JP2012224747A - Aqueous coating material composition - Google Patents
Aqueous coating material composition Download PDFInfo
- Publication number
- JP2012224747A JP2012224747A JP2011093430A JP2011093430A JP2012224747A JP 2012224747 A JP2012224747 A JP 2012224747A JP 2011093430 A JP2011093430 A JP 2011093430A JP 2011093430 A JP2011093430 A JP 2011093430A JP 2012224747 A JP2012224747 A JP 2012224747A
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- JP
- Japan
- Prior art keywords
- parts
- aqueous
- aqueous resin
- resin dispersion
- particle size
- 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.)
- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 238000000576 coating method Methods 0.000 title abstract description 38
- 239000011248 coating agent Substances 0.000 title abstract description 37
- 239000000463 material Substances 0.000 title abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 163
- 229920005989 resin Polymers 0.000 claims abstract description 147
- 239000011347 resin Substances 0.000 claims abstract description 147
- 239000006185 dispersion Substances 0.000 claims abstract description 124
- 239000007787 solid Substances 0.000 claims abstract description 108
- 239000000843 powder Substances 0.000 claims abstract description 54
- 239000011148 porous material Substances 0.000 claims abstract description 46
- 239000004094 surface-active agent Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 100
- 239000008199 coating composition Substances 0.000 claims description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 43
- 239000003973 paint Substances 0.000 claims description 37
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 34
- 244000060011 Cocos nucifera Species 0.000 claims description 34
- 239000003945 anionic surfactant Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000003610 charcoal Substances 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 11
- 229910021536 Zeolite Inorganic materials 0.000 claims description 9
- 125000002091 cationic group Chemical group 0.000 claims description 9
- 239000010457 zeolite Substances 0.000 claims description 9
- 239000005909 Kieselgur Substances 0.000 claims description 8
- 125000000129 anionic group Chemical group 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 5
- 239000003242 anti bacterial agent Substances 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 230000002421 anti-septic effect Effects 0.000 claims description 4
- 239000003429 antifungal agent Substances 0.000 claims description 4
- 229940121375 antifungal agent Drugs 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000003755 preservative agent Substances 0.000 claims description 2
- 230000002335 preservative effect Effects 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 18
- -1 aromatic vinyl compound Chemical class 0.000 description 77
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 66
- 238000006243 chemical reaction Methods 0.000 description 63
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 62
- 239000007864 aqueous solution Substances 0.000 description 62
- 239000011342 resin composition Substances 0.000 description 49
- 239000000178 monomer Substances 0.000 description 47
- 238000009826 distribution Methods 0.000 description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 36
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 33
- 239000002518 antifoaming agent Substances 0.000 description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 26
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 25
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 25
- 239000000047 product Substances 0.000 description 25
- 239000000839 emulsion Substances 0.000 description 23
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 21
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 15
- 235000014113 dietary fatty acids Nutrition 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 15
- 239000000194 fatty acid Substances 0.000 description 15
- 229930195729 fatty acid Natural products 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 14
- 239000002736 nonionic surfactant Substances 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 11
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 11
- 239000004283 Sodium sorbate Substances 0.000 description 10
- 239000003995 emulsifying agent Substances 0.000 description 10
- LROWVYNUWKVTCU-STWYSWDKSA-M sodium sorbate Chemical compound [Na+].C\C=C\C=C\C([O-])=O LROWVYNUWKVTCU-STWYSWDKSA-M 0.000 description 10
- 235000019250 sodium sorbate Nutrition 0.000 description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 9
- 230000035699 permeability Effects 0.000 description 9
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 8
- 238000004332 deodorization Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- 239000000123 paper Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000008719 thickening Effects 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000002843 carboxylic acid group Chemical group 0.000 description 6
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 125000005396 acrylic acid ester group Chemical group 0.000 description 5
- 239000002781 deodorant agent Substances 0.000 description 5
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 5
- 125000006353 oxyethylene group Chemical group 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- FURYAADUZGZUGQ-UHFFFAOYSA-N phenoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 FURYAADUZGZUGQ-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-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
- TURPNXCLLLFJAP-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethyl hydrogen sulfate Chemical compound OCCOCCOCCOS(O)(=O)=O TURPNXCLLLFJAP-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical class CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000008360 acrylonitriles Chemical class 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000003254 anti-foaming effect Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- AJOJTMNIQSTBAP-UHFFFAOYSA-N (1,2,2,6,6-pentamethylpiperidin-3-yl) prop-2-enoate Chemical compound CN1C(C)(C)CCC(OC(=O)C=C)C1(C)C AJOJTMNIQSTBAP-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- JMADMUIDBVATJT-UHFFFAOYSA-N 2-methylprop-2-enamide;propan-2-one Chemical compound CC(C)=O.CC(C)=O.CC(=C)C(N)=O JMADMUIDBVATJT-UHFFFAOYSA-N 0.000 description 1
- YHSYGCXKWUUKIK-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C=C YHSYGCXKWUUKIK-UHFFFAOYSA-N 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N 3-phenylprop-2-enal Chemical compound O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LYJHVEDILOKZCG-UHFFFAOYSA-N Allyl benzoate Chemical compound C=CCOC(=O)C1=CC=CC=C1 LYJHVEDILOKZCG-UHFFFAOYSA-N 0.000 description 1
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- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- MNKABUJTBCYVEK-UHFFFAOYSA-N ethenyl 2-butylbenzoate Chemical compound CCCCC1=CC=CC=C1C(=O)OC=C MNKABUJTBCYVEK-UHFFFAOYSA-N 0.000 description 1
- IGBZOHMCHDADGY-UHFFFAOYSA-N ethenyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC=C IGBZOHMCHDADGY-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
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- 229960004279 formaldehyde Drugs 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical group C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
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- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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- 239000003607 modifier Substances 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- ZHALDANPYXAMJF-UHFFFAOYSA-N octadecanoate;tris(2-hydroxyethyl)azanium Chemical compound OCC[NH+](CCO)CCO.CCCCCCCCCCCCCCCCCC([O-])=O ZHALDANPYXAMJF-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- NLDFTWSUPLJCQD-UHFFFAOYSA-N prop-1-en-2-yl propanoate Chemical compound CCC(=O)OC(C)=C NLDFTWSUPLJCQD-UHFFFAOYSA-N 0.000 description 1
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- ZNZJJSYHZBXQSM-UHFFFAOYSA-N propane-2,2-diamine Chemical compound CC(C)(N)N ZNZJJSYHZBXQSM-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 208000008842 sick building syndrome Diseases 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229940001607 sodium bisulfite Drugs 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 239000004308 thiabendazole Substances 0.000 description 1
- 235000010296 thiabendazole Nutrition 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- 229960004546 thiabendazole Drugs 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N vinyl ethyl ether Natural products CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229940043810 zinc pyrithione Drugs 0.000 description 1
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
本発明は、多孔質材料を含有し、その機能を低下させることなく塗膜化でき、貯蔵安定性、塗工適性に優れる水性塗料組成物に関するものである。 The present invention relates to an aqueous coating composition that contains a porous material, can be formed into a coating without deteriorating its function, and is excellent in storage stability and coating suitability.
近年、地球温暖化問題を背景に省エネルギー化が推進されており、住宅分野においても高気密化、高断熱化された鉄骨造、鉄筋コンクリート造などの建築物および一般戸建住宅が増加している。その反面、建築物の高気密化により室内の換気が不十分になると結露やカビの発生、キシレン、トルエン、ホルムアルデヒドのような揮発性有機化合物やアンモニア、メルカプタンのような悪臭物質の滞留によるシックハウス症候群、化学物質過敏症などの健康被害も増加していることから、これらの問題を解決することが急務となっている。 In recent years, energy saving has been promoted against the background of the global warming problem, and in the housing field, buildings such as steel structures and reinforced concrete structures with high airtightness and high heat insulation and general detached houses are increasing. On the other hand, if the indoor ventilation becomes insufficient due to high airtightness of the building, dew condensation and mold generation, volatile organic compounds such as xylene, toluene and formaldehyde, and sick house syndrome due to retention of malodorous substances such as ammonia and mercaptans As health hazards such as chemical sensitivity increase, there is an urgent need to solve these problems.
このような状況を改善するため、シリカ、ゼオライト、炭、珪藻土等に代表される多孔質材料の持つ吸着機能などを生活環境改善のために幅広く利用することが以前から検討されている。また、このような多孔質材料を粉末化して塗料中に配合し、様々な物品に塗装できる形にすることで更なる活用を目指した検討も行われている。 In order to improve such a situation, it has been studied for a long time to use the adsorption function of porous materials typified by silica, zeolite, charcoal, diatomaceous earth and the like for improving the living environment. In addition, studies have been conducted aiming at further utilization by making such a porous material into powder and blending it into a paint so that it can be applied to various articles.
例えば、特許文献１には、ゼオライトおよびケイ酸マグネシウムの少なくとも一種と無機質バインダーと分散媒より構成した塗料を用いて室内の臭気成分を吸着脱臭する技術が開示されている。また、特許文献２には、樹脂成分またはビヒクルと炭粉を必須成分として含んでなる着色料を、木材等の室内用壁材に塗装することで吸放湿性と脱臭性を付与できる技術が開示されている。さらに、特許文献３には、植物由来の炭を粉末化し、ポリマーエマルション、セルロース系水溶性ポリマー、有機溶剤を含有させることで分散安定性の優れた炭粉末含有塗料を提供する技術が開示されている。 For example, Patent Document 1 discloses a technique for adsorbing and deodorizing indoor odor components using a paint composed of at least one of zeolite and magnesium silicate, an inorganic binder, and a dispersion medium. Patent Document 2 discloses a technique capable of imparting moisture absorption / desorption and deodorizing properties by painting a colorant comprising a resin component or a vehicle and charcoal powder as essential components on a wall material for indoor use such as wood. Has been. Furthermore, Patent Document 3 discloses a technique for providing a charcoal powder-containing coating having excellent dispersion stability by pulverizing plant-derived charcoal and adding a polymer emulsion, a cellulose-based water-soluble polymer, and an organic solvent. Yes.
しかしながら、特許文献１〜３に記載された塗料は、分散媒として健康被害の原因物質の一つである揮発性有機化合物を含んでいたり、塗料の貯蔵安定性が充分でなく、貯蔵経時で増粘したり、沈降分離したりするため、使用時に電動ミキサーなどで撹拌均一化して使用しなければならず、撹拌が不十分であるとブツ等の仕上がり不良の原因にもなる。さらに、多孔質材料の特長である吸油量の高さからその塗料組成物はチクソ性が強く発現し、塗装を行う際に安定した粘性を保持できず、カスレや不均一な膜厚分布となる問題や塗装後に期待していた塗膜性能が発揮されないことさえある。特に特許文献３では、セルロース系水溶性ポリマーおよび有機溶剤を使用して、塗料の分散安定性、保存安定性が改良できるとされているが、セルロース系水溶性ポリマーは塗料粘度を高くするため使用量に限界があり、また有機溶剤を多量に使用することは環境問題から好ましくない。 However, the paints described in Patent Documents 1 to 3 contain a volatile organic compound which is one of the causative substances of health damage as a dispersion medium, and the storage stability of the paint is not sufficient, and the paint increases over time. In order to stick or separate by settling, it must be used after stirring and homogenizing with an electric mixer or the like. Insufficient stirring may also cause defective finish such as blisters. Furthermore, due to the high oil absorption, which is a feature of porous materials, the coating composition has a strong thixotropy and cannot maintain a stable viscosity during coating, resulting in a blur or uneven film thickness distribution. The problem and the coating performance expected after painting may not be exhibited. Particularly in Patent Document 3, it is said that the dispersion stability and storage stability of a paint can be improved by using a cellulose-based water-soluble polymer and an organic solvent. However, a cellulose-based water-soluble polymer is used to increase the viscosity of the paint. The amount is limited, and it is not preferable to use a large amount of an organic solvent because of environmental problems.
本発明の目的は、上記のような塗料の問題点である各種の要求性能を満たし、貯蔵安定性、塗工適性に優れ、配合する多孔質材料粉末が有する機能性を保持したまま塗膜化できる水性塗料組成物を提供することである。 The purpose of the present invention is to satisfy various performance requirements, which are the problems of the paint as described above, to be excellent in storage stability and coating suitability, and to form a coating while maintaining the functionality of the porous material powder to be blended. It is to provide an aqueous coating composition that can be used.
本発明は、水性樹脂分散体の樹脂固形分１００質量部に対して、多孔質材料粉末５〜５００質量部、および界面活性剤の固形分５〜３００質量部を必須成分とする水性塗料組成物であって、
水性樹脂分散体が、平均粒子径５０〜２８０ｎｍの樹脂粒子Ａと平均粒子径３３０〜１２００ｎｍの樹脂粒子Ｂとを質量比率でＡ：Ｂ＝１０：９０〜５０：５０の範囲で含有することを特徴とする、水性塗料組成物である。
The present invention provides an aqueous coating composition containing 5 to 500 parts by weight of a porous material powder and 5 to 300 parts by weight of a solid content of a surfactant as essential components with respect to 100 parts by weight of resin solids of an aqueous resin dispersion. Because
The aqueous resin dispersion contains resin particles A having an average particle size of 50 to 280 nm and resin particles B having an average particle size of 330 to 1200 nm in a mass ratio of A: B = 10: 90 to 50:50. It is the water-based coating composition characterized.
また本発明は、多孔質材料粉末が、椰子殻活性炭粉、備長炭粉、珪藻土および合成ゼオライトから選ばれる少なくとも一種であることを特徴とする。 Further, the present invention is characterized in that the porous material powder is at least one selected from coconut shell activated carbon powder, Bincho charcoal powder, diatomaceous earth, and synthetic zeolite.
また本発明は、多孔質材料粉末の最大粒子径が１００μｍ以下であることを特徴とする。
また本発明は、水性樹脂分散体の最低成膜温度が３０℃以下であることを特徴とする。
In the present invention, the maximum particle size of the porous material powder is 100 μm or less.
The present invention is also characterized in that the minimum film forming temperature of the aqueous resin dispersion is 30 ° C. or lower.
また本発明は、水性樹脂分散体の固形分１００質量部に対して、界面活性剤の固形分が３０〜２５０質量部であることを特徴とする。 In addition, the present invention is characterized in that the solid content of the surfactant is 30 to 250 parts by mass with respect to 100 parts by mass of the solid content of the aqueous resin dispersion.
また本発明は、界面活性剤が親水性基としてアニオン性基、ノニオン性基およびカチオン性基から選ばれる２種以上の官能基を有する界面活性剤であることを特徴とする。 Further, the present invention is characterized in that the surfactant is a surfactant having two or more functional groups selected from an anionic group, a nonionic group and a cationic group as a hydrophilic group.
また本発明は、界面活性剤がノニオン性基としてポリオキシアルキレン基を有するアニオン性の界面活性剤であることを特徴とする。 The present invention is also characterized in that the surfactant is an anionic surfactant having a polyoxyalkylene group as a nonionic group.
また本発明は、消泡剤、増粘剤、防腐剤、防カビ剤、防藻剤、抗菌剤および消臭剤から選ばれる少なくとも１種以上の添加剤を含むことを特徴とする。 Moreover, this invention is characterized by including the at least 1 or more types of additive chosen from an antifoamer, a thickener, antiseptic | preservative, a fungicide, an algae inhibitor, an antibacterial agent, and a deodorizer.
本発明によれば、水性樹脂分散体の樹脂固形分１００質量部に対して、多孔質材料粉末５〜５００質量部、および界面活性剤の固形分５〜３００質量部を必須成分とする水性塗料組成物である。水性樹脂分散体が、平均粒子径５０〜２８０ｎｍの樹脂粒子Ａと平均粒子径３３０〜１２００ｎｍの樹脂粒子Ｂとを質量比率でＡ：Ｂ＝１０：９０〜５０：５０の範囲で含有する。 According to the present invention, an aqueous coating material containing 5 to 500 parts by mass of a porous material powder and 5 to 300 parts by mass of a surfactant as an essential component with respect to 100 parts by mass of resin solids of an aqueous resin dispersion. It is a composition. The aqueous resin dispersion contains resin particles A having an average particle diameter of 50 to 280 nm and resin particles B having an average particle diameter of 330 to 1200 nm in a mass ratio of A: B = 10: 90 to 50:50.
これにより、各種の要求性能、たとえば脱臭、脱色、精製、浄化、調湿性能などの多孔質材料粉末が有する機能性を保持したまま塗膜化でき、かつ塗料の貯蔵安定性、塗工適性を確保することができる。 As a result, various required performances such as deodorization, decolorization, purification, purification, humidity control performance, etc. can be formed into a coating film while maintaining the functionality of porous material powder, and the storage stability and coating suitability of the paint can be improved. Can be secured.
また本発明によれば、多孔質材料粉末として、椰子殻活性炭粉、備長炭粉、珪藻土および合成ゼオライトから選ばれる少なくとも一種を用いることで、脱臭、吸着、調湿などの機能を効率よく付与できる。 Further, according to the present invention, as the porous material powder, by using at least one selected from coconut shell activated carbon powder, Bincho charcoal powder, diatomaceous earth, and synthetic zeolite, functions such as deodorization, adsorption, and humidity control can be efficiently imparted. .
また本発明によれば、多孔質材料粉末の最大粒子径を１００μｍ以下とすることで、多孔質材料粉末の分散性が向上し、塗膜表面が平滑で比較的均一な外観となり、さらに塗料の貯蔵安定性も向上する傾向にある。
また本発明によれば、水性樹脂分散体の最低成膜温度を３０℃以下とすることで、被塗物との付着性がより良好となる。
According to the present invention, the maximum particle size of the porous material powder is 100 μm or less, so that the dispersibility of the porous material powder is improved, the coating film surface is smooth and has a relatively uniform appearance, and Storage stability also tends to improve.
Moreover, according to this invention, adhesiveness with a to-be-coated object becomes more favorable because the minimum film-forming temperature of an aqueous resin dispersion shall be 30 degrees C or less.
また本発明によれば、水性樹脂分散体の固形分１００質量部に対して、界面活性剤の固形分を３０〜２５０質量部とすることで、塗料粘度を適正な範囲とし、塗工適性が確保され、塗料の貯蔵安定性を良好にできる。また脱臭、調湿性能等の多孔質材料粉末が有する機能性を保持したまま塗膜化できる。 According to the present invention, the solid content of the surfactant is 30 to 250 parts by mass with respect to 100 parts by mass of the solid content of the aqueous resin dispersion. It is ensured and the storage stability of the paint can be improved. Moreover, it can be formed into a coating film while maintaining the functionality of the porous material powder such as deodorization and humidity control performance.
また本発明によれば、界面活性剤が親水性基としてアニオン性基、ノニオン性基およびカチオン性基から選ばれる２種以上の官能基を有する界面活性剤であり、ノニオン性基としてポリオキシアルキレン基を有するアニオン性の界面活性剤であることが好ましい。 According to the present invention, the surfactant is a surfactant having two or more functional groups selected from an anionic group, a nonionic group and a cationic group as a hydrophilic group, and the polyoxyalkylene as the nonionic group An anionic surfactant having a group is preferred.
これにより、多孔質材料粉末の分散安定性が向上するため、塗料の貯蔵経時での増粘沈降を防止し、さらに有機溶剤を使用せずに塗料の低粘度化、固形分率の上昇が可能となる。 This improves the dispersion stability of the porous material powder, preventing thickening and sedimentation of the paint over time, and further reducing the viscosity of the paint and increasing the solid content without using organic solvents. It becomes.
また本発明によれば、消泡剤、増粘剤、防腐剤、防カビ剤、防藻剤、抗菌剤および消臭剤から選ばれる少なくとも１種以上の添加剤を含むことで、水性塗料組成物に種々の機能を付加することができる。 Further, according to the present invention, an aqueous coating composition is obtained by including at least one additive selected from an antifoaming agent, a thickener, an antiseptic, an antifungal agent, an algaeproofing agent, an antibacterial agent, and a deodorant. Various functions can be added to objects.
本発明は、水性樹脂分散体と、多孔質材料粉末と、界面活性剤とを含む水性塗料組成物であって、水性樹脂分散体の固形分１００質量部に対して、多孔質材料粉末を５〜５００質量部、界面活性剤を固形分で５〜３００質量部含む。 The present invention relates to an aqueous coating composition containing an aqueous resin dispersion, a porous material powder, and a surfactant, and the amount of the porous material powder is 5 with respect to 100 parts by mass of the solid content of the aqueous resin dispersion. -500 mass parts and 5-300 mass parts of surfactant are included by solid content.
水性樹脂分散体は、平均粒子径５０〜２８０ｎｍの樹脂粒子Ａと平均粒子径３３０〜１２００ｎｍの樹脂粒子Ｂとを、樹脂粒子Ａの質量をＡで表わし、樹脂粒子Ｂの質量をＢで表わしたときに、質量比率でＡ：Ｂ＝１０：９０〜５０：５０の範囲で含有する。 In the aqueous resin dispersion, resin particles A having an average particle diameter of 50 to 280 nm and resin particles B having an average particle diameter of 330 to 1200 nm are represented by A, and the mass of the resin particles B is represented by B. Sometimes, it is contained in a mass ratio of A: B = 10: 90 to 50:50.
以下に、本発明の水性塗料組成物について更に詳細に説明する。
［水性樹脂分散体］
本発明に使用する水性樹脂分散体は、分散樹脂粒子の平均粒子径が５０〜２８０ｎｍの水性樹脂分散体Ａと分散樹脂粒子の平均粒子径が３３０〜１２００ｎｍの水性樹脂分散体Ｂの２種の成分を含む。水性樹脂分散体Ａに分散された樹脂粒子Ａの平均粒子径が、５０ｎｍ未満では透気度が低下してしまい、２８０ｎｍを超えると被塗物への付着性が低下する。また、水性樹脂分散体Ｂに分散された樹脂粒子Ｂの平均粒子径が３３０ｎｍ未満では透気度が低下し、１２００ｎｍを超えると被塗物への付着性が低下してしまう。さらに好ましくは、水性樹脂分散体Ａの分散樹脂粒子の平均粒子径が１００〜２５０ｎｍ、水性樹脂分散体Ｂの分散樹脂粒子の平均粒子径が４３０〜９８０ｎｍである。なお、本発明の水性樹脂分散体は、水に樹脂成分が分散したエマルションである。
Below, the water-based coating composition of this invention is demonstrated in detail.
[Aqueous resin dispersion]
The aqueous resin dispersion used in the present invention is divided into two types: an aqueous resin dispersion A in which the average particle diameter of the dispersed resin particles is 50 to 280 nm and an aqueous resin dispersion B in which the average particle diameter of the dispersed resin particles is 330 to 1200 nm. Contains ingredients. If the average particle diameter of the resin particles A dispersed in the aqueous resin dispersion A is less than 50 nm, the air permeability decreases, and if it exceeds 280 nm, the adhesion to the article to be coated decreases. Further, when the average particle diameter of the resin particles B dispersed in the aqueous resin dispersion B is less than 330 nm, the air permeability decreases, and when it exceeds 1200 nm, the adhesion to an object to be coated decreases. More preferably, the average particle diameter of the dispersed resin particles of the aqueous resin dispersion A is 100 to 250 nm, and the average particle diameter of the dispersed resin particles of the aqueous resin dispersion B is 430 to 980 nm. The aqueous resin dispersion of the present invention is an emulsion in which a resin component is dispersed in water.
また、水性樹脂分散体は、樹脂粒子Ａの質量をＡで表わし、樹脂粒子Ｂの質量をＢで表わしたときに、質量比率でＡ：Ｂ＝１０：９０〜５０：５０の範囲で含有する。すなわち、水性樹脂分散体における水性樹脂分散体Ａの固形分換算比率が１０〜５０質量％、水性樹脂分散体Ｂの固形分換算比率が５０〜９０質量％である。水性樹脂分散体Ａの固形分換算比率が５０質量％より高くなると被塗物への付着性は向上するものの、透気度が低下し、一方水性樹脂分散体Ｂの固形分換算比率が９０質量％より高くなると透気度は向上するものの、被塗物への付着性が低下する。したがって、水性樹脂分散体Ａと水性樹脂分散体Ｂの固形分換算比率を上記の範囲とすることで、透気度と付着性を両立させることができる。さらに好ましい範囲は、水性樹脂分散体Ａの固形分換算比率が２０〜４５質量％、水性樹脂分散体Ｂの固形分換算比率が８０〜５５質量％である。 Further, the aqueous resin dispersion contains A: B = 10: 90 to 50:50 in terms of mass ratio when the mass of the resin particles A is represented by A and the mass of the resin particles B is represented by B. . That is, the solid content conversion ratio of the aqueous resin dispersion A in the aqueous resin dispersion is 10 to 50 mass%, and the solid content conversion ratio of the aqueous resin dispersion B is 50 to 90 mass%. When the solid content conversion ratio of the aqueous resin dispersion A is higher than 50% by mass, the adherence to the object to be coated is improved, but the air permeability is decreased, while the solid content conversion ratio of the aqueous resin dispersion B is 90 mass%. If it is higher than%, the air permeability is improved, but the adhesion to the object to be coated is lowered. Therefore, by setting the solid content conversion ratio of the aqueous resin dispersion A and the aqueous resin dispersion B within the above range, both air permeability and adhesion can be achieved. More preferable ranges are 20 to 45 mass% of the solid content conversion ratio of the aqueous resin dispersion A, and 80 to 55 mass% of the solid content conversion ratio of the aqueous resin dispersion B.
また、水性樹脂分散体としては、塗料、接着剤、紙加工剤、繊維加工剤として広く工業的に利用されているもので、水に樹脂が分散したエマルションであれば特に限定されないが、アクリル系エマルション、アクリルスチレン系エマルション、スチレンブタジエン系エマルション、ウレタン系エマルション、エステル系エマルション、エチレン酢酸ビニル系エマルション、酢酸ビニル系エマルション、塩化ビニル系エマルションなどが挙げられ、アクリル系エマルション、アクリルスチレン系エマルション、スチレンブタジエン系エマルションが好ましく、アクリル系エマルション、アクリルスチレン系エマルションがより好ましい。 The aqueous resin dispersion is widely used industrially as a paint, adhesive, paper processing agent, fiber processing agent, and is not particularly limited as long as it is an emulsion in which a resin is dispersed in water. Emulsions, acrylic styrene emulsions, styrene butadiene emulsions, urethane emulsions, ester emulsions, ethylene vinyl acetate emulsions, vinyl acetate emulsions, vinyl chloride emulsions, acrylic emulsions, acrylic styrene emulsions, styrene A butadiene-based emulsion is preferable, and an acrylic emulsion and an acrylic styrene-based emulsion are more preferable.
上記の水性樹脂分散体の製造方法としては、公知の乳化重合法や懸濁重合法が採用できる。平均粒子径の異なる水性樹脂分散体Ａおよび水性分散体Ｂが混合された水性樹脂分散体を製造する方法を例示すると、
（ｉ）水中にて乳化剤および重合開始剤などの存在下で、重合性単量体を通常４０〜９０℃の加温下で乳化重合した後、塩基性物質にて中和し、さらに重合性単量体を加え乳化重合を行う方法、
（ｉｉ）水中にて乳化剤および重合開始剤などの存在下で、重合性単量体を通常４０〜９０℃の加温下で乳化重合を行う。この工程を異なる容器で各１回行い、平均粒子径の異なる水性樹脂分散体を得て混合する方法、
（ｉｉｉ）水中にて粒子径が大きなシード粒子の存在下で、重合性単量体を通常４０〜９０℃の加温下で乳化重合を行い、その後、粒子径が小さなシード粒子を添加し、さらに重合性単量体を加え乳化重合する方法、
等が挙げられるが、（ｉ）の方法で水性樹脂分散体を製造することが好ましい。
As a method for producing the aqueous resin dispersion, a known emulsion polymerization method or suspension polymerization method can be employed. Illustrating a method for producing an aqueous resin dispersion in which an aqueous resin dispersion A and an aqueous dispersion B having different average particle diameters are mixed,
(I) In the presence of an emulsifier and a polymerization initiator in water, the polymerizable monomer is usually emulsion-polymerized under heating at 40 to 90 ° C., then neutralized with a basic substance, and further polymerizable. A method of performing emulsion polymerization by adding a monomer,
(Ii) In the presence of an emulsifier and a polymerization initiator in water, the polymerizable monomer is usually subjected to emulsion polymerization under heating at 40 to 90 ° C. A method of performing this step once in different containers to obtain and mix aqueous resin dispersions having different average particle diameters,
(Iii) In the presence of seed particles having a large particle size in water, the polymerizable monomer is usually subjected to emulsion polymerization under heating at 40 to 90 ° C., and then seed particles having a small particle size are added, Further, a method of emulsion polymerization by adding a polymerizable monomer,
The aqueous resin dispersion is preferably produced by the method (i).
本発明で用いられる水性樹脂分散体の固形分率については任意に選定できるが、塗料の塗工適性を確保するため、比較的高い方が好ましく、３５〜７０質量％が好ましく、より好ましくは５０〜６８質量％の範囲である。 The solid content ratio of the aqueous resin dispersion used in the present invention can be arbitrarily selected, but is preferably relatively high in order to ensure coating suitability of the paint, preferably 35 to 70 mass%, more preferably 50. It is the range of -68 mass%.
また、本発明で用いられる水性樹脂分散体Ａおよび水性樹脂分散体Ｂは、平均粒子径が異なる２つの粒度分布を有するものであれば、その樹脂組成が同じであっても異なっていても良い。 In addition, the aqueous resin dispersion A and the aqueous resin dispersion B used in the present invention may have the same or different resin composition as long as they have two particle size distributions having different average particle diameters. .
水性樹脂分散体に使用される重合性単量体としては、例えばカルボン酸基を持つ単量体として、アクリル酸、メタクリル酸、イタコン酸、フマール酸、マレイン酸、無水マレイン酸、マレイン酸の半エステル、クロトン酸などがあげられる。また、アクリル酸エステル、メタクリル酸エステル、芳香族ビニル化合物、ジエン類が挙げられる。（メタ) アクリル酸エステルの例としては、アルキル部の炭素数が１〜１８の（メタ) アクリル酸アルキルエステル、アルキル部の炭素数が１〜１８の（メタ）アクリル酸ヒドロキシアルキルエステル、エチレンオキサイド基の数が１〜１００個の（ポリ）オキシエチレン（メタ）アクリレート、プロピレンオキサイド基の数が１〜１００個の（ポリ）オキシプロピレン（メタ）アクリレート、エチレンオキサイド基の数が１〜１００個の（ポリ）オキシエチレンジ（メタ）アクリレート等が挙げられる。（メタ）アクリル酸エステルの例としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸メチルシクロヘキシル、（メタ）アクリル酸ドデシル等が挙げられる。（メタ）アクリル酸ヒドロキシアルキルエステルの例としては、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸２−ヒドロキシシクロヘキシル、（メタ）アクリル酸ドデシル等が挙げられる。（ポリ）オキシエチレン（メタ）アクリレートの例としては、（メタ）アクリル酸エチレングリコール、メトキシ（メタ）アクリル酸エチレングリコール、（メタ） アクリル酸ジエチレングリコール、メトキシ（メタ）アクリル酸ジエチレングリコール、（メタ）アクリル酸テトラエチレングリコール、メトキシ（メタ） アクリル酸テトラエチレングリコール等が挙げられる。（ポリ）オキシプロピレン（メタ）アクリレートの例としては、（メタ）アクリル酸プロピレングリコール、メトキシ（メタ）アクリル酸プロピレングリコール、（メタ）アクリル酸ジプロピレングリコール、メトキシ（メタ）アクリル酸ジプロピレングリコール、（メタ）アクリル酸テトラプロピレングリコール、メトキシ（メタ）アクリル酸テトラプロピレングリコール等が挙げられる。（ポリ）オキシエチレンジ（メタ）アクリレートの例としては、ジ（メタ）アクリル酸エチレングリコール、ジ（メタ）アクリル酸ジエチレングリコール、メトキシ（メタ）アクリル酸ジエチレングリコール、ジ（メタ）アクリル酸テトラエチレングリコール等が挙げられる。また、（メタ）アクリルアミド系単量体、シアン化ビニル類等が挙げられる。（メタ）アクリルアミド系単量体類としては、例えば（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミドなどがあり、シアン化ビニル類としては、例えば（メタ）アクリロニトリルなどがある。アルド基またはケト基を有する重合性単量体としては、アクロレイン、ジアセトンアクリルアミド、ジアセトンメタクリルアミド、ビニルメチルケトン、ビニルエチルケトン、アセトアセトキシエチルメタクリレート、アセトアセトキシエチルアクリレート、ホルミルスチロールなどが挙げられる。芳香族ビニル化合物の例としては、スチレン、ビニルトルエン等が挙げられる。ジエン類の例としては、ブタジエン、クロロプレン、イソプレン等や、それらの併用が挙げられる。 As the polymerizable monomer used in the aqueous resin dispersion, for example, as a monomer having a carboxylic acid group, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, maleic anhydride, maleic acid half Examples thereof include esters and crotonic acid. Moreover, acrylic acid ester, methacrylic acid ester, an aromatic vinyl compound, and dienes are mentioned. Examples of (meth) acrylic acid esters include (meth) acrylic acid alkyl esters having 1 to 18 carbon atoms in the alkyl portion, (meth) acrylic acid hydroxyalkyl esters and ethylene oxide having 1 to 18 carbon atoms in the alkyl portion. (Poly) oxyethylene (meth) acrylate having 1 to 100 groups, (poly) oxypropylene (meth) acrylate having 1 to 100 propylene oxide groups, and 1 to 100 ethylene oxide groups (Poly) oxyethylene di (meth) acrylate and the like. Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, Examples include methyl cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, and the like. Examples of (meth) acrylic acid hydroxyalkyl esters include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxycyclohexyl (meth) acrylate, dodecyl (meth) acrylate, and the like. Is mentioned. Examples of (poly) oxyethylene (meth) acrylate include: ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, diethylene glycol methoxy (meth) acrylate, (meth) acrylic Examples include tetraethylene glycol acid and methoxy (meth) acrylic acid tetraethylene glycol. Examples of (poly) oxypropylene (meth) acrylate include propylene glycol (meth) acrylate, propylene glycol methoxy (meth) acrylate, dipropylene glycol (meth) acrylate, dipropylene glycol methoxy (meth) acrylate, Examples include (meth) acrylic acid tetrapropylene glycol, methoxy (meth) acrylic acid tetrapropylene glycol, and the like. Examples of (poly) oxyethylene di (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol methoxy (meth) acrylate, tetraethylene glycol di (meth) acrylate, etc. Is mentioned. Further, (meth) acrylamide monomers, vinyl cyanides and the like can be mentioned. Examples of (meth) acrylamide monomers include (meth) acrylamide, N-methylol (meth) acrylamide, and N-butoxymethyl (meth) acrylamide. Examples of vinyl cyanides include (meth) acrylonitrile. and so on. Examples of the polymerizable monomer having an aldo group or keto group include acrolein, diacetone acrylamide, diacetone methacrylamide, vinyl methyl ketone, vinyl ethyl ketone, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, and formylstyrene. . Examples of the aromatic vinyl compound include styrene and vinyl toluene. Examples of dienes include butadiene, chloroprene, isoprene, and combinations thereof.
本発明で用いられる水性樹脂分散体Ａおよび水性樹脂分散体Ｂは、アクリル酸ｎ−ブチル、アクリル酸２−エチルヘキシル、メタクリル酸ｎ−ブチル、メタクリル酸メチル、メタクリル酸シクロヘキシル、スチレン、ブタジエン、アクリル酸、メタクリル酸から選ばれる１種以上の単量体を用いることが好ましく、アクリル酸ｎ−ブチル、アクリル酸２−エチルヘキシル、メタクリル酸ｎ−ブチル、メタクリル酸メチル、メタクリル酸シクロヘキシル、スチレン、アクリル酸、メタクリル酸から選ばれる１種以上の単量体を用いることがより好ましい。また、メタクリル酸エステル、アクリル酸エステル、スチレン、ブタジエンから選ばれる１種以上の単量体を９９．５〜９３質量％、カルボン酸基を持つ単量体を０．５〜７質量％用いることが好ましく、メタクリル酸エステル、アクリル酸エステル、スチレン、ブタジエンから選ばれる１種以上の単量体を９９〜９６質量％、カルボン酸基を持つ単量体を１〜４質量％用いることがより好ましい。更に、メタクリル酸エステル、アクリル酸エステル、スチレンから選ばれる１種以上の単量体を９９．５〜９３質量％、カルボン酸基を持つ単量体を０．５〜７質量％用いることが好ましく、メタクリル酸エステル、アクリル酸エステル、スチレンから選ばれる１種以上の単量体を９９〜９６質量％、カルボン酸基を持つ単量体を１〜４質量％用いることがより好ましい。また、上記以外の例としては、エチレン、プロピレン、イソブチレン等のオレフィン類、塩化ビニル、塩化ビニリデン等のハロオレフィン類、酢酸ビニル、プロピオン酸ビニル、ｎ−酪酸ビニル、安息香酸ビニル、ｐ−ｔ−ブチル安息香酸ビニル、ピバリン酸ビニル、２−エチルヘキサン酸ビニル、バーサチック酸ビニル、ラウリン酸ビニル等のカルボン酸ビニルエステル類、酢酸イソプロペニル、プロピオン酸イソプロペニル等のカルボン酸イソプロペニルエステル類、エチルビニルエーテル、イソブチルビニルエーテル、シクロヘキシルビニルエーテル等のビニルエーテル類、酢酸アリル、安息香酸アリル等のアリルエステル類、アリルエチルエーテル、アリルグリシジルエーテル、アリルフェニルエーテル等のアリルエーテル類、さらに、４−（メタ）アクリロイルオキシ−２，２，６，６，−テトラメチルピペリジン、４−（メタ）アクリロイルオキシ−１，２，２，６，６，−ペンタメチルピペリジン、パーフルオロメチル（メタ）アクリレート、パーフルオロプロピル（メタ）アクリレート、パーフルオロプロピロメチル（メタ）アクリレート、ビニルピロリドン、トリメチロールプロパントリ（メタ）アクリレート、（メタ）アクリル酸グリシジル、（メタ）アクリル酸２，３−シクロヘキセンオキサイド、（メタ）アクリル酸アリル等やそれらの併用が挙げられる。 The aqueous resin dispersion A and the aqueous resin dispersion B used in the present invention are n-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, methyl methacrylate, cyclohexyl methacrylate, styrene, butadiene, and acrylic acid. It is preferable to use at least one monomer selected from methacrylic acid, n-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, methyl methacrylate, cyclohexyl methacrylate, styrene, acrylic acid, It is more preferable to use one or more monomers selected from methacrylic acid. In addition, 99.5 to 93% by mass of one or more monomers selected from methacrylic acid esters, acrylic acid esters, styrene and butadiene, and 0.5 to 7% by mass of monomers having a carboxylic acid group are used. It is more preferable to use 99 to 96% by mass of one or more monomers selected from methacrylic acid ester, acrylic acid ester, styrene and butadiene, and 1 to 4% by mass of a monomer having a carboxylic acid group. . Furthermore, it is preferable to use 99.5 to 93% by mass of one or more monomers selected from methacrylic acid esters, acrylic acid esters and styrene, and 0.5 to 7% by mass of monomers having a carboxylic acid group. It is more preferable to use 99 to 96% by mass of one or more monomers selected from methacrylic acid esters, acrylic acid esters and styrene, and 1 to 4% by mass of monomers having a carboxylic acid group. Examples other than the above include olefins such as ethylene, propylene and isobutylene, haloolefins such as vinyl chloride and vinylidene chloride, vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl benzoate, pt- Carboxylic acid vinyl esters such as vinyl butylbenzoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl versatate, vinyl laurate, isopropenyl acetates such as isopropenyl acetate and isopropenyl propionate, ethyl vinyl ether Vinyl ethers such as isobutyl vinyl ether and cyclohexyl vinyl ether, allyl esters such as allyl acetate and allyl benzoate, allyl ethers such as allyl ethyl ether, allyl glycidyl ether and allyl phenyl ether; 4- (meth) acryloyloxy-2,2,6,6, -tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, perfluoromethyl (meta ) Acrylate, perfluoropropyl (meth) acrylate, perfluoropropylmethyl (meth) acrylate, vinylpyrrolidone, trimethylolpropane tri (meth) acrylate, glycidyl (meth) acrylate, 2,3-cyclohexene (meth) acrylate Examples thereof include oxide, allyl (meth) acrylate, and combinations thereof.
本発明で用いられる重合触媒としては、一般に用いられるラジカル重合開始剤であれば特に限定されないが、例えば熱または還元性物質等によってラジカルを生成して重合性単量体の付加重合を起こさせるもので、水溶性または油溶性の過硫酸塩、過酸化物、アゾビス化合物がある。具体的には過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、過酸化水素、ｔ−ブチルハイドロパーオキサイド、ｔ−ブチルパーオキシベンゾエート、２，２−アゾビスイソブチロニトリル、２，２−アゾビス（２−ジアミノプロパン）ハイドロクロライド、２，２−アゾビス（２，４−ジメチルバレロニトリル）等がある。好ましくは水溶性のものであり、単量体に対して０．１〜１質量％で配合することがより好ましい。なお、重合速度の促進や低温反応を望む場合には、重亜硫酸ナトリウム、塩化第一鉄、アスコルビン酸、ホルムアルデヒドスルホオキシレート塩等の還元剤をラジカル重合開始剤と組み合わせて用いることができる。 The polymerization catalyst used in the present invention is not particularly limited as long as it is a radical polymerization initiator that is generally used. For example, a radical that is generated by heat or a reducing substance to cause addition polymerization of a polymerizable monomer. There are water-soluble or oil-soluble persulfates, peroxides, and azobis compounds. Specifically, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis ( 2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like. Preferably it is a water-soluble thing, and it is more preferable to mix | blend with 0.1-1 mass% with respect to a monomer. When acceleration of the polymerization rate or a low temperature reaction is desired, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbic acid, formaldehyde sulfooxylate salt or the like can be used in combination with the radical polymerization initiator.
また、必要に応じて分子量調整剤を使用することができる。具体的にはドデシルメルカプタン、ブチルメルカプタン等が挙げられ、使用方法は特に限定されない。また使用量は、全単量体量の２質量％以下が好ましい。 Moreover, a molecular weight modifier can be used as needed. Specific examples include dodecyl mercaptan and butyl mercaptan, and the method of use is not particularly limited. The amount used is preferably 2% by mass or less of the total monomer amount.
本発明で用いられる重合方法としては、単量体を一括して仕込む単量体一括仕込み法や単量体を連続的に滴下する単量体滴下法、単量体と水と乳化剤とを予め混合乳化しておき、これらを滴下するプレエマルション法、あるいは、これらを組み合わせる方法などが挙げられる。 As a polymerization method used in the present invention, a monomer batch charging method in which monomers are charged in a batch, a monomer dropping method in which a monomer is continuously dropped, a monomer, water, and an emulsifier are added in advance. Examples include a pre-emulsion method in which they are mixed and emulsified and then added dropwise, or a combination of these.
また、本発明で用いられる乳化剤としては、特に限定はなく、例えばアニオン性乳化剤、ノニオン性乳化剤、カチオン性乳化剤、両性乳化剤、高分子乳化剤等を使用することができる。例えば、ラウリル硫酸ナトリウムなどの高級アルコール硫酸エステル塩、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレン多環フェニルエーテル硫酸塩、ポリオキシノニルフェニルエーテルスルホン酸塩、ポリオキシエチレン−ポリオキシプロピレングリコールエーテル硫酸塩、スルホコハク酸系界面活性剤、スルホン酸基又は硫酸エステル基と重合性の不飽和二重結合を分子中に有する、いわゆる反応性乳化剤などのアニオン性界面活性剤、ポリオキシエチレンアルキルエーテルや、ポリオキシエチレンノニルフェニルエーテル、ソルビタン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレン−ポリオキシプロピレンブロックコポリマー、又は前述の骨格と重合性の不飽和二重結合を分子中に有する反応性ノニオン性界面活性剤などのノニオン性界面活性剤、アルキルアミン塩や、第四級アンモニウム塩などのカチオン性界面活性剤（変性）ポリビニルアルコールなどが挙げられる。これらの乳化剤は単独で用いても良いし、数種類を組み合わせて用いても良い。乳化剤の添加量は、単量体に対して０．２〜４質量％が好ましい。 Moreover, there is no limitation in particular as an emulsifier used by this invention, For example, an anionic emulsifier, a nonionic emulsifier, a cationic emulsifier, an amphoteric emulsifier, a polymeric emulsifier etc. can be used. For example, higher alcohol sulfates such as sodium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, polyoxyethylene alkyl ether sulfate, polyoxyethylene polycyclic phenyl ether sulfate, polyoxynonyl phenyl ether sulfonate Anions such as so-called reactive emulsifiers having a salt, polyoxyethylene-polyoxypropylene glycol ether sulfate, sulfosuccinic acid surfactant, sulfonic acid group or sulfate ester group and polymerizable unsaturated double bond in the molecule Surfactant, polyoxyethylene alkyl ether, polyoxyethylene nonylphenyl ether, sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene butyl ester Copolymer, or a nonionic surfactant such as a reactive nonionic surfactant having a polymerizable unsaturated double bond in the molecule and a cationic interface such as an alkylamine salt or a quaternary ammonium salt. Examples include activator (modified) polyvinyl alcohol. These emulsifiers may be used alone or in combination of several kinds. The addition amount of the emulsifier is preferably 0.2 to 4% by mass with respect to the monomer.
水性樹脂分散体は、エマルションの長期の分散安定性を保つため、塩基性物質、例えばアンモニア、ジメチルアミノエタノールなどのアミン類を始めとする塩基性有機化合物、水酸化ナトリウム、水酸化カリウム等のアルカリ金属塩を始めとする塩基性無機化合物等を用いてｐＨ５〜１０の範囲に調整することが好ましい。 In order to maintain long-term dispersion stability of the emulsion, the aqueous resin dispersion is a basic substance, for example, basic organic compounds such as amines such as ammonia and dimethylaminoethanol, and alkalis such as sodium hydroxide and potassium hydroxide. It is preferable to adjust the pH within a range of 5 to 10 using a basic inorganic compound such as a metal salt.
本発明で用いられる水性樹脂分散体の最低成膜温度としては、３０℃以下であることが好ましく、最低成膜温度を比較的低くすることで、被塗物との付着性がより良好となる。最低成膜温度は重合性単量体の種類と量を調節することで制御することが出来る。最低成膜温度を高くするには、ホモポリマーＴｇの高い重合性単量体、例えば、スチレン、メタクリル酸メチル、メタクリル酸シクロヘキシルなどを主に使用すればよく、最低成膜温度を低くするには、ホモポリマーＴｇの低い重合性単量体、例えば、アクリル酸２−エチルヘキシル、アクリル酸ｎ−ブチル、ブタジエンなどを主に使用すればよい。 The minimum film formation temperature of the aqueous resin dispersion used in the present invention is preferably 30 ° C. or less, and the adhesion to the object to be coated becomes better by making the minimum film formation temperature relatively low. . The minimum film formation temperature can be controlled by adjusting the type and amount of the polymerizable monomer. In order to increase the minimum film formation temperature, a polymerizable monomer having a high homopolymer Tg, for example, styrene, methyl methacrylate, cyclohexyl methacrylate, or the like may be mainly used. A polymerizable monomer having a low homopolymer Tg, such as 2-ethylhexyl acrylate, n-butyl acrylate, and butadiene, may be mainly used.
［多孔質材料粉末］
本発明に用いる多孔質材料粉末としては、脱臭、吸着、調湿等に利用されている材料で、多くの細孔を有することで単位体積あたりの表面積が大きく、かつ微粉末化されているものであれば特に限定されないが、例えば炭、シリカゲル、アルミナゲル、合成ゼオライト、珪藻土、焼成炭酸カルシウム等が挙げられる。２種類以上の多孔質材料粉末を併用しても良いが、特に通常の炭よりも多くの細孔と広い表面積を有する活性炭は、脱臭、脱色、精製、浄化、調湿、遠赤効果、電磁波シールド、防ダニ、マイナスイオン発生等の多孔質材料が有する多くの機能性を付与できる点から、全多孔質材料粉末量の５０質量％以上配合することが好ましい。
[Porous material powder]
The porous material powder used in the present invention is a material used for deodorization, adsorption, humidity control, etc., and has a large surface area per unit volume and a fine powder by having many pores. If it is, it will not specifically limit, For example, charcoal, a silica gel, an alumina gel, a synthetic zeolite, diatomaceous earth, a calcination calcium carbonate etc. are mentioned. Two or more kinds of porous material powders may be used in combination, but especially activated carbon having more pores and a larger surface area than ordinary charcoal is deodorized, decolorized, purified, purified, humidity-controlled, far-red effect, electromagnetic wave It is preferable to blend 50% by mass or more of the total amount of the porous material powder from the viewpoint that many functions of the porous material such as shield, mite prevention and negative ion generation can be provided.
本発明で用いられる活性炭粉末としては特に限定されないが、木材、おがくず、木材乾留物、木炭（特に備長炭）、椰子殻及びリグニン等の既知の活性炭原料を好適に用いて製造されており、工業用触媒の担体、脱臭剤、有機溶剤の回収等に利用されている通常の活性炭を塗料、紙加工剤等に利用できるように粉末状に加工したものが好ましく、入手しやすく安価で吸着能力の高い椰子殻を原料に用いることが更に好ましい。 Although it does not specifically limit as activated carbon powder used by this invention, It is manufactured using suitably well-known activated carbon raw materials, such as a wood, a sawdust, a wood distillate, charcoal (especially Bincho charcoal), a coconut husk, and lignin, It is preferable to use ordinary activated carbon used for catalyst carrier, deodorizer, organic solvent recovery, etc., processed into powder so that it can be used for paints, paper processing agents, etc. It is more preferable to use a high coconut shell as a raw material.
多孔質材料粉末の配合量としては、水性樹脂分散体の固形分１００質量部に対し５〜５００質量部が好ましく、５０〜４００質量部であることがさらに好ましい。配合量が５質量部より少なくなると多孔質材料粉末の有する機能性が発揮されなくなり、５００質量部より多くなると塗膜の耐摩耗性が低下し、チョークマークが発生しやすくなるため適さない。上記の範囲においては、塗料の塗工適性、貯蔵安定性が確保され、また脱臭、調湿性能等の多孔質材料粉末が有する機能性を充分発揮させることができる。 As a compounding quantity of porous material powder, 5-500 mass parts is preferable with respect to 100 mass parts of solid content of an aqueous resin dispersion, and it is more preferable that it is 50-400 mass parts. If the blending amount is less than 5 parts by mass, the functionality of the porous material powder is not exhibited. If the blending amount is more than 500 parts by mass, the abrasion resistance of the coating film is lowered and chalk marks are likely to be generated. In the above range, coating applicability and storage stability of the paint can be ensured, and the functions of the porous material powder such as deodorization and humidity control performance can be sufficiently exhibited.
また、多孔質材料粉末の最大粒子径としては、１００μｍ以下が好ましく、５０μｍ以下であることがさらに好ましい。最大粒子径が１００μｍ以下の場合、多孔質材料粉末の分散性が向上し、塗膜表面が平滑で比較的均一な外観となり、さらに塗料の貯蔵安定性も向上する傾向にある。多孔質材料粉末の粒子径は、以下のような方法により測定する。まず、多孔質材料粉末に少量の中性洗剤（市販品）および多量の水を加え、超音波装置を用いて水中に多孔質材料粉末を分散させた分散液を調整する。レーザー回折／散乱式粒度分布測定装置（ＬＡ−９１０、株式会社堀場製作所製）を用いて、分散液の粒度分布を測定し、得られたチャートの頻度分布において最大となる粒子径を多孔質材料粉末の最大粒子径とする。 In addition, the maximum particle size of the porous material powder is preferably 100 μm or less, and more preferably 50 μm or less. When the maximum particle size is 100 μm or less, the dispersibility of the porous material powder is improved, the surface of the coating film is smooth and has a relatively uniform appearance, and the storage stability of the paint tends to be improved. The particle diameter of the porous material powder is measured by the following method. First, a small amount of neutral detergent (commercial product) and a large amount of water are added to the porous material powder, and a dispersion liquid in which the porous material powder is dispersed in water is prepared using an ultrasonic device. Using a laser diffraction / scattering particle size distribution measuring device (LA-910, manufactured by Horiba, Ltd.), the particle size distribution of the dispersion is measured, and the maximum particle size in the frequency distribution of the obtained chart is determined as the porous material. The maximum particle size of the powder.
［界面活性剤］
本発明に用いる界面活性剤としては、塗料、紙加工剤、繊維加工剤等に利用されている界面活性剤であれば特に限定されず、親水性基としてアニオン性基、ノニオン性基またはカチオン性基を有する界面活性剤等を使用することができる。例えば、ラウリン酸ナトリウムなどの脂肪酸石けん、ポリオキシエチレンアルキルエーテルカルボン酸塩、アルキルヒドロキシエーテルカルボン酸塩、ポリ（メタ）アクリル酸塩、ドデシルベンゼンスルホン酸ナトリウムなどのアルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、パラフィンスルホン酸塩、アルカノイルメチルタウライド、ジアルキルスルホコハク酸エステル塩、アルキルスルホコハク酸エステル二塩、ポリオキシエチレンアルキルエーテルスルホコハク酸エステル二塩、ラウリルアルコール硫酸エステルナトリウムなどの高級アルキル硫酸エステル塩、ロート油などの硫酸化油、硫酸化オレイン酸ブチルなどの硫酸化脂肪酸エステル、硫酸化オレフィン、高級アルキルリン酸エステル塩、ポリオキシエチレンアルキルエーテルリン酸エステル塩、ジチオリン酸エステル塩などのアニオン性界面活性剤、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレン多価アルコール脂肪酸エステル、ポリオキシエチレンアルキルアミン、ポリオキシエチレン脂肪酸アミド、ポリオキシエチレンポリオキシプロピレングリコール、グリセリン脂肪酸エステル、ペンタエリスリトール脂肪酸エステル、ソルビトール及びソルビタン脂肪酸エステル、ショ糖脂肪酸エステル、アルキルポリグリコシド、脂肪酸アルカノールアミドなどのノニオン性界面活性剤、ラウリルアミン酢酸塩などのアルキルアミン塩、ジヒドロキシエチルステアリルアミンなどのポリオキシエチレンアルキルアミン、トリエタノールアミンモノステアリン酸エステルギ酸塩などの脂肪酸エステルアミン塩、ステアラミドエチルジエチルアミン酢酸塩などの脂肪酸アミドアミン塩、尿素縮合アミン塩、イミダゾリン型、アルキルトリメチルアンモニウム塩、塩化ベンザルコニウムなどのアルキルベンジルジメチルアンミニウム塩、第四級アンモニウム有機酸塩、脂肪酸アミド型第四級アンモニウム塩などのカチオン性界面活性剤、アミノ酸型やベタイン型に代表されるカルボン酸塩型両性界面活性剤、硫酸エステル塩型、スルホン酸塩型、リン酸エステル塩型両性界面活性剤、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレン多環フェニルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテルスルホン酸塩、ポリオキシエチレン−ポリオキシプロピレングリコールエーテルスルホン酸塩などのノニオン／アニオン性界面活性剤等が挙げられる。
[Surfactant]
The surfactant used in the present invention is not particularly limited as long as it is a surfactant used in paints, paper processing agents, fiber processing agents and the like, and an anionic group, a nonionic group or a cationic group as a hydrophilic group. A surfactant having a group or the like can be used. For example, fatty acid soap such as sodium laurate, polyoxyethylene alkyl ether carboxylate, alkyl hydroxy ether carboxylate, poly (meth) acrylate, alkyl benzene sulfonate such as sodium dodecylbenzene sulfonate, alkyl naphthalene sulfonate Salts, paraffin sulfonates, alkanoyl methyl taurides, dialkyl sulfosuccinic acid ester salts, alkyl sulfosuccinic acid ester di-salts, polyoxyethylene alkyl ether sulfosuccinic acid ester di-salts, higher alkyl sulfates such as sodium lauryl alcohol sulfate, funnels Sulfated oil such as oil, sulfated fatty acid ester such as sulfated butyl oleate, sulfated olefin, higher alkyl phosphate ester salt, polyoxyethylene Anionic surfactants such as alkyl ether phosphates and dithiophosphates, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene polyhydric alcohol fatty acid esters, polyoxyethylene Nonionic surface activity such as alkylamine, polyoxyethylene fatty acid amide, polyoxyethylene polyoxypropylene glycol, glycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol and sorbitan fatty acid ester, sucrose fatty acid ester, alkyl polyglycoside, fatty acid alkanolamide Agents, alkylamine salts such as laurylamine acetate, and polyoxyethylene such as dihydroxyethyl stearylamine Fatty acid ester amine salts such as alkylamines, triethanolamine monostearic acid ester formate, fatty acid amide amine salts such as stearamide ethyl diethylamine acetate, urea condensed amine salts, imidazoline type, alkyltrimethylammonium salts, benzalkonium chloride, etc. Cationic surfactants such as alkylbenzyldimethylammonium salts, quaternary ammonium organic acid salts, fatty acid amide type quaternary ammonium salts, carboxylate type amphoteric surfactants typified by amino acid type and betaine type, sulfuric acid Ester salt type, sulfonate type, phosphate ester type amphoteric surfactant, polyoxyethylene alkyl ether sulfate, polyoxyethylene polycyclic phenyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfonate, polyoxyethylene alkyl ether sulfate Nonionic / anionic surfactants such as oxyethylene-polyoxypropylene glycol ether sulfonate and the like.
さらに、親水性基としてアニオン性基、ノニオン性基およびカチオン性基から選ばれる２種以上の官能基を有した界面活性剤であればより好ましい。界面活性剤の有するアニオン性基としては例えば、カルボン酸基、スルホン酸基、硫酸エステル基、リン酸エステル基等、カチオン性基としてはアミノ基、イミダゾリン基等、ノニオン性基としてはポリオキシエチレン基、ポリオキシプロピレン基等のポリオキシアルキレン基、アルコキシ基、ヒドロキシ基等が挙げられ、アニオンまたはカチオン性基は水分散性を付与するために、アニオン性基はナトリウム、アンモニア、アミン等、カチオン性基は塩酸、酢酸等で全部あるいは一部を中和していることが好ましい。さらに、電解質やｐＨの影響を受けにくく、加水分解安定性にも優れたポリオキシアルキレン基を有するアニオン性界面活性剤を使用すると、併用する多孔質材料粉末の分散安定性が向上するため、塗料の貯蔵経時での増粘沈降を防止し、さらに有機溶剤を使用しない系での塗料の低粘度化、固形分率の上昇が可能となりより好ましい。 Furthermore, a surfactant having two or more functional groups selected from an anionic group, a nonionic group and a cationic group as the hydrophilic group is more preferable. Examples of the anionic group possessed by the surfactant include a carboxylic acid group, a sulfonic acid group, a sulfate ester group, and a phosphate ester group, a cationic group such as an amino group and an imidazoline group, and a nonionic group such as polyoxyethylene. Groups, polyoxyalkylene groups such as polyoxypropylene groups, alkoxy groups, hydroxy groups, and the like. Anionic groups or cationic groups are provided with water dispersibility. It is preferable that all or part of the functional group is neutralized with hydrochloric acid, acetic acid or the like. Furthermore, the use of an anionic surfactant having a polyoxyalkylene group that is not easily affected by electrolytes and pH and has excellent hydrolysis stability improves the dispersion stability of the porous material powder to be used together. This is more preferable because it prevents thickening and sedimentation during storage, and can lower the viscosity of the paint and increase the solid content in a system that does not use an organic solvent.
このような界面活性剤の具体例としてはポリオキシエチレンアルキルエーテルカルボン酸塩、ポリオキシエチレンアルキルエーテルスルホコハク酸エステル二塩、ポリオキシエチレンアルキルエーテルリン酸エステル塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレン多環フェニルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテルスルホン酸塩、ポリオキシエチレン−ポリオキシプロピレングリコールエーテルスルホン酸塩、ポリオキシエチレン−ポリオキシプロピレングリコールエーテル硫酸塩等、また市販品としては、共栄社化学株式会社製「フローレンＧ−７００」「フローレンＧ−７００ＡＭＰ」「フローレンＧＷ−１５００」、サンノプコ株式会社製「ノプコスパース６１００」、ビックケミージャパン株式会社製の「ＤＩＳＰＥＲＢＹＫ−２０９０」「ＤＩＳＰＥＲＢＹＫ−２０１２」、株式会社日新化学研究所製の「ＮＳＤ６１３」「ＮＳＤ６２６」「ＮＳＤ６４２」等を用いることができる。 Specific examples of such surfactants include polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfosuccinate di-salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl ethers Oxyethylene polycyclic phenyl ether sulfate, polyoxyethylene alkylphenyl ether sulfonate, polyoxyethylene-polyoxypropylene glycol ether sulfonate, polyoxyethylene-polyoxypropylene glycol ether sulfate, etc. , "Floren G-700", "Floren G-700AMP", "Floren GW-1500", manufactured by Kyoeisha Chemical Co., Ltd., "Nopcosper 6100", manufactured by San Nopco Co., Ltd., Big Chemie Yapan "DISPERBYK-2090", "DISPERBYK-2012" Co., Ltd., can be used Co. Nisshinkagakukenkyusho made of "NSD613", "NSD626," "NSD642", and the like.
また、界面活性剤は１種または２種以上を任意に選択して使用することが可能であり、界面活性剤の配合量は水性樹脂分散体の固形分１００質量部に対し固形分換算で５〜３００質量部が好ましく、３０〜２５０質量部であることがさらに好ましい。配合量が５質量部より少なくなると塗料の粘度が高くなったり、貯蔵経時で凝集沈降したりするため、塗料化が難しく、貯蔵安定性、塗工適性上の問題から塗料固形分率を下げても、結果的に塗工効率が低下するため適さない。また、３００質量部より多くなると塗工時の泡残りや乾燥時間の遅延、塗膜の耐水性能低下が見られるため適さない。５〜３００質量部の範囲で使用する本発明においては、塗料粘度が適正な範囲にあり、塗工適性が確保され、塗料の貯蔵安定性も良好である。また脱臭、調湿性能等の多孔質材料粉末が有する機能性を保持したまま塗膜化できる。 In addition, one or more surfactants can be arbitrarily selected and used. The amount of the surfactant is 5 in terms of solid content with respect to 100 parts by mass of the solid content of the aqueous resin dispersion. -300 mass parts is preferable, and it is more preferable that it is 30-250 mass parts. If the blending amount is less than 5 parts by mass, the viscosity of the paint will increase or it will coagulate and settle over time, making it difficult to paint and reducing the solids content of the paint due to problems with storage stability and coating suitability. However, as a result, the coating efficiency is not suitable. On the other hand, if the amount is more than 300 parts by mass, it is not suitable because foam residue during coating, delay in drying time, and water resistance performance of the coating film are deteriorated. In the present invention used in the range of 5 to 300 parts by mass, the viscosity of the paint is in an appropriate range, the suitability for coating is ensured, and the storage stability of the paint is also good. Moreover, it can be formed into a coating film while maintaining the functionality of the porous material powder such as deodorization and humidity control performance.
その他、本発明の水性塗料組成物には必要により、添加剤として例えば消泡剤、増粘剤、成膜助剤、可塑剤、凍結防止剤、防腐剤、防カビ剤、防藻剤、抗菌剤、消臭剤等を任意に配合することができる。さらに、得られる塗膜の着色化、厚膜化等のために別途充填材として、例えば非水溶性の有機顔料や無機顔料、顔料以外の粒子状、繊維状または鱗片状のセラミックス、金属または合金、およびこれらの金属の酸化物、水酸化物、炭化物、窒化物、硫化物等を添加、分散させることもできる。これらの添加剤及び充填材については、塗料、紙加工剤、繊維加工剤等に利用されているものであれば特に限定されない。 In addition, the water-based coating composition of the present invention may include additives such as antifoaming agents, thickeners, film forming aids, plasticizers, antifreezing agents, antiseptics, antifungal agents, antialgae agents, antibacterial agents An agent, a deodorant, etc. can be arbitrarily blended. Further, as a separate filler for coloring, thickening, etc. of the obtained coating film, for example, water-insoluble organic pigments and inorganic pigments, particulates other than pigments, fibrous or scale-like ceramics, metals or alloys , And oxides, hydroxides, carbides, nitrides, sulfides and the like of these metals can also be added and dispersed. These additives and fillers are not particularly limited as long as they are used for paints, paper processing agents, fiber processing agents and the like.
本発明の水性塗料組成物は、水性樹脂分散体、多孔質材料粉末、界面活性剤を含み残部を水とすることで、塗料の貯蔵安定性、塗工適性に優れ、配合した多孔質材料粉末の有する機能性を保持したまま塗膜化できることから様々な分野に有用なものである。例えば、一般建築物の内壁、天井、押入、トイレ等の内装用塗料として使用すれば、簡便に塗装可能で居室内の結露やカビの発生防止、揮発性有機化合物や悪臭物質の吸着脱臭、断熱層形成による保温や保冷効果等が期待できる。また、本発明の水性機能性塗料組成物を予め紙、ダンボール、不織布等に塗工したものを成型加工すれば、包装材、フィルター等の様々な製品に、多孔質材料粉末が有する機能性を付与できる。 The aqueous coating composition of the present invention comprises an aqueous resin dispersion, a porous material powder, and a surfactant, and the balance is water, so that the storage stability of the coating and the coating suitability are excellent, and the blended porous material powder It is useful in various fields because it can be formed into a film while maintaining the functionality of For example, if it is used as an interior paint for interior walls, ceilings, closets, toilets, etc. of general buildings, it can be easily painted, preventing condensation and mold generation in the room, adsorption and deodorization of volatile organic compounds and malodorous substances, heat insulation It can be expected to keep warm and cool by layer formation. In addition, if the water-based functional coating composition of the present invention is pre-coated on paper, cardboard, non-woven fabric or the like, the functionality of the porous material powder is added to various products such as packaging materials and filters. Can be granted.
次に実施例および比較例により本発明を詳細に説明するが、本発明はこれらの例によって何ら限定されるものではない。なお、実施例および比較例の説明における部および％は特別な記載がない限り、それぞれ質量部および質量％を表す。また、得られた水性塗料組成物の塗料性状および塗膜性能評価については、以下に示す試験評価方法に従って実施した。 EXAMPLES Next, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited at all by these examples. In the description of Examples and Comparative Examples, “part” and “%” represent “part by mass” and “% by mass”, respectively, unless otherwise specified. Moreover, about the coating property of the obtained aqueous coating composition and coating-film performance evaluation, it implemented according to the test evaluation method shown below.
［試験評価方法］
（１）平均粒子径
水性樹脂分散体の平均粒子径は、リーズ＆ノースラップ社製のマイクロトラック粒度分布計（ＵＰＡ−１５０）を用いて測定（測定時間：３００秒、測定回数：１回、ローディングインデックス：１．５〜３．０）し、得られたチャートの各粒度分布における頻度累積５０％の値とした。得られたチャートに２つの粒度分布が存在する場合、小粒子径側の粒度分布を水性樹脂分散体Ａの粒度分布とし、大粒子径側の粒度分布を水性樹脂分散体Ｂの粒度分布とした。また、得られたチャートを体積分布として再計算を行い、その際の各粒度分布の頻度比率を水性樹脂分散体における質量比率とした。
[Test evaluation method]
(1) Average particle diameter The average particle diameter of the aqueous resin dispersion was measured using a Microtrac particle size distribution meter (UPA-150) manufactured by Leeds & Northrup Co. (measurement time: 300 seconds, number of measurements: once, Loading index: 1.5 to 3.0), and the value of frequency accumulation 50% in each particle size distribution of the obtained chart was obtained. When two particle size distributions exist in the obtained chart, the particle size distribution on the small particle size side is the particle size distribution of the aqueous resin dispersion A, and the particle size distribution on the large particle size side is the particle size distribution of the aqueous resin dispersion B. . The obtained chart was recalculated as a volume distribution, and the frequency ratio of each particle size distribution at that time was defined as the mass ratio in the aqueous resin dispersion.
（２）固形分率
得られた水性樹脂分散体の固形分率は、予め質量の分かっているアルミニウム製の皿に、測定対象物を約１ｇ正確に秤量し、恒温乾燥機で１０５℃にて３時間乾燥した後、シリカゲルを入れたデシケーター中で、３０分放冷後に精秤する。当該物質の乾燥後質量を乾燥前質量で割ったものを固形分率とした。界面活性剤についても同様の方法で固形分率を算出した。
(2) Solid content rate The solid content rate of the obtained aqueous resin dispersion was accurately measured by weighing about 1 g of an object to be measured in an aluminum dish having a known mass at 105 ° C with a constant temperature dryer. After drying for 3 hours, the mixture is allowed to cool for 30 minutes in a desiccator containing silica gel and precisely weighed. The solid content was obtained by dividing the mass after drying of the substance by the mass before drying. For the surfactant, the solid content was calculated in the same manner.
（３）最低成膜温度（ＭＦＴ）
最低成膜温度測定器（マツキ科学社製）を用い、アルミニウム製の板上に０．１ｍｍのアプリケーターで得られた水性樹脂分散体を塗工、乾燥し、その塗膜にクラックの生じた最高の温度を最低成膜温度（ＭＦＴ）とした。
(3) Minimum film formation temperature (MFT)
Using a minimum film-forming temperature measuring instrument (Matsuki Scientific Co., Ltd.), the aqueous resin dispersion obtained with an applicator of 0.1 mm was coated on an aluminum plate, dried, and the highest cracked film was formed. Was defined as the minimum film formation temperature (MFT).
（４）塗料の状態
ＪＩＳ Ｋ ５６００−１−１の４．１．２容器の中の状態「操作及び評価」（液状塗料の場合）に準じて評価した。評価基準は、○：問題なし、△：やや増粘または沈降傾向、×：増粘または沈降激しいとした。
(4) State of paint It evaluated according to the state "operation and evaluation" in 4.1.2 container of JIS K 5600-1-1 (in the case of liquid paint). The evaluation criteria were as follows: ○: no problem, Δ: slightly thickening or sedimentation tendency, ×: thickening or sedimentation severe.
（５）塗膜の外観
ＪＩＳ Ｋ ５６００−１−１の４．４「塗膜の外観」に準じた。但し、試験片は塗料をクラフト紙（５０ｇ／ｍ２）に刷毛にて５０ｇ／ｍ２塗付し、常温乾燥を行ったものを用いた。評価基準は、○：問題なし、△：やや表面が粗い、×：表面が粗いまたは不均一とした。
(5) Appearance of coating film Conforms to 4.4 “Appearance of coating film” of JIS K 5600-1-1. However, the test piece used was a kraft paper (50 g / m 2 ) coated with 50 g / m 2 with a brush and dried at room temperature. Evaluation criteria were as follows: ○: no problem, Δ: slightly rough surface, ×: rough surface or non-uniform.
（６）透気度
王研式透気度計（熊谷理機工業社製）を用いて試験片の透気度を測定した。測定数値（秒）が小さいほど透気度が良いことを表す。
(6) Air permeability The air permeability of the test piece was measured using a Oken type air permeability meter (manufactured by Kumagai Riki Kogyo Co., Ltd.). The smaller the measured value (seconds), the better the air permeability.
（７）付着性
試験片を２３℃、６５％Ｒ．Ｈ．の恒温恒湿室にて１２時間調湿した後、ピック強度ＲＩ印刷試験機（明製作所）を用い、中央部に塗工紙（１．５ｃｍ×２０ｃｍ）を並べて貼った台紙（３０ｃｍ×２５．５ｃｍ）に、印刷インク（東洋インキ社製、商品名：ハイユニティー）０．４ｍｌを２５ｃｍ×２１ｃｍの印刷面積で台紙ごと塗工紙に重ね刷りした。ゴムロールに現れたピックの発生状態を別の台紙に転写して目視評価した。評価は５点法で行い、ピックの発生が少ないものほど高得点とした。
(7) Adhesion The test piece was 23 ° C., 65% R.D. H. After adjusting the humidity in a constant temperature and humidity chamber for 12 hours, using a pick strength RI printing tester (Ming Seisakusho), a mount (30 cm × 25. 5 cm), 0.4 ml of printing ink (manufactured by Toyo Ink Co., Ltd., trade name: High Unity) was overprinted on the coated paper together with the backing paper with a printing area of 25 cm × 21 cm. The occurrence of picks appearing on the rubber roll was transferred to another mount and visually evaluated. Evaluation was performed by a five-point method, and the smaller the number of picks, the higher the score.
（８）簡易消臭性
試験片の塗装面を内側にして封筒（長型３号定形サイズ）を作成し、封筒内に農薬（住友化学園芸株式会社製のＧＦオルトラン粒剤）を一定量入れて封をした後、４Ｌ容量の密閉缶内に１週間保管後、缶内の臭気を評価した。評価基準は、○：臭気なし、△：ほぼ臭気なし、×：臭気ありとした。
(8) Simple deodorant Create an envelope (Long size 3 standard size) with the coated surface of the test piece facing inside, and put a certain amount of pesticide (GF Ortran granule manufactured by Sumitomo Chemical Gardening) into the envelope. After sealing, the odor in the can was evaluated after storing in a 4 L sealed can for 1 week. The evaluation criteria were as follows: ○: no odor, Δ: almost no odor, x: odor.
（９）吸湿性
試験片の塗装面を内側にして封筒（長型３号定形サイズ）を作成し、封筒内に塩化カルシウムを一定量入れて封をして、２３℃、９０％Ｒ．Ｈ．の恒温恒湿室にて２４時間静置した後の質量増分を測定し評価した。評価基準は、○：質量増なし、△：やや質量増、×：質量増（塩化カルシウムの溶解有り）とした。
(9) Hygroscopicity An envelope (Long size 3 standard size) was prepared with the coated surface of the test piece facing inward, and a certain amount of calcium chloride was sealed in the envelope, and sealed at 23 ° C., 90% R.D. H. The mass increment after standing for 24 hours in a constant temperature and humidity chamber was measured and evaluated. The evaluation criteria were as follows: ○: no increase in mass, Δ: slight increase in mass, ×: increase in mass (with dissolution of calcium chloride).
（１０）貯蔵安定性
ＪＩＳ Ｋ ５６００−２−７の６．「常温貯蔵安定性」に準じて評価した。評価基準は、○：貯蔵前と大差なし、△：やや増粘または沈降傾向、×：増粘または沈降傾向とした。
(10) Storage stability 6 of JIS K 5600-2-7. Evaluation was performed according to “room temperature storage stability”. Evaluation criteria were as follows: ○: not much different from that before storage, Δ: slightly thickening or sedimentation tendency, ×: thickening or sedimentation tendency.
（１１）塗装作業性
ＪＩＳ Ｋ ５６００−１−１の４．２「塗装作業性」に準じて評価した。塗装方法はバーコーターＮｏ．９にてクラフト紙に塗料を無希釈のまま塗装を行い評価した。評価基準は、○：問題なし、△：ややカスレ有り、×：カスレ、ブツ有りとした。
(11) Coating workability Evaluation was performed according to 4.2 “Coating workability” of JIS K 5600-1-1. The coating method is Bar Coater No. At 9 the kraft paper was painted and evaluated without dilution. The evaluation criteria were as follows: ○: no problem, Δ: slight blurring, ×: blurring and bumpy.
［水性樹脂分散体の合成］
［合成例１］
撹拌機、還流冷却器、滴下槽および温度計を取り付けた反応容器に水３８５．６部を投入し、反応容器中の温度を８５℃に上げてから、過硫酸アンモニウムの１０％水溶液を１３部添加した５分後に、スチレン２９６．４部、アクリル酸２−エチルヘキシル２１０．６部、メタクリル酸１０．４部、アクリルアミド２．６部、アニオン性界面活性剤（製品名：ラテムルＤ−３−Ｄ、花王（株）製）を２０部、ノニオン性界面活性剤（製品名：エマルゲン１２０、花王（株）製）の２０％水溶液２６部、リン酸水素ニナトリウム十二水の２０％水溶液６５部、過硫酸アンモニウムの１０％の水溶液１５．６部、水１３９．２部からなる乳化混合液を滴下槽より１５０分かけて流入させる。流入中は反応容器の温度を８５℃に保つ。流入が終了してから３０分後に、２５％アンモニア水溶液を５．２部添加する。次にスチレン４４４．６部、アクリル酸２−エチルヘキシル３１９．８部、メタクリル酸１５．６部の混合液と過硫酸アンモニウムの１０％水溶液２３．４部と水３３．６部の混合物を別々に、１５０分かけて流入させる。この流入が完了してから６０分後に温度を７０℃に冷却した。次に、ｔ−ブチルハイドロパーオキサイド２部を添加し３０分後にエルソルビン酸ナトリウムの８％水溶液２５部を３０分かけて流入した。３０分後に室温まで冷却した。
[Synthesis of aqueous resin dispersion]
[Synthesis Example 1]
385.6 parts of water was put into a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, the temperature in the reaction vessel was raised to 85 ° C., and 13 parts of 10% aqueous solution of ammonium persulfate was added. 5 minutes later, 296.4 parts of styrene, 210.6 parts of 2-ethylhexyl acrylate, 10.4 parts of methacrylic acid, 2.6 parts of acrylamide, an anionic surfactant (product name: Latemul D-3-D, 20 parts of a nonionic surfactant (product name: Emulgen 120, manufactured by Kao Corporation), 26 parts of a 20% aqueous solution of disodium hydrogenphosphate twelve water, An emulsified mixed solution consisting of 15.6 parts of a 10% aqueous solution of ammonium persulfate and 139.2 parts of water is allowed to flow from the dropping tank over 150 minutes. During the inflow, the temperature of the reaction vessel is maintained at 85 ° C. Thirty minutes after the end of the inflow, 5.2 parts of 25% aqueous ammonia is added. Next, a mixture of 444.6 parts of styrene, 319.8 parts of 2-ethylhexyl acrylate, 15.6 parts of methacrylic acid, 23.4 parts of a 10% aqueous solution of ammonium persulfate, and 33.6 parts of water was separately obtained. Let it flow in over 150 minutes. The temperature was cooled to 70 ° C. 60 minutes after the inflow was completed. Next, 2 parts of t-butyl hydroperoxide was added and, after 30 minutes, 25 parts of an 8% aqueous solution of sodium sorbate were introduced over 30 minutes. After 30 minutes, it was cooled to room temperature.
室温まで冷却後、２５％アンモニア水溶液を添加してｐＨを８．５に調整してから１００メッシュの金網でろ過した。ろ過された凝集物の乾燥質量は全単量体に対して０．０３％とわずかであった。得られた水性樹脂分散体の固形分率は６５．２％、ＭＦＴは２０℃であった。また、粒度分布には、平均粒子径が１８１ｎｍおよび平均粒子径が６２６ｎｍの２つの分布がみられ、平均粒子径が１８１ｎｍである水性樹脂分散体Ａの固形分換算比率が３５％、平均粒子径が６２６ｎｍである水性樹脂分散体Ｂの固形分換算比率が６５％であった。
このようにして得られた水性樹脂分散体を水性樹脂組成物（Ｒ−１）とした。
After cooling to room temperature, a 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was as small as 0.03% based on the total monomers. The obtained aqueous resin dispersion had a solid content of 65.2% and an MFT of 20 ° C. The particle size distribution includes two distributions having an average particle size of 181 nm and an average particle size of 626 nm. The aqueous resin dispersion A having an average particle size of 181 nm has a solid content conversion ratio of 35%, an average particle size The ratio in terms of solid content of the aqueous resin dispersion B having a thickness of 626 nm was 65%.
The aqueous resin dispersion thus obtained was designated as an aqueous resin composition (R-1).
［合成例２］
撹拌機、滴下槽および温度調節用のジャケットを備える耐圧反応容器に水３８５．６部を投入し、反応容器中の温度を８５℃に上げてから、過硫酸アンモニウムの１０％水溶液を１３部添加した５分後に、スチレン２９６．４部、アクリル酸２−エチルヘキシル２１０．６部、メタクリル酸１０．４部、アクリルアミド２．６部、アニオン性界面活性剤（製品名：ラテムルＤ−３−Ｄ、花王（株）製）を２０部、ノニオン性界面活性剤（製品名：エマルゲン１２０、花王（株）製）の２０％水溶液２６部、リン酸水素ニナトリウム十二水の２０％水溶液６５部、過硫酸アンモニウムの１０％の水溶液１５．６部、水１３９．２部からなる乳化混合液を滴下槽より１５０分かけて流入させる。流入中は反応容器の温度を８５℃に保つ。流入が終了してから３０分後に、２５％アンモニア水溶液を５．２部添加する。次にスチレン４４４．１部、ブタジエン３１９．８部、メタクリル酸１５．６部、アクリル酸４．５部、ラウリルメルカプタン１．０部の混合液と過硫酸アンモニウムの１０％水溶液２３．４部と水３３．６部の混合物を別々に、１５０分かけて流入させる。この流入が完了してから６０分後に温度を７０℃に冷却した。次に、ｔ−ブチルハイドロパーオキサイド２部を添加し３０分後にエルソルビン酸ナトリウムの８％水溶液２５部を３０分かけて流入した。３０分後に室温まで冷却した。
[Synthesis Example 2]
385.6 parts of water was put into a pressure-resistant reaction vessel equipped with a stirrer, a dropping tank and a temperature control jacket, and the temperature in the reaction vessel was raised to 85 ° C., and then 13 parts of a 10% aqueous solution of ammonium persulfate was added. After 5 minutes, 296.4 parts of styrene, 210.6 parts of 2-ethylhexyl acrylate, 10.4 parts of methacrylic acid, 2.6 parts of acrylamide, an anionic surfactant (product name: Latemul D-3-D, Kao) 20 parts of a nonionic surfactant (product name: Emulgen 120, manufactured by Kao Corporation), 65 parts of a 20% aqueous solution of disodium hydrogen phosphate twelve water, An emulsified mixed solution consisting of 15.6 parts of a 10% aqueous solution of ammonium sulfate and 139.2 parts of water is allowed to flow from the dropping tank over 150 minutes. During the inflow, the temperature of the reaction vessel is maintained at 85 ° C. Thirty minutes after the end of the inflow, 5.2 parts of 25% aqueous ammonia is added. Next, a mixture of 444.1 parts of styrene, 319.8 parts of butadiene, 15.6 parts of methacrylic acid, 4.5 parts of acrylic acid, 1.0 part of lauryl mercaptan, 23.4 parts of a 10% aqueous solution of ammonium persulfate and water Allow 33.6 parts of the mixture to flow separately over 150 minutes. The temperature was cooled to 70 ° C. 60 minutes after the inflow was completed. Next, 2 parts of t-butyl hydroperoxide was added and, after 30 minutes, 25 parts of an 8% aqueous solution of sodium sorbate were introduced over 30 minutes. After 30 minutes, it was cooled to room temperature.
室温まで冷却後、２５％アンモニア水溶液を添加してｐＨを８．５に調整してから１００メッシュの金網でろ過した。ろ過された凝集物の乾燥質量は全単量体に対して０．０３％とわずかであった。得られた水性樹脂分散体の固形分率は６５．１％、ＭＦＴは１８℃であった。また、粒度分布には、平均粒子径が１９１ｎｍおよび平均粒子径が５９６ｎｍの２つの分布がみられ、平均粒子径が１９１ｎｍである水性樹脂分散体Ａの固形分換算比率が３８％、平均粒子径が５９６ｎｍである水性樹脂分散体Ｂの固形分換算比率が６２％であった。
このようにして得られた水性樹脂分散体を水性樹脂組成物（Ｒ−２）とした。
After cooling to room temperature, a 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was as small as 0.03% based on the total monomers. The obtained aqueous resin dispersion had a solid content of 65.1% and an MFT of 18 ° C. In addition, in the particle size distribution, two distributions having an average particle size of 191 nm and an average particle size of 596 nm are observed, and the solid resin conversion ratio of the aqueous resin dispersion A having an average particle size of 191 nm is 38%, the average particle size is The ratio in terms of solid content of the aqueous resin dispersion B having a thickness of 596 nm was 62%.
The aqueous resin dispersion thus obtained was designated as an aqueous resin composition (R-2).
［合成例３］
撹拌機、還流冷却器、滴下槽および温度計を取り付けた反応容器に水３７０．２部を投入し、反応容器中の温度を８５℃に上げてから、過硫酸アンモニウムの１０％水溶液を１３部添加した５分後に、スチレン２０１．８部、アクリル酸２−エチルヘキシル１０．４部、アクリル酸ｎ−ブチル２０５部、メタクリル酸ブチル１５部、メタクリル酸メチル５７．４部、アクリル酸１０．４部、アニオン性界面活性剤（製品名：ラテムルＤ−４−Ｄ、花王（株）製）を２０部、ノニオン性界面活性剤（製品名：エマルゲン１４７、花王（株）製）の２０％水溶液２６部、リン酸水素ニナトリウム十二水の２０％水溶液５５部、過硫酸アンモニウムの１０％の水溶液１７．５部、水２００．７部からなる乳化混合液を滴下槽より１５０分かけて流入させる。流入中は反応容器の温度を８５℃に保つ。流入が終了してから３０分後に、２５％アンモニア水溶液を４．８部添加する。次にスチレン３０４．６部、アクリル酸２−エチルヘキシル６０．８部、アクリル酸ｎ−ブチル２９４．５部、メタクリル酸ブチル３０部、メタクリル酸メチル８０部、メタクリル酸シクロヘキシル１０部、メタクリル酸４．５部、アクリル酸１５．６部、ラウリルメルカプタン１．０部の混合液と過硫酸アンモニウムの１０％水溶液２０．４部と水１７３．６部の混合物を別々に、１５０分かけて流入させる。この流入が完了してから６０分後に温度を７０℃に冷却した。次に、ｔ−ブチルハイドロパーオキサイド２部を添加し３０分後にエルソルビン酸ナトリウムの８％水溶液２５部を３０分かけて流入した。３０分後に室温まで冷却した。
[Synthesis Example 3]
370.2 parts of water was put into a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, the temperature in the reaction vessel was raised to 85 ° C., and 13 parts of 10% aqueous solution of ammonium persulfate was added. 5 minutes later, 201.8 parts of styrene, 10.4 parts of 2-ethylhexyl acrylate, 205 parts of n-butyl acrylate, 15 parts of butyl methacrylate, 57.4 parts of methyl methacrylate, 10.4 parts of acrylic acid, 20 parts of anionic surfactant (product name: Latemul D-4-D, manufactured by Kao Corporation), 26 parts of 20% aqueous solution of nonionic surfactant (product name: Emulgen 147, manufactured by Kao Corporation) An emulsified mixed solution consisting of 55 parts of a 20% aqueous solution of sodium disodium phosphate twelve water, 17.5 parts of a 10% aqueous solution of ammonium persulfate, and 200.7 parts of water flows from the dropping tank over 150 minutes. To. During the inflow, the temperature of the reaction vessel is maintained at 85 ° C. 30 minutes after the inflow is completed, 4.8 parts of 25% aqueous ammonia solution is added. Next, 304.6 parts of styrene, 60.8 parts of 2-ethylhexyl acrylate, 294.5 parts of n-butyl acrylate, 30 parts of butyl methacrylate, 80 parts of methyl methacrylate, 10 parts of cyclohexyl methacrylate, 4. A mixture of 5 parts, 15.6 parts of acrylic acid, 1.0 part of lauryl mercaptan, 20.4 parts of a 10% aqueous solution of ammonium persulfate and 173.6 parts of water is allowed to flow separately over 150 minutes. The temperature was cooled to 70 ° C. 60 minutes after the inflow was completed. Next, 2 parts of t-butyl hydroperoxide was added and, after 30 minutes, 25 parts of an 8% aqueous solution of sodium sorbate were introduced over 30 minutes. After 30 minutes, it was cooled to room temperature.
室温まで冷却後、２５％アンモニア水溶液を添加してｐＨを８．５に調整してから１００メッシュの金網でろ過した。ろ過された凝集物の乾燥質量は全単量体に対して０．０５％とわずかであった。得られた水性樹脂分散体の固形分率は５９．８％、ＭＦＴは２１℃であった。また、粒度分布には、平均粒子径が１３０ｎｍおよび平均粒子径が６５７ｎｍの２つの分布がみられ、平均粒子径が１３０ｎｍである水性樹脂分散体Ａの固形分換算比率が２０％、平均粒子径が６５７ｎｍである水性樹脂分散体Ｂの固形分換算比率が８０％であった。 After cooling to room temperature, a 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was only 0.05% with respect to the total monomers. The obtained aqueous resin dispersion had a solid content of 59.8% and an MFT of 21 ° C. The particle size distribution includes two distributions having an average particle size of 130 nm and an average particle size of 657 nm. The aqueous resin dispersion A having an average particle size of 130 nm has a solid content conversion ratio of 20%, an average particle size The ratio in terms of solid content of the aqueous resin dispersion B having a thickness of 657 nm was 80%.
このようにして得られた水性樹脂分散体にエチレングリコールを１部加えたものを水性樹脂組成物（Ｒ−３）とした。 An aqueous resin composition (R-3) was obtained by adding 1 part of ethylene glycol to the aqueous resin dispersion thus obtained.
［合成例４］
撹拌機、滴下槽および温度調節用のジャケットを備える耐圧反応容器に水６００部、ドデシルベンゼンスルホン酸ナトリウム０．５部、あらかじめ調整したシード粒子（Ｔｇ＝３℃、粒子径０．３０μｍ）０．６部を仕込み、内温を８０℃に上昇した。さらにスチレン４６６．６部、ブタジエン３１２．８部、メタクリル酸２０．６部、ｔ−ドデシルメルカプタン（ｔ−ＤＤＭ）０．５部からなる単量体混合物を１８０分かけて一定速度で反応容器内に流入し、添加開始と同時に過硫酸ナトリウムの２０％水溶液を６部、反応器内に投入した。流入中は反応容器の温度を８０℃に保つ。流入が終了してから６０分後に、あらかじめ調整したシード粒子（Ｔｇ＝３℃、粒子径０．０２μｍ）０．１部を仕込み、直後にスチレン１８９．５部、ブタジエン１９５．２部、メタクリル酸メチル１００部、イタコン酸１５．３部からなる単量体混合物と、ｔ−ドデシルメルカプタン０．５部と水２８０部を１２０分かけて一定速度で反応容器内に流入した。流入が完了してから９０分後に室温まで冷却して反応生成物を採取した。得られた反応性生物から未反応単量体を除去し、水酸化ナトリウムと水酸化カリウムの１：１混合物でｐＨを８．５に調製し、固形分率が６５質量％になるまで濃縮した。得られた水性樹脂分散体は、ＭＦＴが５℃であった。また、粒度分布には、平均粒子径が１２５ｎｍおよび平均粒子径が４５３ｎｍの２つの分布がみられ、平均粒子径が１２５ｎｍである水性樹脂分散体Ａの固形分換算比率が２２％、平均粒子径が４５３ｎｍである水性樹脂分散体Ｂの固形分換算比率が７８％であった。
このようにして得られた水性樹脂分散体を水性樹脂組成物（Ｒ−４）とした。
[Synthesis Example 4]
600 parts of water, 0.5 parts of sodium dodecylbenzenesulfonate, pre-adjusted seed particles (Tg = 3 ° C., particle size 0.30 μm) in a pressure-resistant reaction vessel equipped with a stirrer, a dropping tank and a temperature control jacket 6 parts were charged and the internal temperature was raised to 80 ° C. Furthermore, a monomer mixture consisting of 466.6 parts of styrene, 312.8 parts of butadiene, 20.6 parts of methacrylic acid and 0.5 part of t-dodecyl mercaptan (t-DDM) was added to the reaction vessel at a constant rate over 180 minutes. 6 parts of a 20% aqueous solution of sodium persulfate was charged into the reactor simultaneously with the start of addition. During the inflow, the temperature of the reaction vessel is maintained at 80 ° C. Sixty minutes after the end of the inflow, 0.1 parts of pre-adjusted seed particles (Tg = 3 ° C., particle diameter 0.02 μm) were charged, and immediately after that, styrene 189.5 parts, butadiene 195.2 parts, methacrylic acid A monomer mixture consisting of 100 parts of methyl and 15.3 parts of itaconic acid, 0.5 part of t-dodecyl mercaptan and 280 parts of water were allowed to flow into the reaction vessel at a constant rate over 120 minutes. 90 minutes after the inflow was completed, the reaction product was collected by cooling to room temperature. Unreacted monomer was removed from the obtained reactive organism, pH was adjusted to 8.5 with a 1: 1 mixture of sodium hydroxide and potassium hydroxide, and the mixture was concentrated to a solid content of 65% by mass. . The obtained aqueous resin dispersion had an MFT of 5 ° C. In addition, in the particle size distribution, two distributions having an average particle size of 125 nm and an average particle size of 453 nm are observed, the solid content conversion ratio of the aqueous resin dispersion A having an average particle size of 125 nm is 22%, and the average particle size is The ratio in terms of solid content of the aqueous resin dispersion B having a thickness of 453 nm was 78%.
The aqueous resin dispersion thus obtained was designated as an aqueous resin composition (R-4).
［合成例５］
撹拌機、還流冷却器、滴下槽および温度計を取り付けた反応容器に水４２０．８部を投
入し、反応容器中の温度を８５℃に上げてから、過硫酸アンモニウムの１０％水溶液を１３部添加した５分後に、スチレン２２６．４部、アクリル酸２−エチルヘキシル２１３．６部、メタクリル酸メチル７１．８部、メタクリル酸１０．４部、アクリルアミド２．６部、アニオン性界面活性剤（製品名：ラテムルＤ−３−Ｄ、花王（株）製）を１０部、ノニオン性界面活性剤（製品名：エマルゲン１４７、花王（株）製）の２０％水溶液１５部、リン酸水素ニナトリウム十二水の２０％水溶液７５部、過硫酸アンモニウムの１０％の水溶液１２．８部、水９０．７部からなる乳化混合液を滴下槽より１５０分かけて流入させる。流入中は反応容器の温度を８５℃に保つ。流入が終了してから３０分後に、２５％アンモニア水溶液を６．０部添加する。次にスチレン３２６．４部、アクリル酸２−エチルヘキシル３２１．８部、メタクリル酸メチル１１２．５部、メタクリル酸１５．６部、ラウリルメルカプタン０．５部の混合液と過硫酸アンモニウムの１０％水溶液２１．３部と水８４．３部の混合物を別々に、１５０分かけて流入させる。この流入が完了してから９０分後に温度を７０℃に冷却した。次に、ｔ−ブチルハイドロパーオキサイド２部を添加し３０分後にエルソルビン酸ナトリウムの８％水溶液２５部を３０分かけて流入した。３０分後に室温まで冷却した。
[Synthesis Example 5]
420.8 parts of water was put into a reaction vessel equipped with a stirrer, reflux condenser, dripping tank and thermometer, the temperature in the reaction vessel was raised to 85 ° C., and then 13 parts of 10% aqueous solution of ammonium persulfate was added. 5 minutes later, 226.4 parts of styrene, 213.6 parts of 2-ethylhexyl acrylate, 71.8 parts of methyl methacrylate, 10.4 parts of methacrylic acid, 2.6 parts of acrylamide, an anionic surfactant (product name : Latemulu D-3-D, manufactured by Kao Corporation), 10 parts of a nonionic surfactant (product name: Emulgen 147, manufactured by Kao Corporation), 15 parts of a 20% aqueous solution, twelve sodium hydrogen phosphates An emulsion mixture consisting of 75 parts of a 20% aqueous solution of water, 12.8 parts of a 10% aqueous solution of ammonium persulfate and 90.7 parts of water is allowed to flow in over 150 minutes from the dropping tank. During the inflow, the temperature of the reaction vessel is maintained at 85 ° C. After 30 minutes from the end of the inflow, 6.0 parts of 25% aqueous ammonia solution is added. Next, 326.4 parts of styrene, 321.8 parts of 2-ethylhexyl acrylate, 112.5 parts of methyl methacrylate, 15.6 parts of methacrylic acid, 0.5 part of lauryl mercaptan and 10% aqueous solution of ammonium persulfate 21 A mixture of 3 parts and 84.3 parts of water is allowed to flow separately over 150 minutes. The temperature was cooled to 70 ° C. 90 minutes after the inflow was completed. Next, 2 parts of t-butyl hydroperoxide was added and, after 30 minutes, 25 parts of an 8% aqueous solution of sodium sorbate were introduced over 30 minutes. After 30 minutes, it was cooled to room temperature.
室温まで冷却後、２５％アンモニア水溶液を添加してｐＨを８．６に調整してから１００メッシュの金網でろ過した。ろ過された凝集物の乾燥質量は全単量体に対して０．０２％とわずかであった。得られた水性樹脂分散体の固形分率は６３．８％、ＭＦＴは２３℃であった。また、粒度分布には、平均粒子径が２６５ｎｍおよび平均粒子径が１０２６ｎｍの２つの分布がみられ、平均粒子径が２６５ｎｍである水性樹脂分散体Ａの固形分換算比率が４１％、平均粒子径が１０２６ｎｍである水性樹脂分散体Ｂの固形分換算比率が５９％であった。 After cooling to room temperature, a 25% aqueous ammonia solution was added to adjust the pH to 8.6, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was as small as 0.02% based on the total monomers. The obtained aqueous resin dispersion had a solid content of 63.8% and an MFT of 23 ° C. In addition, in the particle size distribution, two distributions having an average particle size of 265 nm and an average particle size of 1026 nm are observed. The solid resin conversion ratio of the aqueous resin dispersion A having an average particle size of 265 nm is 41%, the average particle size is The ratio in terms of solid content of the aqueous resin dispersion B having a thickness of 1026 nm was 59%.
このようにして得られた水性樹脂分散体にエチレングリコールモノブチルエーテル１０部加えたものを水性樹脂組成物（Ｒ−５）とした。 An aqueous resin composition (R-5) was obtained by adding 10 parts of ethylene glycol monobutyl ether to the aqueous resin dispersion thus obtained.
［合成例６］
撹拌機、還流冷却器、滴下槽および温度計を取り付けた反応容器に水４０５．６部を投入し、反応容器中の温度を８５℃に上げてから、過硫酸アンモニウムの１０％水溶液を１５部添加した５分後に、アクリル酸２−エチルヘキシル１５５．３部、アクリル酸ｎ−ブチル１１０．３部、メタクリル酸メチル１７１．４部、メタクリル酸シクロヘキシル７５．９部、アクリル酸１０．４部、アクリルアミド３．０部、アニオン性界面活性剤（製品名：ラテムルＤ−３−Ｄ、花王（株）製）を２２部、ノニオン性界面活性剤（製品名：エマルゲン１２０、花王（株）製）の２０％水溶液２０部、リン酸水素ニナトリウム十二水の２０％水溶液６０部、過硫酸アンモニウムの１０％の水溶液１８．９部、水１５０．１部からなる乳化混合液を滴下槽より１５０分かけて流入させる。流入中は反応容器の温度を８５℃に保つ。流入が終了してから３０分後に、２５％アンモニア水溶液を５．８部添加する。次にアクリル酸２−エチルヘキシル２５３．３部、アクリル酸ｎ−ブチル１９８．２部、メタクリル酸メチル２２２．６部、メタクリル酸シクロヘキシル８５．９部、メタクリル酸５．２部、アクリル酸１０．４部の混合液と過硫酸アンモニウムの１０％水溶液３２．２部と水２３．６部の混合物を別々に、１５０分かけて流入させる。この流入が完了してから１２０分後に室温まで冷却した。
[Synthesis Example 6]
Add 405.6 parts of water to a reaction vessel equipped with a stirrer, reflux condenser, dripping tank and thermometer, raise the temperature in the reaction vessel to 85 ° C., then add 15 parts of 10% aqueous solution of ammonium persulfate. 5 minutes later, 155.3 parts of 2-ethylhexyl acrylate, 110.3 parts of n-butyl acrylate, 171.4 parts of methyl methacrylate, 75.9 parts of cyclohexyl methacrylate, 10.4 parts of acrylic acid, acrylamide 3 0.0 part, 22 parts of anionic surfactant (product name: Latemul D-3-D, manufactured by Kao Corporation), 20 parts of nonionic surfactant (product name: Emulgen 120, manufactured by Kao Corporation) An emulsion mixture consisting of 20 parts of a 20% aqueous solution, 60 parts of a 20% aqueous solution of disodium hydrogen phosphate 12 water, 18.9 parts of a 10% aqueous solution of ammonium persulfate, and 150.1 parts of water Ri is allowed to flow over a period of 150 minutes. During the inflow, the temperature of the reaction vessel is maintained at 85 ° C. 30 minutes after the inflow is completed, 5.8 parts of 25% aqueous ammonia solution is added. Next, 253.3 parts of 2-ethylhexyl acrylate, 198.2 parts of n-butyl acrylate, 222.6 parts of methyl methacrylate, 85.9 parts of cyclohexyl methacrylate, 5.2 parts of methacrylic acid, 10.4 acrylic acid Part of the mixture, 32.2 parts of a 10% aqueous solution of ammonium persulfate and 23.6 parts of water are allowed to flow separately over 150 minutes. 120 minutes after the inflow was completed, the mixture was cooled to room temperature.
室温まで冷却後、２５％アンモニア水溶液を添加してｐＨを８．５に調整してから１００メッシュの金網でろ過した。ろ過された凝集物の乾燥質量は全単量体に対して０．０１％とわずかであった。得られた水性樹脂分散体の固形分率は６５．０％、ＭＦＴは３℃であった。また、粒度分布には、平均粒子径が１５６ｎｍおよび平均粒子径が６３８ｎｍの２つの分布がみられ、平均粒子径が１５６ｎｍである水性樹脂分散体Ａの固形分換算比率が３５％、平均粒子径が６３８ｎｍである水性樹脂分散体Ｂの固形分換算比率が６５％であった。
このようにして得られた水性樹脂分散体を水性樹脂組成物（Ｒ−６）とした。
After cooling to room temperature, a 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was as small as 0.01% with respect to the total monomers. The obtained aqueous resin dispersion had a solid content of 65.0% and MFT of 3 ° C. In addition, in the particle size distribution, two distributions having an average particle size of 156 nm and an average particle size of 638 nm are observed. The solid resin conversion ratio of the aqueous resin dispersion A having an average particle size of 156 nm is 35%, the average particle size is The solid resin conversion ratio of the aqueous resin dispersion B having a thickness of 638 nm was 65%.
The aqueous resin dispersion thus obtained was designated as an aqueous resin composition (R-6).
［合成例７］
撹拌機、還流冷却器、滴下槽および温度計を取り付けた反応容器に水３９６．５部を投入し、反応容器中の温度を８５℃に上げてから、過硫酸アンモニウムの１０％水溶液を１８部添加した５分後に、アクリル酸ｎ−ブチル２１８．８部、メタクリル酸メチル２９０．４部、メタクリル酸８．２部、アクリルアミド２．６部、アニオン性界面活性剤（製品名：ラテムルＤ−４−Ｄ、花王（株）製）を２５部、ノニオン性界面活性剤（製品名：エマルゲン１４７、花王（株）製）の２０％水溶液３０部、リン酸水素二ナトリウム十二水の２０％水溶液７０部、過硫酸アンモニウムの１０％の水溶液２２．３部、水２４４．９部からなる乳化混合液を滴下槽より１８０分かけて流入させる。流入中は反応容器の温度を８５℃に保つ。流入が終了してから９０分後に、２５％アンモニア水溶液を４．７部添加する。次にアクリル酸ｎ−ブチル３２９．８部、メタクリル酸メチル４３０．４部、メタクリル酸１９．８部の混合液と過硫酸アンモニウムの１０％水溶液２３．４部と水２３６．３部の混合物を別々に、１５０分かけて流入させる。この流入が完了してから１５０分後に温度を室温まで冷却した。
[Synthesis Example 7]
396.5 parts of water was put into a reaction vessel equipped with a stirrer, reflux condenser, dripping tank and thermometer, the temperature in the reaction vessel was raised to 85 ° C., and 18 parts of 10% aqueous solution of ammonium persulfate was added. 5 minutes later, 218.8 parts of n-butyl acrylate, 290.4 parts of methyl methacrylate, 8.2 parts of methacrylic acid, 2.6 parts of acrylamide, an anionic surfactant (product name: Latemule D-4- D, 25 parts by Kao Corporation), 30 parts of a 20% aqueous solution of nonionic surfactant (product name: Emulgen 147, produced by Kao Corporation), 70% 20% aqueous solution of disodium hydrogen phosphate twelve water 70 Part, 22.3 parts of a 10% aqueous solution of ammonium persulfate, and 244.9 parts of water are allowed to flow from the dropping tank over 180 minutes. During the inflow, the temperature of the reaction vessel is maintained at 85 ° C. After 90 minutes from the end of the inflow, 4.7 parts of 25% aqueous ammonia solution is added. Next, a mixture of 329.8 parts of n-butyl acrylate, 430.4 parts of methyl methacrylate, 19.8 parts of methacrylic acid, 23.4 parts of a 10% aqueous solution of ammonium persulfate, and 236.3 parts of water was separated. For 150 minutes. 150 minutes after the inflow was completed, the temperature was cooled to room temperature.
室温まで冷却後、２５％アンモニア水溶液を添加してｐＨを８．５に調整してから１００メッシュの金網でろ過した。ろ過された凝集物の乾燥質量は全単量体に対して０．０５％とわずかであった。得られた水性樹脂分散体の固形分率は５６．３％、ＭＦＴは２７℃であった。また、粒度分布には、平均粒子径が９９ｎｍおよび平均粒子径が４０２ｎｍの２つの分布がみられ、平均粒子径が９９ｎｍである水性樹脂分散体Ａの固形分換算比率が３０％、平均粒子径が４０２ｎｍである水性樹脂分散体Ｂの固形分換算比率が７０％であった。
このようにして得られた水性樹脂分散体を水性樹脂組成物（Ｒ−７）とした。
After cooling to room temperature, a 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was only 0.05% with respect to the total monomers. The obtained aqueous resin dispersion had a solid content of 56.3% and an MFT of 27 ° C. The particle size distribution includes two distributions having an average particle size of 99 nm and an average particle size of 402 nm. The aqueous resin dispersion A having an average particle size of 99 nm has a solid content conversion ratio of 30%, an average particle size. The ratio in terms of solid content of the aqueous resin dispersion B having a thickness of 402 nm was 70%.
The aqueous resin dispersion thus obtained was designated as an aqueous resin composition (R-7).
［合成例８］
撹拌機、還流冷却器、滴下槽および温度計を取り付けた反応容器に水３８５．６部を投入し、反応容器中の温度を８５℃に上げてから、過硫酸アンモニウムの１０％水溶液を１３部添加した５分後に、スチレン３５６．４部、アクリル酸２−エチルヘキシル１５０．６部、メタクリル酸１３．０部、アニオン性界面活性剤（製品名：ラテムルＤ−４−Ｄ、花王（株）製）を１８部、ノニオン性界面活性剤（製品名：エマルゲン１２０、花王（株）製）の２０％水溶液２２部、リン酸水素二ナトリウム十二水の２０％水溶液７０部、過硫酸アンモニウムの１０％の水溶液１７．５部、水７０．７部からなる乳化混合液を滴下槽より１５０分かけて流入させる。流入中は反応容器の温度を８５℃に保つ。流入が終了してから３０分後に、２５％アンモニア水溶液を５．２部添加する。次にスチレン５０４．６部、アクリル酸２−エチルヘキシル２５９．８部、メタクリル酸１５．６部の混合液と過硫酸アンモニウムの１０％水溶液２５．１部と水１２６．３部の混合物を別々に、１５０分かけて流入させる。この流入が完了してから６０分後に温度を７０℃に冷却した。次に、ｔ−ブチルハイドロパーオキサイド２部を添加し３０分後にエルソルビン酸ナトリウムの８％水溶液２５部を３０分かけて流入した。３０分後に室温まで冷却した。
[Synthesis Example 8]
385.6 parts of water was put into a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, the temperature in the reaction vessel was raised to 85 ° C., and 13 parts of 10% aqueous solution of ammonium persulfate was added. 5 minutes later, 356.4 parts of styrene, 150.6 parts of 2-ethylhexyl acrylate, 13.0 parts of methacrylic acid, an anionic surfactant (product name: Latemul D-4-D, manufactured by Kao Corporation) 18 parts, 22 parts of a 20% aqueous solution of a nonionic surfactant (product name: Emulgen 120, manufactured by Kao Corporation), 70 parts of a 20% aqueous solution of disodium hydrogen phosphate twelve water, 10% of ammonium persulfate An emulsified mixed solution composed of 17.5 parts of an aqueous solution and 70.7 parts of water is allowed to flow in from the dropping tank over 150 minutes. During the inflow, the temperature of the reaction vessel is maintained at 85 ° C. Thirty minutes after the end of the inflow, 5.2 parts of 25% aqueous ammonia is added. Next, a mixture of 504.6 parts of styrene, 259.8 parts of 2-ethylhexyl acrylate, 15.6 parts of methacrylic acid, 25.1 parts of a 10% aqueous solution of ammonium persulfate and 126.3 parts of water was separately prepared. Let it flow in over 150 minutes. The temperature was cooled to 70 ° C. 60 minutes after the inflow was completed. Next, 2 parts of t-butyl hydroperoxide was added and, after 30 minutes, 25 parts of an 8% aqueous solution of sodium sorbate were introduced over 30 minutes. After 30 minutes, it was cooled to room temperature.
室温まで冷却後、２５％アンモニア水溶液を添加してｐＨを８．５に調整してから１００メッシュの金網でろ過した。ろ過された凝集物の乾燥質量は全単量体に対して０．１０％とわずかであった。得られた水性樹脂分散体の固形分率は６４．３％、ＭＦＴは３８℃であった。また、粒度分布には、平均粒子径が２１１ｎｍおよび平均粒子径が７６４ｎｍの２つの分布がみられ、平均粒子径が２１１ｎｍである水性樹脂分散体Ａの固形分換算比率が３３％、平均粒子径が７６４ｎｍである水性樹脂分散体Ｂの固形分換算比率が６５％であった。 After cooling to room temperature, a 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was as little as 0.10% with respect to the total monomer. The obtained aqueous resin dispersion had a solid content of 64.3% and an MFT of 38 ° C. In addition, in the particle size distribution, two distributions having an average particle diameter of 211 nm and an average particle diameter of 764 nm are observed, and the solid resin conversion ratio of the aqueous resin dispersion A having an average particle diameter of 211 nm is 33%, and the average particle diameter is The solid content conversion ratio of the aqueous resin dispersion B having a thickness of 764 nm was 65%.
このようにして得られた水性樹脂分散体にエチレングリコールモノブチルエーテル３０部加えたものを水性樹脂組成物（Ｒ−８）とした。 An aqueous resin composition (R-8) was obtained by adding 30 parts of ethylene glycol monobutyl ether to the aqueous resin dispersion thus obtained.
［合成例９］
撹拌機、還流冷却器、滴下槽および温度計を取り付けた反応容器に水４２０．８部を投入し、反応容器中の温度を８５℃に上げてから、過硫酸アンモニウムの１０％水溶液を１０部添加した５分後に、スチレン３３４．２部、アクリル酸２−エチルヘキシル１７０．６部、メタクリル酸１２．６部、アクリルアミド２．６部、アニオン性界面活性剤（製品名：ラテムルＤ−３−Ｄ、花王（株）製）を８部、ノニオン性界面活性剤（製品名：エマルゲン１４７、花王（株）製）の２０％水溶液１０部、リン酸水素二ナトリウム十二水の２０％水溶液６５部、過硫酸アンモニウムの１０％の水溶液１０．４部、水１００．４部からなる乳化混合液を滴下槽より１５０分かけて流入させる。流入中は反応容器の温度を８５℃に保つ。流入が終了してから３０分後に、２５％アンモニア水溶液を６．０部添加する。次にスチレン４０４．６部、アクリル酸２−エチルヘキシル３６４．８部、メタクリル酸１０．６部、ラウリルメルカプタン１．０部の混合液と過硫酸アンモニウムの１０％水溶液２１．１部と水５３．２部の混合物を別々に、１５０分かけて流入させる。この流入が完了してから９０分後に温度を７０℃に冷却した。次に、ｔ−ブチルハイドロパーオキサイド２部を添加し３０分後にエルソルビン酸ナトリウムの８％水溶液２５部を３０分かけて流入した。３０分後に室温まで冷却した。
[Synthesis Example 9]
420.8 parts of water was put into a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, the temperature in the reaction vessel was raised to 85 ° C., and 10 parts of 10% aqueous solution of ammonium persulfate was added. 5 minutes later, 334.2 parts of styrene, 170.6 parts of 2-ethylhexyl acrylate, 12.6 parts of methacrylic acid, 2.6 parts of acrylamide, an anionic surfactant (product name: Latemule D-3-D, 8 parts of non-ionic surfactant (product name: Emulgen 147, manufactured by Kao Corporation), 65 parts of 20% aqueous solution of disodium hydrogen phosphate twelve water, An emulsified mixed solution consisting of 10.4 parts of a 10% aqueous solution of ammonium persulfate and 100.4 parts of water is allowed to flow from the dropping tank over 150 minutes. During the inflow, the temperature of the reaction vessel is maintained at 85 ° C. After 30 minutes from the end of the inflow, 6.0 parts of 25% aqueous ammonia solution is added. Next, a mixture of 404.6 parts of styrene, 364.8 parts of 2-ethylhexyl acrylate, 10.6 parts of methacrylic acid, 1.0 part of lauryl mercaptan, 21.1 parts of a 10% aqueous solution of ammonium persulfate, and 53.2 water. The mixture of parts is allowed to flow separately over 150 minutes. The temperature was cooled to 70 ° C. 90 minutes after the inflow was completed. Next, 2 parts of t-butyl hydroperoxide was added and, after 30 minutes, 25 parts of an 8% aqueous solution of sodium sorbate were introduced over 30 minutes. After 30 minutes, it was cooled to room temperature.
室温まで冷却後、２５％アンモニア水溶液を添加してｐＨを８．６に調整してから１００メッシュの金網でろ過した。ろ過された凝集物の乾燥質量は全単量体に対して０．０２％とわずかであった。得られた水性樹脂分散体の固形分率は６４．９％、ＭＦＴは１８℃であった。また、粒度分布には、平均粒子径が３５６ｎｍおよび平均粒子径が１３４４ｎｍの２つの分布がみられ、平均粒子径が３５６ｎｍである水性樹脂分散体の固形分換算比率が３８％、平均粒子径が１３４４ｎｍである水性樹脂分散体の固形分換算比率が６２％であった。 After cooling to room temperature, a 25% aqueous ammonia solution was added to adjust the pH to 8.6, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was as small as 0.02% based on the total monomers. The obtained aqueous resin dispersion had a solid content of 64.9% and an MFT of 18 ° C. In addition, in the particle size distribution, two distributions having an average particle size of 356 nm and an average particle size of 1344 nm are observed, the solid content conversion ratio of the aqueous resin dispersion having an average particle size of 356 nm is 38%, and the average particle size is The solid content conversion ratio of the aqueous resin dispersion having a wavelength of 1344 nm was 62%.
このようにして得られた水性樹脂分散体にエチレングリコールモノブチルエーテル１０部加えたものを水性樹脂組成物（Ｒ−９）とした。 An aqueous resin composition (R-9) was obtained by adding 10 parts of ethylene glycol monobutyl ether to the aqueous resin dispersion thus obtained.
［合成例１０］
撹拌機、還流冷却器、滴下槽および温度計を取り付けた反応容器に水５３０．６部を投入し、反応容器中の温度を８５℃に上げてから、過硫酸アンモニウムの１０％水溶液を１０部添加した５分後に、スチレン７４０．９部、アクリル酸２−エチルヘキシル５３０．４部、メタクリル酸２６．１部、アクリルアミド２．６部、アニオン性界面活性剤（製品名：ラテムルＤ−３−Ｄ、花王（株）製）を１５部、ノニオン性界面活性剤（製品名：エマルゲン１２０、花王（株）製）の２０％水溶液１７部、リン酸水素ニナトリウム十二水の２０％水溶液３５部、過硫酸アンモニウムの１０％の水溶液３３．６部、水１２５．７部からなる乳化混合液を滴下槽より３００分かけて流入させる。流入中は反応容器の温度を８５℃に保つ。この流入が完了してから６０分後に温度を７０℃に冷却した。次に、ｔ−ブチルハイドロパーオキサイド２部を添加し３０分後にエルソルビン酸ナトリウムの８％水溶液２５部を３０分かけて流入した。３０分後に室温まで冷却した。
[Synthesis Example 10]
Into a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 530.6 parts of water was added, the temperature in the reaction vessel was raised to 85 ° C., and 10 parts of 10% aqueous solution of ammonium persulfate was added. 5 minutes later, 740.9 parts of styrene, 530.4 parts of 2-ethylhexyl acrylate, 26.1 parts of methacrylic acid, 2.6 parts of acrylamide, an anionic surfactant (product name: Latemul D-3-D, 15 parts of a nonionic surfactant (product name: Emulgen 120, manufactured by Kao Corporation), 17 parts of a 20% aqueous solution of disodium hydrogenphosphate twelve water, An emulsified mixed solution consisting of 33.6 parts of a 10% aqueous solution of ammonium persulfate and 125.7 parts of water is allowed to flow from the dropping tank over 300 minutes. During the inflow, the temperature of the reaction vessel is maintained at 85 ° C. The temperature was cooled to 70 ° C. 60 minutes after the inflow was completed. Next, 2 parts of t-butyl hydroperoxide was added and, after 30 minutes, 25 parts of an 8% aqueous solution of sodium sorbate were introduced over 30 minutes. After 30 minutes, it was cooled to room temperature.
室温まで冷却後、２５％アンモニア水溶液を添加してｐＨを８．５に調整してから１００メッシュの金網でろ過した。ろ過された凝集物の乾燥質量は全単量体に対して０．１５％とわずかであった。得られた水性樹脂分散体の固形分率は６３．２％、ＭＦＴは２２℃であった。また、粒度分布には、平均粒子径が６７０ｎｍの１つの分布がみられた。 After cooling to room temperature, a 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was as small as 0.15% based on the total monomers. The obtained aqueous resin dispersion had a solid content of 63.2% and an MFT of 22 ° C. In the particle size distribution, one distribution having an average particle diameter of 670 nm was observed.
このようにして得られた水性樹脂分散体を水性樹脂組成物（Ｒ−１０）とした。なお、実施例に用いる場合、水性樹脂組成物（Ｒ−１０）は、水性樹脂分散体Ｂとして使用する。 The aqueous resin dispersion thus obtained was designated as an aqueous resin composition (R-10). In addition, when using for an Example, an aqueous resin composition (R-10) is used as the aqueous resin dispersion B. FIG.
［合成例１１］
撹拌機、還流冷却器、滴下槽および温度計を取り付けた反応容器に水４３０．６部を投入し、反応容器中の温度を８５℃に上げてから、過硫酸アンモニウムの１０％水溶液を１３部添加した５分後に、スチレン７４０．９部、アクリル酸２−エチルヘキシル５３０．４部、メタクリル酸２６．１部、アクリルアミド２．６部、アニオン性界面活性剤（製品名：ラテムルＤ−４−Ｄ、花王（株）製）を２０部、ノニオン性界面活性剤（製品名：エマルゲン１４７、花王（株）製）の２０％水溶液２６部、リン酸水素ニナトリウム十二水の２０％水溶液６５部、過硫酸アンモニウムの１０％の水溶液３５．６部、水４９０．７部からなる乳化混合液を滴下槽より２８０分かけて流入させる。流入中は反応容器の温度を８５℃に保つ。この流入が完了してから６０分後に温度を７０℃に冷却した。次に、ｔ−ブチルハイドロパーオキサイド２部を添加し３０分後にエルソルビン酸ナトリウムの８％水溶液２５部を３０分かけて流入した。３０分後に室温まで冷却した。
[Synthesis Example 11]
430.6 parts of water was put into a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, the temperature in the reaction vessel was raised to 85 ° C., and then 13 parts of a 10% aqueous solution of ammonium persulfate was added. 5 minutes later, 740.9 parts of styrene, 530.4 parts of 2-ethylhexyl acrylate, 26.1 parts of methacrylic acid, 2.6 parts of acrylamide, an anionic surfactant (product name: Latemul D-4-D, 20 parts of a nonionic surfactant (product name: Emulgen 147, produced by Kao Corporation), 65 parts of a 20% aqueous solution of disodium hydrogenphosphate twelve water, An emulsified mixed solution consisting of 35.6 parts of a 10% aqueous solution of ammonium persulfate and 490.7 parts of water is allowed to flow from the dropping tank over 280 minutes. During the inflow, the temperature of the reaction vessel is maintained at 85 ° C. The temperature was cooled to 70 ° C. 60 minutes after the inflow was completed. Next, 2 parts of t-butyl hydroperoxide was added and, after 30 minutes, 25 parts of an 8% aqueous solution of sodium sorbate were introduced over 30 minutes. After 30 minutes, it was cooled to room temperature.
室温まで冷却後、２５％アンモニア水溶液を添加してｐＨを８．５に調整してから１００メッシュの金網でろ過した。ろ過された凝集物の乾燥質量は全単量体に対して０．０４％とわずかであった。得られた水性樹脂分散体の固形分率は５５．２％、ＭＦＴは２０℃であった。また、粒度分布には、平均粒子径が１７１ｎｍの１つの分布がみられた。 After cooling to room temperature, a 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was as small as 0.04% based on the total monomers. The obtained aqueous resin dispersion had a solid content of 55.2% and an MFT of 20 ° C. In the particle size distribution, one distribution having an average particle diameter of 171 nm was observed.
このようにして得られた水性樹脂分散体を水性樹脂組成物（Ｒ−１１）とした。なお、実施例に用いる場合、水性樹脂組成物（Ｒ−１１）は、水性樹脂分散体Ａとして使用する。 The aqueous resin dispersion thus obtained was designated as an aqueous resin composition (R-11). In addition, when using for an Example, an aqueous resin composition (R-11) is used as the aqueous resin dispersion A. FIG.
［合成例１２］
撹拌機、還流冷却器、滴下槽および温度計を取り付けた反応容器に水３８５．６部を投入し、反応容器中の温度を８５℃に上げてから、過硫酸アンモニウムの１０％水溶液を１３部添加した５分後に、スチレン４５５．１部、アクリル酸２−エチルヘキシル３００．８部、メタクリル酸２０．６部、アクリルアミド３．５部、アニオン性界面活性剤（製品名：ラテムルＤ−３−Ｄ、花王（株）製）を２０部、ノニオン性界面活性剤（製品名：エマルゲン１２０、花王（株）製）の２０％水溶液２６部、リン酸水素二ナトリウム十二水の２０％水溶液６５部、過硫酸アンモニウムの１０％の水溶液２３．６部、水１４９．８部からなる乳化混合液を滴下槽より１５０分かけて流入させる。流入中は反応容器の温度を８５℃に保つ。流入が終了してから３０分後に、２５％アンモニア水溶液を５．２部添加する。次にスチレン２５９．１部、アクリル酸２−エチルヘキシル２５２．２部、メタクリル酸８．７部の混合液と過硫酸アンモニウムの１０％水溶液１５．４部と水３３．６部の混合物を別々に、１５０分かけて流入させる。この流入が完了してから６０分後に温度を７０℃に冷却した。次に、ｔ−ブチルハイドロパーオキサイド２部を添加し３０分後にエルソルビン酸ナトリウムの８％水溶液２５部を３０分かけて流入した。３０分後に室温まで冷却した。
[Synthesis Example 12]
385.6 parts of water was put into a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, the temperature in the reaction vessel was raised to 85 ° C., and 13 parts of 10% aqueous solution of ammonium persulfate was added. 5 minutes later, 455.1 parts of styrene, 300.8 parts of 2-ethylhexyl acrylate, 20.6 parts of methacrylic acid, 3.5 parts of acrylamide, an anionic surfactant (product name: Latemul D-3-D, 20 parts of a nonionic surfactant (product name: Emulgen 120, produced by Kao Corporation), 65 parts of a 20% aqueous solution of disodium hydrogenphosphate twelve water, An emulsified mixed solution composed of 23.6 parts of a 10% aqueous solution of ammonium persulfate and 149.8 parts of water is allowed to flow from the dropping tank over 150 minutes. During the inflow, the temperature of the reaction vessel is maintained at 85 ° C. Thirty minutes after the end of the inflow, 5.2 parts of 25% aqueous ammonia is added. Next, a mixture of 259.1 parts of styrene, 252.2 parts of 2-ethylhexyl acrylate, 8.7 parts of methacrylic acid, 15.4 parts of a 10% aqueous solution of ammonium persulfate and 33.6 parts of water was separately obtained. Let it flow in over 150 minutes. The temperature was cooled to 70 ° C. 60 minutes after the inflow was completed. Next, 2 parts of t-butyl hydroperoxide was added and, after 30 minutes, 25 parts of an 8% aqueous solution of sodium sorbate were introduced over 30 minutes. After 30 minutes, it was cooled to room temperature.
室温まで冷却後、２５％アンモニア水溶液を添加してｐＨを８．５に調整してから１００メッシュの金網でろ過した。ろ過された凝集物の乾燥質量は全単量体に対して０．０３％とわずかであった。得られた水性樹脂分散体の固形分率は６４．５％、ＭＦＴは１５℃であった。また、粒度分布には、平均粒子径が１７６ｎｍおよび平均粒子径７４８ｎｍの２つの分布がみられ、平均粒子径が１７６ｎｍである水性樹脂分散体の固形分換算比率が５９％、平均粒子径が７４８ｎｍである水性樹脂分散体の固形分換算比率が４１％であった。
このようにして得られた水性樹脂分散体を水性樹脂組成物（Ｒ−１２）とした。
After cooling to room temperature, a 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was as small as 0.03% based on the total monomers. The obtained aqueous resin dispersion had a solid content of 64.5% and MFT of 15 ° C. In addition, in the particle size distribution, two distributions having an average particle diameter of 176 nm and an average particle diameter of 748 nm are observed. The solid resin conversion ratio of the aqueous resin dispersion having an average particle diameter of 176 nm is 59%, and the average particle diameter is 748 nm. The solid content conversion ratio of the aqueous resin dispersion was 41%.
The aqueous resin dispersion thus obtained was designated as an aqueous resin composition (R-12).
［合成例１３］
撹拌機、還流冷却器、滴下槽および温度計を取り付けた反応容器に水５３０．６部を投入し、反応容器中の温度を８５℃に上げてから、過硫酸アンモニウムの１０％水溶液を１０部添加した５分後に、スチレン７６５．９部、アクリル酸２−エチルヘキシル５３４．１部、アニオン性界面活性剤（製品名：ラテムルＤ−４−Ｄ、花王（株）製）を１５部、ノニオン性界面活性剤（製品名：エマルゲン１４７、花王（株）製）の２０％水溶液１７部、リン酸水素二ナトリウム十二水の２０％水溶液３５部、過硫酸アンモニウムの１０％の水溶液３３．６部、水１２５．７部からなる乳化混合液を滴下槽より３００分かけて流入させる。流入中は反応容器の温度を８５℃に保つ。この流入が完了してから６０分後に温度を７０℃に冷却した。次に、ｔ−ブチルハイドロパーオキサイド２部を添加し３０分後にエルソルビン酸ナトリウムの８％水溶液２５部を３０分かけて流入した。３０分後に室温まで冷却した。
[Synthesis Example 13]
Into a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 530.6 parts of water was added, the temperature in the reaction vessel was raised to 85 ° C., and 10 parts of 10% aqueous solution of ammonium persulfate was added. 5 minutes later, 765.9 parts of styrene, 534.1 parts of 2-ethylhexyl acrylate, 15 parts of an anionic surfactant (product name: Latemul D-4-D, manufactured by Kao Corporation), nonionic interface 17 parts of a 20% aqueous solution of an activator (product name: Emulgen 147, manufactured by Kao Corporation), 35 parts of a 20% aqueous solution of disodium hydrogen phosphate and twelve water, 33.6 parts of a 10% aqueous solution of ammonium persulfate, water An emulsified mixed liquid consisting of 125.7 parts is allowed to flow from the dropping tank over 300 minutes. During the inflow, the temperature of the reaction vessel is maintained at 85 ° C. The temperature was cooled to 70 ° C. 60 minutes after the inflow was completed. Next, 2 parts of t-butyl hydroperoxide was added and, after 30 minutes, 25 parts of an 8% aqueous solution of sodium sorbate were introduced over 30 minutes. After 30 minutes, it was cooled to room temperature.
室温まで冷却後、２５％アンモニア水溶液を添加してｐＨを８．５に調整してから１００メッシュの金網でろ過した。ろ過された凝集物の乾燥質量は全単量体に対して０．３５％とわずかであった。得られた水性樹脂分散体の固形分率は６３．３％、ＭＦＴは２２℃であった。また、粒度分布には、平均粒子径が６８７ｎｍの１つの分布がみられた。 After cooling to room temperature, a 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was as low as 0.35% based on the total monomers. The obtained aqueous resin dispersion had a solid content of 63.3% and an MFT of 22 ° C. In the particle size distribution, one distribution having an average particle diameter of 687 nm was observed.
このようにして得られた水性樹脂分散体を水性樹脂組成物（Ｒ−１３）とした。なお、実施例に用いる場合、水性樹脂組成物（Ｒ−１３）は、水性樹脂分散体Ｂとして使用する。 The aqueous resin dispersion thus obtained was designated as an aqueous resin composition (R-13). In addition, when using for an Example, an aqueous resin composition (R-13) is used as the aqueous resin dispersion B. FIG.
上記の水性樹脂組成物（Ｒ−１）〜（Ｒ−１３）および市販の水性樹脂組成物を用いて実施例１〜１９および比較例１〜１３を調製した。なお、以下の説明において、活性炭などの多孔質材料粉末および界面活性剤の配合量における括弧書きは、水性樹脂分散体の固形分１００質量部に対するそれぞれの固形分換算配合量を示している。 Examples 1 to 19 and Comparative Examples 1 to 13 were prepared using the above aqueous resin compositions (R-1) to (R-13) and commercially available aqueous resin compositions. In the following description, the parentheses in the blending amount of the porous material powder such as activated carbon and the surfactant indicate the respective solid content conversion blending amounts with respect to 100 parts by mass of the solid content of the aqueous resin dispersion.
［実施例１］
水性樹脂組成物（Ｒ−１）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）１５０部（２３０部）、フローレンＧ−７００ＡＭＰ（共栄社化学株式会社製、アニオン界面活性剤、固形分率４５％）７０部（４８部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物１を得た。
[Example 1]
100 parts of aqueous resin composition (R-1), 150 parts (230 parts) of coconut shell activated carbon powder (maximum particle size of 50 μm or less), Floren G-700AMP (manufactured by Kyoeisha Chemical Co., Ltd., anionic surfactant, solid content 45) %) 70 parts (48 parts) and 0.1 part of an antifoaming agent were mixed, and an appropriate amount of water was added so that the total solid content was 45%, whereby an aqueous coating composition 1 was obtained.
［実施例２］
水性樹脂組成物（Ｒ−２）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）１００部（１５４部）、フローレンＧ−７００ＡＭＰ５０部（３５部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物２を得た。
[Example 2]
100 parts of an aqueous resin composition (R-2), 100 parts (154 parts) of coconut shell activated carbon powder (maximum particle size 50 μm or less), 50 parts (35 parts) of Floren G-700AMP, and 0.1 part of an antifoaming agent are mixed. An appropriate amount of water was added so that the total solid content was 45%, to obtain an aqueous coating composition 2.
［実施例３］
水性樹脂組成物（Ｒ−３）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）２５０部（４１８部）、ＮＳＤ６４２（株式会社日新化学研究所製、アニオン界面活性剤、固形分率４０％）１００部（６７部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物３を得た。
[Example 3]
100 parts of an aqueous resin composition (R-3), 250 parts (418 parts) of coconut shell activated carbon powder (maximum particle size of 50 μm or less), NSD642 (manufactured by Nissin Chemical Laboratory Co., Ltd., anionic surfactant, solid content 40 %) 100 parts (67 parts) and 0.1 part of an antifoaming agent were mixed, and an appropriate amount of water was added so that the total solid content was 45%, to obtain an aqueous coating composition 3.
［実施例４］
水性樹脂組成物（Ｒ−４）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）５０部（７７部）、フローレンＧ−７００ＡＭＰ１００部（６９部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物４を得た。
[Example 4]
100 parts of aqueous resin composition (R-4), 50 parts (77 parts) of coconut shell activated carbon powder (maximum particle size 50 μm or less), 100 parts (69 parts) of Floren G-700AMP, and 0.1 part of antifoaming agent are mixed. An appropriate amount of water was added so that the total solid content was 45%, whereby an aqueous coating composition 4 was obtained.
［実施例５］
水性樹脂組成物（Ｒ−５）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）３００部（４７０部）、フローレンＧ−７００ＡＭＰ２００部（１４１部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物５を得た。
[Example 5]
100 parts of an aqueous resin composition (R-5), 300 parts (470 parts) of coconut shell activated carbon powder (maximum particle size of 50 μm or less), 200 parts (141 parts) of Floren G-700AMP, and 0.1 part of an antifoaming agent are mixed. An appropriate amount of water was added so that the total solid content was 45%, whereby an aqueous coating composition 5 was obtained.
［実施例６］
水性樹脂組成物（Ｒ−６）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）１５０部（２３１部）、フローレンＧ−７００ＡＭＰ３００部（２０８部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物６を得た。
[Example 6]
100 parts of aqueous resin composition (R-6), 150 parts (231 parts) of coconut shell activated carbon powder (maximum particle size of 50 μm or less), 300 parts (208 parts) of Floren G-700AMP, and 0.1 part of antifoaming agent are mixed. An appropriate amount of water was added so that the total solid content was 45%, to obtain an aqueous coating composition 6.
［実施例７］
水性樹脂組成物（Ｒ−７）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）２００部（３５５部）、ＤＩＳＰＥＲＢＹＫ−２０９０（ビックケミージャパン株式会社製、アニオン界面活性剤、固形分率８１％）４０部（５８部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物７を得た。
[Example 7]
100 parts of an aqueous resin composition (R-7), 200 parts (355 parts) of coconut shell activated carbon powder (maximum particle size of 50 μm or less), DISPERBYK-2090 (manufactured by Big Chemie Japan Co., Ltd., anionic surfactant, solid fraction 81 %) 40 parts (58 parts) and 0.1 part of an antifoaming agent were mixed, and an appropriate amount of water was added so that the total solid content was 45%, whereby an aqueous coating composition 7 was obtained.
［実施例８］
水性樹脂組成物（Ｒ−８）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）１５０部（２３３部）、フローレンＧ−７００ＡＭＰ７０部（４９部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物８を得た。
[Example 8]
100 parts of an aqueous resin composition (R-8), 150 parts (233 parts) of coconut shell activated carbon powder (maximum particle size 50 μm or less), 70 parts (49 parts) of Floren G-700AMP, and 0.1 part of an antifoaming agent are mixed. An appropriate amount of water was added so that the total solid content was 45%, whereby an aqueous coating composition 8 was obtained.
［実施例９］
水性樹脂組成物（Ｒ−１０）７０部、水性樹脂組成物（Ｒ−１１）３０部、椰子殻活性炭粉（最大粒径５０μｍ以下）１５０部（２４７部）、ＮＳＤ６４２ ７０部（４６部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物９を得た。
[Example 9]
70 parts of aqueous resin composition (R-10), 30 parts of aqueous resin composition (R-11), 150 parts (247 parts) of coconut shell activated carbon powder (maximum particle size 50 μm or less), 70 parts (46 parts) of NSD642, 0.1 part of an antifoaming agent was mixed, and an appropriate amount of water was added so that the total solid content was 45%, whereby an aqueous coating composition 9 was obtained.
［実施例１０］
水性樹脂組成物（Ｒ−１１）３０部、水性樹脂組成物（Ｒ−１３）７０部、椰子殻活性炭粉（最大粒径５０μｍ以下）１５０部（２４６部）、フローレンＧ−７００ＡＭＰ７０部（４６部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物１０を得た。
[Example 10]
30 parts of aqueous resin composition (R-11), 70 parts of aqueous resin composition (R-13), 150 parts (246 parts) of coconut shell activated carbon powder (maximum particle size 50 μm or less), 70 parts of Floren G-700AMP (46 parts) ), 0.1 part of an antifoaming agent was mixed, and an appropriate amount of water was added so that the total solid content was 45%, whereby an aqueous coating composition 10 was obtained.
［実施例１１］
水性樹脂組成物（Ｒ−１）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）１００部（１５４部）、ラヂオライトＦ（昭和化学工業株式会社製、珪藻土粉、平均粒径７μｍ）７０部（１０７部）、フローレンＧ−７００ＡＭＰ７０部（４８部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物１１を得た。
[Example 11]
100 parts of aqueous resin composition (R-1), 100 parts (154 parts) of coconut shell activated carbon powder (maximum particle size 50 μm or less), Radiolite F (manufactured by Showa Chemical Industry Co., Ltd., diatomaceous earth powder, average particle size 7 μm) 70 Parts (107 parts), 70 parts (48 parts) Floren G-700AMP, 0.1 parts of antifoaming agent, and an appropriate amount of water is added so that the total solid content is 45%. Obtained.
［実施例１２］
水性樹脂組成物（Ｒ−１）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）１００部（１５４部）、モレキュラーシーブ４Ａパウダー（ユニオン昭和株式会社製、合成ゼオライト粉、粒径１０μｍ以下）５０部（７６部）、フローレンＧ−７００ＡＭＰ７０部（４８部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物１２を得た。
[Example 12]
Aqueous resin composition (R-1) 100 parts, coconut shell activated carbon powder (maximum particle size 50 μm or less) 100 parts (154 parts), molecular sieve 4A powder (manufactured by Union Showa Co., Ltd., synthetic zeolite powder, particle size 10 μm or less) 50 parts (76 parts), 70 parts (48 parts) of Floren G-700AMP, and 0.1 part of an antifoaming agent are mixed, and an appropriate amount of water is added so that the total solid content is 45%. Got.
［実施例１３］
水性樹脂組成物（Ｒ−１）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）２００部（３０７部）、フローレンＧ−７００ＡＭＰ１００部（６９部）、ジンクピリチオン（抗菌剤）２部、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物１３を得た。
[Example 13]
100 parts of aqueous resin composition (R-1), 200 parts (307 parts) of coconut shell activated carbon powder (maximum particle size of 50 μm or less), 100 parts (69 parts) of Floren G-700AMP, 2 parts of zinc pyrithione (antibacterial agent), antifoaming 0.1 part of the agent was mixed, and an appropriate amount of water was added so that the total solid content was 45%, whereby an aqueous coating composition 13 was obtained.
［実施例１４］
水性樹脂組成物（Ｒ−１）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）１００部（１５３部）、ＤＩＳＰＥＲＢＹＫ−２０９０ ５０部（６２部）、チアベンダゾール（防カビ剤）２部、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物１４を得た。
[Example 14]
Aqueous resin composition (R-1) 100 parts, coconut shell activated carbon powder (maximum particle size 50 μm or less) 100 parts (153 parts), DISPERBYK-2090 50 parts (62 parts), thiabendazole (antifungal agent) 2 parts, 0.1 part of a foaming agent was mixed, and an appropriate amount of water was added so that the total solid content was 45%, whereby an aqueous coating composition 14 was obtained.
［実施例１５］
水性樹脂組成物（Ｒ−１）１００部、椰子殻活性炭粉（最大粒径１５０μｍ以下）３００部（４６０部）、ＤＩＳＰＥＲＢＹＫ−２０９０ １００部（１２４部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物１５を得た。
[Example 15]
100 parts of aqueous resin composition (R-1), coconut shell activated carbon powder (maximum particle size 150 μm or less) 300 parts (460 parts), DISPERBYK-2090 100 parts (124 parts), and 0.1 part of antifoaming agent were mixed. An appropriate amount of water was added so that the total solid content was 45%, whereby an aqueous coating composition 15 was obtained.
［実施例１６］
水性樹脂組成物（Ｒ−１）１００部、備長炭粉（最大粒径５０μｍ以下）１５０部（２３０部）、ＮＳＤ６４２ ５０部（３１部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物１６を得た。
[Example 16]
100 parts of an aqueous resin composition (R-1), 150 parts (230 parts) of Bincho charcoal powder (maximum particle size of 50 μm or less), 50 parts (31 parts) of NSD642, and 0.1 part of an antifoaming agent are mixed together, An appropriate amount of water was added so that the content was 45%, to obtain an aqueous coating composition 16.
［実施例１７］
水性樹脂組成物（Ｒ−１）１００部、ラヂオライトＦ（昭和化学工業株式会社製、珪藻土粉、平均粒径７μｍ）２００部（３０７部）、フローレンＧ−７００ＡＭＰ７０部（４８部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物１７を得た。
[Example 17]
100 parts of aqueous resin composition (R-1), Radiolite F (manufactured by Showa Chemical Industry Co., Ltd., diatomaceous earth powder, average particle size 7 μm) 200 parts (307 parts), Floren G-700AMP 70 parts (48 parts), antifoaming An aqueous coating composition 17 was obtained by mixing 0.1 part of the agent and adding an appropriate amount of water so that the total solid content was 45%.
［実施例１８］
水性樹脂組成物（Ｒ−１）１００部、モレキュラーシーブ４Ａパウダー（ユニオン昭和株式会社製、合成ゼオライト粉、粒径１０μｍ以下）１５０部（２３０部）、フローレンＧ−７００ＡＭＰ７０部（４８部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物１８を得た。
[Example 18]
Aqueous resin composition (R-1) 100 parts, Molecular sieve 4A powder (Union Showa Co., Ltd., synthetic zeolite powder, particle size 10 μm or less) 150 parts (230 parts), Floren G-700AMP 70 parts (48 parts), An aqueous coating composition 18 was obtained by mixing 0.1 part of a foaming agent and adding an appropriate amount of water so that the total solid content was 45%.
［実施例１９］
水性樹脂組成物（Ｒ−１）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）１５０部（２３０部）、ＮＳＤ６１６（株式会社日新化学研究所製、ポリアルキレングリコール成分を含有しないアニオン界面活性剤、固形分率３５％）１００部（５４部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物１９を得た。
[Example 19]
100 parts of aqueous resin composition (R-1), 150 parts (230 parts) of coconut shell activated carbon powder (maximum particle size of 50 μm or less), NSD616 (manufactured by Nisshin Chemical Laboratory Co., Ltd., an anion interface not containing polyalkylene glycol component) Activating agent, solid content rate 35%) 100 parts (54 parts) and antifoaming agent 0.1 part are mixed, and an appropriate amount of water is added so that the total solid content is 45%. Obtained.
［比較例１］
ポリトロンＥ３１６Ｓ（旭化成ケミカルズ社製、アクリル系エマルション、固形分率４５．１％、ＭＦＴ２０℃、平均粒子径１２５ｎｍ）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）２５０部（５５４部）、フローレンＧ−７００ＡＭＰ２００部（２００部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物２０を得た。
[Comparative Example 1]
Polytron E316S (manufactured by Asahi Kasei Chemicals Corporation, acrylic emulsion, solid content 45.1%, MFT 20 ° C., average particle size 125 nm) 100 parts, coconut shell activated carbon powder (maximum particle size 50 μm or less) 250 parts (554 parts), florene 200 parts (200 parts) of G-700AMP and 0.1 part of an antifoaming agent were mixed, and an appropriate amount of water was added so that the total solid content was 45%, whereby an aqueous coating composition 20 was obtained.
［比較例２］
ポリトロンＡ１５００（旭化成ケミカルズ社製、スチレンアクリル系エマルション、固形分率４５．５％、ＭＦＴ３℃、平均粒子径２００ｎｍ）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）１５０部（３３０部）、ＤＩＳＰＥＲＢＹＫ−２０９０ １００部（１７８部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物２１を得た。
[Comparative Example 2]
Polytron A1500 (manufactured by Asahi Kasei Chemicals Corporation, styrene acrylic emulsion, solid content 45.5%, MFT 3 ° C., average particle size 200 nm) 100 parts, coconut shell activated carbon powder (maximum particle size 50 μm or less) 150 parts (330 parts), 100 parts (178 parts) of DISPERBYK-2090 and 0.1 part of an antifoaming agent were mixed, and an appropriate amount of water was added so that the total solid content was 45%, whereby an aqueous coating composition 21 was obtained.
［比較例３］
Ｆ−１８６１（旭化成ケミカルズ社製、スチレンブタジエン系エマルション、固形分率５０．０％、ＭＦＴ５℃、平均粒子径１００ｎｍ）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）２００部（４００部）、ＤＩＳＰＥＲＢＹＫ−２０９０ １００部（１６２部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物２２を得た。
[Comparative Example 3]
F-1861 (manufactured by Asahi Kasei Chemicals Corporation, styrene-butadiene emulsion, solid content rate 50.0%, MFT 5 ° C., average particle size 100 nm) 100 parts, coconut shell activated carbon powder (maximum particle size 50 μm or less) 200 parts (400 parts) 100 parts (162 parts) of DISPERBYK-2090 and 0.1 part of an antifoaming agent were mixed, and an appropriate amount of water was added so that the total solid content was 45%, whereby an aqueous coating composition 22 was obtained.
［比較例４］
水性樹脂組成物（Ｒ−９）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）２００部（３０８部）、フローレンＧ−７００ＡＭＰ２００部（１３９部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物２３を得た。
[Comparative Example 4]
100 parts of aqueous resin composition (R-9), 200 parts (308 parts) of coconut shell activated carbon powder (maximum particle size of 50 μm or less), 200 parts (139 parts) of Floren G-700AMP, and 0.1 part of antifoaming agent are mixed. An appropriate amount of water was added so that the total solid content was 45%, whereby an aqueous coating composition 23 was obtained.
［比較例５］
スミカフレックス２０１ＨＱ（住友化学社製、エチレン−酢酸ビニル共重合エマルション、固形分率５４．８％、ＭＦＴ０℃、平均粒子径６１０ｎｍ）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）１５０部（２７４部）、フローレンＧ−７００ＡＭＰ７０部（５７部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物２４を得た。
[Comparative Example 5]
Sumikaflex 201HQ (manufactured by Sumitomo Chemical Co., Ltd., ethylene-vinyl acetate copolymer emulsion, solid content rate 54.8%, MFT 0 ° C., average particle size 610 nm) 100 parts, coconut shell activated carbon powder (maximum particle size 50 μm or less) 150 parts ( 274 parts), 70 parts (57 parts) of Florene G-700AMP, and 0.1 part of an antifoaming agent were mixed, and an appropriate amount of water was added so that the total solid content would be 45% to obtain an aqueous coating composition 24. .
［比較例６］
水性樹脂組成物（Ｒ−１０）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）１００部（１５８部）、ＮＳＤ６４２ ５０部（３２部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物２５を得た。
[Comparative Example 6]
100 parts of aqueous resin composition (R-10), 100 parts (158 parts) of coconut shell activated carbon powder (maximum particle size of 50 μm or less), 50 parts (32 parts) of NSD642, 0.1 part of antifoaming agent are mixed together. A water-based coating composition 25 was obtained by adding an appropriate amount of water so that the solid content was 45%.
［比較例７］
水性樹脂組成物（Ｒ−１１）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）１００部（１８１部）、フローレンＧ−７００ＡＭＰ５０部（４１部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物２６を得た。
[Comparative Example 7]
100 parts of an aqueous resin composition (R-11), 100 parts (181 parts) of coconut shell activated carbon powder (maximum particle size 50 μm or less), 50 parts (41 parts) of Floren G-700AMP, and 0.1 part of an antifoaming agent are mixed. An appropriate amount of water was added so that the total solid content was 45%, to obtain an aqueous coating composition 26.
［比較例８］
水性樹脂組成物（Ｒ−１２）１００部、椰子殻活性炭粉（最大粒径１５０μｍ以下）１００部（１５５部）、ＤＩＳＰＥＲＢＹＫ−２０９０ ５０部（６３部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物２７を得た。
[Comparative Example 8]
100 parts of aqueous resin composition (R-12), 100 parts (155 parts) of coconut shell activated carbon powder (maximum particle size 150 μm or less), 50 parts (63 parts) DISPERBYK-2090, and 0.1 part of antifoaming agent were mixed. An appropriate amount of water was added so that the total solid content was 45%, whereby an aqueous coating composition 27 was obtained.
［比較例９］
水性樹脂組成物（Ｒ−１３）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）１５０部（２３７部）、フローレンＧ−７００ＡＭＰ７０部（５０部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物２８を得た。
[Comparative Example 9]
100 parts of an aqueous resin composition (R-13), 150 parts (237 parts) of coconut shell activated carbon powder (maximum particle size 50 μm or less), 70 parts (50 parts) of Floren G-700AMP, and 0.1 part of an antifoaming agent are mixed. An appropriate amount of water was added so that the total solid content was 45%, whereby an aqueous coating composition 28 was obtained.
［比較例１０］
水性樹脂組成物（Ｒ−１）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）４００部（６１３部）、フローレンＧ−７００ＡＭＰ３００部（２０７部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物２９を得た。
[Comparative Example 10]
100 parts of aqueous resin composition (R-1), 400 parts (613 parts) of coconut shell activated carbon powder (maximum particle size 50 μm or less), 300 parts (207 parts) of Floren G-700AMP, and 0.1 part of antifoaming agent are mixed. An appropriate amount of water was added so that the total solid content was 45%, whereby an aqueous coating composition 29 was obtained.
［比較例１１］
水性樹脂組成物（Ｒ−１）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）３部（４．６部）、フローレンＧ−７００ＡＭＰ５０部（３５部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物３０を得た。
[Comparative Example 11]
100 parts of aqueous resin composition (R-1), 3 parts (4.6 parts) of coconut shell activated carbon powder (maximum particle size of 50 μm or less), 50 parts (35 parts) of Floren G-700AMP, 0.1 part of antifoaming agent An appropriate amount of water was added so that the total solid content would be 45%, and an aqueous coating composition 30 was obtained.
［比較例１２］
水性樹脂組成物（Ｒ−１）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）３００部（４６０部）、フローレンＧ−７００ＡＭＰ１部（０．７部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物３１を得た。
[Comparative Example 12]
100 parts of an aqueous resin composition (R-1), 300 parts (460 parts) of coconut shell activated carbon powder (maximum particle size 50 μm or less), 1 part (0.7 parts) of Floren G-700AMP, 0.1 part of an antifoaming agent An appropriate amount of water was added so that the total solid content was 45%, and an aqueous coating composition 31 was obtained.
［比較例１３］
水性樹脂組成物（Ｒ−１）１００部、椰子殻活性炭粉（最大粒径５０μｍ以下）２００部（３０７部）、フローレンＧ−７００ＡＭＰ４５０部（３１１部）、消泡剤０．１部を混合し、全固形分が４５％になるように水を適量添加して、水性塗料組成物３２を得た。
[Comparative Example 13]
100 parts of aqueous resin composition (R-1), 200 parts (307 parts) of coconut shell activated carbon powder (maximum particle size of 50 μm or less), 450 parts (311 parts) of Floren G-700AMP, and 0.1 part of antifoaming agent are mixed. An appropriate amount of water was added so that the total solid content was 45%, and an aqueous coating composition 32 was obtained.
得られた水性塗料組成物１〜３２の塗料性状及び塗膜性能評価結果を表１〜４に示す。但し、表中の「−」表示については、塗料の状態で流動性がなかったことから、評価を実施しなかったことを示す。 The paint properties and coating film performance evaluation results of the obtained water-based paint compositions 1 to 32 are shown in Tables 1 to 4. However, “−” in the table indicates that the evaluation was not performed because there was no fluidity in the state of the paint.
本発明の水性塗料組成物を適用することにより、各種の要求性能、例えば脱臭、調湿性能等の多孔質材料粉末が有する機能性を保持したまま塗膜化でき、且つ塗料の貯蔵安定性、塗工適性を確保することができる。また、具体的な用途として、活性炭やゼオライトを用いた消臭脱臭用塗料、ＶＯＣ吸着用塗料、シリカゲルやアルミナゲル、珪藻土を用いた調湿用塗料、断熱塗料等を挙げることができる。 By applying the aqueous coating composition of the present invention, it is possible to form a coating film while maintaining the functionality of the porous material powder such as various required performances such as deodorization and humidity control performance, and the storage stability of the coating material. Coating suitability can be ensured. Specific applications include deodorant and deodorant paints using activated carbon and zeolite, VOC adsorption paints, silica gel, alumina gel, humidity control paints using diatomaceous earth, and heat insulation paints.
Claims (8)
水性樹脂分散体が、平均粒子径５０〜２８０ｎｍの樹脂粒子Ａと平均粒子径３３０〜１２００ｎｍの樹脂粒子Ｂとを質量比率でＡ：Ｂ＝１０：９０〜５０：５０の範囲で含有することを特徴とする、水性塗料組成物。 An aqueous coating composition containing 5 to 500 parts by mass of a porous material powder and 5 to 300 parts by mass of a surfactant as an essential component with respect to 100 parts by mass of a resin solid content of the aqueous resin dispersion,
The aqueous resin dispersion contains resin particles A having an average particle size of 50 to 280 nm and resin particles B having an average particle size of 330 to 1200 nm in a mass ratio of A: B = 10: 90 to 50:50. A water-based paint composition characterized by the above.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5570648B1 (en) * | 2013-12-20 | 2014-08-13 | 株式会社池田工業 | Wallpaper paint |
| JP2014221851A (en) * | 2013-05-13 | 2014-11-27 | アイカ工業株式会社 | Aqueous coating material composition |
| WO2018230120A1 (en) * | 2017-06-16 | 2018-12-20 | パナソニックＩｐマネジメント株式会社 | Coating composition and hydrophilic member |
| JPWO2017164072A1 (en) * | 2016-03-22 | 2019-02-07 | 関西ペイント株式会社 | Water-based paint composition |
| EP3487895B1 (en) | 2016-07-20 | 2023-02-01 | Basf Se | Process for preparing an aqueous polymer dispersion having high chemical resistance |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001200181A (en) * | 2000-01-17 | 2001-07-24 | Kanegafuchi Chem Ind Co Ltd | Aqueous coating composition |
| JP2002302635A (en) * | 2001-02-02 | 2002-10-18 | Taihei Shiki Kk | Adsorptive coating |
| JP2004211049A (en) * | 2002-11-14 | 2004-07-29 | Toto Ltd | Functional coating |
| JP2010174172A (en) * | 2009-01-30 | 2010-08-12 | Hokkaido Univ | Coating agent |
-
2011
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001200181A (en) * | 2000-01-17 | 2001-07-24 | Kanegafuchi Chem Ind Co Ltd | Aqueous coating composition |
| JP2002302635A (en) * | 2001-02-02 | 2002-10-18 | Taihei Shiki Kk | Adsorptive coating |
| JP2004211049A (en) * | 2002-11-14 | 2004-07-29 | Toto Ltd | Functional coating |
| JP2010174172A (en) * | 2009-01-30 | 2010-08-12 | Hokkaido Univ | Coating agent |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014221851A (en) * | 2013-05-13 | 2014-11-27 | アイカ工業株式会社 | Aqueous coating material composition |
| JP5570648B1 (en) * | 2013-12-20 | 2014-08-13 | 株式会社池田工業 | Wallpaper paint |
| JPWO2017164072A1 (en) * | 2016-03-22 | 2019-02-07 | 関西ペイント株式会社 | Water-based paint composition |
| EP3487895B1 (en) | 2016-07-20 | 2023-02-01 | Basf Se | Process for preparing an aqueous polymer dispersion having high chemical resistance |
| WO2018230120A1 (en) * | 2017-06-16 | 2018-12-20 | パナソニックＩｐマネジメント株式会社 | Coating composition and hydrophilic member |
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