JP2011213758A - Crosslinkable aqueous resin composition - Google Patents
Crosslinkable aqueous resin composition Download PDFInfo
- Publication number
- JP2011213758A JP2011213758A JP2010080383A JP2010080383A JP2011213758A JP 2011213758 A JP2011213758 A JP 2011213758A JP 2010080383 A JP2010080383 A JP 2010080383A JP 2010080383 A JP2010080383 A JP 2010080383A JP 2011213758 A JP2011213758 A JP 2011213758A
- Authority
- JP
- Japan
- Prior art keywords
- group
- aqueous resin
- mass
- resin composition
- ethylenically unsaturated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 93
- 239000011347 resin Substances 0.000 claims abstract description 93
- 239000000178 monomer Substances 0.000 claims abstract description 72
- 239000006185 dispersion Substances 0.000 claims abstract description 58
- -1 isocyanate compound Chemical class 0.000 claims abstract description 40
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 11
- 239000012948 isocyanate Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000011258 core-shell material Substances 0.000 claims description 5
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 51
- 238000000576 coating method Methods 0.000 abstract description 51
- 239000002904 solvent Substances 0.000 abstract description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 30
- 229910000077 silane Inorganic materials 0.000 description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 239000003973 paint Substances 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000003995 emulsifying agent Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000000306 component Substances 0.000 description 10
- 229920001228 polyisocyanate Polymers 0.000 description 10
- 239000005056 polyisocyanate Substances 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000004611 light stabiliser Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 7
- 239000006096 absorbing agent Substances 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 6
- 239000012964 benzotriazole Substances 0.000 description 6
- 239000004566 building material Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004908 Emulsion polymer Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 230000008439 repair process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N alpha-Methyl-n-butyl acrylate Natural products CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001246 colloidal dispersion Methods 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000008358 core component Substances 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000006353 oxyethylene group Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- ARVUDIQYNJVQIW-UHFFFAOYSA-N (4-dodecoxy-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 ARVUDIQYNJVQIW-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- SITYOOWCYAYOKL-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(3-dodecoxy-2-hydroxypropoxy)phenol Chemical compound OC1=CC(OCC(O)COCCCCCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 SITYOOWCYAYOKL-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012874 anionic emulsifier Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000005002 finish coating Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- UJRDRFZCRQNLJM-UHFFFAOYSA-N methyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OC)=CC(N2N=C3C=CC=CC3=N2)=C1O UJRDRFZCRQNLJM-UHFFFAOYSA-N 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 239000012875 nonionic emulsifier Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- NWPIOULNZLJZHU-UHFFFAOYSA-N (1,2,2,6,6-pentamethylpiperidin-4-yl) 2-methylprop-2-enoate Chemical compound CN1C(C)(C)CC(OC(=O)C(C)=C)CC1(C)C NWPIOULNZLJZHU-UHFFFAOYSA-N 0.000 description 1
- BUFCQVRLKYIQJP-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) prop-2-enoate Chemical compound CC1(C)CC(OC(=O)C=C)CC(C)(C)N1 BUFCQVRLKYIQJP-UHFFFAOYSA-N 0.000 description 1
- POLSVAXEEHDBMJ-UHFFFAOYSA-N (2-hydroxy-4-octadecoxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 POLSVAXEEHDBMJ-UHFFFAOYSA-N 0.000 description 1
- SXJSETSRWNDWPP-UHFFFAOYSA-N (2-hydroxy-4-phenylmethoxyphenyl)-phenylmethanone Chemical compound C=1C=C(C(=O)C=2C=CC=CC=2)C(O)=CC=1OCC1=CC=CC=C1 SXJSETSRWNDWPP-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- MJZQXNZJXYLXHB-UHFFFAOYSA-N (3-benzoyl-4-hydroxyphenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C(O)C(C(=O)C=2C=CC=CC=2)=C1 MJZQXNZJXYLXHB-UHFFFAOYSA-N 0.000 description 1
- DVVFXZNTIXZGJW-UHFFFAOYSA-N (3-benzoyl-4-hydroxyphenyl) prop-2-enoate Chemical compound OC1=CC=C(OC(=O)C=C)C=C1C(=O)C1=CC=CC=C1 DVVFXZNTIXZGJW-UHFFFAOYSA-N 0.000 description 1
- IMNBHNRXUAJVQE-UHFFFAOYSA-N (4-benzoyl-3-hydroxyphenyl) 2-methylprop-2-enoate Chemical compound OC1=CC(OC(=O)C(=C)C)=CC=C1C(=O)C1=CC=CC=C1 IMNBHNRXUAJVQE-UHFFFAOYSA-N 0.000 description 1
- LJWQJECMFUGUDV-UHFFFAOYSA-N (4-benzoyl-3-hydroxyphenyl) prop-2-enoate Chemical compound OC1=CC(OC(=O)C=C)=CC=C1C(=O)C1=CC=CC=C1 LJWQJECMFUGUDV-UHFFFAOYSA-N 0.000 description 1
- AAZSHFMGBXXYIB-UHFFFAOYSA-N (4-cyano-2,2,6,6-tetramethylpiperidin-4-yl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1(C#N)CC(C)(C)NC(C)(C)C1 AAZSHFMGBXXYIB-UHFFFAOYSA-N 0.000 description 1
- AQNUOTPCFOUIAA-UHFFFAOYSA-N (4-imino-1,2,2,6,6-pentamethylpiperidin-3-yl) 2-methylprop-2-enoate Chemical compound CN1C(C)(C)CC(=N)C(OC(=O)C(C)=C)C1(C)C AQNUOTPCFOUIAA-UHFFFAOYSA-N 0.000 description 1
- WPARMABOLAOINO-UHFFFAOYSA-N 1,2,2,6,6-Pentamethyl-4-piperidinyl acrylate Chemical compound CN1C(C)(C)CC(OC(=O)C=C)CC1(C)C WPARMABOLAOINO-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- OTCWVYFQGYOYJO-UHFFFAOYSA-N 1-o-methyl 10-o-(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound COC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 OTCWVYFQGYOYJO-UHFFFAOYSA-N 0.000 description 1
- XDDLRVYDQACVBC-UHFFFAOYSA-N 10-oxo-10-(1,2,2,6,6-pentamethylpiperidin-4-yl)oxydecanoic acid Chemical compound CN1C(C)(C)CC(OC(=O)CCCCCCCCC(O)=O)CC1(C)C XDDLRVYDQACVBC-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- QHDADHHODABHLK-UHFFFAOYSA-N 2,2-dimethylpentane-1,3-diol Chemical compound CCC(O)C(C)(C)CO QHDADHHODABHLK-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-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
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 description 1
- OHJYHAOODFPJOD-UHFFFAOYSA-N 2-(2-ethylhexoxy)ethanol Chemical compound CCCCC(CC)COCCO OHJYHAOODFPJOD-UHFFFAOYSA-N 0.000 description 1
- JLZIIHMTTRXXIN-UHFFFAOYSA-N 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JLZIIHMTTRXXIN-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
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- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- XQAABEDPVQWFPN-UHFFFAOYSA-N octyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OCCCCCCCC)=CC(N2N=C3C=CC=CC3=N2)=C1O XQAABEDPVQWFPN-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- SQCMCIWNVXFWQF-UHFFFAOYSA-N piperidin-4-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCNCC1 SQCMCIWNVXFWQF-UHFFFAOYSA-N 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- TURAMGVWNUTQKH-UHFFFAOYSA-N propa-1,2-dien-1-one Chemical group C=C=C=O TURAMGVWNUTQKH-UHFFFAOYSA-N 0.000 description 1
- ZNZJJSYHZBXQSM-UHFFFAOYSA-N propane-2,2-diamine Chemical compound CC(C)(N)N ZNZJJSYHZBXQSM-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229940001607 sodium bisulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 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
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Abstract
Description
本発明は、成膜助剤の使用量を低減でき、外観、硬度、光沢、耐屈曲性、耐溶剤性等の塗膜諸物性において優れた性能を有する塗膜を形成し得る架橋性水性樹脂組成物に関する。 The present invention is a crosslinkable aqueous resin capable of reducing the amount of film forming aid used and capable of forming a coating film having excellent performance in coating film properties such as appearance, hardness, gloss, flex resistance and solvent resistance. Relates to the composition.
近年、環境問題の観点等から各種水性塗料の研究が盛んに行われているが、有機溶剤系塗料と比べ塗膜の外観や光沢、硬度等の点でまだ十分な物性が得られていない。 In recent years, various water-based paints have been actively researched from the viewpoint of environmental problems and the like, but sufficient physical properties have not yet been obtained in terms of the appearance, gloss, hardness, etc. of the coating film as compared with organic solvent-based paints.
これらの物性を向上させる目的で、水系塗料中に官能基を導入し、架橋塗膜を形成させることが一般的に行われている。これらの中で、水酸基を導入した水系樹脂とイソシアネート化合物からなる架橋性の水系樹脂組成物から生成するウレタン架橋塗膜は、硬度、耐溶剤性、耐候性に優れた物性を発現するため、注目されている。 For the purpose of improving these physical properties, it is a common practice to introduce a functional group into a water-based paint to form a crosslinked coating film. Among these, urethane cross-linked coating film produced from a crosslinkable aqueous resin composition comprising an aqueous resin and an isocyanate compound into which a hydroxyl group has been introduced exhibits physical properties excellent in hardness, solvent resistance, and weather resistance. Has been.
架橋性水性組成物の分野においては、親水性有機溶剤中で重合させた樹脂を中和し水性化させることによって得られる水性樹脂を主体とした、いわゆるコロイダル・ディスパージョンと、乳化剤と水との存在下で重合を行なう、いわゆる乳化重合体とが、主に検討されて来た。 In the field of the crosslinkable aqueous composition, a so-called colloidal dispersion mainly composed of an aqueous resin obtained by neutralizing a resin polymerized in a hydrophilic organic solvent to make it water, an emulsifier and water. So-called emulsion polymers that polymerize in the presence have been mainly studied.
前者のコロイダル・ディスパージョンは、乳化重合体と比較して分子量が一般に小さいため、成膜した塗膜については光沢や外観は良い反面、初期耐水性や耐久性が悪いという課題がある。また、後者の乳化重合体は、樹脂そのものの分子量が高いものを用いることができるため、良好に成膜した塗膜については優れた塗膜物性が期待できる反面、樹脂が水中に分散した不均一体であることに起因して、イソシアネート化合物と混合した時に微小な凝集物が発生しやすく、塗膜表面に微小なブツとして残るため、塗膜外観はコロイダル・ディスパージョンに比べ劣るという課題があった。 Since the former colloidal dispersion generally has a molecular weight smaller than that of the emulsion polymer, the coated film has good gloss and appearance, but has a problem of poor initial water resistance and durability. In addition, since the latter emulsion polymer can be one having a high molecular weight of the resin itself, excellent coating properties can be expected for a well-formed coating film, while the resin is dispersed in water. Due to the fact that they are integral, minute agglomerates are likely to be generated when mixed with an isocyanate compound, and they remain as fine irregularities on the surface of the coating film. Therefore, there is a problem that the appearance of the coating film is inferior to that of a colloidal dispersion. It was.
この問題に対し、特許文献1では、数平均分子量の大きなコア成分と数平均分子量の小さなシェル成分からなる乳化重合体を使用した架橋性水系被覆組成物を提案している。また、特許文献2では、高Tgのコア成分と低Tgのシェル成分からなる乳化重合体を使用した水性樹脂組成物を提案している。しかし、これらの方法を用いてもなお、塗膜外観の改良効果の更なる向上が求められており、高外観の塗膜が要求される自動車内外装部品や家電製品に用いられるプラスチック基材や自動車補修用のクリアトップコート塗料等の用途では、特にその要求が高まっていた。 For this problem, Patent Document 1 proposes a crosslinkable aqueous coating composition using an emulsion polymer comprising a core component having a large number average molecular weight and a shell component having a small number average molecular weight. Patent Document 2 proposes an aqueous resin composition using an emulsion polymer comprising a high Tg core component and a low Tg shell component. However, even when these methods are used, there is a need for further improvement in the effect of improving the appearance of the coating film, such as plastic substrates used in automobile interior and exterior parts and home appliances that require a high-appearance coating film. In applications such as clear top coat paint for repairing automobiles, the demand has been particularly high.
本発明の目的は、成膜性や硬度、光沢、耐屈曲性、耐溶剤性等の塗膜諸物性に優れ、かつ自動車内外装部品や家電製品に用いられるプラスチック基材や自動車補修用のクリアトップコート塗料等にも好適に使用可能な高外観の塗膜を形成し得る架橋性水性樹脂組成物を提供することである。 The object of the present invention is excellent in coating film properties such as film formability, hardness, gloss, flex resistance, solvent resistance, and clear for plastic substrates and automobile repairs used in automobile interior and exterior parts and home appliances. It is an object of the present invention to provide a crosslinkable aqueous resin composition capable of forming a high-appearance coating film that can be suitably used for a top coat paint or the like.
本発明者は、上記のような問題点を解決するために鋭意研究を重ねた結果、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
即ち、本発明の第1は、
水酸基価10〜200mgKOH/g、酸価8〜50mgKOH/gの樹脂部(A1)を含有する水性樹脂分散体(A)、及び2以上のイソシアネート基を有するイソシアネート化合物(B)を含んでなる架橋性水性樹脂組成物であって、該樹脂部(A1)が、2段階以上の工程で乳化重合して得られるコア部(A1α)及びシェル部(A1β)を有するコアシェル構造を有し、該シェル部(A1β)が、ヒドロキシル基含有エチレン性不飽和単量体(a)から導かれる構成単位12〜50質量%、カルボキシル基含有エチレン性不飽和単量体(b)から導かれる構成単位5〜20質量%、及びその他の重合可能な重合性単量(c)から導かれる構成単位体30〜83質量%からなる重合体を含有することを特徴とする上記架橋性水性樹脂組成物である。
That is, the first of the present invention is
Crosslinking comprising an aqueous resin dispersion (A) containing a resin part (A1) having a hydroxyl value of 10 to 200 mgKOH / g and an acid value of 8 to 50 mgKOH / g, and an isocyanate compound (B) having two or more isocyanate groups Water-based resin composition, wherein the resin part (A1) has a core-shell structure having a core part (A1α) and a shell part (A1β) obtained by emulsion polymerization in two or more steps, and the shell 12 to 50 mass% of structural unit derived from hydroxyl group-containing ethylenically unsaturated monomer (a), part (A1β) is composed of structural unit 5 derived from carboxyl group-containing ethylenically unsaturated monomer (b). The above crosslinkable aqueous resin composition comprising 20% by mass and a polymer composed of 30 to 83% by mass of structural units derived from other polymerizable polymerizable monomer (c). It is.
本発明の第2は、前記シェル部(A1β)が上記単量体(a)、(b)、及び(c)の合計100質量部に対して分子量調整剤(d)(連鎖移動剤が好ましい)を0.1〜5質量部使用して得られたことを特徴とする前記第1の発明の架橋性水性樹脂組成物である。 In the second aspect of the present invention, the shell part (A1β) is preferably a molecular weight modifier (d) (preferably a chain transfer agent) relative to 100 parts by mass of the monomers (a), (b), and (c). The crosslinkable aqueous resin composition according to the first aspect of the present invention, which is obtained by using 0.1 to 5 parts by mass.
本発明の第3は、前記水性樹脂分散体(A)の樹脂部(A1)が、さらに、下記式(1)で表されるSi含有化合物(e)又はこれから得られる重合体を含んでいることを特徴とする前記第1、又は第2の発明の架橋性水性樹脂組成物である。 In the third aspect of the present invention, the resin part (A1) of the aqueous resin dispersion (A) further contains a Si-containing compound (e) represented by the following formula (1) or a polymer obtained therefrom. The crosslinkable aqueous resin composition of the first or second invention, characterized in that
(R1)n −Si−(R2)4-n (1)
(式中nは0から3の整数であり、R1は水素、炭素数1〜16の脂肪族炭化水素基、炭素数5〜10のアリール基、及び炭素数5〜6のシクロアルキル基からなる群より選ばれる。n個のR1は同一であっても、異なってもよい。R2は炭素数1〜8のアルコキシ基、アセトキシ基、及び水酸基からなる群より選ばれる。4−n個のR2は同一であっても、異なってもよい。)
(R1) n-Si- (R2) 4-n (1)
(In the formula, n is an integer of 0 to 3, and R1 is composed of hydrogen, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group having 5 to 10 carbon atoms, and a cycloalkyl group having 5 to 6 carbon atoms. N R1 may be the same or different, and R2 is selected from the group consisting of an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, and a hydroxyl group. May be the same or different.)
本発明の架橋性水性樹脂組成物を使用すれば、VOC(揮発性有機化合物)の低減が可能であり、プラスチック、金属、木材、紙、無機建材等の各種基材に対する密着性に優れ、硬度、光沢、耐屈曲性、耐溶剤性等の塗膜諸物性に優れた塗膜を形成することができる。さらに、自動車内外装部品や家電製品に用いられるプラスチック基材や自動車補修用のクリアトップコート塗料に好適に使用が可能な高外観の塗膜を形成することができる。 If the crosslinkable aqueous resin composition of the present invention is used, VOC (volatile organic compound) can be reduced, and it has excellent adhesion to various substrates such as plastic, metal, wood, paper, inorganic building materials, and hardness. It is possible to form a coating film excellent in various physical properties such as gloss, flex resistance, and solvent resistance. Furthermore, it is possible to form a coating film having a high appearance that can be suitably used for a plastic substrate used for automobile interior / exterior parts and home appliances and a clear top coat paint for automobile repair.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の架橋性水性樹脂組成物は、
水酸基価10〜200mgKOH/g、酸価8〜50mgKOH/gの樹脂部(A1)を含有する水性樹脂分散体(A)、及び2以上のイソシアネート基を有するイソシアネート化合物(B)を含んでなる架橋性水性樹脂組成物であって、該樹脂部(A1)が、2段階以上の工程で乳化重合して得られるコア部(A1α)及びシェル部(A1β)を有するコアシェル構造を有し、該シェル部(A1β)が、ヒドロキシル基含有エチレン性不飽和単量体(a)から導かれる構成単位12〜50質量%、カルボキシル基含有エチレン性不飽和単量体(b)から導かれる構成単位5〜20質量%、及びその他の重合可能な重合性単量(c)から導かれる構成単位体30〜83質量%からなる重合体を含有することを特徴とする上記架橋性水性樹脂組成物であることを特徴とする。
(A)水性樹脂分散体
本発明において使用される水性樹脂分散体(A)は、分散質(固形分)である樹脂部(A1)と、分散媒である水性媒体(A2)とを含有する。
(A1)樹脂部
本発明に用いる水性樹脂分散体(A)を構成する樹脂部(A1)の水酸基価は、10〜200mgKOH/g、好ましくは30〜150mgKOH/gである。水性樹脂分散体の水酸基価が10mgKOH/g以上なので塗膜の架橋が充分であり、200mgKOH/g以下なので重合安定性の低下が抑制でき、さらに水性樹脂分散体の粘度が高くなり過ぎず塗装作業性が良好である。また、本発明の水性樹脂分散体(A)を構成する樹脂部(A1)の酸価は、8〜50mgKOH/g、好ましくは10〜40mgKOH/gである。酸価が8mgKOH/g以上なので目的とする塗膜外観が容易に得られ、50mgKOH/g以下なので、水性樹脂分散体の粘度が高くなり過ぎず塗装作業性が良好である。
The crosslinkable aqueous resin composition of the present invention comprises:
Crosslinking comprising an aqueous resin dispersion (A) containing a resin part (A1) having a hydroxyl value of 10 to 200 mgKOH / g and an acid value of 8 to 50 mgKOH / g, and an isocyanate compound (B) having two or more isocyanate groups Water-based resin composition, wherein the resin part (A1) has a core-shell structure having a core part (A1α) and a shell part (A1β) obtained by emulsion polymerization in two or more steps, and the shell 12 to 50 mass% of structural unit derived from hydroxyl group-containing ethylenically unsaturated monomer (a), part (A1β) is composed of structural unit 5 derived from carboxyl group-containing ethylenically unsaturated monomer (b). The above crosslinkable aqueous resin composition comprising 20% by mass and a polymer composed of 30 to 83% by mass of structural units derived from other polymerizable polymerizable monomer (c). And characterized in that.
(A) Aqueous Resin Dispersion The aqueous resin dispersion (A) used in the present invention contains a resin part (A1) which is a dispersoid (solid content) and an aqueous medium (A2) which is a dispersion medium. .
(A1) Resin Part The hydroxyl value of the resin part (A1) constituting the aqueous resin dispersion (A) used in the present invention is 10 to 200 mgKOH / g, preferably 30 to 150 mgKOH / g. Since the hydroxyl value of the aqueous resin dispersion is 10 mg KOH / g or more, the coating film is sufficiently cross-linked, and since it is 200 mg KOH / g or less, a decrease in polymerization stability can be suppressed, and the viscosity of the aqueous resin dispersion does not become too high. Good properties. Moreover, the acid value of the resin part (A1) which comprises the aqueous resin dispersion (A) of this invention is 8-50 mgKOH / g, Preferably it is 10-40 mgKOH / g. Since the acid value is 8 mgKOH / g or more, the desired coating film appearance can be easily obtained, and since it is 50 mgKOH / g or less, the viscosity of the aqueous resin dispersion does not become too high, and the coating workability is good.
また、本発明の水性樹脂分散体(A)を構成する樹脂部(A1)は、そのシェル成分(A1β)がヒドロキシル基含有エチレン性不飽和単量体(a)から導かれる構成単位12〜50質量%、カルボキシル基含有エチレン性不飽和単量体(b)から導かれる構成単位5〜20質量%、その他重合可能な重合性単量体(c)から導かれる構成単位30〜83質量%からなる重合体を含有する。ヒドロキシル基含有エチレン性不飽和単量体(a)から導かれる構成単位が12質量%以上なので塗膜の架橋が充分であり、50質量%以下なので水性樹脂分散体の粘度が高くなり過ぎず塗装作業性が良好である。また、カルボキシル基含有エチレン性不飽和単量体(b)から導かれる構成単位が5質量%以上なので、目的とする塗膜外観が容易に得られ、20質量%以下なので水性樹脂分散体の粘度が高くなり過ぎず塗装作業性が良好である。 The resin part (A1) constituting the aqueous resin dispersion (A) of the present invention has structural units 12 to 50 in which the shell component (A1β) is derived from the hydroxyl group-containing ethylenically unsaturated monomer (a). From 5% by mass, from 5 to 20% by mass of structural units derived from the carboxyl group-containing ethylenically unsaturated monomer (b), from 30 to 83% by mass of structural units derived from other polymerizable monomer (c). Containing a polymer. Since the structural unit derived from the hydroxyl group-containing ethylenically unsaturated monomer (a) is 12% by mass or more, the coating film is sufficiently crosslinked, and since it is 50% by mass or less, the viscosity of the aqueous resin dispersion does not become too high. Workability is good. Further, since the structural unit derived from the carboxyl group-containing ethylenically unsaturated monomer (b) is 5% by mass or more, the desired coating film appearance can be easily obtained, and since it is 20% by mass or less, the viscosity of the aqueous resin dispersion The coating workability is good without increasing too much.
ここで、上記水酸基価は、樹脂部(A1)1g中の水酸基を無水酢酸でアセチル化して、アセチル化に伴って生成した酢酸を中和するのに要する水酸化カリウムのmg数で表わされる。また、酸価は、樹脂1g中の遊離酸を中和するのに必要な水酸化カリウムのmg数で表わされる。これらの水酸基価、及び酸価は、水性樹脂分散体(A)を合成する際に使用するヒドロキシル基含有エチレン性不飽和単量体(a)等の水酸基含有単量体、及びカルボキシル基含有エチレン性不飽和単量体(b)等の酸基含有単量体の使用量から計算で求めることも可能である。 Here, the hydroxyl value is represented by the number of mg of potassium hydroxide required to neutralize acetic acid produced by acetylating the hydroxyl group in 1 g of the resin part (A1) with acetic anhydride. Moreover, an acid value is represented by mg number of potassium hydroxide required in order to neutralize the free acid in 1g of resin. These hydroxyl value and acid value are determined based on hydroxyl group-containing monomers such as hydroxyl group-containing ethylenically unsaturated monomer (a) used for synthesizing the aqueous resin dispersion (A), and carboxyl group-containing ethylene. It can also be obtained by calculation from the amount of the acid group-containing monomer such as the polymerizable unsaturated monomer (b).
また、本発明で用いる水性樹脂分散体(A)は、シェル部(A1β)が連鎖移動剤(分子量調整剤(d)に該当する。)を上記単量体(a)、(b)、及び(c)の合計100質量部に対して、0.1〜5質量部使用して得られたものであることが望ましい。連鎖移動剤が0.1質量部以上であれば、目的とする塗膜外観が容易に得られ、5質量部以下であれば塗膜の硬度低下が抑制される。また、コア部(A1α)についても、塗膜物性を低下させない程度に連鎖移動剤を使用しても構わない。使用できる連鎖移動剤は、特に限定されるものではないが、具体的にはドデシルメルカプタン、ブチルメルカプタン等が挙げられる。 In the aqueous resin dispersion (A) used in the present invention, the shell part (A1β) is a chain transfer agent (corresponding to the molecular weight modifier (d)) and the monomers (a), (b), and It is desirable to be obtained by using 0.1 to 5 parts by mass with respect to 100 parts by mass in total of (c). If the chain transfer agent is 0.1 parts by mass or more, the desired coating film appearance is easily obtained, and if it is 5 parts by mass or less, a decrease in hardness of the coating film is suppressed. Moreover, you may use a chain transfer agent also to a core part (A1 (alpha)) to such an extent that a physical property of a coating film is not reduced. The chain transfer agent that can be used is not particularly limited, and specific examples include dodecyl mercaptan and butyl mercaptan.
本発明において、水性樹脂分散体(A)の樹脂部(A1)が、通常、数平均分子量100000以上のコア部(A1α)と通常、数平均分子量3000〜100000、好ましくは5000〜80000のシェル部(A1β)からなるコアシェル構造を有し、コア成分/シェル成分(質量比)=30/70〜80/20、好ましくは40/60〜70/30である場合、後述するイソシアネート化合物(B)とからなる架橋性水性樹脂組成物から、成膜助剤を使用しなくても、塗膜外観、硬度、光沢、耐屈曲性、耐溶剤性等に優れた塗膜が形成できるため、非常に好ましい。上記の水性樹脂分散体(A)の樹脂部(A1)がコア、シェル構造であることを確認する方法としてSPM(走査プローブ顕微鏡)を用いることができる。 In the present invention, the resin part (A1) of the aqueous resin dispersion (A) is usually a core part (A1α) having a number average molecular weight of 100,000 or more and a shell part usually having a number average molecular weight of 3000 to 100,000, preferably 5000 to 80000. When it has a core-shell structure consisting of (A1β) and the core component / shell component (mass ratio) = 30/70 to 80/20, preferably 40/60 to 70/30, an isocyanate compound (B) described later and From the crosslinkable aqueous resin composition comprising, it is very preferable because a coating film excellent in appearance, hardness, gloss, bending resistance, solvent resistance, etc. can be formed without using a film forming aid. . SPM (scanning probe microscope) can be used as a method for confirming that the resin part (A1) of the aqueous resin dispersion (A) has a core / shell structure.
さらに、本発明の架橋性水性樹脂組成物は、自動車内外装部品や家電製品に用いられるプラスチック基材や自動車補修用のクリアトップコート等の塗膜硬度が要求される用途を主な目的としているため、本発明の水性樹脂分散体(A)の樹脂部(A1)のガラス転移温度(Tg)は10〜90℃の範囲が好ましく、30〜80℃の範囲がより好ましい。また、成膜性の観点では、シェル部(A1β)のTgをコア部(A1α)のTgより10℃以上低くすることが好ましく、20℃以上低くすることがさらに好ましい。また、塗膜硬度の観点では、シェル部(A1β)のTgとコア部(A1α)のTgより10℃以上高くすることが好ましく、20℃以上高くすることがより好ましい。なお、本発明において、水性樹脂分散体(A)の樹脂部(A1)、そのコア部(A1α)、及びそのシェル部(A1β)のTg(K:絶対温度)は、次のFOX式を用いて計算されるものをいう。 Furthermore, the crosslinkable aqueous resin composition of the present invention is mainly intended for applications requiring coating film hardness such as plastic base materials used in automobile interior and exterior parts and home appliances and clear top coats for automobile repairs. Therefore, the glass transition temperature (Tg) of the resin part (A1) of the aqueous resin dispersion (A) of the present invention is preferably in the range of 10 to 90 ° C, more preferably in the range of 30 to 80 ° C. From the viewpoint of film formability, the Tg of the shell part (A1β) is preferably 10 ° C. or more lower than the Tg of the core part (A1α), more preferably 20 ° C. or more. Further, from the viewpoint of coating film hardness, it is preferably higher by 10 ° C. or more and more preferably by 20 ° C. or more than the Tg of the shell portion (A1β) and the Tg of the core portion (A1α). In the present invention, Tg (K: absolute temperature) of the resin part (A1), the core part (A1α), and the shell part (A1β) of the aqueous resin dispersion (A) is expressed by the following FOX formula. This is what is calculated.
1/Tg=W1/Tg1+W2/Tg2+・・・+Wi/Tgi+・・・Wn/Tgn
[上記FOX式は、n種の単量体からなる重合体を構成する各モノマーのホモポリマーのガラス転移温度をTgi(K)とし、各モノマー単位の質量分率をWiとしている(W1+ W2+・・・+Wi+・・・+Wn=1)。]
シェル部(A1β)
本発明で用いる水性樹脂分散体(A)の樹脂部(A1)のシェル部(A1β)には、ヒドロキシル基含有重合性単量体(a)、カルボキシル基含有重合性単量体(b)、及びその他の重合可能な重合性単量体(c)から得られる重合体が使用される。
なお、同様の単量体から得られる重合体(重合比は、シェル部を構成するものと同一であっても、異なっていてもよい。)を、コア部(A1α)に使用することができる。
ヒドロキシル基含有重合性単量体(a)
ヒドロキシル基含有重合性単量体(a)は少なくとも1のヒドロキシル基(カルボキシル基を構成するものを除く。)、及び少なくとも1の重合性不飽和基を有する化合物であればよく、他に限定はないが、その具体例としては、2−ヒドロキシエチル(メタ)アクリレート、4−ヒドロキシプロピル(メタ)アクリレート、2−ヒドロキシブチル(メタ)アクリレート、カプロラクトン変性(メタ)アクリレート、ポリエチレングリコール(メタ)アクリレート、ポリプロピレングリコール(メタ)アクリレート等であり、これらからなる郡から選ばれた1又は2以上が使用される。特に好ましくは2−ヒドロキシエチル(メタ)アクリレートである。さらにヒドロキシル基含有重合性単量体(a)は、樹脂部(A1)のシェル部(A1β)を構成する重合体を得るために使用する重合性単量体(a)、(b)、及び(c)の合計100質量%に対し、12〜50質量%、好ましくは20〜45質量%使用することが、架橋性と耐水性の観点から重要である。
カルボキシル基含有重合性単量体(b)
カルボキシル基含有重合性単量体(b)は、少なくとも1のカルボキシル基と少なくとも1の重合性不飽和基を有する化合物であればよく、他に限定はないが、その具体例としては、アクリル酸、メタクリル酸、クロトン酸、イタコン酸、マレイン酸、無水マレイン酸等であり、これらからなる群から選ばれた1又は2以上が使用される。特にアクリル酸とメタクリル酸が好ましい。さらに、カルボキシル基含有重合性単量体(b)は、水性樹脂分散体(A)の樹脂部(A1)のシェル部(A1β)を構成する重合体を得るために使用する重合性単量体(a)、(b)、及び(c)の合計100質量%に対し、5〜20質量%、好ましくは5〜15質量%を使用することが、塗膜外観と下地密着性の観点から重要である。
その他の重合可能な重合性単量体(c)
その他重合可能な重合性単量体(c)としては、少なくとも1の重合性不飽和基を有する化合物(前記(a)、又は(b)に該当するものを除く。)であればよく、特に限定されるものではないが、例えば(メタ)アクリル酸エステル、スチレン、ビニルトルエン等の芳香族単量体、酢酸ビニル、プロピオン酸ビニル、バーサチック酸ビニル等のビニルエステル類、(メタ)アクリロニトリル等のシアン化ビニル類、塩化ビニル、塩化ビニリデン等のハロゲン化ビニル類、ブタジエン等が挙げられる。さらに種々の官能性単量体として例えば、アルコキシシラン基含有単量体、(メタ)アクリルアミド、ダイアセトンアクリルアミド、ビニルピロリドン、(メタ)アクリル酸グリシジル、N−メチロールアクリルアミド、N−ブトキシメチルアクリルアミド、ジビニルベンゼン、メチルビニルケトン等が挙げられる。
1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wi / Tgi + ... Wn / Tgn
[In the FOX formula, the glass transition temperature of the homopolymer of each monomer constituting the polymer composed of n types of monomers is Tgi (K), and the mass fraction of each monomer unit is Wi (W1 + W2 + · .. + Wi + ... + Wn = 1). ]
Shell part (A1β)
In the shell part (A1β) of the resin part (A1) of the aqueous resin dispersion (A) used in the present invention, a hydroxyl group-containing polymerizable monomer (a), a carboxyl group-containing polymerizable monomer (b), And other polymers obtained from other polymerizable polymerizable monomers (c) are used.
A polymer obtained from the same monomer (the polymerization ratio may be the same as or different from that constituting the shell portion) can be used for the core portion (A1α). .
Hydroxyl group-containing polymerizable monomer (a)
The hydroxyl group-containing polymerizable monomer (a) may be any compound having at least one hydroxyl group (excluding those constituting a carboxyl group) and at least one polymerizable unsaturated group. Specific examples include 2-hydroxyethyl (meth) acrylate, 4-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, caprolactone-modified (meth) acrylate, polyethylene glycol (meth) acrylate, Polypropylene glycol (meth) acrylate and the like, and one or more selected from the group consisting of these are used. Particularly preferred is 2-hydroxyethyl (meth) acrylate. Furthermore, the hydroxyl group-containing polymerizable monomer (a) is a polymerizable monomer (a), (b) used for obtaining a polymer constituting the shell part (A1β) of the resin part (A1), and From the viewpoint of crosslinkability and water resistance, it is important to use 12 to 50% by mass, preferably 20 to 45% by mass with respect to the total of 100% by mass of (c).
Carboxyl group-containing polymerizable monomer (b)
The carboxyl group-containing polymerizable monomer (b) is not particularly limited as long as it is a compound having at least one carboxyl group and at least one polymerizable unsaturated group. Specific examples thereof include acrylic acid. Methacrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride and the like, and one or more selected from the group consisting of these are used. Acrylic acid and methacrylic acid are particularly preferred. Furthermore, the carboxyl group-containing polymerizable monomer (b) is a polymerizable monomer used for obtaining a polymer constituting the shell part (A1β) of the resin part (A1) of the aqueous resin dispersion (A). From the viewpoint of coating film appearance and base adhesion, it is important to use 5 to 20% by mass, preferably 5 to 15% by mass with respect to the total of 100% by mass of (a), (b) and (c). It is.
Other polymerizable monomer (c)
The other polymerizable monomer (c) may be any compound having at least one polymerizable unsaturated group (excluding those corresponding to the above (a) or (b)). Although not limited, for example, (meth) acrylic acid esters, aromatic monomers such as styrene and vinyl toluene, vinyl esters such as vinyl acetate, vinyl propionate and vinyl versatate, and (meth) acrylonitrile Examples include vinyl cyanides, vinyl halides such as vinyl chloride and vinylidene chloride, and butadiene. Further, as various functional monomers, for example, alkoxysilane group-containing monomers, (meth) acrylamide, diacetone acrylamide, vinyl pyrrolidone, glycidyl (meth) acrylate, N-methylol acrylamide, N-butoxymethyl acrylamide, divinyl Examples thereof include benzene and methyl vinyl ketone.
(メタ)アクリル酸エステルの具体例としては、アルキル部の炭素数が1〜18の(メタ)アクリル酸アルキルエステル、エチレンオキサイド基の数が1〜100個の(ポリ)オキシエチレンモノ(メタ)アクリレート、(ポリ)オキシプロピレンモノ(メタ)アクリレート、アルキル部の炭素数が1〜18の(メタ)アクリル酸ヒドロキシアルキルエステル、エチレンオキサイド基の数が1〜100個の(ポリ)オキシエチレンジ(メタ)アクリレート等がある。(メタ)アクリル酸アルキルエステルの具体例としては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n−ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸t−ブチル、(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸シクロアルキルエステル等が挙げられる。これらからなる群から選ばれた1又は2以上が使用される。
Si含有化合物(e)、又はこれから導かれる重合体
さらに、本発明の水性樹脂分散体(A)の樹脂部(A−1)は、下記式(1)で表されるSi含有化合物(e)又はこれから導かれる重合体をも含んでいることが望ましい。このうち、Si含有化合物(e)から導かれる重合体を使用することが耐候性等の点から好ましい。Si化合物から導かれる重合体としては、例えば環状シロキサン、線状シロキサン、又はアルコキシシランオリゴマーに該当するものを使用することができる。
Specific examples of (meth) acrylic acid esters include (meth) acrylic acid alkyl esters having 1 to 18 carbon atoms in the alkyl moiety, and (poly) oxyethylene mono (meth) having 1 to 100 ethylene oxide groups. Acrylate, (poly) oxypropylene mono (meth) acrylate, (meth) acrylic acid hydroxyalkyl ester having 1 to 18 carbon atoms in the alkyl portion, and (poly) oxyethylene di (1) having 1 to 100 ethylene oxide groups And (meth) acrylate. Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylic acid t-. Examples include butyl, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, and (meth) acrylic acid cycloalkyl ester. One or more selected from the group consisting of these are used.
Si-containing compound (e), or polymer derived therefrom. Furthermore, the resin part (A-1) of the aqueous resin dispersion (A) of the present invention is represented by the following formula (1): Si-containing compound (e) It is also desirable to include a polymer derived therefrom. Among these, it is preferable from points, such as a weather resistance, to use the polymer guide | induced from Si containing compound (e). As the polymer derived from the Si compound, for example, a polymer corresponding to a cyclic siloxane, a linear siloxane, or an alkoxysilane oligomer can be used.
(R1)n−Si−(R2)4−n (1)
(式中nは0〜3の整数であり、R1は水素、炭素数1〜16の脂肪族炭化水素基、炭素数5〜10のアリール基、及び炭素数5〜6のシクロアルキル基からなる群より選ばれる基。n個のR1は同一であっても、異なってもよい。R2は炭素数1〜8のアルコキシ基、アセトキシ基、及び水酸基からなる群より選ばれる基。4−n個のR2は同一であっても、異なってもよい。)
Si含有化合物(e)は、式(1)においてn=0としたシラン(I)及び/又はn=1とおいたシラン(II)の少なくとも1種を含んでいることが好ましく、良好な水分散体の重合安定性を得るためにはn=1のシラン(II)であることがさらに好ましい。シラン(I)のR2はそれぞれ独立して、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、メトキシエトキシ基、又は水酸基が好ましい。シラン(I)の好ましい具体例として、テトラメトキシシラン、テトラエトキシシラン等が挙げられる。
(R1) n-Si- (R2) 4-n (1)
(In the formula, n is an integer of 0 to 3, and R1 is composed of hydrogen, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group having 5 to 10 carbon atoms, and a cycloalkyl group having 5 to 6 carbon atoms. A group selected from the group, n R1s may be the same or different, and R2 is a group selected from the group consisting of an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, and a hydroxyl group. R2 in the above may be the same or different.)
The Si-containing compound (e) preferably contains at least one of silane (I) in which n = 0 in formula (1) and / or silane (II) in which n = 1, and has good water dispersion In order to obtain polymerization stability of the body, n = 1 silane (II) is more preferable. R2 of silane (I) is each independently preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group, or a hydroxyl group. Preferable specific examples of silane (I) include tetramethoxysilane and tetraethoxysilane.
シラン(II)のR1としてはメチル基、フェニル基が好ましく、R2はそれぞれ独立して、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、メトキシエトキシ基、又は水酸基が好ましい。シラン(II)の好ましい具体例としては、メチルトリメトシキシシラン、フェニルトリメトキシシラン、メチルトリエトキシシラン、フェニルトリエトキシシラン、イソブチルトリメトキシシラン等が挙げられる。 R1 of silane (II) is preferably a methyl group or a phenyl group, and R2 is independently preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group, or a hydroxyl group. Preferable specific examples of silane (II) include methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, isobutyltrimethoxysilane and the like.
また、柔軟性を必要とされる場合には、環状シロキサン及び式(1)においてn=2とおいて得られるシラン(III)からなる群より選ばれる少なくとも1種を用いることが好ましい。これは、シラン(II)と、環状シロキサン及びシラン(III)からなる群より選ばれる少なくとも1種を用いることより、Si含有化合物(e)が形成するシリコーン重合体の架橋密度を低くし、重合体の構造が複雑になるのを防ぐことができ、これによって、水性樹脂分散体から提供される塗膜に柔軟性を付与することができるためである。シラン(II)と併用した場合に特に好ましい。
環状シロキサンの具体例としては、オクタメチルシクロテトラシロキサン、オクタフェニルシクロシロキサン、ヘキサメチルシクロトリシロキサン、デカメチルシクロペンタシロキサン、などが挙げられる。
When flexibility is required, it is preferable to use at least one selected from the group consisting of cyclic siloxane and silane (III) obtained by setting n = 2 in formula (1). This is because the use of at least one selected from the group consisting of silane (II), cyclic siloxane and silane (III) reduces the crosslink density of the silicone polymer formed by the Si-containing compound (e), This is because it is possible to prevent the structure of the coalescence from becoming complicated, and thereby to impart flexibility to the coating film provided from the aqueous resin dispersion. Particularly preferred when used in combination with silane (II).
Specific examples of the cyclic siloxane include octamethylcyclotetrasiloxane, octaphenylcyclosiloxane, hexamethylcyclotrisiloxane, decamethylcyclopentasiloxane, and the like.
シラン(III)の具体例として、ジメチルジメトキシシラン、ジフェニルジメトキシシラン、ジメチルジエトキシシラン、ジフェニルジエトキシシラン、メチルフェニルジメトキシシランが挙げられる。 Specific examples of silane (III) include dimethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane.
さらに、加水分解基を有する線状シロキサン、アルコキシシランオリゴマー及び式(1)においてn=3とおいて得られるシラン(IV)からなる群より選ばれる少なくとも1種を用いてもよい。 Furthermore, you may use at least 1 sort (s) chosen from the group which consists of a linear siloxane which has a hydrolysis group, an alkoxysilane oligomer, and silane (IV) obtained by setting n = 3 in Formula (1).
シラン(IV)の具体例として、トリフェニルエトキシシラン、トリメチルメトキシシラン等が挙げられる。 Specific examples of silane (IV) include triphenylethoxysilane and trimethylmethoxysilane.
加水分解基を有する線状シロキサンの例としては、下記の一般式(2)、(3)、(4)で表される化合物が挙げられる。 Examples of the linear siloxane having a hydrolyzable group include compounds represented by the following general formulas (2), (3), and (4).
(式中、R1は水素、炭素数1〜16の脂肪族炭化水素基、炭素数5〜10のアリール基、炭素数5〜6のシクロアルキル基、炭素数1〜10のアクリル酸アルキル基、及び炭素数1〜10のメタクリル酸アルキル基からなる群より選ばれ、各R2はそれぞれ、独立して炭素数1〜8のアルコキシ基、アセトキシ基、水酸基、エポキシ基、アルキレンオキサイド基、及びポリアルキレンオキサイド基からなる群より選ばれ、mは1〜999の正の整数を表す。)
シラン(III)又はシラン(IV)において、R1としてはメチル基、フェニル基が特に好ましく、R2としてはメトキシ基、エトキシ基、プロポキシ基、ブトキシ基、メトキシエトキシ基、水酸基が特に好ましい。
(In the formula, R1 is hydrogen, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group having 5 to 10 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an alkyl acrylate group having 1 to 10 carbon atoms, Each R2 is independently selected from the group consisting of an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, a hydroxyl group, an epoxy group, an alkylene oxide group, and a polyalkylene. (It is selected from the group consisting of oxide groups, and m represents a positive integer of 1 to 999.)
In silane (III) or silane (IV), R1 is particularly preferably a methyl group or phenyl group, and R2 is particularly preferably a methoxy group, ethoxy group, propoxy group, butoxy group, methoxyethoxy group or hydroxyl group.
シラン(II)及び、環状シロキサン、シラン(III)、線状シロキサン、アルコキシシランオリゴマー、シラン(IV)からなる群から選ばれる少なくとも1種に加え、クロロシラン、例えばメチルクロロシラン、メチルジクロロシラン、ジメチルジクロロシラン、トリメチルクロロシラン、フェニルトリクロロシラン、ジフェニルクロロシラン、を使用することができる。 In addition to silane (II) and at least one selected from the group consisting of cyclic siloxane, silane (III), linear siloxane, alkoxysilane oligomer, silane (IV), chlorosilane such as methylchlorosilane, methyldichlorosilane, dimethyldi Chlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenylchlorosilane can be used.
本発明に使用されるSi含有化合物(e)又は上記の各種Si含有化合物によって、本発明の架橋性水性樹脂組成物より得られる塗膜の屋外等に長期曝露における光沢保持性を改善することができる。上記したシラン縮合物の存在は、29SiNMR(29Si核磁気共鳴スペクトル)又は1HNMR(プロトン核磁気共鳴スペクトル)によって知ることができる。例えば、シラン(II)の縮合物は、29SiNMRのケミカルシフトが−40〜−80PPMにピークを示すことで同定することができる。
水性樹脂分散体(A)の製造方法
本発明の水性樹脂分散体(A)の製造方法としては、通常の多段乳化重合法が採用できる。その代表例としては、水中にて乳化剤及び重合開始剤等の存在下で、不飽和単量体(a)、(b)、及び(c)を通常60〜90℃の加温下で乳化重合し、この工程を複数段回繰り返し行う方法が挙げられる。前記乳化重合中のpHは、4以下であることが好ましい。前記乳化剤としては、特に限定はなく、例えばアニオン性乳化剤、ノニオン性乳化剤、カチオン性乳化剤、両性乳化剤、高分子乳化剤等を使用することができる。例えば、脂肪酸石鹸、アルキルスルホン酸塩、アルキルスルホコハク酸塩、ポリオキシエチレンアルキル硫酸塩、ポリオキシエチレンアルキルアリール硫酸塩、ポリオキシエチレンジスチリルフェニルエーテルスルホン酸塩等のアニオン性乳化剤や、例えばアルキルトリメチルアンモニウムブロマイド、アルキルピリジニウムブロマイド、イミダゾリニウムラウリレート等の四級アンモニウム塩、ピリジニウム塩、イミダゾリニウム塩型のカチオン性乳化剤や、例えばポリオキシエチレンアルキルアリールエーテル、ポリオキシエチレンソルビタン脂肪酸エステル、オキシエチレンオキシプロピレンブロックコポリマー、ポリオキシエチレンジスチリルフェニルエーテル等のノニオン性乳化剤等が挙げられる。前記乳化剤の使用量は、特に限定はされないが、例えば、重合性単量体成分(a)、(b)、及び(c)の合計使用量100質量%に対して、好ましくは1.0〜5.0質量%がよい。乳化剤の使用量を多くすると重合安定性が向上し、少なくすると耐水性を向上させることができる。
The Si-containing compound (e) used in the present invention or the above-mentioned various Si-containing compounds can improve the gloss retention in a long-term exposure of the coating film obtained from the crosslinkable aqueous resin composition of the present invention outdoors. it can. The presence of the above-mentioned silane condensate can be known by 29 SiNMR (29Si nuclear magnetic resonance spectrum) or 1 HNMR (proton nuclear magnetic resonance spectrum). For example, a condensate of silane (II) can be identified by 29 SiNMR chemical shift showing a peak at −40 to −80 PPM.
Manufacturing method of aqueous resin dispersion (A) As a manufacturing method of the aqueous resin dispersion (A) of this invention, a normal multistage emulsion polymerization method is employable. A typical example is emulsion polymerization of unsaturated monomers (a), (b), and (c) under normal heating at 60 to 90 ° C. in the presence of an emulsifier and a polymerization initiator in water. And the method of repeating this process in multiple steps is mentioned. The pH during the emulsion polymerization is preferably 4 or less. The emulsifier is not particularly limited, and for example, an anionic emulsifier, a nonionic emulsifier, a cationic emulsifier, an amphoteric emulsifier, a polymer emulsifier, and the like can be used. For example, anionic emulsifiers such as fatty acid soap, alkyl sulfonate, alkyl sulfosuccinate, polyoxyethylene alkyl sulfate, polyoxyethylene alkylaryl sulfate, polyoxyethylene distyryl phenyl ether sulfonate, Quaternary ammonium salts such as ammonium bromide, alkylpyridinium bromide, imidazolinium laurate, pyridinium salts, imidazolinium salt type cationic emulsifiers such as polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan fatty acid ester, oxyethylene Nonionic emulsifiers such as oxypropylene block copolymer and polyoxyethylene distyryl phenyl ether are listed. Although the usage-amount of the said emulsifier is not specifically limited, For example, with respect to the total usage-amount of 100 mass% of polymerizable monomer components (a), (b), and (c), Preferably it is 1.0- 5.0 mass% is good. When the amount of the emulsifier used is increased, the polymerization stability is improved, and when it is decreased, the water resistance can be improved.
本発明の水性樹脂分散体(A)を乳化重合する際の重合方法は、単量体を一括して仕込む単量体一括仕込み法や、単量体を連続的に滴下する単量体滴下法、単量体と水と乳化剤とを予め混合乳化しておき、これらを滴下するプレエマルション法、あるいは、これらを組み合わせる方法等が挙げられる。この時に重合開始剤の使用方法は特に限定されるものではない。また、Si含有化合物(e)の使用方法としては、加水分解性シランの縮合反応と不飽和単量体のラジカル重合を同時に及び/又は加水分解性シランの縮合反応を先行させた後に不飽和単量体のラジカル重合を進行させる乳化重合方法又は不飽和単量体のラジカル重合を進行させた後に加水分解性シランの縮合反応を進行させる方法等が用いられる。 The polymerization method for emulsion polymerization of the aqueous resin dispersion (A) of the present invention includes a monomer batch charging method in which monomers are charged in a batch, and a monomer dropping method in which monomers are continuously dropped. Examples thereof include a pre-emulsion method in which a monomer, water and an emulsifier are mixed and emulsified in advance, and these are added dropwise, or a combination thereof. At this time, the method of using the polymerization initiator is not particularly limited. In addition, the Si-containing compound (e) can be used by simultaneously carrying out the condensation reaction of the hydrolyzable silane and the radical polymerization of the unsaturated monomer and / or preceded by the condensation reaction of the hydrolyzable silane. An emulsion polymerization method for proceeding radical polymerization of a monomer or a method for proceeding condensation reaction of hydrolyzable silane after proceeding radical polymerization of an unsaturated monomer is used.
本発明の水性樹脂分散体を乳化重合する際に使用する重合開始剤としては、一般に用いられるラジカル開始剤である。ラジカル重合開始剤は、熱又は還元性物質等によってラジカルを生成して重合性単量体の付加重合を起こさせるもので、水溶性又は油溶性の過硫酸塩、過酸化物、アゾビス化合物等がある。具体的には過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、過酸化水素、t−ブチルハイドロパーオキサイド、t−ブチルパーオキシベンゾエート、2,2−アゾビスイソブチロニトリル、2,2−アゾビス(2−ジアミノプロパン)ハイドロクロライド、2,2−アゾビス(2,4−ジメチルバレロニトリル)等があり、好ましくは水溶性のものである。なお、重合速度の促進や低温反応を望む場合には、重亜硫酸ナトリウム、塩化第一鉄、アスコルビン酸、ホルムアルデヒドスルホオキシレート塩等の還元剤をラジカル重合開始剤と組み合わせて用いることができる。 The polymerization initiator used for emulsion polymerization of the aqueous resin dispersion of the present invention is a generally used radical initiator. A radical polymerization initiator is one that generates radicals by heat or a reducing substance to cause addition polymerization of a polymerizable monomer. Water-soluble or oil-soluble persulfates, peroxides, azobis compounds, etc. is there. Specifically, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis ( 2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile), and the like, preferably water-soluble. When acceleration of the polymerization rate or a low temperature reaction is desired, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbic acid, formaldehyde sulfooxylate salt or the like can be used in combination with the radical polymerization initiator.
本発明において使用される水性樹脂分散体(A)は、エマルジョンの長期の分散安定性を保つため、塩基性物質、例えばアンモニア、ジメチルアミノエタノール等のアミン類を始めとする塩基性有機化合物、水酸化ナトリウム、水酸化カリウム等のアルカリ金属塩を始めとする塩基性無機化合物等を用いてpH5〜10の範囲に調整することが好ましい。
イソシアネート化合物(B)
本発明において、水性樹脂分散体(A)と2以上のイソシアネート基を有するイソシアネート化合物(B)を組み合わせることにより、成膜助剤を使用しなくとも、外観、硬度、光沢、耐屈曲性、耐溶剤性等の塗膜物性に優れた塗料やコーティング用途等に用いられる架橋性水性樹脂組成物を得ることができる。
The aqueous resin dispersion (A) used in the present invention contains basic substances such as basic organic compounds such as amines such as ammonia and dimethylaminoethanol, water, etc. in order to maintain long-term dispersion stability of the emulsion. It is preferable to adjust the pH within a range of 5 to 10 using a basic inorganic compound such as an alkali metal salt such as sodium oxide or potassium hydroxide.
Isocyanate compound (B)
In the present invention, by combining the aqueous resin dispersion (A) and the isocyanate compound (B) having two or more isocyanate groups, the appearance, hardness, gloss, flex resistance, It is possible to obtain a crosslinkable aqueous resin composition used for paints and coating applications having excellent coating properties such as solvent properties.
本発明において使用されるイソシアネート化合物(B)としては、2個以上のイソシアネート基を分子内に有するものであれば特に限定されないが、その具体例としては、1,6−ヘキサメチレンジイソシアネート、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、メタキシリレンジイソシアネート、及び4,4’−メチレンビス(シクロヘキシルイソシアネート)等のジイソシアネート、これらジイソシアネートの誘導体であるトリメチロールプロパンアダクト体、ビュウレット体、及びイソシアヌレート体等のアダクトポリイシシアネート化合物、上記のイソシアネート基含有重合性単量体を公知の重合方法で単独重合させ、又は他の重合性単量体と共重合させた重合体、並びにこれらの乳化物等を用いることができる。 The isocyanate compound (B) used in the present invention is not particularly limited as long as it has two or more isocyanate groups in the molecule. Specific examples thereof include 1,6-hexamethylene diisocyanate and tolylene diene. Diisocyanates such as isocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, metaxylylene diisocyanate, and 4,4′-methylenebis (cyclohexyl isocyanate), trimethylolpropane adducts, burettes, and isocyanurates that are derivatives of these diisocyanates The adduct polyisocyanate compound such as a polymer, the above isocyanate group-containing polymerizable monomer is homopolymerized by a known polymerization method, or copolymerized with other polymerizable monomers Polymers obtained by, as well as the use of these emulsions and the like.
本発明において使用されるイソシアネート基を有する化合物(B)は、水分散性の点からは、ノニオン性及び/又はイオン性の界面活性剤等により変性処理された水分散性を有するポリイソシアネート化合物が好適である。このようなポリイソシアネート化合物としては、従来公知の手法により親水基を導入してなるものであれば特に制限なく使用でき、例えばアルコキシポリアルキレングリコールとポリイソシアネート化合物との反応生成物や、界面活性能を有するノニオン性基及びイソシアネート反応性基(水酸基等)を含有するビニル系重合体とポリイソシアネート化合物との反応生成物、ジアルカノールアミンとを反応させることにより得られる反応生成物、イセチオン酸アミン塩等のスルホン酸基とイソシアネート反応基を有する化合物とポリイソシアネート化合物の反応生成物を含有するポリイソシアネート化合物を挙げることができる。これらの中で、アルコキシポリアルキレングリコールとポリイソシアネート化合物との反応生成物を含有するポリイソシアネート化合物は水分散性が優れるため、特に好ましい。このような化合物は、市販品としては、商品名「デュラネートWT20−100」、「デュラネートWT30−100」、「デュラネートWB40−100」(以上旭化成ケミカルズ(株)製)等を挙げることができる。
その他の成分
その他、本発明の架橋性水性樹脂組成物には、通常水系塗料に添加配合される成分、例えば、増粘剤、成膜助剤、可塑剤、凍結防止剤、消泡剤、染料、防腐剤、紫外線吸収剤、光安定剤等を任意に配合することができる。
From the viewpoint of water dispersibility, the compound (B) having an isocyanate group used in the present invention is a polyisocyanate compound having water dispersibility modified with a nonionic and / or ionic surfactant or the like. Is preferred. As such a polyisocyanate compound, any compound obtained by introducing a hydrophilic group by a conventionally known method can be used without particular limitation. For example, a reaction product of an alkoxy polyalkylene glycol and a polyisocyanate compound, a surface active ability Reaction product of vinyl polymer containing nonionic group and isocyanate-reactive group (hydroxyl group, etc.) having polyisocyanate and polyisocyanate compound, reaction product obtained by reacting dialkanolamine, isethionate amine salt Examples thereof include a polyisocyanate compound containing a reaction product of a compound having a sulfonic acid group and an isocyanate reactive group and a polyisocyanate compound. Among these, a polyisocyanate compound containing a reaction product of an alkoxy polyalkylene glycol and a polyisocyanate compound is particularly preferable because of its excellent water dispersibility. Examples of such a commercially available product include trade names “Duranate WT20-100”, “Duranate WT30-100”, “Duranate WB40-100” (manufactured by Asahi Kasei Chemicals Corporation) and the like.
In addition to the other components , the crosslinkable aqueous resin composition of the present invention is usually added to a water-based paint, such as a thickener, a film-forming aid, a plasticizer, an antifreezing agent, an antifoaming agent, and a dye. , Preservatives, ultraviolet absorbers, light stabilizers and the like can be optionally blended.
増粘剤の具体例としては、ポリビニルアルコール(部分鹸化ポリ酢酸ビニル等を含む)、メチルセルロース、ヒドロキシエチルセルロース、ポリビニルピロリドン等の高分子分散安定剤等、その他ポリエーテル系、ポリカルボン酸系増粘剤等が挙げられる。 Specific examples of the thickener include polyvinyl alcohol (including partially saponified polyvinyl acetate), polymer dispersion stabilizers such as methylcellulose, hydroxyethylcellulose, and polyvinylpyrrolidone, and other polyether-based and polycarboxylic acid-based thickeners. Etc.
成膜助剤の具体例としては、ジエチレングリコールモノブチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、エチレングリコールモノ2−エチルヘキシルエーテル、2,2,4−トリメチル−1,3−ブタンジオールイソブチレート、グルタル酸ジイソプロピル、プロピレングリコールn−ブチルエーテル、ジプロピレングリコールn−ブチルエーテル、トリプロピレングリコールn−ブチルエーテル、ジプロピレングリコールメチルエーテル、トリプロピレングリコールメチルエーテル、プロピレングリコールメチルエーテルアセテート、ダイアセトンアルコール等が挙げられる。これら成膜助剤は、単独又は併用等任意に配合することができる。なお、本発明の効果により、成膜助剤の使用を省略し、又はその使用量を低減することが可能である。 Specific examples of film forming aids include diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol mono 2-ethylhexyl ether, 2,2,4-trimethyl-1,3-butanediol iso Butyrate, diisopropyl glutarate, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol methyl ether acetate, diacetone alcohol, etc. Can be mentioned. These film-forming aids can be optionally blended alone or in combination. Note that due to the effects of the present invention, it is possible to omit the use of the film forming aid or reduce the amount of use.
可塑剤として具体的には、フタル酸ジブチル、フタル酸ジオクチル等が挙げられる。
凍結防止剤として具体的には、プロピレングリコール、エチレングルコール等が挙げられる。
Specific examples of the plasticizer include dibutyl phthalate and dioctyl phthalate.
Specific examples of the antifreezing agent include propylene glycol and ethylene glycol.
紫外線吸収剤にはベンゾフェノン系、ベンゾトリアゾール系、トリアジン系等があり、ベンゾフェノン系紫外線吸収剤の具体例としては、2,4−ジヒドロキシベンゾフェノン、2−ヒドロキシ−4−メトキシベンゾフェノン、2−ヒドロキシ−4−メトキシベンゾフェノン−5−スルホン酸、2−ヒドロキシ−4−n−オクトキシベンゾフェノン、2−ヒドロキシ−4−n−ドデシルオキシベンゾフェノン、2−ヒドロキシ−4−ベンジルオキシベンゾフェノン、ビス(5−ベンゾイル−4−ヒドロキシ−2−メトキシフェニル)メタン、2,2’−ジヒドロキシ−4−メトキシベンゾフェノン、2,2’−ジヒドロキシ−4,4’ジメトキシベンゾフェノン、2,2’,4,4’−テトラヒドロキシベンゾフェノン、4−ドデシルオキシ−2−ヒドロキシベンゾフェノン、2−ヒドロキシ−4−メトキシ−2’−カルボキシベンゾフェノン、2−ヒドロキシ−4−ステアリルオキシベンゾフェノン等が挙げられる。 Examples of the ultraviolet absorber include benzophenone, benzotriazole, and triazine. Specific examples of the benzophenone ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4. -Methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis (5-benzoyl-4 -Hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy 2-hydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxy benzophenone, 2-hydroxy-4-stearyloxy benzophenone.
ラジカル重合性ベンゾフェノン系の紫外線吸収剤の具体例としては、2−ヒドロキシ4−アクリロキシベンゾフェノン、2−ヒドロキシ−4−メタクリロキシベンゾフェノン、2−ヒドロキシ−5−アクリロキシベンゾフェノン、2−ヒドロキシ−5−メタクリロキシベンゾフェノン、2−ヒドロキシ−4−(アクリロキシ−エトキシ)ベンゾフェノン、2−ヒドロキシ−4−(メタクリロキシ−エトキシ)ベンゾフェノン、2−ヒドロキシ−4−(メタクリロキシ−ジエトキシ)ベンゾフェノン、2−ヒドロキシ−4−(アクリロキシ−トリエトキシ)ベンゾフェノン等が挙げられる。 Specific examples of radical polymerizable benzophenone-based UV absorbers include 2-hydroxy-4-acryloxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-5-acryloxybenzophenone, 2-hydroxy-5- Methacryloxybenzophenone, 2-hydroxy-4- (acryloxy-ethoxy) benzophenone, 2-hydroxy-4- (methacryloxy-ethoxy) benzophenone, 2-hydroxy-4- (methacryloxy-diethoxy) benzophenone, 2-hydroxy-4- ( And acryloxy-triethoxy) benzophenone.
ベンゾトリアゾール系紫外線吸収剤の具体例としては、2−(2’−ヒドロキシ−5’−メチルフェニル)ベンゾトリアゾール、2−(2’−ヒドロキシ−5’−tert−ブチルフェニル)ベンゾトリアゾール、2−(2’−ヒドロキシ−3’,5’−ジ−tert−ブチルフェニル)ベンゾトリアゾール、2−(2−ヒドロキシ−5−tert−オクチルフェニル)ベンゾトリアゾール、2−(2−ヒドロキシ−3,5−ジ−tert−オクチルフェニル)ベンゾトリアゾール、2−〔2’−ヒドロキシ−3’,5’−ビス(α,α’−ジメチルベンジル)フェニル〕ベンゾトリアゾール)、メチル−3−〔3−tert−ブチル−5−(2H−ベンゾトリアゾール−2−イル)−4−ヒドロキシフェニル〕プロピオネートとポリエチレングリコール(分子量300)との縮合物(日本チバガイギー(株)製、製品名:TINUVIN1130)、イソオクチル−3−〔3−(2Hベンゾトリアゾール−2−イル)−5−tert−ブチル−4−ヒドロキシフェニル〕プロピオネート(日本チバガイギー(株)製、製品名:TINUVIN384)、2−(3−ドデシル−5−メチル−2−ヒドロキシフェニル)ベンゾトリアゾール(日本チバガイギー(株)製、製品名:TINUVIN571)、2−(2’−ヒドロキシ−3’−tert−ブチル−5’−メチルフェニル)−5−クロロベンゾトリアゾール、2−(2’ヒドロキシ−3’,5’−ジ−tert−アミルフェニル)ベンゾトリアゾール、2−(2’−ヒドロキシ−4’−オクトキシフェニル)ベンゾトリアゾール、2−〔2’−ヒドロキシ−3’−(3’’,4’’,5’’,6’’−テトラヒドロフタルイミドメチル)−5’−メチルフェニル〕ベンゾトリアゾール、2,2−メチレンビス〔4−(1,1,3,3−テトラメチルブチル)−6−(2H−ベンゾトリアゾール−2−イル)フェノール〕、2−(2H−ベンゾトリアゾール−2−イル)−4,6−ビス(1−メチル−1フェニルエチル)フェノール(日本チバガイギー(株)製、製品名:TINUVIN900)。 Specific examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5- Di-tert-octylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenyl] benzotriazole), methyl-3- [3-tert-butyl -5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene Condensate with glycol (molecular weight 300) (product name: TINUVIN 1130, manufactured by Ciba Geigy Co., Ltd.), isooctyl-3- [3- (2Hbenzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl ] Propionate (manufactured by Ciba Geigy Japan, product name: TINUVIN 384), 2- (3-dodecyl-5-methyl-2-hydroxyphenyl) benzotriazole (manufactured by Ciba Geigy Japan, product name: TINUVIN 571), 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2 -(2'-hydroxy-4'-octoxyphenyl) benzotriazol 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2,2-methylenebis [4 -(1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2H-benzotriazol-2-yl) -4,6-bis (1 -Methyl-1-phenylethyl) phenol (Nippon Ciba-Geigy Co., Ltd., product name: TINUVIN900).
ラジカル重合性ベンゾトリアゾール系の紫外線吸収剤の具体例としては、2−(2’ヒドロキシ−5’−メタクリロキシエチルフェニル)−2H−ベンゾトリアゾール(大塚化学(株)製、製品名:RUVA−93)、2−(2’−ヒドロキシ−5’−メタクリロキシエチル−3−tert−ブチルフェニル)−2H−ベンゾトリアゾール、2−(2’−ヒドロキシ−5’−メタクリリルオキシプロピル−3−tert−ブチルフェニル)5−クロロ−2H−ベンゾトリアゾール、3−メタクリロイル−2−ヒドロキシプロピル−3−〔3’−(2’’−ベンゾトリアゾリル)−4−ヒドロキシ−5−tert−ブチル〕フェニルプロピオネート(日本チバガイギー(株)製、製品名:CGL−104)等が挙げられる。 Specific examples of the radical polymerizable benzotriazole-based UV absorber include 2- (2′hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd., product name: RUVA-93). ), 2- (2′-hydroxy-5′-methacryloxyethyl-3-tert-butylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5′-methacrylyloxypropyl-3-tert- Butylphenyl) 5-chloro-2H-benzotriazole, 3-methacryloyl-2-hydroxypropyl-3- [3 ′-(2 ″ -benzotriazolyl) -4-hydroxy-5-tert-butyl] phenylpropio Nate (Nippon Ciba-Geigy Co., Ltd. product name: CGL-104).
トリアジン系紫外線吸収剤の具体例としては、TINUVIN400(製品名、日本チバガイギー(株)製)等が挙げられる。
光安定剤としては、ヒンダードアミン系光安定剤が好ましく、その中で塩基性の低いものがより好ましく、塩基定数(pKb)が8以上のものが特に好ましい。具体例としては、ビス(2,2,6,6−テトラメチル−4−ピペリジル)サクシネート、ビス(2,2,6,6−テトラメチルピペリジル)セバケート、ビス(1,2,2,6,6−ペンタメチル4−ピペリジル)2−(3,5−ジ−tert−ブチル−4−ヒドロキシベンジル)−2−ブチルマロネート、1−〔2−〔3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピニルオキシ〕エチル〕−4−〔3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピニルオキシ〕−2,2,6,6−テトラメチルピペリジン、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)セバケートとメチル−1,2,2,6,6−ペンタメチル−4−ピペリジル−セバケートの混合物(日本チバガイギー(株)製、製品名:TINUVIN292)、ビス(1−オクトキシ−2,2,6,6−テトラメチル−4−ピペリジル)セバケート、TINUVIN123(製品名、日本チバガイギー(株)製)等が挙げられる。
Specific examples of the triazine ultraviolet absorber include TINUVIN400 (product name, manufactured by Nippon Ciba-Geigy Co., Ltd.).
As the light stabilizer, hindered amine light stabilizers are preferable, among them, those having low basicity are more preferable, and those having a base constant (pKb) of 8 or more are particularly preferable. Specific examples include bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1,2,2,6, 6-pentamethyl 4-piperidyl) 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butyl malonate, 1- [2- [3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propynyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propynyloxy] -2,2,6,6-tetramethylpiperidine, bis A mixture of (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl-sebacate (Nippon Ciba-Geigy Ltd.), product name: Tinuvin 292), bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, TINUVIN123 (trade name, manufactured by Nippon Ciba-Geigy Corporation), and the like.
ラジカル重合性ヒンダードアミン系光安定剤の具体例としては、1,2,2,6,6ペンタメチル−4−ピペリジルメタクリレート、1,2,2,6,6−ペンタメチル−4−ピペリジルアクリレート、2,2,6,6−テトラメチル−4−ピペリジルメタクリレート、2,2,6,6−テトラメチル−4−ピペリジルアクリレート、1,2,2,6,6−ペンタメチル−4−イミノピペリジルメタクリレート、2,2,6,6,−テトラメチル−4−イミノピペリジルメタクリレート、4−シアノ−2,2,6,6−テトラメチル−4−ピペリジルメタクリレート、4−シアノ−1,2,2,6,6−ペンタメチル4−ピペリジルメタクリレート等が挙げられる。 Specific examples of the radical polymerizable hindered amine light stabilizer include 1,2,2,6,6 pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl acrylate, 2,2 , 6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-iminopiperidyl methacrylate, 2,2 , 6,6, -tetramethyl-4-iminopiperidyl methacrylate, 4-cyano-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-cyano-1,2,2,6,6-pentamethyl Examples include 4-piperidyl methacrylate.
本発明において、紫外線吸収剤及び/又は光安定剤は、水性樹脂分散体(A)を製造する乳化重合時に存在させることにより水性樹脂分散体(A)に導入する方法、紫外線吸収剤及び/又は光安定剤を成膜助剤等と混合して水性樹脂分散体(A)に添加することにより導入する方法、紫外線吸収剤及び/又は光安定剤を成膜助剤と混合し、界面活性剤、水を加え乳化させた後、水性樹脂分散体(A)に添加することにより導入する方法が挙げられる。また、紫外線吸収剤と光安定剤を併用すると、相乗効果により卓越した耐久性を示す。 In the present invention, the ultraviolet absorber and / or the light stabilizer is introduced into the aqueous resin dispersion (A) by being present during emulsion polymerization for producing the aqueous resin dispersion (A), the ultraviolet absorber and / or A method of introducing a light stabilizer by mixing it with a film forming auxiliary agent and adding it to the aqueous resin dispersion (A), a UV absorber and / or a light stabilizer mixed with a film forming auxiliary agent, and a surfactant. The method of introducing by emulsifying by adding water and then adding to the aqueous resin dispersion (A) can be mentioned. In addition, when an ultraviolet absorber and a light stabilizer are used in combination, it exhibits excellent durability due to a synergistic effect.
本発明の水性樹脂組成物に使用される水性樹脂分散体(A)は、分散質である樹脂部(A1)の平均粒子径として、30〜500nmであることが好ましい。得られたエマルジョン中の分散質(固形分)である樹脂部(A1)と分散媒としての水性媒体(A2)との質量比は通常70/30以下、好ましくは30/70以上65/35以下である。 The aqueous resin dispersion (A) used in the aqueous resin composition of the present invention preferably has an average particle size of 30 to 500 nm as the dispersoid resin part (A1). The mass ratio of the resin part (A1) which is a dispersoid (solid content) in the obtained emulsion and the aqueous medium (A2) as a dispersion medium is usually 70/30 or less, preferably 30/70 or more and 65/35 or less. It is.
本発明の架橋性水性樹脂組成物は、プラスチック基材に対する密着性や硬度に優れ、高い塗膜外観を有するコーティング被膜が得られるため、自動車内外装部品や家電製品に用いられるプラスチック基材や自動車補修用のクリアトップコート塗料として有用である。また、塗料、建材の仕上げ材、紙加工剤、又は織布、不織布の仕上げ材として有用であり、とくに塗料用、建材の仕上げ材として具体的には、コンクリート、セメントモルタル、スレート板、ケイカル板、石膏ボード、押し出し成形板、発泡性コンクリート等の無機建材、織布あるいは不織布を基材とした建材、金属建材等の各種下地に対する塗料又は建築仕上げ材として、複層仕上げ塗材用の主材及びトップコート、薄付け仕上塗材、厚付け仕上塗材、石材調仕上げ材、グロスペイント等の合成樹脂エマルジョンペイント、金属用塗料、木部塗料、瓦用塗料として有用である。 The crosslinkable aqueous resin composition of the present invention is excellent in adhesion and hardness to a plastic substrate, and a coating film having a high coating film appearance is obtained. It is useful as a clear top coat paint for repair. In addition, it is useful as finishing materials for paints, building materials, paper finishing agents, woven fabrics, and non-woven fabrics. Specifically, as finishing materials for paints and building materials, concrete, cement mortar, slate plates, and calcium plates. Main materials for multi-layer finishing coating materials as paints or building finishing materials for various bases such as inorganic building materials such as plasterboard, extruded boards, foamable concrete, building materials based on woven or non-woven fabrics, and metal building materials It is also useful as a top coat, a thin finish coating material, a thick finish coating material, a stone finish finish material, a synthetic resin emulsion paint such as a gloss paint, a metal paint, a wood part paint, and a tile paint.
以下の水性樹脂分散体(A)の製造例、架橋性水性樹脂組成物の実施例及び比較例により本発明を詳細に説明するが、本発明はこれらの例によって何ら限定されるものでない。尚、水性樹脂分散体(A)の製造例、架橋性水性樹脂組成物の実施例及び比較例中の「部」及び「%」は、別段の言及がない限り、それぞれ質量部、及び質量%を表す。また、得られた架橋性水性樹脂組成物の物性試験については、該水性樹脂分散体(A)を用いて下記に示す配合組成で塗料を調整し、以下に示す試験方法に従って試験を実施した。
(水性樹脂分散体(A)の製造)
[製造例1]
撹拌機、還流冷却器、滴下槽及び温度計を取り付けた反応容器に水62部、アニオン性界面活性剤(製品名:ハイテノールLA−12、第一工業製薬(株)製)の20%水溶液を0.75部投入し、反応容器中の温度を80℃に上げてから、過硫酸アンモニウムの2%水溶液を1.5部添加した5分後に、メタクリル酸メチル50.2部、アクリル酸n−ブチル16.4部、メタクリル酸1.4部、2−ヒドロキシエチルメタアクリレート2部、アニオン性界面活性剤(製品名:ニューコール707SF、日本乳化剤(株)製)の30%水溶液を4.7部、ノニオン性海面活性剤(製品名:エマルゲン120、花王(株)製)の20%水溶液2部、過硫酸アンモニウムの2%の水溶液3.5部、水43.6部からなる乳化混合液を滴下槽より135分かけて流入させる。流入中は反応容器の温度を80℃に保つ。流入が終了してから反応容器の温度を80℃にして30分保つ。
The present invention will be described in detail by the following production examples of the aqueous resin dispersion (A), examples of the crosslinkable aqueous resin composition, and comparative examples, but the present invention is not limited by these examples. In addition, “parts” and “%” in the production examples of the aqueous resin dispersion (A), the examples of the crosslinkable aqueous resin compositions and the comparative examples are “parts by mass” and “% by mass”, respectively, unless otherwise specified. Represents. Moreover, about the physical property test of the obtained crosslinkable aqueous resin composition, the coating material was adjusted with the compounding composition shown below using this aqueous resin dispersion (A), and the test was implemented according to the test method shown below.
(Production of aqueous resin dispersion (A))
[Production Example 1]
A reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 62 parts of water, 20% aqueous solution of anionic surfactant (product name: Haitenol LA-12, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 5 minutes after addition of 1.5 parts of a 2% aqueous solution of ammonium persulfate, 50.2 parts of methyl methacrylate, n-acrylic acid n- 14.7 parts of butyl, 1.4 parts of methacrylic acid, 2 parts of 2-hydroxyethyl methacrylate, 4.7% of a 30% aqueous solution of an anionic surfactant (product name: New Coal 707SF, manufactured by Nippon Emulsifier Co., Ltd.) An emulsion mixture comprising 2 parts of a 20% aqueous solution of a nonionic sea surface active agent (product name: Emulgen 120, manufactured by Kao Corporation), 3.5 parts of a 2% aqueous solution of ammonium persulfate, and 43.6 parts of water. From dripping tank Over a period of 35 minutes is allowed to flow. During the inflow, the temperature of the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature of the reaction vessel is raised to 80 ° C. and maintained for 30 minutes.
次に、メタクリル酸メチル6.8部、アクリル酸n−ブチル9.6部、メタクリル酸1.6部、2−ヒドロキシエチルメタアクリレート12部、ドデシルメルカプタン1部、ニューコール707SFの30%溶液を2部、過硫酸アンモニウムの2%の水溶液1.5部、水17部からなる乳化混合液を90分かけて流入させる。流入中は反応容器の温度を80℃に保つ。流入が終了してから、水7.5部を加え、反応容器の温度を80℃にして90分保つ。 Next, 6.8 parts of methyl methacrylate, 9.6 parts of n-butyl acrylate, 1.6 parts of methacrylic acid, 12 parts of 2-hydroxyethyl methacrylate, 1 part of dodecyl mercaptan, 30% solution of Newcol 707SF An emulsified mixture consisting of 2 parts, 1.5 parts of a 2% aqueous solution of ammonium persulfate and 17 parts of water is allowed to flow in over 90 minutes. During the inflow, the temperature of the reaction vessel is maintained at 80 ° C. After the inflow is completed, 7.5 parts of water is added, and the temperature of the reaction vessel is raised to 80 ° C. and maintained for 90 minutes.
室温まで冷却後、希釈水と25%アンモニア水溶液を添加してpH8、固形分35%に調整してから100メッシュの金網でろ過した。ろ過された凝集物の乾燥質量は全単量体に対して0.002%とわずかであった。得られた水性樹脂分散体(A)の固形分率は35.4%、粒子径110nmで単一分布であった。
[製造例2〜16]
1段目及び2段目の乳化混合液に用いる各成分の種類や量、及び各乳化混合液のフィード時間を表1に示すように変更した以外は、製造例1と同様の方法にて、水性樹脂分散体を得た。得られた水性樹脂分散体について各試験を行った。結果を表1に示す。
After cooling to room temperature, diluted water and 25% aqueous ammonia solution were added to adjust the pH to 8 and the solid content to 35%, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was as small as 0.002% with respect to the total monomers. The obtained aqueous resin dispersion (A) had a solid content of 35.4%, a particle size of 110 nm, and a single distribution.
[Production Examples 2 to 16]
Except for changing the type and amount of each component used in the first stage and second stage emulsified mixed liquid and the feed time of each emulsified mixed liquid as shown in Table 1, in the same manner as in Production Example 1, An aqueous resin dispersion was obtained. Each test was done about the obtained aqueous resin dispersion. The results are shown in Table 1.
なお各重合性単量体の量は、両段で使用した重合性単量体成分合計量100質量部に対する比率(質量部)で示した。
<試験方法>
・水酸基価の測定
水性樹脂分散体の樹脂部(A1)の水酸基価は、水性樹脂分散体の樹脂部(A1)を合成する時に使用するヒドロキシル基含有エチレン性不飽和単量体(a)の質量部(各単量体(a)、(b)、及び(c)の合計を100質量部とする。)から、次式にて計算で求めた。
水酸基価(mgKOH/g)=(aの質量部/100)/(aの分子量)×56.1×1000
・酸価の測定
水性樹脂分散体の樹脂部(A1)の酸価は、水性樹脂分散体の樹脂部(A1)を合成する時に使用するカルボキシル基含有エチレン性不飽和単量体(b)の質量部(各単量体(a)、(b)、及び(c)の合計を100質量部とする。)から、次式にて計算で求めた。
酸価(mgKOH/g)=(bの質量部/100)/(bの分子量)×56.1×1000
・重合安定性の評価
乳化重合後に得られた水性樹脂分散体(A)を100メッシュの濾布で凝固物を濾過し、その残渣質量を水性樹脂分散体(A)の質量で割り、残渣率とした。残渣率が0.01%未満であれば、重合安定性は良好である。
・粘度の測定
乳化重合後に得られた水性樹脂分散体(A)をBM型粘度計を用い、23℃、ローターNo.21又は22又は23、回転数60rpmの条件で測定した。
・粒子径の測定
得られた水性樹脂分散体の平均粒子径を、リーズ&ノースラップ社製のマイクロトラック粒度分布計にて測定した。
・固形分率の測定
予め質量の分かっているアルミ皿に水性樹脂分散体を約1g正確に秤量し、恒温乾燥機で105℃にて3時間乾燥した後、シリカゲルを入れたデシケーター中で、30分放冷後に精秤する。当該物質の乾燥後質量を乾燥前質量で割ったものを固形分率とした。
<塗膜性能の評価方法>
・クリアー光沢
下記の架橋性水性樹脂組成物を黒色のABS板に、100μmの膜厚設定で塗布し、80℃、20分強制乾燥させた後、23℃、1週間乾燥させた。乾燥後の塗膜について、光沢計(マイクロトリグロスμ、BYKガードナー社製)にて60°光沢を測定した。
・塗膜外観
下記の架橋性水性樹脂組成物を透明のPC板に、100μmの膜厚設定で塗布し、80℃、20分強制乾燥させた後、23℃、1週間乾燥させた。乾燥後の塗膜の外観について、微小なブツの発生状況を目視判定した。
◎;なし。
○;少ない。
△;多い。
×;非常に多い。
・鉛筆硬度
下記の架橋性水性樹脂組成物を透明のPC板に、100μmの乾燥膜厚設定で塗布し、80℃、20分強制乾燥させた後、23℃、1週間乾燥させた。乾燥後の塗膜に対し、JIS K5600−5−4(引っかき硬度)に準じて試験を行った。
[実施例1]
製造例1の水性樹脂分散体(固形分35.4%)100部を攪拌機で攪拌し、その中にデュラネートWT30−100(旭化成ケミカルズ(株)製、固形分100%)12.2部、水23.8部を添加し、水性樹脂組成物を得た。この水性樹脂組成物について、上記の各試験を行った。
In addition, the quantity of each polymerizable monomer was shown by the ratio (mass part) with respect to 100 mass parts of polymerizable monomer component total amounts used at both stages.
<Test method>
Measurement of hydroxyl value The hydroxyl value of the resin part (A1) of the aqueous resin dispersion is determined by the hydroxyl group-containing ethylenically unsaturated monomer (a) used when synthesizing the resin part (A1) of the aqueous resin dispersion. It calculated | required by calculation by following Formula from the mass part (The sum total of each monomer (a), (b) and (c) is 100 mass parts).
Hydroxyl value (mg KOH / g) = (part by mass of a / 100) / (molecular weight of a) × 56.1 × 1000
-Acid value measurement The acid value of the resin part (A1) of the aqueous resin dispersion is the same as that of the carboxyl group-containing ethylenically unsaturated monomer (b) used when synthesizing the resin part (A1) of the aqueous resin dispersion. It calculated | required by calculation by following Formula from the mass part (The sum total of each monomer (a), (b) and (c) is 100 mass parts).
Acid value (mgKOH / g) = (part by mass of b / 100) / (molecular weight of b) × 56.1 × 1000
Evaluation of polymerization stability The aqueous resin dispersion (A) obtained after emulsion polymerization was filtered through a 100-mesh filter cloth, and the residue mass was divided by the mass of the aqueous resin dispersion (A) to obtain the residue rate. It was. If the residue rate is less than 0.01%, the polymerization stability is good.
-Viscosity measurement The aqueous resin dispersion (A) obtained after emulsion polymerization was measured using a BM viscometer at 23 ° C, rotor No. The measurement was performed under the conditions of 21 or 22 or 23 and a rotational speed of 60 rpm.
-Measurement of particle diameter The average particle diameter of the obtained aqueous resin dispersion was measured with a Microtrac particle size distribution meter manufactured by Leeds & Northrup.
・ Measurement of solid content rate About 1 g of the aqueous resin dispersion was accurately weighed in an aluminum pan of which the mass was known in advance, dried at 105 ° C. for 3 hours with a constant temperature dryer, and then in a desiccator containing silica gel. Weigh accurately after minute cooling. The solid content was obtained by dividing the mass after drying of the substance by the mass before drying.
<Evaluation method of coating film performance>
Clear gloss The following crosslinkable aqueous resin composition was applied to a black ABS plate at a film thickness of 100 μm, forcedly dried at 80 ° C. for 20 minutes, and then dried at 23 ° C. for 1 week. With respect to the dried coating film, the 60 ° gloss was measured with a gloss meter (Micro Trigloss μ, manufactured by BYK Gardner).
-Appearance of coating film The following crosslinkable aqueous resin composition was applied to a transparent PC plate at a film thickness of 100 μm, forcedly dried at 80 ° C. for 20 minutes, and then dried at 23 ° C. for 1 week. About the appearance of the coating film after drying, the occurrence state of minute irregularities was visually determined.
◎; None.
○: Less.
Δ: Many.
X: Very many.
Pencil Hardness The following crosslinkable aqueous resin composition was applied to a transparent PC plate with a dry film thickness setting of 100 μm, forcedly dried at 80 ° C. for 20 minutes, and then dried at 23 ° C. for 1 week. The coating after drying was tested according to JIS K5600-5-4 (scratch hardness).
[Example 1]
100 parts of the aqueous resin dispersion (solid content 35.4%) of Production Example 1 was stirred with a stirrer, and in that, Duranate WT30-100 (manufactured by Asahi Kasei Chemicals Corporation, solid content 100%) 12.2 parts, water 23.8 parts was added to obtain an aqueous resin composition. Each of the above tests was performed on this aqueous resin composition.
実施例1は、塗膜外観に優れ、光沢、鉛筆硬度とも高く、良好である。
[実施例2〜12]
製造例2〜12の水性樹脂分散体を用い、デュラネートWT30−100、及び水の使用量を表2記載のものに変更したほかは、実施例1と同様な方法にて、架橋性水性樹脂組成物を得た。この水性樹脂組成物について、上記の各試験を行った。結果を表2に示す。
Example 1 is excellent in coating film appearance, high in gloss and pencil hardness, and good.
[Examples 2 to 12]
A crosslinkable aqueous resin composition was prepared in the same manner as in Example 1, except that the aqueous resin dispersions of Production Examples 2 to 12 were used, and Duranate WT30-100 and the amount of water used were changed to those shown in Table 2. I got a thing. Each of the above tests was performed on this aqueous resin composition. The results are shown in Table 2.
実施例2〜12は、いずれも塗膜外観が良好であり、光沢、鉛筆硬度とも高く、良好である。
[比較例1〜4]
製造例13〜16の水性樹脂分散体を用い、デュラネートWT30−100、及び水の使用量を表2記載のものに変更したほかは、実施例1と同様な方法にて、架橋性水性樹脂組成物を得た。この水性樹脂組成物について、各試験を行った。結果を表2に示す。
比較例1は、光沢、鉛筆硬度とも高いが、塗膜外観が不良である。
比較例2は、塗膜外観は良好であるが、光沢が低く、塗膜外観も不良である。
比較例3は、光沢、鉛筆硬度とも高いが、塗膜外観が不良である。
比較例4は、架橋性水性樹脂組成物の粘度が高すぎるため、評価に値する塗膜が得られない。
In Examples 2 to 12, the coating film appearance is good, and both gloss and pencil hardness are high and good.
[Comparative Examples 1-4]
A crosslinkable aqueous resin composition was prepared in the same manner as in Example 1, except that the aqueous resin dispersions of Production Examples 13 to 16 were used, and Duranate WT30-100 and the amount of water used were changed to those shown in Table 2. I got a thing. Each test was done about this aqueous resin composition. The results are shown in Table 2.
Comparative Example 1 has high gloss and pencil hardness, but the coating film appearance is poor.
In Comparative Example 2, the coating film appearance is good, but the gloss is low and the coating film appearance is poor.
Comparative Example 3 has high gloss and pencil hardness, but the coating film appearance is poor.
In Comparative Example 4, since the viscosity of the crosslinkable aqueous resin composition is too high, a coating film worthy of evaluation cannot be obtained.
なお、製造例で用いた重合性単量体の表1等における略称、名称は以下の通りである。また、Foxの式により重合性単量体のガラス転移温度(Tg/℃)を算出するために使用した各々のホモポリマーのTg値を()内に示した。
ヒドロキシル基含有エチレン性不飽和単量体(a)
2HEMA:メタクリル酸2−ヒドロキシエチル(55)
カルボキシル基含有エチレン性不飽和単量体(b)
AA:アクリル酸(87)
MAA:メタクリル酸(144)
その他の重合可能な重合性単量体(c)
MMA:メタクリル酸メチル(105)
BA:アクリル酸n−ブチル(−45)
BMA:メタクリル酸n−ブチル(22)
2EHA:アクリル酸2−エチルへキシル(−55)20
CHMA:メタクリル酸シクロヘキシル(83)
また、製造例で用いた重合性単量体以外に用いた成分は、表1においては略称又は商品名で示すが、その詳細は以下である。
分子量調整剤(d)
t−DDM:ドデシルメルカプタン
Si含有化合物(e)
SZ6030:γ−メタクリロキシプロピルトリメトキシシラン/東レダウコーニング(株)
SZ6070:メチルトリメトキシシラン/東レダウコーニング(株)
AY43−004:ジメチルジメトキシシラン/東レダウコーニング(株)
上記以外の成分
NC707SF:アニオン性乳化剤/日本乳化剤(株)
Em120:ノニオン性乳化剤 エマルゲン120/花王(株)
APS:過硫酸アンモニウム
TINUVIN123:ベンゾトリアゾール系紫外線吸収剤/BASF(株)
TINUVIN400:ヒドロキシフェニルトリアジン系紫外線吸収剤/BASF(株)
The abbreviations and names in Table 1 etc. of the polymerizable monomers used in the production examples are as follows. Moreover, Tg value of each homopolymer used in order to calculate the glass transition temperature (Tg / degreeC) of a polymerizable monomer by Fox formula was shown in ().
Hydroxyl group-containing ethylenically unsaturated monomer (a)
2HEMA: 2-hydroxyethyl methacrylate (55)
Carboxyl group-containing ethylenically unsaturated monomer (b)
AA: Acrylic acid (87)
MAA: Methacrylic acid (144)
Other polymerizable monomer (c)
MMA: Methyl methacrylate (105)
BA: n-butyl acrylate (-45)
BMA: n-butyl methacrylate (22)
2EHA: 2-ethylhexyl acrylate (-55) 20
CHMA: cyclohexyl methacrylate (83)
Moreover, although the component used other than the polymerizable monomer used by the manufacture example is shown by an abbreviation or a brand name in Table 1, the detail is as follows.
Molecular weight regulator (d)
t-DDM: dodecyl mercaptan
Si-containing compound (e)
SZ6030: γ-methacryloxypropyltrimethoxysilane / Toray Dow Corning Co., Ltd.
SZ6070: Methyltrimethoxysilane / Toray Dow Corning Co., Ltd.
AY43-004: Dimethyldimethoxysilane / Toray Dow Corning Co., Ltd.
Components other than the above NC707SF: Anionic emulsifier / Nippon Emulsifier Co., Ltd.
Em120: Nonionic emulsifier Emulgen 120 / Kao Corporation
APS: ammonium persulfate
TINUVIN123: Benzotriazole UV absorber / BASF
TINUVIN400: hydroxyphenyltriazine UV absorber / BASF Corporation
本発明の架橋性水性樹脂組成物は、自動車内外装部品や家電製品に用いられるプラスチック基材や自動車補修用のクリアトップコート塗料やコーティング用途として好適であり、産業上高い利用価値を有する。 The crosslinkable aqueous resin composition of the present invention is suitable as a plastic base material used in automobile interior and exterior parts and home appliances, as a clear top coat paint for automobile repair, and as a coating application, and has a high industrial utility value.
Claims (3)
(R1)n−Si−(R2)4−n(1)
(式中nは0から3の整数であり、R1は水素、炭素数1〜16の脂肪族炭化水素基、炭素数5〜10のアリール基、及び炭素数5〜6のシクロアルキル基からなる群より選ばれる基。n個のR1は同一であっても、異なっても良い。R2は炭素数1〜8のアルコキシ基、アセトキシ基、及び水酸基からなる群より選ばれる基。4−n個のR2は同一であっても、異なっても良い。) The resin part (A1) of the aqueous resin dispersion (A) further contains a Si-containing compound (e) represented by the following formula (1) or a polymer obtained therefrom. Item 3. The crosslinkable aqueous resin composition according to Item 1 or 2.
(R1) n-Si- (R2) 4-n (1)
(In the formula, n is an integer of 0 to 3, and R1 is composed of hydrogen, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group having 5 to 10 carbon atoms, and a cycloalkyl group having 5 to 6 carbon atoms. A group selected from the group, n R1s may be the same or different, and R2 is a group selected from the group consisting of an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, and a hydroxyl group. R2 in the above may be the same or different.)
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JP2018172678A (en) * | 2017-03-31 | 2018-11-08 | 株式会社日本触媒 | Resin emulsion |
JP2020097708A (en) * | 2018-12-19 | 2020-06-25 | 関西ペイント株式会社 | Aqueous coating composition |
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