WO2018051523A1 - Coated metal plate - Google Patents

Coated metal plate Download PDF

Info

Publication number
WO2018051523A1
WO2018051523A1 PCT/JP2016/077822 JP2016077822W WO2018051523A1 WO 2018051523 A1 WO2018051523 A1 WO 2018051523A1 JP 2016077822 W JP2016077822 W JP 2016077822W WO 2018051523 A1 WO2018051523 A1 WO 2018051523A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating film
metal plate
coated metal
film
average
Prior art date
Application number
PCT/JP2016/077822
Other languages
French (fr)
Japanese (ja)
Inventor
尾和　克美
悠悟 中根
杉田　修一
Original Assignee
日新製鋼株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日新製鋼株式会社 filed Critical 日新製鋼株式会社
Priority to CN201680089296.6A priority Critical patent/CN109715390B/en
Publication of WO2018051523A1 publication Critical patent/WO2018051523A1/en

Links

Images

Classifications

    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • 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
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • 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
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • 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
    • B05D7/24—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 for applying particular liquids or other fluent materials
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
    • E04C2/08—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of metal, e.g. sheet metal

Definitions

  • the present invention relates to a painted metal plate.
  • Stainless steel plates with improved design properties by etching, coloring, surface treatment, etc. are used for door materials such as elevators and operation panels. These stainless steel plates are required to be resistant to fingerprints, high contamination resistance, high scratch resistance, and the like. Therefore, usually, a coating film made of resin, wax, oil or the like is formed on the surface of the stainless steel plate.
  • a coating film made of an inorganic material is advantageous in that it hardly changes over time and has high hardness.
  • the coating film made of an inorganic material is thin, the light reflected on the surface of the metal plate and the light reflected on the surface of the coating film are likely to interfere with each other, resulting in color unevenness or coloring (hereinafter also referred to as “interference pattern”). ) Is likely to occur.
  • the thickness of the coating film is increased, the texture (gloss or the like) derived from the metal plate is easily lost, and the design property is easily impaired.
  • it is also considered that an aggregate is included in the coating film, but also in this case, the transparency of the coating film is likely to be lowered and the designability is easily impaired.
  • an object of the present invention is to provide a coated metal plate having excellent stain resistance, no interference pattern, and excellent design.
  • the present invention provides the following coated metal plates.
  • FIG. 1A is an SEM image of the coated metal plate produced in Example (No. 4), and FIG. 1B is an image obtained by measuring the Si distribution of the region with EDS and binarizing the image.
  • 2A is an SEM image of the coated metal plate produced in Example (No. 5), and FIG. 2B is an image obtained by measuring the Si distribution of the region with EDS and binarizing the image.
  • 3A is an SEM image of the coated metal plate produced in Example (No. 8), and FIG. 3B is an image obtained by measuring the Si distribution in the region with EDS and binarizing the image.
  • 4A is an SEM image of the coated metal plate produced in Example (No. 9), and FIG. 4B is an image obtained by measuring the Si distribution in the region by EDS and binarizing the image.
  • the present invention relates to a coated metal plate having a metal plate and a coating film formed discontinuously on the metal plate.
  • the said metal coating plate is applicable to the door material of an elevator, an operation panel, the outer plate
  • the present inventors make it difficult for the interference pattern to be generated by forming the coating film discontinuously. Furthermore, the composition formula K 2 O ⁇ xSiO 2 (3.5 ⁇ x ⁇ substantially). It was found that if the coating film is composed of the composition represented by 6.8), sufficient stain resistance can be obtained even if it is discontinuous.
  • the mechanism that develops stain resistance is considered as follows.
  • potassium is slightly eluted on the surface.
  • oil stains such as sebum and oil-based ink adhere to the surface of the coated metal plate, the stains float on the water film, and the stains can be easily removed by wiping or the like.
  • the coated metal plate according to the present invention since a water film having a sufficient thickness is present on the surface of the coated metal plate, it is difficult for the dirt component to penetrate into the coated metal plate. Furthermore, since the coating film has high hydrophilicity, water easily penetrates between the surface of the coated metal plate and the dirt. Therefore, it becomes possible to remove the dirt adhering to the surface of the painted metal plate by wiping with water or the like.
  • the coating film may be formed only on one surface of the metal plate or may be formed on both surfaces. Moreover, the coating film may be formed only in the one part area
  • the average value of the coating rate per 1 mm 2 (hereinafter also referred to as “average coating rate”) at any 10 locations having a coating is 1 to 90%, preferably 3 to 80 %, More preferably 10 to 80%, still more preferably 15 to 80%.
  • the average coating film coverage is in the above range, an interference pattern is hardly generated and stain resistance is also easily exhibited.
  • the shape of the area (1 mm 2 ) for specifying the coating film coverage is not particularly limited, and may be any shape such as a rectangular shape such as a square or a rectangle, or a circular shape, but is usually a rectangular shape. .
  • the average coating film coverage is specified by the following method.
  • Si element distribution is measured at any 10 locations (1 mm 2 region) out of regions where a coating film is formed by SEM (scanning electron microscope) / EDS (energy dispersive X-ray spectroscopy). .
  • the obtained Si distribution image is binarized by image processing software. In binarization, a region where Si is increased even a little is treated as a region where the coating film exists, based on the Si detection value of the coating film non-formed part (metal plate). Then, from the obtained binarized image, the number of pixels in the area where Si is increasing (area where the coating film exists) is divided by the total number of pixels to calculate the coating film coverage. And let the average value of these coating-film coverage be an average coating-film coverage.
  • the coating film is preferably composed of a plurality of films formed in an island shape.
  • the film formed in an island shape is a film formed discontinuously and separated from other films.
  • the outer peripheral length of each film is often 1600 ⁇ m or less.
  • the shape of each film and the distance between the films are not particularly limited.
  • the plurality of films may be formed in a uniform shape or may be formed in a non-uniform shape. Moreover, these may be formed at a uniform interval or may be formed at a non-uniform interval.
  • the plurality of films are preferably formed on the metal plate with a substantially uniform density.
  • the average maximum width of the film is preferably 500 ⁇ m or less, and more preferably 10 to 200 ⁇ m.
  • the maximum width of each film is obtained from the above-described binarized image, and the average of the maximum widths of any ten films is the average maximum width.
  • the average thickness of the coating film is preferably 0.05 to 3 ⁇ m, and more preferably 0.1 to 0.6 ⁇ m.
  • the average thickness of the coating film is 0.05 ⁇ m or more, the above-described effects are easily obtained.
  • the average thickness of the coating film is 3 ⁇ m or less, the visible light permeability of the coating film is sufficiently high, and it is difficult to impair the texture derived from the metal plate.
  • the average thickness of the coating film is measured by arbitrarily cutting a coated metal plate and observing it from a cross section.
  • an appropriate cross section is prepared by polishing or the like, and a high-precision observation cross section is prepared by ion milling or the like. And about arbitrary 10 places in which a coating film exists, it observes by SEM and TEM, and let the average of 10 thickness be an average thickness.
  • the metal plate in the coated metal plate of the present invention is not particularly limited, and for example, austenitic stainless steel such as SUS304 or SUS316, or ferritic stainless steel such as SUS430 can be used.
  • austenitic stainless steel such as SUS304 or SUS316
  • ferritic stainless steel such as SUS430
  • materials obtained by cold hardening austenitic and ferritic stainless steel martensitic stainless steel plates such as SUS410 and SUS420, and precipitation strengthened stainless steel plates such as SUS631 are used. It is preferable to use it.
  • copper, carbon steel, iron-nickel alloy, various plated steel plates, and aluminum plates may be used.
  • the metal plate may be subjected to surface processing according to a conventional method.
  • the metal plate may have a smooth surface finish such as a BA finish or a mirror finish, and may have been subjected to a linear polishing process such as an HL finish for design and functionality. May be. Further, it may be subjected to curved polishing such as vibration polishing, or may be subjected to dot-like uneven processing. Further, it may be colored by various methods such as oxidation coloring or sputtering coloring.
  • the coating film is substantially composed of a composition represented by the composition formula K 2 O ⁇ xSiO 2 (3.5 ⁇ x ⁇ 6.8), and is composed of potassium silicate (K 2 O ⁇ nSiO 2 (2 ⁇ n ⁇ 4) and colloidal silica (SiO 2 ) can be used to form a film obtained by coating and drying, where the compositional formula K 2 O ⁇ xSiO 2 is the state of the element in the coating film.
  • SiO 2 usually forms a siloxane bond, while potassium becomes a potassium ion, and a silicate ion that is not bonded to a siloxane bond.
  • the coating film shows high hydrophilicity, but the hydrophilicity is high hydration property of potassium ions slightly eluting on the coating surface and the hydrophilicity of silanol groups. It seems to be expressed by sex That.
  • the ratio of silicon oxide (SiO 2 ) to potassium oxide (K 2 O) represented by x in the above composition formula may be 3.5 or more and less than 6.8, but 3.8 or more and 5.2. The following is more preferable.
  • x When the value represented by x is less than 3.5, potassium ions are excessively eluted on the surface of the coating film. In addition, the leached potassium ions are liable to occur as precipitated potassium ions react with carbon dioxide in the atmosphere to form carbonates.
  • the value represented by x is less than 3.5, it is difficult to form a coating film sufficiently, and the average coating film coverage may not be in a desired range.
  • the composition of the said coating film can be adjusted with the mixing ratio etc. of potassium silicate and colloidal silica.
  • the composition of the coating film can be confirmed by EDS, XRF, EPMA, etc., and the chemical bonding state of Si can be confirmed by XPS, IR, or the like.
  • the coating film is obtained by applying a mixed liquid of potassium silicate and colloidal silica on a metal plate by a predetermined method so as to achieve the above-mentioned average coating film coverage, and drying.
  • the potassium silicate and colloidal silica for forming the coating film may be general reagents or industrial chemicals.
  • Examples of commercially available potassium silicate products include “A potassium silicate” and “2K potassium silicate” manufactured by Nippon Chemical Industry Co., Ltd., “No. 2 potassium silicate” manufactured by Fuji Chemical Co., Ltd., “ Snowtex K2 "etc. are included.
  • examples of commercially available colloidal silica include “Adelite AT” manufactured by ADEKA, “Snowtex” manufactured by Nissan Chemical Industries, and “Silica Doll” manufactured by Nippon Chemical Industry.
  • the solid content concentration of the liquid mixture for forming the coating film is appropriately selected according to the method for forming the coating film. From the viewpoint of forming the film discontinuously and controlling the thin film thickness, The concentration is preferably in a relatively low range, and is preferably 1 to 10% by mass.
  • the method for applying the mixed liquid for forming the coating film is not particularly limited as long as the coating film can be formed so that the average coating film coverage is in the above range.
  • a method of applying the mixed solution by a spray gun, an electrostatic atomizer, an ink jet device, a gravure roll transfer device or the like.
  • the spray nozzle diameter of the spray gun or electrostatic atomizer is reduced or the atomization pressure is adjusted to adjust the average coating film coverage. It is preferable to devise such as.
  • the method for drying the mixed solution is not particularly limited as long as the solvent can be sufficiently volatilized.
  • the solvent may be dried at room temperature, but may be heated to 80 to 300 ° C.
  • heating drying of the solvent water is promoted, and film formation is promoted.
  • by heating to 200 ° C. or higher formation of siloxane bonds is promoted, and a strong coating film can be obtained in a short time.
  • discoloration temper color
  • the drying time is usually about 10 to 30 minutes when heating, and 24 hours is sufficient even when drying at room temperature.
  • Painted metal plates were prepared by the following method, and for each, the surface contamination resistance and the presence or absence of interference patterns were confirmed.
  • the metal plates A to E shown in Table 1 below were used.
  • colloidal silica manufactured by Nippon Chemical Industry Co., Ltd., trade name Silica Doll
  • the mixed solution was applied to the metal plates A to E by an atomizing spray so that the average coating film coverage shown in Table 2 was obtained.
  • the coating film was obtained.
  • all the average thickness of the obtained coating film was 0.6 micrometer or less.
  • the average thickness was measured as follows. First, a coated metal plate was cut out, and the cut test piece was embedded in resin and then polished to produce a cross section. Further, a highly accurate observation cross section was prepared by ion milling or the like, and observed with an SEM. Thickness was measured about arbitrary 10 places where a coating film exists, and these average was made into average thickness.
  • the average coating-film coverage per mm ⁇ 2 > was measured as follows. First, using SEM (Hitachi High-Technologies Corporation, trade name: S-3700N) / EDS (Oxford Instruments, trade name: x-act), the element distribution of Si, which is the main component of the coating film, is measured. did. The measurement was performed on arbitrary 10 locations (1 mm 2 ) in the region where the coating film was formed. Next, the obtained Si distribution image was binarized with image processing software (manufactured by Adobe, photoshop). In binarization, a region where Si was slightly increased was treated as a region where the coating film was present, based on the Si detection value of the coating film non-formed part (metal plate).
  • FIGS. 1 to 4 show SEM images and binarized images obtained by measuring the Si distribution in the region with EDS for 4, 5, 8, and 9, respectively.
  • Oil-based ink removal test (contamination resistance) It drew with the oil-based marker (The product made from Teranishi Chemical Industry, brand name: Magic ink (trademark) No. 700 black) on the coating metal plate obtained by the Example and the comparative example. Then, after 1 minute and 1 hour from the drawing, the oil-based ink in the drawing part was wiped off with a cloth impregnated with water (trade name: Bencott M3-II, manufactured by Asahi Kasei Co., Ltd.). The degree was evaluated. The trace of oil-based ink was evaluated according to the following criteria.
  • composition constituting the coating the composition formula K 2 O ⁇ xSiO 2 of x is less than 3.5, efflorescence occurs, the design of the coated metal plate is lowered (No.16). On the other hand, when x was 6.8 or more, film formation was not possible (No. 17).
  • the coated metal plate of the present invention is excellent in stain resistance, has no interference pattern, and is excellent in design. Therefore, the coated metal plate can be applied to door materials and operation panels for elevators, outer plates for home appliances, furniture, furniture, various interior building materials, and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The purpose of the present invention is to provide a coated metal plate that has excellent stain resistance, that does not cause interference patterns to occur, and that has excellent design properties. This coated metal plate comprises a metal plate and a coating film that is formed on at least one of the surfaces of the metal plate and that substantially comprises a composition represented by the compositional formula K2O•xSiO2 (3.5 ≤ x ≤ 6.8). The average value of the coating film coating rate per mm2 at any ten locations having the coating film in the coated metal plate is 1-90%.

Description

塗装金属板Painted metal plate
　本発明は、塗装金属板に関する。 The present invention relates to a painted metal plate.
　エレベータ等のドア材や操作パネル等には、エッチングや着色、表面処理等によって意匠性を高めたステンレス鋼板が用いられている。これらのステンレス鋼板には、指紋等が付着し難いことや、耐汚染性が高いこと、耐擦傷性が高いこと等が求められている。そこで通常、ステンレス鋼板の表面には、樹脂や、ワックス、オイル等からなる塗膜が形成されている。 Stainless steel plates with improved design properties by etching, coloring, surface treatment, etc. are used for door materials such as elevators and operation panels. These stainless steel plates are required to be resistant to fingerprints, high contamination resistance, high scratch resistance, and the like. Therefore, usually, a coating film made of resin, wax, oil or the like is formed on the surface of the stainless steel plate.
　しかしながら、ステンレス鋼板の表面に樹脂からなる塗膜を形成すると、経時変化により、塗膜にクラックや白化等が生じ、意匠性を損ないやすい。また、ワックスやオイルは、定期的に塗り直す必要がある。 However, when a coating film made of a resin is formed on the surface of a stainless steel plate, cracks, whitening, etc. occur in the coating film due to changes over time, and the design properties are likely to be impaired. Moreover, it is necessary to repaint wax and oil regularly.
　そこで、ステンレス鋼板の表面に無機材料からなる塗膜を形成することが検討されている（例えば、特許文献１）。無機材料からなる塗膜は、経時変化が少なく、硬度が高いとの利点がある。 Therefore, it has been studied to form a coating film made of an inorganic material on the surface of a stainless steel plate (for example, Patent Document 1). A coating film made of an inorganic material is advantageous in that it hardly changes over time and has high hardness.
特開２００９－１６８５号公報JP 2009-1685 A
　しかしながら、無機材料からなる塗膜の厚みが薄いと、金属板表面で反射した光と、塗膜表面で反射した光とが干渉しやすく、色ムラや着色等（以下、「干渉模様」とも称する）が生じやすい。一方で、塗膜の厚みを厚くすると、金属板由来の質感（光沢等）が失われやすく、意匠性が損なわれやすい。また、干渉模様を抑制するため、塗膜に骨材を含めることも考えられるが、この場合も、塗膜の透明性が低下しやすく、意匠性が損なわれやすい。 However, if the coating film made of an inorganic material is thin, the light reflected on the surface of the metal plate and the light reflected on the surface of the coating film are likely to interfere with each other, resulting in color unevenness or coloring (hereinafter also referred to as “interference pattern”). ) Is likely to occur. On the other hand, when the thickness of the coating film is increased, the texture (gloss or the like) derived from the metal plate is easily lost, and the design property is easily impaired. Moreover, in order to suppress an interference pattern, it is also considered that an aggregate is included in the coating film, but also in this case, the transparency of the coating film is likely to be lowered and the designability is easily impaired.
　このような状況を鑑み、本発明はなされたものである。すなわち、本発明は、耐汚染性に優れ、干渉模様が生じず、意匠性に優れた塗装金属板の提供を目的とする。 In view of such circumstances, the present invention has been made. That is, an object of the present invention is to provide a coated metal plate having excellent stain resistance, no interference pattern, and excellent design.
　本発明は、以下の塗装金属板を提供する。
　［１］金属板と、前記金属板の少なくとも一方の面に形成された、実質的に組成式Ｋ２Ｏ・ｘＳｉＯ２（３．５≦ｘ＜６．８）で表される組成物からなる塗膜と、を有し、前記塗膜を有する任意の１０箇所の、１ｍｍ２当たりの塗膜被覆率の平均値が１～９０％である、塗装金属板。 The present invention provides the following coated metal plates.
[1] A metal plate and a composition substantially formed by a composition formula K 2 O · xSiO 2 (3.5 ≦ x <6.8) formed on at least one surface of the metal plate. A coated metal plate having an average coating film coverage of 1 to 90% per 1 mm 2 at any 10 locations having the coating film.
　［２］前記塗膜被覆率の平均値が３～８０％である、［１］に記載の塗装金属板。
　［３］前記塗膜が、島状に形成された複数の膜からなり、前記膜の平均最大幅が、５００μｍ以下である［１］または［２］に記載の塗装金属板。 [2] The coated metal plate according to [1], wherein the average value of the coating film coverage is 3 to 80%.
[3] The coated metal plate according to [1] or [2], wherein the coating film includes a plurality of films formed in an island shape, and an average maximum width of the films is 500 μm or less.
　本発明によれば、耐汚染性に優れ、干渉模様が生じず、意匠性に優れた塗装金属板が得られる。 According to the present invention, it is possible to obtain a coated metal plate having excellent stain resistance, no interference pattern, and excellent design.
図１Ａは、実施例（Ｎｏ．４）で作製した塗装金属板のＳＥＭ画像であり、図１Ｂは、ＥＤＳで当該領域のＳｉ分布を測定し、二値化した画像である。1A is an SEM image of the coated metal plate produced in Example (No. 4), and FIG. 1B is an image obtained by measuring the Si distribution of the region with EDS and binarizing the image. 図２Ａは、実施例（Ｎｏ．５）で作製した塗装金属板のＳＥＭ画像であり、図２Ｂは、ＥＤＳで当該領域のＳｉ分布を測定し、二値化した画像である。2A is an SEM image of the coated metal plate produced in Example (No. 5), and FIG. 2B is an image obtained by measuring the Si distribution of the region with EDS and binarizing the image. 図３Ａは、実施例（Ｎｏ．８）で作製した塗装金属板のＳＥＭ画像であり、図３Ｂは、ＥＤＳで当該領域のＳｉ分布を測定し、二値化した画像である。3A is an SEM image of the coated metal plate produced in Example (No. 8), and FIG. 3B is an image obtained by measuring the Si distribution in the region with EDS and binarizing the image. 図４Ａは、実施例（Ｎｏ．９）で作製した塗装金属板のＳＥＭ画像であり、図４Ｂは、ＥＤＳで当該領域のＳｉ分布を測定し、二値化した画像である。4A is an SEM image of the coated metal plate produced in Example (No. 9), and FIG. 4B is an image obtained by measuring the Si distribution in the region by EDS and binarizing the image.
　本発明は、金属板と、当該金属板上に不連続に形成された塗膜と、を有する塗装金属板に関する。当該金属塗装板は、例えばエレベータのドア材や操作パネル、家電製品の外板、家具や調度品、建材等に適用可能である。 The present invention relates to a coated metal plate having a metal plate and a coating film formed discontinuously on the metal plate. The said metal coating plate is applicable to the door material of an elevator, an operation panel, the outer plate | plate of household appliances, furniture, furniture, a building material etc., for example.
　前述のように、金属板の耐汚染性等を高めること等を目的として、金属板表面に無機材料からなる塗膜を形成することが検討されている。しかしながら、金属板表面に比較的薄い塗膜を形成すると、干渉模様が生じやすかった。一方で、塗膜の厚みを厚くすると、金属板の意匠性が損なわれやすかった。なお、従来の塗装金属板では、耐汚染性等の観点から、金属板上に、均一な厚みでムラなく塗膜が形成されていた。 As described above, formation of a coating film made of an inorganic material on the surface of a metal plate has been studied for the purpose of improving the stain resistance of the metal plate. However, when a relatively thin coating film was formed on the surface of the metal plate, an interference pattern was likely to occur. On the other hand, when the thickness of the coating film was increased, the design properties of the metal plate were liable to be impaired. In addition, in the conventional coated metal plate, the coating film was formed uniformly on the metal plate with a uniform thickness from the viewpoint of contamination resistance and the like.
　これに対し、本発明者らは、塗膜を不連続に形成することで、干渉模様が生じ難くなること、さらには、実質的に組成式Ｋ２Ｏ・ｘＳｉＯ２（３．５≦ｘ＜６．８）で表される組成物からなる塗膜であれば、不連続であっても、十分な耐汚染性が得られることを見出した。 On the other hand, the present inventors make it difficult for the interference pattern to be generated by forming the coating film discontinuously. Furthermore, the composition formula K 2 O · xSiO 2 (3.5 ≦ x <substantially). It was found that if the coating film is composed of the composition represented by 6.8), sufficient stain resistance can be obtained even if it is discontinuous.
　金属板を覆う塗膜が不連続であっても、耐汚染性が発現する機構は以下のように考えられる。上記組成物からなる塗膜では、表面にカリウムが微溶出する。そして、カリウムイオンが、大気中の水分と水和し、大気中の水分を引き寄せる。その結果、塗膜の形成領域だけでなく、塗膜どうしの間の領域、すなわち金属板が露出した領域も、薄い水膜で覆われる。したがって、塗装金属板表面に皮脂や油性インク等の油汚れが付着したとしても、汚れが水膜上に浮いた状態となり、拭き取り等によって容易に汚れを除去することが可能となる。 Even if the coating film covering the metal plate is discontinuous, the mechanism that develops stain resistance is considered as follows. In the coating film comprising the above composition, potassium is slightly eluted on the surface. And a potassium ion hydrates with the water | moisture content in air | atmosphere, and draws the water | moisture content in air | atmosphere. As a result, not only the coating film forming region but also the region between the coatings, that is, the region where the metal plate is exposed is covered with a thin water film. Therefore, even if oil stains such as sebum and oil-based ink adhere to the surface of the coated metal plate, the stains float on the water film, and the stains can be easily removed by wiping or the like.
　また一般に、塗装金属板表面に汚れが付着してから時間が経過すると、汚れの一部の成分が塗膜や金属板に含浸し、汚れの除去が困難となることがある。これに対し、本発明での塗装金属板では、塗装金属板表面に十分な厚みの水膜が存在するため、汚れ成分が塗装金属板に浸透し難い。さらに、塗膜の親水性が高いことから、塗装金属板表面と汚れとの間に水が浸透しやすい。したがって、水拭き等によって塗装金属板表面に付着した汚れを剥離することが可能となる。 Also, generally, when time passes after the dirt adheres to the surface of the coated metal plate, some components of the dirt may impregnate the coating film or the metal plate, making it difficult to remove the dirt. On the other hand, in the coated metal plate according to the present invention, since a water film having a sufficient thickness is present on the surface of the coated metal plate, it is difficult for the dirt component to penetrate into the coated metal plate. Furthermore, since the coating film has high hydrophilicity, water easily penetrates between the surface of the coated metal plate and the dirt. Therefore, it becomes possible to remove the dirt adhering to the surface of the painted metal plate by wiping with water or the like.
　上記塗膜は、金属板の一方の面のみに形成されていてもよく、両方の面に形成されていてもよい。また、塗膜は、金属板の一部の領域のみに形成されていてもよく、金属板の一方の面もしくは両面の全ての領域に形成されていてもよい。 The coating film may be formed only on one surface of the metal plate or may be formed on both surfaces. Moreover, the coating film may be formed only in the one part area | region of a metal plate, and may be formed in all the area | regions of one side or both surfaces of a metal plate.
　ここで、塗膜を有する任意の１０箇所の、１ｍｍ２当たりの塗膜被覆率の平均値（以下、「平均塗膜被覆率」とも称する）は１～９０％であり、好ましくは３～８０％であり、より好ましくは１０～８０％であり、さらに好ましくは１５～８０％である。平均塗膜被覆率が上記範囲であると、干渉模様が生じ難く、耐汚染性も発現しやすい。なお、塗膜被覆率を特定する領域（１ｍｍ２）の形状は特に制限されず、例えば正方形や長方形等の矩形状、円形状等、いずれの形状であってもよいが、通常矩形状とする。平均塗膜被覆率は、以下の方法で特定される。 Here, the average value of the coating rate per 1 mm 2 (hereinafter also referred to as “average coating rate”) at any 10 locations having a coating is 1 to 90%, preferably 3 to 80 %, More preferably 10 to 80%, still more preferably 15 to 80%. When the average coating film coverage is in the above range, an interference pattern is hardly generated and stain resistance is also easily exhibited. In addition, the shape of the area (1 mm 2 ) for specifying the coating film coverage is not particularly limited, and may be any shape such as a rectangular shape such as a square or a rectangle, or a circular shape, but is usually a rectangular shape. . The average coating film coverage is specified by the following method.
　ＳＥＭ（走査型電子顕微鏡）／ＥＤＳ（エネルギー分散型Ｘ線分光法）にて、塗膜が形成されている領域のうち、任意の１０箇所（１ｍｍ２の領域）について、Ｓｉ元素分布を測定する。続いて、得られたＳｉの分布画像を画像処理ソフトで２値化する。２値化に際しては、塗膜非形成部（金属板）のＳｉ検出値を基準とし、僅かでもＳｉが増加している領域を塗膜が存在する領域として処理する。そして、得られる２値化画像から、Ｓｉが増加している領域（塗膜が存在する領域）の画素数を、全画素数で除し、塗膜被覆率を算出する。そして、これらの塗膜被覆率の平均値を、平均塗膜被覆率とする。 Si element distribution is measured at any 10 locations (1 mm 2 region) out of regions where a coating film is formed by SEM (scanning electron microscope) / EDS (energy dispersive X-ray spectroscopy). . Subsequently, the obtained Si distribution image is binarized by image processing software. In binarization, a region where Si is increased even a little is treated as a region where the coating film exists, based on the Si detection value of the coating film non-formed part (metal plate). Then, from the obtained binarized image, the number of pixels in the area where Si is increasing (area where the coating film exists) is divided by the total number of pixels to calculate the coating film coverage. And let the average value of these coating-film coverage be an average coating-film coverage.
　ここで、塗膜は島状に形成された複数の膜からなることが好ましい。島状に形成された膜とは、不連続に形成された膜であって、他の膜と分離している膜をいう。上述の平均塗膜被覆率が５０％以下である場合に、島状に膜が形成されやすい。また通常、各膜の外周長さは、１６００μｍ以下となることが多い。なお、各膜の形状や、膜どうしの間隔は特に制限されない。複数の膜は均一な形状に形成されていてもよく、不均一な形状に形成されていてもよい。また、これらは均一な間隔で形成されていてもよく、不均一な間隔で形成されていてもよい。ただし、複数の膜は、金属板上に略均一な密度で形成されていることが好ましい。膜の形成密度に偏りがあると、十分に上述の効果が得られなくなることがある。また、個々の膜の面積が過度に大きいと、膜の有無が視認されやすくなる。そこで、塗膜が島状に形成された複数の膜からなる場合、膜の平均最大幅は、５００μｍ以下であることが好ましく、１０～２００μｍであることがより好ましい。各膜の最大幅は、上述の２値化画像から求められ、任意の１０個の膜の最大幅の平均を、平均最大幅とする。 Here, the coating film is preferably composed of a plurality of films formed in an island shape. The film formed in an island shape is a film formed discontinuously and separated from other films. When the above-mentioned average coating film coverage is 50% or less, a film is easily formed in an island shape. In general, the outer peripheral length of each film is often 1600 μm or less. The shape of each film and the distance between the films are not particularly limited. The plurality of films may be formed in a uniform shape or may be formed in a non-uniform shape. Moreover, these may be formed at a uniform interval or may be formed at a non-uniform interval. However, the plurality of films are preferably formed on the metal plate with a substantially uniform density. If the formation density of the film is uneven, the above effects may not be obtained sufficiently. Further, if the area of each film is excessively large, the presence or absence of the film is easily visually recognized. Therefore, when the coating film is composed of a plurality of films formed in an island shape, the average maximum width of the film is preferably 500 μm or less, and more preferably 10 to 200 μm. The maximum width of each film is obtained from the above-described binarized image, and the average of the maximum widths of any ten films is the average maximum width.
　また、塗膜の平均厚みは、０．０５～３μｍであることが好ましく、０．１～０．６μｍであることがより好ましい。塗膜の平均厚みが０．０５μｍ以上であると、上述の効果が十分に得られやすい。一方で、塗膜の平均厚みが３μｍ以下であると、塗膜の可視光透過性が十分に高くなり、金属板由来の質感を損ない難くなる。塗膜の平均厚みは、塗装金属板を任意に切り出し、断面から観察することにより測定される。具体的には、塗装金属板から切り出した試験片を樹脂で包埋後に研磨等で適当な断面を作製し、さらにイオンミリング加工等で高精度の観察断面を作製する。そして、塗膜が存在する任意の１０箇所について、ＳＥＭやＴＥＭで観察し、１０箇所の厚みの平均を、平均厚みとする。 Further, the average thickness of the coating film is preferably 0.05 to 3 μm, and more preferably 0.1 to 0.6 μm. When the average thickness of the coating film is 0.05 μm or more, the above-described effects are easily obtained. On the other hand, when the average thickness of the coating film is 3 μm or less, the visible light permeability of the coating film is sufficiently high, and it is difficult to impair the texture derived from the metal plate. The average thickness of the coating film is measured by arbitrarily cutting a coated metal plate and observing it from a cross section. Specifically, after embedding a test piece cut out from a coated metal plate with a resin, an appropriate cross section is prepared by polishing or the like, and a high-precision observation cross section is prepared by ion milling or the like. And about arbitrary 10 places in which a coating film exists, it observes by SEM and TEM, and let the average of 10 thickness be an average thickness.
　ここで、本発明の塗装金属板における金属板は特に制限されず、例えばＳＵＳ３０４、ＳＵＳ３１６等のオーステナイト系ステンレス鋼や、ＳＵＳ４３０等のフェライト系ステンレス鋼を用いることができる。機械的強度が要求される用途では、オーステナイト系、フェライト系ステンレス鋼を冷間圧延で加工硬化した材料や、ＳＵＳ４１０、ＳＵＳ４２０系等のマルテンサイト系ステンレス鋼板や、ＳＵＳ６３１等の析出強化型ステンレス鋼板を使用することが好ましい。また、ステンレス鋼板以外に、銅、炭素鋼、鉄－ニッケル系合金、各種めっき鋼板、アルミ板を用いてもよい。 Here, the metal plate in the coated metal plate of the present invention is not particularly limited, and for example, austenitic stainless steel such as SUS304 or SUS316, or ferritic stainless steel such as SUS430 can be used. In applications where mechanical strength is required, materials obtained by cold hardening austenitic and ferritic stainless steel, martensitic stainless steel plates such as SUS410 and SUS420, and precipitation strengthened stainless steel plates such as SUS631 are used. It is preferable to use it. In addition to the stainless steel plate, copper, carbon steel, iron-nickel alloy, various plated steel plates, and aluminum plates may be used.
　これらの金属板は、常法に従って表面加工がなされたものであってもよい。金属板は、例えば、ＢＡ仕上げや鏡面仕上げ等、平滑な表面仕上げを施したものであってもよく、意匠性や機能性のためにＨＬ仕上げ等、直線状の研磨加工を施したものであってもよい。また、バイブレーション研磨等、曲線状の研磨加工を施したものであってもよく、ドット状の凹凸加工を施したもの等であってもよい。さらに、酸化発色やスパッタリング着色等、各種手法によって着色したものであってもよい。 These metal plates may be subjected to surface processing according to a conventional method. For example, the metal plate may have a smooth surface finish such as a BA finish or a mirror finish, and may have been subjected to a linear polishing process such as an HL finish for design and functionality. May be. Further, it may be subjected to curved polishing such as vibration polishing, or may be subjected to dot-like uneven processing. Further, it may be colored by various methods such as oxidation coloring or sputtering coloring.
　一方、塗膜は、実質的に組成式Ｋ２Ｏ・ｘＳｉＯ２（３．５≦ｘ＜６．８）で表される組成物からなり、ケイ酸カリウム（Ｋ２Ｏ・ｎＳｉＯ２（２≦ｎ≦４）とコロイダルシリカ（ＳｉＯ２）との混合液を塗布乾燥して得られる膜とすることができる。なお、上記組成式Ｋ２Ｏ・ｘＳｉＯ２は、塗膜中での元素の状態を示すものではなく、構成元素の比を示すものである。塗膜中では通常、ＳｉＯ２がシロキサン結合を形成している。一方、カリウムは、カリウムイオンとなり、シロキサン結合していないシリケートイオンと電気的に引き合って存在している。前述のように、塗膜は高い親水性を示すが、当該親水性は、塗膜表面に微溶出するカリウムイオンの高い水和性、およびシラノール基の親水性によって発現すると考えられる。 On the other hand, the coating film is substantially composed of a composition represented by the composition formula K 2 O · xSiO 2 (3.5 ≦ x <6.8), and is composed of potassium silicate (K 2 O · nSiO 2 (2 ≦ n ≦ 4) and colloidal silica (SiO 2 ) can be used to form a film obtained by coating and drying, where the compositional formula K 2 O · xSiO 2 is the state of the element in the coating film. In the coating film, SiO 2 usually forms a siloxane bond, while potassium becomes a potassium ion, and a silicate ion that is not bonded to a siloxane bond. As described above, the coating film shows high hydrophilicity, but the hydrophilicity is high hydration property of potassium ions slightly eluting on the coating surface and the hydrophilicity of silanol groups. It seems to be expressed by sex That.
　上記組成式中のｘで表される、酸化カリウム（Ｋ２Ｏ）に対する酸化ケイ素（ＳｉＯ２）の割合は、３．５以上６．８未満であればよいが、３．８以上５．２以下であることがより好ましい。ｘで表される値が３．５未満であると、カリウムイオンが塗膜表面に過剰に溶出する。そして、溶出したカリウムイオンが大気中の二酸化炭素と反応として炭酸塩となり析出する白華現象が生じやすくなる。また、ｘで表される値が３．５未満であると、塗膜が十分に形成され難くなり、平均塗膜被覆率が所望の範囲にならないことがある。一方、ｘで表される値が６．８以上であると、塗膜形成時に、コロイダルシリカを多量に混合する必要がある。その結果、造膜性が低下し、平均塗膜被覆率が所望の範囲にならなかったり、膜として十分な強度を有さないことがある。なお、上記塗膜の組成は、ケイ酸カリウムとコロイダルシリカとの混合比等によって調整することができる。また上記塗膜の組成は、ＥＤＳ、ＸＲＦ、ＥＰＭＡ等で確認することができ、ＸＰＳ、ＩＲ等によりＳｉの化学結合状態を確認することができる。 The ratio of silicon oxide (SiO 2 ) to potassium oxide (K 2 O) represented by x in the above composition formula may be 3.5 or more and less than 6.8, but 3.8 or more and 5.2. The following is more preferable. When the value represented by x is less than 3.5, potassium ions are excessively eluted on the surface of the coating film. In addition, the leached potassium ions are liable to occur as precipitated potassium ions react with carbon dioxide in the atmosphere to form carbonates. Moreover, when the value represented by x is less than 3.5, it is difficult to form a coating film sufficiently, and the average coating film coverage may not be in a desired range. On the other hand, when the value represented by x is 6.8 or more, it is necessary to mix a large amount of colloidal silica at the time of coating film formation. As a result, the film-forming property is lowered, the average coating film coverage may not be in a desired range, or the film may not have sufficient strength. In addition, the composition of the said coating film can be adjusted with the mixing ratio etc. of potassium silicate and colloidal silica. The composition of the coating film can be confirmed by EDS, XRF, EPMA, etc., and the chemical bonding state of Si can be confirmed by XPS, IR, or the like.
　上記塗膜は、金属板上にケイ酸カリウムおよびコロイダルシリカの混合液を、前述の平均塗膜被覆率となるように、所定の方法で塗布し、乾燥させることで得られる。塗膜を形成するためのケイ酸カリウムおよびコロイダルシリカは、一般試薬であってもよく、工業用薬品であってもよい。ケイ酸カリウムの市販品の例には、日本化学工業社製の「Ａケイ酸カリ」や「２Ｋケイ酸カリ」、富士化学社製の「２号ケイ酸カリ」、日産化学社製の「スノーテックスＫ２」等が含まれる。一方、コロイダルシリカの市販品の例には、ＡＤＥＫＡ社製の「アデライトＡＴ」や、日産化学工業社の「スノーテックス」、日本化学工業社の「シリカドール」が含まれる。 The coating film is obtained by applying a mixed liquid of potassium silicate and colloidal silica on a metal plate by a predetermined method so as to achieve the above-mentioned average coating film coverage, and drying. The potassium silicate and colloidal silica for forming the coating film may be general reagents or industrial chemicals. Examples of commercially available potassium silicate products include “A potassium silicate” and “2K potassium silicate” manufactured by Nippon Chemical Industry Co., Ltd., “No. 2 potassium silicate” manufactured by Fuji Chemical Co., Ltd., “ Snowtex K2 "etc. are included. On the other hand, examples of commercially available colloidal silica include “Adelite AT” manufactured by ADEKA, “Snowtex” manufactured by Nissan Chemical Industries, and “Silica Doll” manufactured by Nippon Chemical Industry.
　なお、塗膜形成用の混合液には、ケイ酸カリウムおよびコロイダルシリカと共に、必要に応じて溶剤、レベリング剤、消泡剤等を添加してもよい。また、塗膜形成用の混合液の固形分濃度は、塗膜の形成方法に応じて適宜選択されるが、膜を不連続に形成し、かつ薄い膜厚を制御するとの観点から、固形分濃度は比較的低い範囲であることが好ましく、１～１０質量％であることが好ましい。 In addition, you may add a solvent, a leveling agent, an antifoamer, etc. to the liquid mixture for film formation with potassium silicate and colloidal silica as needed. Further, the solid content concentration of the liquid mixture for forming the coating film is appropriately selected according to the method for forming the coating film. From the viewpoint of forming the film discontinuously and controlling the thin film thickness, The concentration is preferably in a relatively low range, and is preferably 1 to 10% by mass.
　塗膜形成用の混合液の塗布方法は、平均塗膜被覆率が上述の範囲となるように塗膜を形成可能な方法であれば特に制限されない。例えば、スプレーガン、静電霧化装置、インクジェット装置、グラビアロール転写装置等により上記混合液を塗布する方法とすることができる。なお、スプレーガンや静電霧化装置によって塗膜を形成する場合、平均塗膜被覆率の調整のため、スプレーガンや静電霧化装置の吐出ノズル径を小さくしたり、霧化圧力を調整する等の工夫をすることが好ましい。 The method for applying the mixed liquid for forming the coating film is not particularly limited as long as the coating film can be formed so that the average coating film coverage is in the above range. For example, it is possible to use a method of applying the mixed solution by a spray gun, an electrostatic atomizer, an ink jet device, a gravure roll transfer device or the like. When forming a coating film with a spray gun or electrostatic atomizer, the spray nozzle diameter of the spray gun or electrostatic atomizer is reduced or the atomization pressure is adjusted to adjust the average coating film coverage. It is preferable to devise such as.
　また、混合液の乾燥方法は、溶剤を十分に揮発させることが可能であれば、その方法は特に制限されない。例えば、常温で乾燥させてもよいが、８０～３００℃に加熱してもよい。加熱することにより、溶媒の水の乾燥が促進され、造膜が促進される。さらに、２００℃以上に加熱することにより、シロキサン結合の形成が促進され、短時間で強固な塗膜を得ることができる。ただし、加熱する場合は原板の酸化による変色（テンパーカラー）に注意する。乾燥時間は通常、加熱する場合は１０～３０分程度であり、常温乾燥の場合でも２４時間あれば十分である。 Further, the method for drying the mixed solution is not particularly limited as long as the solvent can be sufficiently volatilized. For example, it may be dried at room temperature, but may be heated to 80 to 300 ° C. By heating, drying of the solvent water is promoted, and film formation is promoted. Furthermore, by heating to 200 ° C. or higher, formation of siloxane bonds is promoted, and a strong coating film can be obtained in a short time. However, pay attention to discoloration (temper color) due to oxidation of the original plate when heating. The drying time is usually about 10 to 30 minutes when heating, and 24 hours is sufficient even when drying at room temperature.
　以下、本発明について実施例を参照して詳細に説明するが、本発明は、これらの実施例により限定されない。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
　以下の方法により、塗装金属板を作製し、それぞれについて、表面の耐汚染性、および干渉模様の有無を確認した。なお、金属板は、以下の表１に示す金属板Ａ～Ｅを用いた。 塗装 Painted metal plates were prepared by the following method, and for each, the surface contamination resistance and the presence or absence of interference patterns were confirmed. The metal plates A to E shown in Table 1 below were used.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　［塗装金属板の作製］
　ケイ酸カリウム（富士化学社製、商品名　２号ケイ酸カリ、Ｋ２Ｏ・ｎＳｉＯ２（ｎ＝３．６１）、または富士化学社製、商品名　１号ケイ酸カリ、Ｋ２Ｏ・ｎＳｉＯ２（ｎ＝２．０４））およびコロイダルシリカ（日本化学工業社製、商品名シリカドール）を固形分換算で表２に示す質量比で混合し、混合液を得た。当該混合液を、金属板Ａ～Ｅに表２に示す平均塗膜被覆率となるように、霧化スプレーにより塗布した。その後、２５０℃で２０分乾燥させて、塗膜を得た。なお、得られた塗膜の平均厚みは、いずれも０．６μｍ以下であった。平均厚みは、以下のように測定した。まず、塗装金属板を切り出し、切り出した試験片を樹脂で包埋後に研磨よって断面を作製した。さらにイオンミリング加工等で高精度の観察断面を作製してＳＥＭで観察した。塗膜の存在する任意の１０箇所について、厚みを測定し、これらの平均を、平均厚みとした。 [Preparation of painted metal plate]
Potassium silicate (made by Fuji Chemical Co., Ltd., trade name: No. 2 potassium silicate, K 2 O.nSiO 2 (n = 3.61), or Fuji Chemical Co., Ltd., trade name: No. 1 potassium silicate, K 2 O · nSiO 2 (n = 2.04)) and colloidal silica (manufactured by Nippon Chemical Industry Co., Ltd., trade name Silica Doll) were mixed at a mass ratio shown in Table 2 in terms of solid content to obtain a mixed solution. The mixed solution was applied to the metal plates A to E by an atomizing spray so that the average coating film coverage shown in Table 2 was obtained. Then, it was made to dry at 250 degreeC for 20 minutes, and the coating film was obtained. In addition, all the average thickness of the obtained coating film was 0.6 micrometer or less. The average thickness was measured as follows. First, a coated metal plate was cut out, and the cut test piece was embedded in resin and then polished to produce a cross section. Further, a highly accurate observation cross section was prepared by ion milling or the like, and observed with an SEM. Thickness was measured about arbitrary 10 places where a coating film exists, and these average was made into average thickness.
　また、１ｍｍ２当たりの平均塗膜被覆率は、以下のように測定した。
　まずＳＥＭ（日立ハイテクノロジーズ社製、商品名：Ｓ－３７００Ｎ）／ＥＤＳ（オックスフォードインストゥルメンツ社製、商品名：ｘ－ａｃｔ）を用いて、塗膜の主成分であるＳｉの元素分布を測定した。測定は塗膜が形成されている領域のうち、任意の１０箇所（１ｍｍ２）について行った。次に、得られたＳｉの分布画像を、画像処理ソフト（ａｄｏｂｅ社製、ｐｈｏｔｏｓｈｏｐ）で２値化した。２値化に際しては、塗膜非形成部（金属板）のＳｉ検出値を基準として、わずかでもＳｉが増加している領域を塗膜が存在する領域として処理した。得られた２値化画像からＳｉが増加する領域（塗膜が存在する領域）の画素数を領域内の全画素で除し、塗膜被覆率を算出した。そして、塗膜被覆率の平均値を算出し、これを平均塗膜被覆率とした。Ｎｏ．４、５、８、９について、ＳＥＭ画像、およびＥＤＳで当該領域のＳｉ分布を測定し、二値化した画像を図１～図４に示す。 Moreover, the average coating-film coverage per mm < 2 > was measured as follows.
First, using SEM (Hitachi High-Technologies Corporation, trade name: S-3700N) / EDS (Oxford Instruments, trade name: x-act), the element distribution of Si, which is the main component of the coating film, is measured. did. The measurement was performed on arbitrary 10 locations (1 mm 2 ) in the region where the coating film was formed. Next, the obtained Si distribution image was binarized with image processing software (manufactured by Adobe, photoshop). In binarization, a region where Si was slightly increased was treated as a region where the coating film was present, based on the Si detection value of the coating film non-formed part (metal plate). From the obtained binarized image, the number of pixels in the region where Si increases (region where the coating film exists) is divided by all the pixels in the region to calculate the coating film coverage. And the average value of the coating-film coverage was computed, and this was made into the average coating-film coverage. No. FIGS. 1 to 4 show SEM images and binarized images obtained by measuring the Si distribution in the region with EDS for 4, 5, 8, and 9, respectively.
　［評価］
　各実施例および比較例で得られた塗装金属板について、油性インク除去試験（耐汚染性）、および干渉模様の有無を確認した。結果を表２に示す。 [Evaluation]
About the coated metal plate obtained in each Example and the comparative example, the oil-based ink removal test (contamination resistance) and the presence or absence of an interference pattern were confirmed. The results are shown in Table 2.
　（１）油性インク除去試験（耐汚染性）
　実施例および比較例で得られた塗装金属板に、油性マーカー（寺西化学工業製、商品名：マジックインキ（登録商標）Ｎｏ．７００黒）で描画した。そして、描画部分の油性インクを、描画から１分後および１時間後に、水を含浸させた布（旭化成社製、商品名：ベンコットＭ３－II）で拭き取り、水拭き後の油性インクの痕跡の程度を評価した。油性インクの痕跡は、以下のような基準で評価した。
　◎：痕跡なし（除去率１００％）
　〇：極僅かな痕跡有り（除去率９０％以上～１００％未満）
　△：痕跡有り（除去率５％以上～９０％未満）
　×：殆ど除去されない（除去率５％未満） (1) Oil-based ink removal test (contamination resistance)
It drew with the oil-based marker (The product made from Teranishi Chemical Industry, brand name: Magic ink (trademark) No. 700 black) on the coating metal plate obtained by the Example and the comparative example. Then, after 1 minute and 1 hour from the drawing, the oil-based ink in the drawing part was wiped off with a cloth impregnated with water (trade name: Bencott M3-II, manufactured by Asahi Kasei Co., Ltd.). The degree was evaluated. The trace of oil-based ink was evaluated according to the following criteria.
A: No trace (removal rate 100%)
◯: There is very little trace (removal rate 90% or more to less than 100%)
Δ: Traces (removal rate 5% to less than 90%)
X: Almost no removal (removal rate less than 5%)
　（２）干渉模様の確認
　干渉模様の有無は、標準光源下で目視にて評価した。標準光源装置には、Ｘ－Ｒｉｔｅ社製、商品名：マクベスＪｕｄｇｅIIを用いた。また、参照光は、ＴＬ８４とした。干渉模様は、以下のような基準で評価した。
　〇：発生なし（意匠への影響：なし）
　△：僅かに発生（意匠への影響：軽微）
　×：著しい発生（意匠への影響：有り） (2) Confirmation of interference pattern The presence or absence of the interference pattern was visually evaluated under a standard light source. As the standard light source device, trade name: Macbeth Judge II manufactured by X-Rite was used. The reference light was TL84. The interference pattern was evaluated according to the following criteria.
○: No occurrence (effect on design: none)
△: Slightly generated (effect on design: minor)
×: Significant occurrence (influence on design: yes)
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２に示すように、塗膜を形成しなかった場合（平均塗膜被覆率：０％）には、油性インク試験にて、油性インク痕を除去できなかった（Ｎｏ．１）。これに対し、平均塗膜被覆率が１％以上であれば、いずれも油性インクを除去することができた（Ｎｏ．２～１６、および１８～２１）。ただし、平均塗膜被覆率が９５％以上であると、干渉模様が生じた（Ｎｏ．１２および１３）。 As shown in Table 2, when the coating film was not formed (average coating film coverage: 0%), the oil-based ink trace could not be removed in the oil-based ink test (No. 1). On the other hand, if the average coating film coverage was 1% or more, any oil-based ink could be removed (Nos. 2 to 16 and 18 to 21). However, when the average coating film coverage was 95% or more, an interference pattern occurred (Nos. 12 and 13).
　また、塗膜を構成する組成物について、組成式Ｋ２Ｏ・ｘＳｉＯ２のｘが３．５未満となると、白華が生じ、塗装金属板の意匠性が低下した（Ｎｏ．１６）。一方で、ｘが６．８以上であると、造膜できなかった（Ｎｏ．１７）。 Further, the composition constituting the coating, the composition formula K 2 O · xSiO 2 of x is less than 3.5, efflorescence occurs, the design of the coated metal plate is lowered (No.16). On the other hand, when x was 6.8 or more, film formation was not possible (No. 17).
　本出願は、２０１６年９月１６日出願の特願２０１６－１８１３５６号に基づく優先権を主張する。当該出願明細書および図面に記載された内容は、すべて本願明細書に援用される。 This application claims priority based on Japanese Patent Application No. 2016-181356 filed on Sep. 16, 2016. The contents described in the application specification and the drawings are all incorporated herein.
　本発明の塗装金属板は、耐汚染性に優れ、干渉模様が生じず、意匠性に優れる。したがって、当該塗装金属板は、エレベータのドア材や操作パネル、家電製品の外板、家具や調度品、各種内装建材等に適用が可能である。
  The coated metal plate of the present invention is excellent in stain resistance, has no interference pattern, and is excellent in design. Therefore, the coated metal plate can be applied to door materials and operation panels for elevators, outer plates for home appliances, furniture, furniture, various interior building materials, and the like.

Claims (3)

  1. 　金属板と、
    　前記金属板の少なくとも一方の面に形成された、実質的に組成式Ｋ２Ｏ・ｘＳｉＯ２（３．５≦ｘ＜６．８）で表される組成物からなる塗膜と、
    　を有し、
    　前記塗膜を有する任意の１０箇所の、１ｍｍ２当たりの塗膜被覆率の平均値が１～９０％である、
    　塗装金属板。     A metal plate,
    A coating film formed of at least one surface of the metal plate and made of a composition substantially represented by the composition formula K 2 O · xSiO 2 (3.5 ≦ x <6.8);
    Have
    The average value of the coating ratio per 1 mm 2 at any 10 places having the coating film is 1 to 90%.
    Painted metal plate.
  2. 　前記塗膜被覆率の平均値が３～８０％である、
    　請求項１に記載の塗装金属板。     The average value of the coating film coverage is 3 to 80%.
    The coated metal plate according to claim 1.
  3. 　前記塗膜が、島状に形成された複数の膜からなり、
    　前記膜の平均最大幅が、５００μｍ以下である、
    　請求項１または２に記載の塗装金属板。
          The coating film comprises a plurality of films formed in an island shape,
    The average maximum width of the film is 500 μm or less,
    The painted metal plate according to claim 1 or 2.
PCT/JP2016/077822 2016-09-16 2016-09-21 Coated metal plate WO2018051523A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201680089296.6A CN109715390B (en) 2016-09-16 2016-09-21 Coated metal plate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-181356 2016-09-16
JP2016181356A JP6063088B1 (en) 2016-09-16 2016-09-16 Painted metal plate

Publications (1)

Publication Number Publication Date
WO2018051523A1 true WO2018051523A1 (en) 2018-03-22

Family

ID=57799988

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/077822 WO2018051523A1 (en) 2016-09-16 2016-09-21 Coated metal plate

Country Status (5)

Country Link
JP (1) JP6063088B1 (en)
CN (1) CN109715390B (en)
MY (1) MY179958A (en)
TW (1) TWI596165B (en)
WO (1) WO2018051523A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018095921A (en) * 2016-12-13 2018-06-21 日新製鋼株式会社 Coated metal plate and manufacturing method of the same

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5128650B1 (en) * 1968-08-06 1976-08-20
JPH01168870A (en) * 1987-12-23 1989-07-04 Mitsubishi Alum Co Ltd Aluminum or aluminum alloy material
JPH0995788A (en) * 1995-07-27 1997-04-08 Kobe Steel Ltd Alloyed molten zinc-plated steel sheet excellent in lubricity and chemical convertibility
JPH09228074A (en) * 1995-12-19 1997-09-02 Kobe Steel Ltd Surface treated steel sheet excellent in fingerprint resistance and its production
JPH10330646A (en) * 1997-06-02 1998-12-15 Shiro Tago Water-based inorganic coating composition and formation of coating film
JP2001294779A (en) * 2000-04-12 2001-10-23 Kawatetsu Galvanizing Co Ltd Resin covered material having excellent outdoor stain resistance and surface treating method of resin covered material
JP2008045185A (en) * 2006-08-21 2008-02-28 Nisshin Steel Co Ltd Chemical conversion treated steel sheet having excellent corrosion resistance and blackening resistance

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100213852B1 (en) * 1995-11-13 1999-08-02 구마모토 마사히로 Steel plate with good fire burning properties and the method of same
WO2003022940A1 (en) * 2001-09-11 2003-03-20 Akzo Nobel Coatings International B.V. Coating composition for metal substrates

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5128650B1 (en) * 1968-08-06 1976-08-20
JPH01168870A (en) * 1987-12-23 1989-07-04 Mitsubishi Alum Co Ltd Aluminum or aluminum alloy material
JPH0995788A (en) * 1995-07-27 1997-04-08 Kobe Steel Ltd Alloyed molten zinc-plated steel sheet excellent in lubricity and chemical convertibility
JPH09228074A (en) * 1995-12-19 1997-09-02 Kobe Steel Ltd Surface treated steel sheet excellent in fingerprint resistance and its production
JPH10330646A (en) * 1997-06-02 1998-12-15 Shiro Tago Water-based inorganic coating composition and formation of coating film
JP2001294779A (en) * 2000-04-12 2001-10-23 Kawatetsu Galvanizing Co Ltd Resin covered material having excellent outdoor stain resistance and surface treating method of resin covered material
JP2008045185A (en) * 2006-08-21 2008-02-28 Nisshin Steel Co Ltd Chemical conversion treated steel sheet having excellent corrosion resistance and blackening resistance

Also Published As

Publication number Publication date
JP2018043460A (en) 2018-03-22
CN109715390A (en) 2019-05-03
JP6063088B1 (en) 2017-01-18
TWI596165B (en) 2017-08-21
CN109715390B (en) 2020-03-10
MY179958A (en) 2020-11-19
TW201814008A (en) 2018-04-16

Similar Documents

Publication Publication Date Title
KR102552547B1 (en) Decorative sheet for floors and decorative panel for floors
US20050154112A1 (en) Hydrophilic film, process for producing the same, and paint for formation of hydrophilic film
JP5655981B1 (en) Galvanized steel sheet excellent in blackening resistance and corrosion resistance and method for producing the same
KR20190061068A (en) A method for producing a zinc-base plated steel sheet having a surface-treated film, and a zinc-based plated steel sheet having a surface-
CN108779022A (en) Fatty acid modified resin is used to assign the purposes of glass sheet anti-fingerprint characteristic
JP6063088B1 (en) Painted metal plate
KR101778388B1 (en) Coating composition for excellent anti-corrosion and anti-finger, stainless steel having etching pattern, and method of manufacturing the stainless steel
JP2002519300A (en) Supply of organic paint on glass
JPH0318514B2 (en)
JP2013209832A (en) Building board
JP4767317B2 (en) Coating liquid and coating method
JP6043889B1 (en) Painted metal plate
JP2018095921A (en) Coated metal plate and manufacturing method of the same
US3208874A (en) Surface finishing of stainless steel
JP2002336768A (en) Method for forming antifouling coating film
JP2019022953A (en) Coated steel plate, manufacturing method thereof, and shutter slat
JP5471081B2 (en) Electrical steel sheet with semi-organic insulation coating
TW201520372A (en) Galvanized steel plate having excellent corrosion resistance and blackening resistance, and manufacturing method thereof
JP2006289294A (en) Coating method of metal, inorganic compound and/or organic metallic compound
TW201542723A (en) Surface-treated agent for metal material
JP2006152221A (en) Product with inorganic film and inorganic coatings therefor, and manufacturing method thereof
CN111944338B (en) Alkali metal silicate coating and method for producing same
KR101543926B1 (en) Color-treated magnesium and color-treatment method thereof
EP3954669A1 (en) Nano-inorganic composition and coating method using same
KR102281837B1 (en) Method for forming nano-inorganic film

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16916303

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16916303

Country of ref document: EP

Kind code of ref document: A1