JP2016077998A - Coating formation method - Google Patents
Coating formation method Download PDFInfo
- Publication number
- JP2016077998A JP2016077998A JP2014214383A JP2014214383A JP2016077998A JP 2016077998 A JP2016077998 A JP 2016077998A JP 2014214383 A JP2014214383 A JP 2014214383A JP 2014214383 A JP2014214383 A JP 2014214383A JP 2016077998 A JP2016077998 A JP 2016077998A
- Authority
- JP
- Japan
- Prior art keywords
- coating
- film
- coating film
- paint
- organic solvent
- 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
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- 238000009736 wetting Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、金属調光沢を有する塗膜を形成できる塗膜形成方法に関するものである。 The present invention relates to a coating film forming method capable of forming a coating film having metallic gloss.
塗料を塗装する目的は、主に素材の保護及び美観の付与である。工業製品においては、その商品力を高める点から、美観、なかでも特に「質感」が重要である。消費者が求める工業製品の質感は多様なものであるが、近年、自動車外板、自動車部品、家電製品等の分野において、金属や真珠のような光沢感が求められている（以下、「金属調光沢」と表記する）。 The purpose of applying the paint is mainly to protect the material and impart beauty. In industrial products, aesthetics, in particular, “texture” is particularly important from the standpoint of enhancing its product power. There are various textures of industrial products demanded by consumers, but in recent years, gloss such as metal and pearls has been demanded in the fields of automobile outer panels, automobile parts, home appliances, etc. "Glossy").
金属調光沢とは、鏡面のように表面に粒子感がなく、さらに、塗板に対して垂直に近い状態で見たとき（ハイライト）は光り輝き、塗板に対して斜め上から見たとき（シェード）は暗く見える、すなわちハイライト領域とシェード領域の輝度差が大きいことを特徴とする質感である。 Metallic luster is a mirror-like surface that does not have a grainy appearance. Furthermore, when viewed in a state perpendicular to the coated plate (highlight), it glows, and when viewed obliquely from the coated plate (shade) ) Is a texture that appears dark, that is, has a large luminance difference between the highlight area and the shade area.
かかる金属調光沢を工業製品の表面に付与する技術には、金属めっき処理や金属蒸着処理等（例えば、特許文献１）があるが、塗装によって金属調光沢が付与できれば、簡便さ及びコスト等の観点から有利である。 Techniques for imparting such metallic luster to the surface of industrial products include metal plating treatment and metal vapor deposition treatment (for example, Patent Document 1). However, if the metallic luster can be imparted by coating, simplicity and cost can be improved. It is advantageous from the viewpoint.
特許文献２には、未硬化の塗面に、ノンリーフィングアルミニウムフレークおよび有機溶剤を含有する組成物を塗装し、次いでクリヤ塗料を塗装することを特徴とするメタリック塗膜形成方法が開示されている。 Patent Document 2 discloses a method for forming a metallic coating film characterized in that an uncured coating surface is coated with a composition containing non-leafing aluminum flakes and an organic solvent, and then a clear coating is applied. .
また、特許文献３には、光輝材、樹脂を含む不揮発固形分及び溶剤を含有するメタリック塗料基剤を、高沸点溶剤と低沸点溶剤から成る希釈剤を用いて希釈率１５０〜５００％の割合で希釈し、上記メタリック塗料基剤中の樹脂分１００重量部に対して５〜１０重量部の粘性樹脂を添加して成ることを特徴とするメタリック塗料が開示されている。 In Patent Document 3, a metallic paint base containing a bright material, a non-volatile solid containing a resin, and a solvent is diluted with a diluent composed of a high-boiling solvent and a low-boiling solvent at a rate of 150 to 500%. The metallic paint is characterized in that it is diluted with 5 to 10 parts by weight of a viscous resin with respect to 100 parts by weight of the resin in the metallic paint base.
特許文献４には、光輝材１０〜３０％と、分子量２５，０００〜５０，０００（ＭＷｎ）のセルロースアセテートブチレート樹脂１０〜５０％と、残量としてのアクリル−メラミン樹脂を含有する固形分たる塗料基材を、エステル系溶剤及び／又はケトン系溶剤を用い、上記固形分が１〜１０％となるような希釈率で希釈して成るメタリック塗料が開示されている。 Patent Document 4 discloses a solid content containing 10 to 30% of a glittering material, 10 to 50% of a cellulose acetate butyrate resin having a molecular weight of 25,000 to 50,000 (MWn), and an acrylic-melamine resin as the remaining amount. There is disclosed a metallic paint obtained by diluting a coating base material with an ester solvent and / or a ketone solvent at a dilution rate such that the solid content is 1 to 10%.
特許文献５には、貴金属および／または金属を含むコロイド粒子を含有し、さらに塗膜形成性樹脂および特定の混合溶剤を含有する光輝材含有ベース塗料を使用する複層塗膜形成方法が開示されている。 Patent Document 5 discloses a method for forming a multilayer coating film using a glittering material-containing base coating material containing a noble metal and / or colloidal particles containing a metal, and further containing a coating film-forming resin and a specific mixed solvent. ing.
特許文献６には、貴金属および／または金属を含むコロイド粒子、および塗膜形成性樹脂を含有する特定の光輝材含有ベース塗料を使用し、特定の塗布方法と組み合わせて使用する複層塗膜形成方法が開示されている。 Patent Document 6 discloses the use of a specific glittering material-containing base paint containing a noble metal and / or metal-containing colloidal particles and a film-forming resin, and is used in combination with a specific coating method. A method is disclosed.
特許文献２〜６に開示されている塗料は溶剤系塗料である。しかし近年、低環境負荷等の観点から、金属調塗料の分野においても水性化が求められるようになった。 The paints disclosed in Patent Documents 2 to 6 are solvent-based paints. However, in recent years, from the viewpoint of low environmental load and the like, water-based coatings have also been required in the field of metallic paints.
特許文献７には、蒸着金属膜を粉砕して金属片とした光輝性顔料と、２０〜１５０ｍｇＫＯＨ／ｇ（固形分）の酸価を有する水性セルロース誘導体とを含み、前記水性セルロース誘導体を主たるバインダー樹脂とし、前記光輝性顔料の含有量がＰＷＣで２０〜７０質量％であることを特徴とする水性ベース塗料組成物が開示されている。 Patent Document 7 includes a luster pigment obtained by pulverizing a vapor-deposited metal film into a metal piece, and an aqueous cellulose derivative having an acid value of 20 to 150 mgKOH / g (solid content), and the aqueous cellulose derivative as a main binder. An aqueous base coating composition is disclosed, which is a resin, and the content of the glitter pigment is 20 to 70% by mass in terms of PWC.
しかし、特許文献７に記載の塗料によって形成される塗膜では、金属調光沢が不十分であった。さらに、バインダー樹脂を必須とする点でコスト面でも問題があった。 However, the coating film formed by the paint described in Patent Document 7 has insufficient metal gloss. Furthermore, there is a problem in terms of cost in that the binder resin is essential.
また、特許文献８には、鱗片状光輝性顔料を含んでなる水性ベースコート塗料の塗装方法であって、塗料中の固形分が２０〜４０重量％になるように調整された水性ベースコート塗料（Ａ１）を乾燥膜厚で１〜１５μｍとなるように被塗物に塗装した後、未硬化の塗膜の上に、塗料中の固形分が２〜１５重量％になるように調整された水性ベースコート塗料（Ａ２）を乾燥膜厚で０．１〜５μｍとなるように塗装することを特徴とする水性ベースコート塗料の塗装方法が開示されている。 Further, Patent Document 8 discloses a coating method of an aqueous base coat paint comprising a scaly glittering pigment, wherein the aqueous base coat paint (A1) is adjusted so that the solid content in the paint is 20 to 40% by weight. ) Is applied to an object so that the dry film thickness is 1 to 15 μm, and then the aqueous base coat is adjusted so that the solid content in the paint is 2 to 15% by weight on the uncured coating film. A coating method of an aqueous base coat paint is disclosed, wherein the paint (A2) is applied so as to have a dry film thickness of 0.1 to 5 μm.
しかし、近年、６０°グロス値が１５０以上である鏡面のような金属調光沢を求められているところ、特許文献８に記載の塗装方法によって形成される塗膜では不十分であった。 However, in recent years, a metallic gloss such as a mirror surface having a 60 ° gloss value of 150 or more has been demanded. However, the coating film formed by the coating method described in Patent Document 8 was insufficient.
本発明は、金属調光沢に優れた金属調塗膜を形成することができる塗膜形成方法及び塗装物品を提供することを課題とする。 This invention makes it a subject to provide the coating-film formation method and coating article which can form the metallic-tone coating film excellent in metal-like glossiness.
本発明は、被塗物に、光輝性顔料分散体を塗装し、加熱乾燥させることを含んでなる塗膜形成方法において、
光輝性顔料分散体が、水、有機溶剤（Ａ）、光輝性顔料（Ｂ）及び粘性調整剤（Ｃ）を含み、
上記水を、水、有機溶剤（Ａ）、光輝性顔料（Ｂ）及び粘性調整剤（Ｃ）の合計量１００質量部を基準として５０〜９０質量部含有し、
上記有機溶剤（Ａ）が、２０℃の水に１質量％以上溶解し、
温度２０℃にて１ｍＬの該有機溶剤（Ａ）が９０％以上蒸発するのに必要な時間が２５０秒以上であり、
水と有機溶剤（Ａ）とを質量比で７５／２０で混合させた液体を、温度２０℃にて、Ｂ型粘度計でローター回転速度６０ｒｐｍでの粘度が１００ｍＰａ・ｓとなるように調整したときの、ブリキ板に対する接触角が３〜４０°であることを特徴とする塗膜形成方法に関する。
The present invention relates to a method for forming a coating film comprising applying a glitter pigment dispersion to an object to be coated and drying by heating.
The glitter pigment dispersion contains water, an organic solvent (A), a glitter pigment (B), and a viscosity modifier (C).
The water is contained in an amount of 50 to 90 parts by mass based on 100 parts by mass of water, an organic solvent (A), a glitter pigment (B), and a viscosity modifier (C),
The organic solvent (A) is dissolved by 1% by mass or more in 20 ° C. water,
The time required for 1 mL of the organic solvent (A) to evaporate 90% or more at a temperature of 20 ° C. is 250 seconds or more,
A liquid in which water and an organic solvent (A) were mixed at a mass ratio of 75/20 was adjusted at a temperature of 20 ° C. with a B-type viscometer so that the viscosity at a rotor rotational speed of 60 rpm was 100 mPa · s. It is related with the coating-film formation method characterized by the contact angle with respect to a tin plate being 3-40 degrees.
本発明の塗膜形成方法によれば金属調光沢に優れた外観の塗膜が得られる。 According to the method for forming a coating film of the present invention, a coating film having an appearance excellent in metallic gloss can be obtained.
被塗物
本発明の塗膜形成方法において、被塗物としては、鉄、亜鉛、アルミニウム等の金属やこれらを含む合金などの金属材、及びこれらの金属による成型物、ならびに、ガラス、プラスチックや発泡体などによる成型物等を挙げることができる。これら素材に応じて適宜、脱脂処理や表面処理して被塗物とすることができる。さらに、上記被塗物に下塗り塗膜、中塗り塗膜及びベース塗膜から選ばれる少なくとも１種の塗膜を形成させて被塗物とすることもでき、これらのものが特に好ましい。
In the coating film forming method of the present invention, as the object to be coated, a metal material such as iron, zinc, aluminum or an alloy containing these, and a molded product of these metals, and glass, plastic, A molded product made of foam or the like can be used. Depending on these materials, it can be appropriately subjected to degreasing treatment or surface treatment to obtain an article to be coated. Furthermore, at least one kind of coating film selected from an undercoating film, an intermediate coating film and a base coating film can be formed on the above-mentioned object to be coated, and these are particularly preferable.
上記下塗り塗膜とは、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したり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。この下塗り塗料としては特に限定されるものではなく、例えば、電着塗料、プライマー塗料等を挙げることができる。 The undercoat film is formed to conceal the surface of the material, or to impart corrosion resistance and rust resistance to the material, and is obtained by applying the undercoat paint, drying, and curing. be able to. The undercoat paint is not particularly limited, and examples thereof include an electrodeposition paint and a primer paint.
上記中塗り塗膜とは、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したりするために形成されるものであり、乾燥硬化した下塗り塗膜又は未硬化の下塗り塗膜上に、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。中塗り塗料は、特に限定されるものではなく、既知のものを使用でき、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できる。 The intermediate coating film is formed for concealing the undercoat film or imparting adhesion or chipping resistance, and is a dry-cured undercoat film or an uncured undercoat film. It can be obtained by applying an intermediate coating on top, drying and curing. The intermediate coating is not particularly limited, and known ones can be used. For example, an organic solvent-based or water-based intermediate coating having a thermosetting resin composition and a color pigment as essential components can be preferably used.
上記ベース塗膜とは、得られる塗膜に色味や質感を付与するために形成されるものであり、例えば、熱硬化性樹脂組成物及び着色顔料を必須成分とし、必要に応じて光輝性顔料を含有する有機溶剤系又は水系のベース塗料を好ましく使用できる。 The base coating film is formed in order to impart color and texture to the resulting coating film. For example, a thermosetting resin composition and a coloring pigment are essential components, and if necessary, glitter. An organic solvent-based or water-based base paint containing a pigment can be preferably used.
また、被塗物として、下塗り塗膜、中塗り塗膜及びベース塗膜から選ばれる少なくとも１種の塗膜を形成させる場合においては、該塗膜を加熱し、架橋硬化後に本発明の塗料組成物を塗装することができる。あるいは、下塗り塗膜、中塗り塗膜及びベース塗膜から選ばれる少なくとも１種の塗膜が未硬化の状態で、塗装することもできる。 Further, in the case of forming at least one coating film selected from an undercoat coating film, an intermediate coating film and a base coating film as an object to be coated, the coating composition of the present invention is heated after crosslinking and cured by crosslinking. Objects can be painted. Or at least 1 sort (s) of coating film chosen from an undercoat coating film, an intermediate coating film, and a base coating film can also be applied in an uncured state.
被塗物の素材が金属である場合には、金属素材の上に形成された電着塗膜の上に、中塗り塗料及び／またはベース塗料を塗装し、加熱硬化した塗膜または未硬化の塗膜である被塗物を使用することが好ましい。 When the material of the object to be coated is a metal, an intermediate coating and / or a base coating is applied on the electrodeposition coating formed on the metal material, and a heat-cured coating or an uncured coating is applied. It is preferable to use an object to be coated which is a coating film.
また、被塗物の素材がプラスチックである場合には、プラスチック素材の上にプライマー塗料及び／またはベース塗料を塗装し、加熱硬化した塗膜または未硬化の塗膜である被塗物を使用することが好ましい。 When the material of the object to be coated is plastic, a primer paint and / or base paint is applied on the plastic material, and the object to be coated is a heat-cured or uncured film. It is preferable.
本発明の塗膜形成方法においては、上記の如き被塗物上に光輝性顔料分散体を塗装する。
光輝性顔料分散体
本発明の塗膜形成方法において、光輝性顔料分散体としては、水、特定の有機溶剤（Ａ）、光輝性顔料（Ｂ）及び粘性調整剤（Ｃ）を含み、上記水を、水、特定の有機溶剤（Ａ）、光輝性顔料（Ｂ）及び粘性調整剤（Ｃ）の合計量１００質量部を基準として５０〜９０質量部含有する光輝性顔料分散体である。
In the coating film forming method of the present invention, the glitter pigment dispersion is coated on the object to be coated as described above.
Glitter Pigment Dispersion In the method for forming a coating film of the present invention, the glitter pigment dispersion includes water, a specific organic solvent (A), a glitter pigment (B), and a viscosity modifier (C), Is a glitter pigment dispersion containing 50 to 90 parts by mass of water, a specific organic solvent (A), a glitter pigment (B), and a viscosity modifier (C) based on 100 parts by mass in total.
有機溶剤（Ａ）
光輝性顔料分散体における有機溶剤（Ａ）としては、以下の３つの要件を満足する溶剤である。
Organic solvent (A)
The organic solvent (A) in the glitter pigment dispersion is a solvent that satisfies the following three requirements.
要件１：有機溶剤（Ａ）が、金属調光沢に優れる塗膜を得る観点から、２０℃の水に１質量％以上、好ましくは５質量％以上溶解する。 Requirement 1: The organic solvent (A) dissolves in 1% by mass or more, preferably 5% by mass or more in water at 20 ° C. from the viewpoint of obtaining a coating film having excellent metallic gloss.
本発明において、「有機溶剤が、２０℃の水に１質量％溶解する」とは、有機溶剤１ｇと水１００ｇとを攪拌容器に入れ、２０℃で５分間振とうさせた後、得られる混合液の状態を肉眼で観察した際に、混合液に相分離がなく、均一の状態である有機溶剤をいう。 In the present invention, “the organic solvent dissolves in 1% by mass in 20 ° C. water” means that 1 g of the organic solvent and 100 g of water are placed in a stirring vessel, shaken at 20 ° C. for 5 minutes, and then mixed. When the state of the liquid is observed with the naked eye, it means an organic solvent in which the mixed liquid has no phase separation and is in a uniform state.
要件２：有機溶剤（Ａ）は、金属調光沢に優れる塗膜を得る観点から、温度２０℃にて１ｍＬの有機溶剤が９０％以上蒸発するのに必要な時間が２５０秒以上、好ましくは９００〜５００００秒である。 Requirement 2: From the viewpoint of obtaining a coating film having excellent metallic gloss, the time required for 1 mL of organic solvent to evaporate 90% or more at a temperature of 20 ° C. is 250 seconds or more, preferably 900 ~ 50000 seconds.
要件３：有機溶剤（Ａ）は、金属調光沢に優れる塗膜を得る観点から、水と有機溶剤とを７５／２０で混合させた液体を、温度２０℃にて、Ｂ型粘度計でローター回転速度６０ｒｐｍでの粘度が１００ｍＰａ・ｓとなるように調整したときの、ブリキ板に対する接触角が３〜４０°、好ましくは５〜３０°である。上記Ｂ型粘度計は、ＬＶＤＶ−Ｉ（商品名、ＢＲＯＯＫＦＩＥＬＤ社製）である。 Requirement 3: The organic solvent (A) is a rotor obtained by mixing a liquid in which water and an organic solvent are mixed at 75/20 at a temperature of 20 ° C. with a B-type viscometer from the viewpoint of obtaining a coating film having excellent metallic gloss. When the viscosity at a rotational speed of 60 rpm is adjusted to be 100 mPa · s, the contact angle with respect to the tin plate is 3 to 40 °, preferably 5 to 30 °. The B-type viscometer is LVDV-I (trade name, manufactured by BROOKFIELD).
粘度調整は、ジメチルエタノールアミン及び「プライマルＡＳＥ−６０」（商品名、ダウケミカル社製、固形分２８％）を用いて行ったものである。また、該接触角は、粘度調整後の水／有機溶剤（Ａ）混合液をブリキ板（パルテック社製）上に１０μＬ滴下し３０秒経過後に測定したときの接触角である。このとき、使用する接触角計は、協和界面科学社製 ＣＡ−Ｘ１５０である。 The viscosity is adjusted using dimethylethanolamine and “Primal ASE-60” (trade name, manufactured by Dow Chemical Co., Ltd., solid content: 28%). The contact angle is the contact angle when 10 μL of the water / organic solvent (A) mixed solution after viscosity adjustment is dropped on a tin plate (manufactured by Partec Co., Ltd.) and measured after 30 seconds. At this time, the contact angle meter used is CA-X150 manufactured by Kyowa Interface Science Co., Ltd.
上記有機溶剤（Ａ）としては、例えば、アルコール系溶剤、エーテル系溶剤、エステル系溶剤、ケトン系溶剤等が挙げられる。具体的には例えば以下に列挙したものである。 Examples of the organic solvent (A) include alcohol solvents, ether solvents, ester solvents, ketone solvents, and the like. Specifically, for example, those listed below.
エチレングリコールモノブチルエーテル、３−メトキシブチルアセテート、ジエチレングリコールモノエチルエーテル、３−メチル３−メトキシブタノール、イソプロパノール、ｎ−ブタノール、シクロヘキサノン、ダイアセトンアルコール等。 Ethylene glycol monobutyl ether, 3-methoxybutyl acetate, diethylene glycol monoethyl ether, 3-methyl 3-methoxybutanol, isopropanol, n-butanol, cyclohexanone, diacetone alcohol and the like.
光輝性顔料（Ｂ）
光輝性顔料分散体における光輝性顔料（Ｂ）としては、例えば、蒸着金属フレーク顔料、アルミニウムフレーク顔料、光干渉性顔料等を挙げることができる。中でも金属調光沢に優れた塗膜を得る観点から、蒸着金属フレーク顔料が好適である。
Bright pigment (B)
Examples of the glitter pigment (B) in the glitter pigment dispersion include vapor-deposited metal flake pigments, aluminum flake pigments, and light interference pigments. Among these, vapor-deposited metal flake pigments are preferable from the viewpoint of obtaining a coating film excellent in metallic luster.
蒸着金属フレーク顔料は、ベース基材上に金属膜を蒸着させ、ベース基材を剥離した後、蒸着金属膜を粉砕することにより得られる。上記基材としては、例えばフィルム等を挙げることができる。 The vapor-deposited metal flake pigment is obtained by vapor-depositing a metal film on a base substrate, peeling the base substrate, and then pulverizing the vapor-deposited metal film. As said base material, a film etc. can be mentioned, for example.
上記金属の材質としては、特に限定されるものではないが、例えば、アルミニウム、金、銀、銅、真鍮、チタン、クロム、ニッケル、ニッケルクロム、ステンレス等が挙げられる。なかでも特に入手しやすさ及び取扱いやすさ等の観点から、アルミニウム又はクロムが好適である。本明細書では、アルミニウムを蒸着して得られた蒸着金属フレーク顔料を「蒸着アルミニウムフレーク顔料」と呼び、クロムを蒸着して得られた蒸着金属フレーク顔料を「蒸着クロムフレーク顔料」と呼ぶ。 Although it does not specifically limit as a material of the said metal, For example, aluminum, gold | metal | money, silver, copper, brass, titanium, chromium, nickel, nickel chromium, stainless steel etc. are mentioned. Of these, aluminum or chromium is particularly preferable from the viewpoint of easy availability and handling. In this specification, the vapor-deposited metal flake pigment obtained by vapor-depositing aluminum is referred to as “vapor-deposited aluminum flake pigment”, and the vapor-deposited metal flake pigment obtained by vapor-depositing chromium is referred to as “vapor-deposited chromium flake pigment”.
上記蒸着アルミニウムフレーク顔料として使用できる市販品としては例えば、「Ｈｙｄｒｏｓｈｉｎｅ ＷＳ」シリーズ（商品名、エカルト社製）、「Ｄｅｃｏｍｅｔ」シリーズ（商品名、シュレンク社製）、「Ｍｅｔａｓｈｅｅｎ」シリーズ（商品名、ＢＡＳＦ社製）等を挙げることができる。 Examples of commercially available products that can be used as the above vapor-deposited aluminum flake pigments include the “Hydrosine WS” series (trade name, manufactured by Ecart), the “Decomet” series (trade name, manufactured by Schlenk), and the “Metasheen” series (trade name, BASF). For example).
上記蒸着クロムフレーク顔料として使用できる市販品としては例えば、「Ｍｅｔａｌｕｒｅ Ｌｉｑｕｉｄ Ｂｌａｃｋ」シリーズ（商品名、エカルト社製）等を挙げることができる。 As a commercial item which can be used as the said vapor deposition chromium flake pigment, "Metalure Liquid Black" series (A brand name, the product made by Ecarte) etc. can be mentioned, for example.
上記蒸着金属フレーク顔料の平均厚みは、０．０１〜１．０μｍ、好ましくは、０．０１〜０．１μｍであることが好適である。 The average thickness of the vapor-deposited metal flake pigment is 0.01 to 1.0 μm, preferably 0.01 to 0.1 μm.
蒸着アルミニウムフレーク顔料は、表面がシリカ処理されていることが、貯蔵安定性、及び金属調光沢に優れた塗膜を得る等の観点から好ましい。 The surface of the vapor-deposited aluminum flake pigment is preferably treated with silica from the viewpoint of obtaining a coating film having excellent storage stability and metallic gloss.
アルミニウムフレーク顔料は、一般にアルミニウムをボールミルやアトライターミル中で粉砕媒液の存在下、粉砕助剤を用いて粉砕、摩砕して製造され、塗料用としては通常平均粒子径（Ｄ５０）が１〜５０μｍ程度、特に５〜２０μｍ程度のものが、塗料中における安定性や形成される塗膜の仕上がりの点から使用される。上記平均粒子径は、長径を意味する。粉砕助剤としては、オレイン酸、ステアリン酸、イソステアリン酸、ラウリン酸、パルミチン酸、ミリスチン酸等の高級脂肪酸のほか、脂肪族アミン、脂肪族アミド、脂肪族アルコールが使用される。粉砕媒液としてはミネラルスピリットなどの脂肪族系炭化水素が使用される。 Aluminum flake pigments are generally produced by grinding and grinding aluminum in a ball mill or attritor mill using a grinding aid in the presence of a grinding fluid, and have an average particle size (D50) of 1 for coatings. Those having a thickness of about ˜50 μm, particularly about 5 to 20 μm are used from the viewpoint of the stability in the paint and the finish of the coating film to be formed. The average particle diameter means a long diameter. As the grinding aid, aliphatic amines, aliphatic amides and aliphatic alcohols are used in addition to higher fatty acids such as oleic acid, stearic acid, isostearic acid, lauric acid, palmitic acid and myristic acid. Aliphatic hydrocarbons such as mineral spirits are used as the grinding fluid.
上記アルミニウムフレーク顔料として使用できる市販品としては例えば、「アルペースト」シリーズ（商品名、東洋アルミ社製）等を挙げることができる。 Examples of commercially available products that can be used as the aluminum flake pigment include “Alpaste” series (trade name, manufactured by Toyo Aluminum Co., Ltd.).
上記アルミニウムフレーク顔料の平均厚みは、０．０５〜１．０μｍ、好ましくは、０．１〜０．５μｍであることが好適である。 The average thickness of the aluminum flake pigment is 0.05 to 1.0 μm, preferably 0.1 to 0.5 μm.
アルミニウムフレーク顔料は、表面がシリカ処理されていることが、貯蔵安定性、及び金属調光沢に優れた塗膜を得る等の観点から好ましい。 The aluminum flake pigment is preferably silica-treated on the surface from the viewpoint of obtaining a coating film having excellent storage stability and metallic luster.
上記光干渉性顔料は、透明又は半透明の鱗片状基材に、金属酸化物が被覆された顔料である。 The light interference pigment is a pigment obtained by coating a transparent or translucent scaly substrate with a metal oxide.
該鱗片状基材としては、例えば、天然マイカ、人工マイカ、アルミナフレーク、シリカフレーク、ガラスフレーク等を挙げることができる。該天然マイカとは、鉱石のマイカ（雲母）を粉砕した鱗片状基材である。一方、上記人工マイカとは、フッ素金雲母（ＫＭｇ３ＡｌＳｉ３Ｏ１０Ｆ２）、カリウム四ケイ素雲母（ＫＭｇ２５ＡｌＳｉ４Ｏ１０Ｆ２）、ナトリウム四ケイ素雲母（ＮａＭｇ２５ＡｌＳｉ４Ｏ１０Ｆ２）、Ｎａテニオライト（ＮａＭｇ２ＬｉＳｉ４Ｏ１０Ｆ２）、ＬｉＮａテニオライト（ＬｉＭｇ２ＬｉＳｉ４Ｏ１０Ｆ２）等の工業原料を加熱し、約１５００℃の高温で熔融し、冷却して結晶化させて合成したものであり、天然のマイカと比較した場合において、不純物が少なく、大きさや厚さが均一なものである。 Examples of the scaly substrate include natural mica, artificial mica, alumina flake, silica flake, and glass flake. The natural mica is a scaly substrate obtained by pulverizing ore mica (mica). On the other hand, the above-mentioned artificial mica, fluorphlogopite (KMg 3 AlSi 3 O 10 F 2), potassium tetrasilisic mica (KMg 25 AlSi 4 O 10 F 2), sodium tetrasilicic mica (NaMg 25 AlSi 4 O 10 F 2 ), Na teniolite (NaMg 2 LiSi 4 O 10 F 2 ), LiNa teniolite (LiMg 2 LiSi 4 O 10 F 2 ) and other industrial raw materials are heated, melted at a high temperature of about 1500 ° C., cooled and crystallized. Compared with natural mica, it has less impurities and has a uniform size and thickness.
上記アルミナフレークとは、鱗片状（薄片状）酸化アルミニウムを意味し、無色透明なものである。該酸化アルミニウムは単一成分である必要はなく、他の金属の酸化物を含有するものであってもよい。 The above-mentioned alumina flake means scaly (flaky) aluminum oxide and is colorless and transparent. The aluminum oxide need not be a single component and may contain oxides of other metals.
上記シリカフレークとは、鱗片状のシリカである。上記ガラスフレークとは、鱗片状のガラスである。 The silica flake is scaly silica. The glass flake is scaly glass.
上記金属酸化物とは、酸化チタン、酸化鉄等を挙げることができる。上記鱗片状基材を被覆する金属酸化物の厚さによって異なる干渉色を発現することができるものである。 Examples of the metal oxide include titanium oxide and iron oxide. Different interference colors can be developed depending on the thickness of the metal oxide covering the scaly substrate.
上記光干渉性顔料は、表面処理されていることが、貯蔵安定性、及び耐候性に優れた塗膜を得る等の観点から好ましい。 The optical interference pigment is preferably surface-treated from the viewpoint of obtaining a coating film having excellent storage stability and weather resistance.
上記光干渉性顔料として使用できる市販品としては例えば、「イリオジン」シリーズ（商品名、メルクジャパン社製）、「シラリック」シリーズ（商品名、メルクジャパン社製）等を挙げることができる。 Examples of commercially available products that can be used as the light interference pigment include “Iriodin” series (trade name, manufactured by Merck Japan), “Silary” series (trade name, manufactured by Merck Japan), and the like.
上記光干渉性顔料の平均厚みは、０．１〜１．０μｍ、好ましくは、０．２〜０．８μｍであることが好適である。 The average thickness of the light interference pigment is 0.1 to 1.0 μm, preferably 0.2 to 0.8 μm.
粘性調整剤（Ｃ）
光輝性顔料分散体における粘性調整剤（Ｃ）としては、既知のものを使用できるが、例えば、シリカ系微粉末、鉱物系粘性調整剤、硫酸バリウム微粒化粉末、ポリアミド系粘性調整剤、有機樹脂微粒子粘性調整剤、ジウレア系粘性調整剤、ウレタン会合型粘性調整剤、アクリル膨潤型であるポリアクリル酸系粘性調整剤等を挙げることができる。なかでも金属調光沢に優れた塗膜を得る観点から特に、鉱物系粘性調整剤、ポリアクリル酸系粘性調整剤を使用することが好ましい。
Viscosity modifier (C)
As the viscosity adjusting agent (C) in the glitter pigment dispersion, known ones can be used. For example, silica-based fine powder, mineral-based viscosity adjusting agent, barium sulfate atomized powder, polyamide-based viscosity adjusting agent, organic resin Examples thereof include fine particle viscosity modifiers, diurea viscosity modifiers, urethane-associative viscosity modifiers, and acrylic swellable polyacrylic acid viscosity modifiers. In particular, from the viewpoint of obtaining a coating film excellent in metallic luster, it is preferable to use a mineral viscosity modifier and a polyacrylic acid viscosity modifier.
鉱物系粘性調整剤としては、その結晶構造が２：１型構造を有する膨潤性層状ケイ酸塩が挙げられる。具体的には、天然又は合成のモンモリロナイト、サポナイト、ヘクトライト、スチブンサイト、バイデライト、ノントロナイト、ベントナイト、ラポナイト等のスメクタイト族粘土鉱物や、Ｎａ型テトラシリシックフッ素雲母、Ｌｉ型テトラシリシックフッ素雲母、Ｎａ塩型フッ素テニオライト、Ｌｉ型フッ素テニオライト等の膨潤性雲母族粘土鉱物及びバーミキュライト、又はこれらの置換体や誘導体、或いはこれらの混合物が挙げられる。 Examples of the mineral viscosity modifier include swellable layered silicates whose crystal structure has a 2: 1 type structure. Specifically, smectite clay minerals such as natural or synthetic montmorillonite, saponite, hectorite, stevensite, beidellite, nontronite, bentonite, laponite, Na-type tetrasilicic fluoric mica, Li-type tetralithic fluoric mica Swellable mica group clay minerals such as Na salt type fluorine teniolite and Li type fluorine teniolite and vermiculite, or a substituted or derivative thereof, or a mixture thereof.
ポリアクリル酸系粘性調整剤としては、ポリアクリル酸ソーダ、ポリアクリル酸−（メタ）アクリル酸エステル共重合体等を挙げることができる。 Examples of the polyacrylic acid-based viscosity modifier include polyacrylic acid soda, polyacrylic acid- (meth) acrylic acid ester copolymer, and the like.
該ポリアクリル酸系粘性調整剤の有効成分酸価としては、３０〜３００ｍｇＫＯＨ／ｇ、好ましくは８０〜２８０ｍｇＫＯＨ／ｇの範囲内であることができる。市販品として、例えば、ダウケミカル社製の「プライマルＡＳＥ−６０」、「プライマルＴＴ６１５」、「プライマルＲＭ５」（以上、商品名）、サンノプコ社製の「ＳＮシックナー６１３」、「ＳＮシックナー６１８」、「ＳＮシックナー６３０」、「ＳＮシックナー６３４」、「ＳＮシックナー６３６」（以上、商品名）等が挙げられる。
これらのそれぞれ単独で又は２種以上を適宜組み合わせて使用することができる。
As an active ingredient acid value of this polyacrylic acid type viscosity regulator, it can be in the range of 30-300 mgKOH / g, Preferably it is 80-280 mgKOH / g. As commercially available products, for example, “Primal ASE-60”, “Primal TT615”, “Primal RM5” (above, trade name) manufactured by Dow Chemical Company, “SN thickener 613”, “SN thickener 618” manufactured by San Nopco, Examples thereof include “SN thickener 630”, “SN thickener 634”, “SN thickener 636” (the product name).
Each of these can be used alone or in combination of two or more.
その他の成分
光輝性顔料分散体には、さらに必要に応じて、前記有機溶剤（Ａ）以外の有機溶剤、前記光輝性顔料（Ｂ）以外の顔料、顔料分散剤、沈降防止剤、消泡剤、紫外線吸収剤、表面調整剤等を適宜配合しても良い。
For other component bright pigment dispersions, if necessary, an organic solvent other than the organic solvent (A), a pigment other than the bright pigment (B), a pigment dispersant, an anti-settling agent, and an antifoaming agent. Further, an ultraviolet absorber, a surface conditioner, etc. may be appropriately blended.
光輝性顔料分散体は、基体樹脂や架橋剤を含むことができるが、これらを実質的に含まなくても本発明の効果を発揮することができる。金属調光沢に優れた塗膜を得る観点、及び薄膜化、膜厚安定性、コスト等の観点から基体樹脂及び又は架橋剤を実質的に含まないことが好ましい。 The glitter pigment dispersion can contain a base resin and a cross-linking agent, but the effects of the present invention can be exhibited even if they do not substantially contain them. It is preferable that the base resin and / or the cross-linking agent are not substantially contained from the viewpoint of obtaining a coating film having excellent metallic gloss and from the viewpoints of thinning, film thickness stability, cost and the like.
上記基体樹脂としては、アクリル樹脂、ポリエステル樹脂、アルキド樹脂、ウレタン樹脂などが挙げられる。 Examples of the base resin include acrylic resin, polyester resin, alkyd resin, and urethane resin.
上記架橋剤としては、メラミン樹脂、尿素樹脂、ポリイソシアネート化合物（ブロック体も含む）などが挙げられる。 Examples of the crosslinking agent include melamine resins, urea resins, polyisocyanate compounds (including block bodies), and the like.
光輝性顔料分散体の各成分の配合量
光輝性顔料分散体は、水、有機溶剤（Ａ）、光輝性顔料（Ｂ）及び粘性調整剤（Ｃ）を含む。該光輝性顔料分散体において各成分の配合割合（固形分質量）は、金属調光沢に優れる塗膜を得る観点から下記の範囲内であることが好ましい。
Blending amount of each component of the glitter pigment dispersion The glitter pigment dispersion contains water, an organic solvent (A), a glitter pigment (B), and a viscosity modifier (C). In the glitter pigment dispersion, the blending ratio (solid content mass) of each component is preferably within the following range from the viewpoint of obtaining a coating film having excellent metallic gloss.
水、有機溶剤（Ａ）、光輝性顔料（Ｂ）及び粘性調整剤（Ｃ）の合計量１００質量部を基準として、
水：５０〜９０質量部、好ましくは６０〜８５質量部、さらに好ましくは６５〜８０質量部、
有機溶剤（Ａ）：５〜４５質量部、好ましくは１０〜３５質量部、さらに好ましくは１５〜３０質量部、
光輝性顔料（Ｂ）：０．１〜１０質量部、好ましくは０．２〜５質量部、さらに好ましくは０．３〜３．５質量部、
粘性調整剤（Ｃ）：０．０５〜５質量部、好ましくは０．１〜３質量部、さらに好ましくは０．１５〜２質量部。
Based on 100 parts by mass of the total amount of water, organic solvent (A), glitter pigment (B), and viscosity modifier (C),
Water: 50 to 90 parts by mass, preferably 60 to 85 parts by mass, more preferably 65 to 80 parts by mass,
Organic solvent (A): 5-45 parts by mass, preferably 10-35 parts by mass, more preferably 15-30 parts by mass,
Bright pigment (B): 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass, more preferably 0.3 to 3.5 parts by mass,
Viscosity modifier (C): 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass, more preferably 0.15 to 2 parts by mass.
光輝性顔料分散体の接触角
光輝性顔料分散体の接触角は、金属調光沢に優れる塗膜を得る観点から、３〜４０°、好ましくは５〜３０°である。このとき、使用する接触角計は、協和界面科学社製 ＣＡ−Ｘ１５０であり、光輝性顔料分散体を、予め脱脂したブリキ板（パルテック社製）上に１０μＬ滴下し３０秒経過後に測定した値を指す。
Contact angle of the glitter pigment dispersion The contact angle of the glitter pigment dispersion is 3 to 40 °, preferably 5 to 30 °, from the viewpoint of obtaining a coating film having excellent metallic gloss. At this time, the contact angle meter to be used is CA-X150 manufactured by Kyowa Interface Science Co., Ltd., and a value obtained by dropping 10 μL of the glitter pigment dispersion onto a pre-degreased tin plate (manufactured by Partec Co., Ltd.) and measuring 30 seconds later. Point to.
本発明における塗膜形成方法は、上記被塗物上に、上記光輝性顔料分散体を塗装する工程を含むものである。 The coating film formation method in this invention includes the process of coating the said luster pigment dispersion on the said to-be-coated article.
光輝性顔料分散体の塗装
光輝性顔料分散体は、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。金属調光沢に優れる塗膜を得る観点から、塗装時の固形分含有率を、光輝性顔料分散体に基づいて、０．１５〜５質量％、好ましくは０．３〜４質量％に調整しておくことが好ましい。
Coating of the glitter pigment dispersion The glitter pigment dispersion is prepared by mixing and dispersing the aforementioned components. From the viewpoint of obtaining a coating film excellent in metallic luster, the solid content during coating is adjusted to 0.15 to 5% by mass, preferably 0.3 to 4% by mass, based on the glitter pigment dispersion. It is preferable to keep it.
光輝性顔料分散体の粘度は、金属調光沢に優れる塗膜を得る観点から、温度２０℃にて、６０ｒｐｍで１分後の粘度が５〜１０００ｍＰａ・ｓｅｃ、好ましくは３０〜６００ｍＰａ・ｓｅｃであることが好適である。このとき、使用する粘度計は、ＬＶＤＶ−Ｉ（商品名、ＢＲＯＯＫＦＩＥＬＤ社製、Ｂ型粘度計）である。 The viscosity of the glitter pigment dispersion is 5 to 1000 mPa · sec, preferably 30 to 600 mPa · sec after 1 minute at 60 rpm at a temperature of 20 ° C. from the viewpoint of obtaining a coating film having excellent metallic gloss. Is preferred. At this time, the viscometer used is LVDV-I (trade name, manufactured by BROOKFIELD, B-type viscometer).
光輝性顔料分散体は、静電塗装、エアスプレー、エアレススプレーなどの方法で塗装することができる。本発明の塗膜形成方法においては、特に回転霧化式の静電塗装が好ましい。 The glitter pigment dispersion can be applied by a method such as electrostatic coating, air spray, or airless spray. In the coating film forming method of the present invention, rotary atomizing electrostatic coating is particularly preferable.
例えば、ロボットベル（ＡＢＢ社製）を用いて静電塗装する場合において、塗装時の光輝性顔料分散体固形分含有率が１％の場合、ベル直径が５０〜８０ｍｍ、ベル回転数は２００００〜３００００ｒｐｍ、シェーピングエア圧は１．５〜３．０ｋｇ／ｃｍ２、電圧は−９０〜−４５ｋＶ、被塗物とロボットベルとの距離は２０〜２５ｃｍの条件で塗装することができる。 For example, in the case of electrostatic coating using a robot bell (manufactured by ABB), when the glitter pigment dispersion solid content in coating is 1%, the bell diameter is 50 to 80 mm and the bell rotation speed is 20000. The coating can be performed under conditions of 30000 rpm, a shaping air pressure of 1.5 to 3.0 kg / cm 2 , a voltage of −90 to −45 kV, and a distance between the object to be coated and the robot bell of 20 to 25 cm.
また、例えば、ワイダー１００（アネスト岩田社製、エアスプレーガン）を用いてエアスプレー塗装する場合において、塗装時の光輝性顔料分散体固形分が１％の場合、霧化空気圧力は０．５〜４．０ＭＰａ、塗調開度は０．５〜３．０回転の範囲で調整し、被塗物とワイダー１００との距離は２０〜２５ｃｍの条件で塗装することができる。 Further, for example, when air spray coating is performed using a winder 100 (manufactured by Anest Iwata Corporation, air spray gun), if the solid content of the glitter pigment dispersion at the time of coating is 1%, the atomizing air pressure is 0.5. The coating opening is adjusted in the range of ˜4.0 MPa and the coating opening degree in the range of 0.5 to 3.0 rotation, and the distance between the object to be coated and the weider 100 can be applied under the condition of 20 to 25 cm.
上記光輝性顔料分散体を塗装後、乾燥焼付けを行って塗膜とすることもできるし、上記光輝性顔料分散体を塗装して得られた膜の上に、トップクリヤー塗料を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することもできる。上記光輝性顔料分散体を塗装後、トップクリヤー塗膜を形成する場合には、光輝性顔料分散体を塗装して得られた膜は乾燥していることが好ましい。上記光輝性顔料分散体を塗装して得られた膜を乾燥させる方法に特に制限はないが、例えば、常温で１５〜３０分間放置する方法、５０〜１００℃の温度で３０秒〜１０分間プレヒートを行なう方法、または７０〜１５０℃の温度で２０〜４０分間加熱乾燥させる方法等が挙げられる。 After coating the glitter pigment dispersion, it can be dried and baked to form a coating film. On the film obtained by painting the glitter pigment dispersion, one or two top clear paints are coated. It is also possible to form a top clear coating by coating more than one layer. When a top clear coating film is formed after coating the glitter pigment dispersion, the film obtained by coating the glitter pigment dispersion is preferably dried. The method for drying the film obtained by coating the glitter pigment dispersion is not particularly limited. For example, a method of leaving the film at room temperature for 15 to 30 minutes, a preheating at a temperature of 50 to 100 ° C. for 30 seconds to 10 minutes, Or a method of heating and drying at a temperature of 70 to 150 ° C. for 20 to 40 minutes.
光輝性顔料分散体が被塗物に付着してから３０秒後の膜厚は、金属調光沢に優れる塗膜を得る観点から、３〜１２μｍ、好ましくは３〜１０μｍ、さらに好ましくは３〜７μｍであることが好適である。 The film thickness 30 seconds after the glitter pigment dispersion adheres to the substrate is 3 to 12 μm, preferably 3 to 10 μm, more preferably 3 to 7 μm, from the viewpoint of obtaining a coating film having excellent metallic gloss. It is preferable that
光輝性顔料分散体を塗装することによって形成された膜の厚さは、金属調光沢に優れる塗膜を得る観点から、乾燥膜厚として、０．０１〜１．０μｍ、好ましくは０．０１〜０．８μｍであることが好適である。 The thickness of the film formed by coating the glitter pigment dispersion is from 0.01 to 1.0 μm, preferably from 0.01 to 1.0 μm, as a dry film thickness, from the viewpoint of obtaining a coating film excellent in metallic luster. It is preferable that the thickness is 0.8 μm.
特に、光輝性顔料分散体における光輝性顔料（Ｂ）が蒸着金属フレーク顔料である場合には、該光輝性顔料分散体を塗装することによって形成された膜の厚さは、乾燥膜厚として、０．０１〜１．０μｍ、好ましくは０．０１〜０．５μｍであることが好適である。 In particular, when the glitter pigment (B) in the glitter pigment dispersion is a vapor-deposited metal flake pigment, the thickness of the film formed by coating the glitter pigment dispersion is as follows: It is suitable that the thickness is 0.01 to 1.0 μm, preferably 0.01 to 0.5 μm.
また、光輝性顔料分散体における光輝性顔料（Ｂ）がアルミニウムフレーク顔料である場合には、該光輝性顔料分散体を塗装することによって形成された膜の厚さは、乾燥膜厚として、０．０５〜１．０μｍ、好ましくは０．１〜０．５μｍであることが好適である。 When the glitter pigment (B) in the glitter pigment dispersion is an aluminum flake pigment, the thickness of the film formed by coating the glitter pigment dispersion is 0 as a dry film thickness. It is suitable that the thickness is 0.05 to 1.0 μm, preferably 0.1 to 0.5 μm.
また、光輝性顔料分散体における光輝性顔料（Ｂ）が光干渉性顔料である場合には、該光輝性顔料分散体を塗装することによって形成された膜の厚さは、乾燥膜厚として、０．１〜１．０μｍ、好ましくは０．２〜０．８μｍであることが好適である。
トップクリヤー塗料
トップクリヤー塗料としては、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、シラノール基、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、ポリイソシアネート化合物、ブロックポリイソシアネート化合物、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。
Further, when the glitter pigment (B) in the glitter pigment dispersion is a light interference pigment, the thickness of the film formed by coating the glitter pigment dispersion is as follows: It is suitable that it is 0.1-1.0 micrometer, Preferably it is 0.2-0.8 micrometer.
As the top clear paint , any conventionally known top clear paint 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. As a crosslinking agent, melamine resin, urea resin, polyisocyanate compound, block polyisocyanate compound, epoxy compound or resin, carboxyl group-containing compound or resin, acid anhydride, alkoxysilane group-containing, which can react with the functional group of the base resin Examples thereof include 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.
上記トップクリヤー塗料には、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、該トップクリヤー塗料中のビヒクル形成樹脂組成物１００質量部に対して、３０重量部以下、好ましくは０.０１〜１０重量部である。 A color pigment can be appropriately blended with the top clear coating within a range that does not impair the 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 0.01 to 10 parts by weight with respect to 100 parts by weight of the vehicle-forming resin composition in the top clear paint.
上記トップクリヤー塗料は、静電塗装、エアスプレー、エアレススプレー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。 The top clear coating can be applied by electrostatic coating, air spraying, airless spraying or the like, and the film thickness is preferably in the range of 5 to 40 μm based on the cured coating film.
本発明においては、前記トップクリヤー塗料を塗装した場合においては、トップクリヤー塗料を塗装後、加熱硬化せしめることができる。トップクリヤー塗料は７０〜１５０℃の温度で１０〜３０分間加熱することで架橋硬化させることができる。 In the present invention, when the top clear paint is applied, it can be cured by heating after the top clear paint is applied. The top clear coating can be crosslinked and cured by heating at a temperature of 70 to 150 ° C. for 10 to 30 minutes.
以下、実施例及び比較例を挙げて、本発明をより具体的に説明する。ただし、本発明はこれらの実施例のみに限定されるものではない。なお、「部」及び「％」はいずれも質量基準によるものである。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to only these examples. “Part” and “%” are based on mass.
後述する光輝性顔料分散体の製造に使用する有機溶剤（Ａ）及び光輝性顔料（Ｂ）の性質を、それぞれ表１及び表２に示す。 The properties of the organic solvent (A) and the glitter pigment (B) used in the production of the glitter pigment dispersion described later are shown in Tables 1 and 2, respectively.
（注１）
水／該有機溶剤（Ａ）＝７５／２０の割合で混合させた混合溶液を、予め脱脂したブリキ板（パルテック社製）上に１０μＬ滴下し３０秒経過後に接触角計（ＣＡ−Ｘ１５０、商品名、協和界面科学社製）を用いて測定したときの接触角
(Note 1)
10 μL of the mixed solution mixed at a ratio of water / the organic solvent (A) = 75/20 was dropped on a pre-degreased tin plate (manufactured by Partec Co., Ltd.) and after 30 seconds, a contact angle meter (CA-X150, product) Contact angle when measured using the name, manufactured by Kyowa Interface Science Co., Ltd.
光輝性顔料分散体の製造
製造例１
Ｈｙｄｒｏｓｈｉｎｅ ＷＳ−３００４（水性用蒸着アルミニウムフレーク顔料、Ｅｃｋａｒｔ社製、固形分：１０％、内部溶剤：イソプロパノール、平均粒子径Ｄ５０：１３μｍ、厚さ：０．０５μｍ）５部（固形分で０．５部）、エチレングリコールモノブチルエーテル ２０部、蒸留水 ７５部、Ａｃｒｙｓｏｌ ＡＳＥ−６０（ポリアクリル酸系粘性調整剤、ダウケミカル社製、固形分：２８％）１．５部（固形分で０．４２部）を配合して攪拌混合し、光輝性顔料分散体（Ｘ−１）を調整した。
Production and production example 1 of glitter pigment dispersion
Hydrosine WS-3004 (evaporated aluminum flake pigment for water, manufactured by Eckart, solid content: 10%, internal solvent: isopropanol, average particle diameter D50: 13 μm, thickness: 0.05 μm) 5 parts (0.5% solid content) Part), ethylene glycol monobutyl ether 20 parts, distilled water 75 parts, Acrysol ASE-60 (polyacrylic acid viscosity modifier, manufactured by Dow Chemical Co., Ltd., solid content: 28%) 1.5 parts (solid content 0.42) Part) was mixed and stirred and mixed to prepare the glitter pigment dispersion (X-1).
製造例２〜２０
表３に記載の配合とする以外は全て製造例１と同様にして光輝性顔料分散体（Ｘ−２）〜（Ｘ−２０）を得た。
Production Examples 2 to 20
Luminous pigment dispersions (X-2) to (X-20) were obtained in the same manner as in Production Example 1 except that the formulation shown in Table 3 was used.
製造例２１
アクリル樹脂水溶液Ａ（注２）７０部（固形分）、８０％「サイメル３２５」（商品名、日本サイテックインダストリーズ、メチル化メラミン樹脂）３０ 部（固形分）、りん酸基含有樹脂（注３）１０部（固形分）、「Ｈｙｄｒｏｓｈｉｎｅ ＷＳ−３００４」４０部（固形分）及びイソプロピルアルコール３０部を混合し、さらに増粘剤「ＳＮシックナー６３６」（商品名、サンノプコ社製）及び水を加えて、固形分２％の水性ベースコート塗料（Ｂ−１）を得た。
（注２）アクリル樹脂水溶液Ａ：アクリル酸ｎ−ブチル１６．７部、メタクリル酸メチル１５部、スチレン３０部、アクリル酸２−エチルヘキシル２０部、メタクリル酸２−ヒドロキシルエチル１２部、アクリル酸６．３部からなる単量体成分の共重合体。数平均分子量が４５，０００、水酸基価が５０ｍｇＫＯＨ／ｇ、酸価が５０ｍｇＫＯＨ／ｇ。
（注３）りん酸基含有樹脂：アシッドホスホキシエチルメタクリレート２５部、２−ヒドロキシエチルアクリレート２５部及びメチルメタクリレート５０ 部からなる単量体成分の共重合体。数平均分子量１３，０００、水酸基価１２０ｍｇＫＯＨ／ｇ、酸価１０４ｍｇＫＯＨ／ｇ。
Production Example 21
Acrylic resin aqueous solution A (Note 2) 70 parts (solid content), 80% “Cymel 325” (trade name, Nippon Cytec Industries, methylated melamine resin) 30 parts (solid content), phosphate group-containing resin (Note 3) 10 parts (solid content), "Hydroshine WS-3004" 40 parts (solid content) and 30 parts isopropyl alcohol are mixed, and further thickener "SN thickener 636" (trade name, manufactured by San Nopco) and water are added. An aqueous base coat paint (B-1) having a solid content of 2% was obtained.
(Note 2) Acrylic resin aqueous solution A: n-butyl acrylate 16.7 parts, methyl methacrylate 15 parts, styrene 30 parts, 2-ethylhexyl acrylate 20 parts, 2-hydroxylethyl methacrylate 12 parts, acrylic acid 6. 3 parts monomer component copolymer. The number average molecular weight is 45,000, the hydroxyl value is 50 mgKOH / g, and the acid value is 50 mgKOH / g.
(Note 3) Phosphoric acid group-containing resin: a copolymer of monomer components consisting of 25 parts of acid phosphoxyethyl methacrylate, 25 parts of 2-hydroxyethyl acrylate and 50 parts of methyl methacrylate. Number average molecular weight 13,000, hydroxyl value 120 mgKOH / g, acid value 104 mgKOH / g.
参考例
溶剤系メタリック塗料（ＴＢ−５１６、商品名、関西ペイント社製）に蒸留水を添加したところ、ゲル化して塗装不能となった。
被塗物の調整
製造例２２（被塗物１の作製）
脱脂及びリン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ー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被塗物１を得た。
Reference Example When distilled water was added to a solvent-based metallic paint (TB-516, trade name, manufactured by Kansai Paint Co., Ltd.), it gelled and became unpaintable.
Preparation of coated article 22 (preparation of coated article 1)
Cationic electrodeposition paint "ELECRON 9400HB" (trade name: manufactured by Kansai Paint Co., Ltd., amine-modified epoxy resin-based cationic resin as a curing agent on a degreased and zinc phosphate-treated steel plate (JISG3141, size 400 x 300 x 0.8 mm) A block polyisocyanate compound) was electrodeposited so as to have a film thickness of 20 μm based on the cured coating film, and heated at 170 ° C. for 20 minutes to be crosslinked and cured to obtain an article 1 to be coated.
製造例２３（被塗物２の作製）
ＡＢＳ板（黒色、脱脂処理済み）に、プライマー「ソフレックス１０００」（商品名：関西ペイント社製、ポリオレフィン含有導電性有機溶剤型塗料）を乾燥膜厚で１５μｍになるようにエアスプレー塗装を行ない、８０℃で３０分間加熱し硬化させて被塗物２を得た。
試験板の作成
実施例１〜１５、比較例１〜８
被塗物１上に、中塗塗料「ルーガベーク中塗りグレー」（商品名：関西ペイント社製、ポリエステル樹脂・メラミン樹脂系有機溶剤型塗料）をエアスプレーにて硬化塗膜に基づいて膜厚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、中塗り塗膜を形成した。該中塗り塗膜の上に、前述のように作成した光輝性顔料分散体（Ｘ−１）〜（Ｘ−２０）、及び水性ベースコート（Ｂ−１）を、表４に記載の塗料粘度に調整し、ＡＢＢ社製ロボットベルを用いて、ブース温度２３℃、湿度６８％の条件で、表４に記載の乾燥塗膜となるように塗装した。
その後、室温にて３分間放置し、８０℃で３分間加熱乾燥させた。ついで、これらの乾燥塗面に、トップクリヤー塗料「ＫＩＮＯ６５００」（商品名：関西ペイント株式会社、アクリル樹脂・ウレタン樹脂系２液型有機溶剤型塗料）をＡＢＢ社製ロボットベルを用いて、ブース温度２３℃、湿度６８％の条件で乾燥塗膜として、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各試験板とした。
ここで、表４に記載した乾燥塗膜の膜厚は、下記式から算出した。以下の実施例についても同様である。
ｘ＝ｓｃ／ｓｇ／Ｓ＊１００００
ｘ：膜厚［μｍ］
ｓｃ：塗着固形分［ｇ］
ｓｇ：塗膜比重［ｇ／ｃｍ３］
Ｓ：塗着固形分の評価面積［ｃｍ２］
実施例１６
被塗物１上に、中塗塗料「ＷＰ−５０５Ｔ」（商品名、関西ペイント社製、ポリエステル樹脂系水性中塗り塗料）を回転霧化型のベル型塗装機を用いて、硬化膜厚２０μｍになるように静電塗装し、３分間放置後、８０℃で３分間プレヒートし、さらにその上に、前述のように作成した光輝性顔料分散体（Ｘ−１）を、表４に記載の塗料粘度に調整し、ＡＢＢ社製ロボットベルを用いて、ブース温度２３℃、湿度６８％の条件で、乾燥塗膜として、０．１μｍとなるように塗装した。その後、８０℃にて３分間放置し、ついで、この乾燥塗面に、トップクリヤー塗料「ＫＩＮＯ６５００」（商品名：関西ペイント株式会社、アクリル樹脂・ウレタン樹脂系２液型有機溶剤型塗料）をＡＢＢ社製ロボットベルを用いて、ブース温度２３℃、湿度６８％の条件で乾燥塗膜として、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せしめて試験板とした。
Production Example 23 (Preparation of article 2)
Air-spray coating is applied to an ABS plate (black, degreased) with a primer “SOFLEX 1000” (trade name: manufactured by Kansai Paint Co., Ltd., polyolefin-containing conductive organic solvent type paint) to a dry film thickness of 15 μm. The product 2 was obtained by heating and curing at 80 ° C. for 30 minutes.
Preparation of test plates Examples 1 to 15 and Comparative Examples 1 to 8
An intermediate coating “Luga Bake Intermediate Coating Gray” (trade name: polyester resin / melamine resin organic solvent type coating) manufactured by Kansai Paint Co., Ltd. is applied onto the object 1 by air spray to a film thickness of 30 μm based on the cured coating film. Then, it was heated at 140 ° C. for 30 minutes to be cured by crosslinking to form an intermediate coating film. On the intermediate coating film, the glitter pigment dispersions (X-1) to (X-20) and the aqueous base coat (B-1) prepared as described above were applied to the paint viscosity described in Table 4. It adjusted and it applied so that it might become a dry paint film of Table 4 on condition of booth temperature 23 degreeC and humidity 68% using the robot bell made from ABB.
Then, it was left to stand at room temperature for 3 minutes, and was heat-dried at 80 ° C. for 3 minutes. Next, the top clear paint “KINO6500” (trade name: Kansai Paint Co., Ltd., acrylic resin / urethane resin two-component organic solvent paint) is applied to these dry coated surfaces using a robot bell manufactured by ABB, and the booth temperature. The film was applied as a dry coating film at 25 ° C. and a humidity of 68% so as to be 25 to 35 μm. After coating, the sample was allowed to stand at room temperature for 15 minutes, and then heated in a hot-air circulating drying oven for 30 minutes at 140 ° C., and the multilayer coating film was simultaneously dried and cured to obtain each test plate.
Here, the film thickness of the dry coating film described in Table 4 was calculated from the following formula. The same applies to the following embodiments.
x = sc / sg / S * 10000
x: Film thickness [μm]
sc: solid content of coating [g]
sg: Coating film specific gravity [g / cm 3 ]
S: Evaluation area of solid coating content [cm 2 ]
Example 16
An intermediate coating “WP-505T” (trade name, manufactured by Kansai Paint Co., Ltd., polyester resin-based aqueous intermediate coating) is applied onto the object 1 to a cured film thickness of 20 μm using a rotary atomizing bell type coating machine. After electrostatic coating as such, it was allowed to stand for 3 minutes, preheated at 80 ° C. for 3 minutes, and further the glitter pigment dispersion (X-1) prepared as described above was applied to the paint described in Table 4 The viscosity was adjusted, and using a robot bell manufactured by ABB, the coating was applied to a dry coating film thickness of 0.1 μm under the conditions of a booth temperature of 23 ° C. and a humidity of 68%. After that, it was allowed to stand at 80 ° C. for 3 minutes, and then the top clear paint “KINO6500” (trade name: Kansai Paint Co., Ltd., acrylic resin / urethane resin type two-component organic solvent paint) was applied to this dry coated surface. Using a robot bell manufactured by the company, the coating was applied to a dry coating film thickness of 25 to 35 μm under conditions of a booth temperature of 23 ° C. and a humidity of 68%. 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 the multilayer coating film to obtain a test plate.
実施例１７
被塗物１上に、前述のように作成した光輝性顔料分散体（Ｘ−１）を、表４に記載の塗料粘度に調整し、ＡＢＢ社製ロボットベルを用いて、ブース温度２３℃、湿度６８％の条件で、乾燥塗膜として、０．１μｍとなるように塗装した。その後、室温にて３分間放置し、１４０℃で３０分間加熱乾燥せしめて試験板とした。
Example 17
On the object 1, the glitter pigment dispersion (X-1) prepared as described above was adjusted to the paint viscosity shown in Table 4, and the booth temperature was 23 ° C. using a robot bell manufactured by ABB. The coating was applied at a humidity of 68% to a thickness of 0.1 μm as a dry coating film. Then, it was left to stand at room temperature for 3 minutes, and was heated and dried at 140 ° C. for 30 minutes to obtain a test plate.
実施例１８
被塗物２上に、前述のように作成した光輝性顔料分散体（Ｘ−１）を表４に記載の塗料粘度に調整し、ＡＢＢ社製ロボットベルを用いて、ブース温度２３℃、湿度６８％の条件で、乾燥膜厚で０．１μｍとなるように静電塗装し、８０℃で３分間プレヒート後、クリヤー塗料として「ソフレックス５２００クリヤー」（関西ペイント社製、アクリル樹脂・ウレタン樹脂系２液型有機溶剤型塗料）を乾燥膜厚で約３０μｍとなるように静電塗装して、８０℃で３０分間加熱乾燥させて試験板を作成した。
塗膜評価
上記のようにして得られた各試験板について外観及び性能を評価し、表４にその結果を示した。
Example 18
On the object 2, the glitter pigment dispersion (X-1) prepared as described above was adjusted to the paint viscosity shown in Table 4, and a booth temperature of 23 ° C. and humidity was used using an ABB robot bell. Under 68% conditions, electrostatic coating was applied to a dry film thickness of 0.1 μm, preheating at 80 ° C. for 3 minutes, and then “SOFLEX 5200 Clear” (acrylic / urethane resin, manufactured by Kansai Paint Co., Ltd.) as a clear coating. A two-component organic solvent-based paint) was electrostatically applied to a dry film thickness of about 30 μm and dried by heating at 80 ° C. for 30 minutes to prepare a test plate.
Evaluation of Coating Film Appearance and performance of each test plate obtained as described above were evaluated, and Table 4 shows the results.
外観評価
塗膜外観は、６０°鏡面光沢度、目視、及びはじきの有無によって評価した。
Appearance Evaluation The appearance of the coating film was evaluated by 60 ° specular gloss, visual observation, and presence / absence of repelling.
６０°鏡面光沢度による評価
６０°鏡面光沢度が高い値であるほど、金属調光沢に優れる。該６０°鏡面光沢度は、ＪＩＳ Ｋ ５６００−４−７：１９９９に基づいて測定した。
Evaluation based on 60 ° specular gloss The higher the 60 ° specular gloss, the better the metallic gloss. The 60 ° specular gloss was measured based on JIS K 5600-4-7: 1999.
目視による評価
上記で得られた試験板を、人工太陽灯（セリック社製、色温度６５００Ｋ）で照明し、試照明に対する試験板の角度を変えて観察して、粒子感、ハイライト領域とシェード領域の輝度差を評価した。粒子感が少なく、ハイライト領域とシェード領域の輝度差が大きいほど金属調に優れた塗膜である。評価は、色彩開発に３年以上従事するデザイナー２名と技術者３名の計５名が５点満点で行ない、平均点を採用した。
５：輝度が非常に高く粒子感が無い
４：輝度が高く粒子感が少ない
３：輝度が高いが粒子感が大きい
２：輝度が低く粒子感が大きい
１：輝度が無く、粒子感が非常に大きい
はじきの有無による評価
上記で得られた試験板を、人工太陽灯（セリック社製、色温度６５００Ｋ）で照明し、はじきの有無を観察した。はじきとは試験板に見られる凝集物である。該凝集物のうち、任意の１００個の凝集物の直径を測定し、該直径の平均値が、１ｍｍ以上である場合を「はじきあり」と評価して、表４には「×」と記載した。該直径が１ｍｍ未満である場合を「はじきなし」と評価して、表４には「○」と記載した。
Visual evaluation The test plate obtained above was illuminated with an artificial sun lamp (Ceric, color temperature 6500K), and observed by changing the angle of the test plate with respect to the test illumination, and the particle feeling, highlight area and shade The brightness difference of the area was evaluated. The coating is more excellent in metallic tone as the feeling of particles is less and the brightness difference between the highlight area and the shade area is larger. The evaluation was performed by a total of 5 people, including 2 designers and 3 engineers engaged in color development for 3 years or more, and the average score was adopted.
5: Very high brightness and no particle feeling 4: High brightness and low particle feeling 3: High brightness but large particle feeling 2: Low brightness and large particle feeling 1: No luminance and particle feeling is very high large
Evaluation by presence / absence of repelling The test plate obtained above was illuminated with an artificial sun lamp (manufactured by Celic, color temperature 6500K), and the presence / absence of repelling was observed. Repel is an agglomerate found on the test plate. Of the aggregates, the diameters of 100 arbitrary aggregates were measured, and the case where the average value of the diameters was 1 mm or more was evaluated as “has been repelled”. did. The case where the diameter was less than 1 mm was evaluated as “no repellency”, and “◯” was described in Table 4.
性能評価
塗膜性能は、促進耐候性試験によって評価を行った。
Performance Evaluation The coating film performance was evaluated by an accelerated weather resistance test.
耐候性
各試験板について、ＪＩＳ Ｋ ５６００−７−７に準じ、「スーパーキセノンウエザーメーター」（スガ試験機社製、耐候性試験機）を用いて、試験片ぬれサイクル：１８分／２時間、ブラックパネル温度：６１〜６５℃の条件で、促進耐候性試験を行った。次に、ランプの照射時間が８００時間に達した時点で、試験板の複層塗膜を素地に達するようにカッターで格子状に切り込み、大きさ２ｍｍ×２ｍｍのゴバン目を１００個作った。次いで、その表面に粘着セロハンテープを貼着し、そのテープを急激に剥離した後のゴバン目塗膜の残存状態を調べた。
○：ゴバン目塗膜が１００個残存し、カッターの切り込みの縁において塗膜の小さなフチカケが生じていない
△：ゴバン目塗膜が９０〜９９個残存する
×：ゴバン目塗膜の残存数が８９個以下である。
For each of the weather resistance test plates, in accordance with JIS K 5600-7-7, using a “super xenon weather meter” (manufactured by Suga Test Instruments Co., Ltd., weather resistance tester), test piece wetting cycle: 18 minutes / 2 hours, Black panel temperature: The accelerated weather resistance test was conducted under the conditions of 61 to 65 ° C. Next, when the irradiation time of the lamp reached 800 hours, the multilayer coating film of the test plate was cut into a lattice shape with a cutter so as to reach the substrate, and 100 goblets having a size of 2 mm × 2 mm were made. Next, an adhesive cellophane tape was attached to the surface, and the remaining state of the goby eye coating after the tape was peeled off rapidly was examined.
◯: 100 pieces of Gobang eyes coating film remain, and no small chipping of the coating film occurs at the edge of the cutting of the cutter. Δ: 90-99 pieces of Gobang eyes paint film remain. 89 or less.
総合評価
前記外観評価及び性能評価の結果より総合評価を行った。
○：外観も性能も良い
△：外観は良いが性能が悪い
×：外観も性能も悪い
Comprehensive evaluation Comprehensive evaluation was performed from the results of the appearance evaluation and performance evaluation.
○: Appearance and performance are good △: Appearance is good but performance is poor ×: Appearance and performance are poor
本発明の塗膜形成方法は、各種工業製品、特に自動車車体の内板、外板及び自動車部品に適用できる。 The coating film forming method of the present invention can be applied to various industrial products, in particular, inner plates, outer plates and automobile parts of automobile bodies.
Claims (8)
光輝性顔料分散体が、水、有機溶剤（Ａ）、光輝性顔料（Ｂ）及び粘性調整剤（Ｃ）を含み、
上記水を、水、有機溶剤（Ａ）、光輝性顔料（Ｂ）及び粘性調整剤（Ｃ）の合計量１００質量部を基準として５０〜９０質量部含有し、
上記有機溶剤（Ａ）が、２０℃の水に１質量％以上溶解し、
温度２０℃にて１ｍＬの該有機溶剤（Ａ）が９０％以上蒸発するのに必要な時間が２５０秒以上であり、
水と有機溶剤（Ａ）とを質量比で７５／２０で混合させた液体を、温度２０℃にて、Ｂ型粘度計でローター回転速度６０ｒｐｍでの粘度が１００ｍＰａ・ｓとなるように調整したときの、ブリキ板に対する接触角が３〜４０°であることを特徴とする塗膜形成方法。 In a coating film forming method comprising coating a glitter pigment dispersion on an object to be coated and drying by heating,
The glitter pigment dispersion contains water, an organic solvent (A), a glitter pigment (B), and a viscosity modifier (C).
The water is contained in an amount of 50 to 90 parts by mass based on 100 parts by mass of water, an organic solvent (A), a glitter pigment (B), and a viscosity modifier (C),
The organic solvent (A) is dissolved by 1% by mass or more in 20 ° C. water,
The time required for 1 mL of the organic solvent (A) to evaporate 90% or more at a temperature of 20 ° C. is 250 seconds or more,
A liquid in which water and an organic solvent (A) were mixed at a mass ratio of 75/20 was adjusted at a temperature of 20 ° C. with a B-type viscometer so that the viscosity at a rotor rotational speed of 60 rpm was 100 mPa · s. The contact angle with respect to a tinplate is 3 to 40 degrees, The coating-film formation method characterized by the above-mentioned.
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