JP4292020B2 - Designable coating film, designable coating film forming method and designable coating composition - Google Patents

Description

【００９１】
表１の結果から明らかのように、本実施例は、本発明の意匠性塗膜形成方法により塗膜を形成したもので、部分的金属光沢感を発現する意匠性塗膜が得られた。一方、比較例では、部分的金属光沢感が得られない結果となった。
【００９２】
【発明の効果】
本発明の意匠性塗膜は、部分的金属光沢感を有し、燻し銀調を発現することができる。これは、本発明者らが燻された金属の表面をつぶさに観察して得られたミクロな状態を、種々の塗膜形成成分を用いて再現することができていると考えられる。すなわち、燻された金属の表面では、凹凸形状が光を乱反射しており、燻し工程によると思われる生成物が部分的に存在していることを発見し、これらが合わさって落ち着いた風合いと色調が発現していると考えた。そこで、金属系顔料により、金属光沢を付与するとともに表面に凹凸形状を生じさせる一方、着色顔料により、藁の燻しによる着色効果を与えることで、燻された金属の表面状態を有した塗膜の形成をはじめて可能にした。また、さらに部分的金属光沢感に、特定の領域の色相を加えることにより、燻し銀調を表現し得ることを見出した。
【００９３】
なお、本発明により得られる塗膜は、燻し銀調を呈するため、通信製品、家電製品、自動車、二輪車等の乗物外板、自動車部品（ホイール、バンパー等）、容器外面、コイルコーティングの意匠性が要求される塗膜において好ましく使用される。
【図面の簡単な説明】
【図１】 鏡面光沢度測定器の概略図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a designable coating film, a designable coating film forming method used for obtaining this coating film, and a designable coating composition.
[0002]
[Prior art]
In the field of metal crafts, there is a traditional technique called “bushi”. That is, after forming a rough surface on the metal surface, a surface having a calm texture and color tone can be obtained by wrinkling the wrinkles. This “boshi” is described in “Metallic Coloring Technique” (Hiroshi Nagano, Kenji Io, published by Rigaku Corporation). (See Non-Patent Document 1.)
[0003]
On the other hand, although “blossoming” is not actually performed, those that exhibit the texture and color tone are called “blushing silvery tone”. In addition to ornaments and crafts using silver itself, An example is known in which is applied to roof tiles, floors and wall tiles.
[0004]
In JP-A-5-138629, the material of the lower layer part of the main body that is press-molded into two layers is formed as a base material raw material in which the raw material used for glaze tiles, tiles, etc. is in powder form, The material of the upper layer portion is made into an auxiliary raw material that is made into a powder form by adding a material suitable for glazed roof tiles, for example, a silver cocoon, a silver black cocoon, etc. A ceramic building material by dry press molding exhibiting silvery luster characterized by drying, baking and hatching the main body is described. (For example, refer to Patent Document 1.)
[0005]
Japanese Patent Application Laid-Open No. 11-130514 discloses that a raw material blend containing at least 10% by weight of a clay and the balance containing silicic acid is mixed with an alkali silicate component, an alkaline earth metal chloride, and a low content. There is described a method for producing a glazed tile in which a clay tile base composition containing a melting point metal component is molded and then hatched and sintered. (For example, see Patent Document 2.)
[0006]
These are subjected to a hatching treatment in order to develop a feeling of hazyness. In addition, as an auxiliary material that expresses a feeling of harshness, TiO ₂ , Cr ₂ O _Three , Fe ₂ O _Three , Al ₂ O _Three , SiO ₂ The pigments used for silver candy, silver black candy, etc. are used.
[0007]
However, in these descriptions, although glazed silver or glazed roof tiles are advocated, the range of the color gamut is unclear, indicating so-called silver black in general, and glazed silver-tone with a partial metallic luster feeling. It has not yet achieved the design properties of.
[0008]
On the other hand, metallic paints containing bright pigments such as metal powder and mica are often applied to the top coat of automobiles. For example, as described in JP-A-10-298458, alumina is further added. There have been many attempts to create new designs by adding different brightening agents such as flakes. However, with these metallic paints, it is not possible to obtain a paint film having a tan silver tone having a partial metallic luster. (For example, refer to Patent Document 3.)
[0009]
[Non-Patent Document 1]
"Coloring technique of metalwork" (Hiroshi Nagano, Kenji Io, published by Science and Engineering, pages 2-4)
[Patent Document 1]
JP-A-5-138629
[Patent Document 2]
Japanese Patent Laid-Open No. 11-130514
[Patent Document 3]
JP-A-10-298458
[0010]
[Problems to be solved by the invention]
An object of the present invention is to provide a design coating film, a design coating film forming method, and a design coating composition that exhibit a tanned silver-tone design with a partial metallic luster.
[0011]
[Means for Solving the Problems]
1. (1) 60 degree specular gloss specified by JIS K5400 is 10 to 70, (2) surface roughness Ra is 1.5 to 3.5, and (3) hue H in the display system of Munsell hue ring is 5 YR. 10YR to 5Y, a design coating film having a chroma C of 0.15 to 0.6 and a lightness V of 5 to 7 in the Munsell display system.
[0012]
2. The above-mentioned design coating film containing (A) a vehicle, (B) a metallic pigment, and (C) a colored pigment.
[0013]
3. The design coating film as described above, wherein the metallic pigment contains a metallic pigment and / or a nonmetallic body having metallic luster.
[0014]
4). Said design coating film in which said metallic pigment contains at least 1 sort (s) of pigment chosen from aluminum flake pigment, silver powder pigment, and stainless steel powder pigment.
[0015]
5. The above-mentioned design coating film, wherein the non-metallic body contains at least one pigment selected from glass flakes coated with a metal and a polymer film cut after being coated with a metal.
[0016]
6). The design coating film as described above, wherein the color pigment contains a black color pigment, a yellow color pigment, or a white color pigment.
[0017]
7). Said designable coating film whose solid content in the designable coating film of the said metallic pigment is 0.1-30 mass%.
[0018]
8). The color pigment contains a black color pigment, a yellow color pigment, and a white color pigment, and the solid content ratio of the metal pigment / the black color pigment / the yellow color pigment / the white color pigment is 1 The above-mentioned design coating film which is /0.01 to 1 / 0.02 to 2 / 0.01 to 2.
[0019]
9. Furthermore, the above-mentioned design coating film containing a mica pigment and / or a glass-based pigment.
[0020]
10. The designable coating-film formation method which forms said designable coating film in at least one part on a base material.
[0021]
11. The method for forming a designable coating film as described above, wherein a matte top clear coat is further formed on the designable coating film.
[0022]
12 A design paint composition containing (A) a vehicle, (B) a metallic pigment, and (C) a colored pigment,
(1) 60 degree specular gloss specified by JIS K5400 is 10 to 70, (2) surface roughness Ra is 1.5 to 3.5, and (3) hue H in the display system of Munsell hue ring is 5 YR. A design coating composition capable of forming a design coating film having a color saturation C of 0.15 to 0.6 and a lightness V of 5 to 7 in a Munsell display system.
[0023]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the configuration of the present invention will be described in detail.
[0024]
[Designable coating film]
The designable coating film of the present invention forms a partial metallic luster with a paint. This “partial metallic luster” is the one which has a metallic luster but suppresses the glaring feeling peculiar to the metal, and is called tan silver tone.
[0025]
Furthermore, the designable coating film of the present invention preferably has (1) a 60-degree specular gloss specified by JIS K5400 of 10-70, (2) a surface roughness Ra of 1.5-3.5, and (3) It can be defined that the hue H in the Munsell hue ring display system is 5YR to 10YR to 5Y, the saturation C in the Munsell display system is 0.15 to 0.6, and the lightness V is 5 to 7.
[0026]
If the 60-degree specular gloss is less than 10, the metallic luster due to reflection may be poor and a metal feeling may not be obtained. is there. More preferably, it is 20-50. The 60-degree specular gloss can be measured with a specular gloss measuring instrument, for example, a trade name “micro-TRI-GLOSS” (manufactured by BYK CHEMIE).
[0027]
In FIG. 1, the specular reflected light beam ψs from the sample surface is measured with respect to the incident angle θ. However, the ratio is expressed by the ratio with respect to the specular reflection light beam ψos on the glass surface having the refractive index n = 1.567 under the same conditions. The 60 ° specular glossiness is a value when the incident angle θ and the light receiving angle ψ are 60 ° in the following mathematical formula.
[0028]
[Expression 1]
Gs (θ) = (ψs / ψos) × 100 (%)
[0029]
In FIG. 1, light is emitted from the light source I and the slit S ₁ Through the lens L ₁ And enters the sample surface at an incident angle θ. Then, the light reflected from the sample surface at the light receiving angle ψ is reflected by the lens L. ₂ Through the slit S ₂ And enters the light receiving surface C.
[0030]
When the surface roughness Ra is less than 1.5, the surface is too smooth and the glossiness is emphasized, and there is a risk of damaging the silvery texture. May be emphasized, giving a cast-like texture. More preferably, it is 2.0-3.0. The surface roughness Ra is measured using a surface roughness meter, for example, a trade name “Surf Test 211” (manufactured by Mitutoyo Corporation).
[0031]
When the hue H is out of the range of 5YR to 10YR to 5Y, it is presumably due to oxidation of sulfur components contained mainly in the cocoon, which is characteristically obtained by tanning the metal, and is slightly yellowish A yellowish white hue may not be obtained.
[0032]
If the saturation C in the Munsell display system is less than 0.15, the monotonous blackness may be emphasized and the unique color may be faded. There is a risk that the emphasis on darkness and the darkness of the texture will be lost.
[0033]
If the brightness V in the Munsell display system is less than 5, the partial metallic gloss may be impaired, and if it exceeds 7, the metallic gloss may be emphasized and the harsh feeling may be impaired. The hue H, saturation C, and brightness V in the Munsell display system are measured using a variable angle spectrophotometer, for example, a trade name [GSP-2 type] (manufactured by Murakami Color Research Laboratory).
[0034]
The designable coating film of the present invention contains (A) a vehicle, (B) a metallic pigment, and (C) a colored pigment. The vehicle (A) will be described in the description of the designable coating composition used to form the designable coating film of the present invention, which will be described later. Here, (B) a metal pigment and (C) coloring. The pigment will be described.
[0035]
Examples of the (B) metallic pigment include nonmetallic bodies having metallic luster in addition to general metallic pigments. Each of these may be a single species or a mixture of plural species.
[0036]
Here, the non-metallic body having metallic luster means that the surface itself has metallic luster by performing metal treatment or the like, although it is not itself a metal.
[0037]
The metal pigment is preferably at least one selected from aluminum flake pigment, silver powder pigment, and stainless steel powder pigment. In addition to these, silver and silver have a hue similar to that exhibited by normal exposure conditions, or nickel, titanium or alloys thereof with other dissimilar metals such as copper and zinc, so-called metallic luster Mono pigments can also be used. By including these metal pigments, a metallic luster is imparted.
[0038]
The aluminum flake pigment, silver powder pigment, and stainless steel powder pigment are prepared by an ordinary method in which a raw metal is pulverized with a ball mill. The raw metal is in the form of flakes in the case of aluminum, and in the form of foils in the case of silver and stainless steel. When aluminum flakes are used, they may be leafing, semi-leafing or non-leafing type aluminum flakes, and are usually pulverized with a fatty acid such as stearic acid. These preferred average particle sizes are in the range of 3-100 μm. In addition, the average particle diameter in this invention means the average particle diameter of a major axis. If the average particle size is less than 3 μm, the required metallic gloss may not be obtained. If the average particle size exceeds 100 μm, the pigment may protrude to the surface, which may reduce gloss and feel. More preferably, it is 10-50 micrometers.
[0039]
On the other hand, examples of the non-metallic body having a metallic luster include those having forms such as foil, film, and flakes, such as glass flakes coated with metal and polymer films cut after being coated with metal. Is mentioned.
[0040]
The preferable average particle diameter of the glass flake pigment coated with the metal is 3 to 100 μm, and more preferably 10 to 50 μm. If the average particle size is less than 3 μm, the required metallic gloss may not be obtained, and if it exceeds 100 μm, the smoothness of the coating film becomes insufficient. Examples of the metal of the metal coating include metals such as gold, silver, nickel, platinum, copper, palladium, cobalt, and titanium. Among these, gold or nickel is preferable because it forms a metal layer excellent in acid resistance, alkali resistance, weather resistance, water resistance and salt water resistance by coating. Further, for silver-coated ones, it is preferable that a predetermined surface oxidation prevention treatment (for example, silicon dioxide coating treatment) is performed because the weather resistance is higher than usual. The trade name “Metashine” (manufactured by Nippon Sheet Glass Co., Ltd.) is one of the commercially available pigments as a glass flake pigment coated with such a metal.
[0041]
On the other hand, as a polymer film cut after being coated with a metal, an organic film such as polyester is vapor-deposited and cut into a desired size and shape, the product name “ELG” (manufactured by Oike Kogyo Co., Ltd.) ).
[0042]
The solid content in the design coating film of the metal pigment in the design coating film is preferably 0.1 to 30% by mass. If the content is less than 0.1% by mass, the required partial metallic luster may not be obtained, and if it exceeds 30% by mass, the metallic luster is excessive, which is not preferable. More preferably, it is 1-20 mass%.
[0043]
Next, the (C) color pigment preferably contains a black color pigment, a yellow color pigment, and / or a white color pigment. As the black coloring pigment, black coloring pigments such as carbon black, graphite and black mica pigments, and as yellow coloring pigments, organic pigments such as chromophthalic and indanthrone, iron oxides, Examples thereof include inorganic yellow color pigments such as yellow lead. On the other hand, examples of white color pigments include titanium oxide, but they may be fine particles if necessary.
[0044]
The graphite pigment used as the black colored pigment is scaly graphite, and titanium dioxide is formed on the surface of the graphite flake that has been subjected to oxidation treatment by heating in an oxygen-containing atmosphere and / or oxidation treatment with a water-soluble oxidant. Those uniformly coated are preferably used. Such scaly graphite preferably has an average particle size of 1 to 30 μm, a thickness of 1 μm or less, and good dispersibility. More preferably, the average particle diameter is 1 to 10 μm and the thickness is 0.01 to 0.5 μm. As such scaly graphite, a trade name “GRAPHITAN 7525” (manufactured by Ciba Specialty Chemicals) can be mentioned.
[0045]
In the case where a black color pigment, a yellow color pigment, and a white color pigment are contained as the color pigment, the solid content ratio of the color pigment is based on the metal pigment, and the metal pigment / black color pigment / yellow It is preferable that the color pigment / white color pigment is 1 / 0.01 to 1 / 0.02 to 2 / 0.01 to 2. If it is out of the above range, the intended partial metallic luster may not be obtained.
[0046]
Moreover, it is preferable that the designable coating film of the present invention further contains a mica pigment and / or a glass pigment. When these pigments are contained, the content is preferably equal to or less than the content of the metal pigment. Beyond this, there is a risk of impairing the partial metallic luster. More preferably, solid content in a designable coating film is 30 mass% or less.
[0047]
The mica pigment is preferably a mica pigment obtained by coating a surface of natural muscovite or synthetic mica with a colored pigment in a flaky shape. As such a colored mica pigment, a scaly pigment having a particle size range of 3 to 50 μm, preferably 5 to 20 μm can be used. As the color of the colored mica pigment, a desired interference color can be obtained by adjusting the kind and amount (coating thickness) of the colored pigment to be coated.
[0048]
Examples of the glass pigment include glass chips or glass beads. As glass chip, geometrically irregular and irregular shape, D ₁₀ ~ D ₉₀ Particle size of about 1 to 30 μm (ie D ₁₀ ≧ 1 μm and D ₉₀ ≦ 30 μm), preferably about 1 to 16 μm (ie D ₁₀ ≧ 1 μm and D ₉₀ ≦ 16 μm), more preferably about 2 to 12 μm (ie D ₁₀ ≧ 2 μm and D ₉₀ ≦ 12 μm), and the ratio of average maximum piece length / average minimum piece length is about 1-10, average length is about 1-30 μm and D ₉₀ Those having an average aspect ratio of about 1 to 4 can be preferably used. In the present invention, D ₁₀ Means the particle size when the cumulative amount in the relative cumulative particle size distribution curve is 10% in the long particle size distribution, and D ₉₀ Means the particle size when the cumulative amount in the relative cumulative particle size distribution curve is 90% in the long particle size distribution. In particular, from the viewpoint of environmental protection, it is more preferable to use fine pieces of recycled glass that are geometrically uneven.
[0049]
In addition, the designable coating film of this invention may have not only what exists in the state apply | coated on the base material but the shape of an independent film. The thickness of the film is preferably 20 to 100 μm, more preferably 30 to 80 μm.
[0050]
[Designable coating composition used for forming a designable coating film]
The designable coating composition of the present invention used for forming the designable coating film is obtained by dispersing the metal pigment and the color pigment in a vehicle.
[0051]
The (1) vehicle contained in the designable coating composition of the present invention contains a film-forming resin. As the resin for forming a coating film, (a) acrylic resin, (b) polyester resin, (c) alkyd resin, (d) fluororesin, (e) epoxy resin, (f) polyurethane resin, (g) polyether resin These may be used alone or in combination of two or more, and are preferably acrylic resins or polyester resins.
[0052]
As said (a) acrylic resin, the copolymer of an acryl-type monomer and another ethylenically unsaturated monomer can be mentioned. Acrylic monomers that can be used for the copolymerization include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, 2-ethylhexyl, lauryl, phenyl, benzyl, 2-hydroxy of acrylic acid or methacrylic acid. Esterified compounds such as ethyl and 2-hydroxypropyl, ring-opening adducts of caprolactone of acrylic acid or 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide and N-methylol acrylamide, polyvalent There are (meth) acrylic acid esters of alcohol. Examples of the other ethylenically unsaturated monomers copolymerizable with these include styrene, α-methylstyrene, itaconic acid, maleic acid, and vinyl acetate.
[0053]
Examples of the polyester resin (b) include saturated polyester resins and unsaturated polyester resins, and examples thereof include condensates obtained by heat condensation of a polybasic acid and a polyhydric alcohol. Examples of the polybasic acid include saturated polybasic acids such as phthalic anhydride, terephthalic acid, and succinic acid, and unsaturated polybasic acids such as maleic acid, maleic anhydride, and fumaric acid. Examples of the polyhydric alcohol include dihydric alcohols such as ethylene glycol and diethylene glycol, and trihydric alcohols such as glycerin and trimethylolpropane.
[0054]
The above (c) alkyd resin includes modifiers such as the above-mentioned polybasic acids and polyhydric alcohols, oils and fats and fatty acids (soybean oil, linseed oil, coconut oil, stearic acid, etc.), natural resins (rosin, amber etc.) An alkyd resin obtained by reacting and modifying can be used.
[0055]
The (d) fluororesin comprises any one of vinylidene fluoride resin, tetrafluoroethylene resin or a mixture thereof, a polymerizable compound containing a fluoroolefin and a hydroxy group, and other copolymerizable vinyl compounds. Examples thereof include resins made of various fluorine-based copolymers obtained by copolymerizing monomers.
[0056]
As said (e) epoxy resin, resin etc. which are obtained by reaction of bisphenol and epichlorohydrin can be mentioned. Examples of bisphenol include bisphenol A and F. Examples of the bisphenol-type epoxy resin include Epicoat 828, Epicoat 1001, Epicoat 1004, Epicoat 1007, Epicoat 1009 (all trade names, manufactured by Shell Chemical Co., Ltd.), and the like. A chain-extended product can also be used.
[0057]
Examples of the polyurethane resin (f) include resins having a urethane bond obtained by reaction of various polyol components such as acrylic, polyester, polyether, and polycarbonate with a polyisocyanate compound. Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), and mixtures thereof (TDI), diphenylmethane-4,4 ′. Diisocyanate (4,4′-MDI), diphenylmethane-2,4′-diisocyanate (2,4′-MDI), and mixtures thereof (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3 ′ -Dimethyl-4,4'-biphenylene diisocyanate (TODI), xylylene diisocyanate (XDI), dicyclohexylmethane diisocyanate (hydrogenated HDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), hydrogenated xylylene diene Isocyanate (HXDI) etc. It can be mentioned.
[0058]
The (g) polyether resin is a polymer or copolymer having an ether bond, and is a polyoxyethylene polyether, polyoxypropylene polyether, polyoxybutylene polyether, bisphenol A or bisphenol. Examples thereof include polyether resins having at least two hydroxyl groups per molecule, such as polyethers derived from aromatic polyhydroxy compounds such as F. In addition, the above polyether resin reacts with polyvalent carboxylic acids such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, or reactive derivatives such as these acid anhydrides. Carboxy group-containing polyether resin obtained by causing the reaction to occur.
[0059]
In addition, the coating film-forming resin includes a curable type and a lacquer type. Usually, a curable type is used. It is also possible to use a lacquer-type resin for forming a coating film having no curability together with a type having curability. In the case of a curable type, the vehicle usually contains a crosslinking agent that causes the curing reaction to proceed at room temperature or at room temperature, in addition to the coating film-forming resin. Examples of the crosslinking agent include amino resins, (block) polyisocyanate compounds, amines, polyamides, imidazoles, imidazolines, polyvalent carboxylic acids and the like.
[0060]
When the vehicle includes a crosslinking agent, the ratio of the coating film-forming resin and the crosslinking agent is 90 to 50% by mass of the coating film-forming resin in terms of solid content, and the crosslinking agent is 10 to 50% by mass. Yes, preferably the film-forming resin is 85 to 60% by mass, and the crosslinking agent is 15 to 40% by mass. When the crosslinking agent is less than 10% by mass (when the coating film forming resin exceeds 90% by mass), crosslinking in the coating film is not sufficient. On the other hand, if the crosslinking agent exceeds 50% by mass (if the coating film-forming resin is less than 50% by mass), the storage stability of the design paint decreases and the curing rate increases, resulting in poor coating appearance. In addition, when the curing reaction is based on ultraviolet curing or electron beam curing, a resin obtained by introducing a reactive unsaturated group to be used in the reaction can be used.
[0061]
The description about the (B) metallic pigment and the (C) colored pigment contained in the designable coating composition of the present invention has been described in the above-described designable coating film. Moreover, it mix | blends also about the quantity so that it may become content prescribed | regulated in the designable coating film.
[0062]
In addition to the components described above, the designable coating composition of the present invention includes a polyamide wax which is a lubricating dispersion of an aliphatic amide, a polyethylene wax which is a colloidal dispersion mainly composed of oxidized polyethylene, an antisettling agent, a curing catalyst, Add UV absorbers, antioxidants, leveling agents, surface conditioners such as silicone and organic polymers, anti-sagging agents, thickeners, antifoaming agents, lubricants, crosslinkable polymer particles (microgel), etc. Can be contained. These additives are usually blended at a ratio of 15 parts by mass or less with respect to 100 parts by mass (based on solid content) of the vehicle, respectively, thereby improving the performance of the design paint or coating film. .
[0063]
Moreover, when obtaining a designable coating film by overcoating, the other coloring pigment which was not described in the designable coating film can also be added to any coating composition for forming each layer.
[0064]
The above-mentioned designable coating composition can be obtained by dissolving or dispersing the above-mentioned constituents usually in an organic solvent and / or water. Examples of the organic solvent include those commonly used in the paint field. Examples thereof include hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, cellosolve acetate and butyl cellosolve, alcohols and the like. Water is preferably used when the use of organic solvents is restricted from an environmental point of view. In this case, an appropriate amount of a hydrophilic organic solvent may be contained. Moreover, the said designable coating composition may take the form of the powder coating material.
[0065]
[Designable coating film forming method]
The designable coating film forming method of the present invention forms a designable coating film on at least a part of a substrate using the above-described designable coating composition. Examples of the base material include metals such as iron, aluminum, copper, and alloys thereof; inorganic materials such as glass, cement, and concrete; polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin, polyamide resin, and acrylic resin. Resin such as vinylidene chloride resin, polycarbonate resin, polyurethane resin, epoxy resin and various plastic materials such as FRP; natural or synthetic materials such as wood and fiber materials (paper, cloth, etc.), and processed products thereof It is done.
[0066]
In the designable coating film forming method of the present invention, if necessary, a designable coating film is formed directly or via a base coating film on the base material that has been subjected to the base treatment by degreasing or chemical conversion treatment. The method of forming the coating film is not particularly limited, but when the design paint is liquid, a normal coating method such as a spray method or a roll coater method can be applied, whereas when it is a powder, A fluid immersion method or an electrostatic atomization method can be used. Heating is performed according to the properties of the paint and the base material. For example, by heating at a temperature of 80 to 160 ° C. for a predetermined time, a target design coating film can be obtained.
[0067]
In the case of using a designable paint composition using an ultraviolet curable resin or an electron beam curable resin as a vehicle in the designable coating film forming method of the present invention, first, this designable paint composition was applied onto a polymer film. It is also possible to use a transfer film method in which a sheet is prepared, placed on a base material and pasted, cured by irradiation with ultraviolet rays or an electron beam, and then the polymer film is removed.
[0068]
As for the dry film thickness of the designable coating film obtained by the designable coating film formation method of this invention, 10-100 micrometers is preferable. If the thickness is less than 10 μm, it is difficult to conceal the base. More preferably, it is 15-60 micrometers.
[0069]
In the design coating film forming method of the present invention, a matte top clear coat is further formed on the design coating film thus obtained. For the formation of the matte top clear coat, a matte clear paint containing a matting agent in the clear paint is generally used. Examples of the matting agent include resin fine particles and inorganic fine particles. Examples of the resin fine particles include acrylic resin, polyacrylonitrile, polyurethane, polyamide, and polyimide. The particle diameter of the resin fine particles is preferably 2 to 20 μm. If it is less than 2 μm, the matting effect is insufficient and the tactile feeling becomes too smooth. On the other hand, if it exceeds 20 μm, the rough feeling is emphasized, and there is a risk that the silvery texture will be lost.
[0070]
On the other hand, examples of inorganic fine particles include fine silica powder, clay, talc, and mica. The particle diameter of the inorganic fine particles is preferably 2 to 20 μm as in the case of the resin fine particles. If it is less than 2 μm, the matte effect is insufficient, and if it exceeds 20 μm, the rough feeling may be emphasized.
[0071]
The resin fine particles and inorganic fine particles may be used in combination or may be used alone. The addition amount of the entire matting agent is preferably 5 to 40% by mass based on the solid content with respect to the solid content of the paint. If the addition amount is less than 5% by mass, the matte effect cannot be obtained, and if it exceeds 40% by mass, the strength of the coating film becomes insufficient. As the vehicle contained in the matte clear paint, those described in the above-mentioned designable paint composition can be used.
[0072]
The matte clear paint can contain the black or yellow color pigment as long as the transparency is not impaired. Various extender pigments such as calcium carbonate, barium sulfate, clay and talc can be used in combination.
[0073]
The matte clear paint may be in the form of an organic solvent, water or powder. The organic solvent type and water-based paint may be a one-pack type or a two-pack type such as a two-pack type urethane resin paint.
[0074]
In the design coating film forming method, a matte clear coating film can be formed by a wet-on-wet method when baking is not performed after the design coating film is formed. The dry film thickness of the matte clear coating film is preferably 10 to 100 μm. If it is less than 10 μm, the matte effect is hardly exhibited, and if it exceeds 100 μm, the appearance of the coating film may be poor. More preferably, it is 20-60 micrometers.
[0075]
【Example】
EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited only to these Examples. In addition, unless otherwise indicated, a compounding quantity represents a mass part.
[0076]
[Examples 1 to 12, Comparative Examples 1 to 4]
[Preparation of base materials A and B]
A plastic substrate (material: polycarbonate plate, length 150 mm, width 70 mm, and thickness 3 mm) was degreased to obtain substrate A.
[0077]
Dull steel plate (length 300 mm, width 100 mm and thickness 0.8 mm) was subjected to chemical conversion treatment using a zinc phosphate treating agent (trade name “Surfdyne SD2000”, manufactured by Nippon Paint Co., Ltd.), and then a cationic electrodeposition paint (product) The name “Power Top U-50” (manufactured by Nippon Paint Co., Ltd.) was electrodeposited so that the dry film thickness was 25 μm. Next, after baking at 160 ° C. for 30 minutes, intermediate coating (trade name “Orga S-90”, manufactured by Nippon Paint Co., Ltd.) is applied by air spray so that the dry film thickness is 40 μm, and baking is performed at 140 ° C. for 30 minutes. Thus, a base material B was obtained.
[0078]
[Preparation of Designable Coating Composition 1A]
Acrylic resin (styrene / methyl methacrylate / ethyl methacrylate / hydroxyethyl methacrylate / methacrylic acid copolymer, number average molecular weight about 20,000, hydroxyl value 45, acid value 15, solid content 50% by weight) and melamine resin (trade name “ “Uban 20SE” (manufactured by Mitsui Chemicals, Inc., 60 wt% solid content) was blended at a solid weight ratio of 80:20, and pigments blended in the types and proportions shown in Table 1 were used. . Subsequently, it stirs and mixes with an organic solvent (toluene / xylene / ethyl acetate / butyl acetate weight ratio = 70/15/10/5) so as to obtain an appropriate coating viscosity by a stirrer, and similarly prepares a design coating composition 1A. did.
[0079]
[Adjustment of Designable Coating Composition 1B]
Acrylic resin-based clear paint (trade name “NAX Mighty Lac G-II Clear”, manufactured by Nippon Paint Co., Ltd., solid content 33%) and diisocyanate curing agent (trade name “NAX Mighty Lac hardener”, manufactured by Nippon Paint Co., Ltd. ) And the vehicle obtained by blending so as to have an equivalent ratio of 1: 1. Subsequently, it stirs and mixes with an organic solvent (toluene / xylene / ethyl acetate / butyl acetate weight ratio = 70/15/10/5) with a stirrer so as to obtain an appropriate coating viscosity, and similarly prepares a design coating composition 1B. did.
[0080]
[Adjustment of matte clear paint]
For the matte clear paint, acrylic resin particles (referred to as a matte agent E1) or silica fine powder (referred to as a matte agent E2) were blended in the following two types of clear paints. The blending amounts are shown in Table 1. As the matte clear paint 2A, an acrylic / melamine resin solvent-type clear paint (trade name “Superlac O-150 Clear”, manufactured by Nippon Paint Co., Ltd.) was used. Matte clear paint 2B consists of an acrylic resin solvent-type clear paint (trade name “NAX Mighty Lac G-II Clear” manufactured by Nippon Paint Co., Ltd.) and a diisocyanate curing agent (trade name “NAX Mighty Lac Hardener”, Nippon Paint. The solvent-type clear coating was used so that the equivalent ratio was 1: 1.
[0081]
[Designable coating film forming method]
The design coating composition was air spray coated with the combinations shown in Table 1 so that the dry film thickness was 30 to 35 μm on the substrate A or B, and baked at 140 ° C. for 30 minutes to form a design coating film. . If necessary, if the matte clear paint shown in Table 1 is to be applied on the design coating film, set the design paint film for 3 minutes after coating, and the matte clear paint has a dry film thickness of 35 to 40 μm. Air spray coating was performed, and the coating was set for 3 minutes after coating, and the matte clear coating was baked at a temperature of 140 ° C. for 30 minutes.
[0082]
The following evaluation methods were used to evaluate the effects of metallic gloss, 60-degree specular gloss, surface roughness Ra, hue H, chroma C, lightness V, and tan silver tone in the Munsell hue ring display system. The results are shown in Table 1.
[0083]
[Evaluation methods]
For the metallic luster, the glitter feeling of each coating film obtained above was visually evaluated.
[0084]
2 ... There is a feeling of glitter.
1 ... No glitter.
[0085]
The 60-degree specular gloss was measured with a specular gloss measuring instrument (trade name “micro-TRI-GLOSS” manufactured by BYK CHEMIE).
[0086]
The surface roughness Ra was measured with a surface roughness meter (trade name “Surf Test 211” manufactured by Mitutoyo Corporation).
[0087]
The hue H, saturation C, and brightness V in the Munsell hue ring display system were measured with a variable angle spectrophotometer (trade name “GSP-2”, manufactured by Murakami Color Research Laboratory).
[0088]
For the tanned silver tone, the appearance of each coating film obtained above was visually evaluated.
[0089]
3 ... A unique silver texture is fully expressed due to the unique texture of the color and partial metallic luster.
2 ... Although there is a metallic luster, the color tone and texture are both faint and a silver tone is expressed.
1 ... The metallic luster is too high or there is almost no metallic luster, and both the color and texture are slightly different from the silver tone.
[0090]
[Table 1]

[0091]
As is clear from the results in Table 1, in this example, the coating film was formed by the design coating film forming method of the present invention, and a design coating film expressing a partial metallic gloss was obtained. On the other hand, in the comparative example, a partial metallic luster was not obtained.
[0092]
【The invention's effect】
The designable coating film of the present invention has a partial metallic luster and can exhibit a tanned silver tone. This is considered to be able to reproduce the microscopic state obtained by observing the surface of the metal on which the inventors have been crushed using various coating film forming components. In other words, on the surface of the glazed metal, it was found that the uneven shape was irregularly reflecting the light, and there were some products that seemed to be due to the tanning process, and these were combined to create a calm texture and color tone. Was thought to be expressed. Therefore, the metallic pigment imparts a metallic luster and creates an uneven shape on the surface, while the colored pigment imparts a coloring effect due to the wrinkle of the wrinkle, thereby providing a coating film having the surface state of the wrinkled metal. Formation was made possible for the first time. Furthermore, it has been found that by adding a hue of a specific region to the partial metallic luster, it is possible to express a faint silver tone.
[0093]
In addition, since the coating film obtained by the present invention has a tanned silver tone, vehicle skins for communication products, home appliances, automobiles, motorcycles, automobile parts (wheels, bumpers, etc.), container outer surfaces, and coil coating design properties Is preferably used in coatings that require
[Brief description of the drawings]
FIG. 1 is a schematic view of a specular gloss measuring device.

Claims (7)

(A) a vehicle, (B) a metal pigment having an average particle diameter of 3 to 100 μm (C) a colored pigment and (D) a mica pigment and / or a glass pigment,
The solid content in the design coating film of the metal pigment is 0.1 to 30% by mass,
The color pigment contains a black color pigment, a yellow color pigment, and a white color pigment, and the solid content ratio of the metal pigment / the black color pigment / the yellow color pigment / the white color pigment is 1 /0.01 to 1 / 0.02 to 2 / 0.01 to 2,
The total amount of the mica pigment and / or the glass pigment is 3.1 to 30% by mass, and the coating is not more than the same amount as the content of the metal pigment,
Further, (1) 60 degree specular gloss specified by JIS K5400 is 10 to 70, (2) surface roughness Ra is 1.5 to 3.5, and (3) Hue H in the display system of Munsell hue ring. 5YR to 10YR to 5Y, a chroma paint C in the Munsell display system is 0.15 to 0.6, and a lightness V is 5 to 7. The metallic pigment is, design coating film according to claim 1, further comprising a non-metallic body having a metallic pigment and / or metallic luster. The design coating film according to claim 2 , wherein the metal pigment contains at least one pigment selected from an aluminum flake pigment, a silver powder pigment, and a stainless steel powder pigment. The design coating film according to claim 2 , wherein the non-metallic body contains at least one pigment selected from glass flakes coated with a metal and a polymer film cut after being coated with a metal. The designable coating-film formation method which forms the designable coating film of any one of Claim 1 to 4 in at least one part on a base material. The method for forming a designable coating film according to claim 5 , further comprising forming a matte top clear coat on the designable coating film. (A) vehicle, containing (B) the average particle diameter 3~100μm metal-based Pigment (C) coloring pigments and (D) mica pigment and / or glass-based pigments,
The solid content in the design coating film of the metal pigment is 0.1 to 30% by mass,
The color pigment contains a black color pigment, a yellow color pigment, and a white color pigment, and the solid content ratio of the metal pigment / the black color pigment / the yellow color pigment / the white color pigment is 1 /0.01 to 1 / 0.02 to 2 / 0.01 to 2,
The total amount of the mica pigment and / or the glass pigment is 3.1 to 30% by mass, and the coating is not more than the same amount as the content of the metal pigment,
Further, (1) 60 degree specular gloss specified by JIS K5400 is 10 to 70, (2) surface roughness Ra is 1.5 to 3.5, and (3) Hue H in the display system of Munsell hue ring. 5YR to 10YR to 5Y, a designable coating composition capable of forming a designable coating film having a chroma C of 0.15 to 0.6 and a lightness V of 5 to 7 in the Munsell display system.

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