JP2002138253A - Aqueous metal oxide dispersion composition for electrodeposition coating - Google Patents
Aqueous metal oxide dispersion composition for electrodeposition coatingInfo
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- JP2002138253A JP2002138253A JP2001242224A JP2001242224A JP2002138253A JP 2002138253 A JP2002138253 A JP 2002138253A JP 2001242224 A JP2001242224 A JP 2001242224A JP 2001242224 A JP2001242224 A JP 2001242224A JP 2002138253 A JP2002138253 A JP 2002138253A
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- Prior art keywords
- metal oxide
- electrodeposition coating
- aqueous metal
- oxide dispersion
- dispersion composition
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、内外装用建材、家
電、車両、自動車部品等の各種広範囲な用途に利用でき
る金属製品において、金属表面に形成された酸化皮膜の
着色に用いる電着塗装用水性金属酸化物分散体に関す
る。中でもアルミニウム又はアルミニウム合金製品、又
は、マグネシウム又はマグネシウム合金製品において、
上記金属表面に形成された酸化皮膜上に、高透明性でア
ルミニウム又はマグネシウムの表面色を生かした意匠性
の高い着色塗膜を得ることができ、優れた耐候性、耐水
性、付着性等の塗膜性能が実現でき、経時安定性に優れ
た電着塗装用水性金属酸化物分散体に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrodeposition coating for coloring an oxide film formed on a metal surface of a metal product which can be used for a wide variety of applications such as interior / exterior building materials, home appliances, vehicles, and automobile parts. It relates to an aqueous metal oxide dispersion. Among them, aluminum or aluminum alloy products, or magnesium or magnesium alloy products,
On the oxide film formed on the metal surface, it is possible to obtain a highly designed colored coating film utilizing the surface color of aluminum or magnesium with high transparency, and excellent weather resistance, water resistance, adhesion and the like. The present invention relates to an aqueous metal oxide dispersion for electrodeposition coating, which can achieve coating film performance and has excellent stability over time.
【０００２】[0002]
【従来の技術】従来、アルミニウム又はアルミニウム合
金の酸化皮膜上に電着塗膜を形成する技術として、各種
の電着塗装用水性顔料分散体組成物及び電着塗装方法が
提供されている（特開平８−１６５４４６号、特開平１
０−５３８９６号、特開平４−１５４９９９号）。2. Description of the Related Art Conventionally, various aqueous pigment dispersion compositions for electrodeposition coating and electrodeposition coating methods have been provided as a technique for forming an electrodeposition coating film on an oxide film of aluminum or an aluminum alloy (particularly, Japanese Patent Application Laid-Open No. H11-157556). Japanese Unexamined Patent Publication No. Hei 8-165446,
0-53896, JP-A-4-154999).
【０００３】[0003]
【発明が解決しようとする課題】従来公知の金属酸化物
を着色成分等として含む水性分散体は、一般に金属酸化
物の比重が大きい為、沈降し易いという問題がある。ま
た、上記金属酸化物が微粒化された物である従来公知の
微粒子金属酸化物を着色成分等として含む水性分散体
は、金属酸化物をメジウム中に均一に分散させ、その分
散状態を維持することが難しい。よって、上記のような
従来公知の金属酸化物及び微粒子金属顔料を含む水性分
散体は、経時安定性に問題があった。また、上記の様な
水性分散体は、塗料として各種金属の電着塗装に用いる
と、上記金属酸化物の性質に加えて、無機顔料粒子がつ
ぶれ難い等の理由により、透明で均一な塗膜を得ること
が難しい。よって、金属酸化物が持つ発色や紫外線遮蔽
等の機能を、電着塗膜上に十分に発現させることが困難
であり、また、塗膜の付着性や耐候性に問題があった。An aqueous dispersion containing a conventionally known metal oxide as a coloring component or the like generally has a problem that the specific gravity of the metal oxide is large, and therefore the sedimentation is easy. Further, the aqueous dispersion containing a conventionally known fine particle metal oxide as a coloring component or the like, in which the metal oxide is atomized, uniformly disperses the metal oxide in the medium and maintains the dispersed state. It is difficult. Therefore, the aqueous dispersion containing a conventionally known metal oxide and a fine metal pigment as described above has a problem in stability over time. In addition, when the aqueous dispersion as described above is used for electrodeposition coating of various metals as a coating, in addition to the properties of the metal oxide, the inorganic pigment particles are hardly crushed. Difficult to get. Therefore, it is difficult to sufficiently exhibit the functions of the metal oxide, such as coloring and ultraviolet shielding, on the electrodeposition coating film, and there is a problem in the adhesion and weather resistance of the coating film.
【０００４】中でも、上記の様な金属酸化物を着色成分
とし、アルミニウム又はアルミニウム合金、又は、マグ
ネシウム又はマグネシウム合金の酸化皮膜上に、高透明
性でアルミニウム又はマグネシウムの表面を生かした意
匠性の高い着色電着塗膜を形成し、付着性、耐候性等の
優れた塗膜性能を実現する電着塗装用水性分散体組成物
は提供されていない。[0004] Above all, the above metal oxide is used as a coloring component, and a highly transparent aluminum or magnesium surface is utilized on an oxide film of aluminum or an aluminum alloy or magnesium or a magnesium alloy. No aqueous dispersion composition for electrodeposition coating has been provided which forms a colored electrodeposition coating and realizes excellent coating properties such as adhesion and weather resistance.
【０００５】アルミニウム及びアルミニウムを含む合金
は、比較的軽量な金属であり、また、表面に保護皮膜を
形成する為、防錆性、耐食性に優れる。さらに、加工性
に優れ、目的に応じて表面仕上げを施すことにより高い
意匠性を得ることができる。上記の様な観点から、サッ
シ等の建築材料、飲料缶、車両、航空機等に用いられ、
需要が高い。[0005] Aluminum and alloys containing aluminum are relatively lightweight metals, and since they form a protective film on the surface, they are excellent in rust prevention and corrosion resistance. Furthermore, it is excellent in workability, and a high design property can be obtained by performing surface finishing according to the purpose. From the above viewpoints, building materials such as sashes, beverage cans, vehicles, used in aircraft, etc.,
Demand is high.
【０００６】マグネシウム及びマグネシウムを含む合金
は、実用金属としては最も軽量であり、また、耐くぼみ
性等の強度、剛性に優れる。上記の様な観点からホイー
ル、ステアリングカラム、シートフレーム等の自動車用
部品、ノート型パソコンの筐体、携帯電話、カメラ等の
携帯用製品等に広く用いられ、需要が高い。[0006] Magnesium and alloys containing magnesium are the lightest as practical metals and are excellent in strength and rigidity such as dent resistance. From the above viewpoints, it is widely used in automobile parts such as wheels, steering columns, seat frames and the like, notebook computers, portable products such as mobile phones and cameras, and is in high demand.
【０００７】本発明の目的は、経時安定性に優れ、付着
性、耐候性等の塗膜性能に優れた塗膜を各種金属材料及
びその酸化皮膜上に実現することができ、さらに塗膜の
透明性が高い電着塗装用水性分散体を提供するところに
ある。An object of the present invention is to provide a coating film having excellent stability over time and excellent coating performance such as adhesion and weather resistance on various metal materials and oxide films thereof. An object of the present invention is to provide an aqueous dispersion for electrodeposition coating having high transparency.
【０００８】本発明の目的は、中でもアルミニウム又は
アルミニウム合金の酸化皮膜上に、高透明性でアルミニ
ウム表面の美しさを生かした意匠性の高い着色電着塗膜
を得ることができ、付着性、高耐候性等の塗膜性能を電
着塗膜に高いレベルで実現することができる電着塗装用
水性分散体を提供するところにある。An object of the present invention is to obtain a highly transparent colored electrodeposition coating film having high transparency and utilizing the beauty of the aluminum surface, particularly on an oxide film of aluminum or an aluminum alloy. It is an object of the present invention to provide an aqueous dispersion for electrodeposition coating capable of achieving a coating film performance such as high weather resistance at a high level in an electrodeposition coating film.
【０００９】本発明の目的は、中でもマグネシウム又は
マグネシウム合金の酸化皮膜上に、高透明性でマグネシ
ウム表面の美しさを生かした意匠性の高い着色電着塗膜
を得ることができ、付着性、高耐候性等の塗膜性能を電
着塗膜に高いレベルで実現することができる電着塗装用
水性分散体を提供するところにある。It is an object of the present invention to obtain a highly transparent colored electrodeposition coating film having high designability utilizing the beauty of a magnesium surface, particularly on an oxide film of magnesium or a magnesium alloy. It is an object of the present invention to provide an aqueous dispersion for electrodeposition coating capable of achieving a coating film performance such as high weather resistance at a high level in an electrodeposition coating film.
【００１０】[0010]
【課題を解決するための手段】上記目的を達成するため
鋭意検討した結果、電着塗膜の透明有彩色の着色成分を
構成する微粒子金属酸化物を含有する水性金属酸化物分
散体であれば、これを顔料成分として各種金属に電着塗
装すると、高透明性で、優れた付着性、耐候性等の塗膜
性能を有する電着塗膜を得ることができることを見出し
た。Means for Solving the Problems As a result of intensive studies to achieve the above object, an aqueous metal oxide dispersion containing fine metal oxides constituting a transparent chromatic coloring component of an electrodeposition coating film is required. It has also been found that when this is used as a pigment component for electrodeposition coating on various metals, an electrodeposition coating film having high transparency and excellent coating properties such as excellent adhesion and weather resistance can be obtained.
【００１１】さらに本発明者らは、上記の様な水性金属
酸化物分散体であれば、これを顔料成分としてアルミニ
ウム又はアルミニウム合金酸化皮膜に電着塗装すると、
高透明性でアルミニウムの表面を生かした意匠性の高い
着色電着塗膜を形成することができ、またその電着塗膜
は優れた付着性、耐候性等の塗膜性能を実現することが
できることを見出した。Further, the present inventors have proposed that if the aqueous metal oxide dispersion as described above is used as a pigment component by electrodeposition coating on an aluminum or aluminum alloy oxide film,
It is possible to form highly transparent colored electrodeposition coatings utilizing the surface of aluminum with high transparency, and the electrodeposition coatings can realize coating properties such as excellent adhesion and weather resistance. I found what I could do.
【００１２】さらに本発明者らは、上記の様な水性金属
酸化物分散体であれば、これを顔料成分としてマグネシ
ウム又はマグネシウム合金酸化皮膜に電着塗装すると、
高透明性でマグネシウムの表面を生かした意匠性の高い
着色電着塗膜を形成することができ、またその電着塗膜
は優れた付着性、耐候性等の塗膜性能を実現することが
できることを見出した。Further, the present inventors, when the aqueous metal oxide dispersion as described above, is used as a pigment component by electrodeposition coating on a magnesium or magnesium alloy oxide film.
It is possible to form a highly transparent colored electrodeposition coating film utilizing the surface of magnesium with high transparency, and the electrodeposition coating film can realize excellent coating properties such as excellent adhesion and weather resistance. I found what I could do.
【００１３】本発明の水性金属酸化物分散体を公知の電
着塗装方法によって塗装されたアルミニウム製品は、ア
ルミニウムの無垢材としての美しさや、鏡面加工等の表
面処理を施されたアルミニウム表面を生かした意匠性の
高いものであり、さらに塗膜の付着性、耐久性等に優れ
ることから、上述の様な用途に応じて加工され、用いる
ことができる。[0013] The aluminum product coated with the aqueous metal oxide dispersion of the present invention by a known electrodeposition coating method has a beauty as a solid material of aluminum and an aluminum surface subjected to a surface treatment such as mirror finishing. Since it has a high design property that makes good use of it and further has excellent adhesion and durability of the coating film, it can be processed and used according to the above-mentioned applications.
【００１４】本発明の水性金属酸化物分散体を公知の電
着方法によって塗装されたマグネシウム製品は、マグネ
シウムの金属材料として美しさを生かした意匠性の高い
ものであり、さらに塗膜の付着性、耐久性等に優れるこ
とから、上述の様な用途に応じて加工され、用いること
ができる。The magnesium product obtained by coating the aqueous metal oxide dispersion of the present invention by a known electrodeposition method has a high design property utilizing beauty as a magnesium metal material. Since it is excellent in durability and the like, it can be processed and used according to the above-mentioned applications.
【００１５】[0015]
【発明の実施の形態】（微粒子金属酸化物）本発明で使
用する微粒子金属酸化物は、電着塗膜の透明有彩色の着
色成分を構成する微粒子金属酸化物であることが重要で
ある。DETAILED DESCRIPTION OF THE INVENTION (Fine Particle Metal Oxide) It is important that the fine particle metal oxide used in the present invention is a fine particle metal oxide constituting a transparent chromatic coloring component of an electrodeposition coating film.
【００１６】本発明の微粒子金属酸化物としては、例え
ば、コバルト、アルミニウム、アンチモン、クロム、
鉄、亜鉛、コバルト、マグネシウム、銅、チタン等の酸
化物、及びこれらの金属の複合酸化物を用いることがで
きる。Examples of the particulate metal oxide of the present invention include cobalt, aluminum, antimony, chromium,
Oxides such as iron, zinc, cobalt, magnesium, copper, and titanium, and composite oxides of these metals can be used.
【００１７】上記微粒子金属酸化物の平均粒径は、０．
１μｍ以下、好ましくは０．０７μｍ以下が好適であ
る。微粒子金属酸化物は、後述の様な分散剤を用いて公
知の分散機によって分散することにより０．１μｍ以下
で分散されていても良く、あらかじめ０．１μｍ以下に
分散されたものを用いても良い。微粒子金属酸化物の平
均粒径が０．０７μｍを超え、特に０．１μｍを超えた
場合は、電着塗膜の透明性が低下し、また耐候性が低下
する。尚、本発明でいう平均粒径とは遠心沈降法による
光透過測定方式で測定されたものである。The average particle diameter of the above-mentioned fine particle metal oxide is 0.1.
1 μm or less, preferably 0.07 μm or less is suitable. The fine particle metal oxide may be dispersed at 0.1 μm or less by dispersing with a known disperser using a dispersant as described below, or may be used in advance dispersed at 0.1 μm or less. good. When the average particle size of the fine particle metal oxide exceeds 0.07 μm, particularly when it exceeds 0.1 μm, the transparency of the electrodeposition coating film decreases and the weather resistance decreases. Incidentally, the average particle size referred to in the present invention is a value measured by a light transmission measuring method by a centrifugal sedimentation method.
【００１８】特に、上記平均粒子径を満足する微粒子金
属酸化物としては、α−酸化鉄、コバルトブルー、複合
酸化物を例示できる。α−酸化鉄はα−Ｆｅ２Ｏ３、コ
バルトブルーはＣｏＯ・Ａｌ２Ｏ３として示すことが出
来る。複合酸化物としては例えばＦｅ２Ｏ３−ＺｎＯを
好適に用いることができる。これらの化合物は単独で又
は混合して用いることができる。α−酸化鉄の粒子は、
通常、０．２９μの粒子径であるが、分散剤等を用いる
ことにより、例えば、少なくとも０．０７μｍの平均粒
子径とした場合、アルミニウム又はマグネシウム等の表
面色の上に褐色透明の色相を呈する耐候性のある電着塗
膜が得られる。また、コバルトブルーの粒子は、通常、
０．２１μｍの粒子径であるが、分散剤等を用いること
により、例えば少なくとも０．０６μｍ、特に０．０４
μｍの平均粒子径とした場合、アルミニウム又はマグネ
シウム等の表面色の上に青色透明の色相を呈する耐候性
のある電着塗膜が得られる。また、複合酸化物のＦｅ２
Ｏ３−ＺｎＯは、通常、０．３１μの粒子径であるが、
分散剤等を用いることにより、例えば少なくとも０．０
７μｍの平均粒子径とした場合、アルミニウム又はマグ
ネシウムの表面色の上に褐色透明の色相を呈する耐候性
のある電着塗膜が得られる。In particular, examples of the fine particle metal oxide satisfying the above average particle diameter include α-iron oxide, cobalt blue, and composite oxide. α-iron oxide can be expressed as α-Fe 2 O 3 , and cobalt blue can be expressed as CoO · Al 2 O 3 . As the composite oxide can be suitably used, for example, Fe 2 O 3 -ZnO. These compounds can be used alone or as a mixture. α-iron oxide particles,
Usually, it has a particle diameter of 0.29 μm. However, when a dispersant or the like is used, for example, when the average particle diameter is at least 0.07 μm, a brown transparent hue is exhibited on a surface color such as aluminum or magnesium. An electrodeposition coating film having weather resistance is obtained. Also, cobalt blue particles are usually
It has a particle size of 0.21 μm, but by using a dispersant or the like, for example, at least 0.06 μm, particularly 0.04 μm.
When the average particle diameter is set to μm, a weather-resistant electrodeposited film exhibiting a transparent blue hue on a surface color such as aluminum or magnesium is obtained. In addition, the composite oxide Fe 2
O 3 -ZnO usually has a particle size of 0.31 μm,
By using a dispersant or the like, for example, at least 0.0
When the average particle diameter is 7 μm, a weather-resistant electrodeposited coating film having a brown transparent hue on the surface color of aluminum or magnesium is obtained.
【００１９】本発明で用いる微粒子金属酸化物は、水性
金属酸化物分散体全量に対して１〜４０重量％、好まし
くは１〜３０重量％含有していることがよい。上記微粒
子金属酸化物が水性金属酸化物分散体全量に対して１重
量％未満であると、塗膜の着色性及び耐候性が十分でな
い。上記微粒子金属酸化物が水性金属酸化物分散体全量
に対して４０重量％を超えると、保存安定性が低下す
る。また、電着塗料を含む電着液中での上記微粒子金属
酸化物は、格別限定されないが、電着液全量に対して
０．１〜１０重量％含有していることが好ましい。The fine metal oxide used in the present invention is contained in an amount of 1 to 40% by weight, preferably 1 to 30% by weight, based on the total amount of the aqueous metal oxide dispersion. When the content of the fine metal oxide is less than 1% by weight based on the total amount of the aqueous metal oxide dispersion, the coloring property and weather resistance of the coating film are not sufficient. If the amount of the fine metal oxide exceeds 40% by weight based on the total amount of the aqueous metal oxide dispersion, the storage stability is reduced. The fine metal oxide particles in the electrodeposition solution containing the electrodeposition paint are not particularly limited, but preferably contain 0.1 to 10% by weight based on the total amount of the electrodeposition solution.
【００２０】（分散剤）本発明では、前記金属酸化物を
所定の粒子径に微粒子化することが必要である。かかる
点で、金属酸化物を微粒子化し、分散安定化する一手段
として分散剤の選択が重要となる。また、あらかじめ平
均粒径が０．１μｍ以下である微粒子金属化合物を用い
る場合であっても、分散状態を安定化し、付着性、耐候
性等の塗膜性能を発揮させる為には、上記分散剤を用い
ることが好ましい。本発明で用いられる分散剤として
は、カルボキシル基及びスルホン基の少なくともいずれ
かを含むアニオン性化合物の分散剤が好適に用いられ
る。そして、前記アニオン性化合物は、重合体、共重合
体及び界面活性剤の少なくともいずれかの化合物である
ことが望ましい。例えば、アクリル酸、スチレンスルホ
ン酸、マレイン酸、メタクリル酸等を単量体として含む
重合体又は共重合体のアルカリ金属塩またはアンモニウ
ム塩を例示することができる。また、これらの化合物は
単独で又は混合して用いることができる。(Dispersant) In the present invention, the metal oxide needs to be finely divided into a predetermined particle diameter. In this regard, it is important to select a dispersant as one means for making the metal oxide into fine particles and stabilizing the dispersion. Further, even when a fine particle metal compound having an average particle diameter of 0.1 μm or less is used in advance, the above-mentioned dispersing agent is required in order to stabilize the dispersion state and exhibit coating properties such as adhesion and weather resistance. It is preferable to use As the dispersant used in the present invention, a dispersant of an anionic compound containing at least one of a carboxyl group and a sulfone group is suitably used. The anionic compound is preferably a compound of at least one of a polymer, a copolymer and a surfactant. For example, alkali metal salts or ammonium salts of polymers or copolymers containing acrylic acid, styrene sulfonic acid, maleic acid, methacrylic acid and the like as monomers can be exemplified. These compounds can be used alone or as a mixture.
【００２１】このようなアニオン性化合物の分散剤とし
ては、水性金属酸化物分散体の経時安定性、また、塗膜
の耐久性に優れることから、スチレン−アクリル酸共重
合体、スチレン−マレイン酸共重合体を好適に用いるこ
とができる。Examples of such an anionic compound dispersant include a styrene-acrylic acid copolymer and a styrene-maleic acid, since they have excellent stability over time of an aqueous metal oxide dispersion and excellent durability of a coating film. A copolymer can be suitably used.
【００２２】上記分散剤は、固形分として、上記水性金
属酸化物分散体全量に対して０．２〜１６重量％含まれ
ていることが好ましい。上記分散剤の含有量（固形分）
が上記水性金属酸化物分散体全量に対して０．２重量％
未満であると、経時安定性、付着性が低下する。また上
記分散剤の含有量（固形分）が、上記水性金属酸化物分
散体全量に対して１６重量％を超えると、流動性、塗膜
の耐久性が低下する。The dispersant is preferably contained as a solid content in an amount of 0.2 to 16% by weight based on the total amount of the aqueous metal oxide dispersion. Content of the above dispersant (solid content)
Is 0.2% by weight based on the total amount of the aqueous metal oxide dispersion
If it is less than 1, the stability with time and the adhesiveness are reduced. When the content (solid content) of the dispersant exceeds 16% by weight based on the total amount of the aqueous metal oxide dispersion, fluidity and durability of the coating film are reduced.
【００２３】（溶媒）本発明の分散体は、溶媒である水
及び/又は水溶性有機溶剤に分散されていることが好ま
しい。水としては慣用の水を用いることができる。ま
た、水溶性有機溶剤としては、例えば、エチレングリコ
−ル、ジエチレングリコ−ル、トリエチレングリコ−
ル、プロピレングリコ−ル、ポリエチレングリコ−ル等
のグリコ−ル類、グリセリン等の多価アルコール類、エ
チレングリコ−ルモノメチルエ−テル、ジエチレングリ
コ−ルモノメチルエ−テル、ジプロピレングリコ−ルモ
ノメチルエ−テル、ジプロピレングリコ−ルモノプロピ
ルエ−テル等のグリコ−ルエ−テル類を例示できる。こ
れらの溶媒は１種又は２種以上を混合して用いることが
できる。(Solvent) The dispersion of the present invention is preferably dispersed in water as a solvent and / or a water-soluble organic solvent. Conventional water can be used as the water. Examples of the water-soluble organic solvent include, for example, ethylene glycol, diethylene glycol, and triethylene glycol.
Glycols such as propylene glycol and polyethylene glycol; polyhydric alcohols such as glycerin; ethylene glycol monomethyl ether; diethylene glycol monomethyl ether; dipropylene glycol monomethyl ether; dipropylene glycol. And glycol ethers such as mono-propyl ether. These solvents can be used alone or in combination of two or more.
【００２４】本発明の溶媒、中でも水溶性有機溶剤は、
水性金属酸化物分散体全量に対して１〜３０重量％含ま
れていることが望ましい。水溶性有機溶剤が水性金属酸
化物分散体全量に対して１重量％未満の場合、分散体中
の揮発が多く、３０重量％を超えると、分散体の凝集が
発生し易い。また、水は水性金属酸化物分散体全量に対
して５０重量％以上含まれていることが望ましい。The solvent of the present invention, especially the water-soluble organic solvent,
It is desirable that the content is 1 to 30% by weight based on the total amount of the aqueous metal oxide dispersion. When the amount of the water-soluble organic solvent is less than 1% by weight with respect to the total amount of the aqueous metal oxide dispersion, volatilization in the dispersion is large, and when it exceeds 30% by weight, aggregation of the dispersion is likely to occur. Further, it is desirable that water is contained in an amount of 50% by weight or more based on the total amount of the aqueous metal oxide dispersion.
【００２５】（その他の成分）本発明の微粒子金属酸化
物水性分散体は、必要に応じて、ｐＨ調整剤、潤滑剤、
防錆剤、防腐防黴剤、表面調整剤等を添加することがで
きる。(Other components) The aqueous fine particle metal oxide dispersion of the present invention may contain a pH adjuster, a lubricant,
Rust inhibitors, antiseptic / antifungal agents, surface conditioners and the like can be added.
【００２６】（ｐＨ）また本発明の水性金属酸化物分散
体は、前記金属酸化物を微粒化するために、ｐＨを７以
上にして分散させることが重要である。本発明の水性金
属酸化物分散体のｐＨが７未満の酸性側にある場合、陽
極側に電着させる電着塗装用としては好ましくなく、上
記アニオン性化合物分散剤の析出が起こる。(PH) It is important that the aqueous metal oxide dispersion of the present invention is dispersed at a pH of 7 or more in order to atomize the metal oxide. When the pH of the aqueous metal oxide dispersion of the present invention is on the acidic side of less than 7, it is not preferable for electrodeposition coating for electrodeposition on the anode side, and the anionic compound dispersant precipitates.
【００２７】（製造方法）本発明の微粒子金属酸化物水
性分散体は、例えば以下の様な手順で得ることができ
る。まず、プロピレングリコール及び水を混合し、デゾ
ルバで攪拌しつつ、６０℃前後に加熱する。次に、これ
にトリエチルアミンを少量加え、スチレン−アクリル樹
脂を少量加える。次に、スチレン−アクリル樹脂が溶解
したら、再びトリエチルアミンを少量加え、スチレン−
アクリル樹脂を少量加える。この操作をスチレン−アク
リル酸樹脂がなくなるまで繰り返して分散剤溶液を得
る。或いはまた、分散剤を得る他の方法として、まず、
プロピレングリコール及び水を混合し、デゾルバで攪拌
しつつ、スチレン−アクリル樹脂を加え、６０℃前後に
加熱する。これにトリエチルアミンを加え、樹脂が溶解
するまで攪拌し、分散剤溶液を得る方法でも差し支えな
い。次に、この分散剤溶液に微粒子金属酸化物を加え、
公知のビーズミルにより平均粒径が０．１μｍ以下にな
るまで分散する。次に定着樹脂及びその他の添加剤を加
え、公知の攪拌機で混合して目的の微粒子金属酸化物水
性分散体を得る。かかる調製に際しては、従来公知の分
散方法、脱泡方法、濾過方法などを採用することができ
る。(Production Method) The aqueous dispersion of fine metal oxide particles of the present invention can be obtained, for example, by the following procedure. First, propylene glycol and water are mixed and heated to about 60 ° C. while stirring with a dissolver. Next, a small amount of triethylamine is added thereto, and a small amount of a styrene-acrylic resin is added. Next, when the styrene-acrylic resin is dissolved, a small amount of triethylamine is added again, and the styrene-acrylic resin is added.
Add a small amount of acrylic resin. This operation is repeated until the styrene-acrylic acid resin is exhausted to obtain a dispersant solution. Alternatively, as another method of obtaining a dispersant, first,
Mix propylene glycol and water, add styrene-acrylic resin while stirring with a dissolver, and heat to about 60 ° C. To this, triethylamine is added, and the mixture is stirred until the resin is dissolved to obtain a dispersant solution. Next, the fine particle metal oxide was added to the dispersant solution,
The particles are dispersed by a known bead mill until the average particle diameter becomes 0.1 μm or less. Next, a fixing resin and other additives are added and mixed with a known stirrer to obtain a desired aqueous dispersion of fine metal oxide particles. In such preparation, a conventionally known dispersion method, defoaming method, filtration method and the like can be adopted.
【００２８】[0028]
【実施例】下記表１に示した本発明の実施例及び比較例
に係る水性金属酸化物分散体を上記の様な製造方法によ
り調製した。尚、平均粒径は堀場製作所社製の商品名
「ＣＡＰＡ−７００」によって測定した。EXAMPLES The aqueous metal oxide dispersions according to the examples and comparative examples of the present invention shown in Table 1 below were prepared by the above-mentioned production methods. In addition, the average particle size was measured by HORIBA, Ltd. product name "CAPA-700".
【００２９】[0029]
【表１】 [Table 1]
【００３０】表１中、各原料組成は下記の通りである。 ・α−酸化鉄（Ａ）：商品名「ＦＲＯ−３」（堺化学工
業社製）、色相は褐色、ｐＨ５．１ ・α−酸化鉄（Ｂ）：商品名「バイフェロックスＫＭ１
８０Ｍ」（バイエル社製）、色相は褐色、ｐＨ６．０ ・コバルトブルー（Ａ）：商品名「コバルトブルーＣ」
（東洋顔料工業社製）、色相は青、ｐＨ５．５ ・コバルトブルー（Ｂ）：商品名「コバルトブルーディ
ープ」（東洋顔料工業社製）、色相は青、ｐＨ８．５〜
９．０ ・複合酸化物（Ａ）：Ｆｅ２Ｏ３−ＺｎＯ、商品名「Ｔ
Ｍブラウン＃３２１０」（大日精化工業社製）、色相は
黄色、ｐＨ８ ・複合酸化物（Ｂ）：Ｆｅ２Ｏ３−ＺｎＯ、商品名「Ｔ
Ｍブラウン＃９２１１」（大日精化工業社製）、色相は
黄色、ｐＨ６．０〜８．０In Table 1, the composition of each raw material is as follows. Α-iron oxide (A): trade name “FRO-3” (manufactured by Sakai Chemical Industry Co., Ltd.), hue is brown, pH 5.1. Α-iron oxide (B): trade name “Biferox KM1
80M "(manufactured by Bayer AG), hue is brown, pH 6.0. Cobalt Blue (A): Trade name" Cobalt Blue C "
(Manufactured by Toyo Pigment Industry Co., Ltd.), hue is blue, pH 5.5. Cobalt Blue (B): trade name “Cobalt Blue Deep” (manufactured by Toyo Pigment Industry Co., Ltd.), hue is blue, pH 8.5 to 8.5.
9.0 Complex oxide (A): Fe 2 O 3 —ZnO, trade name “T
M Brown # 3210 "(Dainichiseika Color & Chemicals Mfg. Co., Ltd.), the hue is yellow, pH8 · composite oxide (B): Fe 2 O 3 -ZnO, trade name" T
M Brown # 9211 "(manufactured by Dainichi Seika Industry Co., Ltd.), hue is yellow, pH 6.0 to 8.0
【００３１】・分散剤：表１中の分散剤は下記の表２の
配合の分散樹脂にて調製した。すなわち、まず、プロピ
レングリコール及び水を混合し、デゾルバで攪拌しつ
つ、６０℃前後に加熱する。次に、これにトリエチルア
ミンを少量加え、スチレン−アクリル酸樹脂を少量加え
る。次に、スチレン−アクリル酸樹脂が溶解したら、再
びトリエチルアミンを少量加え、スチレン−アクリル酸
樹脂を少量加える。この操作をスチレン−アクリル酸樹
脂がなくなるまで繰り返して分散剤を得る。Dispersant: The dispersants in Table 1 were prepared using the dispersing resins shown in Table 2 below. That is, first, propylene glycol and water are mixed and heated to about 60 ° C. while stirring with a dissolver. Next, a small amount of triethylamine is added thereto, and a small amount of a styrene-acrylic acid resin is added. Next, when the styrene-acrylic acid resin is dissolved, a small amount of triethylamine is added again, and a small amount of the styrene-acrylic acid resin is added. This operation is repeated until the styrene-acrylic acid resin is exhausted to obtain a dispersant.
【００３２】[0032]
【表２】 [Table 2]
【００３３】（試験サンプルの作成）実施例及び比較例
の水性金属酸化物分散体を用いて、アルミニウム材に電
着塗装をした。使用するアルミニウム材は、Ａ１０５
０，６０６３のアルミニウム材を用いた。まず、前処理
として、かかるアルミニウム材を１０％硝酸水溶液に室
温で１分間浸漬した後、水洗した後、５ｇ／Ｌ水酸化ナ
トリウム水溶液に６０℃で３分間浸漬し、水洗した。続
いて、１０％硝酸水溶液に室温で１分間浸漬し、水洗
し、その後乾燥した。(Preparation of Test Sample) Using the aqueous metal oxide dispersions of Examples and Comparative Examples, an aluminum material was subjected to electrodeposition coating. The aluminum material used is A105
A 0,6063 aluminum material was used. First, as a pretreatment, the aluminum material was immersed in a 10% aqueous nitric acid solution at room temperature for 1 minute, washed with water, then immersed in a 5 g / L aqueous sodium hydroxide solution at 60 ° C. for 3 minutes, and washed with water. Then, it was immersed in a 10% nitric acid aqueous solution at room temperature for 1 minute, washed with water, and then dried.
【００３４】次に、この前処理されたアルミニウム材
を、１７０ｇ／Ｌ硫酸浴中、Ｄ．Ｃ．２Ａ／ｄｍ２の定
電流密度で２０分間電解し、１０μｍの多孔質陽極酸化
皮膜を形成させた。このときの浴温度は２０℃、対極
（陰極）はカーボンを用いた。Next, this pretreated aluminum material was placed in a 170 g / L sulfuric acid bath in a D.I. C. Electrolysis was performed at a constant current density of 2 A / dm 2 for 20 minutes to form a 10 μm porous anodic oxide film. At this time, the bath temperature was 20 ° C., and carbon was used as the counter electrode (cathode).
【００３５】次に、この陽極酸化皮膜が形成されたアル
ミニウム材を、水洗し、８０〜８５℃で５分間湯洗し
た。Next, the aluminum material on which the anodized film was formed was washed with water and washed with hot water at 80 to 85 ° C. for 5 minutes.
【００３６】また、実施例及び比較例の水性金属酸化物
分散体を用いて、マグネシウム材に電着塗装をした。使
用するマグネシウム材は、ＡＺ３１Ｂのマグネシウム材
を用いた。まず、前処理として、かかるマグネシウム材
を３７ｇ／Ｌ水酸化ナトリウム水溶液に９０℃で６分間
浸漬し、その後乾燥した。Using the aqueous metal oxide dispersions of Examples and Comparative Examples, a magnesium material was subjected to electrodeposition coating. The magnesium material used was AZ31B magnesium material. First, as a pretreatment, the magnesium material was immersed in a 37 g / L aqueous sodium hydroxide solution at 90 ° C. for 6 minutes, and then dried.
【００３７】次に、この前処理されたマグネシウム材
を、３６０ｇ／Ｌ酸性フッ化アンモニウム、１００ｇ／
Ｌ重クロム酸ナトリウム、９０ｍｌ／Ｌ８５％リン酸浴
中、Ｄ．Ｃ．５Ａ／ｄｍ２の定電流密度で２０分間電解
し、３０μｍの多孔質陽極酸化皮膜を形成させた。この
ときの浴温度は７５℃、対極（陰極）はマグネシウムを
用いた。Next, 360 g / L ammonium acid fluoride, 100 g / L
L. sodium bichromate in a 90 ml / L 85% phosphoric acid bath; C. Electrolysis was performed at a constant current density of 5 A / dm 2 for 20 minutes to form a 30 μm porous anodic oxide film. The bath temperature at this time was 75 ° C., and magnesium was used as the counter electrode (cathode).
【００３８】次に、この陽極酸化皮膜が形成されたマグ
ネシウム材を、水洗し、８０〜８５℃で５分間湯洗し
た。Next, the magnesium material on which the anodized film was formed was washed with water and washed with hot water at 80 to 85 ° C. for 5 minutes.
【００３９】次に、この湯洗された陽極酸化皮膜が形成
されたアルミニウム材及びマグネシウム材を、ハニー化
成製、商品名「ハニライトＡＬ−８００Ｆ」（物質名：
水溶性アクリル−メラミン樹脂）に、既述した水性金属
酸化物分散体を加えた浴中（浴温：２０℃）にセット
し、Ｄ．Ｃ．１５０Ｖの定電圧で２分３０秒間電着した
後、１８０℃で３０分間焼き付けた。なお、アルミニウ
ム材への電着時の陰極は上記アルミニウム材を、マグネ
シウム材への電着時の陰極は上記マグネシウム材を用い
た。Next, the aluminum material and the magnesium material on which the anodized film was washed with hot water were manufactured by Honey Chemical Co., Ltd. under the trade name “Hanilite AL-800F” (substance name:
A water-soluble acrylic-melamine resin) and the above-mentioned aqueous metal oxide dispersion were added to a bath (bath temperature: 20 ° C.). C. After electrodeposition at a constant voltage of 150 V for 2 minutes and 30 seconds, baking was performed at 180 ° C. for 30 minutes. In addition, the above-mentioned aluminum material was used for the cathode at the time of electrodeposition on the aluminum material, and the above-mentioned magnesium material was used for the cathode at the time of electrodeposition on the magnesium material.
【００４０】（評価試験）上記試験サンプルの色相及び
透明性について評価した。また、耐候性を評価するた
め、デューサイクル（Dew cycle）８０時間後の透明性
についても評価した。アルミニウムを用いた試験サンプ
ルの評価結果を表３に、マグネシウムを用いた試験サン
プルの評価結果を表４に示す。(Evaluation Test) The hue and transparency of the test sample were evaluated. Further, in order to evaluate the weather resistance, the transparency after 80 hours of a Dew cycle was also evaluated. Table 3 shows the evaluation results of the test samples using aluminum, and Table 4 shows the evaluation results of the test samples using magnesium.
【００４１】[0041]
【表３】 [Table 3]
【００４２】[0042]
【表４】 [Table 4]
【００４３】表３及び表４中、塗膜の厚みは、米国イン
ターナショナル社製、超高性能膜厚計「ＣＧＸ−Ｂ２」
（商品名）で測定した。In Tables 3 and 4, the thickness of the coating film was measured using an ultra-high performance film thickness meter "CGX-B2" manufactured by International Corporation of the United States.
(Trade name).
【００４４】また、透明性は光沢度で評価した。光沢度
は、商品名「グロスチェッカー ＩＧ−３１０」（堀場
製作所社製）の光沢度測定機器で評価した。光沢度の数
値が大きいほど透明性が大きいことを示している。な
お、透明性の基準は、光沢度が１００％以上が○、５０
％以上１００％未満が△、５０％未満が×として評価し
た。The transparency was evaluated in terms of gloss. The glossiness was evaluated by a glossiness measuring device of “Gloss Checker IG-310” (trade name, manufactured by Horiba, Ltd.). The higher the value of the gloss, the higher the transparency. The criteria for transparency are as follows.
% To less than 100% was evaluated as Δ, and less than 50% was evaluated as ×.
【００４５】耐候性はスガ試験機社製の商品名「サンシ
ャインウェザメーター WEL-SUN-DC(H)」を用いて電着
塗装アルミニウム板（アルミニウム材）及びマグネシウ
ム板（マグネシウム材）を露光することにより評価し
た。すなわち、まず上記耐候性測定機を、温度６３℃±
３℃（照射時）、湿度を暗黒時９５％以上、試験時間１
時間、照射時間を１時間照射、１時間暗黒の１サイクル
２時間とする、デューサイクル（Dew cycle）用に設定
した。なお、温度は装置内の試験サンプルの表面温度で
ある。次に、各試験サンプルの上半分をアルミニウム箔
で覆ってセッティングした。そして、２０時間ごとにグ
ロスチェッカーで測定した。The weather resistance was measured by exposing an electrodeposited aluminum plate (aluminum material) and a magnesium plate (magnesium material) using “Sunshine Weathermeter WEL-SUN-DC (H)” (trade name, manufactured by Suga Test Instruments Co., Ltd.). Was evaluated. That is, first, the weather resistance measuring instrument was set to a temperature of 63 ° C. ±
3 ° C (at irradiation), humidity 95% or more in darkness, test time 1
The time and the irradiation time were set for a dew cycle in which irradiation was performed for 1 hour, dark for 1 hour, and 2 hours for one cycle. The temperature is the surface temperature of the test sample in the device. Next, the upper half of each test sample was covered with aluminum foil and set. And it measured with the gloss checker every 20 hours.
【００４６】なお、露光による光沢度の変化を更に電着
塗膜の平均表面粗さによっても評価した。平均表面粗さ
の測定は、エリオニクス社製の商品名「ＥＲＡ−８００
０」を用いて測定した。数値が小さいほど平均表面粗さ
が小さく、透明性が良好であることを示している。The change in glossiness due to exposure was further evaluated by the average surface roughness of the electrodeposited coating film. The measurement of the average surface roughness was carried out by the trade name “ERA-800” manufactured by Elionix.
0 ". The smaller the numerical value, the smaller the average surface roughness and the better the transparency.
【００４７】表３及び４に示す様に、実施例１〜３に係
る水性金属酸化物分散体の場合では、アルミニウム酸化
皮膜上及びマグネシウム酸化皮膜上にそれぞれ赤、青、
黄の色相を持った透明性のある電着塗膜を形成できるこ
とが認められた。またその透明性は比較例より大きいこ
とが認められた。また、露光後の透明性に関しても、各
実施例では各比較例と比べて光沢保持率が良好であり、
光沢度の低下を良好に抑止している。As shown in Tables 3 and 4, in the case of the aqueous metal oxide dispersions according to Examples 1 to 3, red, blue,
It was confirmed that a transparent electrodeposition coating film having a yellow hue could be formed. It was also confirmed that the transparency was higher than that of the comparative example. Also, regarding the transparency after exposure, in each example, the gloss retention was better than in each comparative example,
The reduction in gloss is well suppressed.
【００４８】[0048]
【発明の効果】以上の通り、本発明は、電着塗膜の透明
有彩色の着色成分を構成する微粒子金属酸化物、中でも
０．１μｍ以下、好ましくは０．０７μｍ以下の微粒子
金属酸化物を含有する電着塗装用水性金属酸化物分散体
であるので、各種金属及び金属表面に形成された酸化皮
膜上に、高透明性の着色電着塗膜を得ることができ、優
れた付着性、耐候性等の塗膜性能を電着塗膜に実現する
ことができる。中でもアルミニウム又はアルミニウム合
金、又は、マグネシウム又はマグネシウム合金上に形成
された酸化皮膜上に、高透明性で意匠性の高い着色電着
塗膜を得ることができ、付着性、耐候性等の塗膜性能を
高いレベルで電着塗膜に実現することができる。As described above, according to the present invention, the fine metal oxide constituting the transparent chromatic coloring component of the electrodeposition coating film, particularly the fine metal oxide having a particle size of 0.1 μm or less, preferably 0.07 μm or less, is used. Because it is an aqueous metal oxide dispersion for electrodeposition coating containing, it is possible to obtain a highly transparent colored electrodeposition coating film on an oxide film formed on various metals and metal surfaces, and excellent adhesion, Film performance such as weather resistance can be realized in the electrodeposited film. Among them, aluminum or an aluminum alloy, or, on an oxide film formed on magnesium or a magnesium alloy, it is possible to obtain a colored electrodeposition coating film having high transparency and high designability, and a coating film having adhesion, weather resistance, etc. A high level of performance can be achieved for electrodeposition coatings.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 伊藤 征司郎 奈良県生駒市あすか野北３丁目１番11号 Ｆターム(参考） 4J038 CC021 CG031 CG071 HA166 JB01 KA06 KA08 NA01 NA03 NA04 NA12 NA25 PA04 PB04 PB05 PB07 PB08 PB09 PB11 PC02 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Seijiro Ito 3-1-1-11 Asuka Nokita, Ikoma City, Nara Prefecture F-term (reference) 4J038 CC021 CG031 CG071 HA166 JB01 KA06 KA08 NA01 NA03 NA04 NA12 NA25 PA04 PB04 PB05 PB07 PB08 PB09 PB11 PC02
Claims (16)
する微粒子金属酸化物を含有する電着塗装用水性金属酸
化物分散体組成物。1. An aqueous metal oxide dispersion composition for electrodeposition coating containing a fine metal oxide constituting a transparent chromatic coloring component of an electrodeposition coating film.
する微粒子金属酸化物を含有する請求項１記載のアルミ
ニウム又はアルミニウム合金酸化皮膜への電着塗装用水
性金属酸化物分散体組成物。2. The aqueous metal oxide dispersion composition for electrodeposition coating on an aluminum or aluminum alloy oxide film according to claim 1, which contains a fine metal oxide constituting a transparent chromatic coloring component of the electrodeposition coating film. object.
する微粒子金属酸化物を含有する請求項１記載のマグネ
シウム又はマグネシウム合金酸化皮膜への電着塗装用水
性金属酸化物分散体組成物。3. The aqueous metal oxide dispersion composition for electrodeposition coating on a magnesium or magnesium alloy oxide film according to claim 1, which contains a fine metal oxide constituting a transparent chromatic coloring component of the electrodeposition coating film. object.
０．１μｍ以下である請求項１乃至３のいずれかの項に
記載の電着塗装用水性金属酸化物分散体組成物。4. The fine particle metal oxide has an average particle diameter of:
The aqueous metal oxide dispersion composition for electrodeposition coating according to any one of claims 1 to 3, which is 0.1 µm or less.
コバルトブルー、複合酸化物のうち少なくともいずれか
の化合物である請求項１乃至４のいずれかの項に記載の
電着塗装用水性金属酸化物分散体組成物。5. The fine particle metal oxide is α-iron oxide,
The aqueous metal oxide dispersion composition for electrodeposition coating according to any one of claims 1 to 4, wherein the composition is at least one of cobalt blue and a composite oxide.
する微粒子金属酸化物を含有し、上記微粒子金属酸化物
が分散剤を用いて溶媒に分散されている請求項１乃至５
のいずれかに記載の電着塗装用水性金属酸化物分散体組
成物。6. The electrodeposited coating film contains fine metal oxide particles constituting a transparent chromatic coloring component, and the fine metal oxide particles are dispersed in a solvent using a dispersant.
The aqueous metal oxide dispersion composition for electrodeposition coating according to any one of the above.
ホン基の少なくともいずれかを含むアニオン性化合物で
ある請求項１乃至６のいずれかの項に記載の電着塗装用
水性金属酸化物分散体。7. The aqueous metal oxide dispersion for electrodeposition coating according to claim 1, wherein the dispersant is an anionic compound containing at least one of a carboxyl group and a sulfone group.
合体及び界面活性剤の少なくともいずれかである請求項
７記載の電着塗装用水性金属酸化物分散体。8. The aqueous metal oxide dispersion for electrodeposition coating according to claim 7, wherein the anionic compound is at least one of a polymer, a copolymer and a surfactant.
金属酸化物分散体組成物全量に対して１〜４０重量％で
ある請求項１乃至８のいずれかの項に記載の電着塗装用
水性金属酸化物分散体組成物。9. The electrodeposition coating according to claim 1, wherein the content of the fine metal oxide is 1 to 40% by weight based on the total amount of the aqueous metal oxide dispersion composition. Aqueous metal oxide dispersion composition for use.
性金属酸化物分散体組成物全量に対して、０．２〜１６
重量％である請求項１乃至９のいずれかの項に記載の電
着塗装用水性金属酸化物分散体組成物。10. The content (solid content) of the dispersant is 0.2 to 16 with respect to the total amount of the aqueous metal oxide dispersion composition.
The aqueous metal oxide dispersion composition for electrodeposition coating according to any one of claims 1 to 9, wherein the composition is in a weight percent.
溶性有機溶剤の含有量が水性金属酸化物分散体組成物全
量に対して１〜３０重量％である請求項１乃至１０のい
ずれかの項に記載の電着塗装用水性金属酸化物分散体組
成物。11. The method according to claim 1, wherein the solvent contains a water-soluble organic solvent, and the content of the water-soluble organic solvent is 1 to 30% by weight based on the total amount of the aqueous metal oxide dispersion composition. The aqueous metal oxide dispersion composition for electrodeposition coating according to the item.
以上である請求項１乃至１１のいずれかの項に記載の電
着塗装用水性金属酸化物分散体組成物。12. The aqueous metal oxide dispersion having a pH of 7
The aqueous metal oxide dispersion composition for electrodeposition coating according to any one of claims 1 to 11, which is the above.
水性金属酸化物分散体を用いてアルミニウム又はアルミ
ニウム合金酸化皮膜に電着塗装する電着塗装方法。13. An electrodeposition coating method for electrodepositing an aluminum or aluminum alloy oxide film using the aqueous metal oxide dispersion according to claim 1. Description:
水性金属酸化物分散体を用いてマグネシウム又はマグネ
シウム合金酸化皮膜に電着塗装する電着塗装方法。14. An electrodeposition coating method for electrodepositing a magnesium or magnesium alloy oxide film using the aqueous metal oxide dispersion according to claim 1. Description:
化皮膜上に、微粒子金属酸化物を含む透明有彩色の電着
塗膜が形成されているアルミニウム又はアルミニウム合
金製品。15. An aluminum or aluminum alloy product in which a transparent and chromatic electrodeposition coating containing fine metal oxides is formed on an aluminum or aluminum alloy oxide coating.
化皮膜上に、微粒子金属酸化物を含む透明有彩色の電着
塗膜が形成されているマグネシウム又はマグネシウム合
金製品。16. A magnesium or magnesium alloy product in which a transparent and chromatic electrodeposition coating containing fine metal oxides is formed on a magnesium or magnesium alloy oxide coating.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010138373A (en) * | 2008-11-14 | 2010-06-24 | Kansai Paint Co Ltd | Colored anionic electrodeposition coating and method for forming coating film |
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