JP2005220325A - Method for suspension-polymerizing (meth)acrylate monomer - Google Patents
Method for suspension-polymerizing (meth)acrylate monomer Download PDFInfo
- Publication number
- JP2005220325A JP2005220325A JP2004032672A JP2004032672A JP2005220325A JP 2005220325 A JP2005220325 A JP 2005220325A JP 2004032672 A JP2004032672 A JP 2004032672A JP 2004032672 A JP2004032672 A JP 2004032672A JP 2005220325 A JP2005220325 A JP 2005220325A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- suspension polymerization
- aqueous resin
- parts
- monomer
- 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
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- 239000000178 monomer Substances 0.000 title claims abstract description 70
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims abstract description 50
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 49
- 239000006185 dispersion Substances 0.000 claims abstract description 44
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 239000012874 anionic emulsifier Substances 0.000 claims abstract description 3
- -1 acryl skeleton Chemical group 0.000 claims description 39
- 239000002245 particle Substances 0.000 claims description 37
- 239000002562 thickening agent Substances 0.000 claims description 22
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 19
- 239000011342 resin composition Substances 0.000 claims description 14
- 238000010558 suspension polymerization method Methods 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 230000009746 freeze damage Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000008199 coating composition Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 239000002202 Polyethylene glycol Substances 0.000 description 12
- 229920001223 polyethylene glycol Polymers 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000006224 matting agent Substances 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001253 acrylic acids Chemical class 0.000 description 4
- 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 4
- 230000000694 effects Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 3
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- GSNJIHDWUJXETP-UHFFFAOYSA-N 2-[3-(5-tert-butylbenzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=C(C=CC3=N2)C(C)(C)C)=C1 GSNJIHDWUJXETP-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 2
- URLYGBGJPQYXBN-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methyl prop-2-enoate Chemical compound OCC1CCC(COC(=O)C=C)CC1 URLYGBGJPQYXBN-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 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
- 239000000839 emulsion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- AJOJTMNIQSTBAP-UHFFFAOYSA-N (1,2,2,6,6-pentamethylpiperidin-3-yl) prop-2-enoate Chemical compound CN1C(C)(C)CCC(OC(=O)C=C)C1(C)C AJOJTMNIQSTBAP-UHFFFAOYSA-N 0.000 description 1
- GIIUJJXXMYYQQD-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-1-yl) prop-2-enoate Chemical compound CC1(C)CCCC(C)(C)N1OC(=O)C=C GIIUJJXXMYYQQD-UHFFFAOYSA-N 0.000 description 1
- FLYXGBNUYGAFAC-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-(2-hydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1O FLYXGBNUYGAFAC-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical compound CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- 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
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- OFLPBAZQIRUWFV-UHFFFAOYSA-N 2-[3-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=C(Cl)C=CC3=N2)=C1 OFLPBAZQIRUWFV-UHFFFAOYSA-N 0.000 description 1
- UIBLWXYRKDJRSG-UHFFFAOYSA-N 2-[3-(5-cyanobenzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=C(C=CC3=N2)C#N)=C1 UIBLWXYRKDJRSG-UHFFFAOYSA-N 0.000 description 1
- VCYCUECVHJJFIQ-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 VCYCUECVHJJFIQ-UHFFFAOYSA-N 0.000 description 1
- SAOSFCLPXMYGNW-UHFFFAOYSA-N 2-[4-hydroxy-3-(5-methoxybenzotriazol-2-yl)phenyl]ethyl 2-methylprop-2-enoate Chemical compound N1=C2C=C(OC)C=CC2=NN1C1=CC(CCOC(=O)C(C)=C)=CC=C1O SAOSFCLPXMYGNW-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- QUKFNRQNPQSTPD-UHFFFAOYSA-N 2-methylpropanoic acid;pentane-1,3-diol Chemical compound CC(C)C(O)=O.CCC(O)CCO QUKFNRQNPQSTPD-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- LPIQIQPLUVLISR-UHFFFAOYSA-N 2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC(=C)C1=NCCO1 LPIQIQPLUVLISR-UHFFFAOYSA-N 0.000 description 1
- VRBUPQGTJAXZAE-UHFFFAOYSA-N 2-propylidenebutanedioic acid Chemical compound CCC=C(C(O)=O)CC(O)=O VRBUPQGTJAXZAE-UHFFFAOYSA-N 0.000 description 1
- ATZXURVLNCRXQJ-UHFFFAOYSA-N 2-sulfooxyethyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OCCOS(O)(=O)=O ATZXURVLNCRXQJ-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- 102100026788 ATP synthase subunit C lysine N-methyltransferase Human genes 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- 101000833848 Homo sapiens ATP synthase subunit C lysine N-methyltransferase Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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Landscapes
- Polymerisation Methods In General (AREA)
Abstract
Description
本発明は、（メタ）アクリル酸エステル系単量体の懸濁重合方法および水性樹脂組成物に関するものである。さらに詳しくは、塗料、コーティング剤、光学部品、電子材料、医療用検査薬等として有用な水性樹脂組成物ならびに該水性樹脂組成物に使用される水生樹脂を得るための懸濁重合方法に関するものである。 The present invention relates to a suspension polymerization method of an (meth) acrylic acid ester monomer and an aqueous resin composition. More particularly, the present invention relates to an aqueous resin composition useful as a paint, a coating agent, an optical component, an electronic material, a medical test agent, and the like, and a suspension polymerization method for obtaining an aquatic resin used in the aqueous resin composition. is there.
艶消塗料等の艶消剤組成物は、組成物中に無機系または有機系の粒子を含むものが多く、高意匠の目的でその中でも水性のものは、建材表面の塗装に用いられることが多い。 Matting agent compositions such as matting paints often contain inorganic or organic particles in the composition, and water-based ones may be used for the coating of building material surfaces for the purpose of high design. Many.
従来、艶消剤組成物に使用される粒子としては、無機系粒子、特にシリカ系の粉末が主流であり、低コストのために広く使用されているが、吸水性があるので耐水性に問題があり、白化しやすく、耐候性、凍害性にも問題があった。 Conventionally, as particles used in matting agent compositions, inorganic particles, especially silica-based powders, have been the mainstream and widely used for low cost. There was also a problem in weathering and frost damage.
一方、有機系の樹脂粒子を配合する方法としては、水中での懸濁重合法によって得られた樹脂粒子水分散体に、親水性有機溶剤を添加することにより得られる水性樹脂組成物がある（例えば、特許文献１参照。）。 On the other hand, as a method of blending organic resin particles, there is an aqueous resin composition obtained by adding a hydrophilic organic solvent to an aqueous dispersion of resin particles obtained by a suspension polymerization method in water ( For example, see Patent Document 1.)
しかしながら、このような方法で得られる水性樹脂組成物は、ハードケーキの形成は抑制できるが、分離しやすく沈降し、これがハードケーキを形成するので、再分散にはシェアをかける必要があり、工業的には不充分であるという欠点があった。 However, the aqueous resin composition obtained by such a method can suppress the formation of a hard cake, but settles easily and separates, and this forms a hard cake. There was a drawback that it was insufficient.
また、従来の懸濁重合方法により水性樹脂を製造する場合、重合時に反応釜にスケールの生成が多いばかりでなく、得られた水性樹脂を艶消剤として用いた塗膜は、耐候性試験後の艶消剤の抜け落ちが発生するという欠点があった。
したがって、本発明の目的は、新規な（メタ）アクリル酸エステル系単量体の懸濁重合方法を提供することにある。 Accordingly, an object of the present invention is to provide a novel method for suspension polymerization of a (meth) acrylic acid ester monomer.
本発明の他の目的は、耐候性に優れた水性樹脂組成物およびこれに使用される重合体の懸濁重合方法を提供することにある。 Another object of the present invention is to provide an aqueous resin composition having excellent weather resistance and a method for suspension polymerization of a polymer used therein.
本発明のさらに他の目的は、吸水性が低くかつ被膜の透明性に優れた高耐候性および耐凍害性に優れた水性樹脂組成物およびその製造方法を提供することにある。 Still another object of the present invention is to provide an aqueous resin composition having low water absorption and excellent film transparency and excellent weather resistance and frost damage resistance, and a method for producing the same.
本発明の別の目的は、懸濁重合水性分散体に増粘剤を添加することにより粒子間にネットワークを形成し、粒子同士の沈降を抑えてハードケーキの生成が抑制され、かつ得られた水性分散体は数日間にわたって沈降しないという経済的に優れた水性樹脂組成物およびその製造方法を提供することにある。 Another object of the present invention was to form a network between particles by adding a thickener to the suspension polymerization aqueous dispersion, to suppress sedimentation between the particles, and to suppress the formation of a hard cake. It is an object of the present invention to provide an economical aqueous resin composition in which an aqueous dispersion does not settle for several days and a method for producing the same.
上記諸目的は、下記（１）〜（７）により達成される。 The above-mentioned objects are achieved by the following (1) to (7).
（１） 分散剤としての反応性乳化剤の存在下に（メタ）アクリル酸エステル系単量体を懸濁重合することを特徴とする（メタ）アクリル酸エステル系単量体の懸濁重合方法。 (1) A suspension polymerization method of a (meth) acrylate monomer, which comprises suspension polymerization of a (meth) acrylate monomer in the presence of a reactive emulsifier as a dispersant.
（２） 該反応性乳化剤がアニオン性乳化剤である前記（１）に記載の方法。 (2) The method according to (1), wherein the reactive emulsifier is an anionic emulsifier.
（３） 該反応性乳化剤の反応性基が（メタ）アクリル骨格である前記（１）または（２）に記載の方法。 (3) The method according to (1) or (2) above, wherein the reactive group of the reactive emulsifier is a (meth) acryl skeleton.
（４） 該（メタ）アクリル酸エステル系単量体が（メタ）アクリル酸エステルおよび多官能架橋性単量体よりなるものである前記（１）〜（３）のいずれか一つに記載の方法。 (4) The (meth) acrylic acid ester monomer as described in any one of the above (1) to (3), wherein the (meth) acrylic acid ester and a polyfunctional crosslinkable monomer are used. Method.
（５） 前記（１）〜（４）のいずれか一つに記載の方法により得られる水性樹脂分散体。 (5) An aqueous resin dispersion obtained by the method according to any one of (1) to (4).
（６） （メタ）アクリル酸エステル系単量体および反応性乳化剤よりなる平均粒子径が３〜１００μｍの水性樹脂分散体。 (6) An aqueous resin dispersion having an average particle diameter of 3 to 100 μm, comprising a (meth) acrylic acid ester monomer and a reactive emulsifier.
（７） 前記（５）または（６）に記載の水性樹脂分散体および増粘剤よりなる水性樹脂組成物。 (7) An aqueous resin composition comprising the aqueous resin dispersion according to (5) or (6) and a thickener.
本発明は、以上のごとき構成を有しているので、懸濁重合時に粒子同士の接触を抑えてスケールの生成が抑制され、かつ得られる水性分散体は数日間にわたって沈降せず、ハードケーキの生成が抑制されるという利点がある。また、得られる水性樹脂分散体を配合した水性樹脂組成物は、透明性、耐候性、耐凍害性に優れた被膜を形成させることができ、さらに、該塗膜は、耐候性試験後の艶消剤の抜け落ちを防止できる。 Since the present invention has the configuration as described above, the formation of scale is suppressed by suppressing contact between particles during suspension polymerization, and the resulting aqueous dispersion does not settle for several days, There is an advantage that generation is suppressed. In addition, the aqueous resin composition containing the obtained aqueous resin dispersion can form a film having excellent transparency, weather resistance, and frost damage resistance. Can prevent the disinfectant from falling off.
本発明のおいて単量体として使用される（ａ）（メタ）アクリル酸エステルとしては、つぎのものがある。 Examples of the (a) (meth) acrylic acid ester used as a monomer in the present invention include the following.
（ａ）（メタ）アクリル酸エステルとしては、具体的には、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸−２−エチルヘキシル等の（メタ）アクリル酸とＣ１〜Ｃ１８（脂肪族、脂環族、芳香族を含む）のアルコールのエステルである（メタ）アクリル酸エステル類；（メタ）アクリル酸−２−ヒドロキシエチル、（メタ）アクリル酸−２−ヒドロキシプロピル、（メタ）アクリル酸とポリプロピレングリコールとのモノエステル等のヒドロキシ基を有する（メタ）アクリル酸エステル類等が挙げられる。 Specific examples of (a) (meth) acrylic acid ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid-2-ethylhexyl, and the like. (Meth) acrylic acid and (meth) acrylic acid esters which are esters of C1-C18 (including aliphatic, alicyclic, and aromatic) alcohols; (meth) acrylic acid-2-hydroxyethyl, (meta ) (Meth) acrylic acid esters having a hydroxy group such as 2-hydroxypropyl acrylate, monoester of (meth) acrylic acid and polypropylene glycol, and the like.
好ましくは、シクロアルキル基を有する（メタ）アクリル酸類、ｔ−ブチル基を有する（メタ）アクリル酸類が挙げられ、さらに好ましくはシクロアルキル基を有する（メタ）アクリル酸類である。 Preferred are (meth) acrylic acids having a cycloalkyl group and (meth) acrylic acids having a t-butyl group, and more preferred are (meth) acrylic acids having a cycloalkyl group.
上記シクロアルキル基を有する重合性不飽和単量体における、シクロアルキル基構造としては、シクロブチル構造、シクロペンチル構造、シクロヘキシル構造、シクロヘブチル構造、シクロオクチル構造、シクロノニル構造、シクロデシル構造、シクロウンデシル構造、シクロドデシル構造、シクロトリデシル構造、シクロテトラデシル構造、シクロペンタデシル構造、シクロヘキサデシル構造、シクロヘプタデシル構造、シクロオクタデシル構造等が好適である。 The cycloalkyl group structure in the polymerizable unsaturated monomer having a cycloalkyl group includes a cyclobutyl structure, a cyclopentyl structure, a cyclohexyl structure, a cyclohexyl structure, a cyclooctyl structure, a cyclononyl structure, a cyclodecyl structure, a cycloundecyl structure, a cyclo A dodecyl structure, a cyclotridecyl structure, a cyclotetradecyl structure, a cyclopentadecyl structure, a cyclohexadecyl structure, a cycloheptadecyl structure, a cyclooctadecyl structure, and the like are preferable.
上記シクロアルキル基を有する重合性不飽和単量体としては、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、ｔｅｒｔ−ブチルシクロヘキシル（メタ）アクリレート、シクロオクチル（メタ）アクリレート、シクロドデシル（メタ）アクリレート、イソボルニルメタクリレート（共栄社化学社製、商品名：ライトエステルＩＢ−Ｘ）、イソボルニルアクリレート（日立化成工業社製、商品名：ＦＡ−５４４Ａ；共栄社化学社製、商品名：ライトアクリレートＩＢ−ＸＡ）、ジシクロペンタニルメタクリレート（日立化成工業社製、商品名：ＦＡ−５１３Ｍ）、ジシクロペンタニルアクリレート（日立化成工業社製、商品名：ＦＡ−５１３Ａ）、４−メチロールシクロヘキシルメチルアクリレート（日立化成工業社製、商品名：ＣＨＤＭＭＡ）、４−メチルシクロヘキシルメチル（メタ）アクリレート、シクロヘキシルメチル（メタ）アクリレート等が好適であり、これらは１種又は２種以上を用いることができる。これらの中でも、シクロヘキシル（メタ）アクリレート、４−メチルシクロヘキシルメチル（メタ）アクリレート、シクロヘキシルメチル（メタ）アクリレートがより好ましい。 Examples of the polymerizable unsaturated monomer having a cycloalkyl group include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, cyclooctyl (meth) acrylate, and cyclododecyl (meth). Acrylate, isobornyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Ester IB-X), isobornyl acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-544A; trade name: Kyoeisha Chemical Co., Ltd., trade name: Light acrylate) IB-XA), dicyclopentanyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-513M), dicyclopentanyl acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-513A), 4-methylolcyclohexylmethyl Acrylate (Hitachi Adult Industries, Ltd., trade name: CHDMMA), 4- methylcyclohexyl methyl (meth) acrylate, cyclohexylmethyl (meth) acrylate and the like preferred, these can be used alone or in combination. Among these, cyclohexyl (meth) acrylate, 4-methylcyclohexylmethyl (meth) acrylate, and cyclohexylmethyl (meth) acrylate are more preferable.
ｔ−ブチル基を有する（メタ）アクリル酸類としては、メタクリル酸ｔ−ブチル、アクリル酸ｔ−ブチルが挙げられる。 Examples of (meth) acrylic acids having a t-butyl group include t-butyl methacrylate and t-butyl acrylate.
上記（メタ）アクリル酸エステル系単量体は１種又は２種以上を用いることができる。 The said (meth) acrylic acid ester-type monomer can use 1 type (s) or 2 or more types.
その使用量は特に限定されないが、好ましくは５〜９９質量％、より好ましくは３０〜９０質量％である。 Although the usage-amount is not specifically limited, Preferably it is 5-99 mass%, More preferably, it is 30-90 mass%.
本発明においては、上記（メタ）アクリル酸エステル系単量体を、後述するように、反応性乳化剤を分散剤として懸濁重合する。この場合、多官能架橋性単量体を配合して重合することもできる。 In the present invention, the (meth) acrylic acid ester monomer is subjected to suspension polymerization using a reactive emulsifier as a dispersant as described later. In this case, polymerization can be carried out by blending a polyfunctional crosslinking monomer.
（ｂ）多官能架橋性単量体としては（メタ）アクリル酸とエチレングリコール、プロピレングリコール、１，３−ブチレングリコール、ジエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール等の多価アルコールとのエステル；ジビニルベンゼン等の多官能ビニル化合物；（メタ）アクリル酸アリル等の（メタ）アクリル酸とアリルエステル等が挙げられる。その使用量は、特に限定されないが、好ましくは０．１〜２０質量％、より好ましくは５〜１５質量％である。 (B) Polyfunctional crosslinkable monomers such as (meth) acrylic acid and ethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. An ester with a polyhydric alcohol; a polyfunctional vinyl compound such as divinylbenzene; and (meth) acrylic acid such as allyl (meth) acrylate and an allyl ester. Although the usage-amount is not specifically limited, Preferably it is 0.1-20 mass%, More preferably, it is 5-15 mass%.
さらに、紫外線安定基および／または紫外線吸収基を配合して重合することもできる。 Furthermore, it can also superpose | polymerize by mix | blending a ultraviolet-ray stable group and / or a ultraviolet-ray absorption group.
（ｃ）紫外線安定基および／または紫外線吸収基を有する不飽和単量体としては、例えば、２，４−ジヒドロキシベンゾフェノン、または２，２’，４−トリヒドロキシ
ベンゾフェノンとグリシジル（メタ）アクリレートを反応させて得られる２−ヒドロキシ−４−〔３−（メタ）アクリルオキシ−２−ヒドロキシプロポキシ〕ベンゾフェノン、２，２’−ジヒドロキシ−４−〔３−（メタ）アクリルオキシ−２−ヒドロキシプロポキシ
〕ベンゾフェノン等のベンゾフェノン系の単量体、および２−〔２’−ヒドロキシ−５’−（メタクリロイルオキシメチル）フェニル〕−２Ｈ−ベンゾトリアゾール、２−〔２’−ヒドロキシ−５’−（メタクリロイルオキシエチル）フェニル〕−２Ｈ−ベンゾトリアゾール、２−〔２’−ヒドロキシ─５’−（メタクリロイルオキシプロピル〕フェニル〕−２Ｈ−ベンゾトリアゾール、２−〔２’−ヒドロキシ−５’−（メタクリロイルオキシヘキシル〕フェニル〕−２Ｈ−ベンゾトリアゾール、２−〔２’−ヒドロキシ─３’−ｔ−ブチル−５’−（メタクリロイルオキシエチル〕フェニル〕−２−ベンゾトリアゾール、２−〔２’−ヒドロキシ−５’−ｔ−ブチル−３’−（メタクリロイルオキシエチル〕フェニル〕−２Ｈ−ベンゾトリアゾール、２−〔２’−ヒドロキシ−５’−（メタクリロイルオキシエチル）フェニル〕−５−クロロ−２Ｈ−ベンゾトリアゾール、２−〔２’−ヒドロキシ−５’−（メタクリロイルオキシエチル）フェニル〕−５−メトキシ−２Ｈ−ベンゾトリアゾール、２−〔２’−ヒドロキシ−５’−（メタクリロイルオキシエチル）フェニル〕−５−シアノ−２Ｈ−ベンゾトリアゾール、２−〔２’−ヒドロキシ−５’−（メタクリロイルオキシエチル）フェニル〕−５−ｔ−ブチル−２Ｈ−ベンゾトリアゾール、２−〔２’−ヒドロキシ−５’−（メタクリロイルオキシエチル）フェニル〕−５−ｔ−ブチル−２Ｈ−ベンゾトリアゾール等のベンゾトリアゾール系の単量体等の紫外線吸収能を有する単量体；４−（メタ）アクリロイルオキシ−２，２，６，６−テトラメチルピペリジン、４−（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン、４−（メタ）アクリロイルオキシ−１，２，２，６，６−ペンタメチルピペリジン、４−（メタ）アクリロイルアミノ−１，２，２，６，６−ペンタメチルピペリジン、４−シアノ−４−（メタ）アクリロイルオキシ−２，２，６，６−テトラメチルピペリジン、１−（メタ）アクリロイル−４−（メタ）アクリロアミノ−２，２，６，６−テトラメチルピペリジン、４−クロトイルオキシ−２，２，６，６−テトラメチルピペリジン、４−クロトイルアミノ−２，２，６，６−テトラメチルピペリジン、１−クロトイル−４−クロトイルオキシ−２，２，６，６−テトラメチルピペリジン等のピペリジン系の重合性単量体等の紫外線安定化能を有する単量体等がある。
(C) As an unsaturated monomer having an ultraviolet stabilizing group and / or an ultraviolet absorbing group, for example, 2,4-dihydroxybenzophenone or 2,2 ′, 4-trihydroxybenzophenone and glycidyl (meth) acrylate are reacted. 2-hydroxy-4- [3- (meth) acryloxy-2-hydroxypropoxy] benzophenone, 2,2′-dihydroxy-4- [3- (meth) acryloxy-2-hydroxypropoxy] benzophenone Benzophenone monomers such as 2- [2′-hydroxy-5 ′-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) Phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meta Liloyloxypropyl] phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyhexyl] phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-t- Butyl-5 ′-(methacryloyloxyethyl) phenyl] -2-benzotriazole, 2- [2′-hydroxy-5′-t-butyl-3 ′-(methacryloyloxyethyl] phenyl] -2H-benzotriazole, 2 -[2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl] -5-methoxy- 2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] 5-cyano-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -5-tert-butyl-2H-benzotriazole, 2- [2′-hydroxy-5′- (Methacryloyloxyethyl) phenyl] -5-tert-butyl-2H-benzotriazole-based monomers such as benzotriazole-based monomers; 4- (meth) acryloyloxy-2,2, 6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloyloxy-2 2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloamino-2,2,6,6-tetramethylpiperidine, 4-crotoyloxy-2,2,6,6- Piperidine-based polymerizability such as tetramethylpiperidine, 4-crotoylamino-2,2,6,6-tetramethylpiperidine, 1-crotoyl-4-crotoyloxy-2,2,6,6-tetramethylpiperidine There are monomers and the like having a UV-stabilizing ability such as monomers.
このような紫外線安定基および／または紫外線吸収基を有する単量体の使用量は、特に限定されるものではないが、好ましくは０．１〜１０質量％、より好ましくは０．５〜５質量％であり、これにより得られる水性樹脂組成物の耐候性が向上する。 The amount of the monomer having such an ultraviolet stabilizing group and / or ultraviolet absorbing group is not particularly limited, but is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass. %, And the weather resistance of the resulting aqueous resin composition is improved.
以上の単量体混合物中の（ａ）と（ｂ）と（ｃ）との合計は１００質量％である。 The sum of (a), (b) and (c) in the monomer mixture is 100% by mass.
また、本願の方法で使用される単量体において、その他の単量体を使用することもできる。（ｄ）その他の単量体は、必須ではないが、配合してもよい。その使用量は特に限定されるものではないが、好ましくは０〜７０質量％、より好ましくは０〜３０質量％である。 Moreover, in the monomer used by the method of this application, another monomer can also be used. (D) Other monomers are not essential, but may be blended. The amount used is not particularly limited, but is preferably 0 to 70% by mass, and more preferably 0 to 30% by mass.
また、以上の単量体混合物中の（ａ）と（ｂ）と（ｄ）との合計は１００質量％である。 Moreover, the sum total of (a), (b), and (d) in the above monomer mixture is 100 mass%.
このような（ｄ）その他の単量体としては、前記単量体と共重合し得るものであればいずれでも使用できる。主な重合性単量体としては、
・アクリル酸、メタクリル酸、クロトン酸等のエチレン性不飽和モノカルボン酸；フマル酸、イタコン酸の不飽和多価カルボン酸類；マレイン酸モノエチル、イタコン酸モノエチル等のエチレン性不飽和多価モノカルボン酸の部分エステル化合物のカルボキシル基を有する重合性単量体
・（メタ）アクリル酸グリシジル、（メタ）アクリル酸−２−メチルグリシジル、アリルグリシジルエーテル等のエポキシ基を有する重合性単量体
・メタアクリロイルアジリジン、（メタ）アクリル酸−２−アジリジニルエチル等のアジリジニル基を有する重合性単量体
・２−イソプロペニル−２−オキサゾリン、２−ビニル−オキサゾリン等のオキサゾリン基を有する重合性単量体
・（メタ）アクリルアミド、Ｎ−モノエチル（メタ）アクリルアミド、Ｎ−モノメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド等の（メタ）アクリルアミド誘導体類
・（メタ）アクリル酸ジメチルアミノエチル、ジメチルアミノエチル（メタ）アクリルアミド、ビニルピリジン、ビニルイミダゾール、ビニルピロリドン等の塩基性重合性単量体・Ｎ−メチロール（メタ）アクリルアミド、Ｎ−プトキシメチル（メタ）アクリルアミド等の架橋性（メタ）アクリルアミド類
・スチレン、ビニルトルエン、α−メチルスチレン、クロルメチルスチレン等のスチレン誘導体
・（メタ）アクリロニトリル等のシアノ基を有する重合性単量体
・（メタ）アクリル酸−２−スルホン酸エチルおよびその塩、ビニルスルホン酸およびその塩等のスルホン酸基を有する重合性単量体
・ビニルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリメトキシシラン、アリルトリエトキシシラン、トリメトキシシリルプロピルアリルアミン等の有機珪素基を有する不飽和単量体、酢酸ビニル、プロピオン酸ビニル等のビニルエステル類
・フッ化ビニル、フッ化ビニリデン、塩化ビニル、塩化ビニリデン等のハロゲン化単量体類
・ブタジエン、イソプレン等の共役ジエン類
・エチレン、プロピレン、プテン類のオレフィン類等が挙げられる。これらの例示の重合性単量体は１種類のみを用いてもよく、２種類以上を併用してもよい。
As such (d) other monomer, any monomer can be used as long as it can be copolymerized with the monomer. As main polymerizable monomer,
Ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; unsaturated polycarboxylic acids such as fumaric acid and itaconic acid; ethylenically unsaturated polyvalent monocarboxylic acids such as monoethyl maleate and monoethyl itaconic acid Polymerizable monomer having a carboxyl group of a partial ester compound of the present invention. Polymerizable monomer having an epoxy group such as glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and allyl glycidyl ether. Methacryloyl Polymerizable monomer having an aziridinyl group such as aziridine and (meth) acrylic acid-2-aziridinylethyl. Polymerizable monomer having an oxazoline group such as 2-isopropenyl-2-oxazoline and 2-vinyl-oxazoline. Body (meth) acrylamide, N-monoethyl (meth) acrylamide, (Meth) acrylamide derivatives such as N-monomethyl (meth) acrylamide and N, N-dimethyl (meth) acrylamide ・ Dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, vinylpyridine, vinylimidazole, vinyl Basic polymerizable monomers such as pyrrolidone ・ Crosslinking (meth) acrylamides such as N-methylol (meth) acrylamide and N-ptoxymethyl (meth) acrylamide ・ Styrene, vinyltoluene, α-methylstyrene, chloromethylstyrene, etc. Styrene derivatives of -Polymerizable monomers having a cyano group such as (meth) acrylonitrile -Polymerizable monomers having a sulfonic acid group such as ethyl (meth) acrylic acid-2-sulfonate and salts thereof, vinylsulfonic acid and salts thereof Monomer / Vinyl Trimet Unsaturated monomers having an organosilicon group such as xylsilane, γ- (meth) acryloxypropyltrimethoxysilane, allyltriethoxysilane, trimethoxysilylpropylallylamine, and vinyl esters such as vinyl acetate and vinyl propionate Halogenated monomers such as vinyl chloride, vinylidene fluoride, vinyl chloride, and vinylidene chloride. Conjugated dienes such as butadiene and isoprene. Olefin such as ethylene, propylene, and ptenes. These exemplary polymerizable monomers may be used alone or in combination of two or more.
懸濁重合の際に使用される重合開始剤としては、油溶性の開始剤が使用され、例えば、ラウロイルパーオキサイド、ベンゾイルパーオキサイド、ｔ−ブチルパーオキシ−２−エチルケキサノエート、１，１−ジ−ｔ−ブチルパーオキシ−２−メチルシクヘキサン等の過酸化物系開始剤、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス−２，４−ジメチルバレロニトリル等のアゾ系開始剤などを挙げることができる。これらの開始剤は１種類のみを用いてもよく、２種類以上併用してもよい。また、重合開始剤野使用量は、特に限定はされないが、全重合性単量体成分の使用量に対し、好ましくは０．０１〜５質量部であり、よりが好ましくは０．５〜２重量％である。重合開始剤の使用量が多すぎると塗膜の耐水性を低下させ、また、少なすぎると重合速度が遅くなり、未反応の単量体が残存しやすくなるので、いずれも好ましくない。 As the polymerization initiator used in the suspension polymerization, an oil-soluble initiator is used. For example, lauroyl peroxide, benzoyl peroxide, t-butylperoxy-2-ethyl ketanoate, 1,1 -Peroxide initiators such as di-t-butylperoxy-2-methylcyclohexane, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, etc. And azo initiators. These initiators may be used alone or in combination of two or more. Further, the amount of polymerization initiator used is not particularly limited, but is preferably 0.01 to 5 parts by mass, more preferably 0.5 to 2 with respect to the amount of all polymerizable monomer components used. % By weight. When the amount of the polymerization initiator used is too large, the water resistance of the coating film is lowered. When the amount is too small, the polymerization rate is slowed, and unreacted monomers are likely to remain.
平均粒子径３〜１００μｍの樹脂粒子を含有する水性樹脂分散体（Ａ）は、前記単量体（ａ）、（ｂ）、（ｃ）および必要により（ｄ）よりなる単量体混合物または単量体（ａ）、（ｂ）および必要により（ｄ）よりなる単量体混合物を水性媒体中で分散安定剤および重合開始剤の存在下に常法により懸濁重合を行なうことにより得られる。反応温度は、通常５０〜１００℃であり、好ましくは６０〜９０℃である。反応温度は一定であっても、反応途中で変化させてもよい。重合時間は、特に限定はなく、反応の進行状況に応じて適宜選ぶことができるが、重合開始から終了まで、通常１〜１０時間、好ましくは２〜５時間である。 The aqueous resin dispersion (A) containing resin particles having an average particle size of 3 to 100 μm is a monomer mixture or a monomer composed of the monomers (a), (b), (c) and, if necessary, (d). The monomer mixture comprising the monomers (a), (b) and, if necessary, (d) can be obtained by subjecting the monomer mixture to suspension polymerization in an aqueous medium in the presence of a dispersion stabilizer and a polymerization initiator. The reaction temperature is usually 50 to 100 ° C, preferably 60 to 90 ° C. The reaction temperature may be constant or may be changed during the reaction. The polymerization time is not particularly limited and can be appropriately selected according to the progress of the reaction. It is usually 1 to 10 hours, preferably 2 to 5 hours from the start to the end of the polymerization.
前記水性樹脂分散体（Ａ）中の平均粒子径は、３〜１００μｍであるが、好ましくは５〜６０μｍであり、さらに好ましくは１０〜５０μｍである。すなわち、３μｍ未満では艶消し効果が不十分となり、また、１００μｍを越えると、懸濁重合して得られた水性樹脂分散体の貯蔵安定性が著しく低下する。また、該水性樹脂分散体（Ａ）中の固形分濃度は、５〜５０質量％、好ましくは２０〜４０質量％である。 Although the average particle diameter in the said aqueous resin dispersion (A) is 3-100 micrometers, Preferably it is 5-60 micrometers, More preferably, it is 10-50 micrometers. That is, if it is less than 3 μm, the matting effect is insufficient, and if it exceeds 100 μm, the storage stability of the aqueous resin dispersion obtained by suspension polymerization is significantly lowered. Moreover, solid content concentration in this aqueous resin dispersion (A) is 5-50 mass%, Preferably it is 20-40 mass%.
平均粒子径３〜１００μｍの樹脂粒子を含有する水性樹脂分散体（Ａ）の使用形態としては、特に限定はされず、水分散体のまま使用しても粒子粉体としてとりだした後に混合してもよいが、経済的、作業性の観点からも好ましくは水分散体のまま使用する方法が好ましい。 The use form of the aqueous resin dispersion (A) containing resin particles having an average particle diameter of 3 to 100 μm is not particularly limited, and even after being used as an aqueous dispersion, it is mixed after being taken out as a particle powder. However, from the viewpoint of economy and workability, a method of using the aqueous dispersion as it is is preferable.
前記いずれの水性樹脂分散体の製造方法においても、使用される水系媒体としては、通常、水であり、必要に応じて低級アルコールやケトン等の親水性溶媒が併用できる。水性媒体の使用量は、上記全重合性単量体成分の使用量に対して、得られる水性樹脂分散体の固形分含量が上記一定の範囲になるように用いられる。 In any of the methods for producing an aqueous resin dispersion, the aqueous medium to be used is usually water, and a hydrophilic solvent such as a lower alcohol or a ketone can be used in combination as necessary. The amount of the aqueous medium used is used such that the solid content of the obtained aqueous resin dispersion falls within the above-mentioned predetermined range with respect to the amount of the above-mentioned total polymerizable monomer component used.
本発明において使用される反応性乳化剤は、重合系内の単量体と共重合し得る二重結合を分子内に有するとともに、乳化能を持つ分子構造を有しているものであり、該反応性乳化剤としてはアニオン性の反応性乳化剤を使用することが好ましく、さらに、該反応性乳化剤の反応性基として（メタ）アクリロイル基を有するものを使用すると、効果が大きくなる。そして、このような反応性乳化剤を使用した場合には、懸濁重合時に発生するスケール量が低減でき、かつ得られた水性樹脂分散体を使用した塗膜は、耐候性試験後の艶消剤の抜け落ちが抑制される。 The reactive emulsifier used in the present invention has a double bond capable of copolymerizing with a monomer in the polymerization system in the molecule and has a molecular structure having an emulsifying ability. As the reactive emulsifier, an anionic reactive emulsifier is preferably used, and further, the use of the reactive emulsifier having a (meth) acryloyl group as the reactive group increases the effect. When such a reactive emulsifier is used, the amount of scale generated during suspension polymerization can be reduced, and the coating film using the obtained aqueous resin dispersion is a matting agent after the weather resistance test. The omission is suppressed.
このような反応性乳化剤としては、具体的には、例えば、ポリオキシエチレン−１−（アリルアキシメチル）アルキルエーテル硫酸エステルアンモニウム塩「アクアロンＫＨ−１０」（商品名 第一工業製薬株式会社製）、ポリオキシエチレンノニルプロペニルエーテル硫酸エステル塩「アクアロンＨＳ」、「アクアロンＢＣ」（商品名 第一工業製薬株式会社製）、ポリオキシエチレンなリルグリシジルノニルフェニルエーテル硫酸エステル塩「アデカリアソープＳＥ」（商品名 旭電化株式会社製）、アルキルアリルスルホコハク酸ソーダ「エレミノールＪＳ−２」（商品名 三洋化成工業株式会社製）、メタクリル酸ポリオキシアルキレン硫酸エステル塩「エレミノールＲＳ−３０」（商品名 三洋化成工業株式会社製、ビス（ポリオキシエチレン多環フェニルエーテル）メタクリレート硫酸エステル塩「アントックスＭＳ−６０」（商品名 日本乳化剤株式会社製）、エチレングリコールメタクリレート硫酸エステル塩「アントックスＭＳ−２Ｎ」、「アントックスＭＳ−ＮＨ４」（商品名 日本乳化剤株式会社製）、またその他の構達をもつものとして「ラテムル」（商品名 花王株式会社製）、「ニューフロンティア」〈商品名 第一工業製薬製）、「ＲＡ−１８２３」、「ＲＡ−２３２０」（商品名 日本乳化剤株式会社製）等、プロペニル基、アリル基、イソプロペニル基、アクリレート基、メタクリレート基等の反応性基を有するアニオン性反応性乳化剤が挙げられる。またポリオキシエチレンノニルプロペニルエーテル「アクアロンＲＮ」、（商品名 第一工業製薬株式会社製）、ポリオキシエチレンアリルグリシジルノニルフェニルエーテル「アデカリアソープＮＥ」（商品名 旭電化株式会社製）、ポリオキシアルキレングリコールモノアクリレート「プレンマーＡＥＴ」、「プレンマーＡＰＴ」、（商品名 日本油脂株式会社製）、ラウロキシポリエチレンクリコールモノアクリレート「プレンマーＡＬＥ」（商品名 日本油脂株式会社製）、ラウロキシポリエチレングリコールモノメタクリレート「プレンマーＰＳＥ」（商品名 日本油脂株式会社製）、ステアロキシポリエチレングリコールモノメタクリレート「プレンマーＰＳＥ」〈商品名 日本油脂株式会社製〉、ステアロキシポリエチレングリコール−ポリプロピレングリコールモノアクリレート「プレンマーＡＳＥＰ」（商品名 日本油脂株式会社製）、アリロキシポリアルキレシグリコールモノメタクリレート「プレンマーＰＮＥＰ」「プレンマーＰＮＰＥ」（商品名 日本油脂株式会社製）、ノニルフェノキシポリオキシアルキレングリコールモノアクリレート「プレンマー４３ＡＮＥＰ−５００」「プレンマー７０ＡＮＥＰ−５５０」（商品名 日本油脂株式会社製）、ポリエチレングリコール−ポリプロピレングリコールポリエチレングリコールジメタクリレート「プレンマー８０ＰＤＣ」（商品名 日本油脂株式会社製〉、ポリエチレングリコールポリプロピレングリコール−ポリエチレングリコールジアクリレート「プレンマー３０ＡＤＣ」（商品名 日本油脂株式会社製〉等、プロペニル気、アリル基、イソプロペニル基、アクリレート基、メタクリレート基等の反応性基を有するノニオン性反応乳化剤が挙げられる。 As such a reactive emulsifier, specifically, for example, polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium salt “Aqualon KH-10” (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) , Polyoxyethylene nonylpropenyl ether sulfate "AQUALON HS", "AQUALON BC" (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), polyoxyethylene rylglycidyl nonylphenyl ether sulfate "Adekaria soap SE" ( Asahi Denka Co., Ltd.), alkyl allylsulfosuccinate soda “Eleminol JS-2” (trade name, manufactured by Sanyo Chemical Industries Co., Ltd.), polyoxyalkylene sulfate ester salt “Eleminol RS-30” (trade name, Sanyo Kasei) Manufactured by Kogyo Co., Ltd. Ren polycyclic phenyl ether) methacrylate sulfuric ester salt "Ann Krytox MS-60" (trade name Nippon Emulsifier Co., Ltd.), ethylene glycol methacrylate sulfate salts "Ann Krytox MS-2N", "Ann tox MS-NH 4" ( "Latemul" (trade name, manufactured by Kao Corporation), "New Frontier" (trade name, manufactured by Daiichi Kogyo Seiyaku), "RA-1823" An anionic reactive emulsifier having a reactive group such as a propenyl group, an allyl group, an isopropenyl group, an acrylate group, or a methacrylate group, such as “RA-2320” (trade name, manufactured by Nippon Emulsifier Co., Ltd.). In addition, polyoxyethylene nonyl propenyl ether “Aqualon RN” (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), polyoxyethylene allyl glycidyl nonyl phenyl ether “Adekaria soap NE” (trade name, manufactured by Asahi Denka Co., Ltd.), polyoxy Alkylene glycol monoacrylate "Plenmer AET", "Plenmer APT" (trade name, manufactured by Nippon Oil & Fats Co., Ltd.), Lauroxy polyethylene glycol monoacrylate "Plenmer ALE" (trade name, manufactured by Nippon Oil & Fats Co., Ltd.), Lauroxy polyethylene glycol mono Methacrylate "Plenmer PSE" (trade name, manufactured by NOF Corporation), stearoxy polyethylene glycol monomethacrylate "Plenmer PSE" (trade name, manufactured by NOF Corporation), stearoxy polyethylene glycol Polypropylene glycol monoacrylate “Plenmer ASEP” (trade name, manufactured by Nippon Oil & Fats Co., Ltd.), Allyloxy polyalkylene glycol monomethacrylate “Plenmer PNEP” “Plenmer PNPE” (trade name, manufactured by Nippon Oil & Fats Co., Ltd.), Nonylphenoxy polyoxyalkylene glycol Monoacrylate “Plenmer 43ANEP-500” “Plenmer 70ANEP-550” (trade name, manufactured by Nippon Oil & Fats Co., Ltd.), Polyethylene glycol-polypropylene glycol Polyethylene glycol dimethacrylate “Plenmer 80PDC” (trade name: manufactured by Nippon Oil & Fats Co., Ltd.), polyethylene glycol polypropylene Glycol-polyethylene glycol diacrylate “Plenmer 30 ADC” (trade name, manufactured by NOF Corporation) Nonionic reactive emulsifiers having a reactive group such as a phenyl group, an allyl group, an isopropenyl group, an acrylate group, and a methacrylate group.
このような反応性乳化剤の使用量は、特に限定されるものではないが、単量体混合物に対して、好ましくは０．０１〜１０質量％、より好ましくは０．１〜５質量％である。 Although the usage-amount of such a reactive emulsifier is not specifically limited, Preferably it is 0.01-10 mass% with respect to a monomer mixture, More preferably, it is 0.1-5 mass%. .
また、重合時に重合開始剤の他に、必要に応じて、連鎖移動剤を添加することができ、例えば、ｔ−ドデシルメルカプタン等のチオール基を有する化合物やα−メチルスチレンダイマー等を添加することができる。 In addition to the polymerization initiator during polymerization, a chain transfer agent can be added as necessary. For example, a compound having a thiol group such as t-dodecyl mercaptan, α-methylstyrene dimer, or the like is added. Can do.
本発明においては、平均粒径が３〜１００μｍの樹脂粒子を含有する水性樹脂分散体（Ａ）に増粘剤（Ｃ）を添加し、ついで平均粒子径が０．０１〜１μｍの樹脂粒子を含有する水性樹脂分散体を混合することによる水性樹脂組成物が得られる。 In the present invention, the thickener (C) is added to the aqueous resin dispersion (A) containing resin particles having an average particle diameter of 3 to 100 μm, and then resin particles having an average particle diameter of 0.01 to 1 μm are added. An aqueous resin composition is obtained by mixing the aqueous resin dispersion contained therein.
前記増粘剤（Ｃ）としては、特に限定されるものではなく、一例を挙げると、例えば、つぎのものがある。 The thickener (C) is not particularly limited, and examples thereof include the following.
１）水溶性高分子
増粘剤として使用される水溶性高分子の具体例として、例えば、メチルセルロース、セルロースエーテル類（例えば、ヒドロキシプロピルメチルセスロース等）、ポリエチレンオキサイド、ポリプロピレンオキサイド、ポリエチレングリコール、ポリアクリルアミド、ポリビニルアルコールなどが挙げられる。
1) Water-soluble polymer Specific examples of the water-soluble polymer used as a thickener include, for example, methylcellulose, cellulose ethers (for example, hydroxypropylmethylsesulose), polyethylene oxide, polypropylene oxide, polyethylene glycol, poly Examples include acrylamide and polyvinyl alcohol.
２）会合性増粘剤
増粘剤として使用される会合性増粘剤は、一般的には、親水性の高分子主鎖の末端や途中に高級アルキル基等の疎水性ペンダント基をグラフトしたものである。会合性増粘剤の増粘作用の発現メカニズムは、疎水性ペンダント基の二次的結合力（例えば、疎水結合力）による会合性によることが知られている。増粘剤として使用される会合性増粘剤の具体例としては、例えば、ポリエチレングリコール系会合性増粘剤やアクリル系会合性増粘剤が挙げられる。ポリエチレングリコール系会合性増粘剤の一態様は、ポリエチレングリコールの両端に疎水性ペンダント基を結合せしめたものである。
2) Associative thickeners Associative thickeners used as thickeners are generally grafted with a hydrophobic pendant group such as a higher alkyl group at the end or in the middle of the hydrophilic polymer main chain. Is. The expression mechanism of the thickening action of the associative thickener is known to be due to the associative property by the secondary binding force (for example, hydrophobic binding force) of the hydrophobic pendant group. Specific examples of the associative thickener used as the thickener include, for example, polyethylene glycol associative thickeners and acrylic associative thickeners. One aspect of the polyethylene glycol-based associative thickener is one in which hydrophobic pendant groups are bonded to both ends of polyethylene glycol.
３）アクリル系会合性増粘剤
アクリル系会合性増粘剤は、親水性のアクリル系高分子主鎖の末端や途中に高級アルキル基等の疎水性ペンダント基をグラフトしたものである。アクリル系会合性増粘剤の具体例としては、例えば、アクリル系モノマーと、高級アルキル基等の疎水性ペンダント基を有する会合性モノマー（例えば、アルキル基、アラルキル基などの疎水ペンダント基を有し、かつ、アクリル系モノマーと共重合し得るエチレン性不飽和単量体である反応性界面活性剤等）との共重合体が挙げられる。具体的には、特開２００１−２４０６３３号公報に示す増粘剤が好ましい。
3) Acrylic associative thickener An acrylic associative thickener is obtained by grafting a hydrophobic pendant group such as a higher alkyl group on the end or in the middle of a hydrophilic acrylic polymer main chain. Specific examples of the acrylic associative thickener include, for example, an acrylic monomer and an associative monomer having a hydrophobic pendant group such as a higher alkyl group (for example, having a hydrophobic pendant group such as an alkyl group or an aralkyl group). And a reactive surfactant, which is an ethylenically unsaturated monomer that can be copolymerized with an acrylic monomer). Specifically, the thickener shown in JP 2001-240633 A is preferable.
増粘剤（Ｃ）の添加量は、前記平均粒子径が０．０１〜１μｍの樹脂粒子を含有する水性樹脂分散体（Ｂ）１００質量部当り０．０５〜２質量部、好ましくは０．１〜１．５質量部、さらに好ましくは０．１〜０．７質量部である。すなわち、増粘剤（Ｃ）の量が０．０５質量部未満では、増粘効果が発現できず、一方、２質量部を越えると、耐水性が低下するからである。 The addition amount of the thickener (C) is 0.05 to 2 parts by mass, preferably 0.002 per 100 parts by mass of the aqueous resin dispersion (B) containing resin particles having an average particle diameter of 0.01 to 1 μm. 1 to 1.5 parts by mass, more preferably 0.1 to 0.7 parts by mass. That is, if the amount of the thickener (C) is less than 0.05 parts by mass, the thickening effect cannot be exhibited, while if it exceeds 2 parts by mass, the water resistance decreases.
すべての本発明において、平均粒子径が３〜１００μｍの樹脂粒子を含有する水性樹脂分散体（Ａ）の添加量は、前記平均粒子径が０．０１〜１μｍの樹脂粒子を含有する水性樹脂分散体（Ｂ）の固形分１００質量部当り１〜３０質量部、好ましくは５〜２５質量部である。すなわち、水性樹脂分散体（Ａ）の量が１質量部未満では、艶消し効果が不十分であり、一方、３０質量部を越えると、貯蔵安定性が不十分となるためである。 In all the present inventions, the addition amount of the aqueous resin dispersion (A) containing resin particles having an average particle diameter of 3 to 100 μm is the aqueous resin dispersion containing resin particles having an average particle diameter of 0.01 to 1 μm. It is 1-30 mass parts per 100 mass parts of solid content of a body (B), Preferably it is 5-25 mass parts. That is, if the amount of the aqueous resin dispersion (A) is less than 1 part by mass, the matting effect is insufficient, while if it exceeds 30 parts by mass, the storage stability becomes insufficient.
本発明の水性樹脂組成物は、前記水性樹脂分散液のみをそのまま用いたものであってもよいし、必要に応じて種々の添加剤を含有するものであってもよい。添加剤としては、例えば、顔料、成膜助剤、充填剤（フィラー）、トナー、湿潤剤、帯電防止剤、顔料分散剤、可塑剤、酸化防止剤、流れコントロール剤、粘度調整剤等が挙げられる。また、他の水溶性樹脂あるいは水分散性樹脂を、添加、混合して使用してもよい。これら樹脂としては、例えば、スチレンアクリル、アクリル、ウレタン、シリコン、アクリルシリコン、アクリルウレタン、フッ素、アクリルフッ素等が挙げられる。 The aqueous resin composition of the present invention may be one using only the aqueous resin dispersion as it is, or may contain various additives as necessary. Examples of additives include pigments, film forming aids, fillers (fillers), toners, wetting agents, antistatic agents, pigment dispersants, plasticizers, antioxidants, flow control agents, viscosity modifiers, and the like. It is done. Further, other water-soluble resins or water-dispersible resins may be added and mixed for use. Examples of these resins include styrene acrylic, acrylic, urethane, silicon, acrylic silicon, acrylic urethane, fluorine, and acrylic fluorine.
前記添加剤のなかで、特に、顔料としては、酸化チタン、酸化カルシウム、三酸化アンチモン、亜鉛華、リトポン、鉛白等の白色顔料や、カーボンブラック、黄鉛、モリブデン赤、ベンガラ、黄色酸化鉄、黄華等の着色顔料のような無機顔料；ベンジジン、ハンザイエロー等のアゾ化合物やフタロシアニンブルー等のフタロシアニン類のような有機顔料；が挙げられる。これらは、１種類のみを用いてもよいし、２種類以上を併用することもできる。これら例示のなかでも、得られる塗膜の耐候性を低下させないようにするためには、耐候性の良好な顔料を使用することが好ましい。例えば、白色顔料である酸化チタンを使用する場合、アナターゼ型構造の酸化チタンよりもルチル型構造の酸化チタンを用いるほうが好ましい。さらに、ルチル型構造の酸化チタンを使用する場合、長期にわたる耐候性を発現させるためには、硫酸法酸化チタンよりも塩素法酸化チタンを使用するほうが、より好ましい。 Among the additives, in particular, as pigments, white pigments such as titanium oxide, calcium oxide, antimony trioxide, zinc white, lithopone, lead white, carbon black, chrome lead, molybdenum red, red iron oxide, yellow iron oxide And inorganic pigments such as colored pigments such as yellow flower; organic pigments such as azo compounds such as benzidine and Hansa Yellow, and phthalocyanines such as phthalocyanine blue. These may use only 1 type and can also use 2 or more types together. Among these examples, it is preferable to use a pigment having good weather resistance so as not to lower the weather resistance of the resulting coating film. For example, when using titanium oxide, which is a white pigment, it is preferable to use rutile type titanium oxide rather than anatase type titanium oxide. Furthermore, when using rutile-type titanium oxide, it is more preferable to use chlorine-based titanium oxide than sulfuric acid-based titanium oxide in order to develop long-term weather resistance.
つぎに、実施例を挙げて本発明をさらに詳細に説明する。なお、下記に記載する「部」および「％」は、特にことわらない限り、「質量部」および「質量％」を表わす。 Next, the present invention will be described in more detail with reference to examples. “Parts” and “%” described below represent “parts by mass” and “% by mass” unless otherwise specified.
なお、本実施例および比較例における試験方法は、下記のとおりであった。 In addition, the test method in a present Example and a comparative example was as follows.
試験方法
＜ｐＨ＞
ｐＨメーター（株式会社堀場製作所製「Ｆ−２３」）により、２５℃での値測定した。
Test method <pH>
The value at 25 ° C. was measured with a pH meter (“F-23” manufactured by Horiba, Ltd.).
＜粘度＞
ＢＭ型粘度計（東京計器株式会社製）により、３０ｒｐｍ、２５℃にて測定した。また、粘度に応じて使用するローターを選定した。
<Viscosity>
It measured at 30 rpm and 25 degreeC with the BM type | mold viscosity meter (made by Tokyo Keiki Co., Ltd.). Moreover, the rotor to be used was selected according to the viscosity.
＜平均粒子径＞
懸濁重合物の平均粒子径測定は、コールターカウンター（ベックマンコールター社製、機種；コールターマルチサイザーII）にて測定した。
<Average particle size>
The average particle size of the suspension polymer was measured with a Coulter counter (Beckman Coulter, model: Coulter Multisizer II).
＜外艶消し性＞
得られた塗料組成物を、黒色アクリル板（太祐機材製）に４ｍｉｌアプリケーターを使用して塗装する。室温で５分間セッティングした後、１００℃の熱風乾燥機内で１０分間乾燥させた塗装板の光沢（艶）を光沢計（６０°Ｇｌｏｓｓ）で測定した。
<Outer mattness>
The obtained coating composition is applied to a black acrylic plate (manufactured by Taisuke Corporation) using a 4 mil applicator. After setting for 5 minutes at room temperature, the gloss (gloss) of the coated plate dried for 10 minutes in a hot air dryer at 100 ° C. was measured with a gloss meter (60 ° Gloss).
ＧＬ２５以下・・・○
ＧＬ２６以上・・・×
＜透明性＞
上記、外観艶消し性と同様の方法で作成した塗装板の透明性を色差計で測定した。
Less than GL25 ・ ・ ・ ○
GL26 or higher
<Transparency>
The transparency of the coated plate prepared by the same method as the above-mentioned appearance matte property was measured with a color difference meter.
Ｌ値１０以下・・・○
Ｌ値１１以上・・・×
＜吸水率＞
ガラス板状に離型紙を貼り、その上にガムテープ１枚厚（厚さ約３００μｍ）の型枠を形成した。この方枠内に得られた塗料組成物を流し込みキャストする。５分間セッティングした後、１００℃の熱風乾燥機内で１０分間乾燥させて試験フィルムを作成した。該試験フィルムを２４時間室温で放置した後、４×４ｃｍにカットし、重量（Ｗ０）を測定した。その後、常温水中に没水・浸漬させ、１週間後、取り出して表面の水をふき取り、直ちにフィルムの重量を測定した。さらに、該試験フィルムを１５０℃の熱風乾燥機内で１時間乾燥させ、その重量（Ｗ２）を測定した。そして、下記式より、塗膜吸水率を算出した。
L value of 10 or less
L value 11 or more ×
<Water absorption rate>
A release paper was affixed to a glass plate, and a mold frame with a thickness of one gum tape (thickness: about 300 μm) was formed thereon. The obtained coating composition is poured into the frame and cast. After setting for 5 minutes, it was dried in a hot air dryer at 100 ° C. for 10 minutes to prepare a test film. The test film was allowed to stand at room temperature for 24 hours, then cut to 4 × 4 cm, and the weight (W0) was measured. Then, it was immersed in room temperature water, and after 1 week, it was taken out and the surface water was wiped off, and the weight of the film was immediately measured. Further, the test film was dried in a hot air dryer at 150 ° C. for 1 hour, and its weight (W2) was measured. And the coating-film water absorption rate was computed from the following formula.
吸水率＝（Ｗ−Ｗ２）／Ｗ２×１００
＜耐温水試験＞
上記、外観艶消し性と同様の手法で作成した塗装板を室温で２４時間放置した後、６０℃温水中に没水・浸漬させ、１週間経過後の塗装板を引き上げ室温で一日乾燥する。乾燥後の塗装板の外観を未試験板（初期板）と比較する。
Water absorption rate = (W−W2) / W2 × 100
<Hot water resistance test>
The coated plate prepared in the same manner as the matte appearance described above is allowed to stand at room temperature for 24 hours, then immersed in 60 ° C. warm water, pulled up after 1 week, and dried at room temperature for one day. . The appearance of the painted board after drying is compared with an untested board (initial board).
＜耐候性（Ｍ−ＷＯＭ）＞
ストレート板に、溶剤系シーラーをｄｒｙ２０μｍになるように塗装し、室温で１日乾燥させた後、下記配合のベースコート用塗料を４ｍｉｌアプリケーターにて塗装し、５分間セッティングした後、１００℃の熱風乾燥機内で１０分間乾燥させた。室温で１日放置した後、得られた塗料組成物を４ｍｉｌアプリケーターにて塗装し、５分間セッティングした後、１００℃の熱風乾燥機内で１０分間乾燥させ、塗装板を作成した。作成後、１日経過した塗装板を用いて超促進耐候性試験を行なった。
<Weather resistance (M-WOM)>
A straight plate is coated with a solvent sealer to a dry 20 μm, dried at room temperature for 1 day, then coated with a 4 mil applicator with a base coat paint of the following composition, set for 5 minutes, and then dried with hot air at 100 ° C. It was dried for 10 minutes in the machine. After leaving at room temperature for 1 day, the obtained coating composition was coated with a 4 mil applicator, set for 5 minutes, and then dried in a hot air dryer at 100 ° C. for 10 minutes to prepare a coated plate. After the preparation, a super accelerated weather resistance test was performed using a coated plate that had passed one day.
＜超促進耐候性試験：Ｍ−ＷＯＭ条件＞
ダイプラウィンテス社製のダイプラメタルウェザー試験機に上記で作成した塗装板をセットし、照射６時間（温度６８℃−湿度５０％）、シャワー１０秒、結露２時間（温度３０℃−湿度９５％以上）、シャワー１０秒を１サイクルとして、２００時間繰り返し試験を行なった。
<Super accelerated weather resistance test: M-WOM condition>
Set the painted plate prepared above in a die plastic metal weather testing machine manufactured by Daipura Wintes Co., Ltd., irradiation 6 hours (temperature 68 ° C-humidity 50%), shower 10 seconds, condensation 2 hours (temperature 30 ° C-humidity 95%) As described above, the test was repeated for 200 hours with 10 seconds of shower as one cycle.
８００ｈｒ塗膜外観異常なし・・・◎
６００ｈｒ塗膜外観異常なし・・・○
塗膜色変化・・・△
塗膜にクラック発生・・・×
＜ベースコート用塗料の配合＞
◎アクリルエマルション（ＥＸ−３５：株式会社日本触媒製）：３００部
◎白色ペースト（下記の調整ペースト）：１３５部
・分散剤（デモールＥＰ：花王株式会社製）：６０部
（ディスコートＮ−１４：第一工業製薬株式会社製）：５０部
・湿潤剤（エマルゲン９０９：花王株式会社製）：１０部
・エチレングリコール：６０部
・脱イオン水：２１０部
・酸化チタン（ＣＲ−９５：石原産業株式会社製）：１０００部
・ガラスビーズ：５００部
上記をホモディスパー３０００ｒｐｍ攪拌下で配合。全て加えて６０分間攪拌して調整。
800hr paint film appearance no abnormalities ... ◎
No abnormal appearance of 600 hr coating film ... ○
Change in paint film color ... △
Cracks in the coating ... X
<Composition of paint for base coat>
Acrylic emulsion (EX-35: manufactured by Nippon Shokubai Co., Ltd.): 300 parts ◎ White paste (adjusted paste below): 135 parts Dispersant (Demol EP: manufactured by Kao Corporation): 60 parts
(Discoat N-14: Daiichi Kogyo Seiyaku Co., Ltd.): 50 parts Wetting agent (Emulgen 909: Kao Corporation): 10 parts Ethylene glycol: 60 parts Deionized water: 210 parts Titanium oxide ( CR-95: manufactured by Ishihara Sangyo Co., Ltd.): 1000 parts ・ Glass beads: 500 parts The above was mixed under homodisper 3000 rpm stirring. Add everything and stir for 60 minutes to adjust.
◎成膜助剤（ブチルセロソルブ）：１５部
（ＣＳ−１２：チッソ株式会社製）：１５部
◎黒色ペースト（ユニラント８８：横浜化成株式会社製）：１０部
◎抑泡剤（ノプコ８０３４Ｌ：サンノプコ株式会社）：１．５部
＜耐候性試験後テープ剥離＞
上記耐候性試験終了後の塗装板を用い、塗装面にセロハンテープを貼り付けてよく密着させた後、一気にテープを剥離し、テープに付着した艶消し剤の量を比較する。
◎ Film forming aid (butyl cellosolve): 15 parts
(CS-12: manufactured by Chisso Corporation): 15 parts ◎ black paste (Unirant 88: manufactured by Yokohama Chemical Co., Ltd.): 10 parts ◎ foam suppressor (Nopco 8034L: San Nopco Corporation): 1.5 parts <Weather resistance test Rear tape peeling>
Using the coated plate after the weather resistance test is completed, a cellophane tape is applied to the painted surface and brought into close contact, and then the tape is peeled off at once and the amount of the matting agent attached to the tape is compared.
テープへの艶消し剤付着がない・・・○
テープへの艶消し剤付着が確認できる・・・△
テープ剥離後の塗膜外観に変化が見られる・・・×
懸濁重合製造例１
反応容器中で、（ポリオキシエチレン多環フェニルエーテル）メタクリレート化硫酸エステルアンモニウム塩（日本乳化剤株式会社製「アントックスＭＳ−６０」）の２５％水溶液６部を、脱イオン水４３０．２部に溶解させた。この中に、メチルメタクリレート（ＭＭＡ）１３５部、トリメチロールプロパントリメタクリレート（株式会社日本触媒製「ＴＭＰＴＭＡ」）１５部およびラウロイルパーオキサイド（ＬＰＯ）１．５部を添加し、混合攪拌した単量体混合溶液を添加し、攪拌機で攪拌した。光学顕微鏡にて目視で観察した結果、粒子径約２０μｍの単量体分散液を得た。この分散液を１リットルセパラブルフラスコに仕込み、窒素雰囲気化、３００ｒｐｍで攪拌しながら６５℃に昇温した。重合開始後、８５℃まで発熱し、その後８５℃で３時間熟成させることにより水性樹脂分散液を得た。得られた水性樹脂分散液の平均粒子径は、コールターカウンターにて測定した結果、約２０μｍであった。反応後の攪拌翼、セパラブルフラスコに付着したスケールを取り出して１１０℃で１日乾燥させたところ、スケール量は０．２ｇであった。
No matting agent attached to the tape ...
The matting agent can be confirmed on the tape ... △
There is a change in the appearance of the coating film after peeling the tape ... ×
Suspension polymerization production example 1
In a reaction vessel, 6 parts of 25% aqueous solution of (polyoxyethylene polycyclic phenyl ether) methacrylated sulfate ammonium salt (“Antox MS-60” manufactured by Nippon Emulsifier Co., Ltd.) was added to 430.2 parts of deionized water. Dissolved. To this, 135 parts of methyl methacrylate (MMA), 15 parts of trimethylolpropane trimethacrylate (“TMPTMA” manufactured by Nippon Shokubai Co., Ltd.) and 1.5 parts of lauroyl peroxide (LPO) were added and mixed and stirred. The mixed solution was added and stirred with a stirrer. As a result of visual observation with an optical microscope, a monomer dispersion having a particle size of about 20 μm was obtained. This dispersion was charged into a 1 liter separable flask and heated to 65 ° C. while stirring at 300 rpm under a nitrogen atmosphere. After the initiation of polymerization, heat was generated up to 85 ° C., and then aging was carried out at 85 ° C. for 3 hours to obtain an aqueous resin dispersion. The average particle diameter of the obtained aqueous resin dispersion was about 20 μm as a result of measurement with a Coulter counter. The scale adhering to the stirring blade and the separable flask after the reaction was taken out and dried at 110 ° C. for 1 day. The scale amount was 0.2 g.
懸濁重合製造例２
乳化剤をポリオキシエチレンアルキルプロペニルフェニルエーテル硫酸エステルアンモニウム塩（第一工業製薬株式会社製「アクアロンＢＣ−１０」）の２５％水溶液６部とした以外は、懸濁重合製造例１の方法と同様に行なった。得られた水性樹脂分散液の平均粒子径は、コールターカウンターにて測定した結果、約２１μｍであった。反応後の攪拌翼、セパラブルフラスコに付着したスケールを取り出して１１０℃で１日乾燥させたところ、スケール量は１．８ｇであった。
Suspension polymerization production example 2
Similar to the method of Suspension Polymerization Production Example 1 except that the emulsifier was 6 parts of a 25% aqueous solution of ammonium polyoxyethylene alkylpropenyl phenyl ether sulfate (“AQUALON BC-10” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). I did it. The average particle diameter of the obtained aqueous resin dispersion was about 21 μm as a result of measurement with a Coulter counter. The scale adhering to the stirring blade and separable flask after the reaction was taken out and dried at 110 ° C. for 1 day. The scale amount was 1.8 g.
懸濁重合製造例３
乳化剤をメタクロイルオキシアルキレン硫酸エステルナトリウム塩（三洋化成化学工業株式会社製「エレミノールＲＳ−３０」）の２５％水溶液６部とした以外は、懸濁重合製造例１の方法と同様に行なった。得られた水性樹脂分散液の平均粒子径は、コールターカウンターにて測定した結果、約１９μｍであった。反応後の攪拌翼、セパラブルフラスコに付着したスケールを取り出して１１０℃で１日乾燥させたところ、スケール量は０．３ｇであった。
Suspension polymerization production example 3
The same procedure as in Suspension Polymerization Production Example 1 was conducted except that the emulsifier was 6 parts of a 25% aqueous solution of methacryloyloxyalkylene sulfate sodium salt (“Eleminol RS-30” manufactured by Sanyo Chemical Industries, Ltd.). The average particle diameter of the obtained aqueous resin dispersion was about 19 μm as a result of measurement with a Coulter counter. The scale adhering to the stirring blade and separable flask after the reaction was taken out and dried at 110 ° C. for 1 day. The scale amount was 0.3 g.
懸濁重合製造例４
不飽和単量体組成物をシクロヘキシルメタクリレート（ＣＨＭＡ）１３８部およびＴＭＰＴＭＡ１２部とした以外は、懸濁重合製造例１の方法と同様に行なった。得られた水性樹脂分散液の平均粒子径は、コールターカウンターにて測定した結果、約２０μｍであった。反応後の攪拌翼、セパラブルフラスコに付着したスケールを取り出して１１０℃で１日乾燥させたところ、スケール量は０．２ｇであった。
Suspension polymerization production example 4
This was carried out in the same manner as in the suspension polymerization production example 1 except that the unsaturated monomer composition was 138 parts of cyclohexyl methacrylate (CHMA) and 12 parts of TMPTMA. The average particle diameter of the obtained aqueous resin dispersion was about 20 μm as a result of measurement with a Coulter counter. The scale adhering to the stirring blade and the separable flask after the reaction was taken out and dried at 110 ° C. for 1 day. The scale amount was 0.2 g.
懸濁重合製造例５
不飽和単量体組成物をＣＨＭＡ１３０部、ＴＭＰＴＭＡ１７部および４−メタクリロイルオキシー２，６，６−テロラメチルピペリジン（アデカ株式会社製「アデカスタブＬＡ−８７」：以下、ピリペリジンＡとする）３部とした以外は、懸濁重合製造例１の方法と同様に行なった。得られた水性樹脂分散液の平均粒子径は、コールターカウンターにて測定した結果、約２１μｍであった。反応後の攪拌翼、セパラブルフラスコに付着したスケールを取り出して１１０℃で１日乾燥させたところ、スケール量は０．２ｇであった。
Suspension polymerization production example 5
The unsaturated monomer composition was 130 parts of CHMA, 17 parts of TMPTMA, and 3 parts of 4-methacryloyloxy-2,6,6-terolamethylpiperidine (“ADEKA STAB LA-87” manufactured by ADEKA CORPORATION: hereinafter referred to as “piperidine A”). Except for this, the same procedure as in the suspension polymerization production example 1 was performed. The average particle diameter of the obtained aqueous resin dispersion was about 21 μm as a result of measurement with a Coulter counter. The scale adhering to the stirring blade and the separable flask after the reaction was taken out and dried at 110 ° C. for 1 day. The scale amount was 0.2 g.
懸濁重合製造例６
不飽和単量体組成物をターシャリブチルメタクリレート（ｔ−ＢＭＡ）１２５部およびＴＭＰＴＭＡ２５部とした以外は、懸濁重合製造例１の方法と同様に行なった。得られた水性樹脂分散液の平均粒子径は、コールターカウンターにて測定した結果、約２０μｍであった。反応後の攪拌翼、セパラブルフラスコに付着したスケールを取り出して１１０℃で１日乾燥させたところ、スケール量は０．３ｇであった。
Suspension polymerization production example 6
This was carried out in the same manner as in the suspension polymerization production example 1 except that the unsaturated monomer composition was 125 parts of tertiary butyl methacrylate (t-BMA) and 25 parts of TMPTMA. The average particle diameter of the obtained aqueous resin dispersion was about 20 μm as a result of measurement with a Coulter counter. The scale adhering to the stirring blade and the separable flask after the reaction was taken out and dried at 110 ° C. for 1 day. The scale amount was 0.3 g.
懸濁重合製造例７
不飽和単量体組成物を２−エチルヘキシルアクリレート（２−ＥＨＡ）１３０部およびＴＭＰＴＭＡ２０部とした以外は、懸濁重合製造例１の方法と同様に行なった。得られた水性樹脂分散液の平均粒子径は、コールターカウンターにて測定した結果、約２０μｍであった。反応後の攪拌翼、セパラブルフラスコに付着したスケールを取り出して１１０℃で１日乾燥させたところ、スケール量は０．３ｇであった。
Suspension polymerization production example 7
This was carried out in the same manner as in the suspension polymerization production example 1 except that the unsaturated monomer composition was 130 parts 2-ethylhexyl acrylate (2-EHA) and 20 parts TMPTMA. The average particle diameter of the obtained aqueous resin dispersion was about 20 μm as a result of measurement with a Coulter counter. The scale adhering to the stirring blade and separable flask after the reaction was taken out and dried at 110 ° C. for 1 day. The scale amount was 0.3 g.
懸濁重合製造例８
不飽和単量体組成物をＭＭＡ７２部、ＴＭＰＴＭＡ１８部、スチレン（Ｓｔ）６０部とした以外は、懸濁重合製造例１の方法と同様に行なった。得られた水性樹脂分散液の平均粒子径は、コールターカウンターにて測定した結果、約２０μｍであった。反応後の攪拌翼、セパラブルフラスコに付着したスケールを取り出して１１０℃で１日乾燥させたところ、スケール量は０．４ｇであった。
Suspension polymerization production example 8
This was carried out in the same manner as in the suspension polymerization production example 1 except that the unsaturated monomer composition was 72 parts of MMA, 18 parts of TMPTMA, and 60 parts of styrene (St). The average particle diameter of the obtained aqueous resin dispersion was about 20 μm as a result of measurement with a Coulter counter. The scale adhering to the stirring blade and the separable flask after the reaction was taken out and dried at 110 ° C. for 1 day. The scale amount was 0.4 g.
懸濁重合比較例１
乳化剤をポリオキシアルキレンアルキルフェニルエーテル硫酸エステルアンモニウム塩（第一工業製薬株式会社製「ハイテノールＮ−０８」）の２５％水溶液６部とした以外は、懸濁重合製造例１の方法と同様に行なった。得られた水性樹脂分散液の平均粒子径は、コールターカウンターにて測定した結果、約２２μｍであった。反応後の攪拌翼、セパラブルフラスコに付着したスケールを取り出して１１０℃で１日乾燥させたところ、スケール量は２３．３ｇであった。
Suspension polymerization comparative example 1
Except that the emulsifier was 6 parts of 25% aqueous solution of ammonium polyoxyalkylene alkylphenyl ether sulfate (Daiichi Kogyo Seiyaku Co., Ltd. “Hitenol N-08”), the same method as in the suspension polymerization production example 1 I did it. The average particle diameter of the obtained aqueous resin dispersion was about 22 μm as a result of measurement with a Coulter counter. The scale adhering to the stirring blade and the separable flask after the reaction was taken out and dried at 110 ° C. for 1 day. As a result, the scale amount was 23.3 g.
懸濁重合比較例２
乳化剤をポリオキシアルキレンアルキルフェニルエーテル硫酸エステルアンモニウム塩（第一工業製薬株式会社製「ハイテノールＮ−０８」）の２５％水溶液６部とし、重合時の攪拌速度を１５０ｒｐｍとした以外は、懸濁重合製造例１の方法と同様に行なった。得られた水性樹脂分散液の平均粒子径は、コールターカウンターにて測定した結果、約２０μｍであった。反応後の攪拌翼、セパラブルフラスコに付着したスケールを取り出して１１０℃で１日乾燥させたところ、スケール量は１．６ｇであった。
Suspension polymerization comparative example 2
Suspensions except that the emulsifier was 6 parts of 25% aqueous solution of polyoxyalkylene alkylphenyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku Co., Ltd. “Hitenol N-08”) and the stirring speed during polymerization was 150 rpm. The same procedure as in Polymerization Production Example 1 was performed. The average particle diameter of the obtained aqueous resin dispersion was about 20 μm as a result of measurement with a Coulter counter. The scale adhering to the stirring blade and the separable flask after the reaction was taken out and dried at 110 ° C. for 1 day. The scale amount was 1.6 g.
これらの懸濁重合製造例および懸濁重合比較例における各成分の量は、表１に示すとおりであった。なお、同表における数字は質量部を表わす。 The amount of each component in these suspension polymerization production examples and suspension polymerization comparative examples was as shown in Table 1. The numbers in the table represent parts by mass.
実施例１
懸濁重合製造例１で得られた水性樹脂分散液５０部に２５％アンモニア水溶液０．５部と増粘剤プライマルＴＴ−６１５（ローム・アンド・ハース株式会社製：アルカリ可溶型会合性増粘剤、不揮発分５％）６．０部を添加した。粘度は２４００ｍＰａ・ｓであった。これにアクリセットＥＸ−４１（株式会社日本触媒製：アクリルエマルション、不揮発分４４％）１００部と、成膜助剤としてブチルセロソルブ／ＣＳ−１２（チッソ株式会社製：２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレート）＝１／１の混合液５．７部、抑泡剤ＳＮ−デフォーマー７７７（サンノプコ社製）０．２部および希釈水を添加し、クリヤ塗料組成物を得た。スペックは、不揮発分３５．２％、粘度１５００ｍＰａ・ｓ、ｐＨ８．５であった。
Example 1
To 50 parts of the aqueous resin dispersion obtained in Suspension Polymerization Production Example 1, 0.5 part of 25% aqueous ammonia solution and thickener Primal TT-615 (Rohm and Haas Co., Ltd .: increased alkali-soluble associative properties) 6.0 parts) was added. The viscosity was 2400 mPa · s. In addition to this, 100 parts of Acryset EX-41 (manufactured by Nippon Shokubai Co., Ltd .: acrylic emulsion, nonvolatile content 44%) and butyl cellosolve / CS-12 (manufactured by Chisso Corporation: 2,2,4-trimethyl-) as a film forming aid 1,3-pentanediol monoisobutyrate) = 5.7 parts of a mixed solution of 1/1, 0.2 part of foam inhibitor SN-deformer 777 (manufactured by San Nopco) and dilution water were added, and a clear coating composition was added. Got. The specifications were a non-volatile content of 35.2%, a viscosity of 1500 mPa · s, and a pH of 8.5.
実施例２
懸濁重合製造例１の代わりに懸濁重合製造例２を使用した以外は、実施例１と同様にしてクリア塗料組成物を得た。スペックは、不揮発分３５．１％、粘度１４５０ｍＰａ・ｓ、ｐＨ８．５であった。
Example 2
A clear coating composition was obtained in the same manner as in Example 1 except that Suspension Polymerization Production Example 2 was used instead of Suspension Polymerization Production Example 1. The specifications were a non-volatile content of 35.1%, a viscosity of 1450 mPa · s, and a pH of 8.5.
実施例３
懸濁重合製造例１の代わりに懸濁重合製造例３を使用した以外は、実施例１と同様にしてクリア塗料組成物を得た。スペックは、不揮発分３４．７％、粘度１５２０ｍＰａ・ｓ、ｐＨ８．４であった。
Example 3
A clear coating composition was obtained in the same manner as in Example 1 except that Suspension Polymerization Production Example 3 was used instead of Suspension Polymerization Production Example 1. The specifications were a non-volatile content of 34.7%, a viscosity of 1520 mPa · s, and a pH of 8.4.
実施例４
懸濁重合製造例１の代わりに懸濁重合製造例４を使用した以外は、実施例１と同様にしてクリア塗料組成物を得た。スペックは、不揮発分３５．０％、粘度１４２０ｍＰａ・ｓ、ｐＨ８．６であった。
Example 4
A clear coating composition was obtained in the same manner as in Example 1 except that the suspension polymerization production example 4 was used instead of the suspension polymerization production example 1. The specifications were a non-volatile content of 35.0%, a viscosity of 1420 mPa · s, and a pH of 8.6.
実施例５
懸濁重合製造例１の代わりに懸濁重合製造例５を使用した以外は、実施例１と同様にしてクリア塗料組成物を得た。スペックは、不揮発分３５．０％、粘度１４９０ｍＰａ・ｓ、ｐＨ８．５であった。
Example 5
A clear coating composition was obtained in the same manner as in Example 1 except that the suspension polymerization production example 5 was used instead of the suspension polymerization production example 1. The specifications were a non-volatile content of 35.0%, a viscosity of 1490 mPa · s, and a pH of 8.5.
実施例６
懸濁重合製造例１の代わりに懸濁重合製造例６を使用した以外は、実施例１と同様にしてクリア塗料組成物を得た。スペックは、不揮発分３５．１％、粘度１５２０ｍＰａ・ｓ、ｐＨ８．５であった。
Example 6
A clear coating composition was obtained in the same manner as in Example 1 except that the suspension polymerization production example 6 was used instead of the suspension polymerization production example 1. The specifications were a non-volatile content of 35.1%, a viscosity of 1520 mPa · s, and a pH of 8.5.
実施例７
懸濁重合製造例１の代わりに懸濁重合製造例７を使用した以外は、実施例１と同様にしてクリア塗料組成物を得た。スペックは、不揮発分３４．９％、粘度１４５０ｍＰａ・ｓ、ｐＨ８．７であった。
Example 7
A clear coating composition was obtained in the same manner as in Example 1 except that the suspension polymerization production example 7 was used instead of the suspension polymerization production example 1. The specifications were a non-volatile content of 34.9%, a viscosity of 1450 mPa · s, and a pH of 8.7.
実施例８
懸濁重合製造例１の代わりに懸濁重合製造例８を使用した以外は、実施例１と同様にしてクリア塗料組成物を得た。スペックは、不揮発分３４．９％、粘度１４５０ｍＰａ・ｓ、ｐＨ８．５であった。
Example 8
A clear coating composition was obtained in the same manner as in Example 1 except that Suspension Polymerization Production Example 8 was used instead of Suspension Polymerization Production Example 1. The specifications were a non-volatile content of 34.9%, a viscosity of 1450 mPa · s, and a pH of 8.5.
比較例１
懸濁重合製造例１の代わりに懸濁重合比較例２を使用した以外は、実施例１と同様にしてクリア塗料組成物を得た。スペックは、不揮発分３４．７％、粘度１４６０ｍＰａ・ｓ、ｐＨ８．３であった。
Comparative Example 1
A clear coating composition was obtained in the same manner as in Example 1 except that the suspension polymerization comparative example 2 was used instead of the suspension polymerization production example 1. The specifications were a non-volatile content of 34.7%, a viscosity of 1460 mPa · s, and a pH of 8.3.
比較例２
アクリセットＥＸ−４１ １００部にシリカ粉末Ｐ−５２６（水沢化学株式会社製）４．４部、プライマルＴＴ−６１５（不揮発分５％）２．９部、ＳＮ−デフォーマー７７７０．２部および分散剤（ＳＮ−ディスパーサント５０２７：サンノプコ社製）１．０部に希釈液を添加し、塗料組成物を得た。スペックは、不揮発分３５．０％、粘度１４６０ｍＰａ・ｓ、ｐＨ８．３であった。
Comparative Example 2
Acrylic EX-41 100 parts silica powder P-526 (manufactured by Mizusawa Chemical Co., Ltd.) 4.4 parts, Primal TT-615 (non-volatile content 5%) 2.9 parts, SN-deformer 7770.2 parts and dispersant (SN-Dispersant 5027: manufactured by San Nopco) A diluent was added to 1.0 part to obtain a coating composition. The specifications were a non-volatile content of 35.0%, a viscosity of 1460 mPa · s, and a pH of 8.3.
実施例９
実施例１〜９および比較例１〜２で得られたクリア塗料組成物について、物性試験を行なったところ、表２に示す結果が得られた。
Example 9
When the physical property test was performed about the clear coating composition obtained in Examples 1-9 and Comparative Examples 1-2, the result shown in Table 2 was obtained.
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| CN103435740A (en) * | 2013-09-05 | 2013-12-11 | 天津工业大学 | Method for preparing water-soluble polymers |
| CN103435744A (en) * | 2013-09-05 | 2013-12-11 | 天津工业大学 | Method for preparing liquid absorption polymers |
| JP2017179054A (en) * | 2016-03-29 | 2017-10-05 | Jsr株式会社 | Composition for forming cured film and manufacturing method therefor |
| JP2020117668A (en) * | 2019-01-28 | 2020-08-06 | 株式会社日本触媒 | Novel emulsion |
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