JP2001342438A - Aqueous colored thermosetting type base coating material and method for forming coated film by using the same - Google Patents
Aqueous colored thermosetting type base coating material and method for forming coated film by using the sameInfo
- Publication number
- JP2001342438A JP2001342438A JP2001075555A JP2001075555A JP2001342438A JP 2001342438 A JP2001342438 A JP 2001342438A JP 2001075555 A JP2001075555 A JP 2001075555A JP 2001075555 A JP2001075555 A JP 2001075555A JP 2001342438 A JP2001342438 A JP 2001342438A
- Authority
- JP
- Japan
- Prior art keywords
- polymerizable unsaturated
- unsaturated monomer
- water
- anionic
- acrylate
- 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
- 238000000576 coating method Methods 0.000 title claims abstract description 68
- 239000011248 coating agent Substances 0.000 title claims abstract description 65
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 title claims abstract description 13
- 239000010419 fine particle Substances 0.000 claims abstract description 71
- 229920006317 cationic polymer Polymers 0.000 claims abstract description 36
- 125000000129 anionic group Chemical group 0.000 claims abstract description 24
- 239000011342 resin composition Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 239000003973 paint Substances 0.000 claims description 40
- 229920006318 anionic polymer Polymers 0.000 claims description 33
- 239000003995 emulsifying agent Substances 0.000 claims description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 19
- 239000004908 Emulsion polymer Substances 0.000 claims description 16
- 239000012874 anionic emulsifier Substances 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 125000002091 cationic group Chemical group 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 238000004040 coloring Methods 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000007665 sagging Methods 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 78
- -1 alkylamine acetate Chemical class 0.000 description 40
- 239000000839 emulsion Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 20
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- 238000006243 chemical reaction Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 239000008199 coating composition Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
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- 239000012972 dimethylethanolamine Substances 0.000 description 5
- 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 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000012875 nonionic emulsifier Substances 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004640 Melamine resin Substances 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229920003180 amino resin Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009503 electrostatic coating Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- 238000010992 reflux Methods 0.000 description 3
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
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- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 2
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- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 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
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 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
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229940100515 sorbitan Drugs 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 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
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent 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
- Application Of Or Painting With Fluid Materials (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、自動車外板等の保
護、美粧に有用な水性着色ベース熱硬化型塗料、及びそ
れを使用した塗膜形成方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous coloring-based thermosetting paint which is useful for protection of exterior panels of automobiles and cosmetics, and a method for forming a coating film using the same.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
上塗り塗膜、特に自動車外板用上塗り塗膜において、着
色ベース熱硬化型塗料（例えば、メタリックベースコー
ト塗料）を塗布し、続いて未硬化のままでクリヤートッ
プコートを塗装し同時に加熱硬化させる、いわゆる２コ
ート１ベーク方式が主流を占めている。現在、これらに
使用されているメタリックベース塗料として、アクリル
もしくはポリエステルをメラミンで硬化させる有機溶剤
系塗料が多く使用されており、このために塗装、及び焼
き付け時に多量の有機溶剤を発生するために環境汚染や
安全性の点から問題があり、有機溶剤含有量の少ない水
性ベース塗料の開発が強く望まれている。2. Description of the Related Art
In a top coat, particularly a top coat for an automobile outer panel, a so-called colored base thermosetting paint (for example, a metallic base coat paint) is applied, and then a clear top coat is applied while being left uncured and simultaneously heated and cured. The two-coat one-bake system is dominant. At present, as a metallic base paint used for these, an organic solvent-based paint that cures acrylic or polyester with melamine is often used. For this reason, a large amount of organic solvent is generated at the time of painting and baking. There is a problem from the viewpoint of contamination and safety, and there is a strong demand for the development of an aqueous base paint having a low organic solvent content.
【０００３】水性着色ベース熱硬化型塗料として、例え
ば特公平３−１４８６９号公報等には重合体微粒子を水
性着色ベース熱硬化型塗料中に含有させることによっ
て、メタリック粉末のフリップフロップ効果を最大限に
発揮させ、仕上り外観がメタリック感に優れ、かつクリ
ヤー塗膜の表面光沢が高い塗膜を形成する組成物が提案
されている。しかしながら、該組成物は塗装条件、特に
湿度の変化によりタレ、ムラ等の塗膜欠陥が生じやすい
という欠陥があった。[0003] As an aqueous colored base thermosetting coating, for example, Japanese Patent Publication No. 14869/1991 discloses a method of maximizing the flip-flop effect of a metallic powder by incorporating polymer fine particles into the aqueous colored base thermosetting coating. A composition which forms a coating film having an excellent metallic appearance and a clear coating film with high surface gloss. However, the composition has a defect that coating defects such as sagging and unevenness are likely to occur due to changes in coating conditions, particularly humidity.
【０００４】その問題を改良するために、塗料にチキソ
トロピー性を付与するために多くの提案がなされてい
る。従来のチキソトロピー剤としては有機ベントナイ
ト、シリカなどがある。しかしながら、これらを用いる
と特に低湿度の条件下において仕上がり塗膜の光沢が低
下するという欠点を有していた。In order to improve the problem, many proposals have been made to impart thixotropic properties to paints. Conventional thixotropic agents include organic bentonite and silica. However, when these are used, there is a disadvantage that the gloss of the finished coating film is reduced particularly under low humidity conditions.
【０００５】[0005]
【課題を解決するための手段】本発明者らは上記した問
題点を解決するために鋭意研究を重ねた結果、２コート
１ベークに使用されているアニオン型の水性着色ベース
熱硬化型塗料中に、カチオン性重合体微粒子を含有する
ことによって問題点を解決できることを見出し、本発明
を完成するに至った。即ち、本発明は、 １．アニオン型水性熱硬化型樹脂組成物（Ｉ）、及びカ
チオン性重合体微粒子（Ａ）を含んでなる水性着色ベー
ス熱硬化型塗料、 ２．カチオン性重合体微粒子（Ａ）が、水及びカチオン
性乳化剤（ａ）の存在下で、重合性不飽和単量体を用い
て乳化重合して得られるものである１項に記載の水性着
色ベース熱硬化型塗料、 ３．カチオン性重合体微粒子（Ａ）が、水及び乳化剤の
存在下で、アミノ基含有重合性不飽和単量体（ｂ）を含
む重合性不飽和単量体を用いて乳化重合して得られるも
のである１項に記載の水性着色ベース熱硬化型塗料、 ４． アニオン型水性熱硬化型樹脂組成物（Ｉ）が、ア
ニオン性重合体微粒子（Ｂ）、架橋剤（Ｃ）を含有し、
該アニオン性重合体微粒子（Ｂ）が、水及びアニオン性
乳化剤の存在下で、重合性不飽和単量体を用いて多段階
で乳化重合してなる乳化重合体であって、且つ多段のう
ち最後の段階の乳化重合で、長鎖アルキル基含有重合性
不飽和単量体（ｃ）、ヒドロキシル基含有重合性不飽和
単量体（ｄ）、及びカルボキシル基含有重合性不飽和単
量体（ｅ）を共重合成分として含む乳化重合体である１
項ないし３項のいずれか１項に記載の水性着色ベース熱
硬化型塗料、 ５． アニオン型水性熱硬化型樹脂組成物（Ｉ）が、ア
ニオン性重合体微粒子（Ｂ）、架橋剤（Ｃ）を含有し、
該アニオン性重合体微粒子（Ｂ）が、水及びアニオン性
乳化剤の存在下で、重合性不飽和単量体を用いて多段階
で乳化重合して製造される乳化重合体であって、且つ多
段のうち最後の段階の乳化重合で、環状飽和炭化水素基
を有する重合性不飽和単量体（ｆ）、ヒドロキシル基含
有重合性不飽和単量体（ｇ）、及びカルボキシル基含有
重合性不飽和単量体（ｈ）を共重合成分として含む乳化
重合体である１項ないし３項のいずれか１項に記載の水
性着色ベース熱硬化型塗料、 ６． さらに水溶性樹脂（Ｄ）を含む１項ないし５項の
いずれか１項に記載の水性着色ベース熱硬化型塗料、 ７． 被塗装物に１項ないし６項のいずれか１項に記載
の水性着色ベース熱硬化型塗料を塗装し、続いてクリア
ー熱硬化型塗料を塗装した後、これらの塗膜を加熱する
ことにより両塗膜を硬化させる塗膜形成方法、に関す
る。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that an anionic aqueous coloring base thermosetting coating material used for two coats and one bake is used. In addition, they have found that the problems can be solved by containing cationic polymer fine particles, and have completed the present invention. That is, the present invention provides: 1. An aqueous colored base thermosetting paint comprising an anionic aqueous thermosetting resin composition (I) and cationic polymer fine particles (A); 2. The aqueous colored base according to item 1, wherein the cationic polymer fine particles (A) are obtained by emulsion polymerization using a polymerizable unsaturated monomer in the presence of water and the cationic emulsifier (a). 2. thermosetting paint; A cationic polymer fine particle (A) obtained by emulsion polymerization using a polymerizable unsaturated monomer containing an amino group-containing polymerizable unsaturated monomer (b) in the presence of water and an emulsifier. 3. The aqueous coloring-based thermosetting paint according to item 1, which is An anionic aqueous thermosetting resin composition (I) containing anionic polymer fine particles (B) and a crosslinking agent (C),
The anionic polymer fine particles (B) are emulsion polymers obtained by performing emulsion polymerization in multiple stages using a polymerizable unsaturated monomer in the presence of water and an anionic emulsifier; In the last stage of the emulsion polymerization, a polymerizable unsaturated monomer containing a long-chain alkyl group (c), a polymerizable unsaturated monomer containing a hydroxyl group (d), and a polymerizable unsaturated monomer containing a carboxyl group ( 1) which is an emulsion polymer containing e) as a copolymer component
Item 4. The water-based colored thermosetting paint according to any one of items 3 to 3, An anionic aqueous thermosetting resin composition (I) containing anionic polymer fine particles (B) and a crosslinking agent (C),
An emulsion polymer produced by subjecting the anionic polymer fine particles (B) to emulsion polymerization in a multi-stage process using a polymerizable unsaturated monomer in the presence of water and an anionic emulsifier; In the last stage of the emulsion polymerization, a polymerizable unsaturated monomer having a cyclic saturated hydrocarbon group (f), a hydroxyl group-containing polymerizable unsaturated monomer (g), and a carboxyl group-containing polymerizable unsaturated 5. The aqueous colored base thermosetting paint according to any one of items 1 to 3, which is an emulsion polymer containing a monomer (h) as a copolymer component. 6. The aqueous coloring-based thermosetting paint according to any one of items 1 to 5, further comprising a water-soluble resin (D). The object to be coated is coated with the water-based coloring thermosetting paint according to any one of Items 1 to 6, followed by applying a clear thermosetting paint, and then heating these coatings to form a coating. A method for forming a coating film for curing the coating film.
【０００６】[0006]
【発明の実施の形態】本発明の水性着色ベース熱硬化型
塗料は、アニオン型水性熱硬化型樹脂組成物（Ｉ）とカ
チオン性重合体微粒子（Ａ）を含んでなるものである。BEST MODE FOR CARRYING OUT THE INVENTION The aqueous colored base thermosetting coating material of the present invention comprises an anionic aqueous thermosetting resin composition (I) and cationic polymer fine particles (A).
【０００７】カチオン性重合体微粒子（Ａ） まず、カチオン性重合体微粒子（Ａ）について説明す
る。本発明においてカチオン性重合体微粒子は、アニオ
ン型水性熱硬化型樹脂に含まれるアニオン性基、例えば
カルボキシル基に作用して、塗料の粘度を上昇せしめ、
特にメタリック塗装塗膜における仕上り外観を向上させ
るために配合されるものである。[0007] Cationic polymer particles (A) will be described first cationic polymer fine particles (A). In the present invention, the cationic polymer fine particles act on the anionic group contained in the anionic aqueous thermosetting resin, for example, a carboxyl group, to increase the viscosity of the paint,
In particular, it is blended to improve the finished appearance of the metallic coating film.
【０００８】上記カチオン性重合体微粒子（Ａ）は、
水、及び乳化剤の存在下で重合性不飽和単量体を乳化重
合して得られる乳化重合体が好適に使用でき、後述の架
橋剤（Ｃ）と架橋させるため、また仕上り外観、及び粒
子の安定性向上のために水酸基を有するものが好まし
い。カチオン性重合体微粒子（Ａ）の水酸基価としては
１〜２００ｍｇＫＯＨ／ｇ、好ましくは５〜１５０ｍｇ
ＫＯＨ／ｇ、好ましくは５〜１００ｍｇＫＯＨ／ｇの範
囲が好適である。水酸基価が１ｍｇＫＯＨ／ｇ未満で
は、架橋が不充分であり、必要とする耐久性が得られな
い。また、塗装作業性に十分な効果が見られず良好な仕
上がり外観が得られないこともあり、一方、２００ｍｇ
ＫＯＨ／ｇを越えるとカチオン性重合体微粒子（Ａ）の
安定性が悪くなり、また、得られた塗膜の仕上り性が悪
くなるので好ましくない。[0008] The cationic polymer fine particles (A) are
An emulsion polymer obtained by emulsion-polymerizing a polymerizable unsaturated monomer in the presence of water and an emulsifier can be suitably used, and is used for crosslinking with a crosslinking agent (C) described below, and also for the finished appearance and particle size. Those having a hydroxyl group are preferred for improving stability. The hydroxyl value of the cationic polymer fine particles (A) is from 1 to 200 mgKOH / g, preferably from 5 to 150 mgKOH / g.
KOH / g, preferably in the range of 5-100 mg KOH / g, is suitable. If the hydroxyl value is less than 1 mgKOH / g, the crosslinking is insufficient and the required durability cannot be obtained. In addition, there is a case where a satisfactory effect on the coating workability is not obtained and a good finished appearance is not obtained.
If it exceeds KOH / g, the stability of the cationic polymer fine particles (A) deteriorates, and the finish of the obtained coating film deteriorates.
【０００９】本発明においてカチオン性重合体微粒子
（Ａ）として、水及びカチオン性乳化剤（ａ）の存在下
で、重合性不飽和単量体を用いて乳化重合してなる乳化
重合体（カチオン性重合体微粒子（Ａ１）とする）が特
に好適に使用できる。In the present invention, as the cationic polymer fine particles (A), an emulsion polymer (cationic emulsion) obtained by emulsion polymerization using a polymerizable unsaturated monomer in the presence of water and the cationic emulsifier (a). Polymer fine particles (A1)) can be particularly preferably used.
【００１０】上記、カチオン性乳化剤（ａ）としては、
例えば、アルキルアミン酢酸塩、アルキルアミンナトリ
ウム塩、アルキルアミンクロライド、アルキルアミンブ
ロマイド等が挙げられる。また、これらの化合物と不飽
和基を一分子中に有するカチオン性反応性乳化剤も使用
することができる。The above-mentioned cationic emulsifier (a) includes:
For example, alkylamine acetate, alkylamine sodium salt, alkylamine chloride, alkylamine bromide and the like can be mentioned. In addition, a cationic reactive emulsifier having these compounds and an unsaturated group in one molecule can also be used.
【００１１】該カチオン性反応性乳化剤としては、例え
ば下記式As the cationic reactive emulsifier, for example, the following formula
【００１２】[0012]
【化１】 Embedded image
【００１３】（式中、Ｒ１は置換基を有してもよい炭素
数８〜２２の炭化水素基を、Ｒ２およびＲ３は炭素数１
〜３のアルキル基を、Ｒ４は水素原子またはメチル基を
示し、Ｘ(-)は１価の陰イオンを示す。）で表わされる
ものが挙げられる。本発明においては、メタリック塗膜
の仕上り性が良好なことから、特に上記式で表されるカ
チオン性反応性乳化剤のなかでもアルキルアミン酢酸塩
の反応性乳化剤が好適に使用できる。また、本発明にお
いては、カチオン性重合体微粒子（Ａ１）の水中での安
定性を向上させるために、カチオン性乳化剤の他にノニ
オン性乳化剤、両性イオン性乳化剤などの乳化剤を適宜
選択して併用してもよい。(Wherein, R 1 represents a hydrocarbon group having 8 to 22 carbon atoms which may have a substituent, and R 2 and R 3 represent a hydrocarbon group having 1 carbon atom.
And R 4 represents a hydrogen atom or a methyl group, and X (-) represents a monovalent anion. )). In the present invention, a reactive emulsifier of an alkylamine acetate can be suitably used especially among the cationic reactive emulsifiers represented by the above formulas because the finish of the metallic coating film is good. In the present invention, in order to improve the stability of the cationic polymer fine particles (A1) in water, an emulsifier such as a nonionic emulsifier and a zwitterionic emulsifier is appropriately selected in addition to the cationic emulsifier and used in combination. May be.
【００１４】上記ノニオン性乳化剤としては、例えば、
ポリオキシエチレンオレイルエーテル、ポリオキシエチ
レンステアリルエーテル、ポリオキシエチレンラウリル
エーテル、ポリオキシエチレントリデシルエーテル、ポ
リオキシエチレンフェニルエーテル、ポリオキシエチレ
ンノニルフェニルエーテル、ポリオキシエチレンオクチ
ルフェニルエーテル、ポリオキシエチレンモノラウレー
ト、ポリオキシエチレンモノステアレート、ポリオキシ
エチレンモノオレエート、ソルビタンモノラウレート、
ソルビタンモノステアレート、ソルビタンモノステアレ
ート、ソルビタントリオレート、ポリオキシエチレンソ
ルビタンモノラウレート等が挙げられる。As the nonionic emulsifier, for example,
Polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene monolau Rate, polyoxyethylene monostearate, polyoxyethylene monooleate, sorbitan monolaurate,
Sorbitan monostearate, sorbitan monostearate, sorbitan triolate, polyoxyethylene sorbitan monolaurate and the like can be mentioned.
【００１５】両性イオン性乳化剤としては、ジメチルア
ルキルベダイン類、ジメチルアルキルラウリルベダイン
類、アルキルグリシン類等が挙げられる。Examples of the zwitterionic emulsifier include dimethylalkylbedines, dimethylalkyllaurylbedines, alkylglycines and the like.
【００１６】カチオン性乳化剤（ａ）とノニオン性乳化
剤及び／または両性イオン性乳化剤の濃度としては、そ
れらの固形分の合計量がカチオン性重合体微粒子（Ａ
１）の固形分に対して、０．１〜１０重量％、好ましく
は１〜５重量％の範囲がよい。As for the concentration of the cationic emulsifier (a) and the nonionic emulsifier and / or zwitterionic emulsifier, the total amount of the solid content thereof is the cationic polymer fine particle (A).
The range of 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the solid content of 1) is good.
【００１７】重合性不飽和単量体としては、メチル（メ
タ）アクリレート、エチル（メタ）アクリレート、プロ
ピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリ
レート、イソブチル（メタ）アクリレート、ペンチル
（メタ）アクリレート、ヘキシル（メタ）アクリレー
ト、２−エチルヘキシル（メタ）アクリレート、シクロ
ヘキシル（メタ）アクリレート、ラウリル（メタ）アク
リレートなどのアクリル酸またはメタクリル酸の炭素数
１〜２４のモノアルコール類とのモノエステル類、グリ
シジル（メタ）アクリレート、アクリロニトリル、アク
リルアミド、Ｎ−メチルアクリルアミド、Ｎ−メチロー
ルアクリルアミド、Ｎ−ブトキシメチルアクリルアミ
ド、スチレン、フェニルエチル（メタ）アクリレート、
酢酸ビニル、塩化ビニル、アクリル酸、メタクリル酸、
ヒドロキシエチル（メタ）アクリレート、ヒドロキシプ
ロピル（メタ）アクリレートなどが挙げられる。これら
は単独、もしくは２種以上の適宜選択して使用すること
ができる。As the polymerizable unsaturated monomer, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate Monoesters of acrylic acid or methacrylic acid such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate with monoalcohols having 1 to 24 carbon atoms, glycidyl (Meth) acrylate, acrylonitrile, acrylamide, N-methylacrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, styrene, phenylethyl (meth) acrylate,
Vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid,
Examples include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate. These can be used alone or in combination of two or more.
【００１８】本発明では、カチオン性重合体微粒子（Ａ
１）に１分子中に少なくとも２個の重合性不飽和結合を
有する多ビニル化合物を重合し、粒子内を架橋させても
よい。該多ビニル化合物としては具体的にはアリル（メ
タ）アクリレ−ト、エチレングリコ−ルジ（メタ）アク
リレ−ト、トリエチレングリコ−ルジ（メタ）アクリレ
−ト、テトラエチレングリコ−ルジ（メタ）アクリレ−
ト、１，３−ブチレングリコ−ルジ（メタ）アクリレ−
ト、トリメチロ−ルプロパントリ（メタ）アクリレ−
ト、１，４−ブタンジオ−ルジ（メタ）アクリレ−ト、
ネオペンチルグリコ−ルジ（メタ）アクリレ−ト、１，
６−ヘキサンジオ−ルジ（メタ）アクリレ−ト、ペンタ
エリスリト−ルジ（メタ）アクリレ−ト、ペンタエリス
リト−ルテトラ（メタ）アクリレ−ト、グリセロ−ルジ
（メタ）アクリレ−ト、１，１，１−トリスヒドロキシ
メチルエタンジ（メタ）アクリレ−ト、１，１，１−ト
リスヒドロキシメチルエタントリ（メタ）アクリレ−
ト、１，１，１−トリスヒドロキシメチルプロパントリ
（メタ）アクリレ−ト、トリアリルイソシアヌレ−ト、
ジアリルテレフタレ−ト、ジビニルベンゼンなどが挙げ
られる。In the present invention, the cationic polymer fine particles (A
In 1), a polyvinyl compound having at least two polymerizable unsaturated bonds in one molecule may be polymerized to crosslink particles. Specific examples of the polyvinyl compound include allyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. −
G, 1,3-butyleneglycol di (meth) acrylate
G, trimethylolpropane tri (meth) acryle
1,4-butanediol- (meth) acrylate,
Neopentyl glycol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol di (meth) acrylate, 1,1,1 1-trishydroxymethylethanedi (meth) acrylate, 1,1,1-trishydroxymethylethanetri (meth) acrylate
1,1,1-trishydroxymethylpropane tri (meth) acrylate, triallyl isocyanurate,
Diallyl terephthalate, divinylbenzene and the like.
【００１９】また、カチオン性重合体微粒子（Ａ）とし
ては、水及び乳化剤の存在下で、アミノ基含有重合性不
飽和単量体（ｂ）を含む重合性不飽和単量体を用いて乳
化重合してなる乳化重合体（カチオン性重合体微粒子
（Ａ２）とする）も好適に使用できる。アミノ基含有重
合性不飽和単量体（ｂ）としては例えば、Ｎ，Ｎ−ジメ
チルアミノエチル（メタ）アクリレート、Ｎ−ｔ−ブチ
ルアミノエチル（メタ）アクリレート等があげられる。
また、カチオン性重合体微粒子（Ａ１）の説明で列記し
た重合性不飽和単量体、及び多ビニル化合物を必要に応
じて適宜選択し、併用して共重合してもよい。The cationic polymer fine particles (A) are emulsified by using a polymerizable unsaturated monomer containing an amino group-containing polymerizable unsaturated monomer (b) in the presence of water and an emulsifier. An emulsion polymer obtained by polymerization (hereinafter referred to as cationic polymer fine particles (A2)) can also be suitably used. Examples of the amino group-containing polymerizable unsaturated monomer (b) include N, N-dimethylaminoethyl (meth) acrylate, Nt-butylaminoethyl (meth) acrylate, and the like.
Further, the polymerizable unsaturated monomers and the polyvinyl compounds listed in the description of the cationic polymer fine particles (A1) may be appropriately selected as needed, and may be copolymerized in combination.
【００２０】カチオン性重合体微粒子（Ａ２）におい
て、使用可能な乳化剤としては、カチオン性乳化剤、ノ
ニオン性乳化剤、両性イオン性乳化剤が挙げられる。ア
ニオン性乳化剤も使用できるが、重合安定性を保持する
ためにはアルキル硫酸ナトリウム系の乳化剤の使用が好
ましい。In the cationic polymer fine particles (A2), usable emulsifiers include a cationic emulsifier, a nonionic emulsifier and a zwitterionic emulsifier. Although an anionic emulsifier can be used, it is preferable to use a sodium alkyl sulfate emulsifier in order to maintain polymerization stability.
【００２１】アニオン型水性熱硬化型樹脂組成物（Ｉ） 本発明で使用されるアニオン型水性熱硬化型樹脂組成物
（Ｉ）は、従来から公知の水性着色ベース塗料組成物に
使用される、アニオン性基を有する樹脂であれば特に制
限なく使用できる。特に本発明においては、アニオン型
水性熱硬化型樹脂組成物（Ｉ）がアニオン性重合体微粒
子（Ｂ）、架橋剤（Ｃ）を含む組成物が好適である。 Anionic water-based thermosetting resin composition (I) The anionic water-based thermosetting resin composition (I) used in the present invention can be used in a conventionally known water-based colored base coating composition. Any resin may be used as long as it has an anionic group. In particular, in the present invention, a composition in which the anionic aqueous thermosetting resin composition (I) contains the anionic polymer fine particles (B) and the crosslinking agent (C) is preferable.
【００２２】上記アニオン性重合体微粒子（Ｂ）は、
水、及びアニオン性乳化剤の存在下で重合性不飽和単量
体を乳化重合して得られる乳化重合体が好適に使用で
き、水酸基価が１〜１００ｍｇＫＯＨ／ｇ、好ましくは
１０〜８０ｍｇＫＯＨ／ｇ、酸価が１〜１００ｍｇＫＯ
Ｈ／ｇ、好ましくは１０〜８０ｍｇＫＯＨ／ｇの範囲が
好適である。水酸基価が１ｍｇＫＯＨ／ｇ未満ではエマ
ルション安定性が悪くなり、また、架橋性が不十分とな
るので必要とする耐久性がえられない。一方、１００ｍ
ｇＫＯＨ／ｇを超えると塗膜耐水性が悪くなるので好ま
しくない。また、酸価が１ｍｇＫＯＨ／ｇ未満では、中
和後の微粒子に適度な粘度上昇が得られず充分な仕上が
り感、特にメタリック感が得られず、一方１００ｍｇＫ
ＯＨ／ｇを超えると中和後の粘度の上昇が顕著となり得
られた塗料粘度があがりすぎて塗装作業性が困難となり
好ましくない。The anionic polymer fine particles (B) are
An emulsion polymer obtained by emulsion polymerization of a polymerizable unsaturated monomer in the presence of water and an anionic emulsifier can be suitably used, and has a hydroxyl value of 1 to 100 mgKOH / g, preferably 10 to 80 mgKOH / g, Acid value is 1-100mgKO
H / g, preferably in the range of 10-80 mg KOH / g. If the hydroxyl value is less than 1 mgKOH / g, the emulsion stability will be poor and the crosslinkability will be insufficient, so that the required durability cannot be obtained. On the other hand, 100m
If it exceeds gKOH / g, the water resistance of the coating film deteriorates, which is not preferable. If the acid value is less than 1 mgKOH / g, the fine particles after neutralization cannot have an appropriate increase in viscosity and cannot have a sufficient finished feeling, especially a metallic feeling.
If it exceeds OH / g, the increase in viscosity after neutralization becomes remarkable, and the viscosity of the obtained paint becomes too high, which makes the coating workability difficult, which is not preferable.
【００２３】該アニオン性乳化剤としては、アルキルス
ルホン酸、アルキルベンゼンスルホン酸、アルキルリン
酸などのナトリウム塩やアンモニウム塩が挙げられる。
またこれらアニオン性基とポリオキシエチレン、あるい
はポリオキシプロピレン鎖等のノニオン性基を１分子中
に有するノニオン性アニオン性乳化剤やこれらアニオン
性基と重合性不飽和基を１分子中に有する反応性アニオ
ン性乳化剤を使用してもよい。また、必要に応じて上記
カチオン性重合体微粒子（Ａ）の説明で列記したノニオ
ン性乳化剤を適宜選択して併用してもよい。Examples of the anionic emulsifier include sodium salts and ammonium salts of alkylsulfonic acid, alkylbenzenesulfonic acid, alkylphosphoric acid and the like.
Also, a nonionic anionic emulsifier having a nonionic group such as a polyoxyethylene or polyoxypropylene chain in one molecule and a nonionic anionic emulsifier having a polymerizable unsaturated group in one molecule. An anionic emulsifier may be used. If necessary, the nonionic emulsifiers listed in the description of the cationic polymer fine particles (A) may be appropriately selected and used in combination.
【００２４】アニオン性重合体微粒子（Ｂ）における上
記乳化剤の濃度としてはそれらの固形分の合計量が、ア
ニオン性重合体微粒子（Ｂ）の固形分に対して、０．１
〜１０重量％、好ましくは０．５〜５重量％の範囲がよ
い。The concentration of the above emulsifier in the anionic polymer fine particles (B) is such that the total amount of the solids is 0.1% with respect to the solids of the anionic polymer fine particles (B).
The range is from 10 to 10% by weight, preferably from 0.5 to 5% by weight.
【００２５】本発明においては、アニオン性重合体微粒
子（Ｂ）が、水及びアニオン性乳化剤の存在下で、重合
性不飽和単量体を用いて多段階で乳化重合してなる乳化
重合体であって、且つ多段のうち最後の段階の乳化重合
で、長鎖アルキル基含有重合性不飽和単量体（ｃ）、ヒ
ドロキシル基含有重合性不飽和単量体（ｄ）、及びカル
ボキシル基含有重合性不飽和単量体（ｅ）を共重合成分
として含む乳化重合体（アニオン性重合体微粒子（Ｂ
１）とする）が好適に使用できる。In the present invention, an anionic polymer fine particle (B) is an emulsion polymer obtained by emulsion polymerization in a multi-stage process using a polymerizable unsaturated monomer in the presence of water and an anionic emulsifier. And in the last stage of the multi-stage emulsion polymerization, a long-chain alkyl group-containing polymerizable unsaturated monomer (c), a hydroxyl group-containing polymerizable unsaturated monomer (d), and a carboxyl group-containing polymerization Emulsion polymer containing an unsaturated monomer (e) as a copolymer component (anionic polymer fine particles (B
1)) can be preferably used.
【００２６】また、本発明においては、アニオン性重合
体微粒子（Ｂ）が、水及びアニオン性乳化剤の存在下
で、重合性不飽和単量体を用いて多段階で乳化重合して
なる乳化重合体であって、且つ多段のうち最後の段階の
乳化重合で、環状飽和炭化水素基を有する重合性不飽和
単量体（ｆ）、ヒドロキシル基含有重合性不飽和単量体
（ｇ）、及びカルボキシル基含有重合性不飽和単量体
（ｈ）を共重合成分として含む乳化重合体（アニオン性
重合体微粒子（Ｂ２）とする）も同様に好適に使用でき
る。In the present invention, the emulsified polymer obtained by subjecting the anionic polymer fine particles (B) to emulsion polymerization in a multi-stage process using a polymerizable unsaturated monomer in the presence of water and an anionic emulsifier. A polymerizable unsaturated monomer having a cyclic saturated hydrocarbon group (f), a hydroxyl group-containing polymerizable unsaturated monomer (g), and Emulsion polymers (hereinafter referred to as anionic polymer fine particles (B2)) containing a carboxyl group-containing polymerizable unsaturated monomer (h) as a copolymerization component can also be suitably used.
【００２７】上記アニオン性重合体微粒子（Ｂ１）、及
び（Ｂ２）は、まず内層成分を形成する単量体混合物
を、アニオン性乳化剤の存在下で重合開始剤を使用して
第１段階の乳化重合を行い共重合体水分散液を得た後、
該水分散液中に、外層成分を形成する単量体混合物を重
合開始剤を使用して第２段階以降の乳化重合を行い、複
層構造粒子水分散液として得られるものである。第２段
階以降の乳化重合時には、通常、乳化剤を添加しない
か、あるいは添加したとしても新しい粒子を形成しない
程度の量とすることが望ましい。The above-mentioned anionic polymer fine particles (B1) and (B2) are prepared by first emulsifying a monomer mixture forming an inner layer component by using a polymerization initiator in the presence of an anionic emulsifier. After performing polymerization to obtain a copolymer aqueous dispersion,
In the aqueous dispersion, a monomer mixture forming an outer layer component is subjected to emulsion polymerization in the second and subsequent steps using a polymerization initiator to obtain an aqueous dispersion of particles having a multilayer structure. In the emulsion polymerization of the second and subsequent steps, it is usually desirable that the emulsifier is not added, or even if it is added, the amount is such that new particles are not formed.
【００２８】アニオン性重合体微粒子（Ｂ１）、及び
（Ｂ２）における第１段目の反応に用いる重合性不飽和
単量体としては、メチル（メタ）アクリレート、エチル
（メタ）アクリレート、プロピル（メタ）アクリレー
ト、ｎ−ブチル（メタ）アクリレート、イソブチル（メ
タ）アクリレート、ペンチル（メタ）アクリレート、ヘ
キシル（メタ）アクリレート、２−エチルヘキシル（メ
タ）アクリレート、シクロヘキシル（メタ）アクリレー
ト、ラウリル（メタ）アクリレートなどのアクリル酸ま
たはメタクリル酸の炭素数１〜２４のモノアルコール類
とのモノエステル類、グリシジル（メタ）アクリレー
ト、アクリロニトリル、アクリルアミド、Ｎ−メチルア
クリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−ブ
トキシメチルアクリルアミド、スチレン、フェニルエチ
ル（メタ）アクリレート、酢酸ビニル、塩化ビニル、ア
クリル酸、メタクリル酸、ヒドロキシエチル（メタ）ア
クリレート、ヒドロキシプロピル（メタ）アクリレート
などが挙げられる。これらは単独、もしくは２種以上の
組み合わせで使用することができる。The polymerizable unsaturated monomers used in the first-stage reaction in the anionic polymer fine particles (B1) and (B2) include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. A) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, etc. Monoesters of acrylic acid or methacrylic acid with monoalcohols having 1 to 24 carbon atoms, glycidyl (meth) acrylate, acrylonitrile, acrylamide, N-methylacrylamide, N-methylolacrylamide, N-butoxymethylacrylia De, styrene, phenyl ethyl (meth) acrylate, vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate. These can be used alone or in combination of two or more.
【００２９】本発明では、重合安定性を向上させるた
め、及び高湿度条件下における塗膜の仕上り性を確保す
るために、該アニオン性重合体微粒子（Ｂ１）、及び
（Ｂ２）の内層成分に１分子中に少なくとも２個の重合
性不飽和結合を有する多ビニル化合物を重合し、粒子の
内層を架橋することが好適である。１分子中に少なくと
も２個の重合性不飽和結合を有する多ビニル化合物の具
体例としては、カチオン性重合体微粒子（Ａ）の項で列
記したものが挙げられ、これらの中から適宜選択して使
用できる。In the present invention, in order to improve the polymerization stability and to ensure the finish of the coating film under high humidity conditions, the anionic polymer fine particles (B1) and (B2) have an inner layer component. It is preferable to polymerize a polyvinyl compound having at least two polymerizable unsaturated bonds in one molecule to crosslink the inner layer of the particles. Specific examples of the polyvinyl compound having at least two polymerizable unsaturated bonds in one molecule include those listed in the section of the cationic polymer fine particles (A). Can be used.
【００３０】アニオン性重合体微粒子（Ｂ１）におい
て、最外層成分を形成する重合性不飽和単量体は、長鎖
アルキル基含有重合性不飽和単量体（ｃ）、ヒドロキシ
ル基含有重合性不飽和単量体（ｄ）、及びカルボキシル
基含有重合性不飽和単量体（ｅ）を含む。In the anionic polymer fine particles (B1), the polymerizable unsaturated monomer forming the outermost layer component includes a long-chain alkyl group-containing polymerizable unsaturated monomer (c) and a hydroxyl group-containing polymerizable unsaturated monomer. It contains a saturated monomer (d) and a carboxyl group-containing polymerizable unsaturated monomer (e).
【００３１】長鎖アルキル基含有不飽和単量体（ｃ）と
しては、分子中に平均1個の重合性不飽和基と分子末端
にＣ８以上、好ましくはＣ１８以上の長鎖アルキル基を
含有するエチレン性不飽和単量体が使用でき、具体的に
は２−エチルヘキシル（メタ）アクリレート、ラウリル
（メタ）アクリレート、ステアリル（メタ）アクリレー
ト、イソステアリル（メタ）アクリレート等が使用でき
る。また、以下の化学式（１）、（２）に示すようなポ
リオキシアルキレン基を含有する長鎖アルキル基含有重
合性不飽和単量体も使用できる。[0031] The long-chain alkyl group-containing unsaturated monomer (c), the average one polymerizable unsaturated group and the molecular ends to C 8 or more in the molecule, preferably C 18 or higher long-chain alkyl group The contained ethylenically unsaturated monomer can be used, and specifically, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate and the like can be used. Further, a polymerizable unsaturated monomer having a long chain alkyl group containing a polyoxyalkylene group as shown in the following chemical formulas (1) and (2) can also be used.
【００３２】[0032]
【化２】 Embedded image
【００３３】（ｎは１〜１０の整数）本発明において
は、得られる塗膜の平滑性が特に良好なことから長鎖ア
ルキル基含有不飽和単量体（ｃ）として、ステアリルア
クリレート、ステアリルメタクリレートが好適に使用で
きる。(N is an integer of 1 to 10) In the present invention, stearyl acrylate and stearyl methacrylate are used as unsaturated monomers (c) having a long-chain alkyl group since the resulting coating film has particularly good smoothness. Can be preferably used.
【００３４】ヒドロキシル基含有重合性不飽和単量体
（ｄ）としては、例えば、２−ヒドロキシエチル（メ
タ）アクリレート、２−ヒドロキシプロピル（メタ）ア
クリレート、２−ヒドロキシエチル（メタ）アクリレー
トか２−ヒドロキシプロピル（メタ）アクリレートをラ
クトンと付加した付加生成物（ダイセル社製、商品名、
プラクセルＦＡ、及びＦＭシリーズ）等が挙げられる。
これらを単独で使用しても良いし、併用しても良い。Examples of the hydroxyl group-containing polymerizable unsaturated monomer (d) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate. Hydroxypropyl (meth) acrylate and an addition product obtained by adding lactone (manufactured by Daicel, trade name,
Praxel FA and FM series).
These may be used alone or in combination.
【００３５】カルボキシル基含有重合性不飽和単量体
（ｅ）としてはアクリル酸、メタクリル酸、クロトン
酸、イタコン酸、マレイン酸、フマル酸、２−カルボキ
シエチル（メタ）アクリレート、２−カルボキシプロピ
ル（メタ）アクリレート、５−カルボキシペンチル（メ
タ）アクリレートなどが挙げられる。これらの中でもメ
タクリル酸を使用すると、粘度発現が顕著であり、高湿
度条件下での仕上り性が良好であるために特に好まし
い。As the carboxyl group-containing polymerizable unsaturated monomer (e), acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl ( (Meth) acrylate, 5-carboxypentyl (meth) acrylate, and the like. Of these, the use of methacrylic acid is particularly preferable because the development of viscosity is remarkable and the finish under high humidity conditions is good.
【００３６】また、その他の重合性不飽和単量体とし
て、例えばメチル（メタ）アクリレート、エチル（メ
タ）アクリレート、プロピル（メタ）アクリレート、ｎ
-ブチル（メタ）アクリレート、イソブチル（メタ）ア
クリレート、ペンチル（メタ）アクリレート、ヘキシル
（メタ）アクリレート、２−エチルヘキシル（メタ）ア
クリレート、シクロヘキシル（メタ）アクリレート、ラ
ウリル（メタ）アクリレートなどのアクリル酸またはメ
タクリル酸の炭素数１〜２４のモノアルコール類とのモ
ノエステル類、アクリロニトリル、アクリルアミド、Ｎ
−メチルアクリルアミド、Ｎ−メチロールアクリルアミ
ド、Ｎ−ブトキシメチルアクリルアミド、スチレン等の
重合性不飽和単量体を必要に応じて適宜選択して併用し
てもよい。As other polymerizable unsaturated monomers, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n
-Acrylic acid or methacrylic acid such as -butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate Monoesters of an acid with a monoalcohol having 1 to 24 carbon atoms, acrylonitrile, acrylamide, N
Polymerizable unsaturated monomers such as -methylacrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, and styrene may be appropriately selected and used as needed.
【００３７】上記、長鎖アルキル基含有重合性不飽和単
量体（ｃ）の含有量は、最外層成分で使用した全重合性
不飽和単量体中に１〜２０重量％、好ましくは５〜１５
重量％含有することが好適である。１重量％未満では、
仕上り性、特に光沢感、平滑性が不十分であり、２０重
量％を超えると、後述のクリヤー熱硬化型塗料による塗
膜との付着性やリコート付着性が不十分となり、好まし
くない。The content of the long-chain alkyl group-containing polymerizable unsaturated monomer (c) is 1 to 20% by weight, preferably 5 to 20% by weight, based on the total polymerizable unsaturated monomer used in the outermost layer component. ~ 15
It is preferred that the content is contained by weight. If it is less than 1% by weight,
Finishing properties, particularly glossiness and smoothness, are insufficient, and if it exceeds 20% by weight, the adhesion to a coating film and the recoating adhesion of a clear thermosetting paint described below become insufficient, which is not preferable.
【００３８】アニオン性重合体微粒子（Ｂ２）において
最外層成分を形成する重合性不飽和単量体は、環状飽和
炭化水素基を有する重合性不飽和単量体（ｆ）、ヒドロ
キシル基含有重合性不飽和単量体（ｇ）、及びカルボキ
シル基含有重合性不飽和単量体（ｈ）を含む。該環状飽
和炭化水素基を有する重合性不飽和単量体（ｆ）として
は、イソボルニル（メタ）アクリレート、アダマンチル
（メタ）アクリレートなどが挙げられる。ヒドロキシル
基含有重合性不飽和単量体（ｇ）は、ヒドロキシル基含
有重合性不飽和単量体（ｄ）で例示した中から適宜選択
して使用できる。カルボキシル基含有重合性不飽和単量
体（ｈ）はカルボキシル基含有重合性不飽和単量体
（ｅ）で例示したなかから適宜選択して使用できるが、
特にメタクリル酸を使用すると、粘度発現が顕著であ
り、高湿度条件下での仕上り性が良好であるために好ま
しい。The polymerizable unsaturated monomer forming the outermost layer component in the anionic polymer fine particles (B2) includes a polymerizable unsaturated monomer having a cyclic saturated hydrocarbon group (f) and a hydroxyl group-containing polymerizable polymer. It contains an unsaturated monomer (g) and a carboxyl group-containing polymerizable unsaturated monomer (h). Examples of the polymerizable unsaturated monomer (f) having a cyclic saturated hydrocarbon group include isobornyl (meth) acrylate and adamantyl (meth) acrylate. The hydroxyl group-containing polymerizable unsaturated monomer (g) can be appropriately selected and used from those exemplified for the hydroxyl group-containing polymerizable unsaturated monomer (d). The carboxyl group-containing polymerizable unsaturated monomer (h) can be appropriately selected and used from those exemplified for the carboxyl group-containing polymerizable unsaturated monomer (e).
In particular, the use of methacrylic acid is preferable because the viscosity is remarkable and the finish under high humidity conditions is good.
【００３９】また、その他の重合性不飽和単量体とし
て、例えばメチル（メタ）アクリレート、エチル（メ
タ）アクリレート、プロピル（メタ）アクリレート、ｎ
−ブチル（メタ）アクリレート、イソブチル（メタ）ア
クリレート、ペンチル（メタ）アクリレート、ヘキシル
（メタ）アクリレート、２−エチルヘキシル（メタ）ア
クリレート、シクロヘキシル（メタ）アクリレート、ラ
ウリル（メタ）アクリレートなどのアクリル酸またはメ
タクリル酸の炭素数１〜２４のモノアルコール類とのモ
ノエステル類、アクリロニトリル、アクリルアミド、Ｎ
−メチルアクリルアミド、Ｎ−メチロールアクリルアミ
ド、Ｎ−ブトキシメチルアクリルアミド、スチレン等の
重合性不飽和単量体を必要に応じて適宜選択して併用し
てもよい。As other polymerizable unsaturated monomers, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n
Acrylic acid or methacrylic acid such as -butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate; Monoesters of an acid with a monoalcohol having 1 to 24 carbon atoms, acrylonitrile, acrylamide, N
Polymerizable unsaturated monomers such as -methylacrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, and styrene may be appropriately selected and used as needed.
【００４０】環状飽和炭化水素基を有する重合性不飽和
単量体（ｆ）の含有量は、最外層成分で使用した全重合
性不飽和単量体中に１〜６０重量％、好ましくは１０〜
４０重量％含有することが好適である。１重量％未満で
は、塗膜の仕上り性、特に光沢感、平滑性が不十分であ
り、一方、６０重量％を超えると、適度な粘度の発現が
得られず十分な仕上り感、特にメタリック感が得られず
好ましくない。The content of the polymerizable unsaturated monomer (f) having a cyclic saturated hydrocarbon group is 1 to 60% by weight, preferably 10 to 10% by weight, based on the total polymerizable unsaturated monomer used as the outermost layer component. ~
It is preferred to contain 40% by weight. When the amount is less than 1% by weight, the finish of the coating film, particularly glossiness and smoothness, are insufficient. On the other hand, when the amount is more than 60% by weight, a sufficient viscosity cannot be obtained and a sufficient finish, particularly a metallic feeling, is not obtained. Is not preferred.
【００４１】上記アニオン性重合体微粒子（Ｂ１）、及
び（Ｂ２）において最外層成分以外の内層成分と最外層
成分の固形分重量比は、合成のし易さ、及び得られた塗
膜の仕上がり外観の点から、例えば２段階の重合の場
合、１段階目の成分と２段階目の成分の総合計量１００
重量％に対し、１段階目の成分が９９〜２０重量％、好
ましくは９０〜５０重量％、２段階目の成分が１〜８０
重量％、好ましくは１０〜５０重量％の範囲が好まし
い。In the above-mentioned anionic polymer fine particles (B1) and (B2), the solid content ratio of the inner layer component other than the outermost layer component to the outermost layer component is determined by the ease of synthesis and the finish of the obtained coating film. From the viewpoint of appearance, for example, in the case of two-stage polymerization, the total weight of the first-stage components and the second-stage components is 100.
99% to 20% by weight, preferably 90% to 50% by weight of the first stage component and 1% to 80%
% By weight, preferably in the range from 10 to 50% by weight.
【００４２】上記アニオン性重合体微粒子（Ｂ１）、及
び（Ｂ２）は水及びアニオン性乳化剤の存在で重合開始
剤の存在下で重合性不飽和単量体を乳化重合してなるも
のであるが、該重合開始剤の種類としては、過硫酸アン
モニウム、４、４'−アゾビス（４−シアノブタン酸）
などが挙げられ、開始剤濃度としては内層成分重合時に
は、内層成分に使用される全重合性不飽和単量体に対し
て０．０１〜１０重量％、好ましくは０．１〜５重量％
の範囲がよい。最外層重合時には、最外層成分に使用さ
れる全重合性不飽和単量体に対して０．０１〜５重量
％、好ましくは０．０１〜１．０重量％が好ましい。The above-mentioned anionic polymer fine particles (B1) and (B2) are obtained by emulsion-polymerizing a polymerizable unsaturated monomer in the presence of water and an anionic emulsifier in the presence of a polymerization initiator. As the type of the polymerization initiator, ammonium persulfate, 4,4′-azobis (4-cyanobutanoic acid)
And the like, and the initiator concentration is 0.01 to 10% by weight, preferably 0.1 to 5% by weight based on the total amount of the polymerizable unsaturated monomers used in the inner layer component during the polymerization of the inner layer component.
Range is good. At the time of the outermost layer polymerization, the amount is preferably 0.01 to 5% by weight, and more preferably 0.01 to 1.0% by weight, based on the total amount of the polymerizable unsaturated monomers used for the outermost layer component.
【００４３】本発明においては、アニオン性重合体微粒
子（Ｂ１）、及び（Ｂ２）の最外層成分重合時の開始剤
の濃度が０．０１重量％未満では重合率が低下し、一
方、５重量％を超えると分子量が低下し、塗料粘度が低
下して特にメタリック塗膜の仕上り性が不十分となり、
好ましくない。In the present invention, when the concentration of the initiator at the time of polymerization of the outermost layer component of the anionic polymer fine particles (B1) and (B2) is less than 0.01% by weight, the polymerization rate decreases, while 5% by weight. %, The molecular weight decreases, the coating viscosity decreases, and the finish of the metallic coating film in particular becomes insufficient,
Not preferred.
【００４４】架橋剤（Ｃ） 本発明で使用するアニオン型水性熱硬化型樹脂組成物
（Ｉ）に含まれる架橋剤（Ｃ）としては、カチオン性重
合体微粒子（Ａ）及びアニオン性重合体微粒子（Ｂ）に
含まれる水酸基等の活性水素と反応し、架橋構造を形成
するものが好適であり、具体的にはブロックイソシアネ
ート、アミノ樹脂などが使用される。中でもアミノ樹
脂、特に、メラミン樹脂がタレ、ムラのない塗装仕上が
り性及び耐久性に優れた塗膜が形成できることから、こ
のものを用いることが望ましい。 Crosslinking Agent (C) The crosslinking agent (C) contained in the anionic aqueous thermosetting resin composition (I) used in the present invention includes cationic polymer fine particles (A) and anionic polymer fine particles. Those which react with active hydrogen such as a hydroxyl group contained in (B) to form a crosslinked structure are preferable, and specifically, blocked isocyanates, amino resins and the like are used. Among them, an amino resin, particularly a melamine resin, is preferable because it can form a coating film excellent in coating finish and durability without sagging and unevenness.
【００４５】架橋剤（Ｃ）の配合割合は、カチオン性重
合体微粒子（Ａ）、及びアニオン型水性熱硬化型樹脂組
成物（Ｉ）の樹脂固形分の合計１００重量％に対して約
５〜７０重量％、好ましくは１０〜５０重量％の範囲が
望ましい。配合割合が約５重量％未満では塗膜性能が低
下し、一方、配合割合が約７０重量％を越えると塗料貯
蔵安定性、塗膜性能が低下するので好ましくない。The mixing ratio of the crosslinking agent (C) is about 5 to 100% by weight of the total resin solid content of the cationic polymer fine particles (A) and the anionic aqueous thermosetting resin composition (I). A range of 70% by weight, preferably 10 to 50% by weight is desirable. If the compounding ratio is less than about 5% by weight, the coating film performance is reduced. On the other hand, if the compounding ratio exceeds about 70% by weight, the coating storage stability and the coating film performance are undesirably reduced.
【００４６】水溶性樹脂（Ｄ） 本発明で使用するアニオン型水性熱硬化型樹脂組成物
（Ｉ）は、必要に応じて通常水性塗料の塗膜形成成分と
して使用される水溶性樹脂（Ｄ）を含んでいてもよい。
このものとしては、樹脂中に含まれるカルボキシル基等
のアニオン性基を中和して水溶化、または水分散してな
る組成物が挙げられるが、例えば、水溶性アクリル樹
脂、水溶性アルキド系樹脂、水溶性ポリエステル樹脂、
水溶性ポリウレタン樹脂が挙げられる。 Water-Soluble Resin (D) The anionic aqueous thermosetting resin composition (I) used in the present invention may be, if necessary, a water-soluble resin (D) usually used as a film-forming component of an aqueous paint. May be included.
Examples of the resin include a composition obtained by neutralizing an anionic group such as a carboxyl group contained in the resin to make the resin water-soluble or dispersed in water, for example, a water-soluble acrylic resin, a water-soluble alkyd resin , Water-soluble polyester resin,
A water-soluble polyurethane resin is used.
【００４７】上記水溶性樹脂（Ｄ）の配合量は、カチオ
ン性重合体微粒子（Ａ）、及びアニオン性重合体微粒子
（Ｂ）の樹脂固形分の合計に対して１〜９０重量％、好
ましくは５〜６０重量％が好適である。該水溶性樹脂の
配合量が１重量％未満では塗膜の耐チッピング、リコー
ト性が低下するので好ましくなく、一方、９０重量％を
上回ると塗装時にタレを生じやすいので好ましくない。The amount of the water-soluble resin (D) is 1 to 90% by weight, preferably 1 to 90% by weight, based on the total resin solid content of the cationic polymer fine particles (A) and the anionic polymer fine particles (B). 5 to 60% by weight is preferred. If the amount of the water-soluble resin is less than 1% by weight, the chipping resistance and recoating property of the coating film are unfavorably reduced. On the other hand, if the amount is more than 90% by weight, sagging is likely to occur at the time of coating.
【００４８】中和アミン（Ｄ） 上記で得られたアニオン水性熱硬化型樹脂組成物（Ｉ）
に含まれるアニオン性基は中和アミン（Ｄ）によって中
和される。中和アミン（Ｄ）としては、水酸化ナトリウ
ム等のアルカリ性物質；アンモニア水、モノメチルアミ
ン、ジメチルアミン、トリメチルアミン、トリエチルア
ミン、ジイソプロピルアミン、モノエタノールアミン、
ジエタノールアミン、ジメチルエタノールアミン、２−
アミノ−２メチル−１−プロパノール等が挙げられる。
中和方法、順番としては、特に制限がないが、アニオン
性重合体微粒子（Ｂ）を製造してからこれを部分的に中
和を行い、その後これに架橋剤（Ｃ）や水溶性樹脂
（Ｄ）を混合してから再度中和を行う方法が挙げられ
る。 Neutralized amine (D) Anionic aqueous thermosetting resin composition (I) obtained above
Is neutralized by the neutralizing amine (D). As the neutralizing amine (D), alkaline substances such as sodium hydroxide; ammonia water, monomethylamine, dimethylamine, trimethylamine, triethylamine, diisopropylamine, monoethanolamine,
Diethanolamine, dimethylethanolamine, 2-
Amino-2methyl-1-propanol and the like.
The neutralization method and order are not particularly limited, but after the anionic polymer fine particles (B) are produced, they are partially neutralized, and then the crosslinking agent (C) or the water-soluble resin ( D) is mixed and then neutralized again.
【００４９】中和アミン（Ｄ）の中和当量としては、カ
チオン性重合体微粒子（Ａ）、アニオン性重合体微粒子
（Ｂ）、水溶性樹脂（Ｄ）に含まれるカルボキシル基等
のアニオン性基の合計に対し０．３〜１．５当量程度が
好適である。０．３当量未満では仕上がり性が低下し、
１．５当量を越えると塗膜の耐水性が悪くなり好ましく
ない。The neutralization equivalent of the neutralized amine (D) is selected from the following: cationic polymer fine particles (A), anionic polymer fine particles (B), anionic groups such as carboxyl groups contained in the water-soluble resin (D). Is preferably about 0.3 to 1.5 equivalents to the total of If it is less than 0.3 equivalent, the finish is reduced,
If the amount exceeds 1.5 equivalents, the water resistance of the coating film deteriorates, which is not preferable.
【００５０】本発明における水性着色ベース熱硬化型塗
料は、上記で得られたカチオン性重合体微粒子（Ａ）、
及びアニオン型水性熱硬化型樹脂組成物（Ｉ）を含有
し、さらに顔料ペーストを含むものである。The aqueous colored base thermosetting paint of the present invention comprises the cationic polymer fine particles (A) obtained above,
And an anionic aqueous thermosetting resin composition (I), and further contains a pigment paste.
【００５１】本発明で使用する顔料としては、金属フレ
ーク粉末（例えばアルミニウム粉末、青銅粉）、着色マ
イカ粉末、着色剤（例えば二酸化チタン、カーボンブラ
ックなどの無機顔料、フタロシアニンブルー、フタロシ
アニングリーン、キナクリドンなどの有機顔料）が挙げ
られる。これらは必要に応じて適宜選択し使用できる。Examples of the pigment used in the present invention include metal flake powder (eg, aluminum powder and bronze powder), colored mica powder, coloring agents (eg, inorganic pigments such as titanium dioxide and carbon black, phthalocyanine blue, phthalocyanine green, quinacridone, etc.). Organic pigments). These can be appropriately selected and used as needed.
【００５２】本発明組成物においては、さらに必要に応
じて粘度調整剤、消泡剤、紫外線防止剤、表面調整剤、
紫外線吸収剤、酸化防止剤等の塗料用添加物や有機溶剤
を配合してもよい。In the composition of the present invention, if necessary, a viscosity modifier, an antifoaming agent, an ultraviolet ray inhibitor, a surface modifier,
Paint additives such as ultraviolet absorbers and antioxidants and organic solvents may be blended.
【００５３】本発明は、被塗物に本発明の水性着色ベー
ス熱硬化型塗料を塗装し、該塗面上にクリヤー熱硬化型
塗料組成物を塗装した後、両塗膜を加熱により同時に硬
化させてなる塗膜形成方法も提供するものである。According to the present invention, an aqueous colored base thermosetting coating composition of the present invention is applied to an object to be coated, a clear thermosetting coating composition is applied on the coated surface, and both coating films are simultaneously cured by heating. A method for forming a coating film is also provided.
【００５４】被塗物としては、例えば金属又はプラスチ
ックなどの素材に表面処理を施したもの又は未処理のも
の又はこれらの素材にプライマー（電着塗料など）及び
中塗り塗装を施したものが使用できる。塗装方法として
は、エアースプレーガン、エアレススプレーガン、エア
ースプレー方式静電塗装機、エアレススプレー方式静電
塗装機、回転霧化式静電塗装機等を使用することができ
る。As the object to be coated, for example, a material such as metal or plastic which has been subjected to a surface treatment, or an untreated material, or a material obtained by applying a primer (such as an electrodeposition paint) and an intermediate coating to these materials is used. it can. As a coating method, an air spray gun, an airless spray gun, an air spray electrostatic coating machine, an airless spray electrostatic coating machine, a rotary atomizing electrostatic coating machine, or the like can be used.
【００５５】塗膜形成方法としては、水性着色ベース熱
硬化型塗料を、１０〜５０μｍ程度の乾燥塗膜になるよ
うに塗装し、必要に応じてセッティングを行った後、次
いで風乾又は温風乾燥などにより揮発成分が２５重量％
以下程度になるまでに乾燥させ、ついで該塗面上にクリ
ヤー熱硬化型塗料を乾燥膜厚１５〜７０μｍ程度になる
ように塗り重ね、必要に応じてセッティングを行った
後、１２０〜１６０℃程度で１５〜３０分程度加熱して
両塗膜を硬化させる方法が挙げられる。As a method of forming a coating film, a water-based coloring base thermosetting coating material is applied so as to form a dry coating film of about 10 to 50 μm, and, if necessary, setting, and then air drying or hot air drying. 25% by weight volatile components
After drying, the clear thermosetting paint is applied on the coated surface so as to have a dry film thickness of about 15 to 70 μm. After setting as necessary, about 120 to 160 ° C. For about 15 to 30 minutes to cure both coating films.
【００５６】上記で用いられるクリヤー熱硬化型塗料組
成物としては、従来から公知の熱硬化型のクリヤー塗料
組成物が使用でき、具体的には、例えば、アルキド樹
脂、ポリエステル樹脂、アクリル樹脂、シリコン樹脂、
フッ素樹脂、ウレタン樹脂系などの基体樹脂に、アミノ
樹脂、メラミン樹脂、（ブロック）ポリイソシアネート
化合物、ポリカルボン酸、無水酸、反応性シラン化合物
等の硬化剤を、基体樹脂が含有する反応性官能基と適宜
組み合わせてなる塗料組成物が使用できる。As the clear thermosetting coating composition used above, a conventionally known thermosetting clear coating composition can be used. Specifically, for example, alkyd resin, polyester resin, acrylic resin, silicone resin resin,
A reactive resin containing a base resin such as a fluororesin or a urethane resin and a curing agent such as an amino resin, a melamine resin, a (block) polyisocyanate compound, a polycarboxylic acid, an acid anhydride, or a reactive silane compound. A coating composition appropriately combined with a group can be used.
【００５７】また、クリアー熱硬化型塗料としては、環
境問題、省資源の観点からは、有機溶剤の使用量の少な
いハイソリッド型のものが望ましく、更に粉体塗料を用
いることもできる。As the clear thermosetting paint, a high solid type paint which uses a small amount of an organic solvent is desirable from the viewpoint of environmental issues and resource saving, and a powder paint can also be used.
【００５８】[0058]
【実施例】以下、実施例を挙げて詳細に説明する。製造
例及び実施例中の「部」及び「％」は重量基準である。The present invention will be described in detail below with reference to examples. “Parts” and “%” in Production Examples and Examples are based on weight.
【００５９】カチオン性重合体微粒子（Ａ）の製造 製造例１ 温度計、サーモスタット、撹拌器、還流冷却器、及び滴
下装置を備えた反応容器に脱イオン水１３１．１部を仕
込み、窒素気流中で撹拌混合し、９０℃に昇温した。次
いで「ＶＡ−０８６」（注１）の２．４％水溶液１４．２
部を反応容器内に導入し、攪拌して１５分間９０℃で保
持した。その後、下記の組成のモノマー乳化物の１％
分を反応容器内に導入し、２０分間９０℃で保持した。
その後、モノマー乳化物の残りに「ＶＡ−０８６」（注
１）の２．４％水溶液を１４．２部加え、これを５時間
かけて定量ポンプで反応容器内に滴下した。滴下終了
後、２時間熟成を行い、５０℃まで冷却し、「ＫＰ−１
５２Ｋ」（注２）２．５部と脱イオン水８．８部を反応
容器に加えた後１００メッシュのナイロンクロスでろ
過、排出し、平均粒子径０．１μｍ、不揮発分２９．７
重量％、ｐＨ５．１２、水酸基価４８．４ｍｇＫＯＨ／
ｇのカチオン性重合体微粒子（Ａ−１）を得た。Production Example 1 of Cationic Polymer Fine Particles (A) Preparation Example 1 131.1 parts of deionized water was charged into a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, and a dropping device. , And heated to 90 ° C. Next, a "VA-086" (Note 1) 2.4% aqueous solution 14.2
The part was introduced into a reaction vessel, and stirred and maintained at 90 ° C. for 15 minutes. Then, 1% of monomer emulsion of the following composition
Was introduced into the reaction vessel and kept at 90 ° C. for 20 minutes.
Thereafter, 14.2 parts of a 2.4% aqueous solution of "VA-086" (Note 1) was added to the remainder of the monomer emulsion, and this was dropped into the reaction vessel over 5 hours by a metering pump. After completion of the dropwise addition, the mixture was aged for 2 hours, cooled to 50 ° C., and “KP-1
After adding 2.5 parts of "52K" (Note 2) and 8.8 parts of deionized water to the reaction vessel, the mixture was filtered and discharged with a 100-mesh nylon cloth, the average particle diameter was 0.1 μm, and the nonvolatile content was 29.7.
% By weight, pH 5.12, hydroxyl value 48.4 mgKOH /
g of cationic polymer fine particles (A-1) were obtained.
【００６０】 モノマー乳化物 脱イオン水 ４３部 スチレン ４５部 ｎ−ブチルアクリレート ４１部 ヒドロキシルエチルアクリレート １０部 １，６−ヘキサンジオールジアクリレート ４部「 ラテムルＫ−１８０ＡＣ」（注３） ２部「 ＫＰ−１５２Ｋ」（注２） ２．５部 注１）「ＶＡ−０８６」；和光純薬工業株式会社製、商品
名、２，２'−アゾビス｛２−メチル−Ｎ−［−（１−
ヒドロキシブチル）］−プロピルアミド｝ 注２）「ＫＰ−１５２Ｋ」；第１工業製薬社製、商品名、
ポリオキシエチレンオクチルフェニルエーテル、有効成
分８０％ 注３）「ラテムルＫ−１８０ＡＣ」；花王株式会社製、商
品名、アルキルアミン酢酸塩系のカチオン性反応性乳化
剤、有効成分１００％。Monomer emulsion 43 parts of deionized water 45 parts of styrene 41 parts of n-butyl acrylate 10 parts of hydroxylethyl acrylate 4 parts of 1,6-hexanediol diacrylate 4 parts of “Latemul K-180AC” (Note 3) 2 parts of “KP- 152K "(Note 2) 2.5 parts Note 1)" VA-086 "; manufactured by Wako Pure Chemical Industries, Ltd., trade name, 2,2'-azobis @ 2-methyl-N-[-(1- (1-
Hydroxybutyl)]-propylamide｝ Note 2) “KP-152K”;
Polyoxyethylene octyl phenyl ether, active ingredient 80% Note 3) "Latemul K-180AC"; Kao Corporation, trade name, alkylamine acetate-based cationic reactive emulsifier, active ingredient 100%.
【００６１】製造例２ 使用するモノマー乳化物を下記モノマー乳化物とする
以外は製造例１と同様にして、平均粒子径０．１μｍ、
不揮発分２９．９重量％、ｐＨ５．２、水酸基価１９．
３ｍｇＫＯＨ／ｇのカチオン性重合体微粒子（Ａ−２）
を得た。 モノマー乳化物 脱イオン水 ４３部 スチレン ３５部「 ＫＢＭ−５０３」（注４） ２０部 ｎ−ブチルアクリレート ３７部 ヒドロキシルエチルアクリレート ４部 １，６−ヘキサンジオールジアクリレート ４部「 ラテムルＫ−１８０ＡＣ」（注３） ２部「 ＫＰ−１５２Ｋ」（注２） ２．５部 注４）「ＫＢＭ−５０３」；信越シリコーン株式会社製、
商品名、γ−メタクリロイルオキシプロピルトリメトキ
シシラン。Production Example 2 The procedure of Production Example 1 was repeated except that the monomer emulsion used was changed to the following monomer emulsion, and the average particle diameter was 0.1 μm.
29.9% by weight of non-volatile content, pH 5.2, hydroxyl value 19.
3 mg KOH / g cationic polymer fine particles (A-2)
I got Monomer emulsion 43 parts Deionized water 35 parts Styrene 35 parts "KBM-503" (Note 4) 20 parts n-butyl acrylate 37 parts Hydroxyethyl acrylate 4 parts 1,6-hexanediol diacrylate 4 parts "Latemul K-180AC" ( Note 3) 2 parts “KP-152K” (Note 2) 2.5 parts Note 4) “KBM-503”; manufactured by Shin-Etsu Silicone Co., Ltd.
Trade name, γ-methacryloyloxypropyltrimethoxysilane.
【００６２】製造例３ 使用するモノマー乳化物を下記モノマー乳化物とする
以外は製造例１と同様にして、平均粒子径０．１μｍ、
不揮発分２９．５重量％、水酸基価１９．３ｍｇＫＯＨ
／ｇのカチオン性重合体微粒子（Ａ−３）を得た。 モノマー乳化物 脱イオン水 ４３部 スチレン ４５部 ジメチルアミノエチルメタクリレート １０部 ｎ−ブチルアクリレート ３１部 ヒドロキシルエチルアクリレート ４部 １，６−ヘキサンジオールジアクリレート １０部「 ＮＥＷＣＯＬ５６２ＳＮ」（注５） ２部「 ＫＰ−１５２Ｋ」（注２） ２．５部 注５）「Ｎｅｗｃｏｌ５６２ＳＮ」；日本乳化剤社製、商
品名、ポリオキシエチレンアルキルベンゼンスルホン酸
ナトリウム、有効成分６０％。Production Example 3 The same procedure as in Production Example 1 was carried out except that the monomer emulsion used was changed to the following monomer emulsion, and the average particle diameter was 0.1 μm.
Non-volatile content 29.5% by weight, hydroxyl value 19.3mgKOH
/ G of cationic polymer fine particles (A-3). Monomer emulsion Deionized water 43 parts Styrene 45 parts Dimethylaminoethyl methacrylate 10 parts n-butyl acrylate 31 parts Hydroxyethyl acrylate 4 parts 1,6-hexanediol diacrylate 10 parts "NEWCOL562SN" (Note 5) 2 parts "KP- 152K "(Note 2) 2.5 parts Note 5)" Newcol562SN "; trade name, manufactured by Nippon Emulsifier Co., Ltd., sodium polyoxyethylene alkylbenzene sulfonate, active ingredient 60%.
【００６３】アニオン性重合体微粒子（Ｂ−１）の製造 製造例４ 温度計、サーモスタット、撹拌器、還流冷却器、及び滴
下装置を備えた反応容器に脱イオン水１４４．５部、
「Ｎｅｗｃｏｌ ５６２ＳＦ」（注６）１．２部を仕込
み、窒素気流中で撹拌混合し、８０℃に昇温した。次い
で下記のモノマー乳化物のうちの１％と３％過硫酸ア
ンモニウム水溶液５．２部とを反応容器内に導入し１５
分間８０℃で保持した。その後、残りのモノマー乳化物
を3時間かけて定量ポンプで反応器内に滴下し、滴下
終了後1時間、熟成を行った。Production Example 4 of Anionic Polymer Fine Particles (B-1) Production Example 4 144.5 parts of deionized water was placed in a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, and a dropping device.
1.2 parts of “Newcol 562SF” (Note 6) were charged, mixed and stirred in a nitrogen stream, and heated to 80 ° C. Next, 1% of the following monomer emulsion and 5.2 parts of a 3% aqueous ammonium persulfate solution were introduced into the reaction vessel, and
Hold at 80 ° C. for minutes. Thereafter, the remaining monomer emulsion was dropped into the reactor over 3 hours with a metering pump, and aging was performed for 1 hour after the completion of the dropping.
【００６４】その後、下記のモノマー乳化物を２時間
かけて滴下し、０．５時間熟成した後、１．５％ジメチ
ルエタノールアミン水溶液８９部を反応容器に徐々に加
えながら３０℃まで冷却し、１００メッシュのナイロン
クロスでろ過、排出し、平均粒子径０．１μｍ、不揮発
分２５．２％、酸価３０．７ｍｇＫＯＨ／ｇ、水酸基価
２２．１ｍｇＫＯＨ／ｇのアニオン性重合体微粒子（Ｂ
−１）を得た。Thereafter, the following monomer emulsion was added dropwise over 2 hours, and after aging for 0.5 hour, the mixture was cooled to 30 ° C. while gradually adding 89 parts of a 1.5% aqueous dimethylethanolamine solution to the reaction vessel. The mixture was filtered and discharged with a 100-mesh nylon cloth, and anionic polymer fine particles (B having an average particle size of 0.1 μm, a nonvolatile content of 25.2%, an acid value of 30.7 mg KOH / g, and a hydroxyl value of 22.1 mg KOH / g) were used.
-1) was obtained.
【００６５】モノマー乳化物 脱イオン水 ９４．３部 メチルメタクリレート １７部 ｎ−ブチルアクリレート ８０部 アリルメタクリレート ３部「 Ｎｅｗｃｏｌ５６２ＳＦ」（注６） １．２部 モノマー乳化物 脱イオン水 ３９部 メチルメタクリレート １５．４部 ヒドロキシルエチルアクリレート ５．９部 メタクリル酸 ５．１部 ステアリルアクリレート ２．９４部。「 Ｎｅｗｃｏｌ５６２ＳＦ」（注６） ０．５２部 注６）「Ｎｅｗｃｏｌ ５６２ＳＦ」；日本乳化剤株式会
社製、商品名、ポリオキシエチレンアルキルベンゼンス
ルホン酸アンモニウム、有効成分６０％。Monomer emulsion 94.3 parts Deionized water 17 parts Methyl methacrylate 17 parts n-butyl acrylate 80 parts Allyl methacrylate 3 parts "Newcol562SF" (Note 6) 1.2 parts Monomer emulsion Deionized water 39 parts Methyl methacrylate 15. 4 parts Hydroxylethyl acrylate 5.9 parts Methacrylic acid 5.1 parts Stearyl acrylate 2.94 parts. “Newcol 562SF” (Note 6) 0.52 parts Note 6) “Newcol 562SF”; trade name, manufactured by Nippon Emulsifier Co., Ltd., ammonium polyoxyethylene alkylbenzene sulfonate, active ingredient 60%.
【００６６】製造例５ 使用するモノマー乳化物を下記モノマー乳化物とする以
外は製造例４と同様にして、平均粒子径０．１１μｍ、
不揮発分２５．０％、酸価３５．５ｍｇＫＯＨ／ｇ、水
酸基価２２．１ｍｇＫＯＨ／ｇのアニオン性重合体微粒
子（Ｂ−２）を得た。 モノマー乳化物 脱イオン水 ９４．３部 メチルメタクリレート １７部 n−ブチルアクリレート ８０部 アリルメタクリレート ３部「 Ｎｅｗｃｏｌ５６２ＳＦ」（注６） １．２部 モノマー乳化物 脱イオン水 ３９部 メチルメタクリレート ８．８部 ヒドロキシルエチルアクリレート ５．９部 メタクリル酸 ５．９部 イソボルニルアクリレート ８．８部「 Ｎｅｗｃｏｌ５６２ＳＦ」（注６） ０．５２部。Production Example 5 The same procedure as in Production Example 4 was carried out except that the monomer emulsion used was changed to the following monomer emulsion, and the average particle diameter was 0.11 μm.
Anionic polymer fine particles (B-2) having a nonvolatile content of 25.0%, an acid value of 35.5 mgKOH / g and a hydroxyl value of 22.1 mgKOH / g were obtained. Monomer emulsion Deionized water 94.3 parts Methyl methacrylate 17 parts n-butyl acrylate 80 parts Allyl methacrylate 3 parts "Newcol562SF" (Note 6) 1.2 parts Monomer emulsion Deionized water 39 parts Methyl methacrylate 8.8 parts Hydroxyl Ethyl acrylate 5.9 parts Methacrylic acid 5.9 parts Isobornyl acrylate 8.8 parts “Newcol562SF” (Note 6) 0.52 parts.
【００６７】製造例６ 温度計、サーモスタット、撹拌器、還流冷却器、及び滴
下装置を備えた反応容器に、脱イオン水７０部、「Ｎｅ
ｗｃｏｌ７０７ＳＦ」（注７）２．５部を仕込み窒素気
流中で６０℃まで昇温し、３％過硫酸アンモニウム水溶
液３部を反応容器に加えた。次いで、８０℃に温度を上
昇せしめた後、下記のモノマー乳化物を４時間かけて
定量ポンプを用いて反応容器に滴下した。滴下終了後１
時間熟成を行い、温度を８０℃に保持し、さらに、下記
のモノマー乳化物に３％過硫酸アンモニウムを４部加
え、これを１．５時間かけて定量ポンプを用いて反応容
器に滴下した。滴下終了後１時間熟成を行い、３０℃に
冷却し２００メッシュのナイロンクロスでろ過、排出し
た。このものに、脱イオン水とジメチルエタノールアミ
ンでｐＨ、不揮発分を調整し、ｐＨ７．５、平均粒径
０．１μｍ、不揮発分４０％のアニオン性重合体微粒子
（Ｂ−３）を得た。 注７）「Ｎｅｗｃｏｌ７０７ＳＦ」；日本乳化剤社製、
商品名、ポリオキシエチレンアルキルベンゼンスルホン
酸アンモニウム、有効成分３０％ モノマー乳化物 脱イオン水 ４２部 メチルメタクリレート ５５部 スチレン １０部 ｎ−ブチルアクリレート ９部 ２−ヒドロキシエチルアクリレート ５部 １，６−ヘキサンジオールジアクリレート １部「 Ｎｅｗｃｏｌ７０７ＳＦ」（注７） ２．５部 モノマー乳化物 脱イオン水 ３０部 メチルメタクリレート ５部 ｎ−ブチルアクリレート ７部 ２−エチルヘキシルアクリレート ５部 メタクリル酸 ３部 「Ｎｅｗｃｏｌ ７０７ＳＦ」(注７) ０．５部。Production Example 6 In a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, and a dropping device, 70 parts of deionized water, "Ne
2.5 parts of “wcol707SF” (Note 7) were charged, the temperature was raised to 60 ° C. in a nitrogen stream, and 3 parts of a 3% aqueous solution of ammonium persulfate was added to the reaction vessel. Next, after raising the temperature to 80 ° C., the following monomer emulsion was dropped into the reaction vessel over 4 hours using a metering pump. After dripping 1
The mixture was aged for 2 hours, the temperature was maintained at 80 ° C., and 4 parts of 3% ammonium persulfate was added to the following monomer emulsion, and the mixture was added dropwise to the reaction vessel over 1.5 hours using a metering pump. After dropping, the mixture was aged for 1 hour, cooled to 30 ° C., filtered through a 200-mesh nylon cloth, and discharged. The pH and the nonvolatile content were adjusted with deionized water and dimethylethanolamine to obtain anionic polymer fine particles (B-3) having a pH of 7.5, an average particle size of 0.1 μm, and a nonvolatile content of 40%. Note 7) "Newcol707SF"; manufactured by Nippon Emulsifier Co., Ltd.
Trade name, ammonium polyoxyethylene alkylbenzenesulfonate, active ingredient 30%, monomer emulsion Deionized water 42 parts Methyl methacrylate 55 parts Styrene 10 parts n-butyl acrylate 9 parts 2-hydroxyethyl acrylate 5 parts 1,6-hexanediol di Acrylate 1 part “Newcol 707SF” (Note 7) 2.5 parts Monomer emulsion Deionized water 30 parts Methyl methacrylate 5 parts n-butyl acrylate 7 parts 2-ethylhexyl acrylate 5 parts Methacrylic acid 3 parts “Newcol 707SF” (Note 7) 0.5 parts.
【００６８】水溶性樹脂（Ｄ）の製造 製造例７ 反応容器にジエチレングリコールブチルエーテルを３５
部を仕込み、窒素気流中で１１５℃に昇温した。１１５
℃に達した後、下記のモノマー混合物を３時間かけて反
応容器に滴下し、さらに２時間熟成を行った。反応終了
後、ジメチルエタノールアミンで当量中和し、さらにブ
チルセロソルブを２５部加えて酸価４７．ｍｇＫＯＨ／
ｇ、ガードナー粘度Ｚ４、固形分５７％のアクリル系水
溶性樹脂（Ｄ−１）を得た。 モノマー混合物 スチレン ３０部 ｎ−ブチルメタクリレート ３０部 ２−エチルヘキシルアクリレート ２１部 ２−ヒドロキシエチルアクリレート １３部 アクリル酸 ６部 アゾビスイソブチロニトリル １部 ブチルセロソルブ １５部。Production Example 7 of Water-Soluble Resin (D)
And heated to 115 ° C. in a nitrogen stream. 115
After the temperature reached ° C, the following monomer mixture was dropped into the reaction vessel over 3 hours, and aging was performed for 2 hours. After the completion of the reaction, the mixture was neutralized with dimethylethanolamine in an equivalent amount, and 25 parts of butyl cellosolve was added thereto to obtain an acid value of 47. mgKOH /
g, an acrylic water-soluble resin (D-1) having a Gardner viscosity of Z4 and a solid content of 57%. Monomer mixture Styrene 30 parts n-butyl methacrylate 30 parts 2-ethylhexyl acrylate 21 parts 2-hydroxyethyl acrylate 13 parts Acrylic acid 6 parts Azobisisobutyronitrile 1 part Butyl cellosolve 15 parts.
【００６９】アルミニウムペーストの製造 製造例８ アルミニウム顔料ペースト「ＭＧ−５１」（注８）１７部
とブチルセロソルブ２０部を容器に配合し、攪拌混合す
ることによってアルミニウムペーストを得た。 （注８）「ＭＧ−５１」；旭化成株式会社製、商品名、金
属含有量６６．３％。[0069] Aluminum Production Example of a paste 8 aluminum pigment paste "MG-51" (Note 8) was blended 17 parts of butyl cellosolve 20 parts in a container, to obtain an aluminum paste by stirring and mixing. (Note 8) "MG-51"; trade name, metal content 66.3%, manufactured by Asahi Kasei Corporation.
【００７０】実施例１ 容器に「ＳＥＴＡＬ６３０６」(注９)を２５部、「サイメ
ル３２５」（注１０）を３３．３部を仕込みディスパー
で撹拌し、これにアニオン性重合体微粒子（Ｂ−１）を
１６０部加え攪拌し、アニオン型水性熱硬化型樹脂組成
物を得た。ついで、該組成物に製造例１で得たカチオン
性重合体微粒子（Ａ−１）５０部を滴下し、添加したと
ころ、徐々に粘度が上昇した。その後、ジメチルエタノ
ールアミンでｐＨを８．５に調整し、脱イオン水２３
３．４部、ジプロピレングリコール−ｎ−ブチルエーテ
ル５部を加えたのち、アルミニウムペーストを１３．３
部を混合し、水性着色ベース塗料（Ｔ−１）を得た。そ
の時の粘度は、２５℃でＢ型粘度計ＮＯ３ローター回転
速度６ｒｐｍの条件で２２８５ｍＰａ・ｓであった。 注９）「ＳＥＴＡＬ６３０６」；アクゾ社製、商品名、水
溶性ポリエステル樹脂、固形分６０％ 注１０）「サイメル３２５」；三井サイアナミド株式会社
製、商品名、メラミン架橋剤、固形分９０％。Example 1 A container was charged with 25 parts of "SETAL6306" (Note 9) and 33.3 parts of "Symel 325" (Note 10) and stirred with a disper, and the anionic polymer fine particles (B-1) were added thereto. ) Was added and stirred to obtain an anionic aqueous thermosetting resin composition. Then, 50 parts of the cationic polymer fine particles (A-1) obtained in Production Example 1 were added dropwise to the composition, and when added, the viscosity gradually increased. Thereafter, the pH was adjusted to 8.5 with dimethylethanolamine, and the pH was adjusted to 23 with deionized water.
After adding 3.4 parts and 5 parts of dipropylene glycol-n-butyl ether, the aluminum paste was added to 13.3.
Were mixed to obtain an aqueous colored base paint (T-1). The viscosity at that time was 2285 mPa · s at 25 ° C. under the conditions of a B-type viscometer NO3 rotor rotation speed of 6 rpm. Note 9) "SETAL6306"; product name, Akzo Co., Ltd., water-soluble polyester resin, solid content 60% Note 10) "Cymel 325"; product name, Mitsui Cyanamid Co., Ltd., trade name, melamine crosslinking agent, solid content 90%.
【００７１】実施例２ 実施例１において配合する組成を下記表１とする以外は
実施例１と同様の操作を行い、水性着色ベース熱硬化型
塗料（Ｔ−２）〜（Ｔ−９）を得た。尚、表中の数字は
固形分を表す。Example 2 The same operation as in Example 1 was carried out except that the composition to be compounded in Example 1 was as shown in Table 1 below, and the aqueous colored base thermosetting paints (T-2) to (T-9) were prepared. Obtained. The numbers in the table represent solid contents.
【００７２】[0072]
【表１】 [Table 1]
【００７３】塗装 実施例８〜１３、及び比較例４〜７ 冷延ダル鋼板にりん酸亜鉛処理で化成処理した「パルボ
ンド＃３０２０」（日本パーカライジング社製、商品
名）にアミン変性エポキシ樹脂カチオン電着を乾燥膜厚
が２５μｍになるように塗装し、１７０℃で３０分間加
熱硬化させた。そののち「ルーガベークＡＭ」（商品名、
関西ペイント社製、ポリエステル樹脂／メラミン樹脂系
自動車用中塗り塗料）を乾燥膜厚が３０μｍになるよう
に塗装し、１４０℃で３０分間焼き付け、これを被塗物
とした。塗装時のブース環境は、２５℃、相対湿度４０
％の低湿度条件下の場合と２５℃、相対湿度８５％の場
合の高湿度条件下の２通りにて行った。各ブース環境に
て上記被塗物に、上記で得られた各水性着色ベース熱硬
化型塗料（Ｔ−１）〜（Ｔ−９）をエアースプレー塗装
により乾燥膜厚が８〜２０μｍとなるように塗装した。
次に、８０℃、１０分でプレヒートを行い、各塗面上に
続けて「マジクロンＨＫ−４」（関西ペイント社製、商品
名 、アクリルメラミン系有機溶剤型クリヤートップコ
ート用塗料）を乾燥膜厚が３０〜５０μとなるように塗
装した。次いで、各ブース環境下にて１０分間放置して
セッティングを行ったのち、熱風電気乾燥機を用いて１
４０℃、３０分間焼き付けを行い、各塗板を得、下記項
目の評価を行った。 Coating Examples 8 to 13 and Comparative Examples 4 to 7 Palbond # 3020 (trade name, manufactured by Nippon Parkerizing Co., Ltd., trade name) obtained by subjecting a cold-rolled dull steel sheet to a chemical conversion treatment with zinc phosphate was used. The coating was coated so as to have a dry film thickness of 25 μm, and was heated and cured at 170 ° C. for 30 minutes. After that, "Luga Bake AM" (product name,
A polyester resin / melamine resin-based intermediate coating for automobiles manufactured by Kansai Paint Co., Ltd.) was applied to a dry film thickness of 30 μm, and baked at 140 ° C. for 30 minutes to obtain an object to be coated. Booth environment at the time of painting is 25 ℃, relative humidity 40
% And a high humidity condition of 25 ° C. and a relative humidity of 85%. In each booth environment, the above-mentioned aqueous coloring base thermosetting paints (T-1) to (T-9) are applied to the object to be coated by air spray coating so as to have a dry film thickness of 8 to 20 μm. Painted.
Next, preheating was performed at 80 ° C. for 10 minutes, and “Magiclon HK-4” (trade name, manufactured by Kansai Paint Co., trade name, acrylic melamine-based organic solvent type clear top coat paint) was dried on each coated surface. The coating was performed so that the thickness became 30 to 50 μ. Then, after setting for 10 minutes in each booth environment, 1 hour using a hot air electric dryer.
Baking was performed at 40 ° C. for 30 minutes to obtain each coated plate, and the following items were evaluated.
【００７４】試験方法 タレ抵抗性：各条件での塗装時における塗膜のタレ性を
調べた。〇は異常無し、△は若干認められる、×は著し
く認められる。 メタリック感：各塗板を正面からみたメタルのキラリ
感、及び白さを目視により評価した。〇はキラリ感があ
り白い 、△はキラリ感がなく白さに劣る、×はキラリ
感が及び白さが全くない。 リコート付着性：実施例８〜１３及び比較例４〜７で得
られた塗板にこれと同様の組み合わせの各着色ベ−ス塗
料及びクリヤ−塗料を塗り重ね、１２０℃×３０分間焼
付けて塗膜を得た。得られた塗膜にカッタ−ナイフでク
ロスカットを入れその塗面にセロハンテープを貼着しそ
れを急激に剥し１回目と２回目の塗膜間（クリヤ−塗膜
／ベ−ス塗膜）での付着性を評価した。○全く剥離が認
められない、△わずかに剥離が認められる、×著しい剥
離が認められる。 Test Method Sagging Resistance: The sagging resistance of the coating film at the time of coating under each condition was examined. 〇 is normal, △ is slightly recognized, and X is remarkably recognized. Metallic feeling: The glittering feeling and whiteness of the metal as viewed from the front of each coated plate were visually evaluated. 〇 is crisp and white, △ is no crispness and inferior to white, and × is no crispness and no whiteness. Recoat adhesion: Each of the coated base plates obtained in Examples 8 to 13 and Comparative Examples 4 to 7 was overcoated with each of the same colored base paint and clear paint in the same combination, and baked at 120 ° C. for 30 minutes to form a coating film. I got A cross-cut is made on the obtained coating film with a cutter knife, a cellophane tape is stuck on the coated surface, and the cellophane tape is rapidly peeled off, and between the first and second coating films (clear coating film / base coating film). Was evaluated for adhesion. ○ No peeling was observed at all, △ slight peeling was observed, × marked peeling was observed.
【００７５】[0075]
【表２】 [Table 2]
【００７６】[0076]
【表３】 [Table 3]
【００７７】[0077]
【発明の効果】本発明によれば高湿度条件下で塗装して
もタレず、低湿度条件下で塗装しても塗膜表面に平滑感
のある仕上り性の良好な水性着色ベース塗料が得られ
る。とくにメタリック顔料を使用した場合において、ア
ニオン性の樹脂組成物にカチオン性の重合体微粒子を添
加することにより粘度が発現し、これにより塗膜中での
メタリック顔料の配向が制御され、メタリック感、平滑
性が共に良好な塗膜が得られる。According to the present invention, an aqueous colored base paint having a smooth finish on the surface of the coating film and a good finish can be obtained even when applied under low humidity conditions, even when applied under high humidity conditions. Can be Particularly when a metallic pigment is used, the viscosity is developed by adding cationic polymer fine particles to the anionic resin composition, whereby the orientation of the metallic pigment in the coating film is controlled, and the metallic feeling, A coating film having good smoothness is obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｆ 2/28 Ｃ０８Ｆ 2/28 220/04 220/04 220/18 220/18 220/26 220/26 220/34 220/34 Ｃ０９Ｄ 5/00 Ｃ０９Ｄ 5/00 Ｄ 5/02 5/02 // Ｃ０９Ｄ 161/28 161/28 175/04 175/04 (72)発明者 原川 浩美 神奈川県平塚市東八幡４丁目17番１号 関 西ぺイント株式会社内 Ｆターム(参考） 4D075 AA02 AE06 BB26Z CA48 CB13 DA23 DB02 DC12 EA06 EA19 EA60 4J011 KA04 KA08 KA10 4J038 CC021 CD041 CF021 CG002 CG031 CG141 CG161 CG171 CH031 CH041 CH051 CH061 CH081 CH121 CH171 DA162 DB221 DD002 DD232 DG002 DG191 DG301 FA162 GA03 GA06 GA07 GA09 GA10 GA12 GA16 HA156 JB10 JC14 JC23 KA03 KA09 LA02 MA02 MA08 MA10 NA01 NA24 NA27 PA19 PB07 PC02 4J100 AJ01R AJ02R AJ08R AJ09R AL05P AL08P AL08R AL09Q BA04P BA08P BA16R BA30P BA31P BC08P BC09P CA01 CA05 JA01 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C08F 2/28 C08F 2/28 220/04 220/04 220/18 220/18 220/26 220/26 220 / 34 220/34 C09D 5/00 C09D 5/00 D 5/02 5/02 // C09D 161/28 161/28 175/04 175/04 (72) Inventor Hiromi Harakawa 4-17 Higashiyawata, Hiratsuka City, Kanagawa Prefecture No. 1 Seki Nishiinto Co., Ltd. F-term (reference) 4D075 AA02 AE06 BB26Z CA48 CB13 DA23 DB02 DC12 EA06 EA19 EA60 4J011 KA04 KA08 KA10 4J038 CC021 CD041 CF021 CG002 CG031 CG141 CH1 CH051 CH031 DD232 DG002 DG191 DG301 FA162 GA03 GA06 GA07 GA09 GA10 GA12 GA16 HA156 JB10 JC14 JC23 KA03 KA09 LA02 MA02 MA08 MA10 NA01 NA24 NA27 PA19 PB07 PC02 4J100 AJ01R AJ02R AJ08R AJ09R AL05P AL08P AL08P AL08BA BA31P BC08P BC09P CA01 CA05 JA01
Claims (7)
（Ｉ）、及びカチオン性重合体微粒子（Ａ）を含んでな
る水性着色ベース熱硬化型塗料。An aqueous colored base thermosetting paint comprising an anionic aqueous thermosetting resin composition (I) and cationic polymer fine particles (A).
カチオン性乳化剤（ａ）の存在下で、重合性不飽和単量
体を用いて乳化重合して得られるものである請求項１記
載の水性着色ベース熱硬化型塗料。2. The cationic polymer fine particles (A) are obtained by emulsion polymerization using a polymerizable unsaturated monomer in the presence of water and a cationic emulsifier (a). The water-based colored thermosetting paint according to the above.
乳化剤の存在下で、アミノ基含有重合性不飽和単量体
（ｂ）を含む重合性不飽和単量体を用いて乳化重合して
得られるものである請求項１記載の水性着色ベース熱硬
化型塗料。3. Emulsion polymerization of a cationic polymer fine particle (A) using a polymerizable unsaturated monomer including an amino group-containing polymerizable unsaturated monomer (b) in the presence of water and an emulsifier. The water-based coloring base thermosetting paint according to claim 1, which is obtained by:
（Ｉ）が、アニオン性重合体微粒子（Ｂ）、架橋剤
（Ｃ）を含有し、該アニオン性重合体微粒子（Ｂ）が、
水及びアニオン性乳化剤の存在下で、重合性不飽和単量
体を用いて多段階で乳化重合してなる乳化重合体であっ
て、且つ多段のうち最後の段階の乳化重合で、長鎖アル
キル基含有重合性不飽和単量体（ｃ）、ヒドロキシル基
含有重合性不飽和単量体（ｄ）、及びカルボキシル基含
有重合性不飽和単量体（ｅ）を共重合成分として含む乳
化重合体である請求項１ないし３のいずれか１項に記載
の水性着色ベース熱硬化型塗料。4. The anionic aqueous thermosetting resin composition (I) contains an anionic polymer fine particle (B) and a crosslinking agent (C), and the anionic polymer fine particle (B) comprises:
In the presence of water and an anionic emulsifier, an emulsion polymer obtained by emulsion polymerization using a polymerizable unsaturated monomer in multiple steps, and a long-chain alkyl group in the last emulsion polymerization of the multiple steps. Emulsion polymer containing a group-containing polymerizable unsaturated monomer (c), a hydroxyl group-containing polymerizable unsaturated monomer (d), and a carboxyl group-containing polymerizable unsaturated monomer (e) as a copolymerization component The aqueous coloring-based thermosetting paint according to any one of claims 1 to 3, wherein
（Ｉ）が、アニオン性重合体微粒子（Ｂ）、架橋剤
（Ｃ）を含有し、該アニオン性重合体微粒子（Ｂ）が、
水及びアニオン性乳化剤の存在下で、重合性不飽和単量
体を用いて多段階で乳化重合して製造される乳化重合体
であって、且つ多段のうち最後の段階の乳化重合で、環
状飽和炭化水素基を有する重合性不飽和単量体（ｆ）、
ヒドロキシル基含有重合性不飽和単量体（ｇ）、及びカ
ルボキシル基含有重合性不飽和単量体（ｈ）を共重合成
分として含む乳化重合体である請求項１ないし３のいず
れか１項に記載の水性着色ベース熱硬化型塗料。5. The anionic water-based thermosetting resin composition (I) contains an anionic polymer fine particle (B) and a crosslinking agent (C), and the anionic polymer fine particle (B) comprises:
In the presence of water and an anionic emulsifier, an emulsion polymer produced by emulsion polymerization in multiple stages using a polymerizable unsaturated monomer, and in the emulsion polymerization of the last stage of the multiple stages, cyclic A polymerizable unsaturated monomer (f) having a saturated hydrocarbon group,
The emulsion polymer according to any one of claims 1 to 3, wherein the emulsion polymer contains a hydroxyl group-containing polymerizable unsaturated monomer (g) and a carboxyl group-containing polymerizable unsaturated monomer (h) as a copolymerization component. The water-based colored thermosetting paint according to the above.
ないし５のいずれか１項に記載の水性着色ベース熱硬化
型塗料。6. The method according to claim 1, further comprising a water-soluble resin (D).
6. The water-based coloring base thermosetting coating material according to any one of items 5 to 5.
１項に記載の水性着色ベース熱硬化型塗料を塗装し、続
いてクリアー熱硬化型塗料を塗装した後、これらの塗膜
を加熱することにより両塗膜を硬化させる塗膜形成方
法。7. An object to be coated is coated with the water-based colored thermosetting paint according to any one of claims 1 to 6, followed by a clear thermosetting paint, and then these coatings are applied. A coating film forming method in which both coating films are cured by heating.
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Cited By (5)
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| JP2007297545A (en) * | 2006-05-02 | 2007-11-15 | Mazda Motor Corp | Water-based coating composition, method for forming multilayer coating, and coated products |
| JP2008001888A (en) * | 2006-05-22 | 2008-01-10 | Kansai Paint Co Ltd | Water-based paint composition |
| WO2009145223A1 (en) * | 2008-05-27 | 2009-12-03 | 関西ペイント株式会社 | Water-based coating composition |
| CN101544728B (en) * | 2009-03-23 | 2011-05-25 | 广州励宝精细化工有限公司 | Water paint base and water paint containing same |
| WO2014148350A1 (en) * | 2013-03-21 | 2014-09-25 | 日本エクスラン工業株式会社 | Sorbent coating fluid, sorbent-supporting metal plate obtained by applying sorbent coating fluid, and heat exchanger having sorbent-supporting metal plate |
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