JP5411018B2 - Method for producing aqueous urethane-modified (meth) acrylic resin dispersion - Google Patents
Method for producing aqueous urethane-modified (meth) acrylic resin dispersion Download PDFInfo
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- JP5411018B2 JP5411018B2 JP2010037299A JP2010037299A JP5411018B2 JP 5411018 B2 JP5411018 B2 JP 5411018B2 JP 2010037299 A JP2010037299 A JP 2010037299A JP 2010037299 A JP2010037299 A JP 2010037299A JP 5411018 B2 JP5411018 B2 JP 5411018B2
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- Prior art keywords
- meth
- resin dispersion
- monomer
- reaction
- prepolymer
- Prior art date
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- 239000006185 dispersion Substances 0.000 title claims description 114
- 238000004519 manufacturing process Methods 0.000 title claims description 69
- 229920000178 Acrylic resin Polymers 0.000 title claims description 27
- 239000004925 Acrylic resin Substances 0.000 title claims description 27
- 239000000178 monomer Substances 0.000 claims description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 77
- 238000006243 chemical reaction Methods 0.000 claims description 69
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 67
- 238000010526 radical polymerization reaction Methods 0.000 claims description 50
- 125000000524 functional group Chemical group 0.000 claims description 47
- 230000002378 acidificating effect Effects 0.000 claims description 39
- 229920005862 polyol Polymers 0.000 claims description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 33
- 150000003077 polyols Chemical class 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 30
- 238000007259 addition reaction Methods 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 18
- -1 functional group Compound Chemical class 0.000 claims description 15
- 230000003472 neutralizing effect Effects 0.000 claims description 15
- 239000005056 polyisocyanate Substances 0.000 claims description 15
- 229920001228 polyisocyanate Polymers 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 230000001804 emulsifying effect Effects 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 9
- 238000007865 diluting Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 239000011347 resin Substances 0.000 description 109
- 229920005989 resin Polymers 0.000 description 109
- 239000000243 solution Substances 0.000 description 58
- 239000011248 coating agent Substances 0.000 description 37
- 239000000203 mixture Substances 0.000 description 34
- 238000000576 coating method Methods 0.000 description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 30
- 238000000034 method Methods 0.000 description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 27
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 23
- 239000002904 solvent Substances 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 16
- 230000000704 physical effect Effects 0.000 description 16
- 239000003505 polymerization initiator Substances 0.000 description 15
- 239000004970 Chain extender Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 14
- 238000013112 stability test Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 229920000768 polyamine Polymers 0.000 description 11
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 11
- 239000003995 emulsifying agent Substances 0.000 description 10
- 230000035939 shock Effects 0.000 description 10
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 230000002087 whitening effect Effects 0.000 description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- 238000001879 gelation Methods 0.000 description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 7
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- GHJOIQFPDMIKHT-UHFFFAOYSA-N propane-1,2,3-triol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCC(O)CO GHJOIQFPDMIKHT-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000004904 shortening Methods 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
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- OHOVKSFZYUUKHT-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)heptanoic acid Chemical compound CCCCCC(CO)(CO)C(O)=O OHOVKSFZYUUKHT-UHFFFAOYSA-N 0.000 description 2
- VKNBFINDVATXHU-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)nonanoic acid Chemical compound CCCCCCCC(CO)(CO)C(O)=O VKNBFINDVATXHU-UHFFFAOYSA-N 0.000 description 2
- 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 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 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
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000006063 cullet Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229940032296 ferric chloride Drugs 0.000 description 2
- 229940032950 ferric sulfate Drugs 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent 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
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000007342 radical addition reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 229940001584 sodium metabisulfite Drugs 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- 229940075582 sorbic acid Drugs 0.000 description 2
- 239000004334 sorbic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-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
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-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
- KEVOENGLLAAIKA-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl prop-2-enoate Chemical compound CCCCOCCOCCOC(=O)C=C KEVOENGLLAAIKA-UHFFFAOYSA-N 0.000 description 1
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HZMXJTJBSWOCQB-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl prop-2-enoate Chemical compound COCCOCCOC(=O)C=C HZMXJTJBSWOCQB-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- XRIBIDPMFSLGFS-UHFFFAOYSA-N 2-(dimethylamino)-2-methylpropan-1-ol Chemical compound CN(C)C(C)(C)CO XRIBIDPMFSLGFS-UHFFFAOYSA-N 0.000 description 1
- QWDCNUDLDABORJ-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxy)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCC1CO1 QWDCNUDLDABORJ-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- GWIAAIUASRVOIA-UHFFFAOYSA-N 2-aminonaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(N)=CC=C21 GWIAAIUASRVOIA-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- PTJDGKYFJYEAOK-UHFFFAOYSA-N 2-butoxyethyl prop-2-enoate Chemical compound CCCCOCCOC(=O)C=C PTJDGKYFJYEAOK-UHFFFAOYSA-N 0.000 description 1
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 description 1
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- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 description 1
- ULMZOZMSDIOZAF-UHFFFAOYSA-N 3-hydroxy-2-(hydroxymethyl)propanoic acid Chemical compound OCC(CO)C(O)=O ULMZOZMSDIOZAF-UHFFFAOYSA-N 0.000 description 1
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- YHTLGFCVBKENTE-UHFFFAOYSA-N 4-methyloxan-2-one Chemical compound CC1CCOC(=O)C1 YHTLGFCVBKENTE-UHFFFAOYSA-N 0.000 description 1
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
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- 150000007514 bases Chemical class 0.000 description 1
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- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
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- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002596 lactones Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N lysine Chemical compound NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005459 perfluorocyclohexyl group Chemical group 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Description
本発明は、水性ウレタン変性（メタ）アクリル樹脂分散液の製造方法に関する。 The present invention relates to a method for producing an aqueous urethane-modified (meth) acrylic resin dispersion.
従来、コーティング剤、塗料、インキ用の水性樹脂として、アクリル樹脂やウレタン樹脂が使用されている。
アクリル樹脂は、耐候性、光沢、耐アルカリ性などの性能に優れているが、塗膜にした際の硬さと軟さの両立が困難であり、耐屈曲性、耐衝撃性、耐摩耗性などが不十分であった。
一方、ウレタン系樹脂は、機械的物性、密着性、耐磨耗性、柔軟性等に優れているが、耐候性、耐アルカリ性、耐熱性などが不良であり、かつ高価であった。
そこで、両方の樹脂の欠点を補うため、アクリル樹脂とウレタン樹脂を複合化した水性樹脂が提案されている。
Conventionally, acrylic resins and urethane resins have been used as aqueous resins for coating agents, paints, and inks.
Acrylic resin is superior in performance such as weather resistance, gloss, and alkali resistance, but it is difficult to achieve both hardness and softness when applied to a coating film, and it has flexibility, impact resistance, wear resistance, etc. It was insufficient.
On the other hand, the urethane-based resin is excellent in mechanical properties, adhesion, abrasion resistance, flexibility and the like, but has poor weather resistance, alkali resistance, heat resistance and the like, and is expensive.
In order to compensate for the disadvantages of both resins, an aqueous resin in which an acrylic resin and a urethane resin are combined has been proposed.
例えば特許文献１には、活性水素を有しない（メタ）アクリル系モノマー（例えばエチルアクリレート、ブチルアクリレート等）中で、ポリオール（例えばポリプロピレングリコール、ジメチロールプロピオン酸等）と、ポリイソシアネートとを反応させてウレタンプレポリマーを製造し、ついでこれを中和・水分散させ水性分散体とした後、該水性分散体をラジカル重合することで、アクリル樹脂と複合化された水性ウレタン樹脂の製造方法が開示されている。 For example, Patent Document 1 discloses that a polyol (eg, polypropylene glycol, dimethylolpropionic acid, etc.) is reacted with a polyisocyanate in a (meth) acrylic monomer (eg, ethyl acrylate, butyl acrylate, etc.) that does not have active hydrogen. Disclosed is a method for producing an aqueous urethane resin combined with an acrylic resin by radical polymerization of the aqueous dispersion after neutralizing and dispersing in water to form an aqueous dispersion. Has been.
特許文献２には、分子内に、少なくとも２個の水酸基と１個の不飽和基を有する不飽和化合物（例えばグリセリンモノアクリレート等）を必須成分とする不飽和単量体（例えばエチルアクリレート、ブチルアクリレート等）中で、ポリオール（例えばポリプロピレングリコール、ジメチロールプロピオン酸等）と、ポリイソシアネートとを反応させてウレタンプレポリマーを製造し、ついでこれを中和・水分散させ水性分散体とした後、該水性分散体をラジカル重合することで、アクリル樹脂と複合化された水性ウレタン樹脂の製造方法が開示されている。 Patent Document 2 discloses an unsaturated monomer (for example, ethyl acrylate, butyl) having an unsaturated compound (for example, glycerin monoacrylate) having at least two hydroxyl groups and one unsaturated group in the molecule. Acrylate, etc.) in a polyol (for example, polypropylene glycol, dimethylolpropionic acid, etc.) and a polyisocyanate to produce a urethane prepolymer, which is then neutralized and dispersed in water to form an aqueous dispersion. A method for producing an aqueous urethane resin combined with an acrylic resin by radical polymerization of the aqueous dispersion is disclosed.
特許文献３には、活性水素を有しない（メタ）アクリル系モノマー（例えばメチル（メタ）アクリレート等）中で、ジイソシアネート化合物と、ポリオール化合物と、分子中に２個の水酸基と１個のイオン形成官能基を含有する化合物（例えばジメチロールブタン酸等）とを反応させてウレタンプレポリマーを製造し、ついでこれを中和・水添加して乳化した後、水酸基含有（メタ）アクリル系モノマーを混合し、鎖延長と（メタ）アクリル系モノマーのラジカル重合を行うことで、アクリル樹脂とウレタン樹脂が複合化された樹脂組成物水性エマルションが開示されている。 Patent Document 3 discloses that a diisocyanate compound, a polyol compound, two hydroxyl groups and one ion are formed in a (meth) acrylic monomer having no active hydrogen (for example, methyl (meth) acrylate). A urethane prepolymer is produced by reacting with a compound containing a functional group (for example, dimethylolbutanoic acid, etc.), then neutralized, added with water, and emulsified, and then mixed with a hydroxyl group-containing (meth) acrylic monomer. In addition, a resin composition aqueous emulsion in which an acrylic resin and a urethane resin are combined by performing chain extension and radical polymerization of a (meth) acrylic monomer is disclosed.
しかしながら、特許文献１に記載の方法では、ウレタンプレポリマー中にアクリル樹脂と結合する部分（二重結合）がないので、水性分散体をラジカル重合させても（メタ）アクリル系モノマーとウレタンプレポリマーが別々に重合してポリマー（アクリル樹脂とウレタン樹脂）となるだけであり、すなわち、アクリル樹脂とウレタン樹脂の単なる混合物が得られるだけである。よって、得られた水性ウレタン樹脂は溶液安定性が低く、耐アルコールショック性（水性樹脂をアルコール系溶剤で希釈したときの増粘や凝集物の発生）、凍結融解サイクル（水性樹脂を凍結させた後、融解させることを繰り返す操作）に対する耐久性、熱安定性に劣る傾向があった。 However, in the method described in Patent Document 1, since there is no portion (double bond) bonded to the acrylic resin in the urethane prepolymer, even if the aqueous dispersion is radically polymerized, the (meth) acrylic monomer and the urethane prepolymer Are polymerized separately to form a polymer (acrylic resin and urethane resin), that is, a simple mixture of acrylic resin and urethane resin is obtained. Therefore, the obtained water-based urethane resin has low solution stability, resistance to alcohol shock (thickening or aggregation occurs when the water-based resin is diluted with an alcohol solvent), freeze-thaw cycle (freezing the water-based resin) Afterwards, there was a tendency to be inferior in durability and thermal stability to the operation of repeating melting.
特許文献２に記載の方法では、グリセリンモノアクリレートを含むモノマー中でウレタンプレポリマーを製造しているため、ウレタンプレポリマー中に不飽和結合が導入され、不飽和単量体とウレタンプレポリマーとがラジカル重合する。しかし、グリセリンモノアクリレートは不純物としてモノアルコール化合物やトリアルコール化合物を含む場合が多い。そのため、ウレタンプレポリマーの製造工程中に、モノアルコール化合物がウレタンプレポリマーと反応することで反応が停止して低分子量化したり、トリアルコール化合物によってウレタンプレポリマーの増粘やゲル化を引き起こしたりすることがあった。 In the method described in Patent Document 2, since a urethane prepolymer is produced in a monomer containing glycerin monoacrylate, an unsaturated bond is introduced into the urethane prepolymer, and the unsaturated monomer and the urethane prepolymer are separated from each other. Radical polymerization. However, glycerin monoacrylate often contains a monoalcohol compound or a trialcohol compound as an impurity. Therefore, during the production process of urethane prepolymer, the reaction stops due to the monoalcohol compound reacting with the urethane prepolymer, and the trialcohol compound causes the urethane prepolymer to thicken or gel. There was a thing.
特許文献３に記載の方法では、ウレタンプレポリマーを乳化した後に、水酸基含有（メタ）アクリル系モノマーを混合し、鎖延長と（メタ）アクリル系モノマーのラジカル重合を行う。この場合、ウレタンプレポリマー中のイソシアネート基と水酸基含有（メタ）アクリル系モノマーとの反応の方が、鎖延長の反応よりも進行しやすいため、鎖延長の反応はウレタンプレポリマー中の未反応のイソシアネート基と鎖延長剤との反応に限定されやすい。その結果、分子量が制限されやすく、特に高分子量化が困難となる。従って、得られる水性樹脂は低分子量になる傾向にあり、塗膜の耐溶剤性が低下しやすかった。
また、ウレタンプレポリマーの乳化後に添加する（メタ）アクリル系モノマーは活性水素（水酸基）を有するため、得られる水性樹脂全体の親水性が高くなりやすく、塗膜の耐水性が低下しやすかった。
In the method described in Patent Document 3, after emulsifying a urethane prepolymer, a hydroxyl group-containing (meth) acrylic monomer is mixed, and chain extension and radical polymerization of the (meth) acrylic monomer are performed. In this case, since the reaction between the isocyanate group in the urethane prepolymer and the hydroxyl group-containing (meth) acrylic monomer is more likely to proceed than the chain extension reaction, the chain extension reaction is unreacted in the urethane prepolymer. It is easy to be limited to the reaction between an isocyanate group and a chain extender. As a result, the molecular weight is likely to be limited, and it is particularly difficult to increase the molecular weight. Therefore, the aqueous resin obtained tends to have a low molecular weight, and the solvent resistance of the coating film tends to be lowered.
Moreover, since the (meth) acrylic monomer added after emulsification of the urethane prepolymer has active hydrogen (hydroxyl group), the hydrophilicity of the entire aqueous resin obtained tends to be high, and the water resistance of the coating film tends to decrease.
本発明は上記事情に鑑みてなされたもので、耐溶剤性および耐水性が良好な塗膜を形成でき、かつ耐アルコールショック性、凍結融解サイクルに対する耐久性、熱安定性に優れた水性ウレタン変性（メタ）アクリル樹脂分散液の製造方法の提供を課題とする。 The present invention has been made in view of the above circumstances, and can form a coating film having good solvent resistance and water resistance, and can also form an aqueous urethane modification excellent in alcohol shock resistance, durability against freeze-thaw cycles, and thermal stability. An object is to provide a method for producing a (meth) acrylic resin dispersion.
本発明の水性ウレタン変性（メタ）アクリル樹脂分散液の製造方法は、活性水素を有しない（メタ）アクリル系モノマー（Ａ）中で、ポリイソシアネート（ａ）と、分子内に、水酸基及びアミノ基から選ばれる官能基を２つ以上含み、かつ酸性官能基を１つ以上有する化合物（ｂ）と、酸性官能基を有しないポリオール（ｃ）と、分子内にグリシジル基及び重合性不飽和基を有する化合物（ｄ）（ただし、前記（メタ）アクリル系モノマー（Ａ）を除く。）とを反応させて、重合性不飽和基及び酸性官能基を有するイソシアネート末端ウレタンプレポリマー（Ｂ）を製造し、ついで、イソシアネート末端ウレタンプレポリマー（Ｂ）中の酸性官能基を中和し、水希釈して乳化させた後、イソシアネート末端ウレタンプレポリマー（Ｂ）の鎖延長反応と、前記（メタ）アクリル系モノマー（Ａ）およびイソシアネート末端ウレタンプレポリマー（Ｂ）のラジカル重合反応とを行うことを特徴とする。 The method for producing an aqueous urethane-modified (meth) acrylic resin dispersion according to the present invention includes a polyisocyanate (a), a hydroxyl group and an amino group in the molecule in a (meth) acrylic monomer (A) having no active hydrogen. A compound (b) containing two or more functional groups selected from 1 and having at least one acidic functional group, a polyol (c) having no acidic functional group, a glycidyl group and a polymerizable unsaturated group in the molecule. And an isocyanate-terminated urethane prepolymer (B) having a polymerizable unsaturated group and an acidic functional group, by reacting with the compound (d) having the above (excluding the (meth) acrylic monomer (A)). Next, the acidic functional group in the isocyanate-terminated urethane prepolymer (B) is neutralized, diluted with water and emulsified, and then the chain extension of the isocyanate-terminated urethane prepolymer (B). React with, and performing a radical polymerization reaction of the (meth) acrylic monomer (A) and the isocyanate-terminated urethane prepolymer (B).
また、本発明の水性ウレタン変性（メタ）アクリル樹脂分散液の製造方法は、活性水素を有しない（メタ）アクリル系モノマー（Ａ）中で、ポリイソシアネート（ａ）と、分子内に、水酸基及びアミノ基から選ばれる官能基を２つ以上含み、かつ酸性官能基を１つ以上有する化合物（ｂ）と、酸性官能基を有しないポリオール（ｃ）とを反応させて、酸性官能基を有するイソシアネート末端ウレタンプレポリマー（Ｃ）を製造し、ついで、イソシアネート末端ウレタンプレポリマー（Ｃ）中の酸性官能基を中和し、水希釈して乳化させた後、イソシアネート末端ウレタンプレポリマー（Ｃ）の鎖延長反応と、前記（メタ）アクリル系モノマー（Ａ）および分子内にグリシジル基及び重合性不飽和基を有する化合物（ｄ）（ただし、前記（メタ）アクリル系モノマー（Ａ）を除く。）のラジカル重合反応と、イソシアネート末端ウレタンプレポリマー（Ｃ）および前記化合物（ｄ）の付加反応とを行うことを特徴とする。 Moreover, the manufacturing method of the aqueous | water-based urethane-modified (meth) acrylic resin dispersion liquid of this invention is a (meth) acrylic-type monomer (A) which does not have active hydrogen, in a polyisocyanate (a), a molecule | numerator, a hydroxyl group and Isocyanate having an acidic functional group by reacting a compound (b) containing two or more functional groups selected from amino groups and having at least one acidic functional group with a polyol (c) having no acidic functional group After producing the terminal urethane prepolymer (C), neutralizing the acidic functional group in the isocyanate-terminated urethane prepolymer (C), diluting with water and emulsifying, the chain of the isocyanate-terminated urethane prepolymer (C) An extension reaction, the (meth) acrylic monomer (A) and a compound (d) having a glycidyl group and a polymerizable unsaturated group in the molecule (provided that the (meth) Excluding acrylic monomer (A). A radical polymerization reaction), and carrying out the addition reaction of the isocyanate-terminated urethane prepolymer (C) and the compound (d).
本発明の水性ウレタン変性（メタ）アクリル樹脂分散液の製造方法によれば、耐溶剤性および耐水性が良好な塗膜を形成でき、かつ耐アルコールショック性、凍結融解サイクルに対する耐久性、熱安定性に優れた水性ウレタン変性（メタ）アクリル樹脂分散液が得られる。 According to the method for producing an aqueous urethane-modified (meth) acrylic resin dispersion of the present invention, a coating film having good solvent resistance and water resistance can be formed, and alcohol shock resistance, durability against freeze-thaw cycles, and heat stability An aqueous urethane-modified (meth) acrylic resin dispersion having excellent properties can be obtained.
以下、本発明を詳細に説明する。
なお、本明細書において、（メタ）アクリレートは、アクリレートとメタクリレートの両方を示し、（メタ）アクリル酸は、アクリル酸とメタクリル酸の両方を示すものとする。
Hereinafter, the present invention will be described in detail.
In this specification, (meth) acrylate indicates both acrylate and methacrylate, and (meth) acrylic acid indicates both acrylic acid and methacrylic acid.
本発明の水性ウレタン変性（メタ）アクリル樹脂分散液（以下、「水性樹脂分散液」という。）の製造方法は、活性水素を有しない（メタ）アクリル系モノマー（Ａ）（以下、「モノマー（Ａ）」という。）中で、ウレタンプレポリマーを製造し、その後に、ウレタンプレポリマーとモノマー（Ａ）を含む混合物をラジカル重合する方法である。これにより、モノマー（Ａ）とウレタンプレポリマーとがラジカル重合し、アクリル樹脂とウレタン樹脂とが結合した複合体（水性樹脂）の分散液が得られる。 The production method of the aqueous urethane-modified (meth) acrylic resin dispersion (hereinafter referred to as “aqueous resin dispersion”) of the present invention is a (meth) acrylic monomer (A) having no active hydrogen (hereinafter referred to as “monomer ( A) "). In this method, a urethane prepolymer is produced, and then a mixture containing the urethane prepolymer and the monomer (A) is radically polymerized. Thereby, the monomer (A) and the urethane prepolymer undergo radical polymerization, and a dispersion of a composite (aqueous resin) in which the acrylic resin and the urethane resin are combined is obtained.
［モノマー（Ａ）］
モノマー（Ａ）は、分子内に活性水素を有しないアクリル系モノマーである。ここで「活性水素を有しない」とは、カルボキシル基、水酸基、メチロール基、シラノール基、１級アミノ基、２級アミノ基を含有しない、ということである。
このようなモノマー（Ａ）としては、例えば（メタ）アクリル系モノマーが挙げられる。例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニルメタクリレート、ラウリル（メタ）アクリレート、炭素数１２〜１３のアルキルを有するメタクリレート、トリデシルメタクリレート、ステアリルメタクリレート、メトキシエチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、プロポキシエチルアクリレート、ブトキシエチルアクリレート、テトラヒドロフルフリルメタクリレート、メトキシエトキシエチルアクリレート、エトキシエトキシエチルアクリレート、プロポキシエトキシエチルアクリレート、ブトキシエトキシエチルアクリレート等の（メタ）アクリル酸アルキルエステル；（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、Ｎ−メチルアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−イソプロピル（メタ）アクリルアミド等のアミド基を有する不飽和単量体；Ｎ，Ｎ−ジメチルアミノエチルメタクリレート、Ｎ，Ｎ−ジエチルアミノエチルメタクリレート、Ｎ，Ｎ−ジメチルアミノプロピルメタクリレート等の三級アミノ基を有する（メタ）アクリル酸エステル；Ｎ−ビニルピロリドン、Ｎ−ビニルイミダゾール、Ｎ−ビニルカルバゾール等の含窒素不飽和単量体；シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート等の脂環式（メタ）アクリレート；スチレン、α−メチルスチレン、メタクリル酸ベンジル、メタクリル酸フェニル等の芳香族不飽和単量体；ビニルトリエトキシシラン、γ−メタクリロイルオキシプロピルトリメトキシシラン等の含珪素不飽和単量体；オクタフルオロペンチル（メタ）アクリレート、パーフルオロシクロヘキシル（メタ）アクリレート等の含フッ素不飽和単量体；イソシアネート基をブロックした不飽和単量体等の不飽和基を一つ有する単量体類などが挙げられる。
また、モノマー（Ａ）として、活性水素を有しない不飽和基を２つ有する不飽和単量体（例えばジビニルベンゼン、ポリエチレングリコールジ（メタ）アクリレート等）を用いてもよい。
[Monomer (A)]
The monomer (A) is an acrylic monomer having no active hydrogen in the molecule. Here, “having no active hydrogen” means not containing a carboxyl group, a hydroxyl group, a methylol group, a silanol group, a primary amino group, or a secondary amino group.
Examples of such a monomer (A) include a (meth) acrylic monomer. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) Acrylate, nonyl methacrylate, lauryl (meth) acrylate, methacrylate having alkyl having 12 to 13 carbon atoms, tridecyl methacrylate, stearyl methacrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl acrylate, butoxyethyl acrylate , Tetrahydrofurfuryl methacrylate, methoxyethoxyethyl acrylate, ethoxyethoxyethyl acrylate, propoxyethoxy ester (Meth) acrylic acid alkyl esters such as acrylate, butoxyethoxyethyl acrylate; (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-isopropyl (meth) acrylamide (Meth) acrylic acid having a tertiary amino group such as N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, etc. Esters; Nitrogen-containing unsaturated monomers such as N-vinylpyrrolidone, N-vinylimidazole, N-vinylcarbazole; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate Alicyclic (meth) acrylates such as: aromatic unsaturated monomers such as styrene, α-methylstyrene, benzyl methacrylate, phenyl methacrylate; vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, etc. Silicon unsaturated monomer; Fluorine-containing unsaturated monomer such as octafluoropentyl (meth) acrylate and perfluorocyclohexyl (meth) acrylate; one unsaturated group such as unsaturated monomer blocking isocyanate group And the like.
Moreover, you may use the unsaturated monomer (For example, divinylbenzene, polyethyleneglycol di (meth) acrylate, etc.) which has two unsaturated groups which do not have active hydrogen as a monomer (A).
これらのモノマー（Ａ）は１種単独または２種以上を混合して使用することができる。また、モノマー（Ａ）としては、後述する（ａ）〜（ｃ）成分をよく溶解させる化合物を選択することが望ましいが、初期仕込みの段階で完全溶解させなくても、昇温後反応の進行に伴い溶解させるような化合物を選択してもよい。 These monomers (A) can be used individually by 1 type or in mixture of 2 or more types. As the monomer (A), it is desirable to select a compound that dissolves the components (a) to (c) described later well, but the reaction proceeds after the temperature rise without complete dissolution at the initial charging stage. A compound that dissolves along with this may be selected.
［ウレタンプレポリマー］
ウレタンプレポリマーは、ポリイソシアネート（ａ）（以下、「（ａ）成分」という。）と、分子内に、水酸基及びアミノ基から選ばれる官能基を２つ以上含み、かつ酸性官能基を１つ以上有する化合物（ｂ）（以下、「（ｂ）成分」という。）と、酸性官能基を有しないポリオール（ｃ）（以下、「（ｃ）成分」という。）と、分子内にグリシジル基及び重合性不飽和基を有する化合物（ｄ）（以下、「（ｄ）成分」という。）との反応により生成される。
[Urethane prepolymer]
The urethane prepolymer includes polyisocyanate (a) (hereinafter referred to as “component (a)”) and two or more functional groups selected from a hydroxyl group and an amino group in the molecule, and one acidic functional group. Compound (b) having the above (hereinafter referred to as “component (b)”), polyol (c) having no acidic functional group (hereinafter referred to as “component (c)”), glycidyl group in the molecule and It is produced by a reaction with a compound (d) having a polymerizable unsaturated group (hereinafter referred to as “component (d)”).
＜（ａ）成分＞
（ａ）成分は、ポリイソシアネートである。
（ａ）成分としては、分子内にイソシアネート基を２個以上有する化合物が好ましい。このような（ａ）成分としては、例えば脂肪族ポリイソシアネート、芳香族ポリイソシアネート、脂環式ポリイソシアネートおよびその誘導体などが挙げられる。具体的には、キシリレンジイソシアネート、ポリフェニルメタンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、イソホロンジイソシアネート、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、ナフタレンジイソシアネート、水添ジフェニルメタンジイソシアネート、水添キシリレンジイソシアネート、ジシクロヘキシルメタンジイソシアネートなどのジイソシアネートおよびこれらの重合物が挙げられる。
また、（ａ）成分として、例えば上記の４，４’−ジフェニルメタンジイソシアネートなどのポリイソシアネート化合物と、アロファネート結合、イソシアヌレート結合、カルボジイミド結合などを有する化合物との縮合物を用いてもよい。
<(A) component>
The component (a) is polyisocyanate.
As the component (a), a compound having two or more isocyanate groups in the molecule is preferable. Examples of such component (a) include aliphatic polyisocyanates, aromatic polyisocyanates, alicyclic polyisocyanates, and derivatives thereof. Specifically, xylylene diisocyanate, polyphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate And diisocyanates such as these and polymers thereof.
Further, as the component (a), for example, a condensate of a polyisocyanate compound such as the above 4,4′-diphenylmethane diisocyanate and a compound having an allophanate bond, an isocyanurate bond, a carbodiimide bond, or the like may be used.
これら（ａ）成分は、１種単独または２種以上を混合して使用することができる。これら（ａ）成分のうち、詳しくは後述するが、モノマー（Ａ）中で製造されたウレタンプレポリマーを水に分散する際のイソシアネート基と水との反応性、および得られる水性樹脂分散液の耐候性の点から、脂肪族ポリイソシアネート、脂環式ポリイソシアネートが好ましい。さらに、モノマー（Ａ）との相溶性の点から、脂環式ポリイソシアネートが好ましく、中でもイソホロンジイソシアネートが特に好ましい。 These (a) components can be used individually by 1 type or in mixture of 2 or more types. Among these components (a), as will be described in detail later, the reactivity of isocyanate groups and water when the urethane prepolymer produced in the monomer (A) is dispersed in water, and the resulting aqueous resin dispersion From the viewpoint of weather resistance, aliphatic polyisocyanates and alicyclic polyisocyanates are preferred. Furthermore, from the viewpoint of compatibility with the monomer (A), alicyclic polyisocyanates are preferable, and isophorone diisocyanate is particularly preferable.
＜（ｂ）成分＞
（ｂ）成分は、分子内に、水酸基及びアミノ基から選ばれる官能基を２つ以上含み、かつ酸性官能基を１つ以上有する化合物であり、ウレタンプレポリマー中に酸性官能基を導入するために用いられる。
水酸基及びアミノ基は、（ａ）成分のイソシアネート基と反応し得る官能基である。
また、酸性官能基としては、カルボキシル基、スルホン酸基などが挙げられる。
<(B) component>
Component (b) is a compound that contains two or more functional groups selected from a hydroxyl group and an amino group in the molecule and has one or more acidic functional groups, and introduces acidic functional groups into the urethane prepolymer. Used for.
The hydroxyl group and amino group are functional groups that can react with the isocyanate group of component (a).
Examples of the acidic functional group include a carboxyl group and a sulfonic acid group.
このような（ｂ）成分としては、酸性官能基としてカルボキシル基を有する場合、例えばジメチロールプロピオン酸、ジメチロール酢酸、ジメチロールブタン酸、ジメチロールヘプタン酸、ジメチロールノナン酸、ジヒドロキシ安息香酸等の炭素数１〜９のアルカノールカルボン酸類；１−カルボキシ−１，５−ペンチレンジアミン、３，５−ジアミノ安息香酸等のアミノ基含有カルボン酸類；ポリオキシプロピレントリオールと、無水マレイン酸や無水フタル酸とのハーフエステル化合物などが挙げられる。
一方、酸性官能基としてスルホン酸基を有する場合、例えばメタニル酸、２−アミノナフタレン−１−スルホン酸、４−アミノナノフタレン−１−スルホン酸、７−アミノー１，３−ナフタレンジスルホン酸、１−アミノ−２−ナフトール−４−スルホン酸等のアミノ基を有する化合物；５−スルホイソフタル酸のエチレングリコール付加物などが挙げられる。
As such component (b), when having a carboxyl group as an acidic functional group, for example, carbon such as dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutanoic acid, dimethylolheptanoic acid, dimethylolnonanoic acid, dihydroxybenzoic acid, etc. 1-9 alkanol carboxylic acids; amino group-containing carboxylic acids such as 1-carboxy-1,5-pentylenediamine, 3,5-diaminobenzoic acid; polyoxypropylene triol, maleic anhydride and phthalic anhydride; And the like.
On the other hand, when having a sulfonic acid group as an acidic functional group, for example, metanylic acid, 2-aminonaphthalene-1-sulfonic acid, 4-aminonanophthalene-1-sulfonic acid, 7-amino-1,3-naphthalenedisulfonic acid, Examples include compounds having an amino group such as 1-amino-2-naphthol-4-sulfonic acid; and ethylene glycol adducts of 5-sulfoisophthalic acid.
（ｂ）成分としては、酸性官能基としてカルボキシル基を有する化合物が好ましく、中でも、分子内に２個の水酸基と１個以上のカルボキシル基とを有する化合物がより好ましい。このような化合物としては、具体的に、ジメチロールプロピオン酸、ジメチロールブタン酸、ジメチロールヘプタン酸、ジメチロールノナン酸などのジメチロールアルカン酸類が挙げられる。これらの中でも、モノマー（Ａ）への溶解性の観点から、ジメチロールプロピオン酸、ジメチロールブタン酸が特に好ましい。 As the component (b), a compound having a carboxyl group as an acidic functional group is preferable, and among them, a compound having two hydroxyl groups and one or more carboxyl groups in the molecule is more preferable. Specific examples of such compounds include dimethylolalkanoic acids such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolheptanoic acid, and dimethylolnonanoic acid. Among these, dimethylolpropionic acid and dimethylolbutanoic acid are particularly preferable from the viewpoint of solubility in the monomer (A).
＜（ｃ）成分＞
（ｃ）成分は、酸性官能基を有しないポリオールである。
（ｃ）成分としては、分子内に水酸基を２個以上有する化合物が好ましい。このような（ｃ）成分としては、低分子量ポリオール、高分子量ポリオールなどが挙げられる。
低分子量ポリオールとしては、例えばエチレングリコール、ジエチレングリコール、トリメチレングリコール、トリエチレングリコール、プロピレングリコール、ブチレングリコール、ヘキサメチレングリコール、ネオペンチルグリコール等の２価のアルコール；トリメチロールエタン、トリメチロールプロパン、グリセリン、ペンタエリスリトール、ソルビトール等の３価以上のアルコールなどが挙げられる。
<(C) component>
The component (c) is a polyol having no acidic functional group.
As the component (c), a compound having two or more hydroxyl groups in the molecule is preferable. Examples of such component (c) include low molecular weight polyols and high molecular weight polyols.
Examples of the low molecular weight polyol include divalent alcohols such as ethylene glycol, diethylene glycol, trimethylene glycol, triethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, and neopentyl glycol; trimethylolethane, trimethylolpropane, glycerin, Examples thereof include trivalent or higher alcohols such as pentaerythritol and sorbitol.
一方、高分子量ポリオールとしては、ポリエーテルポリオール、ポリエステルポリオール、アクリルポリオール、エポキシポリオールなどが挙げられる。
ポリエーテルポリオールとしては、ポリエチレングリコール、ポリオキシプロピレングリコール、ポリ（エチレン／プロピレン）グリコール、ポリテトラメチレングリコールなどが挙げられる。
ポリエステルポリオールとしては、ジオールと二塩基酸の重縮合物とからなるポリエステルが挙げられる。ジオールとしては、エチレングリコール、ジエチレングリコール、ジプロピレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール、３−メチル１，５−ペンタンジオールなどが挙げられる。二塩基酸としては、アジピン酸、アゼライン酸、セバチン酸、イソフタル酸、テレフタル酸などが挙げられる。また、上述したポリエステル以外にも、例えばポリカプロラクトン、ポリβ−メチル−δ−バレロラクトン等のラクトン系開環重合体ポリオール、ポリカーボネートジオールなどを用いてもよい。
アクリルポリオールとしては、水酸基を有するモノマーの共重合体が挙げられる。水酸基含有モノマーとしては、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチルアクリレート、ジヒドロキシアクリレート等が挙げられる。
エポキシポリオールとしては、アミン変性エポキシ樹脂等がある。
On the other hand, examples of the high molecular weight polyol include polyether polyol, polyester polyol, acrylic polyol, and epoxy polyol.
Examples of the polyether polyol include polyethylene glycol, polyoxypropylene glycol, poly (ethylene / propylene) glycol, and polytetramethylene glycol.
Examples of the polyester polyol include polyester composed of a polycondensate of a diol and a dibasic acid. Examples of the diol include ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and 3-methyl 1,5-pentanediol. Examples of the dibasic acid include adipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid and the like. In addition to the above-described polyester, for example, lactone ring-opening polymer polyols such as polycaprolactone and poly β-methyl-δ-valerolactone, polycarbonate diol, and the like may be used.
Examples of the acrylic polyol include a copolymer of a monomer having a hydroxyl group. Examples of the hydroxyl group-containing monomer include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl acrylate, dihydroxy acrylate and the like.
Examples of the epoxy polyol include an amine-modified epoxy resin.
（ｃ）成分としては、上述したポリオール以外にも、例えばポリブタジエンジオール、ひまし油などを用いてもよい。
これら（ｃ）成分は１種単独または２種以上を混合して使用することができるが、被塗装物への密着性、塗装性、あるいは塗膜物性等のバランスをとるためには、化学構造の異なる２種類以上を混合して使用することが好ましい。また、分子量を適宜選択することによっても達成できる。
As the component (c), in addition to the above-described polyol, for example, polybutadiene diol, castor oil, or the like may be used.
These components (c) can be used alone or in combination of two or more. However, in order to balance the adhesion to the object to be coated, the paintability, or the physical properties of the coating film, the chemical structure It is preferable to use a mixture of two or more different types. It can also be achieved by appropriately selecting the molecular weight.
＜（ｄ）成分＞
（ｄ）成分は、分子内にグリシジル基及び重合性不飽和基を有する化合物（ただし、前記（メタ）アクリル系モノマー（Ａ）を除く。）である。
（ｄ）成分としては、例えばグリシジル（メタ）アクリレート、グリシジルオキシエチルメタクリレート、４−ヒドロキシブチルアクリレートグリシジルエーテル、３，４−エポキシシクロヘキシルメタクリレート、アリルグリシジルエーテルなどが挙げられる。中でもウレタンプレポリマーを製造する際の反応性の面から、グリシジル（メタ）アクリレートが好ましい。
<(D) component>
The component (d) is a compound having a glycidyl group and a polymerizable unsaturated group in the molecule (excluding the (meth) acrylic monomer (A)).
Examples of the component (d) include glycidyl (meth) acrylate, glycidyloxyethyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxycyclohexyl methacrylate, allyl glycidyl ether, and the like. Among these, glycidyl (meth) acrylate is preferable from the viewpoint of reactivity when producing a urethane prepolymer.
［水性樹脂分散液の製造］
上述したように、水性樹脂分散液は、モノマー（Ａ）中でウレタンプレポリマーを製造し、その後に、ウレタンプレポリマーとモノマー（Ａ）を含む混合物をラジカル重合することで得られる。
ここで、水性樹脂分散液の製造について、具体的に説明する。水性樹脂分散液は、以下に示す製造方法（ｉ）または製造方法（ｉｉ）により製造される。
[Production of aqueous resin dispersion]
As described above, the aqueous resin dispersion is obtained by producing a urethane prepolymer in the monomer (A) and then radically polymerizing a mixture containing the urethane prepolymer and the monomer (A).
Here, the production of the aqueous resin dispersion will be specifically described. The aqueous resin dispersion is produced by the following production method (i) or production method (ii).
＜製造方法（ｉ）＞
製造方法（ｉ）は、重合性不飽和基及び酸性官能基を有するイソシアネート末端ウレタンプレポリマー（Ｂ）（以下、「プレポリマー（Ｂ）」という。）を経由して水性樹脂分散液を製造する方法である。
まず、モノマー（Ａ）中でプレポリマー（Ｂ）を製造する。プレポリマー（Ｂ）は、以下に示す製造方法（ｉ−１）〜（ｉ−３）により製造される。
<Manufacturing method (i)>
In the production method (i), an aqueous resin dispersion is produced via an isocyanate-terminated urethane prepolymer (B) having a polymerizable unsaturated group and an acidic functional group (hereinafter referred to as “prepolymer (B)”). Is the method.
First, a prepolymer (B) is produced in the monomer (A). The prepolymer (B) is produced by the production methods (i-1) to (i-3) shown below.
（製造方法（ｉ−１））
製造方法（ｉ−１）では、まず、モノマー（Ａ）中で、（ａ）成分と（ｂ）成分と（ｃ）成分とを反応（ウレタン化反応）させて、（ｂ）成分由来の酸性官能基を有するイソシアネート末端ウレタンプレポリマー（Ｃ）（以下、「プレポリマー（Ｃ）という。」を製造する（第一工程）。
ついで、反応系内に（ｄ）成分を添加して、プレポリマー（Ｃ）中の酸性官能基と（ｄ）成分中のグリシジル基とを付加反応させ、プレポリマー（Ｂ）を得る（第二工程）。
(Manufacturing method (i-1))
In the production method (i-1), first, in the monomer (A), the (a) component, the (b) component, and the (c) component are reacted (urethanization reaction), and the acid derived from the (b) component. An isocyanate-terminated urethane prepolymer (C) having a functional group (hereinafter referred to as “prepolymer (C)”) is produced (first step).
Next, the component (d) is added to the reaction system, and the acidic functional group in the prepolymer (C) and the glycidyl group in the component (d) are subjected to an addition reaction to obtain a prepolymer (B) (second polymer). Process).
（製造方法（ｉ−２））
製造方法（ｉ−２）では、まず、モノマー（Ａ）中に、（ｂ）成分と（ｃ）成分と（ｄ）成分とを仕込み、（ｂ）成分中の酸性官能基と（ｄ）成分中のグリシジル基とを付加反応させて、（ｂ）成分由来の酸性官能基と（ｄ）成分由来の重合性不飽和基を有するポリオール（Ｄ）（以下、ポリオール（Ｄ）という。）を製造する（第一工程）。
ついで、反応系内に（ａ）成分を添加して、（ａ）成分とポリオール（Ｄ）と（ｃ）成分とをウレタン化反応させ、プレポリマー（Ｂ）を得る（第二工程）。
(Manufacturing method (i-2))
In the production method (i-2), first, the monomer (A) is charged with the component (b), the component (c), and the component (d), and the acidic functional group in the component (b) and the component (d) A polyol (D) having an acidic functional group derived from the component (b) and a polymerizable unsaturated group derived from the component (hereinafter referred to as polyol (D)) is produced by addition reaction with the glycidyl group therein. (First step).
Next, the component (a) is added to the reaction system, and the component (a), the polyol (D), and the component (c) are urethanated to obtain a prepolymer (B) (second step).
（製造方法（ｉ−３））
製造方法（ｉ−３）では、モノマー（Ａ）中に、（ａ）成分と（ｂ）成分と（ｃ）成分と（ｄ）成分とを仕込み、（ａ）成分と（ｂ）成分と（ｃ）成分とによるウレタン化反応と、（ｂ）成分中の酸性官能基と（ｄ）成分中のグリシジル基とによる付加反応とを同時に行い、プレポリマー（Ｂ）を得る。
(Manufacturing method (i-3))
In the production method (i-3), the monomer (A) is charged with the components (a), (b), (c), and (d), and the components (a), (b), and ( The urethanization reaction with the component c) and the addition reaction with the acidic functional group in the component (b) and the glycidyl group in the component (d) are simultaneously performed to obtain the prepolymer (B).
上記製造方法（ｉ−１）〜（ｉ−３）のうち、水性樹脂分散液の溶液安定性、および水性樹脂分散液より形成される塗膜の耐水性や耐溶剤性が向上することから、製造方法（ｉ−１）が好ましい。 Among the production methods (i-1) to (i-3), the solution stability of the aqueous resin dispersion and the water resistance and solvent resistance of the coating film formed from the aqueous resin dispersion are improved. Production method (i-1) is preferred.
ついで、上記製造方法（ｉ−１）〜（ｉ−３）のいずれかの方法によって得られたプレポリマー（Ｂ）と、モノマー（Ａ）とを含む混合物に中和剤と水を添加して、プレポリマー（Ｂ）中の酸性官能基を中和すると共に水希釈して、乳化を行う。 Next, a neutralizing agent and water are added to the mixture containing the prepolymer (B) obtained by any one of the production methods (i-1) to (i-3) and the monomer (A). The acidic functional group in the prepolymer (B) is neutralized and diluted with water to emulsify.
その後、プレポリマー（Ｂ）の鎖延長反応と、プレポリマー（Ｂ）およびモノマー（Ａ）のラジカル重合反応とを行うことによって、水性樹脂分散液を得る。
鎖延長反応とラジカル重合反応は同時に行ってもよいし、鎖延長反応を行った後にラジカル重合反応を行ってもよい。
なお、鎖延長反応を行う際には、鎖延長剤として詳しくは後述するが、水やポリアミン等を用いる。鎖延長剤として水を用いる場合には、製造工程の簡略化や工程時間の短縮の面で、鎖延長反応とラジカル重合反応を同時に行うのが好ましい。
一方、鎖延長剤として水以外（ポリアミンなど）を用いる場合には、反応熱緩和の面で、鎖延長反応を行った後にラジカル重合反応を行うのが好ましい。
Thereafter, an aqueous resin dispersion is obtained by performing a chain extension reaction of the prepolymer (B) and a radical polymerization reaction of the prepolymer (B) and the monomer (A).
The chain extension reaction and the radical polymerization reaction may be performed simultaneously, or after the chain extension reaction is performed, the radical polymerization reaction may be performed.
In addition, when performing chain | strand extension reaction, although mentioned later in detail as a chain extender, water, polyamine, etc. are used. When water is used as the chain extender, it is preferable to simultaneously perform the chain extension reaction and the radical polymerization reaction in terms of simplifying the production process and shortening the process time.
On the other hand, when other than water (such as polyamine) is used as the chain extender, it is preferable to perform a radical polymerization reaction after performing a chain extension reaction in terms of reaction heat relaxation.
＜製造方法（ｉｉ）＞
製造方法（ｉｉ）は、プレポリマー（Ｃ）を経由して水性樹脂分散液を製造する方法である。
まず、モノマー（Ａ）中でプレポリマー（Ｃ）を製造する。プレポリマー（Ｃ）は、前記製造方法（ｉ−１）と同様にして製造される。
<Manufacturing method (ii)>
The production method (ii) is a method for producing an aqueous resin dispersion via the prepolymer (C).
First, a prepolymer (C) is produced in the monomer (A). The prepolymer (C) is produced in the same manner as in the production method (i-1).
ついで、プレポリマー（Ｃ）とモノマー（Ａ）とを含む混合物に中和剤と水を添加して、プレポリマー（Ｃ）中の酸性官能基を中和すると共に水希釈して、乳化を行う。 Next, a neutralizing agent and water are added to the mixture containing the prepolymer (C) and the monomer (A) to neutralize acidic functional groups in the prepolymer (C) and dilute with water to emulsify. .
その後、プレポリマー（Ｃ）の鎖延長反応と、モノマー（Ａ）および（ｄ）成分のラジカル重合反応と、プレポリマー（Ｃ）および（ｄ）成分の付加反応とを行うことによって、水性樹脂分散液を得る。
プレポリマー（Ｃ）とモノマー（Ａ）とを含む混合物に（ｄ）成分を添加するタイミングは、混合物に中和剤と水を添加する前でもよいし、後でもよい。
また、鎖延長反応とラジカル重合反応と付加反応は同時に行ってもよいし、鎖延長反応を行った後にラジカル重合反応と付加反応を行ってもよい。後者の場合、ラジカル重合反応と付加反応は同時であってもよいし、付加反応を行った後にラジカル重合反応を行ってもよいし、ラジカル重合反応を行った後に付加反応を行ってもよい。
鎖延長剤として水を用いる場合には、製造工程の簡略化や工程時間の短縮の面で、鎖延長反応とラジカル重合反応と付加反応を同時に行うのが好ましい。
一方、鎖延長剤として水以外（ポリアミンなど）を用いる場合には、反応熱緩和の面で、鎖延長反応を行った後にラジカル重合反応と付加反応を行うのが好ましい。
Then, aqueous resin dispersion is carried out by carrying out chain extension reaction of the prepolymer (C), radical polymerization reaction of the monomers (A) and (d) components, and addition reaction of the prepolymer (C) and (d) components. Obtain a liquid.
The timing of adding the component (d) to the mixture containing the prepolymer (C) and the monomer (A) may be before or after adding the neutralizing agent and water to the mixture.
The chain extension reaction, radical polymerization reaction, and addition reaction may be performed simultaneously, or after the chain extension reaction, the radical polymerization reaction and addition reaction may be performed. In the latter case, the radical polymerization reaction and the addition reaction may be performed simultaneously, the radical polymerization reaction may be performed after the addition reaction, or the addition reaction may be performed after the radical polymerization reaction.
When water is used as the chain extender, it is preferable to simultaneously perform a chain extension reaction, a radical polymerization reaction, and an addition reaction in terms of simplifying the production process and shortening the process time.
On the other hand, when other than water (polyamine or the like) is used as the chain extender, it is preferable to perform a radical polymerization reaction and an addition reaction after performing a chain extension reaction in terms of reaction heat relaxation.
＜各成分の配合割合＞
上述した製造方法（ｉ）、（ｉｉ）においては、ウレタン樹脂とアクリル樹脂の比率が、質量比でウレタン樹脂：アクリル樹脂＝１：９〜９：１となるように、各成分を配合するのが好ましい。より好ましくはウレタン樹脂：アクリル樹脂＝３：７〜７：３であり、この範囲内で各成分を配合すれば、水性樹脂分散液をより安定して製造することができる。
なお、ウレタン樹脂が上述した比率より少ないと、モノマー（Ａ）の分散安定性が低下し、ラジカル重合時にゲル化したり凝集物が発生したりしやすく、製造時の安定性が著しく下がる傾向にある。一方、ウレタン樹脂が上述した比率より多くなると、ウレタン化反応時の粘度が高くなることにより、攪拌効率が低下する傾向にある。
<Combination ratio of each component>
In the production methods (i) and (ii) described above, the respective components are blended so that the ratio of the urethane resin and the acrylic resin is urethane resin: acrylic resin = 1: 9 to 9: 1 by mass ratio. Is preferred. More preferably, urethane resin: acrylic resin = 3: 7 to 7: 3. If each component is blended within this range, the aqueous resin dispersion can be more stably produced.
In addition, when the urethane resin is less than the above-described ratio, the dispersion stability of the monomer (A) is lowered, and gelation or aggregates are easily generated during radical polymerization, and the stability during production tends to be remarkably lowered. . On the other hand, when the amount of the urethane resin is larger than the above-described ratio, the stirring efficiency tends to decrease due to an increase in the viscosity during the urethanization reaction.
また、（ｂ）成分は、ウレタンプレポリマー中に導入される酸性官能基の量、すなわち、ウレタンプレポリマー固形分換算での酸価が２０〜１１０ｍｇＫＯＨ/ｇとなるように配合されるのが好ましく、より好ましくは４０〜９０ｍｇＫＯＨ/ｇである。酸価が低いと、ウレタンプレポリマーの自己乳化性が不足し、分散安定性に劣る傾向がある。一方、酸価が高いと、水性樹脂分散液より形成される塗膜の物性や耐水性に劣る傾向がある。 The component (b) is preferably blended so that the amount of acidic functional groups introduced into the urethane prepolymer, that is, the acid value in terms of urethane prepolymer solids, is 20 to 110 mgKOH / g. More preferably, it is 40-90 mgKOH / g. When the acid value is low, the self-emulsifying property of the urethane prepolymer is insufficient and the dispersion stability tends to be poor. On the other hand, when the acid value is high, the coating film formed from the aqueous resin dispersion tends to have poor physical properties and water resistance.
特に、酸性官能基としてカルボキシル基を有するポリオールを（ｂ）成分として用いる場合、製造方法（ｉ−１）、（ｉｉ）におけるプレポリマー（Ｃ）と（ｄ）成分との付加反応、および製造方法（ｉ−２）、（ｉ−３）における（ｂ）成分と（ｄ）成分との付加反応は、通常、（ｄ）成分のグリシジル基に対して、（ｂ）成分由来のカルボキシル基が過剰に存在する系内で行われる。従って、カルボキシル基とグリシジル基の比率が、モル比でカルボキシル基：グリシジル基＝１：０．０１〜１：１となるように、（ｂ）成分と（ｄ）成分を配合するのが好ましい。より好ましくは、カルボキシル基：グリシジル基＝１：０．１〜１：０．５であり、この範囲内で配合すれば、得られる水性樹脂分散液の溶液安定性と、該水性樹脂分散液より形成される塗膜の耐溶剤性の点でより好ましい。
なお、グリシジル基が上述した比率より少ないと、ウレタンプレポリマー中に導入できる重合性不飽和基量が少なくなり、その結果、ウレタン樹脂−アクリル樹脂間の結合数が減少し、水性樹脂分散液の溶液安定性に劣る傾向がある。一方、グリシジル基が上述した比率より多くなると、ウレタンプレポリマー中の重合性不飽和基量が過剰となる。その結果、製造方法（ｉ）におけるプレポリマー（Ｂ）とモノマー（Ａ）とのラジカル重合時、または製造方法（ｉｉ）におけるプレポリマー（Ｃ）とモノマー（Ａ）とのラジカル重合時に、高粘度化やゲル化したり、凝集物が発生したりし、製造時の安定性が低下する傾向にある。
In particular, when a polyol having a carboxyl group as an acidic functional group is used as the component (b), the addition reaction between the prepolymer (C) and the component (d) in the production methods (i-1) and (ii), and the production method In (i-2) and (i-3), the addition reaction between component (b) and component (d) usually has an excess of carboxyl group derived from component (b) relative to the glycidyl group of component (d). In the system that exists in Therefore, it is preferable to blend the component (b) and the component (d) so that the molar ratio of carboxyl group to glycidyl group is carboxyl group: glycidyl group = 1: 0.01 to 1: 1. More preferably, carboxyl group: glycidyl group = 1: 0.1 to 1: 0.5, and if blended within this range, the solution stability of the resulting aqueous resin dispersion and the aqueous resin dispersion It is more preferable from the viewpoint of solvent resistance of the formed coating film.
If the glycidyl group is less than the above-mentioned ratio, the amount of polymerizable unsaturated groups that can be introduced into the urethane prepolymer is reduced. As a result, the number of bonds between the urethane resin and the acrylic resin is reduced, and the aqueous resin dispersion There is a tendency to be inferior in solution stability. On the other hand, when the glycidyl group is larger than the above-described ratio, the amount of the polymerizable unsaturated group in the urethane prepolymer becomes excessive. As a result, high viscosity is obtained during the radical polymerization of the prepolymer (B) and the monomer (A) in the production method (i) or during the radical polymerization of the prepolymer (C) and the monomer (A) in the production method (ii). Or gelation, aggregates are generated, and the stability during production tends to decrease.
また、製造方法（ｉ−１）、（ｉｉ）においてプレポリマー（Ｃ）を製造する際には、（ａ）成分、（ｂ）成分、（ｃ）成分の比率が、イソシアネート基と水酸基のモル比でイソシアネート基：水酸基＝１：２〜２：１となるように、（ａ）〜（ｃ）成分を配合するのが好ましい。より好ましくは、イソシアネート基：水酸基＝１：１〜２：１であり、この範囲内で配合すれば、末端にイソシアネート基を有するウレタンプレポリマーを容易に製造でき、次工程の鎖延長反応において高分子量化しやすくなるため好ましい。 Moreover, when manufacturing prepolymer (C) in manufacturing method (i-1) and (ii), the ratio of (a) component, (b) component, (c) component is the mole of an isocyanate group and a hydroxyl group. It is preferable to blend the components (a) to (c) so that the ratio of isocyanate group: hydroxyl group = 1: 2 to 2: 1. More preferably, it is isocyanate group: hydroxyl group = 1: 1 to 2: 1. If blended within this range, a urethane prepolymer having an isocyanate group at the terminal can be easily produced, and high in chain extension reaction in the next step. This is preferable because the molecular weight is easily increased.
＜各反応について＞
（ウレタン化反応）
モノマー（Ａ）中で行われるウレタン化反応は、通常、反応系内の温度５０〜１００℃、反応時間３〜１０時間の条件で行うことが好ましい。特に反応時間が短すぎると未反応物質が残る可能性があり、水性樹脂分散液より得られる塗膜の物性が低下しやすくなる。
<About each reaction>
(Urethaneization reaction)
The urethanization reaction carried out in the monomer (A) is usually preferably carried out under conditions of a temperature in the reaction system of 50 to 100 ° C. and a reaction time of 3 to 10 hours. In particular, if the reaction time is too short, unreacted substances may remain, and the physical properties of the coating film obtained from the aqueous resin dispersion tend to deteriorate.
また、ウレタン化反応では、ウレタン化反応の熱によってモノマー（Ａ）が重合するのを防ぐために、空気の存在下でｐ−メトキシフェノール等の重合禁止剤をモノマー（Ａ）１００質量部に対し０．００２〜０．３質量部程度の範囲で、モノマー（Ａ）に加えておいてもよい。 In the urethanization reaction, a polymerization inhibitor such as p-methoxyphenol is added to 100 parts by mass of the monomer (A) in the presence of air in order to prevent the monomer (A) from being polymerized by the heat of the urethanization reaction. It may be added to the monomer (A) in the range of about 0.002 to 0.3 parts by mass.
また、ウレタン化反応では、ウレタン化反応の進行が遅い場合、触媒をウレタンプレポリマー１００質量部に対し０．１〜１．０質量部程度添加してもよい。
触媒としては、例えばジブチルチンジラウレート、ジブチルチンジオクトエート、スタナスオクトエート等の有機スズ化合物；トリエチルアミン、トリエチレンジアミン等の３級アミン化合物などが挙げられる。
In the urethanization reaction, when the urethanization reaction proceeds slowly, the catalyst may be added in an amount of about 0.1 to 1.0 part by mass with respect to 100 parts by mass of the urethane prepolymer.
Examples of the catalyst include organotin compounds such as dibutyltin dilaurate, dibutyltin dioctoate, stannous octoate; and tertiary amine compounds such as triethylamine and triethylenediamine.
（付加反応）
プレポリマー（Ｃ）と（ｄ）成分の付加反応には、以下に示す方法があるが、付加反応効率の点から、（１）が特に好ましい。
（１）製造方法（ｉ‐１）：モノマー（Ａ）中で、プレポリマー（Ｃ）と（ｄ）成分を付加反応させる方法。
（２）製造方法（ｉｉ）：プレポリマー（Ｃ）を中和・水希釈する前に、（ｄ）成分を反応系内に添加し、プレポリマー（Ｃ）を乳化した後、水中でプレポリマー（Ｃ）と（ｄ）成分を付加反応させる方法。
（３）製造方法（ｉｉ）：プレポリマー（Ｃ）を中和・水希釈した後に、（ｄ）成分を反応系内に添加し、プレポリマー（Ｃ）を乳化した後、水中でプレポリマー（Ｃ）と（ｄ）成分を付加反応させる方法。
(Addition reaction)
The addition reaction of the prepolymer (C) and the component (d) includes the following method, but (1) is particularly preferable from the viewpoint of the addition reaction efficiency.
(1) Production method (i-1): A method in which the prepolymer (C) and the component (d) are subjected to an addition reaction in the monomer (A).
(2) Production method (ii): Before neutralizing the prepolymer (C) and diluting with water, the component (d) is added to the reaction system to emulsify the prepolymer (C), and then prepolymer in water. (C) The method of making (d) component addition reaction.
(3) Production method (ii): After neutralizing and diluting the prepolymer (C), the component (d) is added to the reaction system to emulsify the prepolymer (C), and then the prepolymer ( A method in which the components C) and (d) are subjected to an addition reaction.
また、製造方法（ｉ−１）、（ｉｉ）におけるプレポリマー（Ｃ）と（ｄ）成分との付加反応、および製造方法（ｉ−２）、（ｉ−３）における（ｂ）成分と（ｄ）成分との付加反応は、反応系内に触媒がなくても進行するが、触媒を使用すればより容易に進行できる。
触媒としては、例えば水酸化ナトリウム、水酸化カリウム、アンモニア、トリエチルアミン、ジメチルベンジルアミン、ジメチルエタノールアミン、ジルコニウムオクトエート、亜鉛ナフテネート等が挙げられる。
Further, the addition reaction between the prepolymer (C) and the component (d) in the production methods (i-1) and (ii), and the component (b) in the production methods (i-2) and (i-3) ( The addition reaction with component d) proceeds even without a catalyst in the reaction system, but can proceed more easily if a catalyst is used.
Examples of the catalyst include sodium hydroxide, potassium hydroxide, ammonia, triethylamine, dimethylbenzylamine, dimethylethanolamine, zirconium octoate, zinc naphthenate and the like.
（中和・乳化）
ウレタンプレポリマーとモノマー（Ａ）とを含む混合物に中和剤と水を添加して、ウレタンプレポリマーの酸性官能基を中和し、水希釈して乳化させる方法には、以下に示す方法があるが、中和熱が抑制され、さらに乳化が容易になることから、（４）、（６）が特に好ましい。
（４）製造方法（ｉ）：プレポリマー（Ｂ）とモノマー（Ａ）とを含む混合物に、中和剤と水を混合した溶液を徐々に滴下して乳化させる方法。
（５）製造方法（ｉ）：プレポリマー（Ｂ）とモノマー（Ａ）とを含む混合物に、中和剤を添加した後に、水を添加して乳化させる方法。
（６）製造方法（ｉｉ）：プレポリマー（Ｃ）とモノマー（Ａ）とを含む混合物に、中和剤と水を混合した溶液を徐々に滴下して乳化させる方法。
（７）製造方法（ｉｉ）：プレポリマー（Ｃ）とモノマー（Ａ）とを含む混合物に、中和剤を添加した後に、水を添加して乳化させる方法。
(Neutralization / Emulsification)
In the method of adding a neutralizing agent and water to a mixture containing the urethane prepolymer and the monomer (A), neutralizing the acidic functional group of the urethane prepolymer, diluting with water and emulsifying, there are the following methods. However, (4) and (6) are particularly preferred because the heat of neutralization is suppressed and emulsification is facilitated.
(4) Production method (i): A method in which a solution containing a neutralizer and water is gradually added dropwise to a mixture containing the prepolymer (B) and the monomer (A) and emulsified.
(5) Production method (i): A method in which water is added to emulsify after adding a neutralizer to a mixture containing the prepolymer (B) and the monomer (A).
(6) Production method (ii): A method in which a solution containing a neutralizer and water is gradually added dropwise to a mixture containing the prepolymer (C) and the monomer (A) and emulsified.
(7) Production method (ii): A method in which water is added and emulsified after adding a neutralizing agent to a mixture containing the prepolymer (C) and the monomer (A).
中和剤としては、有機アミン類や無機類などの塩基性化合物を用いることができる。
有機アミン類としては、例えばメチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ヘキシルアミン、オクチルアミン、エタノールアミン、プロパノールアミン、ジエタノールアミン、Ｎ−メチルジエタノールアミン、ジメチルアミン、ジエチルアミン、トリエチルアミン、Ｎ，Ｎ−ジメチルエタノールアミン、２−ジメチルアミノ−２−メチル−１−プロパノール、２−アミノ−２−メチル−１−プロパノール、モルホリンなどが挙げられる。
無機類としては、例えばリチウム、カリウム、ナトリウム、水酸化ナトリウム、水酸化カリウム、アンモニアなどが挙げられる。
これらの中でも、塗膜にした後に揮発性を有する点で有機アミン類とアンモニアが好ましく、特にトリエチルアミン、Ｎ，Ｎ−ジメチルエタノールアミンが好ましい。
As the neutralizing agent, basic compounds such as organic amines and inorganics can be used.
Examples of organic amines include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N, N-dimethylethanolamine. 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, morpholine and the like.
Examples of inorganics include lithium, potassium, sodium, sodium hydroxide, potassium hydroxide, and ammonia.
Among these, organic amines and ammonia are preferable in view of volatility after forming a coating film, and triethylamine and N, N-dimethylethanolamine are particularly preferable.
中和剤の添加量は、（ｂ）成分が酸性官能基としてカルボキシル基を有する場合、ウレタンプレポリマー中のカルボキシル基１当量に対して、０．６〜１．２当量（中和率換算で６０〜１２０％）程度が好ましい。中和率が６０％より低いとウレタンプレポリマーの乳化力が低下し、モノマー（Ａ）とのラジカル重合時に、ゲル化や凝集物が発生する傾向にある。中和率が１２０％よりも高くなると、水分散時の系内の粘度が高くなり、乳化が困難となる。また、水性樹脂分散液中に残存する中和剤の量が多くなるため、形成される塗膜の耐水性が低下することがある。 When the component (b) has a carboxyl group as an acidic functional group, the neutralizer is added in an amount of 0.6 to 1.2 equivalents (in terms of neutralization rate) with respect to 1 equivalent of carboxyl groups in the urethane prepolymer. 60 to 120%) is preferable. When the neutralization rate is lower than 60%, the emulsifying power of the urethane prepolymer is reduced, and gelation and aggregates tend to occur during radical polymerization with the monomer (A). When the neutralization rate is higher than 120%, the viscosity in the system at the time of water dispersion becomes high and emulsification becomes difficult. Moreover, since the amount of the neutralizing agent remaining in the aqueous resin dispersion increases, the water resistance of the formed coating film may be lowered.
なお、ウレタンプレポリマーの粘度が高く、あるいは酸価が低いことによって乳化が困難な場合は、反応系内に乳化剤を添加し、中和剤と併用することも可能である。
乳化剤の種類としては、乾燥塗膜の耐水性・耐候性等を考慮し、後述する反応性乳化剤を用いるのが好ましい。
If emulsification is difficult due to the high viscosity of the urethane prepolymer or the low acid value, an emulsifier can be added to the reaction system and used in combination with a neutralizing agent.
As the type of emulsifier, it is preferable to use a reactive emulsifier described later in consideration of the water resistance and weather resistance of the dried coating film.
（鎖延長反応）
製造方法（ｉ）において乳化されたプレポリマー（Ｂ）、および製造方法（ｉｉ）において乳化されたプレポリマー（Ｃ）の鎖延長反応は、反応系内に存在する水がそのまま鎖延長剤として使われるが、ウレタン樹脂をより高分子量化するには、鎖延長剤としてポリアミン類を使用するのが好ましい。
ポリアミン類を使用するとウレタン樹脂中にウレア結合が形成され、ポリウレタン−ウレア樹脂が得られ、ウレタン樹脂部分の高分子量化が図れる。特に、３官能以上のポリアミン類は架橋剤としても作用するので、塗膜の耐溶剤性もより向上する。
ポリアミンとしては、例えばエチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン、トリエチレンテトラミン、イソホロンジアミン、ピペラジン、ジフェニルジアミン等の脂肪族系、脂環式系、芳香族系のジアミン、トリアミンなどが挙げられる。
さらに、単官能のモノアミンを併用すれば鎖延長反応の停止が起こるため、分子量の調整も容易である。
(Chain extension reaction)
In the chain extension reaction of the prepolymer (B) emulsified in the production method (i) and the prepolymer (C) emulsified in the production method (ii), water existing in the reaction system is used as it is as a chain extender. However, to increase the molecular weight of the urethane resin, it is preferable to use polyamines as chain extenders.
When polyamines are used, a urea bond is formed in the urethane resin, a polyurethane-urea resin is obtained, and the molecular weight of the urethane resin portion can be increased. In particular, since trifunctional or higher polyamines also act as a crosslinking agent, the solvent resistance of the coating film is further improved.
Examples of the polyamine include aliphatic, alicyclic, aromatic diamines, and triamines such as ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, isophoronediamine, piperazine, and diphenyldiamine.
Furthermore, when a monofunctional monoamine is used in combination, the chain extension reaction is stopped, so that the molecular weight can be easily adjusted.
水を鎖延長剤として使用する場合、反応系内の温度を７０℃以上にすると、水を介する鎖延長反応が進行しやすくなるので好ましい。また、この鎖延長反応は、後述のモノマー（Ａ）とのラジカル重合と同時に行うことも可能である。 When water is used as a chain extender, it is preferable to set the temperature in the reaction system to 70 ° C. or higher because the chain extension reaction via water tends to proceed. This chain extension reaction can also be performed simultaneously with radical polymerization with the monomer (A) described later.
一方、水以外の鎖延長剤を使用する場合、プレポリマー（Ｂ）やプレポリマー（Ｃ）中のイソシアネート基と水との反応を抑制するため、これらウレタンプレポリマーを乳化させる工程の前に、または乳化工程と同時に、反応系内の温度を７０℃以下に下げることが好ましい。より好ましくは５０℃以下であり、この温度に下げることで、水とイソシアネート基の反応を抑制でき、水以外の鎖延長剤との反応を効率良く進行させ、ウレタンプレポリマーを高分子量化することが可能となる。
特に、ポリアミンを鎖延長剤として用いて鎖延長反応を行う場合は、ポリアミンとイソシアネートの反応性が高いことから、反応系内の温度を２０〜８０℃にするのが好ましい。温度の上限値は６０℃以下が好ましい。また、水に溶解するポリアミンを用いた場合、ポリアミンを適量の水に混合し、その溶液を反応系内に滴下しながら徐々に導入する方法が、反応熱の緩和とウレタン樹脂のゲル化抑制の点から好ましい。
On the other hand, when using a chain extender other than water, in order to suppress the reaction between the isocyanate group in the prepolymer (B) or prepolymer (C) and water, before the step of emulsifying these urethane prepolymers, Or simultaneously with the emulsification step, it is preferable to lower the temperature in the reaction system to 70 ° C. or lower. More preferably, the temperature is 50 ° C. or lower, and by lowering to this temperature, the reaction between water and the isocyanate group can be suppressed, the reaction with a chain extender other than water can be efficiently advanced, and the urethane prepolymer can have a high molecular weight. Is possible.
In particular, when the chain extension reaction is carried out using polyamine as a chain extender, it is preferable to set the temperature in the reaction system to 20 to 80 ° C. because the reactivity of polyamine and isocyanate is high. The upper limit of temperature is preferably 60 ° C. or lower. In addition, when a polyamine that dissolves in water is used, the method of mixing the polyamine with an appropriate amount of water and gradually introducing the solution while dripping the solution into the reaction system reduces the reaction heat and suppresses the gelation of the urethane resin. It is preferable from the point.
（ラジカル重合反応）
製造方法（ｉ）におけるプレポリマー（Ｂ）とモノマー（Ａ）とのラジカル重合反応、および製造方法（ｉｉ）におけるモノマー（Ａ）と（ｄ）成分とのラジカル重合反応には、以下に示す方法があるが、製造工程の簡略化、工程時間の短縮の面で、（８）、（１０）が特に好ましい。
（８）製造方法（ｉ）：モノマー（Ａ）の全量をウレタン化反応時の溶媒として用い、プレポリマー（Ｂ）を乳化した後に、モノマー（Ａ）の全量をそのまま反応器内でラジカル重合させる方法。
（９）製造方法（ｉ）：モノマー（Ａ）の一部をウレタン化反応時の溶媒として用い、プレポリマー（Ｂ）を乳化した後に、残りのモノマー（Ａ）を反応系内に滴下して添加し、ラジカル重合させる方法。
（１０）製造方法（ｉｉ）：モノマー（Ａ）の全量をウレタン化反応時の溶媒として用い、プレポリマー（Ｃ）を乳化した後に、モノマー（Ａ）の全量をそのまま反応器内でラジカル重合させる方法。
（１１）製造方法（ｉｉ）：モノマー（Ａ）の一部をウレタン化反応時の溶媒として用い、プレポリマー（Ｃ）を乳化した後に、残りのモノマー（Ａ）を反応系内に滴下して添加し、ラジカル重合させる方法。
(Radical polymerization reaction)
The radical polymerization reaction between the prepolymer (B) and the monomer (A) in the production method (i) and the radical polymerization reaction between the monomer (A) and the component (d) in the production method (ii) are the following methods: However, (8) and (10) are particularly preferable in terms of simplifying the manufacturing process and shortening the process time.
(8) Production method (i): The total amount of monomer (A) is used as a solvent for the urethanization reaction, and after prepolymer (B) is emulsified, the entire amount of monomer (A) is radically polymerized in the reactor as it is. Method.
(9) Production method (i): A part of the monomer (A) is used as a solvent for the urethanization reaction, and after emulsifying the prepolymer (B), the remaining monomer (A) is dropped into the reaction system. A method of adding and radical polymerization.
(10) Production method (ii): The total amount of monomer (A) is used as a solvent for the urethanization reaction, and after prepolymer (C) is emulsified, the entire amount of monomer (A) is radically polymerized in the reactor as it is. Method.
(11) Production method (ii): A part of the monomer (A) is used as a solvent for the urethanization reaction, and after emulsifying the prepolymer (C), the remaining monomer (A) is dropped into the reaction system. A method of adding and radical polymerization.
ラジカル重合反応を行う際には、通常、重合開始剤を用いる。重合開始剤は水溶性であってもよく、油溶性であってもよい。
重合開始剤としては、例えばアゾビスイソブチロニトリル、アゾビスイソブチルバレロニトリル等のアゾ化合物；過酸化ベンゾイル、イソブチリルパーオキサイド、オクタノイルパーオキサイド、クミルパーオキシオクテート、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシアセテート、ラウリルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ジ−２−エチルヘキシルパーオキシジンカーボネイト等の有機過酸化物；過硫酸カリウム、過硫酸アンモニウム、過酸化水素等の無機パーオキサイド化合物などが挙げられる。
有機または無機パーオキサイド化合物は、還元剤と組み合わせてレドックス系開始剤として使用することも可能である。この場合に用いられる還元剤としては、Ｌ−アスコルビン酸、Ｌ−ソルビン酸、メタ重亜硫酸ナトリウム、硫酸第二鉄、塩化第二鉄、ロンガリットなどが挙げられる。
In carrying out the radical polymerization reaction, a polymerization initiator is usually used. The polymerization initiator may be water-soluble or oil-soluble.
Examples of the polymerization initiator include azo compounds such as azobisisobutyronitrile and azobisisobutylvaleronitrile; benzoyl peroxide, isobutyryl peroxide, octanoyl peroxide, cumylperoxyoctate, t-butylperoxy- Organic peroxides such as 2-ethylhexanoate, t-butylperoxyacetate, lauryl peroxide, di-t-butylperoxide, di-2-ethylhexylperoxydine carbonate; potassium persulfate, ammonium persulfate, peroxysulfate Examples thereof include inorganic peroxide compounds such as hydrogen oxide.
The organic or inorganic peroxide compound can also be used as a redox initiator in combination with a reducing agent. Examples of the reducing agent used in this case include L-ascorbic acid, L-sorbic acid, sodium metabisulfite, ferric sulfate, ferric chloride, Rongalite and the like.
これら重合開始剤は、１種単独または２種以上を混合して使用することができる。
重合開始剤は、モノマー（Ａ）１００質量部に対して０．０５〜５．００質量部の範囲内で使用するのが好ましい。
また、ラジカル重合反応は、通常、４０〜１００℃の温度で行うことが好ましいが、７０℃以下での比較的低温での重合や、重合速度を促進させたい場合は、Ｌ−アスコルビン酸、Ｌ−ソルビン酸、メタ重亜硫酸ナトリウム、硫酸第二鉄、塩化第二鉄、ロンガリット等の還元剤と、過酸化物系の重合開始剤とを組み合わせたレドックス系を用いてもよい。
These polymerization initiators can be used singly or in combination of two or more.
The polymerization initiator is preferably used within a range of 0.05 to 5.00 parts by mass with respect to 100 parts by mass of the monomer (A).
In addition, the radical polymerization reaction is usually preferably carried out at a temperature of 40 to 100 ° C. However, in order to accelerate the polymerization at a relatively low temperature of 70 ° C. or lower or the polymerization rate, L-ascorbic acid, L -You may use the redox type | system | group which combined reducing agents, such as sorbic acid, sodium metabisulfite, ferric sulfate, ferric chloride, Rongalite, and a peroxide type polymerization initiator.
また、重合開始剤として油溶性重合開始剤を用いる場合は、予めウレタンプレポリマーとモノマー（Ａ）を含む混合物中に溶解させておくことが好ましい。
一方、重合開始剤として水溶性重合開始剤を用いる場合は、ウレタンプレポリマーとモノマー（Ａ）を含む混合物を水で希釈した後に、重合開始剤を添加するのが好ましい。重合開始剤を添加する際は、一度に重合開始剤の全量を添加する方法、重合開始剤の全量を時間かけて滴下する方法、始めに重合開始剤の一部を添加し残りを後から添加する方法のいずれの方法で行ってもよい。
Moreover, when using an oil-soluble polymerization initiator as a polymerization initiator, it is preferable to make it melt | dissolve beforehand in the mixture containing a urethane prepolymer and a monomer (A).
On the other hand, when using a water-soluble polymerization initiator as a polymerization initiator, it is preferable to add a polymerization initiator after diluting the mixture containing a urethane prepolymer and a monomer (A) with water. When adding the polymerization initiator, add the polymerization initiator all at once, add the polymerization initiator dropwise over time, add a part of the polymerization initiator first, and add the rest later You may carry out by any method of the method to do.
また、ラジカル重合反応を行う際には、分子量を調節する目的で、公知の連鎖移動剤、例えばオクチルメルカプタン、ラウリルメルカプタン、２−メルカプトエタノール、ターシャルドデシルメルカプタン、チオグリコール酸などを使用してもよい。 In performing the radical polymerization reaction, a known chain transfer agent such as octyl mercaptan, lauryl mercaptan, 2-mercaptoethanol, tert-dodecyl mercaptan, thioglycolic acid or the like may be used for the purpose of adjusting the molecular weight. Good.
ラジカル重合反応では、プレポリマー（Ｂ）やプレポリマー（Ｃ）の乳化力が低い場合、重合中に凝集物、カレットが発生して製造の安定性が低下することがある。
そこで、このような場合には、ラジカル重合反応時に乳化剤を添加するのが好ましく、これにより凝集物・カレットの発生を低減することができる。
ラジカル重合反応時に添加する乳化剤としては、乾燥塗膜の耐水性や耐候性等を考慮し、反応性乳化剤を用いることが好ましい。例えば、反応部位としてアリル基を分子内に有する反応性乳化剤を用いることができる。具体的には、株式会社ＡＤＥＫＡ製の「アデカリアソープＳＲ−１０」、「ＥＲ−１０」、「ＥＲ−３０」等が挙げられる。
また、反応性乳化剤としては、反応部位としてアリル基以外の反応基を持つアニオン性反応性乳化剤を使用することもでき、具体的には花王株式会社製の「ラテムルＰＤ−１０４」等が挙げられる。
In the radical polymerization reaction, when the emulsifying power of the prepolymer (B) or the prepolymer (C) is low, agglomerates and cullet may be generated during the polymerization and the production stability may be lowered.
Therefore, in such a case, it is preferable to add an emulsifier at the time of radical polymerization reaction, thereby reducing the generation of aggregates and cullet.
As the emulsifier added during the radical polymerization reaction, it is preferable to use a reactive emulsifier in consideration of the water resistance and weather resistance of the dried coating film. For example, a reactive emulsifier having an allyl group in the molecule as a reaction site can be used. Specifically, “ADEKA rear soap SR-10”, “ER-10”, “ER-30”, etc., manufactured by ADEKA Corporation are listed.
In addition, as the reactive emulsifier, an anionic reactive emulsifier having a reactive group other than an allyl group as a reactive site can be used, and specifically, “Latemul PD-104” manufactured by Kao Corporation can be used. .
反応性乳化剤の使用量は、ウレタンプレポリマー製造時の重合安定性、並びに塗膜の耐水性および耐候性の点から、モノマー（Ａ）１００質量部に対して、１〜１０質量部とすることが好ましい。 The amount of the reactive emulsifier used is 1 to 10 parts by mass with respect to 100 parts by mass of the monomer (A) from the viewpoints of polymerization stability during production of the urethane prepolymer, and water resistance and weather resistance of the coating film. Is preferred.
以上説明したように本発明によれば、ウレタン樹脂の構成成分の１つとして（ｄ）成分を用いることによって、ウレタンプレポリマーに（ｄ）成分由来の重合性不飽和基を導入できる。よって、本発明により得られる水性樹脂分散液は、ラジカル重合反応時にモノマー（Ａ）とウレタンプレポリマーとがラジカル重合し、アクリル樹脂とウレタン樹脂とが結合した複合体の分散液として得られるので、耐アルコールショック性、凍結融解サイクルに対する耐久性、熱安定性に優れる。 As described above, according to the present invention, the polymerizable unsaturated group derived from the component (d) can be introduced into the urethane prepolymer by using the component (d) as one of the components of the urethane resin. Therefore, the aqueous resin dispersion obtained by the present invention is obtained as a dispersion of a complex in which the monomer (A) and the urethane prepolymer are radically polymerized during the radical polymerization reaction, and the acrylic resin and the urethane resin are combined. Excellent alcohol shock resistance, durability against freeze / thaw cycles, and heat stability.
また、本発明では、アクリル樹脂を構成するアクリル系モノマーとしてモノマー（Ａ）成分を用いる。モノマー（Ａ）は活性水素を有しないので、水性樹脂の親水性が高まるのを抑制できる。加えて、モノマー（Ａ）はウレタンプレポリマー中のイソシアネート基とは反応しにくい。よって、ウレタンプレポリマー中のイソシアネート基と鎖延長剤との反応が妨げられにくいので、ウレタン樹脂部分を容易に高分子量化できる。
従って、本発明により得られる水性樹脂分散液は、耐溶剤性および耐水性が良好な塗膜を形成できる。
Moreover, in this invention, a monomer (A) component is used as an acryl-type monomer which comprises an acrylic resin. Since monomer (A) does not have active hydrogen, it can suppress that the hydrophilic property of aqueous resin increases. In addition, the monomer (A) hardly reacts with the isocyanate group in the urethane prepolymer. Therefore, since the reaction between the isocyanate group in the urethane prepolymer and the chain extender is hardly hindered, the urethane resin portion can be easily made to have a high molecular weight.
Therefore, the aqueous resin dispersion obtained by the present invention can form a coating film having good solvent resistance and water resistance.
本発明により得られる水性樹脂分散液は、そのままコーティング剤、塗料、インキなどとして使用することができる。
なお、水性樹脂分散液をそのままコーティング剤、塗料、インキなどして使用する場合、樹脂固形分については特に限定されないが、通常、３〜５０質量％である。樹脂固形分が高すぎる場合は、所望の値になるように、水性樹脂分散液に水や有機溶剤を配合し、希釈して使用してもよい。
The aqueous resin dispersion obtained by the present invention can be used as it is as a coating agent, paint, ink or the like.
In addition, when using aqueous resin dispersion liquid as it is as a coating agent, a coating material, ink, etc., although resin solid content is not specifically limited, Usually, it is 3-50 mass%. When the resin solid content is too high, water or an organic solvent may be blended in the aqueous resin dispersion so as to obtain a desired value, and may be used after dilution.
以下、本発明について実施例を挙げて具体的に説明する。ただし、本発明はこれらに限定されるものではない。なお、本実施例において、特に断りがない限り「部」は「質量部」を意味する。
各種測定方法、評価方法は以下の通りである。
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these. In this example, “part” means “part by mass” unless otherwise specified.
Various measurement methods and evaluation methods are as follows.
＜水性樹脂分散液の物性測定＞
（樹脂固形分の測定）
予め水性樹脂分散液の質量を測定した。ついで、水性樹脂分散液を１０５±５℃で２時間乾燥させ、残分の質量を測定し、下記式より樹脂固形分を求めた。
樹脂固形分（質量％）＝残分の質量（ｇ）／乾燥前の水性樹脂分散液の質量（ｇ）×１００
<Measurement of physical properties of aqueous resin dispersion>
(Measurement of resin solids)
The mass of the aqueous resin dispersion was measured in advance. Next, the aqueous resin dispersion was dried at 105 ± 5 ° C. for 2 hours, the residual mass was measured, and the resin solid content was determined from the following formula.
Resin solid content (mass%) = residue mass (g) / mass of aqueous resin dispersion before drying (g) × 100
（粘度の測定）
水性樹脂分散液を２５±１℃で２時間放置した後、Ｂ型粘度計（東機産業株式会社製、「ＴＶ−２２形粘度計 スピンドルタイプ」）を用いて、水性樹脂分散液の粘度を測定した。
(Measurement of viscosity)
After leaving the aqueous resin dispersion at 25 ± 1 ° C. for 2 hours, the viscosity of the aqueous resin dispersion is measured using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., “TV-22 type viscometer spindle type”). It was measured.
（ｐＨの測定）
水性樹脂分散液を２５±１℃で２時間放置した後、ｐＨメーター（東亜ディーケーケー株式会社製、「Ｇシリーズ ＨＭ−３０Ｇ」）を用いて、水性樹脂分散液のｐＨを測定した。
(Measurement of pH)
After leaving the aqueous resin dispersion at 25 ± 1 ° C. for 2 hours, the pH of the aqueous resin dispersion was measured using a pH meter (“G Series HM-30G” manufactured by Toa DKK Corporation).
＜溶液安定性試験＞
（耐アルコールショック性の評価）
水性樹脂分散液／イソプロピルアルコール＝１／１（質量比）、または水性樹脂散液／メタノール＝１／１（質量比）で配合し、それぞれを攪拌して水性樹脂水分散液のアルコール配合溶液を作製した。
ついで、得られたアルコール配合液を２５℃で２時間放置した後、Ｂ型粘度計を用いて、アルコール配合液の粘度を測定した。そして、アルコール配合前の水性樹脂分散液の粘度に対する、アルコール配合後の粘度の上昇率を求め、さらに凝集物の発生の有無について目視にて観察し、以下の評価基準に基づき耐アルコールショック性の評価を行った。
５：粘度上昇率が５０％未満であり、凝集物が発生していない。
４：粘度上昇率が５０％以上２００％未満であり、凝集物が発生していない。
３：粘度上昇率が２００％以上５００％未満であり、凝集物が発生していない。
２：粘度上昇率が５００％以上であり、凝集物が発生していない。
１：ゲル化あるいは凝集物が発生し、使用が不可能である。
<Solution stability test>
(Evaluation of alcohol shock resistance)
Aqueous resin dispersion / Isopropyl alcohol = 1/1 (mass ratio) or aqueous resin dispersion / methanol = 1/1 (mass ratio). Produced.
Next, the obtained alcohol blending solution was allowed to stand at 25 ° C. for 2 hours, and then the viscosity of the alcohol blending solution was measured using a B-type viscometer. Then, the increase rate of the viscosity after the alcohol blending with respect to the viscosity of the aqueous resin dispersion before the blending of alcohol is obtained, and further, the presence or absence of aggregates is visually observed, and the alcohol shock resistance resistance is determined based on the following evaluation criteria. Evaluation was performed.
5: Viscosity increase rate is less than 50%, and aggregates are not generated.
4: The viscosity increase rate is 50% or more and less than 200%, and no aggregate is generated.
3: The rate of increase in viscosity is 200% or more and less than 500%, and no aggregate is generated.
2: The viscosity increase rate is 500% or more, and no aggregate is generated.
1: Gelation or agglomerates occur and cannot be used.
（凍結融解サイクルに対する耐久性の評価）
水性樹脂分散液を０℃の条件下において完全に凍結させた後、５０℃の温水中で２時間放置し溶解させた。本操作を５回繰り返し、水性樹脂水分散液の凍結融解サイクル後溶液を作製した。
ついで、得られた凍結融解サイクル後溶液を２５℃で２時間放置した後、Ｂ型粘度計を用いて、凍結融解サイクル後溶液の粘度を測定した。そして、凍結融解サイクル前の水性樹脂分散液の粘度に対する、凍結融解サイクル後の粘度の上昇率を求め、さらに凝集物の発生の有無について目視にて観察し、以下の評価基準に基づき耐アルコールショック性の評価を行った。
５：粘度上昇率が１０％未満であり、凝集物が発生していない。
４：粘度上昇率が１０％以上３０％未満であり、凝集物が発生していない。
３：粘度上昇率が３０％以上５０％未満であり、凝集物が発生していない。
２：粘度上昇率が５０％以上であり、凝集物が発生していない。
１：ゲル化あるいは凝集物が発生し、使用が不可能である。
(Evaluation of durability against freeze-thaw cycles)
The aqueous resin dispersion was completely frozen under the condition of 0 ° C. and then allowed to stand in hot water at 50 ° C. for 2 hours for dissolution. This operation was repeated 5 times to prepare a solution after the freeze-thaw cycle of the aqueous resin aqueous dispersion.
Next, after the obtained solution after the freeze-thaw cycle was allowed to stand at 25 ° C. for 2 hours, the viscosity of the solution after the freeze-thaw cycle was measured using a B-type viscometer. Then, the increase rate of the viscosity after the freeze-thaw cycle with respect to the viscosity of the aqueous resin dispersion before the freeze-thaw cycle is obtained, and further, the presence or absence of aggregates is visually observed. Sexuality was evaluated.
5: Viscosity increase rate is less than 10%, and aggregates are not generated.
4: The viscosity increase rate is 10% or more and less than 30%, and no aggregate is generated.
3: The viscosity increase rate is 30% or more and less than 50%, and no aggregate is generated.
2: The viscosity increase rate is 50% or more, and aggregates are not generated.
1: Gelation or agglomerates occur and cannot be used.
（熱安定性の評価）
水性樹脂分散液を５０℃下で３０日間放置した。放置後の水性樹脂分散液を２５℃で２時間放置した後、Ｂ型粘度計を用いて、放置後の水性樹脂分散液の粘度を測定した。そして、放置前の水性樹脂分散液の粘度に対する、放置後の粘度の上昇率を求め、さらに凝集物の発生の有無について目視にて観察し、以下の評価基準に基づき耐アルコールショック性の評価を行った。
５：粘度上昇率が１０％未満であり、凝集物が発生していない。
４：粘度上昇率が１０％以上３０％未満であり、凝集物が発生していない。
３：粘度上昇率が３０％以上５０％未満であり、凝集物が発生していない。
２：粘度上昇率が５０％以上であり、凝集物が発生していない。
１：ゲル化あるいは凝集物が発生し、使用が不可能である。
(Evaluation of thermal stability)
The aqueous resin dispersion was allowed to stand at 50 ° C. for 30 days. The left aqueous resin dispersion was allowed to stand at 25 ° C. for 2 hours, and then the viscosity of the left aqueous resin dispersion was measured using a B-type viscometer. Then, the rate of increase in viscosity after standing relative to the viscosity of the aqueous resin dispersion before standing is determined, and further, the presence or absence of aggregates is observed visually, and the alcohol shock resistance is evaluated based on the following evaluation criteria. went.
5: Viscosity increase rate is less than 10%, and aggregates are not generated.
4: The viscosity increase rate is 10% or more and less than 30%, and no aggregate is generated.
3: The viscosity increase rate is 30% or more and less than 50%, and no aggregate is generated.
2: The viscosity increase rate is 50% or more, and aggregates are not generated.
1: Gelation or agglomerates occur and cannot be used.
＜塗膜試験＞
（耐溶剤性の評価）
水性樹脂分散液１００部に対し、ブチルセロソルブを１５部配合して、クリヤー塗料を作製した。
ついで、表面をメタノールで拭いた処理済ＰＥＴシートに、バーコーターを用いて乾燥膜厚が２０μｍになるようにクリヤー塗料を塗装し、７０℃×４０分間乾燥させ、評価用塗膜を得た。
トルエン、メチルエチルケトン、酢酸エチル、イソプロピルアルコールのいずれかの溶剤をしみ込ませたガーゼを、評価用塗膜上に５０回ラビングした後、塗膜の外観変化を目視にて観察し、以下の評価基準に基づき耐溶剤性を評価した。
５：曇りや白化が全く無い。
４：曇りや白化がごくわずかにあるが、問題ない。
３：曇り、白化が認められる。
２：かなり白化している。
１：塗膜のキズ、白化が激しい。
<Coating test>
(Evaluation of solvent resistance)
A clear coating was prepared by blending 15 parts of butyl cellosolve with 100 parts of the aqueous resin dispersion.
Then, a clear coating was applied to the treated PET sheet whose surface was wiped with methanol using a bar coater so that the dry film thickness was 20 μm, and dried at 70 ° C. for 40 minutes to obtain a coating film for evaluation.
After rubbing a gauze impregnated with any of toluene, methyl ethyl ketone, ethyl acetate, and isopropyl alcohol on the evaluation coating film 50 times, the appearance change of the coating film was observed visually, and the following evaluation criteria were satisfied. Based on this, the solvent resistance was evaluated.
5: No cloudiness or whitening.
4: There is very little clouding or whitening, but there is no problem.
3: Cloudiness and whitening are recognized.
2: It is considerably whitened.
1: Scratch and whitening of the coating are severe.
（耐水性の評価）
耐溶剤性の評価と同様にして、評価用塗膜を得た。
脱イオン水をしみ込ませたガーゼを、評価用塗膜上に荷重１ｋｇをかけた状態で１００回ラビングした後、塗膜の外観変化を目視にて観察し、以下の評価基準に基づき耐溶剤性を評価した。
５：曇りや白化が全く無い。
４：曇りや白化がごくわずかにあるが、問題ない。
３：曇り、白化が認められる。
２：かなり白化している。
１：塗膜のキズ、白化が激しい。
(Evaluation of water resistance)
An evaluation coating film was obtained in the same manner as in the solvent resistance evaluation.
The gauze soaked with deionized water is rubbed 100 times with a load of 1 kg on the coating film for evaluation, then the appearance change of the coating film is visually observed, and the solvent resistance is based on the following evaluation criteria. Evaluated.
5: No cloudiness or whitening.
4: There is very little clouding or whitening, but there is no problem.
3: Cloudiness and whitening are recognized.
2: It is considerably whitened.
1: Scratch and whitening of the coating are severe.
［実施例１］
製造方法（ｉ−１）を採用し、以下のようにして水性樹脂分散液を得た。
攪拌機、温度計、コンデンサーを備えた四つ口フラスコに、イソホロンジイソシアネートを１１部、ジメチロールブタン酸を５部、ポリオールＡ（３−メチル−１，５−ペンタンジオールとセバシン酸から得られる数平均分子量１０００のポリエステルジオール）を７部、ポリオールＢ（数平均分子量１０００のポリエーテルジオール）を７部、メチルメタクリレートを５２部、２−エチルヘキシルアクリレートを１７部仕込んだ。この混合物を攪拌しながら８０℃に加熱して３時間保持し、ウレタン化反応を行い、酸性官能基を有するイソシアネート末端ウレタンプレポリマー（プレポリマー（Ｃ））の（メタ）アクリル系モノマー溶液を得た。
ついで、反応器内にグリシジルメタクリレートを０．６５部、ジメチルアミノエチルメタクリレートを０．３５部添加し、８０℃で２時間反応させ、重合性不飽和基及び酸性官能基を有するイソシアネート末端ウレタンプレポリマー（プレポリマー（Ｂ））の（メタ）アクリル系モノマー溶液を得た。
ついで、内温が５０℃以下になるまで冷却し、トリエチルアミン３．４部と脱イオン水２２３部を混合した溶液を、３０分間かけて系内に滴下した。溶液が均一に乳化された後、脱イオン水３部に過硫酸カリウム０．１５部を溶解させた溶液を系内に添加し、徐々に昇温した。発熱を確認後、７５℃で制御して１時間保持しラジカル重合を行った。その後脱イオン水３部に過硫酸カリウム０．１５部を溶解させた溶液をさらに追加し、１．５時間ラジカル重合を行い、水性樹脂分散液（Ｐ−１）を得た。
得られた水性樹脂分散液（Ｐ−１）について物性を測定した。結果を表１に示す。また、水性樹脂分散液（Ｐ−１）の溶液安定性試験、および塗膜試験を行った。結果を表３に示す。
[Example 1]
The production method (i-1) was employed to obtain an aqueous resin dispersion as follows.
In a four-necked flask equipped with a stirrer, thermometer, condenser, 11 parts isophorone diisocyanate, 5 parts dimethylolbutanoic acid, polyol A (number average obtained from 3-methyl-1,5-pentanediol and sebacic acid 7 parts of polyester diol having a molecular weight of 1000), 7 parts of polyol B (polyether diol having a number average molecular weight of 1000), 52 parts of methyl methacrylate, and 17 parts of 2-ethylhexyl acrylate were charged. The mixture is heated to 80 ° C. with stirring and held for 3 hours to carry out a urethanization reaction to obtain a (meth) acrylic monomer solution of an isocyanate-terminated urethane prepolymer (prepolymer (C)) having an acidic functional group. It was.
Next, 0.65 part of glycidyl methacrylate and 0.35 part of dimethylaminoethyl methacrylate were added to the reactor and reacted at 80 ° C. for 2 hours to give an isocyanate-terminated urethane prepolymer having a polymerizable unsaturated group and an acidic functional group. A (meth) acrylic monomer solution of (prepolymer (B)) was obtained.
Subsequently, it cooled until internal temperature became 50 degrees C or less, and the solution which mixed 3.4 parts of triethylamine and 223 parts of deionized water was dripped in the system over 30 minutes. After the solution was uniformly emulsified, a solution prepared by dissolving 0.15 part of potassium persulfate in 3 parts of deionized water was added to the system, and the temperature was gradually raised. After confirming the exotherm, it was controlled at 75 ° C. and held for 1 hour to carry out radical polymerization. Thereafter, a solution prepared by dissolving 0.15 part of potassium persulfate in 3 parts of deionized water was further added, and radical polymerization was performed for 1.5 hours to obtain an aqueous resin dispersion (P-1).
The physical properties of the obtained aqueous resin dispersion (P-1) were measured. The results are shown in Table 1. Moreover, the solution stability test of the aqueous resin dispersion (P-1) and the coating-film test were done. The results are shown in Table 3.
［実施例２］
表１に示す組成に変更した以外は、実施例１と同様にして水性樹脂分散液（Ｐ−２）を得た。
得られた水性樹脂分散液（Ｐ−２）について物性を測定した。結果を表１に示す。また、水性樹脂分散液（Ｐ−２）の溶液安定性試験、および塗膜試験を行った。結果を表３に示す。
[Example 2]
An aqueous resin dispersion (P-2) was obtained in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1.
The physical properties of the obtained aqueous resin dispersion (P-2) were measured. The results are shown in Table 1. Moreover, the solution stability test of the aqueous resin dispersion (P-2) and the coating-film test were done. The results are shown in Table 3.
［実施例３］
製造方法（ｉ−１）を採用し、以下のようにして水性樹脂分散液を得た。
攪拌機、温度計、コンデンサーを備えた四つ口フラスコに、イソホロンジイソシアネートを１７部、ジメチロールブタン酸を７．５部、ポリオールＡを８．５部、メチルメタクリレートを５０部、ノルマルブチルメタクリレートを１４．１５部仕込んだ。この混合物を攪拌しながら８０℃に加熱して３時間保持し、ウレタン化反応を行い、プレポリマー（Ｃ）の（メタ）アクリル系モノマー溶液を得た。
ついで、反応器内にグリシジルメタクリレートを２．５部、ジメチルアミノエチルメタクリレートを０．３５部添加し、８０℃で２時間反応させ、プレポリマー（Ｂ）の（メタ）アクリル系モノマー溶液を得た。
ついで、内温が５０℃以下になるまで冷却し、トリエチルアミン５．２部と脱イオン水１５１部を混合した溶液を３０分間かけて系内に滴下した。溶液が均一に乳化された後、脱イオン水２５部にエチレンジアミン０．５部を溶解させた水溶液を３０分間かけて系内に滴下し、内温５０℃で制御して３０分間保持した。
ついで、脱イオン水３部に過硫酸カリウム０．１５部を溶解させた溶液を系内に添加し徐々に昇温した。発熱を確認後、７５℃で制御して１時間保持しラジカル重合を行った。その後、脱イオン水３部に過硫酸カリウム０．１５部を溶解させた溶液をさらに追加し、１．５時間ラジカル重合を行い、水性樹脂分散液（Ｐ−３）を得た。
得られた水性樹脂分散液（Ｐ−３）について物性を測定した。結果を表１に示す。また、水性樹脂分散液（Ｐ−３）の溶液安定性試験、および塗膜試験を行った。結果を表３に示す。
[Example 3]
The production method (i-1) was employed to obtain an aqueous resin dispersion as follows.
In a four-necked flask equipped with a stirrer, thermometer and condenser, 17 parts of isophorone diisocyanate, 7.5 parts of dimethylolbutanoic acid, 8.5 parts of polyol A, 50 parts of methyl methacrylate, 14 parts of normal butyl methacrylate .15 copies were loaded. This mixture was heated to 80 ° C. with stirring and held for 3 hours to carry out a urethanization reaction to obtain a (meth) acrylic monomer solution of prepolymer (C).
Next, 2.5 parts of glycidyl methacrylate and 0.35 part of dimethylaminoethyl methacrylate were added to the reactor and reacted at 80 ° C. for 2 hours to obtain a (meth) acrylic monomer solution of prepolymer (B). .
Subsequently, it cooled until internal temperature became 50 degrees C or less, and the solution which mixed 5.2 parts of triethylamine and 151 parts of deionized water was dripped in the system over 30 minutes. After the solution was uniformly emulsified, an aqueous solution in which 0.5 part of ethylenediamine was dissolved in 25 parts of deionized water was dropped into the system over 30 minutes, and the internal temperature was controlled at 50 ° C. and kept for 30 minutes.
Next, a solution in which 0.15 part of potassium persulfate was dissolved in 3 parts of deionized water was added to the system, and the temperature was gradually raised. After confirming the exotherm, it was controlled at 75 ° C. and held for 1 hour to carry out radical polymerization. Thereafter, a solution prepared by dissolving 0.15 part of potassium persulfate in 3 parts of deionized water was further added, and radical polymerization was performed for 1.5 hours to obtain an aqueous resin dispersion (P-3).
The physical properties of the obtained aqueous resin dispersion (P-3) were measured. The results are shown in Table 1. Moreover, the solution stability test and coating-film test of the aqueous resin dispersion liquid (P-3) were done. The results are shown in Table 3.
［実施例４〜６］
表１に示す組成に変更した以外は、実施例１と同様にして水性樹脂分散液（Ｐ−４）〜（Ｐ−６）を得た。
得られた水性樹脂分散液（Ｐ−４）〜（Ｐ−６）について物性を測定した。結果を表１に示す。また、水性樹脂分散液（Ｐ−４）〜（Ｐ−６）の溶液安定性試験、および塗膜試験を行った。結果を表３に示す。
[Examples 4 to 6]
Aqueous resin dispersions (P-4) to (P-6) were obtained in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1.
The physical properties of the obtained aqueous resin dispersions (P-4) to (P-6) were measured. The results are shown in Table 1. Moreover, the solution stability test and coating-film test of aqueous resin dispersion liquid (P-4)-(P-6) were done. The results are shown in Table 3.
［実施例７］
製造方法（ｉ−２）を採用し、以下のようにして水性樹脂分散液を得た。
攪拌機、温度計、コンデンサーを備えた四つ口フラスコに、ジメチロールブタン酸を５部、ポリオールＡを７部、ポリオールＢを７部、メチルメタクリレートを５２部、２−エチルヘキシルアクリレートを１７部、グリシジルメタクリレートを０．６５部、ジメチルアミノエチルメタクリレートを０．３５部仕込んだ。この混合物系を攪拌しながら８０℃に加熱して２時間保持し、付加反応を行い、酸性官能基と重合性不飽和基を有するポリオール（ポリオール（Ｄ））を得た。
ついで、反応器内にイソホロンジイソシアネートを１１部添加し、８０℃で３時間ウレタン化反応を行い、プレポリマー（Ｂ）の（メタ）アクリル系モノマー溶液を得た。
ついで、内温が５０℃以下になるまで冷却し、トリエチルアミン３．４部と脱イオン水２２３部を混合した溶液を３０分間かけて系内に滴下した。溶液が均一に乳化された後、脱イオン水３部に過硫酸カリウム０．１５部を溶解させた溶液を系内に添加し徐々に昇温した。発熱を確認後、７５℃で制御して１時間保持しラジカル重合を行った。その後、脱イオン水３部に過硫酸カリウム０．１５部を溶解させた溶液をさらに追加し、１．５時間ラジカル重合を行い、水性樹脂分散液（Ｐ−７）を得た。
得られた水性樹脂分散液（Ｐ−７）について物性を測定した。結果を表１に示す。また、水性樹脂分散液（Ｐ−７）の溶液安定性試験、および塗膜試験を行った。結果を表３に示す。
[Example 7]
The production method (i-2) was employed to obtain an aqueous resin dispersion as follows.
In a four-necked flask equipped with a stirrer, thermometer and condenser, 5 parts of dimethylol butanoic acid, 7 parts of polyol A, 7 parts of polyol B, 52 parts of methyl methacrylate, 17 parts of 2-ethylhexyl acrylate, glycidyl 0.65 parts of methacrylate and 0.35 parts of dimethylaminoethyl methacrylate were charged. The mixture system was heated to 80 ° C. with stirring and held for 2 hours, and an addition reaction was performed to obtain a polyol (polyol (D)) having an acidic functional group and a polymerizable unsaturated group.
Next, 11 parts of isophorone diisocyanate was added to the reactor, and a urethanization reaction was performed at 80 ° C. for 3 hours to obtain a (meth) acrylic monomer solution of the prepolymer (B).
Subsequently, it cooled until internal temperature became 50 degrees C or less, and the solution which mixed 3.4 parts of triethylamine and 223 parts of deionized water was dripped in the system over 30 minutes. After the solution was uniformly emulsified, a solution prepared by dissolving 0.15 part of potassium persulfate in 3 parts of deionized water was added to the system, and the temperature was gradually raised. After confirming the exotherm, it was controlled at 75 ° C. and held for 1 hour to carry out radical polymerization. Thereafter, a solution obtained by dissolving 0.15 part of potassium persulfate in 3 parts of deionized water was further added, and radical polymerization was performed for 1.5 hours to obtain an aqueous resin dispersion (P-7).
The physical properties of the obtained aqueous resin dispersion (P-7) were measured. The results are shown in Table 1. Moreover, the solution stability test of the aqueous resin dispersion (P-7) and the coating-film test were done. The results are shown in Table 3.
［実施例８］
製造方法（ｉ−３）を採用し、以下のようにして水性樹脂分散液を得た。
攪拌機、温度計、コンデンサーを備えた四つ口フラスコに、イソホロンジイソシアネートを１１部、ジメチロールブタン酸を５部、ポリオールＡを７部、ポリオールＢを７部、メチルメタクリレートを５２部、２−エチルヘキシルアクリレートを１７部、グリシジルメタクリレートを０．６５部、ジメチルアミノエチルメタクリレートを０．３５部仕込んだ。この混合物系を攪拌しながら８０℃に加熱して５時間保持し、ウレタン化反応と付加反応を同時に行い、プレポリマー（Ｂ）の（メタ）アクリル系モノマー溶液を得た。
ついで、内温が５０℃以下になるまで冷却し、トリエチルアミン３．４部と脱イオン水２２３部を混合した溶液を３０分間かけて系内に滴下した。溶液が均一に乳化された後、脱イオン水３部に過硫酸カリウム０．１５部を溶解させた溶液を系内に添加し徐々に昇温した。発熱を確認後、７５℃で制御して１時間保持しラジカル重合を行った。その後、脱イオン水３部に過硫酸カリウム０．１５部を溶解させた溶液をさらに追加し、１．５時間ラジカル重合を行い、水性樹脂分散液（Ｐ−８）を得た。
得られた水性樹脂分散液（Ｐ−８）について物性を測定した。結果を表１に示す。また、水性樹脂分散液（Ｐ−８）の溶液安定性試験、および塗膜試験を行った。結果を表４に示す。
[Example 8]
The production method (i-3) was employed to obtain an aqueous resin dispersion as follows.
In a four-necked flask equipped with a stirrer, thermometer and condenser, 11 parts isophorone diisocyanate, 5 parts dimethylol butanoic acid, 7 parts polyol A, 7 parts polyol B, 52 parts methyl methacrylate, 2-ethylhexyl 17 parts of acrylate, 0.65 part of glycidyl methacrylate, and 0.35 part of dimethylaminoethyl methacrylate were charged. The mixture system was heated to 80 ° C. with stirring and maintained for 5 hours, and the urethanization reaction and the addition reaction were simultaneously performed to obtain a (meth) acrylic monomer solution of prepolymer (B).
Subsequently, it cooled until internal temperature became 50 degrees C or less, and the solution which mixed 3.4 parts of triethylamine and 223 parts of deionized water was dripped in the system over 30 minutes. After the solution was uniformly emulsified, a solution prepared by dissolving 0.15 part of potassium persulfate in 3 parts of deionized water was added to the system, and the temperature was gradually raised. After confirming the exotherm, it was controlled at 75 ° C. and held for 1 hour to carry out radical polymerization. Thereafter, a solution in which 0.15 part of potassium persulfate was dissolved in 3 parts of deionized water was further added, and radical polymerization was performed for 1.5 hours to obtain an aqueous resin dispersion (P-8).
The physical properties of the obtained aqueous resin dispersion (P-8) were measured. The results are shown in Table 1. Moreover, the solution stability test of the aqueous resin dispersion (P-8) and the coating-film test were done. The results are shown in Table 4.
［実施例９］
製造方法（ｉｉ）を採用し、以下のようにして水性樹脂分散液を得た。
攪拌機、温度計、コンデンサーを備えた四つ口フラスコに、イソホロンジイソシアネートを１２部、ジメチロールブタン酸を５部、ポリオールＡを１６部、メチルメタクリレートを５０部、ノルマルブチルメタクリレートを１４．６５部仕込んだ。この混合物系を攪拌しながら８０℃に加熱して５時間保持し、ウレタン化反応を行い、プレポリマー（Ｃ）の（メタ）アクリル系モノマー溶液を得た。
ついで、反応器内にグリシジルメタクリレートを２部、ジメチルアミノエチルメタクリレートを０．３５部添加し、均一に混合した。内温が５０℃以下になるまで冷却し、トリエチルアミン３．４部と脱イオン水１７６部を混合した溶液を３０分間かけて系内に滴下した。溶液が均一に乳化された後、脱イオン水３部に過硫酸カリウム０．１５部を溶解させた溶液を系内に添加し徐々に昇温した。発熱を確認後、７５℃で制御して１時間保持しラジカル重合を行った。その後、脱イオン水３部に過硫酸カリウム０．１５部を溶解させた溶液をさらに追加し、１．５時間ラジカル重合を行い、水性樹脂分散液（Ｐ−９）を得た。
得られた水性樹脂分散液（Ｐ−９）について物性を測定した。結果を表１に示す。また、水性樹脂分散液（Ｐ−９）の溶液安定性試験、および塗膜試験を行った。結果を表４に示す。
[Example 9]
The production method (ii) was employed to obtain an aqueous resin dispersion as follows.
A four-necked flask equipped with a stirrer, thermometer and condenser is charged with 12 parts isophorone diisocyanate, 5 parts dimethylolbutanoic acid, 16 parts polyol A, 50 parts methyl methacrylate, and 14.65 parts normal butyl methacrylate. It is. This mixture system was heated to 80 ° C. with stirring and held for 5 hours to carry out a urethanization reaction to obtain a (meth) acrylic monomer solution of prepolymer (C).
Next, 2 parts of glycidyl methacrylate and 0.35 part of dimethylaminoethyl methacrylate were added to the reactor and mixed uniformly. It cooled until the internal temperature became 50 degrees C or less, and the solution which mixed 3.4 parts of triethylamine and 176 parts of deionized water was dripped in the system over 30 minutes. After the solution was uniformly emulsified, a solution prepared by dissolving 0.15 part of potassium persulfate in 3 parts of deionized water was added to the system, and the temperature was gradually raised. After confirming the exotherm, it was controlled at 75 ° C. and held for 1 hour to carry out radical polymerization. Thereafter, a solution prepared by dissolving 0.15 part of potassium persulfate in 3 parts of deionized water was further added, and radical polymerization was performed for 1.5 hours to obtain an aqueous resin dispersion (P-9).
The physical properties of the obtained aqueous resin dispersion (P-9) were measured. The results are shown in Table 1. Moreover, the solution stability test of the aqueous resin dispersion (P-9) and the coating-film test were done. The results are shown in Table 4.
［実施例１０］
グリシジルメタクリレートの添加のタイミングを、トリエチルアミンによる中和の後に変更した以外は、実施例９と同様にして水性樹脂分散液（Ｐ−１０）を得た。
得られた水性樹脂分散液（Ｐ−１０）について物性を測定した。結果を表１に示す。また、水性樹脂分散液（Ｐ−１０）の溶液安定性試験、および塗膜試験を行った。結果を表４に示す。
[Example 10]
An aqueous resin dispersion (P-10) was obtained in the same manner as in Example 9 except that the timing of addition of glycidyl methacrylate was changed after neutralization with triethylamine.
The physical properties of the obtained aqueous resin dispersion (P-10) were measured. The results are shown in Table 1. Moreover, the solution stability test of the aqueous resin dispersion (P-10) and the coating-film test were done. The results are shown in Table 4.
［比較例１］
表２に示す組成に変更し、（ｄ）成分を用いなかった以外は、実施例１と同様にして水性樹脂分散液（Ｐ−１１）を得た。
得られた水性樹脂分散液（Ｐ−１１）について物性を測定した。結果を表２に示す。また、水性樹脂分散液（Ｐ−１１）の溶液安定性試験、および塗膜試験を行った。結果を表４に示す。
[Comparative Example 1]
The composition was changed to the composition shown in Table 2, and an aqueous resin dispersion (P-11) was obtained in the same manner as in Example 1 except that the component (d) was not used.
The physical properties of the obtained aqueous resin dispersion (P-11) were measured. The results are shown in Table 2. Moreover, the solution stability test of the aqueous resin dispersion (P-11) and the coating-film test were done. The results are shown in Table 4.
［比較例２］
表２に示す組成に変更し、グリシジルメタクリレートの代わりに、２−ヒドロキシエチルメタクリレートを１．９部用いた以外は、実施例１と同様にして水性樹脂分散液（Ｐ−１２）を得た。
得られた水性樹脂分散液（Ｐ−１２）について物性を測定した。結果を表２に示す。また、水性樹脂分散液（Ｐ−１２）の溶液安定性試験、および塗膜試験を行った。結果を表４に示す。
[Comparative Example 2]
The composition was changed to the composition shown in Table 2, and an aqueous resin dispersion (P-12) was obtained in the same manner as in Example 1 except that 1.9 parts of 2-hydroxyethyl methacrylate was used instead of glycidyl methacrylate.
The physical properties of the obtained aqueous resin dispersion (P-12) were measured. The results are shown in Table 2. Moreover, the solution stability test of the aqueous resin dispersion (P-12) and the coating-film test were done. The results are shown in Table 4.
［比較例３］
表２に示す組成に変更し、グリシジルメタクリレートの代わりに、２−ヒドロキシエチルメタクリレートを１．９部用いた以外は、実施例８と同様にして水性樹脂分散液（Ｐ−１３）を得た。
得られた水性樹脂分散液（Ｐ−１３）について物性を測定した。結果を表２に示す。また、水性樹脂分散液（Ｐ−１３）の溶液安定性試験、および塗膜試験を行った。結果を表４に示す。
[Comparative Example 3]
The composition was changed to the composition shown in Table 2, and an aqueous resin dispersion (P-13) was obtained in the same manner as in Example 8 except that 1.9 parts of 2-hydroxyethyl methacrylate was used instead of glycidyl methacrylate.
The physical properties of the obtained aqueous resin dispersion (P-13) were measured. The results are shown in Table 2. Moreover, the solution stability test of the aqueous resin dispersion (P-13) and the coating-film test were done. The results are shown in Table 4.
［比較例４］
表２に示す組成に変更し、グリシジルメタクリレートの代わりに、２−ヒドロキシエチルメタクリレートを１．９部用いた以外は、実施例９と同様にして水性樹脂分散液（Ｐ−１４）を得た。
得られた水性樹脂分散液（Ｐ−１４）について物性を測定した。結果を表２に示す。また、水性樹脂分散液（Ｐ−１４）の溶液安定性試験、および塗膜試験を行った。結果を表４に示す。
[Comparative Example 4]
The composition was changed to the composition shown in Table 2, and an aqueous resin dispersion (P-14) was obtained in the same manner as in Example 9 except that 1.9 parts of 2-hydroxyethyl methacrylate was used instead of glycidyl methacrylate.
The physical properties of the obtained aqueous resin dispersion (P-14) were measured. The results are shown in Table 2. Moreover, the solution stability test of the aqueous resin dispersion (P-14) and the coating-film test were done. The results are shown in Table 4.
表１〜４から明らかなように、実施例１〜１０で得られた水性樹脂分散液は、溶液安定性（耐アルコールショック性、凍結融解サイクルに対する耐久性、熱安定性）に優れていた。また、これら水性樹脂分散液から形成された塗膜は、耐溶剤性および耐水性も良好であった。
なお、実施例２は、実施例１よりも（ｄ）成分を増量した例であり、水性樹脂分散液のイソプロピルアルコールに対するショック性が特に向上した。
実施例３は、鎖延長剤としてエチレンジアミンを使用した例であり、塗膜の耐溶剤性および耐水性がより向上した。
実施例４は、ウレタン樹脂の比率を多くした例であり、比率の少ないものと同様に水性樹脂分散液の溶液安定性が良好であった。
実施例５、６は、（ｄ）成分の種類を変更した例であり、グリシジルメタクリレートを使用したものと同様に、水性樹脂分散液の液安定が良好であった。
実施例７〜１０は、（ｄ）成分の添加方法を変更した例であり、いずれも水性樹脂分散液の溶液安定性が良好であった。
As is clear from Tables 1 to 4, the aqueous resin dispersions obtained in Examples 1 to 10 were excellent in solution stability (alcohol shock resistance, durability against freeze-thaw cycles, and thermal stability). Moreover, the coating film formed from these aqueous resin dispersions also had good solvent resistance and water resistance.
Example 2 was an example in which the amount of component (d) was increased as compared with Example 1, and the shock resistance of the aqueous resin dispersion to isopropyl alcohol was particularly improved.
In Example 3, ethylenediamine was used as a chain extender, and the solvent resistance and water resistance of the coating film were further improved.
Example 4 was an example in which the ratio of the urethane resin was increased, and the solution stability of the aqueous resin dispersion was good as in the case of a small ratio.
Examples 5 and 6 are examples in which the type of the component (d) was changed, and the liquid stability of the aqueous resin dispersion was good as in the case of using glycidyl methacrylate.
Examples 7 to 10 are examples in which the addition method of the component (d) was changed, and all of the solution stability of the aqueous resin dispersion were good.
一方、比較例１は、（ｄ）成分を用いなかった例であり、水性樹脂分散液の溶液安定性が著しく低下した。
比較例２〜４は、（ｄ）成分の代わりに活性水素を有する（メタ）アクリル系モノマーを用い、さらに添加方法を変更した例であり、水性樹脂分散液の溶液安定性が低下する傾向にあった。また、塗膜の耐溶剤性および耐水性が著しく低下した。
On the other hand, Comparative Example 1 was an example in which the component (d) was not used, and the solution stability of the aqueous resin dispersion was significantly reduced.
Comparative Examples 2 to 4 are examples in which a (meth) acrylic monomer having active hydrogen was used instead of the component (d), and the addition method was further changed, and the solution stability of the aqueous resin dispersion tends to decrease. there were. In addition, the solvent resistance and water resistance of the coating film were significantly reduced.
本発明によれば、耐アルコールショック性、凍結融解サイクルに対する耐久性、熱安定性に優れた水性ウレタン変性（メタ）アクリル樹脂の分散液を、有機溶剤を使用せずに製造することができる。さらに、この分散液から得られる塗膜は耐溶剤性や耐水性に優れるものである。従って、コーティング剤、塗料、インキ用の水性樹脂として工業用有益なものとなる。
According to the present invention, a dispersion of an aqueous urethane-modified (meth) acrylic resin excellent in alcohol shock resistance, durability against freeze / thaw cycles, and thermal stability can be produced without using an organic solvent. Furthermore, the coating film obtained from this dispersion is excellent in solvent resistance and water resistance. Therefore, it becomes industrially useful as a water-based resin for coating agents, paints and inks.
Claims (2)
ついで、イソシアネート末端ウレタンプレポリマー（Ｂ）中の酸性官能基を中和し、水希釈して乳化させた後、
イソシアネート末端ウレタンプレポリマー（Ｂ）の鎖延長反応と、前記（メタ）アクリル系モノマー（Ａ）およびイソシアネート末端ウレタンプレポリマー（Ｂ）のラジカル重合反応とを行う、水性ウレタン変性（メタ）アクリル樹脂分散液の製造方法。 In the (meth) acrylic monomer (A) having no active hydrogen, the polyisocyanate (a) includes two or more functional groups selected from hydroxyl groups and amino groups in the molecule, and one acidic functional group Compound (b) having the above, polyol (c) having no acidic functional group, compound (d) having glycidyl group and polymerizable unsaturated group in the molecule (however, the (meth) acrylic monomer (A)) To produce an isocyanate-terminated urethane prepolymer (B) having a polymerizable unsaturated group and an acidic functional group,
Then, after neutralizing the acidic functional group in the isocyanate-terminated urethane prepolymer (B), diluting with water and emulsifying,
Aqueous urethane-modified (meth) acrylic resin dispersion that performs a chain extension reaction of the isocyanate-terminated urethane prepolymer (B) and a radical polymerization reaction of the (meth) acrylic monomer (A) and the isocyanate-terminated urethane prepolymer (B). Liquid manufacturing method.
ついで、イソシアネート末端ウレタンプレポリマー（Ｃ）中の酸性官能基を中和し、水希釈して乳化させた後、
イソシアネート末端ウレタンプレポリマー（Ｃ）の鎖延長反応と、前記（メタ）アクリル系モノマー（Ａ）および分子内にグリシジル基及び重合性不飽和基を有する化合物（ｄ）（ただし、前記（メタ）アクリル系モノマー（Ａ）を除く。）のラジカル重合反応と、イソシアネート末端ウレタンプレポリマー（Ｃ）および前記化合物（ｄ）の付加反応とを行う、水性ウレタン変性（メタ）アクリル樹脂分散液の製造方法。 In the (meth) acrylic monomer (A) having no active hydrogen, the polyisocyanate (a) includes two or more functional groups selected from hydroxyl groups and amino groups in the molecule, and one acidic functional group The compound (b) having the above and the polyol (c) having no acidic functional group are reacted to produce an isocyanate-terminated urethane prepolymer (C) having an acidic functional group,
Then, after neutralizing the acidic functional group in the isocyanate-terminated urethane prepolymer (C), diluting with water and emulsifying,
Chain extension reaction of the isocyanate-terminated urethane prepolymer (C), the (meth) acrylic monomer (A) and the compound (d) having a glycidyl group and a polymerizable unsaturated group in the molecule (however, the (meth) acrylic) A method for producing an aqueous urethane-modified (meth) acrylic resin dispersion, in which a radical polymerization reaction of the monomer (A) is removed) and an addition reaction of the isocyanate-terminated urethane prepolymer (C) and the compound (d) is performed.
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