JP2008063567A - Aqueous resin dispersion - Google Patents
Aqueous resin dispersion Download PDFInfo
- Publication number
- JP2008063567A JP2008063567A JP2007198784A JP2007198784A JP2008063567A JP 2008063567 A JP2008063567 A JP 2008063567A JP 2007198784 A JP2007198784 A JP 2007198784A JP 2007198784 A JP2007198784 A JP 2007198784A JP 2008063567 A JP2008063567 A JP 2008063567A
- Authority
- JP
- Japan
- Prior art keywords
- resin dispersion
- aqueous resin
- parts
- group
- aqueous
- 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
- 229920005989 resin Polymers 0.000 title claims abstract description 152
- 239000011347 resin Substances 0.000 title claims abstract description 152
- 239000006185 dispersion Substances 0.000 title claims abstract description 110
- 239000000178 monomer Substances 0.000 claims abstract description 84
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 239000003995 emulsifying agent Substances 0.000 claims description 26
- 230000009477 glass transition Effects 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 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
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000005250 alkyl acrylate 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 37
- -1 γ-methacryloxypropyl Chemical group 0.000 description 36
- 239000007864 aqueous solution Substances 0.000 description 30
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 29
- 229910000077 silane Inorganic materials 0.000 description 24
- 230000000903 blocking effect Effects 0.000 description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 20
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 19
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 13
- 239000003973 paint Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000003945 anionic surfactant Substances 0.000 description 10
- 239000003245 coal Substances 0.000 description 10
- 239000000839 emulsion Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004611 light stabiliser Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 8
- 125000000129 anionic group Chemical group 0.000 description 8
- 239000002736 nonionic surfactant Substances 0.000 description 8
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000004566 building material Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000004759 cyclic silanes Chemical class 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000012874 anionic emulsifier Substances 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
- 238000006482 condensation reaction Methods 0.000 description 3
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 239000005002 finish coating Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 239000012875 nonionic emulsifier Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 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
- 239000004094 surface-active agent Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- TURPNXCLLLFJAP-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethyl hydrogen sulfate Chemical compound OCCOCCOCCOS(O)(=O)=O TURPNXCLLLFJAP-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
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 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
- 238000011156 evaluation Methods 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
- 238000005259 measurement Methods 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
- 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
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- HYZQWUZNJVOCCK-UHFFFAOYSA-N (1,2,2,3,3-pentamethylpiperidin-4-yl) 2-methylprop-2-enoate Chemical compound CN1CCC(OC(=O)C(C)=C)C(C)(C)C1(C)C HYZQWUZNJVOCCK-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 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 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
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 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
- 238000005160 1H NMR spectroscopy Methods 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
- 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
- DQYJCFBXVYOJFX-UHFFFAOYSA-N 2,6-ditert-butyl-4-[3-[2-[4-[3-(3,5-ditert-butyl-4-hydroxyphenyl)prop-1-ynoxy]-2,2,6,6-tetramethylpiperidin-1-yl]ethoxy]prop-2-ynyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC#COCCN2C(CC(CC2(C)C)OC#CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(C)C)=C1 DQYJCFBXVYOJFX-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
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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
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000058 polyacrylate 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
- 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
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-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
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 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
- 229940001607 sodium bisulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 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
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
- 239000007962 solid dispersion Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 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
- 230000002463 transducing effect Effects 0.000 description 1
- 150000003918 triazines Chemical class 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
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
本発明は、良好な成膜性を有し、かつ耐候性と耐ブロッキング性に優れた塗料やコーティング用途等に用いられる水性樹脂分散体に関する。ここで、ブロッキングとは、各種被塗物、例えば、金属、木材、紙、プラスチック、無機建材等の基材に水性樹脂分散体が塗装されたものが積み重ねられた際に、塗膜同士が接着する現象を意味する。 The present invention relates to an aqueous resin dispersion having good film formability and excellent in weather resistance and blocking resistance and used for paints and coating applications. Here, blocking refers to various coated objects such as metals, wood, paper, plastics, inorganic building materials, etc., which are coated with water-based resin dispersions, and the coatings adhere to each other. Means the phenomenon.
近年、環境問題の観点から水性塗料の使用が多くなっており、水性樹脂分散体が塗料やコーティング用途に広く用いられている。しかしながら、水性樹脂分散体の造膜（皮膜形成）は、ポリマー粒子の融合により行われるため、その樹脂のガラス転移温度（Ｔｇ）が高いものは造膜助剤を多量に使用して造膜させなければならない。そうすると、塗膜の乾燥が不十分な場合、残存する造膜助剤の影響で耐ブロッキング性が悪くなる問題点があった。また、水性樹脂分散体の該樹脂のガラス転移温度（Ｔｇ）の低いものは常温付近で造膜させる事ができるが、形成された塗膜は乾燥後も粘着性が残り、耐ブロッキング性が悪くなる問題がある。耐ブロッキング性が悪いと塗膜の破損や基材の破壊が生じ、塗装本来の目的である被覆物（基材）の保護や美観を向上させるという目的が達成されないため、塗装用（特に、工場塗装用）等に用いられる水性樹脂分散体には耐ブロッキング性が必要になる。そこで、高いＴｇを有し、且つ造膜助剤が少なくて済むような低い造膜温度（ＭＦＴ）をもつ水性樹脂分散体について様々な検討が行われている。それらの手法として、水性樹脂分散体のコア部に高いＴｇ樹脂成分となる単量体を用い、シェル部に低いＴｇ樹脂成分となる単量体を使用することで前述した特長を示す水性樹脂分散体が特許文献１、特許文献２に開示されている。しかし、特許文献１では高Ｔｇ樹脂成分が１０〜３５質量％と少ないため一定の耐ブロッキング性能は得られるが、過酷な条件下では耐ブロッキング性が不十分という問題があった。また、特許文献２では、耐候性に問題があり、なおかつ過酷な条件下では耐ブロッキング性もまた不十分であった。 In recent years, water-based paints are increasingly used from the viewpoint of environmental problems, and water-based resin dispersions are widely used for paints and coating applications. However, since the film formation (film formation) of the aqueous resin dispersion is performed by fusing polymer particles, those having a high glass transition temperature (Tg) of the resin are formed using a large amount of a film forming aid. There must be. Then, when the coating film is insufficiently dried, there is a problem that the blocking resistance is deteriorated due to the influence of the remaining film forming aid. In addition, although the resin having a low glass transition temperature (Tg) of the aqueous resin dispersion can be formed at around room temperature, the formed coating film remains sticky after drying and has poor blocking resistance. There is a problem. If the blocking resistance is poor, the coating will be damaged or the substrate will be destroyed, and the purpose of the coating (substrate), which is the original purpose of coating, will not be achieved. Aqueous resin dispersions used for coating and the like require blocking resistance. Accordingly, various studies have been conducted on aqueous resin dispersions having a high Tg and a low film-forming temperature (MFT) that requires a small amount of film-forming aid. As these techniques, the aqueous resin dispersion exhibits the above-mentioned features by using a monomer that becomes a high Tg resin component in the core part of the aqueous resin dispersion and a monomer that becomes a low Tg resin component in the shell part. The body is disclosed in Patent Document 1 and Patent Document 2. However, in Patent Document 1, since the high Tg resin component is as small as 10 to 35% by mass, a certain blocking resistance can be obtained, but there is a problem that the blocking resistance is insufficient under severe conditions. Moreover, in patent document 2, there existed a problem in a weather resistance, and also blocking resistance was also inadequate under severe conditions.
本発明は、良好な成膜性を有し、かつ耐候性と耐ブロッキング性に優れた塗膜を形成し得る水性樹脂分散体を提供することである。 An object of the present invention is to provide an aqueous resin dispersion having good film formability and capable of forming a coating film excellent in weather resistance and blocking resistance.
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。
即ち、本発明の第１は、ガラス転移温度（Ｔｇ）が異なる２種類以上の重合性単量体を用いて重合した水性樹脂分散体であって、その水性樹脂分散体は、ガラス転移温度（Ｔｇ）が５０℃以上の高Ｔｇ樹脂成分と、ガラス転移温度（Ｔｇ）が４０℃以下の低Ｔｇ樹脂成分からなり、その水性樹脂分散体の最低成膜温度（ＭＦＴ）が水性樹脂分散体全体のガラス転移温度（Ｔｇ）より１０℃以上低いことを特徴とする水性樹脂分散体である。
発明の第２は、水性樹脂分散体全体のガラス転移温度（Ｔｇ）が４０℃以上であることを特徴とする発明の第１に記載の水性樹脂分散体である。
発明の第３は、高Ｔｇ樹脂成分と低Ｔｇ樹脂成分の質量比が高Ｔｇ樹脂成分／低Ｔｇ樹脂成分（重量比）＝３５／６５〜７０／３０であることを特徴とする発明の第１又は２に記載の水性樹脂分散体である。
As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the first of the present invention is an aqueous resin dispersion polymerized using two or more kinds of polymerizable monomers having different glass transition temperatures (Tg), and the aqueous resin dispersion has a glass transition temperature ( Tg) is composed of a high Tg resin component having a temperature of 50 ° C. or higher and a low Tg resin component having a glass transition temperature (Tg) of 40 ° C. or lower, and the minimum film formation temperature (MFT) of the aqueous resin dispersion is the entire aqueous resin dispersion. It is an aqueous resin dispersion characterized by being 10 ° C. or more lower than the glass transition temperature (Tg).
A second aspect of the invention is the aqueous resin dispersion according to the first aspect of the invention, wherein the glass transition temperature (Tg) of the entire aqueous resin dispersion is 40 ° C. or higher.
According to a third aspect of the invention, the mass ratio of the high Tg resin component and the low Tg resin component is high Tg resin component / low Tg resin component (weight ratio) = 35/65 to 70/30. The aqueous resin dispersion according to 1 or 2.
発明の第４は、水性樹脂分散体の高Ｔｇ樹脂成分にアルコキシシラン基含有重合性単量体（Ａ）及びシクロアルキル基含有重合性単量体（Ｂ）を含むことを特徴とする発明の第１〜３のいずれかに記載の水性樹脂分散体である。
発明の第５は、水性樹脂分散体の高Ｔｇ樹脂成分に、２０℃での水１００ｇに対する溶解度が１０ｇ以上の親水性重合性単量体（Ｃ）及び反応性乳化剤（Ｄ）を含まないことを特徴とする発明の第１〜４のいずれかに記載の水性樹脂分散体である。
発明の第６は、水性樹脂分散体の低Ｔｇ樹脂成分に、架橋性モノマー（Ｅ）を含むことを特徴とする発明の１〜５のいずれかに記載の水性樹脂分散体である。
A fourth aspect of the invention is characterized in that the high Tg resin component of the aqueous resin dispersion contains an alkoxysilane group-containing polymerizable monomer (A) and a cycloalkyl group-containing polymerizable monomer (B). It is the aqueous resin dispersion in any one of 1-3.
The fifth aspect of the invention is that the high Tg resin component of the aqueous resin dispersion does not contain a hydrophilic polymerizable monomer (C) having a solubility in 100 g of water at 20 ° C. of 10 g or more and a reactive emulsifier (D). The aqueous resin dispersion according to any one of the first to fourth aspects of the invention.
A sixth aspect of the invention is the aqueous resin dispersion according to any one of the first to fifth aspects of the invention, wherein the low Tg resin component of the aqueous resin dispersion contains a crosslinkable monomer (E).
発明の第７は、水性樹脂分散体を構成する重合性単量体として、下記式（１）で表されるＳｉ含有化合物（Ｆ）をも含んでいることを特徴とする発明の第１〜６のいずれかに記載の水性樹脂分散体である。
（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、炭素数５〜６のシクロアルキル基、ビニル基、炭素数１〜１０のアクリル酸アルキル基、または炭素数１〜１０のメタクリル酸アルキル基から選ばれる。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、水酸基から選ばれる。４−ｎ個のＲ２は同一であっても、異なっても良い。）
A seventh aspect of the invention includes the Si-containing compound (F) represented by the following formula (1) as a polymerizable monomer constituting the aqueous resin dispersion. 6. The aqueous resin dispersion according to any one of 6 above.
(R 1) n -Si- (R 2) 4-n (1)
(In the formula, n is an integer of 0 to 3, R 1 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, vinyl. Selected from a group, an alkyl acrylate group having 1 to 10 carbon atoms, or an alkyl methacrylate group having 1 to 10 carbon atoms, n R 1 may be the same or different, and R 2 is the number of carbon atoms. (It is selected from 1 to 8 alkoxy groups, acetoxy groups, and hydroxyl groups. 4-n R 2 groups may be the same or different.)
発明の第８は、高Ｔｇ樹脂成分が水性樹脂分散体の中心部分（コア）、低Ｔｇ樹脂成分が水性樹脂分散体の外側部分（シェル）からなる粒子構造を有することを特徴とする発明の第１〜７のいずれかに記載の水性樹脂分散体である。
発明の第９は、２段階以上の工程で乳化重合して得られることを特徴とする発明の第１〜８のいずれかに記載の水性樹脂分散体である。
発明の第１０は、乳化重合中のｐＨが４以下で製造されることを特徴とする発明の第１〜９のいずれかに記載の水性樹脂分散体である。
発明の第１１は、発明の第１〜１０のいずれかに記載の水性樹脂分散体を含む塗料である。
An eighth aspect of the invention is characterized in that the high Tg resin component has a particle structure consisting of the central portion (core) of the aqueous resin dispersion and the low Tg resin component consists of the outer portion (shell) of the aqueous resin dispersion. It is the aqueous resin dispersion in any one of 1-7.
A ninth aspect of the invention is the aqueous resin dispersion according to any one of the first to eighth aspects of the invention, which is obtained by emulsion polymerization in two or more steps.
A tenth aspect of the present invention is the aqueous resin dispersion according to any one of the first to ninth aspects, wherein the pH during emulsion polymerization is 4 or less.
An eleventh aspect of the invention is a paint containing the aqueous resin dispersion according to any one of the first to tenth aspects of the invention.
本発明の水性樹脂分散体を使用すれば低い温度で成膜することができ、耐候性と耐ブロッキング性に優れる塗膜を形成することができる。 If the aqueous resin dispersion of this invention is used, it can form into a film at low temperature and can form the coating film which is excellent in a weather resistance and blocking resistance.
以下、本発明について詳細に説明する。
水性樹脂分散体
本発明における水性樹脂分散体は、ガラス転移温度（Ｔｇ）が異なる複数の重合性単量体成分の個々が重合する過程で一体化してなる水性樹脂分散体であり、高Ｔｇ樹脂成分（以下、単に高Ｔｇ成分ということもある。）のＴｇが５０℃以上、低Ｔｇ樹脂成分（以下、単に低Ｔｇ成分ということもある。）のＴｇが４０℃以下からなるアクリル系重合体の水性分散体である。特に耐ブロッキング性と成膜性から高Ｔｇ成分がコア部、低Ｔｇ成分がシェル部にあり、コア部のＴｇが７０℃以上、シェル部のＴｇが３０℃以下であることが好ましい。
水性樹脂分散体全体のＴｇは、耐ブロッキング性に極めて優れる水性樹脂分散体が得られるため４０℃以上が好ましく、４３℃以上がより好ましく、４５℃以上がさらに好ましい。
なお、本発明において、水性樹脂分散体の高Ｔｇ成分、低Ｔｇ成分及びその全体の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。
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、各モノマーの重量分率をＷｉとしており、（Ｗ１＋Ｗ２＋・・・＋Ｗｉ＋・・・＋Ｗｎ＝１）］
Hereinafter, the present invention will be described in detail.
Aqueous Resin Dispersion The aqueous resin dispersion in the present invention is an aqueous resin dispersion formed by integrating a plurality of polymerizable monomer components having different glass transition temperatures (Tg) in the process of polymerization. An acrylic polymer having a Tg of 50 ° C. or more and a low Tg resin component (hereinafter sometimes simply referred to as a low Tg component) having a Tg of 40 ° C. or less. An aqueous dispersion of In particular, it is preferable that the high Tg component is in the core part and the low Tg component is in the shell part from the blocking resistance and film forming property, the Tg of the core part is 70 ° C. or higher, and the Tg of the shell part is 30 ° C. or lower.
The Tg of the entire aqueous resin dispersion is preferably 40 ° C. or higher, more preferably 43 ° C. or higher, and even more preferably 45 ° C. or higher because an aqueous resin dispersion having extremely excellent blocking resistance can be obtained.
In the present invention, the high Tg component, the low Tg component and the total Tg (K: absolute temperature) of the aqueous resin dispersion are those calculated using the following FOX equation.
1 / Tg = W 1 / Tg 1 + W 2 / Tg 2 +... + W i / Tg i +... W n / Tg n
[In the FOX formula, the glass transition temperature of the homopolymer of each monomer constituting the polymer composed of n types of monomers is Tg i (K), the weight fraction of each monomer is W i , (W 1 + W 2 +... + W i +... + W n = 1)]
また本発明において、高Ｔｇ成分と低Ｔｇ成分の比率は、高Ｔｇ成分／低Ｔｇ成分（重量比）＝３５／６５〜７０／３０であることが重要である。好ましくは、高Ｔｇ成分／低Ｔｇ成分（重量比）＝４０／６０〜６０／４０であるのが良い。高Ｔｇ成分の比率が前記比率より少ないと、耐ブロッキング性が悪くなる。一方、高Ｔｇ成分の比率が前記範囲より多いと、ＭＦＴが上昇し、成膜性を損なうこととなる。
上記した高Ｔｇ成分がコア部、低Ｔｇ成分がシェル部に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。
さらに本発明において、高Ｔｇ成分に２０℃での水１００ｇに対する溶解度が１０ｇ以上の親水性重合性単量体や反応性乳化剤を使用しないことが重要である。これにより、水性樹脂分散体粒子のコア、シェル構造のコントロールがしやすくなり、高Ｔｇ成分がコア部に、低Ｔｇ成分がシェル部により形成しやすくなる。この結果、水性樹脂分散体のＭＦＴを水性樹脂分散体全体のＴｇ（即ち、前記ＦＯＸ式より計算されるＴｇ）より１０℃以上低くすることができる。
In the present invention, it is important that the ratio between the high Tg component and the low Tg component is high Tg component / low Tg component (weight ratio) = 35/65 to 70/30. Preferably, high Tg component / low Tg component (weight ratio) = 40/60 to 60/40. When the ratio of the high Tg component is less than the above ratio, the blocking resistance is deteriorated. On the other hand, if the ratio of the high Tg component is larger than the above range, the MFT rises and the film formability is impaired.
SPM (scanning probe microscope) can be used as a method for confirming that the high Tg component is in the core portion and the low Tg component is in the shell portion.
Furthermore, in the present invention, it is important not to use a hydrophilic polymerizable monomer or reactive emulsifier having a solubility in 100 g of water at 20 ° C. of 10 g or more in the high Tg component. Thereby, it becomes easy to control the core and shell structure of the aqueous resin dispersion particles, and the high Tg component is easily formed in the core portion and the low Tg component is easily formed in the shell portion. As a result, the MFT of the aqueous resin dispersion can be made 10 ° C. or more lower than the Tg of the entire aqueous resin dispersion (that is, Tg calculated from the FOX equation).
アルコキシシラン基含有重合性単量体（Ａ）
本発明に使用されるアルコキシシラン基含有重合性単量体（Ａ）としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、ビニルメチルジメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−アクリロキシプロピルトリメトキシシラン、γ−アクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルメチルジエトキシシランなどであり、これらの群から選ばれた１または２以上が使用される。特に好ましくは、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシランである。さらに、高Ｔｇ樹脂成分のアルコキシシラン基含有重合性単量体（Ａ）の含有量が高Ｔｇ樹脂成分の全単量体中で０．１〜３０質量％であることが重要である。特に、重合安定性と耐ブロッキング性の観点から０．４〜２０質量％が好ましい。
Alkoxysilane group-containing polymerizable monomer (A)
Examples of the alkoxysilane group-containing polymerizable monomer (A) used in the present invention include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinylmethyldimethoxysilane, and γ-methacryloxypropyl. Trimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ -Methacryloxypropylmethyldiethoxysilane, etc., and one or more selected from these groups are used. Particularly preferred are γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane. Furthermore, it is important that the content of the alkoxysilane group-containing polymerizable monomer (A) of the high Tg resin component is 0.1 to 30% by mass in the total monomers of the high Tg resin component. In particular, 0.4 to 20% by mass is preferable from the viewpoints of polymerization stability and blocking resistance.
シクロアルキル基含有重合性単量体（Ｂ）
本発明に使用されるシクロアルキル基含有重合性単量体（Ｂ）としては、シクロヘキシル（メタ）アクリレート、メチルシクロヘキシル（メタ）アクリレート、第３級ブチルシクロヘキシル（メタ）アクリレートなどであり、これらの群から選ばれた１または２以上が使用される。特に好ましくは、シクロヘキシル（メタ）アクリレートである。さらに高Ｔｇ樹脂成分のシクロアルキル基含有重合性単量体（Ｂ）の含有量が高Ｔｇ樹脂成分の全単量体中で１０〜８０重量％であることが重要である。特に重合安定性と耐候性の観点から２０％〜８０％が好ましい。
Cycloalkyl group-containing polymerizable monomer (B)
Examples of the cycloalkyl group-containing polymerizable monomer (B) used in the present invention include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, tertiary butylcyclohexyl (meth) acrylate, and the like. 1 or 2 or more selected from is used. Particularly preferred is cyclohexyl (meth) acrylate. Furthermore, it is important that the content of the cycloalkyl group-containing polymerizable monomer (B) of the high Tg resin component is 10 to 80% by weight in the total monomers of the high Tg resin component. In particular, 20% to 80% is preferable from the viewpoint of polymerization stability and weather resistance.
親水性重合性単量体（Ｃ）
本発明で言う親水性重合性単量体（Ｃ）は、２０℃での水１００ｇに対する溶解度が１０ｇ以上の親水性重合性単量体であり、カルボキシル基含有単量体、水酸基含有単量体、アミド基含有単量体、スルホン酸基含有単量体などが挙げられる。カルボキシル基含有単量体の具体例としては、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、無水マレイン酸などが挙げられる。また、水酸基含有単量体の具体例としては、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）
アクリレートなどが挙げられる。また、アミド基含有単量体の具体例としては、（メタ）アクリルアミド、ダイアセトンアクリルアミド、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などが挙げられる。また、スルホン酸基含有単量体の具体例としては、スチレンスルホン酸ナトリウム、メタアリルスルホン酸ナトリウム、アリルスルホン酸ナトリウム、ビニルスルホン酸ナトリウムなどが挙げられる。２０℃での水１００ｇにたいする溶解度が１０ｇ以上の親水性重合性単量体の具体例を示したが、これらに限定されるものではない。これらの親水性重合性単量体は水性樹脂分散体の高Ｔｇ樹脂成分に使用しないことが重要である。これらの親水性重合性単量体を水性樹脂分散体の高Ｔｇ樹脂成分に使用すると、水性樹脂分散体の成膜性が低下し、目的とする最低成膜温度（ＭＦＴ）が得られない。また、これらの親水性重合性単量体は水性樹脂分散体の低Ｔｇ樹脂成分には使用しても構わないし、成膜性や重合安定性を考慮すると低Ｔｇ樹脂成分には積極的に使用することが望ましい。
Hydrophilic polymerizable monomer (C)
The hydrophilic polymerizable monomer (C) referred to in the present invention is a hydrophilic polymerizable monomer having a solubility in 100 g of water at 20 ° C. of 10 g or more, and includes a carboxyl group-containing monomer and a hydroxyl group-containing monomer. Amide group-containing monomers, sulfonic acid group-containing monomers, and the like. Specific examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride and the like. Specific examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, caprolactone-modified (meth) acrylate, polyethylene glycol ( (Meth) acrylate, polypropylene glycol (meth)
An acrylate etc. are mentioned. Specific examples of the amide group-containing monomer include (meth) acrylamide, diacetone acrylamide, N-methylol acrylamide, N-butoxymethyl acrylamide and the like. Specific examples of the sulfonic acid group-containing monomer include sodium styrene sulfonate, sodium methallyl sulfonate, sodium allyl sulfonate, sodium vinyl sulfonate, and the like. Although the specific example of the hydrophilic polymerizable monomer whose solubility with respect to 100 g of water at 20 degreeC was 10 g or more was shown, it is not limited to these. It is important that these hydrophilic polymerizable monomers are not used in the high Tg resin component of the aqueous resin dispersion. When these hydrophilic polymerizable monomers are used for the high Tg resin component of the aqueous resin dispersion, the film formability of the aqueous resin dispersion is lowered, and the target minimum film formation temperature (MFT) cannot be obtained. In addition, these hydrophilic polymerizable monomers may be used for the low Tg resin component of the aqueous resin dispersion, and are actively used for the low Tg resin component in consideration of film formability and polymerization stability. It is desirable to do.
反応性乳化剤（Ｄ）
本発明で言う反応性乳化剤は、分子内に不飽和二重結合を有する乳化剤であり、例えばアニオン性乳化剤、ノニオン性乳化剤などが挙げられる。例えば、ラウリル硫酸ナトリウムなどの脂肪酸塩や、高級アルコール硫酸エステル塩、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレン多環フェニルエーテル硫酸塩、ポリオキシノニルフェニルエーテルスルホン酸塩、ポリオキシエチレン−ポリオキシプロピレングリコールエーテル硫酸塩、スルホン酸基又は硫酸エステル基と重合性の不飽和二重結合を分子中に有する反応性アニオン性乳化剤、又は前述の骨格と重合性の不飽和二重結合を分子中に有する反応性ノニオン性乳化剤などが挙げられる。これらの反応性乳化剤は、水性樹脂分散体の高Ｔｇ樹脂成分に使用しないことが重要である。これらの反応性乳化剤を水性樹脂分散体の高Ｔｇ樹脂成分に使用すると、水性樹脂分散体の成膜性が低下し、目的とする最低成膜温度（ＭＦＴ）が得られない。また、これらの反応性乳化剤は水性樹脂分散体の低Ｔｇ樹脂成分には使用しても構わない。
Reactive emulsifier (D)
The reactive emulsifier referred to in the present invention is an emulsifier having an unsaturated double bond in the molecule, and examples thereof include an anionic emulsifier and a nonionic emulsifier. For example, fatty acid salts such as sodium lauryl sulfate, higher alcohol sulfate esters, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, polyoxyethylene alkyl ether sulfates, polyoxyethylene polycyclic phenyl ether sulfates, polyoxynonyls Phenyl ether sulfonate, polyoxyethylene-polyoxypropylene glycol ether sulfate, reactive anionic emulsifier having a sulfonic acid group or sulfate ester group and a polymerizable unsaturated double bond in the molecule, or the aforementioned skeleton Examples thereof include a reactive nonionic emulsifier having a polymerizable unsaturated double bond in the molecule. It is important that these reactive emulsifiers are not used in the high Tg resin component of the aqueous resin dispersion. When these reactive emulsifiers are used in the high Tg resin component of the aqueous resin dispersion, the film formability of the aqueous resin dispersion is lowered, and the target minimum film formation temperature (MFT) cannot be obtained. These reactive emulsifiers may be used for the low Tg resin component of the aqueous resin dispersion.
架橋性モノマー（Ｅ）
本発明に使用される架橋性モノマーは、２つ以上の反応性官能基を有する重合性単量体である。その具体例としては、トリメチロールプロパントリアクリレート、エチレングリコールジアクリレート、グリシジルメタアクリレート、アルコキシシラン基含有単量体などが挙げられるが、これらに限定されるものではない。これらの架橋性モノマーは、水性樹脂分散体の低Ｔｇ樹脂成分に使用することが重要である。低Ｔｇ樹脂成分に使用する前記架橋性モノマーの含有量は、低Ｔｇ樹脂成分の全単量体中で０．１〜３重量％であることが重要である。更に望ましくは０．２〜２重量％である。これらの架橋性モノマーの含有量が低Ｔｇ樹脂成分の全単量体中で０．１重量％未満であると、塗膜耐水性向上の効果が不充分であり、目的とする塗膜の耐水性が得られない。また、前記架橋性モノマーの含有量が低Ｔｇ樹脂成分の全単量体中で３重量％を超えると、塗膜の成膜性が著しく低下し、目的とする最低成膜温度（ＭＦＴ）が得られない。
Crosslinkable monomer (E)
The crosslinkable monomer used in the present invention is a polymerizable monomer having two or more reactive functional groups. Specific examples thereof include, but are not limited to, trimethylolpropane triacrylate, ethylene glycol diacrylate, glycidyl methacrylate, and alkoxysilane group-containing monomers. It is important to use these crosslinkable monomers for the low Tg resin component of the aqueous resin dispersion. It is important that the content of the crosslinkable monomer used in the low Tg resin component is 0.1 to 3% by weight in the total monomers of the low Tg resin component. More desirably, the content is 0.2 to 2% by weight. When the content of these crosslinkable monomers is less than 0.1% by weight in all the monomers of the low Tg resin component, the effect of improving the water resistance of the coating film is insufficient, and the water resistance of the target coating film is insufficient. Sex cannot be obtained. Moreover, when the content of the crosslinkable monomer exceeds 3% by weight in all the monomers of the low Tg resin component, the film formability of the coating film is remarkably lowered, and the target minimum film formation temperature (MFT) is reduced. I can't get it.
Ｓｉ含有化合物（Ｆ）
本発明に使用されるＳｉ含有化合物（Ｆ）としては、下記式（１）で表される。
（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、炭素数５〜６のシクロアルキル基、ビニル基、炭素数１〜１０のアクリル酸アルキル基、または炭素数１〜１０のメタクリル酸アルキル基から選ばれる１種以上の基。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、水酸基から選ばれる１種以上の基。４−ｎ個のＲ２は同一であっても、異なっても良い。）
Si-containing compound (F)
The Si-containing compound (F) used in the present invention is represented by the following formula (1).
(R 1) n -Si- (R 2) 4-n (1)
(In the formula, n is an integer of 0 to 3, R 1 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, vinyl. One or more groups selected from a group, an alkyl acrylate group having 1 to 10 carbon atoms, or an alkyl methacrylate group having 1 to 10 carbon atoms, and n R 1 groups may be the same or different. R 2 is one or more groups selected from an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, and a hydroxyl group, and 4-n R 2 may be the same or different.
Ｓｉ含有化合物（Ｃ）には、式（１）においてｎ＝０としたシラン（Ｉ）および／または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、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などがある。
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、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などがある。
The Si-containing compound (C) 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 In order to obtain the polymerization stability of the dispersion, n = 1 silane (II) is more preferable.
R 2 of silane (I) is preferably each independently 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.
R 1 of silane (II) is preferably a methyl group or a phenyl group, and R 2 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、Ｓｉ含有化合物（Ｃ）が、環状シラン及び式（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、環状シラン及びシラン（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（Ｃ）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り、シラン（ＩＩ）と併用した場合に特に好ましい。
環状シラ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、などが上げられる。
Further, when flexibility is required, the Si-containing compound (C) is at least one selected from the group consisting of cyclic silane and silane (III) obtained by setting n = 2 in the formula (1). It is preferable to use it. This is because, by using at least one selected from the group consisting of silane (II), cyclic silane and silane (III), the crosslinking density of the silicone polymer formed by the Si-containing compound (C) is lowered, This is because the structure of the coalescence can be prevented from becoming complicated, and thereby, flexibility can be imparted to the coating film provided from the aqueous resin dispersion, particularly when used in combination with silane (II). preferable.
Specific examples of the cyclic silane 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、メチルフェニルシランが挙げられる。
さらに、Ｓｉ含有化合物（Ｆ）には、加水分解基を有する線状シロキサン、アルコシ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種を含んでも良い。
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などが挙げられる。
Specific examples of silane (III) include dimethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, and methylphenylsilane.
Further, the Si-containing compound (F) includes at least one selected from the group consisting of a linear siloxane having a hydrolyzing group, an alkoxysilane oligomer, and silane (IV) obtained by setting n = 3 in the formula (1). May be included.
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（１）、（２）、（３）で表される化合物が挙げられる。
（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又は炭素数１〜１０のメタクリル酸アルキル基から選ばれ、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又はポリアルキレンオキサイド基から選ばれ、ｍは１〜９９９の正の整数を表す。） (In the formula, R 1 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, and an alkyl acrylate group having 1 to 10 carbon atoms. Or selected from alkyl methacrylate having 1 to 10 carbon atoms, and each R 2 is independently selected from an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, a hydroxyl group, an epoxy group, an alkylene oxide group, or a polyalkylene oxide group. And m represents a positive integer of 1 to 999.)
シラン（ＩＩＩ）またはシラン（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。
Ｓｉ含有化合物（Ｆ）は、シラン（ＩＩ）および、環状シラン、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、を含むことができる。
In silane (III) or silane (IV), R 1 is particularly preferably a methyl group or a phenyl group, and R 2 is particularly preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group or a hydroxyl group.
The Si-containing compound (F) includes silane (II) and at least one selected from the group consisting of cyclic silane, silane (III), linear siloxane, alkoxysilane oligomer, silane (IV), and chlorosilane such as methyl It may include chlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenylchlorosilane.
本発明に使用されるＳｉ含有化合物（Ｆ）によって、本発明の水性樹脂分散体より得られる塗膜の屋外など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）または 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。 The Si-containing compound (F) used in the present invention can improve the gloss retention in a long-term exposure of the coating film obtained from the aqueous resin dispersion of the present invention outdoors. The presence of the above-mentioned silane condensate can be known by 29SiNMR (29Si nuclear magnetic resonance spectrum) or 1HNMR (proton nuclear magnetic resonance spectrum). For example, a condensate of silane (II) can be identified by a 29Si NMR chemical shift having a peak at −40 to −80 PPM.
本発明に使用される（Ａ）〜（Ｆ）以外の重合性単量体としては特に限定はなく、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、パーチサ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、ブタジエン等があり、さらに種々の官能性単量体例えば、ビニルピロリドン、（メタ）アクリル酸グリシジル、ジビニルベンゼン、メチルビニルケトンなどが含まれる。 The polymerizable monomer other than (A) to (F) used in the present invention is not particularly limited. For example, (meth) acrylic acid ester, styrene, vinyl toluene and other aromatic monomers, vinyl acetate, There are vinyl esters such as vinyl propionate and vinyl persuccinate, vinyl cyanides such as (meth) acrylonitrile, vinyl halides such as vinyl chloride and vinylidene chloride, butadiene, and various functional monomers such as Vinyl pyrrolidone, glycidyl (meth) acrylate, divinylbenzene, methyl vinyl ketone and the like.
（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）アクリレートなどがある。
（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などが挙げられる。
Specific examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms in the alkyl portion and (poly) having 1 to 100 ethylene oxide groups.
Oxyethylene mono (meth) acrylate, (poly) oxypropylene mono (meth) acrylate, (meth) acrylic acid hydroxyalkyl ester having 1 to 18 carbon atoms in the alkyl portion, 1 to 100 ethylene oxide groups ( And poly) oxyethylene di (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, and dodecyl (meth) acrylate.
本発明の水性樹脂分散体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などの存在下で、ｐＨが４以下の状態で不飽和単量体を、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、ラウリル硫酸ナトリウムなどの脂肪酸塩や、高級アルコール硫酸エステル塩、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレン多環フェニルエーテル硫酸塩、ポリオキシノニルフェニルエーテルスルホン酸塩、ポリオキシエチレン−ポリオキシプロピレングリコールエーテル硫酸塩、スルホン酸基又は硫酸エステル基と重合性の不飽和二重結合を分子中に有する、いわゆる反応性乳化剤などのアニオン性界面活性剤；ポリオキシエチレンアルキルエーテルや、ポリオキシエチレンノニルフェニルエーテル、ソルビタン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレン−ポリオキシプロピレンブロックコポリマー、又は前述の骨格と重合性の不飽和二重結合を分子中に有する反応性ノニオン性界面活性剤などのノニオン性界面活性剤；アルキルアミン塩や、第四級アンモニウム塩などのカチオン性界面活性剤；（変性）ポリビニルアルコールなどが挙げられる。
As a method for producing the aqueous resin dispersion of the present invention, an ordinary multistage emulsion polymerization method can be employed. As a typical example, an unsaturated monomer is usually emulsion-polymerized in water at a temperature of 60 to 90 ° C. in the presence of an emulsifier and a polymerization initiator in water in a state where the pH is 4 or less. Is a method in which is repeated a plurality of times.
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, fatty acid salts such as sodium lauryl sulfate, higher alcohol sulfate esters, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, polyoxyethylene alkyl ether sulfates, polyoxyethylene polycyclic phenyl ether sulfates, polyoxynonyls Anionic surface activity such as so-called reactive emulsifier having phenyl ether sulfonate, polyoxyethylene-polyoxypropylene glycol ether sulfate, sulfonic acid group or sulfate ester group and polymerizable unsaturated double bond in the molecule Agent: Polyoxyethylene alkyl ether, polyoxyethylene nonylphenyl ether, sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block copolymer Or a nonionic surfactant such as a reactive nonionic surfactant having a skeleton and a polymerizable unsaturated double bond in the molecule; a cationic surfactant such as an alkylamine salt or a quaternary ammonium salt ; (Modified) polyvinyl alcohol and the like.
前記乳化剤の使用量は、特に限定はされないが、例えば、全重合性単量体成分の合計使用量に対して、好ましくは１．０〜５．０重量％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することができる。また、高Ｔｇ成分をコアに低Ｔｇ成分をシェルにするためには、各段の乳化剤使用量について、低Ｔｇ成分をつくる段の使用量よりも高Ｔｇ成分をつくる段の使用量を多くすることが好ましい。 Although the usage-amount of the said emulsifier is not specifically limited, For example, Preferably it is 1.0 to 5.0 weight% with respect to the total usage-amount of all the polymerizable monomer components. 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. Moreover, in order to make a high Tg component into a core and a low Tg component into a shell, the amount of emulsifier used in each stage is increased in the amount used in the stage that produces the high Tg component than the amount used in the stage that produces the low Tg component. It is preferable.
本発明の水性樹脂分散体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などが挙げられる。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（Ｆ）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および／また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また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などが用いられる。 The polymerization method for emulsion polymerization of the aqueous resin dispersion of the present invention is a monomer batch charging method in which monomers are charged in a batch, a monomer dropping method in which monomers are continuously dropped, or a single amount. Examples include a pre-emulsion method in which a body, 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 (F) may be used by simultaneously performing a condensation reaction of hydrolyzable silane and radical polymerization of an unsaturated monomer and / or preceded by a condensation reaction of 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。
必要に応じて乳化重合に際して、分子量調整剤を使用することができる。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。使用方法は特に限定されるものではないが、好ましくはシェル部に使用し、その量は全体単量体量の２％以下が好ましい。
The polymerization initiator used for emulsion polymerization of the aqueous resin dispersion of the present invention is a generally used radical initiator. Radical polymerization initiators generate radicals by heat or reducing substances to cause addition polymerization of polymerizable monomers, and include water-soluble or oil-soluble persulfates, peroxides, and azobis compounds. . 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.
A molecular weight modifier can be used in the emulsion polymerization as required. Specific examples include dodecyl mercaptan and butyl mercaptan. The method of use is not particularly limited, but it is preferably used in the shell part, and the amount is preferably 2% or less of the total monomer amount.
本発明の水性樹脂分散体は、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など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。
その他、本発明の水性樹脂分散体には、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。
In order to maintain long-term dispersion stability of the emulsion, the aqueous resin dispersion of the present invention is a basic substance such as basic organic compounds such as amines such as ammonia and dimethylaminoethanol, sodium hydroxide, potassium hydroxide. 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.
In addition, in the aqueous resin dispersion of the present invention, components usually added and blended in water-based paints, such as thickeners, film forming aids, plasticizers, antifreezing agents, antifoaming agents, dyes, preservatives, ultraviolet rays An absorber, a light stabilizer, etc. can be arbitrarily mix | blended.
増粘剤として具体的には、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。
成膜助剤として具体的には、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、等が挙げられる。これら成膜助剤は、単独または併用など任意に配合することができる。
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 thickeners 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.
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 Examples include butyrate, diisopropyl glutarate, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, dipropylene glycol methyl ether, and tripropylene glycol methyl ether. These film-forming aids can be arbitrarily blended alone or in combination.
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、トリアジン系があり、ベンゾフェノン系紫外線吸収剤として具体的には、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などがある。 There are benzophenone series, benzotriazole series, and triazine series as ultraviolet absorbers. Specific examples of benzophenone ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 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- - hydroxybenzophenone 2-hydroxy-4-methoxy-2'-carboxy benzophenone, and the like 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として具体的には、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）ベンゾフェノンなどがある。 Specific examples of radical polymerizable benzophenone-based UV absorbers include 2-hydroxy-4-acryloxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-5-acryloxybenzophenone, and 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- (Acryloxy-triethoxy) benzophenone.
ベンゾトリアゾール系紫外線吸収剤として具体的には、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）などがある。 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 Corporation), isooctyl-3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxy Phenyl] 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) benzotria 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 (manufactured by 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として具体的には、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）などがある。
トリアジン系紫外線吸収剤として具体的には、ＴＩＮＵＶＩＮ４００（製品名、日本チバガイギー（株）製）などがある。
Specifically, as a radical polymerizable benzotriazole-based ultraviolet absorber, 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] Phenyl propionate (manufactured by Nippon Ciba-Geigy Co., Ltd., product name: CGL-104).
Specific examples of triazine-based ultraviolet absorbers include TINUVIN400 (product name, manufactured by Ciba Geigy Japan).
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。具体的には、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）などがある。 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. Specifically, 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-butylmalonate, 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, A mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl-sebacate (Nippon Ciba Geigy ( ), Product name: TINUVIN292), bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, TINUVIN123 (product name, manufactured by Nihon 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として具体的には、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などがある。 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- Examples include pentamethyl-4-piperidyl methacrylate.
本発明において、紫外線吸収剤および／または光安定剤は、水性樹脂分散体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に導入する方法、紫外線吸収剤および／または光安定剤を成膜助剤などと混合して水性樹脂分散体に添加することにより導入する方法、紫外線吸収剤および／また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 light stabilizer is introduced into the aqueous resin dispersion by being present during emulsion polymerization for producing the aqueous resin dispersion, and the ultraviolet absorber and / or light stabilizer is formed into a film. A method of introducing by mixing with an auxiliary agent and adding to an aqueous resin dispersion, an ultraviolet absorber and / or a light stabilizer are mixed with a film forming auxiliary agent, emulsified by adding a surfactant and water, The method of introduce | transducing by adding to an aqueous resin dispersion is mentioned. In addition, when an ultraviolet absorber and a light stabilizer are used in combination, it exhibits excellent durability due to a synergistic effect.
本発明の水性樹脂分散体は、分散質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）と分散媒としての水性媒体との質量比は７０／３０以下、好ましくは３０／７０以上６５／３５以下である。
本発明の水性樹脂分散体は、塗料、建材の下地処理材または仕上げ材、紙加工剤、または織布、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などの無機建材、織布あるいは不織布を基材とした建材、金属建材などの各種下地に対する塗料または建築仕上げ材として、複層仕上げ塗材用の主材およびトップコート、薄付け仕上塗材、厚付け仕上塗材、石材調仕上げ材、グロスペイントなど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 aqueous resin dispersion of the present invention preferably has an average particle size of the dispersoid of 30 to 500 nm. The mass ratio of the dispersoid (solid content) in the obtained emulsion to the aqueous medium as the dispersion medium is 70/30 or less, preferably 30/70 or more and 65/35 or less.
The water-based resin dispersion of the present invention is useful as a coating material, a ground treatment material or finishing material for building materials, a paper processing agent, or a finishing material for woven fabrics and nonwoven fabrics, and specifically as a finishing material for coating materials and building materials. Paints and finishing materials for various bases such as concrete, cement mortar, slate board, calcium silicate board, gypsum board, extruded board, foamed concrete, building materials based on woven or non-woven fabric, and metal building materials Main materials and top coats for multilayer finish coating materials, thin finish coating materials, thick finish coating materials, stone-like finish materials, synthetic paint emulsion paints such as gloss paint, metal paints, wood paints, tiles It is useful as a coating material.
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、実施例及び比較例中の部及び％はそれぞれ質量部、及び質量％を表す。また、得られた水性樹脂分散体の物性試験については、該水性樹脂分散体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。 The present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, the part and% in an Example and a comparative example represent a mass part and the mass%, respectively. Moreover, about the physical-property test of the obtained aqueous resin dispersion, the coating material was adjusted with the compounding composition shown below using this aqueous resin dispersion, and the test was implemented according to the test method shown below.
＜塗料配合組成＞
・クリアー塗料の作製
各水性樹脂分散体（固形分換算） ５００．００部
成膜助剤（以下の量は耐候性評価の場合）
エチレングリコールモノブチルエーテル５０部と水５０部
の混合液 １００．００部
ＣＳ−１２（製品名、チッソ（株）製） ５０．００部
増粘剤：アデカノールＵＨ−４３８（旭電化工業（株）製）
の１０％水溶液 適量
<Coating composition>
・ Preparation of clear paint Each water-based resin dispersion (solid content conversion) 500.00 parts Film-forming aid (The following amounts are for weather resistance evaluation)
50 parts of ethylene glycol monobutyl ether and 50 parts of water
100.00 parts CS-12 (product name, manufactured by Chisso Corp.) 50.00 parts Thickener: Adecanol UH-438 (Asahi Denka Kogyo Co., Ltd.)
10% aqueous solution
＜試験方法＞
・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の質量で割り、残渣率とした。
（判断基準） ○：残渣率が１００ｐｐｍ未満
△：残渣率が１００ｐｐｍ以上
×：多量の凝集物が発生
<Test method>
-Evaluation of polymerization stability The aqueous resin dispersion obtained after the emulsion polymerization was filtered through a 100-mesh filter cloth, and the residue mass was divided by the mass of the aqueous resin dispersion to obtain the residue rate.
(Judgment criteria) ○: Residue rate is less than 100 ppm
Δ: Residue rate is 100 ppm or more
×: A large amount of aggregate is generated
・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。
・水性樹脂分散体等の固形分率の測定
予め質量の分かっているアルミ皿に、約１ｇの水分散体等固形分率測定対象物を正確に秤量し、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。
・最低成膜温度（ＭＦＴ）
熱勾配試験機の上に置いたアルミ板上に０．１ｍｍのアプリケーターでその対象物を塗工、乾燥し、その塗膜にクラックの生じた最高の温度を最低成膜温度（ＭＦＴ）とした。
-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 fraction of aqueous resin dispersion, etc. Precisely weigh about 1 g of the solid dispersion fraction, such as water dispersion, in an aluminum dish of which mass is known in advance, and measure it at 105 ° C. with a constant temperature dryer. After drying for a period of time, the mixture is allowed to cool for 30 minutes in a desiccator containing silica gel and then weighed accurately. The solid content was obtained by dividing the mass after drying of the substance by the mass before drying.
・ Minimum deposition temperature (MFT)
The object was coated on an aluminum plate placed on a thermal gradient tester with a 0.1 mm applicator and dried, and the highest temperature at which cracks occurred in the coating film was defined as the lowest film formation temperature (MFT). .
・耐候性
上記のクリアー塗料配合物をワイヤーコーターＮｏ．５０を用いて、硫酸アルマイト板に塗布し、５０℃、１週間乾燥させた。引き続きサンシャイン型ウエザオメーター（スガ試験機（株）製、ＷＥＬ−ＳＵＮ−ＤＣ）を使用して曝露試験（降雨サイクル；１８分／２時間、ブラックパネル温度６０〜６６℃）を行った。曝露２０００時間経過後の外観の変化を観察した。判定基準は以下の通り。
◎：変化なし。
○：つやびけが見られる。
△：つやびけと一部にクラックが見られる。
×：つやびけと全面にクラックが見られる。
・ Weather resistance 50 was applied to an alumite sulfate plate and dried at 50 ° C. for 1 week. Subsequently, an exposure test (rain cycle; 18 minutes / 2 hours, black panel temperature 60 to 66 ° C.) was performed using a sunshine type weatherometer (Suga Test Instruments Co., Ltd., WEL-SUN-DC). Changes in appearance after 2000 hours of exposure were observed. Judgment criteria are as follows.
A: No change.
○: Shiny blur is observed.
Δ: Shiny and partially cracked.
X: Cracks are seen on the entire surface with glossiness.
・耐ブロッキング性
上記のクリアー塗料配合物をＭＦＴ１０℃になるように成膜助剤量（エチレングリコールモノブチルエーテルとＣＳ−１２）を調節したものを８ミルのアプリケータで塗装し、１０５℃、１０分間強制乾燥させた後、５０℃の乾燥機内に速やかに移動し１分間放置後に塗膜表面にガーゼをのせ、更にその上におもりを置き、１．０ｋｇ／ｃｍ２の荷重を２時間かけた。そして、常温まで冷却した後、ゆっくりガーゼをはがし、塗膜の状態を目視にて観察し、下記の基準に従って評価した。
◎：ガーゼの痕跡がほとんどなし。
○：ガーゼの痕跡が少し見られる。
△：網目状の痕跡あり。
×：ガーゼの剥離が困難。
Blocking resistance The above clear coating composition was adjusted with an amount of film forming aid (ethylene glycol monobutyl ether and CS-12) so that the MFT was 10 ° C., and then applied with an 8 mil applicator. After forcibly drying for 5 minutes, it was quickly moved into a dryer at 50 ° C. and allowed to stand for 1 minute, after which gauze was placed on the surface of the coating film, a weight was placed thereon, and a load of 1.0 kg / cm 2 was applied for 2 hours. And after cooling to normal temperature, gauze was peeled off slowly, the state of the coating film was observed visually, and it evaluated according to the following reference | standard.
A: There is almost no trace of gauze.
○: Some traces of gauze are seen.
Δ: Reticulated traces.
X: It is difficult to peel off the gauze.
［実施例１］
撹拌機、還流冷却器、滴下槽および温度計を取り付けた反応容器に水６１４部、アニオン性界面活性剤（製品名：ニューコール５６２ＳＦ、日本乳化剤（株）製）の４５％水溶液７部を投入し、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１５部添加した５分後に、メタクリル酸メチル４５５部、メタクリル酸シクロヘキシル４５部、γ―メタクリロキシプロピルトリメトキシシラン（ＳＺ６０３０、東レダウコーニング（株）製）３０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％溶液を４０部、ノニオン性界面活性剤（製品名：エマルゲン１２０、花王（株）製）の２０％水溶液２０部、過硫酸アンモニウムの２％の水溶液２５部、水２６９部からなる乳化混合液を滴下槽より１０５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。
[Example 1]
Into a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 614 parts of water and 7 parts of 45% aqueous solution of an anionic surfactant (product name: New Coal 562SF, manufactured by Nippon Emulsifier Co., Ltd.) are added. 5 minutes after adding 15 parts of a 2% aqueous solution of ammonium persulfate after raising the temperature in the reaction vessel to 80 ° C., 455 parts of methyl methacrylate, 45 parts of cyclohexyl methacrylate, γ-methacryloxypropyltrimethoxysilane (SZ6030, manufactured by Toray Dow Corning Co., Ltd.) 30 parts, 40 parts of a 30% solution of an anionic surfactant (product name: New Coal 707SF, manufactured by Nippon Emulsifier Co., Ltd.), nonionic surfactant (product name) : 20% aqueous solution of Emulgen 120, manufactured by Kao Corporation), 25 parts of 2% aqueous solution of ammonium persulfate, and 269 parts of water. The mixture is flowed over 105 minutes from the dropping funnel. The temperature of the reaction vessel is kept at 80 ° C. during the inflow. 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３０部、メタクリル酸シクロヘキシル８０部、メタクリル酸ｎ−ブチル２１２部、アクリル酸２−エチルヘキシル１３８部、メタクリル酸２−ヒドロキシエチル２０部、メタクリル酸１０部、アクリル酸１０部、アニオン性反応性乳化剤（製品名：アクアロンＫＨ１０、第一工業製薬（株）製）の２５％溶液を１２部、過硫酸アンモニウムの２％の水溶液２５部、水２９１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６７部を加え、反応容器の温度を８０℃にして９０分保つ。
その後、室温まで冷却する。冷却後のｐＨは２．７であった。さらに２５％アンモニア水溶液を用いて、ｐＨを８．５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０．０４％とわずかであった。得られた水性樹脂分散体の固形分率は４１．９％、粒子径１１０ｎｍで単一分布であった。
Next, 30 parts of methyl methacrylate, 80 parts of cyclohexyl methacrylate, 212 parts of n-butyl methacrylate, 138 parts of 2-ethylhexyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 10 parts of methacrylic acid, 10 parts of acrylic acid, An emulsion mixture consisting of 12 parts of a 25% solution of an anionic reactive emulsifier (product name: Aqualon KH10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 25 parts of a 2% aqueous solution of ammonium persulfate and 291 parts of water for 90 minutes Overflow. The temperature of the reaction vessel is kept at 80 ° C. during the inflow. After the inflow is completed, 67 parts of water is added and the temperature of the reaction vessel is raised to 80 ° C. and maintained for 90 minutes.
Then, it cools to room temperature. The pH after cooling was 2.7. Further, the pH was adjusted to 8.5 using a 25% aqueous ammonia solution, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was as small as 0.04% based on the total monomers. The obtained aqueous resin dispersion had a solid content of 41.9%, a particle size of 110 nm, and a single distribution.
［実施例２、３］
１段目および２段目でそれぞれ用いる重合性単量体及び乳化剤の種類および量を表１に示すように変更した以外は、実施例１と同様の方法にて、水性樹脂分散体を得た。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重量部に対する比率で示した。
[Examples 2 and 3]
An aqueous resin dispersion was obtained in the same manner as in Example 1 except that the types and amounts of the polymerizable monomer and the emulsifier used in the first stage and the second stage were changed as shown in Table 1. . In addition, the quantity of each polymerizable monomer was shown by the ratio with respect to 100 weight part of total polymerizable monomer components used in both stages.
［実施例４］
撹拌機、還流冷却器、滴下槽および温度計を取り付けた反応容器に水６１４部、アニオン性界面活性剤（製品名：ニューコール５６２ＳＦ、日本乳化剤（株）製）の４５％水溶液７部を投入し、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１５部添加した５分後に、メタクリル酸メチル３６４部、メタクリル酸シクロヘキシル３６部、γ―メタクリロキシプロピルトリメトキシシラン（ＳＺ６０３０、東レダウコーニング（株）製）３０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％溶液を３３部、ノニオン性界面活性剤（製品名：エマルゲン１２０、花王（株）製）の２０％水溶液１６部、過硫酸アンモニウムの２％の水溶液１６部、水２１５部からなる乳化混合液を滴下槽より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反応容器の温度を８０℃にして３０分保つ。
[Example 4]
Into a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 614 parts of water and 7 parts of 45% aqueous solution of an anionic surfactant (product name: New Coal 562SF, manufactured by Nippon Emulsifier Co., Ltd.) are added. 5 minutes after adding 15 parts of a 2% aqueous solution of ammonium persulfate after raising the temperature in the reaction vessel to 80 ° C., 364 parts of methyl methacrylate, 36 parts of cyclohexyl methacrylate, γ-methacryloxypropyltrimethoxysilane (SZ6030, manufactured by Toray Dow Corning Co., Ltd.) 30 parts, 33 parts of a 30% solution of anionic surfactant (product name: New Coal 707SF, manufactured by Nippon Emulsifier Co., Ltd.), nonionic surfactant (product name) : Emulgen 120, manufactured by Kao Corporation) 16% 20% aqueous solution, ammonium persulfate 2% aqueous solution 16 parts milk, 215 parts water The mixture is flowed over a period of 90 minutes from the dropping funnel. The temperature of the reaction vessel is kept at 80 ° C. during the inflow. 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３６部、メタクリル酸シクロヘキシル９６部、メタクリル酸ｎ−ブチル２５４部、アクリル酸２−エチルヘキシル１６６部、メタクリル酸２−ヒドロキシエチル２４部、メタクリル酸１２部、アクリル酸１２部、ＫＨ１０の２５％溶液を１６部、過硫酸アンモニウムの２％の水溶液３０部、水３４５部からなる乳化混合液を１０５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６７部を加え、反応容器の温度を８０℃にして９０分保つ。
その後、室温まで冷却する。冷却後のｐＨは２．７であった。さらに２５％アンモニア水溶液を添加してｐＨを８．５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０．０５％とわずかであった。得られた水性樹脂分散体の固形分率は４１．７％、粒子径１１５ｎｍで単一分布であった。
Next, 36 parts of methyl methacrylate, 96 parts of cyclohexyl methacrylate, 254 parts of n-butyl methacrylate, 166 parts of 2-ethylhexyl acrylate, 24 parts of 2-hydroxyethyl methacrylate, 12 parts of methacrylic acid, 12 parts of acrylic acid, An emulsion mixture consisting of 16 parts of a 25% solution of KH10, 30 parts of a 2% aqueous solution of ammonium persulfate and 345 parts of water is allowed to flow in over 105 minutes. The temperature of the reaction vessel is kept at 80 ° C. during the inflow. After the inflow is completed, 67 parts of water is added and the temperature of the reaction vessel is raised to 80 ° C. and maintained for 90 minutes.
Then, it cools to room temperature. The pH after cooling was 2.7. Further, a 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was only 0.05% with respect to the total monomers. The obtained aqueous resin dispersion had a solid content of 41.7%, a particle size of 115 nm, and a single distribution.
［実施例５］
撹拌機、還流冷却器、滴下槽および温度計を取り付けた反応容器に水６１４部、アニオン性界面活性剤（製品名：ニューコール５６２ＳＦ、日本乳化剤（株）製）の４５％水溶液７部を投入し、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１５部添加した５分後に、メタクリル酸メチル４５５部、メタクリル酸シクロヘキシル４５部、γ―メタクリロキシプロピルトリメトキシシラン（ＳＺ６０３０、東レダウコーニング（株）製）３０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％溶液を４０部、ノニオン性界面活性剤（製品名：エマルゲン１２０、花王（株）製）の２０％水溶液２０部、過硫酸アンモニウムの２％の水溶液２５部、水２６９部からなる乳化混合液を滴下槽より１０５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。
[Example 5]
Into a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 614 parts of water and 7 parts of 45% aqueous solution of an anionic surfactant (product name: New Coal 562SF, manufactured by Nippon Emulsifier Co., Ltd.) are added. 5 minutes after adding 15 parts of a 2% aqueous solution of ammonium persulfate after raising the temperature in the reaction vessel to 80 ° C., 455 parts of methyl methacrylate, 45 parts of cyclohexyl methacrylate, γ-methacryloxypropyltrimethoxysilane (SZ6030, manufactured by Toray Dow Corning Co., Ltd.) 30 parts, anionic surfactant (product name: New Coal 707SF)
40 parts of 30% solution of Nippon Emulsifier Co., Ltd., 20 parts of 20% aqueous solution of nonionic surfactant (product name: Emulgen 120, produced by Kao Corporation), 25 parts of 2% aqueous solution of ammonium persulfate Then, an emulsified mixed solution composed of 269 parts of water is allowed to flow in from the dropping tank over 105 minutes. The temperature of the reaction vessel is kept at 80 ° C. during the inflow. 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３０部、メタクリル酸シクロヘキシル８０部、メタクリル酸ｎ−ブチル２１２部、アクリル酸２−エチルヘキシル１３８部、メタクリル酸２−ヒドロキシエチル２０部、メタクリル酸１０部、アクリル酸１０部、γ―メタクリロキシプロピルトリメトキシシラン（ＳＺ６０３０、東レダウコーニング（株）製）５部、アニオン性反応性乳化剤（製品名：アクアロンＫＨ１０、第一工業製薬（株）製）の２５％溶液を１２部、過硫酸アンモニウムの２％の水溶液２５部、水２９１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６７部を加え、反応容器の温度を８０℃にして９０分保つ。
その後、室温まで冷却する。冷却後のｐＨは２．７であった。さらに２５％アンモニア水溶液を用いて、ｐＨを８．５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０．０４％とわずかであった。得られた水性樹脂分散体の固形分率は４１．８％、粒子径１０７ｎｍで単一分布であった。
Next, 30 parts of methyl methacrylate, 80 parts of cyclohexyl methacrylate, 212 parts of n-butyl methacrylate, 138 parts of 2-ethylhexyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 10 parts of methacrylic acid, 10 parts of acrylic acid, 5 parts of γ-methacryloxypropyltrimethoxysilane (SZ6030, manufactured by Toray Dow Corning Co., Ltd.), 12 parts of a 25% solution of an anionic reactive emulsifier (Product name: Aqualon KH10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Then, an emulsified mixed solution composed of 25 parts of a 2% aqueous solution of ammonium persulfate and 291 parts of water is allowed to flow in over 90 minutes. The temperature of the reaction vessel is kept at 80 ° C. during the inflow. After the inflow is completed, 67 parts of water is added and the temperature of the reaction vessel is raised to 80 ° C. and maintained for 90 minutes.
Then, it cools to room temperature. The pH after cooling was 2.7. Further, the pH was adjusted to 8.5 using a 25% aqueous ammonia solution, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was as small as 0.04% based on the total monomers. The obtained aqueous resin dispersion had a solid content ratio of 41.8%, a particle size of 107 nm, and a single distribution.
［実施例６］
２段目の架橋性モノマーをトリメチロールプロパントリアクリレートに変更した以外は、実施例５と同様の方法にて、水性樹脂分散体を得た。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重量部に対する比率で示した。
[Example 6]
An aqueous resin dispersion was obtained in the same manner as in Example 5, except that the second-stage crosslinkable monomer was changed to trimethylolpropane triacrylate. In addition, the quantity of each polymerizable monomer was shown by the ratio with respect to 100 weight part of total polymerizable monomer components used in both stages.
［実施例７］
撹拌機、還流冷却器、滴下槽および温度計を取り付けた反応容器に水６１４部、アニオン性界面活性剤（製品名：ニューコール５６２ＳＦ、日本乳化剤（株）製）の４５％水溶液７部を投入し、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１５部添加した５分後に、メタクリル酸メチル４５５部、メタクリル酸シクロヘキシル４５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％溶液を４０部、ノニオン性界面活性剤（製品名：エマルゲン１２０、花王（株）製）の２０％水溶液２０部、過硫酸アンモニウムの２％の水溶液２５部、水２６９部からなる乳化混合液を滴下槽より１０５分かけて流入させる。また、その乳化液が滴下しはじめてから５分後からγ―メタクリロキシプロピルトリメトキシシラン（ＳＺ６０３０、東レダウコーニング（株）製）３０部、ジメチルジメトキシシラン（ＡＹ４３−００４、東レダウコーニング（株）製）３２部、メチルトリメトキシシラン（ＳＺ６０７０、東レダウコーニング（株）製）２０部の混合液を別の滴下槽より９０分かけて滴下する。流入中は反応容器の温度を８０℃に保つ。乳化混合液の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。
[Example 7]
Into a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 614 parts of water and 7 parts of 45% aqueous solution of an anionic surfactant (product name: New Coal 562SF, manufactured by Nippon Emulsifier Co., Ltd.) are added. 5 minutes after adding 15 parts of a 2% aqueous solution of ammonium persulfate after raising the temperature in the reaction vessel to 80 ° C., 455 parts of methyl methacrylate, 45 parts of cyclohexyl methacrylate, an anionic surfactant (product name : New Coal 707SF, 30% solution of Nippon Emulsifier Co., Ltd.), 20 parts of 20% aqueous solution of nonionic surfactant (product name: Emulgen 120, Kao Corporation), 2% of ammonium persulfate An emulsified mixed solution consisting of 25 parts of an aqueous solution and 269 parts of water is allowed to flow from the dropping tank over 105 minutes. In addition, from 5 minutes after the start of dropping of the emulsion, 30 parts of γ-methacryloxypropyltrimethoxysilane (SZ6030, manufactured by Toray Dow Corning), dimethyldimethoxysilane (AY43-004, Toray Dow Corning) A mixed solution of 32 parts of methyltrimethoxysilane (SZ6070, manufactured by Toray Dow Corning Co., Ltd.) is dropped from another dropping tank over 90 minutes. The temperature of the reaction vessel is kept at 80 ° C. during the inflow. After the inflow of the emulsified liquid mixture 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３０部、メタクリル酸シクロヘキシル８０部、メタクリル酸ｎ−ブチル２１２部、アクリル酸２−エチルヘキシル１３８部、メタクリル酸２−ヒドロキシエチル２０部、メタクリル酸１０部、アクリル酸１０部、アニオン性反応性乳化剤（製品名：アクアロンＫＨ１０、第一工業製薬（株）製）の２５％溶液を１２部、過硫酸アンモニウムの２％の水溶液２５部、水２９１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６７部を加え、反応容器の温度を８０℃にして９０分保つ。
その後、室温まで冷却する。冷却後のｐＨは２．７であった。さらに２５％アンモニア水溶液を用いて、ｐＨを８．５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０．０４％とわずかであった。得られた水性樹
脂分散体の固形分率は４２．２％、粒子径１１０ｎｍで単一分布であった。
Next, 30 parts of methyl methacrylate, 80 parts of cyclohexyl methacrylate, 212 parts of n-butyl methacrylate, 138 parts of 2-ethylhexyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 10 parts of methacrylic acid, 10 parts of acrylic acid, An emulsion mixture consisting of 12 parts of a 25% solution of an anionic reactive emulsifier (product name: Aqualon KH10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 25 parts of a 2% aqueous solution of ammonium persulfate and 291 parts of water for 90 minutes Overflow. The temperature of the reaction vessel is kept at 80 ° C. during the inflow. After the inflow is completed, 67 parts of water is added and the temperature of the reaction vessel is raised to 80 ° C. and maintained for 90 minutes.
Then, it cools to room temperature. The pH after cooling was 2.7. Further, the pH was adjusted to 8.5 using a 25% aqueous ammonia solution, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was as small as 0.04% based on the total monomers. The obtained aqueous resin dispersion had a solid content of 42.2%, a particle size of 110 nm, and a single distribution.
［実施例８］
撹拌機、還流冷却器、滴下槽および温度計を取り付けた反応容器に水６１４部、アニオン性界面活性剤（製品名：ニューコール５６２ＳＦ、日本乳化剤（株）製）の４５％水溶液７部を投入し、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１５部添加した５分後に、メタクリル酸メチル４５５部、メタクリル酸シクロヘキシル４５部、紫外線吸収剤（ＴＩＮＵＶＩＮ４００、日本チバガイギー（株）製）を５部、光安定剤（ＴＩＮＵＶＩＮ１２３、日本チバガイギー（株）製）を５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％溶液を４０部、ノニオン性界面活性剤（製品名：エマルゲン１２０、花王（株）製）の２０％水溶液２０部、過硫酸アンモニウムの２％の水溶液２５部、水２６９部からなる乳化混合液を滴下槽より１０５分かけて流入させる。また、その乳化液が滴下しはじめてから５分後からγ―メタクリロキシプロピルトリメトキシシラン（ＳＺ６０３０、東レダウコーニング（株）製）３０部、ジメチルジメトキシシラン（ＡＹ４３−００４、東レダウコーニング（株）製）３２部、メチルトリメトキシシラン（ＳＺ６０７０、東レダウコーニング（株）製）２０部の混合液を別の滴下槽より９０分かけて滴下する。流入中は反応容器の温度を８０℃に保つ。乳化混合液の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。
[Example 8]
Into a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 614 parts of water and 7 parts of 45% aqueous solution of an anionic surfactant (product name: New Coal 562SF, manufactured by Nippon Emulsifier Co., Ltd.) are added. 5 minutes after adding 15 parts of a 2% aqueous solution of ammonium persulfate after raising the temperature in the reaction vessel to 80 ° C., 455 parts of methyl methacrylate, 45 parts of cyclohexyl methacrylate, UV absorber (TINUVIN 400, Ciba Geigy Japan) 5 parts), 5 parts light stabilizer (TINUVIN123, manufactured by Ciba Geigy Japan), 30% solution of anionic surfactant (product name: New Coal 707SF, manufactured by Nippon Emulsifier Co., Ltd.) 40 parts, 20 parts of a 20% aqueous solution of a nonionic surfactant (product name: Emulgen 120, manufactured by Kao Corporation), ammonium persulfate % Aqueous solution 25 parts, to flow over 105 minutes from the dropping tank emulsified mixture consisting of 269 parts of water. In addition, from 5 minutes after the start of dropping of the emulsion, 30 parts of γ-methacryloxypropyltrimethoxysilane (SZ6030, manufactured by Toray Dow Corning), dimethyldimethoxysilane (AY43-004, Toray Dow Corning) A mixed solution of 32 parts of methyltrimethoxysilane (SZ6070, manufactured by Toray Dow Corning Co., Ltd.) is dropped from another dropping tank over 90 minutes. The temperature of the reaction vessel is kept at 80 ° C. during the inflow. After the inflow of the emulsified liquid mixture 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３０部、メタクリル酸シクロヘキシル８０部、メタクリル酸ｎ−ブチル２１２部、アクリル酸２−エチルヘキシル１３８部、メタクリル酸２−ヒドロキシエチル２０部、メタクリル酸１０部、アクリル酸１０部、アニオン性反応性乳化剤（製品名：アクアロンＫＨ１０、第一工業製薬（株）製）の２５％溶液を１２部、過硫酸アンモニウムの２％の水溶液２５部、水２９１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６７部を加え、反応容器の温度を８０℃にして９０分保つ。
その後、室温まで冷却する。冷却後のｐＨは２．７であった。さらに２５％アンモニア水溶液を用いて、ｐＨを８．５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０．０４％とわずかであった。得られた水性樹脂分散体の固形分率は４２．６％、粒子径１１０ｎｍで単一分布であった。
Next, 30 parts of methyl methacrylate, 80 parts of cyclohexyl methacrylate, 212 parts of n-butyl methacrylate, 138 parts of 2-ethylhexyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 10 parts of methacrylic acid, 10 parts of acrylic acid, An emulsion mixture consisting of 12 parts of a 25% solution of an anionic reactive emulsifier (product name: Aqualon KH10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 25 parts of a 2% aqueous solution of ammonium persulfate and 291 parts of water for 90 minutes Overflow. The temperature of the reaction vessel is kept at 80 ° C. during the inflow. After the inflow is completed, 67 parts of water is added and the temperature of the reaction vessel is raised to 80 ° C. and maintained for 90 minutes.
Then, it cools to room temperature. The pH after cooling was 2.7. Further, the pH was adjusted to 8.5 using a 25% aqueous ammonia solution, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was as small as 0.04% based on the total monomers. The obtained aqueous resin dispersion had a solid content of 42.6%, a particle size of 110 nm, and a single distribution.
［比較例１］
撹拌機、還流冷却器、滴下槽および温度計を取り付けた反応容器に水６１４部、アニオン性反応性界面活性剤（製品名：アクアロンＫＨ−１０、第一工業製薬（株）製）１．６部を投入し、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１５部添加した５分後に、メタクリル酸メチル４４０部、メタクリル酸シクロヘキシル４５部、メタクリル酸２−ヒドロキシエチル１０部、メタクリル酸５部、アニオン性反応性界面活性剤（製品名：アクアロンＫＨ−１０、第一工業製薬（株）製）の２５％溶液を４８部、ノニオン性界面活性剤（製品名：エマルゲン１２０、花王（株）製）の２０％水溶液２０部、過硫酸アンモニウムの２％の水溶液２０部、水２９１部からなる乳化混合液を滴下槽より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反応容器の温度を８０℃にして３０分保つ。
[Comparative Example 1]
In a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 614 parts of water, anionic reactive surfactant (product name: Aqualon KH-10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 1.6 5 minutes after adding 15 parts of a 2% aqueous solution of ammonium persulfate, 440 parts of methyl methacrylate, 45 parts of cyclohexyl methacrylate, 2-hydroxy methacrylate 10 parts of ethyl, 5 parts of methacrylic acid, 48 parts of a 25% solution of an anionic reactive surfactant (product name: Aqualon KH-10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), nonionic surfactant (product name) : Emulgen 120, manufactured by Kao Corporation) 20% aqueous solution 20 parts, 2% aqueous solution of ammonium persulfate 20 parts, 291 parts of water emulsified mixture inflow from the dropping tank over 90 minutes To. The temperature of the reaction vessel is kept at 80 ° C. during the inflow. 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３０部、メタクリル酸シクロヘキシル８０部、メタクリル酸ｎ−ブチル２１２部、アクリル酸２−エチルヘキシル１３８部、メタクリル酸２−ヒドロキシエチル２０部、メタクリル酸１０部、アクリル酸１０部、アニオン性反応性乳化剤（製品名：アクアロンＫＨ１０、第一工業製薬（株）製）の２５％溶液を１２部、過硫酸アンモニウムの２％の水溶液２５部、水２９１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６７部を加え、
反応容器の温度を８０℃にして９０分保つ。
その後、室温まで冷却する。冷却後のｐＨは２．７であった。さらに２５％アンモニア水溶液を添加してｐＨを８．５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０．０４％とわずかであった。得られた水性樹脂分散体の固形分率は４１．８％、粒子径１１５ｎｍで単一分布であった。
Next, 30 parts of methyl methacrylate, 80 parts of cyclohexyl methacrylate, 212 parts of n-butyl methacrylate, 138 parts of 2-ethylhexyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 10 parts of methacrylic acid, 10 parts of acrylic acid, An emulsion mixture consisting of 12 parts of a 25% solution of an anionic reactive emulsifier (product name: Aqualon KH10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 25 parts of a 2% aqueous solution of ammonium persulfate and 291 parts of water for 90 minutes Overflow. The temperature of the reaction vessel is kept at 80 ° C. during the inflow. After the inflow is over, add 67 parts of water,
The reaction vessel is brought to 80 ° C. and held for 90 minutes.
Then, it cools to room temperature. The pH after cooling was 2.7. Further, a 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100 mesh wire net. The dry mass of the filtered aggregate was as small as 0.04% based on the total monomers. The obtained aqueous resin dispersion had a solid content ratio of 41.8%, a particle size of 115 nm, and a single distribution.
［比較例２〜５］
１段目および２段目でそれぞれ用いる重合性単量体及び乳化剤の種類および量を表１に示すように変更した以外は、実施例１と同様の方法にて、水性樹脂分散体を得た。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重量部に対する比率で示した。
比較例１は全体Ｔｇに対してＭＦＴが高く、耐ブロッキング性が不良である。比較例２は耐ブロッキング性が不良である。比較例３も耐ブロッキング性が不良である。比較例４は耐ブロッキングが不良であり耐候性も不良である。比較例５も耐ブロッキングが不良であり耐候性も不良である。
[Comparative Examples 2 to 5]
An aqueous resin dispersion was obtained in the same manner as in Example 1 except that the types and amounts of the polymerizable monomer and the emulsifier used in the first stage and the second stage were changed as shown in Table 1. . In addition, the quantity of each polymerizable monomer was shown by the ratio with respect to 100 weight part of total polymerizable monomer components used in both stages.
Comparative Example 1 has a high MFT with respect to the total Tg, and has poor blocking resistance. Comparative Example 2 has poor blocking resistance. Comparative Example 3 also has poor blocking resistance. Comparative Example 4 has poor blocking resistance and poor weather resistance. Comparative Example 5 also has poor blocking resistance and poor weather resistance.
なお、表中の略語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。
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）
ＣＨＭＡ：メタクリル酸シクロヘキシル（８３）
２ＨＥＭＡ：メタクリル酸２−ヒドロキシエチル（５５）
ＡＡ：アクリル酸（８７）
ＭＡＡ：メタクリル酸（１４４）
Abbreviations in the table are as follows. Further, the Tg value of each homopolymer used for calculating the glass transition temperature (Tg / ° C.) of the polymerizable monomer by the Fox formula is shown in parentheses.
MMA: Methyl methacrylate (105)
BA: n-butyl acrylate (-45)
BMA: n-butyl methacrylate (22)
2EHA: 2-ethylhexyl acrylate (-55)
CHMA: cyclohexyl methacrylate (83)
2HEMA: 2-hydroxyethyl methacrylate (55)
AA: Acrylic acid (87)
MAA: Methacrylic acid (144)
本発明の水性樹脂分散体は、塗料やコーティング用途として好適である。 The aqueous resin dispersion of the present invention is suitable for paint and coating applications.
Claims (11)
（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、炭素数５〜６のシクロアルキル基、ビニル基、炭素数１〜１０のアクリル酸アルキル基、又は炭素数１〜１０のメタクルキル酸アルキル基から選ばれる１種以上の基。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、水酸基から選ばれる１種以上の基。４−ｎ個のＲ２は同一であっても、異なっても良い。） The Si-containing compound (F) represented by the following formula (1) is also contained as a polymerizable monomer constituting the aqueous resin dispersion particle, according to any one of claims 1 to 6. An aqueous resin dispersion.
(R 1) n -Si- (R 2) 4-n (1)
(In the formula, n is an integer of 0 to 3, R 1 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, vinyl. One or more groups selected from a group, an alkyl acrylate group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, and the n R 1 groups may be the same or different. R 2 is one or more groups selected from an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, and a hydroxyl group, and 4-n R 2 may be the same or different.
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| JP2020041153A (en) * | 2019-11-20 | 2020-03-19 | 株式会社日本触媒 | Method for producing aqueous resin dispersion |
| JP7051783B2 (en) | 2019-11-20 | 2022-04-11 | 株式会社日本触媒 | Method for manufacturing aqueous resin dispersion |
| JP2021116354A (en) * | 2020-01-27 | 2021-08-10 | 株式会社日本触媒 | Resin emulsion for aqueous ink |
| JP7340467B2 (en) | 2020-01-27 | 2023-09-07 | 株式会社日本触媒 | Resin emulsion for water-based ink |
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