JP2010126638A - Aqueous emulsion composition of thermally crosslinkable polymer, method for producing the same, and fiber treatment agent - Google Patents
Aqueous emulsion composition of thermally crosslinkable polymer, method for producing the same, and fiber treatment agent Download PDFInfo
- Publication number
- JP2010126638A JP2010126638A JP2008302677A JP2008302677A JP2010126638A JP 2010126638 A JP2010126638 A JP 2010126638A JP 2008302677 A JP2008302677 A JP 2008302677A JP 2008302677 A JP2008302677 A JP 2008302677A JP 2010126638 A JP2010126638 A JP 2010126638A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous emulsion
- polymer
- emulsion composition
- ethylenically unsaturated
- unsaturated monomer
- 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.)
- Granted
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 92
- 229920000642 polymer Polymers 0.000 title claims abstract description 71
- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 28
- 239000000835 fiber Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 50
- 238000004132 cross linking Methods 0.000 claims abstract description 49
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 44
- 125000000524 functional group Chemical group 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 28
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- 229920006037 cross link polymer Polymers 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 7
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 4
- 229920006158 high molecular weight polymer Polymers 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 51
- 239000000123 paper Substances 0.000 description 36
- -1 methyl glycidyl Chemical group 0.000 description 15
- 230000004048 modification Effects 0.000 description 13
- 238000012986 modification Methods 0.000 description 13
- 150000007513 acids Chemical class 0.000 description 12
- 238000010828 elution Methods 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 229920003169 water-soluble polymer Polymers 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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 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
- 125000003118 aryl group Chemical group 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- 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
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- FYYIUODUDSPAJQ-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 2-methylprop-2-enoate Chemical compound C1C(COC(=O)C(=C)C)CCC2OC21 FYYIUODUDSPAJQ-UHFFFAOYSA-N 0.000 description 1
- DPTGFYXXFXSRIR-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl prop-2-enoate Chemical compound C1C(COC(=O)C=C)CCC2OC21 DPTGFYXXFXSRIR-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 240000008564 Boehmeria nivea Species 0.000 description 1
- 239000004135 Bone phosphate Chemical class 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000219146 Gossypium Species 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
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N aconitic acid Chemical class OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000013305 flexible fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 240000004308 marijuana Species 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- UFOIOXZLTXNHQH-UHFFFAOYSA-N oxolane-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C1OC(C(O)=O)C(C(O)=O)C1C(O)=O UFOIOXZLTXNHQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
本発明は、塗料、接着剤、粘着剤、紙処理剤及び繊維処理剤等に利用できる熱架橋型高分子重合体水性エマルジョン組成物、その製造方法及び繊維処理剤に関する。 TECHNICAL FIELD The present invention relates to a thermally crosslinkable polymer aqueous emulsion composition that can be used for paints, adhesives, pressure-sensitive adhesives, paper treatment agents, fiber treatment agents, and the like, a production method thereof, and a fiber treatment agent.
近年、省資源及び環境保全の見地から有機溶剤を含まない水性樹脂に関心が向けられている。これらの中でポリマーエマルジョンは乾燥性に優れ、不揮発分を高くしても低粘度化が可能であるため、水性樹脂として、塗料、接着剤、粘着剤、紙処理剤及び繊維処理剤等に広く使用されている。しかしながらポリマーエマルジョンは、エマルジョン粒子を安定に分散させるために、比較的多量の分散安定剤が用いられる。そのため乾燥皮膜は耐水性が劣り、性能が不十分になる傾向がある。また、塗料、接着剤、粘着剤、紙処理剤及び繊維処理剤として用いた場合も同様である。この問題を解決するために、エマルジョンのポリマー分子中に官能基を導入し、該官能基を利用して架橋反応を行い、耐水性等を改善した合成樹脂水性エマルジョンを得る方法が多数提案されている。 In recent years, interest has been directed to water-based resins that do not contain organic solvents from the viewpoint of resource saving and environmental conservation. Among these, polymer emulsions are excellent in drying properties and can be reduced in viscosity even when the non-volatile content is increased. Therefore, they are widely used as paints, adhesives, pressure-sensitive adhesives, paper treatment agents, fiber treatment agents, etc. in use. However, polymer emulsions use a relatively large amount of dispersion stabilizer in order to stably disperse the emulsion particles. Therefore, the dry film has poor water resistance and tends to have insufficient performance. The same applies when used as a paint, adhesive, pressure-sensitive adhesive, paper treatment agent, and fiber treatment agent. In order to solve this problem, many methods have been proposed in which a functional group is introduced into a polymer molecule of an emulsion and a crosslinking reaction is performed using the functional group to obtain a synthetic resin aqueous emulsion having improved water resistance. Yes.
熱架橋エマルジョンとしては、公知の技術として、例えばＮ−メチロール（メタ）アクリルアミド等の加熱縮合反応性官能基を有する重合性単量体を用いたものがある。これらの架橋成分は、架橋に際して加熱装置及び熱エネルギーを必要とし、ホルムアルデヒドを放出することでさらに架橋が進行することが知られている。また、この熱架橋型合成樹脂水性エマルジョンを紙処理剤及び繊維処理剤として使用すると、得られる紙は耐水性に優れ、また得られる繊維は非常に柔らかい。
しかし、発生するホルムアルデヒドは刺激臭のある無色の気体であるだけでなく、発ガン性物質として知られており、例えば、繊維処理工程での作業環境だけでなく、製品として消費者にまで影響が及ぶことが考えられ、近年、安全性指向の高まりと共に、発ガン性のホルムアルデヒドの使用に対する規制や自粛が強化される傾向にある。
As the thermal crosslinking emulsion, there is a known technique using a polymerizable monomer having a heat condensation reactive functional group such as N-methylol (meth) acrylamide. It is known that these crosslinking components require a heating device and thermal energy for crosslinking, and further crosslinking proceeds by releasing formaldehyde. Moreover, when this heat-crosslinking type synthetic resin aqueous emulsion is used as a paper treating agent and a fiber treating agent, the obtained paper is excellent in water resistance, and the resulting fiber is very soft.
However, the formaldehyde generated is not only a colorless gas with an irritating odor, but is also known as a carcinogenic substance. For example, it affects not only the working environment in the fiber treatment process but also the consumer as a product. In recent years, with increasing safety orientation, regulations and self-restraint on the use of carcinogenic formaldehyde tend to be strengthened.
それらを解決するため、熱架橋型エマルジョンに代えて、カルボキシル基と熱架橋反応し得る水酸基を有する水溶性高分子を用いたものがある（特許文献１）。水酸基を有する水溶性高分子として、例えばポリビニルアルコール（ＰＶＡ）等を用いた場合、ホルムアルデヒドを放出せずに架橋が進行する。しかし、水溶性高分子水溶液を高不揮発分化すると、水溶液粘度が著しく上昇し、作業性が低下することとなり、利用分野によっては、大きな障害となる。 In order to solve these problems, there is one using a water-soluble polymer having a hydroxyl group capable of undergoing a thermal crosslinking reaction with a carboxyl group in place of the thermal crosslinking emulsion (Patent Document 1). When, for example, polyvinyl alcohol (PVA) or the like is used as the water-soluble polymer having a hydroxyl group, crosslinking proceeds without releasing formaldehyde. However, when the water-soluble polymer aqueous solution is highly non-volatilely differentiated, the viscosity of the aqueous solution is remarkably increased and the workability is lowered, which is a serious obstacle depending on the application field.
更に、本発明者らは、それらを解決するため、カルボキシル基と熱架橋反応し得る官能基を有する合成樹脂水性エマルジョンとポリカルボン酸を配合してなるエマルジョン組成物を開示した（特許文献２）が、低熱処理条件下では、架橋反応が進行しにくく、紙の耐水性が優れない等の問題があり、使用環境によっては、大きな障害となる。 Furthermore, in order to solve these problems, the present inventors disclosed an emulsion composition comprising a synthetic resin aqueous emulsion having a functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group and a polycarboxylic acid (Patent Document 2). However, under low heat treatment conditions, there are problems such that the cross-linking reaction does not proceed easily and the water resistance of the paper is not excellent, and this is a serious obstacle depending on the use environment.
本発明はこのような状況に鑑み、ホルムアルデヒドを放出せず、熱架橋性を有し、また、紙処理剤として使用すると、低熱処理条件下で得られた紙であっても耐水性に優れ、さらに、繊維処理剤として使用すると、柔軟性に富む繊維が得られる熱架橋型高分子重合体水性エマルジョン組成物、その製造方法及び繊維処理剤の提供を目的とする。 In view of such a situation, the present invention does not release formaldehyde, has thermal crosslinkability, and when used as a paper treatment agent, it is excellent in water resistance even if it is paper obtained under low heat treatment conditions. Furthermore, it aims at provision of the heat-crosslinking-type high molecular weight polymer aqueous emulsion composition from which the fiber which is rich in a flexibility will be obtained when it is used as a fiber processing agent, its manufacturing method, and a fiber processing agent.
かかる課題を解決するために本発明では、従来のカルボキシル基と熱架橋反応し得る官能基を有する高分子重合体水性エマルジョンとポリカルボン酸を配合するものに変えて、ポリカルボン酸存在下、カルボキシル基と熱架橋反応し得る官能基を有するエチレン性不飽和単量体および場合により共重合可能なエチレン性不飽和単量体を乳化重合させて得ることで課題を解決するに至った。 In order to solve this problem, in the present invention, instead of a conventional polymer polymer aqueous emulsion having a functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group and a compound containing polycarboxylic acid, The problem was solved by emulsion-polymerizing an ethylenically unsaturated monomer having a functional group capable of undergoing a thermal crosslinking reaction with a group and optionally copolymerizable ethylenically unsaturated monomer.
すなわち、本発明は、
１．カルボキシル基と熱架橋反応し得る官能基を有する高分子重合体と、ポリカルボン酸とを含む水性エマルジョンであって、前記ポリカルボン酸のカルボキシル基の少なくとも一部が前記高分子重合体の官能基と反応していることを特徴とする熱架橋型高分子重合体水性エマルジョン組成物、
２．前記カルボキシル基と熱架橋反応し得る官能基が、グリシジル基又は水酸基である上記１記載の熱架橋型高分子重合体水性エマルジョン組成物、
３．前記ポリカルボン酸がブタンテトラカルボン酸である上記１又は２記載の熱架橋型高分子重合体水性エマルジョン組成物、
４．前記高分子重合体が、カルボキシル基と熱架橋反応し得る官能基を有するエチレン性不飽和単量体Ａを単独重合してなる高分子単独重合体である上記１〜３のいずれかに記載の熱架橋型高分子重合体水性エマルジョン組成物、
５．前記高分子重合体が、カルボキシル基と熱架橋反応し得る官能基を有するエチレン性不飽和単量体Ａ、並びに他のエチレン性不飽和単量体Ｂを共重合してなる高分子共重合体である上記１〜３のいずれかに記載の熱架橋型高分子重合体水性エマルジョン組成物、
６．上記１〜５のいずれかに記載の熱架橋型高分子重合体水性エマルジョン組成物を用いた繊維処理剤、
７．ポリカルボン酸の存在下、カルボキシル基と熱架橋反応し得る官能基を含むエチレン性不飽和単量体Ａを乳化重合させることを特徴とする上記１〜４のいずれかに記載の熱架橋型高分子重合体水性エマルジョン組成物の製造方法、
８．前記ポリカルボン酸を０．１〜１０質量部及び前記エチレン性不飽和単量体Ａを９０〜９９．９質量部用いる上記７記載の熱架橋型高分子重合体水性エマルジョン組成物の製造方法、
９．ポリカルボン酸の存在下、カルボキシル基と熱架橋反応し得る官能基を含むエチレン性不飽和単量体Ａ及び他のエチレン性不飽和単量体Ｂを乳化重合させることを特徴とする上記１、２、３又は５に記載の熱架橋型高分子重合体水性エマルジョン組成物の製造方法、
１０．前記ポリカルボン酸を０．１〜１０質量部、前記エチレン性不飽和単量体Ａを１〜２０質量部及び前記エチレン性不飽和単量体Ｂを７０〜９８．９質量部用いる上記９記載の熱架橋型高分子重合体水性エマルジョン組成物の製造方法、及び
１１．熱架橋反応の触媒として、ｐ−トルエンスルホン酸を使用する上記７〜１０のいずれかに記載の熱架橋型高分子重合体水性エマルジョン組成物の製造方法、
を提供するものである。
That is, the present invention
1. An aqueous emulsion comprising a polymer having a functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group, and a polycarboxylic acid, wherein at least a part of the carboxyl group of the polycarboxylic acid is a functional group of the polymer. A thermally crosslinkable polymer aqueous emulsion composition characterized by reacting with
2. 2. The thermally crosslinked polymer aqueous emulsion composition according to 1 above, wherein the functional group capable of undergoing a thermal crosslinking reaction with the carboxyl group is a glycidyl group or a hydroxyl group;
3. The heat-crosslinkable polymer aqueous emulsion composition according to 1 or 2, wherein the polycarboxylic acid is butanetetracarboxylic acid,
4). 4. The polymer according to any one of 1 to 3 above, wherein the polymer is a polymer homopolymer obtained by homopolymerizing an ethylenically unsaturated monomer A having a functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group. Thermally crosslinkable polymer aqueous emulsion composition,
5). A polymer copolymer obtained by copolymerizing the ethylenically unsaturated monomer A having a functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group, and another ethylenically unsaturated monomer B. The thermal crosslinkable polymer aqueous emulsion composition according to any one of 1 to 3 above,
6). A fiber treatment agent using the thermally crosslinkable polymer aqueous emulsion composition according to any one of 1 to 5,
7). 5. The heat-crosslinking type high as described in any one of 1 to 4 above, wherein an ethylenically unsaturated monomer A containing a functional group capable of undergoing a heat-crosslinking reaction with a carboxyl group is emulsion-polymerized in the presence of a polycarboxylic acid Method for producing molecular polymer aqueous emulsion composition,
8). The method for producing an aqueous emulsion composition of a heat-crosslinkable polymer polymer according to 7 above, wherein 0.1 to 10 parts by mass of the polycarboxylic acid and 90 to 99.9 parts by mass of the ethylenically unsaturated monomer A are used.
9. The above 1, wherein the ethylenically unsaturated monomer A containing a functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group and other ethylenically unsaturated monomer B are emulsion polymerized in the presence of a polycarboxylic acid. 2, a method for producing a thermally crosslinkable polymer aqueous emulsion composition according to 2, 3 or 5,
10. The above 9 using 0.1 to 10 parts by mass of the polycarboxylic acid, 1 to 20 parts by mass of the ethylenically unsaturated monomer A, and 70 to 98.9 parts by mass of the ethylenically unsaturated monomer B. 10. a method for producing a thermally crosslinkable polymer aqueous emulsion composition of The method for producing a thermally crosslinked polymer aqueous emulsion composition according to any one of 7 to 10 above, wherein p-toluenesulfonic acid is used as a catalyst for the thermal crosslinking reaction,
Is to provide.
本発明によれば、ホルムアルデヒドを放出せず、熱架橋性を有し、また、紙処理剤として使用すると、低熱処理条件下で得られた紙であっても耐水性に優れ、さらに、繊維処理剤として使用すると、柔軟性に富む繊維が得られる。 According to the present invention, it does not release formaldehyde, has thermal crosslinkability, and when used as a paper treating agent, it is excellent in water resistance even if it is paper obtained under low heat treatment conditions. When used as an agent, highly flexible fibers can be obtained.
以下、本発明を詳細に説明する。
本発明の熱架橋型高分子重合体水性エマルジョン組成物は、カルボキシル基と熱架橋反応し得る官能基を有する高分子重合体と、ポリカルボン酸とを含む水性エマルジョンであって、ポリカルボン酸のカルボキシル基の少なくとも一部が高分子重合体の官能基と反応している。
Hereinafter, the present invention will be described in detail.
A thermally crosslinkable polymer aqueous emulsion composition of the present invention is an aqueous emulsion comprising a polymer having a functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group, and a polycarboxylic acid. At least a part of the carboxyl group reacts with the functional group of the polymer.
（高分子重合体）
本発明において用いられる高分子重合体は、カルボキシル基と熱架橋反応し得る官能基（以下、反応性官能基と略すことがある。）を有するものであれば特に限定されず、反応性官能基の具体例としては、エポキシ基、水酸基、カルボジイミド基、アジリジン基、オキサゾリン基、シクロカーボネート基などが挙げられ、好ましくはエポキシ基又は水酸基である。
前記高分子重合体は、カルボキシル基と熱架橋反応し得る官能基を有するエチレン性不飽和単量体Ａを単独重合してなる高分子単独重合体や、カルボキシル基と熱架橋反応し得る官能基を有するエチレン性不飽和単量体Ａ、並びに他のエチレン性不飽和単量体Ｂを共重合してなる高分子共重合体であることが好ましく、特に高分子共重合体が重合時の反応性及び高分子重合体のガラス転移温度の自由度の観点から好ましい。
(High molecular polymer)
The high molecular polymer used in the present invention is not particularly limited as long as it has a functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group (hereinafter sometimes abbreviated as a reactive functional group). Specific examples thereof include an epoxy group, a hydroxyl group, a carbodiimide group, an aziridine group, an oxazoline group, a cyclocarbonate group, and the like, preferably an epoxy group or a hydroxyl group.
The polymer is a polymer homopolymer obtained by homopolymerizing an ethylenically unsaturated monomer A having a functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group, or a functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group. Preferably, the polymer is a polymer copolymer obtained by copolymerizing an ethylenically unsaturated monomer A having the above and another ethylenically unsaturated monomer B. In particular, the polymer copolymer is a reaction during polymerization. From the viewpoint of the flexibility and the degree of freedom of the glass transition temperature of the polymer.
前記エチレン性不飽和単量体Ａは、１分子中に少なくとも１個の反応性官能基を有する。
前記エチレン性不飽和単量体Ａのうち、グリシジル基を含むものの具体例としては、グリシジルアクリレート、グリシジルメタクリレート、アリルグリシジルエーテル、メチルグリシジルアクリレート、メチルグリシジルメタクリレート、３，４−エポキシシクロヘキシルメチルアクリレート、３，４−エポキシシクロヘキシルメチルメタクリレートなどが挙げられ、好ましくはグリシジルメタクリレートである。
前記エチレン性不飽和単量体Ａのうち、水酸基を含むものの具体例としては、ヒドロキシエチルアクリレート、ヒドロキシプロピルアクリレート、ヒドロキシブチルアクリレート、ポリエチレングリコールモノアクリレート、ポリプロピレングリコールモノアクリレート、ポリテトラメチレングリコールモノアクリレート、ポリエチレングリコールポリテトラメチレングリコールモノアクリレート、ポリプロピレングリコールポリテトラメチレングリコールモノアクリレート、ヒドロキシエチルメタクリレート、ヒドロキシプロピルメタクリレート、ヒドロキシブチルメタクリレート、ポリエチレングリコールモノメタクリレート、ポリプロピレングリコールモノメタクリレート、ポリテトラメチレングリコールモノメタクリレート、ポリエチレングリコールポリテトラメチレングリコールモノメタクリレート、ポリプロピレングリコールポリテトラメチレングリコールモノメタクリレート等が挙げられ、好ましくはヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレートである。
これらのエチレン性不飽和単量体Ａは、単独であるいは二種以上を組み合わせて使用することができる。
The ethylenically unsaturated monomer A has at least one reactive functional group in one molecule.
Specific examples of the ethylenically unsaturated monomer A containing a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methyl glycidyl acrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexyl methyl acrylate, 3 , 4-epoxycyclohexylmethyl methacrylate, and the like, preferably glycidyl methacrylate.
Specific examples of the ethylenically unsaturated monomer A containing a hydroxyl group include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polytetramethylene glycol monoacrylate, Polyethylene glycol polytetramethylene glycol monoacrylate, polypropylene glycol polytetramethylene glycol monoacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polytetramethylene glycol monomethacrylate, polyethylene Glycol polytetramethylene glycol monomethacrylate, polypropylene glycol polytetramethylene glycol monomethacrylate, and the like, preferably hydroxyethyl acrylate, hydroxyethyl methacrylate.
These ethylenically unsaturated monomers A can be used alone or in combination of two or more.
前記他のエチレン性不飽和単量体Ｂの具体例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、アリル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、メトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、アクリロニトリル、スチレン、スチレン誘導体、酢酸ビニル、プロピオン酸ビニル、塩化ビニル、塩化ビニリデン、ジビニルベンゼン、エチレン、プロピレン、ブチレン、イソブチレン等を使用することができる。これらエチレン性不飽和単量体Ｂは、単独であるいは二種以上を組み合わせて使用することができる。
なお、熱架橋の際にホルムアルデヒドを発生させるようなエチレン性不飽和単量体は、環境衛生上の観点から、用いないことが肝要である。
Specific examples of the other ethylenically unsaturated monomer B include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, allyl (meth) acrylate, ethylene Glycol di (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, acrylonitrile, styrene, styrene derivatives, vinyl acetate, vinyl propionate, Vinyl chloride, vinylidene chloride, divinylbenzene, ethylene, propylene, butylene, isobutylene and the like can be used. These ethylenically unsaturated monomers B can be used alone or in combination of two or more.
It is important not to use an ethylenically unsaturated monomer that generates formaldehyde during thermal crosslinking from the viewpoint of environmental hygiene.
（ポリカルボン酸）
本発明において使用されるポリカルボン酸としては、１分子中に３個以上のカルボキシル基を有する有機化合物である。そのようなポリカルボン酸としては、例えば、各種の直鎖状脂肪族ポリカルボン酸、分岐状脂肪族ポリカルボン酸、脂環族ポリカルボン酸、芳香族ポリカルボン酸等が使用できる。それらのポリカルボン酸は水酸基、ハロゲン原子、カルボニル基、炭素−炭素二重結合等を有していてもよく、またアミノ酸であってもよい。さらにポリカルボン酸は水溶性であっても、水不溶あるいは難溶性であってもよいが、反応性や作業性の点で水溶性のものがより好ましい。
(Polycarboxylic acid)
The polycarboxylic acid used in the present invention is an organic compound having three or more carboxyl groups in one molecule. Examples of such polycarboxylic acids include various linear aliphatic polycarboxylic acids, branched aliphatic polycarboxylic acids, alicyclic polycarboxylic acids, aromatic polycarboxylic acids, and the like. These polycarboxylic acids may have a hydroxyl group, a halogen atom, a carbonyl group, a carbon-carbon double bond, or the like, or may be an amino acid. Furthermore, the polycarboxylic acid may be water-soluble, water-insoluble or hardly soluble, but is more preferably water-soluble in terms of reactivity and workability.
ポリカルボン酸の例としては、具体的には、トリカルバリル酸、アコニチン酸、メチルシクロヘキセントリカルボン酸等の三塩基酸、ブタンテトラカルボン酸、シクロペンタンテトラカルボン酸、テトラヒドロフランテトラカルボン酸、メチルテトラヒドロフタル酸とマレイン酸のエン付加物等の四塩基酸、トリメリット酸、ピロメリット酸、ビフェニルテトラカルボン酸、ベンゾフェノンテトラカルボン酸、ジフェニルスルホンテトラカルボン酸等の芳香族ポリカルボン酸等が例示できる。これらのポリカルボン酸は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよいが、これらのうち好ましいポリカルボン酸はブタンテトラカルボン酸である。 Specific examples of polycarboxylic acids include tribasal acids, aconitic acids, tribasic acids such as methylcyclohexeric acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, and methyltetrahydrophthalic acid. Examples thereof include tetrabasic acids such as ene adducts of maleic acid and maleic acid, aromatic polycarboxylic acids such as trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and diphenylsulfonetetracarboxylic acid. One of these polycarboxylic acids may be used alone, or two or more thereof may be used in combination. Of these, a preferred polycarboxylic acid is butanetetracarboxylic acid.
本発明の熱架橋型高分子重合体水性エマルジョン組成物においては、前記ポリカルボン酸のカルボキシル基の少なくとも一部が前記高分子重合体の反応性官能基と反応している。具体的には、反応性官能基がグリシジル基である場合には、ポリカルボン酸のカルボキシル基の少なくとも一部と反応してエステル結合を形成している状態が挙げられる。
ポリカルボン酸のカルボキシル基は、少なくともその一部が高分子重合体の反応性官能基と反応していればよいが、ポリカルボン酸の全カルボキシル基に対する反応したカルボキシル基の比率（変性率）が１０〜７０モル％であると好ましく、２０〜５０モル％であるとより好ましい。
In the heat-crosslinking polymer aqueous emulsion composition of the present invention, at least a part of the carboxyl groups of the polycarboxylic acid reacts with the reactive functional groups of the polymer. Specifically, when the reactive functional group is a glycidyl group, a state in which an ester bond is formed by reacting with at least a part of the carboxyl group of the polycarboxylic acid can be mentioned.
The carboxyl group of the polycarboxylic acid may be at least partly reacted with the reactive functional group of the polymer, but the ratio of the reacted carboxyl group to the total carboxyl group of the polycarboxylic acid (modification rate) is It is preferable in it being 10-70 mol%, and it is more preferable in it being 20-50 mol%.
（製造方法）
本発明の熱架橋型高分子重合体水性エマルジョン組成物は、先に調製した高分子重合体とポリカルボン酸とを反応させて製造することもできるが、ポリカルボン酸の存在下、カルボキシル基と熱架橋反応し得る官能基を有するエチレン性不飽和単量体Ａを単独重合させる、あるいは該不飽和単量体Ａと、他のエチレン性不飽和単量体Ｂとを乳化共重合させて製造することが好ましく、特に乳化共重合させて製造することが好ましい。
上記ポリカルボン酸の存在下とは、乳化重合における釜仕込み水もしくはエチレン性不飽和単量体Ａ及びＢの乳化水中にポリカルボン酸を溶解させることである。また、これらのうち一方に溶解させておいてもよく、両者に溶解させておいても構わない。
(Production method)
The heat-crosslinkable polymer aqueous emulsion composition of the present invention can be produced by reacting the previously prepared polymer and polycarboxylic acid. In the presence of polycarboxylic acid, Manufactured by homopolymerizing an ethylenically unsaturated monomer A having a functional group capable of undergoing a thermal crosslinking reaction, or by emulsion copolymerization of the unsaturated monomer A and another ethylenically unsaturated monomer B In particular, it is preferable to produce by emulsion copolymerization.
The presence of the polycarboxylic acid means that the polycarboxylic acid is dissolved in the water charged in the kettle in the emulsion polymerization or the emulsified water of the ethylenically unsaturated monomers A and B. Moreover, you may make it melt | dissolve in one of these, and you may make it melt | dissolve in both.
単独乳化重合の場合には、前記ポリカルボン酸及びエチレン性不飽和単量体Ａの使用量としては、ポリカルボン酸を０．１〜１０質量部及びエチレン性不飽和単量体Ａを９０〜９９．９質量部の比率で用いることが好ましい。また、乳化共重合の場合には、前記ポリカルボン酸、エチレン性不飽和単量体Ａ及びエチレン性不飽和単量体Ｂの使用量としては、ポリカルボン酸を０．１〜１０質量部、エチレン性不飽和単量体Ａを１〜２０質量部、エチレン性不飽和単量体Ｂを７０〜９８．９質量部の比率でそれぞれ用いることが好ましい。ポリカルボン酸の質量比が０．１以上の場合には、エマルジョン組成物の架橋反応性が向上し、紙処理剤に用いた場合、十分な紙の耐水性が得られる。一方、質量比が１０以下である場合には、水性エマルジョン組成物の貯蔵安定性が改善し、短期間で硬化が進んでしまったり、使用不可能となったりしない。乳化共重合においては、エチレン性不飽和単量体量Ａの質量比が１以上の場合には、水性エマルジョン組成物の架橋反応性が向上し、紙処理剤に用いた場合、十分な紙の耐水性が得られる。一方、質量比が２０以下である場合には水性エマルジョン組成物の貯蔵安定性が改善し、短期間で硬化が進んでしまったり、使用不可能となったりしない。 In the case of homoemulsion polymerization, the polycarboxylic acid and the ethylenically unsaturated monomer A are used in an amount of 0.1 to 10 parts by mass of the polycarboxylic acid and 90 to 90% of the ethylenically unsaturated monomer A. It is preferably used at a ratio of 99.9 parts by mass. In the case of emulsion copolymerization, the polycarboxylic acid, the ethylenically unsaturated monomer A and the ethylenically unsaturated monomer B are used in an amount of 0.1 to 10 parts by mass of a polycarboxylic acid, It is preferable to use the ethylenically unsaturated monomer A in a ratio of 1 to 20 parts by mass and the ethylenically unsaturated monomer B in a ratio of 70 to 98.9 parts by mass, respectively. When the mass ratio of the polycarboxylic acid is 0.1 or more, the crosslinking reactivity of the emulsion composition is improved, and when used as a paper treatment agent, sufficient water resistance of paper can be obtained. On the other hand, when the mass ratio is 10 or less, the storage stability of the aqueous emulsion composition is improved, and curing does not proceed or cannot be used in a short period of time. In the emulsion copolymerization, when the mass ratio of the ethylenically unsaturated monomer amount A is 1 or more, the crosslinking reactivity of the aqueous emulsion composition is improved. Water resistance is obtained. On the other hand, when the mass ratio is 20 or less, the storage stability of the aqueous emulsion composition is improved, and curing does not proceed in a short period of time or cannot be used.
本発明の熱架橋型高分子重合体水性エマルジョン組成物の製造においては、熱架橋性を促進するために触媒を用いることができる。例えば、高分子重合体の反応性官能基が水酸基やグリシジル基である場合、熱架橋反応はカルボキシル基と、水酸基又はグリシジル基とのエステル化反応であるため、エステル化反応で通常使用される触媒が使用できる。具体的には、塩基触媒、酸触媒及び金属アルコキシド等が挙げられる。
塩基触媒としては、例えば、水酸化ナトリウム及び水酸化カリウム等の金属水酸化物、並びにトリエチルアミン、Ｎ，Ｎ−ジメチルベンジルアミン及びトリフェニルアミン等のアミン類等が挙げられる。酸触媒としては、硫酸及びｐ−トルエンスルホン酸等が挙げられる。金属アルコキシドとしては、チタン、錫又はジルコニウムのアルコキサイドが好ましい。これら金属アルコキシドの具体例としては、テトラブチルチタネート等のテトラアルキルチタネート；ジブチルスズオキサイド及びモノブチルスズオキサイド等の錫のアルコキサイド；並びにジルコニウムテトラブトキサイド及びジルコニウムイソプロポキサイド等のジルコニウムのアルコキサイド等が挙げられる。上記触媒のうち、好ましくはｐ−トルエンスルホン酸である。
In the production of the thermally crosslinkable polymer aqueous emulsion composition of the present invention, a catalyst can be used to promote thermal crosslinkability. For example, when the reactive functional group of the polymer is a hydroxyl group or a glycidyl group, the thermal crosslinking reaction is an esterification reaction between a carboxyl group and a hydroxyl group or a glycidyl group. Can be used. Specifically, a base catalyst, an acid catalyst, a metal alkoxide, etc. are mentioned.
Examples of the base catalyst include metal hydroxides such as sodium hydroxide and potassium hydroxide, and amines such as triethylamine, N, N-dimethylbenzylamine and triphenylamine. Examples of the acid catalyst include sulfuric acid and p-toluenesulfonic acid. As the metal alkoxide, an alkoxide of titanium, tin or zirconium is preferable. Specific examples of these metal alkoxides include tetraalkyl titanates such as tetrabutyl titanate; tin alkoxides such as dibutyltin oxide and monobutyltin oxide; and zirconium alkoxides such as zirconium tetrabutoxide and zirconium isopropoxide. Of the above catalysts, p-toluenesulfonic acid is preferred.
本発明の熱架橋型高分子重合体水性エマルジョン組成物を乳化重合によって製造する場合には、界面活性剤の存在下で乳化重合を行う。界面活性剤としては、一般に市販されているアニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤及び共重合性乳化剤が使用できる。また、これらの界面活性剤は、単独であるいは二種以上を組み合わせて使用することができる。本発明の熱架橋型高分子重合体水性エマルジョン組成物における界面活性剤量は、特に制限されない。
乳化重合においては、重合開始剤を使用することが好ましい。重合開始剤としては、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、過酸化水素、アゾ系化合物等が使用される。また、これらと還元剤の併用によるレドックス系開始剤を使用することもできる。
また、本発明の水性エマルジョン組成物の乳化重合法としては、一括して仕込み重合する方法、各成分を連続供給しながら重合する方法などが適用できる。重合は通常３０〜８５℃の温度で攪拌下に行われる。
When the heat-crosslinking polymer aqueous emulsion composition of the present invention is produced by emulsion polymerization, the emulsion polymerization is carried out in the presence of a surfactant. As the surfactant, commercially available anionic surfactants, nonionic surfactants, cationic surfactants and copolymerizable emulsifiers can be used. These surfactants can be used alone or in combination of two or more. The amount of the surfactant in the heat crosslinkable polymer aqueous emulsion composition of the present invention is not particularly limited.
In emulsion polymerization, it is preferable to use a polymerization initiator. As the polymerization initiator, persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide, azo compounds and the like are used. Moreover, the redox initiator by using these together with a reducing agent can also be used.
In addition, as the emulsion polymerization method of the aqueous emulsion composition of the present invention, a method of batch polymerization and a method of polymerization while continuously supplying each component can be applied. The polymerization is usually carried out at a temperature of 30 to 85 ° C. with stirring.
本発明はまた、上記熱架橋型高分子重合体水性エマルジョン組成物を用いた繊維処理剤をも提供する。
本発明の熱架橋型高分子重合体水性エマルジョン組成物を処理剤として使用するのに好適な繊維は、綿、亜麻、黄麻、大麻、ラミー及び再生繊維セルロース、レーヨン等のセルロース繊維、ポリビニルアルコール系合成繊維等を３０質量％程度以上含むものである。また、繊維処理剤として使用する場合、繊維の形態は、短繊維（ファイバー）、リンター、ロービング、スライバー、ヤーン、織物、編物、不織布等何れの形態であっても適用することができる。
The present invention also provides a fiber treatment agent using the above heat-crosslinkable polymer aqueous emulsion composition.
Fibers suitable for using the thermally crosslinkable polymer aqueous emulsion composition of the present invention as a treating agent include cellulose fibers such as cotton, flax, jute, cannabis, ramie and regenerated fiber cellulose, rayon, etc., polyvinyl alcohol type It contains about 30% by mass or more of synthetic fibers and the like. Moreover, when using as a fiber processing agent, the form of a fiber is applicable even if it is any form, such as a short fiber (fiber), a linter, a roving, a sliver, a yarn, a woven fabric, a knitted fabric, a nonwoven fabric.
本発明の熱架橋型高分子重合体水性エマルジョン組成物を紙処理剤として使用するのに好適な紙としては、パルプセルロースからなる汎用の紙類が挙げられる。 Examples of paper suitable for using the water-crosslinking polymer aqueous emulsion composition of the present invention as a paper treating agent include general-purpose papers made of pulp cellulose.
以下実施例によって本発明を更に説明するが、本発明はそれらに何ら限定されるものではない。 EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.
実施例及び比較例で得られた水性エマルジョン組成物の物性試験方法及び評価は、以下の通りに行った。
（濾紙強度）
得られた水性エマルジョン組成物を１０質量％に希薄し、濾紙（東洋濾紙株式会社製）に２０〜３０ｇ／ｍ2含浸し、１１０℃にて１０分間乾燥した。こうして、得られた濾紙を濾紙Ａとした。更に、オーブンにて１５０℃で５分間熱処理したものを濾紙Ｂとした。各処理後の濾紙の引っ張り強度を常態濾紙強度とし、また、２３℃の水中に１０分間浸漬した後の濾紙の引っ張り強度を湿潤濾紙強度として測定した（引っ張り速度；２００ｍｍ／分、試験片サイズ；２５×１００ｍｍ、チャック間距離；５０ｍｍ）。強度に関して、１．５ｋｇｆ／２５ｍｍ以上が実用上支障をきたさない強度である。
The physical property test methods and evaluations of the aqueous emulsion compositions obtained in Examples and Comparative Examples were performed as follows.
(Filter paper strength)
The obtained aqueous emulsion composition was diluted to 10% by mass, impregnated with filter paper (manufactured by Toyo Filter Paper Co., Ltd.) at 20 to 30 g / m 2 , and dried at 110 ° C. for 10 minutes. The filter paper thus obtained was designated as filter paper A. Further, filter paper B was heat-treated at 150 ° C. for 5 minutes in an oven. The tensile strength of the filter paper after each treatment was defined as normal filter paper strength, and the tensile strength of the filter paper after being immersed in water at 23 ° C. for 10 minutes was measured as wet filter paper strength (tensile speed; 200 mm / min, test piece size; 25 × 100 mm, distance between chucks: 50 mm). Regarding the strength, 1.5 kgf / 25 mm or more is a strength that does not cause any practical problems.
（剛軟性）
得られた水性エマルジョン組成物を１０質量％に希薄し、布に２０〜３０ｇ／ｍ2含浸し、ピンテンターにて１３０℃で５分間処理した後、ＪＩＳ Ｌ１０９６ ６．１９剛軟性 Ｅ法（ハンドルオメーター法）に準じて、剛軟性を測定した。
(Flexibility)
The obtained aqueous emulsion composition was diluted to 10% by mass, impregnated with 20-30 g / m 2 on a cloth, treated with a pin tenter at 130 ° C. for 5 minutes, and then subjected to JIS L1096 6.19 stiffness / softness E method (handle handle). The bending resistance was measured according to the meter method.
（溶出ホルムアルデヒド量）
得られた水性エマルジョン組成物を１０質量％に希薄し、布に２０〜３０ｇ／ｍ2含浸し、ピンテンターにて１３０℃で５分間処理した後、ＪＩＳ Ｌ１０４１アセチルアセトン法に準じて、溶出ホルムアルデヒド量を測定した。
(Elution formaldehyde amount)
The obtained aqueous emulsion composition was diluted to 10% by mass, impregnated with 20-30 g / m 2 on a cloth, treated with a pin tenter at 130 ° C. for 5 minutes, and the amount of formaldehyde eluted was determined according to JIS L1041 acetylacetone method. It was measured.
（カルボキシル基変性率）
カルボキシル基変性率は、得られた水性エマルジョン組成物を１０質量％に希薄し、残存カルボキシル基量をＫＯＨを用いて滴定することによって測定した。
(Carboxyl group modification rate)
The carboxyl group modification rate was measured by diluting the obtained aqueous emulsion composition to 10% by mass and titrating the amount of residual carboxyl groups using KOH.
実施例１
撹拌機、温度計、還流冷却機、滴下ロートを有する容器中に、イオン交換水を１７８．８質量部仕込み８０℃まで昇温した。一方、イオン交換水２２３質量部およびアニオン性界面活性剤ニューレックスＲ（日油株式会社製 ノルマルドデシルベンゼンスルホン酸ナトリウム）４８質量部、ブタンテトラカルボン酸１４質量部、グリシジルメタクリレート３６質量部、エチルアクリレート３４７質量部、ブチルアクリレート１１１質量部をホモミキサーで乳化し、混合乳化液をつくった。
上記の容器中に、過硫酸カリウム０．５質量部を仕込み、乳化重合を開始した。重合は混合乳化液と３質量％過硫酸カリウム水溶液３０質量部をそれぞれ３時間かけて滴下して行った。この間容器内は８０℃に保った。滴下終了後、１時間、８０℃に保ち、熟成を行った。得られた熱架橋型高分子重合体水性エマルジョン組成物の不揮発分は５０％であった。また、得られた熱架橋型高分子重合体水性エマルジョン組成物について、濾紙強度、剛軟性、溶出ホルムアルデヒド量及びカルボキシル基変性率をそれぞれ測定し、表１に示す結果を得た。
Example 1
In a container having a stirrer, a thermometer, a reflux condenser, and a dropping funnel, 178.8 parts by mass of ion-exchanged water was charged and heated to 80 ° C. On the other hand, 223 parts by mass of ion-exchanged water and 48 parts by mass of anionic surfactant Newlex R (sodium normal dodecylbenzenesulfonate manufactured by NOF Corporation), 14 parts by mass of butanetetracarboxylic acid, 36 parts by mass of glycidyl methacrylate, ethyl acrylate 347 parts by mass and 111 parts by mass of butyl acrylate were emulsified with a homomixer to prepare a mixed emulsion.
In the above container, 0.5 part by mass of potassium persulfate was charged and emulsion polymerization was started. The polymerization was carried out by dropping the mixed emulsion and 30 parts by mass of 3% by mass potassium persulfate aqueous solution over 3 hours. During this time, the inside of the container was kept at 80 ° C. After completion of the dropwise addition, the mixture was kept at 80 ° C. for 1 hour and aged. The resulting thermally crosslinked polymer aqueous emulsion composition had a non-volatile content of 50%. Further, the obtained heat-crosslinking polymer aqueous emulsion composition was measured for filter paper strength, stiffness, elution formaldehyde amount, and carboxyl group modification rate, and the results shown in Table 1 were obtained.
実施例２
熱架橋反応の触媒として、ｐ−トルエンスルホン酸を５質量部添加する以外は、実施例１と同様にして熱架橋型高分子重合体水性エマルジョン組成物を調製した。得られた熱架橋型高分子重合体水性エマルジョン組成物について、濾紙強度、剛軟性、溶出ホルムアルデヒド量及びカルボキシル基変性率をそれぞれ測定し、表１に示す結果を得た。
Example 2
A thermally crosslinked polymer aqueous emulsion composition was prepared in the same manner as in Example 1 except that 5 parts by mass of p-toluenesulfonic acid was added as a catalyst for the thermal crosslinking reaction. The obtained heat-crosslinking polymer aqueous emulsion composition was measured for filter paper strength, stiffness, elution formaldehyde amount, and carboxyl group modification rate, and the results shown in Table 1 were obtained.
実施例３
ブタンテトラカルボン酸の量を３６質量部に変更した以外は、実施例１と同様にして熱架橋型高分子重合体水性エマルジョン組成物を調製した。得られた熱架橋型高分子重合体水性エマルジョン組成物について、濾紙強度、剛軟性、溶出ホルムアルデヒド量及びカルボキシル基変性率をそれぞれ測定し、表１に示す結果を得た。
Example 3
A heat-crosslinkable polymer aqueous emulsion composition was prepared in the same manner as in Example 1 except that the amount of butanetetracarboxylic acid was changed to 36 parts by mass. The obtained heat-crosslinking polymer aqueous emulsion composition was measured for filter paper strength, stiffness, elution formaldehyde amount, and carboxyl group modification rate, and the results shown in Table 1 were obtained.
実施例４
ブタンテトラカルボン酸の量を２８質量部に、グリシジルメタクリレートの量を７２質量部に変更した以外は、実施例１と同様にして熱架橋型高分子重合体水性エマルジョン組成物を調製した。得られた熱架橋型高分子重合体水性エマルジョン組成物について、濾紙強度、剛軟性、溶出ホルムアルデヒド量及びカルボキシル基変性率をそれぞれ測定し、表１に示す結果を得た。
Example 4
A thermally crosslinked polymer aqueous emulsion composition was prepared in the same manner as in Example 1 except that the amount of butanetetracarboxylic acid was changed to 28 parts by mass and the amount of glycidyl methacrylate was changed to 72 parts by mass. The obtained heat-crosslinking polymer aqueous emulsion composition was measured for filter paper strength, stiffness, elution formaldehyde amount, and carboxyl group modification rate, and the results shown in Table 1 were obtained.
実施例５
ブタンテトラカルボン酸の量を１９２質量部に、グリシジルメタクリレートの量を４９４質量部に変更し、エチルアクリレート及びブチルアクリレートを配合しなかった以外は、実施例１と同様にして熱架橋型高分子重合体水性エマルジョン組成物を調製した。得られた熱架橋型高分子重合体水性エマルジョン組成物について、濾紙強度、剛軟性、溶出ホルムアルデヒド量及びカルボキシル基変性率をそれぞれ測定し、表１に示す結果を得た。
Example 5
Except that the amount of butanetetracarboxylic acid was changed to 192 parts by mass, the amount of glycidyl methacrylate was changed to 494 parts by mass, and ethyl acrylate and butyl acrylate were not blended, the heat-crosslinking polymer weight was the same as in Example 1. A combined aqueous emulsion composition was prepared. The obtained heat-crosslinking polymer aqueous emulsion composition was measured for filter paper strength, stiffness, elution formaldehyde amount, and carboxyl group modification rate, and the results shown in Table 1 were obtained.
比較例１
ブタンテトラカルボン酸を使用しない以外は、実施例１と同様にして水性エマルジョン組成物を調製した。得られた水性エマルジョン組成物について、濾紙強度、剛軟性、溶出ホルムアルデヒド量及びカルボキシル基変性率をそれぞれ測定し、表２に示す結果を得た。
Comparative Example 1
An aqueous emulsion composition was prepared in the same manner as in Example 1 except that butanetetracarboxylic acid was not used. The obtained aqueous emulsion composition was measured for filter paper strength, stiffness, elution formaldehyde amount, and carboxyl group modification rate, and the results shown in Table 2 were obtained.
比較例２
グリシジルメタクリレートを使用しない以外は、実施例１と同様にして水性エマルジョン組成物を調製した。得られた水性エマルジョン組成物について、濾紙強度、剛軟性、溶出ホルムアルデヒド量及びカルボキシル基変性率をそれぞれ測定し、表２に示す結果を得た。
Comparative Example 2
An aqueous emulsion composition was prepared in the same manner as in Example 1 except that glycidyl methacrylate was not used. The obtained aqueous emulsion composition was measured for filter paper strength, stiffness, elution formaldehyde amount, and carboxyl group modification rate, and the results shown in Table 2 were obtained.
比較例３
ブタンテトラカルボン酸及びグリシジルメタクリレートを使用しない以外は、実施例１と同様にして水性エマルジョン組成物を調製した。得られた水性エマルジョン組成物について、濾紙強度、剛軟性、溶出ホルムアルデヒド量及びカルボキシル基変性率をそれぞれ測定し、表２に示す結果を得た。
Comparative Example 3
An aqueous emulsion composition was prepared in the same manner as in Example 1 except that butanetetracarboxylic acid and glycidyl methacrylate were not used. The obtained aqueous emulsion composition was measured for filter paper strength, stiffness, elution formaldehyde amount, and carboxyl group modification rate, and the results shown in Table 2 were obtained.
比較例４
グリシジルメタクリレートに代えて、Ｎ−メチロールアクリルアミドを１０質量部使用し、実施例１と同様にして水性エマルジョン組成物を調製した。得られた水性エマルジョン組成物について、濾紙強度、剛軟性、溶出ホルムアルデヒド量及びカルボキシル基変性率をそれぞれ測定し、表２に示す結果を得た。
Comparative Example 4
An aqueous emulsion composition was prepared in the same manner as in Example 1 except that 10 parts by mass of N-methylolacrylamide was used instead of glycidyl methacrylate. The obtained aqueous emulsion composition was measured for filter paper strength, stiffness, elution formaldehyde amount, and carboxyl group modification rate, and the results shown in Table 2 were obtained.
比較例５
乳化重合前にブタンテトラカルボン酸を使用せずに重合を行って水性エマルジョン組成物を調製し、得られた水性エマルジョンにブタンテトラカルボン酸２８質量部を配合した以外は、実施例１と同様にして水性エマルジョン組成物を調製した。得られた水性エマルジョン組成物について、濾紙強度、剛軟性、溶出ホルムアルデヒド量及びカルボキシル基変性率をそれぞれ測定し、表２に示す結果を得た。
Comparative Example 5
Polymerization was carried out without using butanetetracarboxylic acid before emulsion polymerization to prepare an aqueous emulsion composition, and the same procedure as in Example 1 was carried out except that 28 parts by weight of butanetetracarboxylic acid was added to the resulting aqueous emulsion. An aqueous emulsion composition was prepared. The obtained aqueous emulsion composition was measured for filter paper strength, stiffness, elution formaldehyde amount, and carboxyl group modification rate, and the results shown in Table 2 were obtained.
以上詳細に説明したように、本発明の熱架橋型高分子重合体水性エマルジョンを紙処理剤として用いることで、低熱処理条件下で得られた紙であっても耐水性を改善でき、また、繊維処理剤として用いると、柔らかい繊維が得られる。 As explained in detail above, by using the thermally crosslinked polymer aqueous emulsion of the present invention as a paper treatment agent, water resistance can be improved even for paper obtained under low heat treatment conditions, When used as a fiber treating agent, soft fibers can be obtained.
Claims (11)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008302677A JP5255411B2 (en) | 2008-11-27 | 2008-11-27 | Thermally crosslinkable polymer aqueous emulsion composition, method for producing the same, and fiber treating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008302677A JP5255411B2 (en) | 2008-11-27 | 2008-11-27 | Thermally crosslinkable polymer aqueous emulsion composition, method for producing the same, and fiber treating agent |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013014539A Division JP5426787B2 (en) | 2013-01-29 | 2013-01-29 | Method for producing heat-crosslinking polymer aqueous emulsion composition, method for producing treated paper, and method for producing treated fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010126638A true JP2010126638A (en) | 2010-06-10 |
| JP5255411B2 JP5255411B2 (en) | 2013-08-07 |
Family
ID=42327246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008302677A Active JP5255411B2 (en) | 2008-11-27 | 2008-11-27 | Thermally crosslinkable polymer aqueous emulsion composition, method for producing the same, and fiber treating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5255411B2 (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57115417A (en) * | 1981-01-06 | 1982-07-17 | Asahi Chem Ind Co Ltd | Crosslinked-type aqueous dispersion composition |
| JPH02218713A (en) * | 1989-02-20 | 1990-08-31 | Kansai Paint Co Ltd | Aqueous resin dispersion having curability |
| JPH07268064A (en) * | 1994-04-01 | 1995-10-17 | Nippon Paint Co Ltd | Water-base resin composition and its production |
| JP2001048954A (en) * | 1999-08-09 | 2001-02-20 | China Petro Chem Corp | Self emulsifying type aqueous epoxy resin and curing system of its resin composition |
| JP2002293881A (en) * | 2001-03-29 | 2002-10-09 | Dainippon Ink & Chem Inc | Resin composition and metallic sheet with primer layer |
| JP2006328269A (en) * | 2005-05-27 | 2006-12-07 | Showa Highpolymer Co Ltd | Aqueous emulsion composition of thermal crosslinking synthetic resin and paper or fiber treatment agent using the same |
| JP2007528438A (en) * | 2004-03-11 | 2007-10-11 | クナーフ インシュレーション ゲーエムベーハー | Binder composition and related methods |
-
2008
- 2008-11-27 JP JP2008302677A patent/JP5255411B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57115417A (en) * | 1981-01-06 | 1982-07-17 | Asahi Chem Ind Co Ltd | Crosslinked-type aqueous dispersion composition |
| JPH02218713A (en) * | 1989-02-20 | 1990-08-31 | Kansai Paint Co Ltd | Aqueous resin dispersion having curability |
| JPH07268064A (en) * | 1994-04-01 | 1995-10-17 | Nippon Paint Co Ltd | Water-base resin composition and its production |
| JP2001048954A (en) * | 1999-08-09 | 2001-02-20 | China Petro Chem Corp | Self emulsifying type aqueous epoxy resin and curing system of its resin composition |
| JP2002293881A (en) * | 2001-03-29 | 2002-10-09 | Dainippon Ink & Chem Inc | Resin composition and metallic sheet with primer layer |
| JP2007528438A (en) * | 2004-03-11 | 2007-10-11 | クナーフ インシュレーション ゲーエムベーハー | Binder composition and related methods |
| JP2006328269A (en) * | 2005-05-27 | 2006-12-07 | Showa Highpolymer Co Ltd | Aqueous emulsion composition of thermal crosslinking synthetic resin and paper or fiber treatment agent using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5255411B2 (en) | 2013-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102041857B1 (en) | Fluorine containing composition and fluorine containing polymer | |
| JP5459219B2 (en) | Fluoropolymer and water / oil repellent | |
| JPS58127715A (en) | Acryl plastic dispersion and flat fiber product fixation | |
| JPS6364463B2 (en) | ||
| US6506696B2 (en) | High performance synthetic nonwovens using polymers having dual crosslinkable functionality | |
| JP2023022835A (en) | oil repellent composition | |
| JP3687903B2 (en) | Emulsion polymer that can be crosslinked in two ways at ambient conditions | |
| JPH02232287A (en) | Water-soluble, pressure-sensitive adhesive substance and its utilization for manufacture of splice tape having both persistent temperature resistance and adhesiveness to water-containing substance | |
| JPS6241603B2 (en) | ||
| CN104136557B (en) | The low formaldehyde content processing through vinyl acetate ethylene copolymers dispersion or vinyl acetate polymer dispersion and the fiber non-woven base material of high wet strength | |
| MX2007013650A (en) | Salt-sensitive vinyl acetate binder compositions and fibrous articles incorporating same. | |
| JP5255411B2 (en) | Thermally crosslinkable polymer aqueous emulsion composition, method for producing the same, and fiber treating agent | |
| JP5426787B2 (en) | Method for producing heat-crosslinking polymer aqueous emulsion composition, method for producing treated paper, and method for producing treated fiber | |
| JPS62227435A (en) | Novel surface-active agent | |
| JP4703264B2 (en) | Thermally crosslinkable synthetic resin aqueous emulsion composition and paper or fiber treatment agent using the same | |
| CN110461888A (en) | The purposes that aqueous polymer dispersion is bonded in high-molecular porous material interface | |
| JP5785028B2 (en) | Polyvinyl alcohol fiber assembly | |
| EP0510153A1 (en) | Improvements in or relating to non-woven fibrous materials | |
| JP5168508B2 (en) | Fiber treatment agent for composite materials and glass cloth | |
| JP4792226B2 (en) | Two-component adhesive composition | |
| TW202128927A (en) | An adhesive composition | |
| JP5596967B2 (en) | Paper or textile processed product treated with thermosetting oil-in-water emulsion | |
| JP4886046B2 (en) | Aqueous composition for filter media with enhanced wet burst strength | |
| JP6191736B2 (en) | Fluorine-containing composition and fluorine-containing polymer | |
| JP2018521157A (en) | Curable aqueous composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20110202 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110816 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120625 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120731 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120925 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20121030 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130129 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20130226 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130402 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130419 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5255411 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160426 Year of fee payment: 3 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |