KR20160052004A - Non-ionic acrylic emulsion resin, process for producing the same, and cationic antimicrobial paint containing the same - Google Patents
Non-ionic acrylic emulsion resin, process for producing the same, and cationic antimicrobial paint containing the same Download PDFInfo
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- KR20160052004A KR20160052004A KR1020140149751A KR20140149751A KR20160052004A KR 20160052004 A KR20160052004 A KR 20160052004A KR 1020140149751 A KR1020140149751 A KR 1020140149751A KR 20140149751 A KR20140149751 A KR 20140149751A KR 20160052004 A KR20160052004 A KR 20160052004A
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- monomer
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- emulsion resin
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000011347 resin Substances 0.000 title claims abstract description 53
- 229920005989 resin Polymers 0.000 title claims abstract description 53
- 239000000839 emulsion Substances 0.000 title claims abstract description 51
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 47
- 230000000845 anti-microbial effect Effects 0.000 title claims abstract description 30
- 239000003973 paint Substances 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 9
- 230000008569 process Effects 0.000 title claims description 3
- 239000000178 monomer Substances 0.000 claims abstract description 78
- 239000000203 mixture Substances 0.000 claims abstract description 71
- 238000012644 addition polymerization Methods 0.000 claims abstract description 31
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 28
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 20
- 239000002954 polymerization reaction product Substances 0.000 claims abstract description 19
- 150000007524 organic acids Chemical class 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 230000000977 initiatory effect Effects 0.000 claims abstract description 5
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000011248 coating agent Substances 0.000 claims description 34
- -1 acrylic ester Chemical class 0.000 claims description 28
- 239000004599 antimicrobial Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 230000000844 anti-bacterial effect Effects 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- 150000005215 alkyl ethers Chemical class 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- 125000005907 alkyl ester group Chemical group 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002114 octoxynol-9 Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 claims description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- 239000004925 Acrylic resin Substances 0.000 claims 1
- 229920000178 Acrylic resin Polymers 0.000 claims 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 239000000463 material Substances 0.000 description 11
- 125000000129 anionic group Chemical group 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000008199 coating composition Substances 0.000 description 8
- 239000002270 dispersing agent Substances 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000003242 anti bacterial agent Substances 0.000 description 7
- 230000001954 sterilising effect Effects 0.000 description 7
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 7
- 239000007853 buffer solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 5
- 239000001099 ammonium carbonate Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000002688 persistence Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- HFUFUJVRCNBZLX-UHFFFAOYSA-N butyl prop-2-enoate;dodecyl 2-methylprop-2-enoate Chemical compound CCCCOC(=O)C=C.CCCCCCCCCCCCOC(=O)C(C)=C HFUFUJVRCNBZLX-UHFFFAOYSA-N 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
- C08F212/10—Styrene with nitriles
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
- C08F222/08—Maleic anhydride with vinyl aromatic monomers
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- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
- C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
비이온성 아크릴 에멀젼 수지 및 이의 제조방법, 이를 포함하는 양이온성 항균 도료 개시되어 있다. 비이온성 아크릴 에멀젼 수지는 아크릴산 에스테르계 모노머 30 내지 60 중량부, 방향족 비닐계 모노머 20 내지 50 중량부, 유기산계 모노머 0.1 내지 3중량부를 포함하는 모노머 혼합물을 제조하는 단계; 상기 모노머 혼합물 100 중량부 기준으로 비이온성 계면활성제 2.5 내지 6 중량부 및 라디칼 중합개시 촉매 0.1 내지 1 중량부를 혼합하여 부가중합 혼합물을 제조하는 단계; 상기 부가중합 혼합물에 상기 모노머 혼합물을 적하 에멀젼 중합 반응시켜 에멀젼 중합반응물을 형성하는 단계 및 PH조절제를 이용하여 상기 에멀젼 중합 반응물의 PH를 6 내지 9으로 조절하는 단계를 수행함으로서 형성될 수 있다. A nonionic acrylic emulsion resin, a method for producing the same, and a cationic antimicrobial paint containing the same. The nonionic acrylic emulsion resin comprises 30 to 60 parts by weight of an acrylate monomer, 20 to 50 parts by weight of an aromatic vinyl-based monomer, and 0.1 to 3 parts by weight of an organic acid-based monomer; Mixing 2.5 to 6 parts by weight of a nonionic surfactant and 0.1 to 1 part by weight of a radical polymerization initiating catalyst based on 100 parts by weight of the monomer mixture to produce an addition polymerization mixture; Forming the emulsion polymerization reaction product by dropwise emulsion polymerization of the monomer mixture to the addition polymerization mixture, and adjusting the pH of the emulsion polymerization reaction product to 6 to 9 using a pH adjusting agent.
Description
본 발명은 비이온성 아크릴 에멀젼 수지 및 이의 제조방법, 이를 포함하는 양이온성 항균 도료에 관한 것으로, 더욱 상세하게는 우수한 항균성을 갖는 도료에 적용되는 비이온성 아크릴 에멀젼 수지 및 이의 제조방법, 이를 포함하는 양이온성 항균 도료에 관한 것이다. The present invention relates to a nonionic acrylic emulsion resin, a method for producing the same, and a cationic antimicrobial coating composition containing the same. More particularly, the present invention relates to a nonionic acrylic emulsion resin applicable to a coating material having excellent antibacterial properties, The present invention relates to an antimicrobial coating material.
타일보수 용도로 사용되는 도료는 지금까지 일반적으로 음이온성 에멀젼 수지 등의 수성 도료(공개특허 10-2006-0072480)가 일반적으로 사용되고 비이온성 아크릴 에멀젼 및 양이온성 수성도료가 거의 사용되지 않았다. The paint used for tile repair has heretofore generally used an aqueous paint such as an anionic emulsion resin (Patent Document 10-2006-0072480), and almost no nonionic emulsion and cationic water-based paint have been used.
현재 국내에서 사용 중인 음이온성 타일보수 수성 도료는 음이온성 항균제를 사용하고 있다. 음이온성 항균제는 미생물의 음이온성 세포막에 부착이 어려워 지속성이 짧은 문제점이 있다. 양이온성 항균제는 미생물의 음이온 부위에 정전기 현상으로 세포막에 부착해서 영항을 주기 때문에 음이온성 항균제에 비해 살균력이 지속적으로 유지되는 된다. 따라서 양이온성 항균제와의 상용성, 우수한 내수성을 발휘하는 비이온성 아크릴 에멀젼 수지 및 살균력이 지속적으로 유지되는 양이온성 항균 수성 도료의 개발에 대한 요구가 증가하고 있다.Currently, anionic tile repair water-based paints used in Korea are using anionic antimicrobial agents. The anionic antimicrobial agent is difficult to adhere to the anionic membrane of the microorganism and thus has a short persistence. Cationic antimicrobial agents are able to maintain sterilization power compared to anionic antimicrobial agents because they adhere to cell membranes by electrostatic phenomenon at the anion sites of microorganisms and affect the cells. Therefore, there is an increasing demand for the development of cationic antimicrobial water-based paints that are compatible with cationic antimicrobial agents, nonionic acrylic emulsion resins exhibiting excellent water resistance, and persistently maintained sterilizing power.
본 발명의 과제는 이러한 종래기술의 문제점을 해결하고자, 양이온 항균제와의 우수한 상용성, 항균성, 내수성을 발휘하는 비이온성 아크릴 에멀젼 수지 및 이의 제조방법을 제공하는 데 있다. The object of the present invention is to provide a nonionic acrylic emulsion resin exhibiting excellent compatibility with a cationic antimicrobial agent, antimicrobial property and water resistance, and a process for producing the same, in order to solve the problems of the prior art.
본 발명의 다른 과제는 상술한 방법에 의하여 제조된 비이온성 아크릴 에멀젼 수지를 포함하는 양이온성 항균 수성 도료를 제공하는 데 있다.Another object of the present invention is to provide a cationic antimicrobial water-based paint comprising the nonionic acrylic emulsion resin produced by the above-mentioned method.
상기 과제를 달성하기 위한 본 발명의 양이온성 항균 수성 도료에 적용되는 비이온성 아크릴 에멀젼 수지는 아크릴산 에스테르계 모노머 30 내지 60 중량부, 방향족 비닐계 모노머 20 내지 50 중량부, 유기산계 모노머 0.1 내지 3 중량부를 포함하는 모노머 혼합물을 제조하는 단계와, 모노머 혼합물 100 중량부 기준으로 비이온성 계면활성제 2.5 내지 6 중량부 및 라디칼 중합개시 촉매 0.1 내지 1 중량부를 혼합하여 부가중합 혼합물을 제조하는 단계와 상기 부가중합 혼합물에 상기 모노머 혼합물을 적하 에멀젼 중합 반응시켜 에멀젼 중합반응물을 형성하는 단계 및 PH 조절제를 이용하여 상기 에멀젼 중합 반응물의 PH를 6 내지 9으로 조절하는 단계를 수행함으로서 제조될 수 있다. The nonionic acrylic emulsion resin to be applied to the cationic antimicrobial water-based paint of the present invention for achieving the above object comprises 30 to 60 parts by weight of an acrylate monomer, From 20 to 50 parts by weight of an aromatic vinyl monomer, and from 0.1 to 3 parts by weight of an organic acid monomer; mixing 2.5 to 6 parts by weight of a nonionic surfactant and 0.1 to 10 parts by weight of a radical polymerization initiator catalyst To 1 part by weight of an addition polymerization mixture to prepare an addition polymerization mixture; and dropwise emulsion polymerization reaction of said monomer mixture to said addition polymerization mixture to form an emulsion polymerization reaction product; 9, < / RTI >
일 실시예로서, 상기 유기산계 모노머는 아크릴산, 메타크릴산, 푸마르산, 말레산 및 이타콘산으로 이루어진 군에서 적어도 하나의 유기산계 모노머를 선택하여 사용할 수 있다. In one embodiment, the organic acid-based monomer may be selected from at least one organic acid-based monomer selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid, and itaconic acid.
일 실시예로서, 상기 비이온성 계면활성제는 폴리옥시에틸렌노닐페닐에테르, 폴리옥시에칠렌옥틸페닐에텔, 폴리옥시에틸렌알킬에테르, 폴리옥시에틸렌알킬에스테르, 폴리옥시에틸렌알킬아민에테르, 폴리옥시에틸렌폴리옥시프로필렌, 폴리에틸렌글리콜 및 소르비탄지방산에스테르로 이루어진 군에서 적어도 하나의 비이온성 계면활성제를 사용할 수 있다.In one embodiment, the nonionic surfactant is selected from the group consisting of polyoxyethylene nonylphenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine ether, polyoxyethylene polyoxypropylene , Polyethylene glycol, and sorbitan fatty acid esters, may be used as the nonionic surfactant.
상기 과제를 달성하기 위한 본 발명의 양이온성 항균 수성 도료는 비이온성 아크릴 에멀젼 수지 30 내지 60중량%, 양이온 항균제 0.5 내지 3중량%, 실리카 입자 10 내지 30중량%, 첨가제 2 내지 4 중량% 및 여분의 탈이온수를 포함할 수 있다.To achieve the above object, the present invention provides a cationic antibacterial water-based coating composition comprising 30 to 60% by weight of a nonionic acrylic emulsion resin, 0.5 to 3% by weight of a cationic antimicrobial agent, 10 to 30% by weight of silica particles, 2 to 4% Of deionized water.
이때, 상기 비이온성 아크릴 에멀젼 수지는 아크릴산 에스테르계 모노머 30 내지 60 중량부, 방향족 비닐계 모노머 20 내지 50 중량부, 유기산계 모노머 0.1 내지 3 중량부를 포함하는 모노머 혼합물을 제조하는 단계와, 모노머 혼합물 100 중량부 기준으로 비이온성 계면활성제 2.5 내지 6 중량부 및 라디칼 중합개시 촉매 0.1 내지 1 중량부를 혼합하여 부가중합 혼합물을 제조하는 단계와 상기 부가중합 혼합물에 상기 모노머 혼합물을 적하 에멀젼 중합 반응시켜 에멀젼 중합반응물을 형성하는 단계 및 PH 조절제를 이용하여 상기 에멀젼 중합 반응물의 PH를 6 내지 9으로 조절하는 단계를 수행함으로서 제조될 수 있다. In this case, the nonionic acrylic emulsion resin may contain 30 to 60 parts by weight of an acrylate monomer, From 20 to 50 parts by weight of an aromatic vinyl monomer, and from 0.1 to 3 parts by weight of an organic acid monomer; mixing 2.5 to 6 parts by weight of a nonionic surfactant and 0.1 to 10 parts by weight of a radical polymerization initiator catalyst To 1 part by weight of an addition polymerization mixture to prepare an addition polymerization mixture; and dropwise emulsion polymerization reaction of said monomer mixture to said addition polymerization mixture to form an emulsion polymerization reaction product; 9, < / RTI >
본 발명에 따른 비이온성 아크릴 에멀젼 수지는 기존 음이온성 항균제보다 살균 지속성이 우수한 양이온성 항균제와의 우수한 상용성으로 양이온성 항균 수성 도료를 제조하는데 적용가능하다. 상기 비이온성 아크릴 에멀젼 수지를 포함하는 양이온성 항균 도료는 부착성, 내수성 우수할 뿐만 아니라 살균 지속성이 우수한 양이온성 항균제를 포함하고 있어 음이온성 항균제를 포함하는 도료에 비해 우수한 항균성을 갖는다. The nonionic acrylic emulsion resin according to the present invention is applicable to the production of cationic antibacterial water-based coatings with excellent compatibility with cationic antimicrobial agents superior in sterilization persistence than conventional anionic antibacterial agents. The cationic antimicrobial coating composition comprising the nonionic acrylic emulsion resin has excellent antimicrobial properties as compared with the coating composition containing anionic antimicrobial agent because it contains a cationic antimicrobial agent excellent in adhesion and water resistance as well as excellent in sterilization persistence.
이하, 본 발명의 실시예에 따른 비이온성 아크릴 에멀젼 수지, 이의 제조방법 및 이를 포함하는 양이온성 항균 도료에 대하여 상세히 설명하기로 한다. 본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바, 특정 실시예들을 본문에 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 제1, 제2 등의 용어는 다양한 구성요소들을 설명하는데 사용될 수 있지만, 상기 구성요소들은 상기 용어들에 의해 한정되어서는 안 된다. 상기 용어들은 하나의 구성요소를 다른 구성요소로부터 구별하는 목적으로만 사용된다. 예를 들어, 본 발명의 권리 범위를 벗어나지 않으면서 제1 구성요소는 제2 구성요소로 명명될 수 있고, 유사하게 제2 구성요소도 제1 구성요소로 명명될 수 있다.Hereinafter, a nonionic acrylic emulsion resin according to an embodiment of the present invention, a method for producing the same, and a cationic antimicrobial coating material containing the same will be described in detail. While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are further described in the text. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. The terms first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.
본 출원에서 사용한 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, "포함하다" 또는 "가지다" 등의 용어는 명세서 상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, the terms "comprises", "having", and the like are used to specify that a feature, a number, a step, an operation, an element, a part or a combination thereof is described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof.
한편, 다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥 상 가지는 의미와 일치하는 의미를 가지는 것으로 해석되어야 하며, 본 출원에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다.On the other hand, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.
비이온성Nonionic 아크릴 acryl 에멀젼emulsion 수지 및 이의 제조 Resin and its manufacture
본 발명에 따른 양이온 항균 도료에 적용되는 비이온성 아크릴 에멀젼 수지는 아크릴산 에스테르계 모노머 30 내지 60 중량부, 방향족 비닐계 모노머 20 내지 50 중량부, 유기산계 모노머 0.1 내지 3 중량부를 포함하는 모노머 혼합물을 제조하는 단계와, 상기 모노머 혼합물 100 중량부 기준으로 비이온성 계면활성제 2.5 내지 6 중량부 및 라디칼 중합개시 촉매 0.1 내지 1 중량부를 혼합하여 부가중합 혼합물을 제조하는 단계와, 상기 부가중합 혼합물에 상기 모노머 혼합물을 적하 에멀젼 중합 반응시켜 에멀젼 중합반응물을 형성하는 단계와, PH 조절제를 이용하여 상기 에멀젼 중합 반응물의 PH를 6 내지 9으로 조절하는 단계를 수행함으로서 수득될 수 있다. The nonionic acrylic emulsion resin to be applied to the cationic antimicrobial coating material according to the present invention comprises 30 to 60 parts by weight of an acrylate monomer, From 20 to 50 parts by weight of an aromatic vinyl monomer, and from 0.1 to 3 parts by weight of an organic acid monomer; mixing 2.5 to 6 parts by weight of a nonionic surfactant with 100 parts by weight of the monomer mixture, 0.1 to 1 part by weight of an emulsion polymerization initiator to prepare an addition polymerization mixture; dropwise emulsion polymerization of the monomer mixture to form an emulsion polymerization reaction product; Lt; / RTI > to 6-9.
상기 비이온성 아크릴 에멀젼 수지의 구체적인 제조방법은 아래와 같다. 먼저, 아크릴산 에스테르계 모노머 30 내지 60 중량부, 방향족 비닐계 모노머 20 내지 50 중량부 및 유기산계 모노머 0.1 내지 3 중량부를 혼합하여 모노머 혼합물을 제조한다. A specific method for producing the nonionic acrylic emulsion resin is as follows. First, 30 to 60 parts by weight of an acrylic ester monomer, 20 to 50 parts by weight of an aromatic vinyl monomer, and 0.1 to 3 parts by weight of an organic acid monomer are mixed to prepare a monomer mixture.
상기 비이온성 아크릴 에멀젼 수지의 제조시 적용되는 상기 아크릴산 에스테르계 모노머의 예로서는 에틸메타크릴레이트, 메틸메타크릴레이트, 노르말부틸메타크릴레이트,이소프로필메타크릴레이트, 이소부틸메타크릴레이트,라우릴메타크릴레이트, 스테아릴메타크릴레이트, 부틸아크릴레이트, 베타-히드록시부틸메타크릴레이트,디(에틸렌클리콜)모노메타크릴레이트 등을 들 수 있다. 이들은 단독 또는 둘 이상을 혼합하여 사용할 수 있다.Examples of the acrylate monomer to be used in the preparation of the nonionic acrylic emulsion resin include ethyl methacrylate, methyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, lauryl methacrylate Butyl acrylate, beta-hydroxybutyl methacrylate, di (ethylene glycol) monomethacrylate, and the like. These may be used singly or in a mixture of two or more.
상기 아크릴산 에스테르계 모노머의 사용량이 전체 모노머 총중량 100 중량부에 대하여 30 중량부 미만이면, 요구하는 부착성 등의 물성을 갖는 비이온성 아크릴 에멀젼 수지를 얻기 어렵다. 상기 아크릴산 에스테르계 모노머의 사용량이 전체 모노머 총중량 100 중량부에 대하여 60 중량부를 초과하면 양이온 항균 도료로 형성되는 도막의 경도가 떨어진다. 따라서 상기 아크릴산 에스테르계 모노머는 전체 모노머 총량인 100 중량부 기준으로 30 내지 60 중량부 범위 내에서 사용하는 것이 바람직하고, 35 내지 50 중량부 범위 내에서 사용하는 것이 보다 바람직하다.When the amount of the acrylic ester monomer is less than 30 parts by weight based on 100 parts by weight of the total monomer, it is difficult to obtain a nonionic acrylic emulsion resin having desired physical properties such as adhesiveness. When the amount of the acrylate monomer is more than 60 parts by weight based on 100 parts by weight of the total monomer, the hardness of the coating film formed of the cationic antimicrobial coating drops. Accordingly, the acrylate monomer is preferably used in an amount of 30 to 60 parts by weight, more preferably 35 to 50 parts by weight, based on 100 parts by weight of the total amount of all monomers.
상기 비이온성 아크릴 에멀젼 수지의 제조시 적용되는 방향족 비닐계 모노머의 예로서는 스틸렌, α-메틸스티렌, 트랜스- β-메틸스티렌, β-메틸스티렌, 4-메틸스티렌 등을 들 수 있다. 이들은 단독 또는 둘 이상을 혼합하여 사용할 수 있다.Examples of the aromatic vinyl-based monomer to be used in the production of the nonionic acrylic emulsion resin include styrene,? -Methylstyrene, trans-? -Methylstyrene,? -Methylstyrene, and 4-methylstyrene. These may be used singly or in a mixture of two or more.
상기 방향족 비닐계 모노머의 사용량이 전체 모노머 총 중량인 100중량부 기준으로 20 중량부 미만이면, 양이온 항균 도료에서 요구되는 경도의 도막을 형성하기 위한 수지를 얻기 어렵고, 상기 방향족 비닐계 모노머의 사용량이 전체 모노머 총량 100중량부에 대하여 50중량부를 초과하면, 최종 형성되는 도막의 내후성이 매우 취약해지는 문제점이 있다. 따라서 상기 방향족 비닐계 모노머는 전체 모노머 총량인 100 중량부 기준으로 20 내지 50중량부 범위 내에서 사용하는 것이 바람직하다. If the amount of the aromatic vinyl-based monomer is less than 20 parts by weight based on 100 parts by weight of the total weight of the total monomers, it is difficult to obtain a resin for forming a coating film having the hardness required in the cationic antimicrobial coating, and the amount of the aromatic vinyl- If the amount exceeds 50 parts by weight based on 100 parts by weight of the total amount of the total monomers, there is a problem that weather resistance of the final formed coating film becomes very weak. Accordingly, the aromatic vinyl-based monomer is preferably used in an amount of 20 to 50 parts by weight based on 100 parts by weight of the total amount of all monomers.
상기 비이온성 아크릴 에멀젼 수지의 제조시 적용되는 유기산계 모노머의 예로서는 아크릴산, 메타크릴산, 푸마르산, 말레산, 이타콘산 등을 들 수 있다. 이들은 단독으로 또는 두개 이상을 혼합하여 사용할 수 있다.Examples of the organic acid-based monomer to be used in the production of the nonionic acrylic emulsion resin include acrylic acid, methacrylic acid, fumaric acid, maleic acid and itaconic acid. These may be used alone or in combination of two or more.
상기 유기산계 모노머의 사용량이 전체 모노머 총중량인 100중량부 기준에 대하여 0.1중량부 미만이면 에멀젼화가 균일하게 일어나지 않고, 비이온성 아크릴 에멀젼 수지의 냉동안정성 및 부착성이 떨어지는 문제점이 초래된다. If the amount of the organic acid-based monomer is less than 0.1 part by weight based on 100 parts by weight of the total monomer weight, emulsification does not occur uniformly, and the stability and adherence of the nonionic acrylic emulsion resin are deteriorated.
이에 반해 상기 유기산계 모노머의 사용량이 전체 모노머 총 중량 100 중량부에 대하여 3중량부를 초과이면 PH 중화 공정시 수지의 점도 상승 및 내수성이 떨어지는 문제점이 있다. 따라서 상기의 유기산계 모노머는 모노머 총량인 100중량부 기준으로 0.1 내지 3중량부 범위 내에서 사용하는 것이 바람직하다. On the other hand, if the amount of the organic acid-based monomer is more than 3 parts by weight based on 100 parts by weight of the total weight of the total monomers, there is a problem that the viscosity of the resin increases and the water resistance thereof deteriorates during the PH neutralization step. Therefore, the organic acid-based monomer is preferably used in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the total amount of monomers.
일 예로서, 상기 모노머 혼합물 제조시 점도 조절 및 보다 균일한 교반을 수행하기 위해 탈이온수를 적용할 수 있다. 이때 탈이온수는 모노머 혼합물의 20 내지 50중량% 범위 내에서 혼합하여 사용하는 것이 바람직하다.As an example, deionized water may be applied to adjust viscosity and more uniform agitation during the preparation of the monomer mixture. Preferably, the deionized water is used in the range of 20 to 50% by weight of the monomer mixture.
이어서, 상기 방법에 따라 제조된 모노머 혼합물에 적용되는 전체 모노머 100 중량부를 기준으로 비이온성 계면활성제 2.5 내지 6 중량부 및 라디칼 중합 개시촉매 0.1 내지 1 중량부를 혼합하여 부가 중합 혼합물을 제조한다.Next, 2.5 to 6 parts by weight of a nonionic surfactant and 0.1 to 1 part by weight of a radical polymerization initiating catalyst are mixed with 100 parts by weight of the total monomer applied to the monomer mixture prepared according to the above method to prepare an addition polymerization mixture.
상기 부가 중합 혼합물 제조시에 사용되는 비이온성 계면활성제의 예로는 폴리옥시에틸렌노닐페닐에테르, 폴리옥시에칠렌옥틸페닐에텔, 폴리옥시에틸렌알킬에테르, 폴리옥시에틸렌알킬에스테르, 폴리옥시에틸렌알킬아민에테르, 폴리옥시에틸렌폴리옥시프로필렌, 폴리에틸렌글리콜, 소르비탄지방산에스테르 등을 들 수 있다. Examples of the nonionic surfactant used in preparing the addition polymerization mixture include polyoxyethylene nonylphenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine ether, poly Oxyethylene polyoxypropylene, polyethylene glycol, and sorbitan fatty acid esters.
상기 부가 중합 혼합물의 제조시 사용되는 비이온성 계면활성제가 2.5 중량부 미만이면 입자가 불안정하여 도료 적용시 저장성 및 내수성에 문제점이 초래된다. 반면에 상기 비이온성 계면활성제의 사용량이 6중량부를 초과하면 점도 상승으로 도료 적용시 작업성에 문제점이 초래된다. 따라서 상기 비이온성 계면활성제는 2.5 내기 6중량부 범위 내에서 사용하는 것이 바람직하다.If the amount of the nonionic surfactant used in the preparation of the addition polymerization mixture is less than 2.5 parts by weight, the particles may be unstable, resulting in problems of storage stability and water resistance when the coating material is applied. On the other hand, when the amount of the nonionic surfactant is more than 6 parts by weight, the viscosity of the nonionic surfactant is increased, resulting in problems in workability when applying the coating material. Therefore, the nonionic surfactant is preferably used within the range of 2.5 to 6 parts by weight.
특히 본 발명에서 비이온성 계면활성제가 아닌 소듐도데실벤젠설포네이트 등과 같은 음이온성 계면활성제를 사용할 경우 양이온 향균제 적용시 도료가 겔화되어 항균도료서 사용이 어려운 문제점이 발생된다.In particular, when an anionic surfactant such as sodium dodecylbenzenesulfonate is used as a non-ionic surfactant in the present invention, the application of the cationic antibacterial agent causes gelation of the coating, which makes it difficult to use the antibacterial coating agent.
상기 부가 중합 혼합물의 제조시에 사용되는 라디칼 중합 개시 촉매의 예로서는 암모늄퍼설페이트, 소디움퍼설페이트, 포다슘퍼설페이트 등을 들 수 있다. 상기 라디칼 중합 개시 촉매의 사용량이 0.1 이하 이거나, 1 중량부를 초과하면 반응성 및 분자량 크기면에서 바람직하지 않다.Examples of the radical polymerization initiation catalyst used in the preparation of the addition polymerization mixture include ammonium persulfate, sodium persulfate, and pseudosulfur sulfate. If the amount of the radical polymerization initiator used is less than 0.1 or more than 1 part by weight, it is not preferable in terms of reactivity and molecular weight.
본 발명의 일 실시예에 있어서, 상기 부가 중합 혼합물은 모노머 혼합물과 유사한 pH를 갖도록 버퍼용액에 혼합하여 사용할 수 있다. In one embodiment of the present invention, the addition polymerization mixture may be mixed with the buffer solution so as to have a pH similar to that of the monomer mixture.
이어서, 상기 부가중합 혼합물에 상기 모노머 혼합물을 적하 에멀젼 중합 반응시켜 에멀젼 중합반응물을 형성한다. Then, the monomer mixture is subjected to dropwise emulsion polymerization reaction with the addition polymerization mixture to form an emulsion polymerization reaction product.
이어서 상기 중합반응물의 PH를 6 내지 9로 조절하여 비이온성 아크릴 에멀젼 수지를 수득한다. 상기 부가 중합 혼합물의 PH조절은 PH 조절제를 이용하여 수행한다. 상기 PH 조절제의 예로는 암모니아수, 모노에탄올아민, 디에탄올아민, 트리에탄올아민, 1-아미노-2메틸프로판, 2-아미노-2-메틸프로판, 트리에틸아민 등을 들 수 있다. 이 중에서 특히 바람직한 것은 2-아미노-2-메틸프로판이다. Subsequently, the PH of the polymerization reaction product is adjusted to 6 to 9 to obtain a nonionic acrylic emulsion resin. The PH adjustment of the addition polymerization mixture is carried out using a PH modifier. Examples of the pH adjuster include ammonia water, monoethanolamine, diethanolamine, triethanolamine, 1-amino-2-methylpropane, 2-amino-2-methylpropane and triethylamine. Of these, 2-amino-2-methylpropane is particularly preferable.
상기 PH조절제의 사용량은 부가 중합 혼합물 100 중량부에 대하여 0.5 내지 4중량부 범위 내에서 사용하는 것이 바람직하. 이때. PH를 6미만으로 조정하여 비이온성 아크릴 에멀젼 수지를 제조할 경우 저장 중에 점도상승 및 증점제와 상용성 낮아지는 문제점이 초래된다. 이와 반대로 PH를 9 이상으로 조정하여 비이온성 아크릴 에멀젼 수지를 제조할 경우 양이온 항균제와의 상용성 낮아지는 문제점이 초래된다. 따라서, 부가 중합 혼합물의 PH조절은 PH를 6 내지 9 범위 내에서 조절하는 것이 바람직하다.The amount of the PH modifier to be used is preferably in the range of 0.5 to 4 parts by weight based on 100 parts by weight of the addition polymerization mixture. At this time. When the nonionic acrylic emulsion resin is prepared by adjusting the pH to less than 6, there arises a problem that viscosity increases during storage and compatibility with a thickener is lowered. On the other hand, when the nonionic emulsion resin is prepared by adjusting the pH to 9 or more, the compatibility with the cationic antimicrobial agent is lowered. Therefore, it is preferable that the PH of the addition polymerization mixture is controlled within the range of 6 to 9 PH.
상술한 방법을 통해 수득되는 비이온성 아크릴 에멀젼 수지는 -5 내지 10℃의 유리전이 온도를 갖는 것이 바람직하다. 상기 비이온성 아크릴 에멀젼 수지의 유리전이온도가 -5℃미만이면, 건조된 도막에 끈적임이 있으며, 내수성이 불량해진지는 문제점이 발생된다. 이에 반해 상기 비이온성 아크릴 에멀젼 수지의 유리전이온도가 10℃를 초과하면 필름 형성 능력이 불량해져 균일한 도막을 형성할 수 없는 문제점이 초래된다. 또한 균일한 도막을 내기 위해 조막 조제를 적용할 경우 이의 사용량이 증가하여 환경적으로 부적한 문제점을 갖는다. The nonionic acrylic emulsion resin obtained through the above-described method preferably has a glass transition temperature of -5 to 10 캜. If the glass transition temperature of the nonionic acrylic emulsion resin is less than -5 ° C, there is a problem that the dried coating film is sticky and poor in water resistance. On the other hand, when the glass transition temperature of the nonionic acrylic emulsion resin exceeds 10 캜, the film forming ability becomes poor and a uniform coating film can not be formed. In addition, when a coarse coating composition is applied to produce a uniform coating film, the use amount of the coarse coating composition increases, which is environmentally unfavorable.
상술한 방법에 의해 수득한 비이온성 아크릴 에멀젼 수지는 양이온성 항균 도료를 제조하는데 적용되는 바인더로 사용된다. 즉, 비이온성 아크릴 에멀젼 수지는 기존 음이온성 항균제보다 살균 지속성이 우수한 양이온성 항균제와의 우수한 상용성 가짐으로 인해 양이온성 항균 수성 도료에 적용가능하다.The nonionic acrylic emulsion resin obtained by the above-mentioned method is used as a binder to be used for producing a cationic antimicrobial coating. That is, the nonionic acrylic emulsion resin is applicable to cationic antibacterial water-based paints because of its excellent compatibility with cationic antimicrobial agents having superior sterilization persistence than conventional anionic antibacterial agents.
양이온성Cationic 항균 도료 Antimicrobial coating
본 발명의 일 실시예에 따른 양이온성 항균 도료는 상기에서 수득된 비이온성 아크릴 에멀젼 수지 비이온성 아크릴 에멀젼 수지 30 내지 60중량%, 양이온 항균제 0.5 내지 3중량%, 실리카 입자 10 내지 30중량%, 첨가제 2 내지 4 중량% 및 여분의 탈이온수를 포함한다.The cationic antimicrobial coating material according to one embodiment of the present invention may further comprise 30 to 60% by weight of the nonionic acrylic emulsion resin nonionic acrylic emulsion resin obtained above, 0.5 to 3% by weight of cationic antimicrobial agent, 10 to 30% by weight of silica particles, 2 to 4 wt% and extra deionized water.
상기 비이온성 아크릴 에멀젼 수지의 양이 30중량% 미만이면 피도물과의 부착성, 건조도막의 내수성이 불량해 진다. 상기 비이온성 아크릴 에멀젼 수지의 양이 60중량%를 초과이면, 은폐력이 감소되고, 항균성이 불량해진다. 따라서 상기 양이온성 항균 도료는 30 내지 60중량%의 비이온성 아크릴 에멀젼 수지를 포함하는 것이 바람직하다.If the amount of the nonionic acrylic emulsion resin is less than 30% by weight, the adhesion to the substrate and the water resistance of the dried coating film become poor. If the amount of the nonionic acrylic emulsion resin is more than 60% by weight, the hiding power is reduced and the antibacterial property becomes poor. Accordingly, the cationic antimicrobial coating preferably comprises 30 to 60% by weight of a nonionic acrylic emulsion resin.
상기 양이온성 항균 도료에서 양이온 항균제의 함량이 0.5 중량% 미만이면 살균 효과와 지속성이 떨어지는 문제점이 있고, 반면에 상기 양이온 항균제 함량이 3 중량%를 초과하면 저장성 및 도료 칙소성 증가로 작업성이 불량해진다. 따라서 상기 양이온성 항균 도료는 0.5 내지 3중량%의 양이온 항균제를 포함하는 것이 바람직하다.If the amount of the cationic antimicrobial agent in the cationic antimicrobial coating is less than 0.5% by weight, the sterilizing effect and the durability of the cationic antibacterial agent are poor. On the other hand, if the amount of the cationic antibacterial agent exceeds 3% by weight, It becomes. Accordingly, the cationic antimicrobial coating preferably contains 0.5 to 3% by weight of the cationic antimicrobial agent.
상기 양이온성 항균 도료에서 실리카 입자의 함량이 10중량% 미만이면 피도물과의 건조 도막의 내마모성, 내수성이 떨어지고, 30중량%를 초과이면 실리카의 응집현상이 발생하여 외관 불량 및 부착성 불량 현성이 발생하며 저장중 양이온성 항균 도료 내에서 실리카 침전 등이 발생할 수 있다. 이때 적용되는 실리카 입자는 150 내지 325 메쉬의 입자크기를 갖는 것이 바람직하다.If the content of the silica particles in the cationic antimicrobial coating is less than 10% by weight, the abrasion resistance and water resistance of the dried coating film with the substrate deteriorate. When the content of the silica particles exceeds 30% by weight, the aggregation phenomenon of silica occurs, And silica precipitation may occur in the cationic antimicrobial coating during storage. It is preferable that the silica particles to be applied have a particle size of 150 to 325 mesh.
상기 수성 도료 조성물은 분산제, 조막제, 소포제 및 증점제 등과 같은 첨가제를 2 내지 4중량%를 포함할 수 있다. The aqueous coating composition may contain 2 to 4% by weight of an additive such as a dispersing agent, a film forming agent, a defoaming agent, and a thickener.
상기 분산제는 도막의 내수성, 부착성과 도료의 저장성 및 안료, 충진제 등과의 분산 안정성을 확보한다. 상기 분산제의 예로는 모노인산에스테르 분산제, 폴리인상에스테르 분산제, 변성 실리콘계 분산제 등을 들 수 있다. 분산 안정성 면에서 변성 실리콘계 분산제가 가장 바람직하다.The dispersant secures the water resistance of the coating film, the adhesion, the storage stability of the coating material, and the dispersion stability with the pigment, the filler and the like. Examples of the dispersant include a monophosphate ester dispersant, a polyphthalate ester dispersant, and a modified silicone dispersant. The modified silicone dispersant is most preferable in terms of dispersion stability.
또한, 본 발명의 양이온성 항균 도료는 타일 보수제로 사용하기 위해 백색안료가 추가적으로 적용될 수 있다. 상기 백색안료의 예로서는 이산화티탄, 산화아연 등을 들 수 있다. In addition, the cationic antimicrobial coatings of the present invention may additionally include white pigments for use as tile repair agents. Examples of the white pigment include titanium dioxide and zinc oxide.
상기 비이온성 아크릴 에멀젼 수지를 포함하는 양이온성 항균 도료는 부착성, 내수성 우수할 뿐만 아니라 살균 지속성이 우수한 양이온성 항균제를 적용하여도 겔화 현상이 발생하지 않을 뿐만 아니라 음이온성 항균제를 포함하는 항균 도료에 비해 보다 우수한 항균성을 갖는다. The cationic antimicrobial coating material containing the nonionic acrylic emulsion resin is excellent in adhesion and water resistance, and is free from gelation even when a cationic antimicrobial agent excellent in persistence of sterilization is applied. In addition, the cationic antimicrobial coating material containing anionic antibacterial agent And has more excellent antimicrobial activity.
이하, 본 발명을 구체적인 실시예를 통하여 상세히 설명하기로 한다. 단, 본 발명이 이에 한정되는 것은 아니다. Hereinafter, the present invention will be described in detail with reference to specific examples. However, the present invention is not limited thereto.
합성예 1Synthesis Example 1
5ℓ4구 유리제 플라스크에 온도계, 콘덴서, 교반기, 승온 장치를 부착하였다. 탈이온수 410g 수용된 플라스크 용기에 스틸렌 420g, 부틸아크릴레이트 470g, 아크릴산 9.4g을 넣고 교반하여 모노머 혼합물을 제조하였다. 탈이온수 964와 암모늄비카보네이트 2.6g 혼합하여 형성된 버퍼용액이 수용된 플라스크에 비이온계면활성제인 폴리옥시에틸렌알킬에테르 45g 포다슘퍼설페이트 3.5g을 투입하여 부가중합 혼합물을 제조하였다. 상기 모노머 혼합물의 일부(26g)을 부가중합 혼합물이 수용된 플라스크에 투입하여 시드(Seed)폴리머를 합성한 후 남은 모노머 혼합물을 3시간 동안 균일하게 플라스크에 적하 반응시켜 에멀젼 중합반응물을 합성하였다. 이후, 합성된 에멀젼 중합반응물에 PH조절제인 2-아미노-2-메틸프로판 8.2g을 투입하여 반응물의 PH를 7.5로 조절하였다. 이렇게 합성된 비이온성 아크릴 에멀젼 수지의 불휘발분은 36.5%, 점도는 50cps, 유리전이온도는 0℃였다.A thermometer, a condenser, a stirrer, and a temperature raising device were attached to a 5-liter four-necked glass flask. 420 g of styrene, 470 g of butyl acrylate and 9.4 g of acrylic acid were placed in a flask vessel containing 410 g of deionized water and stirred to prepare a monomer mixture. To the flask containing the buffer solution formed by mixing deionized water 964 and 2.6 g of ammonium bicarbonate, 45 g of polyoxyethylene alkyl ether, nonionic surfactant, 3.5 g of pseudosulfate was added to prepare an addition polymerization mixture. A part of the monomer mixture (26 g) was added to a flask containing the addition polymerization mixture to synthesize a seed polymer. The remaining monomer mixture was added dropwise to the flask for 3 hours to prepare an emulsion polymerization reaction product. Then, 8.2 g of 2-amino-2-methylpropane as a pH regulator was added to the synthesized emulsion polymerization reaction product to adjust the PH of the reaction product to 7.5. The non-volatile fraction of the synthesized nonionic acrylic emulsion resin was 36.5%, the viscosity was 50 cps, and the glass transition temperature was 0 占 폚.
합성예 2Synthesis Example 2
5ℓ4구 유리제 플라스크에 온도계, 콘덴서, 교반기, 승온 장치를 부착하였다. 탈이온수 410g 수용된 플라스크 용기에 스틸렌 420g, 부틸아크릴레이트 470g, 아크릴산 9.4g을 넣고 교반하여 모노머 혼합물을 제조하였다. 탈이온수 964와 암모늄비카보네이트 2.6g 혼합하여 형성된 버퍼용액이 수용된 플라스크에 비이온계면활성제인 폴리옥시에틸렌알킬에테르 49.7g 포다슘퍼설페이트 3.5g을 투입하여 부가중합 혼합물을 제조하였다. 상기 모노머 혼합물의 일부(26g)을 부가중합 혼합물이 수용된 플라스크에 투입하여 시드(Seed)폴리머를 합성한 후 남은 모노머 혼합물을 3시간 동안 균일하게 플라스크에 적하 반응시켜 에멀젼 중합반응물을 합성하였다. 이후, 합성된 에멀젼 중합반응물에 PH조절제인 2-아미노-2-메틸프로판 8.2g을 투입하여 반응물의 PH를 7.5로 조절하였다. 이렇게 합성된 비이온성 아크릴 에멀젼 수지의 불휘발분은 36.5%, 점도는 80cps, 유리전이온도는 0℃였다.A thermometer, a condenser, a stirrer, and a temperature raising device were attached to a 5-liter four-necked glass flask. 420 g of styrene, 470 g of butyl acrylate and 9.4 g of acrylic acid were placed in a flask vessel containing 410 g of deionized water and stirred to prepare a monomer mixture. An addition polymerization mixture was prepared by adding 49.7 g of polyoxyethylene alkyl ether, non-ionic surfactant, 3.5 g of pseudocumpersulfate to a flask containing a buffer solution formed by mixing deionized water 964 and 2.6 g of ammonium bicarbonate. A part of the monomer mixture (26 g) was added to a flask containing the addition polymerization mixture to synthesize a seed polymer. The remaining monomer mixture was added dropwise to the flask for 3 hours to prepare an emulsion polymerization reaction product. Then, 8.2 g of 2-amino-2-methylpropane as a pH regulator was added to the synthesized emulsion polymerization reaction product to adjust the PH of the reaction product to 7.5. The non-volatile fraction of the nonionic acrylic emulsion resin thus synthesized was 36.5%, the viscosity was 80 cps, and the glass transition temperature was 0 占 폚.
비교 합성예 1Comparative Synthesis Example 1
5ℓ4구 유리제 플라스크에 온도계, 콘덴서, 교반기, 승온 장치를 부착하였다. 탈이온수 410g 수용된 플라스크 용기에 스틸렌 420g, 부틸아크릴레이트 470g, 아크릴산 9.4g을 넣고 교반하여 모노머 혼합물을 제조하였다. 탈이온수 964와 암모늄비카보네이트 2.6g 혼합하여 형성된 버퍼용액이 수용된 플라스크에 비이온계면활성제인 폴리옥시에틸렌알킬에테르 20g 포다슘퍼설페이트 3.5g을 투입하여 부가중합 혼합물을 제조하였다. 상기 모노머 혼합물의 일부(26g)을 부가중합 혼합물이 수용된 플라스크에 투입하여 시드(Seed)폴리머를 합성한 후 남은 모노머 혼합물을 3시간 동안 균일하게 플라스크에 적하 반응시켜 에멀젼 중합반응물을 합성하였다. 이후, 합성된 에멀젼 중합반응물에 PH조절제인 2-아미노-2-메틸프로판 8.2g을 투입하여 반응물의 PH를 7.5로 조절하였다. 이렇게 합성된 비이온성 아크릴 에멀젼 수지의 불휘발분은 36.5%, 점도는 20cps, 유리전이온도는 0℃였다.A thermometer, a condenser, a stirrer, and a temperature raising device were attached to a 5-liter four-necked glass flask. 420 g of styrene, 470 g of butyl acrylate and 9.4 g of acrylic acid were placed in a flask vessel containing 410 g of deionized water and stirred to prepare a monomer mixture. An additional polymerization mixture was prepared by adding 20 g of polyoxyethylene alkyl ether (nonionic surfactant) and 3.5 g of pseudosulfate to a flask containing a buffer solution formed by mixing deionized water 964 and 2.6 g of ammonium bicarbonate. A part of the monomer mixture (26 g) was added to a flask containing the addition polymerization mixture to synthesize a seed polymer. The remaining monomer mixture was added dropwise to the flask for 3 hours to prepare an emulsion polymerization reaction product. Then, 8.2 g of 2-amino-2-methylpropane as a pH regulator was added to the synthesized emulsion polymerization reaction product to adjust the PH of the reaction product to 7.5. The non-volatile fraction of the synthesized nonionic acrylic emulsion resin was 36.5%, the viscosity was 20 cps, and the glass transition temperature was 0 占 폚.
<비교 합성예 2>≪ Comparative Synthesis Example 2 &
5ℓ4구 유리제 플라스크에 온도계, 콘덴서, 교반기, 승온 장치를 부착하였다. 탈이온수 410g 수용된 플라스크 용기에 스틸렌 420g, 부틸아크릴레이트 470g, 아크릴산 9.4g을 넣고 교반하여 모노머 혼합물을 제조하였다. 탈이온수 964와 암모늄비카보네이트 2.6g 혼합하여 형성된 버퍼용액이 수용된 플라스크에 비이온계면활성제인 폴리옥시에틸렌알킬에테르 67g 포다슘퍼설페이트 3.5g을 투입하여 부가중합 혼합물을 제조하였다. 상기 모노머 혼합물의 일부(26g)을 부가중합 혼합물이 수용된 플라스크에 투입하여 시드(Seed)폴리머를 합성한 후 남은 모노머 혼합물을 3시간 동안 균일하게 플라스크에 적하 반응시켜 에멀젼 중합반응물을 합성하였다. 이후, 합성된 에멀젼 중합반응물에 PH조절제인 2-아미노-2-메틸프로판 8.2g을 투입하여 반응물의 PH를 7.5로 조절하였다. 이렇게 합성된 비이온성 아크릴 에멀젼 수지의 불휘발분은 36.5%, 점도는 850cps, 유리전이온도는 0℃였다.A thermometer, a condenser, a stirrer, and a temperature raising device were attached to a 5-liter four-necked glass flask. 420 g of styrene, 470 g of butyl acrylate and 9.4 g of acrylic acid were placed in a flask vessel containing 410 g of deionized water and stirred to prepare a monomer mixture. An additional polymerization mixture was prepared by adding 67 g of polyoxyethylene alkyl ether, non-ionic surfactant, and 3.5 g of pseudosumper sulfate to a flask containing a buffer solution formed by mixing deionized water 964 and 2.6 g of ammonium bicarbonate. A part of the monomer mixture (26 g) was added to a flask containing the addition polymerization mixture to synthesize a seed polymer. The remaining monomer mixture was added dropwise to the flask for 3 hours to prepare an emulsion polymerization reaction product. Then, 8.2 g of 2-amino-2-methylpropane as a pH regulator was added to the synthesized emulsion polymerization reaction product to adjust the PH of the reaction product to 7.5. The non-volatile fraction of the nonionic acrylic emulsion resin thus synthesized was 36.5%, the viscosity was 850 cps, and the glass transition temperature was 0 占 폚.
<비교 합성예 3>≪ Comparative Synthesis Example 3 >
5ℓ4구 유리제 플라스크에 온도계, 콘덴서, 교반기, 승온 장치를 부착하였다. 탈이온수 410g 수용된 플라스크 용기에 스틸렌 420g, 부틸아크릴레이트 470g, 아크릴산 9.4g을 넣고 교반하여 모노머 혼합물을 제조하였다. 탈이온수 964와 암모늄비카보네이트 2.6g 혼합하여 형성된 버퍼용액이 수용된 플라스크에 음이온계면활성제 소듐알킬디페닐옥사이드설포네이트 32g 포다슘퍼설페이트 3.5g을 투입하여 부가중합 혼합물을 제조하였다. 상기 모노머 혼합물의 일부(26g)을 부가중합 혼합물이 수용된 플라스크에 투입하여 시드(Seed)폴리머를 합성한 후 남은 모노머 혼합물을 3시간 동안 균일하게 플라스크에 적하 반응시켜 에멀젼 중합반응물을 합성하였다. 이후, 합성된 에멀젼 중합반응물에 PH조절제인 2-아미노-2-메틸프로판 8.2g을 투입하여 반응물의 PH를 7.5로 조절하였다. 이렇게 합성된 음이온성 아크릴 에멀젼 수지의 불휘발분은 35.2%, 점도는 100cps, 유리전이온도는 0℃였다A thermometer, a condenser, a stirrer, and a temperature raising device were attached to a 5-liter four-necked glass flask. 420 g of styrene, 470 g of butyl acrylate and 9.4 g of acrylic acid were placed in a flask vessel containing 410 g of deionized water and stirred to prepare a monomer mixture. To a flask containing a buffer solution formed by mixing deionized water 964 and 2.6 g of ammonium bicarbonate, 32 g of an anionic surfactant sodium alkyldiphenyl oxide sulfonate and 3.5 g of pseudosulfate were added to prepare an addition polymerization mixture. A part of the monomer mixture (26 g) was added to a flask containing the addition polymerization mixture to synthesize a seed polymer. The remaining monomer mixture was added dropwise to the flask for 3 hours to prepare an emulsion polymerization reaction product. Then, 8.2 g of 2-amino-2-methylpropane as a pH regulator was added to the synthesized emulsion polymerization reaction product to adjust the PH of the reaction product to 7.5. The nonvolatile fraction of the anionic acrylic emulsion resin thus synthesized was 35.2%, the viscosity was 100 cps, and the glass transition temperature was 0 占 폚
아크릴 에멀젼 수지의 특성 평가Characterization of acrylic emulsion resin
상기 각 합성예 및 비교 합성예에서 수득한 아크릴 에멀젼 수지를 도료화한 후, 도막의 특성을 알아보기 위하여 합성예 1 내지 2 및 비교 합성예 1 내지 3에서 수득한 아크릴 에멀젼 수지를 이용하여 양이온성 항균 도료(실시예 1 내지 2 및 비교예 1 내지 3)을 제조하였다. 하기 표 1에 타일 보수용 양이온성 항균 도료의 조성비를 나타내었다. The acrylic emulsion resin obtained in each of the above Synthesis Examples and Comparative Synthetic Examples was applied as a coating material, and then the properties of the coating film were evaluated. The acrylic emulsion resin obtained in Synthesis Examples 1 to 2 and Comparative Synthesis Examples 1 to 3 was used for cationic Antibacterial paints (Examples 1 to 2 and Comparative Examples 1 to 3) were prepared. The composition ratios of cationic antimicrobial coatings for tile repair are shown in Table 1 below.
(1) 방부제: (주) 선경의 B-95(1) Preservative: Sunkyung B-95
(2) 분산제 : 독일 degussa.의 TEGO Dispers 735W (2) Dispersing agent: TEGO Dispers 735W of Germany degussa.
(3) 소포제: 독일 BYK-Chemie GmbH사의 BYK-024(3) Defoamer: BYK-024 from BYK-Chemie GmbH, Germany
(4) 조막제: Eastman Chemical Company의 Texanol(4) Coating agent: Texanol from Eastman Chemical Company
(5) 증점제: U.C.C.의 ER-4400(5) Thickener: ER-4400 from U.C.C.
상기 표 1의 조성의 각각의 도료 조성물에 대해 주도(KU), 내수성, 내알카리성, 냉동안정성, 열안전성, 부착성, 항균제상용성, 작업성, 항균성을 평가하고, 그 결과를 하기 표 2에 나타내었다. Each coating composition of the composition shown in Table 1 was evaluated for KU, water resistance, alkali resistance, freezing stability, thermal stability, adhesion, compatibility with antibacterial agents, workability and antibacterial property, Respectively.
상기 표 2에서 알 수 있는 바와 같이, 실시예 1 내지 2에서 수득한 양이온 항균 도료는 비교예 들과 달리 높은 항균성을 가질 뿐 아니라 부착성, 내수성, 내알칼리성 등이 모두 우수한 것으로 확인되었다. As can be seen from the above Table 2, the cationic antimicrobial coatings obtained in Examples 1 and 2 were found to have not only high antimicrobial activity but also excellent adhesion, water resistance and alkali resistance.
Claims (8)
아크릴산 에스테르계 모노머 30 내지 60 중량부, 방향족 비닐계 모노머 20 내지 50 중량부, 유기산계 모노머 0.1 내지 3 중량부를 포함하는 모노머 혼합물을 제조하는 단계;
상기 모노머 혼합물 100 중량부 기준으로 비이온성 계면활성제 2.5 내지 6중량부 및 라디칼 중합개시 촉매 0.1 내지 1 중량부를 혼합하여 부가중합 혼합물을 제조하는 단계;
상기 부가중합 혼합물에 상기 모노머 혼합물을 적하 에멀젼 중합 반응시켜 에멀젼 중합반응물을 형성하는 단계; 및
PH조절제를 이용하여 상기 에멀젼 중합 반응물의 PH를 6 내지 9으로 조절하는 단계를 포함하는 비이온성 아크릴 에멀젼 수지의 제조방법. In the resin to be applied to the cationic antimicrobial coating,
30 to 60 parts by weight of an acrylic ester monomer, 20 to 50 parts by weight of an aromatic vinyl-based monomer, and 0.1 to 3 parts by weight of an organic acid-based monomer;
Mixing 2.5 to 6 parts by weight of a nonionic surfactant and 0.1 to 1 part by weight of a radical polymerization initiating catalyst based on 100 parts by weight of the monomer mixture to produce an addition polymerization mixture;
Subjecting the addition polymerization mixture to a dropwise emulsion polymerization reaction of the monomer mixture to form an emulsion polymerization reaction product; And
And adjusting the pH of the emulsion polymerization reaction to 6 to 9 using a pH adjusting agent.
비이온성 아크릴 에멀젼 수지는 아크릴산 에스테르계 모노머 30 내지 60 중량부, 방향족 비닐계 모노머 20 내지 50 중량부, 유기산계 모노머 0.1 내지 3중량부를 포함하는 모노머 혼합물을 제조하는 단계; 상기 모노머 혼합물 100 중량부 기준으로 비이온성 계면활성제 2.5 내지 6 중량부 및 라디칼 중합개시 촉매 0.1 내지 1중량부를 혼합하여 부가중합 혼합물을 제조하는 단계; 상기 부가중합 혼합물에 상기 모노머 혼합물을 적하 에멀젼 중합 반응시켜 에멀젼 중합반응물을 형성하는 단계; 및 PH조절제를 이용하여 상기 에멀젼 중합 반응물의 PH를 6 내지 9으로 조절하는 단계를 수행함으로서 형성되는 것을 특징으로 하는 양이온성 항균 도료.Characterized in that it comprises 30 to 60% by weight of a nonionic acrylic emulsion resin, 0.5 to 3% by weight of a cationic antimicrobial agent, 10 to 30% by weight of silica particles, 2 to 4% by weight of additives and extra deionized water,
The nonionic acrylic emulsion resin comprises 30 to 60 parts by weight of an acrylate monomer, 20 to 50 parts by weight of an aromatic vinyl-based monomer, and 0.1 to 3 parts by weight of an organic acid-based monomer; Mixing 2.5 to 6 parts by weight of a nonionic surfactant and 0.1 to 1 part by weight of a radical polymerization initiating catalyst based on 100 parts by weight of the monomer mixture to produce an addition polymerization mixture; Subjecting the addition polymerization mixture to a dropwise emulsion polymerization reaction of the monomer mixture to form an emulsion polymerization reaction product; And adjusting the PH of the emulsion polymerization reaction to 6 to 9 using a pH adjusting agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115850585A (en) * | 2023-01-04 | 2023-03-28 | 中化泉州石化有限公司 | Biquaternary ammonium salt grafted antibacterial polypropylene and preparation method thereof |
| WO2023101288A1 (en) * | 2021-11-30 | 2023-06-08 | 주식회사 포스코 | Method for preparing acrylic emulsion resin composition having antiviral and antibacterial effects and acrylic emulsion resin composition prepared thereby |
| CN119390913A (en) * | 2024-09-05 | 2025-02-07 | 中国石油天然气集团有限公司 | A high temperature and high salt resistance deformable strong support plugging agent and its preparation method and drilling fluid |
| CN119775500A (en) * | 2025-01-02 | 2025-04-08 | 万华化学集团股份有限公司 | Preparation method of acrylic emulsion with PH response antibacterial function |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023101288A1 (en) * | 2021-11-30 | 2023-06-08 | 주식회사 포스코 | Method for preparing acrylic emulsion resin composition having antiviral and antibacterial effects and acrylic emulsion resin composition prepared thereby |
| JP2024543881A (en) * | 2021-11-30 | 2024-11-26 | ポスコ カンパニー リミテッド | Method for producing acrylic emulsion resin composition having antiviral and antibacterial effects and acrylic emulsion resin composition produced by the same |
| CN115850585A (en) * | 2023-01-04 | 2023-03-28 | 中化泉州石化有限公司 | Biquaternary ammonium salt grafted antibacterial polypropylene and preparation method thereof |
| CN119390913A (en) * | 2024-09-05 | 2025-02-07 | 中国石油天然气集团有限公司 | A high temperature and high salt resistance deformable strong support plugging agent and its preparation method and drilling fluid |
| CN119775500A (en) * | 2025-01-02 | 2025-04-08 | 万华化学集团股份有限公司 | Preparation method of acrylic emulsion with PH response antibacterial function |
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