JP4958090B2 - MULTILAYER COATING FORMATION METHOD AND COATED ARTICLE - Google Patents
MULTILAYER COATING FORMATION METHOD AND COATED ARTICLE Download PDFInfo
- Publication number
- JP4958090B2 JP4958090B2 JP2004012060A JP2004012060A JP4958090B2 JP 4958090 B2 JP4958090 B2 JP 4958090B2 JP 2004012060 A JP2004012060 A JP 2004012060A JP 2004012060 A JP2004012060 A JP 2004012060A JP 4958090 B2 JP4958090 B2 JP 4958090B2
- Authority
- JP
- Japan
- Prior art keywords
- paint
- coating film
- coating
- color
- pigment
- 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.)
- Expired - Fee Related
Links
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
Description
本発明は、光輝感、透明感に優れる塗膜構造、塗膜形成方法及び塗装物品に関する。 The present invention relates to a coating film structure, a coating film forming method and a coated article excellent in glitter and transparency.
着色塗料、金属フレーク顔料を配合したメタリック塗料及びクリヤー塗料を順次塗装して、複層塗膜を形成する方法はすでに知られている。例えば、特許文献1には、透明感及び彩度に優れ、且つ隠蔽性に優れたマイカ塗膜の形成方法として、基材上に、カラーベース塗膜を形成し、焼付け硬化させた後、ベースカラー塗膜、マイカベース塗膜及びクリヤー塗膜を順次形成するマイカ塗膜の形成方法において、上記カラーベース塗膜が呈する色相と、上記ベースカラー塗膜が呈する色相及び上記マイカベース塗膜が呈する色相が同系色であり、且つ、上記マイカベース塗膜を形成するマイカベース塗料が、透明性顔料と非透明性顔料とを重量比で３／１〜２０／１の比で含有することを特徴とする高意匠マイカ塗膜の形成方法が記載されている。しかし、この方法では、明度が低い青系あるいは赤系の塗色においては、十分な透明感は得られない。 A method of forming a multilayer coating film by coating a colored paint, a metallic paint containing a metal flake pigment, and a clear paint in order is already known. For example, in Patent Document 1, as a method for forming a mica coating film having excellent transparency and saturation and excellent concealment property, a color base coating film is formed on a substrate, and after baking and curing, a base color In the method of forming a mica coating film that sequentially forms a coating film, a mica base coating film, and a clear coating film, the hue that the color base coating film exhibits, the hue that the base color coating film exhibits, and the hue that the mica base coating film exhibits The mica base paint that is a similar color and forms the mica base coating film contains a transparent pigment and a non-transparent pigment in a ratio of 3/1 to 20/1 by weight. A method for forming a highly designed mica coating is described. However, with this method, sufficient transparency cannot be obtained for blue or red paint colors with low brightness.
したがって、本発明の目的は、明度が低い青系あるいは赤系の塗色においても光輝感、透明感に優れる塗膜構造、塗膜形成方法及び塗装物品を提供することである。 Accordingly, an object of the present invention is to provide a coating film structure, a coating film forming method, and a coated article that are excellent in glitter and transparency even in a blue or red coating color with low brightness.
本発明は、
１．基材上に着色顔料を含んでなるカラーベースコート塗料（Ａ）による塗膜層、該カラーベースコート塗料（Ａ）による塗膜とＬ＊Ｃ＊ｈ表色系による明度差ΔＬが３０以下かつ色相差Δｈが５０以下かつ彩度差ΔＣが３０以下となるメタリックベース塗料（Ｂ）による塗膜層、及びトップクリヤー塗料（Ｃ）による塗膜層が積層してなることを特徴とする塗膜構造、
２．基材上に着色顔料を含んでなるカラーベースコート塗料（Ａ）、該カラーベースコート塗料（Ａ）による塗膜とＬ＊Ｃ＊ｈ表色系による明度差ΔＬが３０以下かつ色相差Δｈが５０以下かつ彩度差ΔＣが３０以下となる塗膜を形成するように選択された着色顔料及び鱗片状光輝性顔料を含んでなるメタリックベース塗料（Ｂ）、及びトップクリヤー塗料（Ｃ）を順次塗装することを特徴とする複層塗膜形成方法、
３．メタリックベース塗料（Ｂ）による塗膜の可視光領域における光線透過率が４０％以上である１項記載の塗膜構造及び２項記載の複層塗膜形成方法、
４．トップクリヤー塗料（Ｃ）が染料及び／又は着色顔料を含む３項記載の塗膜構造及び複層塗膜形成方法。
５．複層塗膜のＬ＊Ｃ＊ｈ表色系における色相角度ｈが１８０°から３００°である３項記載の塗膜構造及び複層塗膜形成方法、
６．２〜５項のいずれか１項記載の複層塗膜形成方法で得られた塗装物品
に関する。
The present invention
1. Coating layer by color base coat paint (A) comprising a color pigment on the substrate, lightness difference ΔL by the color base coat paint (A) and L * C * h color system is 30 or less, and hue difference A coating film structure comprising a coating layer formed of a metallic base coating (B) having a Δh of 50 or less and a saturation difference ΔC of 30 or less, and a coating layer formed of a top clear coating (C);
2. A color base coat paint (A) comprising a color pigment on a substrate, a lightness difference ΔL of 30 or less and a hue difference Δh of 50 or less according to the coating film of the color base coat paint (A) and the L * C * h color system In addition, a metallic base paint (B) and a top clear paint (C) containing a color pigment and a scale-like glitter pigment selected so as to form a coating film having a saturation difference ΔC of 30 or less are sequentially applied. A method for forming a multilayer coating film,
3. The coating film structure according to 1, wherein the light transmittance in the visible light region of the coating film by the metallic base coating material (B) is 40% or more, and the multilayer coating film forming method according to 2,
4). The coating film structure and multilayer coating film forming method according to claim 3, wherein the top clear coating material (C) contains a dye and / or a coloring pigment.
5. The coating film structure and the multilayer coating film forming method according to claim 3, wherein the hue angle h in the L * C * h color system of the multilayer coating film is 180 ° to 300 °,
It is related with the coated article obtained by the multilayer coating-film formation method of any one of 6.2-5.
本発明は、基材上に、着色顔料を含んでなるカラーベースコート塗料（Ａ）、特定の着色顔料及び鱗片状光輝性顔料を含んでなるメタリックベース塗料（Ｂ）、トップクリヤー塗料（Ｃ）を順次塗装して得られる塗膜構造、複層塗膜形成方法であって、本発明方法によって、明度が低い青系あるいは赤系の塗色においても光輝感、透明感に優れる塗膜を得ることができる。 The present invention provides a color base coat paint (A) comprising a color pigment, a metallic base paint (B) comprising a specific color pigment and a scaly glitter pigment, and a top clear paint (C) on a substrate. It is a coating film structure obtained by sequential coating, a multilayer coating film forming method, and a coating film excellent in glitter and transparency even in a blue or red coating color with low brightness is obtained by the method of the present invention. Can do.
本発明方法において基材としては、鉄、亜鉛、アルミニウム等の金属やこれらを含む合金、これらの金属によるメッキまたは蒸着が施された成型物、及びガラス、プラスチックや発泡体などによる成型物等の素材：ならびにこれらの素材に応じて適宜、脱脂処理や表面処理を実施した処理素材も基材とすることができる。さらに、上記基材に下塗り塗膜及び／又は中塗り塗膜を形成させたものを基材とすることもでき、これらの塗膜形成した基材が特に好ましい。 In the method of the present invention, the base material includes metals such as iron, zinc, and aluminum, alloys containing them, molded products plated or vapor-deposited with these metals, and molded products made of glass, plastic, foam, etc. Material: A treated material subjected to a degreasing treatment or a surface treatment as appropriate according to these materials can also be used as a base material. Furthermore, what formed the undercoat coating film and / or the intermediate coating film on the said base material can also be used as a base material, and the base material in which these coating films were formed is especially preferable.
上記下塗り塗膜は、素材表面を隠蔽したり、素材に防食性及び防錆性などを付与するために形成されるものであり、下塗り塗料を塗装し、乾燥、硬化することによって得ることができる。この下塗り塗料種としては特に限定されるものではなく、例えば、電着塗料、溶剤型プライマー等を挙げることができる。 The undercoat coating film is formed to conceal the surface of the material, or to impart corrosion resistance and rust prevention properties to the material, and can be obtained by applying an undercoat paint, drying and curing. . The type of the undercoat paint is not particularly limited, and examples thereof include an electrodeposition paint and a solvent-type primer.
また、上記中塗り塗膜とは、素材表面や下塗り塗膜を隠蔽したり、付着性や耐チッピング性などを付与するために形成されるものであり、素材表面や下塗り塗膜上に、中塗り塗料を塗装し、乾燥、硬化することによって得ることができる。中塗り塗料種は、特に限定されるものではなく、それ自体既知のものを使用することができ、例えば、熱硬化性樹脂組成物及び着色顔料を必須成分とする有機溶剤系又は水系の中塗り塗料を好ましく使用することができる。 The intermediate coating film is formed to conceal the surface of the material or the undercoating film, or to impart adhesion or chipping resistance. It can be obtained by applying a paint and drying and curing. The type of intermediate coating is not particularly limited, and those known per se can be used, for example, an organic solvent-based or water-based intermediate coating containing a thermosetting resin composition and a color pigment as essential components. A paint can be preferably used.
また、基材として、下塗り塗膜及び／又は中塗り塗膜を形成させた基材を用いる場合においては、下塗り塗膜及び／又は中塗り塗膜を加熱などにより硬化させた後に、後述する次工程の塗料を塗装することができる。また、下塗り塗膜及び／又は中塗り塗膜が未硬化の状態で、次工程の塗料を塗装し、同時に加熱することによって下塗り塗膜及び／又は中塗り塗膜と次工程の塗料を硬化させることもできる。 In the case of using a base material on which an undercoat coating film and / or an intermediate coating film is formed as the base material, after the undercoat coating film and / or the intermediate coating film is cured by heating, the following will be described later. Process paint can be applied. In addition, the undercoat film and / or the intermediate coat film is applied in the uncured state, and the paint of the next process is applied and simultaneously heated to cure the undercoat film and / or the intermediate coat film and the paint of the next process. You can also
本発明では、上述の如き基材上にカラーベースコート塗料（Ａ）を塗装する。カラーベースコート塗料（Ａ）は、基材を隠蔽し、複層塗膜の色相、特にシェード部における色相を決定する塗料であって、着色顔料を必須成分として含有する。該着色顔料としては、インク用、塗料用として従来公知の顔料を１種あるいは２種以上を組み合わせて使用することができる。着色顔料の具体例としては、酸化チタン、酸化鉄等の金属酸化物顔料、チタンイエロー等の複合酸化金属顔料、カーボンブラック、アゾ系顔料、キナクリドン系顔料、ジケトピロロピロール系顔料、ペリレン系顔料、ペリノン系顔料、ベンズイミダゾロン系顔料、イソインドリン系顔料、イソインドリノン系顔料、金属キレートアゾ系顔料、フタロシアニン系顔料、インダンスロン系顔料、ジオキサン系顔料、インジゴ系顔料等を挙げることができる。 In the present invention, the color base coat paint (A) is applied on the substrate as described above. The color base coat paint (A) is a paint that hides the base material and determines the hue of the multilayer coating film, particularly the hue in the shade portion, and contains a color pigment as an essential component. As the colored pigment, conventionally known pigments for ink and paint can be used alone or in combination of two or more. Specific examples of color pigments include metal oxide pigments such as titanium oxide and iron oxide, composite metal oxide pigments such as titanium yellow, carbon black, azo pigments, quinacridone pigments, diketopyrrolopyrrole pigments, and perylene pigments. Perinone pigments, benzimidazolone pigments, isoindoline pigments, isoindolinone pigments, metal chelate azo pigments, phthalocyanine pigments, indanthrone pigments, dioxane pigments, indigo pigments, and the like. .
上記着色顔料の配合量は、得られる塗膜の着色力や仕上がり外観の点からベースコート塗料（Ａ）中のビヒクル固形分１００重量部に対して、１〜１５０重量部、好ましくは３〜１００重量部が適当である。 The blending amount of the color pigment is from 1 to 150 parts by weight, preferably from 3 to 100 parts by weight, based on 100 parts by weight of the vehicle solid content in the base coat paint (A) from the viewpoint of coloring power and finished appearance of the resulting coating film. The part is appropriate.
本発明のカラーベースコート塗料（Ａ）には、着色顔料のほかに、ビヒクルとして、樹脂成分を含有することができる。樹脂成分としては、熱硬化性樹脂組成物が好ましく、具体的には、水酸基などの架橋性官能基を有する、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、尿素樹脂、ポリイソシアネ−ト化合物（ブロック体も含む）などの架橋剤とを併用したものが挙げられ、これらは有機溶剤及び／又は水などの溶媒に溶解または分散させて使用することができる。 In addition to the color pigment, the color base coat paint (A) of the present invention can contain a resin component as a vehicle. The resin component is preferably a thermosetting resin composition, specifically, a base resin such as an acrylic resin, a polyester resin, an alkyd resin, or a urethane resin having a crosslinkable functional group such as a hydroxyl group, a melamine resin, or urea. Examples thereof include those used in combination with a crosslinking agent such as a resin and a polyisocyanate compound (including a block body), and these can be used by dissolving or dispersing in a solvent such as an organic solvent and / or water.
さらに、カラーベースコート塗料（Ａ）には、必要に応じて、水あるいは有機溶剤等の溶媒、レオロジーコントロール剤、顔料分散剤、沈降防止剤、硬化触媒、消泡剤、酸化防止剤、紫外線吸収剤等の各種添加剤、体質顔料などを適宜配合することができる。 Furthermore, for the color base coat paint (A), if necessary, a solvent such as water or an organic solvent, a rheology control agent, a pigment dispersant, an anti-settling agent, a curing catalyst, an antifoaming agent, an antioxidant, an ultraviolet absorber. Various additives such as extender, extender pigments and the like can be appropriately blended.
カラーベースコート塗料（Ａ）は、前述の成分を混合分散せしめることによって調製することができる。カラーベースコート塗料（Ａ）は、塗装に際しては、通常、固形分含有率が３０〜６０重量％、好ましくは３５〜５０重量％、また、２０℃における粘度が１８〜２５秒／フォ−ドカップ＃４となるように調整しておくことが好ましい。 The color base coat paint (A) can be prepared by mixing and dispersing the aforementioned components. The color base coat paint (A) usually has a solid content of 30 to 60% by weight, preferably 35 to 50% by weight, and a viscosity at 20 ° C. of 18 to 25 seconds / Ford cup # 4. It is preferable to adjust so that.
カラーベースコート塗料（Ａ）は、静電塗装、エア−スプレ−、エアレススプレ−などの方法で塗装することができ、その膜厚は硬化塗膜に基づいて１０〜４５μｍの範囲内とするのが、塗膜の平滑性の点から好ましい。カラーベースコート塗料（Ａ）の塗膜それ自体は、通常約７０〜約１５０℃の温度で架橋硬化させることができる。 The color base coat paint (A) can be applied by a method such as electrostatic coating, air spray, airless spray, etc., and its film thickness should be in the range of 10 to 45 μm based on the cured coating film. From the viewpoint of the smoothness of the coating film. The coating itself of the color base coat paint (A) can be crosslinked and cured usually at a temperature of about 70 to about 150 ° C.
本発明方法においては、カラーベースコート塗料（Ａ）を塗装架橋硬化させた塗膜上にメタリックベース塗料（Ｂ）を塗装することができるが、カラーベースコート塗料（Ａ）を加熱硬化させることなく未架橋硬化の状態の塗膜上にメタリックベース塗料（Ｂ）を塗装することができる。 In the method of the present invention, the metallic base paint (B) can be applied on the coating film obtained by coating and curing the color base coat paint (A), but the color base coat paint (A) is not crosslinked without being heated and cured. The metallic base paint (B) can be applied onto the cured coating film.
本発明方法は、カラーベースコート塗料（Ａ）を塗装して得られた塗膜上に、さらにメタリックベース塗料（Ｂ）を塗装して複層塗膜を得ることを特徴とする。メタリックベース塗料（Ｂ）は、複層塗膜において光輝感、ハイライト部の色相を決定する塗料であって、着色顔料及び鱗片状光輝性顔料を必須成分として含有する。 The method of the present invention is characterized in that a multilayer coating film is obtained by further coating a metallic base paint (B) on a coating film obtained by applying the color base coat paint (A). The metallic base paint (B) is a paint that determines the brightness and the hue of the highlight portion in the multilayer coating film, and contains a color pigment and a scale-like glitter pigment as essential components.
本発明方法におけるメタリックベース塗料（Ｂ）に配合せしめる着色顔料は、カラーベース塗料（Ａ）による塗膜とメタリックベース塗料（Ｂ）による塗膜とのＬ＊Ｃ＊ｈ表色系による明度差ΔＬが３０以下かつ色相差Δｈが５０以下かつ彩度差ΔＣが３０以下となるように選択されることが好ましく、より好ましくは、明度差ΔＬが２０以下かつ色相差Δｈが３５以下かつ彩度差ΔＣが２０以下である。具体的には、カラーベース塗料（Ａ）とメタリックベース塗料（Ｂ）をそれぞれ硬化塗膜として３０μｍとなるように平滑なブリキ板上に塗装後、乾燥硬化させた塗膜を「ＳＭカラーコンピューター」（測色計、商品名、スガ試験機社製）にて測色を行うことができる。ここでいうＬ＊Ｃ＊ｈ表色系とは、１９７６年に国際照明委員会で規定され、ＪＩＳ Ｚ ８７２９にも採用されているＬ＊ａ＊ｂ＊表色系を極座標表示したものであって、Ｌ＊は明度を表し、Ｃ＊は原点からの距離として彩度を表す、ｈはＬ＊ａ＊ｂ＊表色系におけるａ＊赤方向の軸を０°として、ここから反時計方向の色相に対して移動した色相角度を表す。 The color pigment compounded in the metallic base paint (B) in the method of the present invention has a lightness difference ΔL due to the L * C * h color system between the paint film by the color base paint (A) and the paint film by the metallic base paint (B). It is preferably selected so that the hue difference Δh is 30 or less, the saturation difference ΔC is 30 or less, and more preferably, the brightness difference ΔL is 20 or less, the hue difference Δh is 35 or less, and the saturation difference ΔC. Is 20 or less. Specifically, the color base paint (A) and the metallic base paint (B) are each coated on a smooth tin plate so as to have a cured coating thickness of 30 μm, and then the dried and cured coating film is “SM color computer” ( Color measurement can be performed with a colorimeter, trade name, manufactured by Suga Test Instruments Co., Ltd.). The L * C * h color system here is a polar coordinate display of the L * a * b * color system specified by the International Commission on Illumination in 1976 and also adopted in JIS Z 8729. L * represents lightness, C * represents saturation as the distance from the origin, h represents the a * red axis in the L * a * b * color system, 0 °, and counterclockwise from here Represents the hue angle moved with respect to the hue of.
本発明のメタリックベース塗料（Ｂ）に含まれる着色顔料としては、インク用、塗料用として従来公知の顔料を１種あるいは２種以上組み合わせて使用することができる。着色顔料の具体例としては、チタンイエロー等の複合酸化金属顔料、アゾ系顔料、キナクリドン系顔料、ジケトピロロピロール系顔料、ペリレン系顔料、ペリノン系顔料、ベンズイミダゾロン系顔料、イソインドリン系顔料、イソインドリノン系顔料、金属キレートアゾ系顔料、フタロシアニン系顔料、インダンスロン系顔料、ジオキサン系顔料、インジゴ系顔料等を挙げることができる。これら着色顔料の好ましい含有量は、塗膜中のビヒクル固形分１００重量部に対して、０.１〜３０重量部が好ましく、より好ましくは１〜２０重量部が適当である。 As the color pigment contained in the metallic base paint (B) of the present invention, one or a combination of two or more conventionally known pigments for ink and paint can be used. Specific examples of color pigments include composite metal oxide pigments such as titanium yellow, azo pigments, quinacridone pigments, diketopyrrolopyrrole pigments, perylene pigments, perinone pigments, benzimidazolone pigments, and isoindoline pigments. And isoindolinone pigments, metal chelate azo pigments, phthalocyanine pigments, indanthrone pigments, dioxane pigments, and indigo pigments. The content of these color pigments is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the vehicle solid content in the coating film.
本発明のメタリックベース塗料（Ｂ）は、複層塗膜の透明感の点から、メタリックベース塗料（Ｂ）による塗膜の可視光領域における光線透過率が４０％以上であることが好ましく、より好ましくは５０％以上である。塗膜の光線透過率とは、具体的には、硬化塗膜として３０μｍとなるように平滑なＰＴＦＥ板に塗装後、乾燥硬化させたものを剥離した塗膜を分光光度計「ＭＰＳ−２４５０」（商品名：島津製作所製）にて測定した可視光領域（波長４００ｎｍ〜７００ｎｍ）における光線透過率である。可視光領域の光線透過率とは、可視光領域の入射光に対する透過光の強度の比であって、入射光量と透過光量をそれぞれ積分して測定することができ、数値が大きいほど透明度が高いことを意味する。 The metallic base coating material (B) of the present invention preferably has a light transmittance of 40% or more in the visible light region of the coating film by the metallic base coating material (B) from the viewpoint of the transparency of the multilayer coating film. Preferably it is 50% or more. Specifically, the light transmittance of the coating film is a spectrophotometer “MPS-2450” obtained by removing the coating film which has been dried and cured after being applied to a smooth PTFE plate so as to have a cured coating film thickness of 30 μm. It is the light transmittance in the visible light region (wavelength 400 nm to 700 nm) measured by (trade name: manufactured by Shimadzu Corporation). The light transmittance in the visible light region is a ratio of the intensity of transmitted light to the incident light in the visible light region, and can be measured by integrating the incident light amount and the transmitted light amount. The higher the numerical value, the higher the transparency. Means that.
本発明のメタリックベース塗料（Ｂ）は、前記の光線透過率を得るために、特に濁り顔料を一定量以上含まないことが望ましい。ここでいう濁り顔料とは、塗料中の樹脂固形分１００重量部に基づいて顔料量が２０重量部となるように配合して塗料化し、硬化塗膜厚が３０μｍとなるように平滑なＰＴＦＥ板に塗装し、硬化、剥離した塗膜を分光光度計「ＭＰＳ−２４５０」（商品名：島津製作所製）にて測定した可視光領域（波長４００ｎｍ〜７００ｎｍ）における光線透過率が５％以下となるような顔料を意味し、具体例としては、粒径が１００ｎｍを超える酸化チタンや酸化鉄等の金属酸化物顔料やカーボンブラックなどが挙げられる。これら濁り顔料は、塗料組成物中の樹脂固形分１００重量部に対して、カーボンブラックにおいては０．２重量部以下、その他の濁り顔料においては２重量部以下であることが特に望ましい。 In order to obtain the light transmittance, the metallic base paint (B) of the present invention preferably does not contain a certain amount of turbid pigment. The term “turbid pigment” as used herein refers to a PTFE plate that is smooth so that the thickness of the cured coating film becomes 30 μm by blending it so that the pigment amount is 20 parts by weight based on 100 parts by weight of the resin solid content in the paint. The light transmittance in the visible light region (wavelength 400 nm to 700 nm) measured with a spectrophotometer “MPS-2450” (trade name: manufactured by Shimadzu Corporation) is 5% or less. Specific examples of such pigments include metal oxide pigments such as titanium oxide and iron oxide having a particle size exceeding 100 nm, carbon black, and the like. It is particularly desirable that these turbid pigments are 0.2 parts by weight or less for carbon black and 2 parts by weight or less for other turbid pigments with respect to 100 parts by weight of resin solid content in the coating composition.
また、本発明のメタリックベースコート塗料（Ａ）における鱗片状光輝性顔料としては、例えば、アルミニウム、銅、ニッケル合金、ステンレス等の鱗片状金属顔料、表面を金属酸化物で被覆した鱗片状金属顔料、表面に着色顔料を化学吸着させた鱗片状金属顔料、表面に酸化還元反応を起こさせることにより酸化アルミニウム層を形成した鱗片状アルミニウム顔料、アルミニウム固溶盤状酸化鉄顔料、ガラスフレーク顔料、表面を金属酸化物で被覆したガラスフレーク顔料、表面に着色顔料を化学吸着させたガラスフレーク顔料、表面を二酸化チタンで被覆した干渉マイカ顔料、干渉マイカ顔料を還元した還元マイカ顔料、表面に着色顔料を化学吸着させたり、表面を酸化鉄で被覆した着色マイカ顔料、表面を二酸化チタンで被覆したグラファイト顔料、表面を二酸化チタンで被覆したシリカフレークやアルミナフレーク顔料、盤状酸化鉄顔料、ホログラム顔料、合成マイカ顔料、らせん構造を持つコレステリック液晶ポリマー顔料、オキシ塩化ビスマス顔料などが挙げられる。これらのうち、干渉マイカ顔料が特に好ましいが、限定されるものではなく、求める光輝感に応じて各種鱗片状光輝性顔料を適宜使用することができる。 Examples of the scaly glitter pigment in the metallic base coat paint (A) of the present invention include scaly metal pigments such as aluminum, copper, nickel alloy, and stainless steel, scaly metal pigments whose surfaces are coated with metal oxides, A scaly metal pigment with a colored pigment chemisorbed on the surface, a scaly aluminum pigment with an aluminum oxide layer formed by causing a redox reaction on the surface, an aluminum solid lamellar iron oxide pigment, a glass flake pigment, a surface Glass flake pigment coated with metal oxide, glass flake pigment with colored pigment chemisorbed on the surface, interference mica pigment coated with titanium dioxide on the surface, reduced mica pigment with reduced interference mica pigment, colored pigment on the surface Colored mica pigments that are adsorbed or coated with iron oxide on the surface, and a glass coated with titanium dioxide on the surface. Aito pigments, silica flakes, alumina flake pigment coated with titanium dioxide surface, disk-shaped iron oxide pigments, holographic pigments, synthetic mica pigments, cholesteric liquid crystal polymer pigments having a helical structure, and the like oxy bismuth pigments chloride. Among these, interference mica pigments are particularly preferable, but are not limited, and various scaly glitter pigments can be used as appropriate according to the desired glitter.
本発明におけるメタリックベース塗料（Ｂ）に基づく塗膜において、鱗片状光輝顔料の好ましい配合量は、光輝感、塗膜外観の点から、塗膜中の樹脂固形分１００重量部に対して、０.１〜３０重量部が好ましく、より好ましくは１〜２０重量部である。 In the coating film based on the metallic base paint (B) in the present invention, the preferred blending amount of the scaly glitter pigment is 0 with respect to 100 parts by weight of the resin solid content in the coating film from the viewpoint of glitter and coating film appearance. 0.1-30 weight part is preferable, More preferably, it is 1-20 weight part.
本発明のメタリックベース塗料（Ｂ）には、着色顔料、鱗片状光輝性顔料のほかに、ビヒクルとして、樹脂成分を含有することができる。樹脂成分としてはカラーベースコート塗料（Ａ）に使用できる樹脂と同様のものを使用することができる。 The metallic base paint (B) of the present invention can contain a resin component as a vehicle in addition to the color pigment and the scaly glitter pigment. As the resin component, the same resin as that which can be used for the color base coat paint (A) can be used.
さらに、メタリックベース塗料（Ｂ）には、必要に応じて、水あるいは有機溶剤等の溶媒、顔料分散剤、沈降防止剤、硬化触媒、消泡剤、酸化防止剤、紫外線吸収剤等の各種添加剤、体質顔料などを適宜配合することができる。 Furthermore, various additives such as a solvent such as water or an organic solvent, a pigment dispersant, an antisettling agent, a curing catalyst, an antifoaming agent, an antioxidant, and an ultraviolet absorber are added to the metallic base paint (B) as necessary. An agent, extender, etc. can be appropriately blended.
本発明方法におけるメタリックベース塗料（Ｂ）は、前述の成分を混合分散せしめることによって調製される。メタリックベース塗料（Ｂ）は塗装の際は固形分含有率を、塗料組成物に基づいて、１５〜５０重量％、好ましくは２０〜４０重量％に、また、２０℃における粘度を１１〜１５秒／フォ−ドカップ＃４に調整しておくことが好ましい。 The metallic base paint (B) in the method of the present invention is prepared by mixing and dispersing the aforementioned components. The metallic base paint (B) has a solid content of 15 to 50% by weight, preferably 20 to 40% by weight based on the paint composition, and a viscosity at 20 ° C. of 11 to 15 seconds. / It is preferable to adjust to the forward cup # 4.
本発明のメタリックベース塗料（Ｂ）は、静電塗装、エア−スプレ−、エアレススプレ−などの方法で塗装することができ、その膜厚は硬化塗膜に基づいて５〜２５μｍの範囲内とするのが好ましい。メタリックベース塗料（Ｂ）の塗膜それ自体は約７０〜約１５０℃の温度で硬化させることができる。 The metallic base paint (B) of the present invention can be applied by a method such as electrostatic coating, air spray, airless spray, and the film thickness is in the range of 5 to 25 μm based on the cured coating film. It is preferable to do this. The coating of the metallic base paint (B) itself can be cured at a temperature of about 70 to about 150 ° C.
本発明においては、メタリックベース塗料（Ｂ）を塗装して得られた塗膜上にさらにトップクリヤー塗料（Ｃ）を１層もしくは２層以上塗装して、トップクリヤー塗膜を形成させることができる。トップクリヤー塗料（Ｃ）は、メタリックベース塗料（Ｂ）の未硬化もしくは硬化させてなる塗面に塗装することができる。 In the present invention, it is possible to form a top clear coating film by further coating one or more top clear coatings (C) on the coating obtained by applying the metallic base coating (B). . The top clear paint (C) can be applied to the uncured or cured surface of the metallic base paint (B).
本発明のトップクリヤー塗料（Ｃ）としては、従来公知のものが制限なく使用できる。例えば、基体樹脂及び架橋剤を含有する液状もしくは粉体状の塗料組成物が適用できる。基体樹脂の例としては、水酸基、カルボキシル基、シラノ−ル基、エポキシ基などの架橋性官能基を含有する、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が挙げられる。架橋剤としては、前記基体樹脂の官能基と反応しうるメラミン樹脂、尿素樹脂、ポリイソシアネ−ト化合物、ブロックポリイソシアネ−ト化合物、エポキシ化合物又は樹脂、カルボキシル基含有化合物又は樹脂、酸無水物、アルコキシシラン基含有化合物又は樹脂等が挙げられる。また、必要に応じて、水や有機溶剤等の溶媒、硬化触媒、消泡剤、紫外線吸収剤等の添加剤を適宜配合することができる。 As the top clear paint (C) of the present invention, conventionally known ones can be used without limitation. For example, a liquid or powdery coating composition containing a base resin and a crosslinking agent can be applied. Examples of the base resin include acrylic resin, polyester resin, alkyd resin, fluororesin, urethane resin, and silicon-containing resin containing a crosslinkable functional group such as a hydroxyl group, a carboxyl group, a silanol group, and an epoxy group. It is done. As a crosslinking agent, a melamine resin capable of reacting with the functional group of the base resin, urea resin, polyisocyanate compound, block polyisocyanate compound, epoxy compound or resin, carboxyl group-containing compound or resin, acid anhydride, Examples thereof include alkoxysilane group-containing compounds or resins. Moreover, additives, such as solvents, such as water and an organic solvent, a curing catalyst, an antifoamer, and a ultraviolet absorber, can be suitably mix | blended as needed.
本発明におけるトップクリヤー塗料（Ｃ）には、透明性を損なわない範囲内において、着色顔料を適宜配合することができる。着色顔料としては、インク用、塗料用として従来公知の顔料を１種あるいは２種以上を組み合わせて配合することができる。その添加量は、適宜決定されて良いが、クリヤー塗膜中の樹脂１００固形分重量部に対して、３０重量部以下、好ましくは０.１〜１０重量部である。 In the top clear paint (C) in the present invention, a color pigment can be appropriately blended within a range not impairing transparency. As the color pigment, one or a combination of two or more conventionally known pigments for ink and paint can be blended. The amount of addition may be appropriately determined, but is 30 parts by weight or less, preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the solid content of the resin in the clear coating film.
本発明におけるクリヤー塗料は、静電塗装、エア−スプレ−、エアレススプレ−などの方法で塗装することができ、その膜厚は硬化塗膜に基づいて５〜４０μｍの範囲内とするのが好ましい。トップクリヤー塗料（Ｃ）の塗膜それ自体は約７０〜約１５０℃の温度で架橋硬化させることができる。 The clear paint in the present invention can be applied by a method such as electrostatic coating, air spray, airless spray, and the film thickness is preferably in the range of 5 to 40 μm based on the cured coating film. . The top clear coating (C) coating itself can be crosslinked and cured at a temperature of about 70 to about 150 ° C.
本発明方法で得られる複層塗膜は、明度が低い色域であるＬ＊Ｃ＊ｈ表色系における色相角度ｈが１２０°以上且つ６０°以下であることが好ましく、より好ましくは１８０°〜３００°である。ここでいう色相角度は、具体的には、本発明の方法で得られた複層塗膜を「ＳＭカラーコンピューター」（測色計、商品名、スガ試験機社製）にて測色して求めることができる。 The multilayer coating film obtained by the method of the present invention preferably has a hue angle h in the L * C * h color system, which is a color gamut with low lightness, of 120 ° to 60 °, more preferably 180 °. ~ 300 °. Specifically, the hue angle here is obtained by measuring the color of the multilayer coating film obtained by the method of the present invention with an “SM color computer” (colorimeter, trade name, manufactured by Suga Test Instruments Co., Ltd.). Can be sought.
次に、実施例を挙げて、本発明をより具体的に説明する。
実施例１〜６及び比較例１、２
基材の調整
脱脂及びりん酸亜鉛処理した鋼板（ＪＩＳＧ３１４１、大きさ４００×３００×０．８ｍｍ）にカチオン電着塗料「エレクロン９４００ＨＢ」（商品名：関西ペイント株式会社製、アミン変性エポキシ樹脂系カチオン樹脂に硬化剤としてブロックポリイソシアネ−ト化合物を使用したもの）を硬化塗膜に基づいて膜厚２０μｍになるように電着塗装し、１７０℃で２０分加熱して架橋硬化させて電着塗膜を得た。
Next, an Example is given and this invention is demonstrated more concretely.
Examples 1 to 6 and Comparative Examples 1 and 2
Preparation of base material Degreased and zinc phosphate-treated steel plate (JISG3141, size 400 x 300 x 0.8 mm), cationic electrodeposition paint "Electron 9400HB" (trade name: manufactured by Kansai Paint Co., Ltd., amine-modified epoxy resin cation Electrodeposition of a resin using a block polyisocyanate compound as a curing agent) to a film thickness of 20 μm based on the cured coating film, followed by heating at 170 ° C. for 20 minutes for crosslinking and electrodeposition A coating film was obtained.
得られた電着塗面に、中塗塗料「ル−ガベ−ク中塗りグレ−」（商品名：関西ペイント株式会社製、ポリエステル樹脂・メラミン樹脂系有機溶剤型塗料）をエアスプレーにて硬化塗膜にμ膜厚３０μｍになるように塗装し、１４０℃で３０分加熱して架橋硬化させて、中塗塗膜を形成した塗板を基材とした。
塗料の調整
水酸基含有アクリル樹脂（水酸基価１００、数平均分子量２００００）及びメラミン樹脂からなる樹脂成分１００重量部（固形分）あたり、光輝材及び必要に応じて着色顔料を表１に示す比率で配合して攪拌混合し、塗装に適正な粘度に希釈して、固形分約２５％の有機溶剤型塗料を調整し、各実施例及び比較例に使用するカラーベース塗料、メタリックベース塗料を作成した。
On the surface of the resulting electrodeposition, an intermediate coating “Lugerbake intermediate coating gray” (trade name: polyester resin / melamine resin organic solvent-based coating manufactured by Kansai Paint Co., Ltd.) is applied by air spray. A coated plate on which an intermediate coating film was formed was applied as a base material by coating the film to a thickness of 30 μm and heating at 140 ° C. for 30 minutes to cure by crosslinking.
Preparation of coating material Lubricant and, if necessary, coloring pigments are blended in proportions shown in Table 1 per 100 parts by weight (solid content) of a hydroxyl group-containing acrylic resin (hydroxyl value 100, number average molecular weight 20000) and melamine resin. Then, the mixture was stirred and mixed, diluted to an appropriate viscosity for coating, and an organic solvent-type paint having a solid content of about 25% was prepared to prepare a color base paint and a metallic base paint used in each of Examples and Comparative Examples.
また、トップクリヤー塗料としては、実施例１〜４及び比較例１、２についてはクリヤー塗料（ル−ガベ−ククリヤ−、関西ペイント製、商品名、アクリル樹脂・アミノ樹脂系、有機溶剤型）塗装に適正な粘度に希釈した。実施例５、６については、表１に示す比率でクリヤー塗料（ル−ガベ−ククリヤ−、関西ペイント製、商品名、アクリル樹脂・アミノ樹脂系、有機溶剤型）に着色顔料を配合し、ビーズミルにて分散し、クリヤー塗料を作成した。 As the top clear paint, Examples 1 to 4 and Comparative Examples 1 and 2 were applied with a clear paint (Lugabe Kukuriya, manufactured by Kansai Paint, trade name, acrylic resin / amino resin system, organic solvent type). Diluted to an appropriate viscosity. For Examples 5 and 6, coloring pigments were blended into the clear paint (Lugabe Kukuriya, Kansai Paint, trade name, acrylic resin / amino resin type, organic solvent type) at the ratio shown in Table 1, and the beads mill To obtain a clear paint.
測色
（２）で調整したカラーベース塗料、メタリックベース塗料をそれぞれ平滑なブリキ板にエアスプレーにて硬化塗膜に基づいて３０μｍとなるように塗装し、１４０℃で３０分加熱して架橋硬化させて形成した塗板を「ＳＭカラーコンピューター」（測色計、商品名、スガ試験機社製）にて測色して、１０度視野、照明としてＤ６５を使用したときのカラーベース塗料とメタリックベース塗料の明度差ΔＬ、彩度差ΔＣ、色相角度差Δｈを算出した。結果を表２に示す。
光線透過率の測定
（２）で調整したメタリックベース塗料をそれぞれ平滑なＰＴＦＥ板にエアスプレーにて硬化塗膜に基づいて３０μｍとなるように塗装し、１４０℃で３０分加熱して架橋硬化させて形成した塗膜を剥離させて、分光光度計「ＭＰＳ−２４５０」（商品名：島津製作所製）にて、可視光領域（波長４００ｎｍ〜７００ｎｍ）における光線透過率を測定した。結果を表２に示す。
Color base paint and metallic base paint prepared in color measurement (2) are each applied to a smooth tin plate by air spraying to a thickness of 30 μm based on the cured coating, and heated at 140 ° C. for 30 minutes for crosslinking and curing. The coated plate formed in this way is measured by “SM Color Computer” (colorimeter, trade name, manufactured by Suga Test Instruments Co., Ltd.), and the color base paint and metallic base paint when D65 is used as the 10 ° field of view and illumination. A brightness difference ΔL, a saturation difference ΔC, and a hue angle difference Δh were calculated. The results are shown in Table 2.
Measurement of light transmittance The metallic base paint prepared in (2) was applied to a smooth PTFE plate by air spraying to a thickness of 30 μm based on the cured coating film, and heated at 140 ° C. for 30 minutes to be crosslinked and cured. The film formed was peeled, and the light transmittance in the visible light region (wavelength 400 nm to 700 nm) was measured with a spectrophotometer “MPS-2450” (trade name: manufactured by Shimadzu Corporation). The results are shown in Table 2.
試験板の作成
以下の手順にて、表１に示す構成となるようにカラーベース塗料、ベースコート塗料、を塗装し、トップクリヤー塗料を塗装して試験板とした。
Preparation of test plate In the following procedure, a color base paint and a base coat paint were applied so as to have the constitution shown in Table 1, and a top clear paint was applied to obtain a test plate.
（カラーベース塗料の塗装）
(１)で作成した中塗り塗板に、（２）で作成したカラーベース塗料をミニベル型回転式静電塗装機を用いて、ブ−ス温度２０℃、湿度７５％の条件で塗装した。塗装後、室温にて１５分間放置した後に、熱風循環式乾燥炉内を使用して、１４０℃で３０分間加熱し、３０μｍの膜厚の硬化塗膜を得た。
(Color base paint application)
The color base paint prepared in (2) was applied to the intermediate coating plate prepared in (1) under the conditions of a boot temperature of 20 ° C. and a humidity of 75% using a mini-bell type rotary electrostatic coating machine. After coating, the mixture was allowed to stand at room temperature for 15 minutes, and then heated in a hot-air circulating drying furnace at 140 ° C. for 30 minutes to obtain a cured coating film having a thickness of 30 μm.
（メタリックベース塗料の塗装）
カラーベース塗膜上に、（２）で作成したメタリックベース塗料をＲＥＡガンを用いて、ブ−ス温度２０℃、湿度７５％の条件で、硬化塗膜として、７〜１５μｍとなるように塗装した。
(Painting of metallic base paint)
On the color base coating film, the metallic base paint prepared in (2) was applied using a REA gun under the conditions of a boot temperature of 20 ° C. and a humidity of 75% so as to be 7 to 15 μm as a cured coating film. .
（トップクリヤー塗料の塗装）
メタリックベース塗料を塗装後に、室温にて１５分間放置し、ついで、これらの未硬化塗面に、（２）で作成したトップクリヤー塗料をミニベル型回転式静電塗装機を用いて、ブ−ス温度２０℃、湿度７５％の条件で硬化塗膜として、２５〜３５μｍとなるように塗装した。塗装後、室温にて１５分間放置した後に、熱風循環式乾燥炉内を使用して、１４０℃で３０分間加熱し、複層塗膜を同時に乾燥硬化せしめて試験板とした。
(Coating of top clear paint)
After painting the metallic base paint, it is allowed to stand at room temperature for 15 minutes, and then the top clear paint prepared in (2) is applied to these uncured paint surfaces using a minibell rotary electrostatic coater. The cured coating film was coated to a thickness of 25 to 35 μm under the conditions of a temperature of 20 ° C. and a humidity of 75%. After coating, the sample was allowed to stand at room temperature for 15 minutes, and then heated in a hot air circulating drying oven at 140 ° C. for 30 minutes to simultaneously dry and cure the multilayer coating film to obtain a test plate.
（評価試験）
実施例１〜６及び比較例１、２で得られた試験板について、目視にて、光輝感、透明感を評価した。また、得られた複層塗膜をそれぞれ「ＳＭカラーコンピューター」（測色計、商品名、スガ試験機社製）にて測色して、１０度視野、照明としてＤ６５を使用したときの色相角度ｈを算出した。表３にその結果を示す。
(Evaluation test)
The test panels obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were visually evaluated for brightness and transparency. In addition, each of the obtained multi-layer coating films is color-measured by “SM color computer” (colorimeter, trade name, manufactured by Suga Test Instruments Co., Ltd.), hue when using D65 as a 10 ° field of view and illumination. The angle h was calculated. Table 3 shows the results.
本発明の塗膜形成方法は、各種工業製品、特に自動車車体の外板に適用できる。
The coating film forming method of the present invention can be applied to various industrial products, particularly to the outer plate of an automobile body.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004012060A JP4958090B2 (en) | 2004-01-20 | 2004-01-20 | MULTILAYER COATING FORMATION METHOD AND COATED ARTICLE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004012060A JP4958090B2 (en) | 2004-01-20 | 2004-01-20 | MULTILAYER COATING FORMATION METHOD AND COATED ARTICLE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005205262A JP2005205262A (en) | 2005-08-04 |
| JP4958090B2 true JP4958090B2 (en) | 2012-06-20 |
Family
ID=34898560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004012060A Expired - Fee Related JP4958090B2 (en) | 2004-01-20 | 2004-01-20 | MULTILAYER COATING FORMATION METHOD AND COATED ARTICLE |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4958090B2 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5057841B2 (en) * | 2007-05-09 | 2012-10-24 | 関西ペイント株式会社 | Multilayer pattern coating film forming method |
| CN107073515B (en) * | 2014-10-23 | 2020-09-29 | 关西涂料株式会社 | Method for forming multilayer coating film |
| JP6587404B2 (en) * | 2015-03-27 | 2019-10-09 | 日本ペイント・オートモーティブコーティングス株式会社 | Formation method of multilayer coating film |
| JP6330743B2 (en) * | 2015-07-08 | 2018-05-30 | マツダ株式会社 | Laminated coatings and painted products |
| JP6330742B2 (en) * | 2015-07-08 | 2018-05-30 | マツダ株式会社 | Laminate coating design method |
| RU2686175C1 (en) * | 2015-12-02 | 2019-04-24 | Мазда Мотор Корпорейшн | Multilayer coating film and article with coating |
| WO2017146150A1 (en) * | 2016-02-26 | 2017-08-31 | マツダ株式会社 | Laminated coating film, and coated article |
| JP6250220B1 (en) * | 2016-08-19 | 2017-12-20 | エーエスペイント株式会社 | Multi-layer coating formation method |
| CN111615431B (en) * | 2018-01-15 | 2022-05-06 | 关西涂料株式会社 | Method for forming multilayer coating film |
| US11740532B2 (en) | 2018-12-17 | 2023-08-29 | Viavi Solutions Inc. | Article including light valves |
| US11118061B2 (en) * | 2018-12-17 | 2021-09-14 | Viavi Solutions Inc. | Article including at least one metal portion |
| JP2022094523A (en) * | 2020-12-15 | 2022-06-27 | 日本ペイント・オートモーティブコーティングス株式会社 | Multilayer coating film and method for forming multilayer coating film |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0716534A (en) * | 1993-06-30 | 1995-01-20 | Nippon Paint Co Ltd | Formation of double-layered film |
| JP3386222B2 (en) * | 1994-03-03 | 2003-03-17 | 日本ペイント株式会社 | Design film formation method |
| JPH1028926A (en) * | 1996-05-14 | 1998-02-03 | Yamaha Motor Co Ltd | Metallic coating film structure and formation of metallic coating film |
| US6165621A (en) * | 1996-06-14 | 2000-12-26 | Kansai Paint Co., Ltd. | Method for forming multi-layer metallic coating film |
| JP4226743B2 (en) * | 1999-12-22 | 2009-02-18 | 関西ペイント株式会社 | Repair coating method of multilayer coating film |
| JP2003236462A (en) * | 2002-02-20 | 2003-08-26 | Nippon Paint Co Ltd | Pearl coating film formation method and layered coating film |
-
2004
- 2004-01-20 JP JP2004012060A patent/JP4958090B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005205262A (en) | 2005-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4886994B2 (en) | Multi-layer coating formation method | |
| JP5567297B2 (en) | Coating method | |
| US10239091B2 (en) | Method for forming multilayer coating film | |
| JP6360809B2 (en) | Multi-layer coating formation method | |
| US20050214483A1 (en) | Method for forming multilayered coating film | |
| JP4916319B2 (en) | Multilayer pattern coating film forming method | |
| JP2007106925A (en) | Metallic coating composition, method for forming coating film, coating-film structure and coated article | |
| JP4958090B2 (en) | MULTILAYER COATING FORMATION METHOD AND COATED ARTICLE | |
| JP2011026543A (en) | Paint composition and method of forming paint film | |
| JP5547526B2 (en) | Coating composition, coating film forming method and coating film structure | |
| JP4824958B2 (en) | METALLIC COATING COMPOSITION, COATING FORMATION METHOD, COATING STRUCTURE AND COATED ARTICLE | |
| JP4851393B2 (en) | Coating method | |
| JP6805401B1 (en) | Multi-layer coating film forming method | |
| JP4676150B2 (en) | High chroma metallic coating composition, coating film forming method, and coated article | |
| JP4971611B2 (en) | Metallic coating composition, multilayer coating film forming method, coating film structure and coated article | |
| JP6583898B2 (en) | Paint composition | |
| JP5156194B2 (en) | Red metallic paint composition | |
| JP4751043B2 (en) | MULTILAYER COATING FORMATION METHOD AND COATED ARTICLE | |
| JP5611629B2 (en) | Coating method | |
| JP2006239519A (en) | Japanese lacquer tone multi-layer coating film forming method and coated article | |
| JP2005177642A (en) | Method of forming multilayer coating film, and coated article | |
| JP2005334717A (en) | Method for forming multi-layer coating film, film structure and coated article | |
| JPH111641A (en) | Process for forming double-layer coating film | |
| WO2021100238A1 (en) | Method for forming multilayer coating film | |
| JP5057841B2 (en) | Multilayer pattern coating film forming method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061211 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090525 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090602 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20090908 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091202 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20091217 |
|
| A912 | Re-examination (zenchi) completed and case transferred to appeal board |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20100122 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20111215 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120203 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120313 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150330 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4958090 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150330 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |