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JP2001293428A - Method for depositing double-layered coating film - Google Patents

Method for depositing double-layered coating film

Info

Publication number
JP2001293428A
JP2001293428A JP2000115088A JP2000115088A JP2001293428A JP 2001293428 A JP2001293428 A JP 2001293428A JP 2000115088 A JP2000115088 A JP 2000115088A JP 2000115088 A JP2000115088 A JP 2000115088A JP 2001293428 A JP2001293428 A JP 2001293428A
Authority
JP
Japan
Prior art keywords
paint
coating
coating film
water
parts
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
Application number
JP2000115088A
Other languages
Japanese (ja)
Other versions
JP4489905B2 (en
Inventor
Hiroyuki Nagano
裕幸 永野
Shigeru Nakamura
茂 中村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kansai Paint Co Ltd
Original Assignee
Kansai Paint Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kansai Paint Co Ltd filed Critical Kansai Paint Co Ltd
Priority to JP2000115088A priority Critical patent/JP4489905B2/en
Publication of JP2001293428A publication Critical patent/JP2001293428A/en
Application granted granted Critical
Publication of JP4489905B2 publication Critical patent/JP4489905B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a method for depositing a new metallic double-layered coating film using a scaly bright pigment. SOLUTION: The face coated with an uncured water-base coating is coated with a brilliant coating consisting essentially of the scaly brilliant pigment and an organic solvent to deposit a double-layered coating film by this method.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、りん片状光輝性顔
料を使用した新規なメタリック複層塗膜を形成する方法
に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a novel metallic multilayer coating film using a flaky glittering pigment.

【0002】[0002]

【従来の技術とその課題】アルミニウムフレークなどの
光輝性顔料を含有するメタリック塗料を塗装し、その塗
膜を硬化させることなく、クリヤ塗料を塗装し、加熱し
てこれらの両塗膜を同時に硬化せしめて得られるメタリ
ック複層塗膜は、キラキラとした光輝感があって意匠性
にすぐれており、自動車車体の外板部の上塗り塗膜とし
て広く採用されている。しかしながら、このメタリック
塗料の単独塗膜は、主に樹脂成分、アルミニウムフレー
ク及び着色顔料で構成されており、このうちアルミニウ
ムフレークは、その塗膜内において塗面に対して平行に
配向していることが理想であるが、実際は不規則に配向
することが多いために、アルミニウムフレークが本来的
に有している白くかつ金属光沢感にすぐれ、しかもフリ
ップフロップ性の強いメタリック塗膜を形成させること
を困難にしている。
2. Description of the Related Art A metallic paint containing a brilliant pigment such as aluminum flakes is applied, and a clear paint is applied without curing the paint film, and both the paint films are cured simultaneously by heating. The metallic multi-layer coating film obtained at least has a glittering glitter and excellent design, and is widely used as a top coating film on the outer plate of an automobile body. However, a single coating of this metallic paint is mainly composed of a resin component, aluminum flakes and coloring pigments, and among these, the aluminum flakes are oriented parallel to the coating surface in the coating. Is ideal, but in fact, it is often irregularly oriented, so it is necessary to form a metallic coating film that aluminum flakes originally have excellent whiteness and metallic luster and have strong flip-flop properties. Making it difficult.

【0003】[0003]

【課題を解決するための手段】本発明の目的は、りん片
状光輝性顔料を使用したメタリック複層塗膜の形成方法
に関し、特に、りん片状光輝性顔料を塗膜内において塗
面に対して平行に配向せしめ、このりん片状光輝性顔料
が本来的に有している白くかつ金属光沢感などの特性に
すぐれ、しかもフリップフロップ性の強いメタリック塗
膜を形成させる新規な方法を提供することである。その
特徴は、水性塗料の未硬化塗面に、りん片状光輝性顔料
及び有機溶剤を主成分とする光輝性塗料を塗装するとこ
ろにある。
SUMMARY OF THE INVENTION An object of the present invention is to provide a method for forming a metallic multilayer coating film using a scaly glittering pigment, and more particularly, to a method for applying a scaly glittering pigment to a coated surface in a coating film. Provide a new method of forming a metallic coating film that is oriented in parallel to the flake-like brilliant pigment and has excellent characteristics such as white and metallic luster, which are inherently possessed by this scaly brilliant pigment, and has strong flip-flop properties. It is to be. The feature is that a glitter paint containing a flaky glitter pigment and an organic solvent as main components is applied to the uncured coating surface of the water-based paint.

【0004】しかして本発明によれば、水性塗料(A)
の未硬化塗面に、りん片状光輝性顔料及び有機溶剤を主
成分とする光輝性塗料(B)を塗装することを複層塗膜
形成方法(以下、本方法という)が提供される。
Thus, according to the present invention, the aqueous paint (A)
A method of forming a multi-layer coating film (hereinafter referred to as the present method), which comprises applying a glittering paint (B) containing a flaky glitter pigment and an organic solvent as main components to the uncured coating surface.

【0005】以下に、本方法について詳細に説明する。Hereinafter, the present method will be described in detail.

【0006】本方法による複層塗膜を形成させるための
被塗物として金属製品及びプラスチック製品などがあげ
られ、これらの素材を用いて形成された乗用車、トラッ
ク、オートバイ、バスなどの自動車車体の外板部が特に
好適である。これらの被塗物は、水性塗料(A)の塗装
に先立って、あらかじめ表面処理などを行ない、さらに
必要に応じてカチオン電着塗装及び中塗り塗装を行な
い、これらの塗膜を硬化しておくことが好ましい。
[0006] Metal articles and plastic articles are examples of objects to be coated to form a multi-layer coating film according to the present method, and automobile bodies such as passenger cars, trucks, motorcycles, buses, etc. formed using these materials. The skin is particularly suitable. Prior to the application of the water-based paint (A), these objects are subjected to a surface treatment and the like, and if necessary, a cationic electrodeposition coating and an intermediate coating are performed to cure these coating films. Is preferred.

【0007】水性塗料(A)は、光輝性塗料(B)に先
立って被塗物に塗装する塗料であり、水を主たる溶媒又
は分散媒とする水性塗料であり、具体的には、ビニル樹
脂及びポリエステル樹脂などの基体樹脂及び硬化剤を含
有する熱硬化型水性塗料が好適に使用できる。
The water-based paint (A) is a paint to be applied to an object to be coated prior to the glittering paint (B), and is a water-based paint containing water as a main solvent or a dispersion medium. And a thermosetting water-based paint containing a base resin such as a polyester resin and a hardener.

【0008】ビニル樹脂として、それ自体既知のものが
使用でき、例えば、カルボキシル基含有重合性単量体、
水酸基含有重合性単量体及びその他の重合性単量体を共
重合して得られる、数平均分子量約3000〜約400
00、酸価約20〜約100、水酸基価約20〜約20
0のアクリル樹脂やビニル樹脂をあげることができる。
As the vinyl resin, those known per se can be used, for example, a carboxyl group-containing polymerizable monomer,
A number average molecular weight of about 3,000 to about 400, obtained by copolymerizing a hydroxyl group-containing polymerizable monomer and other polymerizable monomers.
00, acid value about 20 to about 100, hydroxyl value about 20 to about 20
0 acrylic resin and vinyl resin.

【0009】カルボキシル基含有重合性単量体として
は、(メタ)アクリル酸、マレイン酸、イタコン酸など
のモノエチレン性不飽和カルボン酸類;水酸基含有重合
性単量体としては、(メタ)アクリル酸2−ヒドロキシ
エチル、(メタ)アクリル酸2−ヒドロキシプロピルな
どのモノエチレン性不飽和カルボン酸のヒドロキシアル
キルエステル類などがあげられる。その他の重合性単量
体としては、(メタ)アクリル酸メチル、(メタ)アク
リル酸エチル、(メタ)アクリル酸n−ブチル、(メ
タ)アクリル酸イソブチル、(メタ)アクリル酸2−エ
チルヘキシル、(メタ)アクリル酸ラウリル、(メタ)
アクリル酸デシルなどのモノエチレン性不飽和カルボン
酸のアルキルエステル類、(メタ)アクリルアミド、N
−メチロール(メタ)アクリルアミド、ジアセトンアク
リルアミドなどのアクリルアミド誘導体、(メタ)アク
リル酸グリシジルなどのモノエチレン性不飽和カルボン
酸のグリシジルエステル類、酢酸ビニル、プロピオン酸
ビニルなどの飽和カルボン酸のビニルエステル類、スチ
レン、α−メチルスチレン、ビニルトルエンなどの芳香
族不飽和単量体をあげることができる。
The carboxyl group-containing polymerizable monomers include monoethylenically unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, and itaconic acid; and the hydroxyl group-containing polymerizable monomers include (meth) acrylic acid. Examples include hydroxyalkyl esters of monoethylenically unsaturated carboxylic acids such as 2-hydroxyethyl and 2-hydroxypropyl (meth) acrylate. Other polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( (Meth) lauryl acrylate, (meth)
Alkyl esters of monoethylenically unsaturated carboxylic acids such as decyl acrylate, (meth) acrylamide, N
-Acrylamide derivatives such as methylol (meth) acrylamide and diacetone acrylamide; glycidyl esters of monoethylenically unsaturated carboxylic acids such as glycidyl (meth) acrylate; vinyl esters of saturated carboxylic acids such as vinyl acetate and vinyl propionate And aromatic unsaturated monomers such as styrene, α-methylstyrene and vinyltoluene.

【0010】かくして得られるアクリル樹脂やビニル樹
脂は、アンモニア又はトリエチルアミン、モノエタノー
ルアミン、ジエタノールアミン、トリエタノールアミ
ン、ジメチルアミノエタノールなどのアミン類、水酸化
ナトリウムなどのアルカリ金属の水酸化物などの塩基性
物質で中和することにより水性にすることができる。ま
た、カルボキシル基含有重合性単量体を使用して、又は
使用せずに、水酸基含有重合性単量体及びその他の重合
性単量体を用いて共重合体を水中に分散せしめてなる水
分散体も使用できる。
The acrylic resin and the vinyl resin thus obtained can be used in the form of a basic compound such as ammonia or amines such as triethylamine, monoethanolamine, diethanolamine, triethanolamine and dimethylaminoethanol; and alkali metal hydroxides such as sodium hydroxide. It can be made aqueous by neutralizing with a substance. Further, with or without using a carboxyl group-containing polymerizable monomer, water is obtained by dispersing a copolymer in water using a hydroxyl group-containing polymerizable monomer and other polymerizable monomers. Dispersions can also be used.

【0011】水性ポリエステル樹脂としては、それ自体
既知のものが使用でき、例えば、多価アルコールと多塩
基酸とのエステル化反応により得られる、数平均分子量
約1000〜約20000、酸価約20〜約100、水
酸基価約20〜約200のポリエステル樹脂をあげるこ
とができる。多価アルコールとして、エチレングリコー
ル、ジエチレングリコール、プロピレングリコール、ブ
タンジオール、ペンタンジオール、2,2−ジメチルプ
ロパンジオール、グリセリン、トリメチロールプロパ
ン、ペンタエリスリトールなど、多塩基酸として無水フ
タル酸、イソフタル酸、テトラヒドロ無水フタル酸、ヘ
キサヒドロ無水フタル酸、無水マレイン酸、無水コハク
酸、アジピン酸、セバチン酸、無水トリメリット酸、無
水ピロメリット酸などが使用でき、さらに必要に応じて
安息香酸やt−ブチル安息香酸などの一塩基酸やヒマシ
油、桐油、サフラワー油、大豆油、アマニ油、トール
油、ヤシ油及びこれらの脂肪酸の油成分を用いることが
できる。
As the aqueous polyester resin, those known per se can be used. For example, a number average molecular weight of about 1,000 to about 20,000, an acid value of about 20 to about 20, obtained by an esterification reaction of a polyhydric alcohol and a polybasic acid. Polyester resins having a hydroxyl value of about 100 and a hydroxyl value of about 20 to about 200 can be used. Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol, 2,2-dimethylpropanediol, glycerin, trimethylolpropane, and pentaerythritol; and polybasic acids such as phthalic anhydride, isophthalic acid, and tetrahydroanhydride Phthalic acid, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, adipic acid, sebacic acid, trimellitic anhydride, pyromellitic anhydride, etc. can be used, and if necessary, benzoic acid or t-butylbenzoic acid, etc. Monobasic acid, castor oil, tung oil, safflower oil, soybean oil, linseed oil, tall oil, coconut oil, and oil components of these fatty acids can be used.

【0012】かくしてポリエステル樹脂は、アンモニア
又はトリエチルアミン、モノエタノールアミン、ジエタ
ノールアミン、トリエタノールアミン、ジメチルアミノ
エタノールなどのアミン類、水酸化ナトリウムなどのア
ルカリ金属の水酸化物などの塩基性物質で中和すること
により水性にすることができる。
Thus, the polyester resin is neutralized with ammonia or basic substances such as amines such as triethylamine, monoethanolamine, diethanolamine, triethanolamine and dimethylaminoethanol, and alkali metal hydroxides such as sodium hydroxide. By doing so, it can be made aqueous.

【0013】また、硬化剤として、メラミン樹脂、ベン
ゾグアナミン樹脂などが好適に使用でき、これらは、親
水性及び疎水性のいずれでも差し支えなく使用できる。
As the curing agent, a melamine resin, a benzoguanamine resin or the like can be suitably used, and these can be used regardless of hydrophilicity or hydrophobicity.

【0014】水性塗料(A)における、基体樹脂と硬化
剤との比率は、両者の合計固形分重量を基準として、基
体樹脂が約50〜約90重量%、好ましくは約60〜約
85重量%、硬化剤が約10〜約50重量%、好ましく
は約15〜約40重量%の範囲内で使用される。
The ratio of the base resin and the curing agent in the water-based coating composition (A) is preferably about 50 to about 90% by weight, preferably about 60 to about 85% by weight, based on the total solid content of both. The curing agent is used in the range of about 10 to about 50% by weight, preferably about 15 to about 40% by weight.

【0015】水性塗料(A)による単独塗膜は、無色透
明、有色透明、着色不透明のいずれでも差支えない。着
色はソリッドカラ−調の塗膜が適している。
The single coating film of the water-based paint (A) may be colorless and transparent, colored and transparent, or colored and opaque. For coloring, a solid color tone coating film is suitable.

【0016】水性塗料(A)は、塗装時粘度をフォード
カップ#4で約10〜約50秒(20℃)に調整し、エ
アスプレー塗装、エアレススプレー塗装、静電塗装など
により、上記の被塗物に塗装することができる。その膜
厚は、硬化塗膜に基ずいて約5〜約30μm、特に約1
0〜約20μmが好ましい。
The water-based paint (A) is adjusted to a viscosity of about 10 to about 50 seconds (20 ° C.) with a Ford cup # 4 at the time of coating, and is subjected to the above coating by air spray coating, airless spray coating, electrostatic coating or the like. Can be applied to painted objects. Its film thickness is about 5 to about 30 μm, especially about 1 μm, based on the cured coating film.
0 to about 20 μm is preferred.

【0017】本方法では、被塗物に塗装した水性塗料
(A)の未硬化塗面に、りん片状光輝性顔料及び有機溶
剤を主成分とする光輝性塗料(B)を塗装することを特
徴としており、特に、光輝性塗料(B)を塗装する時点
での水性塗料(A)の未硬化塗膜は、水分含有率50〜
90重量%、特に60〜80重量%、粘度1000セン
チポイズ以上(20℃)、特に1300〜2000セン
チポイズ(20℃)で、ゲル分率10重量%以下あるこ
とが好ましい。水性塗料(A)の未硬化塗膜の水分含有
率、粘度及びゲル分率を上記の範囲に調整するために、
被塗物に塗装された水性塗料(A)の未硬化塗膜を室温
乃至100℃で1〜30分放置することが好ましい。
In the present method, the glitter coating (B) containing a scaly glitter pigment and an organic solvent as main components is applied to the uncured coating surface of the aqueous coating (A) applied to the object to be coated. In particular, the uncured coating film of the water-based paint (A) at the time of applying the glitter paint (B) has a water content of 50 to 50%.
It is preferably 90% by weight, especially 60 to 80% by weight, viscosity of 1000 centipoise or more (20 ° C), particularly 1300 to 2000 centipoise (20 ° C), and a gel fraction of 10% by weight or less. In order to adjust the water content, viscosity and gel fraction of the uncured coating film of the water-based paint (A) to the above ranges,
It is preferable that the uncured coating film of the water-based paint (A) applied to the object is left at room temperature to 100 ° C. for 1 to 30 minutes.

【0018】水性塗料(A)の「未硬化塗膜」の粘度
は、その塗料をガラス板に実際に即した条件で塗装し、
所定の時間放置してから、ガラスビンに捕集し、それを
コーンアンドプレート型粘時計でズリ速度10sec-1
における粘度を読み取ることにより測定した。水分含有
率は同様にして捕集した塗料約2gを100℃で3時間
加熱して、加熱前との減量率を測定した。ゲル分率は、
同様にして捕集した塗料をアセトンで3時間還流温度で
抽出した後の残存率を測定した(顔料は除いて計算し
た)。
The viscosity of the “uncured coating film” of the water-based coating material (A) is determined by applying the coating material to a glass plate under conditions that are practically applicable.
After leaving it for a predetermined time, it was collected in a glass bottle, and it was sheared at a shear rate of 10 sec -1 using a cone and plate viscometer.
Was measured by reading the viscosity at. In the same manner, about 2 g of the collected paint was heated at 100 ° C. for 3 hours, and the weight loss rate before heating was measured. The gel fraction is
In the same manner, the residual ratio after extracting the collected paint with acetone for 3 hours at the reflux temperature was measured (calculated excluding the pigment).

【0019】本方法において、光輝性塗料(B)は、水
分含有率、粘度及びゲル分率を上記範囲に調整された、
水性塗料(A)の未硬化塗膜の塗面に塗装する塗料であ
り、りん片状光輝性顔料及び有機溶剤を主成分とする光
輝性塗料である。
In the present method, the glittering paint (B) has a water content, a viscosity and a gel fraction adjusted to the above ranges.
This is a paint to be applied to the uncured coating surface of the water-based paint (A), and is a glitter paint containing a scaly glitter pigment and an organic solvent as main components.

【0020】光輝性塗料(B)はりん片状光輝性顔料及
び有機溶剤を含有する光輝性塗料であり、さらに必要に
応じて塗料用樹脂組成物、沈降防止剤、静電助剤などを
適宜配合することは可能である。
The brilliant paint (B) is a brilliant paint containing a flaky brilliant pigment and an organic solvent, and may further contain, if necessary, a resin composition for a paint, an anti-settling agent, an electrostatic assistant, etc. It is possible to mix.

【0021】りん片状光輝性顔料は、キラキラとした金
属光沢感又は光干渉感を示すフレーク状の顔料が使用で
き、具体的には、アルミニウム(リーフィング、ノンリ
ーフィング)、蒸着アルミニウム、塩化オキシビスマ
ス、アルミナ(酸化アウミニウム)、雲母、グラファイ
ト、雲母状酸化鉄、酸化チタン被服雲母、酸化鉄被覆雲
母などがあげられる。これらの形状はいずれもりん片状
であって、長手方向の大きさが2〜50μm、厚さが
0.001〜2μmであることが好ましい。また、有機
溶剤として、通常の塗料に使用されている炭化水素系、
エステル系、エーテル系、アルコール系、ケトン系など
の溶剤が使用できる。
As the scaly brilliant pigment, a flake pigment exhibiting a glittering metallic luster or light interference can be used. Specifically, aluminum (leafing, non-leafing), vapor-deposited aluminum, oxybismuth chloride , Alumina (auminium oxide), mica, graphite, mica-like iron oxide, titanium oxide coated mica, iron oxide coated mica and the like. Each of these shapes is scaly, and preferably has a size in the longitudinal direction of 2 to 50 μm and a thickness of 0.001 to 2 μm. In addition, as organic solvents, hydrocarbons used in ordinary paints,
Ester, ether, alcohol, and ketone solvents can be used.

【0022】りん片状光輝性顔料と有機溶剤との比率
は、これらの両成分の合計重量を基準に、りん片状光輝
性顔料は1〜60重量%、特に2〜10重量%、有機溶
剤は99〜40重量%、特に98〜90重量%の範囲内
が適している。
The ratio of the flaky brilliant pigment to the organic solvent is based on the total weight of these two components, and the flaky brilliant pigment is 1 to 60% by weight, particularly 2 to 10% by weight, Is suitably in the range of 99 to 40% by weight, especially 98 to 90% by weight.

【0023】光輝性塗料(B)において、上記の両成分
に加えて、必要に応じて含有せしめることが可能な塗料
用樹脂組成物として、水酸基などの官能基を有するアク
リル樹脂、ポリエステル樹脂、アルキド樹脂、ウレタン
樹脂などの基体樹脂とメラミン樹脂、(ブロック)ポリ
イソシアネート化合物などの硬化剤からなる組成物があ
げられる。これらの塗料用樹脂組成物の配合量は、りん
片状光輝性顔料100重量部あたり、300重量部以
下、特に0.1〜100重量部の範囲内が適している。
沈降防止剤として、例えば、脂肪酸アマイドワックス、
酸化ポリエチレンなどがあげられ、これらの配合量は、
りん片状光輝性顔料100重量部あたり、50重量部以
下、特に0.1〜30重量部の範囲内が適している。
In the glittering paint (B), in addition to the above-mentioned two components, a paint resin composition which can be contained as required includes acrylic resins, polyester resins and alkyds having a functional group such as a hydroxyl group. Examples of the composition include a resin, a base resin such as a urethane resin, and a curing agent such as a melamine resin and a (block) polyisocyanate compound. The compounding amount of these resin compositions for paints is suitably not more than 300 parts by weight, especially in the range of 0.1 to 100 parts by weight, per 100 parts by weight of the flaky glittering pigment.
As an anti-settling agent, for example, fatty acid amide wax,
Oxidized polyethylene and the like.
A suitable amount is 50 parts by weight or less, especially 0.1 to 30 parts by weight, per 100 parts by weight of the flaky glittering pigment.

【0024】本方法は、水性塗料(A)の未硬化塗面
に、光輝性塗料(B)を、塗装時粘度をフォードカップ
#4で約10〜約50秒(20℃)に調整し、エアスプ
レー塗装、エアレススプレー塗装、静電塗装などによ
り、塗装することができる。その膜厚は、一般に、硬化
塗膜(りん片状光輝性顔料のみ、又は塗料用樹脂などが
併存することもある)として、約0.5〜約5μm、特
に約0.8〜約2μmが好ましい。
In the present method, the glitter coating (B) is applied to the uncured coating surface of the water-based coating (A) by adjusting the viscosity during coating to about 10 to about 50 seconds (20 ° C.) with a Ford cup # 4. The coating can be performed by air spray coating, airless spray coating, electrostatic coating, or the like. The film thickness is generally from about 0.5 to about 5 μm, particularly from about 0.8 to about 2 μm, as a cured coating film (only a flaky glittering pigment or a resin for a coating may coexist). preferable.

【0025】水性塗料(A)の未硬化塗面に、有機溶剤
系光輝性塗料(B)を塗装すると、水面に油をを流した
ように、光輝性塗料(B)が未硬化塗面に速やかにかつ
均一に延展し、その結果、りん片状光輝性顔料が均一か
つち密に未硬化塗面に平行に配向し、りん片状光輝性顔
料が本来的に有しているそれぞれの特性、例えば、りん
片状アルミニウムでは白くかつ金属光沢感にすぐれ、し
かもフリップフロップ性の強いメタリック塗膜を形成さ
せることができる。
When an organic solvent-based brilliant paint (B) is applied to the uncured coating surface of the water-based paint (A), the brilliant paint (B) is applied to the uncured coating surface as if the oil was poured on the water surface. It spreads quickly and uniformly, and as a result, the scaly glittering pigment is uniformly and densely oriented parallel to the uncured coating surface, and each characteristic that the scaly glittering pigment originally has, For example, flaky aluminum can form a metallic coating film that is white, has excellent metallic luster, and has strong flip-flop properties.

【0026】本方法では、水性塗料(A)の未硬化塗面
に光輝性塗料(B)を塗装した後、室温で放置し、又は
さらに50〜100℃で1〜30分程度強制乾燥して、
100〜170℃で10〜40分程度加熱して、水性塗
料(A)の塗膜、さらに光輝性塗料(B)の塗膜を同時
に硬化することにより本発明の目的とするメタリック複
層塗膜を形成することができる。
In the present method, the glitter coating (B) is applied to the uncured surface of the water-based coating (A) and then left at room temperature or further forcibly dried at 50 to 100 ° C. for about 1 to 30 minutes. ,
By heating at 100 to 170 ° C. for about 10 to 40 minutes to simultaneously cure the water-based coating (A) coating and the glittering coating (B) coating, the metallic multilayer coating of the present invention is intended. Can be formed.

【0027】さらに、本方法では、水性塗料(A)及び
光輝性塗料(B)を上記のように塗装し、必要に応じて
これらの塗膜を加熱硬化してから、光輝性塗料(B)の
塗面にクリヤ塗料(C)を塗装することができる。
Further, in the present method, the water-based paint (A) and the glitter paint (B) are applied as described above, and if necessary, these coating films are heated and cured, and then the glitter paint (B) is applied. Can be coated with the clear paint (C).

【0028】クリヤ塗料(C)は、無色透明又は有色透
明の塗膜を形成する塗料であり、複層塗膜の美化粧、仕
上り外観、耐候性、耐薬品性、耐水性、耐湿性などをよ
り一層向上させることができる。具体的には、水酸基、
カルボキシル基、シラノール基、エポキシ基などの官能
基を有するアクリル樹脂、ポリエステル樹脂、アルキド
樹脂、フッ素樹脂、ウレタン樹脂、シリコン含有樹脂な
どの基体樹脂に、メラミン樹脂、(ブロック)ポリイソ
シアネート化合物、エポキシ樹脂又は化合物、カルボキ
シル基含有樹脂又は化合物、酸無水物、アルコキシシラ
ン基含有樹脂又は化合物などの架橋剤とからなる熱硬化
性樹脂組成物をビヒクル成分とする有機溶剤型又は非水
分散液型の塗料が挙げられる。これらのクリヤ塗料に
は、紫外線吸収剤、着色剤などを適宜配合することもで
きる。
The clear paint (C) is a paint that forms a colorless and transparent or colored and transparent coating film. The clear coating material (C) has a multi-layer coating film which has good cosmetic, finished appearance, weather resistance, chemical resistance, water resistance, moisture resistance and the like. It can be further improved. Specifically, a hydroxyl group,
Base resins such as acrylic resin, polyester resin, alkyd resin, fluororesin, urethane resin and silicon-containing resin having functional groups such as carboxyl group, silanol group and epoxy group, melamine resin, (block) polyisocyanate compound, epoxy resin Or, an organic solvent-based or non-aqueous dispersion type paint containing a thermosetting resin composition comprising a compound, a carboxyl group-containing resin or a compound, an acid anhydride, a crosslinker such as an alkoxysilane group-containing resin or a compound as a vehicle component. Is mentioned. An ultraviolet absorber, a coloring agent, and the like can be appropriately compounded in these clear paints.

【0029】クリヤ塗料(C)は、公害防止、省資源の
観点から、高固形分型であることが好ましく、具体的に
は、塗装時の不揮発分濃度を約35重量%以上、好まし
くは約40〜約80重量%、更に好ましくは約45〜約
80重量%に調整したものが望ましい。
The clear paint (C) is preferably of a high solid content type from the viewpoint of preventing pollution and saving resources. Specifically, the non-volatile content at the time of coating is about 35% by weight or more, preferably about 35% by weight. It is preferably adjusted to 40 to about 80% by weight, more preferably to about 45 to about 80% by weight.

【0030】クリヤ塗料(C)は、エアスプレー塗装、
エアレススプレー塗装、静電塗装などにより塗装するこ
とができ、硬化塗膜に基ずいて約5〜約50μmの膜厚
に塗装することが好ましい。
The clear paint (C) is an air spray paint,
It can be applied by airless spray coating, electrostatic coating, or the like, and is preferably applied to a thickness of about 5 to about 50 μm based on the cured coating film.

【0031】本方法による複層塗膜は、上記した水性塗
料(A)及び光輝性塗料(B)、さらに必要に応じてク
リヤ塗料(C)を塗装することにより形成することがで
きる。
The multilayer coating film according to the present method can be formed by applying the above-mentioned water-based paint (A), glitter paint (B), and, if necessary, clear paint (C).

【0032】[0032]

【発明の効果】水性塗料(A)の未硬化塗膜面に有機溶
剤系光輝性塗料(B)を塗装すると、水面に油を浮かべ
たように、塗料(A)の塗面に塗料(B)が薄く均一に
延展しやすく、しかも塗料(B)は主に有機溶剤とりん
片状光輝性顔料とからなっているので、りん片状光輝性
顔料は未硬化塗面に全体に均一かつその塗面に対して平
行方向に配向しやすく、その結果、従来のメタリック塗
料を塗装したものと比べて、アルミニウムフレークの場
合は、白く、金属光沢感にすぐれ、しかもフリップフロ
ップ性の強いメタリック塗膜を形成することが可能にな
った。
When the organic solvent-based glittering paint (B) is applied to the uncured coating surface of the water-based paint (A), the paint (B) is applied to the coating surface of the paint (A) as if oil was floating on the water surface. ) Is thin and easy to spread uniformly, and since the paint (B) is mainly composed of an organic solvent and a scaly glittering pigment, the scaly glittering pigment is uniformly and uniformly applied to the uncured coating surface. It is easy to orient in the direction parallel to the painted surface. As a result, aluminum flakes are white, have excellent metallic luster, and have a strong flip-flop property compared to those coated with conventional metallic paint. Can be formed.

【0033】[0033]

【実施例】以下に本発明に関する実施例及び比較例につ
いて説明する。部及び%はいずれも重量を基準ににして
おり、塗膜の膜厚は硬化塗膜についてである。 1.試料の調製 1)被塗物 りん酸亜鉛化成処理を施した厚さ0.8mmのダル鋼板
に、熱硬化性エポキシ樹脂系カチオン電着塗料(「エレ
クロン9600」、関西ペイント社製、商品名)を膜厚
20μmになるように電着塗装し、170℃で30分間
加熱し塗膜を硬化させてから、自動車用中塗り塗料
(「TP−37プライマーサーフェーサー」、関西ペイ
ント社製、商品名、熱硬化性ポリエステル樹脂・メラミ
ン樹脂有機溶剤系)を膜厚25μmになるようにエアス
プレー塗装し、140℃で30分間加熱し塗膜を硬化さ
せて被塗物とした。 2)水性塗料(A) a):重合体(イ)(注1)25部、重合体(ロ)(注
2)60部、「サイメル327」(サイテック社製、商
品名、メラミン樹脂)15部、チタン白顔料80部を混
合し、水を加えて粘度40秒/フォードカップ#4/2
0℃に調整し水性塗料(A)(a)を得た。(配合比率
は固形分比である) (注1)重合体(イ):スチレン15部、メチルメタク
リレート20部、エチルアクリレート25部、n−ブチ
ルアクリレート20部、ヒドロキシエチルアクリレート
15部及びアクリル酸5部からなる重合体(水酸基価7
2、酸価39、数平均分子量12000)をジメチルエ
タノールアミンで中和したもの。 (注2)重合体(ロ):スチレン15部、メチルメタク
リレート20部、エチルアクリレート25部、n−ブチ
ルアクリレート25部、アクリル酸5部及びジアセトン
アクリルアミド10部からなる重合体(水酸基価0、酸
価39、カルボニル価0.6mmol/g/固形分、数
平均分子量12000)をジメチルエタノールアミンで
中和したもの。 b):重合体(ハ)(注3)80部及び「サイメル32
7」20部を混合し、水を加えて粘度40秒/フォード
カップ#4/20℃に調整した。(配合比率は固形分比
である) (注3)重合体(ハ):スチレン15部、メチルメタク
リレート20部、エチルアクリレート25部、n−ブチ
ルアクリレート15部、ヒドロキシエチルアクリレート
15部、アクリル酸5部及びジアセトンアクリルアミド
5部からなる重合体(水酸基価72、酸価39、カルボ
ニル価0.3mmol/g/固形分、数平均分子量12
000)をジメチルエタノールアミンで中和したもの。
EXAMPLES Examples and comparative examples according to the present invention will be described below. All parts and percentages are based on weight, and the thickness of the coating film is based on the cured coating film. 1. Preparation of sample 1) Coating object Thermosetting epoxy resin-based cationic electrodeposition paint (“Elecron 9600”, trade name, manufactured by Kansai Paint Co., Ltd.) on a 0.8 mm thick dull steel plate that has been subjected to zinc phosphate conversion treatment. Is electrodeposited so as to have a film thickness of 20 μm, and heated at 170 ° C. for 30 minutes to cure the coating film. Then, an intermediate coating for automobiles (“TP-37 Primer Surfacer”, manufactured by Kansai Paint Co., trade name, A thermosetting polyester resin / melamine resin organic solvent system) was applied by air spraying so as to have a film thickness of 25 μm, and heated at 140 ° C. for 30 minutes to cure the coating film to obtain an object to be coated. 2) Aqueous paint (A) a): 25 parts of polymer (a) (Note 1), 60 parts of polymer (B) (Note 2), "Cymel 327" (trade name, melamine resin, manufactured by Scitech) 15 Parts and 80 parts of titanium white pigment, and water was added to the mixture to obtain a viscosity of 40 seconds / Ford Cup # 4/2
The temperature was adjusted to 0 ° C. to obtain water-based paints (A) and (a). (The compounding ratio is the solid content ratio.) (Note 1) Polymer (a): 15 parts of styrene, 20 parts of methyl methacrylate, 25 parts of ethyl acrylate, 20 parts of n-butyl acrylate, 15 parts of hydroxyethyl acrylate and 5 parts of acrylic acid Of a polymer having a hydroxyl value of 7
2, acid value 39, number average molecular weight 12000) neutralized with dimethylethanolamine. (Note 2) Polymer (b): Polymer composed of 15 parts of styrene, 20 parts of methyl methacrylate, 25 parts of ethyl acrylate, 25 parts of n-butyl acrylate, 5 parts of acrylic acid and 10 parts of diacetone acrylamide (hydroxyl value 0, Acid value 39, carbonyl value 0.6 mmol / g / solid content, number average molecular weight 12000) neutralized with dimethylethanolamine. b): 80 parts of polymer (c) (Note 3) and Cymel 32
7 "was mixed, and water was added to adjust the viscosity to 40 seconds / Ford cup # 4/20 ° C. (The compounding ratio is a solid content ratio.) (Note 3) Polymer (C): 15 parts of styrene, 20 parts of methyl methacrylate, 25 parts of ethyl acrylate, 15 parts of n-butyl acrylate, 15 parts of hydroxyethyl acrylate, 5 parts of acrylic acid And a polymer consisting of 5 parts by weight of diacetone acrylamide (hydroxyl value 72, acid value 39, carbonyl value 0.3 mmol / g / solid content, number average molecular weight 12
000) neutralized with dimethylethanolamine.

【0034】3)光輝性塗料(B) a):ノンリーフィングアルニウムフレーク(注4)5
部及び「スワゾール1000」95部からなる混合物。 (注4)ノンリーフィングアルニウムフレーク:「アル
ペースト7680NS」(東洋アルミニウム社製、商品
名、長手寸法13μm、厚さ0.1〜2μm) b):ノンリーフィングアルニウムフレーク(注4)5
部、樹脂組成物(注5)2部及び「スワゾール100
0」93部からなる混合物。 (注5)樹脂組成物:水酸基価100、数平均分子量1
5000のアクリル樹脂/ブチルエーテル化メラミン樹
脂=75/25(重量比)からなる混合物。 c)ノンリーフィングアルニウムフレーク(注4)1
部、樹脂組成物(注5)6部及び「スワゾール100
0」93部からなる混合物。
3) Bright paint (B) a): Non-leafing aluminum flake (Note 4) 5
And 95 parts of "Swazol 1000". (Note 4) Non-leafing aluminum flakes: "Alpaste 7680NS" (manufactured by Toyo Aluminum Co., Ltd., trade name, longitudinal dimension 13 μm, thickness 0.1 to 2 μm) b): Non-leafing aluminum flakes (Note 4) 5
Parts, 2 parts of the resin composition (Note 5) and “Swazol 100
0 "a mixture of 93 parts. (Note 5) Resin composition: hydroxyl value 100, number average molecular weight 1
A mixture consisting of 5000 acrylic resin / butyl etherified melamine resin = 75/25 (weight ratio). c) Non-leafing aluminum flakes (Note 4) 1
Parts, 6 parts of the resin composition (Note 5) and “Swazol 100
0 "a mixture of 93 parts.

【0035】2.実施例及び比較例 実施例 1 被塗物に水性塗料(A)(a)を膜厚25μmになるよ
うに塗装し、室温で15分間放置してから(この未硬化
塗膜の粘度は1500センチポイズ、水分含有率は65
%、ゲル分率は0%であった)、光輝性塗料(B)(a)
を膜厚1μmに塗装し、室温で3分間放置してから、
「マジクロンクリヤ」(関西ペイント社製、商品名、有
機溶剤型熱硬化性アクリル樹脂系クリヤ塗料)を膜厚4
0μmに塗装し、室温で3分間放置してから、140℃
で30分間加熱してこれらの複層塗膜を同時に硬化せし
めた。
2. Examples and Comparative Examples Example 1 A water-based paint (A) (a) was applied to an object to be coated so as to have a film thickness of 25 μm, and allowed to stand at room temperature for 15 minutes (the viscosity of the uncured coating film was 1500 centipoise). , Moisture content is 65
%, The gel fraction was 0%), and the glittering paint (B) (a)
Is coated to a thickness of 1 μm and left at room temperature for 3 minutes.
"Magiclon clear" (manufactured by Kansai Paint Co., Ltd., trade name, organic solvent type thermosetting acrylic resin clear paint) with a film thickness of 4
0 μm, leave at room temperature for 3 minutes,
For 30 minutes to simultaneously cure these multilayer coating films.

【0036】水性塗料(A)(a)の未硬化塗面に光輝
性塗料(B)(a)を塗装すると、水面に油を浮かべた
ように、塗料(A)(a)の塗面に塗料(B)(a)が薄
く均一に延展し、しかも塗料(B)(a)は主に有機溶
剤とりん片状アルミニウム顔料とからなっているので、
りん片状アルミニウム顔料は未硬化塗面に全体に均一か
つその塗面に対して平行方向に配向しており、その結
果、比較例1に比べ、白く、金属光沢感にすぐれ、しか
もフリップフロップ性の強いメタリック塗膜を形成する
ことができた。
When the glitter coating (B) (a) is applied to the uncured coating surface of the water-based coating (A) (a), the coating surface of the coating (A) (a) is applied to the coating surface as if oil was floating on the water surface. Since the paint (B) (a) spreads thinly and uniformly, and because the paint (B) (a) is mainly composed of an organic solvent and flaky aluminum pigment,
The scaly aluminum pigment is entirely uniform on the uncured coating surface and is oriented in a direction parallel to the coating surface. As a result, compared to Comparative Example 1, the aluminum pigment is white, has excellent metallic luster, and has flip-flop properties. , A metallic coating film having a strong

【0037】実施例 2 被塗物に水性塗料(A)(b)を膜厚25μmになるよ
うに塗装し、室温で15分間放置してから(この未硬化
塗膜の粘度は1500センチポイズ、水分含有率は65
%、ゲル分率は0%であった)、光輝性塗料(B)
(b)を膜厚1μmに塗装し、室温で3分間放置してか
ら、「マジクロンクリヤ」(関西ペイント社製、商品
名、有機溶剤型熱硬化性アクリル樹脂系クリヤ塗料)を
膜厚40μmに塗装し、室温で3分間放置してから、1
40℃で30分間加熱してこれらの複層塗膜を同時に硬
化せしめた。
Example 2 A water-based paint (A) (b) was applied to an object to be coated so as to have a film thickness of 25 μm, and was allowed to stand at room temperature for 15 minutes. Content rate is 65
%, The gel fraction was 0%), and the glittering paint (B)
(b) was coated to a thickness of 1 μm, left at room temperature for 3 minutes, and then coated with “MAGICRON CLEAR” (trade name, manufactured by Kansai Paint Co., Ltd., organic solvent type thermosetting acrylic resin clear coating) to a thickness of 40 μm. And leave it at room temperature for 3 minutes.
These multilayer coatings were simultaneously cured by heating at 40 ° C. for 30 minutes.

【0038】水性塗料(A)(b)の未硬化塗面に光輝
性塗料(B)(b)を塗装すると、水面に油を浮かべた
ように、塗料(A)(b)の塗面に塗料(B)(b)が薄
く均一に延展し、しかも塗料(B)(b)は主に有機溶
剤とりん片状アルミニウム顔料とからなっているので、
りん片状アルミニウム顔料は未硬化塗面に全体に均一か
つその塗面に対して平行方向に配向しており、その結
果、比較例1に比べ、白く、金属光沢感にすぐれ、しか
もフリップフロップ性の強いメタリック塗膜を形成する
ことができた。
When the glitter coatings (B) and (b) are applied to the uncured coating surfaces of the aqueous coatings (A) and (b), the coating surfaces of the coatings (A) and (b) are applied as if oil were floating on the water surface. Since the paints (B) and (b) spread thinly and uniformly, and because the paints (B) and (b) are mainly composed of an organic solvent and flaky aluminum pigment,
The scaly aluminum pigment is entirely uniform on the uncured coating surface and is oriented in a direction parallel to the coating surface. As a result, compared to Comparative Example 1, the aluminum pigment is white, has excellent metallic luster, and has flip-flop properties. , A metallic coating film having a strong

【0039】比較例 1 被塗物に水性塗料(A)(a)を膜厚25μmになるよ
うに塗装し、室温で15分間放置してから(この未硬化
塗膜の粘度は1500センチポイズ、水分含有率は65
%、ゲル分率は0%であった)、光輝性塗料(B)(c)
を膜厚1μmに塗装し、室温で3分間放置してから、
「マジクロンクリヤ」(関西ペイント社製、商品名、有
機溶剤型熱硬化性アクリル樹脂系クリヤ塗料)を膜厚4
0μmに塗装し、室温で3分間放置してから、140℃
で30分間加熱してこれらの複層塗膜を同時に硬化せし
めた。
COMPARATIVE EXAMPLE 1 A water-based paint (A) (a) was applied to an object to be coated so as to have a film thickness of 25 μm, and allowed to stand at room temperature for 15 minutes. Content rate is 65
%, The gel fraction was 0%), and the brilliant paint (B) (c)
Is coated to a thickness of 1 μm and left at room temperature for 3 minutes.
"Magiclon clear" (manufactured by Kansai Paint Co., Ltd., trade name, organic solvent type thermosetting acrylic resin clear paint) with a film thickness of 4
0 μm, leave at room temperature for 3 minutes,
For 30 minutes to simultaneously cure these multilayer coating films.

【0040】水性塗料(A)(a)の未硬化塗面に光輝
性塗料(B)(c)を塗装すると、塗料(A)(a)の塗
面に塗料(B)(c)が薄く均一に延展せず、しかも塗
料(B)(c)は塗料用樹脂が多量含有しているので、
りん片状アルミニウム顔料を未硬化塗面に全体に均一か
つその塗面に対して平行方向に配向させることは困難で
あり、その結果、実施例1、2に比べ、白さが劣り、金
属光沢感も十分でなく、しかもフリップフロップ性も弱
かった。
When the glitter coatings (B) and (c) are applied to the uncured coating surface of the aqueous coatings (A) and (a), the coatings (B) and (c) become thin on the coating surfaces of the coatings (A) and (a). It does not spread uniformly, and paints (B) and (c) contain a large amount of paint resin.
It is difficult to orient the flaky aluminum pigment uniformly on the uncured coating surface and in a direction parallel to the coating surface. As a result, the whiteness is inferior to that of Examples 1 and 2, and the metallic luster is low. The feeling was not enough, and the flip-flop property was weak.

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) C09D 201/00 C09D 201/00 Fターム(参考) 4D075 CB13 EA06 EB52 EB56 EC23 4J038 CG031 CG071 CG141 CH121 CJ021 CJ101 CJ131 CJ141 DD061 DD081 DD231 GA03 GA06 HA066 HA216 HA546 JA01 JA17 JA25 JA32 JA55 KA06 KA08 KA20 MA07 MA08 MA15 NA01 PA19 PB07 PC02Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (reference) C09D 201/00 C09D 201/00 F term (reference) 4D075 CB13 EA06 EB52 EB56 EC23 4J038 CG031 CG071 CG141 CH121 CJ021 CJ101 CJ131 CJ141 DD061 DD081 DD231 GA03 GA06 HA066 HA216 HA546 JA01 JA17 JA25 JA32 JA55 KA06 KA08 KA20 MA07 MA08 MA15 NA01 PA19 PB07 PC02

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】水性塗料(A)の未硬化塗面に、りん片状
光輝性顔料及び有機溶剤を主成分とする光輝性塗料
(B)を塗装することを複層塗膜形成方法。
1. A method for forming a multi-layer coating film, comprising applying a glitter paint (B) containing a flaky glitter pigment and an organic solvent as main components to the uncured coating surface of the aqueous paint (A).
【請求項2】水性塗料(A)の未硬化塗膜が、水分含有
率20〜80重量%、粘度1000センチポイズ以上
(20℃)である請求項1記載の複層塗膜形成方法。
2. The method for forming a multilayer coating film according to claim 1, wherein the uncured coating film of the water-based coating material (A) has a water content of 20 to 80% by weight and a viscosity of 1000 centipoise or more (20 ° C.).
JP2000115088A 2000-04-17 2000-04-17 Multi-layer coating formation method Expired - Lifetime JP4489905B2 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009013853A1 (en) * 2007-07-25 2009-01-29 Basf Coatings Japan Ltd. Method for formation of multi-layered coating film, and coated article

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Publication number Priority date Publication date Assignee Title
JPS6121761A (en) * 1984-07-11 1986-01-30 Kansai Paint Co Ltd Metallic finishing method
JPH0292974A (en) * 1988-09-30 1990-04-03 Kansai Paint Co Ltd Water-dispersible paint and method for forming coating film using the paint
JPH09187722A (en) * 1996-01-12 1997-07-22 Kansai Paint Co Ltd Method for forming coating film
JPH10296171A (en) * 1997-04-28 1998-11-10 Nippon B Chem Kk Method for coating plastic base material
JPH10328615A (en) * 1997-05-29 1998-12-15 Kansai Paint Co Ltd Compound layer film forming method
JPH1157605A (en) * 1997-08-26 1999-03-02 Kansai Paint Co Ltd Metallic coating method
JPH1190318A (en) * 1997-07-25 1999-04-06 Kansai Paint Co Ltd Formation of metallic coating film
JP2000000517A (en) * 1998-06-15 2000-01-07 Kansai Paint Co Ltd Method for repairing multi layered coating

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6121761A (en) * 1984-07-11 1986-01-30 Kansai Paint Co Ltd Metallic finishing method
JPH0292974A (en) * 1988-09-30 1990-04-03 Kansai Paint Co Ltd Water-dispersible paint and method for forming coating film using the paint
JPH09187722A (en) * 1996-01-12 1997-07-22 Kansai Paint Co Ltd Method for forming coating film
JPH10296171A (en) * 1997-04-28 1998-11-10 Nippon B Chem Kk Method for coating plastic base material
JPH10328615A (en) * 1997-05-29 1998-12-15 Kansai Paint Co Ltd Compound layer film forming method
JPH1190318A (en) * 1997-07-25 1999-04-06 Kansai Paint Co Ltd Formation of metallic coating film
JPH1157605A (en) * 1997-08-26 1999-03-02 Kansai Paint Co Ltd Metallic coating method
JP2000000517A (en) * 1998-06-15 2000-01-07 Kansai Paint Co Ltd Method for repairing multi layered coating

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009013853A1 (en) * 2007-07-25 2009-01-29 Basf Coatings Japan Ltd. Method for formation of multi-layered coating film, and coated article
JP2009028607A (en) * 2007-07-25 2009-02-12 Basf Coatings Japan Ltd Method for formation of multi-layered coating film and coated article

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