JP4695829B2 - Water-based paint composition - Google Patents
Water-based paint composition Download PDFInfo
- Publication number
- JP4695829B2 JP4695829B2 JP2003377960A JP2003377960A JP4695829B2 JP 4695829 B2 JP4695829 B2 JP 4695829B2 JP 2003377960 A JP2003377960 A JP 2003377960A JP 2003377960 A JP2003377960 A JP 2003377960A JP 4695829 B2 JP4695829 B2 JP 4695829B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- weight
- water
- group
- resin emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 53
- 239000000203 mixture Substances 0.000 title claims description 28
- 239000003973 paint Substances 0.000 title claims description 22
- 239000000839 emulsion Substances 0.000 claims description 51
- 239000007787 solid Substances 0.000 claims description 23
- 229920003002 synthetic resin Polymers 0.000 claims description 23
- 239000000057 synthetic resin Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 22
- -1 dimethylsiloxane compound Chemical class 0.000 claims description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 19
- 239000000049 pigment Substances 0.000 claims description 17
- 125000003700 epoxy group Chemical group 0.000 claims description 16
- 239000005871 repellent Substances 0.000 claims description 13
- 230000002940 repellent Effects 0.000 claims description 13
- 125000003277 amino group Chemical group 0.000 claims description 12
- 239000008199 coating composition Substances 0.000 claims description 10
- 239000001023 inorganic pigment Substances 0.000 claims description 10
- 239000004606 Fillers/Extenders Substances 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 7
- 239000012463 white pigment Substances 0.000 claims description 7
- 238000006757 chemical reactions by type Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000011941 photocatalyst Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 description 63
- 239000011248 coating agent Substances 0.000 description 62
- 239000000178 monomer Substances 0.000 description 36
- 239000000463 material Substances 0.000 description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 17
- 238000002156 mixing Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 11
- 125000000524 functional group Chemical group 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 238000010422 painting Methods 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 7
- 229920000178 Acrylic resin Polymers 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
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- 230000005856 abnormality Effects 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000010454 slate Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 125000005370 alkoxysilyl group Chemical group 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
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- 238000001035 drying Methods 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- 239000011505 plaster Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000012674 dispersion polymerization Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000000843 powder Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- 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 2
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- GLLRIXZGBQOFLM-UHFFFAOYSA-N Xanthorin Natural products C1=C(C)C=C2C(=O)C3=C(O)C(OC)=CC(O)=C3C(=O)C2=C1O GLLRIXZGBQOFLM-UHFFFAOYSA-N 0.000 description 2
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- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000003429 antifungal agent Substances 0.000 description 2
- 229940121375 antifungal agent Drugs 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
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- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- WDQKICIMIPUDBL-UHFFFAOYSA-N n-[2-(dimethylamino)ethyl]prop-2-enamide Chemical compound CN(C)CCNC(=O)C=C WDQKICIMIPUDBL-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
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- 125000002560 nitrile group Chemical group 0.000 description 1
- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 229910001562 pearlite Inorganic materials 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged 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
- 239000005053 propyltrichlorosilane Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011044 quartzite Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012508 resin bead Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 208000008842 sick building syndrome Diseases 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- UQMGAWUIVYDWBP-UHFFFAOYSA-N silyl acetate Chemical class CC(=O)O[SiH3] UQMGAWUIVYDWBP-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
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- 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
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- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- YZVRVDPMGYFCGL-UHFFFAOYSA-N triacetyloxysilyl acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)OC(C)=O YZVRVDPMGYFCGL-UHFFFAOYSA-N 0.000 description 1
- GIHPVQDFBJMUAO-UHFFFAOYSA-N tributoxy(ethyl)silane Chemical compound CCCCO[Si](CC)(OCCCC)OCCCC GIHPVQDFBJMUAO-UHFFFAOYSA-N 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- INUOIYMEJLOQFN-UHFFFAOYSA-N tributoxy(phenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C1=CC=CC=C1 INUOIYMEJLOQFN-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-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
- 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
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-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
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-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
- 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 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
Description
本発明は、建築物の壁面や天井面等の表面化粧に適用可能な水性塗料組成物に関するものである。 The present invention relates to a water-based coating composition applicable to surface makeup such as a wall surface and a ceiling surface of a building.
建築物の壁面、天井面等においては、その表面の美観性を高めるために各種乾式建材が使用されている。このうち内装用の材料としては、壁紙・ビニールクロス等の材料が汎用的である。しかし、このような材料では、結露発生の問題、揮発性有機化合物に起因するシックハウス症候群の問題等がクローズアップされている。一方、外装用の材料としては、サイディングボード等の乾式建材がよく使用されているが、その外観は人工的な印象を与える場合が少なくない。 Various dry building materials are used on the wall surfaces, ceiling surfaces, etc. of buildings in order to enhance the aesthetics of the surfaces. Of these materials, wallpaper, vinyl cloth, etc. are widely used as interior materials. However, with such materials, the problem of dew condensation, the problem of sick house syndrome caused by volatile organic compounds, etc. are highlighted. On the other hand, a dry building material such as a siding board is often used as an exterior material, but its appearance often gives an artificial impression.
これに対し、最近では漆喰等の塗材による仕上げが見直されている。漆喰は古来の伝統的な材料であり、表面美観性、呼吸性等において優れた特性を有している。漆喰を構成する成分は、主に土や砂等の天然無機質成分、消石灰等であり、これらを塗付時に水と混練して使用する。その塗膜では、消石灰が空気中の二酸化炭素を吸収することによって硬化が進行する。
ところが、漆喰は一度に厚塗りすると割れが発生しやすくなるため、複数回薄く塗り重ねる必要があり、工期が長期化するという欠点を有している。また、下地との密着性が低く、剥離等が発生するおそれもある。さらには、塗付後の強度発現に時間を要するため、硬化段階の降雨等に対する抵抗性が不十分で、耐水性に劣るという問題もある。
On the other hand, recently, finishing with plaster and other coating materials has been reviewed. Stucco is an ancient and traditional material, and has excellent characteristics such as surface aesthetics and breathability. The components constituting the plaster are mainly natural inorganic components such as soil and sand, slaked lime, etc., and these are used by kneading with water at the time of application. In the coating film, curing proceeds by slaked lime absorbing carbon dioxide in the air.
However, since plaster tends to generate cracks when thickly applied at once, it has to be applied thinly several times and has the disadvantage that the construction period is prolonged. In addition, the adhesiveness to the base is low, and peeling or the like may occur. Furthermore, since it takes time to develop the strength after application, there is a problem that the resistance to rain at the curing stage is insufficient and the water resistance is poor.
特開平４−６８１５５号公報（特許文献１）、特開２００２−３１７１４３号公報（特許文献２）では、割れ防止性、剥離防止性等を高めるため、消石灰等の粉末成分に合成樹脂エマルションを混合することが記載されている。
しかしながら、上記特許文献に記載の材料は、消石灰を主成分とするものであるため、硬化段階における耐水性の問題については依然として未解決のままである。
合成樹脂エマルション及び各種艶消し剤を主成分とする壁面用艶消し塗料（例えば特開平１１−２１５１４号公報等）では、耐水性等に優れた塗膜が形成可能であるが、その仕上塗膜は肉厚感に乏しく、漆喰調の外観を表出することは困難である。
In JP-A-4-68155 (Patent Document 1) and JP-A-2002-317143 (Patent Document 2), a synthetic resin emulsion is mixed with a powder component such as slaked lime in order to enhance crack prevention properties, peeling prevention properties, and the like. It is described to do.
However, since the materials described in the above-mentioned patent documents are mainly composed of slaked lime, the water resistance problem in the curing stage remains unsolved.
With a matte paint for wall surfaces (for example, Japanese Patent Application Laid-Open No. 11-21514) mainly composed of a synthetic resin emulsion and various matting agents, a coating film having excellent water resistance can be formed. Is not thick and it is difficult to express a stucco-like appearance.
本発明は、このような点に鑑みなされたものであり、漆喰が有する種々の問題点を解決するとともに、漆喰調の質感を表出することができる水性塗料組成物を提供することを目的とするものである。 This invention is made | formed in view of such a point, and it aims at providing the water-based coating composition which can express the texture of a stucco tone while solving the various problems which a stucco has. To do.
これらの課題を解決するため本発明者は鋭意検討を行い、合成樹脂エマルション、水分散型撥水剤、及び無機質顔料を必須成分とし、無機質顔料として、特定の物性を有するものを複数種併用することにより、消石灰を使用しなくても漆喰調の外観を表出することができ、耐水性、割れ防止性、剥離防止性等の塗膜物性にも優れる水性塗料組成物が得られることを見出し、本発明を完成させるに至った。
すなわち、本発明は以下の特徴を有するものである。
In order to solve these problems, the present inventor has intensively studied and uses a synthetic resin emulsion, a water-dispersed water repellent, and an inorganic pigment as essential components, and a plurality of inorganic pigments having specific physical properties are used in combination. It is found that a water-based coating composition that can exhibit a stucco-like appearance without using slaked lime and is excellent in coating properties such as water resistance, anti-cracking property and anti-peeling property can be obtained. The present invention has been completed.
That is, the present invention has the following characteristics.
１．合成樹脂エマルション、水分散型撥水剤、及び無機質顔料を含有する水性塗料組成物であって、
合成樹脂エマルションがカルボキシル基及びエポキシ基を含有する架橋反応型合成樹脂エマルションであり、
水分散型撥水剤がアミノ基含有ジメチルシロキサン化合物の乳化分散体であり、
合成樹脂エマルションの固形分１００重量部に対し、水分散型撥水剤を固形分で１〜１００重量部含み、
顔料容積濃度が３０〜９０％であり、
無機質顔料として、平均粒子径０．１〜１μｍ、白色度９５以上の白色顔料、及び平均粒子径０．１〜２００μｍ、白色度８０以上９５未満の体質顔料を含み、白色顔料と体質顔料の体積比率が１：５〜１：５０であり、
消石灰を含有しないことを特徴とする水性塗料組成物。
1. An aqueous coating composition containing a synthetic resin emulsion, a water-dispersed water repellent, and an inorganic pigment,
The synthetic resin emulsion is a crosslinking reaction type synthetic resin emulsion containing a carboxyl group and an epoxy group,
The water-dispersed water repellent is an emulsified dispersion of an amino group-containing dimethylsiloxane compound ,
1-100 parts by weight of a water-dispersible water repellent with a solid content with respect to 100 parts by weight of the solid content of the synthetic resin emulsion,
The pigment volume concentration is 30-90%,
The inorganic pigment includes a white pigment having an average particle diameter of 0.1 to 1 μm and a whiteness of 95 or more, and an extender having an average particle diameter of 0.1 to 200 μm and a whiteness of 80 to less than 95, and the volume of the white pigment and the extender pigment The ratio is 1: 5 to 1:50,
An aqueous paint composition characterized by not containing slaked lime.
２．合成樹脂エマルションが、少なくともコア部及びシェル部の２層を含み、コア部にエポキシ基、シェル部にカルボキシル基を有する多層構造エマルションであることを特徴とする１．に記載の水性塗料組成物。2. 1. The synthetic resin emulsion is a multilayer structure emulsion comprising at least two layers of a core part and a shell part, and having an epoxy group in the core part and a carboxyl group in the shell part. The water-based paint composition described in 1.
３．無機質顔料として、さらに平均粒子径０．１μｍ未満の光触媒を、合成樹脂エマルションの固形分１００重量部に対し０．１〜５０重量部含むことを特徴とする１．〜２．のいずれかに記載の水性塗料組成物。
3. As an inorganic pigment, 0.1 to 50 parts by weight of a photocatalyst having an average particle diameter of less than 0.1 μm is further contained with respect to 100 parts by weight of the solid content of the synthetic resin emulsion. ~ 2. The water-based coating composition according to any one of the above.
４．建築物表面に対し、１．〜３．のいずれかに記載の水性塗料組成物を塗付した後、透明被膜が形成可能な上塗材を塗付する塗装方法。 4). For the building surface: ~ 3. A coating method of applying a topcoat material capable of forming a transparent film after applying the water-based coating composition according to any one of the above.
５．上塗材が、反応性シリル基を有する化合物及び／または重合体を含有する上塗材である４．に記載の塗装方法 5. 3. The topcoat material is a topcoat material containing a compound and / or polymer having a reactive silyl group. Painting method described in
本発明によれば、漆喰が有する種々の問題点を解決するとともに、漆喰調の質感を表出することができる水性塗料組成物を得ることができる。 ADVANTAGE OF THE INVENTION According to this invention, while solving the various problems which plaster has, the water-based coating composition which can express the texture of a stucco tone can be obtained.
以下、本発明をその実施の形態とともに詳細に説明する。
本発明の水性塗料組成物は、（ａ）合成樹脂エマルション（以下「（ａ）成分」という）、（ｂ）水分散型撥水剤（以下「（ｂ）成分」という）、及び（ｃ）無機質顔料（以下「（ｃ）成分」という）を含有するものである。
Hereinafter, the present invention will be described in detail together with embodiments thereof.
The aqueous coating composition of the present invention comprises (a) a synthetic resin emulsion (hereinafter referred to as “component (a)”), (b) a water-dispersed water repellent (hereinafter referred to as “component (b)”), and (c). An inorganic pigment (hereinafter referred to as “component (c)”) is contained.
このうち（ａ）成分は、本発明組成物のバインダーとして機能するものである。
具体的に（ａ）成分としては、例えば、酢酸ビニル樹脂エマルション、塩化ビニル樹脂エマルション、エポキシ樹脂エマルション、アクリル樹脂エマルション、ウレタン樹脂エマルション、アクリルシリコン樹脂エマルション、フッ素樹脂エマルション等、あるいはこれらの複合系等を挙げることができる。これらは１種または２種以上で使用することができる。
Among these, (a) component functions as a binder of this invention composition.
Specifically, as the component (a), for example, a vinyl acetate resin emulsion, a vinyl chloride resin emulsion, an epoxy resin emulsion, an acrylic resin emulsion, a urethane resin emulsion, an acrylic silicon resin emulsion, a fluororesin emulsion, or a composite system thereof. Can be mentioned. These can be used alone or in combination of two or more.
また、（ａ）成分は架橋反応性を有するものであってもよい。（ａ）成分が架橋反応型合成樹脂エマルションである場合は、塗膜の耐水性、剥離防止性等を高めることができる。架橋反応型合成樹脂エマルションは、それ自体で架橋反応を生じるもの、あるいは別途混合する架橋剤によって架橋反応を生じるもののいずれであってもよい。このような架橋反応性は、例えば、カルボキシル基と金属イオン、カルボキシル基とカルボジイミド基、カルボキシル基とエポキシ基、カルボキシル基とアジリジン基、カルボキシル基とオキサゾリン基、水酸基とイソシアネート基、カルボニル基とヒドラジド基、エポキシ基とアミノ基、アルコキシル基どうし等の反応性官能基を組み合わせることによって付与することができる。 Further, the component (a) may have crosslinking reactivity. When the component (a) is a crosslinking reaction type synthetic resin emulsion, it is possible to improve the water resistance, anti-peeling property and the like of the coating film. The crosslinking reaction type synthetic resin emulsion may be either one that causes a crosslinking reaction by itself or one that causes a crosslinking reaction by a separately mixed crosslinking agent. Such crosslinking reactivity includes, for example, carboxyl group and metal ion, carboxyl group and carbodiimide group, carboxyl group and epoxy group, carboxyl group and aziridine group, carboxyl group and oxazoline group, hydroxyl group and isocyanate group, carbonyl group and hydrazide group. It can be provided by combining reactive functional groups such as epoxy groups with amino groups and alkoxyl groups.
（ａ）成分の製造方法は特に限定されないが、例えば、乳化重合、ソープフリー乳化重合、分散重合、フィード乳化重合、フィード分散重合、シード乳化重合、シード分散重合等を採用することができる。 Although the manufacturing method of (a) component is not specifically limited, For example, emulsion polymerization, soap-free emulsion polymerization, dispersion polymerization, feed emulsion polymerization, feed dispersion polymerization, seed emulsion polymerization, seed dispersion polymerization, etc. are employable.
（ａ）成分のガラス転移温度（以下「Ｔｇ」という）は通常−３０〜６０℃、好ましくは−１０〜４０℃に設定する。Ｔｇが−３０℃より低い場合は、塗膜表面に汚染物質が付着しやすくなる。Ｔｇが６０℃より高い場合は、塗膜に割れが発生しやすくなる。なお、本発明におけるＴｇは、（ａ）成分を構成するモノマーの種類とその構成比率から、Ｆｏｘの計算式によって求められる値である。
（ａ）成分の平均粒子径は、通常０．０５〜０．２μｍ程度である。
The glass transition temperature (hereinafter referred to as “Tg”) of the component (a) is usually set to −30 to 60 ° C., preferably −10 to 40 ° C. When Tg is lower than −30 ° C., contaminants easily adhere to the coating film surface. When Tg is higher than 60 ° C., cracks are likely to occur in the coating film. The Tg in the present invention is a value obtained from the formula of Fox from the type of monomer constituting the component (a) and its constituent ratio.
(A) The average particle diameter of a component is about 0.05-0.2 micrometer normally.
本発明における（ａ）成分としては、
（ａ−１）少なくともコア部及びシェル部の２層を含み、前記コア部にエポキシ基、前記シェル部にカルボキシル基を有し、ガラス転移温度が−３０〜６０℃である多層構造エマルション（以下「（ａ−１）成分」という）が好適である。特に、（ａ−１）成分においては、コア部のガラス転移温度よりシェル部のガラス転移温度が高いことが望ましい。なお、ここで言うコア部とは、多層構造エマルションの内層部を意味し、最外層部以外の層である。シェル部とは、多層構造エマルションの最外層部を意味するものである。（ａ−１）成分は、複数のコア部とシェル部からなる多層構造を有するものであってもよい。
本発明組成物において、このような（ａ−１）成分を使用すれば、下地の変位に対する追従性を付与することができ、さらに塗膜の耐汚染性を高めることもできる。また、塗膜の水蒸気透過性能が向上するため、基材内部に滞留した水分を外部に放散させる効果が高まり、塗膜の膨れ・剥れ等の発生を十分に防止することもできる。したがって、漆喰調の外観を長期にわたり維持することが可能となる。
As the component (a) in the present invention,
(A-1) A multilayer structure emulsion comprising at least two layers of a core part and a shell part, having an epoxy group in the core part, a carboxyl group in the shell part, and a glass transition temperature of -30 to 60 ° C. “(A-1) component”) is preferred. In particular, in the component (a-1), the glass transition temperature of the shell part is preferably higher than the glass transition temperature of the core part. In addition, the core part said here means the inner layer part of a multilayer structure emulsion, and is layers other than an outermost layer part. A shell part means the outermost layer part of a multilayer structure emulsion. The component (a-1) may have a multilayer structure composed of a plurality of core portions and shell portions.
In the composition of the present invention, when such a component (a-1) is used, it is possible to impart followability to the displacement of the base, and it is possible to improve the stain resistance of the coating film. Moreover, since the water vapor permeation performance of the coating film is improved, the effect of dissipating moisture remaining inside the base material is increased, and the occurrence of swelling and peeling of the coating film can be sufficiently prevented. Therefore, it becomes possible to maintain the stucco-like appearance for a long time.
具体的に、（ａ−１）成分のコア部にエポキシ基を生成させるためには、コア部を構成するモノマーとしてエポキシ基含有モノマーを使用すればよい。エポキシ基含有モノマーとしては、例えばグリシジル（メタ）アクリレート、ジグリシジル（メタ）アクリレート、アリルグリシジルエーテル等が挙げられる。このうち、特にグリシジル（メタ）アクリレートが好適である。 Specifically, in order to generate an epoxy group in the core part of the component (a-1), an epoxy group-containing monomer may be used as a monomer constituting the core part. Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, diglycidyl (meth) acrylate, and allyl glycidyl ether. Of these, glycidyl (meth) acrylate is particularly preferred.
（ａ−１）成分のシェル部にカルボキシル基を生成させるためには、シェル部を構成するモノマーとしてカルボキシル基含有モノマーを使用すればよい。カルボキシル基含有モノマーとしては、アクリル酸、メタクリル酸、クロトン酸、マレイン酸またはそのモノアルキルエステル、イタコン酸またはそのモノアルキルエステル、フマル酸またはそのモノアルキルエステル等、あるいはこれらのアンモニウム塩、有機アミン塩、アルカリ金属塩等が挙げられる。このうち、特にアクリル酸、メタクリル酸から選ばれる１種以上が好適である。 In order to generate a carboxyl group in the shell part of the component (a-1), a carboxyl group-containing monomer may be used as a monomer constituting the shell part. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, maleic acid or a monoalkyl ester thereof, itaconic acid or a monoalkyl ester thereof, fumaric acid or a monoalkyl ester thereof, or ammonium salts or organic amine salts thereof. And alkali metal salts. Among these, at least one selected from acrylic acid and methacrylic acid is particularly preferable.
上述のエポキシ基含有モノマー、カルボキシル基含有モノマーと共重合可能なモノマーとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｎ−アミル（メタ）アクリレート、イソアミル（メタ）アクリレート、ｎ−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、オクチル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート等の（メタ）アクリル酸エステル系モノマー；
Ｎ−メチルアミノエチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジメチルアミノエチルビニルエーテル、Ｎ−（２−ジメチルアミノエチル）アクリルアミド、Ｎ−（２−ジメチルアミノエチル）メタクリルアミド等のアミノ基含有モノマー；
ビニルピリジン等のピリジン系モノマー；
２−ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート等の水酸基含有モノマー；
酢酸ビニル、プロピオン酸ビニル等のビニルエステル系モノマー；
アクリロニトリル、メタアクリロニトリル等のニトリル基含有モノマー；
スチレン、２−メチルスチレン、ビニルトルエン、ｔ−ブチルスチレン、クロルスチレン、ビニルアニソール、ビニルナフタレン、ジビニルベンゼン等の芳香族モノマー；
アクリルアミド、メタクリルアミド、マレイン酸アミド、Ｎ−メチロール（メタ）アクリルアミド、ジアセトンアクリルアミド等のアミド基含有モノマー；
アクロレイン、ダイアセトン（メタ）アクリルアミド、ビニルメチルケトン、ビニルエチルケトン、ビニルブチルケトン等のカルボニル基含有モノマー；
ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−（メタ）アクリロイルオキシプロピルトリメトキシシラン、γ−（メタ）アクリロイルオキシプロピルトリエトキシシラン、γ−（メタ）アクリロイルオキシプロピルメチルジメトキシシラン等のアルコキシシリル基含有モノマー；
塩化ビニリデン、フッ化ビニリデン等のハロゲン化ビニリデン系モノマー；
その他、エチレン、プロピレン、イソプレン、ブタジエン、ビニルピロリドン、塩化ビニル、ビニルエーテル、ビニルケトン、ビニルアミド、クロロプレン等が挙げられる。これらは１種または２種以上で使用することができる。
As a monomer copolymerizable with the above-mentioned epoxy group-containing monomer and carboxyl group-containing monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) (Meth) acrylic acid ester monomers such as acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate;
Contains amino groups such as N-methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminoethyl vinyl ether, N- (2-dimethylaminoethyl) acrylamide, N- (2-dimethylaminoethyl) methacrylamide monomer;
Pyridine monomers such as vinylpyridine;
Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate;
Vinyl ester monomers such as vinyl acetate and vinyl propionate;
Nitrile group-containing monomers such as acrylonitrile and methacrylonitrile;
Aromatic monomers such as styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, vinylanisole, vinylnaphthalene, divinylbenzene;
Amide group-containing monomers such as acrylamide, methacrylamide, maleic acid amide, N-methylol (meth) acrylamide and diacetone acrylamide;
Carbonyl group-containing monomers such as acrolein, diacetone (meth) acrylamide, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone;
Alkoxysilyl groups such as vinyltrimethoxysilane, vinyltriethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane Containing monomers;
Vinylidene halide monomers such as vinylidene chloride and vinylidene fluoride;
Other examples include ethylene, propylene, isoprene, butadiene, vinyl pyrrolidone, vinyl chloride, vinyl ether, vinyl ketone, vinyl amide, and chloroprene. These can be used alone or in combination of two or more.
エポキシ基含有モノマーの使用量は、多層構造エマルションを構成する全モノマー量に対し、通常０．１〜４０重量％、好ましくは０．５〜２０重量％とする。
カルボキシル基含有モノマーの使用量は、多層構造エマルションを構成する全モノマー量に対し、通常０．１〜４０重量％、好ましくは０．５〜２０重量％とする。
コア部とシェル部に用いるモノマーの重量比率は、通常１０／９０〜９０／１０である。
The amount of the epoxy group-containing monomer used is usually 0.1 to 40% by weight, preferably 0.5 to 20% by weight, based on the total amount of monomers constituting the multilayer emulsion.
The amount of the carboxyl group-containing monomer used is usually 0.1 to 40% by weight, preferably 0.5 to 20% by weight, based on the total amount of monomers constituting the multilayer emulsion.
The weight ratio of the monomers used for the core part and the shell part is usually 10/90 to 90/10.
本発明組成物における（ｂ）成分は水分散型撥水剤である。本発明では、このような（ｂ）成分が含まれることにより、厚塗り塗装を行った場合の乾燥過程における湿気、降雨等の影響を抑制することができる。すなわち、塗膜硬化段階における耐水性を高めることができる。
（ｂ）成分の形態は、水中に分散した形態であれば特に制限されず、界面活性剤を用いた強制乳化型エマルション、あるいは自己乳化型エマルションのいずれであってもよい。
The component (b) in the composition of the present invention is a water-dispersed water repellent. In the present invention, by including such a component (b), it is possible to suppress the influence of moisture, rainfall, and the like in the drying process when thick coating is performed. That is, the water resistance in the coating film curing stage can be increased.
The form of (b) component will not be restrict | limited especially if it is the form disperse | distributed in water, Any of the forced emulsification type emulsion using surfactant or a self-emulsification type emulsion may be sufficient.
（ｂ）成分の混合比率は、（ａ）成分の固形分１００重量部に対し、固形分換算で通常１〜１００重量部、好ましくは２〜５０重量部、より好ましくは３〜３０重量部である。（ｂ）成分が１重量部より少ない場合は、塗膜硬化段階において湿気、降雨等の影響を受けやすくなる。（ｂ）成分が１００重量部より多い場合は、塗膜の耐汚染性が低下するおそれがある。また、相対的にバインダー比率が低下するため、塗膜に割れが発生するおそれもある。 The mixing ratio of the component (b) is usually 1 to 100 parts by weight, preferably 2 to 50 parts by weight, more preferably 3 to 30 parts by weight in terms of the solid content with respect to 100 parts by weight of the solid content of the component (a). is there. When the amount of the component (b) is less than 1 part by weight, the component is easily affected by moisture, rainfall, and the like in the coating curing stage. When there is more (b) component than 100 weight part, there exists a possibility that the stain resistance of a coating film may fall. Moreover, since a binder ratio falls relatively, there exists a possibility that a crack may generate | occur | produce in a coating film.
（ｂ）成分としては、（ｂ−１）アミノ基、カルボキシル基、エポキシ基から選ばれる少なくとも１種の官能基を有する水分散型撥水剤（以下「（ｂ−１）成分」という）が好適である。このような（ｂ−１）成分を使用すれば、塗膜形成後の耐水性を十分に高めることができる。さらに、基材内部への水の浸入を長期にわたり防止することもできる。特に、本発明では（ａ−１）成分と（ｂ−１）成分を併用することが望ましい。 As the component (b), (b-1) a water-dispersed water repellent (hereinafter referred to as “component (b-1)”) having at least one functional group selected from an amino group, a carboxyl group, and an epoxy group. Is preferred. If such (b-1) component is used, the water resistance after coating film formation can fully be improved. Furthermore, it is possible to prevent water from entering the base material for a long time. In particular, in the present invention, it is desirable to use the component (a-1) and the component (b-1) in combination.
（ｂ−１）成分は、通常下記式（１）、（２）で示される単位を有するものである。 The component (b-1) usually has units represented by the following formulas (1) and (2).
このうち（ｂ−１）成分の官能基としては、アミノ基が好適である。アミノ基としては、例えば−ＮＨ２、−ＮＨＣＨ３、−Ｎ（ＣＨ３）２、−ＮＨ（ＣＨ２）２ＮＨ２、−ＮＨ（ＣＨ２）２ＮＨＣＨ３、−ＮＨ（ＣＨ２）２Ｎ（ＣＨ３）２等が挙げられる。 Among these, as a functional group of (b-1) component, an amino group is suitable. As an amino group, for example, —NH 2 , —NHCH 3 , —N (CH 3 ) 2 , —NH (CH 2 ) 2 NH 2 , —NH (CH 2 ) 2 NHCH 3 , —NH (CH 2 ) 2 N (CH 3) 2 or the like can be mentioned.
本発明組成物における（ｃ）成分としては、
（ｃ−１）平均粒子径０．１〜１μｍ、白色度９５以上の白色顔料（以下「（ｃ−１）成分」という）、及び
（ｃ−２）平均粒子径０．１〜２００μｍ、白色度８０以上９５未満の体質顔料（以下「（ｃ−２）成分」という）を必須成分とし、その体積比率が、（ｃ−１）成分：（ｃ−２）成分＝１：５〜１：５０（好ましくは１：８〜１：３０、より好ましくは１：１０〜１：２０）となるように混合して使用する。なお、本発明における白色度は、酸化マグネシウムの白色度を１００、暗闇の状態を０とした場合の白色計（ケット式光電管白色度計）による比較値である。
本発明では、このような（ｃ−１）成分と（ｃ−２）成分を特定混合比率で併用することによって、漆喰調の質感を表出することができる。（ｃ−１）成分が上記比率より多い場合は、肉厚感が得られ難く、漆喰調の質感を表出することができない。（ｃ−１）成分が上記比率より少ない場合は、塗膜の隠ぺい率が低下し、全体的に透けたような仕上りとなってしまう。
As the component (c) in the composition of the present invention,
(C-1) An average particle size of 0.1 to 1 μm, a white pigment having a whiteness of 95 or more (hereinafter referred to as “(c-1) component”), and (c-2) an average particle size of 0.1 to 200 μm, white An extender pigment having a degree of 80 or more and less than 95 (hereinafter referred to as “component (c-2)”) is an essential component, and the volume ratio thereof is (c-1) component: (c-2) component = 1: 5 to 1: 50 (preferably 1: 8 to 1:30, more preferably 1:10 to 1:20). In addition, the whiteness in this invention is a comparison value by a white meter (ket type phototube whiteness meter) when the whiteness of magnesium oxide is 100 and the dark state is 0.
In the present invention, by using such a component (c-1) and component (c-2) in combination at a specific mixing ratio, a stucco-like texture can be expressed. (C-1) When there are more components than the said ratio, a thick feeling is hard to be acquired and a stucco-like texture cannot be expressed. (C-1) When there are few components than the said ratio, the concealment rate of a coating film will fall and it will be the finish which was transparent as a whole.
（ｃ−１）成分、（ｃ−２）成分としては、上述の条件を満たす限り各種の無機質顔料を使用することができる。
このうち（ｃ−１）成分としては、例えば、酸化チタン、酸化亜鉛、酸化アルミニウム、酸化マグネシウム、中空樹脂粒子等が挙げられる。このうち、本発明では酸化チタンが好適である。
（ｃ−１）成分の白色度は９５以上、好ましくは９７以上である。（ｃ−１）成分の平均粒子径は０．１〜１μｍ、好ましくは０．１〜０．５μｍである。（ｃ−１）成分の白色度が９５より小さい場合は、塗膜の隠ぺい性が低下してしまう。（ｃ−１）成分の平均粒子径が上記の範囲外である場合も、塗膜の隠ぺい性が低下してしまう。
As the component (c-1) and the component (c-2), various inorganic pigments can be used as long as the above conditions are satisfied.
Among these, examples of the component (c-1) include titanium oxide, zinc oxide, aluminum oxide, magnesium oxide, and hollow resin particles. Of these, titanium oxide is preferred in the present invention.
The whiteness of the component (c-1) is 95 or more, preferably 97 or more. (C-1) The average particle diameter of a component is 0.1-1 micrometer, Preferably it is 0.1-0.5 micrometer. When the whiteness of the component (c-1) is less than 95, the concealability of the coating film is lowered. Even when the average particle diameter of the component (c-1) is out of the above range, the concealability of the coating film is lowered.
（ｃ−２）成分としては、例えば、重質炭酸カルシウム、沈降性炭酸カルシウム、クレー、カオリン、陶土、チャイナクレー、珪藻土、シリカ、珪石粉、タルク、バライト粉、硫酸バリウム、沈降性硫酸バリウム、炭酸バリウム等が挙げられる。本発明では、これらの２種以上を組合わせて使用することが望ましく、特に、白色度が異なる２種以上の（ｃ−２）成分を併用することが望ましい。これにより、漆喰調の質感を高めることができる。
（ｃ−２）成分の白色度は８０以上９５未満、好ましくは８５以上９５未満である。（ｃ−２）成分の平均粒子径は０．１〜２００μｍ、好ましくは１〜１５０μｍ、より好ましくは１０〜１００μｍである。（ｃ−２）成分の白色度が８０より小さい場合は、漆喰特有の白味が損われ、９５より大きい場合は、肉厚感が得られにくくなる。また、（ｃ−２）成分の平均粒子径が２００μｍより大きい場合は形成塗膜表面の平滑性が損われ、０．１μｍより小さい場合は顔料容積濃度を高く設定し難くなり、いずれの場合においても漆喰調の質感を得ることが困難となる。
As the component (c-2), for example, heavy calcium carbonate, precipitated calcium carbonate, clay, kaolin, china clay, china clay, diatomaceous earth, silica, quartzite powder, talc, barite powder, barium sulfate, precipitated barium sulfate, Examples include barium carbonate. In the present invention, it is desirable to use a combination of two or more of these, and it is particularly desirable to use two or more (c-2) components having different whiteness. Thereby, the stucco-like texture can be enhanced.
The whiteness of the component (c-2) is 80 or more and less than 95, preferably 85 or more and less than 95. (C-2) The average particle diameter of a component is 0.1-200 micrometers, Preferably it is 1-150 micrometers, More preferably, it is 10-100 micrometers. When the whiteness of the component (c-2) is smaller than 80, the whiteness peculiar to stucco is damaged, and when it is larger than 95, it is difficult to obtain a thick feeling. Further, when the average particle size of the component (c-2) is larger than 200 μm, the smoothness of the formed coating film surface is impaired, and when it is smaller than 0.1 μm, it is difficult to set the pigment volume concentration high. It is difficult to obtain a stucco-like texture.
本発明における（ｃ）成分は、形成塗膜における顔料容積濃度が３０〜９０％、好ましくは５０〜８０％、より好ましくは５５〜７５％となるように配合する。このような顔料容積濃度であれば、漆喰調の質感を表出することが可能となる。また、耐汚染性と割れ防止性のバランスに優れた塗膜を形成することができる。顔料容積濃度が３０％より小さい場合は、肉厚感が得られ難く、また塗膜の耐汚染性が低下する傾向となる。顔料容積濃度が９０％より大きい場合は、塗膜に割れが発生しやすくなる。
なお、本発明における顔料容積濃度は、乾燥塗膜中に含まれる（ｃ）成分の容積百分率であり、下記式によって算出される値である。（ｂ）成分は実質的に造膜性能を有さないため、顔料容積濃度算出の際には除外しておく。
The component (c) in the present invention is blended so that the pigment volume concentration in the formed coating film is 30 to 90%, preferably 50 to 80%, more preferably 55 to 75%. With such a pigment volume concentration, it is possible to express a stucco-like texture. Moreover, the coating film excellent in the balance of stain resistance and crack prevention property can be formed. When the pigment volume concentration is less than 30%, it is difficult to obtain a thick feeling and the stain resistance of the coating film tends to be lowered. When the pigment volume concentration is larger than 90%, the coating film is easily cracked.
In addition, the pigment volume concentration in this invention is a volume percentage of (c) component contained in a dry coating film, and is a value computed by a following formula. Since the component (b) has substantially no film forming performance, it is excluded when calculating the pigment volume concentration.
＜式＞ 顔料容積濃度（％）＝［（ｃｗ／ｃρ）／｛（ａｗ／ａρ）＋（ｃｗ／ｃρ）｝］×１００
（式中、ａｗは（ａ）成分固形分の混合量、ａρは（ａ）成分固形分の比重、ｃｗは（ｃ）成分の混合量、ｃρは（ｃ）成分の比重を示す。）
<Formula> Pigment volume concentration (%) = [(c w / c ρ ) / {(a w / a ρ ) + (c w / c ρ )}] × 100
(Wherein, a w is (a) mixing of the component solids, a [rho component (a) solids content of the specific gravity, the mixing amount of c w component (c), the c [rho specific gravity of component (c) Show.)
本発明では、（ｃ）成分として（ｃ−３）平均粒子径０．１μｍ未満の光触媒（以下「（ｃ−３）成分」という）を含むことができる。本発明では、このような（ｃ−３）成分を混合することにより、形成塗膜表面に種々の汚染物質（特に有機系汚染物質）が付着した場合に、それらを分解することが可能となり、耐汚染性をいっそう高めることができ、漆喰調の質感を維持することができる。（ｃ−１）成分の混合によって、ホルムアルデヒド等の揮発性有機化合物の分解機能を付与することもできる。さらに、本発明では（ｂ）成分が必須成分として含まれるため、（ｃ−１）成分による（ａ）成分の劣化を抑制することもできる。
（ｃ−１）成分を混合する場合、（ａ）成分としてアクリルシリコン樹脂エマルション、フッソ樹脂エマルション、重合性紫外線吸収剤及び／または重合性光安定剤が共重合された合成樹脂エマルションのいずれかを使用すれば、（ａ）成分の劣化抑制の点でより好適である。このうち、重合性紫外線吸収剤及び／または重合性光安定剤が共重合された合成樹脂エマルションにおいては、例えば２−ヒドロキシ−４−アクリロキシベンゾフェノン、２−（２’−ヒドロキシ−５’−メタクリロキシエチルフェニル）−２Ｈ−ベンゾトリアゾール等の重合性紫外線吸収剤、４−メタクリロイルオキシ−２，２，６，６−テトラメチルピペリジン、４−メタクリロイルオキシ−１，２，２，６，６−ペンタメチルピペリジン等の重合性光安定剤が使用できる。
In the present invention, as the component (c), (c-3) a photocatalyst (hereinafter referred to as “(c-3) component”) having an average particle diameter of less than 0.1 μm can be included. In the present invention, by mixing such a component (c-3), when various pollutants (especially organic pollutants) adhere to the surface of the formed coating film, they can be decomposed, Contamination resistance can be further increased, and a stucco-like texture can be maintained. (C-1) The decomposition function of volatile organic compounds, such as formaldehyde, can also be provided by mixing of a component. Furthermore, in this invention, since (b) component is contained as an essential component, deterioration of (a) component by (c-1) component can also be suppressed.
When the component (c-1) is mixed, any one of the acrylic resin resin emulsion, the fluororesin emulsion, the polymerizable ultraviolet absorber and / or the synthetic light stabilizer copolymerized with the polymerizable light stabilizer is used as the component (a). If used, it is more suitable in terms of suppressing deterioration of component (a). Among these, in synthetic resin emulsions in which a polymerizable ultraviolet absorber and / or a polymerizable light stabilizer are copolymerized, for example, 2-hydroxy-4-acryloxybenzophenone, 2- (2′-hydroxy-5′-methacrylic). Polymerizable ultraviolet absorbers such as (Roxyethylphenyl) -2H-benzotriazole, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-penta A polymerizable light stabilizer such as methylpiperidine can be used.
（ｃ−３）成分の平均粒子径は通常０．１μｍ未満であるが、好ましくは０．００１μｍ以上０．１μｍ未満、より好ましくは０．００５μｍ以上０．０５μｍ以下である。
（ｃ−３）成分としては、例えばＴｉＯ２、ＺｎＯ、Ｂｉ２Ｏ３、ＢｉＶＯ４、ＳｒＴｉＯ３、ＣｄＳ、ＩｎＰ、ＩｎＰｂ、ＧａＰ、ＧａＡｓ、ＢａＴｉＯ３、ＢａＴｉＯ４、ＢａＴｉ４Ｏ９、Ｋ２ＮｂＯ３、Ｎｂ２Ｏ５、Ｆｅ２Ｏ３、Ｔａ２Ｏ５、Ｔａ３Ｎ５、Ｋ３Ｔａ３Ｓｉ２Ｏ３、ＷＯ３、ＳｎＯ２、ＮｉＯ、Ｃｕ２Ｏ、ＳｉＣ、ＭｏＳ２、ＲｕＯ２、ＣｅＯ２等の他、これらと金属、金属酸化物、多孔体、層状化合物等との複合体等が挙げられる。
（ｃ−３）成分の混合量は、（ａ）成分の固形分１００重量部に対し、通常０．１〜５０重量部、好ましくは０．５〜２０重量部とする。（ｃ−３）成分が０．１重量部より少ない場合は、耐汚染性等の向上効果が期待できない。（ｃ−３）成分が５０重量部より多い場合は、（ａ）成分を劣化させるおそれがある。
The average particle size of the component (c-3) is usually less than 0.1 μm, preferably 0.001 μm or more and less than 0.1 μm, more preferably 0.005 μm or more and 0.05 μm or less.
As the component (c-3), for example, TiO 2 , ZnO, Bi 2 O 3 , BiVO 4 , SrTiO 3 , CdS, InP, InPb, GaP, GaAs, BaTiO 3 , BaTiO 4 , BaTi 4 O 9 , K 2 NbO 3 , Nb 2 O 5 , Fe 2 O 3 , Ta 2 O 5 , Ta 3 N 5 , K 3 Ta 3 Si 2 O 3 , WO 3 , SnO 2 , NiO, Cu 2 O, SiC, MoS 2 , RuO 2 In addition to CeO 2 and the like, composites of these with metals, metal oxides, porous bodies, layered compounds and the like can be mentioned.
The mixing amount of the component (c-3) is usually 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the solid content of the component (a). When the amount of the component (c-3) is less than 0.1 parts by weight, an improvement effect such as contamination resistance cannot be expected. (C-3) When there are more components than 50 weight part, there exists a possibility of degrading (a) component.
本発明組成物においては、上述の成分の他に、通常塗料に使用可能な成分を含むこともできる。このような成分としては、例えば、有機質顔料、染料、骨材、繊維、増粘剤、造膜助剤、レベリング剤、湿潤剤、可塑剤、凍結防止剤、ｐＨ調整剤、防腐剤、防黴剤、防藻剤、抗菌剤、分散剤、消泡剤、紫外線吸収剤、酸化防止剤、触媒、架橋剤等が使用可能である。 In the composition of the present invention, in addition to the above-described components, components that can be used in ordinary paints can also be included. Examples of such components include organic pigments, dyes, aggregates, fibers, thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreezing agents, pH adjusting agents, preservatives, and antifungal agents. An agent, an anti-algae agent, an antibacterial agent, a dispersant, an antifoaming agent, an ultraviolet absorber, an antioxidant, a catalyst, a crosslinking agent, and the like can be used.
本発明の水性塗料組成物は、建築物内外壁や土木構築物等の基材表面に対して塗装することができる。適用可能な基材としては、例えば、コンクリート、モルタル、磁器タイル、繊維混入セメント板、セメント珪酸カルシウム板、スラグセメントパーライト板、石綿セメント板、ＡＬＣ板、サイディング板、押出成形板、石膏ボード、合板、鋼板、プラスチック板等が挙げられる。これら基材の表面は、何らかの表面処理（例えば、シーラー、サーフェーサー、フィラー等）が施されたものでもよく、既に塗膜が形成されたものや、既に壁紙が貼り付けられたもの等であってもよい。 The water-based paint composition of the present invention can be applied to the surface of a base material such as a building inner / outer wall or a civil engineering structure. Applicable base materials include, for example, concrete, mortar, porcelain tile, fiber-mixed cement board, cement calcium silicate board, slag cement pearlite board, asbestos cement board, ALC board, siding board, extrusion board, gypsum board, plywood , Steel plate, plastic plate and the like. The surface of these base materials may have been subjected to some surface treatment (for example, a sealer, a surfacer, a filler, etc.), and has already been provided with a coating film, or has already been applied with wallpaper. Also good.
本発明組成物を塗装する際には、スプレー、ローラー、鏝、刷毛等の各種塗装器具を使用することができる。
塗装の際には、水を用いて希釈することも可能である。水の混合量は、塗装器具の種類、塗装下地の状態、塗装時の温度等を勘案して適宜設定すればよいが、通常は塗料１００重量部に対し０〜１０重量部程度である。
本発明組成物の塗付量は、通常０．５〜２ｋｇ／ｍ２である。また、本発明組成物を塗装した後の乾燥は通常、常温で行えばよいが、加熱することも可能である。乾燥時間は、通常、常温で０．５〜４時間程度である。
When painting the composition of the present invention, various painting tools such as sprays, rollers, scissors and brushes can be used.
In the case of painting, it is also possible to dilute with water. The mixing amount of water may be appropriately set in consideration of the type of coating equipment, the state of the coating base, the temperature at the time of coating, and the like, but is usually about 0 to 10 parts by weight with respect to 100 parts by weight of the paint.
The application amount of the composition of the present invention is usually 0.5 to 2 kg / m 2 . In addition, drying after coating the composition of the present invention is usually performed at room temperature, but can be performed. The drying time is usually about 0.5 to 4 hours at room temperature.
本発明の水性塗料組成物を塗付した後、透明被膜が形成可能な上塗材を塗付することもできる。この場合、上塗材として艶消し塗料乃至３分艶塗料を使用すれば、本発明組成物の質感を阻害せずに、塗膜の耐候性、耐水性、耐汚染性等を高めることができる。 After applying the water-based coating composition of the present invention, a top coating material capable of forming a transparent film can also be applied. In this case, if a matte paint or a three-minute gloss paint is used as the top coating material, the weather resistance, water resistance, stain resistance, etc. of the coating film can be enhanced without impairing the texture of the composition of the present invention.
特に、上塗材としては、反応性シリル基を有する化合物及び／または重合体を含有する上塗材が好適である。この上塗材は、下塗材塗膜に対して優れた密着性を示すとともに、耐汚染性に優れた塗膜を形成することができるものである。また、適度な水蒸気透過性能を有するため、基材内部に滞留した水分を外部に放散させることもできる。 In particular, as the top coating material, a top coating material containing a compound having a reactive silyl group and / or a polymer is suitable. This top coating material can form a coating film having excellent adhesion to the primer coating film and having excellent stain resistance. Moreover, since it has moderate water vapor permeation performance, it is possible to dissipate the moisture remaining inside the substrate.
上塗材における反応性シリル基としては、珪素原子にアルコキシル基、フェノキシ基、メルカプト基、アミノ基、ハロゲン等が結合したものが挙げられる。このうち、珪素原子にアルコキシル基が結合したアルコキシシリル基が好適である。 Examples of the reactive silyl group in the top coating material include those in which an alkoxyl group, a phenoxy group, a mercapto group, an amino group, a halogen, or the like is bonded to a silicon atom. Of these, alkoxysilyl groups in which an alkoxyl group is bonded to a silicon atom are preferred.
本発明における上塗材としては、
（ｉ）固形分中のシリコン成分量がＳｉＯ２換算で０．１〜５０重量％である重合体を含む合成樹脂エマルションを含有するもの、あるいは、
（ｉｉ）合成樹脂エマルションの固形分１００重量部に対し、アルコキシシラン化合物をＳｉＯ２換算で０．１〜５０重量部含有するもの
が好適である。
As the top coating material in the present invention,
(I) those silicon component content in the solid component contains synthetic resin emulsion containing polymer from 0.1 to 50% by weight in terms of SiO 2, or,
The solid content 100 parts by weight of (ii) a synthetic resin emulsion is suitable alkoxysilane compounds those containing 0.1 to 50 parts by weight in terms of SiO 2.
このうち（ｉ）に示す上塗材は、バインダー成分として、
（ｐ）固形分中のシリコン成分量がＳｉＯ２換算で０．１〜５０重量％である重合体を含む合成樹脂エマルション（以下「（ｐ）成分」という）を含有するものである。この（ｐ）成分は、（ｍ）反応性シリル基含有化合物（以下「（ｍ）成分」という）を必須成分として得られるものである。（ｐ）成分において、（ｍ）成分を導入する方法としては、特に限定されず各種の方法を採用することができるが、例えば、
（１）反応性シリル基含有ビニル系単量体を共重合する方法
（２）反応性シリル基含有ビニル系単量体、水酸基含有ビニル系単量体、カルボキシル基含有ビニル系単量体から選ばれる少なくとも１種以上の単量体を共重合した後に、シラン化合物を反応させる方法、
（３）樹脂中の官能基と、該官能基と反応可能な官能基を有するカップリング剤を反応させる方法、
（４）樹脂中の官能基と、該官能基と反応可能な官能基を有するカップリング剤を反応させた後に、シラン化合物を反応させる方法、
等が挙げられる。
Of these, the top coating material shown in (i) is used as a binder component.
(P) It contains a synthetic resin emulsion (hereinafter referred to as “(p) component”) containing a polymer whose solid content is 0.1 to 50% by weight in terms of SiO 2 . This component (p) is obtained by using (m) a reactive silyl group-containing compound (hereinafter referred to as “(m) component”) as an essential component. In the component (p), the method for introducing the component (m) is not particularly limited, and various methods can be adopted.
(1) Method of copolymerizing reactive silyl group-containing vinyl monomer (2) Selected from reactive silyl group-containing vinyl monomer, hydroxyl group-containing vinyl monomer, carboxyl group-containing vinyl monomer A method of reacting a silane compound after copolymerizing at least one or more monomers,
(3) A method of reacting a functional group in the resin with a coupling agent having a functional group capable of reacting with the functional group,
(4) A method of reacting a silane compound after reacting a functional group in the resin with a coupling agent having a functional group capable of reacting with the functional group,
Etc.
（１）、（２）における反応性シリル基含有ビニル系単量体は、反応性シリル基と重合性二重結合を含有する化合物であり、例えば、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−ｎ−ブトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、アリルトリメトキシシラン、トリメトキシシリルエチルビニルエーテル、トリエトキシシリルエチルビニルエーテル、トリメトキシシリルプロピルビニルエーテル、トリエトキシシリルプロピルビニルエーテル、γ−（メタ）アクリロイルオキシプロピルトリメトキシシラン、γ−（メタ）アクリロイルオキシプロピルトリエトキシシラン、γ−（メタ）アクリロイルオキシプロピルメチルジメトキシシラン、ビニルメチルジメトキシシラン、メチルジメトキシシリルエチルビニルエーテル、メチルジメトキシシリルプロピルビニルエーテル等があげられ、これらの１種または２種以上を使用することができる。 The reactive silyl group-containing vinyl monomer in (1) and (2) is a compound containing a reactive silyl group and a polymerizable double bond, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethyl. -N-butoxysilane, vinyltris (β-methoxyethoxy) silane, allyltrimethoxysilane, trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, triethoxysilylpropyl vinyl ether, γ- (meth) acryloyl Oxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, vinylmethyldimethoxysilane, methyldimethoxysilyl Chill vinyl ether, and methyl dimethoxy silyl propyl vinyl ether and the like, can be used one or two or more thereof.
（２）における水酸基含有ビニル系単量体としては、例えば、２−ヒドロキシエチル（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、３−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等が挙げられる。
（２）におけるカルボキシル基含有ビニル系単量体としては、例えば、（メタ）アクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸、無水マレイン酸、無水イタコン酸等が挙げられる。
Examples of the hydroxyl group-containing vinyl monomer in (2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, and the like. Can be mentioned.
Examples of the carboxyl group-containing vinyl monomer in (2) include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride and the like.
（２）、（４）におけるシラン化合物としては、反応性シリル基を一分子中に２個以上有するものが用いられ、例えば、テトラエトキシシラン、テトラメトキシシラン、テトラブトキシシラン等の４官能アルコキシシラン類；メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリブトキシシラン、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、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、フェニルトリブトキシシラン等の３官能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、ジメチルジブトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジプロピルジメトキシシラン、ジプロピルジエトキシシラン、ジブチルジメトキシシラン、ジブチルジエトキシシラン、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、ジフェニルジブトキシシラン、メチルフェニルジメトキシシラン、メチルフェニルジエトキシシラン等の２官能アルコキシシラン類；テトラクロロシラン、メチルトリクロロシラン、エチルトリクロロシラン、プロピルトリクロロシラン、フェニルトリクロロシラン、ビニルトリクロロシラン、ジメチルジクロロシラン、ジエチルジクロロシラン、ジフェニルジクロロシラン、メチルフェニルジクロロシラン等のクロロシラン類；テトラアセトキシシラン、メチルトリアセトキシシラン、フェニルトリアセトキシシラン、ジメチルジアセトキシシラン、ジフェニルジアセトキシシラン等のアセトキシシラン類などがあげられ、これらの１種または２種以上を使用することができる。また、反応性シリル基を一分子中に１個有する化合物を併用することもできる。 As the silane compounds in (2) and (4), those having two or more reactive silyl groups in one molecule are used. For example, tetrafunctional alkoxysilanes such as tetraethoxysilane, tetramethoxysilane, and tetrabutoxysilane. Class: methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxy Trifunctional alkoxysilanes such as silane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, diethyldi Toxisilane, Diethyldiethoxysilane, Dipropyldimethoxysilane, Dipropyldiethoxysilane, Dibutyldimethoxysilane, Dibutyldiethoxysilane, Diphenyldimethoxysilane, Diphenyldiethoxysilane, Diphenyldibutoxysilane, Methylphenyldimethoxysilane, Methylphenyldiethoxy Bifunctional alkoxysilanes such as silane; tetrachlorosilane, methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane, etc. Chlorosilanes: tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxy Orchids, dimethyldiacetoxysilane, such as acetoxy silanes such as diphenyl diacetoxy silane and the like, can be used one or two or more thereof. Moreover, the compound which has one reactive silyl group in 1 molecule can also be used together.
（３）、（４）における官能基の組み合わせとしては、水酸基とイソシアネート基、アミノ基とイソシアネート基、カルボキシル基とエポキシ基、アミノ基とエポキシ基、アルコキシシリル基どうし等があげられる。カップリング剤は、例えば、一分子中に、少なくとも１個以上の反応性シリル基とそのほかの置換基を有する化合物であり、具体的には、β−（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、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、Ｎ−（β−アミノエチル）−γ−アミノプロピルメチルジメトキシシラン、Ｎ−（β−アミノエチル）−γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、イソシアネート官能性シランなどがあげられ、これらの１種または２種以上を使用することができる。 Examples of combinations of the functional groups in (3) and (4) include a hydroxyl group and an isocyanate group, an amino group and an isocyanate group, a carboxyl group and an epoxy group, an amino group and an epoxy group, and an alkoxysilyl group. The coupling agent is, for example, a compound having at least one reactive silyl group and other substituents in one molecule, specifically, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. , Γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ- Examples thereof include aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, isocyanate functional silane, and the like, and one or more of these can be used.
（ｐ）成分の共重合モノマーとしては、特に限定されないが、各種アクリル系モノマー等を用いることができる。 Although it does not specifically limit as a copolymerization monomer of (p) component, Various acrylic monomers etc. can be used.
（ｐ）成分の重量平均分子量は３００００以上、さらには５００００以上であることが望ましい。分子量が３００００以上であることにより、耐候性、硬度、耐汚染性、耐水性等を向上させることができる。また、（ｐ）成分のＴｇは−１０〜８０℃であることが望ましい。Ｔｇが−１０℃より低い場合は汚染物質が付着しやすくなり、８０℃より高い場合は塗膜に割れが生じやすくなる。 The weight average molecular weight of the component (p) is preferably 30,000 or more, more preferably 50,000 or more. When the molecular weight is 30000 or more, weather resistance, hardness, stain resistance, water resistance and the like can be improved. The Tg of the component (p) is desirably -10 to 80 ° C. When Tg is lower than −10 ° C., contaminants are likely to adhere, and when it is higher than 80 ° C., cracks are likely to occur in the coating film.
（ｐ）成分におけるシリコン成分量は、（ｐ）成分の固形分中にＳｉＯ２換算で０．１〜５０重量％、好ましくは１〜３０重量％である。シリコン成分量がこのような範囲であることにより、十分な硬度及び耐候性を有する被膜が形成される。（ｐ）成分のシリコン成分が少なすぎる場合は、密着性が不十分となるおそれがある。また、汚染物質が付着しやすくなり、耐候性も低下してしまう。シリコン成分が多すぎる場合は、塗膜の割れを引き起こすおそれがある。 The amount of the silicon component in the component (p) is 0.1 to 50% by weight, preferably 1 to 30% by weight in terms of SiO 2 in the solid content of the component (p). When the silicon component amount is in such a range, a film having sufficient hardness and weather resistance is formed. When there is too little silicon component of (p) component, there exists a possibility that adhesiveness may become inadequate. Moreover, it becomes easy for a contaminant to adhere and a weather resistance will also fall. When there are too many silicon components, there exists a possibility of causing the crack of a coating film.
なお、ＳｉＯ２換算とは、Ｓｉ−Ｏ結合をもつ化合物を、完全に加水分解した後に、９００℃で焼成した際にシリカ（ＳｉＯ２）となって残る重量分にて表したものである。
一般に、アルコキシシランやシリケート等は、水と反応して加水分解反応が起こりシラノールとなり、さらにシラノールどうしやシラノールとアルコキシにより縮合反応を起こす性質を持っている。この反応を究極まで行うと、シリカ（ＳｉＯ２）となる。これらの反応は一般式、
ＲＯ（Ｓｉ（ＯＲ）２Ｏ）ｎＲ＋（ｎ＋１）Ｈ２Ｏ→ｎＳｉＯ２＋（２ｎ＋２）ＲＯＨ
という反応式で表されるが、この反応式をもとに残るシリカ成分の量を換算したものである。
The term “SiO 2 conversion” refers to the weight remaining as silica (SiO 2 ) when the compound having a Si—O bond is completely hydrolyzed and then baked at 900 ° C.
In general, alkoxysilanes, silicates, and the like have the property of reacting with water to cause hydrolysis reaction to form silanol, and further causing condensation reaction between silanols or silanol and alkoxy. When this reaction is performed to the ultimate, silica (SiO 2 ) is obtained. These reactions have the general formula:
RO (Si (OR) 2 O) n R + (n + 1) H 2 O → nSiO 2 + (2n + 2) ROH
The amount of the remaining silica component is converted based on this reaction equation.
工程（２）における上塗材（ｉｉ）は、
（ｑ）合成樹脂エマルション（以下「（ｑ）成分」という）の固形分１００重量部に対し、（ｒ）アルコキシシラン化合物（以下「（ｒ）成分」という）をＳｉＯ２換算で０．１〜５０重量部含有するもの
である。
The top coating material (ii) in step (2) is:
(Q) (r) an alkoxysilane compound (hereinafter referred to as “(r) component”) is 0.1 to 0.1 parts in terms of SiO 2 with respect to 100 parts by weight of the solid content of the synthetic resin emulsion (hereinafter referred to as “(q) component”). It contains 50 parts by weight.
（ｑ）成分としては、例えば、酢酸ビニル樹脂エマルション、塩化ビニル樹脂エマルション、エポキシ樹脂エマルション、アクリル樹脂エマルション、ウレタン樹脂エマルション、アクリルシリコン樹脂エマルション、フッ素樹脂エマルション等、あるいはこれらの複合系等を挙げることができる。上述の（ｐ）成分を使用することもできる。これらは１種または２種以上で使用することができる。
（ｑ）成分のＴｇは−１０〜８０℃であることが望ましい。Ｔｇが−１０℃より低い場合は汚染物質が付着しやすくなり、８０℃より高い場合は塗膜に割れが生じやすくなる。
Examples of the component (q) include a vinyl acetate resin emulsion, a vinyl chloride resin emulsion, an epoxy resin emulsion, an acrylic resin emulsion, a urethane resin emulsion, an acrylic silicon resin emulsion, a fluororesin emulsion, or a composite system thereof. Can do. The component (p) described above can also be used. These can be used alone or in combination of two or more.
The Tg of the component (q) is desirably -10 to 80 ° C. When Tg is lower than −10 ° C., contaminants are likely to adhere, and when it is higher than 80 ° C., cracks are likely to occur in the coating film.
（ｒ）成分としては、一分子中に少なくとも１個以上のアルコキシシリル基を有する化合物が使用できる。（ｒ）成分は、単一のアルコキシシラン化合物、２種以上のアルコキシシラン化合物の混合物、１種以上のアルコキシシラン化合物の重縮合物、及びこれらの変性物等を適宜選択して使用することができる。（ｒ）成分を構成する化合物としては、例えば、上述の（ｐ）成分において説明したシラン化合物のうち、アルコキシシリル基を含有するもの等が使用可能である。 As the component (r), a compound having at least one alkoxysilyl group in one molecule can be used. As the component (r), a single alkoxysilane compound, a mixture of two or more alkoxysilane compounds, a polycondensate of one or more alkoxysilane compounds, a modified product thereof, and the like may be appropriately selected and used. it can. As a compound which comprises (r) component, the thing etc. which contain an alkoxy silyl group etc. can be used among the silane compounds demonstrated in the above-mentioned (p) component, for example.
（ｒ）成分の混合比率は、（ｑ）成分の固形分１００重量部に対して、ＳｉＯ２換算で０．１〜５０重量部、好ましくは１〜３０重量部とする。０．１重量部未満では密着性や耐汚染性が不十分となるおそれがある。５０重量部を超えると、塗膜に割れが生じやすくなる。 The mixing ratio of the component (r) is 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight in terms of SiO 2 with respect to 100 parts by weight of the solid content of the component (q). If it is less than 0.1 part by weight, the adhesion and stain resistance may be insufficient. If it exceeds 50 parts by weight, the coating film tends to crack.
本発明における（ｒ）成分としては、特に（ｒ−１）繰り返し単位の炭素数が１〜４のポリオキシアルキレン基と、炭素数が１〜４のアルコキシル基を含有するアルコキシシランの縮合物（以下「（ｒ−１）成分」という）が好適である。このような（ｒ−１）成分は、合成樹脂エマルションとの相溶性が良好であり、耐汚染性に優れた塗膜を形成することができる。
（ｒ−１）成分のアルコキシル基の炭素数は１〜４である。炭素数が４を超えると、耐汚染性が低下する傾向となる。
ポリオキシアルキレン基の平均分子量は、１５０〜２０００であることが望ましい。平均分子量が１５０未満の場合は、（ｑ）成分との相溶性が低下し、２０００を超えると被膜の耐水性、強度等が低下する傾向となる。
また、（ｒ−１）の平均縮合度は１〜２０であることが望ましい。平均縮合度が２０を超えると、取り扱いが不便になる。
As the component (r) in the present invention, (r-1) a condensate of an alkoxysilane containing a polyoxyalkylene group having 1 to 4 carbon atoms in a repeating unit and an alkoxyl group having 1 to 4 carbon atoms ( Hereinafter, “(r-1) component”) is preferable. Such (r-1) component has good compatibility with the synthetic resin emulsion, and can form a coating film excellent in stain resistance.
Carbon number of the alkoxyl group of (r-1) component is 1-4. When the number of carbons exceeds 4, the contamination resistance tends to decrease.
The average molecular weight of the polyoxyalkylene group is desirably 150 to 2,000. When the average molecular weight is less than 150, the compatibility with the component (q) decreases, and when it exceeds 2000, the water resistance and strength of the coating film tend to decrease.
The average degree of condensation of (r-1) is preferably 1-20. When the average degree of condensation exceeds 20, handling becomes inconvenient.
（ｒ−１）成分は、公知の方法により製造することが可能であるが、例えば、アルコキシシラン縮合物の１種または２種以上の混合物を、ポリオキシアルキレン基含有化合物１種または２種以上でエステル交換反応させる方法、カップリング剤を用いて付加反応させる方法等があげられる。 The component (r-1) can be produced by a known method. For example, one or two or more mixtures of alkoxysilane condensates are used as one or more polyoxyalkylene group-containing compounds. For example, a transesterification method using a coupling agent, and an addition reaction method using a coupling agent.
上述の（ｐ）成分、（ｑ）成分は、エポキシ基を含有するものが好適である。これにより、下塗材における（ｂ−１）成分との相互作用により、より密着性を高めることができる。 The above-mentioned component (p) and component (q) are preferably those containing an epoxy group. Thereby, adhesiveness can be improved more by interaction with the (b-1) component in undercoat.
上塗材においては、上述の成分の他に、通常塗料に使用可能な成分を本発明の効果を阻害しない範囲内で適宜混合することもできる。このような成分としては、例えば、着色顔料、体質顔料、染料、骨材、繊維、増粘剤、造膜助剤、レベリング剤、湿潤剤、可塑剤、凍結防止剤、ｐＨ調整剤、防腐剤、防黴剤、防藻剤、抗菌剤、分散剤、消泡剤、紫外線吸収剤、酸化防止剤、触媒、架橋剤等が挙げられる。 In the top coating material, in addition to the above-described components, components that can be used in ordinary paints can be appropriately mixed within a range that does not impair the effects of the present invention. Examples of such components include coloring pigments, extender pigments, dyes, aggregates, fibers, thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreezing agents, pH adjusting agents, preservatives. , Antifungal agents, algaeproofing agents, antibacterial agents, dispersants, antifoaming agents, ultraviolet absorbers, antioxidants, catalysts, crosslinking agents, and the like.
上塗材を塗装する際には、スプレー、ローラー、刷毛等の各種塗装器具を使用することができる。
塗装の際には、水を用いて希釈することも可能である。上塗材の塗付量は、通常０．１〜０．５ｋｇ／ｍ２程度である。また、上塗材を塗装した後の乾燥は通常、常温で行えばよいが、加熱することも可能である。
When painting the top coat material, various painting tools such as sprays, rollers, and brushes can be used.
In the case of painting, it is also possible to dilute with water. The coating amount of the top coating material is usually about 0.1 to 0.5 kg / m 2 . In addition, drying after applying the top coating material is usually performed at room temperature, but heating is also possible.
以下に実施例及び比較例を示し、本発明の特徴をより明確にする。 Examples and Comparative Examples are shown below to clarify the features of the present invention.
［塗料の製造］
・配合例１
樹脂Ａ２００重量部に対し、撥水剤８重量部、白色顔料３６重量部、体質顔料Ａ７４重量部、体質顔料Ｂ１８４重量部、体質顔料Ｃ１１０重量部、造膜助剤２４重量部、分散剤１０重量部、繊維２２重量部、消泡剤４重量部を常法により混合・攪拌することによって塗料を製造した。
・配合例２〜７
表１に示す配合に従い、配合例１と同様にして塗料を製造した。
なお、原料としては下記のものを使用した。
[Manufacture of paint]
・ Composition example 1
8 parts by weight of water repellent, 36 parts by weight of white pigment, 74 parts by weight of extender pigment A, 184 parts by weight of extender pigment B, 110 parts by weight of extender pigment C, 24 parts by weight of a film-forming aid, and 10 parts by weight of dispersing agent A paint was prepared by mixing and stirring parts, 22 parts by weight of fibers, and 4 parts by weight of an antifoaming agent by a conventional method.
・ Composition examples 2-7
According to the formulation shown in Table 1, paints were produced in the same manner as in Formulation Example 1.
In addition, the following were used as a raw material.
・樹脂Ａ：アクリル樹脂エマルション（メチルメタクリレート−スチレン−２−エチルヘキシルアクリレート−メタクリル酸共重合体、固形分５０重量％、Ｔｇ５℃）
・樹脂Ｂ：コアシェル型アクリル樹脂エマルション（メチルメタクリレート−スチレン−２−エチルヘキシルアクリレート−グリシジルメタクリレート−メタクリル酸共重合体、固形分５０重量％、トータルＴｇ５℃、コアＴｇ−２０℃、シェルＴｇ２５℃）
・樹脂Ｃ：コアシェル型アクリル樹脂エマルション（メチルメタクリレート−スチレン−２−エチルヘキシルアクリレート−グリシジルメタクリレート−メタクリル酸−４−メタクリロイルオキシ−２，２，６，６−テトラメチルピペリジン共重合体、固形分５０重量％、トータルＴｇ５℃、コアＴｇ−２０℃、シェルＴｇ２５℃）
・撥水剤：水分散型撥水剤（アミノ基含有ジメチルシロキサン化合物の乳化分散体、固形分５０重量％）
・白色顔料：ルチル型酸化チタン（平均粒子径０．２μｍ、白色度９７）
・体質顔料Ａ：タルク（平均粒子径８μｍ、白色度９３）
・体質顔料Ｂ：珪石粉（平均粒子径６０μｍ、白色度９０）
・体質顔料Ｃ：炭酸カルシウム（平均粒子径６０μｍ、白色度８９）
・体質顔料Ｄ：珪藻土（平均粒子径３０μｍ、白色度８８）
・光触媒：アナターゼ型酸化チタン（平均粒子径０．０２μｍ）
・造膜助剤：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
・分散剤：ポリカルボン酸系分散剤（固形分３０重量％）
・繊維：パルプ繊維（平均繊維長０．１ｍｍ）
・増粘剤：ヒドロキシエチルセルロース３重量％水溶液
・消泡剤：鉱物油系消泡剤
Resin A: acrylic resin emulsion (methyl methacrylate-styrene-2-ethylhexyl acrylate-methacrylic acid copolymer, solid content 50% by weight, Tg 5 ° C.)
Resin B: Core-shell type acrylic resin emulsion (methyl methacrylate-styrene-2-ethylhexyl acrylate-glycidyl methacrylate-methacrylic acid copolymer, solid content 50% by weight, total Tg 5 ° C., core Tg-20 ° C., shell Tg 25 ° C.)
Resin C: Core-shell type acrylic resin emulsion (methyl methacrylate-styrene-2-ethylhexyl acrylate-glycidyl methacrylate-methacrylic acid-4-methacryloyloxy-2,2,6,6-tetramethylpiperidine copolymer, solid content 50 weight %, Total Tg5 ° C, core Tg-20 ° C, shell Tg25 ° C)
Water repellent: Water-dispersed water repellent (emulsified dispersion of amino group-containing dimethylsiloxane compound, solid content 50% by weight)
White pigment: rutile titanium oxide (average particle size 0.2 μm, whiteness 97)
・ External pigment A: talc (average particle size 8 μm, whiteness 93)
・ External pigment B: Silica powder (average particle size 60 μm, whiteness 90)
・ External pigment C: calcium carbonate (average particle size 60 μm, whiteness 89)
・ External pigment D: diatomaceous earth (average particle size 30 μm, whiteness 88)
Photocatalyst: anatase type titanium oxide (average particle size 0.02 μm)
・ Film-forming auxiliary: 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate ・ Dispersant: polycarboxylic acid-based dispersant (solid content 30% by weight)
・ Fiber: Pulp fiber (average fiber length 0.1 mm)
・ Thickener: Hydroxyethylcellulose 3% by weight aqueous solution ・ Defoamer: Mineral oil-based defoamer
［試験例１］
得られた塗料について、以下の方法で仕上り性と耐水性を確認した。
[Test Example 1]
About the obtained coating material, the finish and water resistance were confirmed by the following methods.
・仕上り性
９０×９０ｃｍのスレート板に対し、各塗料を塗付量１ｋｇ／ｍ２でスプレー塗装し、温度２３℃・相対湿度５０％雰囲気（以下、標準状態）で１４日間養生した後、その質感と隠ぺい性を確認した。質感については、漆喰調の質感が得られたものを「○」として３段階で評価した。隠ぺい性については、下地を完全に隠ぺいしたものを「○」とし３段階で評価した。
・ Finish: 90 × 90cm slate plate sprayed with 1kg / m 2 of each paint, and cured for 14 days at 23 ° C and 50% relative humidity (standard condition) The texture and concealment were confirmed. The texture was evaluated in three stages as “◯” when the stucco-like texture was obtained. Concealing property was evaluated in three stages with “○” indicating that the ground was completely hidden.
・初期耐水性
各塗料を、０．５ｍｍのフィルムアプリケータを用いてガラス板に塗付し、５℃雰囲気にて乾燥させ、水に浸漬したときに溶出しなくなるまでの時間を測定した。評価は、１８０分未満を「○」、１８０分以上２４０分未満を「△」、２４０分以上を「×」とした。
-Initial water resistance Each coating material was applied to a glass plate using a 0.5 mm film applicator, dried in an atmosphere of 5 ° C, and the time until it was not eluted when immersed in water was measured. The evaluation was evaluated as “◯” when less than 180 minutes, “Δ” when 180 minutes or more and less than 240 minutes, and “X” when 240 minutes or more.
・耐水性
１５×７ｃｍのスレート板に対し、各塗料を塗付量１ｋｇ／ｍ２でスプレー塗装し、標準状態で１４日間養生することにより試験体を作製した。得られた試験体を、２３℃の水中に７日間浸漬した後、膨れ等の異常が発生していないか確認を行った。評価は、全く異常が認められないものを「◎」、ほとんど異常が認められなかったものを「○」、一部異常が認められたものを「△」、明らかに異常が認められたものを「×」とした。
· To waterproof 15 × 7 cm slate plate, and spraying each paint coat-weight 1 kg / m 2, to produce a test body by curing in normal conditions for 14 days. The obtained specimen was immersed in water at 23 ° C. for 7 days, and then it was confirmed whether or not abnormality such as swelling occurred. The evaluation is “◎” when no abnormality is observed, “○” when there is almost no abnormality, “△” when some abnormality is observed, and those with obvious abnormality. It was set as “x”.
試験結果を表２に示す。
配合例１〜３の塗料では、いずれの試験においても良好な結果を得ることができた。
これに対し、配合例４の塗料は、塗膜の仕上り性は良好であったが、耐水性に劣る結果となった。配合例５、配合例６及び配合例７の塗料では、仕上り性が悪く、耐水性も不十分な結果となった。
The test results are shown in Table 2.
In the paints of Formulation Examples 1 to 3, good results could be obtained in any test.
On the other hand, the paint of Formulation Example 4 had good finish of the coating film, but was inferior in water resistance. In the paints of Formulation Example 5, Formulation Example 6 and Formulation Example 7, the finish was poor and the water resistance was insufficient.
［試験例２］
１５×７ｃｍのスレート板に対し、各塗料を塗付量１ｋｇ／ｍ２でスプレー塗装し、標準状態で１４日間養生することにより試験体を作製した。通気孔を設けた容器内に試験体を入れ、タバコに火をつけて燃焼させた。次いで、通気孔を閉じて２４時間放置した。その後、試験板を取り出し、試験板表面に紫外線ランプを２４時間照射し、照射後の状態を目視により確認した。その結果、配合例３の塗料ではヤニの黄色が消失した。他の配合例ではヤニの黄色が残存した。
[Test Example 2]
Each paint was spray-coated at a coating amount of 1 kg / m 2 on a 15 × 7 cm slate plate and cured for 14 days in a standard state to prepare a test specimen. The specimen was placed in a container provided with a vent, and the cigarette was ignited and burned. Next, the vent hole was closed and left for 24 hours. Thereafter, the test plate was taken out, the surface of the test plate was irradiated with an ultraviolet lamp for 24 hours, and the state after irradiation was visually confirmed. As a result, the yellowish color of the paint in Formulation Example 3 disappeared. In other blending examples, the yellow color of the spider remained.
［試験例３］
アクリル樹脂エマルション（メチルメタクリレート−シクロヘキシルメタクリレート−２−エチルヘキシルアクリレート−グリシジルメタクリレート−アクリル酸共重合体、Ｔｇ２５℃、固形分５０重量％）２００重量部に、ポリオキシエチレン基含有アルコキシシラン化合物（エチルシリケートとポリオキシエチレングリコールモノセチルエーテルとの反応物）をＳｉＯ２換算で１０重量部、ポリエチレン樹脂ビーズを１０重量部均一に混合分散させることにより、上塗材Ａを製造した。
９０×９０ｃｍのスレート板に対し、配合例２の塗料を塗付量１ｋｇ／ｍ２でスプレー塗装し、標準状態で２４時間乾燥後、上述の上塗材Ａを塗付量０．２ｋｇ／ｍ２でスプレー塗装した。標準状態で１４日間養生した後、その質感と隠ぺい性を確認した。また、塗装後のスレート板を１５×７ｃｍの大きさに切り出したものを耐水性試験に供し、膨れ等の異常が発生していないか確認を行った。その結果、質感及び隠ぺい性については「○」、耐水性については「◎」となった。
さらに、上記塗装後のスレート板を１５×７ｃｍの大きさに切り出したものの表面に、汚れ成分（カーボンブラック水分散液）を滴下し、標準状態で２４時間放置後、流水によって洗浄した。その結果、汚れ成分は完全に除去された。
[Test Example 3]
To 200 parts by weight of an acrylic resin emulsion (methyl methacrylate-cyclohexyl methacrylate-2-ethylhexyl acrylate-glycidyl methacrylate-acrylic acid copolymer, Tg 25 ° C., solid content 50% by weight), a polyoxyethylene group-containing alkoxysilane compound (ethyl silicate and The top coating material A was produced by uniformly mixing and dispersing 10 parts by weight of the reaction product of polyoxyethylene glycol monocetyl ether) in terms of SiO 2 and 10 parts by weight of polyethylene resin beads.
A 90 × 90 cm slate plate is spray-coated with the coating material of Formulation Example 2 at a coating amount of 1 kg / m 2 , dried for 24 hours in a standard state, and then coated with the above-mentioned top coating material A at a coating amount of 0.2 kg / m 2. Spray painted with. After curing for 14 days in the standard state, the texture and concealment were confirmed. Moreover, what cut out the slate board after a painting to the magnitude | size of 15x7 cm was used for the water resistance test, and it was confirmed whether abnormality, such as a swelling, had generate | occur | produced. As a result, the texture and concealment were “◯” and the water resistance was “◎”.
Further, a soil component (carbon black water dispersion) was dropped onto the surface of the slate plate after the coating was cut out to a size of 15 × 7 cm, left in a standard state for 24 hours, and then washed with running water. As a result, the soil component was completely removed.
Claims (2)
合成樹脂エマルションがカルボキシル基及びエポキシ基を含有する架橋反応型合成樹脂エマルションであり、
水分散型撥水剤がアミノ基含有ジメチルシロキサン化合物の乳化分散体であり、
合成樹脂エマルションの固形分１００重量部に対し、水分散型撥水剤を固形分で１〜１００重量部含み、
顔料容積濃度が３０〜９０％であり、
無機質顔料として、平均粒子径０．１〜１μｍ、白色度９５以上の白色顔料、及び平均粒子径０．１〜２００μｍ、白色度８０以上９５未満の体質顔料を含み、白色顔料と体質顔料の体積比率が１：５〜１：５０であり、
消石灰を含有しないことを特徴とする水性塗料組成物。 An aqueous coating composition containing a synthetic resin emulsion, a water-dispersed water repellent, and an inorganic pigment,
The synthetic resin emulsion is a crosslinking reaction type synthetic resin emulsion containing a carboxyl group and an epoxy group,
The water-dispersed water repellent is an emulsified dispersion of an amino group-containing dimethylsiloxane compound ,
1-100 parts by weight of a water-dispersible water repellent with a solid content with respect to 100 parts by weight of the solid content of the synthetic resin emulsion,
The pigment volume concentration is 30-90%,
The inorganic pigment includes a white pigment having an average particle diameter of 0.1 to 1 μm and a whiteness of 95 or more, and an extender having an average particle diameter of 0.1 to 200 μm and a whiteness of 80 to less than 95, and the volume of the white pigment and the extender pigment The ratio is 1: 5 to 1:50,
An aqueous paint composition characterized by not containing slaked lime.
The water-based paint composition according to claim 1, further comprising 0.1 to 50 parts by weight of a photocatalyst having an average particle diameter of less than 0.1 µm as an inorganic pigment with respect to 100 parts by weight of the solid content of the synthetic resin emulsion. .
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| JPH11106681A (en) * | 1997-10-06 | 1999-04-20 | Sunstar Eng Inc | Surface protection of diatomaceous earth |
| JP2000313843A (en) * | 1999-10-22 | 2000-11-14 | Rikuo Himeno | Coating material composition |
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| JP2004217897A (en) | 2004-08-05 |
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