JPH0522743B2 - - Google Patents
Info
- Publication number
- JPH0522743B2 JPH0522743B2 JP59164859A JP16485984A JPH0522743B2 JP H0522743 B2 JPH0522743 B2 JP H0522743B2 JP 59164859 A JP59164859 A JP 59164859A JP 16485984 A JP16485984 A JP 16485984A JP H0522743 B2 JPH0522743 B2 JP H0522743B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- group
- parts
- coating
- ethylenically unsaturated
- 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
- 229920005989 resin Polymers 0.000 claims description 81
- 239000011347 resin Substances 0.000 claims description 81
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 49
- 150000001875 compounds Chemical class 0.000 claims description 30
- -1 methacryloxy Chemical group 0.000 claims description 25
- 239000008199 coating composition Substances 0.000 claims description 24
- 230000036961 partial effect Effects 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000002894 organic compounds Chemical group 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 34
- 238000000576 coating method Methods 0.000 description 32
- 239000010408 film Substances 0.000 description 29
- 239000011248 coating agent Substances 0.000 description 27
- 239000004925 Acrylic resin Substances 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000178 monomer Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- 229920000178 Acrylic resin Polymers 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000001723 curing Methods 0.000 description 12
- 239000005062 Polybutadiene Substances 0.000 description 11
- 239000003822 epoxy resin Substances 0.000 description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 11
- 238000000016 photochemical curing Methods 0.000 description 11
- 229920002857 polybutadiene Polymers 0.000 description 11
- 229920000647 polyepoxide Polymers 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000002265 prevention Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 238000005452 bending Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000013007 heat curing Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 150000003961 organosilicon compounds Chemical class 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000007870 radical polymerization initiator Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000007496 glass forming Methods 0.000 description 3
- 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 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 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 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-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
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 235000010338 boric acid Nutrition 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- LHEFLUZWISWYSQ-CVBJKYQLSA-L cobalt(2+);(z)-octadec-9-enoate Chemical compound [Co+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LHEFLUZWISWYSQ-CVBJKYQLSA-L 0.000 description 2
- 229940120693 copper naphthenate Drugs 0.000 description 2
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-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
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WIKUXHHNKRKVGJ-UHFFFAOYSA-N (2-chlorophenyl)-(4-methylphenyl)methanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1Cl WIKUXHHNKRKVGJ-UHFFFAOYSA-N 0.000 description 1
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- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229940093920 gynecological arsenic compound Drugs 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 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
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HLXDKGBELJJMHR-UHFFFAOYSA-N methyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)OC(C)C HLXDKGBELJJMHR-UHFFFAOYSA-N 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- 229960000990 monobenzone Drugs 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010352 sodium erythorbate Nutrition 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- GIHPVQDFBJMUAO-UHFFFAOYSA-N tributoxy(ethyl)silane Chemical compound CCCCO[Si](CC)(OCCCC)OCCCC GIHPVQDFBJMUAO-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- NVAZFWGSXWKRIF-UHFFFAOYSA-N triethoxysilyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)OC(=O)C(C)=C NVAZFWGSXWKRIF-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- QLUOOUIRXJWVBN-UHFFFAOYSA-N triphenylene-1,2,3,4-tetramine Chemical compound C1(=C(C(=C(C=2C3=CC=CC=C3C3=CC=CC=C3C12)N)N)N)N QLUOOUIRXJWVBN-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Paints Or Removers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Description
〔産業上の利用分野〕
本発明は被覆用組成物に関する。さらに詳しく
は、アルコキシシラン化合物類と樹脂類および重
合開始剤を含有する新規な組成成分の配合からな
る光硬化性および／または熱硬化性の被覆用組成
物に関するものである。
該被覆用組成物は、表面硬度が高く、加工性、
防錆性、耐薬品性に優れた被膜を形成することを
目的として、ステンレス鋼、亜鉛メツキ鋼等の金
属表面に、あるいはプラスチツク表面に、また、
防曇性被膜を形成することを目的としてガラス表
面等に適用され、さらにまた、感光性塗料、電絶
ワニスとして適用されるものである。
〔従来技術〕
各種基板表面処理用の被覆用組成物として、そ
れらを採用して形成される被膜の性能の１つある
いは複数が改良されることを作用効果とする提案
は、枚挙にいとまのない程数多くある。これらの
多くは、その目的によつても異るが、有機高分子
化合物例えばアクリル系樹脂、エポキシ系樹脂な
どを樹脂骨格とする樹脂を主成分とするものであ
り、基板に塗布した後、熱硬化または光硬化する
ことにより形成される被覆は、可撓性に富む利点
を有するものの、表面硬度が低く、耐溶剤性が劣
り、また特に金属表面に適用した場合、防錆性が
不足する等の欠点を有している。近年、表面硬度
が高く、耐溶剤性に優れた被覆の形成が可能な被
覆用組成物として有機ケイ素化合物を成分として
含有するものが数多く提案されている。その主な
ものは、具体的な文献を挙げるまでもなく、重合
性の不飽和結合を有する置換基を導入した有機ケ
イ素化合物を主成分とする組成物である。これら
においては、主剤である有機ケイ素化合物の合成
が極めて複雑な工程を経て行われるため高価であ
るばかりでなく、有機ケイ素化合物あるいは、そ
れを主成分とする組成物は、安定性の悪い欠陥が
ある。被覆用組成物に比較的に安価な有機ケイ素
化合物を導入するものとして、特開昭51−33128
号公報に、テトラアルコキシシランとアルキルア
ルコキシシランとの共部分加水分解物、アクリル
系共重合体およびエーテル化メチロールメラミン
を溶剤に溶解した被覆用組成物が提案されてい
る。該組成物は、基板に塗布した後、熱硬化によ
り被膜を形成するものであり、表面硬度が高く、
耐摩耗性、耐熱水性、ヒートサイクル性等に優れ
ている。しかしながら、該組成物を用いた被膜は
可撓性が乏しく、曲げ加工等により容易に割れや
剥離を生ずる欠点がある。
また特開昭59−4611号公報には、エチレン性不
飽和結合を有するプレポリマーとモノマー、光重
合開始剤およびチタン系カツプリング剤で処理さ
れたメチルシリケートの３次元縮合物からなる感
光性樹脂組成物が開示されており、基板上に光硬
化被膜を形成する実施例が記載されている。該組
成物に添加されるメチルシリケートの３次元縮合
物は、実質的にSiO2の粒子であり充填剤として
被膜の表面硬度の向上に寄与するものと考えら
れ、また得られる被膜は、基板との密着性、被膜
の外観等に優れているものの形成される被膜は可
撓性に乏しく、被膜形成後の変形加工性の際に被
膜が容易に割れ、剥離して曲げ加工性の点で問題
があつた。
〔発明が解決しようとする問題点〕
本発明は、前述の如き曲げ加工性の問題点を解
消し、表面硬度が高く、耐溶剤性、密着性、耐良
性および可撓性に優れた被膜が形成される光硬化
性および／または熱硬化性の被覆用組成物を提供
せんとするものである。
〔問題を解決するための手段よおび作用〕
本発明者らは、前述の目的を達成すべく鋭意検
討を重ねた結果、アルコキシシラン化合物類、ヒ
ドロキシル基を有し、かつ不飽和結合を有する樹
脂またはヒドロキシル基を有する化合物と不飽和
結合を有する化合物の混合物、および光重合開始
剤を主要成分として含有してなる特定の被覆用組
成物を用いることにより所期を目的を達成するこ
とを見い出し本発明を完成するに至つた。
すなわち本発明は、
(A) 一般式 RnSi（OR′）4-o ……〔１〕
（式中、Ｒは炭素数１〜６のアルキル基、アリ
ール基、アルケニル基およびメタクリロキシを
有する有機基から選ばれた同種または異種の基
を示し、R′は炭素数１〜４のアルキル基の同
種または異種を示し、ｎは０〜２である。）
で表されるアルコキシシラン化合物および／ま
たは該アルコキシシラン化合物の部分加水分解
物
(B) 下記(イ)成分および／または(ロ)成分の樹脂
(イ) １分子中に少なくとも１個のヒドロキシル
基を有し、かつエチレン性不飽和基有する平
均分子量500〜50000の樹脂
(ロ) １分子中に２個以上のヒドロキシル基を有
する平均分子量500〜50000の樹脂と１分子中
に２個以上のエチレン性不飽和基を有する平
均分子量500〜50000の樹脂との混合物
(C) 光重合開始剤
上記(A)、(B)および(C)成分を主要成分として含有
してなることを特徴とする被覆用組成物である。
以下、本発明を詳細に説明する。
本発明に用いる(A)成分であるアルコキシシラン
化合物は、前記一般式
RnSi（OR′）4-o……〔１〕
で表され、式中のＲは炭素数１〜６のアルキル
基、アリール基、アルケニル基およびメタクリロ
キシを有する有機基から選ばれた同種または異種
の基を示し、R′は炭素数１〜４のアルキル基の
同種または異種を示し、ｎは０〜２である。
ここで、ｎが０の場合は、R′が同種または異
種の炭素数１〜４のアルキル基であるテトラアル
コキシシラン化合物であり、ｎが１の場合は、Ｒ
が炭素数１〜６のアルキル基、アルール基、アル
ケニル基およびメタクリロキシ基を含む１価の有
機基から選ばれた同種または異種の基で、かつ
R′が同種または異種の炭素数１〜４のアルキル
基であるトリアルコキシシラン化合物であり、ｎ
が２の場合は、Ｒ、R′がｎが１の場合と同様な
ものからなるジアルコキシシラン化合物である。
これらの代表的な化合物として、式中のｎが０
であるテトラメトキシシラン、テトラエトキシシ
ラン、テトライソプロポキシシラン、テトラブト
キシシラン、ジメトキシジエトキシシラン、ジメ
トキシジイソプロポキシシラン、ジエトキシジイ
ソプロポキシシラン、ジエトキシジブトキシシラ
ン等のテトラアルコキシシラン化合物類；式中の
ｎが１であるメチルトリメトキシシラン、メチル
トリエトキシシラン、メチルトリイソプロポキシ
シラン、エチルトリイソプロポキシシラン、エチ
ルトリブトキシシラン、フエニルトリメトキシシ
ラン、フエニルトリエトキシシラン、ビニルトリ
メトキシシラン、ビニルトリエトキシシラン、ア
リルトリエトキシシラン、メタクリルオキシプロ
ピルトリメトキシシラン、メタクリルオキシトリ
エトキシシラン等のトリアルコキシシラン化合物
類；式中のｎが２であるジメチルジメトキシシラ
ン、ジメチルジエトキシシラン、ジエチルジイソ
プロポキシシラン、ジエチルジブトキシシラン、
フエニルメチルジメトキシシラン等のジアルコキ
シシラン化合物類が挙げられる。
また、(A)成分としてこれらアルコキシシラン化
合物の単独または２種以上の混合物を酸性触媒ま
たはアルカリ性触媒の存在下に加水分解すること
により得られらアルコキシシラン化合物の部分加
水物解物シロキサン重合体が用いられる。
これらのアルコキシシラン化合物の部分加水分
解物は、前記一般式〔１〕で表されるアルコキシ
シラン化合物の単独または２種以上の混合物を有
機溶媒中において、塩酸、硫酸、硝酸、リン酸、
ホウ酸等の無機酸類、酢酸、プロピオン酸、シユ
ウ酸、フマル酸、マレイン酸、コハク酸等の有機
酸類の１種または２種以上の酸性触媒、または水
酸化ナトリウム、水酸化カリウム、アンモニア水
等のアルカリ触媒の存在下に加水分解することに
より、一般式〔１〕中のR′で表されるアルキル
基の離脱により重合して得られるシロキサン重合
体である。
本発明において、(A)成分として、前記一般式
〔１〕で表されるテトラ、トリ、ジアルコキシシ
ラン類、および該アルコキシシラン化合物の部分
加水分解物よりなる群からなる単独または２種以
上の混合物を使用することができる。特に、アル
コキシシラン化合物の部分加水分解物は、大気中
の水分を吸収して起る加水分解性に対して安定で
あるため好ましく使用される。
なお、前記一般式RnSi（OR′）4-oにおいて、ｎ
が２を超える場合はアルコキシシラン化合物ある
いは該アルコキシシラン化合物の部分加水分解物
中に存在する反応性官能基が少なくなり、従つて
(B)成分のヒドロキシル基との結合が充分でなく、
得られる被膜の硬化性が不足し、被膜の表面硬
度、耐溶剤性、耐食性および可撓性等の諸性能が
充分に得られない。
本発明に用いる(B)成分である(イ)の１分子中に少
なくとも１個のヒドロキシル基を有し、かつエチ
レン性不飽和基を有する平均分子量500〜50000の
樹脂は、樹脂骨格中に１個以上のヒドロキシル基
と光硬化せしめ程度のエチレン性不飽和基を含有
するものであればよく、例えば不飽和ポリエステ
ル系樹脂、アクリル系樹脂、ウレタンアクリレー
ト系樹脂、エポキシアクリレート系樹脂、ポリブ
タジエン系樹脂、ポリエーテルアクリレート系樹
脂、ポリエステルアクリレート系樹脂等を樹脂骨
格としてヒドロキシル基およびエチレン性不飽和
基を導入せしめたものであり、代表的化合物とし
て、
(i) エポキシアクリレート系樹脂：エポキシ樹脂
と（メタ）アクリル酸との付加反応またはグリ
シジルアクリレートとビスフエノールＡとの付
加反応によつて得られる樹脂であり、また分子
中のヒドロキシル基を一部利用して変性したウ
レタン変性樹脂等も挙げられる。前記エポキシ
樹脂は特に限定されるものでなく、通常用いら
れるビスフエノールＡ型エポキシ樹脂、ノボラ
ツク型エポキシ樹脂、脂環型エポキシ樹脂、エ
チレンまたはプロピレングリコールのジグリシ
ジルエーテルグリセリンまたはトリメチロール
プロパンのポリグリシジルエーテル等である。
(ii) アクリルおよびウレタンアクリレート系樹
脂：（メタ）アクリル酸エステル共重合体等の
反応性基（ヒドロキシル基、カルボキシル基、
エポキシ基等）を利用して、その側鎖に光重合
性の（メタ）アクリル酸エステル類を導入して
得られる樹脂で、例えば、次の方法によつて製
造される樹脂等が挙げられる。
(a) ヒドロキシル基含有アクリル樹脂に、グリ
シジル基を含有する不飽和モノマーを付加し
て、ヒドロキシル基にエチレン性不飽和基を
導入せしめる。
該グリシジル基含有不飽和モノマーとして
は例えばグリシジルアクリレート、グリシジ
ルメタクリレート等が用いられる。
(b) カルボキシル基含有アクリル樹脂に、グリ
シジル基を含有する不飽和モノマーを付加し
て、ヒドロキシル基とエチレン性不飽和基を
導入せしめる。
該グリシジル基含有の不飽和モノマーとし
ては前記(a)に記載したものが用いられる。
(c) グリシジル基含有アクリル樹脂に、カルボ
キシル基を含有する不飽和モノマーを付加し
て、ヒドロキシル基とエチレン性不飽和基を
導入せしめる。
該カルボキシル基含有不飽和モノマーとし
ては例えばアクリル酸、メタクリル酸、クロ
トン酸等が使用できる。
前記(a)〜(c)におけるエチレン性不飽和基を導入
せしめるヒドロキシル基、カルボキシル基または
グリシジル基を含有するアクリル樹脂は、これら
のヒドロキシル基、カルボキシル基またはグリシ
ジル基などの官能基を含有する不飽和モノマーと
その他のアクリル系不飽和モノマーとを共重合せ
しめることによつて得られる樹脂が用いられる。
なお、ヒドロキシル基含有不飽和モノマーとして
は例えば２−ヒドロキシエチルアクリレート、２
−ヒドロキシエチルメタクリレート、ヒドロキシ
プロピルアクリレート、ヒドロキシプロピルメタ
クリレート等が用いられる。
また、ウレタンアクリレート系樹脂としては、
(a)のヒドロキシル基含有アクリル樹脂または(b)(c)
によつて生成したヒドロキシル基含有樹脂にジイ
ソシアネートを付加反応し、さらにヒドロキシル
基含有不飽和モノマーを付加反応せしめるか、ま
たはジイソシアネートとヒドロキシル基含有不飽
和モノマーを付加反応した後に、ヒドロキシル基
含有アクリル系樹脂と付加反応せしめることによ
つて得られる。
(iii) ポリブタジエン系樹脂
(a) 両末端にヒドロキシル基を有するポリブタ
ジエン樹脂またはその（メタ）アクリル変性
樹脂
(b) 両末端にカルボキシル基を有するポリブタ
ジエン樹脂とエポキシ樹脂を反応せしめ、次
いで分子中に存在するエポキシ基、水酸基を
利用して前述のアクリルおよびウレタンアク
リレート系樹脂で記載したようにエチレン性
不飽和基含有モノマーの導入したアクリル変
性樹脂あるいはジイソシアネートを介して得
られるウレタン変性樹脂
(c) 両末端および／または内部にエポキシ基を
含有するエポキシ化ポリブタジエンと前述の
カルボキシル基含有不飽和モノマーを反応得
られる樹脂等である。
本発明の(B)成分である(イ)樹脂が１分子内に１個
以上のヒドロキシル基を有し、かつエチレン性不
飽和基を有する樹脂であるが、分子内にヒドロキ
シル基を有しない場合は、被膜硬化の際にヒドロ
キシル基と(A)成分であるアルコキシシラン化合物
あるいは該アルコキシシランの部分加水分解物に
存在する反応性官能基との結合がなく、従つて被
膜の硬化性が不足し、期待する被膜の諸性能が得
られない。また、エチレン性不飽和基においても
光照射によつて硬化しうる範囲内で含有すること
が必要であり、１分子当り２個以上が望ましい。
また、分子量が500以下では被膜の可撓性が得ら
れず、逆に50000以上であると樹脂変性配合等の
作業性の点で欠けるため、好ましくは1000〜
10000である。
これら(A)成分の(イ)樹脂にも多種あるが可撓性の
付与のためには樹脂骨格にウレタン結合を有する
変性樹脂がより好ましい。
本発明の(B)成分である(ロ)の１分子中に２個以上
のヒドロキシル基を有する平均分子量500〜50000
の樹脂（以下、HC樹脂と称す）と１分子中に２
個以上のエチレン性不飽和基を有する平均分子量
500〜50000の樹脂（以下、UR樹脂と称す）との
混合物は、
HC樹脂の代表的な樹脂として、例えばポリエ
ステルポリオール樹脂、ポリエーテルポリオール
樹脂、アルキツド樹脂、飽和ポリエステル樹脂、
ポリブタジエングリコール樹脂、ヒドロキシル基
を有するエポキシ樹脂、ヒドロキシル基含有ビニ
ル重合体樹脂（アクリルポリオール樹脂）、ヒド
ロキシル基を有するポリウレタン樹脂またはポリ
ウレタンアクリレート樹脂、フエノール樹脂等が
挙げられる。
UR樹脂は、前述したヒドロキシル基を含有
し、かつエチレン性不飽和基を有する樹脂の合成
でヒドロキシル基を有しないまたは未導入樹脂の
エチレン性不飽和基を有する樹脂であり、例えば
不飽和ポリエステル系樹脂、アクリル系樹脂、ウ
レタンアクリル系樹脂、エポキシアクリレート樹
脂およびポリブタジエン系樹脂もしくはこれらの
変性樹脂が挙げられる。
本発明の(B)成分である(ロ)の樹脂混合物におい
て、HC樹脂とUR樹脂との混合樹脂系でHC樹脂
中のヒドロキシル基またはUR樹脂中のエチレン
性不飽和基が２個未満であると、期待する被覆の
諸性能が得られない。このことはヒドロキシル基
が少ないと光硬化および／または熱硬化の際に
HC樹脂と(A)成分であるアルコキシシラン化合物
あるいは該アルコキシシラン化合物の部分加水分
解物中に存在する反応性官能基との結合が少な
く、またUR樹脂のエチレン性不飽和基が少ない
と光硬化の際に硬化反応が進まず、従つて得られ
る被膜の架橋密度が小さく硬化性が不足のため良
好な性能が得られない。
また、HC樹脂、UR樹脂の平均分子量が500〜
50000であるが500以下または50000以上では(A)成
分である(イ)の樹脂と同様に性能性、作業性に欠け
る。好ましくは1000〜10000である。
なお、HC樹脂とUR樹脂の配合割合は、70〜
30／30〜70（重量比）で用いられる。
本発明に用いられる(C)成分の光重合開始剤は、
活性光線を照射した際に重合を開始させ得る公知
のものであり、その代表的な化合物としては、ベ
ンゾイン、ベンゾインメチルエーテル、ベンゾイ
ンエチルエーテル、ベンゾインイソプロピルエー
テル、ベンゾインイソブチルエーテル、酢酸ベン
ゾイン、ベンゾフエノン、２−ク・ルベンゾフエ
ノン、４−メトキシベンゾフエノン、４・4′−ジ
メチルベンゾフエノン、４−ブロムベンゾフエノ
ン、２・2′、４・4′−テトラクロルベンゾフエノ
ン、２−クロル−4′−メチルベンゾフエノン、３
−メチルベンゾフエノン、４−ｔ−ブチルベンゾ
フエノン、ベンジル、ベンジル酸、ベンジルジメ
チルケタール、ジアセチル、メチレンブルー、ア
セトフエノン、２・２−ジエトキシアセトフエノ
ン、９・10−フエナントレンキノン、２−メチル
アントラキノン、２−エチルアントラキノン、２
−ｔ−ブチルアントラキノン、ジフエニルジスル
フイツド、ジチオカ−バメート、α−クロルメチ
ルナフタリン、アントラセン、塩化鉄、１・４−
ナフトキノン等である。特に好適なのは、ベンジ
ルジメチルケタール、２・２−ジエトキシアセト
フエノン、２，２−ジメトキシ−２−フエニルア
セトフエノン、ベンゾイソプロピルエーテル、ベ
ンゾインブチルエーテル２−エチルアントラキノ
ンおよびチオキサントンである。これらの光重合
開始剤は単独あるいは２種以上併用して用いられ
る。
本発明における前述の(A)、(B)および(C)成分を主
要成分としてなる被覆用組成物は、(A)、(B)および
(C)成分の配合割合（固形分換算）が(A)／(B)＝１〜
100／100（重量比）、(C)／(B)＝0.05〜10／100（重量
比）であり、好ましくは(A)／(B)＝15〜70／100、
(C)／(B)＝0.1〜５／100である。
(A)成分の量が１／100未満で少ない場合、光お
よび／または熱硬化して得られる被膜の耐食性、
表面硬度が不充分となり、一方、100／100を超え
ると光硬化被膜の基板への密着性が低下し、また
光硬化後の基板の変形加工性が著しく悪くなるの
で好ましくない。
本発明において本発明の組成物に、必要に応じ
て例えば(A)(B)成分の製造時、あるいは組成物の粘
度調整の際に有機溶剤が用いられるが、これらの
有機溶剤は(A)、(B)および(C)成分に不活性で、かつ
溶解性に富むものが好ましく用いられ、例えば(A)
成分の溶剤としてメタノール、エタノール、イソ
プロパノール、ｎ−ブタノール等の低級アルコー
ル類；酢酸メチル、酢酸エチル、酢酸ブチル等の
エステル類；アセトン、メチルエチルケトン、ア
セチルアセトン等のケトン類；多価アルコール類
あるいはそのエーテル類が挙げられ、これらの単
独または２種以上の混合系で用いられる。
また(B)および(C)成分の溶剤としてトルエン、キ
シレン等の芳香族炭化水素類：ケロシン、ミネラ
ルスピリツト等の脂肪族炭化水素類；酢酸エチ
ル、酢酸ブチル等のエステル類；四塩化炭素、
１・１・１−トリクロルエタン、バークロルエチ
レン、クロルベンゼン、ジクロルベンゼン等のハ
ロゲン化炭化水素類等が挙げられ、これらの単独
または２種以上の混合系で用いられる。
これらの(A)および(B)および(C)成分の列挙した溶
剤は、必ずしも(A)成分の溶剤は(B)、(C)成分を、
(B)、(C)成分の溶剤は(A)成分を溶解するものでない
ので(A)、(B)および(C)成分の組成物の溶解性を損わ
ない範囲内で量的な配合も配慮し、適宜選択して
用いられる。
本発明において、本発明の組成物にさらに所望
により各種添加剤を添加することができる。これ
らの添加剤として、光重合促進剤、ラジカル重合
開始剤、ラジカル重合開始剤と併用される硬化促
進剤、安定剤（重合禁止剤）ガラス質形成剤、ケ
イ素化合物以外の有機金属化合物類、顔料等が挙
げられる。光重合促進剤は、光硬化、特に紫外線
硬化の際に硬化速度を著しく促進し、かつ、酸素
等による重合阻害作用を防止するので、(C)成分の
光重合開始剤と併用して用いられる。このような
光重合促進剤としてアミン類があり、例えば、ブ
チルアミン、ヘキサメチレンジアミン、ジエチレ
ントリアミン、トリエチレンテトラミン、モノエ
タノールアミン等の第１級アミン；ジエチルアミ
ン、ジメチルアニリン、ジメチル−パラートルイ
ジン、ピリジン、Ｎ，N′−ジメチルクロヘキシ
ルアミン、ジエタノールアミン、トリエタノール
アミン、ミヒラ−ケトン等の第二級アミンおよび
第三級アミン等が挙げられる。
前記ラジカル重合開始剤としては、ジアシルパ
ーオキサイド類、例えば過酸化ベンゾイル、２・
４−ジクロル過酸化ベンゾイル、オクタノイルパ
ーオキサイド、ラウロイルパーオキサイド等；ジ
アルキルパーオキサイド類、例えばジ−第３ブチ
ルパーオキサイド、ジクミルパーオキサイド等；
パーオキシエステル類、例えば第３ブチルパーベ
ンゾエート、第３ブチルパーアセテート、ジ−第
３ブチルパーフタレート、２・５−ジメチル−
２・５−ジ（ベンゾイルパーオキシ）ヘキサン
等；ケトンパーオキサイド類、例えばメチルエチ
ルケトンパーオキサイド、シクロヘキサノンパー
オキサイド等；ハイドロパーオキサイド類、例え
ば第３ブチルヒドロパーオキサイド、クメンハイ
ドロパーオキサイド、α−フエニルエチルヒドロ
パーオキサイド、シクロヘキセニルヒドロパーオ
キサイド等およびこれらの混合物が適当であつて
発泡性のないものが好ましく、その使用量は(B)成
分の樹脂（固形分）に対し、0.1〜10重量％、好
ましくは0.5ないし５重量％である。
また、前記ラジカル重合開始剤と併用される硬
化促進剤としては、例えばナフテン酸コバルト、
ナフテン酸マンガン、ナフテン酸銅、ナフテン酸
鉄、オレイン酸コバルト等の金属石けん類；塩化
コバルト、酢酸マンガン等の水溶性金属塩類；ア
スコルビン酸、アラボアスコルビン酸等の強力な
還元剤；チオシアン酸アンモニウム、チオシアン
酸カリウム等のチオシアン酸塩；チオ尿素、テト
ラメチルチオ尿素、ジトリルチオ尿素、エチレン
チオ尿素、２−メルカプトベンゾチアゾール、２
−メルカプトベンゾイミダゾール等のチオ尿素類
が有効である。
またジメチルアニリン、ジエチルアニリン、ト
リエチルアミン、トリエタノールアミン、オクチ
ルアミン、ブチルアミン、ジエチレントリアミ
ン、トリエチレンテトラミン、ペンタエチレンヘ
キサミン、テトラエチレンペンタミン、アニシジ
ン、ピロリジン、トルイジン、２・2′−ピピリジ
ル−４・4′−ジアミノジフエニルメタン、ベンジ
ジン、トリフエニレンテトラミン等のアミン類は
ラジカル発生の促進作用が大きい。
硬化促進剤の添加量は(B)成分の樹脂（固形分）
に対し、0.001〜30％であり、0.001以下であれば
効果がなく、30％以上であれば表面硬度、耐薬品
性、可撓性などの諸性能が低下する。
硬化促進剤は数種組み合せて用いるとさらに優
れた硬化促進能力を現わす。前記ラジカル重合開
始剤や硬化促進剤は解してもよいし、トリクロル
エチレン、クロロホルム、酢酸エチル、エタノー
ル、イソプロパノール、アセトン、メチルエチル
ケトン、エーテル、メチルクロロホルム、水等の
単独または混合系溶剤に溶解し使用しても良い。
なお、前記硬化促進剤のうち、ナフテン酸コバ
ルト、ナフテン酸マンガン、ナフテン酸銅、ナフ
テン酸鉄、オレイン酸コバルト等の金属石けん類
は単独で硬化剤として添加することもできる。
また成分(B)のエチレン性不飽和結合を有する樹
脂の加熱処理および貯蔵中における早期架橋を阻
止するために、安定剤（重合禁止剤）を混入する
のが望ましい。この安定剤としては、ジ−ｔ−ブ
チル−ｐ−クレゾール、ハイドロキノンモノメチ
ルエーテル、ピロガロール、キノン、ハイドロキ
ノン、ｔ−ブチルカテコール、ハイドロキノンモ
ノベンジルエーテル、メチルハイドロキノン、ア
ミルキノン、フエノール、ハイドロキノンモノプ
ロピルエーテル、フエノチアジン、ニトロベンゼ
ン等が挙げられる。これらの安定剤は、被覆用組
成物の配合時または貯蔵時における早期架橋を防
止する。
ガラス質形成剤は、有機シラン化合物と共に加
熱することによりガラス質を形成するものであ
り、本発明の被覆用組成物に添加して、被覆を行
う場合、必ずしもガラス質を形成するものではな
いが、形成される被膜の表面硬度および耐食性、
特に耐アルカリ性を向上させる。ガラス質形成剤
として、リン酸類、リンアルコキシド誘導体等の
リン化合物；ホウ酸類、ホウ素アルコキシド誘導
体等のホウ素化合物類、；ヒ素酸類、ヒ素アルコ
キシド誘導体等のヒ素化合物；アンチモン酸類、
アンチモンアルコキジド誘導体等のアンチモン化
合物；有機ガリウム化合物；カルボン酸亜鉛、亜
鉛アルコキシド等の亜鉛化合物；カルボン酸鉛、
鉛アルコキシド等の鉛化合物等およびこれらの混
合物を添加使用することができる。
ケイ素化合物以外の有機金属化合物も、前記ガ
ラス質形成剤と同様に、形成される被膜特性を向
上させる作用を有する。これらの有機金属化合物
として、チタン、タンタル、アルミニウム、また
はジルコニウムのアルコキシド類、キレート化
体、アシル化体、およびこれらの混合物が好まし
く使用できる。
顔料の添加は、透明な着色被膜を与える。例え
ば、CIBA−GEIGY社製のMierolith Blue4G−
Ｔ、Cromophtal Orange2G、Mierolith Green
Ｇ−Ｔ等を使用することにより、ブルー、オレン
ジ、グリーン等の透明な着色被膜を形成すること
ができる。
本発明において、前記した被覆用組成物を各種
基板に均一な厚さに塗布し、必要に応じて溶剤を
乾燥除去した後、活性光線を照射して基板表面に
光硬化被膜を形成する。光硬化用光源として、(C)
成分の光重合開始剤および所望により添加される
光重合促進剤を活性化し得る200〜500nｍの波長
域の紫外線を発生する高圧水銀灯、超高圧水銀
灯、カーボンアーク灯等が使用できる。被覆用組
成物の基板への塗布方法には特に制限はなく、浸
漬法、スプレー法、ロールコート法、フローコー
ト法等の均一な塗膜厚さの得られる方法が好まし
く採用される。
光硬化により形成される被膜は、それを被覆し
た各種基板の保護被覆としての充分な特性を有す
るが、さらに80〜300℃の温度下に0.5〜120分間
熱処理することにより熱硬化が進み、被覆特性、
特に、表面硬度、耐薬品性、耐食性、特に金属基
板に被覆した場合、その防錆性が著しく向上した
被膜が形成される。また、ステンレス鋼板、亜鉛
メツキ鋼板等の金属基板の変形加工表面の防食、
防錆等を目的とする被覆を形成する場合、平面基
板に被覆用組成物を塗布して光硬化した後、所望
の変形加工を行いついで熱硬化することにより、
所望の被覆を形成することができる。
なお、光硬化することなしに単に80〜300℃の
温度で0.5〜120分間熱処理した場合でも被膜形式
が可能である。
〔実施例〕
以下、本発明を合成例、実施例および比較例を
挙げてより具体的に説明するが、本発明は何らこ
れらの実施例のみに限定されるものではない。
なお、例中の部および％は重量部および重量％
を示す。
合成例 １
撹拌機、温度計および還流冷却器を備えた反応
容器に、テトラエトキシシラン186部、エタノー
ル643部および酢酸206部を仕込み、さらに35％塩
酸0.3部を加え、撹拌下に加熱して、溶剤を還流
させながら45時間反応を行つた。生成したアルコ
キシシラン化合物の部分加水分解のSiO2に換算
した濃度が５％となるよう溶剤量を調整し、さら
にSiO2の2.5％に相当するP2O5を添加溶解せしめ
て調製液〔〕を得た。
合成例 ２
撹拌機、温度計および滴下装置を備えた反応容
器にメチルトリエトキシシラン200部、テトラエ
トキシシラン250部、エタノール2500部および20
％塩酸1.5部を仕込み、撹拌混合した後、滴下装
置により水150部を反応液温を70℃に保持しなが
ら滴下した。水の滴下終了後、さらに70℃の温度
で５時間保持して反応を行つた。生成した部分加
水分解のSiO2換算濃度が4.5％となるよう溶剤量
を調整せしめて調製液〔〕を得た。
合成例 ３
合成例２と同様な反応容器にテトラブトキシシ
ラン115部、エタノール163部、20％塩酸0.15部お
よび水22部を仕込み、撹拌下で70℃の温度に加温
して４時間反応を行つた。次いで反応液を室温ま
で冷却した後、テトラブトキシチタン3.3部を加
えて溶解し、さらに生成した部分加水分解物の
SiO2換算濃度が7.0％となるよう溶剤量を調整せ
しめて調製液〔〕を得た。
合成例 ４
イソプロピルアルコール70ｇに四エトキシ珪素
66.7ｇとメチルトリエトキシ珪素33.3ｇを溶解
し、さらに0.05規定塩酸水溶液30ｇを加えて室温
で撹拌して加水分解を行つた。反応後室温で20時
間以上熟成して〔〕とした。得れらて溶液
〔〕はSiO2として計算された四エトキシ珪素部
分加水分解物9.6％、CH3SiO1.5として計算された
メチルトリエトキシ珪素部分加水分解物6.3％を
含んでいた。（比較用）
合成例 ５
イソプロピルトリイソステアロイルチタネート
（味の素(株)発売：プレンアクトTTS）をトルエン
で希釈した１％の溶液：100部に、メチルシリケ
ートの３次元縮合物（日興フアインプロダクツ(株)
発売：MSP・Ｓ「SiO2粒状物」）：50部を添加混合
した後、加熱減圧下でトルエンを揮発させて除去
し、〔〕とした。〔〕には、チタン系カツプリ
ング剤：TTSが２％付着したメチルシリケート
の３次元縮合物：MSP・Ｓであつた。（比較用）
合成例 ６
撹拌機、温度計およびガス導入口備えた反応容
器に１，２−ジフエニルベンゼンを溶解したテト
ラヒドロフランにナトリウム分散体を加えた系に
−60℃においてブタジエンを添加して生成したリ
ビング重合反応液を二酸化炭素を処理して製造さ
れた数平均分子量（以下分子量と略す）1550、
1.2−ビニル結合90.7％、1.4−トランス結合9.3％
の微細構造、酸価59.6（純分１グラム当りのKOH
mgで表示、以下同様）の分子末端にカルボキシル
基を有するポリブタジエンNISSO−PBC−1000
（日本曹達(株)製、商品名）1000部に対してビスフ
エノールＡ−ジグリシジルエーテル型エポキシ樹
脂エピコート828（油化シエルエポキシ(株)製、商品
名）1000部、Ｎ−Ｎジメチルベンジルアミン５部
を仕込み、反応容器内に窒素を吹き込みながら、
100℃で４時間反応すると、反応混合物の酸価は
0.1以下となり、得られた反応物のエポキシ酸素
含有量3.3％のポリブタジエン変性エポキシ樹脂
3.3を得た。引続いて、乾燥空気を10分間吹き込
み、メタアクリル酸400部、ハイドロキノン５部
加えて100℃で７時間加熱撹拌し、ヒドロキシル
基含有ポリブタジエン変性不飽和樹脂〔Ｒ−〕
を得た。
合成例 ７
合成例１と同様な反応容器に１分子中にヒドロ
キシル基１個とエポキシ基３個を有するジグリセ
ロールポリグリシジルエーテルデナコールEX−
421（長瀬産業製、商品名）346部、トルエン616
部、Ｎ−N′ジメチルベンジルアミン１部、ハイ
ドロキノン３部およびアクリル酸252部を仕込み、
乾燥空気を少量吹き込みながら約100℃で７時間
加熱撹拌し、ヒドロキシル基含有ポリグリシジル
エーテル変性不飽和樹脂〔Ｒ−〕を得た。
合成例 ８
合成例１と同様な反応容器にポリエチレングリ
コールジグリシジルエーテルデナコールEX−832
（長瀬産業製、商品名）526部、酢酸ブチル684部
Ｎ−N′ジメチルベンジルアミン1.5部、ハイドロ
キノン２部、およびアクリル酸158部を仕込み、
乾燥空気を少量吹き込みながら約100℃で10時間
加熱撹拌し、ヒドロキシル基含有ポリエチレング
リコールジグリシジルエーテル変性不飽和樹脂
〔Ｒ−〕を得た。
合成例 ９
ビスフエノールＡ型エポキシ樹脂エピコート
1001（油化シエルエポキシ(株)製、商品名、エポキ
シ当量900）900部、アクリル酸144部、メチルエ
チルクトン1044部、トリエチルアミン1.0部、お
よびハイドロキノン0.1部を反応容器中に入れ、
100℃で酸価が５以下になるまで反応せしめて分
子内中にヒドロキシル基を有し、かつエチレン性
不飽和基を有する樹脂〔Ｒ−〕を得た。
次に上記〔Ｒ−〕樹脂500部に予じめ合成し
ておいたトリレンジイソシアネート174部と２−
エチルヒドロキシルアクリレート130部からなる
イソシアネート基を有するウレタンプレポリマー
の204部およびメチルエチルケトン204部を加え、
〔Ｒ−〕樹脂の一部のヒドロキシル基とウレタ
ンプレポリマーのイソシアネート基を80℃で２時
間反応せしめて１分子中にヒドロキシル基を有
し、かつエチレン性不飽和基を有する樹脂〔Ｒ−
−Ａ〕を得た。
合成例 10
合成例１で用いた同様な反応容器にメチルメタ
クリレート601部、メチルアクリレート401部、ｎ
−ブチルアクリレート601部、グリシジルメタク
リレート401部、トルエン200部、アゾビスイソブ
チロニトリル61部を仕込み、撹拌しながら110℃
で５時間保ちグリシジル基含有アクリル樹脂を合
成した。これに、アクリル酸144部およびテトラ
エチルアンモニウムブロマイドを５部添加して
110℃で３時間反応して、ヒドロキシル基を有し、
かつエチレン性不飽和基を有するアクリル系樹脂
〔Ｒ−〕を得た。
合成例 11
撹拌機、温度計、窒素ガス導入口、滴下装置お
よび還流冷却器を備えた反応容器に１・１・１−
トリメチロールプロパン60部、２・４−トリレン
ジイソシアネート80％と２・６−トリレンジイソ
シアネート20％からなるトリレンジイソシアネー
ト240部および酢酸ｎ−ブチル120部を入れ、窒素
置換後、かきまぜながら除々に加温して80℃で２
時間反応させた。次いで、予め数平均分子量
2000、水酸基価50（KOHmg／ｇ、以下同様）、重
合体鎖のブタジエン単位の91.7％が１・２−結合
からなるポリブタジエンジオール70部をトルエン
370部、酢酸エチル90部、酢酸ｎ−ブチル90部お
よびエチレングリコールモノエチエーテルアセテ
ート90部の混合溶液に良く溶解したものを、約２
時間かけて反応容器内に滴下した。滴下終了後、
さらに窒素ガスを反応容器に少量通じながら、80
℃で２時間反応を継続した。斯くして得れらたポ
リイソシアネート化合物は、淡黄色透明な溶液で
遊離イソシアネートを24％含有し、粘度はＶ（20
℃、泡粘度計、以下同様）であつた。次に、導入
する窒素ガスを乾燥空気に切り替えて少量通じな
がら、滴下装置から２−ヒドロキシエチルアクリ
レート116部を２時間かけて滴下し、滴下終了後、
さらに80℃で3.5時間反応を継続してエチレン性
不飽和基を含有するポリブタジエン系変性樹脂
〔Ｒ−XI〕を得た。
合成例 12
ブチルアクリレート40部、２−ヒドロキシエチ
ルメタクリレート10部、およびアゾビスイソブチ
リロニトリル0.5部をエタノール300部と共に反応
容器に仕込み、窒素雰囲気下、70℃の温度に５時
間撹拌保持し重合させた。反応終了後石油エーテ
ルを用いて未反応モノマーを抽出除去しヒドロキ
シル基を有するアクリル樹脂〔Ｒ−XII〕を得た。
（比較用）
合成例 13
ビニルエステル樹脂（昭和高分子(株)製、商品名
VR−90）100部をエチレン性飽和基を有するモ
ノマである1.6−ヘキサンジオールジアクリレー
ト70部に溶解してビニルエステル樹脂溶液〔Ｒ−
〕を得た。（比較用）
実施例１〜20、比較例１〜４
合成例１〜13によつて得られた(A)成分である調
製液〔〕〜〔〕または市販のアルコキシ化合
物、(B)成分である樹脂類〔Ｒ−〕〜〔Ｒ−〕
および重合開始剤（ベンジルジメチルケタール）
を用い表−１、表−２に示す諸配合で本発明の実
施例１〜実施例20の調製被覆用組成物（Ｓ−１〜
Ｓ−20）を得た。
また、同様にして表−２に示す諸配合で比較例
１〜４の調製被覆用組成物（Ｃ−１〜Ｃ−４）を
得た。次に、これらの被覆組成物のＳ−１〜Ｓ−
20、Ｃ−１〜Ｃ−４を用いて各種基板に浸漬法で
均一な膜厚にコートした後、UV硬化および／ま
たは熱硬化を行い、その得られた被膜の諸性能に
ついて次に記す試験法で測定および試験を行つ
た。その被覆条件と結果を表−３、表−４に示
す。
＜試験法＞
(a) 膜厚測定：薄膜段差測定器を用いて測定し
た。
(b) 表面硬度：JIS−Ｇ−3320に準じ鉛筆硬度を
測定した。判定は、20倍の拡大鏡で観察し、キ
ズのつかない鉛筆の硬度とした。
(c) 曲げ加工性：直径２mmφの曲げ試験機を用い
て被覆基板の180度折り曲げを行つた後、５％
塩酸97c.c.と30％H2O2水溶液３c.c.との混合溶液
中に30秒間浸漬し、曲げ部を100倍の拡大鏡で
観察した。被膜にクラツクまたは剥離が認めら
れないものを(A)、被膜にクラツクの認められる
ものを(B)、被膜の剥離したものを(C)として判定
した。
(d) 防錆性：前記(c)項で曲げ加工を行つた被膜基
板上に、NaCl：28ｇ／、MgSO4：７ｇ／
およびMgCl2：５ｇ／の組成の人工海水を吹
き付け、赤外線ランプを用いて乾燥後、相対湿
度50％（25℃）に保持したデシケーター中に６
日間放置した。発錆の認められないものを(A)、
加工部に点状錆の発生したものを(B)、全体に点
状錆の発生したものを(C)と判定した。
(e) 耐溶剤性：被膜上にメチルエチルケトンを滴
下し、１分間放置し現後、被膜面の表面観察を
行つた。被膜面に異常の認められないものを
(A)、僅ずかに痕跡の認められるものを(B)、明ら
かに痕跡の認められるものを(C)と判定した。
(f) 密着性：JIS Ｄ−0202によりセロテープ・ゴ
バン目剥離試験を行つた。剥離しなかつたマス
目が100／100を(A)、99〜91／100を(B)、90以
下／100を(C)と判定した。
実施例 21
実施例18の組成配合の調製液（Ｓ−18）を脱
脂、乾燥した電気亜鉛メツキ鋼板（0.5×50×150
mm）の両面に浸漬法で所定の膜厚に均一にコート
した後、UV照射を3KW水銀灯を用いて10cmの距
離から30秒間行つて約2μｍと0.8μｍ膜厚の各被膜
鋼板を得た。次いで、得られた各々の被膜鋼板を
５mmのエリクセン押出処理し、そのうち0.8μｍ被
膜鋼板を市販のエポキシウレタン系カチオン電着
塗料液を用いて200V印加電圧で２分間電着後、
180℃で20分間焼付乾燥をなし、約20μｍの電着
膜厚の処理鋼板を得た。この得られた処理鋼板を
用いソルトスプレーテスト（JIS−Ｚ−2371）を
200時間行い、その防錆性を評価した。これらの
結果を表−５に示す。
比較例 ５
実施例21において、組成配合調製液（Ｓ−18）
に代りに合成例１で得られたアルコシシラン溶液
〔〕を用いて電気亜鉛メツキ鋼板上に浸漬法で
コートし、300℃で30分硬化せしめて約0.2μｍの
SiO2被膜を形成した。以下、実施例21と全く同
様に処理して防錆試験を行つた。その結果を表−
５に示す。
比較例 ６
実施例21において、組成配合調製液（Ｓ−18）
をコートしないで、電気亜鉛メツキ鋼板上に実施
例21と全く同様にエポキシウレタン系カチオン電
着塗膜を形成せしめた後、その防錆試験を行つ
た。その結果を表−５に示す。
〔発明の効果〕
本発明の被覆用組成物は、光硬化および／また
は熱硬化することによつて表面硬度、耐溶剤性、
耐食性および可撓性等に優れた被膜を得ることが
でき、特に光硬化し、次いで熱硬化することによ
り、光硬化によつて形成された被膜性能を劣化さ
せることなく、極めて表面硬度の高い被膜を形成
せしめ、かつ曲げ加工性に優れたものであり、さ
らに金属基板に対する防錆性が極めて優れた被覆
用組成物である。
[Industrial Field of Application] The present invention relates to coating compositions. More specifically, the present invention relates to a photocurable and/or thermosetting coating composition comprising a novel composition containing an alkoxysilane compound, a resin, and a polymerization initiator. The coating composition has high surface hardness, processability,
For the purpose of forming a coating with excellent rust prevention and chemical resistance, it can be used on metal surfaces such as stainless steel and galvanized steel, or on plastic surfaces.
It is applied to glass surfaces etc. for the purpose of forming an anti-fogging film, and is also applied as a photosensitive paint and an electrical insulation varnish. [Prior Art] There are too many proposals to improve one or more of the properties of the film formed by using these coating compositions for surface treatment of various substrates. There are so many. Although most of these products differ depending on their purpose, their main component is a resin whose resin skeleton is an organic polymer compound such as acrylic resin or epoxy resin. Although coatings formed by curing or photocuring have the advantage of being highly flexible, they have low surface hardness, poor solvent resistance, and lack of rust prevention, especially when applied to metal surfaces. It has the following disadvantages. In recent years, many coating compositions containing organosilicon compounds as components have been proposed as coating compositions capable of forming coatings with high surface hardness and excellent solvent resistance. The main one is a composition whose main component is an organosilicon compound into which a substituent having a polymerizable unsaturated bond is introduced, without citing any specific literature. In these products, the organosilicon compound, which is the main ingredient, is not only expensive because it is synthesized through an extremely complicated process, but also the organosilicon compound or the composition containing it as the main ingredient has poor stability and defects. be. Japanese Patent Application Laid-Open No. 51-33128 describes the introduction of relatively inexpensive organosilicon compounds into coating compositions.
JP-A-2006-100003 proposes a coating composition in which a co-partial hydrolyzate of tetraalkoxysilane and alkylalkoxysilane, an acrylic copolymer, and etherified methylolmelamine are dissolved in a solvent. The composition forms a film by heat curing after being applied to a substrate, and has high surface hardness.
Excellent abrasion resistance, hot water resistance, heat cycle resistance, etc. However, the coating using this composition has a drawback of poor flexibility and easily cracking or peeling due to bending or the like. Furthermore, JP-A No. 59-4611 discloses a photosensitive resin composition comprising a three-dimensional condensate of methyl silicate treated with a prepolymer having ethylenically unsaturated bonds, a monomer, a photopolymerization initiator, and a titanium-based coupling agent. Embodiments are disclosed for forming photocured coatings on substrates. The three-dimensional condensate of methyl silicate added to the composition is substantially SiO 2 particles and is thought to contribute to improving the surface hardness of the coating as a filler, and the resulting coating has a good bond with the substrate. Although the film has excellent adhesion and appearance, the formed film has poor flexibility, and the film easily cracks and peels off when deformed after forming, causing problems in terms of bending workability. It was hot. [Problems to be Solved by the Invention] The present invention solves the above-mentioned problems in bending workability, and provides a coating with high surface hardness, excellent solvent resistance, adhesion, good resistance, and flexibility. It is an object of the present invention to provide a photocurable and/or thermosetting coating composition. [Means and effects for solving the problem] As a result of intensive studies to achieve the above-mentioned object, the present inventors have developed a resin containing alkoxysilane compounds, a hydroxyl group, and an unsaturated bond. Or, it was discovered that the desired purpose could be achieved by using a specific coating composition comprising a mixture of a compound having a hydroxyl group and a compound having an unsaturated bond, and a photopolymerization initiator as main components. The invention was completed. That is, the present invention has the following formula: (A) General formula RnSi(OR') 4-o ...[1] (wherein R is an organic group having an alkyl group, an aryl group, an alkenyl group, and a methacryloxy group having 1 to 6 carbon atoms; represents the same or different selected groups, R' represents the same or different alkyl groups having 1 to 4 carbon atoms, and n is 0 to 2) and/or the alkoxysilane compound represented by Partial hydrolyzate of silane compound (B) Resin of component (a) and/or (b) below (a) Average molecular weight having at least one hydroxyl group and ethylenically unsaturated group in one molecule 500 to 50,000 resins (b) Resins with an average molecular weight of 500 to 50,000 that have two or more hydroxyl groups in one molecule and resins with an average molecular weight of 500 to 50,000 that have two or more ethylenically unsaturated groups in one molecule. (C) A photopolymerization initiator A coating composition characterized by containing the above components (A), (B) and (C) as main components. The present invention will be explained in detail below. The alkoxysilane compound that is the component (A) used in the present invention is represented by the general formula RnSi(OR') 4-o ...[1], where R is an alkyl group having 1 to 6 carbon atoms, an aryl group, and an alkyl group having 1 to 6 carbon atoms. R' represents the same or different types of alkyl groups having 1 to 4 carbon atoms, and n is 0 to 2. Here, when n is 0, it is a tetraalkoxysilane compound in which R' is the same or different alkyl group having 1 to 4 carbon atoms, and when n is 1, R
are the same or different groups selected from monovalent organic groups having 1 to 6 carbon atoms, including alkyl groups, allyl groups, alkenyl groups, and methacryloxy groups, and
A trialkoxysilane compound in which R' is the same or different alkyl group having 1 to 4 carbon atoms, and n
When is 2, it is a dialkoxysilane compound in which R and R' are the same as when n is 1. As these representative compounds, n in the formula is 0
Tetraalkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, dimethoxydiisopropoxysilane, diethoxydiisopropoxysilane, diethoxydibutoxysilane; Methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxy, where n in the formula is 1 Trialkoxysilane compounds such as silane, vinyltriethoxysilane, allyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxytriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyl where n is 2; Diisopropoxysilane, diethyldibutoxysilane,
Examples include dialkoxysilane compounds such as phenylmethyldimethoxysilane. In addition, as component (A), a siloxane polymer obtained by hydrolyzing a single or a mixture of two or more of these alkoxysilane compounds in the presence of an acidic or alkaline catalyst may be used. used. Partial hydrolysates of these alkoxysilane compounds can be obtained by adding hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid,
One or more acidic catalysts such as inorganic acids such as boric acid, organic acids such as acetic acid, propionic acid, oxalic acid, fumaric acid, maleic acid, and succinic acid, or sodium hydroxide, potassium hydroxide, aqueous ammonia, etc. This is a siloxane polymer obtained by hydrolysis in the presence of an alkali catalyst and polymerization by elimination of the alkyl group represented by R' in the general formula [1]. In the present invention, as component (A), one or more of tetra-, tri-, and dialkoxysilanes represented by the general formula [1] and a partial hydrolyzate of the alkoxysilane compound are used. Mixtures can be used. In particular, a partially hydrolyzed alkoxysilane compound is preferably used because it is stable against hydrolysis caused by absorption of moisture in the atmosphere. In addition, in the general formula RnSi(OR') 4-o , n
When is more than 2, the number of reactive functional groups present in the alkoxysilane compound or the partial hydrolyzate of the alkoxysilane compound decreases;
(B) The bond with the hydroxyl group of component is not sufficient,
The curability of the obtained coating is insufficient, and various properties such as surface hardness, solvent resistance, corrosion resistance, and flexibility of the coating cannot be obtained sufficiently. The resin having an average molecular weight of 500 to 50,000 and having at least one hydroxyl group in one molecule and having an ethylenically unsaturated group as component (B) used in the present invention has one hydroxyl group in one molecule and an ethylenically unsaturated group. Any material may be used as long as it contains at least one hydroxyl group and a photocurable ethylenically unsaturated group, such as unsaturated polyester resin, acrylic resin, urethane acrylate resin, epoxy acrylate resin, polybutadiene resin, Hydroxyl groups and ethylenically unsaturated groups are introduced into the resin skeleton of polyether acrylate resin, polyester acrylate resin, etc. Typical compounds include (i) Epoxy acrylate resin: Epoxy resin and (meth) It is a resin obtained by an addition reaction with acrylic acid or an addition reaction between glycidyl acrylate and bisphenol A, and also includes urethane-modified resins modified by partially utilizing the hydroxyl groups in the molecule. The epoxy resin is not particularly limited, and includes commonly used bisphenol A type epoxy resins, novolak type epoxy resins, alicyclic type epoxy resins, diglycidyl ether glycerin of ethylene or propylene glycol, or polyglycidyl ether of trimethylolpropane. etc. (ii) Acrylic and urethane acrylate resins: reactive groups such as (meth)acrylic acid ester copolymers (hydroxyl groups, carboxyl groups,
It is a resin obtained by introducing a photopolymerizable (meth)acrylic acid ester into the side chain using an epoxy group (such as an epoxy group), and includes, for example, a resin produced by the following method. (a) An unsaturated monomer containing a glycidyl group is added to a hydroxyl group-containing acrylic resin to introduce an ethylenically unsaturated group into the hydroxyl group. Examples of the glycidyl group-containing unsaturated monomer include glycidyl acrylate and glycidyl methacrylate. (b) Adding an unsaturated monomer containing a glycidyl group to a carboxyl group-containing acrylic resin to introduce a hydroxyl group and an ethylenically unsaturated group. As the glycidyl group-containing unsaturated monomer, those described in (a) above are used. (c) An unsaturated monomer containing a carboxyl group is added to a glycidyl group-containing acrylic resin to introduce a hydroxyl group and an ethylenically unsaturated group. As the carboxyl group-containing unsaturated monomer, for example, acrylic acid, methacrylic acid, crotonic acid, etc. can be used. The acrylic resin containing a hydroxyl group, a carboxyl group or a glycidyl group into which an ethylenically unsaturated group is introduced in (a) to (c) above is an unsaturated resin containing a functional group such as a hydroxyl group, a carboxyl group or a glycidyl group. A resin obtained by copolymerizing a saturated monomer and another acrylic unsaturated monomer is used.
In addition, examples of the hydroxyl group-containing unsaturated monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate,
-Hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc. are used. In addition, as urethane acrylate resin,
(a) hydroxyl group-containing acrylic resin or (b)(c)
A hydroxyl group-containing acrylic resin is produced by adding a diisocyanate to the hydroxyl group-containing resin produced by the method, and then adding a hydroxyl group-containing unsaturated monomer, or by adding a diisocyanate and a hydroxyl group-containing unsaturated monomer to the hydroxyl group-containing acrylic resin. It can be obtained by addition reaction with (iii) Polybutadiene resin (a) Polybutadiene resin having hydroxyl groups at both ends or its (meth)acrylic modified resin (b) Polybutadiene resin having carboxyl groups at both ends and epoxy resin are reacted, and then the polybutadiene resin present in the molecule (c) Urethane-modified resin obtained via diisocyanate or acrylic-modified resin into which an ethylenically unsaturated group-containing monomer is introduced as described above for acrylic and urethane acrylate resins using epoxy groups and hydroxyl groups. and/or resins obtained by reacting epoxidized polybutadiene containing an epoxy group therein with the aforementioned unsaturated monomer containing a carboxyl group. When the resin (A), which is the component (B) of the present invention, has one or more hydroxyl groups in one molecule and has an ethylenically unsaturated group, but does not have a hydroxyl group in the molecule. When the film is cured, there is no bond between the hydroxyl group and the reactive functional group present in the alkoxysilane compound (A) or the partial hydrolyzate of the alkoxysilane, and therefore the film has insufficient curability. , the expected performance of the coating cannot be obtained. Furthermore, the ethylenically unsaturated group must be contained within a range that can be cured by light irradiation, and two or more per molecule is desirable.
In addition, if the molecular weight is less than 500, the flexibility of the film cannot be obtained, and if it is more than 50,000, workability such as resin modification compounding will be lacking.
It is 10000. Although there are many types of resins (i) of component (A), modified resins having urethane bonds in the resin skeleton are more preferred in order to impart flexibility. Component (B) of the present invention (B) has two or more hydroxyl groups in one molecule and has an average molecular weight of 500 to 50,000
of resin (hereinafter referred to as HC resin) and 2 in one molecule.
Average molecular weight with more than 1 ethylenically unsaturated group
500 to 50,000 resin (hereinafter referred to as UR resin), typical resins of HC resin include polyester polyol resin, polyether polyol resin, alkyd resin, saturated polyester resin,
Examples include polybutadiene glycol resin, epoxy resin having a hydroxyl group, vinyl polymer resin containing a hydroxyl group (acrylic polyol resin), polyurethane resin or polyurethane acrylate resin having a hydroxyl group, and phenol resin. UR resin is a resin that contains the aforementioned hydroxyl group and has an ethylenically unsaturated group of a resin that does not have a hydroxyl group or has not been introduced in the synthesis of a resin that has an ethylenically unsaturated group, such as an unsaturated polyester-based resin. Examples include resins, acrylic resins, urethane acrylic resins, epoxy acrylate resins, polybutadiene resins, and modified resins thereof. In the resin mixture of (B), which is the component (B) of the present invention, in the mixed resin system of HC resin and UR resin, the number of hydroxyl groups in the HC resin or the ethylenically unsaturated groups in the UR resin is less than two. As a result, the expected coating performance cannot be obtained. This means that if there are few hydroxyl groups, it will be difficult to cure during photocuring and/or heat curing.
If there is little bonding between the HC resin and the reactive functional groups present in the alkoxysilane compound or the partial hydrolyzate of the alkoxysilane compound, which is component (A), and if there are few ethylenically unsaturated groups in the UR resin, photocuring is possible. During this process, the curing reaction does not proceed, and the resulting film has a low crosslinking density and insufficient curability, making it impossible to obtain good performance. In addition, the average molecular weight of HC resin and UR resin is 500~
50,000, but if it is less than 500 or more than 50,000, it will lack performance and workability like the resin of (B), which is component (A). Preferably it is 1000-10000. The blending ratio of HC resin and UR resin is 70~
Used in a ratio of 30/30 to 70 (weight ratio). The photopolymerization initiator as component (C) used in the present invention is:
It is a known compound that can initiate polymerization when irradiated with actinic rays, and its representative compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin acetate, benzophenone, -rubenzophenone, 4-methoxybenzophenone, 4,4'-dimethylbenzophenone, 4-bromobenzophenone, 2,2',4,4'-tetrachlorobenzophenone, 2-chlor-4 '-Methylbenzophenone, 3
-Methylbenzophenone, 4-t-butylbenzophenone, benzyl, benzylic acid, benzyl dimethyl ketal, diacetyl, methylene blue, acetophenone, 2,2-diethoxyacetophenone, 9,10-phenanthrenequinone, 2 -Methylanthraquinone, 2-ethylanthraquinone, 2
-t-Butylanthraquinone, diphenyl disulfide, dithiocarbamate, α-chloromethylnaphthalene, anthracene, iron chloride, 1,4-
Naphthoquinone, etc. Particularly preferred are benzyl dimethyl ketal, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, benzoisopropyl ether, benzoin butyl ether 2-ethylanthraquinone and thioxanthone. These photopolymerization initiators may be used alone or in combination of two or more. In the present invention, the coating composition comprising the above-mentioned components (A), (B) and (C) as main components includes (A), (B) and
The blending ratio (solid content equivalent) of (C) component is (A)/(B) = 1~
100/100 (weight ratio), (C)/(B) = 0.05 to 10/100 (weight ratio), preferably (A)/(B) = 15 to 70/100,
(C)/(B)=0.1 to 5/100. (A) When the amount of component is less than 1/100, the corrosion resistance of the coating obtained by photo and/or heat curing,
On the other hand, if the surface hardness exceeds 100/100, the adhesion of the photocured film to the substrate will decrease, and the deformability of the substrate after photocuring will be extremely poor, which is not preferable. In the present invention, an organic solvent is used in the composition of the present invention as necessary, for example, when producing components (A) and (B) or when adjusting the viscosity of the composition. , (B) and (C) components and are highly soluble are preferably used. For example, (A)
Lower alcohols such as methanol, ethanol, isopropanol, and n-butanol as solvents; esters such as methyl acetate, ethyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, and acetylacetone; polyhydric alcohols or their ethers These can be used alone or in a mixture of two or more. In addition, as a solvent for components (B) and (C), aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as kerosene and mineral spirits; esters such as ethyl acetate and butyl acetate; carbon tetrachloride,
Examples include halogenated hydrocarbons such as 1,1,1-trichloroethane, verchlorethylene, chlorobenzene, dichlorobenzene, etc., which may be used alone or in a mixture of two or more. The listed solvents for components (A), (B), and (C) are not necessarily the same as those for component (A), (B), and (C).
Since the solvents for components (B) and (C) do not dissolve component (A), they should be mixed in amounts within a range that does not impair the solubility of the composition of components (A), (B), and (C). They are also selected and used as appropriate. In the present invention, various additives may be further added to the composition of the present invention if desired. These additives include photopolymerization accelerators, radical polymerization initiators, curing accelerators used in combination with radical polymerization initiators, stabilizers (polymerization inhibitors), glass forming agents, organometallic compounds other than silicon compounds, and pigments. etc. A photopolymerization accelerator is used in combination with the photopolymerization initiator of component (C) because it significantly accelerates the curing speed during photocuring, especially ultraviolet curing, and prevents the polymerization inhibiting effect caused by oxygen, etc. . Such photopolymerization accelerators include amines, such as primary amines such as butylamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, monoethanolamine; diethylamine, dimethylaniline, dimethyl-paratoluidine, pyridine, N , N'-dimethylchlorohexylamine, diethanolamine, triethanolamine, Michler's ketone, and other secondary and tertiary amines. As the radical polymerization initiator, diacyl peroxides such as benzoyl peroxide, 2.
4-Dichlorobenzoyl peroxide, octanoyl peroxide, lauroyl peroxide, etc.; dialkyl peroxides, such as di-tert-butyl peroxide, dicumyl peroxide, etc.;
Peroxy esters, such as tert-butyl perbenzoate, tert-butyl peracetate, di-tert-butyl perphthalate, 2,5-dimethyl-
2,5-di(benzoylperoxy)hexane, etc.; ketone peroxides, such as methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.; hydroperoxides, such as tert-butyl hydroperoxide, cumene hydroperoxide, α-phenyl Ethyl hydroperoxide, cyclohexenyl hydroperoxide, etc., and mixtures thereof are suitable and preferably non-foaming, and the amount used is 0.1 to 10% by weight based on the resin (solid content) of component (B). , preferably 0.5 to 5% by weight. Further, examples of the curing accelerator used in combination with the radical polymerization initiator include cobalt naphthenate,
Metal soaps such as manganese naphthenate, copper naphthenate, iron naphthenate, and cobalt oleate; water-soluble metal salts such as cobalt chloride and manganese acetate; strong reducing agents such as ascorbic acid and araboascorbic acid; ammonium thiocyanate , thiocyanates such as potassium thiocyanate; thiourea, tetramethylthiourea, ditolylthiourea, ethylenethiourea, 2-mercaptobenzothiazole, 2
- Thioureas such as mercaptobenzimidazole are effective. Also dimethylaniline, diethylaniline, triethylamine, triethanolamine, octylamine, butylamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, tetraethylenepentamine, anisidine, pyrrolidine, toluidine, 2,2'-pipyridyl-4,4' -Amines such as diaminodiphenylmethane, benzidine, and triphenylenetetramine have a strong effect of promoting radical generation. The amount of curing accelerator added is based on the resin (solid content) of component (B).
On the other hand, it is 0.001 to 30%, and if it is less than 0.001, there is no effect, and if it is more than 30%, various performances such as surface hardness, chemical resistance, and flexibility will deteriorate. When several types of curing accelerators are used in combination, even better curing accelerating ability is exhibited. The radical polymerization initiator and curing accelerator may be dissolved or dissolved in a single or mixed solvent such as trichlorethylene, chloroform, ethyl acetate, ethanol, isopropanol, acetone, methyl ethyl ketone, ether, methyl chloroform, water, etc. You may do so. Among the curing accelerators, metal soaps such as cobalt naphthenate, manganese naphthenate, copper naphthenate, iron naphthenate, and cobalt oleate can also be added alone as a curing agent. Further, in order to prevent early crosslinking of the resin having an ethylenically unsaturated bond (B) during heat treatment and storage, it is desirable to mix a stabilizer (polymerization inhibitor). Examples of the stabilizer include di-t-butyl-p-cresol, hydroquinone monomethyl ether, pyrogallol, quinone, hydroquinone, t-butylcatechol, hydroquinone monobenzyl ether, methylhydroquinone, amylquinone, phenol, hydroquinone monopropyl ether, phenothiazine, Examples include nitrobenzene. These stabilizers prevent premature crosslinking during formulation or storage of the coating composition. The vitreous forming agent forms a vitreous substance by heating together with an organic silane compound, and does not necessarily form a vitreous substance when added to the coating composition of the present invention for coating. , surface hardness and corrosion resistance of the formed film,
In particular, it improves alkali resistance. As glass forming agents, phosphorus compounds such as phosphoric acids and phosphorus alkoxide derivatives; boron compounds such as boric acids and boron alkoxide derivatives; arsenic compounds such as arsenic acids and arsenic alkoxide derivatives; antimonic acids,
Antimony compounds such as antimony alkoxide derivatives; organic gallium compounds; zinc compounds such as zinc carboxylates and zinc alkoxides; lead carboxylates;
Lead compounds such as lead alkoxides and mixtures thereof can be used in addition. Organometallic compounds other than silicon compounds also have the effect of improving the properties of the formed film, similar to the glass forming agent. As these organometallic compounds, titanium, tantalum, aluminum, or zirconium alkoxides, chelates, acylates, and mixtures thereof can be preferably used. Addition of pigments gives transparent colored coatings. For example, Mierolith Blue4G manufactured by CIBA-GEIGY
T, Cromophtal Orange2G, Mierolith Green
By using G-T or the like, transparent colored films such as blue, orange, and green can be formed. In the present invention, the coating composition described above is applied to various substrates to a uniform thickness, and after drying and removing the solvent as necessary, actinic light is irradiated to form a photocured film on the substrate surface. As a light source for photocuring, (C)
High-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, and the like that generate ultraviolet rays in the wavelength range of 200 to 500 nm that can activate the component photopolymerization initiator and optionally added photopolymerization accelerator can be used. There are no particular restrictions on the method of applying the coating composition to the substrate, and methods that provide a uniform coating thickness, such as dipping, spraying, roll coating, and flow coating, are preferably employed. The film formed by photocuring has sufficient properties as a protective coating for the various substrates coated with it, but heat curing progresses by further heat treatment at a temperature of 80 to 300°C for 0.5 to 120 minutes, and the coating Characteristic,
In particular, a coating with significantly improved surface hardness, chemical resistance, and corrosion resistance, especially when coated on a metal substrate, is formed. We also provide corrosion protection for deformed surfaces of metal substrates such as stainless steel plates and galvanized steel plates.
When forming a coating for the purpose of rust prevention, etc., a coating composition is applied to a flat substrate, photocured, then subjected to desired deformation processing, and then thermally cured.
A desired coating can be formed. Note that even if the film is simply heat treated at a temperature of 80 to 300° C. for 0.5 to 120 minutes without photocuring, a film format is possible. [Examples] Hereinafter, the present invention will be explained in more detail with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to these Examples in any way. In addition, parts and percentages in the examples are parts by weight and percentages by weight.
shows. Synthesis Example 1 186 parts of tetraethoxysilane, 643 parts of ethanol, and 206 parts of acetic acid were placed in a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, and 0.3 part of 35% hydrochloric acid was added, and the mixture was heated with stirring. The reaction was carried out for 45 hours while refluxing the solvent. The amount of solvent was adjusted so that the concentration of the partially hydrolyzed alkoxysilane compound converted to SiO 2 was 5%, and P 2 O 5 equivalent to 2.5% of SiO 2 was added and dissolved to obtain a prepared solution [] I got it. Synthesis Example 2 200 parts of methyltriethoxysilane, 250 parts of tetraethoxysilane, 2500 parts of ethanol and 20
After adding 1.5 parts of % hydrochloric acid and stirring and mixing, 150 parts of water was added dropwise using a dropping device while maintaining the reaction liquid temperature at 70°C. After the dropwise addition of water was completed, the reaction was continued at a temperature of 70° C. for an additional 5 hours. A prepared solution [] was obtained by adjusting the amount of solvent so that the SiO 2 equivalent concentration of the generated partial hydrolysis was 4.5%. Synthesis Example 3 In a reaction vessel similar to Synthesis Example 2, 115 parts of tetrabutoxysilane, 163 parts of ethanol, 0.15 parts of 20% hydrochloric acid, and 22 parts of water were charged, heated to 70°C with stirring, and reacted for 4 hours. I went. Next, after cooling the reaction solution to room temperature, 3.3 parts of tetrabutoxytitanium was added and dissolved, and the resulting partial hydrolyzate was dissolved.
A prepared solution [] was obtained by adjusting the amount of solvent so that the concentration in terms of SiO 2 was 7.0%. Synthesis example 4 Tetraethoxy silicon in 70g of isopropyl alcohol
66.7 g and 33.3 g of methyltriethoxy silicon were dissolved, and 30 g of a 0.05N aqueous hydrochloric acid solution was further added and the mixture was stirred at room temperature to perform hydrolysis. After the reaction, it was aged at room temperature for 20 hours or more to obtain [ ]. The resulting solution [] contained 9.6% of tetraethoxy silicon partial hydrolyzate calculated as SiO 2 and 6.3% of methyltriethoxy silicon partial hydrolyzate calculated as CH 3 SiO 1.5 . (For comparison) Synthesis Example 5 A three-dimensional condensate of methyl silicate (Nikko Fine Products Co., Ltd.) was added to 100 parts of a 1% solution of isopropyl triisostearoyl titanate (Plenact TTS, sold by Ajinomoto Co., Inc.) diluted with toluene. )
Release: MSP・S "SiO 2 granules"): After adding and mixing 50 parts, toluene was removed by volatilization under heating and reduced pressure to obtain []. [ ] contained a titanium-based coupling agent: a three-dimensional condensate of methyl silicate with 2% TTS attached: MSP.S. (For comparison) Synthesis Example 6 In a reaction vessel equipped with a stirrer, a thermometer, and a gas inlet, butadiene was added at -60°C to a system in which 1,2-diphenylbenzene was dissolved in tetrahydrofuran and a sodium dispersion was added. Number average molecular weight (hereinafter abbreviated as molecular weight) 1550, produced by treating the generated living polymerization reaction solution with carbon dioxide;
1.2-vinyl bond 90.7%, 1.4-trans bond 9.3%
microstructure, acid value 59.6 (KOH per gram of pure content)
NISSO-PBC-1000, a polybutadiene with a carboxyl group at the end of the molecule (expressed in mg, the same applies hereinafter)
(manufactured by Nippon Soda Co., Ltd., trade name) 1000 parts of bisphenol A-diglycidyl ether type epoxy resin Epicoat 828 (manufactured by Yuka Ciel Epoxy Co., Ltd., trade name) 1000 parts, N-N dimethylbenzylamine After charging 5 parts, while blowing nitrogen into the reaction vessel,
After reacting at 100℃ for 4 hours, the acid value of the reaction mixture is
0.1 or less, and the resulting reactant has an epoxy oxygen content of 3.3% polybutadiene-modified epoxy resin
Got 3.3. Subsequently, dry air was blown in for 10 minutes, 400 parts of methacrylic acid and 5 parts of hydroquinone were added, and the mixture was heated and stirred at 100°C for 7 hours to obtain a hydroxyl group-containing polybutadiene-modified unsaturated resin [R-].
I got it. Synthesis Example 7 In a reaction vessel similar to Synthesis Example 1, diglycerol polyglycidyl ether denacol EX-, which has one hydroxyl group and three epoxy groups in one molecule, was added.
421 (manufactured by Nagase Sangyo, product name) 346 parts, toluene 616
1 part, N-N' dimethylbenzylamine, 3 parts of hydroquinone, and 252 parts of acrylic acid.
The mixture was heated and stirred at about 100° C. for 7 hours while blowing a small amount of dry air to obtain a hydroxyl group-containing polyglycidyl ether modified unsaturated resin [R-]. Synthesis Example 8 Polyethylene glycol diglycidyl ether denacol EX-832 was placed in the same reaction vessel as in Synthesis Example 1.
(manufactured by Nagase Sangyo, trade name) 526 parts, butyl acetate 684 parts N-N'dimethylbenzylamine 1.5 parts, hydroquinone 2 parts, and acrylic acid 158 parts.
The mixture was heated and stirred at about 100° C. for 10 hours while blowing a small amount of dry air to obtain a hydroxyl group-containing polyethylene glycol diglycidyl ether modified unsaturated resin [R-]. Synthesis example 9 Bisphenol A type epoxy resin Epicoat
1001 (manufactured by Yuka Ciel Epoxy Co., Ltd., trade name, epoxy equivalent: 900), 900 parts of acrylic acid, 144 parts of methyl ethyl lactone, 1.0 part of triethylamine, and 0.1 part of hydroquinone were placed in a reaction vessel.
The reaction was carried out at 100°C until the acid value became 5 or less to obtain a resin [R-] having a hydroxyl group and an ethylenically unsaturated group in the molecule. Next, 174 parts of tolylene diisocyanate synthesized in advance with 500 parts of the above [R-] resin and 2-
204 parts of a urethane prepolymer having isocyanate groups consisting of 130 parts of ethyl hydroxyl acrylate and 204 parts of methyl ethyl ketone are added;
[R-] Some of the hydroxyl groups of the resin and the isocyanate groups of the urethane prepolymer are reacted at 80°C for 2 hours to produce a resin that has a hydroxyl group in one molecule and an ethylenically unsaturated group [R-]
-A] was obtained. Synthesis Example 10 Into the same reaction vessel used in Synthesis Example 1, 601 parts of methyl methacrylate, 401 parts of methyl acrylate, n
- 601 parts of butyl acrylate, 401 parts of glycidyl methacrylate, 200 parts of toluene, and 61 parts of azobisisobutyronitrile were charged and heated to 110°C while stirring.
The mixture was kept for 5 hours to synthesize a glycidyl group-containing acrylic resin. To this, 144 parts of acrylic acid and 5 parts of tetraethylammonium bromide were added.
React at 110°C for 3 hours to obtain a hydroxyl group,
An acrylic resin [R-] having an ethylenically unsaturated group was obtained. Synthesis Example 11 In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet, a dropping device, and a reflux condenser, 1.1.1-
Add 60 parts of trimethylolpropane, 240 parts of tolylene diisocyanate consisting of 80% 2,4-tolylene diisocyanate and 20% 2,6-tolylene diisocyanate, and 120 parts of n-butyl acetate, and after purging with nitrogen, gradually stir while stirring. Heat to 80℃ 2
Allowed time to react. Next, the number average molecular weight
2000, hydroxyl value 50 (KOHmg/g, the same applies hereinafter), 70 parts of polybutadiene diol in which 91.7% of the butadiene units in the polymer chain are 1,2-bonds was mixed with toluene.
370 parts, 90 parts of ethyl acetate, 90 parts of n-butyl acetate, and 90 parts of ethylene glycol monoethyether acetate.
It was dropped into the reaction vessel over time. After finishing dropping,
Furthermore, while passing a small amount of nitrogen gas into the reaction vessel,
The reaction was continued for 2 hours at °C. The polyisocyanate compound thus obtained is a pale yellow transparent solution containing 24% free isocyanate and a viscosity of V(20
℃, foam viscometer, the same applies hereafter). Next, while changing the introduced nitrogen gas to dry air and passing a small amount, 116 parts of 2-hydroxyethyl acrylate was dripped from the dropping device over 2 hours, and after the dropping was completed,
The reaction was further continued at 80° C. for 3.5 hours to obtain a polybutadiene-based modified resin [R-XI] containing an ethylenically unsaturated group. Synthesis Example 12 40 parts of butyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, and 0.5 parts of azobisisobutyrilonitrile were charged into a reaction vessel together with 300 parts of ethanol, and the mixture was stirred and maintained at a temperature of 70°C for 5 hours under a nitrogen atmosphere to polymerize. I let it happen. After the reaction was completed, unreacted monomers were extracted and removed using petroleum ether to obtain an acrylic resin having a hydroxyl group [R-XII].
(For comparison) Synthesis example 13 Vinyl ester resin (manufactured by Showa Kobunshi Co., Ltd., trade name
VR-90) was dissolved in 70 parts of 1,6-hexanediol diacrylate, a monomer having an ethylenic saturated group, to obtain a vinyl ester resin solution [R-
] was obtained. (For comparison) Examples 1 to 20, Comparative Examples 1 to 4 Preparation solutions [] to [] which are component (A) obtained in Synthesis Examples 1 to 13 or commercially available alkoxy compounds, component (B) Certain resins [R-] ~ [R-]
and polymerization initiator (benzyl dimethyl ketal)
The coating compositions (S-1 to 20) of Examples 1 to 20 of the present invention were prepared using
S-20) was obtained. Similarly, coating compositions (C-1 to C-4) of Comparative Examples 1 to 4 were obtained using various formulations shown in Table 2. Next, these coating compositions S-1 to S-
20. After coating various substrates with C-1 to C-4 to a uniform thickness by dipping, UV curing and/or heat curing were performed, and the following tests were conducted on the various performances of the resulting coatings. Measurements and tests were carried out using the method. The coating conditions and results are shown in Tables 3 and 4. <Test method> (a) Film thickness measurement: Measured using a thin film step measuring device. (b) Surface hardness: Pencil hardness was measured according to JIS-G-3320. Judgment was made by observing with a 20x magnifying glass and determining the hardness of a pencil without scratching. (c) Bending workability: 5% after bending the coated substrate 180 degrees using a bending tester with a diameter of 2 mmφ.
It was immersed in a mixed solution of 97 c.c. of hydrochloric acid and 3 c.c. of 30% H 2 O 2 aqueous solution for 30 seconds, and the bent portion was observed with a 100x magnifying glass. Those with no cracks or peeling on the film were evaluated as (A), those with cracks on the film as (B), and those with peeling of the film as (C). (d) Rust prevention: NaCl: 28 g/, MgSO 4 : 7 g/
After spraying artificial seawater with a composition of 5 g /MgCl2 and drying using an infrared lamp, the cells were placed in a desiccator kept at a relative humidity of 50% (25°C).
I left it for days. (A) where no rust is observed;
A specimen with rust spots on the processed part was classified as (B), and a specimen with rust spots on the entire surface was classified as (C). (e) Solvent resistance: Methyl ethyl ketone was dropped onto the film, left to stand for 1 minute, and then the surface of the film was observed. No abnormalities are observed on the coating surface.
(A), those with slight traces were classified as (B), and those with obvious traces were classified as (C). (f) Adhesion: A sellotape/goban peel test was conducted according to JIS D-0202. The number of squares that did not peel off was determined to be 100/100 as (A), 99 to 91/100 as (B), and 90 or less/100 as (C). Example 21 A prepared solution (S-18) having the composition of Example 18 was degreased and dried on an electrogalvanized steel sheet (0.5×50×150
After uniformly coating both sides of the steel sheet to a predetermined thickness using a dipping method, UV irradiation was performed for 30 seconds from a distance of 10 cm using a 3KW mercury lamp to obtain coated steel plates with film thicknesses of approximately 2 μm and 0.8 μm. Next, each of the obtained coated steel plates was subjected to Erichsen extrusion treatment to a thickness of 5 mm, and the 0.8 μm coated steel plates were electrodeposited for 2 minutes at an applied voltage of 200 V using a commercially available epoxy urethane cationic electrodeposition paint solution.
Baking and drying was carried out at 180° C. for 20 minutes to obtain a treated steel sheet with an electrodeposited film thickness of about 20 μm. A salt spray test (JIS-Z-2371) was conducted using this treated steel plate.
The test was carried out for 200 hours and its rust prevention properties were evaluated. These results are shown in Table-5. Comparative Example 5 In Example 21, composition blend preparation liquid (S-18)
Instead, the alkoxysilane solution obtained in Synthesis Example 1 was coated on an electrogalvanized steel plate by dipping, and cured at 300°C for 30 minutes to form a film with a thickness of approximately 0.2 μm.
A SiO 2 film was formed. Thereafter, a rust prevention test was conducted in exactly the same manner as in Example 21. Table the results.
5. Comparative Example 6 In Example 21, composition blend preparation liquid (S-18)
An epoxy urethane-based cationic electrodeposited coating film was formed on an electrogalvanized steel sheet in exactly the same manner as in Example 21 without coating, and then a rust prevention test was conducted. The results are shown in Table-5. [Effects of the Invention] The coating composition of the present invention improves surface hardness, solvent resistance,
A coating with excellent corrosion resistance and flexibility can be obtained.In particular, by photocuring and then heat curing, a coating with extremely high surface hardness can be obtained without deteriorating the coating performance formed by photocuring. This coating composition has excellent bending workability and excellent rust prevention properties for metal substrates.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
＊９：表−３に同じ
[Table] *9: Same as Table-3
【表】【table】
Claims (1)
ール基、アルケニル基およびメタクリロキシを
有する有機基から選ばれた同種または異種の基
を示し、R′は炭素数１〜４のアルキル基の同
種または異種を示し、ｎは０〜２である。） で表されるアルコキシシラン化合物および／ま
たは該アルコキシシラン化合物の部分加水分解
物 (B) 下記(イ)成分および／または(ロ)成分の樹脂 (イ) １分子中に少なくとも１個のヒドロキシル
基を有し、かつエチレン性不飽和基有する平
均分子量500〜50000の樹脂 (ロ) １分子中に２個以上のヒドロキシル基を有
する平均分子量500〜50000の樹脂と１分子中
に２個以上のエチレン性不飽和基を有する平
均分子量500〜50000の樹脂との混合物 (C) 光重合開始剤 上記(A)、(B)および(C)成分を主要成分として含有
してなることを特徴とする被覆用組成物。 ２ (A)、(B)および(C)成分の配合割合（固形分換
算）が、(A)／(B)＝１〜100／100（重量比）、(C)／(B)
＝0.05〜10／100（重量比）である特許請求の範囲
第１項記載の被覆用組成物。[Scope of Claims] 1 (A) General formula RnSi(OR') 4-o ... [1] (wherein, R is an organic compound having an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, and a methacryloxy group) The alkoxysilane compound and/or Partial hydrolyzate of the alkoxysilane compound (B) Resin of component (a) and/or component (b) below (a) Having at least one hydroxyl group in one molecule and having an ethylenically unsaturated group Resins with an average molecular weight of 500 to 50,000 (b) Resins with an average molecular weight of 500 to 50,000 that have two or more hydroxyl groups in one molecule and average molecular weights of 500 to 50,000 that have two or more ethylenically unsaturated groups in one molecule (C) A photopolymerization initiator A coating composition comprising the above components (A), (B), and (C) as main components. 2 The blending ratio of components (A), (B), and (C) (in terms of solid content) is (A)/(B) = 1 to 100/100 (weight ratio), (C)/(B)
The coating composition according to claim 1, wherein the ratio is 0.05 to 10/100 (weight ratio).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59164859A JPS6143665A (en) | 1984-08-08 | 1984-08-08 | Coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59164859A JPS6143665A (en) | 1984-08-08 | 1984-08-08 | Coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6143665A JPS6143665A (en) | 1986-03-03 |
| JPH0522743B2 true JPH0522743B2 (en) | 1993-03-30 |
Family
ID=15801271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59164859A Granted JPS6143665A (en) | 1984-08-08 | 1984-08-08 | Coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6143665A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0738123Y2 (en) * | 1991-12-06 | 1995-08-30 | 大日本紙業株式会社 | Paper dividers for gift boxes |
| AU2056402A (en) * | 2000-09-25 | 2002-04-02 | Chemteall Gmbh | Method for coating metallic surfaces and use of substrates coated in such a way or coatings produced in such a way |
| US20100036012A1 (en) * | 2006-05-12 | 2010-02-11 | Nobuo Kimura | Organic-inorganic composite body |
| CN101702891A (en) * | 2007-07-03 | 2010-05-05 | 日本曹达株式会社 | Molding sheet for forming hard coat layer |
| JP5013526B2 (en) * | 2007-10-05 | 2012-08-29 | 日本曹達株式会社 | Hard coat film |
| WO2013118201A1 (en) * | 2012-02-08 | 2013-08-15 | 日本曹達株式会社 | Organic-inorganic composite thin film |
| US9255210B2 (en) * | 2012-03-02 | 2016-02-09 | Nippon Soda Co., Ltd. | Olefin based polymer-combined organic-inorganic composite and composition for forming same |
| TWI512058B (en) * | 2014-12-25 | 2015-12-11 | Chi Mei Corp | Photo-curing coating composition, photo-curing coating film and touch panel |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60199072A (en) * | 1984-03-24 | 1985-10-08 | Nippon Soda Co Ltd | Composition for coating and method of coating with it |
-
1984
- 1984-08-08 JP JP59164859A patent/JPS6143665A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60199072A (en) * | 1984-03-24 | 1985-10-08 | Nippon Soda Co Ltd | Composition for coating and method of coating with it |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6143665A (en) | 1986-03-03 |
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