JP2010013634A - Aqueous coating resin composition - Google Patents
Aqueous coating resin composition Download PDFInfo
- Publication number
- JP2010013634A JP2010013634A JP2009133196A JP2009133196A JP2010013634A JP 2010013634 A JP2010013634 A JP 2010013634A JP 2009133196 A JP2009133196 A JP 2009133196A JP 2009133196 A JP2009133196 A JP 2009133196A JP 2010013634 A JP2010013634 A JP 2010013634A
- Authority
- JP
- Japan
- Prior art keywords
- water
- resin composition
- weight
- group
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000000576 coating method Methods 0.000 title claims abstract description 58
- 239000011342 resin composition Substances 0.000 title claims abstract description 37
- 239000011248 coating agent Substances 0.000 title abstract description 55
- 239000000839 emulsion Substances 0.000 claims abstract description 66
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 39
- 230000007062 hydrolysis Effects 0.000 claims abstract description 37
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 37
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 14
- 239000000057 synthetic resin Substances 0.000 claims abstract description 14
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 89
- -1 III Chemical class 0.000 claims description 81
- 239000003973 paint Substances 0.000 claims description 53
- 239000000178 monomer Substances 0.000 claims description 47
- 238000009833 condensation Methods 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 31
- 230000005494 condensation Effects 0.000 claims description 29
- 125000005370 alkoxysilyl group Chemical group 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 23
- 239000004925 Acrylic resin Substances 0.000 claims description 11
- 229920000178 Acrylic resin Polymers 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000003945 anionic surfactant Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000012736 aqueous medium Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- 150000002896 organic halogen compounds Chemical group 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 238000003860 storage Methods 0.000 abstract description 16
- 239000000306 component Substances 0.000 description 46
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 33
- 239000010408 film Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 24
- 238000000034 method Methods 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 17
- 229920002554 vinyl polymer Polymers 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 238000007654 immersion Methods 0.000 description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 15
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 239000002320 enamel (paints) Substances 0.000 description 9
- 235000021317 phosphate Nutrition 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 239000004480 active ingredient Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 230000005660 hydrophilic surface Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000000872 buffer Substances 0.000 description 4
- 239000006172 buffering agent Substances 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 3
- UDWIZRDPCQAYRF-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C=C UDWIZRDPCQAYRF-UHFFFAOYSA-N 0.000 description 3
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 3
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 3
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 3
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 2
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 2
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 2
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- JMGZKPMMFXFSGK-UHFFFAOYSA-N 3-tri(propan-2-yloxy)silylpropyl prop-2-enoate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCOC(=O)C=C JMGZKPMMFXFSGK-UHFFFAOYSA-N 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 2
- 229940043264 dodecyl sulfate Drugs 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- FURYAADUZGZUGQ-UHFFFAOYSA-N phenoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 FURYAADUZGZUGQ-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000010454 slate Substances 0.000 description 2
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- 150000004688 heptahydrates Chemical class 0.000 description 1
- VRINOTYEGADLMW-UHFFFAOYSA-N heptyl(trimethoxy)silane Chemical compound CCCCCCC[Si](OC)(OC)OC VRINOTYEGADLMW-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000479 mixture part Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- LUZMYRZQOMVJCU-UHFFFAOYSA-N n-[2-(diethylamino)ethyl]-2-(5-methyl-2-propan-2-ylphenoxy)acetamide;4-methylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1.CCN(CC)CCNC(=O)COC1=CC(C)=CC=C1C(C)C LUZMYRZQOMVJCU-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- DCUJJWWUNKIJPH-UHFFFAOYSA-N nitrapyrin Chemical compound ClC1=CC=CC(C(Cl)(Cl)Cl)=N1 DCUJJWWUNKIJPH-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000005459 perfluorocyclohexyl group Chemical group 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011178 precast concrete Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 150000003342 selenium Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- DEWNCLAWVNEDHG-UHFFFAOYSA-M sodium;2-(2-methylprop-2-enoyloxy)ethanesulfonate Chemical compound [Na+].CC(=C)C(=O)OCCS([O-])(=O)=O DEWNCLAWVNEDHG-UHFFFAOYSA-M 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 1
- FHVAUDREWWXPRW-UHFFFAOYSA-N triethoxy(pentyl)silane Chemical compound CCCCC[Si](OCC)(OCC)OCC FHVAUDREWWXPRW-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
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- HILHCDFHSDUYNX-UHFFFAOYSA-N trimethoxy(pentyl)silane Chemical compound CCCCC[Si](OC)(OC)OC HILHCDFHSDUYNX-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
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- JZZBTMVTLBHJHL-UHFFFAOYSA-N tris(2,3-dichloropropyl) phosphate Chemical compound ClCC(Cl)COP(=O)(OCC(Cl)CCl)OCC(Cl)CCl JZZBTMVTLBHJHL-UHFFFAOYSA-N 0.000 description 1
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
本発明は、建築内外装、屋根、窯業系建材、自動車、家電用品、プラスチックなどに対する各種塗装の水性塗料として好適に用いられる、親水性表面を形成し得る水性塗料用樹脂組成物に関する。 The present invention relates to a resin composition for water-based paints capable of forming a hydrophilic surface, which is suitably used as a water-based paint for various coatings on architectural exteriors, roofs, ceramic building materials, automobiles, household appliances, plastics and the like.
近年、塗料の分野においても、公害対策あるいは省資源の観点より、有機溶剤を使用するものから、水溶性あるいは水分散樹脂への転換が試みられている。しかし、水性塗料は溶剤系塗料に比べ、塗膜性能が劣る傾向にあった。こういった状況下、水性塗料においても溶剤系塗料と同等の塗膜物性が要求され、特に耐汚染性といった高度な性能付与が要求されている。 In recent years, in the field of paints, from the viewpoint of pollution control or resource saving, attempts have been made to switch from using organic solvents to water-soluble or water-dispersed resins. However, water-based paints tended to be inferior in coating film performance compared to solvent-based paints. Under such circumstances, water-based paints are also required to have the same coating film properties as solvent-based paints, and in particular, are required to have high performance such as stain resistance.
塗料への耐汚染性付与方法としては、塗料中に加水分解性のシリコン化合物、特にオルガノシリケートを配合する方法が知られている（特許文献１）。この方法により形成した親水性塗膜は、油性の汚染物質の付着を抑制、さらに付着した汚染物質を降雨等の水滴で洗い流すことが可能であり、耐汚染性を発現する。また、上記方法の水性塗料への適用にあたり、アルコキシシリル基の加水分解・縮合を促進する化合物を併用することで耐汚染性を向上させることも知られている（特許文献２）。 As a method for imparting stain resistance to a paint, a method is known in which a hydrolyzable silicon compound, particularly an organosilicate is blended in the paint (Patent Document 1). The hydrophilic coating film formed by this method can suppress the adhesion of oily contaminants, and can wash away the adhered contaminants with water droplets such as rain, thereby exhibiting stain resistance. In addition, when applying the above method to water-based paints, it is also known to improve stain resistance by using a compound that promotes hydrolysis and condensation of alkoxysilyl groups (Patent Document 2).
しかしながら、上記方法の水性塗料への適用は、加水分解性のシリコン化合物を必然的に水を含有する水性塗料に添加することから、塗料中でシリコン化合物の加水分解・縮合が進行し、最終的に反応性が消失、耐汚染性が損なわれることとなり、アルコキシシリル基の加水分解・縮合を促進する化合物を併用すれば、さらに問題となる。このため、塗装においてシリコン化合物および／またはアルコキシシリル基の加水分解・縮合を促進する化合物を含む組成物を塗装開始時に添加し、シリコン化合物の反応性が消失する以前に完了させる、２液型の塗料形態とせざるを得ず、操作の煩雑さに欠点を有していた。 However, when the above method is applied to water-based paints, the hydrolyzable silicon compound is inevitably added to the water-based paint containing water. Further, the reactivity is lost and the stain resistance is impaired, and if a compound that promotes hydrolysis / condensation of the alkoxysilyl group is used in combination, a further problem arises. For this reason, a two-pack type composition that includes a silicon compound and / or a composition containing a compound that promotes hydrolysis / condensation of alkoxysilyl groups in coating is added at the start of coating, and is completed before the reactivity of the silicon compound disappears. It had to be in the form of a paint, and had a drawback in the complexity of operation.
本発明が解決しようとする課題は、１液型の塗料形態も可能な安定性と良好な耐汚染性を示す、シリコン化合物による親水性表面を形成し得る水性塗料用樹脂組成物を提供することである。 The problem to be solved by the present invention is to provide a resin composition for water-based paints capable of forming a hydrophilic surface with a silicon compound, which is capable of forming a one-component paint form and exhibits good stain resistance. It is.
本発明者は、合成樹脂エマルジョン、シリコン化合物および光酸発生剤を含有する水性樹脂組成物が通常の塗料の貯蔵条件である暗所での安定性を有する１液型の組成物となり得ること、得られる塗膜が通常の被塗物の使用条件である屋外暴露、その他の光暴露により優れた親水性表面を形成し得ることを見出した。
すなわち、
１）．
（Ｉ）合成樹脂エマルジョン
（II）下記一般式（１）で示されるシリコン化合物および／またはその部分加水分解縮合物
（Ｒ1Ｏ）4-aＳｉＲ2 a （１）
（式中、Ｒ1は同じかまたは異なり、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基または炭素数７〜１０のアラルキル基、Ｒ2は同じかまたは異なり、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基、または炭素数７〜１０のアラルキル基、ａは０〜２の整数。）
（III）光酸発生剤
を含有する水性塗料用樹脂組成物、
２）．
前記（II）シリコン化合物および／またはその部分加水分解縮合物が、オルガノシリケート（下記一般式（２）で示される化合物および／またはその部分加水分解縮合物）および／またはその変性物
（Ｒ3Ｏ）4Ｓｉ （２）
（式中、Ｒ3は同じかまたは異なり、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基または炭素数７〜１０のアラルキル基である１）に記載の水性塗料用樹脂組成物、
３）．
前記（II）シリコン化合物および／またはその部分加水分解縮合物をノニオン系界面活性剤および／またはアニオン系界面活性剤を用いて水性媒体中に分散して得られる乳化物として添加する１）または２）に記載の水性塗料用樹脂組成物、
４）．
前記（Ｉ）合成樹脂エマルジョンが、アルコキシシリル基含有単量体単位を有するアクリル系樹脂エマルジョンである１）〜３）のいずれか１項に記載の水性塗料用樹脂組成物、
５）．
さらに（IV）酸により活性化するアルコキシシリル基の加水分解・縮合を促進する化合物を含有する１）〜４）のいずれか１項に記載の水性塗料用樹脂組成物、
６）．
（IV）酸により活性化するアルコキシシリル基の加水分解・縮合を促進する化合物が酸性リン酸化合物の塩である５）に記載の水性塗料用樹脂組成物、
７）
（III）光酸発生剤が、有機ハロゲン化合物である１）〜６）の何れか１項に記載の水性塗料用樹脂組成物、
８）
（III）光酸発生剤が、ハロゲン含有トリアジン化合物、塩化ビニリデン共重合体、塩化ビニル共重合体、塩素化ポリオレフィンである１）〜７）の何れか１項に記載の水性塗料用樹脂組成物、
９）
１）〜８）の何れか１項に記載の（Ｉ）、（II）、（III）および必要に応じて（IV）を含有してなる一液型水性塗料用樹脂組成物、
に関する。
The inventor of the present invention is that an aqueous resin composition containing a synthetic resin emulsion, a silicon compound and a photoacid generator can be a one-component composition having stability in a dark place, which is a storage condition for ordinary paints. It was found that the obtained coating film can form an excellent hydrophilic surface by outdoor exposure or other light exposure which is a normal use condition of the object to be coated.
That is,
1).
(I) Synthetic resin emulsion (II) Silicon compound represented by the following general formula (1) and / or its partial hydrolysis condensate (R 1 O) 4-a SiR 2 a (1)
(Wherein R 1 is the same or different, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, R 2 is the same or different and has 1 carbon atom) C-10 alkyl group, C6-C10 aryl group, or C7-C10 aralkyl group, a is an integer of 0-2.)
(III) A resin composition for water-based paints containing a photoacid generator,
2).
The (II) silicon compound and / or a partial hydrolysis condensate thereof is an organosilicate (a compound represented by the following general formula (2) and / or a partial hydrolysis condensate thereof) and / or a modified product thereof (R 3 O 4 Si (2)
(In the formula, R 3 is the same or different and is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms). object,
3).
The above (II) silicon compound and / or a partially hydrolyzed condensate thereof is added as an emulsion obtained by dispersing it in an aqueous medium using a nonionic surfactant and / or an anionic surfactant 1) or 2 ) Resin composition for water-based paints according to
4).
The resin composition for water-based paints according to any one of 1) to 3), wherein the (I) synthetic resin emulsion is an acrylic resin emulsion having an alkoxysilyl group-containing monomer unit,
5).
The resin composition for water-based paints according to any one of 1) to 4), further comprising (IV) a compound that promotes hydrolysis and condensation of an alkoxysilyl group activated by an acid,
6).
(IV) The resin composition for aqueous coatings according to 5), wherein the compound that promotes hydrolysis / condensation of an alkoxysilyl group activated by an acid is a salt of an acidic phosphoric acid compound,
7)
(III) The resin composition for water-based paints according to any one of 1) to 6), wherein the photoacid generator is an organic halogen compound,
8)
(III) The resin composition for an aqueous coating material according to any one of 1) to 7), wherein the photoacid generator is a halogen-containing triazine compound, a vinylidene chloride copolymer, a vinyl chloride copolymer, or a chlorinated polyolefin. ,
9)
1) to 8) one-component water-based paint resin composition comprising (I), (II), (III) and (IV) as necessary,
About.
本発明の水性塗料用樹脂組成物は、貯蔵安定性が高く１液型の塗料形態が可能である。また本発明の組成物は、通常の被塗物の使用条件である屋外暴露、その他の光暴露により優れた親水性を有する塗膜形成し得る。 The resin composition for water-based paints of the present invention has high storage stability and can be in the form of a one-component paint. Further, the composition of the present invention can form a coating film having excellent hydrophilicity by outdoor exposure, which is a normal use condition of an object to be coated, or by other light exposure.
以下に本発明をその実施の形態に基づき詳細に説明する。 Hereinafter, the present invention will be described in detail based on an embodiment thereof.
（Ｉ）合成樹脂エマルジョン
本発明に使用可能な合成樹脂エマルションとしては、アクリル系樹脂エマルジョン、ウレタン樹脂エマルジョン、ふっ素樹脂エマルジョン、エポキシ樹脂エマルジョン、ポリエステル樹脂エマルジョン、アルキド樹脂エマルジョン、メラミン樹脂エマルジョンなどが挙げられるが、これらに限定されるわけではない。また、これらは単独で使用しても２種以上を併用しても良い。これらの中でコスト、樹脂設計の自由度の高さなどからアクリル系樹脂エマルジョンが有利である。
(I) Synthetic resin emulsion Examples of the synthetic resin emulsion that can be used in the present invention include acrylic resin emulsion, urethane resin emulsion, fluorine resin emulsion, epoxy resin emulsion, polyester resin emulsion, alkyd resin emulsion, and melamine resin emulsion. However, it is not limited to these. These may be used alone or in combination of two or more. Among these, acrylic resin emulsions are advantageous because of their high cost and high degree of freedom in resin design.
アクリル系樹脂エマルジョンは、（Ａ）アクリル系単量体、（Ｂ）（Ａ）と共重合可能な単量体とをラジカル共重合により得られるものが使用できる。 As the acrylic resin emulsion, those obtained by radical copolymerization of (A) an acrylic monomer and (B) a monomer copolymerizable with (A) can be used.
（Ａ）アクリル系単量体はアルキルまたはアラルキル基を有するメタアクリレートおよび／またはアクリレートであり、その具体例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｉｓｏ−プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉｓｏ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ベンジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、イソデシル（メタ）メタクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボニル（メタ）アクリレートなどが上げられる。尚、(メタ)アクリレートとは、本明細書中ではメタアクリレートおよび／またはアクリレートを表すこととする。 (A) The acrylic monomer is a methacrylate and / or acrylate having an alkyl or aralkyl group, and specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) methacrylate, Examples include lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, and isobonyl (meth) acrylate. In this specification, (meth) acrylate represents methacrylate and / or acrylate.
この中で、炭素数３以上、１２以下のアルキル基を有する（メタ）アクリレート単量体を用いれば、安定な乳化重合が可能となるとともに、塗膜の耐候性などの耐久性の点で好ましく、特に、分岐アルキル基および／または環状アルキル基を有する（メタ）アクリレート単量体、たとえばｉｓｏ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、イソボニル（メタ）アクリレートが好ましい。 Among these, if a (meth) acrylate monomer having an alkyl group having 3 or more and 12 or less carbon atoms is used, stable emulsion polymerization is possible and preferable from the viewpoint of durability such as weather resistance of the coating film. In particular, (meth) acrylate monomers having branched and / or cyclic alkyl groups, such as iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate and isobornyl (meth) acrylate are preferred.
単量体総量中の（Ａ）成分の量は特に限定されないが、単量体の総量１００重量部に対して５０〜９９重量部が塗膜の耐候性などの耐久性の点で好ましい。さらに好ましくは、８０〜９９重量部である。 The amount of component (A) in the total amount of monomers is not particularly limited, but 50 to 99 parts by weight with respect to 100 parts by weight of the total amount of monomers is preferable in terms of durability such as weather resistance of the coating film. More preferably, it is 80-99 weight part.
（Ｂ）（Ａ）と共重合可能な単量体は、（Ａ）とは異なり、これらと共重合可能なものであれば、特に限定はされない。その具体例としては、スチレン、α−メチルスチレン、クロロスチレン、４−ヒドロキシスチレン、ビニルトルエンなどの芳香族炭化水素系ビニル単量体；酢酸ビニル、プロピオン酸ビニル、バーサチック酸ビニル、ジアリルフタレートなどのビニルエステルやアリル化合物；（メタ）アクリロニトリルなどのニトリル基含有ビニル系単量体；グリシジル（メタ）アクリレートなどのエポキシ基含有ビニル系単量体；２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシエチルビニルエーテル、ヒドロキシスチレン、アロニクスＭ−５７００（東亜合成化学（株）製）、ｐｌａｃｃｅｌＦＡ−１、ｐｌａｃｃｅｌＦＡ−４、ｐｌａｃｃｅｌＦＭ−１、ｐｌａｃｃｅｌＦＭ−４（以上、ダイセル化学（株）製）、ＨＥ−１０、ＨＥ−２０、ＨＰ−１０、ＨＰ−２０（以上日本触媒化学（株）製）、ブレンマーＰＥＰシリーズ、ブレンマーＮＫＨ−５０５０、ブレンマーＧＬＭ（以上日本油脂（株）製）、水酸基含有ビニル系変性ヒドロキシアルキルビニル系モノマーなどの水酸基含有ビニル系単量体；東亜合成化学（株）製のマクロモノマーであるＡＳ−６、ＡＮ−６、ＡＡ−６、ＡＢ−６、ＡＫ−５などの化合物、ビニルメチルエーテル、プロピレン、ブタジエン等が挙げられる。 (B) Unlike (A), the monomer copolymerizable with (A) is not particularly limited as long as it is copolymerizable with these. Specific examples thereof include aromatic hydrocarbon vinyl monomers such as styrene, α-methylstyrene, chlorostyrene, 4-hydroxystyrene, and vinyl toluene; vinyl acetate, vinyl propionate, vinyl versatate, diallyl phthalate, and the like. Vinyl esters and allyl compounds; Nitrile group-containing vinyl monomers such as (meth) acrylonitrile; Epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate; 2-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, 2-hydroxyethyl vinyl ether, hydroxystyrene, Aronics M-5700 (manufactured by Toa Gosei Kagaku Co., Ltd.), packageFA-1, packageFA-4, packageFM-1, and packageFM-4 (and above) Daicel Chemical Co., Ltd.), HE-10, HE-20, HP-10, HP-20 (manufactured by Nippon Shokubai Chemical Co., Ltd.), Bremer PEP series, Bremer NKH-5050, Bremer GLM Co., Ltd.), hydroxyl-containing vinyl monomers such as hydroxyl-containing vinyl-modified hydroxyalkyl vinyl monomers; AS-6, AN-6, AA-6, AB which are macromonomers manufactured by Toa Synthetic Chemical Co., Ltd. -6, compounds such as AK-5, vinyl methyl ether, propylene, butadiene and the like.
さらに、親水性を有するビニル系単量体も使用可能である。使用可能な親水性基を有するビニル系単量体としては、スチレンスルホン酸ナトリウム、２−スルホエチルメタクリレートナトリウム、２−スルホエチルメタクリレートアンモニウム、ポリオキシアルキレン鎖を有するビニル系単量体が挙げられる。ポリオキシアルキレン鎖を有するビニル系単量体に限定はないが、ポリオキアルキレン鎖を有するアクリル酸エステル又はメタクリル酸エステルが好ましく、具体例としては日油（株）製ブレンマーＰＥ−９０、ＰＥ−２００、ＰＥ−３５０、ＡＥ−９０、ＡＥ−２００、ＡＥ−３５０、ＰＰ−５００、ＰＰ−８００、ＰＰ−１０００、ＡＰ−４００、ＡＰ−５５０、ＡＰ−８００、７００ＰＥＰ−３５０Ｂ、１０ＰＥＰ−５５０Ｂ、５５ＰＥＴ−４００、３０ＰＥＴ−８００、５５ＰＥＴ−８００、３０ＰＰＴ−８００、５０ＰＰＴ−８００、７０ＰＰＴ−８００、ＰＭＥ−１００、ＰＭＥ−２００、ＰＭＥ−４００、ＰＭＥ−１０００、ＰＭＥ−４０００、ＡＭＥ−４００、５０ＰＯＥＰ−８００Ｂ、５０ＡＯＥＰ−８００Ｂ、ＡＥＰ、ＡＥＴ、ＡＰＴ、ＰＬＥ、ＡＬＥ、ＰＳＥ、ＡＳＥ、ＰＫＥ、ＡＫＥ、ＰＮＥ、ＡＮＥ、ＰＮＰ、ＡＮＰ、ＰＮＥＰ−６００、共栄社化学（株）製ライトエステル１３０ＭＡ、０４１ＭＡ、ＭＴＧ、ライトアクリレートＥＣ−Ａ、ＭＴＧ−Ａ、１３０Ａ、ＤＰＭ−Ａ、Ｐ−２００Ａ、ＮＰ−４ＥＡ、ＮＰ−８ＥＡ、ＥＨＤＧ−Ａ、日本乳化剤（株）製ＭＡ−３０、ＭＡ−５０、ＭＡ−１００、ＭＡ−１５０、ＲＭＡ−１１２０、ＲＭＡ−５６４、ＲＭＡ−５６８、ＲＭＡ−５０６、ＭＰＧ１３０−ＭＡ、Ａｎｔｏｘ ＭＳ−６０、ＭＰＧ−１３０ＭＡ、ＲＭＡ−１５０Ｍ、ＲＭＡ−３００Ｍ、ＲＭＡ−４５０Ｍ、ＲＡ−１０２０、ＲＡ−１１２０、ＲＡ−１８２０、新中村化学工業（株）製ＮＫ−ＥＳＴＥＲ Ｍ−２０Ｇ、Ｍ−４０Ｇ、Ｍ−９０Ｇ、Ｍ−２３０Ｇ、ＡＭＰ−１０Ｇ、ＡＭＰ−２０Ｇ、ＡＭＰ−６０Ｇ、ＡＭ−９０Ｇ、ＬＡなどがあげられる。 Furthermore, hydrophilic vinyl monomers can also be used. Examples of the vinyl monomer having a hydrophilic group that can be used include sodium styrenesulfonate, sodium 2-sulfoethyl methacrylate, 2-sulfoethyl methacrylate ammonium, and vinyl monomers having a polyoxyalkylene chain. Although there is no limitation in the vinyl-type monomer which has a polyoxyalkylene chain, the acrylic acid ester or methacrylic acid ester which has a polyoxyalkylene chain is preferable, As a specific example, Blenmer PE-90, PE- by NOF Corporation is mentioned. 200, PE-350, AE-90, AE-200, AE-350, PP-500, PP-800, PP-1000, AP-400, AP-550, AP-800, 700PEP-350B, 10PEP-550B, 55PET-400, 30PET-800, 55PET-800, 30PPT-800, 50PPT-800, 70PPT-800, PME-100, PME-200, PME-400, PME-1000, PME-4000, AME-400, 50POEP- 800B, 50AOEP-800B, AEP, ET, APT, PLE, ALE, PSE, ASE, PKE, AKE, PNE, ANE, PNP, ANP, PNEP-600, Kyoeisha Chemical Co., Ltd. light ester 130MA, 041MA, MTG, light acrylate EC-A, MTG- A, 130A, DPM-A, P-200A, NP-4EA, NP-8EA, EHDG-A, MA-30 manufactured by Nippon Emulsifier Co., Ltd., MA-50, MA-100, MA-150, RMA-1120, RMA-564, RMA-568, RMA-506, MPG130-MA, Antox MS-60, MPG-130MA, RMA-150M, RMA-300M, RMA-450M, RA-1020, RA-1120, RA-1820, new Nakamura Chemical Co., Ltd. NK-ESTER M-20G, M-40G, M-9 G, M-230G, AMP-10G, AMP-20G, AMP-60G, AM-90G, LA, and the like.
また、ポリエチレングリコールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、トリアリルシアヌレート、アリル（メタ）アクリレート、ジビニルベンゼンなどの重合性の不飽和結合を２つ以上有する単量体を使用することも可能である。この場合、生成した粒子内部に架橋を有する構造となり、形成した塗膜の耐水性が向上する。 In addition, a monomer having two or more polymerizable unsaturated bonds such as polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, triallyl cyanurate, allyl (meth) acrylate, divinylbenzene or the like is used. It is also possible. In this case, the generated particles have a structure having cross-linking, and the water resistance of the formed coating film is improved.
また、トリフルオロ（メタ）アクリレート、ペンタフルオロ（メタ）アクリレート、パーフルオロシクロヘキシル（メタ）アクリレート、２，２，３，３−テトラフルオロプロピルメタクリレート、β−（パーフルオロオクチル）エチル（メタ）アクリレートなどのふっ素含有ビニル系単量体を使用することにより高度な撥水・撥油を付与することも可能である。 Moreover, trifluoro (meth) acrylate, pentafluoro (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, β- (perfluorooctyl) ethyl (meth) acrylate, etc. It is also possible to impart high water and oil repellency by using a fluorine-containing vinyl monomer.
また、ダイアセトンアクリルアミド、メチルビニルケトン等のカルボニル基含有ビニル系単量体を用い、ヒドラジンおよび／またはヒドラジド基を含有する化合物を配合することにより、架橋性を付与することも可能であり、形成した塗膜の耐水性が向上する。 It is also possible to impart crosslinkability by using a carbonyl group-containing vinyl monomer such as diacetone acrylamide or methyl vinyl ketone and blending a compound containing hydrazine and / or hydrazide group. The water resistance of the coated film is improved.
単量体総量中の（Ｂ）成分の量は特に限定されないが、単量体の総量１００重量部に対して（Ｂ）成分が０．１〜５０重量部含まれていることが、経済性、架橋性などの機能付与、エマルジョンの安定性の点で好ましい。親水性を有するビニル系単量体について、さらに好ましくは、０．５〜３重量部である。 The amount of component (B) in the total amount of monomers is not particularly limited, but it is economical that component (B) is contained in an amount of 0.1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers. From the viewpoint of imparting functions such as crosslinkability and stability of the emulsion. The vinyl monomer having hydrophilicity is more preferably 0.5 to 3 parts by weight.
さらに（Ｃ）成分としてアルコキシシリル基含有単量体を用いれば、塗膜の耐水性、耐候性などの耐久性向上、（II）のシリコン化合物および／またはその部分加水分解縮合物による耐汚染性効果を向上させることから好ましい。 Furthermore, if an alkoxysilyl group-containing monomer is used as the component (C), durability of the coating film is improved, such as water resistance and weather resistance, and contamination resistance due to the silicon compound and / or its partial hydrolysis condensate of (II) It is preferable because the effect is improved.
（Ｃ）アルコキシシリル基含有単量体は、
Ｒ4Ｒ5 (3-b)Ｓｉ（ＯＲ6）b （３）
（式中、Ｒ4は重合性二重結合を有する１価有機基、Ｒ5は炭素数１〜４のアルキル基、Ｒ6は炭素数１〜４のアルキル基、ｂは１〜３）で示される有機ケイ素化合物で、アルコキシ基を有し、反応性二重結合を有する化合物である。その具体例としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリプロポキシシラン、ビニルトリイソプロポキシシラン、ビニルメチルジメトキシシラン、ビニルメチルジエトキシシランなどのビニルシラン類；γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルトリプロポキシシラン、γ−（メタ）アクリロキシプロピルトリイソプロポキシシラン、γ−（メタ）アクリロキシプロピルトリブトキシシラン、γ−（メタ）アクリロキシプロピルメチルジメトキシシラン、γ−（メタ）アクリロキシプロピルメチルジエトキシシラン、γ−（メタ）アクリロキシプロピルメチルジプロポキシシラン、γ−（メタ）アクリロキシプロピルメチルジイソプロポキシシラン、γ−（メタ）アクリロキシプロピルメチルジブトキシシランなどのアクリルシラン類などがあげられ、これらを１種又は２種以上併用して用いることができる。
(C) The alkoxysilyl group-containing monomer is
R 4 R 5 (3-b) Si (OR 6 ) b (3)
(Wherein R 4 is a monovalent organic group having a polymerizable double bond, R 5 is an alkyl group having 1 to 4 carbon atoms, R 6 is an alkyl group having 1 to 4 carbon atoms, and b is 1 to 3). The organosilicon compound shown is a compound having an alkoxy group and a reactive double bond. Specific examples thereof include vinylsilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane; γ- (meth) acryloxypropyl Trimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltripropoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, γ- (meth) acryloxypropyltri Butoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxy Propyl methyl diisopropoxy silane, acrylic silane such as .gamma. (meth) acryloxy propyl methyl dibutoxy silane and the like, can be used in combination of these one or more.
（Ｃ）成分の使用量は特に限定されないが、単量体の総量１００重量部に対して０．１〜２０重量部が好ましく、さらに好ましくは０．５〜１０重量部用いることによって、組成物の貯蔵時の架橋、過度の架橋による脆化を抑制し、耐久性を向上させることができる。 Although the usage-amount of (C) component is not specifically limited, 0.1-20 weight part is preferable with respect to 100 weight part of total amounts of a monomer, More preferably, by using 0.5-10 weight part, it is a composition. It is possible to suppress cross-linking during storage and embrittlement due to excessive cross-linking and improve durability.
（Ｃ）成分のＲ6の炭素数は、アルコキシシリル基の加水分解・縮合の反応性と反比例し、炭素数が増えるにつれ反応性は低下する傾向がある。エマルジョン中での安定性を考慮すれば、２〜４が好ましく、上記具体例のなかでγ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルトリイソプロポキシシラン、γ−（メタ）アクリロキシプロピルメチルジエトキシシランが好ましい。また、コア／シェル型エマルジョンとした（Ｉ）において、コア部にＲ6の炭素数の低い（Ｃ）成分（たとえばメトキシシリル基を有するγ−（メタ）アクリロキシプロピルメチルジメトキシシラン）、シェル部にＲ6の炭素数の高い（Ｃ）成分（たとえばエトキシシリル基を有するγ−（メタ）アクリロキシプロピルトリエトキシシラン）を用いれば、コア部に緩やかな架橋構造が導入され、柔軟性を損なうことなく、シェル部の安定化された反応性とともに耐水性、塗膜強度を向上させることができる。 The carbon number of R 6 of the component (C) is inversely proportional to the reactivity of hydrolysis / condensation of the alkoxysilyl group, and the reactivity tends to decrease as the carbon number increases. Considering the stability in the emulsion, 2 to 4 are preferable. Among the above specific examples, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, γ- (Meth) acryloxypropylmethyldiethoxysilane is preferred. Further, in (I), which is a core / shell type emulsion, the component (C) having a low carbon number of R 6 (for example, γ- (meth) acryloxypropylmethyldimethoxysilane having a methoxysilyl group) in the core portion, shell portion If a component (C) having a high carbon number of R 6 (for example, γ- (meth) acryloxypropyltriethoxysilane having an ethoxysilyl group) is used, a moderate cross-linked structure is introduced into the core portion and the flexibility is impaired. In addition, the water resistance and the coating strength can be improved together with the stabilized reactivity of the shell portion.
（Ｃ）成分を用いる場合、（Ａ）成分に炭素数４以上のアルキル基および／又はシクロアルキル基を有するメタクリル酸エステルを単量体の総量１００重量部中に６０重量部以上使用するとエマルジョン中のアルコキシシリル基の安定性が大きく向上する。 When component (C) is used, if component (A) is 60 parts by weight or more of a methacrylic acid ester having an alkyl group and / or cycloalkyl group having 4 or more carbon atoms in 100 parts by weight of the total monomer, This greatly improves the stability of the alkoxysilyl group.
（Ｂ）成分に、水酸基含有ビニル系単量体および／またはポリオキシアルキレン鎖を有するビニル系単量体を単量体の総量１００重量部中に０．５〜２０重量部用いると、（Ｃ）成分、（II）のシリコン化合物および／またはその部分加水分解縮合物のアルコキシシリル基の安定性を向上させ、さらにエマルジョンの機械的安定性、化学的安定性を向上させることができる。なかでも、ポリオキシアルキレン鎖を有するビニル系単量体が特に有効である。 When 0.5 to 20 parts by weight of a hydroxyl group-containing vinyl monomer and / or a vinyl monomer having a polyoxyalkylene chain is used as the component (B) in 100 parts by weight of the total monomer, (C ), The stability of the alkoxysilyl group of the component (II) silicon compound and / or its partially hydrolyzed condensate, and the mechanical and chemical stability of the emulsion can be improved. Of these, vinyl monomers having a polyoxyalkylene chain are particularly effective.
次にアクリル系樹脂エマルジョンの製造方法について説明する。 Next, the manufacturing method of an acrylic resin emulsion is demonstrated.
（Ａ）、（Ｂ）成分からなる単量体混合物を公知の乳化重合法、たとえばバッチ重合法、モノマー滴下重合法、乳化モノマー滴下重合法などにより重合して得られる。 A monomer mixture comprising the components (A) and (B) is obtained by polymerization by a known emulsion polymerization method, for example, a batch polymerization method, a monomer dropping polymerization method, an emulsion monomer dropping polymerization method or the like.
また、コア／シェル型エマルションの製造は、コア部をなす単量体混合物を公知の乳化重合法で重合し、得られたコア成分の水性分散液の存在下に、シェル部をなす単量体混合物を公知の乳化重合法で重合し、シェル成分を導入する。なお、コア部、シェル部各成分内の重合は、何回かに分割して行ってもよい。 In addition, the production of the core / shell type emulsion is carried out by polymerizing the monomer mixture forming the core part by a known emulsion polymerization method, and in the presence of the obtained aqueous dispersion of the core component, the monomer forming the shell part. The mixture is polymerized by a known emulsion polymerization method, and a shell component is introduced. In addition, you may divide | segment several times and superpose | polymerize in each component of a core part and a shell part.
乳化重合に際しては、通常用いられるアニオン系またはノニオン系の界面活性剤を用いることができる。 In emulsion polymerization, a commonly used anionic or nonionic surfactant can be used.
乳化重合に用いる水性媒体としては、水を必須成分として含有していればよく、他の有機溶剤を含有していても構わない。他の有機溶剤としては、エタノール、イソプロパノールなどのアルコール系溶剤；プロピレングリコールなどのグリコール系溶剤；エチレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールジメチルエーテルなどのエーテル系溶剤、プロピレングリコールモノブチルエーテルアセテート、（株）チッソ製ＣＳ−１２などのエステル系溶剤があげられるが、エマルジョンの重合時の安定性や環境の観点から有機溶剤は含有しない方が好ましい。 The aqueous medium used for the emulsion polymerization only needs to contain water as an essential component, and may contain other organic solvents. Other organic solvents include alcohol solvents such as ethanol and isopropanol; glycol solvents such as propylene glycol; ether solvents such as ethylene glycol monobutyl ether, propylene glycol monobutyl ether and propylene glycol dimethyl ether, propylene glycol monobutyl ether acetate, An ester solvent such as CS-12 manufactured by Chisso Corporation may be mentioned, but it is preferable not to contain an organic solvent from the viewpoint of stability during polymerization of the emulsion and the environment.
アニオン系界面活性剤としては、たとえばポリオキシエチレンノニルフェニルエーテルサルフェート、ポリオキシエチレン多環フェニルエーテルサルフェートなどのポリオキシエチレンアリールエーテルサルフェート、ポリオキシエチレントリデシルエーテルサルフェートなどのポリオキシエチレンアルキルエーテルサルフェートなどのポリオキシエチレン鎖を有する硫酸エステル；ラウリルスルホン酸、ドデシルベンゼンスルホン酸、アルキルナフタレンスルホン酸などのスルホン酸；ラウリルサルフェートなどの硫酸エステル；ジ（２−エチルヘキシル）スルホコハク酸などのアルキルスルホコハク酸などおよびそれらの塩があげられる。 Examples of the anionic surfactant include polyoxyethylene aryl ether sulfate such as polyoxyethylene nonyl phenyl ether sulfate, polyoxyethylene polycyclic phenyl ether sulfate, and polyoxyethylene alkyl ether sulfate such as polyoxyethylene tridecyl ether sulfate. Sulfates having a polyoxyethylene chain; sulfonic acids such as lauryl sulfonic acid, dodecylbenzene sulfonic acid, alkylnaphthalene sulfonic acid; sulfate esters such as lauryl sulfate; alkyl sulfosuccinic acids such as di (2-ethylhexyl) sulfosuccinic acid, and the like These salts are mentioned.
アニオン系界面活性剤の中和カチオン種は種々選択できるが、アルカリ金属、たとえばナトリウムまたはカリウムイオンを用いた界面活性剤を用いれば、（II）シリコン化合物、（Ｃ）成分の安定性を向上させることができる。 Various types of neutralized cation species of an anionic surfactant can be selected. If a surfactant using an alkali metal such as sodium or potassium ion is used, the stability of (II) silicon compound and (C) component is improved. be able to.
また、ノニオン系界面活性剤としては、たとえばポリオキシエチレンアルキルエ−テル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン−ポリオキシプロピレンブロック共重合体、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステルなどのポリオキシエチレン鎖を有するもの；ソルビタン脂肪酸エステル、グリセリン脂肪酸エステルなどの水酸基を有するもの；信越化学工業（株）製ＫＦ−３５１、ＫＦ−３５２、ＫＦ−３５３、ＫＦ−３５４、ＫＦ−３５５、ＫＦ−６１５、ＫＦ−６１８、ＫＦ−９４５、ＫＦ−９０７、Ｘ−２２−６００８、Ｘ−２２−８１１、Ｘ−２２−８１２、東レ・ダウコーニング社製ＳＨ３７４８、ＳＨ３７４９、ＳＨ３７７１、ＳＨ８４００、ＳＦ８４１０、ＳＦ８７００などの片末端および／または両末端および／または側鎖をポリアルキレンオキシドで変性したポリオルガノシロキサンであるシリコーン系界面活性剤などがあげられる。 Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid. Those having a polyoxyethylene chain such as ester; those having a hydroxyl group such as sorbitan fatty acid ester and glycerin fatty acid ester; KF-351, KF-352, KF-353, KF-354, KF- manufactured by Shin-Etsu Chemical Co., Ltd. 355, KF-615, KF-618, KF-945, KF-907, X-22-6008, X-22-811, X-22-812, SH3748, SH3749, SH3771, SH8400 manufactured by Toray Dow Corning SF8410, such as one terminal and / or both ends and / or side chains of the silicone-based surfactant is a modified polyorganosiloxane polyalkylene oxides such SF8700 and the like.
本発明においては、界面活性剤として１分子中に不飽和基を有する、いわゆる反応性乳化剤を用いることが組成物およびこれを用いた水性塗料での泡立ち抑制、得られる塗膜の耐水性、耐候性の点で好ましい。また、特に分子内にポリオキシアルキレン基を有する反応性乳化剤を用いた場合には、機械的安定性を向上させることができる。 In the present invention, the use of a so-called reactive emulsifier having an unsaturated group in one molecule as a surfactant suppresses foaming in a composition and an aqueous paint using the composition, and the water resistance and weather resistance of the resulting coating film. From the viewpoint of sex. In particular, when a reactive emulsifier having a polyoxyalkylene group in the molecule is used, the mechanical stability can be improved.
かかる反応性乳化剤の具体例としては、たとえば、(株)ＡＤＥＫＡ製アデカリアソープＳＲ−０５、ＳＲ−１０、ＳＲ−２０、ＳＲ−１０２５、ＳＲ−２０２５、ＳＲ−３０２５，ＳＲ−１０Ｓ、ＮＥ−１０、ＮＥ−２０、ＮＥ−３０、ＮＥ−４０、ＳＥ−１０、ＳＥ−２０、ＳＥ−１０Ｓ、ＥＲ−１０、ＥＲ−２０、ＥＲ−３０、ＥＲ−４０）、日本乳化剤（株）製Ａｎｔｏｘ−ＭＳ−６０、ＲＭＡ−１１２０、ＲＭＡ−５６４、ＲＭＡ−５６８、ＲＭＡ−５０６、第一工業製薬（株）製アクアロンＫＨ−０５、ＫＨ−１０、ＲＮ−２０、ＲＮ−３０、ＲＮ−５０、ＲＮ−２０２５、ＨＳ−１０、ＨＳ−２０、ＨＳ−１０２５、ＢＣ０５、ＢＣ１０、ＢＣ０５１５、ＢＣ１０２５、三洋化成工業（株）製エレミノールＪＳ−２、ＪＳ−２０、ＲＳ−３０、花王（株）製ラテムルＳ−１８０、Ｓ−１８０Ａ、ＰＤ−１０４、ＰＤ−４２０、ＰＤ−４３０などがあげられる。 Specific examples of such a reactive emulsifier include, for example, Adeka Soap SR-05, SR-10, SR-20, SR-1025, SR-2025, SR-3025, SR-3025, SR-10S, NE-A manufactured by ADEKA Corporation. 10, NE-20, NE-30, NE-40, SE-10, SE-20, SE-10S, ER-10, ER-20, ER-30, ER-40), Antox manufactured by Nippon Emulsifier Co., Ltd. -MS-60, RMA-1120, RMA-564, RMA-568, RMA-506, Aqualon KH-05, KH-10, RN-20, RN-30, RN-50, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. RN-2025, HS-10, HS-20, HS-1025, BC05, BC10, BC0515, BC1025, Elyonol JS-2, JS-20 manufactured by Sanyo Chemical Industries, Ltd. RS-30, manufactured by Kao Corp. LATEMUL S-180, S-180A, such as PD-104, PD-420, PD-430 and the like.
前記界面活性剤は、単独または２種以上を混合して用いることができる。界面活性剤の総使用量は、単量体全量１００重量部に対して有効成分量として１０重量部以下、好ましくは０．５〜８重量部である。 The surfactants can be used alone or in admixture of two or more. The total amount of the surfactant used is 10 parts by weight or less, preferably 0.5 to 8 parts by weight as the amount of active ingredient with respect to 100 parts by weight of the total amount of monomers.
重合開始剤としては、特に限定はなく、アゾビス−２−メチルブチロニトリルなどのアゾ化合物；過硫酸カリウムなどの無機過酸化物；クメンハイドロパーオキサイドなどの有機過酸化物；過酸化物と還元剤を組み合わせるレドックス系などの公知の重合開始剤を挙げることができる。それらの中でも重合をより安定に行なうために、重合開始剤としてレドックス系を用いることが望ましい。また、重合中の混合液の安定性を保持し、重合を安定に行なうためには、温度は７０℃以下、好ましくは４０〜６５℃であり、塩基および／または緩衝剤を用いてｐＨは５〜９に調整することが好ましい。 The polymerization initiator is not particularly limited. An azo compound such as azobis-2-methylbutyronitrile; an inorganic peroxide such as potassium persulfate; an organic peroxide such as cumene hydroperoxide; a peroxide and a reduction Known polymerization initiators such as a redox system combined with an agent can be exemplified. Among them, it is desirable to use a redox system as a polymerization initiator in order to perform polymerization more stably. Further, in order to maintain the stability of the mixed solution during the polymerization and perform the polymerization stably, the temperature is 70 ° C. or lower, preferably 40 to 65 ° C., and the pH is 5 using a base and / or a buffer. It is preferable to adjust to ~ 9.
前記レドックス系に用いる開始剤として、たとえば、過硫酸カリウム、過硫酸アンモニウム、過酸化水素、ｔ−ブチルハイドロパーオキサイド、ベンゾイルパーオキサイド、クメンハイドロパーオキサイド、ｔ−ブチルパーオキシラウレートなどがあげられ、これらに組み合わせる還元剤としては、酸性亜硫酸ナトリウム、ロンガリット（Ｂｒｕｇｇａｍａｎｎ Ｃｈｅｍｉｃａｌ ＵＳ製、Ｓｏｄｉｕｍ ｆｏｒｍａｌｄｅｈｙｄｅ ｓｕｌｆｏｘｙｌａｔｅ）、Ｂｒｕｇｇｏｌｉｔｅ ＦＦ−６（Ｂｒｕｇｇａｍａｎｎ Ｃｈｅｍｉｃａｌ ＵＳ製、２−ｈｙｄｒｏｘｙ−２−ｓｕｌｆｉｎａｔｅ−ａｃｅｔｉｃ−ａｃｉｄ ｄｉ−ｓｏｄｉｕｍ ｓａｌｔ、Ｓｏｄｉｕｍ ｓｕｌｆｉｔｅ、２−ｈｙｄｒｏｘｙ−２−ｓｕｌｆｏｎａｔｅ−ａｃｅｔｉｃ−ａｃｉｄ ｄｉ−ｓｏｄｉｕｍ ｓａｌｔ混合物）、二酸化チオ尿素、Ｌ−アスコルビン酸などがあげられる。特に、ｔ−ブチルハイドロパーオキサイド、ベンゾイルパーオキサイド、クメンハイドロパーオキサイド等の有機過酸化物とロンガリット、Ｂｒｕｇｇｏｌｉｔｅ ＦＦ−６または二酸化チオ尿素との組み合わせが好ましい。 Examples of the initiator used for the redox system include potassium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, t-butyl peroxylaurate, and the like. Examples of the reducing agent to be combined with these include acidic sodium sulfite, Rongalite (manufactured by Bruggamann Chemical US, Sodium formaldehydrate sulfonate), Bruggolite FF-6 (manufactured by Brugmann Chemical US, 2-hyultic in USA) Sodium sulfide, 2-hydroxy-2-sulfonate-a etic-acid di-sodium salt mixture), thiourea dioxide, etc. L- ascorbic acid. In particular, a combination of an organic peroxide such as t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide and the like and Rongalite, Bruggolite FF-6 or thiourea dioxide is preferable.
なお、還元剤は、環境への配慮からホルムアルデヒド発生のないＢｒｕｇｇｏｌｉｔｅ ＦＦ−６、二酸化チオ尿素が特に好ましい。 Note that the reducing agent is particularly preferably Bruggolite FF-6 or thiourea dioxide which does not generate formaldehyde in consideration of the environment.
前記重合開始剤の使用量は、単量体全量１００重量部に対して０．０１〜１０部、好ましくは０．０５〜５重量部である。かかる重合開始剤の使用量が０．０１重量部未満である場合には、重合が進行しにくくなることがあり、１０重量部を超える場合には、生成する重合体の分子量が低下する傾向がある。 The amount of the polymerization initiator used is 0.01 to 10 parts, preferably 0.05 to 5 parts by weight based on 100 parts by weight of the total amount of monomers. When the amount of the polymerization initiator used is less than 0.01 parts by weight, the polymerization may be difficult to proceed. When the amount exceeds 10 parts by weight, the molecular weight of the produced polymer tends to decrease. is there.
また、重合開始剤の触媒活性を安定的に付与するために、硫酸鉄などの２価の鉄イオンを含む化合物とエチレンジアミン四酢酸二ナトリウムなどのキレート化剤を用いてもよい。かかるキレート化剤の使用量は、単量体全量１００重量部に対して０．０００１〜１重量部、好ましくは０．００１〜０．５重量部である。 In order to stably impart the catalytic activity of the polymerization initiator, a compound containing a divalent iron ion such as iron sulfate and a chelating agent such as disodium ethylenediaminetetraacetate may be used. The amount of the chelating agent used is 0.0001 to 1 part by weight, preferably 0.001 to 0.5 part by weight, based on 100 parts by weight of the total amount of monomers.
重合体の分子量を調節するために連鎖移動剤の添加も可能である。連鎖移動剤としては公知のもの、たとえば、ｎ−ドデシルメルカプタン、ｔｅｒｔ−ドデシルメルカプタン、ｎ−ブチルメルカプタン、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン、γ−メルカプトプロピルメチルジエトキシシラン等のメルカプタン系化合物、クロロホルム、四塩化炭素等の有機ハロゲン化物、スルフィドベンゼン、イソプロピルベンゼン、塩化第二鉄等が挙げられる。かかる連鎖移動剤の使用量は、単量体全量１００重量部に対して０．０１〜５重量部、好ましくは０．０５〜１重量部である。 Chain transfer agents can be added to control the molecular weight of the polymer. Known chain transfer agents such as n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, Examples include mercaptan compounds such as γ-mercaptopropylmethyldiethoxysilane, organic halides such as chloroform and carbon tetrachloride, sulfide benzene, isopropylbenzene, and ferric chloride. The amount of the chain transfer agent used is 0.01 to 5 parts by weight, preferably 0.05 to 1 part by weight based on 100 parts by weight of the total amount of monomers.
エマルジョンの安定性を保持するため、重合完了後に塩基および／または緩衝剤によりｐＨを６〜１０に保つのが好ましい。この調整、維持は、塩基および／または緩衝剤は、一般に使用されるものであれば、特に限定されないが、塩基としては水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物；アンモニア、有機アミン類など、緩衝剤としては、たとえば炭酸水素ナトリウム、リン酸水素２ナトリウムなどの炭酸塩、リン酸塩またはカルボン酸塩があげられる。 In order to maintain the stability of the emulsion, it is preferable to maintain the pH at 6 to 10 with a base and / or a buffer after completion of the polymerization. The adjustment and maintenance are not particularly limited as long as the base and / or buffering agent are generally used. Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; ammonia and organic amines. Examples of buffering agents include carbonates such as sodium hydrogen carbonate and disodium hydrogen phosphate, phosphates, and carboxylates.
これらのｐＨ調整剤、緩衝剤において、アルカリ金属を含むものを用いれば、（II）シリコン化合物、（Ｃ）成分の安定性を向上させることができ、炭酸水素ナトリウムの使用がより好ましい。 If these pH adjusting agents and buffering agents containing an alkali metal are used, the stability of the (II) silicon compound and the (C) component can be improved, and the use of sodium bicarbonate is more preferable.
アクリル系樹脂エマルジョン中の樹脂固形分濃度は、２０〜７０重量％が好ましく、さらに好ましくは３０〜６０重量％となるように調整する。かかる樹脂固形分濃度が７０重量％を超える場合には、系の粘度が著しく上昇するため、重合反応に伴なう発熱を除去することが困難になったり、重合器からの取り出しに長時間を要するようになる傾向がある。また、樹脂固形分濃度が２０重量％未満である場合には、重合操作の面では何ら問題は生じないものの、１回の重合操作によって生じる樹脂量が少なく、経済面で不利となるとともに、得られる塗膜の膜厚が薄くなるなど、塗装作業性、塗膜性能低下の点で不利となる。 The resin solid content concentration in the acrylic resin emulsion is preferably 20 to 70% by weight, and more preferably 30 to 60% by weight. When the resin solid content concentration exceeds 70% by weight, the viscosity of the system is remarkably increased, so that it becomes difficult to remove heat generated by the polymerization reaction, or it takes a long time to take out from the polymerization vessel. There is a tendency to become necessary. Further, when the resin solid content concentration is less than 20% by weight, there is no problem in the aspect of the polymerization operation, but the amount of resin generated by one polymerization operation is small, which is disadvantageous in terms of economy. This is disadvantageous in terms of coating workability and coating film performance degradation, such as a reduced coating film thickness.
本発明のアクリル系樹脂エマルジョンは、平均粒子径が０．０２〜１．０μｍ程度が好ましい。平均粒子径は、重合初期に仕込む界面活性剤の量で調整することが可能である。 The average particle diameter of the acrylic resin emulsion of the present invention is preferably about 0.02 to 1.0 μm. The average particle diameter can be adjusted by the amount of surfactant charged at the initial stage of polymerization.
（II）シリコン化合物および／またはその部分加水分解縮合物
本発明における（II）成分であるシリコン化合物は、一般式（１）で示される。
（Ｒ1Ｏ）4-aＳｉＲ2 a （１）
（式中、Ｒ1は同じかまたは異なり、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基または炭素数７〜１０のアラルキル基、Ｒ2は同じかまたは異なり、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基、または炭素数７〜１０のアラルキル基、ａは０〜２の整数。）
(II) Silicon Compound and / or Partially Hydrolyzed Condensate thereof The silicon compound as the component (II) in the present invention is represented by the general formula (1).
(R 1 O) 4-a SiR 2 a (1)
(Wherein R 1 is the same or different, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, R 2 is the same or different and has 1 carbon atom) C-10 alkyl group, C6-C10 aryl group, or C7-C10 aralkyl group, a is an integer of 0-2.)
シリコン化合物および／またはその部分加水分解縮合物としては、たとえば、テトラメチルシリケート、テトラエチルシリケート、テトラ−ｎ−プロピルシリケート、テトラ−ｉ−プロピルシリケート、テトラ−ｎ−ブチルシリケート、テトラ−ｉ−ブチルシリケート、テトラ−ｔ−ブチルシリケートなどのテトラアルキルシリケート類；メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、ブチルトリメトキシシラン、ブチルトリエトキシシラン、ペンチルトリメトキシシラン、ペンチルトリエトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、ヘプチルトリメトキシシラン、ヘプチルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、オクタデシルトリエトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−（メタ）アクリロキシプロピルトリメトキシシラン、３−（メタ）アクリロキシプロピ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などのトリアルコキシシラン類；ジメチルジメトキシシラン、ジメチルジエトキシシラン、メチルフェニルジメトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−（メタ）アクリロキシプロピルメチルジメトキシシラン、３−（メタ）アクリロキシプロピルメチルジエトキシシランなどのジアルコキシシラン類などのシランおよび／またはこれらのシランから選択される１種または２種以上の部分加水分解縮合物があげられる。また、これらは１種単独でもよく、２種以上を併用しても良い。 Examples of silicon compounds and / or partial hydrolysis condensates thereof include tetramethyl silicate, tetraethyl silicate, tetra-n-propyl silicate, tetra-i-propyl silicate, tetra-n-butyl silicate, and tetra-i-butyl silicate. Tetraalkyl silicates such as tetra-t-butyl silicate; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyl Triethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyl Ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octadecyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxy Trialkoxysilanes such as silane, vinyltrimethoxysilane, vinyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane Sialkoxysilanes such as 3- (meth) acryloxypropylmethyldimethoxysilane and 3- (meth) acryloxypropylmethyldiethoxysilane Emissions and / or one or more partially hydrolyzed condensate chosen from silanes and the like. These may be used alone or in combination of two or more.
上記のシリコン化合物および／またはその部分加水分解縮合物の中で、下記一般式（２）で示される化合物および／またはその部分加水分解縮合物であるオルガノシリケートおよび／またはその変性物が塗膜に親水性を付与し、耐汚染性を発現せしめる効果に優れることから好ましい。
（Ｒ3Ｏ）4Ｓｉ （２）
（式中、Ｒ3は同じかまたは異なり、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基または炭素数７〜１０のアラルキル基）
Among the above silicon compounds and / or partial hydrolysis condensates thereof, a compound represented by the following general formula (2) and / or an organosilicate which is a partial hydrolysis condensate thereof and / or a modified product thereof are added to the coating film. It is preferable because it is excellent in the effect of imparting hydrophilicity and developing stain resistance.
(R 3 O) 4 Si (2)
(Wherein R 3 is the same or different and is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms)
オルガノシリケートとしては、たとえば上記のテトラメチルシリケート、テトラエチルシリケート、テトラ−ｎ−プロピルシリケート、テトラ−ｉ−プロピルシリケート、テトラ−ｎ−ブチルシリケート、テトラ−ｉ−ブチルシリケート、テトラ−ｔ−ブチルシリケートなどテトラアルキルシリケート類、これらから選択される１種または２種以上の部分加水分解縮合物があげられる。 Examples of the organosilicate include tetramethyl silicate, tetraethyl silicate, tetra-n-propyl silicate, tetra-i-propyl silicate, tetra-n-butyl silicate, tetra-i-butyl silicate, tetra-t-butyl silicate, etc. Examples thereof include tetraalkyl silicates and one or more partially hydrolyzed condensates selected from these.
オルガノシリケートのＲ3は、炭素数が多い、また分岐のあるもので加水分解・縮合の反応性が低下し、組成物の貯蔵安定性および耐汚染性とを考慮すれば、炭素数２〜４のアルキル基が好ましい。また、Ｒ3として、短鎖アルキル（たとえばエチル）と長鎖または分岐アルキル（たとえばｉ−プロピル）の２種以上の選択により反応性に幅を持たせ、貯蔵安定性および耐汚染性の双方を向上させることもできる。 R 3 of the organosilicate has a large number of carbon atoms and is branched and the reactivity of hydrolysis / condensation is lowered, and considering the storage stability and stain resistance of the composition, it has 2 to 4 carbon atoms. Are preferred. Further, as R 3 , the reactivity is widened by selecting two or more kinds of short-chain alkyl (for example, ethyl) and long-chain or branched alkyl (for example, i-propyl), so that both storage stability and stain resistance are achieved. It can also be improved.
また、部分加水分解縮合物とすれば、耐汚染性を向上させることができる。その縮合度は２〜２０、好ましくは３〜１５である。 Moreover, if it is set as a partial hydrolysis-condensation product, stain resistance can be improved. The degree of condensation is 2-20, preferably 3-15.
また、ポリオキシアルキレン、ポリオキシアルキレンモノアルキルエーテルなどの水酸基を含有する親水性のポリエーテルをエステル交換反応等により導入すること、γ−アミノプロピルトリエトキシシランなどの親水性基含有シラン化合物を共縮合することなどで親水性基を導入する変性により、水性媒体中での分散性を向上させることもできる。 In addition, a hydrophilic polyether containing a hydroxyl group such as polyoxyalkylene or polyoxyalkylene monoalkyl ether is introduced by transesterification or the like, and a hydrophilic group-containing silane compound such as γ-aminopropyltriethoxysilane is used together. Dispersibility in an aqueous medium can also be improved by modification that introduces a hydrophilic group by condensation or the like.
（II）の添加方法は、特に限定されないが、（Ｉ）または（Ｉ）を用いた水性塗料組成物に直接添加、たとえば特開平８−２５９８９２号公報に記載される乳化物としての添加、特開平９−２２１６１１号公報に記載される（II）とγ−アミノプロピルトリエトキシシランなどの親水性基含有シラン化合物を共縮合することなどによる水溶化を行ったのちの添加、ＷＯ１９９９／０５２２８号公報に記載されるポリオキシアルキレン基を有する（II）の変性物としての添加、特開平８−３３７７５４号公報に記載される水溶性又は自己乳化型の（ブロック）イソシアネート基含有化合物および／またはカルボジイミド化合物などと（II）の混合物としての添加、特開２００２−１３８１２３号公報に記載される（II）を包含させた（Ｉ）合成樹脂エマルジョンの使用などがあげられる。 The addition method of (II) is not particularly limited, but it is directly added to the aqueous coating composition using (I) or (I), for example, as an emulsion described in JP-A-8-259892. Addition after water-solubilization by co-condensing (II) described in Kaihei 9-221611 and a hydrophilic group-containing silane compound such as γ-aminopropyltriethoxysilane, WO 1999/05228 (II) as a modified product having a polyoxyalkylene group described in JP-A-8-337754, a water-soluble or self-emulsifying type (block) isocyanate group-containing compound and / or carbodiimide compound And (II) as a mixture, and (I) synthetic resin including (II) described in JP-A-2002-138123 Such as the use of Marujon and the like.
上記の（II）の添加方法の中で、乳化物としての添加、特に(II）シリコン化合物および／またはその部分加水分解縮合物をアニオン系界面活性剤および／またはノニオン系界面活性剤を用いて水性媒体中に分散して得られる乳化物としての添加は、水性塗料組成物での貯蔵安定性、得られる塗膜の外観などを向上させる点で好ましい。 Among the addition methods of (II) above, addition as an emulsion, in particular, (II) silicon compounds and / or partially hydrolyzed condensates thereof using anionic surfactants and / or nonionic surfactants Addition as an emulsion obtained by dispersing in an aqueous medium is preferable in terms of improving storage stability in the aqueous coating composition, appearance of the resulting coating film, and the like.
この乳化物に用いる水性媒体は、水を必須成分として含有していればよく、他の有機溶剤を含有していても構わない。他の有機溶剤としては、エタノール、イソプロパノールなどのアルコール系溶剤；プロピレングリコールなどのグリコール系溶剤；エチレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールジメチルエーテルなどのエーテル系溶剤、プロピレングリコールモノブチルエーテルアセテート、（株）チッソ製ＣＳ−１２などのエステル系溶剤があげられるが、乳化物の安定性や環境の観点から有機溶剤は含有しない方が好ましい。 The aqueous medium used for this emulsion should just contain water as an essential component, and may contain the other organic solvent. Other organic solvents include alcohol solvents such as ethanol and isopropanol; glycol solvents such as propylene glycol; ether solvents such as ethylene glycol monobutyl ether, propylene glycol monobutyl ether and propylene glycol dimethyl ether, propylene glycol monobutyl ether acetate, Although ester solvents such as CS-12 manufactured by Chisso Corporation are listed, it is preferable not to contain an organic solvent from the viewpoint of stability of the emulsion and the environment.
また、アニオン系界面活性剤のアニオンとしては、たとえばポリオキシエチレンノニルフェニルエーテルサルフェート、ポリオキシエチレン多環フェニルエーテルサルフェートなどのポリオキシエチレンアリールエーテルサルフェート、ポリオキシエチレントリデシルエーテルサルフェートなどのポリオキシエチレンアルキルエーテルサルフェートなどのポリオキシエチレン鎖を有する硫酸エステル；ラウリルサルフェートなどの硫酸エステル；ラウリルスルホン酸、ドデシルベンゼンスルホン酸、アルキルナフタレンスルホン酸、アルキルジフェニルエーテルジスルホン酸などのスルホン酸；ジ（２−エチルヘキシル）スルホコハク酸などのアルキルスルホコハク酸；アルキルリン酸エステル、ポリオキシエチレンアルキルエーテルリン酸エステルなどのリン酸エステルなどがあげられる。 Examples of the anion of the anionic surfactant include polyoxyethylene nonylphenyl ether sulfate, polyoxyethylene aryl ether sulfate such as polyoxyethylene polycyclic phenyl ether sulfate, and polyoxyethylene such as polyoxyethylene tridecyl ether sulfate. Sulfate ester having polyoxyethylene chain such as alkyl ether sulfate; Sulfate ester such as lauryl sulfate; Sulfonic acid such as lauryl sulfonic acid, dodecylbenzene sulfonic acid, alkylnaphthalene sulfonic acid, alkyl diphenyl ether disulfonic acid; Di (2-ethylhexyl) Alkylsulfosuccinic acid such as sulfosuccinic acid; alkyl phosphate ester, polyoxyethylene alkyl ether phosphoric acid And phosphoric acid esters such as ester, and the like.
アニオン系界面活性剤の中和カチオン種は、種々選択できるが、アルカリ金属、好ましくはナトリウムまたはカリウムイオンを用いれば、乳化物および水性塗料組成物での（II）シリコン化合物および／またはその部分加水分解縮合物の安定性を向上させることができる。 Various neutralizing cationic species of the anionic surfactant can be selected. If an alkali metal, preferably sodium or potassium ion, is used, the (II) silicon compound and / or its partial hydrolysis in emulsions and aqueous coating compositions are used. The stability of the decomposition condensate can be improved.
また、ノニオン系界面活性剤としては、たとえばポリオキシエチレンアルキルエ−テル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン−ポリオキシプロピレンブロック共重合体、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステルなどのポリオキシエチレン鎖を有するもの；ソルビタン脂肪酸エステル、グリセリン脂肪酸エステルなどの水酸基を有するもの；信越化学工業（株）製ＫＦ−３５１、ＫＦ−３５２、ＫＦ−３５３、ＫＦ−３５４、ＫＦ−３５５、ＫＦ−６１５、ＫＦ−６１８、ＫＦ−９４５、ＫＦ−９０７、Ｘ−２２−６００８、Ｘ−２２−８１１、Ｘ−２２−８１２、東レ・ダウコーニング社製ＳＨ３７４８、ＳＨ３７４９、ＳＨ３７７１、ＳＨ８４００、ＳＦ８４１０、ＳＦ８７００などの片末端および／または両末端および／または側鎖をポリアルキレンオキシドで変性したポリオルガノシロキサンであるシリコーン系界面活性剤；アセチレングリコール系界面活性剤、ポリビニルアルコール、ヒドロキシエチルセルロース、アクリルアミド共重合体などの水溶性高分子系などがあげられる。 Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid. Those having a polyoxyethylene chain such as ester; those having a hydroxyl group such as sorbitan fatty acid ester and glycerin fatty acid ester; KF-351, KF-352, KF-353, KF-354, KF- manufactured by Shin-Etsu Chemical Co., Ltd. 355, KF-615, KF-618, KF-945, KF-907, X-22-6008, X-22-811, X-22-812, SH3748, SH3749, SH3771, SH8400 manufactured by Toray Dow Corning Silicone surfactants that are polyorganosiloxanes modified with polyalkylene oxide at one and / or both ends and / or side chains, such as SF8410 and SF8700; acetylene glycol surfactants, polyvinyl alcohol, hydroxyethyl cellulose, acrylamide Examples thereof include water-soluble polymer systems such as polymers.
これらの界面活性剤は、単独で用いてもよく、２種以上を併用してもよい。界面活性剤の使用量は、シリコン化合物１００重量部に対して有効成分量として０．０５〜５０重量部、好ましくは、０．１〜３０重量部である。０．０５重量部未満では安定な乳化物が得られず、貯蔵安定性も低下する。５０重量部を越えると得られる塗膜の外観や耐水性の低下などの問題が発生する。 These surfactants may be used alone or in combination of two or more. The amount of the surfactant used is 0.05 to 50 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the silicon compound. If it is less than 0.05 part by weight, a stable emulsion cannot be obtained, and the storage stability is also lowered. If it exceeds 50 parts by weight, problems such as the appearance of the resulting coating film and a decrease in water resistance occur.
この乳化物は、ｐＨを６〜１０に保つのが好ましい。この範囲外では、シリコン化合物および／またはその部分加水分解縮合物の加水分解・縮合が起こりやすくなり貯蔵安定性が低下する傾向がある。特に、ｐＨ６未満では加水分解が促進されるため、縮合が速く進行する。また、ｐＨ１０を超えると不安定になるだけでなく作業上の問題も生じる。 This emulsion preferably has a pH of 6-10. Outside this range, hydrolysis / condensation of the silicon compound and / or its partially hydrolyzed condensate tends to occur and storage stability tends to decrease. In particular, when the pH is less than 6, hydrolysis is accelerated, and thus condensation proceeds rapidly. Moreover, when the pH is exceeded, not only is it unstable, but there are also operational problems.
ｐＨの調整、維持の方法あるいは順序については、特に限定しないが、乳化物作製時点から行うことが好ましい。ｐＨの調整に用いる酸、塩基、ｐＨの維持に用いる緩衝剤は、一般に使用されるものであれば、特に限定されないが、塩基としては水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物；アンモニア、有機アミン類など、緩衝剤としては、たとえば炭酸水素ナトリウム、リン酸水素２ナトリウムなどの炭酸塩、リン酸塩またはカルボン酸塩があげられる。これらのｐＨ調整剤、緩衝剤において、アルカリ金属を含むものが好ましく、炭酸水素ナトリウムの使用がより好ましい。 The method or order for adjusting and maintaining the pH is not particularly limited, but it is preferably performed from the time of preparation of the emulsion. The acid used to adjust the pH, the base, and the buffer used to maintain the pH are not particularly limited as long as they are generally used. Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; Examples of buffers such as ammonia and organic amines include carbonates such as sodium hydrogen carbonate and disodium hydrogen phosphate, phosphates, and carboxylates. Among these pH adjusters and buffering agents, those containing an alkali metal are preferred, and the use of sodium bicarbonate is more preferred.
この乳化物中のシリコン化合物および／またはその部分加水分解縮合物の固形分濃度は、５〜６０重量％が好ましく、１０〜４０重量％がより好ましい。固形分濃度が６０重量％を超える場合には、（II）の粘度が上昇、乳化安定性を損なう等の問題が生じる可能性があり、５重量％未満の場合には、得られる塗膜の膜厚が薄くなるなど、塗装作業性、塗膜性能低下の点で不利となる。 The solid content concentration of the silicon compound and / or its partially hydrolyzed condensate in the emulsion is preferably 5 to 60% by weight, more preferably 10 to 40% by weight. If the solid content concentration exceeds 60% by weight, the viscosity of (II) may increase, and the emulsion stability may be impaired. If it is less than 5% by weight, It is disadvantageous in terms of coating workability and coating film performance degradation, such as a thin film thickness.
乳化物の作製は、上記の各成分と水性媒体を一般的な乳化方法により乳化することによる。乳化方法としては、シリコン化合物および／またはその部分加水分解縮合物と界面活性剤を混合、これに水をゆっくりと添加し、油中水型乳化物から水中油型乳化物に相反転させる、いわゆる転相乳化法；各成分を混合後、また予備乳化後にディスパー、高圧ホモジナイザーなどで機械的に微分散する方法などがあげられる。 The preparation of the emulsion is performed by emulsifying the above components and the aqueous medium by a general emulsification method. As the emulsification method, a silicon compound and / or a partially hydrolyzed condensate thereof and a surfactant are mixed, water is slowly added thereto, and the phase inversion from a water-in-oil emulsion to an oil-in-water emulsion is so-called. Phase inversion emulsification method: a method in which each component is mixed, or after preliminary emulsification, mechanically finely dispersed with a disper, a high-pressure homogenizer, or the like.
（II）の添加量は、（Ｉ）合成樹脂エマルジョンの固形分１００重量部に対し、１〜５０重量部、好ましくは３〜２０重量部となる量である。１重量部未満では得られる塗膜の耐汚染性が十分ではない傾向にあり、５０重量部を越えると塗膜外観の低下やクラックなどの問題が発生する傾向にある。 (II) is added in an amount of 1 to 50 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the solid content of (I) the synthetic resin emulsion. If the amount is less than 1 part by weight, the resulting coating film tends to have insufficient stain resistance. If the amount exceeds 50 parts by weight, problems such as deterioration of the coating film appearance and cracks tend to occur.
（III）光酸発生剤
本発明における（III）成分である光酸発生剤は、光暴露により酸を発生する化合物であり、たとえばトルエンスルホン酸などの強酸または四フッ化ホウ素などのスルホニウム塩、アンモニウム塩、ホスホニウム塩、ヨードニウム塩またはセレニウム塩などのオニウム塩類；鉄−アレン錯体類；シラノール−金属キレート錯体類；ジスルホン類、ジスルホニルジアゾメタン類、ジスルホニルメタン類、スルホニルベンゾイルメタン類、イミドスルホネート類、ベンゾインスルホネート類などのスルホン酸誘導体；有機ハロゲン化合物類など、特開平５−１３４４１２号公報に示される放射線の照射により酸を発生する化合物があげられる。
(III) Photoacid generator The photoacid generator as a component (III) in the present invention is a compound that generates an acid upon exposure to light. For example, a strong acid such as toluenesulfonic acid or a sulfonium salt such as boron tetrafluoride, Onium salts such as ammonium salts, phosphonium salts, iodonium salts or selenium salts; iron-allene complexes; silanol-metal chelate complexes; disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imide sulfonates And sulfonic acid derivatives such as benzoin sulfonates; organic halogen compounds and the like, and compounds that generate an acid upon irradiation with radiation as disclosed in JP-A-5-34412.
上記の光酸発生剤の中で、イオン性を有しないスルホン酸誘導体、有機ハロゲン化合物類は、特に（Ｉ）合成樹脂エマルジョンがイオン性界面活性剤で分散安定性を付与している場合において、組成物の安定性への影響が小さい点で好ましい。スルホン酸誘導体としては、たとえば米国特許第４６１８５６４号公報に示されるベンソイントシレート、ニトロベンジルトシレート、コハク酸イミドトシルスルホネートなどのスルホン酸エステル類；米国特許第４５４０５９８号公報、特開平６−６７４３３号公報に示されるα−（４−トシルオキシイミノ）−４−メトキシベンジルシアニドなどのオキシムスルホネート類；特開平６−３４８０１５号公報に示されるトリス（メタンスルホニルオキシ）ベンゼンなど；特開昭６４−１８１４３号公報に示される９，１０−ジアルコキシアントラセンスルホン酸ニトロベンジルエステルなど；Ｎ−（ｐ−ドデシルベンゼンスルホニルオキシ）−１，８−ナフタルイミドなどがあげられる。有機ハロゲン化合物類としては、たとえば２−（４−メトキシフェニル）−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−（３，４−ジメトキシスチリル）−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（５−メチルフラン−２−イル）ビニル）−４，６−ビス（トリクロロメチル）−１，３，５−トリアジンなどの特開昭５５−３２０７０号公報、特開昭４８−３６２８１号公報、特開昭６３−２３８３３９号公報に示されるハロゲン含有トリアジン化合物；特開平２−３０４０５９号公報に示される２−ピリジル−トリブロモメチルスルホンなどのハロゲン含有スルホン化合物；トリス（２−クロロプロピル）ホスフェート、トリス（２，３−ジクロロプロピル）ホスフェート、トリス（２，３−ジブロモプロピル）ホスフェートなどのハロゲン化アルキルリン酸エステル；２−クロロ−６−（トリクロロメチル）ピリジンなどのハロゲン含有へテロ環状化合物；１，１−ビス［ｐ−クロロフェニル］−２，２，２−トリクロロエタン、塩化ビニリデン共重合体、塩化ビニル共重合体、塩素化ポリオレフィンなどのハロゲン含有炭化水素化合物などがあげられる。 Among the photoacid generators described above, sulfonic acid derivatives and organic halogen compounds having no ionicity are particularly (I) when the synthetic resin emulsion is provided with dispersion stability by an ionic surfactant. This is preferable in that the influence on the stability of the composition is small. Examples of the sulfonic acid derivatives include sulfonic acid esters such as benzoin tosylate, nitrobenzyl tosylate, and succinimide tosyl sulfonate disclosed in US Pat. No. 4,618,564; US Pat. No. 4,540,598 and JP-A-6-67433. Oxime sulfonates such as α- (4-tosyloxyimino) -4-methoxybenzylcyanide shown in Japanese Patent Publication No. 6-348015; tris (methanesulfonyloxy) benzene shown in Japanese Patent Publication No. 6-348015; And 9,10-dialkoxyanthracenesulfonic acid nitrobenzyl ester shown in No. 18143; N- (p-dodecylbenzenesulfonyloxy) -1,8-naphthalimide and the like. Examples of the organic halogen compounds include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-dimethoxystyryl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-methylfuran-2-yl) vinyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, etc. Halogen-containing triazine compounds disclosed in JP-A-55-32070, JP-A-48-36281, and JP-A-63-238339; 2-pyridyl-tri described in JP-A-2-304059 Halogen-containing sulfone compounds such as bromomethylsulfone; tris (2-chloropropyl) phosphate, tris (2,3-dichloropropyl) phosphate, tri Halogenated alkyl phosphates such as (2,3-dibromopropyl) phosphate; halogen-containing heterocyclic compounds such as 2-chloro-6- (trichloromethyl) pyridine; 1,1-bis [p-chlorophenyl] -2 , 2,2-trichloroethane, vinylidene chloride copolymers, vinyl chloride copolymers, halogen-containing hydrocarbon compounds such as chlorinated polyolefins, and the like.
（III）の添加方法は、特に限定されないが、たとえば（II）に溶解させて添加する、成膜助剤または溶剤に溶解させて添加する、（III）が固体の場合には粉末として添加する、エマルジョン形態の（III）を添加するなどがあげられる。 The method of adding (III) is not particularly limited. For example, it is added after being dissolved in (II), added after being dissolved in a film forming aid or solvent, and added as a powder when (III) is solid. And (III) in the form of an emulsion are added.
（III）の添加量は、生成する酸の発生量、発生速度に応じて調整が必要だが、（Ｉ）合成樹脂エマルジョンの固形分１００重量部に対し、０．０５〜３０重量部、好ましくは３〜２０重量部となる量である。０．０５重量部未満では生成する酸が不足し、得られる塗膜の耐汚染性が十分ではない傾向にあり、３０重量部を越えると塗膜外観の低下や着色などの問題が発生する傾向にある。 The amount of (III) added needs to be adjusted according to the amount of acid generated and the rate of generation, but (I) 0.05 to 30 parts by weight, preferably 100 parts by weight of the solid content of the synthetic resin emulsion, The amount is 3 to 20 parts by weight. If the amount is less than 0.05 parts by weight, the acid generated is insufficient, and the resulting coating film tends to have insufficient stain resistance. If the amount exceeds 30 parts by weight, problems such as deterioration of the coating film appearance and coloration tend to occur. It is in.
上記（Ｉ）〜（III）から得られた組成物は、暗所での安定性を有する１液型の組成物とすることができ、さらに塗膜の光暴露により（III）から生じた酸が（II）の加水分解・縮合反応の触媒となり、優れた親水性表面を形成することが可能である。 The composition obtained from the above (I) to (III) can be a one-component composition having stability in a dark place, and further the acid generated from (III) by light exposure of the coating film. Becomes a catalyst for the hydrolysis / condensation reaction of (II), and can form an excellent hydrophilic surface.
この親水性をさらに向上させるため、さらに（IV）酸により活性化するアルコキシシリル基の加水分解・縮合を促進する化合物の添加を行うことができる。（IV）成分は、酸性ではアルコキシシリル基の加水分解・縮合を促進するが、塩基性ではこの活性が抑制されているものであり、たとえば（III）に該当するものを除く硫酸化合物、スルホン酸化合物、カルボン酸化合物、リン酸化合物などの酸性有機化合物のエステルまたは塩などがあげられる。具体例としては、ｔ−ブチル（メタ）アクリレート共重合体などのｔ−ブチルエステル類；アルキルホスホン酸、酸性リン酸エステルなどのナトリウム塩、カルシウム塩などのアルカリ金属、アルカリ土類金属塩などがあげられる。 In order to further improve the hydrophilicity, (IV) a compound that promotes hydrolysis / condensation of an alkoxysilyl group activated by an acid can be added. Component (IV) promotes hydrolysis / condensation of alkoxysilyl groups when acidic, but its activity is suppressed when basic. For example, sulfuric acid compounds and sulfonic acids except those corresponding to (III) Examples thereof include esters or salts of acidic organic compounds such as compounds, carboxylic acid compounds, and phosphoric acid compounds. Specific examples include t-butyl esters such as t-butyl (meth) acrylate copolymers; sodium salts such as alkylphosphonic acid and acidic phosphate esters, alkali metals such as calcium salts, and alkaline earth metal salts. can give.
上記の酸性有機化合物のエステルまたは塩の中で、酸性リン酸化合物の塩は、塗膜の表面親水性向上および組成物の安定性への影響が小さい点で好ましい。酸性リン酸化合物の塩としては、たとえばモノ−２−エチルヘキシル−２−エチルヘキシルホスホネートなどのアルキルホスホン酸；ジブチルホスフェート、２−エチルヘキシルアシッドホスフェート、ジ−２−エチルヘキシルホスフェート、モノイソデシルアシッドホスフェート、ジイソデシルホスフェート、ラウリルアシッドホスフェート、オレイルアシッドホスフェート、ステアリルアシッドホスフェート等の酸性リン酸エステルなどのナトリウム、カリウムなどのアルカリ金属塩、マグネシウム、カルシウムなどのアルカリ土類金属塩などがあげられる。 Among the above-mentioned esters or salts of acidic organic compounds, salts of acidic phosphoric acid compounds are preferred in that the surface hydrophilicity of the coating film is improved and the effect on the stability of the composition is small. Examples of the salt of the acidic phosphoric acid compound include alkylphosphonic acids such as mono-2-ethylhexyl-2-ethylhexylphosphonate; dibutyl phosphate, 2-ethylhexyl acid phosphate, di-2-ethylhexyl phosphate, monoisodecyl acid phosphate, diisodecyl phosphate , Alkali metal salts such as sodium and potassium such as acidic phosphates such as lauryl acid phosphate, oleyl acid phosphate and stearyl acid phosphate, and alkaline earth metal salts such as magnesium and calcium.
（IV）の添加量は、（III）の添加量、（III）から生成する酸の発生量、発生速度に応じて調整が必要だが、（Ｉ）合成樹脂エマルジョンの固形分１００重量部に対し、０．０５〜２０重量部、好ましくは１〜１０重量部となる量である。０．０５重量部未満ではアルコキシシリル基の加水分解・縮合の反応促進が不足し、得られる塗膜の耐汚染性が向上作用が十分ではない傾向にあり、２０重量部を越えると塗膜耐水性の低下などの問題が発生する傾向にある。 The amount of addition of (IV) needs to be adjusted according to the amount of addition of (III), the amount of acid generated from (III), and the rate of generation, but (I) to 100 parts by weight of the solid content of the synthetic resin emulsion , 0.05 to 20 parts by weight, preferably 1 to 10 parts by weight. If the amount is less than 0.05 parts by weight, the hydrolysis / condensation reaction of the alkoxysilyl group is insufficiently promoted, and there is a tendency that the antifouling property of the obtained coating film is not sufficiently improved. There is a tendency to cause problems such as a decrease in sex.
水性塗料用樹脂組成物の作製
本発明の水性塗料用樹脂組成物は、（Ｉ）合成樹脂エマルジョン、（II）シリコン化合物および／またはその部分加水分解縮合物、（III）光酸発生剤、必要であれば（IV）加水分解・縮合を促進する化合物を、任意の順番で加え混合することにより得られる。混合方法は、一般的な混合方法を使用することができ特に限定されない。
Preparation of Resin Composition for Aqueous Paints The resin composition for aqueous paints of the present invention comprises (I) a synthetic resin emulsion, (II) a silicon compound and / or a partially hydrolyzed condensate thereof, (III) a photoacid generator, necessary If so, it can be obtained by adding (IV) compounds that promote hydrolysis and condensation in any order and mixing. The mixing method can use a general mixing method, and is not specifically limited.
本発明の水性塗料用樹脂組成物の配合形態については、全ての配合物を配合した１液型の配合形態が可能である。本発明の水性塗料用樹脂組成物の貯蔵安定性は良好で、全ての配合物を配合し、遮光した密閉状態で、室温もしくは５０℃２８日間安定であり、得られる塗膜の物性の低下は起こらない。 About the compounding form of the resin composition for water-based paints of this invention, the 1 liquid type compounding form which mix | blended all the compounds is possible. The storage stability of the resin composition for water-based paints of the present invention is good, all formulations are blended, and it is stable at room temperature or 50 ° C. for 28 days in a sealed state where light is shielded. Does not happen.
得られた組成物には、必要に応じて、通常塗料に用いられる顔料、たとえば二酸化チタン、炭酸カルシウム、カオリンクレー、タルク、硫酸バリウム、ホワイトカーボン、カーボン、弁柄、黄土、シアニンブルーなど、成膜助剤、たとえばベンジルアルコールなどのアルコール類；エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノブチルエーテルなどのグリコール類、エチレングリコールモノブチルエーテルアセテート、２，２，４−トリメチル−１,３−ペンタンジオールモノイソブチレートなどのグリコールエステル類など、コロイダルシリカ、可塑剤、溶剤、分散剤、湿潤剤、増粘剤、防腐剤、凍結防止剤、光安定剤、紫外線吸収剤、消泡剤などの通常塗料に用いられる添加剤を添加することもできる。 If necessary, the obtained composition may contain pigments commonly used in paints such as titanium dioxide, calcium carbonate, kaolin clay, talc, barium sulfate, white carbon, carbon, petal, ocher, cyanine blue, and the like. Membrane aids such as alcohols such as benzyl alcohol; glycols such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, 2 Glycol esters such as 1,2,4-trimethyl-1,3-pentanediol monoisobutyrate, colloidal silica, plasticizers, solvents, dispersants, wetting agents, Additives usually used in paints such as a sticking agent, preservative, antifreezing agent, light stabilizer, ultraviolet absorber and antifoaming agent can also be added.
本発明の組成物は、例えば建築内外装用、メタリックベースあるいはメタリックベース上のクリアーなどの自動車用、アルミニウム、ステンレスなどの金属直塗用、スレート、コンクリート、瓦、モルタル、石膏ボード、石綿スレート、アスベストボード、プレキャストコンクリート、軽量気泡コンクリート、硅酸カルシウム板、タイル、レンガなどの窯業系直塗用、ガラス用、天然大理石、御影石等の石材用の塗料あるいは上面処理剤として用いられる。 The composition of the present invention is used for, for example, interior / exterior of buildings, automotive such as metallic base or clear on metallic base, direct coating of metal such as aluminum and stainless steel, slate, concrete, roof tile, mortar, gypsum board, asbestos slate, asbestos It is used as a paint for ceramics such as board, precast concrete, lightweight cellular concrete, calcium oxalate plate, tile, brick, etc., for glass, natural marble, granite and other stones, or as a top treatment.
以下に、本発明を実施例に基づいて説明するが、本発明はこれによって限定されるものではない。 Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto.
（アクリル系樹脂エマルジョンの合成例）
撹拌機、還流冷却器、窒素ガス導入管および滴下ロートを備えた反応容器に、初期仕込みとして脱イオン水１６０重量部、Ｎｅｗｃｏｌ−７０７ＳＮ（日本乳化剤（株）製：有効成分３０％、ポリオキシエチレン多環フェニルエーテル硫酸エステルナトリウム塩）０．３５重量部、５％炭酸水素ナトリウム水溶液０．２５重量部を仕込み、窒素ガスを導入しつつ５０℃に昇温した。昇温後、７％ｔ−ブチルハイドロパーオキサイド水溶液０．５重量部、２０％Ｂｒｕｇｇｏｌｉｔｅ ＦＦ−６水溶液０．２８重量部、０．１０％硫酸第一鉄・７水和物と０．４０％エチレンジアミン四酢酸二ナトリウムの混合水溶液０．３５部を添加し、１段目として２−エチルヘキシルアクリレート１６．０４重量部、ブチルメタクリレート３３重量部、γ−メタクリロキシプロピルメチルジメトキシシラン０．９４重量部の混合物５０重量部にアデカリアソープＳＲ−１０Ｓ（(株)ＡＤＥＫＡ製：有効成分１００％、ポリオキシエチレン−１−アルコキシメチル−２−（２−プロペニルオキシ）エチルエーテル硫酸エステルナトリウム塩）０．７５重量部、アデカリアソープＥＲ−２０（(株)ＡＤＥＫＡ製：有効成分７５％、ポリオキシエチレン−１−アルコキシメチル−２−（２−プロペニルオキシ）エチルエーテル）０．４７重量部、および脱イオン水２０重量部を加え乳化したモノマー乳化液を２００分かけて等速追加した。その間、７％ｔ−ブチルハイドロパーオキサイド水溶液０．５５重量部および２．５％Ｂｒｕｇｇｏｌｉｔｅ ＦＦ−６水溶液０．４３重量部を３回に分けて添加した。モノマー乳化液追加終了後、１時間後重合を行った。さらに、７％ｔ−ブチルハイドロパーオキサイド水溶液０．２５重量部、２．５％Ｂｒｕｇｇｏｌｉｔｅ ＦＦ−６水溶液０．５５重量部および０．１０％硫酸第一鉄・７水和物と０．４０％エチレンジアミン四酢酸二ナトリウムの混合水溶液０．３５部を添加し、２段目としてメチルメタクリレート９．２５重量部、ブチルメタクリレート３７重量部、γ−メタクリロキシプロピルトリエトキシシラン０．５重量部、ポリオキシエチレン鎖を有するビニル系単量体であるブレンマーＰＥ−２００（日油(株）製)３重量部、ｎ−ドデシルメルカプタン０．２５重量部の混合物５０重量部にアデカリアソープＳＲ−１０Ｓ ０．７５重量部、アデカリアソープＥＲ−２０ ０．４７重量部、および脱イオン水２０重量部を加え乳化したモノマー乳化液を２００分かけて等速追加した。その間、７％ｔ−ブチルハイドロパーオキサイド水溶液０．６重量部および２．５％Ｂｒｕｇｇｏｌｉｔｅ ＦＦ−６水溶液０．８５重量部を４回に分けて添加した。モノマー乳化液追加終了後、１．５時間後重合を行った。得られたエマルジョンに５％炭酸水素ナトリウム水溶液５．５部を添加後、脱イオン水で固形分５０％に調整しアクリル系樹脂エマルジョン（Ｉ−１）を得た。得られたエマルジョンは、日機装（株）製動的光散乱法粒子径測定機ＭＩＣＲＯＴＲＡＣ ＵＰＡ ＭＯＤＥＬ９３４０−ＵＰＡによる体積平均粒子径が２００ｎｍであった。
(Synthesis example of acrylic resin emulsion)
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen gas inlet tube and dropping funnel, 160 parts by weight of deionized water as an initial charge, Newcol-707SN (manufactured by Nippon Emulsifier Co., Ltd .: 30% active ingredient, polyoxyethylene) Polycyclic phenyl ether sulfate sodium salt) 0.35 parts by weight, 0.25 parts by weight of 5% aqueous sodium hydrogen carbonate solution were charged, and the temperature was raised to 50 ° C. while introducing nitrogen gas. After the temperature rise, 0.5 parts by weight of 7% t-butyl hydroperoxide aqueous solution, 0.28 parts by weight of 20% Bruggolite FF-6 aqueous solution, 0.10% ferrous sulfate and heptahydrate and 0.40% 0.35 part of a mixed aqueous solution of ethylenediaminetetraacetic acid disodium was added, and the first stage was 16.04 parts by weight of 2-ethylhexyl acrylate, 33 parts by weight of butyl methacrylate, 0.94 parts by weight of γ-methacryloxypropylmethyldimethoxysilane. ADEKA rear soap SR-10S (manufactured by ADEKA: 100% active ingredient, polyoxyethylene-1-alkoxymethyl-2- (2-propenyloxy) ethyl ether sulfate sodium salt) 0.75 in 50 parts by weight of the mixture Part by weight, Adekaria soap ER-20 (manufactured by ADEKA Corporation: 75% active ingredient, polyoxye A monomer emulsion obtained by adding 0.47 part by weight of tylene-1-alkoxymethyl-2- (2-propenyloxy) ethyl ether) and 20 parts by weight of deionized water was added at a constant rate over 200 minutes. Meanwhile, 0.55 parts by weight of 7% t-butyl hydroperoxide aqueous solution and 0.43 parts by weight of 2.5% Bruggolite FF-6 aqueous solution were added in three portions. Polymerization was performed after 1 hour after the addition of the monomer emulsion was completed. Further, 0.25 parts by weight of a 7% t-butyl hydroperoxide aqueous solution, 0.55 parts by weight of a 2.5% Bruggolite FF-6 aqueous solution, and 0.10% ferrous sulfate heptahydrate and 0.40% Add 0.35 parts of a mixed aqueous solution of ethylenediaminetetraacetic acid disodium, and in the second stage, 9.25 parts by weight of methyl methacrylate, 37 parts by weight of butyl methacrylate, 0.5 parts by weight of γ-methacryloxypropyltriethoxysilane, polyoxy Adecalia Soap SR-10S in a mixture of 3 parts by weight of Blemmer PE-200 (manufactured by NOF Corporation), a vinyl monomer having an ethylene chain, and 0.25 parts by weight of n-dodecyl mercaptan. Monomer emulsion emulsified by adding 75 parts by weight, 0.47 parts by weight of Adeka Soap ER-20, and 20 parts by weight of deionized water Was added at a constant speed over 200 minutes. Meanwhile, 0.6 part by weight of 7% t-butyl hydroperoxide aqueous solution and 0.85 part by weight of 2.5% Bruggolite FF-6 aqueous solution were added in four portions. After completion of the addition of the monomer emulsion, polymerization was carried out 1.5 hours later. After adding 5.5 parts of 5% aqueous sodium hydrogen carbonate solution to the obtained emulsion, the solid content was adjusted to 50% with deionized water to obtain an acrylic resin emulsion (I-1). The obtained emulsion had a volume average particle size of 200 nm by a dynamic light scattering particle size measuring device MICROTRAC UPA MODEL 9340-UPA manufactured by Nikkiso Co., Ltd.
（シリコン化合物の乳化物の製造例１）
室温にて、縮合度５〜６のテトラ−ｎ−プロピルシリケート部分加水分解縮合物３０重量部とネオコールＳＷ−Ｃ（第一工業製薬（株）製：有効成分７０％、ジアルキルスルホコハク酸ナトリウム塩）１０重量部を攪拌しながら、脱イオン水を６０重量部を滴下して、有効固形分濃度３０％のシリコン化合物（II−１）の乳化物を得た。
(Production Example 1 of Emulsion of Silicon Compound)
At room temperature, 30 parts by weight of a tetra-n-propyl silicate partial hydrolysis condensate having a condensation degree of 5 to 6 and Neocor SW-C (Daiichi Kogyo Seiyaku Co., Ltd .: active ingredient 70%, dialkylsulfosuccinic acid sodium salt) While stirring 10 parts by weight, 60 parts by weight of deionized water was added dropwise to obtain an emulsion of silicon compound (II-1) having an effective solid content concentration of 30%.
（シリコン化合物の乳化物の製造例２）
室温にて、縮合度５〜６のテトラエチルシリケート部分加水分解縮合物３０重量部とネオコールＳＷ−Ｃ（第一工業製薬（株）製：有効成分７０％、ジアルキルスルホコハク酸ナトリウム塩）１０重量部、ハイテノールＸＪ−６３０Ｓ（第一工業製薬（株）製：有効成分３０％、ポリオキシアルキレンデシルエーテル硫酸エステルナトリウム塩）５重量部を混合し、攪拌しながら、脱イオン水を５５重量部を滴下して、有効固形分濃度３０％のシリコン化合物（II−２）の乳化物を得た。
(Production Example 2 of Emulsion of Silicon Compound)
At room temperature, 30 parts by weight of a tetraethyl silicate partial hydrolysis condensate having a degree of condensation of 5 to 6 and 10 parts by weight of Neocor SW-C (Daiichi Kogyo Seiyaku Co., Ltd .: active ingredient 70%, dialkylsulfosuccinic acid sodium salt) Hytenol XJ-630S (Daiichi Kogyo Seiyaku Co., Ltd .: active ingredient 30%, polyoxyalkylene decyl ether sulfate sodium salt) 5 parts by weight was mixed and 55 parts by weight of deionized water was added dropwise with stirring. Thus, an emulsion of the silicon compound (II-2) having an effective solid content concentration of 30% was obtained.
（シリコン化合物の乳化物の製造例３）
室温にて、縮合度５〜６、エチル基／ｉ−プロピル基が８／２ ｍｏｌ／ｍｏｌであるテトラアルコキシシランの部分加水分解縮合物３０重量部とポリオキシエチレンラウリル硫酸エステルナトリウム塩５重量部、ポリオキシエチレンノニルフェニルエーテル３重量部を混合し、１０００ｒｐｍ以上で高速攪拌しながら、ゆっくりと脱イオン水を６２重量部加えて、有効固形分濃度３０％のシリコン化合物（II−３）の乳化物を得た。
(Production Example 3 of Silicon Compound Emulsion)
30 parts by weight of a partially hydrolyzed condensate of tetraalkoxysilane having a degree of condensation of 5 to 6 and an ethyl group / i-propyl group of 8/2 mol / mol at room temperature and 5 parts by weight of polyoxyethylene lauryl sulfate sodium salt Then, 3 parts by weight of polyoxyethylene nonylphenyl ether is mixed, and 62 parts by weight of deionized water is slowly added while stirring at a high speed of 1000 rpm or more to emulsify the silicon compound (II-3) having an effective solid content of 30%. I got a thing.
（水性樹脂組成物の製造例）
アクリル系樹脂エマルジョン（Ｉ−１）１００重量部に、シリコン化合物の乳化物の製造例１〜３のシリコン化合物（II−１）〜（II−３）の乳化物１６．７重量部｛（Ｉ）の固形分１００重量部に対し、（II）のシリコン化合物および／またはその部分加水分解縮合物１０重量部｝を加え、室温下、攪拌機により３０分混合した。この混合物に表１に示す光酸発生剤（III−１）〜（III−５）の溶液、懸濁液または水分散液を添加、混合して水性樹脂組成物Ａ〜Ｋを得た。
(Production example of aqueous resin composition)
16.7 parts by weight of the emulsion of silicon compounds (II-1) to (II-3) of Production Examples 1 to 3 of the emulsion of silicon compound in 100 parts by weight of the acrylic resin emulsion (I-1) {(I ) Was added to the solid content of 100 parts by weight of (II), and / or 10 parts by weight of the partially hydrolyzed condensate thereof, and mixed at room temperature with a stirrer for 30 minutes. To this mixture, solutions, suspensions or aqueous dispersions of the photoacid generators (III-1) to (III-5) shown in Table 1 were added and mixed to obtain aqueous resin compositions AK.
実施例１〜６、比較例１、２
水性樹脂組成物Ａ〜Ｃ、Ｉに表２に示す添加剤を室温、攪拌下で加えクリアー塗料を得た。これらを６ミルのアプリケーターを使用してガラス板上に塗装し、表２に示す露光、養生を行って塗板を作製した。これらの塗板の露光、養生完了時の水接触角（初期）および室温で１４日水浸漬し、室内で約６時間乾燥後の水接触角（水浸漬後）の測定を行った。結果を表２に示す。
Examples 1 to 6, Comparative Examples 1 and 2
The additives shown in Table 2 were added to the aqueous resin compositions A to C and I at room temperature with stirring to obtain a clear paint. These were coated on a glass plate using a 6 mil applicator and subjected to exposure and curing shown in Table 2 to prepare a coated plate. Exposure of these coated plates, water contact angle upon completion of curing (initial), and water immersion for 14 days at room temperature, and measurement of water contact angle (after water immersion) after drying for about 6 hours indoors were performed. The results are shown in Table 2.
実施例７、８、比較例３、４
実施例７、８は、水性樹脂組成物Ｄ、Ｅに表３に示す添加剤を室温、攪拌下で加えクリアー塗料を得た。これらを密閉容器に入れ、直射日光の当たらない条件下で表３に示す貯蔵を行った後、６ミルのアプリケーターを使用してガラス板上に塗装し、表３に示す露光、養生を行って塗板を作製した。比較例３、４は、水性樹脂組成物Ｉ、Ｊに表４に示す成膜助剤を室温、攪拌下で加えてクリアー塗料とし、これらにアルコキシシリル基の加水分解・縮合を促進する化合物である加水分解縮合触媒を加えて混合し、混合後３０分後もしくは１日後に塗装を行う、２液形態とした。これらの塗板の露光、養生完了時の水接触角（初期）および室温で７日水浸漬し、室内で約６時間乾燥後の水接触角（水浸漬後）の測定を行った。結果を表３、表４に示す。
Examples 7 and 8, Comparative Examples 3 and 4
In Examples 7 and 8, the additives shown in Table 3 were added to the aqueous resin compositions D and E at room temperature under stirring to obtain clear paints. After putting these in a sealed container and storing them in a condition not exposed to direct sunlight, they are coated on a glass plate using a 6 mil applicator and exposed and cured as shown in Table 3. A coated plate was prepared. Comparative Examples 3 and 4 are compounds that add the film-forming aid shown in Table 4 to the aqueous resin compositions I and J under stirring at room temperature to form a clear paint, which promotes hydrolysis and condensation of alkoxysilyl groups. A certain hydrolysis-condensation catalyst was added and mixed, and coating was performed 30 minutes or 1 day after mixing to obtain a two-component form. Exposure of these coated plates, water contact angle upon completion of curing (initial), and water immersion for 7 days at room temperature, and measurement of the water contact angle after drying for about 6 hours indoors (after water immersion) were performed. The results are shown in Tables 3 and 4.
実施例９、１０、比較例５、６
水性樹脂組成物Ｆ、Ｋに表５に示す添加剤を室温、攪拌下で加えクリアー塗料を得た。これらを密閉容器に入れ、直射日光の当たらない条件下で表５に示す貯蔵を行った後、６ミルのアプリケーターを使用してガラス板上に塗装し、表５に示す露光、養生を行って塗板を作製した。比較例６は、比較例５のクリアー塗料に室温でアルコキシシリル基の加水分解・縮合を促進する化合物である加水分解縮合触媒を加えて混合、３０分後に塗装を行う、２液形態とした。これらの塗板の露光、養生完了時の水接触角（初期）および室温で１４日水浸漬し、室内で約６時間乾燥後の水接触角（水浸漬後）の測定を行った。結果を表５に示す。
Examples 9 and 10, Comparative Examples 5 and 6
The additives shown in Table 5 were added to the aqueous resin compositions F and K at room temperature with stirring to obtain a clear paint. After putting these in a sealed container and storing them in a condition not exposed to direct sunlight, they are coated on a glass plate using a 6 mil applicator and exposed and cured as shown in Table 5. A coated plate was prepared. The comparative example 6 was made into the 2 liquid form which adds and mixes the hydrolysis-condensation catalyst which is a compound which accelerates | stimulates hydrolysis and condensation of an alkoxy silyl group at room temperature to the clear coating material of the comparative example 5, and coats it 30 minutes later. Exposure of these coated plates, water contact angle upon completion of curing (initial), and water immersion for 14 days at room temperature, and measurement of water contact angle (after water immersion) after drying for about 6 hours indoors were performed. The results are shown in Table 5.
実施例１１、１２、比較例７、８、９
水性樹脂組成物Ｄ、Ｉに表６に示す顔料ペースト、表７に示す添加剤を室温、攪拌下で加え白エナメル塗料を得た。比較例８は、比較例７の白エナメル塗料に室温でアルコキシシリル基の加水分解・縮合を促進する化合物である加水分解縮合触媒を加えて混合、３０分後に塗装を行う、２液形態とした。比較例９は、市販の１液水系アクリル塗料である亜細亜工業（株）製ネオグロスＧ−８０（白）をそのまま用いた。厚さ４ｍｍ、幅４０ｍｍ、長さ１５０ｍｍのＪＩＳ Ａ５４３０スレート板に関西ペイント（株）製アレスゴムタイルシーラーを室温下エアスプレーで塗装、１日乾燥し、これに白エナメル塗料を室温下、塗装間隔２４時間でエアスプレー２回塗装（塗布量合計約０．３Ｋｇ／ｍ2）、直射日光の当たらない室内で室温下、７日養生を行って塗板を作製した。これらの塗板を兵庫県高砂市内で南面４５°で固定し、屋外暴露を行った。この際の養生完了時の水接触角（初期）および各暴露期間での水接触角、各暴露期間での耐汚染性、養生完了時の光沢の測定を行った。結果を表７に示す。
Examples 11 and 12, Comparative Examples 7, 8, and 9
The pigment paste shown in Table 6 and the additive shown in Table 7 were added to aqueous resin compositions D and I under stirring at room temperature to obtain a white enamel paint. In Comparative Example 8, the white enamel paint of Comparative Example 7 was mixed with a hydrolysis-condensation catalyst, which is a compound that promotes hydrolysis / condensation of alkoxysilyl groups at room temperature, and the coating was performed after 30 minutes. . In Comparative Example 9, Neogros G-80 (white) manufactured by Asia Industries, which is a commercially available one-component water-based acrylic paint, was used as it was. ARES rubber tile sealer manufactured by Kansai Paint Co., Ltd. with a thickness of 4 mm, width 40 mm, and length 150 mm is coated with air spray at room temperature and dried for one day, and then white enamel paint is coated at room temperature at a coating interval of 24 Air spray was applied twice over time (a total coating amount of about 0.3 kg / m 2 ), and curing was performed for 7 days at room temperature in a room not exposed to direct sunlight to prepare a coated plate. These coated plates were fixed at a south surface of 45 ° in Takasago City, Hyogo Prefecture, and exposed outdoors. At this time, the water contact angle at the completion of curing (initial), the water contact angle at each exposure period, the contamination resistance at each exposure period, and the gloss at the completion of curing were measured. The results are shown in Table 7.
実施例１３、１４、１５、１６比較例１０、１１
水性樹脂組成物Ｅ、Ｇ、Ｈ、Ｊに表６に示す顔料ペースト、表８に示す添加剤を室温、攪拌下で加え白エナメル塗料を得た。比較例１１は、比較例１０の白エナメル塗料に室温でアルコキシシリル基の加水分解・縮合を促進する化合物である加水分解縮合触媒を加えて混合、３０分後に塗装を行う、２液形態とした。厚さ４ｍｍ、幅４０ｍｍ、長さ１５０ｍｍのＪＩＳ Ａ５４３０スレート板に関西ペイント（株）製アレスゴムタイルシーラーを室温下エアスプレーで塗装、１日乾燥し、これに白エナメル塗料を室温下、塗装間隔２４時間でエアスプレー２回塗装（塗布量合計約０．３Ｋｇ／ｍ2）、直射日光の当たらない室内で室温下、７日養生を行って塗板を作製した。これらの塗板を兵庫県高砂市内で南面４５°で固定し、屋外暴露を行った。
Examples 13, 14, 15, 16 Comparative Examples 10, 11
The pigment paste shown in Table 6 and the additive shown in Table 8 were added to aqueous resin compositions E, G, H, and J under stirring at room temperature to obtain a white enamel paint. In Comparative Example 11, the white enamel paint of Comparative Example 10 was mixed with a hydrolysis-condensation catalyst, which is a compound that promotes hydrolysis / condensation of alkoxysilyl groups at room temperature, and the coating was performed after 30 minutes. . ARES rubber tile sealer manufactured by Kansai Paint Co., Ltd. with a thickness of 4 mm, width 40 mm, and length 150 mm is coated with air spray at room temperature and dried for one day, and then white enamel paint is coated at room temperature at a coating interval of 24 Air spray was applied twice over time (a total coating amount of about 0.3 kg / m 2 ), and curing was performed for 7 days at room temperature in a room not exposed to direct sunlight to prepare a coated plate. These coated plates were fixed at a south surface of 45 ° in Takasago City, Hyogo Prefecture, and exposed outdoors.
さらに、上記方法にて作成した白エナメル塗料を遮光密閉下５０℃に静置した。１０日間静置後の塗料を使用して、同様の方法にて塗板を作成し、屋外曝露を実施した。この際の養生完了時の水接触角（初期）および各暴露期間での水接触角、各暴露期間での耐汚染性、養生完了時の光沢の測定を行った。結果を表８に示す。 Furthermore, the white enamel paint prepared by the above method was allowed to stand at 50 ° C. in a light-tight sealed state. Using the paint after standing for 10 days, a coated plate was prepared in the same manner and exposed outdoors. At this time, the water contact angle at the completion of curing (initial), the water contact angle at each exposure period, the contamination resistance at each exposure period, and the gloss at the completion of curing were measured. The results are shown in Table 8.
なお、測定は下記の方法によった。
・水接触角
協和界面科学（株）製接触角測定機ＣＡ−Ｓ１５０を使用し、純水の接触角を測定した。値が低いほど表面親水性が高く、耐汚染性に優れることを示し、７０°以下であれば実際の屋外暴露試験での耐汚染性の効果が顕著となる傾向がある。特に水浸漬後の値は、降雨後の状態を想定しており、この値が低いことは、表面親水性の耐久性、持続性が高く、長期にわたる耐汚染性の効果が顕著となる傾向がある。
・耐汚染性
ミノルタ（株）製測色計ＣＲ−３００を使用し、暴露開始前と各暴露期間でＬ＊、ａ＊、ｂ＊値を測定し、各暴露期間でのＬ＊と暴露開始前のＬ＊から明度差（ΔＬ）を算出した。値が大きい（０に近い）ほど汚染物質の付着による色相変化が小さく、耐汚染性に優れることを示す。
・光沢
ミノルタ（株）製光沢計Ｍｕｌｔｉ−Ｇｌｏｓｓ２６８を使用し、入射角６０°の光沢値を測定した。値が高いほど外観に優れることを示す。
The measurement was performed according to the following method.
-Water contact angle The contact angle measuring device CA-S150 by Kyowa Interface Science Co., Ltd. was used, and the contact angle of pure water was measured. The lower the value, the higher the surface hydrophilicity and the better the stain resistance. If it is 70 ° or less, the effect of the stain resistance in the actual outdoor exposure test tends to be remarkable. In particular, the value after water immersion assumes the state after rain, and this low value tends to have a high durability and long-lasting surface hydrophilic property, and a long-term antifouling effect tends to be prominent. is there.
・ Contamination resistance Using a CR-300 color meter manufactured by Minolta Co., Ltd., measured L *, a *, and b * values before the start of exposure and during each exposure period. L * and start of exposure during each exposure period The brightness difference (ΔL) was calculated from the previous L *. A larger value (closer to 0) indicates a smaller change in hue due to the adhesion of contaminants, indicating superior stain resistance.
Gloss Using a gloss meter Multi-Gloss 268 manufactured by Minolta Co., Ltd., the gloss value at an incident angle of 60 ° was measured. Higher values indicate better appearance.
実施例１〜６は、塗膜の水浸漬後の水接触角が室内養生で８４°以上であるが、ＵＶ照射または屋外暴露を行った後では室内養生に対して１０°程度低下し、露光による表面親水化の効果が認められた。特に（IV）成分としてジ−２−エチルヘキシルホスフェートのナトリウム塩を用いる実施例４〜６は、露光時の水浸漬後の水接触角がより低く、親水性向上が認められた。 In Examples 1 to 6, the water contact angle after water immersion of the coating film is 84 ° or more in indoor curing, but after UV irradiation or outdoor exposure, the contact angle decreases by about 10 ° with respect to indoor curing. The effect of hydrophilizing the surface was observed. In particular, Examples 4 to 6 using a sodium salt of di-2-ethylhexyl phosphate as the component (IV) had a lower water contact angle after water immersion during exposure, and improved hydrophilicity was observed.
比較例１、２は、（III）成分を含有しておらず、露光の有無によらず塗膜の水浸漬後の水接触角が８２°以上となり、表面親水性が十分ではなかった。 Comparative Examples 1 and 2 did not contain the component (III), the water contact angle after water immersion of the coating film was 82 ° or more regardless of the presence or absence of exposure, and the surface hydrophilicity was not sufficient.
実施例７、８は、クリアー塗料の室温５日貯蔵後で、塗膜の水浸漬後の水接触角が室内養生で７６°以上であるが、ＵＶ照射を行った後で１０°程度低下し、比較例３、４の（III）成分を含有せず、アルコキシシリル基の加水分解・縮合を促進する化合物を塗装時に添加する２液形態の塗装時間３０分での水浸漬後の水接触角と同等となり、露光による表面親水化の効果が認められた。さらに、クリアー塗料の５０℃、２８日貯蔵後でも同様の水接触角挙動となっており、表面親水性の貯蔵安定性が良好であった。 In Examples 7 and 8, after the clear paint was stored at room temperature for 5 days, the water contact angle after water immersion of the coating film was 76 ° or more by indoor curing, but it decreased by about 10 ° after UV irradiation. The water contact angle after immersion in water in a coating time of 30 minutes in a two-component form in which a compound that does not contain the component (III) of Comparative Examples 3 and 4 and accelerates hydrolysis / condensation of alkoxysilyl groups is added during coating The effect of surface hydrophilization by exposure was recognized. Furthermore, even after the clear paint was stored at 50 ° C. for 28 days, the water contact angle behavior was the same, and the storage stability of the hydrophilic surface was good.
比較例３、４は、（III）成分を含有せず、アルコキシシリル基の加水分解・縮合を促進する化合物を塗装時に添加する２液形態であるが、塗膜の水浸漬後の水接触角が塗装時間３０分では７３°以下となるが、塗装時間１日では８３°以上となり、アルコキシシリル基の加水分解・縮合を促進する化合物である通常の加水分解縮合触媒の添加では表面親水性の貯蔵安定性が十分ではなかった。 Comparative Examples 3 and 4 are two-component forms in which a compound that does not contain the component (III) and accelerates hydrolysis / condensation of alkoxysilyl groups is added during coating, but the water contact angle after water immersion of the coating film However, when the coating time is 30 minutes, it is 73 ° or less, but when the coating time is 1 day, it is 83 ° or more. With the addition of a normal hydrolysis-condensation catalyst which is a compound that promotes hydrolysis / condensation of alkoxysilyl groups, Storage stability was not sufficient.
実施例９、１０は、クリアー塗料の室温１日貯蔵後で、塗膜の水浸漬後の水接触角が室内養生では、比較例５の（III）成分を含有しないものと同等の７８°であるが、ＵＶ照射を行った後で１０°程度低下し、比較例６の（III）成分を含有せず、アルコキシシリル基の加水分解・縮合を促進する化合物を塗装時に添加する２液形態での水浸漬後の水接触角と同等の６７°以下となり、露光による表面親水化の効果が認められた。さらに、クリアー塗料の室温、２８日貯蔵後でも同様の水接触角挙動となっており、表面親水性の貯蔵安定性が良好であった。 In Examples 9 and 10, the clear water paint was stored at room temperature for 1 day, and the water contact angle after water immersion of the coating film was 78 ° which was the same as that of Comparative Example 5 not containing the component (III). However, in a two-part form, a compound that decreases about 10 ° after UV irradiation and does not contain the component (III) of Comparative Example 6 and accelerates hydrolysis / condensation of alkoxysilyl groups is added during coating. It became 67 degrees or less equivalent to the water contact angle after water immersion, and the effect of surface hydrophilization by exposure was recognized. Further, even after the clear paint was stored at room temperature for 28 days, the water contact angle behavior was the same, and the storage stability of the hydrophilic surface was good.
実施例１１、１２は、白エナメル塗料の塗板の屋外暴露において、水接触角が期間に応じて低下し、耐汚染性が比較例８の（III）成分を含有せず、アルコキシシリル基の加水分解・縮合を促進する化合物を塗装時に添加する２液形態と同等であり、実使用条件の暴露による表面親水化、耐汚染性付与の効果が認められた。 In Examples 11 and 12, when the white enamel coating plate was exposed outdoors, the water contact angle decreased according to the period, the contamination resistance did not contain the component (III) of Comparative Example 8, and the alkoxysilyl group was hydrolyzed. This is equivalent to the two-component form in which a compound that promotes decomposition / condensation is added at the time of coating, and the effect of imparting surface hydrophilicity and contamination resistance by exposure under actual use conditions was recognized.
比較例７は、（III）成分を含有せず、塗板の屋外暴露で水接触角の低下が小さく、耐汚染性が比較例９の市販の１液水系アクリル塗料と同等であり悪く、表面親水化、耐汚染性付与の効果が十分ではなかった。 Comparative Example 7 does not contain the component (III), the decrease in water contact angle is small when exposed to the coating plate, the stain resistance is equivalent to the commercially available one-component water-based acrylic paint of Comparative Example 9, and the surface hydrophilicity is poor. And the effect of imparting stain resistance was not sufficient.
実施例１３、１４、１５、１６は、白エナメル塗料の塗板の屋外暴露において、水接触角が期間に応じて低下し、耐汚染性が比較例１１の（III）成分を含有せず、アルコキシシリル基の加水分解・縮合を促進する化合物を塗装時に添加する２液形態と同等であり、実使用条件の暴露による表面親水化、耐汚染性付与の効果が認められた。 In Examples 13, 14, 15, and 16, when the white enamel coating plate was exposed outdoors, the water contact angle decreased with time, the stain resistance did not contain the component (III) of Comparative Example 11, and the alkoxy This is equivalent to the two-component form in which a compound that promotes hydrolysis / condensation of silyl groups is added at the time of coating, and the effect of imparting surface hydrophilicity and imparting stain resistance by exposure under actual use conditions was recognized.
さらに５０℃で１０日間保存後の塗料を使用しても、曝露により表面の親水化および耐汚染性の効果が認められた。 Further, even when the paint after storage at 50 ° C. for 10 days was used, the effects of surface hydrophilization and stain resistance were recognized by exposure.
比較例１０は、（III）成分を含有せず、塗板の屋外暴露で水接触角の低下が小さく、耐汚染性が悪く、表面親水化、耐汚染性付与の効果が十分ではなかった。 In Comparative Example 10, the component (III) was not contained, and the decrease in the water contact angle was small due to outdoor exposure of the coated plate, the stain resistance was poor, and the effect of imparting surface hydrophilization and stain resistance was not sufficient.
比較例１１は、初期の表面親水化および耐汚染性の効果は良好なものの、５０℃で１０日間保存した後には、何れの効果も確認できなかった。 In Comparative Example 11, although the effects of the initial surface hydrophilization and stain resistance were good, none of the effects could be confirmed after storage at 50 ° C. for 10 days.
以上のように本発明の水性樹脂組成物は、１液型の塗料形態においても良好な表面親水性およびその貯蔵安定性を有していることが確認され、耐汚染性に優れた塗膜を与える水性樹脂組成物として有用であることが確認された。 As described above, it is confirmed that the aqueous resin composition of the present invention has good surface hydrophilicity and storage stability even in the form of a one-pack type paint, and a coating film excellent in stain resistance is obtained. It was confirmed to be useful as an aqueous resin composition.
Claims (9)
（II）下記一般式（１）で示されるシリコン化合物および／またはその部分加水分解縮合物
（Ｒ1Ｏ）4-aＳｉＲ2 a （１）
（式中、Ｒ1は同じかまたは異なり、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基または炭素数７〜１０のアラルキル基、Ｒ2は同じかまたは異なり、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基、または炭素数７〜１０のアラルキル基、ａは０〜２の整数。）
（III）光酸発生剤
を含有する水性塗料用樹脂組成物。 (I) Synthetic resin emulsion (II) Silicon compound represented by the following general formula (1) and / or its partial hydrolysis condensate (R 1 O) 4-a SiR 2 a (1)
(Wherein R 1 is the same or different, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, R 2 is the same or different and has 1 carbon atom) C-10 alkyl group, C6-C10 aryl group, or C7-C10 aralkyl group, a is an integer of 0-2.)
(III) A resin composition for water-based paints containing a photoacid generator.
（Ｒ3Ｏ）4Ｓｉ （２）
（式中、Ｒ3は同じかまたは異なり、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基または炭素数７〜１０のアラルキル基）である請求項１記載の水性塗料用樹脂組成物。 The (II) silicon compound and / or its partially hydrolyzed condensate is an organosilicate (a compound represented by the following general formula (2) and / or a partially hydrolyzed condensate thereof) and / or a modified product thereof (R 3 O 4 Si (2)
The resin for water-based paint according to claim 1, wherein R 3 is the same or different and is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. Composition.
A resin composition for a one-component water-based paint comprising (I), (II), (III) according to any one of claims 1 to 8, and (IV) as required.
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| JPWO2015008777A1 (en) * | 2013-07-16 | 2017-03-02 | 株式会社カネカ | Active energy ray-curable resin composition for organic / inorganic substrate coating |
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|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |