JP2016020462A - Hydrophilic treatment coating composition and hydrophilic treatment method - Google Patents
Hydrophilic treatment coating composition and hydrophilic treatment method Download PDFInfo
- Publication number
- JP2016020462A JP2016020462A JP2014145542A JP2014145542A JP2016020462A JP 2016020462 A JP2016020462 A JP 2016020462A JP 2014145542 A JP2014145542 A JP 2014145542A JP 2014145542 A JP2014145542 A JP 2014145542A JP 2016020462 A JP2016020462 A JP 2016020462A
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- Japan
- Prior art keywords
- group
- hydrophilic
- silane coupling
- coupling agent
- functional group
- Prior art date
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- 238000011282 treatment Methods 0.000 title claims abstract description 43
- 239000008199 coating composition Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 13
- 150000002433 hydrophilic molecules Chemical class 0.000 claims abstract description 59
- 125000000524 functional group Chemical group 0.000 claims abstract description 53
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000002344 surface layer Substances 0.000 claims abstract description 27
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 27
- 125000003277 amino group Chemical group 0.000 claims abstract description 26
- -1 alkali metal salt Chemical class 0.000 claims abstract description 25
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 24
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 20
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 16
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 150000001720 carbohydrates Chemical class 0.000 claims description 3
- 230000009257 reactivity Effects 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- 229910052571 earthenware Inorganic materials 0.000 abstract description 11
- 238000004140 cleaning Methods 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 abstract description 4
- 229910052791 calcium Inorganic materials 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 3
- 230000007423 decrease Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000010410 layer Substances 0.000 description 28
- 239000011248 coating agent Substances 0.000 description 27
- 238000000576 coating method Methods 0.000 description 27
- 239000007864 aqueous solution Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 125000005372 silanol group Chemical group 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 239000004202 carbamide Substances 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- GWLWWNLFFNJPDP-UHFFFAOYSA-M sodium;2-aminoethanesulfonate Chemical compound [Na+].NCCS([O-])(=O)=O GWLWWNLFFNJPDP-UHFFFAOYSA-M 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- 229930006000 Sucrose Natural products 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- IMYBWPUHVYRSJG-UHFFFAOYSA-M potassium;2-aminoethanesulfonate Chemical compound [K+].NCCS([O-])(=O)=O IMYBWPUHVYRSJG-UHFFFAOYSA-M 0.000 description 3
- LADXKQRVAFSPTR-UHFFFAOYSA-M sodium;2-hydroxyethanesulfonate Chemical compound [Na+].OCCS([O-])(=O)=O LADXKQRVAFSPTR-UHFFFAOYSA-M 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 2
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 2
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 239000004386 Erythritol Substances 0.000 description 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 2
- 235000019414 erythritol Nutrition 0.000 description 2
- 229940009714 erythritol Drugs 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229940102253 isopropanolamine Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- FHWJIBJQYPWBNC-UHFFFAOYSA-M sodium 3-(oxiran-2-yl)propane-1-sulfonate Chemical compound C(C1CO1)CCS(=O)(=O)[O-].[Na+] FHWJIBJQYPWBNC-UHFFFAOYSA-M 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 2
- KSVSZLXDULFGDQ-UHFFFAOYSA-M sodium;4-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C=C1 KSVSZLXDULFGDQ-UHFFFAOYSA-M 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XUFXOAAUWZOOIT-SXARVLRPSA-N (2R,3R,4R,5S,6R)-5-[[(2R,3R,4R,5S,6R)-5-[[(2R,3R,4S,5S,6R)-3,4-dihydroxy-6-methyl-5-[[(1S,4R,5S,6S)-4,5,6-trihydroxy-3-(hydroxymethyl)-1-cyclohex-2-enyl]amino]-2-oxanyl]oxy]-3,4-dihydroxy-6-(hydroxymethyl)-2-oxanyl]oxy]-6-(hydroxymethyl)oxane-2,3,4-triol Chemical compound O([C@H]1O[C@H](CO)[C@H]([C@@H]([C@H]1O)O)O[C@H]1O[C@@H]([C@H]([C@H](O)[C@H]1O)N[C@@H]1[C@@H]([C@@H](O)[C@H](O)C(CO)=C1)O)C)[C@@H]1[C@@H](CO)O[C@@H](O)[C@H](O)[C@H]1O XUFXOAAUWZOOIT-SXARVLRPSA-N 0.000 description 1
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- VSFYNOPUGFDOEQ-UHFFFAOYSA-N 2-(diethylamino)ethanol;2-(dimethylamino)ethanol Chemical compound CN(C)CCO.CCN(CC)CCO VSFYNOPUGFDOEQ-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
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- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- RXCMFQDTWCCLBL-UHFFFAOYSA-N 4-amino-3-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(N)=C(O)C=C(S(O)(=O)=O)C2=C1 RXCMFQDTWCCLBL-UHFFFAOYSA-N 0.000 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
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- SBVKVAIECGDBTC-UHFFFAOYSA-N 4-hydroxy-2-methylidenebutanamide Chemical compound NC(=O)C(=C)CCO SBVKVAIECGDBTC-UHFFFAOYSA-N 0.000 description 1
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- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
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- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- OBESRABRARNZJB-UHFFFAOYSA-N aminomethanesulfonic acid Chemical compound NCS(O)(=O)=O OBESRABRARNZJB-UHFFFAOYSA-N 0.000 description 1
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- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- IIYKIPRBEOUOJY-UHFFFAOYSA-L calcium;2-hydroxyethanesulfonate Chemical compound [Ca+2].OCCS([O-])(=O)=O.OCCS([O-])(=O)=O IIYKIPRBEOUOJY-UHFFFAOYSA-L 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
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- 235000019425 dextrin Nutrition 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
- 235000006694 eating habits Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IBKNSIPMTGYUNZ-UHFFFAOYSA-N ethenyl(methoxy)silane Chemical compound CO[SiH2]C=C IBKNSIPMTGYUNZ-UHFFFAOYSA-N 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002972 pentoses Chemical class 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 235000014786 phosphorus Nutrition 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- BTAAXEFROUUDIL-UHFFFAOYSA-M potassium;sulfamate Chemical compound [K+].NS([O-])(=O)=O BTAAXEFROUUDIL-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- WUWHFEHKUQVYLF-UHFFFAOYSA-M sodium;2-aminoacetate Chemical compound [Na+].NCC([O-])=O WUWHFEHKUQVYLF-UHFFFAOYSA-M 0.000 description 1
- KYXOYPPMBYKBFL-UHFFFAOYSA-M sodium;2-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=CC=C1S([O-])(=O)=O KYXOYPPMBYKBFL-UHFFFAOYSA-M 0.000 description 1
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 150000003538 tetroses Chemical class 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 150000003641 trioses Chemical class 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、陶器、ガラス、金属などの無機化合物を含有する表面層の洗浄性を向上させるために、その表面層を親水化する処理を行う組成物及びその方法に関するものである。 The present invention relates to a composition and method for performing a treatment for hydrophilizing a surface layer in order to improve the detergency of the surface layer containing an inorganic compound such as earthenware, glass or metal.
従来、便器、洗面台など水回りに設置される陶器類などに対して、表面の汚れを洗浄し易くするために種々の表面処理が行われている。近年における人の食生活の欧米化の影響により汚れには油成分が増加しているため、それら陶器類の表面の汚れを充分に洗浄することが難しくなってきている。 Conventionally, various surface treatments have been performed on ceramics installed around water such as toilets and washstands in order to facilitate cleaning of surface dirt. In recent years, due to the influence of westernization of human dietary habits, oil components have increased in the soil, and it has become difficult to sufficiently clean the surface soil of these ceramics.
特許文献１には、ガラス板などの基材表面に防汚性、耐摩擦性などに優れた親水性膜を形成するために、エポキシ基又はイソシアネート基を含むシランカップリング剤と、それらエポキシ基又はイソシアネート基と反応させる官能基及びスルホン酸カリウムなどの親水基を有する親水性ポリマーと、テトラアルコキシシランなどのアルコキシド化合物などを含む組成物が開示されている。 In Patent Document 1, a silane coupling agent containing an epoxy group or an isocyanate group, and those epoxy groups are used to form a hydrophilic film excellent in antifouling property, friction resistance, etc. on the surface of a substrate such as a glass plate. Alternatively, a composition comprising a hydrophilic polymer having a functional group to be reacted with an isocyanate group and a hydrophilic group such as potassium sulfonate and an alkoxide compound such as tetraalkoxysilane is disclosed.
しかしながら、特許文献１に記載の組成物は、ガラス基板などの表面に製膜したときに、親水性ポリマーの重量平均分子量が３０００〜９９００と主鎖が長いために親水基が表面に集約されにくく、塗膜の親水性が充分ではないことが懸念される。 However, when the composition described in Patent Document 1 is formed on the surface of a glass substrate or the like, the hydrophilic group is not easily concentrated on the surface because the weight average molecular weight of the hydrophilic polymer is 3000 to 9900 and the main chain is long. There is a concern that the hydrophilicity of the coating film is not sufficient.
そこで、本発明は、便器、洗面台など水回りに設置され、酸化ケイ素などの無機化合物が含有される陶器類などに対して、カルシウムなどの沈着を防ぐとともに、菌の繁殖や臭気の原因となる油性の汚れも洗浄しやすくすることによって、清掃回数を低減することができる親水化処理剤及びその親水化処理方法を提供することを課題とする。 Therefore, the present invention is installed around the water, such as toilet bowls and washstands, and prevents the deposition of calcium and the like on ceramics containing inorganic compounds such as silicon oxide, and causes the growth of bacteria and odors. It is an object of the present invention to provide a hydrophilization treatment agent and a hydrophilization treatment method capable of reducing the number of times of cleaning by facilitating washing of oily dirt.
〔１〕すなわち、本発明は、無機化合物を含有する表面層を、イソシアネート基、エポキシ基、アミノ基、メルカプト基から選ばれる少なくとも一つの反応性官能基を含有するシランカップリング剤によって処理した後に、前記シランカップリング剤の反応性官能基に対して反応させる組成物であって、アミノ基、水酸基、メルカプト基、エポキシ基から選ばれる少なくとも一つであって、前記シランカップリング剤の反応性官能基と反応する官能基と、スルホン酸又はスルホン酸基のアルカリ金属塩を含有し、分子鎖の端部以外に親水部を含有しない親水性化合物と、極性を有する相溶化剤を含有する親水処理塗料組成物である。 [1] That is, in the present invention, a surface layer containing an inorganic compound is treated with a silane coupling agent containing at least one reactive functional group selected from an isocyanate group, an epoxy group, an amino group, and a mercapto group. A composition that reacts with a reactive functional group of the silane coupling agent, wherein the composition is at least one selected from an amino group, a hydroxyl group, a mercapto group, and an epoxy group, and the reactivity of the silane coupling agent A hydrophilic group containing a functional group that reacts with a functional group, a sulfonic acid or an alkali metal salt of a sulfonic acid group, a hydrophilic compound that does not contain a hydrophilic part other than the end of the molecular chain, and a compatibilizer having polarity It is a processing coating composition.
〔２〕そして、無機化合物を含有する表面層に対して反応させる組成物であって、（ａ）イソシアネート基、エポキシ基、アミノ基、メルカプト基から選ばれる少なくとも一つの反応性官能基を含有するシランカップリング剤と、（ｂ）アミノ基、水酸基、メルカプト基、エポキシ基から選ばれる少なくとも一つであって、前記シランカップリング剤の反応性官能基と反応する官能基と、スルホン酸基又はスルホン酸基のアルカリ金属塩を含有し、分子鎖の端部以外に親水部を含有しない親水性化合物と、（ｃ）極性を有する相溶化剤を含有する親水処理塗料組成物である。 [2] A composition that reacts with a surface layer containing an inorganic compound, and (a) contains at least one reactive functional group selected from an isocyanate group, an epoxy group, an amino group, and a mercapto group. A silane coupling agent, and (b) at least one selected from an amino group, a hydroxyl group, a mercapto group, and an epoxy group, a functional group that reacts with a reactive functional group of the silane coupling agent, a sulfonic acid group, or It is a hydrophilic treatment coating composition containing a hydrophilic compound containing an alkali metal salt of a sulfonic acid group and containing no hydrophilic part other than the molecular chain end, and (c) a compatibilizer having polarity.
〔３〕そして、前記シランカップリング剤の反応性官能基と前記親水性化合物の官能基との反応を促進する反応触媒を含有することを特徴とする前記〔１〕又は前記〔２〕に記載の親水処理塗料組成物である。 [3] The method according to [1] or [2], further comprising a reaction catalyst that promotes a reaction between the reactive functional group of the silane coupling agent and the functional group of the hydrophilic compound. This is a hydrophilic treatment coating composition.
〔４〕そして、前記親水性化合物の数平均分子量が、７０〜５００であることを特徴とする前記〔１〕から前記〔３〕のいずれかに記載の親水処理塗料組成物である。 [4] The hydrophilic treatment coating composition according to any one of [1] to [3], wherein the hydrophilic compound has a number average molecular weight of 70 to 500.
〔５〕そして、前記相溶化剤が、アミド化合物、非プロトン性極性溶媒、多価アルコール、糖類、極性を有する樹脂、無機塩類から選択される少なくとも一種であることを特徴とする前記〔１〕から前記〔４〕のいずれかに記載の親水処理塗料組成物である。 [5] The compatibilizer is at least one selected from amide compounds, aprotic polar solvents, polyhydric alcohols, saccharides, polar resins, and inorganic salts. [1] To [4].
〔６〕そして無機化合物を含有する表面層を、イソシアネート基、エポキシ基、アミノ基、メルカプト基から選ばれる少なくとも一つの反応性官能基を含有するシランカップリング剤によって処理し、前記シランカップリング剤と結合した前記表面層に、アミノ基、水酸基、メルカプト基から選ばれる少なくとも一つであって、前記シランカップリング剤の反応性官能基と反応する官能基と、スルホン酸又はスルホン酸基のアルカリ金属塩を含有し、分子鎖の端部以外に親水部を含有しない親水性化合物と、極性を有する相溶化剤を含有する親水処理塗料組成物を塗布し、熱により前記シランカップリング剤の反応性官能基と前記親水性化合物の官能基を反応させることを特徴とする親水化処理方法である。 [6] The surface layer containing an inorganic compound is treated with a silane coupling agent containing at least one reactive functional group selected from an isocyanate group, an epoxy group, an amino group, and a mercapto group, and the silane coupling agent The surface layer bonded to the silane coupling agent is at least one selected from an amino group, a hydroxyl group, and a mercapto group, the functional group reacting with the reactive functional group of the silane coupling agent, and an alkali of a sulfonic acid or a sulfonic acid group A hydrophilic treatment coating composition containing a hydrophilic compound containing a metal salt and not containing a hydrophilic part other than the molecular chain end and a compatibilizer having polarity is applied, and the reaction of the silane coupling agent by heat is applied. The hydrophilic treatment method is characterized by reacting a functional group with a functional group of the hydrophilic compound.
〔７〕そして、無機化合物を含有する表面層を、イソシアネート基、エポキシ基、アミノ基、メルカプト基から選ばれる少なくとも一つの反応性官能基を含有するシランカップリング剤によって処理し、前記シランカップリング剤と結合した前記表面層に、アミノ基、水酸基、メルカプト基から選ばれる少なくとも一つであって、前記シランカップリング剤の反応性官能基と反応する官能基とスルホン酸基を含有し、分子鎖の端部以外に親水部を含有しない親水性化合物と、極性を有する相溶化剤を含有する親水処理塗料組成物を塗布し、熱により前記シランカップリング剤の反応性官能基と前記親水性化合物の官能基を反応させ、前記親水性化合物のスルホン酸基をアルカリ金属の水酸化物で反応させることによりスルホン酸塩を形成させることを特徴とする親水化処理方法である。 [7] The surface layer containing an inorganic compound is treated with a silane coupling agent containing at least one reactive functional group selected from an isocyanate group, an epoxy group, an amino group, and a mercapto group, and the silane coupling is performed. The surface layer bonded to the agent contains at least one selected from an amino group, a hydroxyl group, and a mercapto group, and includes a functional group that reacts with a reactive functional group of the silane coupling agent and a sulfonic acid group, and a molecule. A hydrophilic compound containing no hydrophilic part other than the chain end and a hydrophilic treatment coating composition containing a polar compatibilizing agent is applied, and the reactive functional group of the silane coupling agent and the hydrophilicity are applied by heat. The sulfonate is formed by reacting the functional group of the compound and reacting the sulfonic acid group of the hydrophilic compound with an alkali metal hydroxide. It is hydrophilic treatment method comprising.
本発明によれば、便器、洗面台など水回りに設置され、酸化ケイ素などの無機化合物が含有される陶器類などに対して、カルシウムなどの無機化合物の沈着を防ぐとともに、菌の繁殖や臭気の原因となる油性の汚れも洗浄しやすくすることによって、清掃回数を低減することができる。 According to the present invention, in addition to preventing the deposition of inorganic compounds such as calcium on pottery and the like that are installed around the water, such as toilets and washstands, and contain inorganic compounds such as silicon oxide, the growth of bacteria and odor The number of cleanings can be reduced by facilitating the cleaning of oily dirt that causes water.
以下、本発明に係る親水処理塗料組成物及び親水化処理方法に関する実施形態について詳しく説明する。なお、数量の範囲を示す表現は上限と下限を含むものである。 Hereinafter, embodiments relating to the hydrophilic treatment coating composition and the hydrophilic treatment method according to the present invention will be described in detail. The expression indicating the range of quantities includes an upper limit and a lower limit.
便器、洗面台など水回りに設置される陶器類は、素焼きにした陶器類の表面に灰釉などの釉薬を釉掛けし、焼成することで、陶器類の表面にガラス質の層が形成されるという表面処理が行われている。この釉薬による表面処理が行われることにより、その表面層には無機化合物である酸化ケイ素が多数存在するためシラノール基も多数存在する。 Ceramics installed around the water, such as toilets and washstands, are glazed with a glaze such as ash glaze on the surface of unglazed ceramics, and a glassy layer is formed on the surface of the ceramics. Surface treatment is performed. By performing the surface treatment with this glaze, a large number of silanol groups are also present in the surface layer because there are a large number of silicon oxides which are inorganic compounds.
本発明の親水処理塗料組成物を塗布する前段階で、陶器類の表面層を、イソシアネート基、エポキシ基、アミノ基、メルカプト基から選ばれる少なくとも一つの反応性官能基を含有するシランカップリング剤によって処理されたプライマー層が設けられてもよい。プライマー層は、陶器類の表面層と、本発明の親水処理塗料組成物との間に位置し、本発明の親水処理塗料組成物の一部を陶器類の表面層に結合させるためのバインダーの役割を果たす。 A silane coupling agent containing at least one reactive functional group selected from an isocyanate group, an epoxy group, an amino group, and a mercapto group in the surface layer of the earthenware before the application of the hydrophilic treatment coating composition of the present invention A primer layer treated by may be provided. The primer layer is located between the surface layer of the earthenware and the hydrophilic treatment coating composition of the present invention, and is a binder layer for binding a part of the hydrophilic treatment coating composition of the present invention to the surface layer of the earthenware. Play a role.
上記イソシアネート基、エポキシ基、アミノ基、メルカプト基から選ばれる少なくとも一つの反応性官能基を含有するシランカップリング剤は、具体的には、３−イソシアネートプロピルトリメトキシシラン、３−イソシアネートプロピルトリエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルトリエトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルメチルジメトシキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリエトキシシシラン、３−アミノプロピルトリメトシキシシラン、３−アミノプロピルトリエトシキシシラン、３−トリエトキシシリル−Ｎ−（１，３−ジメチル−ブチリデン）プロピルアミン、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン、Ｎ−（ビニルベンジル）−２−アミノエチル−３−アミノプロピルトリメトキシシランの塩酸塩、３−メルカプトプロピルメチルジメトキシシラン、３−メルカプトプロピルトリメトキシシランなどが好ましい。また、ケイ素原子に結合する加水分解基として、上記メトキシ基やエトキシ基などのアルコキシ基の他に、２−メトキシエトキシル基（ＣＨ３ＯＣＨ２ＣＨ２−Ｏ−）を有していてもよい。これらの市販品として、信越化学工業株式会社のＫＢＥ−９００７、ＫＢＭ−３０３、ＫＢＭ−４０２、ＫＢＭ−４０３、ＫＢＥ−４０２、ＫＢＥ−４０３、ＫＢＭ−６０２、ＫＢＭ−６０３、ＫＢＭ−９０３、ＫＢＥ−９０３、ＫＢＥ−９１０３、ＫＢＭ−５７３、ＫＢＭ−５７５、ＫＢＭ−８０２、ＫＢＭ−８０３、モーメンティブ・パフォーマンス・マテリアルズ合同会社のＹ−５１８７などを使用することができる。 Specific examples of the silane coupling agent containing at least one reactive functional group selected from the isocyanate group, epoxy group, amino group, and mercapto group include 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxy. Silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrime Tosoxysilane, 3-amino Propyl triethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl- Preference is given to hydrochloride of 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like. Further, as the hydrolyzable group bonded to a silicon atom, in addition to alkoxy groups, such as the methoxy group and an ethoxy group may have 2-methoxyethoxy Le based on (CH 3 OCH 2 CH 2 -O- ). As these commercially available products, KBE-9007, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-602, KBM-603, KBM-903, KBE- from Shin-Etsu Chemical Co., Ltd. 903, KBE-9103, KBM-573, KBM-575, KBM-802, KBM-803, Y-5187 of Momentive Performance Materials LLC, and the like can be used.
上記シランカップリング剤のアルコキシシランを加水分解して、生じたシラノール基を、陶器類の表面層に存在するシラノール基と脱水縮合反応させる。このとき、アルコキシシランを加水分解する触媒としては、酸性触媒；塩酸水溶液、硫酸水溶液、硝酸水溶液、リン酸水溶液、蟻酸、酢酸、プロピオン酸などのカルボン酸を有する化合物の水溶液、塩基性触媒；アンモニア水溶液、モルホリン、Ｎ−メチルモルホリン、Ｎ−エチルモルホリン、ピペラジン、ヒドロキシエチルピペラジン、２−メチルピペラジン、トランス２，５−ジメチルピペラジン、シス２，６−ジメチルピペラジン、トリエチルアミン、Ｎ，Ｎ−ジメチルエタノールアミン、Ｎ，Ｎ−ジエチルエタノールアミン、Ｎ−（β―アミノエチル）エタノールアミン、Ｎ−メチルジエタノールアミン、Ｎ−ｎ−ブチルエタノールアミン、Ｎ−ｎ−ブチルジエタノールアミン、Ｎ−ｔ−ブチルエタノールアミン、Ｎ−ｔ−ブチルジエタノールアミン、Ｎ−（β―アミノエチル）イソプロパノールアミン、Ｎ，Ｎ−ジエチルイソプロパノールアミン、２−アミノ−２−メチル−１−プロパノール、水酸化ナトリウム水溶液、水酸化カリウム水溶液などが好ましい。 The alkoxysilane of the silane coupling agent is hydrolyzed, and the resulting silanol group is subjected to a dehydration condensation reaction with the silanol group present in the surface layer of the earthenware. At this time, as a catalyst for hydrolyzing alkoxysilane, acidic catalyst; aqueous solution of hydrochloric acid, aqueous solution of sulfuric acid, aqueous solution of nitric acid, aqueous solution of phosphoric acid, aqueous solution of compound having carboxylic acid such as formic acid, acetic acid, propionic acid, basic catalyst; ammonia Aqueous solution, morpholine, N-methylmorpholine, N-ethylmorpholine, piperazine, hydroxyethylpiperazine, 2-methylpiperazine, trans 2,5-dimethylpiperazine, cis 2,6-dimethylpiperazine, triethylamine, N, N-dimethylethanolamine N, N-diethylethanolamine, N- (β-aminoethyl) ethanolamine, N-methyldiethanolamine, Nn-butylethanolamine, Nn-butyldiethanolamine, Nt-butylethanolamine, N- t-Butyl di Ethanolamine, N-(beta-aminoethyl) isopropanolamine, N, N-diethyl-isopropanolamine, 2-amino-2-methyl-1-propanol, aqueous sodium hydroxide, potassium hydroxide solution is preferred.
また、プライマー層を作成する組成物の溶剤として、メタノール、エタノール、イソプロピルアルコール、ｎ−プロピルアルコール、１−メトキシ−２−プロパノールなどのアルコール類、メチルエチルケトン、メチルイソブチルケトンなどのケトン類、酢酸エチルなどのエステル類などの有機溶媒、及び水が好ましい。 Further, as a solvent for the composition for forming the primer layer, alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, etc. Organic solvents such as esters and water are preferred.
プライマー層を作成する組成物において、上記シランカップリング剤の配合量は、０．０１〜１０重量％であることが好ましく、０．０５〜５重量％であることがさらに好ましく、０．１〜２重量％であることがもっとも好ましい。上記シランカップリング剤の配合量が０．０１重量％未満であるとプライマー層が十分に形成されず、後に結合される親水性化合物が少なくなるため親水性が低下する。また、上記シランカップリング剤の配合量が１０重量％を超えると前記カップリング剤同士が縮合反応してゲル化が生じたり、形成されたプライマー層に凹凸が生じたりする。 In the composition for forming the primer layer, the amount of the silane coupling agent is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, Most preferably, it is 2% by weight. When the blending amount of the silane coupling agent is less than 0.01% by weight, the primer layer is not sufficiently formed, and the hydrophilic compound to be bonded later decreases, so that the hydrophilicity is lowered. Moreover, when the compounding quantity of the said silane coupling agent exceeds 10 weight%, the said coupling agents will carry out a condensation reaction, gelling will arise, or an unevenness | corrugation will arise in the formed primer layer.
プライマー層は、具体的に下記に示すように作成される。 The primer layer is specifically created as shown below.
（プライマー層１）
３−イソシアネートプロピルトリメトキシシラン０．５重量部、１−メトキシ−２−プロパノール９９重量部を室温で攪拌混合した後に、３％塩酸水溶液０．５重量部を加えて、さらに３０分間攪拌し、加水分解を行う。そして得られた溶液を、予めメタノールで脱脂した陶器類の表面層に塗布した後に、電気オーブンを用いて６０℃下で３０分静置し、熱により溶媒などを揮発させるとともに３−イソシアネートプロピルトリメトキシシランから生じたシラノール基と陶器類の表面層のシラノール基を脱水縮合反応させてプライマー層を得た。
(Primer layer 1)
After stirring and mixing 0.5 parts by weight of 3-isocyanatopropyltrimethoxysilane and 99 parts by weight of 1-methoxy-2-propanol at room temperature, 0.5 part by weight of 3% hydrochloric acid aqueous solution was added and further stirred for 30 minutes. Hydrolyze. And after apply | coating the obtained solution to the surface layer of the ceramics degreased previously with methanol, it left still at 60 degreeC for 30 minutes using an electric oven, volatilizes a solvent etc. with a heat | fever, and also 3-isocyanate propyl tri A primer layer was obtained by dehydration condensation reaction of silanol groups generated from methoxysilane and silanol groups on the surface layer of the earthenware.
（プライマー層２）
３−グリシドキシプロピルトリメトキシシラン０．５重量部、１−メトキシ−２−プロパノール９９重量部を室温で攪拌混合した後に、３％塩酸水溶液０．５重量部を加えて、さらに３０分間攪拌し、加水分解を行う。そして得られた溶液を陶器類の表面層に塗布した後に、電気オーブンを用いて６０℃下で３０分静置し、熱により溶媒などを揮発させるとともにビニルメトキシシランから生じたシラノール基と陶器類の表面層のシラノール基を脱水縮合反応させてプライマー層を得た。
(Primer layer 2)
After 0.5 parts by weight of 3-glycidoxypropyltrimethoxysilane and 99 parts by weight of 1-methoxy-2-propanol were stirred and mixed at room temperature, 0.5 parts by weight of 3% hydrochloric acid aqueous solution was added and stirred for another 30 minutes. And hydrolyze. And after apply | coating the obtained solution to the surface layer of earthenware, it left still at 60 degreeC for 30 minutes using an electric oven, volatilizes a solvent etc. with heat, and the silanol group produced from vinyl methoxysilane, and earthenware The primer layer was obtained by subjecting the silanol group of the surface layer to dehydration condensation reaction.
こうして得られたプライマー層に対して、本発明の親水処理塗料組成物を反応させる表面処理を行う。当該親水処理塗料組成物としては、アミノ基、水酸基、メルカプト基、エポキシ基から選ばれる少なくとも一つであって、前記シランカップリング剤の反応性官能基と反応する官能基とスルホン酸基のアルカリ金属塩を含有し、分子鎖の端部以外に親水部を含有しない親水性化合物と、極性を有する相溶化剤を含有する。 The primer layer thus obtained is subjected to a surface treatment for reacting the hydrophilic treatment coating composition of the present invention. The hydrophilic treatment coating composition includes at least one selected from an amino group, a hydroxyl group, a mercapto group, and an epoxy group, and a functional group that reacts with a reactive functional group of the silane coupling agent and an alkali of a sulfonic acid group. A hydrophilic compound containing a metal salt and not containing a hydrophilic part other than the end of the molecular chain, and a compatibilizer having polarity are contained.
上記親水性化合物は、一端にシランカップリング剤のイソシアネート基、エポキシ基、アミノ基、メルカプト基から選ばれる少なくとも一つの反応性官能基と反応するアミノ基、水酸基、メルカプト基、エポキシ基から選ばれる少なくとも一つの官能基を有しており、他端にスルホン酸又はスルホン酸基のアルカリ金属塩を有しており、分子鎖の端部以外に親水基を有していない。このような構造を有することにより、親水性化合物の親水基を塗膜表面に集約し、便器、洗面台など水による洗浄が頻繁になされる陶器類に用いても十分な洗浄性を持たせることができる。また、親水基を特定の方向に配向させるために、親水性化合物には分岐鎖を有していないことがさらに好ましい。 The hydrophilic compound is selected at one end from an amino group, a hydroxyl group, a mercapto group, and an epoxy group that reacts with at least one reactive functional group selected from an isocyanate group, an epoxy group, an amino group, and a mercapto group of a silane coupling agent. It has at least one functional group, has a sulfonic acid or an alkali metal salt of a sulfonic acid group at the other end, and has no hydrophilic group other than the end of the molecular chain. By having such a structure, the hydrophilic group of the hydrophilic compound is concentrated on the surface of the coating film, and it has sufficient detergency even when used for pottery that is frequently washed with water, such as toilets and washstands. Can do. In order to orient the hydrophilic group in a specific direction, it is more preferable that the hydrophilic compound does not have a branched chain.
上記親水性化合物の他端にあるスルホン酸基のアルカリ金属塩は、ナトリウム塩、カリウム塩が好ましい。上記親水性化合物としては、具体的には、２−アミノエチルスルホン酸ナトリウム、２−アミノエチルスルホン酸カリウム、４−アミノベンゼンスルホン酸ナトリウム、２−ヒドロキシエチルスルホン酸ナトリウム、３−メルカプト−１−プロパンスルホン酸ナトリウム、２−グリシジルエチルスルホン酸ナトリウム、アミノスルホン酸ナトリウム、アミノスルホン酸カリウム、アミノメタンスルホン酸、３−アミノプロパンスルホン酸、２−アミノベンゼンスルホン酸、４−アミノベンゼンスルホン酸、１−アミノ−２−ナフトール−４−スルホン酸、６−アミノ−４−ヒドロキシ−２−ナフタレンスルホン酸、ヒドロキシメタンスルホサン酸ナトリウム、４−ヒドロキシ−１−ブタンスルホン酸などが好ましい。性状としては、固形物、水溶液などのものを使用することができる。上記の各種スルホン酸を水酸化ナトリウム又は水酸化カリウムなどにより中和反応を行って合成するなどして使用することができる。 The alkali metal salt of the sulfonic acid group at the other end of the hydrophilic compound is preferably a sodium salt or a potassium salt. Specific examples of the hydrophilic compound include sodium 2-aminoethylsulfonate, potassium 2-aminoethylsulfonate, sodium 4-aminobenzenesulfonate, sodium 2-hydroxyethylsulfonate, 3-mercapto-1- Sodium propanesulfonate, sodium 2-glycidylethylsulfonate, sodium aminosulfonate, potassium aminosulfonate, aminomethanesulfonic acid, 3-aminopropanesulfonic acid, 2-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 1 -Amino-2-naphthol-4-sulfonic acid, 6-amino-4-hydroxy-2-naphthalenesulfonic acid, sodium hydroxymethanesulfosanoate, 4-hydroxy-1-butanesulfonic acid and the like are preferable. As the properties, solids, aqueous solutions and the like can be used. The above-mentioned various sulfonic acids can be used by synthesizing by neutralizing with sodium hydroxide or potassium hydroxide.
例えば、上記２−アミノエチルスルホン酸ナトリウムは、以下のように合成することができる。
（合成例）
２−アミノエチルスルホン酸３７．９重量部、水酸化ナトリウム１２．１重量部、イオン交換水５０．２重量部を２０〜２５℃の室温で１時間程度攪拌して合成した。ｐＨが中性領域に達したことで反応が終了したことを確認した。
For example, the sodium 2-aminoethylsulfonate can be synthesized as follows.
(Synthesis example)
Synthesis was performed by stirring 37.9 parts by weight of 2-aminoethylsulfonic acid, 12.1 parts by weight of sodium hydroxide, and 50.2 parts by weight of ion-exchanged water at room temperature of 20 to 25 ° C. for about 1 hour. It was confirmed that the reaction was completed when the pH reached the neutral range.
また、上記２−アミノエチルスルホン酸カリウム、４−アミノベンゼンスルホン酸ナトリウム、２−ヒドロキシエチルスルホン酸ナトリウム、３−メルカプト−１−プロパンスルホン酸ナトリウム、２−グリシジルエチルスルホン酸ナトリウムなどにおいても、上記合成例と同様に合成することができる。 Further, in the above potassium 2-aminoethylsulfonate, sodium 4-aminobenzenesulfonate, sodium 2-hydroxyethylsulfonate, sodium 3-mercapto-1-propanesulfonate, sodium 2-glycidylethylsulfonate, etc. It can be synthesized in the same manner as in the synthesis example.
上記親水性化合物の数平均分子量が、７０〜５００であることが好ましく、１００〜４００であることがさらに好ましい。上記親水性化合物の数平均分子量が、７０未満であるとアミノ基、水酸基、メルカプト基、エポキシ基から選ばれる少なくとも一つの官能基とスルホン酸基のアルカリ金属塩を含有することが困難であり、親水性の塗膜を形成することができない。上記親水性化合物の数平均分子量が、５００を超えると立体障害のために反応率が低下し、ひいては親水基の量が低下するために塗膜の親水性が低下する。 The number average molecular weight of the hydrophilic compound is preferably 70 to 500, and more preferably 100 to 400. When the number average molecular weight of the hydrophilic compound is less than 70, it is difficult to contain an alkali metal salt of at least one functional group selected from an amino group, a hydroxyl group, a mercapto group, and an epoxy group and a sulfonic acid group, A hydrophilic coating film cannot be formed. When the number average molecular weight of the hydrophilic compound exceeds 500, the reaction rate is lowered due to steric hindrance, and the hydrophilic group amount is lowered, so that the hydrophilicity of the coating film is lowered.
さらに、上記プライマー層のイソシアネート基、エポキシ基、アミノ基、メルカプト基から選ばれる少なくとも一つの反応性官能基に対して、２−アミノエチルスルホン酸など一端にアミノ基、水酸基、メルカプト基、エポキシ基から選ばれる少なくとも一つの官能基を有し、他端にスルホン酸を有し、分子鎖の端部以外に親水部を有していない化合物を反応させた後に、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属の水酸化物水溶液で中和させて、スルホン酸塩を形成する処理を行うこともできる。 Furthermore, with respect to at least one reactive functional group selected from the isocyanate group, epoxy group, amino group, and mercapto group of the primer layer, an amino group, a hydroxyl group, a mercapto group, and an epoxy group at one end such as 2-aminoethylsulfonic acid After reacting a compound having at least one functional group selected from, having a sulfonic acid at the other end and not having a hydrophilic portion other than the end of the molecular chain, sodium hydroxide, potassium hydroxide, etc. It is also possible to carry out a treatment for forming a sulfonate by neutralizing with an aqueous alkali metal hydroxide solution.
上記親水性化合物を溶解、又は分散させるために、溶媒を加えることができる。溶媒としては、水、メタノール、エタノール、イソプロピルアルコール、ｎ−プロピルアルコールなどが好ましい。溶媒を添加することにより、上記親水性化合物の固形分濃度を、０．１〜６０重量％と調節することが好ましい。上記親水性化合物の固形分濃度が０．１重量％未満であると、形成された塗膜に親水基が数なく親水性が低くなる。また、上記親水性化合物の固形分濃度が６０重量％を超えると、上記親水性化合物を溶解、又は分散させる溶媒、極性を有する相溶化剤を均一に混合することが困難になり、一定の親水性を有さなくなる。 A solvent can be added to dissolve or disperse the hydrophilic compound. As the solvent, water, methanol, ethanol, isopropyl alcohol, n-propyl alcohol and the like are preferable. It is preferable to adjust the solid content concentration of the hydrophilic compound to 0.1 to 60% by weight by adding a solvent. When the solid content concentration of the hydrophilic compound is less than 0.1% by weight, the formed coating film has few hydrophilic groups and has low hydrophilicity. On the other hand, when the solid content concentration of the hydrophilic compound exceeds 60% by weight, it becomes difficult to uniformly mix a solvent for dissolving or dispersing the hydrophilic compound and a compatibilizer having polarity, and a certain hydrophilicity is obtained. No longer have sex.
極性を有する相溶化剤は、上記親水性化合物を結晶化させずに均一に溶解させ得る材料である。通常、分子鎖の端部以外に親水部を含有しない上記親水性化合物を用いて組成物を作成すると結晶化してしまい組成物が均一にならないため、形成される塗膜の親水性が不十分であったり、ムラが生じたりするところ、上記相溶化剤を配合することにより、分子鎖の端部以外に親水部を含有しない上記親水性化合物を用いてもその結晶化を抑制し、得られる組成物を均一に溶解させることができる。 The polar compatibilizing agent is a material that can uniformly dissolve the hydrophilic compound without crystallizing it. Usually, if a composition is prepared using the above hydrophilic compound that does not contain a hydrophilic part other than the end of the molecular chain, the composition will not crystallize and the composition will not be uniform. When the above-mentioned hydrophilic compound that does not contain a hydrophilic part other than the end of the molecular chain is used, the crystallization is suppressed by blending the above-described compatibilizing agent. A thing can be dissolved uniformly.
上記相溶化剤としては、尿素、メラミン、アクリロイルモルホリン、ジメチルアクリルアミド、ジメチルアミノプロピルアクリルアミド、イソプロピルアクリルアミド、ジエチルアクリルアミド、ヒドロキシエチルアクリルアミドなどのアミド化合物、ジメチルスルホキシド、アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミドなどの非プロトン性極性溶媒、エチレングリコール、グリセリン、トリメチロールプロパン、ジトリメチロールプロパン、エリトリトール、エリスリトール、ジペンタエリスリトールなどの多価アルコール、トリオース、テトロース、ペントース、ヘキソース、セドヘプルロース、グルコース、マルトース、スクロース（ショ糖）、ラクトース、セロビオース、ラフィノース、アカルボース、オリゴ糖、シクロデキストリン、デキストリン、デンプンなどの糖類、カルボキシメチルセルロースナトリウム、ポリビニルピロリドン、ポリアクリル酸ナトリウム、変性ウレアなどの極性を有する樹脂、炭酸水素ナトリウム、炭酸ナトリウム、硫酸水素ナトリウム、硫酸ナトリウムなどの無機塩類等が好ましい。これらの市販品として、各社の試薬を使用することでき、樹脂については、第一工業製薬株式会社のセロゲンＷＳ−Ｃ、ピッツコールＫ−３０Ｌ、シャロール、ビックケミー・ジャパン株式会社のＢＹＫＥＴＯｌ−ＰＣなどを使用することができる。また、上記相溶化剤は１種、又は２種以上混合して使用することもできる。 Examples of the compatibilizer include urea, melamine, acryloylmorpholine, dimethylacrylamide, dimethylaminopropylacrylamide, isopropylacrylamide, diethylacrylamide, hydroxyethylacrylamide and other amide compounds, dimethyl sulfoxide, acetonitrile, N, N-dimethylformamide and the like. Protic polar solvents, ethylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, erythritol, erythritol, dipentaerythritol and other polyhydric alcohols, triose, tetrose, pentose, hexose, sedheptulose, glucose, maltose, sucrose , Lactose, cellobiose, raffinose, acarbose, oligosaccharide, cyclodex Saccharides such as phosphorus, dextrin and starch, polar resins such as sodium carboxymethylcellulose, polyvinylpyrrolidone, sodium polyacrylate and modified urea, inorganic salts such as sodium hydrogen carbonate, sodium carbonate, sodium hydrogen sulfate and sodium sulfate are preferred. . Reagents from each company can be used as these commercially available products. For resins, Serogen WS-C from Daiichi Kogyo Seiyaku Co., Ltd., Pitzkor K-30L, Charol, BYKETOl-PC from Big Chemie Japan Co., Ltd., etc. Can be used. Moreover, the said compatibilizer can also be used 1 type or in mixture of 2 or more types.
上記相溶化剤の配合量は、上記親水性化合物の固形分重量に対して１０〜２００重量％が好ましく、３０〜１２０重量％がさらに好ましい。上記相溶化剤の配合量が１０重量％未満であると上記親水性化合物が結晶化、粉体化して反応率が低下して形成される塗膜の親水性が低くなる。上記相溶化剤の配合量が２００重量％を超えると上記親水性化合物の濃度が相対的に低くなり反応率が低下して形成される塗膜の親水性が低くなる。 10-200 weight% is preferable with respect to the solid content weight of the said hydrophilic compound, and, as for the compounding quantity of the said compatibilizer, 30-120 weight% is more preferable. When the blending amount of the compatibilizer is less than 10% by weight, the hydrophilic compound is crystallized and powdered to reduce the reaction rate, thereby reducing the hydrophilicity of the coating film formed. When the compounding amount of the compatibilizer exceeds 200% by weight, the concentration of the hydrophilic compound is relatively lowered, the reaction rate is lowered, and the hydrophilicity of the formed coating film is lowered.
さらに、上記シランカップリング剤と上記親水性化合物の反応を促進するために反応触媒を、本発明の親水処理塗料組成物に配合することができる。例えば、イソシアネート基を有するシランカップリング剤と水酸基を有する親水性化合物と反応させるときに、ジラウリン酸ジブチルすずなどの有機すず触媒を用いることが好ましい。さらに、グリシジル基を有するシランカップリング剤と水酸基又はメルカプト基を有する親水性化合物と反応させるときに、Ｎ，Ｎ−ジメチルベンジルアミン、トリフェニルホスフィン、１，８−ジアザビシクロ（５，４，０）ウンデセンー７、２−ヘプタデシルイミダゾールなどの化合物を用いることが好ましい。 Furthermore, a reaction catalyst can be blended in the hydrophilic treatment coating composition of the present invention in order to promote the reaction between the silane coupling agent and the hydrophilic compound. For example, when reacting with a silane coupling agent having an isocyanate group and a hydrophilic compound having a hydroxyl group, it is preferable to use an organic tin catalyst such as dibutyltin dilaurate. Further, when the silane coupling agent having a glycidyl group is reacted with a hydrophilic compound having a hydroxyl group or a mercapto group, N, N-dimethylbenzylamine, triphenylphosphine, 1,8-diazabicyclo (5,4,0) It is preferable to use a compound such as undecen-7,2-heptadecylimidazole.
本発明の親水処理塗料組成物は、上述した成分以外にも他の添加剤を含むことができる。他の添加剤として、表面調整剤、レベリング剤、可塑剤、消泡剤、紫外線吸収剤、酸化防止剤、粘性制御剤などを使用することができる。また、添加剤を２種以上組み合わせて使用することもできる。 The hydrophilic treatment coating composition of the present invention can contain other additives in addition to the components described above. As other additives, surface conditioners, leveling agents, plasticizers, antifoaming agents, ultraviolet absorbers, antioxidants, viscosity control agents, and the like can be used. Two or more additives may be used in combination.
こうして得られた本発明の親水処理塗料組成物をプライマー層と反応させるために、熱を使用する。熱を発生させる装置として、電気オーブン、熱風乾燥機、赤外線照射装置などを使用することができる。これらの市販品として、ＴＲＰ商事株式会社のＵＷＬ−３００Ｎなどを使用することができる。 Heat is used to react the hydrophilic treatment coating composition of the present invention thus obtained with the primer layer. As a device for generating heat, an electric oven, a hot air dryer, an infrared irradiation device, or the like can be used. As these commercial products, TWL Shoji Co., Ltd. UWL-300N etc. can be used.
そして、本発明の親水処理塗料組成物をプライマー層と反応させて形成された塗膜を、プライマー層と反応しない成分を水などで洗い流して、所望の親水処理化処理を終了する。 Then, the coating film formed by reacting the hydrophilic treatment coating composition of the present invention with the primer layer is washed away with a component that does not react with the primer layer with water, and the desired hydrophilic treatment treatment is completed.
また、上記プライマー層を設けることなく、陶器など無機化合物を含有する表面層に対して反応させる組成物として、上記シランカップリング剤と、上記親水性化合物と、上記相溶化剤を含有する親水処理塗料組成物を用いることもできる。上記シランカップリング剤によるプライマー処理の工程と、上記シランカップリング剤に対して上記親水性化合物を反応させることによる親水性処理の工程を一度に行うことができるので、例えば、家屋やオフィスなどのすでに設置されている便器、洗面台などの陶器類に対して用いると、その設置場所で作業する時間を短縮することができる。 Moreover, the hydrophilic treatment containing the said silane coupling agent, the said hydrophilic compound, and the said compatibilizing agent as a composition made to react with respect to the surface layer containing inorganic compounds, such as earthenware, without providing the said primer layer A coating composition can also be used. Since the step of the primer treatment with the silane coupling agent and the step of hydrophilic treatment by reacting the hydrophilic compound with the silane coupling agent can be performed at one time, for example, in a house or office When it is used for pottery such as toilets and washstands that have already been installed, it is possible to shorten the work time at the installation location.
さらに、上記シランカップリング剤などを含有する第一の液と、上記親水性化合物及び上記相溶化剤などを含有する第二の液とを分けておき、上記表面層に対して作業を行う直前に、第一の液と第二の液を混合して用いることもできる。予め第一の液と第二の液として分液しておくと、上記親水性化合物の官能基などの触媒作用による上記シランカップリング剤の加水分解を抑制することができる。そのため、生成したシラノール基同士が脱水縮合して上記表面層との反応性を低下させることがないばかりか、粒状物の生成を防ぐことができる。また、第二の液には、上記シランカップリング剤のアルコキシシランにおける加水分解を促進させる触媒を含有させることもできる。 Furthermore, the first liquid containing the silane coupling agent and the like and the second liquid containing the hydrophilic compound and the compatibilizing agent are separated, and immediately before working on the surface layer. In addition, the first liquid and the second liquid can be mixed and used. When the liquid is separated in advance as the first liquid and the second liquid, hydrolysis of the silane coupling agent due to a catalytic action such as a functional group of the hydrophilic compound can be suppressed. Therefore, the generated silanol groups do not dehydrate and condense, and the reactivity with the surface layer is not lowered, and generation of particulates can be prevented. The second liquid can also contain a catalyst that promotes hydrolysis of the silane coupling agent in alkoxysilane.
以下、実施例および比較例を挙げて本発明をより詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these.
（実施例１）
上記プライマー層１に対して反応させるために、イオン交換水３０．０重量部、尿素１０重量部を混合して尿素が溶解するまで攪拌した後、２−アミノエチルスルホン酸ナトリウム（５０重量％水溶液，数平均分子量１４７．２）５０．０重量部、イソプロピルアルコール１０．０重量部を加え、透明な均一溶液となるまで攪拌し、実施例１の組成物を１００重量部得た。
Example 1
In order to react with the primer layer 1, 30.0 parts by weight of ion exchange water and 10 parts by weight of urea were mixed and stirred until the urea was dissolved, and then sodium 2-aminoethylsulfonate (50% by weight aqueous solution). , Number average molecular weight 147.2) 50.0 parts by weight and 10.0 parts by weight of isopropyl alcohol were added and stirred until a transparent uniform solution was obtained to obtain 100 parts by weight of the composition of Example 1.
（実施例２）
親水性化合物として、２−アミノエチルスルホン酸カリウム（５０重量％水溶液，数平均分子量１６３．３）５０．０重量部を用いた以外は、実施例１と同様にして、実施例２の組成物を１００重量部得た。
(Example 2)
The composition of Example 2 was the same as Example 1, except that 50.0 parts by weight of potassium 2-aminoethylsulfonate (50% by weight aqueous solution, number average molecular weight 163.3) was used as the hydrophilic compound. Of 100 parts by weight was obtained.
（実施例３、４）
親水性化合物として、２−アミノエチルスルホン酸（５０重量％水溶液，数平均分子量１２５．２）５０．０重量部を用いた以外は、実施例１と同様にして、実施例３、４の組成物を１００重量部得た。
(Examples 3 and 4)
The compositions of Examples 3 and 4 were the same as Example 1 except that 50.0 parts by weight of 2-aminoethylsulfonic acid (50% by weight aqueous solution, number average molecular weight 125.2) was used as the hydrophilic compound. 100 parts by weight of the product was obtained.
（実施例５〜１０）
上記相溶化剤として、ジメチルスルホキシド２５．０重量部、グリセリン２５．０重量部、スクロース（ショ糖）１０．０重量部、カルボキシメチルセルロースナトリウム３０％水溶液３３．３重量部、ポリビニルピロリドン３０％水溶液３３．３重量部、炭酸水素ナトリウム１０．０重量部それぞれ用いた以外は、実施例１と同様にして、実施例５〜１０の組成物を１００重量部得た。
(Examples 5 to 10)
As the compatibilizing agent, 25.0 parts by weight of dimethyl sulfoxide, 25.0 parts by weight of glycerin, 10.0 parts by weight of sucrose (sucrose), 33.3 parts by weight of a 30% aqueous solution of sodium carboxymethylcellulose, and 33% aqueous solution of polyvinylpyrrolidone 33 100 parts by weight of the compositions of Examples 5 to 10 were obtained in the same manner as in Example 1 except that 3 parts by weight and 10.0 parts by weight of sodium bicarbonate were used.
（実施例１１）
親水性化合物として、アミノベンゼンスルホン酸ナトリウム（４０重量％水溶液，数平均分子量１９５．１）５０．０重量部を用いた以外は、実施例１と同様にして、実施例１１の組成物を１００重量部得た。
(Example 11)
In the same manner as in Example 1, except that 50.0 parts by weight of sodium aminobenzenesulfonate (40 wt% aqueous solution, number average molecular weight 195.1) was used as the hydrophilic compound, the composition of Example 11 was 100. Part by weight was obtained.
（実施例１２）
親水性化合物として、２−ヒドロキシエチルスルホン酸ナトリウム（６０重量％水溶液，数平均分子量１４８．１）５０．０重量部、反応触媒としてジラウリン酸ジブチルすず０．１重合部を用いた以外は、実施例１と同様にして、実施例１２の組成物を１００重量部得た。
(Example 12)
Implemented except that 50.0 parts by weight of sodium 2-hydroxyethylsulfonate (60% by weight aqueous solution, number average molecular weight 148.1) was used as the hydrophilic compound, and 0.1 polymer part of dibutyltin dilaurate was used as the reaction catalyst. In the same manner as in Example 1, 100 parts by weight of the composition of Example 12 was obtained.
（実施例１３）
上記プライマー層２に対して反応させるために、実施例１と全く同様に、実施例１３の組成物を１００重量部得た。
(Example 13)
In order to make the primer layer 2 react, 100 parts by weight of the composition of Example 13 was obtained in the same manner as in Example 1.
（実施例１４）
上記プライマー層２に対して反応させるために、親水性化合物として、３−メルカプト−１−プロパンスルホン酸ナトリウム（５０重量％水溶液，数平均分子量１７８．２）５０．０重量部、反応触媒としてＮ，Ｎ−ジメチルベンジルアミン１．０重合部を用いた以外は、実施例１と同様にして、実施例１４の組成物を１００重量部得た。
(Example 14)
In order to react with the primer layer 2, 50.0 parts by weight of sodium 3-mercapto-1-propanesulfonate (50% by weight aqueous solution, number average molecular weight 178.2) as a hydrophilic compound, N as a reaction catalyst 100 parts by weight of the composition of Example 14 was obtained in the same manner as in Example 1 except that 1.0 polymer part of N, dimethylbenzylamine was used.
（実施例１５）
上記プライマー層１〜２を設けることなく、上記シランカップリング剤として３−イソシアネートプロピルトリメトキシシラン０．５重量部、溶剤としてメタノール１９．５重量部を均一混合したＡ液２０部を予め用意する。そして、メタノール１９．２重量部、尿素１０重量部を混合して尿素が溶解するまで攪拌した後、２−アミノエチルスルホン酸ナトリウム（５０重量％水溶液，数平均分子量１４７．２）５０．０重量部、前記シランカップリング剤を加水分解するＮ−メチルモルホリン１．０重量部を加え、透明な均一溶液となるまで攪拌したＢ液８０部を別途用意する。被塗布物に塗布する直前に前記Ａ液と前記Ｂ液を均一に混合して、実施例１５の組成物を１００重量部得た。
(Example 15)
Without providing the primer layers 1 and 2, 20 parts of A liquid prepared by uniformly mixing 0.5 parts by weight of 3-isocyanatopropyltrimethoxysilane as the silane coupling agent and 19.5 parts by weight of methanol as the solvent are prepared in advance. . Then, after 19.2 parts by weight of methanol and 10 parts by weight of urea were mixed and stirred until the urea was dissolved, sodium 2-aminoethylsulfonate (50 wt% aqueous solution, number average molecular weight 147.2) 50.0 wt. 80 parts of B liquid which added 1.0 part weight of N-methylmorpholine which hydrolyzes the said silane coupling agent and stirred until it became a transparent uniform solution is prepared separately. Immediately before application to the object, the liquid A and the liquid B were mixed uniformly to obtain 100 parts by weight of the composition of Example 15.
（比較例１）
上記プライマー層１に対して反応させるために、親水性化合物として、２−ヒドロキシエチルスルホン酸カルシウム（４０重量％水溶液）６２．５重量部を用いた以外は、実施例１と同様にして、比較例１の組成物を１００重量部得た。
(Comparative Example 1)
In the same manner as in Example 1, except that 62.5 parts by weight of calcium 2-hydroxyethylsulfonate (40% by weight aqueous solution) was used as the hydrophilic compound in order to react with the primer layer 1. 100 parts by weight of the composition of Example 1 were obtained.
（比較例２）
上記相溶化剤として尿素を添加しなかった以外は、実施例１と同様にして、比較例２の組成物を１００重量部得た。
(Comparative Example 2)
100 parts by weight of the composition of Comparative Example 2 was obtained in the same manner as in Example 1 except that urea was not added as the compatibilizer.
（比較例３）
親水性化合物として、グリシンナトリウム（４０重量％水溶液）６２．５重量部を用いた以外は、実施例１と同様にして、比較例３の組成物を１００重量部得た。
(Comparative Example 3)
100 parts by weight of the composition of Comparative Example 3 was obtained in the same manner as in Example 1 except that 62.5 parts by weight of sodium glycine (40% by weight aqueous solution) was used as the hydrophilic compound.
（比較例４）
親水性化合物として、２−アミノ−２−メチル−１−プロパノール（９０重量％水溶液，ダウケミカル社製ＡＭＰ−９０）２７．８重量部を用いた以外は、実施例１と同様にして、比較例４の組成物を１００重量部得た。
(Comparative Example 4)
In the same manner as in Example 1, except that 27.8 parts by weight of 2-amino-2-methyl-1-propanol (90% by weight aqueous solution, AMP-90 manufactured by Dow Chemical Co., Ltd.) was used as the hydrophilic compound. 100 parts by weight of the composition of Example 4 were obtained.
（比較例５）
親水性化合物として、リン酸二水素−２−アミノエチルジナトリウム（４０重量％水溶液）２５．０重量部を用いた以外は、実施例１と同様にして、比較例５の組成物を１００重量部得た。
(Comparative Example 5)
100% by weight of the composition of Comparative Example 5 was used in the same manner as in Example 1 except that 25.0 parts by weight of dihydrogen-2-aminoethyl disodium phosphate (40% by weight aqueous solution) was used as the hydrophilic compound. I got a part.
（比較例６）
親水性化合物として、（２−ヒドロキシエチル）トリメチルアンモニウムクロリド（４０重量％水溶液）２５．０重量部を用いた以外は、実施例１と同様にして、比較例６の組成物を１００重量部得た。
(Comparative Example 6)
100 parts by weight of the composition of Comparative Example 6 was obtained in the same manner as in Example 1 except that 25.0 parts by weight of (2-hydroxyethyl) trimethylammonium chloride (40% by weight aqueous solution) was used as the hydrophilic compound. It was.
（比較例７）
親水性化合物として、テトラヒドロフルフリルアルコール（１００重量％液体）２５．０重量部を用いた以外は、実施例１と同様にして、比較例７の組成物を１００重量部得た。
(Comparative Example 7)
100 parts by weight of the composition of Comparative Example 7 was obtained in the same manner as in Example 1 except that 25.0 parts by weight of tetrahydrofurfuryl alcohol (100% by weight liquid) was used as the hydrophilic compound.
（比較例８）
親水性化合物として、ポリオキシエチレンラウリルエーテル（４０重量％水溶液，第一工業製薬製セロゲンＷＳ−Ｃ）６２．５重量部、反応触媒としてジラウリン酸ジブチルすず０．１重量部を用いた以外は、実施例１と同様にして、比較例８の組成物を１００重量部得た。
(Comparative Example 8)
Except for using 62.5 parts by weight of polyoxyethylene lauryl ether (40% by weight aqueous solution, Daiichi Kogyo Seerogen WS-C) as a hydrophilic compound and 0.1 parts by weight of dibutyltin dilaurate as a reaction catalyst, In the same manner as in Example 1, 100 parts by weight of the composition of Comparative Example 8 was obtained.
（比較例９）
上記プライマー層２に対して反応させるために、親水性化合物として、ポリオキシエチレンアルキルスルホコハク酸二ナトリウム（２５重量％水溶液，第一工業製薬製ネオハイテノールＳ−７０）８９．０重量部、反応触媒としてＮ，Ｎ−ジメチルベンジルアミン１．０重量部を用い、尿素を添加しなかった以外は、実施例１と同様にして、比較例９の組成物を１００重量部得た。
(Comparative Example 9)
In order to react with the primer layer 2, 89.0 parts by weight of a polyoxyethylene alkylsulfosuccinate disodium (25% by weight aqueous solution, Neo Haitenol S-70 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a hydrophilic compound 100 parts by weight of the composition of Comparative Example 9 was obtained in the same manner as in Example 1 except that 1.0 part by weight of N, N-dimethylbenzylamine was used as a catalyst and urea was not added.
（比較例１０）
プライマー層を設けずに、実施例１と同様に、比較例１０の組成物を１００重量部得た。
(Comparative Example 10)
100 parts by weight of the composition of Comparative Example 10 was obtained in the same manner as in Example 1 without providing the primer layer.
実施例１〜１５、比較例１〜１０の組成物を、表１〜２に示す。 The compositions of Examples 1-15 and Comparative Examples 1-10 are shown in Tables 1-2.
そして、酸化ケイ素を表面に含有する陶器に対して作成された表１〜表２に記載された上記プライマー層１〜２に対して、各組成物を塗布し、電気オーブンを用いて６０℃下で３０分乾燥し、３０分室温にて静置した後、電気オーブンを用いて１２０℃で３０分間加熱を行い、塗膜を形成した。実施例３の組成物については、加熱を行った後に、５重量％水酸化ナトリウム水溶液を浸漬した綿布を塗膜に塗布し、５分後に水洗し、親水基であるスルホン酸基を中和してスルホン酸ナトリウムとした。また、実施例１５においては、上記プライマー層１〜２を設けることなく、上記Ａ液及びＢ液を配合させて塗布した後に、上記方法と同様にして乾燥、加熱を行って塗膜を形成した。 And each composition was apply | coated with respect to the said primer layers 1-2 described in Table 1-2 created with respect to the earthenware which contains a silicon oxide on the surface, and it was 60 degreeC below using electric oven. Was dried for 30 minutes and allowed to stand at room temperature for 30 minutes, and then heated at 120 ° C. for 30 minutes using an electric oven to form a coating film. For the composition of Example 3, after heating, a cotton cloth soaked with 5% by weight sodium hydroxide aqueous solution was applied to the coating film, washed with water after 5 minutes, and neutralized sulfonic acid groups, which are hydrophilic groups. To obtain sodium sulfonate. Moreover, in Example 15, after providing and apply | coating the said A liquid and B liquid, without providing the said primer layers 1-2, it dried and heated like the said method, and formed the coating film. .
便器、洗面台など水回りに設置される陶器類などに対して上記塗膜を作成したときを想定し、洗浄剤等により洗浄したときの塗膜の耐久性、及び、汚れである油脂などの有機物や無機物に対する塗膜の洗浄性について、以下の方法により評価した。 Assuming that the above-mentioned coating film is created for pottery installed around the water, such as toilet bowls, washstands, etc., durability of the coating film when washed with a cleaning agent, etc. The following method evaluated the washability of the coating film with respect to an organic substance and an inorganic substance.
まず、形成された塗膜の耐久性を評価する基準として、ＪＩＳ Ｒ ３２５７「基板ガラス表面のぬれ性試験方法」（試験方法の種類として、静滴法を採用）に準じて、塗膜表面の水滴の接触角を用いた。具体的には、水滴の接触角の測定について、ＫＲＵＳＳ社製のＤＳＡ２０Ｅを用い、蒸留水４μＬを塗膜に滴下して６０秒後の接触角を測定した。形成された塗膜に物理的又は化学的処理を行い、塗膜に物理的又は化学的変化が起こった場合、水滴の接触角が変化することを利用したものである。塗膜に対して何も処理を行わないものを「初期」とし、４０℃のイオン交換水に２４０時間浸漬処理を行ったものを「耐水性」として、２０〜２５℃の水中においてジョンソン株式会社製の流せるトイレブラシを用い５００ｇｆの荷重を掛けて１０００往復したものを「耐摩耗性」として、４０℃のサンポール（登録商標，大日本除虫菊株式会社製）に２４時間浸漬処理を行ったものを「耐洗浄性（酸性）」として、４０℃のトイレマジックリン（登録商標，花王株式会社製）に２４時間浸漬処理を行ったものを「耐洗浄性（中性）」として、４０℃のカビキラー（登録商標，ジョンソン株式会社製）に２４時間浸漬処理を行ったものを「耐洗浄性（アルカリ性）」として、それぞれ水滴の接触角を測定し評価を行った。いずれも水滴の接触角が１０°以下のものは◎、１０°より大きく２０°以下のものは○、２０°より大きく４０°以下のものは△、４０°より大きいものは×として評価し、◎、○、△を良好、×を不良と判断した。 First, as a standard for evaluating the durability of the formed coating film, according to JIS R 3257 “Test method for wettability of substrate glass surface” (adopting a sessile drop method as the type of test method) The contact angle of the water droplet was used. Specifically, for the measurement of the contact angle of water droplets, 4 μL of distilled water was dropped onto the coating film using DSA20E manufactured by KRUS, and the contact angle after 60 seconds was measured. When the formed coating film is subjected to a physical or chemical treatment and a physical or chemical change occurs in the coating film, the contact angle of the water droplet is changed. Johnson does not perform any treatment on the coating film as “initial”, and what is immersed in 40 ° C. ion exchange water for 240 hours as “water resistance” in water at 20 to 25 ° C. What was subjected to a dipping treatment for 24 hours in a 40 ° C. sun pole (registered trademark, manufactured by Dainippon Insect Chrysanthemum Co., Ltd.) using a toilet brush that can be made to flow and reciprocating 1000 times with a load of 500 gf as “wear resistance” Is "washing resistance (acidic)" and 40 ° C toilet magiclin (registered trademark, manufactured by Kao Corporation) for 24 hours is used as "washing resistance (neutral)" What was immersed in mold killer (registered trademark, manufactured by Johnson Co., Ltd.) for 24 hours was regarded as “cleaning resistance (alkaline)”, and the contact angle of each water droplet was measured and evaluated. In all cases, water droplets having a contact angle of 10 ° or less were evaluated as ◎: those greater than 10 ° and 20 ° or less, ◯ that were greater than 20 ° and 40 ° or less, △, and those that were larger than 40 ° as x. ◎, ○, and △ were judged as good, and × as bad.
そして、形成された塗膜の洗浄性を評価する基準として、油脂など有機物と無機物に対する洗浄性をそれぞれ評価した。油脂などの有機物については、食品において汎用に使用されるオレイン酸を用いて「オレイン酸除去性」として、塗膜に対して３００μＬのオレイン酸を滴下した後に静かに水に浸漬し、オレイン酸が塗膜表面から浮き上がるまでの時間を測定した。オレイン酸が塗膜表面から浮き上がるまでの時間が３０秒以下のものは◎、３０秒より長く６０秒以下のものは○、６０秒より長く１２０秒以下のものは△、１２０秒より長いものは×として評価し、◎、○、△を良好、×を不良と判断した。 And as a reference | standard which evaluates the washability of the formed coating film, the washability with respect to organic substances, such as fats and oils, and an inorganic substance was evaluated, respectively. For organic substances such as fats and oils, oleic acid, which is commonly used in foods, is used as “oleic acid removability”. After 300 μL of oleic acid is dropped on the coating film, it is gently dipped in water. The time to lift from the coating surface was measured. Oleic acid lifts from the surface of the coating film for 30 seconds or less: ◎, longer than 30 seconds to 60 seconds or less: ○, longer than 60 seconds to 120 seconds or less: Δ, longer than 120 seconds It evaluated as x, and (double-circle), (circle), (triangle | delta) was judged favorable, and x was judged to be bad.
また、無機物については、カルシウム及びマグネシウムを所定量以上含有する硬水であるｅｖｉａｎ（登録商標）を用いて「ミネラル除去性」として、塗膜に対して５００μＬの硬水を滴下し４０℃で２４時間乾燥させて白色の水滴斑を作成した後に、２０〜２５℃の水中においてジョンソン株式会社製の流せるトイレブラシを用い５００ｇｆの荷重を掛けて１０又は２０往復し残存する水滴斑を目視にて観察した。ブラシによる洗浄において、１０往復で水滴斑が見られないものは◎、２０往復で水滴斑が見られないものは○、２０往復で水滴斑が若干見られるものは△、２０往復で水滴斑がはっきり見られるものは×として評価し、◎、○、△を良好、×を不良と判断した。 In addition, for inorganic materials, 500 μL of hard water is added dropwise to the coating film and dried at 40 ° C. for 24 hours as “mineral removability” using evian (registered trademark), which is hard water containing a predetermined amount or more of calcium and magnesium. After creating white water droplet spots, the remaining water droplet spots were visually observed by applying a load of 500 gf and reciprocating 10 or 20 times in water at 20 to 25 ° C. using a toilet brush. In the case of washing with a brush, ◎ when water droplets are not seen after 10 reciprocations, ○ when water droplets are not seen after 20 reciprocations, △ when water droplets are slightly seen after 20 reciprocations, and water droplets after 20 reciprocations. Those clearly seen were evaluated as x, and ◎, ○, and Δ were judged good, and x was judged bad.
上述したように耐久性と洗浄性を測定し、実施例及び比較例ごとにまとめたものを表３〜表４に示す。いずれの評価でも不良である×を有さないものを市場性があるとして「良」と判断し、いずれかの評価で不良である×を有するものを市場性がないとして「不可」と判断した。 The durability and detergency were measured as described above, and those summarized for each of the examples and comparative examples are shown in Tables 3 to 4. Those that do not have a bad x in any evaluation are judged as “good” as being marketable, and those that have a bad x in any evaluation are judged as “impossible” as having no marketability. .
Claims (7)
アミノ基、水酸基、メルカプト基、エポキシ基から選ばれる少なくとも一つであって、前記シランカップリング剤の反応性官能基と反応する官能基と、スルホン酸基又はスルホン酸基のアルカリ金属塩を含有し、分子鎖の端部以外に親水部を含有しない親水性化合物と、
極性を有する相溶化剤を
含有する親水処理塗料組成物。 After the surface layer containing an inorganic compound is treated with a silane coupling agent containing at least one reactive functional group selected from an isocyanate group, an epoxy group, an amino group, and a mercapto group, the reactivity of the silane coupling agent A composition that reacts with a functional group,
It is at least one selected from an amino group, a hydroxyl group, a mercapto group, and an epoxy group, and contains a functional group that reacts with a reactive functional group of the silane coupling agent and an alkali metal salt of a sulfonic acid group or a sulfonic acid group A hydrophilic compound that does not contain a hydrophilic part other than the end of the molecular chain;
A hydrophilic treatment coating composition containing a compatibilizer having polarity.
イソシアネート基、エポキシ基、アミノ基、メルカプト基から選ばれる少なくとも一つの反応性官能基を含有するシランカップリング剤と、
アミノ基、水酸基、メルカプト基、エポキシ基から選ばれる少なくとも一つであって、前記シランカップリング剤の反応性官能基と反応する官能基と、スルホン酸基又はスルホン酸基のアルカリ金属塩を含有し、分子鎖の端部以外に親水部を含有しない親水性化合物と、
極性を有する相溶化剤を
含有する親水処理塗料組成物。 A composition for reacting with a surface layer containing an inorganic compound,
A silane coupling agent containing at least one reactive functional group selected from an isocyanate group, an epoxy group, an amino group, and a mercapto group;
It is at least one selected from an amino group, a hydroxyl group, a mercapto group, and an epoxy group, and contains a functional group that reacts with a reactive functional group of the silane coupling agent and an alkali metal salt of a sulfonic acid group or a sulfonic acid group A hydrophilic compound that does not contain a hydrophilic part other than the end of the molecular chain;
A hydrophilic treatment coating composition containing a compatibilizer having polarity.
前記シランカップリング剤と結合した前記表面層に、アミノ基、水酸基、メルカプト基から選ばれる少なくとも一つであって、前記シランカップリング剤の反応性官能基と反応する官能基と、スルホン酸又はスルホン酸基のアルカリ金属塩を含有し、分子鎖の端部以外に親水部を含有しない親水性化合物と、極性を有する相溶化剤を含有する親水処理塗料組成物を塗布し、
熱により前記シランカップリング剤の反応性官能基と前記親水性化合物の官能基を反応させることを特徴とする親水化処理方法。 Treating the surface layer containing the inorganic compound with a silane coupling agent containing at least one reactive functional group selected from an isocyanate group, an epoxy group, an amino group, and a mercapto group;
The surface layer bonded to the silane coupling agent is at least one selected from an amino group, a hydroxyl group, and a mercapto group, and a functional group that reacts with a reactive functional group of the silane coupling agent, sulfonic acid or Applying a hydrophilic treatment coating composition containing a hydrophilic compound that contains an alkali metal salt of a sulfonic acid group and does not contain a hydrophilic part other than the end of the molecular chain, and a compatibilizer having polarity,
A hydrophilic treatment method comprising reacting a reactive functional group of the silane coupling agent with a functional group of the hydrophilic compound by heat.
前記シランカップリング剤と結合した前記表面層に、アミノ基、水酸基、メルカプト基から選ばれる少なくとも一つであって、前記シランカップリング剤の反応性官能基と反応する官能基とスルホン酸基を含有し、分子鎖の端部以外に親水部を含有しない親水性化合物と、極性を有する相溶化剤を含有する親水処理塗料組成物を塗布し、
熱により前記シランカップリング剤の反応性官能基と前記親水性化合物の官能基を反応させ、
前記親水性化合物のスルホン酸基をアルカリ金属の水酸化物で反応させることによりスルホン酸塩を形成させることを特徴とする親水化処理方法。 Treating the surface layer containing the inorganic compound with a silane coupling agent containing at least one reactive functional group selected from an isocyanate group, an epoxy group, an amino group, and a mercapto group;
The surface layer bonded to the silane coupling agent has at least one selected from an amino group, a hydroxyl group, and a mercapto group, and a functional group that reacts with a reactive functional group of the silane coupling agent and a sulfonic acid group. Containing, applying a hydrophilic treatment coating composition containing a hydrophilic compound that does not contain a hydrophilic part other than the end of the molecular chain, and a compatibilizer having polarity,
The reactive functional group of the silane coupling agent is reacted with the functional group of the hydrophilic compound by heat,
A hydrophilization method comprising forming a sulfonate by reacting a sulfonic acid group of the hydrophilic compound with an alkali metal hydroxide.
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| WO2019188412A1 (en) * | 2018-03-29 | 2019-10-03 | 株式会社Ｌｉｘｉｌ | Primer composition, functional member, and method for producing functional member |
| KR20220162707A (en) | 2020-03-13 | 2022-12-08 | 가부시키가이샤 리쿠시루 | Hydrophilic treatment paint composition and hydrophilization treatment method |
| DE112021006565T5 (en) | 2020-12-21 | 2023-10-26 | Lixil Corporation | Surface treatment agent, hydrophilized inorganic substrate and process for producing the same |
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| JPH05202216A (en) * | 1991-10-21 | 1993-08-10 | Sekisui Chem Co Ltd | Production of anti-fogging plastics |
| JPH0827290A (en) * | 1994-07-19 | 1996-01-30 | Sekisui Chem Co Ltd | Production of antifogging coated article |
| JP2014111745A (en) * | 2012-11-09 | 2014-06-19 | Toto Ltd | Hydrophilic coating composition, hydrophilic coating film, water section product and manufacturing method of hydrophilic coating film |
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| JPS60240769A (en) * | 1984-05-16 | 1985-11-29 | Nippon Steel Chem Co Ltd | Production of inorganic material having hydrophobic surface |
| JPH05202216A (en) * | 1991-10-21 | 1993-08-10 | Sekisui Chem Co Ltd | Production of anti-fogging plastics |
| JPH0827290A (en) * | 1994-07-19 | 1996-01-30 | Sekisui Chem Co Ltd | Production of antifogging coated article |
| JP2014111745A (en) * | 2012-11-09 | 2014-06-19 | Toto Ltd | Hydrophilic coating composition, hydrophilic coating film, water section product and manufacturing method of hydrophilic coating film |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019188412A1 (en) * | 2018-03-29 | 2019-10-03 | 株式会社Ｌｉｘｉｌ | Primer composition, functional member, and method for producing functional member |
| KR20220162707A (en) | 2020-03-13 | 2022-12-08 | 가부시키가이샤 리쿠시루 | Hydrophilic treatment paint composition and hydrophilization treatment method |
| DE112021001608T5 (en) | 2020-03-13 | 2022-12-29 | Lixil Corporation | Coating composition for hydrophilic treatment and a method for hydrophilic treatment |
| DE112021006565T5 (en) | 2020-12-21 | 2023-10-26 | Lixil Corporation | Surface treatment agent, hydrophilized inorganic substrate and process for producing the same |
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| JP6300098B2 (en) | 2018-03-28 |
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