JP2016204571A - Water dispersion of polyurethane urea-acrylic composite resin - Google Patents
Water dispersion of polyurethane urea-acrylic composite resin Download PDFInfo
- Publication number
- JP2016204571A JP2016204571A JP2015090429A JP2015090429A JP2016204571A JP 2016204571 A JP2016204571 A JP 2016204571A JP 2015090429 A JP2015090429 A JP 2015090429A JP 2015090429 A JP2015090429 A JP 2015090429A JP 2016204571 A JP2016204571 A JP 2016204571A
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- Japan
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- parts
- group
- water
- composite resin
- acrylic composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000006185 dispersion Substances 0.000 title claims abstract description 68
- 239000000805 composite resin Substances 0.000 title claims abstract description 67
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 30
- 239000004814 polyurethane Substances 0.000 title claims abstract description 30
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 83
- -1 amine compound Chemical class 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 12
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 16
- 125000003172 aldehyde group Chemical group 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920003226 polyurethane urea Polymers 0.000 claims description 10
- 125000000129 anionic group Chemical group 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 42
- 239000000203 mixture Substances 0.000 abstract description 36
- 239000003960 organic solvent Substances 0.000 abstract description 13
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 66
- 239000007864 aqueous solution Substances 0.000 description 63
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 57
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 45
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 38
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 33
- 239000002253 acid Substances 0.000 description 26
- 229920005862 polyol Polymers 0.000 description 25
- 238000006116 polymerization reaction Methods 0.000 description 24
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 22
- 239000005058 Isophorone diisocyanate Substances 0.000 description 22
- 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 22
- 150000003077 polyols Chemical class 0.000 description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 21
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 20
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 20
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 19
- 235000010265 sodium sulphite Nutrition 0.000 description 19
- 238000001816 cooling Methods 0.000 description 18
- 238000004132 cross linking Methods 0.000 description 18
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 17
- 230000001588 bifunctional effect Effects 0.000 description 17
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 229920000058 polyacrylate Polymers 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 238000004945 emulsification Methods 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 7
- 230000002349 favourable effect Effects 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 239000005056 polyisocyanate Substances 0.000 description 6
- 229920001228 polyisocyanate Polymers 0.000 description 6
- 229920005749 polyurethane resin Polymers 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920005906 polyester polyol Polymers 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 150000001261 hydroxy acids Chemical class 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 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 2
- JWTGRKUQJXIWCV-UHFFFAOYSA-N 1,2,3-trihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(O)C(O)CO JWTGRKUQJXIWCV-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-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
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- RKOOOVKGLHCLTP-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol Chemical compound CC(=C)C(O)=O.OCC(O)CO RKOOOVKGLHCLTP-UHFFFAOYSA-N 0.000 description 2
- IGDCJKDZZUALAO-UHFFFAOYSA-N 2-prop-2-enoxypropane-1,3-diol Chemical compound OCC(CO)OCC=C IGDCJKDZZUALAO-UHFFFAOYSA-N 0.000 description 2
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 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
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000011346 highly viscous material Substances 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- LLHSEQCZSNZLRI-UHFFFAOYSA-M sodium;3,5-bis(methoxycarbonyl)benzenesulfonate Chemical compound [Na+].COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1 LLHSEQCZSNZLRI-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 description 1
- ZODNDDPVCIAZIQ-UHFFFAOYSA-N (2-hydroxy-3-prop-2-enoyloxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(=O)C=C ZODNDDPVCIAZIQ-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- SNVRDQORMVVQBI-OWOJBTEDSA-N (e)-but-2-enedihydrazide Chemical compound NNC(=O)\C=C\C(=O)NN SNVRDQORMVVQBI-OWOJBTEDSA-N 0.000 description 1
- SNVRDQORMVVQBI-UPHRSURJSA-N (z)-but-2-enedihydrazide Chemical compound NNC(=O)\C=C/C(=O)NN SNVRDQORMVVQBI-UPHRSURJSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- OYLCUJRJCUXQBQ-UHFFFAOYSA-N 1-hepten-3-one Chemical compound CCCCC(=O)C=C OYLCUJRJCUXQBQ-UHFFFAOYSA-N 0.000 description 1
- NMRJTPABHJLURO-UHFFFAOYSA-N 1-n-ethyl-4-methylbenzene-1,3-diamine Chemical compound CCNC1=CC=C(C)C(N)=C1 NMRJTPABHJLURO-UHFFFAOYSA-N 0.000 description 1
- RHNJVKIVSXGYBD-UHFFFAOYSA-N 10-prop-2-enoyloxydecyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCCOC(=O)C=C RHNJVKIVSXGYBD-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- BWDHJINUKACSDS-UHFFFAOYSA-N 2,3-bis(prop-2-enoxy)propan-1-ol Chemical compound C=CCOC(CO)COCC=C BWDHJINUKACSDS-UHFFFAOYSA-N 0.000 description 1
- RJTQLJDSJFPMQT-UHFFFAOYSA-N 2,4-diaminobutane-2-sulfonic acid Chemical compound OS(=O)(=O)C(N)(C)CCN RJTQLJDSJFPMQT-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 1
- CTNICFBTUIFPOE-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=C(O)C=C1 CTNICFBTUIFPOE-UHFFFAOYSA-N 0.000 description 1
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- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は、ポリウレタンウレア-アクリル複合樹脂の水分散体に関する。 The present invention relates to an aqueous dispersion of a polyurethane urea-acrylic composite resin.
水系ポリウレタン樹脂は、従来から、接着剤、コーティング剤、塗料、改質剤、バインダー等として有用な材料であり、広範な用途で使用されている。このような水系ポリウレタン樹脂としては、ウレタン樹脂骨格中にアニオン性、カチオン性、非イオン性等の親水性基を含有させて自己乳化分散させる方法が、粒子径を微細にでき、しかも性能的に優れていることが知られているが、さらに耐水性、耐溶剤性の向上が望まれている。
その解決策として、イソシアネート系、エポキシ系、アジリジン系、カルボジイミド系、金属キレート系架橋剤を配合する方法が知られているが、配合後の安定性が悪く、またその架橋特性を得る為には加熱処理が必要とされる。また、通常、水性ポリウレタン樹脂の製造には、有機溶剤中で親水性基含有ウレタンプレポリマーを合成し、アニオン性、カチオン性樹脂では、塩形成剤を使用して乳化後、多価アミン化合物（Ｙ）で高分子量化させて製造するが、この方法では脱溶媒が必要となる。脱溶媒には多大なエネルギーと煩雑な操作に伴い非常に不経済であるとともに、得られた水性ポリウレタン樹脂からは、使用した有機溶剤を完全に除去することは困難である。
常温下で架橋し、かつ乳化安定性が良好な対応策として、ヒドラジド基とカルボニル基もしくはアルデヒド基との間の自己架橋を利用する方法が種々提案されている(特許文献１〜４）。具体的には、ヒドラジド基またはカルボニル基もしくはアルデヒド基を導入した水系ポリウレタン樹脂に反応するカルボニル基もしくはアルデヒド基またはヒドラジド基含有架橋剤や樹脂を配合したものが開示されている。
A water-based polyurethane resin has hitherto been a material useful as an adhesive, a coating agent, a paint, a modifier, a binder, and the like, and has been used in a wide range of applications. As such an aqueous polyurethane resin, a method in which a hydrophilic group such as anionic, cationic, nonionic, etc. is contained in a urethane resin skeleton and self-emulsified and dispersed can make the particle diameter fine and in terms of performance. Although it is known to be excellent, further improvement in water resistance and solvent resistance is desired.
As a solution, a method of blending an isocyanate-based, epoxy-based, aziridine-based, carbodiimide-based, or metal chelate-based crosslinking agent is known, but the stability after blending is poor, and in order to obtain its crosslinking characteristics Heat treatment is required. In general, an aqueous polyurethane resin is produced by synthesizing a hydrophilic group-containing urethane prepolymer in an organic solvent. For anionic and cationic resins, after emulsification using a salt forming agent, a polyvalent amine compound ( Y) is produced by increasing the molecular weight, but this method requires solvent removal. Solvent removal is very uneconomical due to enormous energy and complicated operations, and it is difficult to completely remove the used organic solvent from the aqueous polyurethane resin obtained.
Various methods using self-crosslinking between a hydrazide group and a carbonyl group or an aldehyde group have been proposed as countermeasures for crosslinking at room temperature and good emulsion stability (Patent Documents 1 to 4). Specifically, a blend of a carbonyl group, an aldehyde group, or a hydrazide group-containing crosslinking agent or resin that reacts with an aqueous polyurethane resin into which a hydrazide group, a carbonyl group, or an aldehyde group has been introduced is disclosed.
本発明者らは上記に鑑み、従来技術以上の架橋特性を示し、また界面活性剤や有機溶剤を使用することなく合成を行うべく検討を行ったところ、特許文献１に記載の方法では、例示のカルボニル基含有アルコールの架橋特性は弱く、また、ジエポキシドとケトカルボン酸の反応物では、反応物の合成時点で著しい着色が認められ好ましくない。特許文献２に記載の方法では、水系ウレタン中でカルボニル基含有アクリル系重合体を乳化重合するが、アクリル系重合体は不飽和基が単官能化合物の重合体であり、またウレタン骨格とカルボニル基含有アクリル系重合体が架橋しないことから、その架橋効果は弱い。また、アクリル系重合体の乳化重合時に界面活性剤を必要とする事から耐水性に劣る。特許文献３に記載の方法では、ヒドラジド末端ウレタンとする事で、カルボニル基含有アクリル系重合体と架橋させるが、アクリル系重合体は不飽和基が単官能化合物の重合体であり、ヒドラジド末端ウレタンの分子量は制限され、また、ヒドラジド基の導入量にも限界がある事から、その架橋特性には限界がある。また、ウレタンプレポリマーの合成時点で有機溶媒を使用しなければならず、またカルボニル基含有アクリル系重合体の乳化重合には界面活性剤を必要とする。特許文献４に記載の方法では、不飽和結合導入ウレタン部にカルボニル基含有アクリル系重合体を共重合しているが、実質的に開示されているのはＯＨ末端プレポリマーを使用したものであり、ウレタン分子量は低分子である事からウレタンの特性が失われる。またウレタンプレポリマーの合成時点で有機溶媒を使用しなければならず、またカルボニル基含有アクリル系重合体の乳化重合には乳化剤を必要とする。 In view of the above, the inventors of the present invention have exhibited crosslinking properties that are higher than those of the prior art and have studied to synthesize without using a surfactant or an organic solvent. The crosslinking property of the carbonyl group-containing alcohol is weak, and a reaction product of diepoxide and ketocarboxylic acid is not preferable because remarkable coloring is observed at the time of synthesis of the reaction product. In the method described in Patent Document 2, an carbonyl group-containing acrylic polymer is emulsion-polymerized in an aqueous urethane. The acrylic polymer is a polymer having a monofunctional unsaturated group, and the urethane skeleton and carbonyl group. Since the contained acrylic polymer does not crosslink, its crosslinking effect is weak. Moreover, since a surfactant is required at the time of emulsion polymerization of an acrylic polymer, the water resistance is poor. In the method described in Patent Document 3, a hydrazide-terminated urethane is crosslinked with a carbonyl group-containing acrylic polymer. The acrylic polymer is a polymer of a monofunctional compound having an unsaturated group, and is a hydrazide-terminated urethane. The molecular weight is limited, and the amount of hydrazide groups introduced is also limited, so that its crosslinking properties are limited. Moreover, an organic solvent must be used at the time of synthesis of the urethane prepolymer, and a surfactant is required for emulsion polymerization of the carbonyl group-containing acrylic polymer. In the method described in Patent Document 4, a carbonyl group-containing acrylic polymer is copolymerized in the unsaturated bond-introducing urethane portion, but what is substantially disclosed is the use of an OH-terminated prepolymer. Because of the low molecular weight of urethane, the properties of urethane are lost. In addition, an organic solvent must be used at the time of synthesis of the urethane prepolymer, and an emulsifier is required for emulsion polymerization of the carbonyl group-containing acrylic polymer.
本発明の発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、特定割合で、特定構造のエチレン性不飽和基含有化合物（Ａ）およびＮＣＯ基末端ウレタンプレポリマー（Ｘ）を、水中に乳化分散した後、多価アミン化合物（Ｙ）で鎖伸張し、さらにエチレン性不飽和基を重合することにより得られる、ポリウレタンウレア-アクリル複合樹脂の水分散体により、上記課題を解決できることを見いだし、本発明を完成させるに至った。 As a result of intensive studies to solve the above problems, the inventors of the present invention have a specific ratio of the ethylenically unsaturated group-containing compound (A) having a specific structure and the NCO group-terminated urethane prepolymer (X), The above problem can be solved by an aqueous dispersion of a polyurethaneurea-acrylic composite resin obtained by emulsifying and dispersing in water, then chain-extending with a polyvalent amine compound (Y), and further polymerizing an ethylenically unsaturated group. As a result, the present invention has been completed.
すなわち、本発明は下記に掲げる発明に関する。
（１） エチレン性不飽和基含有化合物（Ａ）およびＮＣＯ基末端ウレタンプレポリマー（Ｘ）を、水中に乳化分散した後、多価アミン化合物（Ｙ）で鎖伸張し、さらにエチレン性不飽和基を重合することにより得られる、ポリウレタンウレア-アクリル複合樹脂の水分散体であって、前記（Ａ）が２以上のエチレン性不飽和基を有する化合物（Ａ１）を含有し、（Ｘ）と（Ａ１）の混合割合が、（Ｘ）１０００［ｇ］に対して（Ａ１）が０．３〜７．０［ｍｏｌ×（Ａ１）中の平均不飽和基数］である、ポリウレタンウレア-アクリル複合樹脂の水分散体。
（２） 前記（Ａ）が、さらにエチレン性不飽和基数が１以上のカルボニル基もしくはアルデヒド基含有エチレン性不飽和単量体（Ａ２）を含有し、（Ｘ）と（Ａ２）の混合割合が、（Ｘ）１０００［ｇ］に対して（Ａ２）が０．１〜２．０［ｍｏｌ］である、（１）記載のポリウレタンウレア-アクリル複合樹脂の水分散体。
（３） 前記ＮＣＯ基末端ウレタンプレポリマー（Ｘ）が、（Ｘ）１０００［ｇ］に対してエチレン性不飽和基を０．００５〜１．０［ｍｏｌ］有するように、エチレン性不飽和基含有ＮＣＯ基末端ウレタンプレポリマー（Ｘ１）を含有する（１）または（２）記載のポリウレタンウレア-アクリル複合樹脂の水分散体。
（４） さらに、（Ａ）中のカルボニル基もしくはアルデヒド基に対して０．３〜１．２当量のヒドラジド基となるようにヒドラジド誘導体を混合させて得られる（２）または（３）記載のポリウレタンウレア-アクリル複合樹脂の水分散体。
（５） 前記多価アミン化合物（Ｙ）が、少なくともヒドラジド誘導体（Ｙ１）を含有し、かつ多価アミン化合物（Ｙ）で鎖伸長後の水系ポリウレタンウレア樹脂の末端アミノ基がヒドラジド基である、（２）〜（４）のいずれか記載のポリウレタンウレア-アクリル複合樹脂の水分散体。
（６） ＮＣＯ基末端ウレタンプレポリマー（Ｘ）が、アニオン性基を有する、（１）〜（５）のいずれか記載のポリウレタンウレア-アクリル複合樹脂の水分散体。
（７） 実質的に無溶剤で、かつ界面活性剤を実質的に含有しないで製造される（１）〜（６）のいずれか記載のポリウレタンウレア-アクリル複合樹脂の水分散体。
（８） エチレン性不飽和基含有化合物（Ａ）およびＮＣＯ基末端ウレタンプレポリマー（Ｘ）を、水中に乳化分散する工程と、多価アミン化合物（Ｙ）で鎖伸張する工程と、さらにエチレン性不飽和基を重合する工程を含む、ポリウレタンウレア-アクリル複合樹脂の水分散体の製造方法であって、前記（Ａ）が２以上のエチレン性不飽和基を有する化合物（Ａ１）を含有し、（Ｘ）と（Ａ１）の混合割合は（Ｘ）１０００［ｇ］に対して（Ａ１）が０．３〜７．０［ｍｏｌ×（Ａ１）中の平均不飽和基数］である、ポリウレタンウレア-アクリル複合樹脂の水分散体の製造方法。
That is, this invention relates to the invention hung up below.
(1) An ethylenically unsaturated group-containing compound (A) and an NCO group-terminated urethane prepolymer (X) are emulsified and dispersed in water, then chain-extended with a polyvalent amine compound (Y), and further an ethylenically unsaturated group An aqueous dispersion of a polyurethaneurea-acrylic composite resin obtained by polymerizing (A), wherein the (A) contains a compound (A1) having two or more ethylenically unsaturated groups, and (X) and ( A polyurethane urea-acrylic composite resin in which the mixing ratio of A1) is (X) 1000 [g] and (A1) is 0.3 to 7.0 [mol × average number of unsaturated groups in (A1)] Water dispersion.
(2) The (A) further contains a carbonyl group or aldehyde group-containing ethylenically unsaturated monomer (A2) having one or more ethylenically unsaturated groups, and the mixing ratio of (X) and (A2) is (X) The aqueous dispersion of polyurethane urea-acrylic composite resin according to (1), wherein (A2) is 0.1 to 2.0 [mol] with respect to 1000 [g].
(3) The ethylenically unsaturated group so that the NCO group-terminated urethane prepolymer (X) has 0.005 to 1.0 [mol] of ethylenically unsaturated group with respect to (X) 1000 [g]. An aqueous dispersion of a polyurethaneurea-acrylic composite resin according to (1) or (2), which contains the NCO group-terminated urethane prepolymer (X1).
(4) The method according to (2) or (3), which is further obtained by mixing a hydrazide derivative so that a hydrazide group is 0.3 to 1.2 equivalents relative to the carbonyl group or aldehyde group in (A). An aqueous dispersion of polyurethaneurea-acrylic composite resin.
(5) The polyvalent amine compound (Y) contains at least the hydrazide derivative (Y1), and the terminal amino group of the aqueous polyurethane urea resin after chain extension with the polyvalent amine compound (Y) is a hydrazide group. An aqueous dispersion of the polyurethaneurea-acrylic composite resin according to any one of (2) to (4).
(6) The aqueous dispersion of a polyurethaneurea-acrylic composite resin according to any one of (1) to (5), wherein the NCO group-terminated urethane prepolymer (X) has an anionic group.
(7) The aqueous dispersion of a polyurethane urea-acrylic composite resin according to any one of (1) to (6), which is produced substantially without a solvent and substantially free of a surfactant.
(8) The step of emulsifying and dispersing the ethylenically unsaturated group-containing compound (A) and the NCO group-terminated urethane prepolymer (X) in water, the step of extending the chain with the polyvalent amine compound (Y), and the ethylenic property A method for producing an aqueous dispersion of a polyurethaneurea-acrylic composite resin comprising a step of polymerizing an unsaturated group, wherein (A) comprises a compound (A1) having two or more ethylenically unsaturated groups, The mixing ratio of (X) and (A1) is polyurethane urea in which (A1) is 0.3 to 7.0 [mol × average number of unsaturated groups in (A1)] with respect to (X) 1000 [g] -Manufacturing method of aqueous dispersion of acrylic composite resin.
本発明によれば、実質的に有機溶剤および界面活性剤を使用することなく、乳化安定性が良好かつ得られる塗膜の耐水性および耐溶剤性も良好なポリウレタンウレア-アクリル複合樹脂の水分散体を提供することができる。 According to the present invention, an aqueous dispersion of a polyurethaneurea-acrylic composite resin having good emulsion stability and good water resistance and good solvent resistance without substantially using an organic solvent and a surfactant. The body can be provided.
本発明のポリウレタンウレア-アクリル複合樹脂の水分散体は、エチレン性不飽和基含有化合物（Ａ）およびＮＣＯ基末端ウレタンプレポリマー（Ｘ）を、水中に乳化分散した後、多価アミン化合物（Ｙ）で鎖伸張し、さらにエチレン性不飽和基を重合することにより得られる。 The aqueous dispersion of the polyurethaneurea-acrylic composite resin of the present invention comprises an ethylenically unsaturated group-containing compound (A) and an NCO group-terminated urethane prepolymer (X) emulsified and dispersed in water, and then a polyvalent amine compound (Y ) And then polymerizing ethylenically unsaturated groups.
本発明においてエチレン性不飽和基含有化合物（Ａ）は、２以上のエチレン性不飽和基を有する化合物（Ａ１）を含有するものであれば、特に限定されない。例えば、トリシクロデカンジメタノールジアクリレート、１，９−ノナンジオールジアクリレート、１，１０−デカンジオールジアクリレート、１，４−ブタンジオールジアクリレート、グリセリンジアクリレート、１，６−ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート、トリエチエレングルコールジアクリレート、ジプロピレングリコールジアクリレート、トリプロピレングリコールジアクリレート、ポリプロピレングリコールジアクリレート、ポリエチレングリコールジアクリレート、プロポキシ化エトキシ化ビスフェノールＡジアクリレート、エトキシ化ビスフェノールＡジアクリレート、９，９−ビス［４−（２−アクリロイルオキシエトキシ）フェニル］フルオレン、プロポキシ化ビスフェノールＡジアクリレート、エトキシ化イソシアヌル酸トリアクリレート、ε-カプロラクトン変性トリス−（２−アクリロキシエチル)イソシアヌレート、ペンタエリスリトールトリアクリレート、トリメチロールプロパントリアクリレート、ジトリメチロールプロパンテトラアクリレート、エトキシ化ペンタエリスリトールテトラアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールポリアクリレート、ジペンタエリスリトールヘキサアクリレート、２−メタクロイロキシエチルアシッドホスフェート、２−ヒドロキシ−３−アクリロイロキシプロピルメタクリレート、エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ポリエチレングリコール ジメタクリレート、エトキシ化ビスフェノールＡジメタクリレート、トリシクロデカンジメタノールジメタクリレート、１，６−ヘキサンジオールジメタクリレート、ネオペンチルグリコールジメタクリレート、１，９−ノナンジオールジメタクリレート、１，１０−デカンジオールジメタリレート、グリセリンジメタクリレート、ポリプロピレングリコールジメタクリレート、トリメチロールプロパントリメタクリレートなどが挙げられる。
これらのうち、耐溶剤性発現効果、臭気や粘度等の取り扱いやすさの観点から、ジペンタエリスリトールヘキサアクリレート、ペンタエリスリトールテトラアクリレート、１，６−ヘキサンジオールジアクリレート、トリメチロールプロパントリアクリレートが好ましい。
In the present invention, the ethylenically unsaturated group-containing compound (A) is not particularly limited as long as it contains the compound (A1) having two or more ethylenically unsaturated groups. For example, tricyclodecane dimethanol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 1,4-butanediol diacrylate, glycerin diacrylate, 1,6-hexanediol diacrylate, Neopentyl glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol diacrylate, propoxylated ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A di Acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, propoxylated bisphenol A Acrylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, pentaerythritol triacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, penta Erythritol tetraacrylate, dipentaerythritol polyacrylate, dipentaerythritol hexaacrylate, 2-methacryloylethyl acid phosphate, 2-hydroxy-3-acryloyloxypropyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol di Methacrylate, polyethylene glycol Dimethacrylate, ethoxylated bisphenol A dimethacrylate, tricyclodecane dimethanol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimetall Examples thereof include rate, glycerin dimethacrylate, polypropylene glycol dimethacrylate, and trimethylolpropane trimethacrylate.
Of these, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, 1,6-hexanediol diacrylate, and trimethylolpropane triacrylate are preferable from the viewpoint of solvent resistance expression effect and ease of handling such as odor and viscosity.
本発明においてエチレン性不飽和基含有化合物（Ａ）は、さらに（Ａ１）に含まれないエチレン性不飽和基数が１以上のカルボニル基もしくはアルデヒド基含有エチレン性不飽和単量体（Ａ２）を含有することが好ましい。（Ａ２）のエチレン性不飽和基数は１以上であることが好ましく、取り扱い性、入手性の観点から、より好ましくは１である。本発明において、カルボニル基もしくはアルデヒド基とは、架橋性のケト基もしくはアルド基であり、エステル結合からなるカルボニル基は含まない。 In the present invention, the ethylenically unsaturated group-containing compound (A) further contains a carbonyl group or aldehyde group-containing ethylenically unsaturated monomer (A2) having one or more ethylenically unsaturated groups not included in (A1). It is preferable to do. The number of ethylenically unsaturated groups in (A2) is preferably 1 or more, and more preferably 1 from the viewpoints of handleability and availability. In the present invention, the carbonyl group or aldehyde group is a crosslinkable keto group or aldo group, and does not include a carbonyl group comprising an ester bond.
カルボニル基もしくはアルデヒド基含有エチレン性不飽和単量体（Ａ２）としては、特に限定されないが、例えば、アクロレイン、ダイアセトン（メタ）アクリルアミド、ホルミルスチロール、ビニルアルキルケトン（たとえばビニルメチルケトン、ビニルエチルケトン、ビニルブチルケトン）、アセトアセトキシエチルアクリレート、アセトアセトキシエチルメタクリレートなどがあげられる。これらのうち、反応性、入手容易性の観点から、ダイアセトン（メタ）アクリルアミドが好ましい。ダイアセトン（メタ）アクリルアミドの等の水溶性エチレン性不飽和単量体を使用する場合、重合開始前の乳化物に混合後重合開始することも、また水溶液を添加しながら重合する事も可能である。 Although it does not specifically limit as a carbonyl group or an aldehyde group containing ethylenically unsaturated monomer (A2), For example, acrolein, diacetone (meth) acrylamide, formyl styrene, vinyl alkyl ketone (For example, vinyl methyl ketone, vinyl ethyl ketone) Vinyl butyl ketone), acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, and the like. Of these, diacetone (meth) acrylamide is preferred from the viewpoints of reactivity and availability. When using a water-soluble ethylenically unsaturated monomer such as diacetone (meth) acrylamide, it is possible to start polymerization after mixing into the emulsion before polymerization, or to polymerize while adding an aqueous solution. is there.
２以上のエチレン性不飽和基を有する化合物（Ａ１）を含有するとは、少なくとも２以上のエチレン性不飽和基を有する化合物（Ａ１）を含有すれば、１つのエチレン性不飽和基を有する化合物を含有することを妨げるものではない。（Ａ２）を除くエチレン性不飽和基を１個有するエチレン性不飽和単量体（Ａ３）を含有してもよい。（Ａ３）としては、特に限定されないが、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、２−エチルヘキシル（ メタ） アクリレート、ラウリル（メタ）アクリレート、（イソ）ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレ−ト、等のアルキル又はシクロアルキル（メタ）アクリレート； イソボルニル（メタ）アクリレート等のイソボルニル基を有するエチレン性不飽和基含有化合物、アダマンチル（メタ）アクリレート等のアダマンチル基を有するエチレン性不飽和基含有化合物、 スチレンなどのビニル芳香族化合物、 ビニルトリメトキシシラン、ビニルトリエトキシシランなどのアルコキシシリル基を有するエチレン性不飽和基含有化合物、パーフルオロブチルエチル（メタ）アクリレート、等のフッ素化アルキル基を有するエチレン性不飽和基含有化合物、マレイミド基等の光重合性官能基を有するエチレン性不飽和基含有化合物； Ｎ − ビニルピロリドン等のビニル化合物、（メタ）アクリル酸、マレイン酸、クロトン酸、β − カルボキシエチルアクリレート等のカルボキシル基を有する化合物、アリル（メタ）アクリレ−トがあげられる。また、水酸基を有するヒドロキシエチル（メタ）アクリレ−トなどの水酸基を有する（メタ）アクリレート、ポリエチレングリコールーモノ（メタ）アクリレート、ポリプロピレングリコールーモノ（メタ）アクリレート等のエチレン性不飽和基含有化合物も（Ｘ）のＮＣＯ基と反応させない条件化での使用が可能である。また、分子末端がアルコキシ基であるポリオキシエチレン鎖を有する（メタ）アクリレート、スチレンスルホン酸ナトリウム塩等のスルホン酸基を有するエチレン性不飽和基含有化合物が挙げられる。 “Containing compound (A1) having two or more ethylenically unsaturated groups” means containing a compound (A1) having at least two or more ethylenically unsaturated groups as a compound having one ethylenically unsaturated group. It does not prevent inclusion. You may contain the ethylenically unsaturated monomer (A3) which has one ethylenically unsaturated group except (A2). Although it does not specifically limit as (A3), For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate , (Iso) stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and other alkyl or cycloalkyl (meth) acrylates; ethylenically unsaturated group-containing compounds having an isobornyl group such as isobornyl (meth) acrylate, adamantyl ( Ethylenically unsaturated group-containing compounds having an adamantyl group such as (meth) acrylate, vinyl aromatic compounds such as styrene, vinylsilyl groups such as vinyltrimethoxysilane and vinyltriethoxysilane N-containing compounds, ethylenically unsaturated group-containing compounds having a fluorinated alkyl group such as perfluorobutylethyl (meth) acrylate, and ethylenically unsaturated group-containing compounds having a photopolymerizable functional group such as a maleimide group; N -Vinyl compounds such as vinylpyrrolidone, (meth) acrylic acid, maleic acid, crotonic acid, compounds having a carboxyl group such as β-carboxyethyl acrylate, and allyl (meth) acrylate. Also, ethylenically unsaturated group-containing compounds such as (meth) acrylate having a hydroxyl group such as hydroxyethyl (meth) acrylate having a hydroxyl group, polyethylene glycol-mono (meth) acrylate, polypropylene glycol-mono (meth) acrylate, etc. It can be used under conditions that do not react with the NCO group of (X). Moreover, the ethylenically unsaturated group containing compound which has sulfonic acid groups, such as (meth) acrylate which has a polyoxyethylene chain whose molecular terminal is an alkoxy group, and a styrenesulfonic acid sodium salt is mentioned.
これらエチレン性不飽和基含有化合物（Ａ）は得られる水性樹脂分散体に望まれる性能や製造条件などに応じて一種または二種以上を使用することができる。また、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、２−エチルヘキシル（ メタ） アクリレート、１，６−ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート、のような活性水素原子をもたず低粘度の（メタ）アクリレート化合物はウレタンプレポリマー反応時の減粘剤としての効果を有することから好ましい。 These ethylenically unsaturated group-containing compounds (A) may be used alone or in combination of two or more depending on the performance and production conditions desired for the obtained aqueous resin dispersion. Also, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, Such a (meth) acrylate compound having no active hydrogen atom and having a low viscosity is preferable because it has an effect as a thickener during the urethane prepolymer reaction.
本発明においてＮＣＯ基末端ウレタンプレポリマー（Ｘ）は、２個以上のヒドロキシル基を有するポリオール成分（ｘ１）と、ポリイソシアネート成分（ｘ２）を用いて得られる。 In the present invention, the NCO group-terminated urethane prepolymer (X) is obtained using a polyol component (x1) having two or more hydroxyl groups and a polyisocyanate component (x2).
本発明において、少なくとも２個以上のヒドロキシル基を有するポリオール成分（ｘ１）としては、特に限定されないが、例えば、多価アルコール、ポリエーテルポリオール、ポリエステルポリオール、ポリエーテルエステルポリオール、ポリカーボネートポリオール、ポリオレフィンポリオール、ポリアクリルポリオール、ポリアセタールポリオール、ポリブタジエンポリオール、ポリシロキサンポリオール、フッ素ポリオール等の分子末端または分子内に２個以上のヒドロキシル基を有する化合物などがあげられる。多価アルコールとしては、特に限定されないが、例えば、エチレングリコール、ジエチレングリコール、ブタンジオール、プロピレングリール、ヘキサンジオール、ビスフェノールＡ、ビスフェノールＢ、ビスフェノールＳ、水素添加ビスフェノールＡ，ジブロムビスフェノールＡ，１，４−シクロヘキサンジメタノール、ジヒドロキシエチルテレフタレート、ハイドロキノンジヒドロキシエチルエーテル、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などがあげられる。ポリエーテルポリオールとしては、特に限定されないが、例えば、多価アルコールのアルキレン誘導体、ポリテトラメチレングリコール、ポリチオエーテルポリオールなどがあげられる。ポリエステルポリオール、ポリエーテルエステルポリオールとしては特に限定されないが、例えば、多価アルコール、多価カルボン酸、多価カルボン酸無水物、ポリエーテルポリオール、多価カルボン酸エステルからのエステル化物、ヒマシ油ポリオール、ポリカプロラクトンポリオールなどがあげられる。ポリオレフィンポリオールとしては特に限定されないが、例えば、ポリブタジエンポリオール、ポリイソプレンポリオールやこれらの水素添加ポリオールなどがあげられる。これらのうち、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオールが好ましい。これらは一種または二種以上を使用することができる。 In the present invention, the polyol component (x1) having at least two or more hydroxyl groups is not particularly limited. For example, polyhydric alcohol, polyether polyol, polyester polyol, polyether ester polyol, polycarbonate polyol, polyolefin polyol, Examples thereof include compounds having two or more hydroxyl groups in the molecular terminal or molecule, such as polyacryl polyol, polyacetal polyol, polybutadiene polyol, polysiloxane polyol, and fluorine polyol. The polyhydric alcohol is not particularly limited. For example, ethylene glycol, diethylene glycol, butanediol, propylene glycol, hexanediol, bisphenol A, bisphenol B, bisphenol S, hydrogenated bisphenol A, dibromobisphenol A, 1, 4 -Cyclohexanedimethanol, dihydroxyethyl terephthalate, hydroquinone dihydroxyethyl ether, trimethylolpropane, glycerin, pentaerythritol and the like. The polyether polyol is not particularly limited, and examples thereof include an alkylene derivative of a polyhydric alcohol, polytetramethylene glycol, and polythioether polyol. Polyester polyol, polyether ester polyol is not particularly limited, for example, polyhydric alcohol, polycarboxylic acid, polyhydric carboxylic acid anhydride, polyether polyol, esterified product from polycarboxylic acid ester, castor oil polyol, Examples thereof include polycaprolactone polyol. The polyolefin polyol is not particularly limited, and examples thereof include polybutadiene polyol, polyisoprene polyol, and hydrogenated polyols thereof. Of these, polyether polyol, polyester polyol, and polycarbonate polyol are preferred. These can use 1 type, or 2 or more types.
本発明において、前記ポリオール成分の数平均分子量としては、特に限定されないが、乳化性や乳化安定性の観点から５０〜１００００が好ましく、５００〜５,０００がより好ましい。 In the present invention, the number average molecular weight of the polyol component is not particularly limited, but is preferably 50 to 10,000 and more preferably 500 to 5,000 from the viewpoints of emulsification and emulsion stability.
本発明において、前記ポリイソシアネート成分（ｘ２）としては、特に限定されないが、例えば芳香族、脂肪族、脂環族、芳香脂肪等の有機ポリイソシアネートがあげられる。これらのうち、乳化水との反応容易に制御でき、また多価アミン化合物（Ｙ）との反応時に凝集物が発生しないことから、脂肪族、脂環族、芳香脂肪等の有機ポリイソシアネート、およびこれらの多量変性体（二量体、三量体等）や、あるいは上記した有機ポリイソシアネートと水との反応により生成するビウレット変性体等が好ましい。４，４’−ジシクロヘキシ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、水素添加キシリレンジイソシアネート〔ビス（イソシアネナトメチル）シクロヘキサン〕、ヘキサメチレンジイソシアネート、リジンジイソシアネート、ノルボルナンジイソシアネート、キシリレンジイソシアネート等の有機ポリイソシアネート、これらの変性体がより好ましい。また４，４’−ジシクロヘキシ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がより好ましい。これらは一種または二種以上を使用することができる。 In the present invention, the polyisocyanate component (x2) is not particularly limited, and examples thereof include organic polyisocyanates such as aromatic, aliphatic, alicyclic, and aromatic fats. Of these, the reaction with the emulsified water can be easily controlled, and since no aggregates are generated during the reaction with the polyvalent amine compound (Y), organic polyisocyanates such as aliphatic, alicyclic, and arabic fats, and These multi-modified products (dimers, trimers, etc.), or biuret-modified products produced by the reaction of the above-described organic polyisocyanate with water are preferred. Organic polyisocyanates such as 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate [bis (isocyanenatomethyl) cyclohexane], hexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, xylylene diisocyanate, and modified products thereof Is more preferable. Further, 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate are more preferable. These can use 1 type, or 2 or more types.
本発明においてＮＣＯ基末端ウレタンプレポリマー（Ｘ）は、さらに活性水素基含有アニオン性塩形成基含有化合物（ｘ３）を用いて得られるものが好ましい。（ｘ３）を用いることにより、アニオン性基を有するＮＣＯ基末端ウレタンプレポリマーを得ることができる。 In the present invention, the NCO group-terminated urethane prepolymer (X) is preferably obtained using the active hydrogen group-containing anionic salt-forming group-containing compound (x3). By using (x3), an NCO group-terminated urethane prepolymer having an anionic group can be obtained.
本発明において、活性水素基含有アニオン性塩形成基含有化合物（ｘ３）とは、１個以上の活性水素基およびイオン性塩形成基を有する化合物をいう。本発明において活性水素基はＮＣＯ基と反応性の活性水素原子を有する官能基であれば特に限定されないが、例えば、水酸基、アミノ基、チオール基などがあげられる。 In the present invention, the active hydrogen group-containing anionic salt-forming group-containing compound (x3) refers to a compound having one or more active hydrogen groups and an ionic salt-forming group. In the present invention, the active hydrogen group is not particularly limited as long as it is a functional group having an active hydrogen atom reactive with the NCO group, and examples thereof include a hydroxyl group, an amino group, and a thiol group.
本発明において、活性水素基含有アニオン性塩形成基含有化合物（ｘ３）およびそれに対応する塩形成剤としては特に限定されないが、例えば、塩形成性のカルボン酸またはスルホン酸基を有する化合物及び対応する塩形成剤および対応する塩形成剤などが挙げられる。例えば、ヒドロキシ酸、アミノスルホン酸、ヒドロキシスルホン酸、アミノカルボン酸、多価ヒドロキシ酸類などがあげられる。前記ヒドロキシ酸としては、特に限定されないが、例えば、グリコール酸、リンゴ酸、ジメチロールプロピオン酸、ジメチロールブタン酸などがあげられる。前記アミノカルボン酸としては、特に限定されないが、例えば、グリシン、アミノ安息香酸、アラニンなどがあげられる。前記アミノスルホン酸としては、特に限定されないが、例えば、アミノエチルスルホン酸、（アミノエチル）アミノエタンスルホン酸などがあげられる。前記ヒドロキスルホン酸としては、特に限定されないが、２−ヒドロキシエタンスルホン酸、５−スルホイソフタル酸ジメチルナトリウムと多価アルコールのエステル化物などがあげられる。これらのうち、ヒドロキシ酸、ヒドロキスルホン酸が好ましく、ジメチロールプロピオン酸、ジメチロールブタン酸、５−スルホイソフタル酸ジメチルナトリウムと多価アルコールのエステル化物がより好ましい。また、対応する塩形成剤としては、特に限定されないが、例えば、１価の金属水酸化物、３級アミン化合物などがあげられる。前記１価の金属水酸化物としては、特に限定されないが、例えば、水酸化カリウム、水酸化ナトリウム、水酸化カルシウムなどがあげられる。前記３級アミン化合物としては、特に限定されないが、例えば、１価の金属水酸化物やアンモニア、トリメチルアミン、トリエチルアミンなどがあげられる。これらのうち、３級アミン化合物が好ましく、トリエチルアミンがより好ましい。 In the present invention, the active hydrogen group-containing anionic salt-forming group-containing compound (x3) and the corresponding salt-forming agent are not particularly limited, and examples thereof include compounds having a salt-forming carboxylic acid or sulfonic acid group and the corresponding compounds. Examples include salt forming agents and corresponding salt forming agents. Examples thereof include hydroxy acid, amino sulfonic acid, hydroxy sulfonic acid, amino carboxylic acid, and polyvalent hydroxy acids. Although it does not specifically limit as said hydroxy acid, For example, glycolic acid, malic acid, dimethylol propionic acid, dimethylol butanoic acid etc. are mention | raise | lifted. The aminocarboxylic acid is not particularly limited, and examples thereof include glycine, aminobenzoic acid, and alanine. The aminosulfonic acid is not particularly limited, and examples thereof include aminoethylsulfonic acid and (aminoethyl) aminoethanesulfonic acid. The hydroxysulfonic acid is not particularly limited, and examples thereof include esterified products of 2-hydroxyethanesulfonic acid, dimethyl sodium 5-sulfoisophthalate and polyhydric alcohol. Of these, hydroxy acid and hydroxysulfonic acid are preferable, and dimethylolpropionic acid, dimethylolbutanoic acid, dimethyl sodium 5-sulfoisophthalate and polyhydric alcohol are more preferable. The corresponding salt forming agent is not particularly limited, and examples thereof include monovalent metal hydroxides and tertiary amine compounds. Although it does not specifically limit as said monovalent metal hydroxide, For example, potassium hydroxide, sodium hydroxide, calcium hydroxide etc. are mention | raise | lifted. The tertiary amine compound is not particularly limited, and examples thereof include monovalent metal hydroxide, ammonia, trimethylamine, and triethylamine. Of these, tertiary amine compounds are preferred, and triethylamine is more preferred.
本発明において、ＮＣＯ末端ウレタンプレポリマー（Ｘ）の酸価としては、特に限定されないが、７〜５０ｍｇＫＯＨ／ｇであることが好ましく、１０〜３０ｍｇＫＯＨ／ｇであることがより好ましい。７〜５０ｍｇＫＯＨ／ｇであれば、エチレン性不飽和基含有化合物（Ａ）を混合しても、ＮＣＯ基末端ウレタンプレポリマーの乳化物粒子径が微細となり、多価アミン化合物（Ｙ）で鎖伸長した水系ウレタンウレア樹脂、またその後、カルボニル基もしくはアルデヒド基含有エチレン性不飽和単量体及び他のエチレン性不飽和単量体重合後のエマルジョン粒子も細かく、また乳化安定性に優れることから好ましい。酸価が５０ｍｇＫＯＨ／ｇ以下であれば、プレポリマーの粘度が好適で無溶剤での製造が容易となり、また耐水性、耐ＭＥＫ性も良好である。 In the present invention, the acid value of the NCO-terminated urethane prepolymer (X) is not particularly limited, but is preferably 7 to 50 mgKOH / g, and more preferably 10 to 30 mgKOH / g. If it is 7-50 mgKOH / g, even if it mixes an ethylenically unsaturated group containing compound (A), the emulsion particle diameter of NCO group terminal urethane prepolymer will become fine, and chain extension will be carried out with a polyvalent amine compound (Y). The water-based urethane urea resin and the emulsion particles after polymerization of the carbonyl group or aldehyde group-containing ethylenically unsaturated monomer and other ethylenically unsaturated monomers are also fine and preferable because they are excellent in emulsion stability. When the acid value is 50 mgKOH / g or less, the viscosity of the prepolymer is suitable, the production without solvent is easy, and the water resistance and MEK resistance are also good.
本発明において、ＮＣＯ末端ウレタンプレポリマーを得るために用いるイソシアネート基と水酸基の割合(モル当量比)は（イソシアネート（ＮＣＯ）基:水酸基=)１．０５以上：１であれば特に限定されないが、ＮＣＯ末端ウレタンプレポリマーを低粘度とし、また安定な乳化物を得ることができることから１．５〜３．０：１が好ましく、１．６〜２．２：１であることがより好ましい。１．５モル当量以上であればプレポリマーの粘度が低く、無溶剤系でポリウレタンウレア-アクリル複合樹脂の生産が容易となる。また、エマルジョン粒子径も細かく、乳化安定性も良好となる。 In the present invention, the ratio of the isocyanate group to the hydroxyl group (molar equivalent ratio) used to obtain the NCO-terminated urethane prepolymer is not particularly limited as long as it is (isocyanate (NCO) group: hydroxyl group =) 1.05 or more, The NCO-terminated urethane prepolymer has a low viscosity and a stable emulsion can be obtained, so 1.5 to 3.0: 1 is preferable, and 1.6 to 2.2: 1 is more preferable. If it is 1.5 molar equivalents or more, the viscosity of the prepolymer is low, and production of a polyurethaneurea-acrylic composite resin in a solvent-free system becomes easy. In addition, the emulsion particle size is fine and the emulsion stability is good.
本発明において、ＮＣＯ末端ウレタンプレポリマーが、エチレン性不飽和基含有ＮＣＯ基末端ウレタンプレポリマー（Ｘ１）を含有することも好ましい態様である。得られるポリウレタンウレア-アクリル複合樹脂の耐水性、耐ＭＥＫ性も良好となることから好ましい。 In the present invention, it is also a preferred embodiment that the NCO-terminated urethane prepolymer contains the ethylenically unsaturated group-containing NCO group-terminated urethane prepolymer (X1). The resulting polyurethaneurea-acrylic composite resin is preferable because the water resistance and MEK resistance are also good.
エチレン性不飽和基含有ＮＣＯ基末端ウレタンプレポリマー（Ｘ１）は、ポリオール成分として、１個以上のヒドロキシル基およびエチレン性不飽和基を有するヒドロキシル基含有エチレン性不飽和単量体を使用して得られる。前記エチレン性不飽和基とは特に限定されないが、例えば（メタ）アクリロイル基、ビニル基、ビニルエーテル基、アリル基及びアリルエーテル基が挙げられる。これらのうち、反応性および皮膜の変色抑止性の観点から、（メタ）アクリロイル基、アリル基が好ましい。ヒドロキシル基含有エチレン性不飽和単量体としては、特に限定されないが、例えば、（メタ）アクリレート類、アリル化合物、およびこれらのアルキレンオキシド付加物などがあげられる。前記（メタ）アクリレート類としては、特に限定されないが、例えば、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（メタ）アクリレート、及びこれらのε−カプロラクトンやβ−メチル−δ−バレロラクトンの重付加物、ポリエチレングリコールーモノ（メタ）アクリレート、ポリエチレングリコールーモノ（メタ）アクリレート、ポリプロピレングリコールーモノ（メタ）アクリレート、グリセロールモノ（メタ）アクリレート、グリセロールジ（メタ）アクリレートなどの（メタ）アクリレート類などがあげられる。前記アリル化合物としては、特に限定されないが、例えば、アリルアルコール、グリセロールモノアリルエーテル、グリセロールジアリルエーテルなどがあげられる。これらのうち、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、グリセロールモノ（メタ）アクリレート、グリセロールモノアリルエーテルが好ましい。これらは一種または二種以上を使用することができる。 The ethylenically unsaturated group-containing NCO group-terminated urethane prepolymer (X1) is obtained using a hydroxyl group-containing ethylenically unsaturated monomer having one or more hydroxyl groups and ethylenically unsaturated groups as a polyol component. It is done. Although it does not specifically limit with the said ethylenically unsaturated group, For example, a (meth) acryloyl group, a vinyl group, a vinyl ether group, an allyl group, and an allyl ether group are mentioned. Of these, a (meth) acryloyl group and an allyl group are preferable from the viewpoint of reactivity and film discoloration suppression. The hydroxyl group-containing ethylenically unsaturated monomer is not particularly limited, and examples thereof include (meth) acrylates, allyl compounds, and alkylene oxide adducts thereof. The (meth) acrylates are not particularly limited, and examples thereof include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and ε-caprolactone and β-methyl-δ-. Valerolactone polyadducts, polyethylene glycol-mono (meth) acrylate, polyethylene glycol-mono (meth) acrylate, polypropylene glycol-mono (meth) acrylate, glycerol mono (meth) acrylate, glycerol di (meth) acrylate, etc. And (meth) acrylates. The allyl compound is not particularly limited, and examples thereof include allyl alcohol, glycerol monoallyl ether, and glycerol diallyl ether. Of these, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, and glycerol monoallyl ether are preferred. These can use 1 type, or 2 or more types.
エチレン性不飽和基含有ＮＣＯ基末端ウレタンプレポリマー（Ｘ１）中のエチレン性不飽和基の量は、（Ｘ）１０００［ｇ］に対してエチレン性不飽和基を０．００５〜１．０［ｍｏｌ］であることが好ましく、０．０１〜０．６［ｍｏｌ］であることがより好ましい。 The amount of the ethylenically unsaturated group in the ethylenically unsaturated group-containing NCO group-terminated urethane prepolymer (X1) is 0.005 to 1.0 [ mol] is preferable, and 0.01 to 0.6 [mol] is more preferable.
本発明において、ＮＣＯ末端ウレタンプレポリマーの平均分子量は、乳化性や乳化安定性の観点から、１００００以下が好ましく、４０００以下が、より好ましい。ここでいう平均分子量とは、仕込み原料の数平均分子量から算出される理論値をいう。 In the present invention, the average molecular weight of the NCO-terminated urethane prepolymer is preferably 10,000 or less, more preferably 4000 or less, from the viewpoints of emulsifying properties and emulsion stability. The average molecular weight here means a theoretical value calculated from the number average molecular weight of the charged raw materials.
本発明において、（Ｘ）と（Ａ）の混合割合（重量比）は、（Ｘ）／（Ａ）が ９５／５〜６０／４０であることが好ましい。より好ましくは９５／５〜７０／３０であり、さらに好ましくは９０／１０〜７５／２５である。これらの範囲であれば架橋特性が良好となり、得られる塗膜の耐水性および耐溶剤性も良好となる。また、粒子径が粗くならず乳化安定性に優れる。ポリウレタンウレア量が好適であることから、柔軟性や屈曲性、接着性等が良好である In the present invention, the mixing ratio (weight ratio) of (X) and (A) is preferably such that (X) / (A) is 95/5 to 60/40. More preferably, it is 95 / 5-70 / 30, More preferably, it is 90 / 10-75 / 25. If it is these ranges, a crosslinking characteristic will become favorable and the water resistance and solvent resistance of the coating film obtained will also become favorable. Further, the particle diameter is not coarse and the emulsion stability is excellent. Since the amount of polyurethane urea is suitable, flexibility, flexibility, adhesion, etc. are good.
本発明において、（Ｘ）と（Ａ１）の混合割合は、（Ｘ）１０００［ｇ］に対して（Ａ１）が０．３〜７．０［ｍｏｌ×（Ａ１）中の平均不飽和基数］である。架橋特性や性状の観点から、好ましくは０．５〜６．０［ｍｏｌ×（Ａ１）中の平均不飽和基数］であり、より好ましくは１．０〜０．４［ｍｏｌ×（Ａ１）中の平均不飽和基数］である。これらの範囲であれば、架橋特性が良好となり、得られる塗膜の耐水性および耐溶剤性も良好となる。また得られるポリウレタンウレア-アクリル複合樹脂水分散体の粒子径も細かく粗粒子物が少ない。また、粘度が著しく高く、ゲル状となることがないことから、良好である。なお、本明細書等において［ｍｏｌ×（Ａ１）中の平均不飽和基数］とは、［ｍｏｌ］と［（Ａ１）中の平均不飽和基数］の積を示す。また、平均不飽和基数は、（Ａ１）の重量割合に基づき、加重平均により算出される。 In the present invention, the mixing ratio of (X) and (A1) is such that (A1) is 0.3 to 7.0 [average number of unsaturated groups in mol × (A1)] with respect to (X) 1000 [g]. It is. From the viewpoint of crosslinking characteristics and properties, it is preferably 0.5 to 6.0 [average number of unsaturated groups in mol × (A1)], more preferably 1.0 to 0.4 [mol × (A1). Average number of unsaturated groups]. If it is these ranges, a crosslinking characteristic will become favorable and the water resistance and solvent resistance of the coating film obtained will also become favorable. Further, the resulting polyurethane urea-acrylic composite resin aqueous dispersion has a fine particle size and few coarse particles. Moreover, since the viscosity is remarkably high and it does not become a gel, it is favorable. In addition, in this specification and the like, [mol × average number of unsaturated groups in (A1)] represents a product of [mol] and [average number of unsaturated groups in (A1)]. The average unsaturated group number is calculated by a weighted average based on the weight ratio of (A1).
本発明において、（Ｘ）と（Ａ２）の混合割合は、架橋特性の観点から、（Ｘ）１０００［ｇ］に対して（Ａ２）が０．１〜２．０［ｍｏｌ］であることが好ましい。架橋特性や性状の観点から、より好ましくは０．２〜１．５［ｍｏｌ］であり、さらに好ましくは０．３〜１．０［ｍｏｌ］である。これらの範囲であれば、架橋特性が良好となり、得られる塗膜の耐水性および耐溶剤性も良好となる。また得られるポリウレタンウレア-アクリル複合樹脂水分散体の粘度が著しく高く、ゲル状となることがないことから、良好である。 In the present invention, the mixing ratio of (X) and (A2) is such that (A2) is 0.1 to 2.0 [mol] with respect to (X) 1000 [g] from the viewpoint of crosslinking properties. preferable. From the viewpoint of cross-linking properties and properties, it is more preferably 0.2 to 1.5 [mol], and still more preferably 0.3 to 1.0 [mol]. If it is these ranges, a crosslinking characteristic will become favorable and the water resistance and solvent resistance of the coating film obtained will also become favorable. Further, the obtained polyurethane urea-acrylic composite resin aqueous dispersion has a very high viscosity and does not become a gel.
本発明において、（Ａ）および（Ｘ）を水中に乳化分散する際には、使用する原材料やそのウレタンプレポリマー組成により、どうしても高粘性体での乳化が必要となる場合には、適宜、ノニオン系界面活性剤、アニオン系界面活性剤およびカチオン系界面活性剤のような界面活性剤を使用することも可能である。しかし本発明によれば、高粘性体とならない場合においては、実質的に含有することなく乳化分散することができる。界面活性剤を実質的に含有しないことにより、さらに優れた耐水性、耐溶剤性を得ることができることから、界面活性剤を実質的に含有しないことは、好ましい態様のひとつである。ここで実質的に含有しないとは、（Ａ）および（Ｘ）の重量和に対して０．５重量％以下のことをいうが、まったく含まないことが好ましい。 In the present invention, when (A) and (X) are emulsified and dispersed in water, depending on the raw materials used and the urethane prepolymer composition, emulsification with a high-viscosity material is absolutely necessary. Surfactants such as system surfactants, anionic surfactants and cationic surfactants can also be used. However, according to the present invention, when it does not become a highly viscous material, it can be emulsified and dispersed without being substantially contained. Since a further excellent water resistance and solvent resistance can be obtained by substantially not containing the surfactant, it is one of preferred embodiments that the surfactant is not substantially contained. Here, “substantially not containing” means 0.5% by weight or less with respect to the sum of the weights of (A) and (X), but it is preferably not contained at all.
本発明における多価アミン化合物（Ｙ）としては、特に限定されないが、例えば、ヒドラジド誘導体（Ｙ１）、（Ｙ１）に含まれないポリアミン類（Ｙ２）があげられる。前記ヒドラジド誘導体（Ｙ１）としては、特に限定されないが、例えば、シュウ酸ジヒドラジド，マロン酸ジヒドラジド，アジピン酸ジヒドラジド， アゼライン酸ジヒドラジド，コハク酸ジヒドラジド，セバシン酸ジヒドラジド， マレイン酸ジヒドラジド，フマル酸ジヒドラジド，イタコン酸ジヒドラジド、１，３− ビス（ヒドラジノカルボエチル）−５−イソプロピルヒダントイン、カルボヒドラジド、ドデカンジオヒドラジド、イソフタル酸ジヒドラジド、ヒドラジンなどがあげられる。また、分子末端遊離イソシアネート基を有するポリウレタンプレポリマーに対して１分子中に２個以上のヒドラジド基を有する化合物やヒドラジンを反応させて得られる、分子末端に−ＮＨＮＨ２基を有するポリウレタンプレポリマーも使用することができる。前記（Ｙ１）に含まれないポリアミン類としては、特に限定されないが、例えば、エチレンジアミン、プロピレンジアミン、ヘキシレンジアミン、イソホロンジアミン、キシリレンジアミン、ピペラジン、ジフェニルメタンジアミン、エチルトリレンジアミン、ジエチレントリアミン、ジプロピレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミンなどがあげられる。 The polyvalent amine compound (Y) in the present invention is not particularly limited, and examples thereof include polyamines (Y2) not included in the hydrazide derivatives (Y1) and (Y1). The hydrazide derivative (Y1) is not particularly limited, and examples thereof include oxalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, succinic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, Examples thereof include dihydrazide, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, carbohydrazide, dodecanediohydrazide, isophthalic acid dihydrazide, hydrazine and the like. In addition, a polyurethane prepolymer having a —NHNH 2 group at a molecular end obtained by reacting a compound having two or more hydrazide groups in one molecule or hydrazine with a polyurethane prepolymer having a molecular end free isocyanate group. Can be used. The polyamines not included in the (Y1) are not particularly limited. For example, ethylenediamine, propylenediamine, hexylenediamine, isophoronediamine, xylylenediamine, piperazine, diphenylmethanediamine, ethyltolylenediamine, diethylenetriamine, dipropylene. Examples include triamine, triethylenetetramine, and tetraethylenepentamine.
ポリウレタンウレア樹脂の末端は、アミノ基であることが好ましく、末端がヒドラジド基であることが、より好ましい。末端をアミノ基とする観点から、（多価アミン化合物（Ｙ）のアミノ基）／（ＮＣＯ末端ウレタンプレポリマー（Ｘ）の末端ＮＣＯ基）＝１．０５／１〜１．５／１となる範囲で鎖伸長させる事が好ましい。これらの範囲にすることにより、架橋特性により耐水性、耐溶剤性を飛躍的に向上させ、かつ乳化安定性にも優れるポリウレタンウレア-アクリル系複合樹脂水分散体を得ることができる。本発明において、多価アミン化合物（Ｙ）としては、少なくともヒドラジド誘導体（Ｙ１）を含有するものであれば、ヒドラジド誘導体（Ｙ１）単独であってもよいし、あるいはヒドラジド誘導体（Ｙ１）およびポリアミン類（Ｙ２）を両方用いてもよい。また、ヒドラジド基末端とすることにより、架橋特性により耐水性、耐溶剤性を飛躍的に向上させ、かつ乳化安定性にも優れるポリウレタンウレア-アクリル系複合樹脂水分散体を得ることができることから好ましい。また、エチレン性不飽和基含有ＮＣＯ基末端ウレタンプレポリマー（Ｘ１）を含有する系では、カルボニル基とポリウレタンウレア樹脂が反応することで架橋特性が向上し、さらに好ましい。 The terminal of the polyurethane urea resin is preferably an amino group, and more preferably a terminal is a hydrazide group. From the viewpoint of making the terminal an amino group, (amino group of polyvalent amine compound (Y)) / (terminal NCO group of NCO-terminated urethane prepolymer (X)) = 1.05 / 1 to 1.5 / 1. It is preferable to extend the chain in the range. By setting the content within these ranges, it is possible to obtain a polyurethaneurea-acrylic composite resin water dispersion that drastically improves water resistance and solvent resistance due to crosslinking properties and is excellent in emulsion stability. In the present invention, as the polyvalent amine compound (Y), as long as it contains at least the hydrazide derivative (Y1), the hydrazide derivative (Y1) alone may be used, or the hydrazide derivative (Y1) and polyamines may be used. Both (Y2) may be used. Further, it is preferable to use a hydrazide group terminal because a polyurethaneurea-acrylic composite resin aqueous dispersion can be obtained which drastically improves water resistance and solvent resistance due to crosslinking properties and is excellent in emulsion stability. . Moreover, in the system containing the ethylenically unsaturated group-containing NCO group-terminated urethane prepolymer (X1), the carbonyl group and the polyurethane urea resin react with each other, so that the cross-linking property is improved.
本発明においてヒドラジド誘導体（Ｙ１）の混合量としては、特に限定されないが、例えば、（Ａ）中のカルボニル基もしくはアルデヒド基に対して０．３〜１．２当量のヒドラジド基となるようにヒドラジド誘導体を混合させることが好ましく、０．５〜１．０当量がより好ましい。０．３当量以上であれば、架橋が十分となり、耐水、耐薬品性が良好となる。１．３当量以下であれば、耐水、耐ＭＥＫ性が良好となり、また未反応ヒドラジド化合物がブリードアウトすることもなく、透明性や耐水、耐ＭＥＫ性が低下することもない。 In the present invention, the mixing amount of the hydrazide derivative (Y1) is not particularly limited. For example, the amount of hydrazide is 0.3 to 1.2 equivalents of hydrazide group relative to the carbonyl group or aldehyde group in (A). It is preferable to mix a derivative, and 0.5 to 1.0 equivalent is more preferable. If it is 0.3 equivalent or more, crosslinking is sufficient and water resistance and chemical resistance are improved. If it is 1.3 equivalents or less, water resistance and MEK resistance will be good, unreacted hydrazide compounds will not bleed out, and transparency, water resistance and MEK resistance will not be reduced.
本発明において、エチレン性不飽和基を重合するとは、（Ａ）と（Ｘ）に含まれるエチレン性不飽和単量体を重合することをいう。重合する際には、重合開始剤を用いることが好ましい。重合開始剤としては、特に限定されないが、例えば、油溶性、水溶性の重合開始剤などがあげられる。前記油溶性の重合開始剤としては、特に限定されないが、例えば、ベンゾイルパーオキシド等の有機過酸化物、 アゾビスイソブチロニトリルなどが挙げられる。前記水溶性の重合開始剤としては、特に限定されないが、例えば、クメンハイドロパーオキサイド、ｔｅｒｔ−ブチルパーオキサイド等の有機過酸化物、アゾビス（２−メチルプロピオンニトリル）等のアゾ化合物、過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム等の過硫酸塩などがあげられる。これらは一種または二種以上を使用することができる。また、前記重合開始剤に、必要に応じて、糖、ナトリウムホルムアルデヒドスルホキシレート、亜硫酸ナトリウム等の還元剤と組み合わせて使用するとこができる。前記重合開始剤の使用量は、得られるポリウレタンウレア-アクリル系複合樹脂の量を基準にして、０．０１〜１重量％、特に０．０２〜０．５重量％の範囲内が好ましい。 In the present invention, polymerizing an ethylenically unsaturated group means polymerizing ethylenically unsaturated monomers contained in (A) and (X). When polymerizing, it is preferable to use a polymerization initiator. The polymerization initiator is not particularly limited, and examples thereof include oil-soluble and water-soluble polymerization initiators. The oil-soluble polymerization initiator is not particularly limited, and examples thereof include organic peroxides such as benzoyl peroxide and azobisisobutyronitrile. The water-soluble polymerization initiator is not particularly limited, and examples thereof include organic peroxides such as cumene hydroperoxide and tert-butyl peroxide, azo compounds such as azobis (2-methylpropiononitrile), and potassium persulfate. And persulfates such as ammonium persulfate and sodium persulfate. These can use 1 type, or 2 or more types. Further, the polymerization initiator can be used in combination with a reducing agent such as sugar, sodium formaldehyde sulfoxylate, sodium sulfite, etc., if necessary. The amount of the polymerization initiator used is preferably in the range of 0.01 to 1% by weight, particularly 0.02 to 0.5% by weight, based on the amount of the polyurethane urea-acrylic composite resin obtained.
本発明のポリウレタンウレア-アクリル系複合樹脂の水分散体の製造方法としては、エチレン性不飽和基含有化合物（Ａ）およびＮＣＯ基末端ウレタンプレポリマー（Ｘ）を、水中に乳化分散する工程と、多価アミン化合物（Ｙ）で鎖伸張する工程と、さらにエチレン性不飽和基を重合する工程を含む。前記（Ａ）が２以上のエチレン性不飽和基を有する化合物（Ａ１）を含有し、（Ｘ）と（Ａ１）の混合割合は（Ｘ）１０００［ｇ］に対して（Ａ１）が０．３〜７．０［ｍｏｌ×（Ａ１）中の平均不飽和基数］である。 As a method for producing an aqueous dispersion of the polyurethane urea-acrylic composite resin of the present invention, an ethylenically unsaturated group-containing compound (A) and an NCO group-terminated urethane prepolymer (X) are emulsified and dispersed in water; It includes a step of chain extending with the polyvalent amine compound (Y) and a step of polymerizing an ethylenically unsaturated group. The (A) contains the compound (A1) having two or more ethylenically unsaturated groups, and the mixing ratio of (X) and (A1) is (A1) is 0.1 with respect to (X) 1000 [g]. 3 to 7.0 [mol × (average number of unsaturated groups in (A1)]].
本発明の水中に乳化分散する工程における攪拌装置としては特に限定されない。低粘度のＮＣＯ末端プレポリマーであれば高せん断力を必要とせず通常の攪拌装置が好ましく使用でき、高粘度のＮＣＯ末端プレポリマーであれば、高エネルギーせん断能力を有する分散機、例えば、高圧ホモジナイザー、インライン・ローター・ステーター式ミキサーなどが好適に使用される。 The stirring device in the step of emulsifying and dispersing in water of the present invention is not particularly limited. A low-viscosity NCO-terminated prepolymer does not require a high shearing force and a normal stirring device can be preferably used. If a high-viscosity NCO-terminated prepolymer, a disperser having a high energy shearing capability, such as a high-pressure homogenizer An inline rotor-stator mixer or the like is preferably used.
本発明において、ポリウレタンウレア-アクリル系複合樹脂中の水分散体を得るためには、使用する原材料やそのウレタンプレポリマー組成により、どうしても高粘性体での乳化が必要となる場合には、有機溶剤を使用することも可能である。しかし本発明によれば、高粘性体とならない場合においては、実質的に有機溶剤を含有しないことは、好ましい態様のひとつである。有機溶剤を使用しないことにより、経済的にポリウレタンウレア-アクリル系複合樹脂中の水分散体を得ることができる。ここで実質的に含有しないとは、（Ａ）および（Ｘ）の重量和に対して０．５重量％以下のことをいうが、まったく含まないことが好ましい。 In the present invention, in order to obtain an aqueous dispersion in a polyurethaneurea-acrylic composite resin, depending on the raw materials used and the urethane prepolymer composition, an emulsification with a highly viscous material is absolutely necessary, an organic solvent Can also be used. However, according to the present invention, it is one of preferred embodiments that the organic solvent is not substantially contained in the case where the high viscosity body is not obtained. By not using an organic solvent, an aqueous dispersion in a polyurethane urea-acrylic composite resin can be obtained economically. Here, “substantially not containing” means 0.5% by weight or less with respect to the sum of the weights of (A) and (X), but it is preferably not contained at all.
本発明の水中に乳化分散する工程に使用するＮＣＯ末端ウレタンプレポリマーの温度としては特に限定されないが、例えば、８０℃以下であることが好ましく、６０℃以下であることがより好ましい。 Although it does not specifically limit as a temperature of the NCO terminal urethane prepolymer used for the process of emulsifying and dispersing in water of this invention, For example, it is preferable that it is 80 degrees C or less, and it is more preferable that it is 60 degrees C or less.
本発明において多価アミン化合物（Ｙ）で鎖伸張する工程としては、特に限定されないが、多価アミン化合物（Ｙ）の水溶液を徐々に加えながら鎖伸長することが好ましい。 In the present invention, the step of chain extension with the polyvalent amine compound (Y) is not particularly limited, but it is preferable to extend the chain while gradually adding an aqueous solution of the polyvalent amine compound (Y).
本発明において好ましい実施形態の、末端アミノ基がヒドラジド基である水系ポリウレタンウレア樹脂は、前記多価アミン化合物（Ｙ）が、少なくともヒドラジド誘導体（Ｙ１）を含有することで得られるが、ヒドラジド誘導体（Ｙ１）が高価であることからポリアミン類（Ｙ２）で鎖伸張をした後に、ヒドラジド誘導体（Ｙ１）を用いてヒドラジド末端とする、二段階で反応を行なうことが好ましい。 In the preferred embodiment of the present invention, the water-based polyurethane urea resin in which the terminal amino group is a hydrazide group is obtained when the polyvalent amine compound (Y) contains at least the hydrazide derivative (Y1). Since Y1) is expensive, it is preferable to carry out the reaction in two steps, after chain extension with polyamines (Y2) and then using hydrazide derivative (Y1) to make a hydrazide end.
本発明においてエチレン性不飽和基を重合する工程における重合開始剤の添加方法としては、特に限定されず、乳化前プレポリマーに添加してもよいが、水溶性開始剤では重合開始段階で水溶液として加えることが好ましい。 In the present invention, the addition method of the polymerization initiator in the step of polymerizing the ethylenically unsaturated group is not particularly limited, and may be added to the prepolymer before emulsification. It is preferable to add.
本発明においてエチレン性不飽和基を重合する工程における重合温度としては、特に限定されないが、例えば、８０℃以下であることが好ましく、６０℃以下であることがより好ましい。８０℃を超えると乳化物が凝集する。また開始剤や還元剤の添加は乳化物が凝集しないように希薄水溶液を徐々に添加する必要がある。 In the present invention, the polymerization temperature in the step of polymerizing the ethylenically unsaturated group is not particularly limited, but is preferably, for example, 80 ° C. or less, and more preferably 60 ° C. or less. When it exceeds 80 degreeC, an emulsion will aggregate. In addition, it is necessary to gradually add a dilute aqueous solution so that the emulsion does not aggregate in the addition of the initiator and the reducing agent.
本発明のポリウレタンウレア-アクリル系複合樹脂の水分散体中の不揮発分の重量は、ＪＩＳ Ｋ６８２８に準じて測定される値が１５〜６０％であることが経済性、安定性の観点から好ましい。 The weight of the nonvolatile content in the aqueous dispersion of the polyurethaneurea-acrylic composite resin of the present invention is preferably 15 to 60% as measured in accordance with JIS K6828 from the viewpoints of economy and stability.
本発明のポリウレタンウレア-アクリル系複合樹脂の水分散体の粘度は、乳化安定性、使用性の観点から、２０℃において、ＢＭ型粘度計（東京計器社製）を使用し、ＪＩＳ Ｚ８８０３に準じて測定される値が５〜１００００（２０℃ ｍＰａ・ｓ）であることが好ましい。 The viscosity of the aqueous dispersion of the polyurethane urea-acrylic composite resin of the present invention is in accordance with JIS Z8803 using a BM viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 20 ° C. from the viewpoint of emulsion stability and usability. The measured value is preferably 5 to 10,000 (20 ° C. mPa · s).
本発明のポリウレタンウレア-アクリル系複合樹脂の水分散体の粒子径は、乳化安定性の観点から、ＭｉｃｒｏｔｒａｃＵＰＡ−ＵＺ１５２（日機装社製）にて測定し、５０％平均値を粒子径として算出される値が０．６μｍ以下であることが好ましい。 The particle size of the aqueous dispersion of the polyurethane urea-acrylic composite resin of the present invention is measured with MicrotracUPA-UZ152 (manufactured by Nikkiso Co., Ltd.) from the viewpoint of emulsion stability, and the 50% average value is calculated as the particle size. The value is preferably 0.6 μm or less.
本発明のポリウレタンウレア-アクリル系複合樹脂の乳化安定性は、実施例に記載の方法において、粘度変化や沈降のないことが好ましい。 The emulsification stability of the polyurethane urea-acrylic composite resin of the present invention is preferably such that there is no change in viscosity or sedimentation in the methods described in the examples.
本発明のポリウレタンウレア-アクリル系複合樹脂の水分散体の硬化物の耐水性は、実施例に記載の方法において、１５０％以下が好ましく、７０％以下がより好ましい。また膨潤やタックが少なく、白化やまた強度低下の少ないことが好ましい。 The water resistance of the cured product of the aqueous dispersion of the polyurethaneurea-acrylic composite resin of the present invention is preferably 150% or less, more preferably 70% or less in the method described in the examples. Moreover, it is preferable that there is little swelling and tack, and there is little whitening and a strength fall.
本発明のポリウレタンウレア-アクリル系複合樹脂の水分散体の硬化物の耐MEK性は、実施例に記載の方法において、３００％以下が好ましく、２００％以下がより好ましい。また膨潤やタックが少なく、また強度低下の少ないことが好ましい。 The MEK resistance of the cured product of the aqueous dispersion of the polyurethaneurea-acrylic composite resin of the present invention is preferably 300% or less, more preferably 200% or less in the method described in the examples. Moreover, it is preferable that there is little swelling and tackiness, and there is little decrease in strength.
本発明のポリウレタンウレア-アクリル系複合樹脂中の水分散体には本発明の効果を阻害しない範囲内で、充填剤、難燃剤、消泡剤、防菌剤、防錆剤、安定剤、可塑剤、増粘剤、防黴剤、他の水系分散樹脂等の添加剤を含むことができる。 The aqueous dispersion in the polyurethane urea-acrylic composite resin of the present invention has a filler, a flame retardant, an antifoaming agent, an antibacterial agent, a rust preventive, a stabilizer, a plasticizer, as long as the effects of the present invention are not impaired. Additives such as an agent, a thickener, an antifungal agent, and other aqueous dispersion resins can be included.
以下、実施例及び比較例に基づいて、本発明のポリウレタンウレア-アクリル系複合樹脂中の水分散体について詳細に説明する。本発明はこれらの実施例に限定されるものではない。なお、本明細書中に於ける「部」、「％」は、特に明示した場合を除き、「質量部」、「質量％」をそれぞれ表している。 Hereinafter, based on an Example and a comparative example, the water dispersion in the polyurethane urea-acrylic-type composite resin of this invention is demonstrated in detail. The present invention is not limited to these examples. In the present specification, “parts” and “%” represent “parts by mass” and “mass%”, respectively, unless otherwise specified.
（実施例１）
２官能のプロピレングリコール（数平均分子量２０００）６４８部、ジメチロールプロピオン酸４８部、イソホロンジイソシアネート３０４部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量５．７％、カルボキシル基酸価２０ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーにジペンタエリスリトールヘキサアクリレート２００部を混合し６０℃迄冷却後、トリエチルアミン３６部を混合後、乳化水（２０℃）１７００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン３７部を水２００部に稀釈した水溶液を仕込み高分子量化した。得られた乳化物を３０℃まで冷却後、ｔｅｒｔ−ブチルパーオキサイド２部を水５０部に稀釈した水溶液を仕込み、その後亜硫酸ソーダ２部を水５０部に稀釈した水溶液を仕込み重合を開始した。その後５０℃の温度にて３０分反応させて、ポリウレタンウレア-アクリル系複合樹脂の水分散体を得た。
Example 1
648 parts of bifunctional propylene glycol (number average molecular weight 2000), 48 parts of dimethylolpropionic acid, and 304 parts of isophorone diisocyanate were charged and reacted at a temperature of 90 ° C. for 60 minutes to obtain an isocyanate group content of 5.7% and a carboxyl group. A urethane prepolymer having an acid value of 20 mgKOH / g was obtained. 200 parts of dipentaerythritol hexaacrylate was mixed with the obtained urethane prepolymer, cooled to 60 ° C., mixed with 36 parts of triethylamine, charged with 1700 parts of emulsified water (20 ° C.), and a homomixer (Homomixer MARKII manufactured by PRIMIX Co., Ltd.). And emulsified. Next, an aqueous solution in which 37 parts of ethylenediamine was diluted in 200 parts of water was added to increase the molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution in which 2 parts of tert-butyl peroxide was diluted in 50 parts of water was charged, and then an aqueous solution in which 2 parts of sodium sulfite was diluted in 50 parts of water was charged to initiate polymerization. Thereafter, the mixture was reacted at a temperature of 50 ° C. for 30 minutes to obtain an aqueous dispersion of a polyurethane urea-acrylic composite resin.
（実施例２）
２官能のプロピレングリコール（数平均分子量２０００）６４８部、ジメチロールプロピオン酸４８部、イソホロンジイソシアネート３０４部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量５．７％、カルボキシル基酸価２０ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーにペンタエリスリトールテトラアクリレート２００部を混合し６０℃迄冷却後、トリエチルアミン３６部を混合後、乳化水（２０℃）１７００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン３７部を水２００部に稀釈した水溶液を仕込み高分子量化した。得られた乳化物を３０℃まで冷却後、ｔｅｒｔ−ブチルパーオキサイド２部を水５０部に稀釈した水溶液を仕込み、その後亜硫酸ソーダ２部を水５０部に稀釈した水溶液を仕込み重合を開始した。その後５０℃の温度にて３０分反応させて、ポリウレタンウレア-アクリル系複合樹脂の水分散体を得た。
(Example 2)
648 parts of bifunctional propylene glycol (number average molecular weight 2000), 48 parts of dimethylolpropionic acid, and 304 parts of isophorone diisocyanate were charged and reacted at a temperature of 90 ° C. for 60 minutes to obtain an isocyanate group content of 5.7% and a carboxyl group. A urethane prepolymer having an acid value of 20 mgKOH / g was obtained. 200 parts of pentaerythritol tetraacrylate was mixed with the obtained urethane prepolymer, cooled to 60 ° C., mixed with 36 parts of triethylamine, charged with 1700 parts of emulsified water (20 ° C.), and put into a homomixer (Homomixer MARKII manufactured by Primics). Mixed and emulsified. Next, an aqueous solution in which 37 parts of ethylenediamine was diluted in 200 parts of water was added to increase the molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution in which 2 parts of tert-butyl peroxide was diluted in 50 parts of water was charged, and then an aqueous solution in which 2 parts of sodium sulfite was diluted in 50 parts of water was charged to initiate polymerization. Thereafter, the mixture was reacted at a temperature of 50 ° C. for 30 minutes to obtain an aqueous dispersion of a polyurethane urea-acrylic composite resin.
（実施例３）
２官能のプロピレングリコール（数平均分子量２０００）６４８部、ジメチロールプロピオン酸４８部、イソホロンジイソシアネート３０４部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量５．７％、カルボキシル基酸価２０ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーにジペンタエリスリトールヘキサアクリレート１００部、ダイアセトンアクリルアミド１００部を混合し６０℃迄冷却後、トリエチルアミン３６部を混合後、乳化水（２０℃）２７００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン３７部を水２００部に稀釈した水溶液を仕込み高分子量化した。得られた乳化物を３０℃まで冷却後、ｔｅｒｔ−ブチルパーオキサイド２部を水５０部に稀釈した水溶液を仕込み、その後亜硫酸ソーダ２部を水５０部に稀釈した水溶液を仕込み重合を開始した。その後５０℃の温度にて３０分反応させて、ポリウレタンウレア-アクリル系複合樹脂の水分散体を得た。
Example 3
648 parts of bifunctional propylene glycol (number average molecular weight 2000), 48 parts of dimethylolpropionic acid, and 304 parts of isophorone diisocyanate were charged and reacted at a temperature of 90 ° C. for 60 minutes to obtain an isocyanate group content of 5.7% and a carboxyl group. A urethane prepolymer having an acid value of 20 mgKOH / g was obtained. To the obtained urethane prepolymer, 100 parts of dipentaerythritol hexaacrylate and 100 parts of diacetone acrylamide were mixed, cooled to 60 ° C, mixed with 36 parts of triethylamine, charged with 2700 parts of emulsified water (20 ° C), and homomixer ( The mixture was mixed and emulsified with a homomixer MARKII manufactured by Primix. Next, an aqueous solution in which 37 parts of ethylenediamine was diluted in 200 parts of water was added to increase the molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution in which 2 parts of tert-butyl peroxide was diluted in 50 parts of water was charged, and then an aqueous solution in which 2 parts of sodium sulfite was diluted in 50 parts of water was charged to initiate polymerization. Thereafter, the mixture was reacted at a temperature of 50 ° C. for 30 minutes to obtain an aqueous dispersion of a polyurethane urea-acrylic composite resin.
（実施例４）
２官能のプロピレングリコール（数平均分子量２０００）６４８部、ジメチロールプロピオン酸４８部、イソホロンジイソシアネート３０４部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量５．７％、カルボキシル基酸価２０ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーにジペンタエリスリトールヘキサアクリレート１００部、ダイアセトンアクリルアミド１００部を混合し６０℃迄冷却後、トリエチルアミン３６部を混合後、乳化水（２０℃）２７００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン３７部を水２００部に稀釈した水溶液を仕込み高分子量化した。得られた乳化物を３０℃まで冷却後、ｔｅｒｔ−ブチルパーオキサイド２部を水５０部に稀釈した水溶液を仕込み、その後亜硫酸ソーダ２部を水５０部に稀釈した水溶液を仕込み重合を開始した。その後５０℃の温度にて３０分反応させ、さらにアジピン酸ジヒドラジドを５１部混合溶解することで、ポリウレタンウレア-アクリル系複合樹脂の水分散体を得た。
Example 4
648 parts of bifunctional propylene glycol (number average molecular weight 2000), 48 parts of dimethylolpropionic acid, and 304 parts of isophorone diisocyanate were charged and reacted at a temperature of 90 ° C. for 60 minutes to obtain an isocyanate group content of 5.7% and a carboxyl group. A urethane prepolymer having an acid value of 20 mgKOH / g was obtained. To the obtained urethane prepolymer, 100 parts of dipentaerythritol hexaacrylate and 100 parts of diacetone acrylamide were mixed, cooled to 60 ° C, mixed with 36 parts of triethylamine, charged with 2700 parts of emulsified water (20 ° C), and homomixer ( The mixture was mixed and emulsified with a homomixer MARKII manufactured by Primix. Next, an aqueous solution in which 37 parts of ethylenediamine was diluted in 200 parts of water was added to increase the molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution in which 2 parts of tert-butyl peroxide was diluted in 50 parts of water was charged, and then an aqueous solution in which 2 parts of sodium sulfite was diluted in 50 parts of water was charged to initiate polymerization. Thereafter, the mixture was reacted at a temperature of 50 ° C. for 30 minutes, and 51 parts of adipic acid dihydrazide was mixed and dissolved to obtain an aqueous dispersion of a polyurethaneurea-acrylic composite resin.
（実施例４−２）
２官能のプロピレングリコール（数平均分子量２０００）６４８部、ジメチロールプロピオン酸４８部、イソホロンジイソシアネート３０４部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量５．７％、カルボキシル基酸価２０ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーにジペンタエリスリトールヘキサアクリレート５０部、ダイアセトンアクリルアミド１００部を混合し６０℃迄冷却後、トリエチルアミン３６部を混合後、乳化水（２０℃）２７００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン３７部を水２００部に稀釈した水溶液を仕込み高分子量化した。得られた乳化物を３０℃まで冷却後、ｔｅｒｔ−ブチルパーオキサイド２部を水５０部に稀釈した水溶液を仕込み、その後亜硫酸ソーダ２部を水５０部に稀釈した水溶液を仕込み重合を開始した。その後５０℃の温度にて３０分反応させ、さらにアジピン酸ジヒドラジドを５１部混合溶解することで、ポリウレタンウレア-アクリル系複合樹脂の水分散体を得た。
(Example 4-2)
648 parts of bifunctional propylene glycol (number average molecular weight 2000), 48 parts of dimethylolpropionic acid, and 304 parts of isophorone diisocyanate were charged and reacted at a temperature of 90 ° C. for 60 minutes to obtain an isocyanate group content of 5.7% and a carboxyl group. A urethane prepolymer having an acid value of 20 mgKOH / g was obtained. The obtained urethane prepolymer was mixed with 50 parts of dipentaerythritol hexaacrylate and 100 parts of diacetone acrylamide, cooled to 60 ° C., mixed with 36 parts of triethylamine, and charged with 2700 parts of emulsified water (20 ° C.). The mixture was mixed and emulsified with a homomixer MARKII manufactured by Primix. Next, an aqueous solution in which 37 parts of ethylenediamine was diluted in 200 parts of water was added to increase the molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution in which 2 parts of tert-butyl peroxide was diluted in 50 parts of water was charged, and then an aqueous solution in which 2 parts of sodium sulfite was diluted in 50 parts of water was charged to initiate polymerization. Thereafter, the mixture was reacted at a temperature of 50 ° C. for 30 minutes, and 51 parts of adipic acid dihydrazide was mixed and dissolved to obtain an aqueous dispersion of a polyurethaneurea-acrylic composite resin.
（実施例４−３）
２官能のプロピレングリコール（数平均分子量２０００）６４８部、ジメチロールプロピオン酸４８部、イソホロンジイソシアネート２７４部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量４．８％、カルボキシル基酸価２１ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーに、１，６−ヘキサンジオールジアクリレート５００部、ダイアセトンアクリルアミド１００部を混合し６０℃迄冷却後、トリエチルアミン３６部を混合後、乳化水（２０℃）２７００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン３２部を水２００部に稀釈した水溶液を仕込み高分子量化した。得られた乳化物を３０℃まで冷却後、ｔｅｒｔ−ブチルパーオキサイド２部を水５０部に稀釈した水溶液を仕込み、その後亜硫酸ソーダ２部を水５０部に稀釈した水溶液を仕込み重合を開始した。その後５０℃の温度にて３０分反応させ、さらにアジピン酸ジヒドラジドを５１部混合溶解することで、ポリウレタンウレア-アクリル系複合樹脂の水分散体を得た。
(Example 4-3)
648 parts of a bifunctional propylene glycol (number average molecular weight 2000), 48 parts of dimethylolpropionic acid, and 274 parts of isophorone diisocyanate were charged and reacted at a temperature of 90 ° C. for 60 minutes to have an isocyanate group content of 4.8% and a carboxyl group. A urethane prepolymer having an acid value of 21 mgKOH / g was obtained. The obtained urethane prepolymer was mixed with 500 parts of 1,6-hexanediol diacrylate and 100 parts of diacetone acrylamide, cooled to 60 ° C., mixed with 36 parts of triethylamine, and charged with 2700 parts of emulsified water (20 ° C.). The mixture was mixed and emulsified with a homomixer (Homomixer MARKII manufactured by PRIMIX Corporation). Next, an aqueous solution obtained by diluting 32 parts of ethylenediamine in 200 parts of water was added to increase the molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution in which 2 parts of tert-butyl peroxide was diluted in 50 parts of water was charged, and then an aqueous solution in which 2 parts of sodium sulfite was diluted in 50 parts of water was charged to initiate polymerization. Thereafter, the mixture was reacted at a temperature of 50 ° C. for 30 minutes, and 51 parts of adipic acid dihydrazide was mixed and dissolved to obtain an aqueous dispersion of a polyurethaneurea-acrylic composite resin.
（実施例５）
２官能のプロピレングリコール（数平均分子量２０００）６４８部、ジメチロールプロピオン酸４８部、イソホロンジイソシアネート３０４部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量５．６％、カルボキシル基酸価２０ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーに１，６−ヘキサンジオールジアクリレート２００部、ダイアセトンアクリルアミド１５０部を混合溶解し６０℃迄冷却後、トリエチルアミン３６部を混合後、乳化水（２０℃）２９００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン３３部を水１００部に稀釈した水溶液を仕込み高分子量化した後、５分後にアジピン酸ジヒドラジド４２部を４０℃温水２００部に稀釈した水溶液を仕込み高分子量化した。さらに、得られた乳化物を３０℃まで冷却後、ｔｅｒｔ−ブチルパーオキサイド２部を水５０部に稀釈した水溶液を仕込み、その後亜硫酸ソーダ２部を水５０部に稀釈した水溶液を仕込み重合を開始した。その後５０℃の温度にて３０分反応させ、さらにアジピン酸ジヒドラジドを５６部混合溶解することで、ポリウレタンウレア-アクリル系複合樹脂の水分散体を得た。
(Example 5)
648 parts of bifunctional propylene glycol (number average molecular weight 2000), 48 parts of dimethylolpropionic acid, and 304 parts of isophorone diisocyanate were charged and reacted at a temperature of 90 ° C. for 60 minutes to have an isocyanate group content of 5.6% and a carboxyl group. A urethane prepolymer having an acid value of 20 mgKOH / g was obtained. 200 parts of 1,6-hexanediol diacrylate and 150 parts of diacetone acrylamide are mixed and dissolved in the obtained urethane prepolymer, cooled to 60 ° C., mixed with 36 parts of triethylamine, and charged with 2900 parts of emulsified water (20 ° C.). The mixture was mixed and emulsified with a homomixer (Homomixer MARKII manufactured by PRIMIX Corporation). Next, an aqueous solution in which 33 parts of ethylenediamine was diluted in 100 parts of water was charged to increase the molecular weight, and after 5 minutes, an aqueous solution in which 42 parts of adipic dihydrazide was diluted in 200 parts of 40 ° C. warm water was charged to increase the molecular weight. Furthermore, after cooling the obtained emulsion to 30 ° C., an aqueous solution in which 2 parts of tert-butyl peroxide was diluted in 50 parts of water was added, and then an aqueous solution in which 2 parts of sodium sulfite was diluted in 50 parts of water was added to initiate polymerization. did. Thereafter, the mixture was reacted at a temperature of 50 ° C. for 30 minutes, and 56 parts of adipic acid dihydrazide was mixed and dissolved to obtain an aqueous dispersion of a polyurethane urea-acrylic composite resin.
（実施例５−２）
３メチル−１，５−ペンタンジオールとアジピン酸からなるポリエステルポリオール（数平均分子量２０００）６４８部、ジメチロールプロピオン酸４８部、イソホロンジイソシアネート３０４部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量５．６％、カルボキシル基酸価２０ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーに１，６−ヘキサンジオールジアクリレート２００部、ダイアセトンアクリルアミド２００部を混合溶解し６０℃迄冷却後、トリエチルアミン３６部を混合後、乳化水（２０℃）３１００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン３３部を水１００部に稀釈した水溶液を仕込み高分子量化した後、５分後にアジピン酸ジヒドラジド４２部を４０℃温水２００部に稀釈した水溶液を仕込み高分子量化した。さらに、得られた乳化物を３０℃まで冷却後、ｔｅｒｔ−ブチルパーオキサイド２部を水５０部に稀釈した水溶液を仕込み、その後亜硫酸ソーダ２部を水５０部に稀釈した水溶液を仕込み重合を開始した。その後５０℃の温度にて３０分反応させ、さらにアジピン酸ジヒドラジドを８２部混合溶解することで、ポリウレタンウレア-アクリル系複合樹脂の水分散体を得た。
(Example 5-2)
648 parts of a polyester polyol (number average molecular weight 2000) composed of 3-methyl-1,5-pentanediol and adipic acid, 48 parts of dimethylolpropionic acid, and 304 parts of isophorone diisocyanate were charged and reacted at a temperature of 90 ° C. for 60 minutes. A urethane prepolymer having an isocyanate group content of 5.6% and a carboxyl group acid value of 20 mgKOH / g was obtained. 200 parts of 1,6-hexanediol diacrylate and 200 parts of diacetone acrylamide are mixed and dissolved in the obtained urethane prepolymer, cooled to 60 ° C., mixed with 36 parts of triethylamine, and charged with 3100 parts of emulsified water (20 ° C.). The mixture was mixed and emulsified with a homomixer (Homomixer MARKII manufactured by PRIMIX Corporation). Next, an aqueous solution in which 33 parts of ethylenediamine was diluted in 100 parts of water was charged to increase the molecular weight, and after 5 minutes, an aqueous solution in which 42 parts of adipic dihydrazide was diluted in 200 parts of 40 ° C. warm water was charged to increase the molecular weight. Furthermore, after cooling the obtained emulsion to 30 ° C., an aqueous solution in which 2 parts of tert-butyl peroxide was diluted in 50 parts of water was added, and then an aqueous solution in which 2 parts of sodium sulfite was diluted in 50 parts of water was added to initiate polymerization. did. Thereafter, the mixture was reacted at a temperature of 50 ° C. for 30 minutes, and further 82 parts of adipic acid dihydrazide was mixed and dissolved to obtain an aqueous dispersion of a polyurethane urea-acrylic composite resin.
（実施例５−３）
３メチル−１，５−ペンタンジオールとアジピン酸からなるポリエステルポリオール（数平均分子量２０００）６７３部、ジメチロールプロピオン酸４１部、イソホロンジイソシアネート２８６部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量５．４％、カルボキシル基酸価１７ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーに１，６−ヘキサンジオールジアクリレート２００部、ダイアセトンアクリルアミド２５０部を混合溶解し６０℃迄冷却後、トリエチルアミン３６部を混合後、乳化水（２０℃）３３００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン３１部を水１００部に稀釈した水溶液を仕込み高分子量化した後、５分後にアジピン酸ジヒドラジド４２部を４０℃温水２００部に稀釈した水溶液を仕込み高分子量化した。さらに、得られた乳化物を３０℃まで冷却後、ｔｅｒｔ−ブチルパーオキサイド２部を水５０部に稀釈した水溶液を仕込み、その後亜硫酸ソーダ２部を水５０部に稀釈した水溶液を仕込み重合を開始した。その後５０℃の温度にて３０分反応させ、さらにアジピン酸ジヒドラジドを８２部混合溶解することで、ポリウレタンウレア-アクリル系複合樹脂の水分散体を得た。
(Example 5-3)
673 parts of a polyester polyol (number average molecular weight 2000) consisting of 3-methyl-1,5-pentanediol and adipic acid, 41 parts of dimethylolpropionic acid, and 286 parts of isophorone diisocyanate are charged and reacted at a temperature of 90 ° C. for 60 minutes. A urethane prepolymer having an isocyanate group content of 5.4% and a carboxyl group acid value of 17 mgKOH / g was obtained. 200 parts of 1,6-hexanediol diacrylate and 250 parts of diacetone acrylamide are mixed and dissolved in the obtained urethane prepolymer, cooled to 60 ° C., mixed with 36 parts of triethylamine, and charged with 3300 parts of emulsified water (20 ° C.). The mixture was mixed and emulsified with a homomixer (Homomixer MARKII manufactured by PRIMIX Corporation). Next, an aqueous solution in which 31 parts of ethylenediamine was diluted in 100 parts of water was charged to increase the molecular weight, and 5 minutes later, an aqueous solution in which 42 parts of adipic dihydrazide was diluted in 200 parts of 40 ° C. warm water was charged to increase the molecular weight. Furthermore, after cooling the obtained emulsion to 30 ° C., an aqueous solution in which 2 parts of tert-butyl peroxide was diluted in 50 parts of water was added, and then an aqueous solution in which 2 parts of sodium sulfite was diluted in 50 parts of water was added to initiate polymerization. did. Thereafter, the mixture was reacted at a temperature of 50 ° C. for 30 minutes, and further 82 parts of adipic acid dihydrazide was mixed and dissolved to obtain an aqueous dispersion of a polyurethane urea-acrylic composite resin.
（実施例６）
２官能のプロピレングリコール（数平均分子量２０００）６４８部、ジメチロールプロピオン酸４８部、イソホロンジイソシアネート３０４部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量５．６％、カルボキシル基酸価２０ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーにジペンタエリスリトールヘキサアクリレート２００部、ダイアセトンアクリルアミド１００部を混合溶解し６０℃迄冷却後、トリエチルアミン３６部を混合後、乳化水（２０℃）２１００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン２９部を水１００部に稀釈した水溶液を仕込み高分子量化した後、５分後にアジピン酸ジヒドラジド６４部を４０℃温水２００部に稀釈した水溶液を仕込み高分子量化した。さらに、得られた乳化物を３０℃まで冷却後、ｔｅｒｔ−ブチルパーオキサイド２部を水５０部に稀釈した水溶液を仕込み、その後亜硫酸ソーダ２部を水５０部に稀釈した水溶液を仕込み重合を開始した。その後５０℃の温度にて３０分反応させてポリウレタンウレア-アクリル系複合樹脂の水分散体を得た。
(Example 6)
648 parts of bifunctional propylene glycol (number average molecular weight 2000), 48 parts of dimethylolpropionic acid, and 304 parts of isophorone diisocyanate were charged and reacted at a temperature of 90 ° C. for 60 minutes to have an isocyanate group content of 5.6% and a carboxyl group. A urethane prepolymer having an acid value of 20 mgKOH / g was obtained. 200 parts of dipentaerythritol hexaacrylate and 100 parts of diacetone acrylamide are mixed and dissolved in the obtained urethane prepolymer, cooled to 60 ° C., mixed with 36 parts of triethylamine, and charged with 2100 parts of emulsified water (20 ° C.). The mixture was mixed and emulsified with a homomixer MARKII manufactured by PRIMIX. Next, an aqueous solution in which 29 parts of ethylenediamine was diluted in 100 parts of water was charged to increase the molecular weight, and 5 minutes later, an aqueous solution in which 64 parts of adipic acid dihydrazide was diluted in 200 parts of warm water at 40 ° C. was charged to increase the molecular weight. Furthermore, after cooling the obtained emulsion to 30 ° C., an aqueous solution in which 2 parts of tert-butyl peroxide was diluted in 50 parts of water was added, and then an aqueous solution in which 2 parts of sodium sulfite was diluted in 50 parts of water was added to initiate polymerization. did. Thereafter, the mixture was reacted at a temperature of 50 ° C. for 30 minutes to obtain an aqueous dispersion of a polyurethane urea-acrylic composite resin.
（実施例７）
２官能のプロピレングリコール（数平均分子量２０００）６４５部、ジメチロールプロピオン酸４８部、ヒドロキシエチルアクリレート１．３部、イソホロンジイソシアネート３０５部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量５．７％、カルボキシル基酸価２０ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーにダイアセトンアクリルアミド１００部、ジペンタエリスリトールヘキサアクリレート２００部を混合し６０℃迄冷却後、トリエチルアミン３６部を混合後、乳化水（２０℃）１９００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン３７部を水２００部に稀釈した水溶液を仕込み高分子量化した。得られた乳化物を３０℃まで冷却後、ｔｅｒｔ−ブチルパーオキサイド２部を水１００部に稀釈した水溶液を仕込み、その後亜硫酸ソーダ２部を水１００部に稀釈した水溶液を仕込み重合を開始した。その後５０℃の温度にて３０分反応させ、さらにアジピン酸ジヒドラジドを５１部混合溶解することで、ポリウレタンウレア-アクリル系複合樹脂の水分散体を得た。
(Example 7)
645 parts of bifunctional propylene glycol (number average molecular weight 2000), 48 parts of dimethylolpropionic acid, 1.3 parts of hydroxyethyl acrylate, 305 parts of isophorone diisocyanate are charged and reacted at a temperature of 90 ° C. for 60 minutes. A urethane prepolymer having a content of 5.7% and a carboxyl group acid value of 20 mgKOH / g was obtained. The obtained urethane prepolymer was mixed with 100 parts of diacetone acrylamide and 200 parts of dipentaerythritol hexaacrylate, cooled to 60 ° C., mixed with 36 parts of triethylamine, and charged with 1900 parts of emulsified water (20 ° C.). The mixture was mixed and emulsified with a homomixer MARKII manufactured by Primix. Next, an aqueous solution in which 37 parts of ethylenediamine was diluted in 200 parts of water was added to increase the molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution in which 2 parts of tert-butyl peroxide was diluted in 100 parts of water was charged, and then an aqueous solution in which 2 parts of sodium sulfite was diluted in 100 parts of water was charged to initiate polymerization. Thereafter, the mixture was reacted at a temperature of 50 ° C. for 30 minutes, and 51 parts of adipic acid dihydrazide was mixed and dissolved to obtain an aqueous dispersion of a polyurethaneurea-acrylic composite resin.
（実施例７-２）
２官能のプロピレングリコール（数平均分子量２０００）５４４部、ジメチロールプロピオン酸４６部、ヒドロキシエチルアクリレート４７部、イソホロンジイソシアネート３６３部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量６．９％、カルボキシル基酸価１９ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーにダイアセトンアクリルアミド１００部、ジペンタエリスリトールヘキサアクリレート２００部を混合し６０℃迄冷却後、トリエチルアミン３６部を混合後、乳化水（２０℃）１９００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン４６部を水２００部に稀釈した水溶液を仕込み高分子量化した。得られた乳化物を３０℃まで冷却後、ｔｅｒｔ−ブチルパーオキサイド２部を水１００部に稀釈した水溶液を仕込み、その後亜硫酸ソーダ２部を水１００部に稀釈した水溶液を仕込み重合を開始した。その後５０℃の温度にて３０分反応させ、さらにアジピン酸ジヒドラジドを５１部混合溶解することで、ポリウレタンウレア-アクリル系複合樹脂の水分散体を得た。
(Example 2-2)
544 parts of bifunctional propylene glycol (number average molecular weight 2000), 46 parts of dimethylolpropionic acid, 47 parts of hydroxyethyl acrylate and 363 parts of isophorone diisocyanate were charged and reacted at 90 ° C. for 60 minutes to obtain an isocyanate group content of 6 A urethane prepolymer having a carboxyl group acid value of 19 mgKOH / g was obtained. The obtained urethane prepolymer was mixed with 100 parts of diacetone acrylamide and 200 parts of dipentaerythritol hexaacrylate, cooled to 60 ° C., mixed with 36 parts of triethylamine, and charged with 1900 parts of emulsified water (20 ° C.). The mixture was mixed and emulsified with a homomixer MARKII manufactured by Primix. Next, an aqueous solution in which 46 parts of ethylenediamine was diluted in 200 parts of water was added to increase the molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution in which 2 parts of tert-butyl peroxide was diluted in 100 parts of water was charged, and then an aqueous solution in which 2 parts of sodium sulfite was diluted in 100 parts of water was charged to initiate polymerization. Thereafter, the mixture was reacted at a temperature of 50 ° C. for 30 minutes, and 51 parts of adipic acid dihydrazide was mixed and dissolved to obtain an aqueous dispersion of a polyurethaneurea-acrylic composite resin.
（実施例８）
２官能のプロピレングリコール（数平均分子量２０００）６４５部、ジメチロールプロピオン酸４８部、ヒドロキシエチルアクリレート１．３部、イソホロンジイソシアネート３０５部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量５．７％、カルボキシル基酸価２０ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーにダイアセトンアクリルアミド１００部、１，６−ヘキサンジオールアクリレート３００部を混合し６０℃迄冷却後、トリエチルアミン３６部を混合後、乳化水（２０℃）２１００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン３７部を水２００部に稀釈した水溶液を仕込み高分子量化した。得られた乳化物を３０℃まで冷却後、ｔｅｒｔ−ブチルパーオキサイド２部を水１００部に稀釈した水溶液を仕込み、その後亜硫酸ソーダ２部を水１００部に稀釈した水溶液を仕込み重合を開始した。その後５０℃の温度にて３０分反応させ、さらにアジピン酸ジヒドラジドを５１部混合溶解することで、ポリウレタンウレア-アクリル系複合樹脂の水分散体を得た。
(Example 8)
645 parts of bifunctional propylene glycol (number average molecular weight 2000), 48 parts of dimethylolpropionic acid, 1.3 parts of hydroxyethyl acrylate, 305 parts of isophorone diisocyanate are charged and reacted at a temperature of 90 ° C. for 60 minutes. A urethane prepolymer having a content of 5.7% and a carboxyl group acid value of 20 mgKOH / g was obtained. To the obtained urethane prepolymer, 100 parts of diacetone acrylamide and 300 parts of 1,6-hexanediol acrylate were mixed, cooled to 60 ° C., mixed with 36 parts of triethylamine, and charged with 2100 parts of emulsified water (20 ° C.). The mixture was mixed and emulsified with a mixer (Homomixer MARKII manufactured by PRIMIX Corporation). Next, an aqueous solution in which 37 parts of ethylenediamine was diluted in 200 parts of water was added to increase the molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution in which 2 parts of tert-butyl peroxide was diluted in 100 parts of water was charged, and then an aqueous solution in which 2 parts of sodium sulfite was diluted in 100 parts of water was charged to initiate polymerization. Thereafter, the mixture was reacted at a temperature of 50 ° C. for 30 minutes, and 51 parts of adipic acid dihydrazide was mixed and dissolved to obtain an aqueous dispersion of a polyurethaneurea-acrylic composite resin.
（実施例９）
２官能のプロピレングリコール（数平均分子量２０００）６４１部、ジメチロールプロピオン酸４８部、グリセリンモノメタクリレート３部、イソホロンジイソシアネート３０９部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量５．８％、カルボキシル基酸価２０ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーにダイアセトンアクリルアミド１００部、ジペンタエリスリトールヘキサアクリレート２００部を混合し６０℃迄冷却後、トリエチルアミン３６部を混合後、乳化水（２０℃）２１００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン３９部を水２００部に稀釈した水溶液を仕込み高分子量化した。得られた乳化物を３０℃まで冷却後、ｔｅｒｔ−ブチルパーオキサイド２部を水１００部に稀釈した水溶液を仕込み、その後亜硫酸ソーダ２部を水１００部に稀釈した水溶液を仕込み重合を開始した。その後５０℃の温度にて３０分反応させ、さらにアジピン酸ジヒドラジドを５１部混合溶解することで、ポリウレタンウレア-アクリル系複合樹脂の水分散体を得た。
Example 9
A difunctional propylene glycol (number average molecular weight 2000) 641 parts, dimethylolpropionic acid 48 parts, glycerin monomethacrylate 3 parts, isophorone diisocyanate 309 parts were charged and reacted at 90 ° C. for 60 minutes to give an isocyanate group content of 5 A urethane prepolymer having a carboxyl group acid value of 20 mgKOH / g was obtained. The obtained urethane prepolymer was mixed with 100 parts of diacetone acrylamide and 200 parts of dipentaerythritol hexaacrylate, cooled to 60 ° C, mixed with 36 parts of triethylamine, charged with 2100 parts of emulsified water (20 ° C), and homomixer ( The mixture was mixed and emulsified with a homomixer MARKII manufactured by Primix. Next, an aqueous solution in which 39 parts of ethylenediamine was diluted in 200 parts of water was added to increase the molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution in which 2 parts of tert-butyl peroxide was diluted in 100 parts of water was charged, and then an aqueous solution in which 2 parts of sodium sulfite was diluted in 100 parts of water was charged to initiate polymerization. Thereafter, the mixture was reacted at a temperature of 50 ° C. for 30 minutes, and 51 parts of adipic acid dihydrazide was mixed and dissolved to obtain an aqueous dispersion of a polyurethaneurea-acrylic composite resin.
（実施例１０）
２官能のプロピレングリコール（数平均分子量３０００）７１０部、ジメチロールプロピオン酸３５部、グリセリンモノメタクリレート２６部、イソホロンジイソシアネート２２８部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量３．１％、カルボキシル基酸価１５ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーにダイアセトンアクリルアミド１００部、ジペンタエリスリトールヘキサアクリレート２００部を混合し６０℃迄冷却後、トリエチルアミン２６部を混合後、乳化水（２０℃）２１００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン１９部を水２００部に稀釈した水溶液を仕込み高分子量化した。得られた乳化物を３０℃まで冷却後、ｔｅｒｔ−ブチルパーオキサイド２部を水１００部に稀釈した水溶液を仕込み、その後亜硫酸ソーダ２部を水１００部に稀釈した水溶液を仕込み重合を開始した。その後５０℃の温度にて３０分反応させ、さらにアジピン酸ジヒドラジドを５１部混合溶解することで、ポリウレタンウレア-アクリル系複合樹脂の水分散体を得た。
(Example 10)
710 parts of bifunctional propylene glycol (number average molecular weight 3000), 35 parts of dimethylolpropionic acid, 26 parts of glycerin monomethacrylate, 228 parts of isophorone diisocyanate were added and reacted at a temperature of 90 ° C. for 60 minutes to obtain an isocyanate group content of 3 0.1% of urethane prepolymer having a carboxyl group acid value of 15 mgKOH / g was obtained. The resulting urethane prepolymer was mixed with 100 parts of diacetone acrylamide and 200 parts of dipentaerythritol hexaacrylate, cooled to 60 ° C., mixed with 26 parts of triethylamine, and charged with 2100 parts of emulsified water (20 ° C.). The mixture was mixed and emulsified with a homomixer MARKII manufactured by Primix. Next, an aqueous solution in which 19 parts of ethylenediamine was diluted in 200 parts of water was added to increase the molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution in which 2 parts of tert-butyl peroxide was diluted in 100 parts of water was charged, and then an aqueous solution in which 2 parts of sodium sulfite was diluted in 100 parts of water was charged to initiate polymerization. Thereafter, the mixture was reacted at a temperature of 50 ° C. for 30 minutes, and 51 parts of adipic acid dihydrazide was mixed and dissolved to obtain an aqueous dispersion of a polyurethaneurea-acrylic composite resin.
（比較例１）
２官能のプロピレングリコール（数平均分子量２０００）６４８部、ジメチロールプロピオン酸４８部、イソホロンジイソシアネート３０４部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量５．７％、カルボキシル基酸価２０ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーを６０℃迄冷却後、トリエチルアミン３７部を混合後、乳化水（２０℃）１５００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン３６部を水２００部に稀釈した水溶液を仕込み高分子量化しポリウレタンウレアの水分散体を得た。
(Comparative Example 1)
648 parts of bifunctional propylene glycol (number average molecular weight 2000), 48 parts of dimethylolpropionic acid, and 304 parts of isophorone diisocyanate were charged and reacted at a temperature of 90 ° C. for 60 minutes to obtain an isocyanate group content of 5.7% and a carboxyl group. A urethane prepolymer having an acid value of 20 mgKOH / g was obtained. The obtained urethane prepolymer was cooled to 60 ° C., mixed with 37 parts of triethylamine, charged with 1500 parts of emulsified water (20 ° C.), and mixed and emulsified with a homomixer (Homomixer MARKII manufactured by Primics). Next, an aqueous solution obtained by diluting 36 parts of ethylenediamine in 200 parts of water was charged to increase the molecular weight, and an aqueous dispersion of polyurethane urea was obtained.
（比較例２）
２官能のプロピレングリコール（数平均分子量２０００）６４８部、ジメチロールプロピオン酸４８部、イソホロンジイソシアネート３０４部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量５．７％、カルボキシル基酸価２０ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーにメチルメタクリレート１００部を混合し６０℃迄冷却後、トリエチルアミン３６部を混合後、乳化水（２０℃）１７００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン３７部を水２００部に稀釈した水溶液を仕込み高分子量化した。得られた乳化物を３０℃まで冷却後、ｔｅｒｔ−ブチルパーオキサイド２部を水５０部に稀釈した水溶液を仕込み、その後亜硫酸ソーダ２部を水５０部に稀釈した水溶液を仕込み重合を開始した。その後５０℃の温度にて３０分反応させて、ポリウレタンウレア-アクリル系複合樹脂の水分散体を得た。
(Comparative Example 2)
648 parts of bifunctional propylene glycol (number average molecular weight 2000), 48 parts of dimethylolpropionic acid, and 304 parts of isophorone diisocyanate were charged and reacted at a temperature of 90 ° C. for 60 minutes to obtain an isocyanate group content of 5.7% and a carboxyl group. A urethane prepolymer having an acid value of 20 mgKOH / g was obtained. 100 parts of methyl methacrylate is mixed with the obtained urethane prepolymer, cooled to 60 ° C., mixed with 36 parts of triethylamine, charged with 1700 parts of emulsified water (20 ° C.), and mixed with a homomixer (Homomixer MARKII manufactured by Primics). Emulsified. Next, an aqueous solution in which 37 parts of ethylenediamine was diluted in 200 parts of water was added to increase the molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution in which 2 parts of tert-butyl peroxide was diluted in 50 parts of water was charged, and then an aqueous solution in which 2 parts of sodium sulfite was diluted in 50 parts of water was charged to initiate polymerization. Thereafter, the mixture was reacted at a temperature of 50 ° C. for 30 minutes to obtain an aqueous dispersion of a polyurethane urea-acrylic composite resin.
（比較例３）
２官能のプロピレングリコール（数平均分子量２０００）６４８部、ジメチロールプロピオン酸４８部、イソホロンジイソシアネート３０４部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量５．７％、カルボキシル基酸価２０ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーにメチルメタクリレート１００部、ダイアセトンアクリルアミド１００部を混合し６０℃迄冷却後、トリエチルアミン３６部を混合後、乳化水（２０℃）１７００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン３７部を水１７０部に稀釈した水溶液を仕込み高分子量化した。得られた乳化物を３０℃まで冷却後、ｔｅｒｔ−ブチルパーオキサイド２部を水５０部に稀釈した水溶液を仕込み、その後亜硫酸ソーダ２部を水５０部に稀釈した水溶液を仕込み重合を開始した。その後５０℃の温度にて３０分反応させて、ポリウレタンウレア-アクリル系複合樹脂の水分散体を得た。
(Comparative Example 3)
648 parts of bifunctional propylene glycol (number average molecular weight 2000), 48 parts of dimethylolpropionic acid, and 304 parts of isophorone diisocyanate were charged and reacted at a temperature of 90 ° C. for 60 minutes to obtain an isocyanate group content of 5.7% and a carboxyl group. A urethane prepolymer having an acid value of 20 mgKOH / g was obtained. 100 parts of methyl methacrylate and 100 parts of diacetone acrylamide were mixed with the obtained urethane prepolymer, cooled to 60 ° C., mixed with 36 parts of triethylamine, charged with 1700 parts of emulsified water (20 ° C.), and homomixer (manufactured by Primix Co., Ltd.). The mixture was mixed and emulsified with a homomixer MARKII). Next, an aqueous solution in which 37 parts of ethylenediamine was diluted with 170 parts of water was charged to increase the molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution in which 2 parts of tert-butyl peroxide was diluted in 50 parts of water was charged, and then an aqueous solution in which 2 parts of sodium sulfite was diluted in 50 parts of water was charged to initiate polymerization. Thereafter, the mixture was reacted at a temperature of 50 ° C. for 30 minutes to obtain an aqueous dispersion of a polyurethane urea-acrylic composite resin.
（比較例４）
２官能のプロピレングリコール（数平均分子量２０００）６４８部、ジメチロールプロピオン酸４８部、イソホロンジイソシアネート３０４部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量５．７％、カルボキシル基酸価２０ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーにメチルメタクリレート１００部、ダイアセトンアクリルアミド１００部を混合し６０℃迄冷却後、トリエチルアミン３６部を混合後、乳化水（２０℃）１７００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にエチレンジアミン３７部を水１７０部に稀釈した水溶液を仕込み高分子量化した。得られた乳化物を３０℃まで冷却後、ｔｅｒｔ−ブチルパーオキサイド２部を水５０部に稀釈した水溶液を仕込み、その後亜硫酸ソーダ２部を水５０部に稀釈した水溶液を仕込み重合を開始した。その後５０℃の温度にて３０分反応させて得られたポリウレタンウレア-アクリル系複合樹脂の水分散体にアジピン酸ヒドラジドを５１部混合溶解した。
(Comparative Example 4)
648 parts of bifunctional propylene glycol (number average molecular weight 2000), 48 parts of dimethylolpropionic acid, and 304 parts of isophorone diisocyanate were charged and reacted at a temperature of 90 ° C. for 60 minutes to obtain an isocyanate group content of 5.7% and a carboxyl group. A urethane prepolymer having an acid value of 20 mgKOH / g was obtained. 100 parts of methyl methacrylate and 100 parts of diacetone acrylamide were mixed with the obtained urethane prepolymer, cooled to 60 ° C., mixed with 36 parts of triethylamine, charged with 1700 parts of emulsified water (20 ° C.), and homomixer (manufactured by Primix Co., Ltd.). The mixture was mixed and emulsified with a homomixer MARKII). Next, an aqueous solution in which 37 parts of ethylenediamine was diluted with 170 parts of water was charged to increase the molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution in which 2 parts of tert-butyl peroxide was diluted in 50 parts of water was charged, and then an aqueous solution in which 2 parts of sodium sulfite was diluted in 50 parts of water was charged to initiate polymerization. Thereafter, 51 parts of adipic hydrazide was mixed and dissolved in an aqueous dispersion of a polyurethaneurea-acrylic composite resin obtained by reacting at 50 ° C. for 30 minutes.
（比較例５）
２官能のプロピレングリコール（数平均分子量２０００）６４８部、ジメチロールプロピオン酸４８部、イソホロンジイソシアネート３０４部を仕込み、９０℃の温度にて６０分反応させて、イソシアネート基含量５．７％、カルボキシル基酸価２０ｍｇＫＯＨ／ｇのウレタンプレポリマーを得た。得られたウレタンプレポリマーを６０℃迄冷却後、トリエチルアミン３７部を混合後、乳化水（２０℃）１５００部を仕込み、ホモミキサー（プライミクス社製ホモミクサーＭＡＲＫＩＩ）にて混合乳化した。次にジエチレントリアミン４１部を水１５０部に稀釈した水溶液を仕込み高分子量化しポリウレタンウレアの水分散体を得た。
(Comparative Example 5)
648 parts of bifunctional propylene glycol (number average molecular weight 2000), 48 parts of dimethylolpropionic acid, and 304 parts of isophorone diisocyanate were charged and reacted at a temperature of 90 ° C. for 60 minutes to obtain an isocyanate group content of 5.7% and a carboxyl group. A urethane prepolymer having an acid value of 20 mgKOH / g was obtained. The obtained urethane prepolymer was cooled to 60 ° C., mixed with 37 parts of triethylamine, charged with 1500 parts of emulsified water (20 ° C.), and mixed and emulsified with a homomixer (Homomixer MARKII manufactured by Primics). Next, an aqueous solution obtained by diluting 41 parts of diethylenetriamine in 150 parts of water was charged to increase the molecular weight, and an aqueous dispersion of polyurethane urea was obtained.
（試験片の作成方法）
得られたポリウレタンウレア-アクリル系複合樹脂の水分散体を、膜厚２００μｍとなるようにテフロン(登録商標)コーティングシャーレに投入し、２０℃で３日間乾燥し、試験片を作製した。
(How to create a test piece)
The obtained polyurethane urea-acrylic composite resin aqueous dispersion was put into a Teflon (registered trademark) coating petri dish so as to have a film thickness of 200 μm, and dried at 20 ° C. for 3 days to prepare a test piece.
（評価方法）
ウレタンプレポリマー温度：乳化直前の温度を測定した。
外観：ポリウレタンウレア-アクリル系複合樹脂の水分散体の外観を目視で評価した。
不揮発分の重量％：ＪＩＳ Ｋ ６８２８に準じて測定した。
ｐＨ：ＪＩＳ Ｚ８８０２に従い、評価した。
粘度：ＪＩＳ Ｚ８８０３に準じて、Ｂ８Ｍ型粘度計（東京計器社製）を用いて２０℃にて測定した。
粒子径：ＭｉｃｒｏｔｒａｃＵＰＡ−ＵＺ１５２（日機装社製）にて測定し、５０％平均値を粒子径として算出した。
(Evaluation method)
Urethane prepolymer temperature: The temperature immediately before emulsification was measured.
Appearance: The appearance of the aqueous dispersion of polyurethaneurea-acrylic composite resin was visually evaluated.
Non-volatile content% by weight: Measured according to JIS K 6828.
pH: Evaluated according to JIS Z8802.
Viscosity: Measured at 20 ° C. using a B8M viscometer (manufactured by Tokyo Keiki Co., Ltd.) according to JIS Z8803.
Particle size: Measured with MicrotracUPA-UZ152 (manufactured by Nikkiso Co., Ltd.), and the 50% average value was calculated as the particle size.
（乳化安定性）
４０℃恒温器中に３０日間保存し乳化安定性を下記の基準で評価した。
◎：粘度変化および沈降が全くない
○：粘度変化あるいは沈降がわずかに認められる
×：粘度変化が大きいあるいは沈降が多い
(Emulsification stability)
The emulsion was stored in a 40 ° C. incubator for 30 days, and the emulsion stability was evaluated according to the following criteria.
A: No change in viscosity and no settling O: A slight change in viscosity or settling is observed x: A large change in viscosity or a lot of settling
（皮膜外観）
上記試験皮膜を目視により確認した。
(Film appearance)
The test film was visually confirmed.
（耐水性）
上記試験皮膜を所定の大きさ（２ｃｍ×４ｃｍ）に切断することにより評価サンプルを作製した。試験液として、水道水を使用した。試験片を２０℃の試験液に４時間浸漬し、初期重量に対する重量増加率を下記式により求めた。
重量増加率＝(浸漬後重量−初期重量)／初期重量×１００
(water resistant)
An evaluation sample was prepared by cutting the test film into a predetermined size (2 cm × 4 cm). Tap water was used as a test solution. The test piece was immersed in a test solution at 20 ° C. for 4 hours, and the weight increase rate relative to the initial weight was determined by the following formula.
Weight increase rate = (weight after immersion−initial weight) / initial weight × 100
（耐ＭＥＫ性）
上記試験皮膜を所定の大きさ（２ｃｍ×４ｃｍ）に切断することにより評価サンプルを作製した。試験液として、ＭＥＫ（メチルエチルケトン）を使用した。試験片を２０℃の試験液に４時間浸漬し、初期重量に対する重量増加率を下記式により求めた。
重量増加率＝(浸漬後重量−初期重量)／初期重量×１００
(MEK resistance)
An evaluation sample was prepared by cutting the test film into a predetermined size (2 cm × 4 cm). MEK (methyl ethyl ketone) was used as a test solution. The test piece was immersed in a test solution at 20 ° C. for 4 hours, and the weight increase rate relative to the initial weight was determined by the following formula.
Weight increase rate = (weight after immersion−initial weight) / initial weight × 100
比較例１の耐ＭＥＫ性はＭＥＫに溶解したことから、評価できなかった。
The MEK resistance of Comparative Example 1 could not be evaluated because it was dissolved in MEK.
＜評価結果＞
実施例１〜１０から分かるように、本発明のポリウレタンウレア-アクリル複合樹脂の水分散体は、実質的に有機溶剤および界面活性剤を使用することなく、乳化安定性が良好かつ得られる塗膜の耐水性および耐溶剤性も良好であることが分かる。
<Evaluation results>
As can be seen from Examples 1 to 10, the aqueous dispersion of the polyurethaneurea-acrylic composite resin of the present invention has a good emulsion stability without substantially using an organic solvent and a surfactant. It can be seen that the water resistance and the solvent resistance of are also good.
一方、比較例１のようにＡを含有せず重合工程を行なわなかった場合、耐ＭＥＫに溶解し、不良であった。比較例２のようにＡ中にＡ１を含まずに重合した場合、耐ＭＥＫ性の膨潤は大きく不良であった。比較例３のようにＡ中にＡ１は含まないがＡ２を含ませて重合した場合でも、耐ＭＥＫ性の膨潤は大きく不良であった。比較例４のようにＡ中にＡ１は含まないがＡ２を含ませて重合した水分散体にアジピン酸ヒドラジドを混合した場合でも、耐ＭＥＫ性の膨潤は不良であった。比較例５ではＡを含有せず三官能アミンの使用によりポリウレタンウレア樹脂を架橋体としたが耐水性および耐ＭＥＫ性試験後の皮膜は非常にもろく、不良であった。 On the other hand, when A was not contained and the polymerization process was not performed as in Comparative Example 1, it was dissolved in MEK resistance and was defective. When polymerized without A1 in A as in Comparative Example 2, the MEK-resistant swelling was very poor. Even when A1 was not included in A as in Comparative Example 3, but polymerization was performed with A2 included, the MEK-resistant swelling was very poor. Even in the case where adipic acid hydrazide was mixed with an aqueous dispersion polymerized by containing A2 but not A1 in A as in Comparative Example 4, the MEK-resistant swelling was poor. In Comparative Example 5, the polyurethane urea resin was cross-linked by using a trifunctional amine without containing A, but the film after the water resistance and MEK resistance test was very brittle and poor.
本発明のポリウレタンウレア-アクリル複合樹脂の水分散体は、優れた架橋特性により耐水性、耐溶剤性を飛躍的に向上出来、また乳化安定性にも優れている。また、界面活性剤を使用しないことでさらに優れた耐水性、耐溶剤性を示し、さらには、有機溶剤を使用しなくても、粒子径が微細であり貯蔵安定性に優れたポリウレタンウレア-アクリル複合樹脂を製造することができ、有機溶剤を使用しない為、生産性にも優れる。このような特性から、従来水系ポリウレタン樹脂が使用される分野、接着剤、コーティング剤、塗料、改質剤、バインダー等に幅広く好適に使用される。 The aqueous dispersion of the polyurethane urea-acrylic composite resin of the present invention can drastically improve water resistance and solvent resistance due to excellent cross-linking properties, and also has excellent emulsion stability. In addition, polyurethane urea-acrylic has excellent water resistance and solvent resistance by not using a surfactant, and has a fine particle size and excellent storage stability without using an organic solvent. A composite resin can be produced, and since no organic solvent is used, the productivity is excellent. Because of these characteristics, it is suitably used widely in fields where water-based polyurethane resins are conventionally used, adhesives, coating agents, paints, modifiers, binders and the like.
Claims (8)
前記（Ａ）が２以上のエチレン性不飽和基を有する化合物（Ａ１）を含有し、
（Ｘ）と（Ａ１）の混合割合が、（Ｘ）１０００［ｇ］に対して（Ａ１）が０．３〜７．０［ｍｏｌ×（Ａ１）中の平均不飽和基数］である、
ポリウレタンウレア-アクリル複合樹脂の水分散体。 The ethylenically unsaturated group-containing compound (A) and the NCO group-terminated urethane prepolymer (X) are emulsified and dispersed in water, and then chain-stretched with the polyvalent amine compound (Y) to further polymerize the ethylenically unsaturated group. An aqueous dispersion of a polyurethaneurea-acrylic composite resin obtained by
The (A) contains a compound (A1) having two or more ethylenically unsaturated groups,
The mixing ratio of (X) and (A1) is such that (A1) is 0.3 to 7.0 [mol × average number of unsaturated groups in (A1)] with respect to (X) 1000 [g].
An aqueous dispersion of polyurethaneurea-acrylic composite resin.
（Ｘ）と（Ａ２）の混合割合が、（Ｘ）１０００［ｇ］に対して（Ａ２）が０．１〜２．０［ｍｏｌ］である、
請求項１記載のポリウレタンウレア-アクリル複合樹脂の水分散体。 (A) further contains a carbonyl group or aldehyde group-containing ethylenically unsaturated monomer (A2) having one or more ethylenically unsaturated groups,
The mixing ratio of (X) and (A2) is such that (A2) is 0.1 to 2.0 [mol] with respect to (X) 1000 [g].
The aqueous dispersion of polyurethane urea-acrylic composite resin according to claim 1.
請求項２〜４のいずれか記載のポリウレタンウレア-アクリル複合樹脂の水分散体。 The polyvalent amine compound (Y) contains at least the hydrazide derivative (Y1), and the terminal amino group of the aqueous polyurethane urea resin after chain extension with the polyvalent amine compound (Y) is a hydrazide group.
An aqueous dispersion of the polyurethaneurea-acrylic composite resin according to any one of claims 2 to 4.
多価アミン化合物（Ｙ）で鎖伸張する工程と、
さらにエチレン性不飽和基を重合する工程を含む、
ポリウレタンウレア-アクリル複合樹脂の水分散体の製造方法であって、
前記（Ａ）が２以上のエチレン性不飽和基を有する化合物（Ａ１）を含有し、
（Ｘ）と（Ａ１）の混合割合は（Ｘ）１０００［ｇ］に対して（Ａ１）が０．３〜７．０［ｍｏｌ×（Ａ１）中の平均不飽和基数］である、
ポリウレタンウレア-アクリル複合樹脂の水分散体の製造方法。 Emulsifying and dispersing the ethylenically unsaturated group-containing compound (A) and the NCO group-terminated urethane prepolymer (X) in water;
A step of chain extending with the polyvalent amine compound (Y);
And further comprising a step of polymerizing ethylenically unsaturated groups,
A method for producing an aqueous dispersion of a polyurethaneurea-acrylic composite resin,
The (A) contains a compound (A1) having two or more ethylenically unsaturated groups,
The mixing ratio of (X) and (A1) is such that (A1) is 0.3 to 7.0 [mol × (average number of unsaturated groups in (A1)] with respect to (X) 1000 [g].
A method for producing an aqueous dispersion of a polyurethaneurea-acrylic composite resin.
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| JP2017014500A (en) * | 2015-07-03 | 2017-01-19 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion, and coating composition and coating agent composition comprising the same |
| JP7458545B1 (en) | 2023-09-06 | 2024-03-29 | 第一工業製薬株式会社 | Release coating agents for polyester base materials, release sheets and laminates |
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