合せて、こうし
た溶媒中で行なわれる。その場合、温度は常温〜
200℃、反応時間は２〜30時間が適当である。
また、重合開始剤としてはベンゾイルパーオキ
サイドもしくはジ−tert−ブチルパーオキサイド
などの過酸化物；あるいはアゾビスイソブチロニ
トリルなどのアゾ化合物が用いられるし、公知慣
用のレドツクス系で重合させることも可能であ
る。
さらに、必要に応じてラウリルメルカプタンあ
るいはチオグリコール酸オクチルなどの連鎖移動
剤を用いて分子量を調節することも可能である。
別に、必要に応じて、かくして得られた共重合
体はその製造時に、あるいは製造後において、た
とえば不飽和ポリエステル樹脂、アルキド樹脂、
エポキシ樹脂あるいは天然もしくは合成樹脂酸な
どにより変性することもできる。
このようにして得られた共重合体は数平均分子
量約1000〜100000の範囲のものが好ましい。
本発明の樹脂組成物はこの共重合体を主成分と
し、必要に応じてこれに適当な硬化剤などが添加
配合され、常温乾燥あるいは60℃〜300℃での焼
付により諸性能のすぐれた硬化塗膜を得ることが
できる。
本発明の樹脂組成物の塗料形態は、溶剤タイ
プ、液状無溶剤型、水溶性、水分散型、粉体等が
可能で、目的、用途に応じて適宜選択することが
できる。
実施例１〜２および比較例１〜３
温度計、撹拌装置および還流冷却器を備えたフ
ラスコに、キシレン670部、ジ−tert−ブチルパ
ーオキサイド10部を仕込み、120℃に加熱して表
１の各実施例および比較例に示すモノマー混合物
とアゾビスイソブチロニトリル15部とから成る混
合液を６時間かけて滴下した。さらに15時間120
℃に保ち各樹脂溶液を得た。
得られた各樹脂溶液にスーパーベツカミンＬ−
117−60（ブチル化メラミン樹脂；大日本インキ化
学工業(株)製）およびエピクロン1050（ビスフエノ
ールタイプエポキシ樹脂；大日本インキ化学工業
(株)製）を70／20／10（ソリツド比）でブレンドし、
タイペークＲ−580（ルチル型酸化チタン、石原産
業(株)製）にて、PWC50％で練肉し、塗装後160℃
で20分焼付けした。
得られた塗膜の物性を表１に示す。又、宮崎県
で塗膜の屋外曝露試験を行なつた。その結果は第
１図に示す。[Formula] R 4 is an alkyl group having 1 to 18 carbon atoms)
0.05 to 10% by weight (abbreviated simply as %) (B) At least one monomer selected from styrene, acrylonitrile, and alkyl methacrylate 20 to 99.95% (C) Other copolymerizable monomers 0 to 79.95% A resin composition for coating material containing a polymer is provided. The amount of the monomer represented by the above general formula used in the present invention is 0.05 to 10%, preferably 0.1 to 3%, but if the amount is less than 0.05%, sufficient weather resistance will not be provided; Exceeding this is not preferable as it may cause problems with the painted surface condition, gloss, leveling, etc. Representative examples of such monomers include: 2-Hydroxy-4-(meth)acryloxybenzophenone 2,2-dihydroxy-4-(meth)acryloxybenzophenone Examples include 2,2'-dihydroxy-4,4'-di(meth)acryloxybenzophenone. Moreover, the monomer of the above general formula is usually combined with acrylic acid chloride or methacrylic acid chloride and 2,4
-dihydroxybenzophenone or its derivatives. A specific synthesis example is shown below. 12 parts (by weight) of sodium hydroxide and methanol
Dissolve 64.2 parts of 2,4-dihydroxybenzophenone into the solution prepared by mixing 200 parts. Next, the solvent is distilled off in vacuo, and the remaining monosodium compound is dried and suspended in 500 parts of anhydrous benzene. 27 parts of acrylic acid chloride was cooled and added dropwise to this while stirring, and the mixture was stirred at room temperature for 1 hour and briefly heated to 60°C.
The sodium chloride formed is filtered off with suction. Benzene is distilled off from this filtrate in vacuo to obtain the acrylic acid ester as an oily residue. This acrylic ester crystallizes when an ethanol aqueous solution is added. If the crystals thus obtained are crystallized twice from an aqueous ethanol solution, 2-hydroxy-
4-Acryloxybenzophenone Approximately 51 parts (64% of the theoretical amount) has a melting point of 80°C (uncorrected)
Obtained as yellow shiny flaky crystals. In the present invention, the amount of at least one monomer selected from styrene, acrylonitrile, and methacrylic acid alkyl ester is 20 to 99.95%, preferably 35 to 99.9%, but if the amount is less than 20%, the hardness of the coating film , solvent resistance, stain resistance, etc. are deteriorated, which is not preferable. Among these monomers, the methacrylic acid alkyl ester is preferably one in which the alkyl group has 1 to 4 carbon atoms, and specifically, methyl methacrylate, ethyl methacrylate, n-methacrylate, etc.
propyl, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate,
Examples include sec-butyl methacrylate and ter-butyl methacrylate. Other copolymerizable monomers used in the present invention include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, lauryl methacrylate, vinyltoluene, α
-Methylstyrene, dimethylstyrene, (meth)
Acrylamide, N-methylol (meth)acrylamide, vinyl acetate, diethyl maleate, dibutyl maleate, diethyl fumarate, dibutyl fumarate, diethyl itaconate, dibutyl itaconate, 2-hydroxyethyl (meth)acrylate,
2-Hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, ethylene glycol di(meth)acrylate, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, ethylglycidyl (meth)acrylate, ( Examples include meth)acrylic acid, maleic acid (anhydride), fumaric acid, itaconic acid, monobutyl maleate, monobutyl fumarate, monobutyl itaconate, and the like. These monomers can be used in combination of two or more. Copolymers of the above monomers can be easily obtained by known methods such as emulsion polymerization, suspension polymerization, and bulk polymerization, but it is extremely convenient to produce them by solution polymerization. In this case, polymerization is usually carried out in a hydrocarbon solvent such as toluene, xylene, ethylbenzene or ethylcyclohexane, or a mixture thereof; an alcohol solvent such as n-butanol; an ester solvent such as butyl acetate; a ketone solvent such as methyl isobutyl ketone. ; Alternatively, the reaction may be carried out in an ether alcohol solvent such as cellosolve alone or in a combination of two or more. In that case, the temperature is room temperature ~
A temperature of 200°C and a reaction time of 2 to 30 hours are appropriate. In addition, as a polymerization initiator, a peroxide such as benzoyl peroxide or di-tert-butyl peroxide; or an azo compound such as azobisisobutyronitrile is used, and polymerization can also be carried out using a known and commonly used redox system. It is possible. Furthermore, if necessary, it is also possible to adjust the molecular weight using a chain transfer agent such as lauryl mercaptan or octyl thioglycolate. Separately, if necessary, the copolymer thus obtained may be used during or after its production, such as unsaturated polyester resins, alkyd resins, etc.
It can also be modified with epoxy resins or natural or synthetic resin acids. The copolymer thus obtained preferably has a number average molecular weight in the range of about 1,000 to 100,000. The resin composition of the present invention has this copolymer as its main component, and if necessary, an appropriate curing agent is added thereto, and cured with excellent performance by drying at room temperature or baking at 60°C to 300°C. A coating film can be obtained. The coating form of the resin composition of the present invention can be a solvent type, a liquid non-solvent type, a water-soluble type, a water-dispersible type, a powder type, etc., and can be appropriately selected depending on the purpose and use. Examples 1 to 2 and Comparative Examples 1 to 3 670 parts of xylene and 10 parts of di-tert-butyl peroxide were charged into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and heated to 120°C. A liquid mixture consisting of the monomer mixture shown in each of the Examples and Comparative Examples and 15 parts of azobisisobutyronitrile was added dropwise over 6 hours. Another 15 hours 120
Each resin solution was obtained by maintaining the temperature at °C. Supervecamine L- was added to each resin solution obtained.
117-60 (butylated melamine resin; manufactured by Dainippon Ink and Chemicals Co., Ltd.) and Epiclon 1050 (bisphenol type epoxy resin; manufactured by Dainippon Ink and Chemicals)
Co., Ltd.) at a ratio of 70/20/10 (solid ratio).
Mixed with 50% PWC using Taipeke R-580 (rutile titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.) and heated to 160℃ after painting.
I baked it for 20 minutes. Table 1 shows the physical properties of the resulting coating film. Additionally, an outdoor exposure test of the paint film was conducted in Miyazaki Prefecture. The results are shown in FIG.
第１図は実施例１〜２および比較例１〜３の各
硬化塗膜の屋外曝露試験による曝露時間と光沢保
持率との関係を示すグラフである。
……実施例１、……実施例２、……比較
例３、……比較例２、……比較例１
FIG. 1 is a graph showing the relationship between exposure time and gloss retention rate in an outdoor exposure test of each cured coating film of Examples 1 to 2 and Comparative Examples 1 to 3. ...Example 1, ...Example 2, ...Comparative example 3, ...Comparative example 2, ...Comparative example 1
Claims (1)
−OH、R3は−Ｈ、−OH、−OR4又は
【式】R4は炭素数１〜18のアル キル基） で表わされるモノマー 0.05〜10重量％ (B) スチレン、アクリロニトリルおよびメタクリ
ル酸アルキルエステルから選ばれる少なくとも
一種のモノマー 20〜99.95重量％ (C) その他の共重合性モノマー０〜79.95重量％ から得られる共重合体を含有してなる塗料用樹脂
組成物。[Claims] 1 (A) General formula (In the formula, R 1 is -H or -CH 3 , R 2 is -H or -OH, R 3 is -H, -OH, -OR 4 or [Formula] R 4 is an alkyl group having 1 to 18 carbon atoms) ) Monomer represented by 0.05 to 10% by weight (B) At least one monomer selected from styrene, acrylonitrile, and alkyl methacrylate 20 to 99.95% by weight (C) Obtained from 0 to 79.95% by weight of other copolymerizable monomers A resin composition for paint containing a copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2923580A JPH0245642B2 (en) | 1980-03-10 | 1980-03-10 | TORYOYOJUSHISOSEIBUTSU |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2923580A JPH0245642B2 (en) | 1980-03-10 | 1980-03-10 | TORYOYOJUSHISOSEIBUTSU |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56125414A JPS56125414A (en) | 1981-10-01 |
| JPH0245642B2 true JPH0245642B2 (en) | 1990-10-11 |
Family
ID=12270562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2923580A Expired - Lifetime JPH0245642B2 (en) | 1980-03-10 | 1980-03-10 | TORYOYOJUSHISOSEIBUTSU |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0245642B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3333502A1 (en) * | 1983-09-16 | 1985-04-18 | Röhm GmbH, 6100 Darmstadt | THERMOPLASTIC PLASTIC MOLDS CONTAINING UV ABSORBER |
| JPS6123628A (en) * | 1984-07-11 | 1986-02-01 | Nippon Paint Co Ltd | Fine resin particle having high weather resistance function |
| JPS6136375A (en) * | 1984-07-30 | 1986-02-21 | Nippon Telegr & Teleph Corp <Ntt> | Coating compound composition |
| JP2800152B2 (en) * | 1989-04-27 | 1998-09-21 | 東芝ケミカル株式会社 | Conductive paste |
| US5518818A (en) * | 1992-02-05 | 1996-05-21 | Toray Industries, Inc. | Primer and multilayer coated article |
| CN106893023B (en) * | 2017-02-27 | 2024-02-20 | 杭州启明医疗器械股份有限公司 | Ultraviolet cross-linking anti-leakage film material and preparation method thereof |
-
1980
- 1980-03-10 JP JP2923580A patent/JPH0245642B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56125414A (en) | 1981-10-01 |
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