WO2017164234A1 - プレコート金属板 - Google Patents
プレコート金属板 Download PDFInfo
- Publication number
- WO2017164234A1 WO2017164234A1 PCT/JP2017/011440 JP2017011440W WO2017164234A1 WO 2017164234 A1 WO2017164234 A1 WO 2017164234A1 JP 2017011440 W JP2017011440 W JP 2017011440W WO 2017164234 A1 WO2017164234 A1 WO 2017164234A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal plate
- pigment
- coating film
- coating
- white pigment
- Prior art date
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
Definitions
- the present invention relates to a precoated metal sheet.
- Metal plates used in the fields of home appliances, building materials, automobiles, etc. are often painted after processing.
- the surface of a metal plate may be coated with a pre-colored coating film (colored coating film) and processed with the coating film coated.
- a metal plate to be coated after processing may be referred to as a post-coated metal plate, and a metal plate processed in a state where a colored coating film is coated may be referred to as a pre-coated metal plate.
- high-grade design is required for pre-coated metal plates, and a design that applies metallic coating to the surface of pre-coated metal plates is often used. Consumers' demands for paint colors are diversified, and one of them is metallic paint, which has a small difference in color tone and brightness change depending on the line-of-sight direction.
- pre-coated metal plate that has been subjected to metallic coating may be simply referred to as a pre-coated metal plate, or may be referred to as a metallic pre-coated metal plate.
- a post-coated metal plate that has been subjected to metallic coating may be simply referred to as a post-coated metal plate, or may be referred to as a metallic post-coated metal plate.
- a change in color tone and brightness due to the line-of-sight direction may be referred to as flip-flop property.
- a large flip-flop property means that the color tone and the glitter property change greatly depending on the line-of-sight direction
- a small flip-flop property means that the color tone and the glitter property hardly change depending on the line-of-sight direction.
- Patent Document 1 In order to form a coating film having excellent whiteness and metallic luster and having a large flip-flop property, aluminum flakes are oriented parallel to the coating surface, and an uncured base coating material is used. An aqueous dispersion of aluminum flakes is applied to the coated surface.
- Patent Documents 2 and 3 in order to produce a metallic coating film having a large flip-flop property or a thermoplastic resin composition for molded articles having a metallic feeling, a scaly aluminum pigment or a high aspect ratio aluminum powder is used. Describes a technique of adding scaly graphite pigment or interference pearl mica.
- Patent Document 4 describes a metallic paint composition that exhibits a pearl-like milky white feeling and an iris feeling that suppresses the color tone of blackness, and is excellent in base concealing properties, other than titanium dioxide pigment, pigment-supported scaly aluminum pigment, and titanium dioxide.
- a metallic paint composition comprising a color pigment, a pearl pigment and a film-forming resin as composition components is disclosed.
- Patent Document 5 describes a method for producing a metallic finish with a glittering finish, and a mica-like iron oxide powder containing 60% by weight or more of ⁇ -iron oxide on a metal plate with or without a primer coating film. Discloses a method of applying an organic solvent-type paint containing a coating film-forming resin and a color pigment.
- Patent Document 6 contains a vehicle, a metal oxide-coated alumina flake pigment (A), and an aluminum flake pigment or a fine-particle titanium dioxide pigment (B-1) and has a concealing property, We are disclosing things.
- Patent Document 7 discloses (1) an aluminum flake pigment, (2) an interference mica pigment having a dark region, (3) an interference bright pigment other than the interference mica pigment having the dark region of (2), and (4).
- a glittering coating composition containing a vehicle is disclosed.
- Patent Document 8 discloses a fatty acid-modified polyester having a number average molecular weight of 5000 to 30000, a hydroxyl value of 5 to 100 mgKOH / g, and an oil length of 3 to 30% as a coating composition capable of forming a coating film excellent in chemical resistance and weather resistance.
- Polyester resin component (A) containing 50 to 100% by mass of resin (A1), melamine resin component (B) containing 50 to 100% by mass of butyl etherified melamine resin (B1), and bright pigment component (C) A coating composition is disclosed.
- Patent Document 9 shows that there is no hue fluctuation due to a mixed layer of a metallic base coating film and a clear coating film when applied by a 2-coat 1-bake coating method, excellent transparency, a fine glitter, and flip-flop properties.
- a solvent-type metallic base coating composition containing a urea-modified acrylic resin (A), a urethane-modified polyester resin (B), a curing agent (C), a glitter pigment (D), and inorganic fine particles (E) as a strong coating film. Disclosure.
- Patent Document 10 discloses a coating film ⁇ (film thickness: 1.5 to 10 ⁇ m) containing a flaky aluminum pigment C whose organic resin A is a film-forming component on at least one surface of a metal plate and whose surface is inactivated. A chromate-free painted metal plate having a metallic appearance is disclosed.
- Japanese Unexamined Patent Publication No. 2000-000514 Japanese Unexamined Patent Publication No. 2000-271536 Japanese Unexamined Patent Publication No. 2000-319521 Japanese Unexamined Patent Publication No. 6-299100 Japanese Unexamined Patent Publication No. 2-212564 Japanese Unexamined Patent Publication No. 2000-86945 Japanese Unexamined Patent Publication No. 2001-164191 Japanese Unexamined Patent Publication No. 2014-9288 Japanese Unexamined Patent Publication No. 2005-220289 International publication WO2013 / 065354
- the coating film thickness including the corner portion needs to be 30 to 100 ⁇ m in order to have a sufficient metallic feeling even at the corner portion where the coating tends to be thin.
- the drying time after coating requires time corresponding to the film thickness of the coating film.
- a metallic precoated metal plate (particularly a metallic precoated steel plate) is produced on a continuous production line, and therefore, the length of the heating and drying line after coating is limited, and it is necessary to complete drying in a short time. Therefore, the film thickness of the coating film is 3 to 30 ⁇ m, which is thin compared to the coating film thickness of the metallic post-coated metal plate.
- the solvent in the film rapidly heats and evaporates, resulting in frequent boiling, and a defect called “Waki” occurs frequently in the metal pre-coated metal plate. The appearance of is deteriorated.
- the coating film of the metallic pre-coated metal plate is thin, the flake-like (scale-like) glitter pigment is strongly oriented, and the glitter pigment is arranged in a state where the flat surface of the glitter pigment is aligned parallel to the coating film surface. .
- the appearance of the metallic pre-coated metal plate tends to have a strong metallic feeling when viewed from one direction and a weak metallic feeling when viewed from another direction (that is, the flip-flop property becomes strong).
- Patent Documents 1 to 10 aim to improve the metallic feeling of the metallic pre-coated metal plate or obtain a metallic pre-coated metal plate having strong flip-flop properties. That is, as in the present invention, there has been almost no prior art relating to a metallic pre-coated metal plate having a small change in color tone and brightness due to the viewing direction (that is, having a weak flip-flop property).
- the present invention has been made in view of the above circumstances, and provides a pre-coated metal plate (metallic pre-coated metal plate) having a small change in color tone and brightness depending on the line-of-sight direction, that is, having a weak flip-flop property. Objective.
- the present invention adopts the following means in order to solve the above problems and achieve the object.
- a precoated metal plate according to an aspect of the present invention is provided on at least one surface of a metal plate and the metal plate, and has a luster pigment, an average particle size of 200 to 400 nm, and a content of 0.5. And a coating film having a film thickness of 5 to 30 ⁇ m, the white pigment comprising titanium oxide, zinc oxide, barium sulfate, basic carbonate, and silica.
- the content of the bright pigment in the coating film is A in mass% unit and the content of the white pigment is B in mass% unit, B / The value of A is 0.03 to 0.27.
- the average particle diameter of the white pigment may be 250 to 350 nm.
- the bright pigment may be aluminum flakes.
- the B / A value may be 0.05 to 0.20.
- the surface of the coating film may further have a clear coating film.
- the present inventors first investigated the difference in properties of the coating film between the post-coated metal plate and the pre-coated metal plate. As a result of the investigation, in the post-coated metal plate, the film thickness of the coating film is relatively large with respect to the thickness of the bright pigment. It was found that the incident light tends to diffusely reflect.
- the present inventors have found the following points regarding the pre-coated metal sheet. That is, since the film thickness of the coating film is relatively small with respect to the thickness of the bright pigment, the flat surface of the bright pigment is oriented in a direction parallel to the coating film surface in the coating film. As a result, the light incident on the precoated metal plate is often specularly reflected, which increases the difference in color tone and brightness depending on the line-of-sight direction (that is, the flip-flop property increases).
- the present inventors have found that the flip-flop property can be reduced by mixing an appropriate amount of a fine white pigment in the coating film in order to reduce the flip-flop property in the pre-coated metal plate. It came.
- the present inventors investigated the cause of the difference in flip-flop properties in the post-coated metal plate according to the prior art, the pre-coated metal plate according to the prior art, and the pre-coated metal plate according to the present embodiment.
- FIG. 1 is a diagram showing the principle of color tone measurement using a variable angle color difference meter.
- incident light is applied to the measurement surface (painted surface) from the upper left 45 ° direction, and the right oblique 45 ° direction corresponding to regular reflection is set as a reference angle (0 °) (that is, light Measuring the lightness L, etc. by placing light receivers in the directions of 15 °, 25 °, 45 ° (vertically upward), 75 °, and 110 ° on the incident light side. Is shown.
- human vision can be expressed in Lab (sometimes expressed as L * a * b) space, where a is the red direction, -a is the green direction, b is the yellow direction, -b Represents the blue direction, and L represents lightness (brightness).
- L represents lightness (brightness).
- the present inventors have found that among the above-mentioned indicators, the difference in flip-flop property of the metallic coating film is mainly caused by the difference in L value representing lightness. That is, the present inventors have found that the flip-flop property is large when the L value difference is large depending on the angle, and the flip-flop property is small when the L value difference depending on the angle is small.
- the present inventors have found that the difference ⁇ L between the L value at 15 ° and the L value at 110 ° is 70 or less, even in the pre-coated metal plate, It was found that flip-flop properties similar to post-coated metal plates can be realized.
- FIG. 2A is a schematic diagram showing a cross-sectional structure of a post-coated metal plate according to the prior art.
- FIG. 2B is a schematic diagram showing a cross-sectional structure of a pre-coated metal plate according to the prior art.
- FIG. 2C is a schematic diagram showing a cross-sectional structure of the precoated metal sheet according to the present embodiment.
- the film thickness of the coating film is relatively thick as 30 to 100 ⁇ m, so that the orientation of the glitter pigment 5 in the coating film is small, that is, the glitter The pigment 5 exists in various directions.
- a light ray incident from the upper left is reflected on the flat surface of the bright pigment 5 directed in various directions, so that the reflected light travels in various directions.
- the flip-flop property is small on the surface of the post-coated metal plate.
- the film thickness of the coating film is relatively small (about 3 to 30 ⁇ m)
- the bright pigment 5 is substantially parallel to the coating film surface in the coating film. Orient to the angle. Thereby, the probability that the light incident on the precoated metal plate is regularly reflected is increased, and the flip-flop property is increased.
- the precoated metal plate As shown in FIG. 2C, in the precoated metal plate according to this embodiment, an appropriate amount of fine white pigment 7 is mixed in the coating film.
- the white pigment 7 diffuses incident light before reaching the bright pigment 5 and reflected light reflected by the bright pigment 5.
- the flip-flop property is smaller than that of the conventional precoated metal plate.
- the diameter of the white pigment 7 is enlarged and displayed.
- the precoated metal sheet according to the present embodiment can reduce changes in color tone and glitter (flip-flop property) depending on the line-of-sight direction by containing an appropriate amount of fine white pigment 7 in the coating film.
- precoat metal plate 10 which concerns on embodiment is demonstrated with reference to drawings.
- Pre-coated metal plate 10 First, the precoat metal plate 10 will be described. 3 and 4 are schematic views showing the configuration of the precoated metal plate 10.
- the pre-coated metal plate 10 is provided on the metal plate 1 and at least one surface of the metal plate 1, and the bright pigment 5, the average particle diameter is 200 to 400 nm, and the content is 0. And a coating film 3 containing 5 to 4.0% by mass of white pigment 7 and having a thickness of 5 to 30 ⁇ m.
- the white pigment 7 is at least one selected from the group consisting of titanium oxide, zinc oxide, barium sulfate, basic carbonate, and silica.
- the precoat metal plate 10 includes the metal plate 1 as a base material.
- the metal plate 1 is not specifically limited, A well-known metal plate can be used and an alloy material may be used. Examples of such a metal plate 1 include a steel plate, a stainless steel plate, an aluminum plate, an aluminum alloy plate, a titanium plate, and a copper plate.
- the metal plate 1 may be plated on the surface. Examples of the type of plating include zinc plating, aluminum plating, copper plating, nickel plating and the like. These alloy platings may be used.
- steel plates In the case of steel plates, generally known steel plates and plated steel plates such as hot dip galvanized steel plates, electrogalvanized steel plates, zinc-nickel alloy plated steel plates, hot galvannealed steel plates, aluminum plated steel plates, aluminum-zinc alloyed steel plates, etc. Can be used.
- the pre-coated metal plate 10 is provided on at least one surface of the metal plate 1, and the bright pigment 5 and the white pigment 7 having an average particle diameter of 200 to 400 nm and a content of 0.5 to 4.0 mass%. And a coating film 3 having a film thickness of 5 to 30 ⁇ m. As shown in FIG. 3, the coating film 3 may be provided on one side of the metal plate 1, or may be provided on both sides of the metal plate 1 as shown in FIG. 4.
- the coating film 3 has a bright pigment 5.
- the bright pigment 5 is a generic term for pigments having a bright feeling, such as pearl pigments, glass flake pigments, metallic pigments and the like.
- the pearl pigment generally known pearl pigments such as mica and synthetic mica can be used, and commercially available ones may be used.
- the glass flake pigment is glass powder made into flakes, and a surface coated with metal or metal oxide may be used.
- a commercially available glass flake pigment may be used.
- the metallic pigment for example, metal fine particles such as aluminum and silver, flaky fine particles, and the like can be used.
- As the bright pigment 5 a metallic pigment capable of obtaining a suitable metallic appearance is preferable, and aluminum flakes are particularly preferable.
- Patent Document 4 metallic pigment in which an organic or inorganic colored pigment is chemically adsorbed on the surface of the scaly aluminum pigment
- Patent Document Use of the mica-like iron oxide powder described in No. 5 or the metal oxide-coated alumina flake pigment described in Patent Document 6 is not preferable because a suitable flip-flop property cannot be obtained. Although this reason is not certain, when the above-mentioned pigment is added to the coating film 3, some interaction acts between the above-mentioned pigment and the white pigment 7 described later, and a suitable flip-flop property cannot be obtained. It is thought that.
- the shape of the bright pigment 5 is not particularly limited, but is preferably a flake shape in order to reflect light appropriately.
- the flake shape generally means that the aspect ratio (average particle diameter D50 (cumulative weight 50% particle diameter) / thickness ratio) is 5 to 20.
- the size of the bright pigment 5 is not particularly limited, but in order to obtain suitable flip-flop properties, the average particle size (D50 (cumulative weight 50% particle size)) is preferably 20 to 50 ⁇ m, and the thickness is 0.00. It is preferably 5 to 5.0 ⁇ m.
- the coating film 3 contains a white pigment 7 having an average particle diameter of 200 to 400 nm and a content of 0.5 to 4.0% by mass. Depending on the type, particle size, and addition amount of the white pigment 7, the effect as the white pigment 7 is manifested, and the coating film 3 becomes cloudy, loses gloss, or the color tone becomes a blue gray tone. It is necessary to appropriately select the type, particle size and amount of addition.
- the white pigment 7 is at least one selected from the group consisting of titanium oxide, zinc oxide, barium sulfate, basic carbonate, and silica. It is preferable that the white pigment 7 contained in the coating film 3 is any one or more of the above-mentioned compounds because suitable flip-flop properties can be obtained.
- the average particle diameter of the white pigment 7 is 200 to 400 nm. If the average particle diameter of the white pigment 7 is 200 nm or less, a sufficient diffuse reflection effect cannot be obtained, which is not preferable. Moreover, when the average particle diameter of the white pigment 7 exceeds 400 nm, an effect as a white pigment is manifested, and for example, the color tone becomes a blue gray tone, and the metallic feeling is lost, which is not preferable.
- the average particle diameter of the white pigment 7 is preferably 250 to 350 nm.
- the coating film 3 contains 0.5 to 4.0% by mass of the white pigment 7.
- the content of the white pigment 7 is less than 0.5% by mass, a suitable flip-flop property cannot be obtained, which is not preferable.
- the content of the white pigment 7 is more than 4% by mass, the transparency of the coating film 3 is lowered, and the metallic feeling may be lost.
- the coating film 3 preferably contains 1.0 to 3.0% by mass of white pigment 7 and more preferably contains 1.5 to 2.5% by mass.
- the light irradiated on the surface of the precoated metal plate 10 is suitably reflected.
- the light irradiated on the pre-coated metal plate 10 is reflected in a manner close to irregular reflection.
- the diffuse reflection of a very small amount of white pigment 7 reflects in a manner that raises a metallic feeling other than regular reflection.
- the resin that is the main component of the coating film 3 is not particularly limited. Since the transparency is high, the resin of the coating film 3 is preferably polyethylene, polyester, acrylic, or the like. Similar to the conventional metallic coating film, a colorant (dye) and various additives can be mixed in the coating film 3, or a clear coating film (not shown) may be formed on the surface. As the colorant (dye) to be added to the coating film 3, known azo dyes, anthraquinone dyes, indigoid dyes, sulfur dyes, phthalocyanine dyes, diphenylmethane and triphenylmethane dyes, other nitro dyes, acridine dyes and the like are used. .
- the coating film 3 contains the bright pigment 5 and the white pigment 7, but in order to achieve suitable flip-flop properties, the content (unit: mass%) of the bright pigment 5 in the coating film 3 is set.
- the value of B / A needs to be 0.03 to 0.27.
- the value of B / A is 0.05 to 0.20, more preferably 0.06 to 0.18.
- additives that can be added to the coating film 3 include additives such as antifoaming agents, leveling agents, and dispersion aids, and organic wax components such as polyethylene, polypropylene, ester, paraffin, and fluorine.
- organic wax components such as polyethylene, polypropylene, ester, paraffin, and fluorine.
- Inorganic wax components such as molybdenum disulfide, diluents for reducing paint viscosity, solvents, water and the like.
- the pre-coated metal plate 10 can be manufactured by using a general continuous coating line or a coating line for a cut plate, appropriately selecting a necessary process, and performing the selected process. As a typical production process of a painting line, washing, drying, chemical conversion treatment, drying, painting, drying and baking, cooling, and drying are performed in this order. However, the manufacturing process of the precoat metal plate 10 in this embodiment is not limited to this.
- a clear coat film (not shown) is formed on the surface of the coating film 3
- a clear coating film paint (hereinafter referred to as "clear paint”) is applied. Then, drying and baking hardening may be performed.
- the clear paint is applied together with the paint for the coating film by wet-on-wet or multilayer simultaneous application method
- the two laminated layers may be simultaneously dried and baked and cured.
- the wet-on-wet or multi-layer simultaneous coating method is more preferable because the manufacturing process is further omitted.
- the metal plate 1 is a galvanized steel sheet, in a line having a wet-on-wet coating facility or a simultaneous multi-layer coating facility after the plating step in the continuous electroplated steel sheet facility or the continuous hot dip galvanized steel sheet facility By being manufactured, it can be applied before the oxide film on the surface of the plated metal is formed, and appearance defects due to the oxide film can be prevented.
- multi-layer simultaneous application means that a plurality of coating liquids are dispensed by a device capable of discharging different paints from two or more parallel slits such as a slot die coater or a slide hopper type curtain coater. It is a method in which the laminated coating liquid is applied to a substrate in the state of being simultaneously laminated, and the laminated coating liquid is simultaneously dried and baked.
- Wet-on-wet coating is a multilayer coating solution in which a coating solution is applied on a substrate and then wet before the coating solution dries. Are simultaneously dried and baked.
- a coating layer such as roll coating, dip coating, curtain flow coating, or roller curtain coating is applied, and then the coating layer is dried.
- a method that can be applied without contact with the substrate such as curtain flow coating, roller curtain coating, slide hopper curtain coating, slot die coating, etc.
- a method of simultaneously drying and baking the laminated multilayer coating film in a wet state for example, a method of simultaneously drying and baking the laminated multilayer coating film in a wet state.
- baking ovens for paints such as hot air drying ovens, direct heating ovens, induction heating, etc.
- a furnace, an infrared heating furnace, a heating furnace using these in combination, or the like can be used.
- Polyester was used as the resin for forming the coating film.
- a paint base was prepared by changing the composition of the coating film as described in the table, and a coating film having the film thickness described in the table was formed on a galvanized steel sheet to prepare a sample. For each sample, flip-flop properties ( ⁇ L), metallic feeling and appearance were evaluated by the methods described below.
- the flip-flop property was evaluated as follows according to the value of ⁇ L. VeryGood: ⁇ L ⁇ 60 Good: 60 ⁇ L ⁇ 65 Fair: 65 ⁇ L ⁇ 70 Bad: 70 ⁇ L In the above four-step evaluation, those evaluated as VeryGood, Good, and Fair were regarded as acceptable.
- the metallic feeling was evaluated as follows. Eight evaluators skilled in evaluating the metallic feeling of the pre-coated metal plate evaluated the metallic feeling of the pre-coated metal plate under natural daylight in the following three stages. 3 points: Metallic feeling 2 points: Low metallic feeling 1 point: No metallic feeling The metallic feeling was evaluated in the following four stages based on the total score by 8 people. Very Good: 20 points or more and 24 points or less Good: 16 points or more and less than 20 points Fair: 12 points or more and less than 16 points Bad: 8 points or more and less than 12 points In the above four-step evaluation, those evaluated as Very Good, Good, and Fair Was passed.
- the appearance was evaluated as follows. One evaluator skilled in evaluating the appearance of the precoated metal sheet observed the appearance of the precoated metal sheet in natural daylight. The appearance was evaluated in the following two stages. Good: When a defect is not recognized Bad: When a defect of 1 mm ⁇ or more is recognized What was evaluated as Good in the above two-stage evaluation was regarded as acceptable.
- Tables 1 to 5 show the conditions and evaluation results of the examples and comparative examples.
- Example 2 Next, the conditions regarding the bright pigment and the white pigment were not changed, and the kind of the resin in the coating film was changed, and the flip-flop property, metallic feeling and appearance were examined in the same manner as in Example 1. The evaluation results are shown in Table 6.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
Abstract
Description
本願は、2016年3月22日に、日本に出願された特願2016-56852号に基づき優先権を主張し、その内容をここに援用する。
近年、インテリア嗜好性の高まり等を反映して、プレコート金属板において高級な意匠性が求められており、プレコート金属板表面にメタリック塗装を施すデザインが多用されている。消費者の塗色に対する要求は多様化しており、視線方向による色調及び光輝性の変化の差の小さいメタリック塗装はその1つである。
例えば、特許文献1では、白色度及び金属光沢感に優れ、かつ、フリップフロップ性の大きい塗膜を形成するために、アルミフレークを塗面に対して平行に配向させるとともに、未硬化のベース塗料の塗面にアルミフレークの水分散液を塗布している。
特許文献2、3では、フリップフロップ性の大きいメタリック塗膜や、メタリック感を有する成形品用熱可塑性樹脂組成物を製造するために、光輝顔料である鱗片状アルミニウム顔料や高アスペクト比のアルミニウム粉に、鱗片状グラファイト顔料や、干渉パールマイカを添加する技術が記載されている。
特許文献5は、光輝感のあるメタリック仕上げのプレコートメタルの製法として、金属板上にプライマー塗膜を介して、もしくは介さずに、α-酸化鉄を60重量%以上含有する雲母状酸化鉄粉、塗膜形成樹脂及び着色顔料を含有する有機溶剤型塗料を塗装する方法を開示している。
特許文献7は、(1)アルミニウムフレーク顔料、(2)暗部領域を有する干渉マイカ顔料、(3)前記(2)の暗部領域を有する干渉マイカ顔料以外の干渉性光輝性顔料、および(4)ビヒクルを含有する光輝性塗料組成物を開示している。
特許文献9は、2コート1ベーク塗装方法で塗装した場合に、メタリックベース塗膜とクリヤー塗膜との混層による色相変動がなく、透明感に優れ、緻密な光輝感があり、フリップフロップ性が強い塗膜として、ウレア変性アクリル樹脂(A)、ウレタン変性ポリエステル樹脂(B)、硬化剤(C)、光輝性顔料(D)および無機微粒子(E)を含有する溶剤型メタリックベース塗料組成物を開示している。
なお、膜厚の厚い塗膜を短時間で急激に乾燥させると、塗膜中の溶媒が急速に加熱蒸発することにより突沸し、塗膜にワキと呼ばれる欠陥が多発して、メタリックプレコート金属板の外観が劣化する。
本発明者らは、上記課題を解決するために、まず、ポストコート金属板と、プレコート金属板とにおける、塗膜の性状の違いを調査した。
調査の結果、ポストコート金属板では、光輝顔料の厚みに対して相対的に塗膜の膜厚が大きいため、塗膜内において、光輝顔料の配向性の自由度が高く、ポストコート金属板に入射した光が拡散反射する傾向があることを知見した。
本発明者らは、上述の指標のうち、メタリック塗膜のフリップフロップ性の差異は、主として明度を表すL値の差異に起因することを知見した。
つまり、本発明者らは、角度によってL値の差異が大きい場合にはフリップフロップ性が大きく、角度によるL値の差異が小さい場合にはフリップフロップ性が小さいことを知見した。
図2Aに示すように、従来技術に係るポストコート金属板では、塗膜の膜厚が30~100μmと相対的に厚いために、塗膜中の光輝顔料5の配向性が小さい、つまり、光輝顔料5は様々な方向を向いて存在している。左斜め上から入射した光線は様々な方向を向いた光輝顔料5の偏平面で反射する結果、反射光は様々な方向に進む。これにより、ポストコート金属板の表面では、フリップフロップ性が小さい。
なお、図2Cにおいては、白色顔料7の径を実際より拡大して表示している。
(プレコート金属板10)
最初に、プレコート金属板10について説明する。
図3及び4は、プレコート金属板10の構成を示す模式図である。
プレコート金属板10は、基材として金属板1を備える。金属板1は特に限定されず、公知の金属板を用いることができ、合金材料製であってもよい。そのような金属板1の例として、鋼板、ステンレス鋼板、アルミ板、アルミ合金板、チタン板、銅板等が挙げられる。
金属板1は、表面にめっきが施されていてもよい。めっきの種類としては、亜鉛めっき、アルミめっき、銅めっき、ニッケルめっき等が挙げられる。これらの合金めっきであってもよい。鋼板の場合は、溶融亜鉛めっき鋼板、電気亜鉛めっき鋼板、亜鉛-ニッケル合金めっき鋼板、溶融合金化亜鉛めっき鋼板、アルミめっき鋼板、アルミ-亜鉛合金化めっき鋼板等、一般に公知の鋼板及びめっき鋼板を用いることができる。
プレコート金属板10は、金属板1の少なくとも一方の表面に設けられ、光輝顔料5と、平均粒径が200~400nmであり含有量が0.5~4.0質量%である白色顔料7とを含有し、膜厚が5~30μmである塗膜3とを備える。
塗膜3は、図3に示すように、金属板1の片面に設けられていてもよく、図4に示すように、金属板1の両面に設けられていてもよい。
塗膜3は、光輝顔料5を有する。ここで、光輝顔料5とは、パール顔料、ガラスフレーク顔料、メタリック顔料等の光輝感を持つ顔料の総称である。
具体的には、パール顔料としては、マイカ、合成マイカなどの一般に公知のパール顔料を用いることができ、市販のものを使用してもよい。
メタリック顔料としては、例えば、アルミニウム、銀等の金属の微粒子やフレーク状の微粒子などを用いることができる。
光輝顔料5としては、好適なメタリック外観を得ることのできるメタリック顔料が好ましく、特にアルミニウムフレークが好ましい。
この理由は定かではないが、上述の顔料を塗膜3中に添加した場合、上述の顔料と後述する白色顔料7との間に何らかの相互作用が働き、好適なフリップフロップ性が得られないためであると考えられる。
光輝顔料5の大きさも特に限定されないが、好適なフリップフロップ性を得るために、平均粒子径(D50(累積重量50%粒子径))が20~50μmであることが好ましく、厚さが0.5~5.0μmであることが好ましい。
塗膜3は、平均粒径が200~400nmであり含有量が0.5~4.0質量%である白色顔料7を含有する。
白色顔料7の種類、粒径及び添加量によっては、白色顔料7としての作用が発現して、塗膜3に曇りや光沢喪失、或いは、色調がブルーグレー調となってしまうので、白色顔料7の種類、粒径及び添加量を適宜選択する必要がある。
白色顔料7の平均粒径が200nm以下では、十分な拡散反射作用を得ることができないため好ましくない。また、白色顔料7の平均粒径が400nm超では、白色顔料としての作用が発現して、例えば色調がブルーグレー調となり、メタリック感が喪失してしまうため好ましくない。白色顔料7の平均粒径は、250~350nmが好ましい。
白色顔料7の含有量が0.5質量%未満の場合、好適なフリップフロップ性が得られないため好ましくない。白色顔料7の含有量が4質量%超の場合、塗膜3の透明性が低下して、メタリック感が喪失するおそれがあるため好ましくない。
塗膜3は、白色顔料7を1.0~3.0質量%含有することが好ましく、1.5~2.5質量%含有することがより好ましい。
一方、本実施形態では、白色塗膜を形成するために白色顔料7を添加しているのではなく、塗膜3が好適なフリップフロップ性を有するために白色顔料7を添加している。そのため、従来技術と比較して、塗膜3への白色顔料7の添加量が大幅に少なく、0.5~4.0質量%である。
従来のメタリック塗膜と同様に、塗膜3中に着色剤(染料)や各種添加剤を混入できる他、表面にクリア塗膜(不図示)を重ねて形成してもよい。塗膜3に添加する着色剤(染料)としては、アゾ染料、アントラキノン染料、インジゴイド染料、硫化染料、フタロシアニン染料、ジフェニルメタンおよびトリフェニルメタン染料、その他ニトロ染料、アクリジン染料等、公知のものが用いられる。
上述したように、塗膜3は光輝顔料5と白色顔料7とを含有するが、好適なフリップフロップ性を奏するためには、塗膜3における光輝顔料5の含有量(単位:質量%)をA、塗膜3における白色顔料7の含有量(単位:質量%)をBとしたときに、B/Aの値が0.03~0.27である必要がある。好ましくは、B/Aの値は0.05~0.20であり、より好ましくは0.06~0.18である。
次に、プレコート金属板10の製造方法について説明する。
塗膜を形成する樹脂としてポリエステルを用いた。塗膜の組成を表中に記載するように変化させて塗料ベースを作成し、亜鉛めっき鋼板上に表中に記載の膜厚を有する塗膜を形成して試料とした。各試料に対して、フリップフロップ性(ΔL)、メタリック感及び外観を後述の方法で評価した。
各試料のフリップフロップ性は、次のようにして測定した。まず、X-RITE社製の変角色差計MA-68IIを使用して、15°におけるL値であるL15と、110°におけるL値であるL110とを測定した。次に、L15-L110=△Lの式で表されるΔLを算出し、ΔLをフリップフロップ性の指標とした。
VeryGood:ΔL≦60
Good:60<ΔL≦65
Fair:65<ΔL≦70
Bad:70<ΔL
上述の4段階評価で、VeryGood、Good、Fairと評価されたものを合格とした。
メタリック感は次のように評価した。
プレコート金属板のメタリック感の評価に熟練した評価者8名が、自然昼光下におけるプレコート金属板のメタリック感を、以下の3段階で評価した。
3点:メタリック感がある
2点:メタリック感が低い
1点:メタリック感が無い
8名による合計得点により、メタリック感は、次の4段階で評価した。
Very Good:20点以上24点以下
Good:16点以上20点未満
Fair:12点以上16点未満
Bad:8点以上12点未満
上述の4段階評価で、VeryGood、Good、Fairと評価されたものを合格とした。
外観は次のように評価した。
プレコート金属板の外観の評価に熟練した評価者1名が、自然昼光におけるプレコート金属板の外観を観察した。
外観は、次の2段階で評価した。
Good:欠陥が認められない場合
Bad:1mmφ以上の欠陥が認められた場合
上述の2段階評価で、Goodと評価されたものを合格とした。
一方、表4及び5に示すように、本発明の条件を充足しない比較例では、フリップフロップ性、メタリック感又は外観のいずれかの評価が不適であった。
次に、光輝顔料及び白色顔料に関する条件は変えずに、塗膜中の樹脂の種類を変えて、実施例1と同様にフリップフロップ性、メタリック感及び外観について調べた。
評価結果を表6に示す。
なお、表1~表6において、光輝顔料として用いられているアルミニウムは、アルミニウムフレークを指す。
3 塗膜
5 光輝顔料
7 白色顔料
10 プレコート金属板
Claims (6)
- 金属板と;
前記金属板の少なくとも一方の表面に設けられ、光輝顔料と、平均粒径が200~400nmであり含有量が0.5~4.0質量%である白色顔料とを含有し、膜厚が5~30μmである塗膜と;
を備え、
前記白色顔料が、酸化チタン、酸化亜鉛、硫酸バリウム、塩基性炭酸塩及びシリカからなる群から選ばれる少なくとも1種であり、
前記塗膜での前記光輝顔料の含有量を質量%単位でAとし、前記白色顔料の含有量を質量%単位でBとしたときに、B/Aの値が0.03~0.27である
ことを特徴とするプレコート金属板。 - 前記白色顔料の前記平均粒径が、250~350nmである
ことを特徴とする、請求項1に記載のプレコート金属板。 - 前記光輝顔料が、アルミニウムフレークである
ことを特徴とする、請求項1又は2に記載のプレコート金属板。 - 前記B/Aの値が、0.05~0.20である
ことを特徴とする、請求項1~3の何れか1項に記載のプレコート金属板。 - 表面に対して入射角45°で光を入射させ、前記光の正反射光が出射する角度を0°とし、前記光の入射位置を90°としたとき、変角色差計を用いて測定した15°における明度であるL15と、110°における明度であるL110との差分であるL15-L110が、70以下である
ことを特徴とする、請求項1~4の何れか1項に記載のプレコート金属板。 - 前記塗膜の表面に、更にクリア塗膜を有する
ことを特徴とする、請求項1~5の何れか1項に記載のプレコート金属板。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018502438A JP6424980B2 (ja) | 2016-03-22 | 2017-03-22 | プレコート金属板 |
MYPI2018703276A MY190599A (en) | 2016-03-22 | 2017-03-22 | Precoated metal sheet |
CN201780017868.4A CN109070546B (zh) | 2016-03-22 | 2017-03-22 | 预涂金属板 |
KR1020187026861A KR102157565B1 (ko) | 2016-03-22 | 2017-03-22 | 프리코팅 금속판 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016056852 | 2016-03-22 | ||
JP2016-056852 | 2016-03-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017164234A1 true WO2017164234A1 (ja) | 2017-09-28 |
Family
ID=59900263
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2017/011440 WO2017164234A1 (ja) | 2016-03-22 | 2017-03-22 | プレコート金属板 |
Country Status (6)
Country | Link |
---|---|
JP (1) | JP6424980B2 (ja) |
KR (1) | KR102157565B1 (ja) |
CN (1) | CN109070546B (ja) |
MY (1) | MY190599A (ja) |
TW (1) | TWI617636B (ja) |
WO (1) | WO2017164234A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019225765A1 (ja) * | 2018-05-25 | 2019-11-28 | 日本製鉄株式会社 | 表面処理鋼板 |
JP2020006609A (ja) * | 2018-07-10 | 2020-01-16 | 本田技研工業株式会社 | 車両用成形品 |
WO2024014543A1 (ja) * | 2022-07-14 | 2024-01-18 | 日本製鉄株式会社 | ホットスタンプ用アルミめっき鋼板 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06254484A (ja) * | 1993-03-04 | 1994-09-13 | Kansai Paint Co Ltd | メタリック塗膜形成法 |
JPH07316475A (ja) * | 1994-05-20 | 1995-12-05 | Ishihara Sangyo Kaisha Ltd | 塗料組成物 |
JPH11172202A (ja) * | 1997-12-15 | 1999-06-29 | Mitsui Mining & Smelting Co Ltd | 耐食性、付着性、フリップ・フロップ性に優れた被覆合金製品の製造方法 |
JP2002045786A (ja) * | 2000-08-07 | 2002-02-12 | Nisshin Steel Co Ltd | メタリック調外観に優れた塗装金属板 |
JP2011122036A (ja) * | 2009-12-10 | 2011-06-23 | Dainichiseika Color & Chem Mfg Co Ltd | カラーフリップフロップ効果を示す樹脂組成物 |
WO2011087054A1 (ja) * | 2010-01-13 | 2011-07-21 | 関西ペイント株式会社 | 塗料組成物及び塗膜形成方法 |
JP2011231194A (ja) * | 2010-04-27 | 2011-11-17 | Kansai Paint Co Ltd | 塗料組成物及び塗膜形成方法 |
JP2013169507A (ja) * | 2012-02-21 | 2013-09-02 | Kansai Paint Co Ltd | 塗膜形成方法 |
WO2014024884A1 (ja) * | 2012-08-07 | 2014-02-13 | 日本ペイント株式会社 | 光輝性塗料組成物、それを用いた複層塗膜形成方法および複層塗膜 |
JP2015051385A (ja) * | 2013-09-05 | 2015-03-19 | 日本ペイントホールディングス株式会社 | 複層塗膜の形成方法、それを用いて得られた複層塗膜 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02212564A (ja) | 1989-02-10 | 1990-08-23 | Kansai Paint Co Ltd | 光輝感を有するプレコートメタルの製法 |
JPH02245072A (ja) * | 1989-03-17 | 1990-09-28 | Nippon Paint Co Ltd | 塗料組成物 |
JP2829813B2 (ja) | 1993-04-16 | 1998-12-02 | 日本ペイント株式会社 | メタリック塗料組成物およびメタリック塗膜の形成法 |
JP2000000514A (ja) | 1998-06-16 | 2000-01-07 | Kansai Paint Co Ltd | メタリック塗膜形成方法 |
JP2000086945A (ja) | 1998-09-10 | 2000-03-28 | Nippon Paint Co Ltd | 光輝性塗料組成物 |
JP2000271536A (ja) | 1999-03-25 | 2000-10-03 | Nippon Paint Co Ltd | メタリック塗膜の形成方法 |
JP2000319521A (ja) | 1999-05-14 | 2000-11-21 | Dainichiseika Color & Chem Mfg Co Ltd | フリップフロップ性メタリック感を有する成形品用熱可塑性樹脂組成物 |
JP2001164191A (ja) | 1999-12-07 | 2001-06-19 | Nippon Paint Co Ltd | 光輝性塗料組成物、塗膜形成方法および塗装物 |
GB2411173B (en) * | 2001-11-29 | 2005-11-30 | Honda Canada Inc | A process of forming a finished paint coating of a predetermined colour |
JP2005220289A (ja) | 2004-02-09 | 2005-08-18 | Nippon Paint Co Ltd | メタリックベース塗料組成物および積層塗膜の形成方法 |
DE102005061684A1 (de) * | 2005-12-21 | 2007-06-28 | Eckart Gmbh & Co. Kg | Weißes, IR-Strahlung reflektierendes Pigment, dessen Herstellung und Verwendung |
MY167813A (en) | 2011-10-31 | 2018-09-26 | Nippon Steel & Sumitomo Metal Corp | Chromate-free precoated metal sheet having metallic appearance and water-based coating composition used in the same |
JP2014009288A (ja) | 2012-06-29 | 2014-01-20 | Kansai Paint Co Ltd | メタリック塗料組成物 |
-
2017
- 2017-03-22 JP JP2018502438A patent/JP6424980B2/ja active Active
- 2017-03-22 CN CN201780017868.4A patent/CN109070546B/zh active Active
- 2017-03-22 WO PCT/JP2017/011440 patent/WO2017164234A1/ja active Application Filing
- 2017-03-22 TW TW106109588A patent/TWI617636B/zh active
- 2017-03-22 MY MYPI2018703276A patent/MY190599A/en unknown
- 2017-03-22 KR KR1020187026861A patent/KR102157565B1/ko active IP Right Grant
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06254484A (ja) * | 1993-03-04 | 1994-09-13 | Kansai Paint Co Ltd | メタリック塗膜形成法 |
JPH07316475A (ja) * | 1994-05-20 | 1995-12-05 | Ishihara Sangyo Kaisha Ltd | 塗料組成物 |
JPH11172202A (ja) * | 1997-12-15 | 1999-06-29 | Mitsui Mining & Smelting Co Ltd | 耐食性、付着性、フリップ・フロップ性に優れた被覆合金製品の製造方法 |
JP2002045786A (ja) * | 2000-08-07 | 2002-02-12 | Nisshin Steel Co Ltd | メタリック調外観に優れた塗装金属板 |
JP2011122036A (ja) * | 2009-12-10 | 2011-06-23 | Dainichiseika Color & Chem Mfg Co Ltd | カラーフリップフロップ効果を示す樹脂組成物 |
WO2011087054A1 (ja) * | 2010-01-13 | 2011-07-21 | 関西ペイント株式会社 | 塗料組成物及び塗膜形成方法 |
JP2011231194A (ja) * | 2010-04-27 | 2011-11-17 | Kansai Paint Co Ltd | 塗料組成物及び塗膜形成方法 |
JP2013169507A (ja) * | 2012-02-21 | 2013-09-02 | Kansai Paint Co Ltd | 塗膜形成方法 |
WO2014024884A1 (ja) * | 2012-08-07 | 2014-02-13 | 日本ペイント株式会社 | 光輝性塗料組成物、それを用いた複層塗膜形成方法および複層塗膜 |
JP2015051385A (ja) * | 2013-09-05 | 2015-03-19 | 日本ペイントホールディングス株式会社 | 複層塗膜の形成方法、それを用いて得られた複層塗膜 |
Non-Patent Citations (1)
Title |
---|
ENSOHO SANKA, TITANIUM (RUTILE-GATA) SEIHIN JOHO, Retrieved from the Internet <URL:https://www.iskweb.co.jp/products/spec022.html?iiframe=true> [retrieved on 20170518] * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019225765A1 (ja) * | 2018-05-25 | 2019-11-28 | 日本製鉄株式会社 | 表面処理鋼板 |
JP6680412B1 (ja) * | 2018-05-25 | 2020-04-15 | 日本製鉄株式会社 | 表面処理鋼板 |
JP2020006609A (ja) * | 2018-07-10 | 2020-01-16 | 本田技研工業株式会社 | 車両用成形品 |
WO2024014543A1 (ja) * | 2022-07-14 | 2024-01-18 | 日本製鉄株式会社 | ホットスタンプ用アルミめっき鋼板 |
JP7469732B1 (ja) | 2022-07-14 | 2024-04-17 | 日本製鉄株式会社 | ホットスタンプ用アルミめっき鋼板 |
Also Published As
Publication number | Publication date |
---|---|
KR20180112858A (ko) | 2018-10-12 |
TWI617636B (zh) | 2018-03-11 |
MY190599A (en) | 2022-04-27 |
KR102157565B1 (ko) | 2020-09-18 |
JP6424980B2 (ja) | 2018-11-21 |
CN109070546A (zh) | 2018-12-21 |
CN109070546B (zh) | 2020-12-25 |
TW201736530A (zh) | 2017-10-16 |
JPWO2017164234A1 (ja) | 2018-04-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10071396B2 (en) | Laminated coating film and coated article | |
US10441970B2 (en) | Method for forming multilayer coated film | |
RU2569356C1 (ru) | Способ формирования превосходного многослойного пленочного покрытия | |
JP5567297B2 (ja) | 塗膜形成方法 | |
CN107073515B (zh) | 用于形成多层涂膜的方法 | |
CA2991282C (en) | Multilayer coating film and coated article | |
JP6658769B2 (ja) | 積層塗膜及び塗装物 | |
WO2017164234A1 (ja) | プレコート金属板 | |
JP6323932B2 (ja) | 塗料組成物及び塗膜形成方法 | |
JP6468554B2 (ja) | 複層塗膜形成方法 | |
JP2011136317A (ja) | 光輝性複層塗膜の形成方法 | |
US20040005471A1 (en) | Color clear coated metal sheet | |
CN107922758A (zh) | 高性能涂层 | |
JP2011251253A (ja) | 複層塗膜形成方法 | |
WO2011034214A1 (ja) | プレコート金属板およびその製造方法 | |
JP2011025101A (ja) | 光輝性複層塗膜の形成方法 | |
JPH06316683A (ja) | 発泡金属酸化物を含有する乳光塗料 | |
JP5611629B2 (ja) | 塗膜形成方法 | |
WO2024116735A1 (ja) | 積層塗膜及び塗装物 | |
JP2004223436A (ja) | 光変色性複層塗膜形成方法及び塗装物 | |
JP2024079381A (ja) | 積層塗膜及び塗装物 | |
JP6796005B2 (ja) | 塗装亜鉛系めっき鋼板およびその製造方法 | |
JP2016138231A (ja) | 光輝性塗料組成物 | |
JP5580145B2 (ja) | 塗料組成物、それを用いた塗膜形成方法及び塗膜 | |
JP6045101B2 (ja) | 塗料組成物及び塗膜形成方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2018502438 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20187026861 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020187026861 Country of ref document: KR |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17770274 Country of ref document: EP Kind code of ref document: A1 |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17770274 Country of ref document: EP Kind code of ref document: A1 |