JPS63258913A - Hardening water-based resin dispersion - Google Patents
Hardening water-based resin dispersionInfo
- Publication number
- JPS63258913A JPS63258913A JP9322987A JP9322987A JPS63258913A JP S63258913 A JPS63258913 A JP S63258913A JP 9322987 A JP9322987 A JP 9322987A JP 9322987 A JP9322987 A JP 9322987A JP S63258913 A JPS63258913 A JP S63258913A
- Authority
- JP
- Japan
- Prior art keywords
- polymerizable monomer
- polymer
- parts
- water
- polymerization
- 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
- 239000006185 dispersion Substances 0.000 title claims abstract description 38
- 239000011347 resin Substances 0.000 title claims description 43
- 229920005989 resin Polymers 0.000 title claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 87
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 22
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 18
- -1 alkyl mercaptan Chemical compound 0.000 claims abstract description 16
- 150000003839 salts Chemical group 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 239000012736 aqueous medium Substances 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000009257 reactivity Effects 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 20
- 238000003860 storage Methods 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 29
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 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 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000010556 emulsion polymerization method Methods 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- 239000011345 viscous material Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 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
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 108010002352 Interleukin-1 Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-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
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
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- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds 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
- 150000001412 amines Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
（産業上の利用分野）
本発明は硬化性水性樹脂分散液に関し、さらに詳しくは
良好な貯蔵安定性を示し、水を飛散させて被膜とした際
には乳化剤と乳化重合樹脂が架橋反応して特に耐水性に
優れた透明な硬化被膜を形成しうる硬化性水性樹脂分散
液に関する。
（従来の技術）
水性樹脂分散液は、従来よシ各種乳化剤を用いて乳化重
合法によシ製造されておシ、その無公害性、作業性の良
さ、省資源といった利点を生かして、塗料、接着剤、紙
加工剤、繊維加工剤、モルタル改質剤など広範な応用用
途を持っている。
しかしながら、乳化重合に用いた親水性の乳化剤は水を
飛散させて被膜とした後も被膜中に残存し、しかも≠粒
子界面に局在化し易いために、被膜の耐水性など諸物性
に悪影響を及ぼす原因となっている。この様な水性樹脂
分散液の本質的な欠点を改良するために、過硫酸カリウ
ムなどを多量に用いるソーｆ７リー乳化重合法、高分子
乳化剤を用いた乳化重合法、重合性不飽和基と分子内に
有する反応性乳化剤を用いた乳化重合法等が提案されて
いるが、耐水性に関してはいまだ不十分である。
一方、従来よ勺各種架橋反応によシ被膜の耐溶剤性及び
強度の向上が図られている。最も広く行なわれている方
法としては、Ｎ−メチロール（メタ）アクリルアミドや
Ｎ−ブトキシメチル（メタ）アクリルアミド等の官能性
単量体を共重合成分に用いる方法があるが、この方法に
よシ得られる水性樹脂分散液は一般に液の安定性が悪く
、また架橋被膜を形成する過程でホルマリンを発生する
問題点を有する。
（発明が解決しようとする問題点）
本発明は、従来の水性樹脂分散液が有していた前記問題
点を解消するものであり、従ってその目的は水分散液の
状態では極めて安定で、しかも被膜を形成するに際して
はホルマリン等の有害物質を発生することなく硬化して
、耐水性、耐溶剤性、強度に優れた被膜を与える硬化性
水性樹脂分散液を提供することにある。
（問題点を解決するための手段および作用）本発明者ら
は、鋭意研究を進めた結果、特定の方法によシ得られる
末端アルキル基を有する重合体を乳化剤に用い、特定成
分の重合性単量体を乳化重合して得られる硬化性水性樹
脂分散液が、前記目的を達成しうるものであることを見
いだし、本発明を完成するに至った。
即ち、本発明は不飽和カルボン酸を必須成分として含む
重合性単量体成分（４）を炭素数が６〜１８のアルキル
メルカプタン（Ｂ）の存在下に重合して得られる酸価が
２００以上の水溶性もしくは水分散性の末端アルキル基
を有する重合体〔Ｉ〕および／またはその塩を乳化剤に
用いて、カルブキシル基との反応性を有する基を含有す
る重合性単量体（ａ）０．５〜４０重量％および他の重
合性単量体（ｂ）６０〜９９．５重量％（但し、重合性
単量体（ａ）および（ｂ）の合計は１００重′！ｊｋｅ
Ｉｋである。）からなる重合性単量体成分（ＩＩ）を水
性媒体中で乳化重合して得られることを特徴とする硬化
性水性樹脂分散液に関するものである。
本発明において乳化剤に用いる重合体ＣＤは前記の手順
で得られるものであるが、乳化重合時の安定性や得られ
る樹脂の被膜の耐水性、耐溶剤性、強度等の諸物性の面
で、酸価が２００以上でなければならない。また、その
分子量は３００〜７０００、特に４００〜４０００の範
囲とするのが好適でちる。分子量がこの範囲以外のもの
を使用すると十分な乳化安定性が得られなかったり、耐
水性、耐溶剤性、強度のすべてに優れた樹脂の被膜が得
られなかったりする場合がある。
重合体〔■〕の合成に用いる不飽和カルボン酸は、重合
体〔！〕にカルブキシル基を導入して親水性を付与する
と共に、得られる硬化性樹脂を硬化する際の官能基とす
るために使用するものでアシ、分子内にカルがキシル基
および／またはその塩と重合性不飽和基とと有するもの
であれば特に制限されず、例えば（メタ）アクリル酸、
クロトン酸、マレイン酸、フマル酸、イタコン酸もしく
はこれらの半エステルまたはこれらの塩等が挙げられ、
これらの１種または２種以上の混合物と使用できる。
重合体（１）を合成する際の重合性単量体成分（４）は
、不飽和カルボン酸だけから構成されてもよいが、必要
によシネ飽和カルボン酸以外の重合性単量体を併用して
もよい。使用できる重合性単量体としては、不飽和カル
がン酸と共重合性のあるものであれば特に制限されず、
例えばスチレン、ビニルトルエン、α−メチルスチレン
、クロルメチルスチレン、スチレンスルホン酸及びその
塩などのスチレン誘導体煩；（メタ）アクリルアミド、
Ｎ−モノメチル（メタ）アクリルアミド、Ｎ−モノエテ
ル（メタ）アクリルアミド、Ｎ、Ｎ−ジメチル（メタ）
アクリルアミドなどの（メタ）アクリルアミド９誘導体
類；（メタ）アクリル酸メチル、（メタ）アクリル酸エ
チル、（メタ）アクリル酸ブチルなどの（メタ）アクリ
ル酸とＣ１〜Ｃ，８Ｏアルコールのエステル化によシ合
成される（メタ）アクリル酸エステル類；（メタ）アク
リル酸２−ヒドロキシエチル、（メタ）アクリル酸２−
ヒドロキシプロピル、（メタ）アクリル酸とポリプロピ
レングリコールもしくはポリエチレングリコールとのモ
ノエステルなどのヒドロキシル基含有（メタ）アクリル
酸エステル類；（メタ）アクリル酸２−スルホン酸エチ
ル及びその塩、ビニルスルホン酸及びその塩、酢酸ビニ
ル、（メタ）アクリロニトリル等を挙げることができ、
これらの１種または２種以上の混合物を使用できる。不
飽和カルボン酸以外の重合性単量体は得られる重合体〔
■〕の酸価が２００未満とならない量で使用する。
また、得られる重合体（１）を用いて乳化重合する際に
生成するポリマー成分との相溶性を考慮して、その栓類
と量を選択することが好ましい。
ては、例えばｎ−へキシルメルカプタン、ｎ−オクチル
メルカプタン、ｎ−ドデシルメルカプタン、ｔ−ドデシ
ルメルカプタン、セチルメルカプタン、ステアリルメル
カプタン等と挙げることができ、これらの１洩または２
種以上の混合物が使用できる。アルキルメルカプタン中
）は、重合体〔■〕の末端にアルキル基を導入して界面
活性能を付与するために使用するもので、炭素数が６未
満のアルキルメルカプタンは乳化重合時の安定性及び貯
蔵安定性の面で使用することができない。アルキルメル
カプタン０）の使用量は所望する重合体［１）の分子量
により決定するものであるが、通常重合性単量体成分（
Ａ）１００重量部に対し、２〜３００重社部の範囲で使
用する。
重合性単量体成分（Ａ）の重合に用いる重合開始剤は、
周知の油溶性、水溶性の重合開始剤が使用できるが、末
端アルキル基を有する重合体（１）を効率よく製造する
ために、その使用量はアルキルメルカプタン（Ｂ） １
−Ｅ−ルに対し１モル以下、より好ましくは０．１モル
以下の割合とするのが好適である。
重合体（１）は、その性状によシ塊状重合、溶液重合、
懸濁重合いずれの方法でも製造することができる。重合
温度としては５０〜１５０℃、重合時間は１〜８時間が
良い。溶液重合の溶剤としては、重合性単量体成分（Ａ
）、アルキルメルカプタン（Ｂ）、ラジカル重合開始剤
が溶解し、ラジカル重合を阻害しないものであるならば
何でも使用することができる。
重合体〔Ｉ〕は、それ自体十分な界面活性能を有するが
、乳化重合に用いて目的とする重合時の安定性及び貯蔵
安定性の良好な硬化性水性樹脂分散液を得るために、カ
ルブキシル基の一部もしくは全量を中和して重合体〔！
〕の塩として使用に供するのが好ましい。
中和剤としては、通常のもの？使用することができ、例
えば水酸化ナトリウム、水酸化カリウムなどのアルカリ
金属化合物；水酸化カルシウム、炭酸カルシウムなどの
アルカリ土類金属化合物；アンモニア；モノメチルアミ
ン、ジメチルアミン、トリメチルアミン、モノエチルア
ミン、ジエチルアミン、トリエチルアミン、モノプロピ
ルアミン、ジメチルプロピルアミン、モノエタノールア
ミン、ジェタノールアミン、トリエタノールアミン、エ
チレンジアミン、ジエチレントリアミンなどの水溶性有
機アミン類が挙げられ、これらの群から選ばれる１種ま
たは２種以上の混合物で使用することができる。硬化被
膜の耐水性をより向上させたい場合は、常温るるいは加
熱によル飛散する、例えばアンモニア、モノメチルアミ
ン、ジメチルアミン、トリメチルアミンなどの低沸点ア
ミン類を使用することが好ましい。
本発明の硬化性水性樹脂分散液の製造に用いら酸グリシ
ジル、（メタ）アクリル酸２−メチルグリシジル、アリ
ルグリシジルエーテルなどの工Ｉキシ基台有重合性単量
体類：（メタ）アクリロイルアジリジン、（メタ）アク
リル酸２−アジリジニルエチルなどのアジリジニル基含
有重合性単量体類；２−イングロペニルー２−オキサゾ
リン、２−ビニル−２−オキサゾリンなどのオキサゾリ
ン基含有重合性単量体類等を挙げることができ、これら
の１抛または２ｆ！！以上の混合物を使用することがで
きる。重合性単量体（ａ）の使用量は、乳化重合に用い
る重合性単量体成分（ＩＩ）中０．５〜４０重量％であ
シ、よシ好ましくは３〜１５重量％である。重合性単量
体（、）の使用量が０．５重量−未満では、乳化剤とし
て用いた重合体〔Ｉ〕のカルがキシル基が未反応として
多量に残ると共に架橋が不十分となるため、耐水性、耐
溶剤性、強度に改善が認められない。一方、４００重量
を越えて使用すると、乳化重合時の安定性及び貯蔵安定
性が悪くなるので好ましくない。
本発明の乳化重合に用いられる重合性単量体（−）以外
の重合性単量体（ｂ）は、重合性のものであれば特に限
定されないが、目的、用途に応じてその中の１種あるい
は２種以上を組合わせて使用することができる。これら
重合性単量体としては、例えば、重合体〔Ｉ〕の合成に
用いた前記重合性単量体成分−Ｗがそのまま挙げられる
他、（メタ）アクリル酸ジメチルアミンエチル、ジメチ
ルアミノエチル（メタ）アクリルアミド、ジメチルアミ
ンプロピル（メタ）アクリルアミド、ビニルピリジン、
ビニルイミダゾール、ビニルピロリドンなどの塩基性不
飽和単量体類；（メタ）アクリル酸とエチレングリコー
ル、１，３−ブチレングリコール、ジエチレングリコー
ル、１．６−ヘキサンクリコール、ネオペンチルグリコ
ール、ポリエチレングリコール、ポリプロピレングリコ
ール、トリメチロールプロパン、ペンタエリスリトール
、ジペンタエリスリトールなどの多価アルコールとのエ
ステルなどの分子内に重合性不飽和基を２個以上有する
多官能（メタ）アクリル酸エステル類；Ｎ−゛メチロー
ル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ
）アクリルアミドなどの（メタ）アクリルアミド類；ビ
ニルトリメトキシシラン、γ−（メタ）アクリロキシグ
ロビルトリメトキシシラン、アリルトリエトキシシラン
、トリメトキシシリルグロピル了りルアミンなどの有情
ケイ素基含有不飽和単量体類；及び弗化ビニル、弗化ビ
ニリデン、塩化ビニル、塩化ビニリデン、ジビニルベン
ゼン、シアリルフタレートなどを挙げることができる。
本発明は、前記重合体ＣＩＩおよび／またはその塩を乳
化剤として、重合性単量体（−）および他の重合性早世
体色）からなる重合性単量体成分（Ｉｆ）を水性媒体中
で乳化重合してなる硬化性樹脂分散液に関するものであ
シ、その重合方法については従来公知のあらゆる乳化重
合法が適用できる。例えば、重合触媒、水、前記重合体
〔Ｉ〕および／またはその塩、重合性単量体（、）を含
む重合性単量体成分〔■〕を一括混合して重合する方法
もしくはいわゆるモノマー滴下法、プレエマルション法
などの方法により本発明の硬化性水性樹脂分散液？合成
することができる。重合温度としては０〜１００℃、好
ましくは５０〜８０℃、重合時間は１−１０時間である
。乳化重合の際、親水性溶媒を加えること及び他の公知
の乳化剤、添加剤を加えることは、その被ｊ漠の物性に
悪影響を及ぼさない範囲において可能である。
重合体〔Ｉ〕および／またはその塩の使用量は重合性単
量体成分（ｉｆ） １００重量部に対して０．５〜２０
０重Ｊ訛部の範囲が好ましく、よシ好ましくは１〜１５
重量部である。０．５重量部未満の使用量では乳化重合
の安定性が悪く、２００重量部を越して使用すると重合
中にグル化が起こるなど、やけシ安定性が悪くなる。
重合触媒としては、従来公知のものならば何でも使用す
ることができる。ただし、更に耐水性に優れた被膜を与
える硬化性樹脂分散液を得るためには、過酸化水素、ジ
−ｔ−ブチル・や−オキサイド、過酢酸、２．２’−ア
ゾビス（２−アミジノプロノ母ン）二塩酸［，４，４’
−アゾビス（４−シアノペンクン酸）などの硫酸根を残
さない重合触媒の１槙または２種以上の混合物？使用す
るのが好ましい。より好ましくは、重合性単量体（ａ）
の反応性基に対して高い反応性と有するアミジノ基、カ
ルボキシル基などを分子内に含有する２、２′−アゾビ
ス（２−アミ・ジノプロパン）二塩酸塩、４．４’−ア
ゾビス（４−シアノペンタン酸）などが挙ケラレる・重
合触媒の使用量は、通常重合性単量体成分（ＩＩ）１０
０重量部に対して０．０１〜５重量部の範囲である。
乳化重合に際して、重合性単量体成分〔ＩＩ）を１種以
上の重合性単量体（、）を含む重合性単量体成分（ＩＩ
−ａ）と１種以上の該重合性単量体（ＩＬ）を含まぬ重
合性単量体成分ＣＩＩ−ｂ：］とに分割し、これら全多
段重合することは、このようにして得られた硬化性水性
樹脂分散液の被膜の耐水性、耐溶剤性、強度の向上が特
に著しいので好ましい。その際、重合性単量体成分（Ｉ
Ｉ−ａ：）及び重合性単量体成分〔ＩＩ−ｂ″ｌをそれ
ぞれ何段階に分けて乳化重合しても良く、重合する順序
をもとわない。
多段重合は、硬化被膜の耐水性、耐溶剤性、強度を著し
く向上させるものであるが、特に最後段に重合する成分
として重合性単量体成分ｃｍ−ｂ：＋を用いると、硬化
被膜の上記物性とよシ向上させるはかシでなく、貯蔵安
定性？飛躍的に向上させるので好ましい。
以上のようにして製造された硬化性水性樹脂分散液は、
それ自体常温もしくは加熱により自己架橋して耐水性、
耐溶剤性の良好な高強度の硬化被膜を形成するものであ
るが、必要によりアミノプラスト樹脂、多官能ブロック
イソシアネート、エポキシ樹脂、顔料、消泡剤、成膜助
剤などを添加して使用することができる。
（発明の効果）
本発明の硬化性水性樹脂分散液は、不飽和カルボン酸を
含む重合性単量体成分に）を炭素数が６〜１８のアルキ
ルメルカプタン（Ｂ）存在下、ラジカル重合して得られ
る重合体〔Ｉ〕を乳化剤として、カルブキシル基との反
応性を有する基を含有する重合性単量体（ａ）および他
の重合性単量体（′ｂ）からなる重合性単量体成分〔Ｉ
Ｉ）を水性媒体中で乳化重合しｔ ｉ！ｉらｈるもので
あり、貯蔵安定性が良好で、水を飛散させた際には乳化
剤が乳化重合樹脂中に拡散して親水性基であるカルブキ
シル基と反応しホルマリンの発生なく架橋構造を形成す
るため、耐水性、耐溶剤性、強度など諸物性の非常に優
れた被膜と与えるものである。それ故、当硬化性水性樹
脂分散液は、塗料、接着剤、紙加工剤、繊維加工剤、モ
ルタル改質剤など広範な用途、特に耐水性、耐溶剤性の
要求される分野において有用なものである。
（一実施例）
以下実施例によって本発明の詳細な説明するが、本発明
の範囲がこれら実施例のみに限定されるものではない。
尚、実施例中に特にことわりのない限りチは重量％金、
部は重量部をそれぞれ示すものとする。
参考例１
攪拌機、還流冷却器、窒素導入管、温度計、滴下ロート
を備えたフラスコにイソプロピルアルコール１８０部を
仕込み、窒素を吹き込みながら８１℃まで内温を上昇さ
せて、イソプロピルアルコールを１０分間還流させた。
次に予め用意しておいた、アクリル酸１７４部、ｎ−ド
デシルメルカプタン３６部、及び２，２′−アゾビスイ
ソブチロニトリル０．４２部からなる重合性単量体混合
物を１時間かけて滴下、重合した。滴下終了後、還流状
態で１時間熟成を行い、固形分５３．９％の重合体（１
）の溶液を得た。該重合体（１）は、下記一般式にて代
表される構造？有する、酸価６４５、数平均分子量１２
００の白色粉末状物であった。
参考例２
参考例１と同様のフラスコに、イソプロピルアルコール
１８０部と仕込み、窒素を吹き込みながら８１℃まで内
温を上げて、イソプロピルアルコールを１０分間還流さ
せた。続いて予め用意しておいたアクリル酸８６部、ア
クリル酸２−ヒドロキシエチル１３９部、ｎ−ドデシル
メルカプタン３６部、イソプロピルアルコール３０部及
び２，２′−アゾビスインブチロニトリル０．３０部か
らなる重合性単量体混合ｖｌＪヲ１時間かけて滴下、重
合した。滴下終了後、還流状態で１時間熟成を行い固形
分５５．４チの重合体（２）の溶液と得た。該重合体（
２）は下記一般式にて代表される構造を有する、酸価２
５６数平均分子量１５００の白色粘稠物であった。
比較参考例１
参考例１と同様のフラスコに、イソプロピルアルコール
１８０部を仕込み、窒素を吹き込みながら８１℃まで内
温を上げて、イソプロピルアルコールを１０分間還流さ
せた。続いて予め用意しておいたアクリル酸１０部、メ
タクリル酸２−ヒドロキシエチル２０部、メタクリル酸
メチル４０部、アクリル酸ｎ−ブチル２０部、スチレン
１０部及び２，２′−アゾビスイソブチロニトリル４部
からなる重合性単量体混合物襟参と３時間かけて滴下、
重合した。滴下終了後、還流状態で１時間熟成を行い、
固形分５２．９ ％の比較用重合体（１′）の溶液を得
た。該重合体（１′）は、酸価°３８、数平均分子ｉ７
５００の白色樹脂状物であった。
比較参考例２
参考例１と同様のフラスコに、インプロピルアルコール
１８０部を仕込み、窒素を吹き込みながら８１℃まで内
温を上げて、イソプロピルアルコールを１０分間還流さ
せた。続いて予め用意しておいたアクリル酸８６部、ア
クリル酸２−ヒドロキシエチル１３９部、チオグリコー
ル１４部及び２．２′−アゾビスイソブチロニトリル０
．３０部からなる重合性単量体混合物＃４！＝を１時間
かけて滴下、重合した。滴下終了後、還流状態で１時間
熟成を行い、固形分５６．９％の比較用重合体（２つ溶
液と得た。該重合体（２′）は、下記一般式にて代表さ
れる構造を有する酸価２８０、数平均分子１１４００の
白色粘稠物であった。
実施例１
滴下ロート、攪拌機、窒素導入管、温度計及び還流冷却
器と備えたフラスコに純水１５０部、参るやかに窒素ガ
スを吹き込みながら６５℃に加熱した。滴下ロートにア
クナル酸ブチル５５部、メタクリル酸メチル３５部、メ
タクリル酸グリシジル１０部からなる重合性単量体混合
物を調製し、その内１０チ量をフラスコに滴下した。続
いて２．２′−アゾビス（２−アミジノグロノ９ン）二
塩酸塩の５％水溶液４部を注入した。１０分後、残シの
重合性単量体混合物の滴下？始め、１．５時間で完全に
滴下と終了した。滴下中は、温度を６５〜７０℃に保持
し、さらに滴下終了後同温度で１時間攪拌して重合を終
了させ、不揮発分３９．５チｐＨ＝８．３の硬化性水性
樹脂分散液〔１〕を得た。
中和剤の量及び種類、重合性単量体混合物の種類を第１
表に示した通シとする他は実施例１と同様の操作？ｉｌ
−繰返して硬化性水性樹脂分散液〔２〕〜〔５〕を得た
。その結果をまとめて第１表に示した。
実施例６
実施例１において、２．２’−アゾビス（２−アミソノ
ノロ／４’ン）二塩酸塩の５チ水溶液の代わりに、過硫
酸カリウムの５％水溶液を同量使用する他は、実施例１
と同様の操作を繰返して硬化性水性樹脂分散液〔６〕を
得た。その結果を第１表に示した。
比較例１
実施例Ｉにおいて、カル？キシル基との反応性を有する
重合性単量体（ａ）〔メタクリル酸グリシツル〕を含ま
ない、アクリル酸ブチル５５部、メタクリル酸メチル４
５部よフなる重合性単量体混合物を使用した他は、実施
例１と同様の操作を繰り返して比較用水性樹脂分散液〔
１′〕を得た。その結果ｔ−第１表に示した。
比較例２〜３
実施例１において、乳化剤として重合体（１）のアンモ
ニア中和物の代わシに、市販の乳化剤を使用する他は実
施例１と同様の操作を繰返して比較用水性樹脂分散液〔
２′〕〜〔３′〕を得た。その結果をまとめて第１表に
示した。
比較例４
実施例Ｉにおいて、重合体（１）の溶液の代わりに比較
用令室合体（１′）の溶液を同量、２８チアンモニア水
の代わシにジメチルエタノールアミン０．１８部を使用
する他は同様の操作を繰返して乳化重合を行なった。し
かしながら、滴下の後半で凝集物が多量に生成し、重合
続行が不可能な状態となりた。
比較例５
実施例１において、重合体（１）の溶液の代わりに比較
用令室合体（１′）の溶液を３５部、２８チアンモニア
水の代わシにジメチルエタノールアミン１．１２部を使
用し、重合性単量体の使用量を第１表に示した通シとす
る他は同様の操作を繰返して比較用水性樹脂分散液〔５
′〕を得た。その結果を第１表に示した。
比較例６
実施例１において、重合体（１）の溶液の代わりに比較
用生型合体（２′）の溶液を同量、２８チアンモニア水
を１．６部使用する以外は同様の操作を繰返して乳化重
合を行なった。しかしながら、滴下の後半で凝集物が多
量に生成し、重合続行が不可能な状態となった。
比較例７
実施例１において、重合性単量体混合物としてアクリル
酸ブチル５５部、メタクリル酸グリシジル４５部からな
る混合物を使用する以外は同様の操作を繰返して乳化重
合を行なった。しかしながら、滴下の後半で凝集物が多
量に生成し、重合続行が不可能な状態となった。
実施例７
実施例１と同様のフラスコに純水１５０部、参考例１で
得られた重合体（２）の溶液５．６部を仕込み、２８％
アンモニア水２．１部茫加えて中和した。ゆるやかに窒
素ガス上吹き込みながら６５℃に加熱した。滴下ロート
にアクリル酸ブチル２０部、メタクリル酸グリシジル１
０部からなる重合性単量（ＩＬン
体動を含んでなる重合性単量体混合物〔イ）Ｌ−調整し
、その内１０部をフラスコに滴下した。続いて２．２′
−アゾビス（２−アミジノグロパン）二塩酸塩の５チ水
溶液４部を注入した。１０分後、残シの重合性単量体混
合物〔イ〕の滴下を始め、２０分間で完全に滴下を終了
した。３０分間攪拌を続けた後、第２段の重合として滴
下ロートにアクリル酸ブチル３５部、メタクリル酸メチ
ル３５部からなる重合性単量体＊を含まない重合性単量
体混合物〔口〕を調整し、１時間かけて滴下した。重合
中は、温度を６５〜７０℃に保持し、さらに第２段の滴
下終了後同温度で１時間攪拌して重合を終了させ、不揮
発分３９．４チ、ｐ）Ｉ＝８．４の硬化性水性樹脂分散
液〔７〕を得た。
実施例８〜９
悴）
実施例７と同様にして、重合性単量体件を含んでなる重
合性単量体混合物〔イ〕を重合した後、第（Ａ）
２段の′重合として重合性単量体−を含まない重合性単
量体混合物〔口〕の重合を行い、硬化性水性樹脂分散液
〔８〕〜(Industrial Application Field) The present invention relates to a curable aqueous resin dispersion, and more specifically, it exhibits good storage stability, and when water is splashed to form a film, the emulsifier and the emulsion polymerized resin undergo a crosslinking reaction. In particular, it relates to a curable aqueous resin dispersion that can form a transparent cured film with excellent water resistance. (Prior art) Aqueous resin dispersions have conventionally been produced by emulsion polymerization using various emulsifiers. It has a wide range of applications, including adhesives, paper processing agents, fiber processing agents, and mortar modifiers. However, the hydrophilic emulsifier used in emulsion polymerization remains in the film even after water is dispersed to form a film, and moreover, it tends to be localized at particle interfaces, which has a negative impact on various physical properties such as water resistance of the film. This is the cause of In order to improve the essential drawbacks of such aqueous resin dispersions, we have developed methods such as the Sor F7 emulsion polymerization method using a large amount of potassium persulfate, the emulsion polymerization method using a polymeric emulsifier, and polymerizable unsaturated groups and molecules. Emulsion polymerization methods using reactive emulsifiers have been proposed, but they are still insufficient in terms of water resistance. On the other hand, attempts have been made to improve the solvent resistance and strength of coatings by various crosslinking reactions. The most widely used method is to use a functional monomer such as N-methylol (meth)acrylamide or N-butoxymethyl (meth)acrylamide as a copolymerization component; The aqueous resin dispersions generally have poor stability and also have the problem of generating formalin during the process of forming a crosslinked film. (Problems to be Solved by the Invention) The present invention solves the above-mentioned problems that conventional aqueous resin dispersions have, and therefore, its purpose is to provide an aqueous dispersion that is extremely stable and yet The object of the present invention is to provide a curable aqueous resin dispersion that hardens without emitting harmful substances such as formalin when forming a film, and provides a film with excellent water resistance, solvent resistance, and strength. (Means and effects for solving the problem) As a result of intensive research, the present inventors have discovered that a polymer having a terminal alkyl group obtained by a specific method is used as an emulsifier to improve the polymerizability of specific components. The present inventors have discovered that a curable aqueous resin dispersion obtained by emulsion polymerization of monomers can achieve the above object, and have completed the present invention. That is, the present invention provides a monomer component (4) containing an unsaturated carboxylic acid as an essential component, which is obtained by polymerizing the polymerizable monomer component (4) in the presence of an alkyl mercaptan (B) having 6 to 18 carbon atoms, and which has an acid value of 200 or more. Polymer [I] having a water-soluble or water-dispersible terminal alkyl group and/or a salt thereof is used as an emulsifier to form a polymerizable monomer (a) containing a group reactive with a carboxyl group (a) 0 .5 to 40% by weight and other polymerizable monomers (b) 60 to 99.5% by weight (however, the total of polymerizable monomers (a) and (b) is 100% by weight!
It is Ik. The present invention relates to a curable aqueous resin dispersion obtained by emulsion polymerizing a polymerizable monomer component (II) consisting of the following in an aqueous medium. The polymer CD used as the emulsifier in the present invention is obtained by the above-mentioned procedure, but in terms of stability during emulsion polymerization and physical properties of the resulting resin film such as water resistance, solvent resistance, and strength, The acid value must be 200 or higher. The molecular weight is preferably in the range of 300 to 7,000, particularly 400 to 4,000. If a polymer having a molecular weight outside this range is used, sufficient emulsion stability may not be obtained, or a resin film having excellent water resistance, solvent resistance, and strength may not be obtained. The unsaturated carboxylic acid used in the synthesis of polymer [■] is polymer [! ] is used to impart hydrophilicity by introducing a carboxyl group into the curable resin, and to use it as a functional group when curing the resulting curable resin. It is not particularly limited as long as it has a polymerizable unsaturated group, such as (meth)acrylic acid,
Examples include crotonic acid, maleic acid, fumaric acid, itaconic acid, half esters thereof, or salts thereof,
It can be used alone or in combination with two or more of these. The polymerizable monomer component (4) when synthesizing the polymer (1) may be composed only of an unsaturated carboxylic acid, but if necessary, a polymerizable monomer other than the saturated carboxylic acid may be used in combination. You may. The polymerizable monomer that can be used is not particularly limited as long as it is copolymerizable with unsaturated carboxylic acid.
For example, styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, chloromethylstyrene, styrenesulfonic acid and its salts; (meth)acrylamide,
N-monomethyl (meth)acrylamide, N-monoether (meth)acrylamide, N,N-dimethyl (meth)
(Meth)acrylamide 9 derivatives such as acrylamide; by esterification of (meth)acrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate with C1-C,8O alcohol. Synthesized (meth)acrylic esters; 2-hydroxyethyl (meth)acrylate, 2-(meth)acrylate
Hydroxyl group-containing (meth)acrylic esters such as hydroxypropyl, monoester of (meth)acrylic acid and polypropylene glycol or polyethylene glycol; ethyl (meth)acrylate 2-sulfonate and its salts, vinylsulfonic acid and its salt, vinyl acetate, (meth)acrylonitrile, etc.
One or a mixture of two or more of these can be used. Polymerizable monomers other than unsaturated carboxylic acids are used in the resulting polymer [
(2)] is used in an amount that does not result in an acid value of less than 200. Further, it is preferable to select the plugs and the amount thereof in consideration of compatibility with the polymer component generated when emulsion polymerization is performed using the obtained polymer (1). Examples of these include n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, cetyl mercaptan, stearyl mercaptan, etc.
Mixtures of more than one species can be used. (among alkyl mercaptans) is used to introduce an alkyl group to the end of the polymer [■] to impart surfactant ability, and alkyl mercaptans with less than 6 carbon atoms are used for stability during emulsion polymerization and for storage. Unable to use due to stability. The amount of alkyl mercaptan 0) to be used is determined depending on the molecular weight of the desired polymer [1), but usually the amount of the polymerizable monomer component (
A) It is used in an amount of 2 to 300 parts by weight per 100 parts by weight. The polymerization initiator used for polymerizing the polymerizable monomer component (A) is
Well-known oil-soluble and water-soluble polymerization initiators can be used, but in order to efficiently produce the polymer (1) having a terminal alkyl group, the amount used is alkyl mercaptan (B) 1
The ratio is preferably 1 mol or less, more preferably 0.1 mol or less, based on -E-. Depending on its properties, the polymer (1) can undergo bulk polymerization, solution polymerization,
It can be produced by any method of suspension polymerization. The polymerization temperature is preferably 50 to 150°C, and the polymerization time is preferably 1 to 8 hours. As a solvent for solution polymerization, the polymerizable monomer component (A
), alkyl mercaptan (B), and any radical polymerization initiator can be used as long as it dissolves and does not inhibit radical polymerization. Polymer [I] itself has sufficient surface-active ability, but in order to obtain a curable aqueous resin dispersion with good stability during polymerization and storage stability when used in emulsion polymerization, it is necessary to add carboxyl. Neutralize some or all of the groups to form a polymer [!
] It is preferable to use it as a salt. Is it a normal neutralizing agent? Can be used, for example, alkali metal compounds such as sodium hydroxide, potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide, calcium carbonate; ammonia; monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine , monopropylamine, dimethylpropylamine, monoethanolamine, jetanolamine, triethanolamine, ethylenediamine, diethylenetriamine, etc., and one type or a mixture of two or more types selected from these groups. can be used. If it is desired to further improve the water resistance of the cured film, it is preferable to use low-boiling amines such as ammonia, monomethylamine, dimethylamine, trimethylamine, etc., which scatter at room temperature or upon heating. Polymerizable monomers having an I-oxy group such as glycidyl chloride, 2-methylglycidyl (meth)acrylate, and allylglycidyl ether used in the production of the curable aqueous resin dispersion of the present invention: (meth)acryloyl aziridine , aziridinyl group-containing polymerizable monomers such as 2-aziridinylethyl (meth)acrylate; oxazoline group-containing polymerizable monomers such as 2-ingropenyl-2-oxazoline, 2-vinyl-2-oxazoline, etc. You can list these 1 or 2 f! ! Mixtures of the above can be used. The amount of the polymerizable monomer (a) used is 0.5 to 40% by weight, preferably 3 to 15% by weight in the polymerizable monomer component (II) used for emulsion polymerization. If the amount of the polymerizable monomer (,) used is less than 0.5 weight, a large amount of xyl groups of the polymer [I] used as an emulsifier remain unreacted, and crosslinking becomes insufficient. No improvement was observed in water resistance, solvent resistance, or strength. On the other hand, if it exceeds 400 weight, the stability during emulsion polymerization and storage stability will deteriorate, which is not preferable. The polymerizable monomer (b) other than the polymerizable monomer (-) used in the emulsion polymerization of the present invention is not particularly limited as long as it is polymerizable, but one of them may be used depending on the purpose and use. One species or a combination of two or more species can be used. Examples of these polymerizable monomers include the polymerizable monomer component -W used in the synthesis of polymer [I] as is, dimethylamine ethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, etc. ) acrylamide, dimethylamine propyl (meth)acrylamide, vinylpyridine,
Basic unsaturated monomers such as vinyl imidazole and vinyl pyrrolidone; (meth)acrylic acid and ethylene glycol, 1,3-butylene glycol, diethylene glycol, 1,6-hexane glycol, neopentyl glycol, polyethylene glycol, polypropylene Polyfunctional (meth)acrylic acid esters having two or more polymerizable unsaturated groups in the molecule, such as esters with polyhydric alcohols such as glycol, trimethylolpropane, pentaerythritol, and dipentaerythritol; (Meth)acrylamides such as meth)acrylamide and N-butoxymethyl(meth)acrylamide; vinyltrimethoxysilane, γ-(meth)acryloxyglobiltrimethoxysilane, allyltriethoxysilane, trimethoxysilylglopyru unsaturated monomers containing a silicon group such as polyamine; and vinyl fluoride, vinylidene fluoride, vinyl chloride, vinylidene chloride, divinylbenzene, sialyl phthalate, and the like. The present invention provides a method for preparing a polymerizable monomer component (If) consisting of a polymerizable monomer (-) and other polymerizable premature body color in an aqueous medium using the polymer CII and/or its salt as an emulsifier. This invention relates to a curable resin dispersion obtained by emulsion polymerization, and any conventionally known emulsion polymerization method can be applied to the polymerization method. For example, a method in which a polymerization catalyst, water, the polymer [I] and/or its salt, a polymerizable monomer component [■] containing a polymerizable monomer (,) is mixed all at once, or a so-called monomer dropwise addition method is used. The curable aqueous resin dispersion of the present invention can be prepared by a method such as a pre-emulsion method or a pre-emulsion method. Can be synthesized. The polymerization temperature is 0 to 100°C, preferably 50 to 80°C, and the polymerization time is 1 to 10 hours. During emulsion polymerization, it is possible to add a hydrophilic solvent and other known emulsifiers and additives as long as the physical properties of the mixture are not adversely affected. The amount of polymer [I] and/or its salt used is 0.5 to 20 parts by weight per 100 parts by weight of the polymerizable monomer component (if).
The range of 0 double J accent is preferable, more preferably 1 to 15
Parts by weight. If the amount used is less than 0.5 parts by weight, emulsion polymerization stability will be poor, and if more than 200 parts by weight is used, gluing will occur during polymerization, resulting in poor burn stability. As the polymerization catalyst, any conventionally known catalyst can be used. However, in order to obtain a curable resin dispersion that provides a film with even better water resistance, hydrogen peroxide, di-t-butyl oxide, peracetic acid, 2,2'-azobis(2-amidinopronopronobase), etc. dihydrochloric acid [,4,4'
-A mixture of one or more polymerization catalysts that do not leave sulfate groups, such as azobis(4-cyanopencunic acid)? It is preferable to use More preferably, the polymerizable monomer (a)
2,2'-azobis(2-ami dinopropane) dihydrochloride, 4,4'-azobis(4- Cyanopentanoic acid) etc. ・The amount of polymerization catalyst used is usually 10% of the polymerizable monomer component (II).
The amount is in the range of 0.01 to 5 parts by weight relative to 0 parts by weight. During emulsion polymerization, the polymerizable monomer component [II] is converted into a polymerizable monomer component (II) containing one or more types of polymerizable monomers (,).
-a) and the polymerizable monomer component CII-b: which does not contain one or more of the polymerizable monomers (IL), and carry out multi-stage polymerization of all of them. The curable aqueous resin dispersion is preferred because the water resistance, solvent resistance, and strength of the coating film are particularly markedly improved. At that time, the polymerizable monomer component (I
The emulsion polymerization of I-a:) and the polymerizable monomer component [II-b''l may be carried out in several stages, and the order of polymerization does not matter. However, if the polymerizable monomer component cm-b:+ is used as the component to be polymerized in the last stage, it is difficult to improve the above physical properties of the cured film. It is preferable because it dramatically improves the storage stability.The curable aqueous resin dispersion produced as described above is
It self-crosslinks at room temperature or when heated, making it water resistant.
It forms a high-strength cured film with good solvent resistance, but if necessary, aminoplast resin, polyfunctional block isocyanate, epoxy resin, pigment, antifoaming agent, film-forming aid, etc. may be added. be able to. (Effects of the Invention) The curable aqueous resin dispersion of the present invention is obtained by radical polymerizing a polymerizable monomer component containing an unsaturated carboxylic acid) in the presence of an alkyl mercaptan (B) having 6 to 18 carbon atoms. Using the obtained polymer [I] as an emulsifier, a polymerizable monomer consisting of a polymerizable monomer (a) containing a group having reactivity with a carboxyl group and another polymerizable monomer ('b) Ingredients [I
I) is emulsion polymerized in an aqueous medium and t i! It has good storage stability, and when water is splashed, the emulsifier diffuses into the emulsion polymerized resin and reacts with the hydrophilic carboxyl group, forming a crosslinked structure without generating formalin. Because of its formation, it provides a coating with extremely excellent physical properties such as water resistance, solvent resistance, and strength. Therefore, this curable aqueous resin dispersion is useful in a wide range of applications such as paints, adhesives, paper processing agents, fiber processing agents, and mortar modifiers, especially in fields where water resistance and solvent resistance are required. It is. (One Example) The present invention will be described in detail below with reference to Examples, but the scope of the present invention is not limited only to these Examples. In addition, unless otherwise specified in the examples, Q is weight% gold,
Each part indicates a part by weight. Reference Example 1 180 parts of isopropyl alcohol was placed in a flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, and while blowing nitrogen, the internal temperature was raised to 81°C, and the isopropyl alcohol was refluxed for 10 minutes. I let it happen. Next, a previously prepared polymerizable monomer mixture consisting of 174 parts of acrylic acid, 36 parts of n-dodecylmercaptan, and 0.42 parts of 2,2'-azobisisobutyronitrile was added over 1 hour. It was added dropwise and polymerized. After the dropwise addition was completed, it was aged for 1 hour under reflux to obtain a polymer with a solid content of 53.9% (1
) was obtained. The polymer (1) has a structure represented by the following general formula? has an acid value of 645 and a number average molecular weight of 12.
00 white powder. Reference Example 2 A flask similar to Reference Example 1 was charged with 180 parts of isopropyl alcohol, and the internal temperature was raised to 81° C. while blowing nitrogen, and the isopropyl alcohol was refluxed for 10 minutes. Next, from 86 parts of acrylic acid, 139 parts of 2-hydroxyethyl acrylate, 36 parts of n-dodecylmercaptan, 30 parts of isopropyl alcohol, and 0.30 parts of 2,2'-azobisinbutyronitrile prepared in advance. The polymerizable monomer mixture vlJ was added dropwise over 1 hour and polymerized. After completion of the dropwise addition, the solution was aged under reflux for 1 hour to obtain a solution of polymer (2) with a solid content of 55.4%. The polymer (
2) has a structure represented by the following general formula, and has an acid value of 2
It was a white viscous substance with a number average molecular weight of 1,500. Comparative Reference Example 1 A flask similar to Reference Example 1 was charged with 180 parts of isopropyl alcohol, and the internal temperature was raised to 81° C. while blowing nitrogen, and the isopropyl alcohol was refluxed for 10 minutes. Next, 10 parts of acrylic acid, 20 parts of 2-hydroxyethyl methacrylate, 40 parts of methyl methacrylate, 20 parts of n-butyl acrylate, 10 parts of styrene, and 2,2'-azobisisobutyro which had been prepared in advance were added. A polymerizable monomer mixture consisting of 4 parts of nitrile was added dropwise over 3 hours.
Polymerized. After the addition was completed, the mixture was aged for 1 hour under reflux.
A solution of comparative polymer (1') with a solid content of 52.9% was obtained. The polymer (1') has an acid value of °38 and a number average molecular weight of i7.
500 white resinous material. Comparative Reference Example 2 In a flask similar to Reference Example 1, 180 parts of inpropyl alcohol was charged, and while blowing nitrogen, the internal temperature was raised to 81° C., and the isopropyl alcohol was refluxed for 10 minutes. Subsequently, 86 parts of acrylic acid, 139 parts of 2-hydroxyethyl acrylate, 14 parts of thioglycol, and 0 of 2,2'-azobisisobutyronitrile, which had been prepared in advance, were added.
．． Polymerizable monomer mixture #4 consisting of 30 parts! = was added dropwise over 1 hour to polymerize. After completion of the dropwise addition, aging was carried out for 1 hour under reflux to obtain a comparative polymer (two solutions) with a solid content of 56.9%. The polymer (2') had a structure represented by the following general formula. It was a white viscous substance with an acid value of 280 and a number average molecular weight of 11,400. Example 1 A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser was charged with 150 parts of pure water and a boiling water bottle. was heated to 65°C while blowing nitrogen gas into the solution.A polymerizable monomer mixture consisting of 55 parts of butyl acinate, 35 parts of methyl methacrylate, and 10 parts of glycidyl methacrylate was prepared in a dropping funnel, and 10 parts of the mixture was added to the dropping funnel. Then, 4 parts of a 5% aqueous solution of 2,2'-azobis(2-amidinogulonone) dihydrochloride was injected into the flask.After 10 minutes, the remaining polymerizable monomer mixture was added dropwise. The dropwise addition was completed in 1.5 hours.During the dropwise addition, the temperature was maintained at 65-70°C, and after the dropwise addition was completed, the polymerization was completed by stirring at the same temperature for 1 hour. A curable aqueous resin dispersion [1] with pH = 8.3 was obtained.The amount and type of neutralizing agent and the type of polymerizable monomer mixture were adjusted to
Is the operation the same as in Example 1 except for the procedures shown in the table? il
-Repeatedly to obtain curable aqueous resin dispersions [2] to [5]. The results are summarized in Table 1. Example 6 The same procedure as in Example 1 was carried out, except that the same amount of a 5% aqueous solution of potassium persulfate was used instead of the 5% aqueous solution of 2,2'-azobis(2-amisononoro/4'-en) dihydrochloride. Example 1
The same operation as above was repeated to obtain a curable aqueous resin dispersion [6]. The results are shown in Table 1. Comparative Example 1 In Example I, Cal? 55 parts of butyl acrylate, 4 parts of methyl methacrylate, which does not contain the polymerizable monomer (a) [glycityl methacrylate] that has reactivity with xyl groups.
A comparative aqueous resin dispersion was prepared by repeating the same operation as in Example 1, except that 5 parts of the polymerizable monomer mixture was used.
1′] was obtained. The results are shown in Table 1. Comparative Examples 2 to 3 Comparative aqueous resin dispersions were prepared by repeating the same operations as in Example 1, except that a commercially available emulsifier was used instead of the ammonia-neutralized product of polymer (1) as the emulsifier. liquid〔
2'] to [3'] were obtained. The results are summarized in Table 1. Comparative Example 4 In Example I, the same amount of the solution of the comparative polymer (1') was used instead of the solution of the polymer (1), and 0.18 part of dimethylethanolamine was used instead of the 28 thiammonia water. Emulsion polymerization was carried out by repeating the same procedure except for the following steps. However, in the latter half of the dropping process, a large amount of aggregates formed, making it impossible to continue the polymerization. Comparative Example 5 In Example 1, 35 parts of a solution of comparative polymer (1') was used instead of the solution of polymer (1), and 1.12 parts of dimethylethanolamine was used instead of 28% ammonia water. The same procedure was repeated except that the amount of polymerizable monomer used was the same as shown in Table 1 to prepare a comparative aqueous resin dispersion [5].
′] was obtained. The results are shown in Table 1. Comparative Example 6 The same operation as in Example 1 was carried out except that the same amount of comparative green polymer (2') solution and 1.6 parts of 28 thiammonia water were used instead of the polymer (1) solution. Emulsion polymerization was carried out repeatedly. However, in the latter half of the dropping process, a large amount of aggregates formed, making it impossible to continue the polymerization. Comparative Example 7 Emulsion polymerization was carried out by repeating the same procedure as in Example 1 except that a mixture of 55 parts of butyl acrylate and 45 parts of glycidyl methacrylate was used as the polymerizable monomer mixture. However, in the latter half of the dropping process, a large amount of aggregates formed, making it impossible to continue the polymerization. Example 7 In a flask similar to Example 1, 150 parts of pure water and 5.6 parts of the solution of polymer (2) obtained in Reference Example 1 were charged to give a 28%
2.1 parts of aqueous ammonia was added to neutralize the mixture. The mixture was heated to 65° C. while being gently bubbled with nitrogen gas. Add 20 parts of butyl acrylate and 1 part of glycidyl methacrylate to the dropping funnel.
A polymerizable monomer mixture (a) consisting of 0 parts of polymerizable monomers (polymerizable monomer mixture containing IL-1) was prepared, and 10 parts of it was added dropwise to the flask. Then 2.2'
- 4 parts of an aqueous solution of azobis(2-amidinoglopane) dihydrochloride was injected. After 10 minutes, dropwise addition of the remaining polymerizable monomer mixture [A] was started, and the dropwise addition was completely completed in 20 minutes. After continuing stirring for 30 minutes, as the second stage polymerization, a polymerizable monomer mixture containing no polymerizable monomers* consisting of 35 parts of butyl acrylate and 35 parts of methyl methacrylate was prepared in the dropping funnel. The mixture was added dropwise over 1 hour. During the polymerization, the temperature was maintained at 65 to 70°C, and after the completion of the second stage addition, stirring was continued at the same temperature for 1 hour to complete the polymerization. A curable aqueous resin dispersion [7] was obtained. Examples 8 to 9) In the same manner as in Example 7, a polymerizable monomer mixture [A] containing a polymerizable monomer substance was polymerized, and then polymerization was carried out as the second stage (A) polymerization. A curable aqueous resin dispersion [8] ~
〔９〕を得た。その結果をまとめて第２表に示
した。
比較例８〜９
実施例７と同様にして、重合性単量体混合物〔イ〕、〔
口〕の種類及び量を第２表に示した通シとする他は実施
例７と同様の操作を繰り返して比較用水性樹脂分散液〔
８′〕〜〔９′〕を得た。その結果をまとめて第２表に
示した。
実施例１０
実施例１〜９及び比較例１〜９で得られた硬化性水性樹
脂分散液〔１〕〜[9] was obtained. The results are summarized in Table 2. Comparative Examples 8 to 9 In the same manner as in Example 7, polymerizable monomer mixtures [A], [
A comparative aqueous resin dispersion was prepared by repeating the same operation as in Example 7, except that the type and amount of the resin were as shown in Table 2.
8'] to [9'] were obtained. The results are summarized in Table 2. Example 10 Curable aqueous resin dispersion [1] obtained in Examples 1 to 9 and Comparative Examples 1 to 9
〔９〕、比較用水性樹脂分散ｉ （１
’Ｅ〜Ｃ９’〕ｅテフロン板上で乾燥時の膜厚が０、２
〜０．３鰭になるようにキャスティングし、２０℃で１
日乾燥して成膜させ、次いで１２０℃で３分間加熱して
試験フィルムを作成した。
得られたフィルムについて下記の性能試験を行い、各水
性樹脂分散液の性能を評価した。その結＜ＣＬ＞
該重合体（１）もしくは重合性単量体部の単独使用系に
は見られない著しい耐水性、耐溶剤性、強度（ａ）
の向上が認められた。また、重合性単量体部を含んでな
る重合性単量体混合物を乳化重合した後、（Ａ）
第２段の重合として重合性単量体部を含まない重合性単
量体混合物の乳化重合を行なった系は、さ１、 耐水性
試験フィルムを約２０．角に切シ取シ秤量した（Ｗｅ）
。フィルムを３日間脱イオン水に浸漬し、引上げてフィ
ルム表面の水分を軽くふき取った後秤量した（Ｗ！ ）
。さらにそのフィルムを１００℃で１時間乾燥し、放冷
後押量した（Ｗ、）。
下記計算式によシ吸水率及び溶出率を求め試験フィルム
の耐水性？評価した。
フィルム外観；３日間脱イオン水に浸漬したフィルムの
透明性を評価した。
○・・・透明のまま変化なし
Δ・・・青白くなる
×・・・白化する
２、 耐溶剤性
試験フィルムを２０嘔角に切り取シ、５０℃メチルセロ
ソルブ中に１５分間浸漬した。しかる後にフィルムを取
り出し面積膨潤率を測定した。また、試験後フィルムを
乾燥して溶出率を算出した。
３、 フィルム強度
ＪＩＳ Ｋ−６７３２記載の試験方法に基づきフィルム
の引張強度を測定した。
４、貯蔵安定性
硬化性水性樹脂分散液（１−５０℃、３０日間放置した
前後での最低造膜温度の変化゛
○・・・全く変化がなかった。
△・・・０℃〜５℃の範囲で変化した。
×・・・５℃以上変化した。[9], Comparative aqueous resin dispersion i (1
'E~C9']e Film thickness when drying on Teflon plate is 0, 2
Cast to ~0.3 fins and heat at 20°C.
A film was formed by drying in the sun, and then heated at 120° C. for 3 minutes to prepare a test film. The following performance tests were conducted on the obtained films to evaluate the performance of each aqueous resin dispersion. As a result <CL> Significant improvements in water resistance, solvent resistance, and strength (a) were observed that were not observed in systems in which the polymer (1) or the polymerizable monomer moiety was used alone. Further, after emulsion polymerization of a polymerizable monomer mixture containing a polymerizable monomer part, (A) emulsification of a polymerizable monomer mixture not containing a polymerizable monomer part as a second stage polymerization. The polymerized system had a rating of 1, and the water resistance test film had a rating of 20. I cut it into a corner and weighed it (We)
. The film was immersed in deionized water for 3 days, pulled out, and the moisture on the film surface was gently wiped off before being weighed (W!)
. The film was further dried at 100° C. for 1 hour, left to cool, and then pressed (W,). Calculate the water absorption rate and dissolution rate using the formula below and check the water resistance of the test film. evaluated. Film appearance: The transparency of the film immersed in deionized water for 3 days was evaluated. ○: No change as it remains transparent Δ: Becomes pale ×: Whitening 2. Solvent resistance test The film was cut into 20-square pieces and immersed in 50° C. methyl cellosolve for 15 minutes. Thereafter, the film was taken out and the area swelling rate was measured. Furthermore, after the test, the film was dried and the dissolution rate was calculated. 3. Film strength The tensile strength of the film was measured based on the test method described in JIS K-6732. 4. Storage-stable curable aqueous resin dispersion (1-50°C, change in minimum film-forming temperature before and after standing for 30 days゛○...No change at all. △...0°C to 5°C Changed within the range of ×... Changed by 5°C or more.
Claims (1)
体成分（Ａ）を炭素数が６〜１８のアルキルメルカプタ
ン（Ｂ）の存在下に重合して得られる酸価が２００以上
の水溶性もしくは水分散性の末端アルキル基を有する重
合体〔 I 〕および／またはその塩を乳化剤に用いて、
カルボキシル基との反応性を有する基を含有する重合性
単量体（ａ）０．５〜４０重量％および他の重合性単量
体（ｂ）６０〜９９．５重量％（但し、重合性単量体（
ａ）および（ｂ）の合計は１００重量％である。）から
なる重合性単量体成分〔II〕を水性媒体中で乳化重合し
て得られることを特徴とする硬化性水性樹脂分散液。 ２、重合性単量体成分〔II〕を、１種以上のカルボキシ
ル基との反応性を有する基を含有する重合性単量体（ａ
）を含む重合性単量体成分〔II−ａ〕と１種以上の該重
合性単量体（ａ）を含まぬ重合性単量体成分〔II−ｂ〕
とに分割し、これらを多段重合する特許請求の範囲第１
項記載の硬化性水性樹脂分散液。 ３、少なくとも最後段目に重合する成分が重合性単量体
成分〔II−ｂ〕である特許請求の範囲第２項記載の硬化
性水性樹脂分散液。[Claims] 1. An acid value obtained by polymerizing a polymerizable monomer component (A) containing an unsaturated carboxylic acid as an essential component in the presence of an alkyl mercaptan having 6 to 18 carbon atoms (B) Using a polymer [I] having a water-soluble or water-dispersible terminal alkyl group of 200 or more and/or a salt thereof as an emulsifier,
0.5 to 40% by weight of a polymerizable monomer (a) containing a group having reactivity with a carboxyl group and 60 to 99.5% by weight of another polymerizable monomer (b) (however, polymerizable Monomer (
The sum of a) and (b) is 100% by weight. ) A curable aqueous resin dispersion obtained by emulsion polymerization of a polymerizable monomer component [II] consisting of ) in an aqueous medium. 2. Polymerizable monomer component [II] is a polymerizable monomer containing a group having reactivity with one or more carboxyl groups (a
) and a polymerizable monomer component [II-b] that does not contain one or more of the polymerizable monomers (a).
Claim 1, in which the invention is divided into two parts, and these are polymerized in multiple stages.
The curable aqueous resin dispersion described in . 3. The curable aqueous resin dispersion according to claim 2, wherein the component polymerized at least in the last stage is a polymerizable monomer component [II-b].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62093229A JPH0798849B2 (en) | 1987-04-17 | 1987-04-17 | Curable aqueous resin dispersion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62093229A JPH0798849B2 (en) | 1987-04-17 | 1987-04-17 | Curable aqueous resin dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63258913A true JPS63258913A (en) | 1988-10-26 |
| JPH0798849B2 JPH0798849B2 (en) | 1995-10-25 |
Family
ID=14076713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62093229A Expired - Fee Related JPH0798849B2 (en) | 1987-04-17 | 1987-04-17 | Curable aqueous resin dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0798849B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0525366A (en) * | 1990-11-22 | 1993-02-02 | Nippon Shokubai Co Ltd | Epoxy resin composition and its production |
| WO1993010184A1 (en) * | 1991-11-18 | 1993-05-27 | Nippon Shokubai Co., Ltd. | Highly weather-resistant one-pack cross-linking emulsion |
| WO1994010241A1 (en) * | 1991-08-13 | 1994-05-11 | Nippon Shokubai Co., Ltd. | Epoxy resin composition and production thereof |
| JPH0820617A (en) * | 1994-07-11 | 1996-01-23 | Kanegafuchi Chem Ind Co Ltd | Cold-setting composition |
| US5691416A (en) * | 1992-11-05 | 1997-11-25 | Nippon Shokubai Co., Ltd. | (Meth)acrylate polymer particles dispersed in epoxy resin |
| WO2004076581A1 (en) * | 2003-02-28 | 2004-09-10 | Soken Chemical & Engineering Co., Ltd. | Emulsion-type pressure sensitive adhesive and process for producing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5321224A (en) * | 1976-08-10 | 1978-02-27 | Nippon Paint Co Ltd | Coating compositions |
| JPS5480334A (en) * | 1977-12-08 | 1979-06-27 | Dainippon Ink & Chem Inc | Thermosetting aqueous coating composition |
| JPS6053552A (en) * | 1983-09-02 | 1985-03-27 | Dainippon Ink & Chem Inc | Synthetic resin aqueous dispersion |
-
1987
- 1987-04-17 JP JP62093229A patent/JPH0798849B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5321224A (en) * | 1976-08-10 | 1978-02-27 | Nippon Paint Co Ltd | Coating compositions |
| JPS5480334A (en) * | 1977-12-08 | 1979-06-27 | Dainippon Ink & Chem Inc | Thermosetting aqueous coating composition |
| JPS6053552A (en) * | 1983-09-02 | 1985-03-27 | Dainippon Ink & Chem Inc | Synthetic resin aqueous dispersion |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0525366A (en) * | 1990-11-22 | 1993-02-02 | Nippon Shokubai Co Ltd | Epoxy resin composition and its production |
| WO1994010241A1 (en) * | 1991-08-13 | 1994-05-11 | Nippon Shokubai Co., Ltd. | Epoxy resin composition and production thereof |
| WO1993010184A1 (en) * | 1991-11-18 | 1993-05-27 | Nippon Shokubai Co., Ltd. | Highly weather-resistant one-pack cross-linking emulsion |
| AU661519B2 (en) * | 1991-11-18 | 1995-07-27 | Nippon Shokubai Co., Ltd. | Highly weather-resistant one-pack cross-linking emulsion |
| US5534579A (en) * | 1991-11-18 | 1996-07-09 | Nippon Shokubai Co., Ltd. | Highly weather-resistant, single package, crosslinkable emulsion |
| US5691416A (en) * | 1992-11-05 | 1997-11-25 | Nippon Shokubai Co., Ltd. | (Meth)acrylate polymer particles dispersed in epoxy resin |
| JPH0820617A (en) * | 1994-07-11 | 1996-01-23 | Kanegafuchi Chem Ind Co Ltd | Cold-setting composition |
| WO2004076581A1 (en) * | 2003-02-28 | 2004-09-10 | Soken Chemical & Engineering Co., Ltd. | Emulsion-type pressure sensitive adhesive and process for producing the same |
| US7375161B2 (en) | 2003-02-28 | 2008-05-20 | Soken Chemical & Engineering Co., Ltd. | Emulsion-type pressure sensitive adhesive and process for producing the same |
| US7608656B2 (en) | 2003-02-28 | 2009-10-27 | Soken Chemical & Engineering Co., Ltd. | Emulsion pressure-sensitive adhesive and process for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0798849B2 (en) | 1995-10-25 |
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