JPH0586324A - Water-base coating composition - Google Patents
Water-base coating compositionInfo
- Publication number
- JPH0586324A JPH0586324A JP27477791A JP27477791A JPH0586324A JP H0586324 A JPH0586324 A JP H0586324A JP 27477791 A JP27477791 A JP 27477791A JP 27477791 A JP27477791 A JP 27477791A JP H0586324 A JPH0586324 A JP H0586324A
- Authority
- JP
- Japan
- Prior art keywords
- water
- resin
- coating composition
- polyester resin
- weight
- 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.)
- Pending
Links
- 239000008199 coating composition Substances 0.000 title claims description 22
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 46
- 229920001225 polyester resin Polymers 0.000 claims abstract description 37
- 239000004645 polyester resin Substances 0.000 claims abstract description 37
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920003180 amino resin Polymers 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- -1 butoxymethyl Chemical group 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- 125000004849 alkoxymethyl group Chemical group 0.000 claims 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 claims 1
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 48
- 239000011248 coating agent Substances 0.000 abstract description 46
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- WVJOGYWFVNTSAU-UHFFFAOYSA-N dimethylol ethylene urea Chemical compound OCN1CCN(CO)C1=O WVJOGYWFVNTSAU-UHFFFAOYSA-N 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 239000003973 paint Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 229920001807 Urea-formaldehyde Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229940014800 succinic anhydride Drugs 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 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
- 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
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 1
- RSPWVGZWUBNLQU-FOCLMDBBSA-N 3-[(e)-hexadec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCCCCCC\C=C\C1CC(=O)OC1=O RSPWVGZWUBNLQU-FOCLMDBBSA-N 0.000 description 1
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 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
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は新規な水系塗料組成物、
さらに詳しくは、良好な外観品質と優れた耐チッピング
性を有する硬化塗膜を与える水溶性ポリエステル樹脂と
アミノプラスト樹脂と水溶性エチレン尿素系樹脂とを含
有する水系塗料組成物に関するものである。The present invention relates to a novel water-based coating composition,
More specifically, the present invention relates to a water-based coating composition containing a water-soluble polyester resin, an aminoplast resin, and a water-soluble ethyleneurea resin, which gives a cured coating film having good appearance quality and excellent chipping resistance.
【０００２】[0002]
【従来の技術】近年、大気汚染防止や省資源の観点か
ら、水を希釈剤として用いる水系塗料が注目されてお
り、すでに工業用として焼付け硬化型の水系塗料が開発
されている。この焼付け硬化型の水系塗料においては、
通常塗膜形成成分として、カルボキシル基を有するポリ
エステル樹脂とアミノプラスト樹脂との混合物が用いら
れ、焼付け時に、該ポリエステル樹脂とアミノプラスト
樹脂とが縮重合することにより硬化し、塗膜が形成され
る（例えば、特開昭６１−３１４７２号公報）。ところ
で、自動車用中塗り塗料の分野においては、高級感を付
与するために、見た目に美しい高外観品質が要求される
とともに、小石などの衝突から素材を保護するために耐
チッピング性が要求され、そして近年この要求品質はま
すます高いものになってきている。しかしながら、従来
の焼付け硬化型水系塗料においては、通常硬化剤として
アミノプラスト樹脂のみが用いられているため、仕上が
り外観品質及び耐チッピング性共に十分に満足しうる塗
膜が得られないという欠点があった。また、耐チッピン
グ性向上のために、硬化剤としてブロック化ポリイソシ
アネート化合物を用いた水系分散型塗料組成物が開示さ
れているが（特開平３−１８１５７５号公報）、この組
成物は得られる塗膜の外観品質が不十分であるという欠
点を有している。2. Description of the Related Art In recent years, water-based paints using water as a diluent have been drawing attention from the viewpoints of preventing air pollution and saving resources, and bake-curable water-based paints have already been developed for industrial use. In this bake-curable water-based paint,
Usually, a mixture of a polyester resin having a carboxyl group and an aminoplast resin is used as a coating film-forming component, and the polyester resin and the aminoplast resin are cured by polycondensation during baking to form a coating film. (For example, JP-A-61-31472). By the way, in the field of intermediate coatings for automobiles, in order to impart a high-class feeling, a visually high quality appearance is required, and chipping resistance is required in order to protect the material from collision such as pebbles, In recent years, the required quality has become higher and higher. However, in conventional bake-curable water-based coatings, since only aminoplast resin is usually used as a curing agent, there is a drawback that a coating film that is not sufficiently satisfactory in terms of finished appearance quality and chipping resistance cannot be obtained. It was Further, an aqueous dispersion type coating composition using a blocked polyisocyanate compound as a curing agent for improving chipping resistance is disclosed (JP-A-3-181575). It has the disadvantage that the appearance quality of the membrane is insufficient.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、このような
従来の焼付け硬化型の水系塗料が有する欠点を克服し、
良好な外観品質と優れた耐チッピング性とを合わせもつ
硬化塗膜を与える水系塗料組成物を提供することを目的
としてなされたものである。SUMMARY OF THE INVENTION The present invention overcomes the drawbacks of the conventional bake-curable water-based coating composition,
The object of the present invention is to provide an aqueous coating composition which gives a cured coating film having both good appearance quality and excellent chipping resistance.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記の好
ましい性質を有する水系塗料組成物を開発すべく鋭意研
究を重ねた結果、塗膜形成成分として、水溶性ポリエス
テル樹脂とアミノプラスト樹脂と特定の割合の補助架橋
剤としての水溶性エチレン尿素系樹脂とを含有して成る
組成物により、その目的を達成しうることを見い出し、
この知見に基づいて本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies to develop an aqueous coating composition having the above-mentioned preferable properties, the present inventors have found that a water-soluble polyester resin and an aminoplast resin are used as a coating film forming component. It has been found that the object can be achieved by a composition containing a water-soluble ethylene urea-based resin as an auxiliary cross-linking agent in a specific ratio and
The present invention has been completed based on this finding.
【０００５】すなわち、本発明は、（Ａ）水溶性ポリエ
ステル樹脂及び（Ｂ）アミノプラスト樹脂を主成分とす
る熱硬化性水系塗料組成物において、補助架橋剤として
（Ｃ）水溶性エチレン尿素系樹脂を、該（Ａ）成分１０
０重量部に対し３〜３０重量部の割合で含有させたこと
を特徴とする水系塗料組成物を提供するものである。以
下、本発明を詳細に説明する。本発明組成物において
は、（Ａ）成分として水溶性ポリエステル樹脂が用いら
れる。この水溶性ポリエステル樹脂としては、例えば一
般式That is, the present invention provides a thermosetting water-based coating composition containing (A) a water-soluble polyester resin and (B) an aminoplast resin as main components, and (C) a water-soluble ethylene urea resin as an auxiliary crosslinking agent. The component (A) 10
The present invention provides a water-based coating composition characterized in that it is contained in an amount of 3 to 30 parts by weight with respect to 0 parts by weight. Hereinafter, the present invention will be described in detail. In the composition of the present invention, a water-soluble polyester resin is used as the component (A). Examples of the water-soluble polyester resin include those represented by the general formula
【０００６】[0006]
【化３】 [Chemical 3]
【０００７】（式中のＲは炭素数８〜２０のアルキル基
又はアルケニル基である）で表される酸無水物から形成
される単位５〜５０重量％を含有するものが好ましく用
いられる。このポリエステル樹脂の原料として該酸無水
物を使用するのは、オイルフリーポリエステル樹脂で
は、樹脂の表面張力が高いため被塗物への濡れ性が悪
く、塗装時にはじき、へこみなどの塗膜欠陥が生じやす
いし、脂肪酸変性ポリエステル樹脂では多層塗りを施す
場合、塗膜物性として層間付着性に問題が生じるおそれ
があるためである。Those containing 5 to 50% by weight of a unit formed from an acid anhydride represented by the formula (wherein R is an alkyl or alkenyl group having 8 to 20 carbon atoms) are preferably used. The acid anhydride is used as a raw material for the polyester resin in the oil-free polyester resin because the surface tension of the resin is high, the wettability to the article to be coated is poor, and coating defects such as cissing and dents occur during coating. This is because the fatty acid-modified polyester resin is likely to occur, and when multi-layer coating is performed, a problem may occur in the interlayer adhesion as a physical property of the coating film.
【０００８】前記水溶性ポリエステル樹脂中の該酸無水
物から形成される単位の含有量が５重量％未満では樹脂
の表面張力が高いため被塗物への濡れ性が悪く、塗装時
にはじき、へこみなどの塗膜欠陥が生じやすいし、５０
重量％を超えると塗膜の層間付着性が十分でなくなるお
それが生じる。前記酸無水物におけるアルキル基又はア
ルケニル基は、炭素数が８〜２０、好ましくは１０〜１
８の範囲にあれば、直鎖状であってもよいし、分枝を有
するものであってもよい。該アルキル基又はアルケニル
基の炭素数が２０を超えると、炭素鎖が長くなる割には
耐チッピング性の向上効果が十分に発揮されない上、む
しろ工業的に入手することが困難となり、実用上不適当
である。If the content of the unit formed from the acid anhydride in the water-soluble polyester resin is less than 5% by weight, the surface tension of the resin is high, so that the wettability to the article to be coated is poor and crevices and dents occur during coating. Coating film defects such as
If the amount exceeds 5% by weight, the interlayer adhesion of the coating film may become insufficient. The alkyl group or alkenyl group in the acid anhydride has 8 to 20 carbon atoms, preferably 10 to 1 carbon atoms.
If it is in the range of 8, it may be linear or branched. When the number of carbon atoms of the alkyl group or alkenyl group exceeds 20, the effect of improving the chipping resistance is not sufficiently exhibited despite the lengthening of the carbon chain, and it is rather difficult to obtain industrially, which is not practical. Appropriate.
【０００９】このような酸無水物としては、例えばオク
チル、ノニル、デシル、ウンデシル、ドデシル、トリデ
シル、テトラデシル、ペンタデシル、ヘキサデシル、ヘ
プタデシル、オクタデシルなどのアルキル基を有する無
水コハク酸、オクテニル、ノネニル、デセニル、ウンデ
セニル、トリデセニル、テトラデセニル、ペンタデセニ
ル、ヘキサデセニル、ヘプタデセニル、オクタデセニル
などのアルケニル基を有する無水コハク酸が挙げられ
る。これらの酸無水物は１種用いてもよいし、２種以上
を組み合わせて用いてもよい。Examples of such acid anhydrides include succinic anhydride having an alkyl group such as octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octenyl, nonenyl, decenyl, Examples thereof include succinic anhydride having an alkenyl group such as undecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl and octadecenyl. These acid anhydrides may be used alone or in combination of two or more.
【００１０】本発明で用いられる水溶性ポリエステル樹
脂は、酸価が２５〜１００KOHmg／ｇの範囲にあり、か
つ水酸基が５０〜２００KOHmg／ｇの範囲にあるのが望
ましい。該酸価が２５KOHmg／ｇ未満では塗料の安定性
が不十分となるおそれがあるし、１００KOHmg／ｇを超
えると塗膜の耐アルカリ性が著しく低下する傾向がみら
れる。また、該水酸基価はポリエステル樹脂の水性媒体
に対する溶解性及び架橋点にとって重要であり、この水
酸基価が５０KOHmg／ｇ未満では親水性が不足し、かつ
架橋点が少なすぎて塗膜の耐水性や強度が不十分となる
おそれがあるし、２００KOHmg／ｇを超えると塗膜の耐
水性が低下する傾向がみられる。The water-soluble polyester resin used in the present invention preferably has an acid value in the range of 25 to 100 KOHmg / g and a hydroxyl group in the range of 50 to 200 KOHmg / g. If the acid value is less than 25 KOHmg / g, the stability of the coating may be insufficient, and if it exceeds 100 KOHmg / g, the alkali resistance of the coating film tends to be remarkably reduced. Further, the hydroxyl value is important for the solubility of the polyester resin in an aqueous medium and the cross-linking point, and when the hydroxyl value is less than 50 KOHmg / g, the hydrophilicity is insufficient, and the cross-linking point is too small so that the water resistance of the coating film is reduced. The strength may be insufficient, and if it exceeds 200 KOHmg / g, the water resistance of the coating film tends to decrease.
【００１１】さらに、該水溶性ポリエステル樹脂は、そ
の数平均分子量が５００〜５,０００の範囲にあるもの
が好適である。この数平均分子量が５００未満では塗膜
の耐水性、耐チッピング性、耐久性に劣り、本発明の目
的が十分に達せられないし、５,０００を超えると粘度
が高くなりすぎるため、焼付け時の流動性が低下し、塗
膜の平滑性が損なわれる傾向がみられる。本発明で用い
られる水溶性ポリエステル樹脂は、前記の酸無水物、及
び通常のポリエステル樹脂の原料として慣用されている
多価アルコール、多塩基酸、必要に応じて用いられる油
脂類などを原料として使用し、公知の方法によって製造
することができる。Further, the water-soluble polyester resin preferably has a number average molecular weight in the range of 500 to 5,000. If the number average molecular weight is less than 500, the water resistance, chipping resistance, and durability of the coating film are poor, and the object of the present invention cannot be fully achieved. If it exceeds 5,000, the viscosity becomes too high. There is a tendency that the fluidity decreases and the smoothness of the coating film is impaired. The water-soluble polyester resin used in the present invention uses, as a raw material, the above-mentioned acid anhydride, and polyhydric alcohols, polybasic acids, and fats and oils used as necessary, which are commonly used as raw materials for ordinary polyester resins. However, it can be manufactured by a known method.
【００１２】前記多価アルコールとしては、例えばエチ
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、１,４−ブタンジオール、１,６−ヘキ
サンジオール、ジエチレングリコール、ジプロピレング
リコール、ネオペンチルグリコール、トリエチレングリ
コール、水素化ビスフェノールＡ、グリセリン、トリメ
チロールエタン、トリメチロールプロパン、ペンタエリ
トリット、ジペンタエリトリットなどが挙げられる。こ
れらの多価アルコールはそれぞれ単独で用いてもよい
し、２種以上を組み合わせて用いてもよい。また、多塩
基酸としては、例えば無水フタル酸、イソフタル酸、テ
レフタル酸、無水コハク酸、アジピン酸、アゼライン
酸、セバシン酸、無水マレイン酸、フマル酸、イタコン
酸、無水トリメリット酸などを挙げることができる。こ
れらの多塩基酸はそれぞれ単独で用いてもよいし、２種
以上を組み合わせて用いてもよい。Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol and triethylene. Glycol, hydrogenated bisphenol A, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and the like can be mentioned. These polyhydric alcohols may be used alone or in combination of two or more. Examples of polybasic acids include phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, maleic anhydride, fumaric acid, itaconic acid and trimellitic anhydride. You can These polybasic acids may be used alone or in combination of two or more.
【００１３】このようにして得られた水溶性ポリエステ
ル樹脂は通常塩基性物質で中和される。この際、塩基性
物質は、水溶性ポリエステル樹脂に含まれているカルボ
キシ基の４０〜１００モル％を中和するのに必要な量を
用いるのが好ましく、その使用量が４０モル％未満では
該ポリエステル樹脂は水溶化されないおそれがあるし、
１００モル％を超えると得られる塗料の安定性が低下す
る傾向がみられる。The water-soluble polyester resin thus obtained is usually neutralized with a basic substance. At this time, the basic substance is preferably used in an amount necessary to neutralize 40 to 100 mol% of the carboxy groups contained in the water-soluble polyester resin, and when the amount used is less than 40 mol%, The polyester resin may not be solubilized,
If it exceeds 100 mol%, the stability of the obtained coating composition tends to decrease.
【００１４】本発明組成物における（Ｂ）成分のアミノ
プラスト樹脂としては、アルコキシメチルメラミン樹
脂、アルコキシル基以外にメチロール基やイミノ基を有
するメラミン樹脂、トリアジン環が２分子以上縮合した
いわゆる縮合型メラミン樹脂などを用いることができる
が、特にヘキサアルコキシメチルメラミン樹脂が好適で
ある。このヘキサアルコキシメチルメラミン樹脂として
は、そのアルコキシル基がメトキシ、エトキシ、プロポ
キシ、ブトキシのいずれかであるもの及びそれらの２つ
以上を含有する混合アルコキシメチルメラミン樹脂が適
当である。これらの中でメトキシメチル及びブトキシメ
チル混合型のメラミン樹脂であって、樹脂の表面張力を
低下させて被塗物に対する濡れ性を向上させるために、
トリアジン環当たり、約２モル以上のブトキシメチル基
を導入したものが特に望ましい。本発明組成物において
は、補助架橋剤として、（Ｃ）成分、すなわち水溶性エ
チレン尿素系樹脂が用いられる。この水溶性エチレン尿
素系樹脂としては、一般式The component (B) aminoplast resin in the composition of the present invention is an alkoxymethylmelamine resin, a melamine resin having a methylol group or an imino group in addition to an alkoxyl group, a so-called condensed melamine in which two or more triazine rings are condensed. A resin or the like can be used, but a hexaalkoxymethylmelamine resin is particularly preferable. As the hexaalkoxymethylmelamine resin, a resin whose alkoxyl group is methoxy, ethoxy, propoxy or butoxy and a mixed alkoxymethylmelamine resin containing two or more thereof are suitable. Among these, a melamine resin of methoxymethyl and butoxymethyl mixed type, in order to reduce the surface tension of the resin and improve the wettability to the article to be coated,
Those having about 2 mol or more butoxymethyl groups introduced per triazine ring are particularly desirable. In the composition of the present invention, the component (C), that is, a water-soluble ethylene urea resin is used as an auxiliary crosslinking agent. This water-soluble ethylene urea resin has a general formula
【００１５】[0015]
【化４】 [Chemical 4]
【００１６】［式中のＸ及びＹはそれぞれ水素原子又は
−(ＣＨ2)n−ＯＨであるが、少なくとも一方は−(Ｃ
Ｈ2)n−ＯＨ（ｎは１〜３の整数）である］で表される
ものが好ましく用いられる。このような水溶性エチレン
尿素系樹脂としては、例えばＮ,Ｎ'−ジメチロールエチ
レン尿素、Ｎ,Ｎ'−ジエタノールエチレン尿素、Ｎ,Ｎ'
−ジプロパノールエチレン尿素、Ｎ−モノエタノールエ
チレン尿素などが挙げられる。これらの中で、容易に入
手しうるものとしては、例えばＮ,Ｎ'−ジメチロールエ
チレン尿素であるＳＭＩＴＥＸ ＲＥＳＩＮ ９０１
［住友化学工業(株)製、商品名、固形分５０重量％］、
Ｎ−モノエタノールエチレン尿素であるＵＣＡＲ Ｒｅ
ａｃｔｉｖｅ Ｄｉｌｕｅｎｔ ＲＤ ６５−２（ユニ
オンカーバイド社製、商品名、固形分７５重量％、以
下、ＲＤ６５−２と略記する）などが挙げられる。[In the formula, X and Y are each a hydrogen atom or-(CH 2 ) n --OH, but at least one is-(C
H 2) n -OH (n is preferably used those represented by a is] an integer of 1 to 3). Examples of such water-soluble ethylene urea-based resin include N, N'-dimethylol ethylene urea, N, N'-diethanol ethylene urea, N, N '
-Dipropanol ethylene urea, N-monoethanol ethylene urea, etc. are mentioned. Among these, as those that are easily available, for example, N, N′-dimethylolethylene urea SMITEX RESIN 901 is available.
[Sumitomo Chemical Co., Ltd., trade name, solid content 50% by weight],
UCAR Re which is N-monoethanol ethylene urea
active Diluent RD 65-2 (manufactured by Union Carbide Co., trade name, solid content 75% by weight, hereinafter abbreviated as RD 65-2) and the like.
【００１７】本発明組成物における前記水溶性エチレン
尿素系樹脂の含有量は、（Ａ）成分の水溶性ポリエステ
ル樹脂１００重量部当たり３〜３０重量部の範囲で選ば
れる。この含有量が３重量部未満では外観品質及び耐チ
ッピング性の向上効果が十分に発揮されないし、３０重
量部を超えると塗膜の硬度が高くなりすぎ、耐チッピン
グ性が不十分となる。The content of the water-soluble ethylene urea-based resin in the composition of the present invention is selected in the range of 3 to 30 parts by weight per 100 parts by weight of the water-soluble polyester resin as the component (A). If the content is less than 3 parts by weight, the effect of improving the appearance quality and chipping resistance will not be sufficiently exhibited, and if it exceeds 30 parts by weight, the hardness of the coating film will be too high and the chipping resistance will be insufficient.
【００１８】本発明の水系塗料組成物の調製方法につい
ては特に制限はなく、公知の方法を用いることができ
る。例えば、まず水性媒体中において、（Ａ）成分の水
溶性ポリエステル樹脂を所要量の塩基性物質を用いて中
和したのち、これに所要量の（Ｂ）成分のアミノプラス
ト樹脂を加えて均質に混合し、水系樹脂溶液を調製し、
次いで、これに所要量の（Ｃ）成分である水溶性エチレ
ン尿素系樹脂を加え、均質に混合し、さらに必要に応
じ、硬化促進剤、他の硬化剤、他の水溶性樹脂、塗面調
整剤などを加え、公知の手段を用い、均質に混合するこ
とにより、所望の水系塗料組成物が得られる。また、顔
料着色水系塗料組成物とする場合には、（Ａ）成分のポ
リエステル樹脂の一部を使用して、常法により顔料ペー
ストを調製し、これを該水系樹脂溶液と混合してもよい
し、顔料を直接該水系樹脂溶液に練り込んでもよい。こ
のようにして調製された本発明の水系塗料組成物は、従
来の水系塗料と同様に、刷毛塗り、スプレー塗装、浸漬
塗装、静電塗装などの方法を用いて、被塗物に塗装した
のち、焼付け処理することにより、良好な外観品質と高
度の耐チッピング性を有する硬化塗膜を形成することが
できる。The method for preparing the water-based coating composition of the present invention is not particularly limited, and known methods can be used. For example, first, in a water-based medium, a water-soluble polyester resin of component (A) is neutralized with a required amount of a basic substance, and then a required amount of aminoplast resin of component (B) is added to homogenize it. Mix, prepare an aqueous resin solution,
Then, the required amount of the component (C), a water-soluble ethylene urea resin, is added and mixed homogeneously, and if necessary, a curing accelerator, another curing agent, another water-soluble resin, and a coating surface adjustment. A desired water-based coating composition is obtained by adding an agent and the like and using a known means to uniformly mix them. Further, in the case of preparing a pigmented water-based coating composition, a pigment paste may be prepared by a conventional method using a part of the polyester resin as the component (A), and this may be mixed with the water-based resin solution. However, the pigment may be directly kneaded into the aqueous resin solution. The water-based coating composition of the present invention thus prepared is applied to an object to be coated by a method such as brush coating, spray coating, dip coating, electrostatic coating or the like, as in the conventional water-based coating composition. By performing the baking treatment, it is possible to form a cured coating film having good appearance quality and a high degree of chipping resistance.
【００１９】[0019]
【実施例】次に、実施例により本発明をさらに詳細に説
明するが、本発明はこれらの例によってなんら限定され
るものではない。なお、塗膜性能は次の方法に従い評価
した。 （１）耐チッピング性 ダイヤモンドショット試験機（スガ試験機株式会社製、
ＫＳＳ−１型）を用い、−２０℃に冷却した塗膜に、９
０、１３０、１７０km／ｈのスピードでダイヤモンドを
それぞれ１０発ずつショットし、その部位に幅２４mmの
セロハン粘着テープを密着させ、上方に一気に引いて塗
膜が剥離した面積の合計を３で割り、その数値を剥離面
積とし、また鋼板素地まで到達した割合を、塩水噴霧試
験（ＪＩＳ Ｋ-５４００（１９９０）９.１耐塩水噴霧
性による）を７２時間行ったのちの錆の発生点数より求
め、素地傷到達率とした。 （２）外観品質 表面粗皮計（ＳＵＲＦＴＥＳＴ ２０１ ミツトヨ社
製）を用いて表面粗度Ｒａ値を測定することにより中塗
り外観品質を評価した。またＰＧＤ計（ＰＧＤIV型 日
本色彩研究所製）を用いてＰＧＤ値を、写像鮮明度測定
機（ＩＣＮ−１スガ試験機社製）を用いてＮＳＩＣ値を
測定することにより、上塗り塗装後の外観品質を評価し
た。 （３）鏡面光沢度 ＪＩＳ Ｋ-５４００（１９９０）７.６鏡面光沢度によ
る。 （４）鉛筆硬度 ＪＩＳ Ｋ-５４００（１９９０）８.４.２手かき法に準
拠し、鉛筆（三菱ユニ、三菱鉛筆株式会社製、商品名）
の木質部のみを削り、芯を塗装鋼板面に４５°の角度で
当接摩擦し、塗装面に傷が付く直前の鉛筆硬度でもって
表示した。 （５）付着性 ＪＩＳ Ｋ-５４００（１９９０）８.５.２碁盤目テープ
法に準拠し、試験片に鋭利な薄い刃物（ＮＴカッターな
ど）で１mmの等間隔平行線１１本をたがいに直交させて
引き、１mmの正方形１００個をつくり、それに幅２４mm
のセロハン粘着テープを密着させ、上方に一気に引き、
はがれずに残ったものの数をχとして、付着性をχ／１
００で表示した。 （６）耐湿性 温度５０℃、湿度９８％の耐湿試験器に３６０時間放置
したのちの塗膜の外観を観察した［ＪＩＳ Ｋ-５４００
（１９９０）９.２.１固定式による］。EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The coating film performance was evaluated according to the following method. (1) Chipping resistance Diamond shot tester (manufactured by Suga Test Instruments Co., Ltd.,
KSS-1 type), the coating film cooled to −20 ° C.
Shot 10 diamonds each at a speed of 0, 130, 170 km / h, attach a cellophane adhesive tape with a width of 24 mm to that part, pull it all at once in a stretch and divide the total area of the coating film divided by 3, The numerical value was taken as the peeling area, and the ratio of reaching the steel plate substrate was obtained from the number of rust occurrence points after a salt spray test (according to JIS K-5400 (1990) 9.1 salt spray resistance) was carried out for 72 hours, The rate of damage to the base material was used. (2) Appearance quality The intermediate coating appearance quality was evaluated by measuring the surface roughness Ra value using a surface roughness tester (SURFTEST 201 manufactured by Mitutoyo). Also, by measuring the PGD value using a PGD meter (PGD IV type manufactured by Japan Color Research Institute) and the NSIC value using a mapping sharpness measurement device (ICN-1 Suga Test Instruments Co., Ltd.), the appearance after topcoat coating Evaluated the quality. (3) Specular glossiness According to JIS K-5400 (1990) 7.6 specular glossiness. (4) Pencil hardness Based on JIS K-5400 (1990) 8.4.2 Hand-shaking method, pencil (Mitsubishi Uni, manufactured by Mitsubishi Pencil Co., Ltd., trade name)
Only the wood part was scraped, and the core was rubbed against the coated steel plate surface at an angle of 45 °, and the pencil hardness immediately before the coated surface was scratched was displayed. (5) Adhesion According to JIS K-5400 (1990) 8.5.2 cross-cut tape method, the test piece is orthogonal to 11 equally spaced parallel lines with a sharp blade (NT cutter, etc.) Draw and make 100 squares of 1mm, width 24mm
Adhere the cellophane adhesive tape from and pull it all at once,
The adhesiveness is χ / 1, where χ is the number of those that remain without peeling.
Displayed with 00. (6) Moisture resistance The appearance of the coating film was observed after leaving it in a humidity resistance tester at a temperature of 50 ° C and a humidity of 98% for 360 hours [JIS K-5400.
(1990) 9.2.1 According to fixed type].
【００２０】製造例１ 水溶性ポリエステル樹脂Ａ−１の製造 かくはん機、温度計、還流冷却器及び窒素ガス導入管を
取り付けた四つ口フラスコに、イソフタル酸２０.０重
量部、無水トリメリット酸１０.０重量部、アジピン酸
９.３重量部、ヘキサデセニル無水コハク酸２５.０重量
部、１,４−ブタンジオール２０.８重量部、トリメチロ
ールプロパン１４.９重量部を仕込み、２２０℃で２時
間、次いで１９０℃で２時間エステル化反応を行って、
酸価５０、水酸基価１２０、数平均分子量１,６００の
水溶性ポリエステル樹脂を得た。得られた樹脂反応物の
温度を１００℃まで下げ、これにブチルセロソルブを加
えて、加熱残分８０重量％の水溶性ポリエステル樹脂Ａ
−１を得た。Production Example 1 Production of Water-Soluble Polyester Resin A-1 A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube was charged with 20.0 parts by weight of isophthalic acid and trimellitic anhydride. 10.0 parts by weight, 9.3 parts by weight of adipic acid, 25.0 parts by weight of hexadecenyl succinic anhydride, 20.8 parts by weight of 1,4-butanediol and 14.9 parts by weight of trimethylolpropane were charged at 220 ° C. The esterification reaction was carried out for 2 hours and then at 190 ° C. for 2 hours,
A water-soluble polyester resin having an acid value of 50, a hydroxyl value of 120 and a number average molecular weight of 1,600 was obtained. The temperature of the obtained resin reaction product was lowered to 100 ° C., butyl cellosolve was added thereto, and a heating residue of 80% by weight was applied to the water-soluble polyester resin A.
-1 was obtained.
【００２１】製造例２ 水溶性ポリエステル樹脂Ａ−２の製造 製造例１と同様にかくはん機、温度計、還流冷却器及び
窒素ガス導入管を取り付けた四つ口フラスコに、イソフ
タル酸２０.０重量部、無水トリメリット酸６.６重量
部、ドデシル無水コハク酸３０.９重量部、ポリエチレ
ングリコール（分子量２００）１５.０重量部、１,４−
ブタンジオール８.７重量部、トリメチロールプロパン
１８.８重量部を仕込み、２２０℃で２時間、次いで１
９０℃で２時間エステル化反応を行って、酸価３５、水
酸基価１５０、数平均分子量１,４００の水溶性ポリエ
ステル樹脂を得た。得られた樹脂反応物の温度を１００
℃まで下げ、ブチルセロソルブを加え、加熱残分８０重
量％の水溶性ポリエステル樹脂Ａ−２を得た。Production Example 2 Production of Water-Soluble Polyester Resin A-2 In the same manner as in Production Example 1, a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube was charged with 20.0 parts by weight of isophthalic acid. Parts, 6.6 parts by weight of trimellitic anhydride, 30.9 parts by weight of dodecyl succinic anhydride, 15.0 parts by weight of polyethylene glycol (molecular weight 200), 1,4-
Charge 8.7 parts by weight of butanediol and 18.8 parts by weight of trimethylolpropane, and heat at 220 ° C. for 2 hours, then 1
An esterification reaction was carried out at 90 ° C. for 2 hours to obtain a water-soluble polyester resin having an acid value of 35, a hydroxyl value of 150 and a number average molecular weight of 1,400. The temperature of the obtained resin reactant is set to 100.
The temperature was lowered to ℃, and butyl cellosolve was added to obtain a water-soluble polyester resin A-2 having a heating residue of 80% by weight.
【００２２】実施例１〜６ 製造例１で得られた水溶性ポリエステル樹脂Ａ−１、製
造例２で得られた水溶性ポリエステル樹脂Ａ−２の温度
を６０℃まで下げ、ホモディスパーで撹拌しながら、樹
脂中のカルボキシル基０.７５モル当量に相当するジメ
チルエタノールアミンを加えて均一に中和したのち、こ
れにヘキサメトキシメチルメラミン樹脂「ニカラックＭ
Ｗ−３０」（三和ケミカル社製、商品名、加熱残分１０
０％）及びブチルセロソルブを加え混合した。同温度を
維持しながら、脱イオン水を徐々に加え、強い青味を呈
した加熱残分４０重量％の水系樹脂溶液［１］及び
［２］を得た。これらの水系樹脂溶液の配合組成を第１
表に示す。Examples 1 to 6 The temperatures of the water-soluble polyester resin A-1 obtained in Production Example 1 and the water-soluble polyester resin A-2 obtained in Production Example 2 were lowered to 60 ° C. and stirred with a homodisper. However, dimethylethanolamine corresponding to 0.75 molar equivalent of the carboxyl group in the resin was added to uniformly neutralize it, and then the hexamethoxymethylmelamine resin "Nicalac M" was added.
W-30 "(manufactured by Sanwa Chemical Co., Ltd., trade name, heating residue 10
0%) and butyl cellosolve were added and mixed. While maintaining the same temperature, deionized water was gradually added to obtain aqueous resin solutions [1] and [2] having a strong blue tint and a heating residue of 40% by weight. The composition of these aqueous resin solutions is
Shown in the table.
【００２３】[0023]
【表１】 [Table 1]
【００２４】次いで、前記水系樹脂溶液［１］及び
［２］それぞれ３０重量部、酸化チタン６０重量部、脱
イオン水１０重量部をサンドミルで１時間混合分散し、
白色ペースト［１］及び［２］を調製した。この白色ペ
ーストそれぞれに、前記の水系樹脂溶液［１］又は
［２］、Ｎ,Ｎ'−ジメチロールエチレン尿素樹脂「ＳＵ
ＭＩＴＥＸ ＲＥＳＩＮ９０１」又はＮ−モノエタノー
ルエチレン尿素樹脂「ＲＤ６５−２」、硬化触媒として
のキャタリスト６０００［三井東圧化学(株)製、商品
名］及び水性塗料用添加剤「アジトールＸＶ３２９」
（ヘキスト社製、商品名）を第３表に示す割合で加え、
均一になるまでよく撹拌し、白色の水系塗料を調製し
た。Next, 30 parts by weight of each of the aqueous resin solutions [1] and [2], 60 parts by weight of titanium oxide, and 10 parts by weight of deionized water were mixed and dispersed in a sand mill for 1 hour,
White pastes [1] and [2] were prepared. To each of the white pastes, the above-mentioned aqueous resin solution [1] or [2], N, N′-dimethylol ethylene urea resin “SU
MITEX RESIN 901 "or N-monoethanol ethylene urea resin" RD65-2 ", Catalyst 6000 [trade name of Mitsui Toatsu Chemicals, Inc.] as a curing catalyst, and" Azitol XV329 "additive for water-based paint.
(Hoechst, trade name) is added at the ratio shown in Table 3,
The mixture was stirred well until it became uniform to prepare a white water-based paint.
【００２５】比較例１〜５ 実施例１〜６における水系樹脂溶液［１］及び［２］と
同様にして、第２表に示す配合組成の水系樹脂溶液
［３］を調製し、さらに、白色ペースト［１］及び
［２］と同様の配合割合で白色ペースト［３］を調製し
た。次に、実施例１〜６と同様にして第３表に示す配合
組成の白色の水系塗料を調製した。Comparative Examples 1 to 5 In the same manner as the aqueous resin solutions [1] and [2] in Examples 1 to 6, aqueous resin solutions [3] having the compounding compositions shown in Table 2 were prepared and further white A white paste [3] was prepared with the same mixing ratio as the pastes [1] and [2]. Next, white aqueous paints having the composition shown in Table 3 were prepared in the same manner as in Examples 1 to 6.
【００２６】[0026]
【表２】 [Table 2]
【００２７】注 １）住友バイエルウレタン(株)製、ブ
ロック化イソシアネート、商品名、固形分７５重量％、
ＮＣＯ含有率１１.２重量％、数平均分子量８７０Note 1) Sumitomo Bayer Urethane Co., Ltd., blocked isocyanate, trade name, solid content 75% by weight,
NCO content 11.2% by weight, number average molecular weight 870
【００２８】[0028]
【表３】 [Table 3]
【００２９】[0029]
【表４】 [Table 4]
【００３０】試験例１ リン酸亜鉛処理を施した厚さ０.８mmのダル鋼板に、カ
チオン電着塗料［アクアＮｏ.４２００、日本油脂(株)
製、商品名］を乾燥膜厚２０μｍとなるように電着塗装
し、１７５℃で２５分間焼付けしたのち、実施例１〜６
及び比較例１〜５で調製した白色水系塗料を脱イオン水
で希釈してフォードカップ＃４による秒数を２０℃で３
０秒に粘度調整した希釈塗料を、温度２５℃、湿度７５
％の条件でエアロベル（デビルビス社製、商品名）にて
乾燥塗膜厚が３５μｍになるように塗装して、２５℃で
１０分間セッティングし、１６０℃で３０分間焼付け
た。この塗膜の上に上塗り塗料［メラミＮｏ.２００
０、日本油脂(株)製、商品名］を同様にエアロベルを用
いて乾燥塗膜厚が３５μｍとなるように塗装し、１４０
℃で３０分間焼付けした。なお、水性塗料も、上塗り塗
料も、水平部は水平塗装／水平セット／水平焼付け、垂
直部は垂直塗装／垂直セット／垂直焼付けにて行った。
このようにして得られた塗膜の耐チッピング性、外観品
質、光沢、硬度、付着性、耐湿性を求めた。その結果を
第４表に示す。Test Example 1 A 0.8 mm thick dull steel plate treated with zinc phosphate was coated with a cationic electrodeposition coating [Aqua No. 4200, NOF Corporation].
Manufactured, trade name] to a dry film thickness of 20 μm, and baked for 25 minutes at 175 ° C.
And the white water-based paints prepared in Comparative Examples 1 to 5 were diluted with deionized water, and the number of seconds by Ford cup # 4 was 3 at 20 ° C.
Diluted paint with viscosity adjusted to 0 seconds, temperature 25 ℃, humidity 75
% Was applied by Aerobell (trade name, manufactured by Devilbiss Co., Ltd.) so that the dry coating film thickness would be 35 μm, set at 25 ° C. for 10 minutes, and baked at 160 ° C. for 30 minutes. On top of this coating, top coat paint [Merami No. 200
0, Nippon Oil & Fats Co., Ltd. product name] was similarly coated using an aerobell so that the dry coating film thickness would be 35 μm.
It was baked at 30 ° C. for 30 minutes. Both the water-based paint and the top-coat paint were subjected to horizontal coating / horizontal setting / horizontal baking for the horizontal part and vertical coating / vertical setting / vertical baking for the vertical part.
The chipping resistance, appearance quality, gloss, hardness, adhesion and moisture resistance of the coating film thus obtained were determined. The results are shown in Table 4.
【００３１】[0031]
【表５】 [Table 5]
【００３２】[0032]
【表６】 [Table 6]
【００３３】第４表から明らかなように実施例１〜６の
水系塗料は、比較例１〜４の水系塗料と比較して光沢、
硬度、付着性、耐湿性を損なうことなく、耐チッピング
性が剥離面積、素地傷到達率とも大幅に改善され、かつ
外観品質も向上していることが分かる。これに対し、水
溶性エチレン尿素系樹脂／水溶性ポリエステル樹脂重量
比が３／１００未満の比較例１は耐チッピング性、塗膜
外観に劣り、該重量比が３０／１００を超える比較例２
は耐チッピング性（剥離面積）に劣る。また、水溶性エ
チレン尿素系樹脂を使用しない比較例３及び４はそれぞ
れ耐チッピング性、塗膜外観に劣る。さらに、硬化剤と
してブロック化イソシアネート化合物を用いた比較例５
は耐チッピング性は向上しているものの塗膜外観に劣
る。As is apparent from Table 4, the water-based paints of Examples 1 to 6 have a gloss higher than that of the water-based paints of Comparative Examples 1 to 4,
It can be seen that the chipping resistance is greatly improved in both the peeled area and the base damage arrival rate, and the appearance quality is also improved without deteriorating the hardness, adhesion and moisture resistance. In contrast, Comparative Example 1 in which the weight ratio of water-soluble ethylene urea resin / water-soluble polyester resin was less than 3/100 was inferior in chipping resistance and coating film appearance, and Comparative Example 2 in which the weight ratio exceeded 30/100.
Is inferior in chipping resistance (peeling area). Further, Comparative Examples 3 and 4 in which the water-soluble ethylene urea resin is not used are inferior in chipping resistance and coating film appearance, respectively. Furthermore, Comparative Example 5 using a blocked isocyanate compound as a curing agent
Has improved chipping resistance but is inferior in the appearance of the coating film.
【００３４】[0034]
【発明の効果】本発明の水系塗料組成物は、補助架橋剤
として水溶性エチレン尿素系樹脂を用いることにより、
塗料固形分及び耐溶剤性などが向上するとともに、架橋
塗膜は破断エネルギー及び塗膜強度が向上し、かつリニ
ヤーな架橋により脆くなることがない。このため、硬化
塗膜は上塗り塗料中の溶剤により侵されることがなく、
良好な外観品質、光沢、硬度、付着性、耐湿性を有する
上、耐チッピング性に優れている。本発明の水系塗料組
成物は、例えば自動車用中塗り塗料などとして好適に用
いられる。The water-based coating composition of the present invention contains a water-soluble ethylene urea resin as an auxiliary cross-linking agent.
The solid content of coating material and solvent resistance are improved, the breaking energy and the strength of the coating film are improved, and the crosslinked coating film does not become brittle due to linear crosslinking. Therefore, the cured coating film is not attacked by the solvent in the top coating,
It has good appearance quality, gloss, hardness, adhesion, and moisture resistance, as well as excellent chipping resistance. The water-based coating composition of the present invention is suitably used as, for example, an intermediate coating for automobiles.
Claims (4)
アミノプラスト樹脂を主成分とする熱硬化性水系塗料組
成物において、補助架橋剤として（Ｃ）水溶性エチレン
尿素系樹脂を、該（Ａ）成分１００重量部に対し３〜３
０重量部の割合で含有させたことを特徴とする水系塗料
組成物。1. A water-soluble polyester resin (A) and (B)
In a thermosetting water-based coating composition containing an aminoplast resin as a main component, (C) a water-soluble ethylene urea-based resin as an auxiliary crosslinking agent is added in an amount of 3 to 3 with respect to 100 parts by weight of the (A) component.
A water-based coating composition, characterized in that it is contained in an amount of 0 part by weight.
一般式 【化１】 （式中のＲは炭素数８〜２０のアルキル基又はアルケニ
ル基である）で表される酸無水物から形成される単位５
〜５０重量％を含有する、酸価２５〜１００KOHmg／
ｇ、水酸基価５０〜２００KOHmg／ｇ及び数平均分子量
５００〜５,０００の水溶性ポリエステル樹脂である請
求項１記載の水系塗料組成物。2. A water-soluble polyester resin as component (A),
General formula: A unit 5 formed from an acid anhydride represented by (R in the formula is an alkyl group or an alkenyl group having 8 to 20 carbon atoms).
Acid value 25-100 KOHmg /
The water-based coating composition according to claim 1, which is a water-soluble polyester resin having g, a hydroxyl value of 50 to 200 KOHmg / g, and a number average molecular weight of 500 to 5,000.
シメチル、エトキシメチル、プロポキシメチル及びブト
キシメチルの中から選ばれた少なくとも１種のアルコキ
シメチル基で変性されたアルコキシメチルメラミン樹脂
である請求項１又は２記載の水系塗料組成物。3. The component (B) aminoplast resin is an alkoxymethylmelamine resin modified with at least one alkoxymethyl group selected from methoxymethyl, ethoxymethyl, propoxymethyl and butoxymethyl. The water-based coating composition according to 1 or 2.
が、一般式 【化２】 ［式中のＸ及びＹはそれぞれ水素原子又は−(ＣＨ2)n−
ＯＨであるが、少なくとも一方は−(ＣＨ2)n−ＯＨ（ｎ
は１〜３の整数）である］で表されるものである請求項
１、２又は３記載の水系塗料組成物。4. The water-soluble ethylene urea-based resin as the component (C) has the general formula: [X and Y in the formula are each a hydrogen atom or a - (CH 2) n -
Is a OH, at least one of - (CH 2) n -OH ( n
Is an integer of 1 to 3]]. The water-based coating composition according to claim 1, 2 or 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27477791A JPH0586324A (en) | 1991-09-26 | 1991-09-26 | Water-base coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27477791A JPH0586324A (en) | 1991-09-26 | 1991-09-26 | Water-base coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0586324A true JPH0586324A (en) | 1993-04-06 |
Family
ID=17546421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27477791A Pending JPH0586324A (en) | 1991-09-26 | 1991-09-26 | Water-base coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0586324A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008144064A (en) * | 2006-12-12 | 2008-06-26 | Nippon Paint Co Ltd | Waterborne intermediate coating composition for automobiles |
-
1991
- 1991-09-26 JP JP27477791A patent/JPH0586324A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008144064A (en) * | 2006-12-12 | 2008-06-26 | Nippon Paint Co Ltd | Waterborne intermediate coating composition for automobiles |
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