JPH06264010A - Electrodeposition coating material, electrodeposition coated member, and production of the member - Google Patents
Electrodeposition coating material, electrodeposition coated member, and production of the memberInfo
- Publication number
- JPH06264010A JPH06264010A JP25590393A JP25590393A JPH06264010A JP H06264010 A JPH06264010 A JP H06264010A JP 25590393 A JP25590393 A JP 25590393A JP 25590393 A JP25590393 A JP 25590393A JP H06264010 A JPH06264010 A JP H06264010A
- Authority
- JP
- Japan
- Prior art keywords
- electrodeposition coating
- electrodeposition
- resin
- weight
- coating
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、光学機器、電子機器、
音響機器、通信機器、家電機器あるいは事務機等の製
品、更にはクリーンルーム等の壁材に用いられる、静電
気対策および化粧性表面形成に適する電着塗料、電着塗
装部材およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to optical equipment, electronic equipment,
The present invention relates to an electrodeposition coating material, which is suitable for use as a wall material in a clean room or the like, for products such as audio equipment, communication equipment, home electric appliances or office machines, and which is suitable for forming a cosmetic surface, an electrodeposition coating member, and a manufacturing method thereof.
【０００２】[0002]
【従来の技術】従来、光学機器、電子機器、音響機器、
通信機器、家電機器あるいは事務機等の製品、更にはク
リーンルーム等の壁材に用いられる、静電気対策塗装部
材を形成する方法としては、適当な基材に導電性塗料を
スプレー塗装によって塗膜形成する方法が主流で、その
他樹脂中に導電性フィラーを充填する方法、あるいは界
面活性剤を樹脂中に混入する方法等が挙げられる。2. Description of the Related Art Conventionally, optical equipment, electronic equipment, audio equipment,
As a method of forming antistatic coating members used for products such as communication equipment, home appliances or office machines, and for wall materials in clean rooms, etc., a conductive coating is spray-coated on a suitable base material. The method is mainly used, and other methods include a method of filling the resin with a conductive filler, a method of mixing a surfactant into the resin, and the like.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記の
従来の方法には、次のような欠点があった。即ち、適当
な基板上に導電性塗料を用い、スプレー塗装で、塗膜部
材を形成する方法が知られているが、まず、導電性フイ
ラーのアスペクト比によって抵抗値が変動する。例え
ば、球形の導電性フィラーは低アスペクト比のため、塗
料中の含有量が５０重量％以上でないと、目標とする抵
抗値が得られない欠点がある。また、導電性フィラーの
含有量が過多になると塗膜の耐久性が低下し、製品への
適用は難しく、またコストが高い欠点がある。However, the above-mentioned conventional method has the following drawbacks. That is, there is known a method of forming a coating film member by spray coating using a conductive paint on an appropriate substrate. First, the resistance value varies depending on the aspect ratio of the conductive filler. For example, the spherical conductive filler has a low aspect ratio, so that the target resistance value cannot be obtained unless the content in the coating material is 50% by weight or more. Further, when the content of the conductive filler is excessively high, the durability of the coating film is deteriorated, and it is difficult to apply it to products, and there is a drawback that the cost is high.
【０００４】上記の問題を解決する手段として、短繊
維、針状、リン片状あるいは、球形でシャープな突起が
ある高アスペクト比の導電性フィラーを塗料に含有する
ことにより、球状フィラーに比べ少量の混入量で発揮で
きるとされているが、ここにも大きな欠点があり、実用
的ではない。例えば、長い形状の導電性フイラーは樹脂
や塗料に分散しくにいことや、導電性フィラーが折れて
しまい、高アスペクト比を下げてしまう問題があり量産
的ではない。As a means for solving the above problems, a short aspect, a needle-like shape, a scaly shape, or a spherical and high aspect ratio conductive filler having sharp projections is contained in the coating material, so that the amount thereof is smaller than that of the spherical filler. It is said that it can be demonstrated by the mixed amount of, but this also has a big defect and is not practical. For example, a long-shaped conductive filler is not mass-producible because it has a problem in that it is difficult to disperse in a resin or a paint, and the conductive filler is broken to lower the high aspect ratio.
【０００５】一方、導電性フィラー以外に界面活性剤を
混入するものがあるが、温度や光により経時変化し、あ
るいは大気の乾燥時には効果がなく商品価値の低下が問
題である。また、プラスチック射出成形時のフィラーの
不均一や導電性に異方性が生ずる問題がある。On the other hand, there are some which mix a surface active agent in addition to the conductive filler, but there is a problem that it changes with time due to temperature and light, or it is ineffective when it is dried in the air and the commercial value is lowered. Further, there are problems that the filler is non-uniform and the conductivity is anisotropic during plastic injection molding.
【０００６】本発明は、上記の従来技術の欠点を改善す
るためになされたもので、フィラーの形状を問わず、均
質性及び静電シールド性に優れ、かつ化粧塗装として製
品に適用できる電着塗料、電着塗装部材およびその製造
方法を提供することを目的とするものである。The present invention has been made to solve the above-mentioned drawbacks of the prior art, and has excellent homogeneity and electrostatic shielding property regardless of the shape of the filler and can be applied to products as a cosmetic coating. It is an object of the present invention to provide a paint, an electrodeposition coated member and a method for producing the same.
【０００７】[0007]
【課題を解決するための手段】本発明の電着塗料は、少
なくとも金属酸化物を含有する多相構造微粒子からなる
微粉体を、樹脂に含有したものである。The electrodeposition coating composition of the present invention comprises a resin containing a fine powder of multiphase structure fine particles containing at least a metal oxide.
【０００８】また、本発明の電着塗装部材は、上記の電
着塗料により形成した電着塗装被膜を、基板上に有する
ものである。The electrodeposition coating member of the present invention has an electrodeposition coating film formed of the above electrodeposition coating material on a substrate.
【０００９】更に、本発明の電着塗装部材の製造方法
は、上記の電着塗料を用い、基板上に電着塗装法で電着
塗装被膜を形成する工程と、前記電着塗装被膜を硬化さ
せる工程とを有するものである。Further, the method for producing an electrodeposition coating member of the present invention comprises the steps of forming an electrodeposition coating film on a substrate by the electrodeposition coating method using the above electrodeposition coating material, and curing the electrodeposition coating film. And the process of making it.
【００１０】本発明の電着塗料は、光学機器や電気製品
等の塗装に使用して電着塗装被膜とし、静電気シールド
及び外観の化粧性の向上を図るものである。電着塗装被
膜とは、電着塗装法で形成した被膜を意味する。本発明
の電着塗料は、電着可能な樹脂にフィラーを含有して、
電着塗装法に使用するものである。電着塗装法とは、電
着塗料中に一対の電極を配置して直流電圧を加えること
により電極上に電着塗料中の物質を付着させるものであ
る。従って、塗装を行なう対象を一方の電極として用い
る。他方の電極には、例えばステンレス板を用いるとよ
い。The electrodeposition coating composition of the present invention is used as a coating for electrodeposition coating when it is used for coating optical equipment, electric products, etc. to improve the electrostatic shield and the cosmetic appearance. The electrodeposition coating film means a film formed by the electrodeposition coating method. The electrodeposition coating composition of the present invention contains a filler in a resin capable of electrodeposition,
It is used in the electrodeposition coating method. The electrodeposition coating method is a method in which a pair of electrodes are arranged in the electrodeposition coating material and a direct current voltage is applied to deposit the substance in the electrodeposition coating material on the electrodes. Therefore, the object to be coated is used as one electrode. A stainless plate, for example, may be used for the other electrode.
【００１１】本発明の電着塗料に用いられる電着可能な
樹脂には、低温硬化型樹脂が用いられ、例えばアクリル
・メラミン系，アクリル系，エポキシ系，ウレタン系，
フッ素系，アルキッド系等が挙げられる。As the electrodepositable resin used in the electrodeposition coating composition of the present invention, a low temperature curing type resin is used. For example, acryl / melamine type, acryl type, epoxy type, urethane type,
Fluorine type, alkyd type and the like can be mentioned.
【００１２】本発明の電着塗料に用いられる電着可能な
樹脂は、アニオン系樹脂でもカチオン系樹脂でもかまわ
ないが、実用的にはカルボキシル基を有する水溶性樹脂
あるいは水分散性樹脂が好ましい。The electrodepositable resin used in the electrodeposition coating composition of the present invention may be an anion resin or a cation resin, but a water-soluble resin having a carboxyl group or a water-dispersible resin is preferable for practical use.
【００１３】本発明の電着塗料は、所望の樹脂を水に溶
解または分散して作製するのが好ましいが、電着塗料中
に、更にアルコール系やグリコールエーテル系等の有機
溶剤を含有してもかまわない。有機溶剤の含有量は数パ
ーセントで十分である。The electrodeposition coating composition of the present invention is preferably prepared by dissolving or dispersing a desired resin in water. However, the electrodeposition coating composition further contains an organic solvent such as alcohol or glycol ether. I don't care. A few percent of organic solvent content is sufficient.
【００１４】本発明の電着塗料中の樹脂濃度は、７〜２
０重量％、更には７〜１７重量％が好ましい。また、本
発明の電着塗料には、必要に応じて従来公知の顔料等を
添加して着色することができる。着色のための顔料の添
加量としては、１〜３重量％が好ましい。The resin concentration in the electrodeposition coating composition of the present invention is 7-2.
It is preferably 0% by weight, more preferably 7 to 17% by weight. Further, the electrodeposition coating composition of the present invention can be colored by adding a conventionally known pigment or the like, if necessary. The addition amount of the pigment for coloring is preferably 1 to 3% by weight.
【００１５】本発明の電着塗料中には、少なくとも金属
酸化物を含有する多相構造微粒子からなる微粉体をフィ
ラーとして含有する。多相構造の微粒子とは、粒子が、
コーティング層でコーティングされたもの、あるいは粒
子表面からドーピング材料をドーピングしたもの等、複
数の材料を用いて材料の種類や配合比が部位により異な
るように構成したものである。The electrodeposition coating composition of the present invention contains, as a filler, a fine powder composed of multi-phase structure fine particles containing at least a metal oxide. Particles with a multiphase structure mean that the particles are
A plurality of materials, such as one coated with a coating layer or one doped with a doping material from the particle surface, is used so that the type and mixing ratio of the material are different depending on the site.
【００１６】また、本発明で使用する多相構造の微粒子
からなる微粉体には、金属酸化物を含有する。即ち、微
粒子を構成する複数の材料のうち、少なくとも１つの材
料は金属酸化物である。The fine powder composed of fine particles having a multiphase structure used in the present invention contains a metal oxide. That is, at least one of the plurality of materials forming the fine particles is a metal oxide.
【００１７】微粉体を構成する粒子に含有する金属酸化
物としては、例えば酸化チタン、酸化スズ、酸化アンチ
モン、酸化インジウム、あるいは酸化亜鉛等が好ましく
用いられる。As the metal oxide contained in the particles constituting the fine powder, for example, titanium oxide, tin oxide, antimony oxide, indium oxide, zinc oxide or the like is preferably used.
【００１８】金属酸化物以外で、微粒子を構成する材料
としては、例えばアンチモン、ホウ酸アルミニウム、更
にはカーボンブラック等が挙げられる。Other than the metal oxide, examples of the material forming the fine particles include antimony, aluminum borate, and carbon black.
【００１９】多相構造の微粉体の好ましいものとして
は、例えば酸化チタン粒子表面に酸化スズをコーティン
グした粒子からなる粉体、酸化スズ粒子表面にアンチモ
ンをドーピングした粒子からなる粉体、酸化スズ粒子表
面に酸化アンチモンをドーピングした粒子からなる粉
体、酸化インジウム粒子表面に酸化アンチモンをドーピ
ングした粒子からなる粉体、酸化チタン粒子表面に酸化
スズをコーティングし、さらに酸化アンチモンをドーピ
ングした粒子からなる粉体、酸化チタン粒子表面に酸化
亜鉛をコーティングした粒子からなる粉体、酸化亜鉛粒
子表面にアンチモンをドーピングした粒子からなる粉
体、酸化亜鉛粒子表面に酸化アンチモンをドーピングし
た粒子からなる粉体、ホウ酸アルミニウム粒子表面に酸
化スズ、あるいは酸化亜鉛をコーティングした粒子から
なる粉体等が挙げられる。コーティング層あるいはドー
パントの含有する層の厚みは、粒子径の１／２００〜１
／１０が好ましい。Preferred fine powders having a multi-phase structure are, for example, powder composed of particles of titanium oxide particles coated with tin oxide, powder composed of particles of tin oxide particles doped with antimony, and tin oxide particles. Powder consisting of particles doped with antimony oxide on the surface, powder consisting of particles doped with antimony oxide on the surface of indium oxide particles, powder composed of particles coated with tin oxide on the surface of titanium oxide particles and further doped with antimony oxide Body, powder composed of particles of titanium oxide particles coated with zinc oxide, powder composed of particles of zinc oxide particles doped with antimony, powder composed of particles of zinc oxide particles doped with antimony oxide, boron Tin oxide or suboxide on the surface of aluminum oxide particles Powder and the like made of coated particles. The thickness of the coating layer or the layer containing the dopant is 1/200 to 1 of the particle diameter.
/ 10 is preferable.
【００２０】多相構造の微粒子の平均粒子径は、０．０
１〜５μｍ、更には０．０１〜２．０μｍが好ましい。
０．０１μｍ未満では二次凝集作用で分散性に問題を生
じ易く、また５μｍよりも大きいと化粧性あるいは沈降
性の点で問題を生じ易い。The average particle size of the fine particles having a multiphase structure is 0.0
The thickness is preferably 1 to 5 μm, more preferably 0.01 to 2.0 μm.
If it is less than 0.01 μm, a problem of dispersibility tends to occur due to the secondary aggregation action, and if it is more than 5 μm, a problem of cosmeticity or sedimentation tends to occur.
【００２１】本発明において、微粒子の粒径は、遠心沈
降式粒度分布測定器を用いて測定した値である。この測
定器として実際に用いたものはＳＡＣＰ−３（島津製作
所製）である。In the present invention, the particle size of the fine particles is a value measured by using a centrifugal sedimentation type particle size distribution measuring device. SACP-3 (manufactured by Shimadzu Corporation) was actually used as this measuring device.
【００２２】本発明の電着塗料において、多相構造の微
粉体の含有量は、電着可能な樹脂１００重量部に対し
て、２〜１５０重量部、更には、７〜４０重量部が好ま
しい。２重量部よりも少ないと静電防止効果が薄れ、又
１５０重量部よりも多いと化粧性および耐久性に問題を
生じ易い。In the electrodeposition coating composition of the present invention, the content of the fine powder having a multiphase structure is 2 to 150 parts by weight, preferably 7 to 40 parts by weight, based on 100 parts by weight of the electrodepositable resin. . When the amount is less than 2 parts by weight, the antistatic effect is weakened, and when the amount is more than 150 parts by weight, cosmetic properties and durability are likely to cause problems.
【００２３】粉体の共析はＸ線マイクロアナライザーに
より確認され、その共析量は熱重量分析で解析すること
により測定することができる。The eutectoid of the powder is confirmed by an X-ray microanalyzer, and the eutectoid amount can be measured by analyzing it by thermogravimetric analysis.
【００２４】本発明の電着塗料には、多相構造の微粒子
からなる微粉体以外にフィラーとしてセラミック粉体や
カーボンブラックを含有してもよい。セラミック粉体と
しては、例えばアルミナ、シリカ、ジルコニア、マグネ
シア、酸化チタン、窒化ケイ素、炭化ケイ素、窒化アル
ミニウム等が使用できる。セラミック粉体及びカーボン
ブラックの平均粒子径は、０．０１〜３μｍ、更には
０．２〜２μｍが好ましい。０．０１μｍ未満では二次
凝集作用で分散性に問題を生じ易く、４μｍより大きい
と化粧性あるいは沈降性の点で問題を生じ易い。The electrodeposition coating composition of the present invention may contain ceramic powder or carbon black as a filler in addition to fine powder composed of fine particles having a multiphase structure. As the ceramic powder, for example, alumina, silica, zirconia, magnesia, titanium oxide, silicon nitride, silicon carbide, aluminum nitride or the like can be used. The average particle diameter of the ceramic powder and carbon black is preferably 0.01 to 3 μm, more preferably 0.2 to 2 μm. If it is less than 0.01 μm, a problem of dispersibility tends to occur due to the secondary aggregation action, and if it is more than 4 μm, a problem of cosmeticity or sedimentation tends to occur.
【００２５】本発明の電着塗料に、セラミック粉体ある
いはカーボンブラックを含有する場合、セラミック粉体
の含有量は、多相構造の微粒子からなる微粉体１００重
量部に対して２〜１５０重量部の範囲が好ましい。When the electrodeposition coating composition of the present invention contains ceramic powder or carbon black, the content of the ceramic powder is 2 to 150 parts by weight based on 100 parts by weight of fine powder composed of fine particles having a multiphase structure. Is preferred.
【００２６】本発明の電着塗料を用いることにより、静
電気をシールドするのに適当な抵抗値を有する電着塗装
被膜を形成することができる。静電気シールドに好まし
い体積抵抗値は、１０2〜１０9Ω・ｃｍである。By using the electrodeposition coating composition of the present invention, an electrodeposition coating film having a resistance value suitable for shielding static electricity can be formed. A preferable volume resistance value for the electrostatic shield is 10 2 to 10 9 Ω · cm.
【００２７】本発明の電着塗装部材は、金属基材、又は
表面に金属薄膜を有する非金属基材の上に、本発明の電
着塗料を用いて電着塗装法により電着塗装被膜を形成し
たものである。The electrodeposition coated member of the present invention has a metal base material or a non-metal base material having a metal thin film on its surface, and an electrodeposition coating film is formed by the electrodeposition coating method using the electrodeposition coating material of the present invention. It was formed.
【００２８】図１において、本発明の電着塗装部材は、
金属薄膜２を有する非金属基材１上に付着性向上被膜
３、およびフィラーの共析した電着塗装被膜４を設けて
なるものである。付着性向上被膜３は必要に応じて設け
るものである。In FIG. 1, the electrodeposition coated member of the present invention is
The non-metal substrate 1 having a metal thin film 2 is provided with an adhesion-improving coating 3 and an electrodeposition coating coating 4 containing a codeposited filler. The adhesion improving coating 3 is provided as needed.
【００２９】次に、図１に示す本発明の電着塗装部材の
製造方法について説明する。Next, a method for manufacturing the electrodeposition coated member of the present invention shown in FIG. 1 will be described.
【００３０】まず、非金属基材１表面に金属薄膜２を形
成し、さらに付着性向上のために、化学処理により付着
性向上被膜３を施す。First, the metal thin film 2 is formed on the surface of the non-metal substrate 1, and the adhesion improving coating 3 is applied by chemical treatment to improve the adhesion.
【００３１】非金属基材１としては、特に制限すること
はなく電子機器、通信機器、家電製品等の筺体に用いら
れるプラスチックで、例えばＡＢＳ、ポリカーボネイ
ト、ポリカーボネイト／ＡＢＳ、変性ＰＰＥあるいはこ
れらにガラス繊維、炭素繊維等を含有したプラスチック
等が挙げられる。The non-metal base material 1 is not particularly limited and is a plastic used for housings of electronic equipment, communication equipment, home electric appliances, etc., such as ABS, polycarbonate, polycarbonate / ABS, modified PPE or glass fiber thereof. , And plastics containing carbon fiber and the like.
【００３２】前記非金属基材１に金属薄膜２を形成する
方法は無電界銅めっき、電界めっき、あるいはドライプ
レイティング、蒸着等により行なうことが好ましい。金
属薄膜は膜厚５μｍ以下、好ましくは０．１〜２μｍが
好適である。めっきによる金属薄膜２を形成する場合、
一般に知られているプラスチック上のめっき法で行なわ
れているように、エッチングし触媒処理した後、金属薄
膜２を形成する。金属薄膜２としては、ニッケル、銅、
金、銀、アルミニウム、クロム又はその合金が挙げられ
る。The metal thin film 2 is preferably formed on the non-metal substrate 1 by electroless copper plating, electric field plating, dry plating, vapor deposition or the like. The metal thin film has a film thickness of 5 μm or less, preferably 0.1 to 2 μm. When forming the metal thin film 2 by plating,
The metal thin film 2 is formed after etching and catalytic treatment as is done by the commonly known plating method on plastics. As the metal thin film 2, nickel, copper,
Examples thereof include gold, silver, aluminum, chromium and alloys thereof.
【００３３】さらに、金属薄膜２上に付着性向上のため
に必要に応じて施す処理は、例えばクロム酸処理、化学
着色処理、界面活性剤処理、ブラッククロムめっき処理
等が挙げられる。このように、金属薄膜２表面に化学的
あるいは、電気化学的処理を施すことで、電着塗料浴へ
の金属溶出も防止される。付着性向上被膜の厚みは、
０．１〜０．５μｍが好ましい。Further, examples of the treatment to be performed on the metal thin film 2 for improving the adhesion include chromic acid treatment, chemical coloring treatment, surfactant treatment, black chrome plating treatment and the like. As described above, by chemically or electrochemically treating the surface of the metal thin film 2, metal elution into the electrodeposition coating bath is also prevented. The thickness of the adhesion improving coating is
0.1 to 0.5 μm is preferable.
【００３４】次に、本発明の電着塗料を用いて前記基材
に電着塗装法により電着塗装被膜４を形成する。電界条
件としては２０〜２５℃、ｐＨ８〜９で３０〜１２０Ｖ
が望ましい。Next, an electrodeposition coating film 4 is formed on the above-mentioned base material by the electrodeposition coating method using the electrodeposition coating material of the present invention. The electric field conditions are 20 to 25 ° C., pH 8 to 9 and 30 to 120 V.
Is desirable.
【００３５】最後に、電着塗装被膜４を低温硬化させる
ことにより本発明の電着塗装部材を得ることができる。
硬化条件としては、硬化温度９０〜１００℃のオーブン
で２０〜１８０分間で硬化するのが望ましい。Finally, the electrodeposition coating film 4 is cured at a low temperature to obtain the electrodeposition coating member of the present invention.
As curing conditions, it is desirable to cure in an oven at a curing temperature of 90 to 100 ° C. for 20 to 180 minutes.
【００３６】図２は本発明の電着塗装部材の構成の他の
例を示す断面図である。図２に示す電着塗装部材は、金
属基材５の上に、付着性向上被膜３を必要に応じて設
け、付着性向上被膜３の上にフィラーの含有する電着塗
装被膜４を設けてなるものである。FIG. 2 is a sectional view showing another example of the constitution of the electrodeposition coated member of the present invention. In the electrodeposition coating member shown in FIG. 2, an adhesion improving coating 3 is provided on a metal substrate 5 as necessary, and an electrodeposition coating coating 4 containing a filler is provided on the adhesion improving coating 3. It will be.
【００３７】金属基材５には、例えば銅、黄銅、アルミ
ニウム、鉄あるいはその合金等が用いられる。For the metal base material 5, for example, copper, brass, aluminum, iron or an alloy thereof is used.
【００３８】また、図２に示す本発明の電着塗装部材の
製造方法は、金属基材５として、例えば黄銅基材の上
に、図１に示した方法と同様の方法、例えばアルカリに
よる酸化銅の形成により付着性向上被膜３を形成し、そ
の上に図１に示した電着塗装法と同様の方法により電着
塗装被膜４を形成し、該電着塗装被膜４を低温硬化させ
ることにより電着塗装部材を得ることができる。In the method for producing the electrodeposition coated member of the present invention shown in FIG. 2, the metal base material 5 is, for example, a brass base material, and the same method as that shown in FIG. Forming an adhesion-enhancing coating 3 by forming copper, forming an electrodeposition coating film 4 thereon by a method similar to the electrodeposition coating method shown in FIG. 1, and curing the electrodeposition coating film 4 at a low temperature. Thus, an electrodeposition coated member can be obtained.
【００３９】本発明の電着塗装部材において、電着塗装
被膜の膜厚は、通常５〜４０μｍ、好ましくは７〜３０
μｍが望ましい。In the electrodeposition coated member of the present invention, the film thickness of the electrodeposition coating film is usually 5 to 40 μm, preferably 7 to 30.
μm is desirable.
【００４０】また、電着膜４中のフィラーの共析量は１
０〜６０重量％、特に１０〜５０重量％、更には１０〜
３５重量％が好ましい。The codeposition amount of the filler in the electrodeposition film 4 is 1
0 to 60% by weight, particularly 10 to 50% by weight, and further 10 to
35% by weight is preferred.
【００４１】本発明の電着塗装部材は、金属酸化物を含
有する多相構造の微粉体を共析した電着塗装被膜を有し
ているため、静電対策および化粧性も良好となり、商品
価値が高められる効果がある。Since the electrodeposition coating member of the present invention has the electrodeposition coating film obtained by co-depositing the fine powder having a multi-phase structure containing a metal oxide, the antistatic property and the cosmetic property are also improved, and the product It has the effect of increasing the value.
【００４２】図３は、３種類の電着塗料について、それ
ぞれ電着塗装を行ない、電流−時間曲線を求めたもので
ある。この電流−時間曲線から塗膜の緻密性がわかる。FIG. 3 shows current-time curves obtained by performing electrodeposition coating on each of the three kinds of electrodeposition coatings. The current-time curve shows the denseness of the coating film.
【００４３】作成した電着塗装部材は、いずれも図１に
示す構成のもので、非金属基材１にはＡＢＳ樹脂を使用
し、このＡＢＳ樹脂上に金属薄膜としてはアルミニウム
膜を形成し、更に化学処理により付着性向上被膜３を形
成した。最後に、３種類の電着塗料を用いて、それぞれ
電着塗装被膜を形成して３種類の電着塗装部材を作成し
た。Each of the prepared electrodeposition coated members had the structure shown in FIG. 1, ABS resin was used for the non-metal substrate 1, and an aluminum film was formed as a metal thin film on this ABS resin. Further, an adhesion improving coating 3 was formed by chemical treatment. Finally, three kinds of electrodeposition coating materials were used to form electrodeposition coating films, and three kinds of electrodeposition coating members were prepared.
【００４４】３種類の電着塗料のうちの第１のものは、
アクリル・メラミン系樹脂１００重量部に、ＴｉＯ2に
ＳｎＯ2をコーティングした微粒子からなる多相構造の
微粒子からなる微粉体を５重量部分散したものである。
第１の電着塗料に使用した微粉体の平均粒子径は０．２
μｍであった。この電着塗装についての電流−時間曲線
を、グラフ（ａ）で示した。The first of the three types of electrodeposition paint is:
It is a dispersion of 5 parts by weight of fine powder of fine particles having a multi-phase structure, which is composed of fine particles of TiO 2 coated with SnO 2 , in 100 parts by weight of an acrylic melamine resin.
The average particle size of the fine powder used in the first electrodeposition coating is 0.2
was μm. The current-time curve for this electrodeposition coating is shown in graph (a).
【００４５】第２の電着塗料は、アクリル・メラミン系
樹脂１００重量部に、ＴｉＯ2にＳｎＯ2をコーティング
した微粒子からなる多相構造粒子からなる微粉体７０重
量部及びアルミナ粉体３０重量部を分散したものであ
る。第２の電着塗料に使用した多層構造粒子からなる微
粉体の平均粒子径は０．２μｍで、アルミナの平均粒子
径は０．５μｍであった。この電着塗装についての電流
−時間曲線をグラフ（ｂ）で示した。The second electrodeposition coating composition is 100 parts by weight of acrylic melamine resin, 70 parts by weight of fine powder composed of multi-phase structured particles composed of fine particles of TiO 2 coated with SnO 2 , and 30 parts by weight of alumina powder. Is dispersed. The average particle size of the fine powder composed of multi-layered particles used in the second electrodeposition coating was 0.2 μm, and the average particle size of alumina was 0.5 μm. The current-time curve for this electrodeposition coating is shown in graph (b).
【００４６】第３の電着塗料には、フィラーがなくアク
リル・メラミン系樹脂のみで構成されている。この電着
塗料についての電流−時間曲線をグラフ（ｃ）で示し
た。The third electrodeposition paint has no filler and is composed only of acrylic / melamine resin. The current-time curve for this electrodeposition coating is shown in graph (c).
【００４７】電着塗装は、いずれの場合も印加電圧９０
Ｖで２分間通電することにより行なった。In any case, the electrodeposition coating is applied voltage 90
It was carried out by energizing with V for 2 minutes.
【００４８】図３から明らかなように、第１及び第２の
電着塗料では（グラフ（ａ）及び（ｂ））、フィラーを
含有しない第３の電着塗装部材に比較して、時間の経過
と共に急激な電流減衰が見られ、析出された塗膜は緻密
性が高いことがわかる。As is apparent from FIG. 3, in the first and second electrodeposition coating materials (graphs (a) and (b)), compared with the third electrodeposition coating member containing no filler, A rapid current decay is observed with the passage of time, and it can be seen that the deposited coating film is highly dense.
【００４９】[0049]
【実施例】以下、実施例を示し本発明をさらに具体的に
説明するが、本発明は係る実施例のみに限定されるもの
ではない。EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
【００５０】実施例１ 縦１００ｍｍ，横５０ｍｍ，厚み０．７ｍｍのＡＢＳ基
板（電気化学工業社製）をＣｒＯ3−Ｈ2ＳＯ4−Ｈ2Ｏ系
エッチング液で１分間処理し、水洗後、センシタイザー
液として塩化第一スズ３０ｇ／ｌ、塩酸２０ｍｌ／ｌを
用いて、室温で２分間処理し、水洗した。次いで、アク
チベータ液として、塩化パラジウム０．３ｇ／ｌ、塩酸
３ｍｌ／ｌを用いて、室温で２分間処理し、この基板を
導通化した。この基板に、無電解銅めっき液（奥野製薬
工業社製）ｐＨ１３．０を用いて浴温７０℃にて３分間
めっきを施し、０．２μｍの厚さの銅薄膜を形成した。
次いで、水酸化ナトリウム５％、過硫酸カリウム１％の
水溶液で、７０℃、３０秒間処理し前記銅薄膜に化学着
色被膜である銅の酸化被膜を形成した。Example 1 An ABS substrate (made by Denki Kagaku Kogyo Co., Ltd.) having a length of 100 mm, a width of 50 mm and a thickness of 0.7 mm was treated with a CrO 3 —H 2 SO 4 —H 2 O type etching solution for 1 minute, washed with water, As a sensitizer solution, stannous chloride (30 g / l) and hydrochloric acid (20 ml / l) were used for treatment at room temperature for 2 minutes and washed with water. Next, as an activator solution, 0.3 g / l of palladium chloride and 3 ml / l of hydrochloric acid were used for treatment at room temperature for 2 minutes to make the substrate conductive. This substrate was plated with an electroless copper plating solution (Okuno Pharmaceutical Co., Ltd.) pH 13.0 at a bath temperature of 70 ° C. for 3 minutes to form a copper thin film having a thickness of 0.2 μm.
Then, it was treated with an aqueous solution of sodium hydroxide 5% and potassium persulfate 1% at 70 ° C. for 30 seconds to form a copper oxide film as a chemically colored film on the copper thin film.
【００５１】そして、アクリル・メラミン系樹脂（商品
名：ハニブライトＣ−ＩＬ、ハニー化成社製）１００重
量部に、平均粒子径０．２μｍのフィラー（ＴｉＯ2に
ＳｎＯ2をコーティングした粒子からなる粉体。商品名
ＥＴ−５００Ｗ、石原産業社製）を７０重量部含有し
て、ボールミルで３０時間分散した後、脱塩水にて１５
重量％に希釈し、さらに着色のためにカーボンブラック
を２．０重量％添加した塗液を用いて、浴温２５℃、ｐ
Ｈ８〜９の条件で、上記基板を陽極とし、対極として厚
み０．５ｍｍのステンレス板を用いて、印加電圧１００
Ｖで２分間電着した。電着後に水洗し、９７℃±１℃の
オーブンにて６０分間加熱して硬化し外観が良好な本発
明の電着塗装部材を得た。A powder composed of 100 parts by weight of an acrylic melamine resin (trade name: Hanibright C-IL, manufactured by Honey Kasei Co., Ltd.) and filler (TiO 2 coated with SnO 2 ) having an average particle diameter of 0.2 μm. 70 parts by weight of trade name ET-500W (manufactured by Ishihara Sangyo Co., Ltd.) was dispersed in a ball mill for 30 hours and then deionized water was added to 15
Using a coating liquid diluted to 2.0% by weight and further containing 2.0% by weight of carbon black for coloring, bath temperature 25 ° C., p
Under the conditions of H8 to 9, the substrate was used as an anode, and a stainless plate having a thickness of 0.5 mm was used as a counter electrode, and an applied voltage of 100
Electroplated with V for 2 minutes. After electrodeposition, it was washed with water and heated in an oven at 97 ° C. ± 1 ° C. for 60 minutes to be cured to obtain an electrodeposition coated member of the present invention having a good appearance.
【００５２】この電着塗装部材に形成された電着塗装被
膜の膜厚は２０μｍ、共析量は３０重量％であった。ま
た、この電着塗装被膜の付着性（ＪＩＳ Ｋ５４００
碁盤目試験に準拠）、耐食性（ＪＩＳ Ｋ５４００ 塩
水噴霧試験に準拠）についてそれぞれ試験を行なった。The film thickness of the electrodeposition coating film formed on this electrodeposition coating member was 20 μm, and the amount of eutectoid was 30% by weight. Also, the adhesion of this electrodeposition coating film (JIS K5400
Tests were performed for the cross-cut test) and the corrosion resistance (based on JIS K5400 salt spray test).
【００５３】付着性試験の結果は１００／１００、即ち
電着塗装被膜の剥離は発生しなかった。また、耐食性試
験の結果、試験時間５００時間経過後も電着塗装被膜の
腐食によるフクレは全く発生しなかった。The result of the adhesion test was 100/100, that is, peeling of the electrodeposition coating film did not occur. Further, as a result of the corrosion resistance test, no blistering due to corrosion of the electrodeposition coating film occurred even after the test time of 500 hours.
【００５４】更に、静電気シールド効果について、電着
塗装部材の体積抵抗率を測定することにより確認した。
この測定には、電着塗料中のフィラー含有量を表１に示
すように変え、その他は上記の電着塗装部材と同様にし
て作成した電着塗装部材を用いた。測定はＪＩＳＫ６９
１１に準拠して行なった。測定結果を表１に示した。Further, the electrostatic shield effect was confirmed by measuring the volume resistivity of the electrodeposition coated member.
For this measurement, the content of the filler in the electrodeposition coating was changed as shown in Table 1, and the other components were used in the same manner as the above electrodeposition coating member. Measurement is JISK69
It carried out according to 11. The measurement results are shown in Table 1.
【００５５】[0055]
【表１】 [Table 1]
【００５６】表１から明らかなように、電着塗装被膜中
に多相構造の微粉体を含有することにより、満足できる
抵抗値となった。As is clear from Table 1, the inclusion of the fine powder having a multiphase structure in the electrodeposition coating film gave a satisfactory resistance value.
【００５７】比較例 １ 電着塗装被膜中に微粉体を含有せず、その他は実施例１
と同様にして電着塗装部材を形成し、この電着塗装部材
の体積抵抗率を実施例１と同様にして測定した。その結
果、この電着塗装部材の体積抵抗率は１０13（Ω・ｃ
ｍ）と高いものであった。Comparative Example 1 The fine powder was not contained in the electrodeposition coating film, and the others were in Example 1.
An electrodeposition coated member was formed in the same manner as in 1. and the volume resistivity of this electrodeposition coated member was measured in the same manner as in Example 1. As a result, the volume resistivity of this electrodeposition coated member was 10 13 (Ω · c).
m) was high.
【００５８】実施例２ 実施例１と同様のＡＢＳ基板（電気化学工業社製）を、
実施例１と同様にして導通化した。この基板に、無電解
銅めっき液（奥野製薬工業社製）ｐＨ１３．０を用い
て、浴温７０℃にて１０分間めっきを施し、０．５μｍ
の厚さの銅薄膜を形成した。次いで、重クロム酸カリウ
ム０．１％の水溶液で、７０℃，１分間処理し前記銅薄
膜にクロム被膜を形成した。Example 2 The same ABS substrate (manufactured by Denki Kagaku Kogyo) as in Example 1 was used.
Conduction was performed in the same manner as in Example 1. This substrate was plated with an electroless copper plating solution (Okuno Pharmaceutical Co., Ltd.) pH 13.0 at a bath temperature of 70 ° C. for 10 minutes to give 0.5 μm.
A copper thin film having a thickness of 1 was formed. Then, it was treated with an aqueous solution of 0.1% potassium dichromate at 70 ° C. for 1 minute to form a chromium film on the copper thin film.
【００５９】そして、アクリル・メラミン系樹脂（商品
名：ハニブライトＣ−ＩＬ、ハニー化成社製）１００重
量部に、平均粒子径０．１μｍのフィラー（酸化スズに
酸化アンチモンをドーピングした粒子からなる粉体。商
品名Ｔ−１，三菱マテリアル社製）７０重量部及び平均
粒子径１μｍのアルミナ４０重量部を含有して、ボール
ミルで３０時間分散した後、脱塩水にて１５重量％に希
釈し、さらに着色のためにシアニンブルーを２．０重量
％添加した塗液を用いて、浴温２５℃、ｐＨ８〜９の条
件で、上記基板を陽極とし、対極として厚み０．５ｍｍ
ステンレス板を用いて、印加電圧７０Ｖで３分間電着し
た。電着後に水洗し、９７℃±１℃のオーブンにて６０
分間加熱して硬化し外観が良好な本発明の電着塗装部材
を得た。Then, 100 parts by weight of an acrylic / melamine resin (trade name: Hanibright C-IL, manufactured by Honey Chemical Co., Ltd.) was added to a powder (particles of tin oxide doped with antimony oxide) having a mean particle diameter of 0.1 μm. Body, trade name T-1, manufactured by Mitsubishi Materials Corporation) 70 parts by weight and 40 parts by weight of alumina having an average particle diameter of 1 μm are dispersed in a ball mill for 30 hours and then diluted with demineralized water to 15% by weight, Further, using a coating liquid added with 2.0% by weight of cyanine blue for coloring, the above substrate was used as an anode under conditions of a bath temperature of 25 ° C. and a pH of 8 to 9 and a thickness of 0.5 mm as a counter electrode.
Using a stainless steel plate, electrodeposition was performed at an applied voltage of 70 V for 3 minutes. Rinse with water after electrodeposition and 60 in an oven at 97 ℃ ± 1 ℃
An electrodeposition coated member of the present invention having a good appearance was obtained by curing by heating for minutes.
【００６０】この電着塗装部材に形成された電着塗装被
膜の膜厚は２０μｍ、共析量は４０重量％であった。ま
た、この電着塗装部材を用いて実施例１と同様の試験を
行なった結果、実施例１と同様の良好な効果が得られ
た。The film thickness of the electrodeposition coating film formed on this electrodeposition coating member was 20 μm, and the amount of eutectoid was 40% by weight. Further, as a result of conducting the same test as in Example 1 using this electrodeposition coated member, the same good effect as in Example 1 was obtained.
【００６１】実施例３ 縦１００ｍｍ，横５０ｍｍ，厚み０．７ｍｍのＡＢＳ／
ＰＣアロイ基板（電気化学工業社製）に、アルミニウム
蒸着膜を１μｍを施し、重クロム酸カリウム１％水溶液
で７０℃，１分間処理した。Example 3 ABS / 100 mm long, 50 mm wide, 0.7 mm thick ABS /
A PC alloy substrate (manufactured by Denki Kagaku Kogyo Co., Ltd.) was coated with an aluminum vapor deposition film having a thickness of 1 μm and treated with a 1% potassium dichromate aqueous solution at 70 ° C. for 1 minute.
【００６２】そして、アクリル・メラミン系樹脂（商品
名：ハニブライトＣ−ＩＬ、ハニー化成社製）１００重
量部に対して、平均粒子径０．０７μｍのフィラー（Ｔ
ｉＯ2にＳｎＯ2をコーティングした粒子からなる粉体，
商品名ＦＴ−２０００，石原産業社製）５０重量部及び
平均粒子径１μｍのアルミナ２重量部を含有して、ボー
ルミルで３０時間分散した後、脱塩水にて５重量％に希
釈し、さらに着色のためにカーボンブラックを２．０重
量％添加した塗液を用いて、その他は実施例２と同様に
して外観が良好な本発明の電着塗装部材を得た。Then, with respect to 100 parts by weight of an acrylic / melamine resin (trade name: Hanibright C-IL, manufactured by Honey Chemical Co., Ltd.), a filler (T
a powder consisting of particles obtained by coating SnO 2 on iO 2 ,
(FT-2000, trade name, manufactured by Ishihara Sangyo Co., Ltd.) and 2 parts by weight of alumina having an average particle size of 1 μm, and dispersed in a ball mill for 30 hours, then diluted to 5% by weight with demineralized water and further colored. For this purpose, a coating liquid containing 2.0% by weight of carbon black was used, and otherwise the same as in Example 2 to obtain an electrodeposition coated member of the present invention having a good appearance.
【００６３】この電着塗装部材に形成された電着塗装被
膜の膜厚は１０μｍ、共析量は３５重量％であった。ま
た、この電着塗装部材を用いて実施例１と同様の試験を
行なった結果、実施例１と同様の良好な効果が得られ
た。The film thickness of the electrodeposition coating film formed on this electrodeposition coating member was 10 μm, and the amount of eutectoid was 35% by weight. Further, as a result of conducting the same test as in Example 1 using this electrodeposition coated member, the same good effect as in Example 1 was obtained.
【００６４】実施例４ 縦１００ｍｍ，横５０ｍｍ，厚み０．７ｍｍの黄銅基板
に対し、溶剤脱脂、電解脱脂等のめっき前処理を行なっ
た。次いで、水酸化ナトリウム５％、過硫酸カリウム１
％の水溶液を用いて、７０℃で１分間処理し、この基板
に銅の酸化被膜を形成した。Example 4 A brass substrate having a length of 100 mm, a width of 50 mm and a thickness of 0.7 mm was subjected to plating pretreatment such as solvent degreasing and electrolytic degreasing. Next, sodium hydroxide 5%, potassium persulfate 1
% Aqueous solution at 70 ° C. for 1 minute to form a copper oxide film on this substrate.
【００６５】そして、アクリル・メラミン系樹脂（商品
名エレコート，シミズ社製）１００重量部に対して、平
均粒子径０．２μｍのフィラー（酸化亜鉛にアンチモン
をドーピングした粒子からなる粉体。商品名パストラン
２２１０，三井金属社製）６０重量部及び平均粒子径１
μｍのアルミナ３重量部を含有して、ボールミルで３０
時間分散した後、脱塩水にて１５重量％に希釈し、着色
のためにカーボンブラック２．０重量％添加した塗液を
用いて、その他は実施例２と同様にして外観が良好な本
発明の電着塗装部材を得た。A powder (particles consisting of particles in which zinc oxide is doped with antimony) having an average particle diameter of 0.2 μm is added to 100 parts by weight of an acrylic / melamine resin (trade name: Elecoat, manufactured by Shimizu Co., Ltd.). Pastran 2210, manufactured by Mitsui Kinzoku Co., Ltd.) 60 parts by weight and average particle size 1
30 parts by ball mill containing 3 parts by weight of μm alumina.
The present invention having a good appearance in the same manner as in Example 2 except that the coating liquid was dispersed in demineralized water to 15% by weight after being dispersed for 15 hours, and 2.0% by weight of carbon black was added for coloring. An electrodeposition coated member of was obtained.
【００６６】この電着塗装部材に形成された電着塗装被
膜の膜厚は２０μｍ、共析量は４０重量％であった。ま
た、この電着塗装部材を用いて実施例１と同様の試験を
行なった結果、実施例１と同様の良好な効果が得られ
た。The film thickness of the electrodeposition coating film formed on this electrodeposition coating member was 20 μm, and the amount of eutectoid was 40% by weight. Further, as a result of conducting the same test as in Example 1 using this electrodeposition coated member, the same good effect as in Example 1 was obtained.
【図１】本発明の電着塗装部材の一例を示す断面図であ
る。FIG. 1 is a cross-sectional view showing an example of an electrodeposition coated member of the present invention.
【図２】本発明の電着塗装部材の他の例を示す断面図で
ある。FIG. 2 is a sectional view showing another example of the electrodeposition coated member of the present invention.
【図３】電着塗装被膜形成時の電流−時間曲線を示すグ
ラフである。FIG. 3 is a graph showing a current-time curve at the time of forming an electrodeposition coating film.
１ 非金属基材 ２ 金属薄膜 ３ 付着性向上被膜 ４ 電着塗装被膜 ５ 金属基材 1 Non-metal substrate 2 Metal thin film 3 Adhesion improving film 4 Electrodeposition coating film 5 Metal substrate
Claims (7)
造微粒子からなる微粉体を、樹脂に含有したことを特徴
とする電着塗料。1. An electrodeposition coating composition comprising a resin containing a fine powder of multi-phase structure fine particles containing at least a metal oxide.
ズ、酸化アンチモン、酸化インジウム及び酸化亜鉛から
選ばれたものである請求項１記載の電着塗料。2. The electrodeposition coating composition according to claim 1, wherein the metal oxide is selected from titanium oxide, tin oxide, antimony oxide, indium oxide and zinc oxide.
るコーティング層を有するものである請求項１記載の電
着塗料。3. The electrodeposition coating composition according to claim 1, wherein the fine particles have a coating layer containing the metal oxide.
ングしたものである請求項１記載の電着塗料。4. The electrodeposition coating composition according to claim 1, wherein the fine particles are doped with the metal oxide.
た電着塗装被膜を、基板上に有することを特徴とする電
着塗装部材。5. An electrodeposition coating member having an electrodeposition coating film formed from the electrodeposition coating composition according to claim 1 on a substrate.
付着性向上被膜を有する請求項５記載の電着塗装部材。6. The electrodeposition coating member according to claim 5, further comprising an adhesion improving coating between the electrodeposition coating film and the substrate.
上に電着塗装法で電着塗装被膜を形成する工程と、前記
電着塗装被膜を硬化させる工程とを有することを特徴と
する電着塗装部材の製造方法。7. A method of forming an electrodeposition coating film on a substrate by using the electrodeposition coating composition according to claim 1 by an electrodeposition coating method, and curing the electrodeposition coating film. And a method for producing an electrodeposition coated member.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25590393A JP3236148B2 (en) | 1992-10-27 | 1993-10-13 | Electroplated member and method of manufacturing electrodeposited member |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-288849 | 1992-10-27 | ||
| JP28884992 | 1992-10-27 | ||
| JP25590393A JP3236148B2 (en) | 1992-10-27 | 1993-10-13 | Electroplated member and method of manufacturing electrodeposited member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06264010A true JPH06264010A (en) | 1994-09-20 |
| JP3236148B2 JP3236148B2 (en) | 2001-12-10 |
Family
ID=26542461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25590393A Expired - Fee Related JP3236148B2 (en) | 1992-10-27 | 1993-10-13 | Electroplated member and method of manufacturing electrodeposited member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3236148B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10237362A (en) * | 1997-02-26 | 1998-09-08 | Catalysts & Chem Ind Co Ltd | Electrodeposition coating material and electrodeposition coating |
| JP2002138253A (en) * | 2000-08-25 | 2002-05-14 | Sakura Color Prod Corp | Aqueous metal oxide dispersion composition for electrodeposition coating |
| JP2002146296A (en) * | 2000-11-13 | 2002-05-22 | Kansai Paint Co Ltd | Anion-type electrodeposition coating material |
| JP2007288258A (en) * | 2006-04-12 | 2007-11-01 | Pioneer Electronic Corp | Structural component for speaker apparatus and speaker apparatus |
| JP2010040889A (en) * | 2008-08-07 | 2010-02-18 | Nec Electronics Corp | Semiconductor device and inspection method of semiconductor device |
| JP2011521031A (en) * | 2008-05-14 | 2011-07-21 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング | Electrodeposition primer composition |
-
1993
- 1993-10-13 JP JP25590393A patent/JP3236148B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10237362A (en) * | 1997-02-26 | 1998-09-08 | Catalysts & Chem Ind Co Ltd | Electrodeposition coating material and electrodeposition coating |
| JP2002138253A (en) * | 2000-08-25 | 2002-05-14 | Sakura Color Prod Corp | Aqueous metal oxide dispersion composition for electrodeposition coating |
| JP2002146296A (en) * | 2000-11-13 | 2002-05-22 | Kansai Paint Co Ltd | Anion-type electrodeposition coating material |
| JP2007288258A (en) * | 2006-04-12 | 2007-11-01 | Pioneer Electronic Corp | Structural component for speaker apparatus and speaker apparatus |
| JP2011521031A (en) * | 2008-05-14 | 2011-07-21 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング | Electrodeposition primer composition |
| US9309415B2 (en) | 2008-05-14 | 2016-04-12 | Basf Coatings Gmbh | Electrodeposition paint composition |
| JP2010040889A (en) * | 2008-08-07 | 2010-02-18 | Nec Electronics Corp | Semiconductor device and inspection method of semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3236148B2 (en) | 2001-12-10 |
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