JPH0425579A - Production of resin for water paint and water paint - Google Patents
Production of resin for water paint and water paintInfo
- Publication number
- JPH0425579A JPH0425579A JP13080790A JP13080790A JPH0425579A JP H0425579 A JPH0425579 A JP H0425579A JP 13080790 A JP13080790 A JP 13080790A JP 13080790 A JP13080790 A JP 13080790A JP H0425579 A JPH0425579 A JP H0425579A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- pts
- water
- resin
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000003973 paint Substances 0.000 title claims abstract description 42
- 229920005989 resin Polymers 0.000 title claims abstract description 40
- 239000011347 resin Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- -1 fatty acid ester Chemical class 0.000 claims abstract description 41
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 31
- 239000000194 fatty acid Substances 0.000 claims abstract description 31
- 229930195729 fatty acid Natural products 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 16
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000003822 epoxy resin Substances 0.000 claims abstract description 11
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 11
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 11
- 239000004593 Epoxy Substances 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 229930185605 Bisphenol Natural products 0.000 claims description 5
- 239000007870 radical polymerization initiator Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 13
- 239000003960 organic solvent Substances 0.000 abstract description 9
- 239000003505 polymerization initiator Substances 0.000 abstract description 3
- 238000007259 addition reaction Methods 0.000 abstract description 2
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 238000001035 drying Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000005395 methacrylic acid group Chemical group 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 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 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000002202 Polyethylene glycol Substances 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- JYGXADMDTFJGBT-VWUMJDOOSA-N hydrocortisone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 JYGXADMDTFJGBT-VWUMJDOOSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- QNRSQFWYPSFVPW-UHFFFAOYSA-N 5-(4-cyanobutyldiazenyl)pentanenitrile Chemical compound N#CCCCCN=NCCCCC#N QNRSQFWYPSFVPW-UHFFFAOYSA-N 0.000 description 1
- RWHRFHQRVDUPIK-UHFFFAOYSA-N 50867-57-7 Chemical class CC(=C)C(O)=O.CC(=C)C(O)=O RWHRFHQRVDUPIK-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010008631 Cholera Diseases 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 235000003385 Diospyros ebenum Nutrition 0.000 description 1
- 241000792913 Ebenaceae Species 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- 244000062793 Sorghum vulgare Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical compound CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- XKUKSGPZAADMRA-UHFFFAOYSA-N glycyl-glycyl-glycine Natural products NCC(=O)NCC(=O)NCC(O)=O XKUKSGPZAADMRA-UHFFFAOYSA-N 0.000 description 1
- 108010067216 glycyl-glycyl-glycine Proteins 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 235000019713 millet Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- JMCVCHBBHPFWBF-UHFFFAOYSA-N n,n-diethyl-2-methylprop-2-enamide Chemical compound CCN(CC)C(=O)C(C)=C JMCVCHBBHPFWBF-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 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 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、水性塗料用樹脂の製造法及びこれにより得ら
れる水性塗料用樹脂を用いてなる水性塗料に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a resin for water-based paints and a water-based paint using the resin for water-based paints obtained thereby.
（従来の技術）
塗料には９通常、大量の有機溶剤を使用するため、塗装
の際に大気中に有機溶剤が排出され、大気汚染の原因と
なっており、また火災の危険性も高い。近年、有機溶剤
量を低減する努力が種々なされ、ハイソリッド塗料、粉
体塗料、電子線・紫外線硬化塗料、水性塗料等がその目
的のために開発されている。特に、水性塗料は危険性の
ない。(Prior Art) Since paints usually use large amounts of organic solvents, the organic solvents are emitted into the atmosphere during painting, causing air pollution and increasing the risk of fire. In recent years, various efforts have been made to reduce the amount of organic solvents, and high solid paints, powder paints, electron beam/ultraviolet curing paints, water-based paints, etc. have been developed for this purpose. In particular, water-based paints are non-hazardous.
また経済性の高い水を利用し、ざらに従来の塗装設備か
らの転用が容易であることから注目を集めている。しか
しながら、従来の水性塗料には、塗料の乾燥が遅い、耐
水性及び耐食性が劣るという欠点がある。It is also attracting attention because it uses water, which is highly economical, and can easily be used as a substitute for conventional painting equipment. However, conventional water-based paints have drawbacks such as slow drying of the paint and poor water resistance and corrosion resistance.
このような欠点を改良するために、これまでに様々な方
法が考えられ１例えば水性アルキド樹脂塗料において樹
脂成分中に、フェノール樹脂９石油樹脂、エポキシ樹脂
等全含有させる方法９重合性単量体を重合させる方法等
が挙げられる。In order to improve these drawbacks, various methods have been considered so far. 1. For example, in water-based alkyd resin paints, the resin component contains all phenol resins, 9 petroleum resins, epoxy resins, etc. 9. Polymerizable monomers Examples include a method of polymerizing.
こレラのひとつに、ビスフェノール型エポキシ樹脂と脂
肪酸のエステルを基体とした。水希釈可能なビニル変性
エポキシ脂肪酸エステル樹脂が知られている。これは、
エポキシ樹脂を用いることにより、高い耐食性を有しま
た脂肪酸エステルにより常温乾燥型としても使用できる
という利点がある。One type of cholera is based on bisphenol-type epoxy resin and fatty acid ester. Water-dilutable vinyl-modified epoxy fatty acid ester resins are known. this is,
The use of epoxy resin has the advantage that it has high corrosion resistance and can also be used as a room temperature drying type due to the fatty acid ester.
（発明が解決しようとする課題） このビニル変性エポキシ脂肪酸エステルＩＩＱ＆は。(Problem to be solved by the invention) This vinyl-modified epoxy fatty acid ester IIQ&.
一般にビニル単量体中にカルボキシル基含有単量体を必
須成分として合成され、導入されたカルボキシル基をさ
らにアミン等で中和することにより。Generally, it is synthesized using a carboxyl group-containing monomer as an essential component in a vinyl monomer, and the introduced carboxyl group is further neutralized with an amine or the like.
樹脂中に、親水性部分を形成し、水性としている。A hydrophilic part is formed in the resin, making it water-based.
安定な水性樹脂を得るためには、ビニル変性エポキシ脂
肪酸エステル樹脂の酸価は、３０〜５０と溶剤型に比べ
高くする必要があるが、エポキシ脂肪酸エステル部分に
グラフトしたビニル単量体の重合部分について考えれば
、その部分酸価はさらに高いものとなっている。そのた
め、塗膜としたときに耐水性、耐加水分解性、耐アルカ
リ性に著しく劣る原因となっている。In order to obtain a stable aqueous resin, the acid value of the vinyl-modified epoxy fatty acid ester resin must be 30 to 50, which is higher than that of the solvent type resin. If you think about it, its partial acid value is even higher. Therefore, when formed into a coating film, it becomes significantly inferior in water resistance, hydrolysis resistance, and alkali resistance.
一方、アルキド樹脂等を水性化する方法としてポリオキ
シエチレングリコールを樹脂中に導入する方法が知られ
ている。ポリオキシエチレングリコールを併用すること
で水性樹脂の酸価を低減できるため加熱残分が高く、ま
た、耐食性、耐水性にも優れた！１Ｋを与えることが可
能である。しかし、これらの方法では、ポリオキシエチ
レンクリコールが比較的低分子量の部分にオリゴマー、
あるいは未反応の状態で逼圧するため２例えば、耐水性
、耐湿性において、溶剤型に比べて十分な性能が得られ
ていない。On the other hand, a method of introducing polyoxyethylene glycol into the resin is known as a method for making alkyd resins and the like water-based. By using polyoxyethylene glycol in combination, the acid value of the aqueous resin can be reduced, resulting in a high heating residue, and it also has excellent corrosion resistance and water resistance! It is possible to give 1K. However, in these methods, polyoxyethylene glycol contains oligomers and
Alternatively, because the pressure is applied in an unreacted state, for example, in terms of water resistance and humidity resistance, sufficient performance is not obtained compared to the solvent type.
本発明は９以上の問題点を解決するものであり。The present invention solves nine or more problems.
安定でかつ、塗膜としての耐水性、耐加水分解性。Stable, water resistant and hydrolytic resistant as a coating film.
耐アルカリ性に優れ、その上塗料の乾燥性にも優れる水
性塗料用樹脂の製造法及び水性塗料を提供するものであ
る。The present invention provides a method for producing a resin for water-based paint, which has excellent alkali resistance and also has excellent paint drying properties, and provides a water-based paint.
（課題を解決するための手段）
本発明は、脂肪酸（ａ）２５〜６０重量部、ビスフェノ
ール型エポキシ樹脂（ｂ）７０〜２０重量部及び１分子
中に１〜４個のグリシジル基を有する脂肪族系エポキシ
化合物（ｃ）０〜４０重量部を合計が１００重量部とな
るように配合し、付加、縮合して得られる脂肪酸エステ
ル（Ｉ）１０〜９０重量部。(Means for Solving the Problems) The present invention provides 25 to 60 parts by weight of a fatty acid (a), 70 to 20 parts by weight of a bisphenol type epoxy resin (b), and a fat having 1 to 4 glycidyl groups in one molecule. 10 to 90 parts by weight of a fatty acid ester (I) obtained by adding and condensing 0 to 40 parts by weight of a group-based epoxy compound (c) to a total of 100 parts by weight.
−形成
％式％
（ただし２式中Ｒは水素または低級アルキル基であり、
Ｒ′は、水素、低級アルキル基またはハロゲンであり、
ｎは３以上の整数である）で示される化合物（［［１１
〜２０重量部、並びに他の重合性ビニル単量体（ＩＩＩ
）８９〜０重量部を（１）成分、（■）成分及び＠）成
分の合計が１００重量部となるように配合した混合物中
に、ラジカル重合開始剤を滴下して重合することを特徴
とする水性塗料用樹脂の製造法。- Formation % formula % (However, in formula 2, R is hydrogen or a lower alkyl group,
R' is hydrogen, a lower alkyl group or a halogen,
n is an integer of 3 or more) ([[11
~20 parts by weight, as well as other polymerizable vinyl monomers (III
) 89 to 0 parts by weight are blended so that the total of components (1), (■) and @) is 100 parts by weight, and a radical polymerization initiator is added dropwise to polymerize. A method for producing resin for water-based paints.
該製造法により得られる水性塗料用樹脂を含有してなる
水性塗料に関する。The present invention relates to a water-based paint containing a water-based paint resin obtained by the production method.
本発明に使用する（ａ）成分である脂肪酸としては。The fatty acids as component (a) used in the present invention include:
乾性油又は半乾性油から誘導されうる脂肪酸及び合成脂
肪酸があり９例えば桐油、大豆油、アマニ油、ヒマシ油
、脱水ヒマ７油、サフラワー油、綿実油等から得られる
脂肪酸９合成により得られるバーサチック酸（ンエルケ
ミカル社商品名）等が挙げられる。（ａ）成分としては
、Ｅ性油又は半乾性油から誘導されうる脂肪酸を使用す
るのが、常温硬化性を付与できるので好ましいが、不乾
性油から誘導されうる脂肪酸を使用してもよい。ｔａ＋
成分は一種又は二種以上使用芒れる。その使用量は。There are fatty acids that can be derived from drying or semi-drying oils and synthetic fatty acids, such as tung oil, soybean oil, linseed oil, castor oil, dehydrated castor oil, safflower oil, cottonseed oil, etc. Examples include acids (trade name of Ner Chemical Co., Ltd.). As component (a), it is preferable to use fatty acids derived from E-type oils or semi-drying oils because they can impart room-temperature curability, but fatty acids derived from non-drying oils may also be used. ta+
One or more ingredients can be used. What is its usage?
（ａ）、 （ｂ）及び（ｃｌ成分の合計１００重量部に
対して２５〜６０重量部、好ましくは３０〜５５重量部
である。ｆａｔ成分の使用量が２５重量部未満であると
塗膜の可とう性が低下し、（ａ）成分の使用量が６０重
量部を超えると塗膜の硬さ及び耐食性が低下する。It is 25 to 60 parts by weight, preferably 30 to 55 parts by weight, based on a total of 100 parts by weight of components (a), (b) and (Cl). If the amount of the fat component used is less than 25 parts by weight, the coating film If the amount of component (a) used exceeds 60 parts by weight, the hardness and corrosion resistance of the coating film will decrease.
（ｂ）成分であるビスフェノール型エポキシ樹脂トハ、
ビスフェノールＡ、ビスフェノールＦ等のビスフェノー
ルとエピクロルヒドリンの反応によって得られるエポキ
シ樹脂であり１例えば、エピコート８２８．エピコート
１００１． エピコート１００４、 エピコート１
００７．エピコート１００９（いずれも、シェルケミカ
ル社商品名）等として市販されているものが使用できる
。（ｂ）成分は一攬又は二種以上使用されるが、軟化点
が６０°Ｃ以上のものが、塗膜性能の観点から特に好せ
しい。（ｂ）成分は、 （ａ）、 （ｂ）及び（ｃ）成
分の合計１００重量部に対して７０〜２０重量部、好ま
しくは６０〜３０重量部配合爪部る。（ｂ）成分の使用
量が２０重量部未満でろると塗膜の硬き及び耐食性が低
下し、７０重量部を超えると塗膜の可とう性が低下する
。(b) Component bisphenol type epoxy resin toha,
It is an epoxy resin obtained by the reaction of bisphenols such as bisphenol A and bisphenol F with epichlorohydrin. For example, Epicote 828. Epicote 1001. Epicort 1004, Epicort 1
007. A commercially available product such as Epicoat 1009 (all trade names of Shell Chemical Co., Ltd.) can be used. One or more types of component (b) may be used, but those having a softening point of 60°C or higher are particularly preferred from the viewpoint of coating film performance. Component (b) is added in an amount of 70 to 20 parts by weight, preferably 60 to 30 parts by weight, based on a total of 100 parts by weight of components (a), (b) and (c). If the amount of component (b) used is less than 20 parts by weight, the hardness and corrosion resistance of the coating film will decrease, and if it exceeds 70 parts by weight, the flexibility of the coating film will decrease.
（ｃ）成分でおる１分子中に１〜４個のグリンンル基を
有する脂肪族系エポキシ化合物は、必要に応じて使用さ
れる。該化合物としては、ラウリルアルコール、アリル
アルコール等のｍ個脂肪族アルコールのクリシジルエー
テル、エチレンクリコール、プロピレングリコール、ブ
チレングリコール等のアルキレングリコール、ジエチレ
ングリコール、ポリエチレングリコール、ジフロビレン
グリコール、ポリプロピレングリコール、ポリ（テトラ
メチレングリコール）、１．６−ヘキサンジオール、ネ
オペンチルグリコールなどの二価脂肪族アルコールのジ
グリンジルエーテル、トリメチロールフロパン、グリセ
リン等の三価脂肪族アルコールのジー又はトリージグリ
フジルエーテル、ペンタエリスリトール、ソルビトール
、グリセリン二量体、グリセリン多量体等の四価以上の
脂肪族アルコールのジー トリー又はテトラーグリノン
ルエーテル、アジピン酸、テトラメチレンジカルボン酸
等の脂肪族ジカルボン酸のジグリンジルエステルなどが
ある。ｆｃ）成分は一種又は二種以上使用することがで
きる。（ｃ）成分はｔａ）、 （ｂ）及び（ｃ）成分の
合計１００重量部に対して０〜４０重量部、好ましくは
５〜２０重量部使用きれる。（ｃ）成分の使用量が４０
重量部を超えると塗料の安定性が劣る。Component (c), an aliphatic epoxy compound having 1 to 4 phosphorus groups in one molecule, is used as necessary. Examples of the compound include chrycidyl ether of m aliphatic alcohols such as lauryl alcohol and allyl alcohol, alkylene glycols such as ethylene glycol, propylene glycol, and butylene glycol, diethylene glycol, polyethylene glycol, difluorylene glycol, polypropylene glycol, and polypropylene glycol. (tetramethylene glycol), 1,6-hexanediol, diglyndyl ether of dihydric aliphatic alcohols such as neopentyl glycol, di- or tri-diglyngyl ether of trihydric aliphatic alcohols such as trimethylolfuropane, glycerin, penta Diglyndyl esters of tetrahydric or higher aliphatic alcohols such as erythritol, sorbitol, glycerin dimer, glycerin polymer, etc. or tetraglynonyl ether, aliphatic dicarboxylic acids such as adipic acid, tetramethylene dicarboxylic acid, etc. . One or more types of fc) components can be used. Component (c) can be used in an amount of 0 to 40 parts by weight, preferably 5 to 20 parts by weight, based on a total of 100 parts by weight of components ta), (b) and (c). (c) The amount of ingredient used is 40
If it exceeds parts by weight, the stability of the paint will be poor.
脂肪酸エステル（１）は、前記！ａ）成分、（ｂ）成分
及び（ｃ）成分を反応させて得られる。反応方法は公知
の方法により、付加、縮合反応させられる。例えば１８
０〜２５０°Ｃで加熱すればよい。この反応はキシレン
、トルエン等の（ａ）成分、（ｂ）成分及び（Ｃ）成分
と反応しない有機溶剤中で行なってもよい。また９反応
は、（ａ）成分、（ｂ）成分及びｔｃ）成分を同時に混
合して反応させてもよ＜ 、 （ａ）成分とｔｂ＋成分
又は（ｃ）成分全反応させたのち、（Ｃ）成分又は（ｂ
）成分を添加し反応ζぜてもよい。生成物は、（ａ）成
分とｔｂ’ｌ成分のエステル及び（ａ）成分と（Ｃ）成
分のエステルの混合物となる。これらのエステルを別個
に製造しておき、混合して使用すると特性が低下しやす
いので好ましくない。このようにして得られる脂肪酸エ
ステルｆＩ）の存在下に、以下の重合性ビニル単量体を
配合し９重合させる。The fatty acid ester (1) is as described above! It is obtained by reacting component a), component (b) and component (c). Addition and condensation reactions are carried out using known methods. For example 18
It may be heated at 0 to 250°C. This reaction may be carried out in an organic solvent such as xylene or toluene that does not react with components (a), (b) and (C). In addition, in reaction 9, components (a), (b) and tc) may be mixed and reacted at the same time. ) component or (b
) components may be added to carry out the reaction. The product is a mixture of esters of component (a) and tb'l and esters of component (a) and (C). It is not preferable to produce these esters separately and use them in a mixture because the properties tend to deteriorate. In the presence of the fatty acid ester fI) thus obtained, the following polymerizable vinyl monomers are blended and polymerized.
本発明に使用される上記の一般式で示される化合物（ｎ
）としては、該一般式において、ＲがＨ，ＣＨ３゜Ｃ２
Ｈ５、Ｃ３Ｈ７等、Ｒ′がＨ、ＣＨ３，Ｃ２Ｈ５，Ｃ３
Ｈ７，Ｃ１，Ｂ ｒ等の組み合わくのものが挙げられ、
さらに具体的ニハ、ポリエチレングリコールモノアクリ
レートポリエテレングリコールモノメタクリレート等が
挙げられる。一般式において、ｎは３以上であり。The compound (n
), in the general formula, R is H, CH3°C2
H5, C3H7, etc., R' is H, CH3, C2H5, C3
Examples include combinations of H7, C1, Br, etc.
More specific examples include polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, and the like. In the general formula, n is 3 or more.
特に５以上であるのが好ましい。ｎが３未満であると充
分な効果が得られず、ｎが５未満であると効果が低下す
る傾向にある。市販品としては、フレ７７ＰＥ ３５
０ （Ｒ；Ｈ，Ｒ’：ＣＨ３，ｎ ；７〜９９日本油脂
■製）、ブレンマーＰＥ−２００（Ｒ；Ｈ，Ｒ’漬ＣＨ
３，ｎ ； ４〜５ ）などが使用できる。これらは、
−穐又は二種以上使用することができる。（旧成分は、
前記（Ｉ）成分、（旧成分及び後述する■）成分の合計
１００重量部に対して１〜２０重量部となるように使用
される。（旧成分が１重量部未満であると樹脂の安定性
が低下し、２０重１部を超えると塗膜の耐水性が低下す
る。In particular, it is preferably 5 or more. When n is less than 3, sufficient effects cannot be obtained, and when n is less than 5, the effects tend to decrease. As a commercially available product, Fure 77PE 35
0 (R; H, R': CH3, n; 7-99 manufactured by NOF ■), Blenmar PE-200 (R; H, R' pickled CH
3,n; 4-5), etc. can be used. these are,
- One or more types can be used. (The old ingredients are
It is used in an amount of 1 to 20 parts by weight based on a total of 100 parts by weight of the above-mentioned component (I) and component (old component and component (2) described below). (If the old component is less than 1 part by weight, the stability of the resin will decrease, and if it exceeds 20 parts by weight, the water resistance of the coating will decrease.
本発明に使用する他の重合性ビニル単量体（（■）成分
）としては、アクリル酸、メタクリル酸、マレイン酸、
無水マレイン酸、フマル酸、クロトン酸、イタコン酸
等のカルボキシル基を含有するもの、アクリル酸メチル
、アクリル酸エチル、アクリルｍｎ−プロピル、アクリ
ル酸インプロピル。Other polymerizable vinyl monomers ((■) component) used in the present invention include acrylic acid, methacrylic acid, maleic acid,
Those containing a carboxyl group such as maleic anhydride, fumaric acid, crotonic acid, itaconic acid, methyl acrylate, ethyl acrylate, mn-propyl acrylate, impropyl acrylate.
アクリル酸ｎ−ブチル、アクリル酸ｔｅｒｔ−ブチル。n-butyl acrylate, tert-butyl acrylate.
アクリル酸イソブチル、アクリル酸２−エチルヘキシル
等のアクリル酸エステル、メタクリル酸メチル、メタク
リル酸エチル、メタクリル酸ｎ−プロピル、メタクリル
酸イソプロピル、メタクリル酸ｎ−ブチル、メタクリル
酸ｔｅｒｔ−ブチル、メタクリル酸インブチル、メタク
リル酸２−エチルヘキシル等のメタクリル酸エステル、
スチレン、ビニルトルエン、α−メチルスチレン等のス
チレン系モノマー、酢酸ビニル、アクリル酸β−ヒドロ
キシエチル、アクリル酸グリシジル、メタクリル酸グリ
シジル、アクリルアミド、Ｎ、Ｎ−ジエチルメタクリル
アミド、アクリロニトリル、メタクリロニトリル等が挙
げられ、これらは一種又は二穫以上使用することができ
る。Acrylic acid esters such as isobutyl acrylate and 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, inbutyl methacrylate, methacrylate methacrylic acid esters such as 2-ethylhexyl acid;
Styrenic monomers such as styrene, vinyltoluene, α-methylstyrene, vinyl acetate, β-hydroxyethyl acrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide, N,N-diethylmethacrylamide, acrylonitrile, methacrylonitrile, etc. One or more of these can be used.
他の重合性ビニル単量体（ＩＩＩ）は、前記（Ｉ）、
ｆｉｌ）成分の残部、すなわち８９〜０重量部配爪部れ
る。Other polymerizable vinyl monomers (III) include the above (I),
The remainder of the component fil), ie, 89 to 0 parts by weight, is included in the nail arrangement part.
他の重合性ビニル単量体（ＩＩＩ）として、カルボキシ
ル基含有重合性ビニル単量体を使用すると９本発明によ
り得られる樹脂にカルボキシル基が導入され、これを、
アミン等で中和、親水化することにより＋Ｉｔｊ式で表
わされる化合物中の親水性部分とともに水性化が可能に
なり、良好な特性を与えるので好ましい。該カルボキシ
ル基含有重合性ビニル単量体は１本発明により得られる
樹脂の酸価が５〜４０になるように調整して配合される
のが好ましい。When a carboxyl group-containing polymerizable vinyl monomer is used as the other polymerizable vinyl monomer (III), a carboxyl group is introduced into the resin obtained by the present invention.
Neutralization and hydrophilization with an amine or the like makes it possible to make the compound water-soluble together with the hydrophilic moiety in the compound represented by the +Itj formula, which is preferable because it provides good properties. The carboxyl group-containing polymerizable vinyl monomer is preferably blended so that the acid value of the resin obtained by the present invention is 5 to 40.
前記一般式で表わされる化合物（ＩＩ）及び他の重合性
ビニル単量体（ＩＩｌ）は、前記脂肪酸エステル（１）
の存在下に重合される。この場合、脂肪酸エステル／重
合性ビニル単量体（（■）および（ＩＩＩ）成分）の重
量比が１０／９０〜９０／１０．好ましくは５０１５０
〜８０／２０になるような割合で配合される。この重量
比が小さすぎると水希釈性が劣り、大きすぎると塗膜の
乾燥性が低下しやすくなる。The compound (II) represented by the above general formula and the other polymerizable vinyl monomer (IIl) are the fatty acid ester (1)
is polymerized in the presence of In this case, the weight ratio of fatty acid ester/polymerizable vinyl monomer (components (■) and (III)) is 10/90 to 90/10. Preferably 50150
They are blended in a ratio of ~80/20. If this weight ratio is too small, the water dilutability will be poor, and if it is too large, the drying properties of the coating film will tend to decrease.
本発明における重合性ビニル単量体の重合は。Polymerization of the polymerizable vinyl monomer in the present invention.
上記の脂肪酸エステル（■）、前記一般式で示される化
合物（Ｉｌｌ及び他の重合性ビニル単量体（ｍｉｌｌを
配合した混合物中に、ラジカル重合開始剤を滴下して重
合する。A radical polymerization initiator is added dropwise into a mixture containing the above fatty acid ester (■), the compound represented by the above general formula (Ill), and another polymerizable vinyl monomer (mill), and polymerization is carried out.
この場合、 （１１，（ｎｌ及び（ＩＩ）成分の混合物
１重合開始剤は各々有機溶剤と混合又は有機溶剤に溶解
しておくのが好ましい。In this case, (11, (nl) and (II) component mixture 1) It is preferable that each polymerization initiator be mixed with or dissolved in an organic solvent.
有機溶剤としては親水性溶剤が好ましく、このようなも
のとしては９例えば、メチルセロソルブ。The organic solvent is preferably a hydrophilic solvent, such as methyl cellosolve.
エチルセロソルブ、プチルセロソルフ、 ｊｅｒｔ−
フテルセロソルプ、イソプロピルセロソルブ、イングロ
ビルアルコール、ブチルアルコール、 ｊｅｒｔ−ブ
チルアルコール、イソブチルアルコール等を使用するこ
とができる。Ethyl cellosolve, butyl cellosolve, jet-
Phentercellosolve, isopropylcellosolve, inglovir alcohol, butyl alcohol, jet-butyl alcohol, isobutyl alcohol, and the like can be used.
滴下する重合開始剤の有機溶剤中の濃度は、脂肪酸エス
テル（１）の分子量９重合濃度１合成温度等の条件によ
り適宜決定される。滴下時間及び滴下速度は９合成温度
等により適宜選択されるが１通常２〜４時間で均一に滴
下するのが好ましい。滴下時間が短かすぎる（すなわち
滴下速度が大きすぎる）とゲル化、粘度上昇等の問題が
生じやすく。The concentration of the polymerization initiator to be added dropwise in the organic solvent is appropriately determined based on conditions such as the molecular weight, the polymerization concentration, and the synthesis temperature of the fatty acid ester (1). The dropping time and dropping rate are appropriately selected depending on the synthesis temperature, etc., but it is preferable to drop the mixture uniformly over a period of usually 2 to 4 hours. If the dropping time is too short (that is, the dropping rate is too high), problems such as gelation and increased viscosity are likely to occur.
長ずざると分子量が小さくなる傾向にあり、優れた特性
が得られにくい。また２合成温度は８０〜１４０℃が好
ましい。If the length is too long, the molecular weight tends to decrease, making it difficult to obtain excellent properties. Moreover, the synthesis temperature of 2 is preferably 80 to 140°C.
本発明においては、前述のようにラジカル重合開始剤を
滴下しつつ重合することが必須要件であり、このため９
重合濃度が高くなりエポキシ脂肪酸エステル（１）にビ
ニル単量体（Ｉｆ）及び（Ｉ［）成分がグラフトされや
すくなって高分子量化され、高分子量部分が多くなる。In the present invention, as mentioned above, it is essential to polymerize while dropping the radical polymerization initiator, and therefore
As the polymerization concentration increases, the vinyl monomer (If) and (I[) components are easily grafted onto the epoxy fatty acid ester (1), resulting in a high molecular weight, and the high molecular weight portion increases.
そのために塗膜性能を維持したまま塗料の乾燥性が著し
く向上できる。Therefore, the drying properties of the paint can be significantly improved while maintaining the film performance.
こうして得られる樹脂の酸価は５〜４０の範囲であるよ
うに調整されるのが好ましい。酸価が５未満であると塗
料安定性が劣る傾向にあり、酸価が４０を越えると、塗
膜の耐水性及び耐アルカリ性が劣る傾向がある。酸価の
調整は脂肪酸エステル（１１の酸価とカルボキシル基含
有重合性単量体の使用量を調整することにより行なうこ
とができる。The acid value of the resin thus obtained is preferably adjusted to be in the range of 5 to 40. If the acid value is less than 5, the coating stability tends to be poor, and if the acid value exceeds 40, the water resistance and alkali resistance of the coating film tend to be poor. The acid value can be adjusted by adjusting the acid value of the fatty acid ester (11) and the amount of the carboxyl group-containing polymerizable monomer used.
また９分子量（数平均、Ｍｎ）は、 ４，０００〜７，
０００ 。In addition, the molecular weight (number average, Mn) is 4,000 to 7,
000.
特に４，５００〜６，５００であるのが好ましく１分子
量分散度（重量平均分子ｉｔ／数平均分子量、Ｍｗ／Ｍ
ｎ）は４〜７．特に４．５〜６．５であるのが好ましい
。分子量が４． ＯＯ０未満または分子量分散度が４未
満では充分な乾燥性が得られに＜＜、−ノ分子量が７．
ＯＯＯを超えるかまたは分子量分散用が７を超えると
、粘度が高くなりすぎたりゲルイ）したりして塗料とし
て使用できなくなることが冴る。In particular, it is preferably 4,500 to 6,500 1 molecular weight dispersity (weight average molecular it/number average molecular weight, Mw/M
n) is 4 to 7. In particular, it is preferably 4.5 to 6.5. The molecular weight is 4. If the molecular weight is less than OO or the molecular weight dispersity is less than 4, sufficient drying properties cannot be obtained.
If it exceeds OOO or if the molecular weight dispersion exceeds 7, the viscosity may become too high or it may become gelatinous, making it impossible to use it as a paint.
使用するラジカル重合開始剤としては、アゾヒスイソブ
チロニトリル、アゾビスバレロニトリル等のアゾビスニ
ドｌｊル型触媒、ベンゾイルパーオキシド、ブチルパー
ベンゾエート等の過酸化物等が用いられる。Examples of the radical polymerization initiator used include azobisnidol-type catalysts such as azohisisobutyronitrile and azobisvaleronitrile, and peroxides such as benzoyl peroxide and butyl perbenzoate.
このようにして得られた樹脂は、中和後、前記した親水
性溶剤と水の混合溶剤又は水に溶解ないし分散させて（
水希釈して）使用に供することができる。中和及び水希
釈は、前記重合を親水性溶剤中で行なったときは９重合
完了後、ひきつづいて中和し、さらに水を添加すること
によって行なうことができるが９重合後、脱溶したのち
、中和及び水希釈することもできる。After neutralization, the resin thus obtained is dissolved or dispersed in the above-mentioned mixed solvent of hydrophilic solvent and water or in water (
(diluted with water). When the above polymerization is carried out in a hydrophilic solvent, neutralization and water dilution can be carried out by continuing to neutralize after the completion of 9 polymerization and further adding water; , neutralization and water dilution.
上記中和は、 ｐＨが好ましくは、７〜１ｏになるよ
うに、樹脂中のカルボキシル基の一部又は全部を中和剤
により中和して行なわれる。中和剤としては、アンモニ
ア、トリエチルアミン、ジメチルエタノールアミン等の
アミン、水酸化ナトリウム。The above neutralization is carried out by neutralizing some or all of the carboxyl groups in the resin with a neutralizing agent so that the pH is preferably 7 to 1o. Examples of neutralizing agents include ammonia, triethylamine, amines such as dimethylethanolamine, and sodium hydroxide.
水酸化カリウム等のアルカリ金属の水酸化物、炭酸ナト
ｌ）ラム等のアルカリ金属の炭ｆＩｉ塩２重炭酸ナトリ
ウム等の重炭酸塩等を使用することができる。Alkali metal hydroxides such as potassium hydroxide, alkali metal carbonyl salts such as sodium carbonate, and bicarbonates such as sodium bicarbonate can be used.
このようにして得られる水性塗料用樹脂は、水希釈後、
水性塗料としてそのまま使用することができるが、その
他の成分として顔料、可塑剤、溶剤１着色剤等全添加し
たり、ｆ性アミノ樹脂、エボキ／樹脂、ポリエステル樹
脂、アクリル樹脂等の広範囲の水溶性又は水分散性樹脂
全配合することもできる。例えば、変性アミン樹脂、エ
ポキシ樹脂等と組み合わせることにより、焼付用塗料と
して使用することができ２％に本発明により得られる水
性樹脂のうち、乾性油又は半乾性油の脂肪酸を用いた場
合には、金属乾燥剤を添加したものは、常温硬化型塗料
として有用である。これらは。After diluting the water-based paint resin thus obtained,
It can be used as is as a water-based paint, but other components such as pigments, plasticizers, solvents, colorants, etc. may be added, or a wide range of water-soluble materials such as f-based amino resins, ebony/resins, polyester resins, acrylic resins, etc. Alternatively, all water-dispersible resins can be blended. For example, by combining with modified amine resins, epoxy resins, etc., it can be used as a baking paint. Among the aqueous resins obtained by the present invention, when 2% of the fatty acids of drying oil or semi-drying oil are used. , and those to which a metal drying agent is added are useful as room temperature curing paints. these are.
更に通常使用される顔料９表面処理剤、有機溶剤等を用
いることにより塗料化できる。塗料組成物は反漬法、刷
毛塗り、スプレー塗り、ロール塗り等の方法によって塗
装することができ、木材１紙。Furthermore, it can be made into a paint by using commonly used pigment 9 surface treatment agents, organic solvents, etc. The paint composition can be applied by methods such as anti-dip coating, brush coating, spray coating, and roll coating, and is coated on one piece of wood paper.
繊維、プラスチック、セラミック、鉄、非鉄金属等の表
面に塗装することができる。It can be applied to textiles, plastics, ceramics, iron, non-ferrous metals, etc.
（実施例）
次に、実施例により本発明を詳述するが２本発明はこれ
らに限定されるものではない。(Examples) Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.
実施例１
囚 攪拌機、温度計、還流脱水装置及び窒素ガス導入管
を付けた１１！のガラス製フラスコ中にキシレン１０９
．大豆油脂肪酸３００９及びビスフェノール型エポキシ
樹脂（エビコー）１００１．シェルケミカル社製）２４
０９金入れ、窒素ガスを吹き込みながら２３０ ℃で２
時間反応きぜた後冷却し、エポキシ化合物としてトリメ
チロールプロパンのジグリシジルエーテル及びトリメチ
ロールプロパンのトリグリシンルエーテルの混合物（「
デナコールＥＸ３２１Ｊ、ナガセ化成工業■商品名）４
０９を加え、還流しながら２２０’Ｃまで加熱し。Example 1 Prisoner 11 equipped with a stirrer, thermometer, reflux dehydrator and nitrogen gas inlet tube! xylene 109 in a glass flask
．． Soybean oil fatty acid 3009 and bisphenol type epoxy resin (Ebiko) 1001. Shell Chemical Co.) 24
09 Place the gold in the container and heat it at 230℃ while blowing in nitrogen gas.
After stirring the reaction for a time, it was cooled and a mixture of diglycidyl ether of trimethylolpropane and triglycine ether of trimethylolpropane was used as an epoxy compound ("
Denacol EX321J, Nagase Chemical Industry ■Product name) 4
Add 09 and heat to 220'C under reflux.
酸価が１以下になるまで付加、縮合奮進め、この後、キ
シレンを留去して、脂肪酸エステルを得た。Addition and condensation were continued until the acid value became 1 or less, and then xylene was distilled off to obtain a fatty acid ester.
（Ｂ）攪拌機、温度計、還流脱水装置及び窒素ガス導入
管を付けたｌｌのガラス製フラスコ中に（至）で得うレ
タ脂肪酸エステル２５２ｇ、ブチルセコソルブ１２０ｇ
、スチレン８０ｇ、ブレンマーＰＥ−３５Ｏｆ日本油脂
株式会社製、商品名１１８ｇ。(B) In a 1 liter glass flask equipped with a stirrer, a thermometer, a reflux dehydrator, and a nitrogen gas inlet tube, 252 g of letha fatty acid ester obtained in (to) and 120 g of butyl secosolve are placed.
, 80 g of styrene, 118 g of Blenmar PE-35Of Nippon Oil & Fats Co., Ltd., trade name.
メタクリルｆｉｌ ＯＱｉ入れ１００℃に加熱攪拌する
。これにアゾビスイソブチロニトリル９９とフチルセロ
ソルブ７３ｇ１混合したものを２時間かけて均一に滴下
し更に３時間保温する。８０℃に冷却後、トリエチルア
ミンｔｏ、ｓｇｌ添加し攪拌する。水２８０９全加え加
熱残分４７．３％、粘度７０ポアズ（２５℃）、ｐＨ７
，９の水性樹脂を得た。Add methacrylic fil OQi and heat to 100°C with stirring. A mixture of 99 g of azobisisobutyronitrile and 73 g of phtyl cellosolve was added dropwise uniformly to this mixture over 2 hours, and the mixture was kept warm for an additional 3 hours. After cooling to 80°C, triethylamine to and sgl were added and stirred. Added all 2809 water and heated residue 47.3%, viscosity 70 poise (25℃), pH 7
, 9 was obtained.
実施例２
実施例１の（Ｂ）においてスチレン１７３ｇ、ブレンマ
ーＰＥ−３５０を２５９に変更した以外は。Example 2 Example 1 (B) except that 173 g of styrene and Blenmar PE-350 were changed to 259.
実施例】と同様に操作し、加熱残分４５．５％、粘度８
５ポアズ（２５℃）、ｐＨ８，０の水性樹脂を得た。Example] The heating residue was 45.5% and the viscosity was 8.
An aqueous resin having a temperature of 5 poise (25° C.) and a pH of 8.0 was obtained.
実施例３
実施例１の（ＢＪにおいて、スチレンに７０ｇ、７’Ｌ
／ン７−ＰＥ−３５０に２５ ｇ、 メタクリＡ［ｔ−
１３９、トリエチルアミン’１１４９に変更した以外は
、実施例１と同様に操作し、加熱残分４１．９チ、粘度
７５ポアズ（２５℃）、ｐＨ８，２の水性樹脂を得九。Example 3 Example 1 (in BJ, 70g, 7'L of styrene
/N7-PE-350, 25 g, Methacrylic A [t-
139 and triethylamine '1149, the same procedure as in Example 1 was carried out to obtain an aqueous resin having a heating residue of 41.9 cm, a viscosity of 75 poise (25° C.), and a pH of 8.2.
比較例１
実施例１の囚で得られた脂肪酸エステル２５２９及びブ
チルセロソルブ１９３９ｉ入れ１００℃に加熱攪拌する
。スチレン８０ｇ、プレンマーＰＥ−３５０１８９，メ
タクリルａ！１０９及びアゾビスイソブチロニトリル９
ｇを混合し、２時間かけて均一に滴下し、更に３時間保
温する。以下、実施例１と同様に操作し、加熱残分４７
．５％粘度６０ポアズ（２５℃）、ｐＨ７，９の水性樹
脂を得た。Comparative Example 1 Fatty acid ester 2529 obtained in Example 1 and butyl cellosolve 1939i were added and heated to 100°C with stirring. Styrene 80g, Premar PE-350189, Methacrylic a! 109 and azobisisobutyronitrile 9
g was mixed, uniformly added dropwise over 2 hours, and kept warm for an additional 3 hours. Hereinafter, the same operation as in Example 1 was carried out, and the heating residue was 47
．． An aqueous resin having a 5% viscosity of 60 poise (25° C.) and a pH of 7.9 was obtained.
比較例２
比較例１０の）において、スチレンを７３ｇ、プレンマ
ーＰＥ−３５０を２５９に変更した以外は比較例１と同
様に操作し加熱残分４５．４％、粘度７５ポアズ（２５
℃）、ｐＨ＆ｏの水性樹脂を得た。Comparative Example 2 In Comparative Example 10), the same procedure as Comparative Example 1 was performed except that styrene was changed to 73 g and Premer PE-350 was changed to 259.
℃), pH&o aqueous resin was obtained.
比較例３
比較例１の■）において、スチレンを７０ｇ、プレンマ
ーＰＥ−３５０を２５ｇ、メタクリル酸を１３９、トリ
エチルアミンを１４９に変更した以外は比較例１と同様
に操作し、加熱残分４２．０％。Comparative Example 3 The same procedure as Comparative Example 1 was carried out except that in (■) of Comparative Example 1, styrene was changed to 70 g, Premer PE-350 was changed to 25 g, methacrylic acid was changed to 139, and triethylamine was changed to 149, and the heating residue was 42.0. %.
粘度６５ポアズ（２５℃）、ｐＨ８，２の水性樹脂を得
た。An aqueous resin having a viscosity of 65 poise (25° C.) and a pH of 8.2 was obtained.
比較例４
比較例１のＣＢ）において、七ツマ−としてスチレン８
０ｇ、メタクリル９２８９を使用し、プレンマーＰＥ−
３５０を使用しない以外は、比較例１と同様な方法で操
作し、加熱残分３５．５％、粘度９９ポアズ（２５℃）
、ｐＨ９，２の水性樹脂を得た。Comparative Example 4 In CB) of Comparative Example 1, styrene 8 was used as the 7-mer.
0g, using methacrylic 9289, premar PE-
The procedure was the same as in Comparative Example 1 except that 350 was not used, and the heating residue was 35.5% and the viscosity was 99 poise (25°C).
, an aqueous resin having a pH of 9.2 was obtained.
比較例５（樹脂組成）
比較例１の（Ｂ）において、モノマーとしてステン７８
８ｇ、メタクリル［２０９を使用し、プレンマーＰＢ−
３５０を使用しない以外は、比較例１と同様な方法で操
作し、加熱残分４０．５％、粘度８５ポアズ（２５℃）
、ｐＨ８，９の水性樹脂を得た。Comparative Example 5 (Resin Composition) In (B) of Comparative Example 1, Sten 78 was used as the monomer.
8g, using methacrylic [209, premar PB-
The procedure was the same as in Comparative Example 1 except that 350 was not used, and the heating residue was 40.5% and the viscosity was 85 poise (25°C).
, an aqueous resin having a pH of 8.9 was obtained.
各実施例及び比較例１〜３により得られた水性樹脂の分
子量分布を以下の方法で測定し、その数平均分子量及び
分子量分散度を表１に示すとともに、チャートを第１図
に示した。The molecular weight distribution of the aqueous resins obtained in each Example and Comparative Examples 1 to 3 was measured by the following method, and the number average molecular weight and molecular weight dispersity are shown in Table 1, and a chart is shown in FIG.
分子量分布測定法；高速液体クロマトグラフィー法
測定条件 ポンプ：６５５Ａ−１１（＠日立製作成製）
検出器；ＲＩ６５５Ａ−３０Ｃ
カラム；ゲルパックＲ，４００Ｍ、Ｒ４４０，Ｒ４５０
（いずれも日立化成工業■製）
を３本直列に接続
溶 媒；テトラヒドロフラン
流量； ２ｒｎｅ／ ｍｉｎ
試料濃度、０．１５９１５艷
各実施例及び比較例によシ得られた水性樹脂液を下記の
ように塗料化し、試験を行なった。Molecular weight distribution measurement method; high performance liquid chromatography measurement conditions Pump: 655A-11 (manufactured by Hitachi) Detector: RI655A-30C Column: Gelpack R, 400M, R440, R450
(all manufactured by Hitachi Chemical Co., Ltd.) were connected in series. Solvent: Tetrahydrofuran Flow rate: 2 rne/min Sample concentration: 0.15915 The aqueous resin liquid obtained in each Example and Comparative Example was treated as follows. It was made into a paint and tested.
白エナメル塗料配合
前記成分をガラスピーズの存在下にサントグラインダー
を用いて１２５０ｒｐｍで６０分間分散させ、カラスビ
ーズを除いて白エナメル（［）’を得た後。White enamel paint formulation The above components were dispersed in the presence of glass beads using a sand grinder at 1250 rpm for 60 minutes, and the glass beads were removed to obtain white enamel ([)'.
下記の組成物を添加して白エナメルｆｉｔ）を得た。A white enamel (fit) was obtained by adding the following composition.
このようにして得られた白エナメル（■）を適量の水で
希釈し、フォードカップφ４で３０〜３５秒に調製した
。この塗料の安定性及び塗膜の特性試験結果を表ＩＫ示
す。The white enamel (■) thus obtained was diluted with an appropriate amount of water and prepared in a Ford cup φ4 for 30 to 35 seconds. The stability of this paint and the test results of the film properties are shown in Table IK.
試験板作成条件
基材：ボンデライトナ１０フフ処理鋼板（日本テストパ
ネル社、厚さ０．８ ｏｎ ）塗装：エアスプレー（岩
田ライダ６１９口径１、５ ｏｎ ） ＋空気圧４ｋｇ
／Ｃｌｌ１１２乾燥＝２２〜２４℃で３日間。Test plate creation conditions Base material: Bonderite Tona 10 fufu treated steel plate (Japan Test Panel Co., Ltd., thickness 0.8 on) Painting: Air spray (Iwata Rider 619 caliber 1,5 on) + air pressure 4 kg
/Cll112 drying = 3 days at 22-24°C.
評価基準
塗料安定性；５０℃で７日間放置後も塗料成分が均一に
溶解ないし分散しているものを良好とした。Evaluation Criteria Paint Stability: A film in which the paint components were uniformly dissolved or dispersed even after being left at 50°C for 7 days was considered good.
耐 食 性１ＪＩｓ Ｋ ５４００の塩素噴霧試験
に準じて行なった。きび幅が１−以下のものを良好とし
た。Corrosion resistance 1 JIs K 5400 chlorine spray test was conducted. Those with a millet width of 1 or less were considered good.
耐 水 性；２３℃の水に７日間浸漬後、ブリスタ発生
なしのものを良好とした。Water resistance: No blisters were observed after immersion in water at 23°C for 7 days.
（発明の効果）
本発明の製造法により、得られる水性塗料用樹脂を含有
してなる水性塗料は、耐食性が優れ、塗料固形分が高く
、また塗料安定性も良好でかつ。(Effects of the Invention) The water-based paint containing the water-based paint resin obtained by the production method of the present invention has excellent corrosion resistance, high paint solid content, and good paint stability.
塗料の乾燥性の優れたものである。It has excellent paint drying properties.
第１図は不発明の実施例及び比較例で得られた水性樹脂
の高速液体クロマトグラフィー法によって測定された分
子量分布を示すチャートである。
μ「−）
代理人 弁理士 若 林 邦 彦″′１７ウー、二″−
′
溶
出
容
（ｍＺ）
第
図FIG. 1 is a chart showing the molecular weight distribution measured by high performance liquid chromatography of the aqueous resins obtained in Examples and Comparative Examples. μ"-) Agent Patent Attorney Kunihiko Wakabayashi"'17 Woo, 2"-
' Elution volume (mZ) Figure
Claims (1)
エポキシ樹脂（ｂ）７０〜２０重量部及び１分子中に１
〜４個のグリシジル基を有する脂肪族系エポキシ化合物
（ｃ）０〜４０重量部を、合計が１００重量部となるよ
うに配合し、付加、縮合して得られる脂肪酸エステル（
I ）１０〜９０重量部、一般式▲数式、化学式、表等
があります▼ （ただし、式中Ｒは水素または低級アルキル基であり、
Ｒ′は、水素、低級アルキル基またはハロゲンであり、
ｎは３以上の整数である）で示される化合物（II）１〜
２０重量部、並びに他の重合性ビニル単量体（III）８
９〜０重量部を（ I ）成分、（II）成分及び（II）成
分の合計が１００重量部となるように配合した混合物中
に、ラジカル重合開始剤を滴下して重合することを特徴
とする水性塗料用樹脂の製造法。 ２、請求項１記載の製造法により得られる水性塗料用樹
脂を含有してなる水性塗料。[Claims] 1. 25 to 60 parts by weight of fatty acid (a), 70 to 20 parts by weight of bisphenol type epoxy resin (b), and 1 part by weight per molecule.
Fatty acid ester obtained by blending 0 to 40 parts by weight of an aliphatic epoxy compound (c) having ~4 glycidyl groups in a total of 100 parts by weight, addition and condensation (
I) 10 to 90 parts by weight, general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R is hydrogen or a lower alkyl group,
R' is hydrogen, a lower alkyl group or a halogen,
n is an integer of 3 or more) Compounds (II) 1-
20 parts by weight, and other polymerizable vinyl monomer (III) 8
A radical polymerization initiator is added dropwise to a mixture containing 9 to 0 parts by weight of components (I), (II), and (II) so that the total amount is 100 parts by weight. A method for producing resin for water-based paints. 2. A water-based paint containing a water-based paint resin obtained by the production method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13080790A JPH086067B2 (en) | 1990-05-21 | 1990-05-21 | Method for producing resin for water-based paint and water-based paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13080790A JPH086067B2 (en) | 1990-05-21 | 1990-05-21 | Method for producing resin for water-based paint and water-based paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0425579A true JPH0425579A (en) | 1992-01-29 |
| JPH086067B2 JPH086067B2 (en) | 1996-01-24 |
Family
ID=15043170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13080790A Expired - Lifetime JPH086067B2 (en) | 1990-05-21 | 1990-05-21 | Method for producing resin for water-based paint and water-based paint |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH086067B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011084663A (en) * | 2009-10-16 | 2011-04-28 | Kansai Paint Co Ltd | Aqueous coating composition and method of coating |
-
1990
- 1990-05-21 JP JP13080790A patent/JPH086067B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011084663A (en) * | 2009-10-16 | 2011-04-28 | Kansai Paint Co Ltd | Aqueous coating composition and method of coating |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH086067B2 (en) | 1996-01-24 |
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