JPH0742436B2 - Method for producing aqueous coating film - Google Patents
Method for producing aqueous coating filmInfo
- Publication number
- JPH0742436B2 JPH0742436B2 JP60275036A JP27503685A JPH0742436B2 JP H0742436 B2 JPH0742436 B2 JP H0742436B2 JP 60275036 A JP60275036 A JP 60275036A JP 27503685 A JP27503685 A JP 27503685A JP H0742436 B2 JPH0742436 B2 JP H0742436B2
- Authority
- JP
- Japan
- Prior art keywords
- coating film
- water
- monomer
- polymerization
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000576 coating method Methods 0.000 title claims description 100
- 239000011248 coating agent Substances 0.000 title claims description 99
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000000178 monomer Substances 0.000 claims description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- 229920000642 polymer Polymers 0.000 claims description 49
- 239000002245 particle Substances 0.000 claims description 41
- 239000000839 emulsion Substances 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 30
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 49
- 239000000243 solution Substances 0.000 description 34
- 238000000034 method Methods 0.000 description 30
- WLPAQAXAZQUXBG-UHFFFAOYSA-N 1-pyrrolidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCC1 WLPAQAXAZQUXBG-UHFFFAOYSA-N 0.000 description 20
- 239000012153 distilled water Substances 0.000 description 20
- 239000011734 sodium Substances 0.000 description 18
- 230000008961 swelling Effects 0.000 description 16
- 150000003926 acrylamides Chemical class 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- RESPXSHDJQUNTN-UHFFFAOYSA-N 1-piperidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCCC1 RESPXSHDJQUNTN-UHFFFAOYSA-N 0.000 description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- -1 silica compound Chemical class 0.000 description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 7
- 239000004809 Teflon Substances 0.000 description 7
- 229920006362 Teflon® Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 3
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UGODCLHJOJPPHP-AZGWGOJFSA-J tetralithium;[(2r,3s,4r,5r)-5-(6-aminopurin-9-yl)-4-hydroxy-2-[[oxido(sulfonatooxy)phosphoryl]oxymethyl]oxolan-3-yl] phosphate;hydrate Chemical compound [Li+].[Li+].[Li+].[Li+].O.C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP([O-])(=O)OS([O-])(=O)=O)[C@@H](OP([O-])([O-])=O)[C@H]1O UGODCLHJOJPPHP-AZGWGOJFSA-J 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- RASDUGQQSMMINZ-UHFFFAOYSA-N 2-methyl-1-piperidin-1-ylprop-2-en-1-one Chemical compound CC(=C)C(=O)N1CCCCC1 RASDUGQQSMMINZ-UHFFFAOYSA-N 0.000 description 2
- LVCMKNCJDCTPIB-UHFFFAOYSA-N 2-methyl-1-pyrrolidin-1-ylprop-2-en-1-one Chemical compound CC(=C)C(=O)N1CCCC1 LVCMKNCJDCTPIB-UHFFFAOYSA-N 0.000 description 2
- NRVQUYCYEAKQIF-UHFFFAOYSA-N 2-phenyl-2-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound C=CC(=O)NC(CS(O)(=O)=O)(C)C1=CC=CC=C1 NRVQUYCYEAKQIF-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 235000013611 frozen food Nutrition 0.000 description 2
- 108010025899 gelatin film Proteins 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- HNKNCTHACSPOPO-UHFFFAOYSA-N 1-(azepan-1-yl)prop-2-en-1-one Chemical compound C=CC(=O)N1CCCCCC1 HNKNCTHACSPOPO-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-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
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- JNDVNJWCRZQGFQ-UHFFFAOYSA-N 2-methyl-N,N-bis(methylamino)hex-2-enamide Chemical compound CCCC=C(C)C(=O)N(NC)NC JNDVNJWCRZQGFQ-UHFFFAOYSA-N 0.000 description 1
- SXXWNCNXSWHLQO-UHFFFAOYSA-N 2-methyl-n,n-bis(oxiran-2-ylmethyl)prop-2-enamide Chemical compound C1OC1CN(C(=O)C(=C)C)CC1CO1 SXXWNCNXSWHLQO-UHFFFAOYSA-N 0.000 description 1
- BKMQIHWHYNMCNW-UHFFFAOYSA-N 2-methyl-n-[4-(oxiran-2-ylmethoxy)butyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCCCCOCC1CO1 BKMQIHWHYNMCNW-UHFFFAOYSA-N 0.000 description 1
- YQIGLEFUZMIVHU-UHFFFAOYSA-N 2-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C(C)=C YQIGLEFUZMIVHU-UHFFFAOYSA-N 0.000 description 1
- CCIDRBFZPRURMU-UHFFFAOYSA-N 2-methyl-n-propylprop-2-enamide Chemical compound CCCNC(=O)C(C)=C CCIDRBFZPRURMU-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- GCCYYQQSMJMZSV-UHFFFAOYSA-N 4-hydroxy-N-prop-2-enoylbut-2-enamide Chemical compound OCC=CC(=O)NC(C=C)=O GCCYYQQSMJMZSV-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 241001370313 Alepes vari Species 0.000 description 1
- BLQBZHOHSZPHKC-UHFFFAOYSA-M C(C=C)(=O)NC(C(C)C1=CC=CC=C1)S(=O)(=O)[O-].[Na+] Chemical compound C(C=C)(=O)NC(C(C)C1=CC=CC=C1)S(=O)(=O)[O-].[Na+] BLQBZHOHSZPHKC-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000007976 Ketosis Diseases 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001323 aldoses Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- BRXCDHOLJPJLLT-UHFFFAOYSA-N butane-2-sulfonic acid Chemical compound CCC(C)S(O)(=O)=O BRXCDHOLJPJLLT-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002584 ketoses Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- QRWZCJXEAOZAAW-UHFFFAOYSA-N n,n,2-trimethylprop-2-enamide Chemical compound CN(C)C(=O)C(C)=C QRWZCJXEAOZAAW-UHFFFAOYSA-N 0.000 description 1
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 description 1
- OALVDEJWUQUDTF-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)prop-2-enamide Chemical compound C1OC1CN(C(=O)C=C)CC1CO1 OALVDEJWUQUDTF-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- RKSYJNCKPUDQET-UHFFFAOYSA-N n,n-dipropylprop-2-enamide Chemical compound CCCN(CCC)C(=O)C=C RKSYJNCKPUDQET-UHFFFAOYSA-N 0.000 description 1
- YRDNVESFWXDNSI-UHFFFAOYSA-N n-(2,4,4-trimethylpentan-2-yl)prop-2-enamide Chemical compound CC(C)(C)CC(C)(C)NC(=O)C=C YRDNVESFWXDNSI-UHFFFAOYSA-N 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
- KCTMTGOHHMRJHZ-UHFFFAOYSA-N n-(2-methylpropoxymethyl)prop-2-enamide Chemical compound CC(C)COCNC(=O)C=C KCTMTGOHHMRJHZ-UHFFFAOYSA-N 0.000 description 1
- LSWADWIFYOAQRZ-UHFFFAOYSA-N n-(ethoxymethyl)prop-2-enamide Chemical compound CCOCNC(=O)C=C LSWADWIFYOAQRZ-UHFFFAOYSA-N 0.000 description 1
- ULYOZOPEFCQZHH-UHFFFAOYSA-N n-(methoxymethyl)prop-2-enamide Chemical compound COCNC(=O)C=C ULYOZOPEFCQZHH-UHFFFAOYSA-N 0.000 description 1
- BLIQQXSBYNKXAC-UHFFFAOYSA-N n-[4-(oxiran-2-ylmethoxy)butyl]prop-2-enamide Chemical compound C=CC(=O)NCCCCOCC1CO1 BLIQQXSBYNKXAC-UHFFFAOYSA-N 0.000 description 1
- CDJQLDOSFSALHP-UHFFFAOYSA-N n-[5-(oxiran-2-ylmethoxy)pentyl]prop-2-enamide Chemical compound C=CC(=O)NCCCCCOCC1CO1 CDJQLDOSFSALHP-UHFFFAOYSA-N 0.000 description 1
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- FYCBGURDLIKBDA-UHFFFAOYSA-N n-hexyl-2-methylprop-2-enamide Chemical compound CCCCCCNC(=O)C(C)=C FYCBGURDLIKBDA-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は水性塗膜の製造方法に関する。更に詳しくは特
定の単量体を特定状態で重合してなる重合体と水よりな
る水性組成物を塗布、乾燥して製造する水性塗膜の製造
方法に関する。TECHNICAL FIELD The present invention relates to a method for producing an aqueous coating film. More specifically, it relates to a method for producing an aqueous coating film, which is produced by applying an aqueous composition comprising a polymer obtained by polymerizing a specific monomer in a specific state and water, and drying the composition.
近年、衣類の高機能化、住宅の気密化、冷暖房設備の一
般化、冷凍食品の普及等衣食住に大きな変化が起ってい
る。その変化に応じて衣類では、たとえば汗をかいても
むれないような通気性のある素材が要求されている。住
宅関連では住宅の気密化に伴い室内の湿度の制御、すな
わち調湿及び結露防止が問題になっている。また、冷暖
房設備及び冷凍食品等の普及により熱交換機関の多様化
が進むとともにエネルギー消費に占めるこれら熱交換仕
事の比率が高まっている。その際運転費用の節減及び省
エネルギーの立場より熱交換効率の向上が強く求められ
ている。その方策として種々のものが考えられるが、た
とえば、熱交換部位のフィンと空気との流通接触を十分
に行わせることなどもその１つとしてあげられ、具体的
にはフィン間への水の凝縮等を防止する種々の方策がと
られている。In recent years, there have been major changes in clothing, clothing, and housing such as high-performance clothing, airtight housing, generalization of air-conditioning equipment, and spread of frozen food. In response to such changes, clothing is required to have a breathable material that will not be damaged by sweat, for example. With respect to housing, the control of indoor humidity, that is, humidity control and prevention of dew condensation, has become a problem as housing becomes airtight. In addition, the spread of air-conditioning equipment, frozen foods, and the like has led to the diversification of heat exchange engines, and the ratio of these heat exchange jobs to energy consumption has increased. At that time, improvement of heat exchange efficiency is strongly demanded from the viewpoint of saving operating cost and energy saving. There are various possible measures to achieve this. One of them is, for example, sufficient flow contact between the fins at the heat exchange site and air, and more specifically, water condensation between the fins. Various measures have been taken to prevent such problems.
従来、上記した問題点を解決する一般的方法として水蒸
気と接触する面を親水化して、水とのなじみをよくし、
場合によっては水を吸収させてしまう等の方法が検討さ
れてきた。たとえば親水性または水溶性のアクリル樹脂
またはセルロース誘導体を塗布して塗膜を形成させる方
法あるいはシリカ化合物のような親水性の無機物を有機
系のバインダーで塗膜として固定化する方法等が考えら
れる。Conventionally, as a general method for solving the above-mentioned problems, the surface that comes into contact with water vapor is made hydrophilic to improve compatibility with water,
In some cases, methods such as absorbing water have been studied. For example, a method of applying a hydrophilic or water-soluble acrylic resin or a cellulose derivative to form a coating film, or a method of fixing a hydrophilic inorganic substance such as a silica compound as a coating film with an organic binder can be considered.
しかし、上記した方法においても親水性は不充分であっ
て、前記した要求を満足するに至っていない。However, even in the above method, the hydrophilicity is insufficient, and the above requirements have not been satisfied.
本発明者らは先に特定のアクリルアミドまたはメタアク
リルアミド誘導体（以下（メタ）アクリルアミド誘導体
と略記する）よりなる重合体がまわりの環境変化に応じ
て吸水、吸湿または放水、放湿することを見い出してい
る（特開昭60−90010号）が、未だ上記した特徴を発揮
できる塗膜の製造技術の開発には到っていない。具体的
に塗膜を製造する方法としては該（メタ）アクリルアミ
ド誘導体を重合して得られる重合体溶液を塗布、乾燥し
て行う方法が採用される。その時、塗膜としての要求さ
れる性能として水不溶性と表面平滑性がある。すなわ
ち、該（メタ）アクリルアミド誘導体の重合体はまわり
の環境変化に応じて水の吸収及び放出を行うので、塗膜
として使用する時には水不溶性は吸水した時の塗膜の流
動性をなくすために要求され、また表面平滑性は塗膜の
吸水または放水をムラなく一様に行わせかつ塗膜強度を
保つために要求される。更には表面平滑性と水不溶性と
の間には相関があり、表面平滑性の高いもの程、水不溶
性に優れる塗膜となる。The present inventors have previously found that a polymer composed of a specific acrylamide or methacrylamide derivative (hereinafter abbreviated as (meth) acrylamide derivative) absorbs water, absorbs moisture, or releases moisture depending on environmental changes. (Japanese Patent Laid-Open No. 60-90010), yet the development of a coating film manufacturing technique capable of exhibiting the above-mentioned characteristics has not yet been achieved. Specifically, as a method for producing a coating film, a method in which a polymer solution obtained by polymerizing the (meth) acrylamide derivative is applied and dried is employed. At that time, the performance required as a coating film is water insolubility and surface smoothness. That is, since the polymer of the (meth) acrylamide derivative absorbs and releases water in accordance with changes in the surrounding environment, water-insolubility when used as a coating film eliminates fluidity of the coating film when absorbing water. Surface smoothness is required in order to uniformly and evenly absorb water or to discharge the coating film and to maintain the coating strength. Furthermore, there is a correlation between the surface smoothness and the water insolubility, and the higher the surface smoothness, the more excellent the water insolubility is.
従来、水不溶化技術としては架橋性単量体を添加して重
合する方法または加熱等により架橋を引き起こすＮ−メ
チロールアクリルアクリルアミドのような後架橋性単量
体を予め共重合しておく方法等の技術が知られている。
しかし、それらの技術を塗膜製造に適用しても、後述の
比較例に示すごとく塗布するに十分な流動性が得られな
いあるいは塗膜がヒビ割れを起こす等の問題点があり、
それらの方法は塗膜の製造法に適用できない。Conventionally, water insolubilization techniques include a method of polymerizing by adding a crosslinkable monomer or a method of preliminarily copolymerizing a postcrosslinkable monomer such as N-methylolacrylacrylamide which causes crosslinking by heating. The technology is known.
However, even if these techniques are applied to coating film production, there is a problem that sufficient fluidity cannot be obtained for coating or a coating film is cracked as shown in Comparative Examples described later,
Those methods cannot be applied to the manufacturing method of the coating film.
更には、特開昭60−233182号にエマルション重合して得
た重合体を用いて水不溶性の膜を製造した例が示されて
いるが、後述の比較例に示すごとく表面が平滑でなく厚
みの均一な膜とはならず、ただ単にエマルション重合し
て得た重合体を用いただけでは、本発明の目的とする水
不溶性及び表面平滑性に優れる塗膜の製造法として適用
できない。Further, JP-A-60-233182 shows an example of producing a water-insoluble film using a polymer obtained by emulsion polymerization, but as shown in Comparative Examples described later, the surface is not smooth and the thickness is However, the use of a polymer obtained simply by emulsion polymerization cannot be applied as a method for producing a coating film having excellent water-insolubility and surface smoothness, which is the object of the present invention.
本発明者らは上記した点に鑑み、水の吸収及び放出能を
有する特定の（メタ）アクリルアミド誘導体よりなる重
合体の塗膜の水不溶性の抑制すなわち水不溶化及び表面
平滑化について鋭意検討した結果、該（メタ）アクリル
アミド誘導体をシード粒子を形成させてエマルション状
態で重合してなる重合体を含んでなる水性組成物を塗
布、乾燥して製造した塗膜は水不溶性でありかつその表
面は平滑であり、塗膜として優れていることを見い出し
て本発明に到達した。更にはシード粒子を形成させてエ
マルション状態で重合したものであれば架橋性単量体ま
たは後架橋性単量体との共重合による水不溶化法も本発
明の塗膜の製造に適用できることも見い出した。In view of the above points, the present inventors have diligently studied suppression of water insolubility of a coating film of a polymer composed of a specific (meth) acrylamide derivative having water absorption and release ability, that is, water insolubilization and surface smoothing. A coating film produced by coating and drying an aqueous composition containing a polymer obtained by polymerizing the (meth) acrylamide derivative to form seed particles and polymerizing it in an emulsion state is water-insoluble and has a smooth surface. The present invention has been achieved by finding that the coating film is excellent. Furthermore, it was also found that a water insolubilization method by copolymerization with a crosslinkable monomer or a postcrosslinkable monomer can be applied to the production of the coating film of the present invention as long as seed particles are formed and polymerized in an emulsion state. It was
即ち、本発明は一般式（Ｉ）または一般式（II） 一般式 （上式でR1は水素原子またはメチル基、R2は水素原子、
メチル基またはエチル基、R3はメチル基、エチル基また
はプロピル基を表わす。） 一般式 （上式でR1は水素原子またはメチル基、ＡはCH2 ｎ
でｎは４〜６またはCH2 2OCH2 ２を表わす。） で表わされる単量体の単独重合体若しくは共重合体、ま
たは上記した単量体と共重合可能な他の単量体との共重
合体を含んでなる水性組成物を塗布、乾燥して塗膜を製
造する方法において、上記単独重合体または共重合体は
一般式（Ｉ）若しくは一般式（II）で表わされる単量体
又は他の単量体の１種以上の重合体のシード粒子を核と
してエマルション状態で重合させたものであることを特
徴とする水性塗膜の製造方法である。That is, the present invention relates to general formula (I) or general formula (II) (In the above formula, R 1 is a hydrogen atom or a methyl group, R 2 is a hydrogen atom,
A methyl group or an ethyl group, and R 3 represents a methyl group, an ethyl group or a propyl group. ) General formula (In the above formula, R 1 is a hydrogen atom or a methyl group, A is CH 2 n
In n represents 4-6 or CH 2 2 OCH 2 2. ) A homopolymer or copolymer of the monomer represented by: or an aqueous composition comprising a copolymer of the above-mentioned monomer and another monomer copolymerizable with In the method for producing a coating film, the homopolymer or copolymer is a seed particle of one or more polymers of a monomer represented by the general formula (I) or the general formula (II) or another monomer. It is a method for producing an aqueous coating film, characterized in that it is polymerized in an emulsion state by using as a core.
本発明で使用される特定の（メタ）アクリルアミド誘導
体とは一般式（Ｉ）及び（II）で表わされるＮ−アルキ
ルまたはＮ−アルキレン置換（メタ）アクリルアミドで
あり、具体的には、たとえばＮ−エチルアクリルアミ
ド、N,N−ジエチルアクリルアミド、Ｎ−エチルメタク
リルアミド、N,N−ジメチルアクリルアミド、N,N−ジメ
チルメタクリルアミド、Ｎ−イソプロピルアクリルアミ
ド、Ｎ−ｎ−プロピルアクリルアミド、Ｎ−イソプロピ
ルメタクリルアミド、Ｎ−ｎ−プロピルメタクリルアミ
ド、Ｎ−アクリロイルピロリジン、Ｎ−メタクリロイル
ピロリジン、Ｎ−アクリロイルピペリジン、Ｎ−メタク
リロイルピペリジン、Ｎ−アクリロイルヘキサヒドロア
ゼピン、Ｎ−アクリロイルモルホリン等をあげることが
できる。The specific (meth) acrylamide derivative used in the present invention is an N-alkyl or N-alkylene substituted (meth) acrylamide represented by the general formulas (I) and (II), and specifically, for example, N- Ethyl acrylamide, N, N-diethyl acrylamide, N-ethyl methacrylamide, N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, N-isopropyl acrylamide, Nn-propyl acrylamide, N-isopropyl methacrylamide, N Examples thereof include -n-propylmethacrylamido, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylhexahydroazepine, and N-acryloylmorpholine.
上記した単量体の中で、液体状のモノマーが重合を行う
上で好ましく、更には該モノマーの重合体が水溶液中で
加温により曇りを生じる性質を有する単量体が好まし
く、具体的にはN,N−ジエチルアクリルアミド、Ｎ−ｎ
−プロピルアクリルアミド、Ｎ−ｎ−プロピルメタクリ
ルアミド、Ｎ−アクリロイルピロリジン、Ｎ−メタクリ
ロイルピロリジン、Ｎ−アクリロイルピペリジン、Ｎ−
メタクリロイルピペリジン等である。更に特に好ましい
単量体としてはＮ−アクリロイルピロリジン、Ｎ−アク
リロイルピペリジン等である。Among the above-mentioned monomers, a liquid monomer is preferable for carrying out the polymerization, and further, a monomer having a property that a polymer of the monomer causes clouding due to heating in an aqueous solution is preferable. Is N, N-diethylacrylamide, Nn
-Propylacrylamide, N-n-propylmethacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-
Methacryloyl piperidine and the like. More particularly preferable monomers are N-acryloylpyrrolidine, N-acryloylpiperidine and the like.
また、上記した単量体と共重合可能な単量体としては、
親水性単量体、イオン性単量体、親油性単量体等があげ
られ、それらの一種以上の単量体が適用できる。具体的
には親水性単量体として、たとえばアクリルアミド、メ
タクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−
メチロールメタクリルアミド、ジアセトンアクリルアミ
ド、メチレンビスアクリルアミド、ヒドロキシエチルメ
タクリレート、ヒドロキシエチルアクリレート、ヒドロ
キシプロピルメタクリレート、ヒドロキシプロピルアク
リレート、各種のメトキシポリエチレングリコール（メ
タ）アクリレート、各種のモノまたはポリエチレングリ
コールジ（メタ）アクリレート、Ｎ−ビニル−２−ピロ
リドン等をあげることができるし、また、酢酸ビニル、
グリシジルメタクリレート等を共重合により導入して、
それを加水分解して親水性を賦与することもできる。イ
オン性単量体としては、たとえばアクリル酸、メタクリ
ル酸、ビニルスルホン酸、アリルスルホン酸、メタリル
スルホン酸、スチレンスルホン酸、２−アクリルアミド
−２−フエニルプロパンスルホン酸、２−アクリルアミ
ド−２−メチル−プロパンスルホン酸等の酸及びそれら
の塩、N,N−ジメチルアミノエチルメタクリレート、N,N
−ジエチルアミノエチルメタクリレート、N,N−ジメチ
ルアミノエチルアクリレート、N,N−ジメチルアミノプ
ロピルメタクリルアミド、N,N−ジメチルアミノプロピ
ルアクリルアミド等のアミン及びそれらの塩等をあげる
ことができる。Further, as the monomer copolymerizable with the above-mentioned monomer,
Examples thereof include hydrophilic monomers, ionic monomers, lipophilic monomers and the like, and one or more kinds of these monomers can be applied. Specifically, as hydrophilic monomers, for example, acrylamide, methacrylamide, N-methylol acrylamide, N-
Methylol methacrylamide, diacetone acrylamide, methylene bis acrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, various methoxy polyethylene glycol (meth) acrylates, various mono or polyethylene glycol di (meth) acrylates, N-vinyl-2-pyrrolidone and the like can be mentioned, and vinyl acetate,
Introducing glycidyl methacrylate etc. by copolymerization,
It can also be hydrolyzed to impart hydrophilicity. Examples of the ionic monomer include acrylic acid, methacrylic acid, vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-phenylpropane sulfonic acid, 2-acrylamido-2- Acids such as methyl-propanesulfonic acid and salts thereof, N, N-dimethylaminoethyl methacrylate, N, N
Examples include amines such as -diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl methacrylamide, and N, N-dimethylaminopropyl acrylamide, and salts thereof.
また、各種アクリレート、メタクリレート、アクリルア
ミド、メタクリルアミド、アクリロニトリル等を共重合
により導入して、それを加水分解してイオン性を賦与す
ることもできる。親油性単量体としては、たとえばN,N
−ジ−ｎ−プロピルアクリルアミド、Ｎ−ｎ−ブチルア
クリルアミド、Ｎ−ｎ−ヘキシルアクリルアミド、Ｎ−
ｎ−ヘキシルメタクリルアミド、Ｎ−ｎ−オクチルアク
リルアミド、Ｎ−ｎ−オクチルメタクリルアミド、Ｎ−
tert−オクチルアクリルアミド、Ｎ−ｎ−ドデシルアク
リルアミド、Ｎ−ｎ−ドデシルメタクリルアミド等のＮ
−アルキル（メタ）アクリルアミド誘導体、Ｎ−メトキ
シメチルアクリルアミド、Ｎ−エトキシメチルアクリル
アミド、Ｎ−ｎ−プロポキシメチルアクリルアミド、Ｎ
−ｎ−ブトキシメチルアクリルアミド、Ｎ−ｎ−ブトキ
シメチルメタアクリルアミド、Ｎ−イソブトキシメチル
アクリルアミド、Ｎ−ｔ−オクトキシメチルアクリルア
ミド等のＮ−アルコキシメチル（メタ）アクリルアミド
誘導体、N,N−ジグリシジルアクリルアミド、N,N−ジグ
リシジルメタクリルアミド、Ｎ−（４−グリシドキシブ
チル）アクリルアミド、Ｎ−（４−グリシドキシブチ
ル）メタクリルアミド、Ｎ−（５−グリシドキシペンチ
ル）アクリルアミド、Ｎ−（６−グリシドキシヘキシ
ル）アクリルアミド等のＮ−（ω−グリシドキシアルキ
ル）（メタ）アクリルアミド誘導体、エチルアクリレー
ト、メチルメタクリレート、ブチルメタクリレート、ブ
チルアクリレート、ラウリルアクリレート、２−エチル
ヘキシルメタクリレート、グリシジルメタクリレート等
の（メタ）アクリレート誘導体、アクリロニトリル、メ
タクリロニトリル、酢酸ビニル、塩化ビニル、塩化ビニ
リデン、エチレン、プロピレン、ブテン等のオレフィン
類、スチレン、ジビニルベンゼン、α−メチルスチレ
ン、ブタジエン、イソプレン等をあげることができる。It is also possible to introduce various acrylates, methacrylates, acrylamides, methacrylamides, acrylonitriles and the like by copolymerization and hydrolyze them to impart ionicity. Examples of lipophilic monomers include N, N
-Di-n-propyl acrylamide, Nn-butyl acrylamide, Nn-hexyl acrylamide, N-
n-hexyl methacrylamide, Nn-octyl acrylamide, Nn-octyl methacrylamide, N-
N such as tert-octylacrylamide, Nn-dodecylacrylamide, Nn-dodecylmethacrylamide
-Alkyl (meth) acrylamide derivative, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, Nn-propoxymethylacrylamide, N
N-alkoxymethyl (meth) acrylamide derivatives such as -n-butoxymethylacrylamide, Nn-butoxymethylmethacrylamide, N-isobutoxymethylacrylamide, Nt-octoxymethylacrylamide, N, N-diglycidylacrylamide , N, N-diglycidyl methacrylamide, N- (4-glycidoxybutyl) acrylamide, N- (4-glycidoxybutyl) methacrylamide, N- (5-glycidoxypentyl) acrylamide, N- ( N- (ω-glycidoxyalkyl) (meth) acrylamide derivative such as 6-glycidoxyhexyl) acrylamide, ethyl acrylate, methyl methacrylate, butyl methacrylate, butyl acrylate, lauryl acrylate, 2-ethylhexyl methacrylate (Meth) acrylate derivatives such as glycidyl methacrylate, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, olefins such as ethylene, propylene, butene, styrene, divinylbenzene, α-methylstyrene, butadiene, isoprene, etc. I can give you.
上記した単量体のうち、Ｎ−メチロール（メタ）アクリ
ルアミド、Ｎ−アルコキシメチル（メタ）アクリルアミ
ドは後架橋性単量体として有用である。Among the above-mentioned monomers, N-methylol (meth) acrylamide and N-alkoxymethyl (meth) acrylamide are useful as post-crosslinkable monomers.
上記した単量体の重合体を含有してなる水性組成物は温
度により親水性疎水性の変化が起り、たとえば水溶性の
場合には、加温により疎水化し、曇りを生じる（その時
の温度を曇点と言う）。また、水性組成物がエマルショ
ンを形成している場合にはその溶液の粘度は加温により
低下する。An aqueous composition containing a polymer of the above-mentioned monomers changes in hydrophilicity and hydrophobicity depending on temperature. For example, when the composition is water-soluble, it becomes hydrophobic by heating and fog occurs. Called cloud point). Further, when the aqueous composition forms an emulsion, the viscosity of the solution is lowered by heating.
また、前記した他の共重合しうる単量体としての親水性
単量体及びイオン性単量体はエマルション表面の改質及
びエマルションそのものの安定化に有用である。The hydrophilic monomer and ionic monomer as the other copolymerizable monomers described above are useful for modifying the emulsion surface and stabilizing the emulsion itself.
前記一般式（Ｉ）または（II）で示される（メタ）アク
リルアミド誘導体と上記した種々の他の単量体との量的
関係について次に述べる。The quantitative relationship between the (meth) acrylamide derivative represented by the general formula (I) or (II) and the various other monomers described above will be described below.
（メタ）アクリルアミド誘導体と上記した種々の他の単
量体との量的比率は、それら単量体の組合せにより変化
し、一概には言えない。しかし、概ね親水性またはイオ
ン性単量体は単量体総量中各々60重量％または30重量％
以下であり、好ましくは各々40重量％または20重量％以
下である。一方親油性単量体は単量体総量中80重量％以
下、好ましくは60重量％以下である。The quantitative ratio of the (meth) acrylamide derivative to the various other monomers described above varies depending on the combination of those monomers and cannot be generally stated. However, in general, hydrophilic or ionic monomers account for 60% or 30% by weight of the total amount of monomers, respectively.
Or less, and preferably 40% by weight or 20% by weight or less, respectively. On the other hand, the lipophilic monomer content is 80% by weight or less, preferably 60% by weight or less, based on the total amount of the monomers.
親水性またはイオン性単量体の占める割合が高くなりす
ぎると、塗膜の水溶性を抑制できず、水との接触により
溶解してしまう。一方、親油性単量体の比率が高くなり
すぎると塗膜の親水性が損われてくる。一方、（メタ）
アクリルアミド誘導体単独またはそれらの共重合によっ
てもエマルションを形成できる。If the proportion of the hydrophilic or ionic monomer is too high, the water solubility of the coating film cannot be suppressed and the coating film will be dissolved by contact with water. On the other hand, if the ratio of the lipophilic monomer becomes too high, the hydrophilicity of the coating film will be impaired. Meanwhile, (meta)
The emulsion can also be formed by the acrylamide derivative alone or by copolymerization thereof.
上記の単量体もしくはそれらの単量体混合物を使用して
エマルション状態で重合して、水不溶性に優れ表面の平
滑な塗膜を形成する重合体を得るためには、シード粒子
を形成させてエマルション重合することが必須となる。In order to obtain a polymer which is polymerized in an emulsion state using the above-mentioned monomers or a mixture of those monomers and which is excellent in water insolubility and forms a smooth coating film on the surface, form seed particles. Emulsion polymerization is essential.
具体的には、まず重合すべき単量体の一部を重合してエ
マルション粒子の核となるシード粒子を形成させる。つ
いで、更に単量体を添加してシード粒子中で重合を行わ
せエマルション重合を進行させてゆくことが不可欠とな
る。Specifically, first, a part of the monomer to be polymerized is polymerized to form seed particles which become the core of the emulsion particles. Then, it is indispensable to further add a monomer to carry out polymerization in the seed particles to promote emulsion polymerization.
上記の方法の採用により、水不溶性及び表面平滑性に優
れた塗膜の製造がはじめて可能となった。以下、その具
体的な重合方法について記述してゆく。By adopting the above method, it becomes possible for the first time to produce a coating film having excellent water insolubility and surface smoothness. The specific polymerization method will be described below.
すなわち、反応媒体としては水が使用され、具体的には
イオン交換水、蒸留水、上水、工業用水等が使用され
る。親油性単量体を併用する場合においては、アルキル
硫酸塩、アルキルアリールスルホン酸塩、脂肪酸石けん
等の通常の界面活性剤、または前記したイオン性単量体
を必要に応じて使用することにより、単量体の乳化状態
を形成でき、それに引き続いて乳化重合を行いうる。一
方、本発明の（メタ）アクリルアミド誘導体単独もしく
は親水性またはイオン性単量体を併用する場合において
は、単量体は通常水溶性であるので乳化できないが、重
合開始剤の存在下必要に応じて前記した界面活性剤また
はイオン性単量体を溶解し、重合体の曇点以上の重合開
始温度に加温しておき、そこに前記した単量体を添加し
てゆくことにより重合体の乳化がおこり、重合体エマル
ションを製造できる。That is, water is used as the reaction medium, and specifically ion-exchanged water, distilled water, tap water, industrial water, etc. are used. In the case of using a lipophilic monomer in combination, an alkyl sulfate, an alkyl aryl sulfonate, a normal surfactant such as fatty acid soap, or by using the above-mentioned ionic monomer as necessary, An emulsion state of the monomer can be formed, which can be followed by emulsion polymerization. On the other hand, when the (meth) acrylamide derivative of the present invention is used alone or in combination with a hydrophilic or ionic monomer, the monomer is usually water-soluble and therefore cannot be emulsified, but if necessary in the presence of a polymerization initiator. The above-mentioned surfactant or ionic monomer is dissolved, the polymer is heated to a polymerization start temperature not lower than the cloud point of the polymer, and the above-mentioned monomer is added thereto to form a polymer. Emulsification occurs and a polymer emulsion can be produced.
また、上記した重合温度条件は重合体エマルションの製
造中必ずしも一定に保つ必要はなく、重合体エマルショ
ンが一度形成された後は温度を上げたり下げたりして重
合する速度を調節して行ってもよい。Further, the above-mentioned polymerization temperature conditions do not necessarily need to be kept constant during the production of the polymer emulsion, and even after the polymer emulsion is once formed, the temperature may be raised or lowered to control the polymerization rate. Good.
重合に用いられる重合開始剤としては過硫酸塩などの水
溶性ラジカル重合開始剤であれば、何れも使用すること
ができ、当然レドックス系開始剤の使用も可能である。
具体的には、たとえば過硫酸アンモニウム、過硫酸カ
リ、過酸化水素、tert−ブチルパーオキシド及びレドッ
クス系開始剤として、上記した酸化剤と組合せる還元剤
としては、たとえば亜硫酸塩、亜硫酸水素塩、鉄、銅、
コバルトなどの低次のイオン価の塩、アニリン等の有機
アミン更にはアルドース、ケトース等の還元糖をあげる
ことができる。またアゾ化合物としては、2,2′−アゾ
ビス−２−アミジノプロパン塩酸塩、2,2′−アゾビス
−2,4−ジメチルバレロニトリル、4,4′−アゾビス−４
−シアノバレイン酸及びその塩等を使用することができ
る。また、上記した重合開始剤を２種以上併用すること
も可能である。重合温度は使用する重合開始剤により変
化するが、通常０〜100℃、好ましくは５〜90℃で、か
つ該重合体の曇点以上の範囲である。As the polymerization initiator used for the polymerization, any water-soluble radical polymerization initiator such as persulfate can be used, and of course, a redox initiator can also be used.
Specifically, for example, ammonium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl peroxide, and a redox-based initiator, examples of the reducing agent in combination with the above-mentioned oxidizing agent include sulfite, bisulfite, and iron. ,copper,
Examples thereof include salts of low ionic value such as cobalt, organic amines such as aniline, and reducing sugars such as aldose and ketose. Examples of the azo compound include 2,2'-azobis-2-amidinopropane hydrochloride, 2,2'-azobis-2,4-dimethylvaleronitrile and 4,4'-azobis-4.
-Cyanovaleic acid and its salts can be used. It is also possible to use two or more of the above-mentioned polymerization initiators in combination. The polymerization temperature varies depending on the polymerization initiator used, but is usually 0 to 100 ° C., preferably 5 to 90 ° C., and is in the range above the cloud point of the polymer.
水性組成物中の重合体含量となる重合体濃度は特に限定
はないが、概ね５〜60％である。The concentration of the polymer, which is the polymer content in the aqueous composition, is not particularly limited, but is generally 5 to 60%.
重合体エマルションの具体的製造法としては、まず重合
体が不溶化する温度以上でシード粒子を製造することが
必須となる。シードを構成する単量体は前記一般式で示
される（メタ）アクリルアミド誘導体単独でもよいし、
親油性単量体単独でもよいし、それらの混合物でもよい
し、更には親水性単量体を併用してもよい。シード粒子
を製造するために添加する単量体の全単量体に占める比
率は重量比で0.1〜40％、好ましくは0.25〜30％であ
る。添加量の比率がそのように幅広い範囲にわたる原因
は重合体濃度が高くなるとシードの比率を低下させるこ
とが好ましく、一方重合体濃度が低くなるとシードの比
率を高めることができることにある。しかし、シードの
比率が低くなりすぎると重合中粒子の発生が起こり、粒
径の均一性が損われると同時にエマルションの安定性
が、低下する。一方、シードの比率が高くなりすぎても
エマルションの均一性が損われ、重合体のヒモ状折出ま
たはエマルション粒子の会合が起こり、塗膜にムラが出
来、平滑性が損われる。As a specific method for producing a polymer emulsion, first, it is essential to produce seed particles at a temperature at which the polymer becomes insoluble or higher. The monomer constituting the seed may be the (meth) acrylamide derivative represented by the above general formula alone,
The lipophilic monomer may be used alone, a mixture thereof may be used, or a hydrophilic monomer may be used in combination. The weight ratio of the monomers added to the seed particles to the total monomers is 0.1 to 40%, preferably 0.25 to 30%. The reason why the ratio of the added amount is in such a wide range is that it is preferable to decrease the seed ratio when the polymer concentration is high, while it is possible to increase the seed ratio when the polymer concentration is low. However, if the seed ratio becomes too low, particles will be generated during the polymerization, and the uniformity of the particle size will be impaired, and at the same time, the stability of the emulsion will decrease. On the other hand, if the seed ratio becomes too high, the homogeneity of the emulsion will be impaired, the polymer string-like protrusions or the association of emulsion particles will occur, the coating film will become uneven, and the smoothness will be impaired.
更に、シード粒子の形成後に添加する単量体が二種以上
の場合には、それらの単量体の混合したものを添加して
もよいし、経時的に混合すべき比率を変えて添加しても
よいし、混合しないで単量体毎に添加してもよい。上記
した単量体の組合せにより均質なエマルションまたは不
均質なエマルションの製造のいづれも可能となる。しか
し、本発明の水性塗膜の製造方法においては不均質なエ
マルションのほうが好適な水性塗膜を製造できて好都合
である。Further, when the number of the monomers to be added after the formation of the seed particles is two or more, a mixture of the monomers may be added, or the ratio to be mixed may be changed with time. Alternatively, they may be added for each monomer without mixing. The combination of the above-mentioned monomers allows either the production of homogeneous emulsions or heterogeneous emulsions. However, in the method for producing a water-based coating film of the present invention, a heterogeneous emulsion is advantageous because it can produce a suitable water-based coating film.
また、エマルションの粒径は界面活性剤、イオン性単量
体等の種類及び添加量によりコントロールできる。一般
にそれら物質の添加量を多くした場合、粒径は小さくな
る。Further, the particle size of the emulsion can be controlled by the kind and the addition amount of the surfactant, the ionic monomer and the like. Generally, when the amount of addition of these substances is increased, the particle size becomes smaller.
それらの中でもイオン性単量体を使用すると該単量体が
重合体中に取り込まれる結果、生成するエマルションは
界面活性剤を使用した場合に比べると水溶性化合物の残
存量が少なくなり、塗膜の水への溶解性が抑制され好ま
しい。イオン性単量体としては各種のものが使用される
が、それらの中でも２−アクリルアミド−２−メチルプ
ロパンスルホン酸塩、２−アクリルアミド−２−フェニ
ルプロパンスルホン酸塩等のスルホン酸型モノマーが好
ましい。それらの添加量は全単量体あたり0.1〜10重量
％、好ましくは0.5〜５重量％であり、シード粒径の形
成時に全量添加してもよいし、添加する単量体とともに
分割添加してもよい。Among them, when an ionic monomer is used, the monomer is incorporated into the polymer, and the resulting emulsion has a smaller residual amount of the water-soluble compound than when a surfactant is used. The solubility in water is suppressed, which is preferable. Various kinds of ionic monomers are used, and among them, sulfonic acid type monomers such as 2-acrylamido-2-methylpropanesulfonate and 2-acrylamido-2-phenylpropanesulfonate are preferable. . The addition amount thereof is 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the total amount of the monomers, and the total amount may be added when the seed particle size is formed, or may be divided and added together with the added monomers. Good.
次に重合時間であるが、シード粒子形成の重合時間は10
〜120分であり、必ずしも重合が完結する必要はなく、
重合液が白濁して粒子が形成されれば十分である。つい
で、そこに単量体を添加してエマルション重合を行うの
であるが、その際単量体全量を一度に添加してもよい
が、重合を安定的に行うには連続的または遂次的に添加
したほうが好ましい。その際重合開始剤も単量体添加と
併行して添加してもよい。その添加に要する時間は添加
すべき単量体量に依存し、一概には述べられないが１〜
10時間である。更には添加後も残存する単量体を重合し
て消失させるために、１〜５時間引き続き重合を行わせ
ることが好ましい。Next is the polymerization time, but the polymerization time for seed particle formation is 10
~ 120 minutes, it is not necessary to complete the polymerization,
It is sufficient that the polymerization liquid becomes cloudy and particles are formed. Then, the monomer is added thereto to carry out emulsion polymerization, and at that time, the entire amount of the monomer may be added at one time, but in order to stably carry out the polymerization, it may be continuously or sequentially added. It is preferable to add it. At that time, a polymerization initiator may be added concurrently with the addition of the monomer. The time required for the addition depends on the amount of the monomer to be added, and although it cannot be generally stated,
10 hours. Furthermore, it is preferable to continue the polymerization for 1 to 5 hours in order to polymerize and eliminate the residual monomer after the addition.
上記の重合を通じて、重合を速やかに行わせるために重
合系内の雰囲気はチッ素のような不活性ガスで空気等の
酸素含有ガスを置換しておいたほうがよい。In order to carry out the polymerization rapidly through the above-mentioned polymerization, the atmosphere in the polymerization system should be replaced with an oxygen-containing gas such as air by an inert gas such as nitrogen.
上記した方法により製造される重合体エマルションは粒
子凝集物等の粒子の会合体の生成の起りにくい、均一な
粒径分布を有する安定性にすぐれたものである。特にエ
マルション水溶液の温度を変化させても粒子の凝集等の
起きにくい安定なエマルションである。従って塗膜とし
て使用した場合、粒径の均一性にすぐれ重合体の分子量
が大きいので塗膜は水不溶性及び表面平滑性にすぐれた
ものになる。The polymer emulsion produced by the above-mentioned method is excellent in stability and has a uniform particle size distribution in which the formation of aggregates of particles such as particle aggregates is unlikely to occur. In particular, it is a stable emulsion in which aggregation of particles does not easily occur even when the temperature of the emulsion aqueous solution is changed. Therefore, when used as a coating film, the particle size is excellent in uniformity and the polymer has a large molecular weight, so that the coating film is excellent in water insolubility and surface smoothness.
また、上記した単量体のエマルションは（ｉ）親油性単
量体の比率が相対的に高い場合には、温度を変化させて
もエマルションとして存在できるが、（ii）親油性単量
体の比率が低下し、前記した（メタ）アクリルアミド誘
導体の比率が相対的に高くなると、重合体の曇点以上で
はエマルションとなり、曇点以下では水溶液または水性
ゲルとなる。通常曇点以下では水溶液となるのである
が、重合体の分子量が高い場合、メチレンビスアクリル
アミド、各種のモノまたはポリエチレングリコールジ
（メタ）アクリレートのような架橋性単量体と共重合さ
せた場合またはアクリロニトリルのような親油性単量体
をエマルション重合の後期に添加して共重合させた場合
などでは、曇点以下では重合体がゲル状を呈する場合が
ある。Further, the emulsion of the above-mentioned monomer can exist as an emulsion even if the temperature is changed when (i) the ratio of the lipophilic monomer is relatively high. When the ratio is lowered and the ratio of the (meth) acrylamide derivative is relatively high, the polymer becomes an emulsion above the cloud point and becomes an aqueous solution or an aqueous gel below the cloud point. Normally, it will be an aqueous solution below the cloud point, but when the molecular weight of the polymer is high, when it is copolymerized with a crosslinkable monomer such as methylenebisacrylamide, various mono- or polyethylene glycol di (meth) acrylates, or When a lipophilic monomer such as acrylonitrile is added and copolymerized in the latter stage of emulsion polymerization, the polymer may take a gel form at a point below the cloud point.
上記した方法で製造される水性組成物を塗布する基材と
しては、特に限定はなく各種の材料が使用できる。具体
的には繊維、不織布、紙、パルプ、フィルム、シート、
板状成形体、金属板、ガラス板等の材料があげられる。
いづれのものも天然、半合成及び合成のものが使用で
き、それら材料表面に本発明の塗膜を形成させることに
より水を吸収及び放出させる能力を賦与できる。The substrate to which the aqueous composition produced by the above method is applied is not particularly limited, and various materials can be used. Specifically, fiber, non-woven fabric, paper, pulp, film, sheet,
Examples of the material include a plate-shaped molded product, a metal plate, a glass plate and the like.
Any of these may be natural, semi-synthetic or synthetic, and the ability to absorb and release water can be imparted by forming the coating film of the present invention on the surface of these materials.
実際に塗布する場合、塗布する材料表面の極性に応じて
水性組成物をそのまま使用してもよいし、アルコール、
モノまたはポリエチレングリコールのモノアルキルエー
テル等の水溶性の有機化合物を添加してもよいし、また
水性組成物の界面張力を低下させるために界面活性剤を
使用してもよい。一般に材料表面の極性が高い場合には
水性組成物をそのまま使用できるが、極性が低い場合に
は水溶性有機化合物及び界面活性剤等を添加して塗布し
たようが好結果が得られる場合がある。また、水性組成
物にポリエチレングリコール等のポリアルキレングリコ
ール、グリセリン等の多価水酸基置換化合物、塩化カル
シウム等の水溶性無機化合物、シリカ、チタン白等の各
種顔料、アクリルエマルション等の疎水性エマルション
等の変性剤を添加して塗膜を製造してもよい。更には、
表面が平滑の場合はサンディング等の方法で表面を粗面
化した後、塗布してもよい。一方金属またはガラス表面
の場合には、エポキシ樹脂、アクリル樹脂、メラミン樹
脂等のプレコート用樹脂で表面処理したものを使用して
もよい。具体的に塗布する方法として、コーティング、
浸漬及び吹きつけ等の各種の方法が採用でき、塗布する
材料の形状に応じて、任意に選択できる。具体的にはコ
ーティング法としてはブレードコータ、ロールコータ、
スピンコータ更にはハケ塗り等種々の方法が採用でき
る。浸漬及び吹きつけ等についても同様に種々の方法が
採用できる。When actually applied, the aqueous composition may be used as it is, depending on the polarity of the material surface to be applied, alcohol,
Water-soluble organic compounds such as mono- or polyethylene glycol mono-alkyl ethers may be added, and surfactants may be used to reduce the interfacial tension of the aqueous composition. Generally, when the polarity of the material surface is high, the aqueous composition can be used as it is, but when the polarity is low, it may be possible to obtain good results by adding a water-soluble organic compound and a surfactant. . Further, polyalkylene glycol such as polyethylene glycol in the aqueous composition, polyvalent hydroxyl group-substituted compound such as glycerin, water-soluble inorganic compound such as calcium chloride, silica, various pigments such as titanium white, hydrophobic emulsion such as acrylic emulsion You may add a modifier and manufacture a coating film. Furthermore,
When the surface is smooth, it may be applied after roughening the surface by a method such as sanding. On the other hand, in the case of a metal or glass surface, those surface-treated with a precoat resin such as an epoxy resin, an acrylic resin or a melamine resin may be used. As a specific application method, coating,
Various methods such as dipping and spraying can be adopted, and can be arbitrarily selected according to the shape of the material to be applied. Specifically, as a coating method, a blade coater, a roll coater,
Various methods such as spin coating and brush coating can be adopted. Similarly, various methods can be adopted for dipping and spraying.
本発明で使用する水性組成物は、その粘度が温度により
変化し、加温に伴い粘度は低下する。従って、水性組成
物の温度を制御することにより、その水性組成物の粘度
を塗布に適した状態に設定できる。粘度が高い場合には
塗布量が多くなり、一方低くなると塗布量が少なくなり
目的に応じて粘度調節を行なえばよい。したがって、塗
布する際の水性組成物の温度は広範囲に設定することが
必要となり一概には述べられないが、塗工機等の設備的
制約があり、概ね５〜80℃であり、好ましくは10〜70℃
であり、特に好ましくは15〜60℃である。The viscosity of the aqueous composition used in the present invention changes with temperature, and the viscosity decreases with heating. Therefore, by controlling the temperature of the aqueous composition, the viscosity of the aqueous composition can be set to a state suitable for coating. When the viscosity is high, the coating amount increases, while when it is low, the coating amount decreases, and the viscosity may be adjusted according to the purpose. Therefore, it is necessary to set the temperature of the aqueous composition at the time of application in a wide range, which cannot be generally described. However, there are facility restrictions such as a coating machine, and the temperature is generally 5 to 80 ° C., preferably 10 ~ 70 ° C
And particularly preferably 15 to 60 ° C.
次に上記した塗布物を乾燥して塗膜を製造するのである
が、多種の乾燥方法が適用できる。乾燥機としては塗工
機と一体化したものでも、別個にあるものでも、いづれ
の方法も適用できる。具体的には箱形乾燥器、真空乾燥
器、トンネル乾燥器、バンド乾燥器、回転乾燥器、撹拌
乾燥器、気流乾燥器、円筒乾燥器、噴霧乾燥器、流動乾
燥器、赤外線乾燥器、高周波乾燥器等をあげられる。乾
燥温度は乾燥方法及び乾燥時間に依存し一概には言えな
いが、概ね50〜250℃であり、好ましくは75℃〜200℃で
ある。温度が低すぎると乾燥速度が遅くなり、結果とし
て乾燥時間が長時間になる。一方、温度が高すぎると塗
膜の着色等変性が起り好ましくない。Next, the coating material is dried to produce a coating film, and various drying methods can be applied. As the dryer, either one integrated with the coating machine or one separately provided, either method can be applied. Specifically, box dryers, vacuum dryers, tunnel dryers, band dryers, rotary dryers, stirring dryers, airflow dryers, cylinder dryers, spray dryers, fluidized dryers, infrared dryers, high-frequency dryers. A dryer etc. can be mentioned. The drying temperature depends on the drying method and the drying time and cannot be generally stated, but is generally 50 to 250 ° C, preferably 75 ° C to 200 ° C. If the temperature is too low, the drying speed will be slow, resulting in a long drying time. On the other hand, if the temperature is too high, the coating film is unfavorably modified such as coloring.
本発明の方法により、水不溶性の表面平滑性に優れる塗
膜を製造することができ、下記の特徴を有する。By the method of the present invention, a water-insoluble coating film having excellent surface smoothness can be produced and has the following characteristics.
（１）架橋性単量体を使用して架橋しなくても得られる
塗膜は水に実質的に溶解せず、その表面は平滑である。(1) The coating film obtained even if it is not crosslinked using a crosslinkable monomer is substantially insoluble in water and its surface is smooth.
（２）架橋性単量体を使用した場合でも、製膜時の作業
性が優れ、得られる塗膜は厚みムラがなく、表面が滑ら
かである。(2) Even when a crosslinkable monomer is used, the workability during film formation is excellent, and the resulting coating film has no thickness unevenness and the surface is smooth.
（３）水性組成物の粘度が温度により変化するので、温
度により塗布量を制御できる。加温して粘度を低くして
塗布量を少なめに、一方逆に冷却して粘度を高めにして
塗布量を多くできる。(3) Since the viscosity of the aqueous composition changes with temperature, the coating amount can be controlled by the temperature. The coating amount can be increased by heating to lower the viscosity to reduce the coating amount, while conversely cooling to increase the viscosity.
（４）水性組成物を塗布乾燥して塗膜を製造するので、
その工程で蒸発するのは水蒸気が主成分であるので、溶
剤型塗膜の製造法に比べ環境の汚染がなく、工程上の安
全性が高い。(4) Since an aqueous composition is applied and dried to produce a coating film,
Since water vapor is the main component that evaporates in that process, there is less environmental pollution than in the method of producing a solvent-based coating film, and the safety in the process is high.
本発明の方法により製造される塗膜は下記の特徴を有し
ている。The coating film produced by the method of the present invention has the following characteristics.
（１）低温または高温度の条件では水蒸気を吸収し、高
温または低温度の条件では吸収した水蒸気を放出すると
いう水蒸気の呼吸作用を有している。その時、吸収また
は放出する水蒸気の量はまわりの温度及び湿度の条件及
び塗膜の組成等により異なり、一様には述べられない
が、その最大値で概ね塗膜1g当り10gである。(1) It has a breathing action of water vapor that absorbs water vapor under low temperature or high temperature conditions and releases the absorbed water vapor under high temperature or low temperature conditions. At that time, the amount of water vapor absorbed or released varies depending on the surrounding temperature and humidity conditions, the composition of the coating film, etc., and cannot be stated uniformly, but the maximum value is approximately 10 g per 1 g of the coating film.
（２）本発明の方法により製造される塗膜は水への溶解
性を極力抑えられているので、水中に塗膜を浸漬させて
も塗膜は溶解せずに膨潤してゲル状または膜状に形状を
保持することができる。その時の膨潤量は温度に依存
し、低温ほど膨潤量は大きくなり、加温により減少す
る。具体的に、たとえば10℃と50℃との間での膨潤量の
比は塗膜の組成等により変化するが、概ね50℃での膨潤
量を１とした場合10℃においては1.3〜10の範囲にあ
る。その時の膨潤量そのものは10℃において概ね乾燥塗
膜の自重の５〜100倍である。(2) Since the coating film produced by the method of the present invention has the solubility in water suppressed as much as possible, the coating film does not dissolve even when immersed in water and swells to form a gel or a film. The shape can be retained. The swelling amount at that time depends on the temperature, and the swelling amount increases as the temperature decreases, and decreases with heating. Specifically, for example, the ratio of the swelling amount between 10 ° C. and 50 ° C. varies depending on the composition of the coating film, etc. In range. At that time, the swelling amount itself is about 5 to 100 times the weight of the dry coating film at 10 ° C.
（３）塗膜を形成する重合体の性質の１つとして広範囲
な物質との相容性がよいので、前記した変性剤の添加に
より、各種用途に適した塗膜を製造できる。具体的に
は、たとえば水蒸気の吸放出用には水溶性の無機化合物
または有機化合物を添加して吸湿量を向上させることも
可能であるし、一方吸水させる場合には、疎水性エマル
ション等を添加して耐水性を向上させることも可能とな
る。(3) As one of the properties of the polymer forming the coating film, the compatibility with a wide range of substances is good, and therefore the addition of the above-mentioned modifier makes it possible to produce a coating film suitable for various applications. Specifically, for example, for absorbing and releasing water vapor, it is possible to add a water-soluble inorganic compound or organic compound to improve the moisture absorption amount, while when absorbing water, a hydrophobic emulsion or the like is added. Then, it becomes possible to improve the water resistance.
本発明の方法により製造される水性塗膜は水不溶性で、
かつ、周囲の環境の変化に応じて水を吸収したり放出す
るという性質を有し、各種素材の表面にそのような性質
を賦与する表面変性剤として非常に広範囲な用途に応用
できる。The aqueous coating film produced by the method of the present invention is water-insoluble,
In addition, it has a property of absorbing and releasing water according to changes in the surrounding environment, and can be applied to a very wide range of uses as a surface modifier that imparts such a property to the surface of various materials.
具体的用途として、室内の結露防止、調湿、メガネ、ガ
ラス等の防曇、アクリル繊維等の繊維の改質、気体或い
は溶液中に含まれる水の脱水、気体の加湿、除湿、保
湿、熱交換器フィンの表面処理、汚泥、液状廃棄物の脱
水凝固等の分野への応用が可能である。Specific applications include prevention of dew condensation in the room, humidity control, anti-fog on glasses, glass, etc., modification of fibers such as acrylic fiber, dehydration of gas or water contained in a solution, humidification of gas, dehumidification, heat retention, heat It can be applied to fields such as surface treatment of exchanger fins, sludge, and dehydration and solidification of liquid waste.
更にはシリコン或いはテフロンもしくはそれらの処理を
施した表面或いは金属表面等の剥離性のよい表面で塗膜
を形成させて、その後表面より塗膜を剥離してフィルム
または膜を製造することも可能であるし、また、繊維用
の中間原料としても有用である。Further, it is also possible to form a coating film on a surface having good releasability such as silicon or Teflon or a surface treated with them or a metal surface, and then peeling the coating film from the surface to produce a film or film. However, it is also useful as an intermediate raw material for fibers.
以下実施例、比較例により本発明を具体的に説明する。 The present invention will be specifically described below with reference to examples and comparative examples.
実施例１ 蒸留水170gにＮ−アクリロイルピロリジン4.5g及び２−
アクリルアミド−２−フェニルプロパンスルホン酸ナト
リウム（以下APPS−Naと略す。）0.3gを添加し、反応器
内を窒素ガスで置換した後、60℃に加温した。ついで反
応液に過硫酸カリウム0.6gを添加し重合を開始し、60分
間重合し、シード粒子分散液を得た。このようにして得
たシード粒子分散液にＮ−アクリロイルピロリジン5.5g
を添加し、引きつづいてアクリロニトリル5g添加した。
添加終了後、該反応液を更に４時間60℃で反応させた。
重合は重合体のヒモ状折出等もなく、均一なエマルショ
ン状態で進行した。得られた重合液の粘度を50℃、25℃
及び10℃で測定し、結果を表−１に示した。その時重合
液は50℃では乳化状態であり、25℃及び10℃では半透明
な水性ゲルであった。Example 1 In 170 g of distilled water, 4.5 g of N-acryloylpyrrolidine and 2-
After adding 0.3 g of sodium acrylamido-2-phenylpropanesulfonate (hereinafter abbreviated as APPS-Na) and replacing the inside of the reactor with nitrogen gas, the mixture was heated to 60 ° C. Then, 0.6 g of potassium persulfate was added to the reaction solution to start polymerization, and polymerization was carried out for 60 minutes to obtain a seed particle dispersion liquid. 5.5 g of N-acryloylpyrrolidine was added to the seed particle dispersion thus obtained.
Was added, followed by the addition of 5 g of acrylonitrile.
After the addition was completed, the reaction solution was further reacted for 4 hours at 60 ° C.
The polymerization proceeded in a uniform emulsion state without any string-like protrusion of the polymer. The viscosity of the obtained polymerization liquid is 50 ℃, 25 ℃
And at 10 ° C, and the results are shown in Table-1. At that time, the polymerization liquid was in an emulsified state at 50 ° C and was a translucent aqueous gel at 25 ° C and 10 ° C.
また、上記した重合液を12cm×12cm角のテフロン製シー
トに刷毛塗りし、それを125℃で２時間乾燥して塗膜を
作った。得られた塗膜は厚みムラがなく、表面も滑らか
であった。Further, the above-mentioned polymerization solution was brush-coated on a 12 cm × 12 cm square Teflon sheet, which was dried at 125 ° C. for 2 hours to form a coating film. The resulting coating film had no thickness unevenness and had a smooth surface.
塗膜をテフロン製シートよりはがし、その厚みを測定し
たところ0.2mmであり、該塗膜を水中に浸漬すると吸水
して含水ゲル膜となった。その時浸漬する水の温度を1
0、25、50℃に変え、塗膜1g当りの膨潤量を測定し、表
−１に示した。吸水した塗膜もその表面はなめらかであ
り、重合体の溶出はなかった。The coating film was peeled off from the Teflon sheet and its thickness was measured to be 0.2 mm. When the coating film was immersed in water, it absorbed water to form a hydrous gel film. The temperature of the water to be immersed at that time is 1
The swelling amount per 1 g of the coating film was measured by changing the temperature to 0, 25 and 50 ° C. and shown in Table 1. The water-absorbed coating film had a smooth surface, and no polymer was eluted.
比較例１ 100mlの４ツ口丸底フラスコに窒素ガス流通下で撹拌し
ながら、蒸留水45.0g、Ｎ−アクリロイルピロリジン5.0
gを添加した。その後、過硫酸アンモニウム0.5g及び亜
硫酸水素ナトリウム0.23gを添加し、15〜30℃で４時間
重合し、Ｎ−アクリロイルピロリジンの重合体の10％水
溶液を得た。該水溶液の粘膜を測定したところ、25℃で
3.5cpsであった。Comparative Example 1 45.0 g of distilled water and 5.0 of N-acryloylpyrrolidine were stirred in a 100 ml four-necked round bottom flask under a nitrogen gas stream while stirring.
g was added. Thereafter, 0.5 g of ammonium persulfate and 0.23 g of sodium hydrogen sulfite were added, and the mixture was polymerized at 15 to 30 ° C. for 4 hours to obtain a 10% aqueous solution of a polymer of N-acryloylpyrrolidine. When the mucous membrane of the aqueous solution was measured, it was
It was 3.5 cps.
次に上記重合液を使用して実施例１と同様にして塗膜を
作った。該塗膜をテフロン製シートよりはがし、水中に
浸漬したところ水に溶解した。Next, a coating film was prepared in the same manner as in Example 1 using the above polymerization solution. When the coating film was peeled off from the Teflon sheet and immersed in water, it was dissolved in water.
比較例２ 蒸留水170gにＮ−アクリロイルピロリジン10g及びAPPS
−Na0.3gを添加し、反応器内を窒素ガスで置換した後、
60℃に加温した。ついで反応液に過硫酸カリウム0.6gを
添加し重合を開始し、３時間重合した。ついで該反応液
にアクリロニトリル5gを添加した。添加終了後、該反応
液を更に３時間60℃で反応させた。得られた重合液の粘
度を50℃、25℃及び10℃で測定したところ、50℃で13×
102、25℃で704×102、10℃で1660×102であった。Comparative Example 2 N-acryloylpyrrolidine 10 g and APPS in 170 g of distilled water
-Na0.3g was added and after replacing the inside of the reactor with nitrogen gas,
Heated to 60 ° C. Then, 0.6 g of potassium persulfate was added to the reaction solution to start the polymerization, and the polymerization was carried out for 3 hours. Then, 5 g of acrylonitrile was added to the reaction solution. After the addition was completed, the reaction solution was further reacted for 3 hours at 60 ° C. When the viscosity of the obtained polymerization liquid was measured at 50 ° C, 25 ° C and 10 ° C, it was 13 × at 50 ° C.
It was 704 × 10 2 at 10 2 and 25 ° C. and 1660 × 10 2 at 10 ° C.
なお、上記重合液中には重合体のヒモ状に析出したもの
が浮遊しており、50℃以下では水性ゲルとなった。In addition, in the above-mentioned polymerization liquid, a string of polymer deposited was suspended, and it became an aqueous gel at 50 ° C or lower.
次に上記重合液を使用して実施例１と同様にして塗膜を
作った。得られた塗膜はその表面にブツブツが観察さ
れ、平滑でなかった。該塗膜をテフロン製シートよりは
がし、水中に浸漬したところ吸水して含水ゲル膜となっ
た。その時浸漬する水の温度を50、25、10℃に変え、塗
膜1g当りの膨潤量を測定したところ、38.5、45.3、69.3
gと得られた。ただし、その吸水した表面には凹凸が多
数存在し、膨んだ部所に接触したところ、糸洩性があり
一部水溶性のあることが確認された。Next, a coating film was prepared in the same manner as in Example 1 using the above polymerization solution. The obtained coating film was not smooth, with burrs observed on its surface. When the coating film was peeled off from the Teflon sheet and immersed in water, it absorbed water to form a hydrogel film. At that time, the temperature of the water to be immersed was changed to 50, 25, and 10 ° C, and the swelling amount per 1 g of the coating film was measured to be 38.5, 45.3, 69.3.
got g. However, it was confirmed that the water-absorbed surface had many irregularities, and when it came into contact with the swollen portion, it had thread leakage and was partially water-soluble.
比較例３ 蒸留水45.0gにＮ−アクリロイルピロリジン5.0g及びメ
チレンビスアクリルアミド0.5gを添加し、反応器内をチ
ッ素ガスで置換した後20℃に保って過硫酸アンモニウム
0.5g及び亜硫酸水素ナトリウム0.2gを添加し、４時間重
合した。Comparative Example 3 5.0 g of N-acryloylpyrrolidine and 0.5 g of methylenebisacrylamide were added to 45.0 g of distilled water, and the inside of the reactor was replaced with nitrogen gas and then kept at 20 ° C. to give ammonium persulfate.
0.5 g and 0.2 g of sodium hydrogen sulfite were added and polymerized for 4 hours.
得られた重合液を使用して実施例１と全く同様にして塗
膜を製造しようとしたが、重合液は溶液にならずゲル状
で塗布できなかった。An attempt was made to produce a coating film using the obtained polymerization liquid in exactly the same manner as in Example 1, but the polymerization liquid did not become a solution and could not be applied in gel form.
比較例４ 蒸留水45.0gにＮ−アクリロイルピロリジン5.0g及びＮ
−メチロールアクリルアミド1.5gを添加し、反応器内を
チッ素ガスで置換した後20℃に保って過硫酸アンモニウ
ム0.5g及び亜硫酸水素ナトリウム0.2gを添加し、４時間
重合した。Comparative Example 4 N-acryloylpyrrolidine 5.0 g and N were added to distilled water 45.0 g.
-Methylol acrylamide (1.5 g) was added, and the inside of the reactor was replaced with nitrogen gas. Then, 0.5 g of ammonium persulfate and 0.2 g of sodium bisulfite were added, and the mixture was polymerized for 4 hours.
得られた重合液を使用して実施例１と全く同様にして塗
膜を製造した。しかし、乾燥物は至るところヒビ割れし
ており塗膜とはならなかった。A coating film was produced in the same manner as in Example 1 by using the obtained polymerization liquid. However, the dried product was cracked everywhere and did not form a coating film.
実施例２ 蒸留水83gにＮ−アクリロイルピロリジン2.0g及びAPPS
−Na0.1gを添加し、反応器内をチッ素で置換した後、60
℃に加温した。ついで反応液に過硫酸カリウム0.06gを
添加し重合を開始し、30分間重合した。反応液は重合が
進行するにつれて、徐々に白濁し、シード粒子が生成し
た。このようにして得られたシード粒子分散液に蒸留水
10g、Ｎ−アクリロイルピロリジン4.9g及びAPPS−Na0.1
gよりなる水溶液をそのままの温度で１時間かけてゆっ
くり滴下し、その後更に５時間重合した。Example 2 2.0 g of N-acryloylpyrrolidine and APPS in 83 g of distilled water
-After adding 0.1 g of Na and replacing the inside of the reactor with nitrogen, 60
Warmed to ° C. Then, 0.06 g of potassium persulfate was added to the reaction solution to start polymerization, and polymerization was continued for 30 minutes. The reaction liquid gradually became cloudy as the polymerization proceeded, and seed particles were generated. Distilled water was added to the seed particle dispersion thus obtained.
10 g, N-acryloylpyrrolidine 4.9 g and APPS-Na0.1
An aqueous solution consisting of g was slowly added dropwise at the same temperature over 1 hour, and then polymerized for 5 hours.
得られた重合液の粘度を50℃、25℃及び10℃で測定し、
結果を表−１に示した。なお、その時重合液は50℃では
乳化状態であり、25℃及び10℃では透明であった。The viscosity of the obtained polymerization liquid was measured at 50 ° C, 25 ° C and 10 ° C,
The results are shown in Table-1. At that time, the polymerization liquid was in an emulsified state at 50 ° C and transparent at 25 ° C and 10 ° C.
また、上記した重合液を12cm×12cm角のテフロン製シー
トに刷毛塗りし、それを125℃で２時間乾燥して塗膜を
作った。得られた塗膜は厚みムラがなく、表面も滑らか
であった。塗膜をテフロン製シートよりはがし、その厚
みを測定したところ0.2mmであり、該塗膜を水中に浸漬
すると吸水して含水ゲル膜となった。その時浸漬する水
の温度を10、25、50℃に変え、塗膜1g当りの膨潤量を測
定し、表−１に示した。Further, the above-mentioned polymerization solution was brush-coated on a 12 cm × 12 cm square Teflon sheet, which was dried at 125 ° C. for 2 hours to form a coating film. The resulting coating film had no thickness unevenness and had a smooth surface. The coating film was peeled off from the Teflon sheet and its thickness was measured to be 0.2 mm. When the coating film was immersed in water, it absorbed water to form a hydrous gel film. The temperature of the water soaked at that time was changed to 10, 25 and 50 ° C., and the amount of swelling per 1 g of the coating film was measured and shown in Table 1.
実施例３〜５ 実施例２と単量体の種類及びその濃度、更には重合方法
は全く同様にしてエマルション重合を行った。ただし、
単量体水溶液を添加終了後１時間そのまま重合した後、
実施例３では２−ヒドロシエチルメタクリレート2.1g
を、実施例４ではエチルアクリレート2.1gを、実施例５
ではスチレン2.1gを30分かけて滴下し、その後、そのま
まの状態で５時間反応を行った。Examples 3 to 5 Emulsion polymerization was carried out in exactly the same manner as in Example 2 except for the type and concentration of the monomer and the polymerization method. However,
After completion of addition of the aqueous monomer solution, polymerization is continued for 1 hour, then,
In Example 3, 2.1 g of 2-hydroxyethylmethacrylate
In Example 4, 2.1 g of ethyl acrylate, Example 5
Then, 2.1 g of styrene was added dropwise over 30 minutes, and then the reaction was performed for 5 hours in that state.
得られた重合液は実施例２と全く同様にして、その溶液
粘度及び塗膜の膨潤量を測定して、その結果を表−１に
示した。なお重合液は冷却する事により水性ゲル状を呈
した。The obtained polymer solution was measured in the same manner as in Example 2 for its solution viscosity and coating film swelling amount, and the results are shown in Table 1. The polymer solution was in the form of an aqueous gel upon cooling.
実施例６ 実施例２と全く同様にしてシード粒子を製造した。ただ
し、APPS−Na0.1gのかわりに２−アクリルアミド−２−
メチルプロパンスルホン酸ナトリウム（以下、AMPS−Na
と略す。）0.1gを使用した。このようにして得たシード
粒子分散液に蒸留水10g、Ｎ−アクリロイルピロリジン
2.7g、アクリロニトリル2.3g及びAMPS−Na0.1gよりなる
水溶液をそのままの温度で１時間かけて滴下し、その後
更に４時間重合した。Example 6 Seed particles were produced in exactly the same manner as in Example 2. However, instead of APPS-Na 0.1g, 2-acrylamido-2-
Sodium methyl propane sulfonate (hereinafter AMPS-Na
Abbreviated. ) 0.1 g was used. 10 g of distilled water and N-acryloylpyrrolidine were added to the seed particle dispersion thus obtained.
An aqueous solution consisting of 2.7 g, acrylonitrile 2.3 g and AMPS-Na 0.1 g was added dropwise at the same temperature over 1 hour, and then polymerized for 4 hours.
得られた重合液は実施例２と全く同様にして、その溶液
粘度及び塗膜の膨潤量を測定して、その結果を表−１に
示した。The obtained polymer solution was measured in the same manner as in Example 2 for its solution viscosity and coating film swelling amount, and the results are shown in Table 1.
実施例７ 実施例２と全く同様にしてシード粒子を製造した。この
ようにして得たシード粒子分散液に蒸留水10g、Ｎ−ア
クリロイルピロリジン2.7g及びAPPS−Na0.1gよりなる水
溶液をそのままの温度で１時間かけて滴下し、その後１
時間重合した。重合後、更にアクリロニトリル2.3gを滴
下しその後更に４時間重合した。Example 7 Seed particles were manufactured in exactly the same manner as in Example 2. An aqueous solution consisting of 10 g of distilled water, 2.7 g of N-acryloylpyrrolidine and 0.1 g of APPS-Na was added dropwise to the seed particle dispersion thus obtained at that temperature for 1 hour, and then 1
Polymerized for hours. After the polymerization, 2.3 g of acrylonitrile was further added dropwise, and then the polymerization was further continued for 4 hours.
得られた重合液は実施例２と全く同様にして、その溶液
粘度及び塗膜の膨潤量を測定して、その結果を表−１に
示した。The obtained polymer solution was measured in the same manner as in Example 2 for its solution viscosity and coating film swelling amount, and the results are shown in Table 1.
実施例８ 実施例２と全く同様にしてシード粒子を製造した。ただ
し、APPS−Na0.1gのかわりにAMPS−Na0.1gを使用した。
このようにして得たシード粒子分散液に蒸留水10g、Ｎ
−アクリロイルピロリジン2.7g及びAMPS−Na0.1gよりな
る水溶液をそのままの温度で１時間かけて滴下し、その
後引きつづいてアクリロニトリル2.3gを滴下し、その後
更に４時間重合した。Example 8 Seed particles were manufactured in exactly the same manner as in Example 2. However, 0.1 g of AMPS-Na was used instead of 0.1 g of APPS-Na.
10 g of distilled water and N were added to the seed particle dispersion thus obtained.
An aqueous solution of 2.7 g of acryloylpyrrolidine and 0.1 g of AMPS-Na was added dropwise at the same temperature for 1 hour, followed by 2.3 g of acrylonitrile, followed by polymerization for 4 hours.
得られた重合液は実施例２と全く同様にして、その溶液
粘度及び塗膜の膨潤量を測定して、その結果を表−１に
示した。The obtained polymer solution was measured in the same manner as in Example 2 for its solution viscosity and coating film swelling amount, and the results are shown in Table 1.
実施例９ 蒸留水100g、Ｎ−アクリロイルピペリジン4.0g及びAPPS
−Na0.2gを使用した以外は実施例２と全く同様にしてシ
ード粒子を製造した。このようにして得たシード粒子分
散液に蒸留水10g、Ｎ−アクリロイルピペリジン5.0g、
Ｎ−メチロールメタクリルアミド1.0g及びAPPS−Na0.1g
よりなる水溶液をそのままの温度で１時間かけて滴下
し、その後更に４時間重合した。Example 9 100 g distilled water, 4.0 g N-acryloylpiperidine and APPS
Seed particles were produced in exactly the same manner as in Example 2 except that 0.2 g of Na was used. To the seed particle dispersion thus obtained, 10 g of distilled water, 5.0 g of N-acryloylpiperidine,
N-methylolmethacrylamide 1.0g and APPS-Na 0.1g
The resulting aqueous solution was added dropwise at the same temperature over 1 hour and then polymerized for 4 hours.
得られた重合液は実施例２と全く同様にして、その溶液
粘度及び塗膜の膨潤量を測定して、その結果を表−１に
示した。The obtained polymer solution was measured in the same manner as in Example 2 for its solution viscosity and coating film swelling amount, and the results are shown in Table 1.
実施例10 蒸留水110g、Ｎ−アクリロイルピロリジン0.7g、Ｎ−ア
クリロイルピペリジン2.1g、AMPS−Na0.2g及び過硫酸カ
リウム0.1gを使用した以外は実施例２と全く同様にして
シード粒子を製造した。このようにして得たシード粒子
分散液に蒸留水35g、Ｎ−アクリロイルピロリジン2.1
g、Ｎ−アクリロイルピペリジン6.2g、AMPS−Na0.2gよ
りなる水溶液をそのままの温度で１時間かけて滴下し、
引き続いて蒸留水17.5g、２−ヒドロキシエチルメタク
リレート1.1g及びポリエチレングリコールジアクリレー
ト（新中村化学社製14EGA）0.12gよりなる水溶液を30分
で滴下した。その後、４時間重合を行った。Example 10 Seed particles were produced in exactly the same manner as in Example 2 except that 110 g of distilled water, 0.7 g of N-acryloylpyrrolidine, 2.1 g of N-acryloylpiperidine, 0.2 g of AMPS-Na and 0.1 g of potassium persulfate were used. . 35 g of distilled water and N-acryloylpyrrolidine 2.1 were added to the seed particle dispersion thus obtained.
g, N-acryloylpiperidine 6.2 g, AMPS-Na 0.2 g aqueous solution was added dropwise at the same temperature over 1 hour,
Subsequently, an aqueous solution containing 17.5 g of distilled water, 1.1 g of 2-hydroxyethyl methacrylate and 0.12 g of polyethylene glycol diacrylate (14EGA manufactured by Shin-Nakamura Chemical Co., Ltd.) was added dropwise over 30 minutes. Then, polymerization was performed for 4 hours.
得られた重合液は実施例２と全く同様にして、その溶液
粘度及び塗膜の膨潤量を測定して、その結果を表−１に
示した。The obtained polymer solution was measured in the same manner as in Example 2 for its solution viscosity and coating film swelling amount, and the results are shown in Table 1.
実施例11 蒸留水110g、Ｎ−アクリロイルピロリジン0.5g、Ｎ−ア
クリロイルピペリジン1.5g、AMPS−Na0.2g及び過硫酸カ
リウム0.1gを使用した以外は実施例２と全く同様にして
シード粒子を製造した。このようにして得たシード粒子
分散液に蒸留水35g、Ｎ−アクリロイルピロリジン1.5
g、Ｎ−アクリロイルピペリジン4.4g及びAMPS−Na0.2g
よりなる水溶液をそのままの温度で１時間かけて滴下
し、引き続いて蒸留水17.5g、２−ヒドロキシエチルメ
タクリレート0.77g及びＮ−メチロールメタクリルアミ
ド3.7gよりなる水溶液を30分で滴下した。その後４時間
重合を行った。Example 11 Seed particles were produced in exactly the same manner as in Example 2 except that 110 g of distilled water, 0.5 g of N-acryloylpyrrolidine, 1.5 g of N-acryloylpiperidine, 0.2 g of AMPS-Na and 0.1 g of potassium persulfate were used. . 35 g of distilled water and 1.5 g of N-acryloylpyrrolidine were added to the seed particle dispersion thus obtained.
g, N-acryloylpiperidine 4.4 g and AMPS-Na 0.2 g
The resulting aqueous solution containing 17.5 g of distilled water, 0.77 g of 2-hydroxyethyl methacrylate and 3.7 g of N-methylolmethacrylamide was added dropwise over 30 minutes at the same temperature. Then, polymerization was performed for 4 hours.
得られた重合液は実施例２と全く同様にして、その溶液
粘度及び塗膜の膨潤量を測定して、その結果を表−１に
示した。The obtained polymer solution was measured in the same manner as in Example 2 for its solution viscosity and coating film swelling amount, and the results are shown in Table 1.
実施例12 蒸留水189gにアクリル酸エチル0.075g、アクリル酸ブチ
ル0.025g、２−ヒドロキシエチルメタクリレート0.005g
及びAMPS−Na0.3gを添加し、反応器内を窒素ガスで置換
した後75℃に加温した。ついで反応液に過硫酸カリウム
0.18gを添加し重合を開始し、20分間重合し、シード粒
子分散液を得た。ついで、温度を60℃に下げて水90gに
Ｎ−アクリロイルピロリジン14.9g、アクリル酸6.0g及
びAMPS−Na0.3gを溶解した溶液を30分間かけて連続的に
添加し、その後５時間重合した。Example 12 Ethyl acrylate 0.075 g, butyl acrylate 0.025 g, and 2-hydroxyethyl methacrylate 0.005 g in 189 g of distilled water.
And 0.3 g of AMPS-Na were added and the inside of the reactor was replaced with nitrogen gas, and then heated to 75 ° C. Then add potassium persulfate to the reaction mixture.
Polymerization was started by adding 0.18 g, and polymerization was carried out for 20 minutes to obtain a seed particle dispersion liquid. Then, the temperature was lowered to 60 ° C., and a solution prepared by dissolving 14.9 g of N-acryloylpyrrolidine, 6.0 g of acrylic acid and 0.3 g of AMPS-Na in 90 g of water was continuously added over 30 minutes, and then polymerized for 5 hours.
得られた重合液は実施例２と全く同様にして、その溶液
粘度及び塗膜の膨潤量を測定して、その結果を表−１に
示した。The obtained polymer solution was measured in the same manner as in Example 2 for its solution viscosity and coating film swelling amount, and the results are shown in Table 1.
実施例13 実施例12においてシード成分としてメタクリル酸メチル
1.0g、２−ヒドロキシエチルメタクリレート0.5g及びAM
PS−Na0.3gを使用した以外は実施例12と全く同様にして
エマルション重合を行った。Example 13 Methyl methacrylate as a seed component in Example 12
1.0 g, 2-hydroxyethyl methacrylate 0.5 g and AM
Emulsion polymerization was performed in exactly the same manner as in Example 12 except that 0.3 g of PS-Na was used.
得られた重合液は実施例２と同様にして、その溶液粘度
及び塗膜の膨潤量を測定して、その結果を表−１に示し
た。The solution viscosity and the amount of swelling of the coating film of the obtained polymerization liquid were measured in the same manner as in Example 2, and the results are shown in Table 1.
〔発明の効果〕 上記より明らかなように本発明によれば従来困難であっ
た水不溶性の水性塗膜を極めて容易に提供することがで
き、かつ得られた塗膜の表面状態は極めて良好なもので
あり、各種素材へ容易に塗布することができ、調湿、結
露防止等への応用などに有用である。 [Effects of the Invention] As is clear from the above, according to the present invention, a water-insoluble aqueous coating film, which has heretofore been difficult, can be provided very easily, and the surface state of the obtained coating film is extremely good. Since it can be easily applied to various materials, it is useful for applications such as humidity control and dew condensation prevention.
Claims (1)
れる （上式でR1は水素原子またはメチル基、R2は水素原子、
メチル基またはエチル基、R3はメチル基、エチル基また
はプロピル基を表す。） （上式でR1は水素原子またはメチル基、ＡはCH2 ｎ
でｎは４〜６またはCH2 2OCH2 ２である。） で表わされる単量体の単独重合体若しくは共重合体、ま
たは上記した単量体と共重合可能な他の単量体との共重
合体を含んでなる水性組成物であって、該単独重合体ま
たは共重合体が一般式（Ｉ）または（II）で表わされる
単量体又は他の単量体の１種以上の重合体のシード粒子
を核としてエマルション状態で重合させた重合体エマル
ションからなる水性組成物をまず形成し、該水性組成物
を、５〜80℃で基材上に塗布して塗膜を形成し、50〜25
0℃で乾燥せしめる、温度に依存して水蒸気の吸収・放
出作用を有する表面平滑性にすぐれた水不溶性の水性塗
膜の製造方法。1. A compound represented by formula (I) or formula (II) (In the above formula, R 1 is a hydrogen atom or a methyl group, R 2 is a hydrogen atom,
A methyl group or an ethyl group, R 3 represents a methyl group, an ethyl group or a propyl group. ) (In the above formula, R 1 is a hydrogen atom or a methyl group, A is CH 2 n
In n is 4-6 or CH 2 2 OCH 2 2. ) A homopolymer or copolymer of the monomer represented by: or an aqueous composition comprising a copolymer of the above-mentioned monomer and another monomer copolymerizable with the monomer, Polymer emulsion in which a polymer or copolymer is polymerized in an emulsion state with seed particles of one or more polymers of the monomer represented by the general formula (I) or (II) or one or more other monomers as cores. First, an aqueous composition consisting of is formed, and the aqueous composition is applied on a substrate at 5 to 80 ° C. to form a coating film,
A method for producing a water-insoluble aqueous coating film which is dried at 0 ° C. and has a water vapor absorption / release effect depending on temperature and which has excellent surface smoothness.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60275036A JPH0742436B2 (en) | 1985-12-09 | 1985-12-09 | Method for producing aqueous coating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60275036A JPH0742436B2 (en) | 1985-12-09 | 1985-12-09 | Method for producing aqueous coating film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62135573A JPS62135573A (en) | 1987-06-18 |
| JPH0742436B2 true JPH0742436B2 (en) | 1995-05-10 |
Family
ID=17549970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60275036A Expired - Lifetime JPH0742436B2 (en) | 1985-12-09 | 1985-12-09 | Method for producing aqueous coating film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0742436B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101960738B1 (en) * | 2018-08-13 | 2019-03-21 | 윤인용 | Sheet manufacturing method using water base acrylic coating agent and blowing preventing and waterproof method of roof shingle using thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006241339A (en) * | 2005-03-04 | 2006-09-14 | Nippon Shokubai Co Ltd | Polyaniline-containing composition and method for producing the same |
| WO2007148506A1 (en) * | 2006-06-19 | 2007-12-27 | Denki Kagaku Kogyo Kabushiki Kaisha | Resin composition, and temporary fixation method and surface protection method for member to be processed each using the resin composition |
| GB201512725D0 (en) | 2015-07-20 | 2015-08-26 | Life Technologies As | Polymeric particles |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS170001B1 (en) * | 1973-07-31 | 1976-08-27 | ||
| JPS5949243B2 (en) * | 1975-06-17 | 1984-12-01 | キヨウワガスカガクコウギヨウ カブシキガイシヤ | Method for producing hydrophilic polymer |
| JPS6026064A (en) * | 1983-07-21 | 1985-02-08 | Nippon Sheet Glass Co Ltd | Coated article having surface having excellent water-wettability |
| JP2587808B2 (en) * | 1983-10-22 | 1997-03-05 | 三井東圧化学株式会社 | Water separation retention release agent |
| JPS62124156A (en) * | 1985-11-25 | 1987-06-05 | Mitsui Toatsu Chem Inc | Production of aqueous coating film |
-
1985
- 1985-12-09 JP JP60275036A patent/JPH0742436B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101960738B1 (en) * | 2018-08-13 | 2019-03-21 | 윤인용 | Sheet manufacturing method using water base acrylic coating agent and blowing preventing and waterproof method of roof shingle using thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62135573A (en) | 1987-06-18 |
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