JP2019112701A - Low-glossiness chemical coloring stainless steel processed product coated with transparent coating film, and method of manufacturing the same - Google Patents

Abstract

To provide a chemical coloring stainless steel processed product that is superior in wear resistance and scratch resistance, free of color shading on a surface, superior in visual angle color tone discriminability, and made high in level of an industrial color tone, and uses a chemical coloring technique, and a method of manufacturing the same.SOLUTION: There is provided a chemical coloring stainless steel processed product which has a 60° specular gloss [Gs(60°)] of 5-50 on an irregular surface. A grinding process uses a sand blast processing alone or the sand blast processing and electrolytic polishing processing in combination. There is provided a manufacturing method comprises: a sand blast processing stage; an electrolytic polishing processing stage; a coloring processing stage of forming a coloring coating film by dipping in a coloring processing liquid consisting of a mixed solution of chromic acid and sulfuric acid; a curing processing stage of dipping a stainless steel processing product having been subjected to the coloring processing in a curing processing liquid consisting of the mixed solution of chromic acid and sulfuric acid; and a coating processing stage of coating a surface of the stainless steel processed article having been subjected to the curing processing with an inorganic or organic coating composition.SELECTED DRAWING: Figure 1

Description

  The present invention is excellent in abrasion resistance and abrasion resistance by covering with a transparent coating film, and has low glossiness and low dependency of the color tone change of the surface on the viewing angle, that is, less variation in color tone depending on the viewing angle Hereinafter, it is referred to as “excellent in visual angle color distinction”. In particular, it is a chemically colored stainless steel processed product which has a low surface gloss and is excellent in visual angle color tone discrimination, which has been subjected to a chemical coloring treatment by roughening the surface with an abrasive, and imparts wear resistance and scratch resistance. The present invention relates to a chemically processed stainless steel processed article having no change in surface gloss and visual angle discrimination even if a coating film is formed on the surface, and a method of manufacturing the same.

Stainless steel materials are widely adopted as stainless steel products such as industrial products and household products because they are excellent in corrosion resistance. However, the stainless steel material has a strong silver-white metallic luster, so the design of the processed stainless steel product has a cool color tone, and there is a problem that the user who desires a warm color tone has a sense of resistance. For this reason, there is a demand for stainless steel products with warm colors.
As a method of coloring the processed stainless steel, there is a method of oxidizing and coloring the surface of the processed stainless steel to form a colored film and then electrolytically treating it to cure the film, and the oxidized coloring by the inco method using chromic acid is widely used. It is adopted (patent document 1). However, since the technique for uniformly controlling the thickness of the oxide film having a color forming function is not sufficient, there is a problem that color unevenness easily occurs.

  Further, in order to impart abrasion resistance, scratch resistance and fingerprint resistance while making the most of the appearance of a processed stainless steel, the surface of the processed stainless steel is coated with a transparent coating film (Patent Document 2). . However, by coating the coating film, although abrasion resistance, scratch resistance and fingerprint resistance are provided, there is a problem that the color tone of the stainless steel product is changed before and after the coating film is coated. Patent Document 2 does not disclose the problem that the color tone of the stainless steel product changes.

  There is disclosed a method for producing a surface-treated steel sheet in which the surface gloss and brightness of the surface-treated steel sheet are controlled by controlling the pickling operation conditions such as acid pickling time, acid component, acid concentration, acid temperature and the like (Patent Literature 3). However, Patent Document 3 corresponds to chemical polishing processing, so-called wet etching processing, and does not utilize dry etching processing such as sand blast processing.

  As a pretreatment to form a low-friction fluorocarbon resin coating on the inner surface of the washing tank, the stainless steel material is blasted using # 80 to # 100 mesh alumina sand to increase the adhesion between the stainless steel material and the coating film. It has been disclosed that the appearance of the coating film is kept inconspicuous by making a scratch produced in the coating film (Patent Document 4). However, Patent Document 4 is a surface treatment for improving coating film adhesion, and does not relate to a processed stainless steel product which has been subjected to a chemical coloring treatment, has a low surface glossiness, and a high visual angle color distinction.

JP-A-54-10245 JP 2001-316848 A Japanese Patent Application Laid-Open No. 11-106986 Japanese Patent Application Laid-Open No. 2002-360989

  The present invention is a chemical coloration technology that is excellent in abrasion resistance, scratch resistance and fingerprint resistance, has no surface color unevenness, is excellent in visual angle color discrimination, and has advanced industrial color tone. It is an object of the present invention to provide a colored stainless steel processed product and a method of manufacturing the same.

  The problems of the present invention can be solved by the following aspects. In particular,

(Aspect 1) A chemically processed stainless steel product having an uneven surface formed by grinding treatment covered with a transparent coating film, wherein the 60 ° specular gloss [Gs (60 °) of the uneven surface covered with the transparent coating film ] Is 5 to 50. It is a chemically colored stainless steel product characterized in that it is 5 to 50. The surface of a processed stainless steel product with uneven surface by grinding process has less specular reflection, and the processed chemically developed stainless steel product manufactured by subjecting the surface of such a processed stainless steel product to chemical coloring treatment is less noticeable in color unevenness and distinguishes visual angle color tone It is because it is excellent in the nature. In addition, when the 60-degree specular gloss [Gs (60 °)] is in the range of 5 to 50, color unevenness is less noticeable, and an effect of excellent visual angle color distinction is obtained. Furthermore, by coating with a transparent coating film, abrasion resistance, scratch resistance, and fingerprint resistance are provided.

(Aspect 2) The chemically developed stainless steel product described in (Aspect 1) is characterized in that the grinding process is a sandblasting process. The sand blasting process in which the abrasive is directly sprayed on the surface of the processed stainless steel product is excellent in safety, productivity, easy in equipment, and excellent in processability.

(Aspect 3) The chemically developed stainless steel product described in (Aspect 1) is characterized in that the grinding treatment is a grinding treatment using a combination of sand blasting and electrolytic polishing. By using the sandblasting treatment and the electrolytic polishing treatment in combination, it is possible to realize a region (for example, 30 to 50) in which a 60 degree specular gloss [Gs (60 °)] of the uneven surface is moderate.

(Aspect 4) The chemical coloring described in any one of Aspects 1 to 3 characterized in that the transparent coating film is a film formed by applying an inorganic or organic coating composition. It is a processed stainless steel product. A transparent coating film formed by application of an inorganic or organic coating composition can form a transparent film on the surface of a chemically processed stainless steel product by coating and drying, and has abrasion resistance, scratch resistance and fingerprint resistance. There is no color unevenness and color tone change before and after the formation of the coating film, and the 60 degree mirror gloss [Gs (60 °)] is also within the range of 5 to 50. In addition, as compared with a film (electrodeposition film) formed by electrolytic treatment or a film (vapor deposition film) formed by sputtering, no special equipment is required, and therefore, cost and productivity are excellent.

(Aspect 5) A sand blasting process for forming an irregular surface on the surface of a processed stainless steel by spraying a mixture of an abrasive and compressed air onto the surface of the processed stainless steel Immersed in a color processing solution consisting of a mixed solution to form a colored film on the surface of a processed stainless steel product, and immerse the color processed stainless processed product in a hardening solution consisting of a mixed solution of chromic acid and phosphoric acid And a coating treatment step of applying an inorganic or organic coating composition to the surface of the cured stainless steel product surface, and curing treatment step of curing the color film formed in the color treatment step. It is a manufacturing method of a chemically colored stainless steel processed product. By sequentially performing the sandblasting treatment and the chemical coloring treatment, it is possible to realize a chemically colored stainless steel which is less likely to be uneven in color and has an effect of being excellent in visual angle color tone discrimination.

(Aspect 6) A sand blasting process for forming an irregular surface on the surface of the processed stainless steel by spraying a mixture of abrasive and compressed air on the surface of the processed stainless steel, and electrolytically polishing the surface of the processed stainless sand processed sandblasted surface. Polishing process step, the electroprocessed polished stainless steel product is immersed in a coloring treatment solution composed of a mixed solution of chromic acid and sulfuric acid to form a colored coating film on the surface of the stainless finished product surface The processed product is immersed in a hardening treatment solution consisting of a mixed solution of chromic acid and phosphoric acid to harden the color-forming film formed in the color forming treatment step, and an inorganic or hardened stainless steel processed product surface. A coating treatment step of applying an organic coating composition, and a chemically colored stainless steel characterized by comprising It is a method of manufacturing a pyrotechnic. By performing the electrolytic polishing treatment after the sand blasting treatment, it is possible to accurately realize a chemically colored stainless steel in a region (for example, 30 to 50) where the 60 degree specular gloss [Gs (60 °)] of the uneven surface is large.

  According to the present invention, it is possible to accurately provide a colored stainless steel processed product using a chemical coloring technology in which the 60 ° specular gloss [Gs (60 °)] of the surface coated with a transparent coating film is in the range of 5 to 50. . As a result, it is possible to realize a colored stainless steel processed product which is excellent in abrasion resistance, scratch resistance, fingerprint resistance, without color unevenness, excellent in visual angle color discrimination and advanced in industrial color tone.

It is process drawing which shows the flow of the process which comprises the manufacturing method of the coloring stainless steel processed goods of this invention.

The colored stainless steel processed article of the present invention has a low 60 ° specular gloss [Gs (60 °)] of 5 to 50 on its surface, is less noticeable in color unevenness, and is excellent in visual angle color distinction and has a transparent coating film It is characterized by being excellent in abrasion resistance, scratch resistance, and fingerprint resistance by covering with. The colored stainless steel processed article of the present invention, as shown in FIG. 1, is a sandblasting step of forming irregularities on the stainless steel surface in order to develop a 60 degree specular gloss [Gs (60 °)] of the stainless steel surface to 5 to 50. And electrolytic polishing process, color forming process of forming a chemically colored film on a stainless steel surface, curing process of curing the chemically colored film, and coating process of covering a transparent coated film on a colored stainless steel product Can. However, the electrolytic polishing process step is a process employed to develop a region (eg, 30 to 50) in which the 60 ° specular gloss [Gs (60 °)] of the surface is moderate, and it is a stainless steel by sandblasting alone. Irregularities can be formed on the surface.
Hereinafter, in the present invention, the metal material and the processed metal material to be treated, and the sandblasting process, the electrolytic polishing process, the color forming process, the curing process, and the coating process will be described in order. The evaluation method is also described. In addition, this invention is not limited to the aspect for implementing the following invention.

(1) Metal Material The metal material used in the present invention is austenitic stainless steel, ferrite, as long as it is a metal material which can be processed to have surface irregularities by sand blasting and electrolytic polishing and can be subjected to chemical coloring treatment. It is not limited to stainless steel such as stainless steel. Specifically, aluminum, aluminum alloy, iron, iron alloy, stainless steel, nickel, nickel alloy, titanium, titanium alloy, magnesium, magnesium alloy, tungsten, tungsten alloy, molybdenum, molybdenum alloy, zinc or zinc alloy etc. Known metal materials may also be used.

  As aluminum and an aluminum alloy, for example, an alloy containing 40% by mass or more of Al, 80% by mass or more, or 99% by mass or more can be used. For example, aluminum and aluminum alloy standardized in JIS H 4000 to JIS H 4180, JIS H 5202, JIS H 5303 or JIS Z 3232 to JIS Z 3263 can be used. For example, aluminum: 99.00 mass% or more of aluminum represented by aluminum alloy number 1085, 1080, 1070, 1050, 1100, 1200, 1N00, 1N30, or an alloy thereof or the like specified in JIS H 4000 is used. be able to.

As the iron alloy, for example, stainless steel, mild steel, carbon steel, iron nickel alloy, steel or the like can be used. For example, iron or iron alloys described in JIS G 3101 to JIS G 7603, JIS C 2502 to JIS C 8380, JIS A 5504 to JIS A 6514, or JIS E 1101 to JIS E 5402-1 can be used.
As stainless steel, SUS 301, SUS 304, SUS 310, SUS 316, SUS 430, SUS 631 (all of which are JIS standards) can be used. As the mild steel, a mild steel having carbon of 0.15% by mass or less can be used, and the mild steel described in JIS G3141 can be used. The iron-nickel alloy contains 35 to 85% by mass of Ni and the balance is Fe and unavoidable impurities. Specifically, the iron-nickel alloy described in JIS C2531 can be used.

  As nickel and a nickel alloy, what contains 40 mass% or more of Ni, or 80 mass% or more, or 99.0 mass% or more can be used, for example. For example, nickel or a nickel alloy standardized in JIS H 4541 to JIS H 4554, JIS H 5701 or JIS G 7604 to JIS G 7605, JIS C 2531 can be used. Further, for example, nickel represented by alloy numbers NW2200 and NW2201 described in JIS H4551 and nickel of 99.0% by mass or more or an alloy thereof can be used.

  As titanium and a titanium alloy, for example, one containing 40% by mass or more of Ti, 80% by mass or more, or 99.0% by mass or more can be used. For example, titanium and titanium alloys specified in JIS H 4600 to JIS H 4675 and JIS H 5801 can be used.

  As magnesium and a magnesium alloy, an alloy containing, for example, 40% by mass or more of Mg, or 80% by mass or more, or 99.0% by mass or more can be used. For example, magnesium and magnesium alloys standardized in JIS H 4201 to JIS H 4204, JIS H 5203 to JIS H 5303, and JIS H 6125 can be used.

  As tungsten and a tungsten alloy, for example, one containing 40% by mass or more of W, or 80% by mass or more, or 99.0% by mass or more can be used. For example, tungsten and a tungsten alloy standardized in JIS H 4463 can be used.

  As molybdenum and a molybdenum alloy, what contains 40 mass% or more of Mo, 80 mass% or more, or 99.0 mass% or more can be used, for example.

(2) Metal material processed article A metal material processed article of the present invention is a metal material processed article which exhibits excellent appearance by performing chemical coloring treatment, that is, a metal processed article having excellent designability, a finished product or part It does not matter. Specifically, building materials (eg, nails, bolts, nuts, screws, files, wires, pipes, steel plates, hose joints, keyhole caps, etc.), daily necessities (eg, mugs, spoons, hawks, eyeglass frames, bookmarks, Baskets, chairs, desks, thermos, toys, nail clippers, etc., water accessories (sinks, tubs, system kitchens, drain plates, wash baskets, etc.), fashion accessories (hooks, buttons, hips, buckles, fasteners, medals, etc.) , Mechanical parts (chains, friction rings, manifolds, car bodies, bicycle frames, wheelchair frames, etc.), and other advertising panels.
The processed metal material may be either a processed metal material subjected to a chemical coloring treatment or a processed metal material and then subjected to a chemical coloring treatment.

(3) Sandblasting treatment The sandblasting treatment is to carry out surface treatment by causing a projectile (sometimes referred to as an abrasive or an abrasive) to collide with the object to be treated. There are a mechanical method, a pneumatic method, and a wet method as a projection method of a projection material. There are two types of pneumatics: a vacuum type that transports the projection material by negative pressure and a direct pressure type that transports the projection material by positive pressure.
In the sand blasting process, the projectile used in this process to efficiently process the surface of the metal material has a higher hardness than the metal material (for example, a Mohs hardness of 6 or more, more preferably 8 or more). It is preferable to use an inorganic material, preferably angular particles such as spheres or polygons, and particularly preferably angular particles. Specific examples include glass beads, zirconia particles, steel grids, alumina particles, silica particles, silicon carbide particles and the like.

  The particle size (count) of the shot material is preferably # 70 to # 800, and more preferably # 90 to # 500. If the particle size is smaller than # 70, the particle size is large, the haze of the treated product tends to be high, and the visibility tends to decrease. If the particle size exceeds # 800, sandblasting tends to be inefficient because the particle size is small.

  0.05-1 Mpa is preferable and, as for the projection pressure when a projection material is projected on a metal material, 0.1-0.5 Mpa is more preferable. When the projection pressure is less than 0.05, the sandblasting process becomes inefficient because the projection pressure is low, and uneven surface with unevenness tends to be formed. When the projection pressure exceeds 1 MPa, the collision energy when the projection material reaches the metal material surface tends to be large, the shape of the irregularities on the treated surface becomes large, and the color tone of the metal material surface subjected to the chemical coloring treatment is inferior. It is because

  The projection angle when the projection material is projected onto the metal material is preferably 10 to 90 ° when the surface of the metal material is 0 °. If it is less than 10 °, the sandblasting process tends to be inefficient. In consideration of the efficiency, the projection angle is preferably 15 ° or more, more preferably 20 ° or more.

  5-300 mm is preferable and, as for the projection distance (distance from a projection start position to a metal-material board surface) when projecting a projection material on the metal material surface, 10-250 mm is more preferable. If it is less than 1 mm, the collision energy becomes large, the haze of the metal material treated surface becomes high, and the visibility decreases. If it exceeds 400 mm, sandblasting tends to be inefficient.

  The amount of projection when the projection material is projected onto the surface of the metal material is preferably 50 to 300 g / min, and more preferably 100 to 200 g / min. If it is less than 50 g / min, sandblasting tends to be inefficient, and if it is more than 300 g / min, unevenness to the extent that can be visually confirmed in the treated product tends to occur.

(4) Electrolytic polishing In electrolytic polishing according to metal, direct current is applied with metal as plus in electrolytic polishing solution according to metal, and the metal surface is smoothed and dissolved by dissolution of the convex part of the metal surface with fine unevenness. Polishing method. It is possible to remove dirt, foreign matter, and process-altered layers generated by physical polishing such as buffing.

  The type of the electropolishing liquid is preferably a single or mixed acidic aqueous solution of hydrogen peroxide water, glacial butyric acid, phosphoric acid, sulfuric acid, nitric acid, chromic acid, sodium bichromate and the like. In addition, ethylene glycol monoethyl ether, ethylene glycol monobutyl ester and glycerin can be used as additives. These additives have the effect of stabilizing the electrolytic solution and widening the proper electrolytic range against concentration change, temporal change, and deterioration due to use.

Specifically, in an electrolytic solution consisting of 40 to 80 vol% phosphoric acid, 5 to 30 vol% sulfuric acid, 15 to 20 vol% water, and 0 to 35 vol% ethylene glycol, direct current (10 to 70 ° C., 3 to 10 min. It can be carried out at 30 V, ^{3 to} 60 A / dm ³ ).

(5) Coloring treatment By the coloring treatment, an extremely thin light transmitting oxide film (hereinafter referred to as “coloring coating”) is formed on the surface of the metal material which has undergone sandblasting and electrolytic polishing. The metallic material develops a color by utilizing the interference of light by the colored film. It is possible to express a quaint color tone that reflects the beautifulness of the metal substrate surface. The following will describe stainless steel products as specific examples.

(5-1) Coloring treatment As a coloring method, electrolysis of a processed stainless steel as an anode was performed in a mixed solution of sulfuric acid and chromic acid (hereinafter referred to as "coloring solution"), and electrolysis was performed by a direct current and immersed in an aqueous solution. A so-called inco method is employed in which a desired color-forming film is formed by the potential difference with the reference electrode (see JP-A-48-011243).
When the thickness of the colored film is optically determined from the interference peak of light, the thickness of the colored film formed on the surface of the processed stainless steel is proportional to the potential difference between the anode and the reference electrode (hereinafter referred to as "colored potential"). Do. The values are 6 mV (blue: 90 nm), 13 mV (gold: 150 nm), 16 mV (red: 180 nm) and 19.5 mV (green: 220 nm) in each color tone (Takeuchi Takeshi, Practical Surface Technology 33 11) No. 1986)). The thickness of the colored film is significantly larger than the thickness (1 to 3 nm) of the passive film formed on the stainless steel product.
Therefore, since the color unevenness produced in the colored stainless steel processed product is caused by the dispersion of the thickness of the colored film, it is important to control the thickness of the colored film.

(5-2) Chromogenic Coating By lowering the formation rate of the chromogenic coating, it is possible to moderate the expression of color tone and reduce color unevenness. This is because the thickness of the coloring film formed on the surface of the processed stainless steel is correlated with the coloring potential.
The mixing ratio of sulfuric acid to chromic acid (chromic acid / sulfuric acid) in the coloring solution is preferably 40 to 50 wt / vl% with respect to 15 to 30 wt / vl% of chromic acid. By reducing the concentration of chromic acid, it is possible to reduce the formation rate of the colored film, and to control precisely the formed thickness of the colored film.
The formation rate of the color film can be controlled by the color potential (mV / sec). The coloring potential velocity is 0.02 to 0.08 mV / sec, preferably 0.050 to 0.065 mV / sec. This is because if the coloring potential velocity is less than 0.02 mV / sec, the formation of a colored film is delayed and the productivity is reduced. If the color development potential velocity exceeds 0.08 mV / sec, the thickness of the formed color film will be non-uniform, which may cause discomfort in color tone and color unevenness.

(5-3) Manganese Ion Manganese ion (Mn ²⁺ ) can be added in order to compensate for the formation rate of the colored film due to the reduction of the chromic acid concentration in the coloring solution. Manganese salts (MnCl ₂ ), manganese sulfate (MnSO ₄ ), manganese nitrate (Mn (NO ₃ ) ₂ ), etc. may be used as the manganese salt used in the color forming solution, and one or more of these may be used. Can. The concentration of manganese ion (Mn ²⁺ ) in the coloring solution is preferably 0.5 to 300 mmol / L, and more preferably 5 to 150 mmol / L. If the manganese ion (Mn ²⁺ ) concentration is less than 0.5 mmol / L, there is no effect to promote the formation of a colored film, and if the manganese ion (Mn ²⁺ ) concentration exceeds 300 mmol / L, insoluble parts remain and It affects the generation.

(6) Curing treatment A stainless steel product on which a coloring film is formed by oxidation coloring is electrolytically treated to cure the coloring film. In this hardening treatment, the coloring film is hardened by embedding chromium in the porous portion of the coloring film by electrolysis in a mixed solution of phosphoric acid and chromic acid. It is designed to give a color tone.

(7) Coating treatment The coating treatment of the present invention imparts abrasion resistance, scratch resistance and fingerprint resistance, and forms a transparent coating film with little color tone change on the surface of a colored stainless steel product. Specifically, by applying a coating composition (clear paint) capable of imparting abrasion resistance, scratch resistance, fingerprint resistance and forming a transparent coating film with little color tone change on the surface of a chemically colored stainless steel product Form.
The coating composition of the present invention is an inorganic coating composition as long as it imparts abrasion resistance, scratch resistance and fingerprint resistance, and forms a transparent coating film with little color tone change on the surface of a colored stainless steel product. And organic coating compositions can be used.

As an inorganic coating composition, a coating containing an inorganic polysilazane (for example, perhydroxypolysilazane (PHPS)) capable of forming a coating film composed of an inorganic (glassy) material composed of a silica-based compound, a diluting solvent and a catalyst There is a composition (see WO 2002-088269). The inorganic polysilazane reacts with the moisture in the air to introduce a silyl group and condenses to form a glassy film of SiO ₂ while generating basic ammonium.
The catalyst has the function of converting the inorganic polysilazane into silica at normal temperature. Specifically, N-heterocyclic compounds (for example, 1-methylpiperazine, pyrrole, imidazole and the like), amines (methylamine, propylamine and the like).
The dilution solvent can dissolve the inorganic polysilazane and the catalyst, has no reactivity with the inorganic polysilazane, and is excellent in storage stability. Specifically, petroleum solvents, aromatic solvents and cycloaliphatic solvents are preferably used.
In addition, an inorganic coating composition (see JP-A-2-129269), which contains as a main component silica obtained by heating and dissolving alkali potassium silicate and ultrafine particle silica (see JP-A-2-129269), alumina sol in which boehmite particles are dispersed in a dispersion medium, and dispersion. There is an inorganic coating composition (see Japanese Patent Application Laid-Open No. 2007-099884) or the like which is mixed with a silica sol in which silica particles are dispersed in a medium.

As the organic coating composition, known coating resin (for example, polyester resin, polyurethane resin, acrylic resin, fluorocarbon resin, epoxy resin, etc.) and a lubricant (for example, polytetrafluoroethylene (PTFE), polyethylene, microcrystalline, etc. Etc.), leveling agent, wax etc. are added. It may be either oily or aqueous.
The oily coating composition is a coating composition using an organic solvent (eg, xylene, cyclohexane, methyl ethyl ketone etc.) as a dilution solvent. For example, there is one in which an acidic catalyst is added to a mixed solution of a polyester resin and a melamine resin.
The aqueous coating composition is a coating composition using a water-based solvent as a dilution solvent. For example, one obtained by adding a curing agent (melamine resin, polyisocyanate compound etc.), silica particles (spherical silica etc.) and a lubricant (polyethylene resin particles etc.) to an aqueous resin (polyester resin, urethane resin, acrylic resin etc.) is there.
As organic material,

Any known method may be used as a method of applying the coating composition to the surface of the colored stainless steel product. Specifically, there are spray coating, roller coating, dip coating and the like.
The coating amount of the coating composition is preferably such that the film thickness after drying is about 0.1 to 2 μm.

(7) Evaluation The appearance of the colored stainless steel product was evaluated by “color tone”, “visual angle color distinction” and “60 degree specular gloss [Gs (60 °)]”. As for the color tone, it conforms to “visual recognition” and L ^* , a ^* , b ^* color system (JIS Z 878 1-4: 2013) determined by the CIE (International Lighting Commission) in 1976 (hereinafter referred to as “ "CIELAB", described in detail below.

(7-1) Color tone evaluation The test product of color-processed stainless steel processed product (see FIG. 2, hereinafter referred to as “this test product”) is visually identified in color, and a spectrocolorimeter (manufactured by Konica Minolta, CM- CIELAB was measured by 2600 d).
Here, CIELAB is an almost complete color space, which was developed by the International Commission on Illumination (CIE). It can describe all colors visible to the human eye, and can be used as a basis for device-specific models. Three coordinates of CIELAB, lightness of color (L ^* = 0 is black, L ^* = 100 is diffuse color), position between red / magenta and green (a ^* <0 is green, a ^* > 0 Corresponds to the position between magenta and yellow / blue (b ^* <0 for blue, b ^* > 0 for yellow).

(7-2) Visual angle color distinction When the line of sight of the test product is placed at a position shifted 60 ° from the vertical direction with respect to the test product placed horizontally (when the test product is viewed at a depression angle of 30 °) The color tone change of the test product was evaluated. Those with no change in color tone were judged as “○”, and those with change in color tone were judged as “x”.

(7-3) 60 degree specular gloss (Gs 60 °)
In order to express the mirror surface state of the surface of the test article as a numerical value, 60 ° mirror gloss method (Gs 60 °) was used. The measuring method of 60 degree specular gloss is described in JIS Z8741 "mirror gloss-measuring method", and based on this description, the glossiness of the colored stainless steel processed article surface was measured. As a measuring device, a gloss meter (Gloss Meter U manufactured by Toyo Seiki Seisaku-sho, Ltd.) was used.

(7-4) Wear resistance Abrasion resistance test is performed according to the flat plate rotational wear test method (taper type wear test method) presented in the method for testing the wear resistance of plating (JIS H 8503-1989), and the substrate is exposed The number of times was measured.

  Next, an embodiment exhibiting the effects of the present invention will be shown as an example. The summary is shown in Table 1.

Example 1
(1) Sandblasting The test piece (30 × 30 × 1 mmt) is placed in a sandblasting apparatus (not shown), and the blast material: alumina particles (# 200), the blasting pressure: 0 against the main surface of the test specimen plate. Sandblasting treatment was performed with a pressure of 3 MPa, a projection angle of 40 °, a projection time of 15 seconds, a projection distance of 50 mm, and a projection amount of 450 g / min.

(2) Coloring Treatment The sandblasted product 1 was subjected to a coloring treatment under the following conditions to produce a color-treated product 1.
[Coloring treatment conditions]
・ Colorant composition 250 g / L of chromium oxide, 500 g / L of sulfuric acid
· Processing temperature 80 ° C
Processing time 8 min
・ Color development potential 9mV

(3) Curing treatment The color-treated product 1 was cured under the following conditions to produce a cured product 1.
[Curing treatment conditions]
・ Curing liquid composition Chromium oxide 250 g / L, phosphoric acid 2.5 g / L
Processing temperature 25 ° C
Processing time 10 min
・ Current density 0.5A / dm ²

(4) Coating Treatment A cured coating 1 was coated with a silica-based coating agent (Protector HB-LTC 2 manufactured by Okuno Pharmaceutical Industry Co., Ltd.) to prepare a coating treated product 1 coated with a transparent coating film.

(5) Color tone evaluation The color tone of the cured product 1 and the coated product 1 was visually confirmed. The color tone was all "mochi". Furthermore, about the coating process goods 1, CIELAB was measured with the spectrophotometer (Konica Minolta make, CM-2600d). CIELAB was as shown in Table 1.

(6) Evaluation of visual angle color distinction For the cured product 1 and the coated product 1, when the line of sight is placed at a position shifted 60 ° from the vertical direction with respect to the present test product placed horizontally (tested at an included angle of 30 ° The presence or absence of the color tone change of the test product of when it looked at goods was evaluated. There was almost no change in color tone in any of the cured product 1 and the coated product 1, and it was judged as "o."

(7) Evaluation of 60 degree specular gloss (Gs 60 °) For the cured product 1 and the test item 1, a 60 degree specular gloss (Gs 60 °) is a gloss meter according to JIS Z8741 (Gloss Meter U manufactured by Toyo Seiki Seisakusho Co., Ltd.) Was measured at an incident angle of 60 degrees. The glossiness was, as shown in Table 1, before coating (12.0%) and after coating (31.5%), both being 50% or less.

(8) Abrasion resistance For the coated article 1, according to the plate rotational abrasion test method (taper abrasion test method) presented in the abrasion resistance test method for plating (JIS H 8503-1989), under the following conditions: The abrasion test was done. The number of exposures to substrate exposure was 40 times.
[Abrasion resistance test conditions]
・ Abrasive paper Kraft paper (Cw)
Abrasive material Silicon carbide abrasive material (C), particle size: P600
・ Test load 5.20N

Example 2
A cured product 2 and a coated product 2 were produced by performing the same processing as in Example 1 except that the coating processing was changed to an acrylic coating agent (Body Pen Clear manufactured by Soft 99 Corporation).

(1) Color tone evaluation The color tone of the cured product 2 and the coated product 2 was visually confirmed. The color tone was all "mochi". Furthermore, about the coating process goods 2, CIELAB was measured with the spectrophotometer (Konica Minolta make, CM-2600d). CIELAB was as shown in Table 1.

(2) Evaluation of visual angle color distinction The line of sight of the cured product 2 and the coated product 2 was placed at a position shifted 60 ° from the vertical direction with respect to this test product placed horizontally (tested at an included angle of 30 ° The presence or absence of the color tone change of the test product of when it looked at goods was evaluated. In both the cured product 2 and the coated product 2, there was almost no change in color tone, and it was judged as "o."

(3) 60 degree specular gloss (Gs 60 °) evaluation With respect to the cured product 2 and the test item 2, a 60 degree specular gloss (Gs 60 °) is a gloss meter according to JIS Z8741 (Gloss Meter U manufactured by Toyo Seiki Seisakusho Co., Ltd.) Was measured at an incident angle of 60 degrees. The glossiness was, as shown in Table 1, before coating (12.0%) and after coating (36.8%), both being 50% or less.

(4) Wear resistance A wear resistance test was conducted on the coated product 2 under the same conditions as in Example 1. The number of exposures to substrate exposure was 60.

Example 3
(1) Sandblasting Treatment Under the same conditions as in Example 1, a sandblasted product 3 was produced.

(2) Electrolytic Polishing Treatment The sandblasted article 3 was subjected to electrolytic polishing treatment under the following conditions to produce an electropolished treatment article 3.
[Electrolytic polishing treatment conditions]
Electrolytic polishing liquid composition 70 ml / L phosphoric acid, 20 ml / L sulfuric acid, 0.2 ml / L ethylene glycol
· Processing temperature 70 ° C
Processing time 5 min
・ Current density 10A / dm ²
(3) Coloring Treatment The electropolished product 3 was subjected to a coloring treatment under the same conditions as in Example 1 to produce a color-treated product 3.

(4) Curing Treatment The color-treated product 3 was cured under the same conditions as in Example 1 to produce a cured product 3.

(5) Coating treatment The same silica-based coating agent (Protector HB-LTC2 manufactured by Okuno Pharmaceutical Co., Ltd.) as in Example 1 was applied to the cured product 3 to prepare a coated product 3 coated with a transparent coating film.

(6) Color tone evaluation The color tone of the cured product 3 and the coated product 3 was visually confirmed. The color tone was all "mochi". Furthermore, about the coating process goods 3, CIELAB was measured by the spectrophotometer (Konica Minolta make, CM-2600d). CIELAB was as shown in Table 1.

(7) Evaluation of visual angle color distinction For the cured product 3 and the coated product 3, when the line of sight is placed at a position shifted 60 ° from the vertical direction with respect to the present test product placed horizontally (tested at a depression angle of 30 ° The presence or absence of the color tone change of the test product of when it looked at goods was evaluated. Almost no change in color tone was found in any of the cured product 3 and the coated product 3, and it was judged as "o."

(8) Evaluation of 60 degree mirror gloss (Gs 60 °) For the cured product 3 and the coated product 3, the 60 degree mirror gloss (Gs 60 °) is a gloss meter according to JIS Z8741 (Gross Meter U manufactured by Toyo Seiki Seisakusho Co., Ltd. Was measured at an incident angle of 60 degrees. As shown in Table 1, the degree of gloss was before coating (36.7%) and after coating (44.95%), both being 50% or less.

(9) Wear Resistance A wear resistance test was conducted on the coated product 3 under the same conditions as in Example 1. The number of exposures to substrate exposure was 40 times.

Example 4
A cured product 4 and a coated product 4 were produced in the same process as in Example 3 except that the coating process was changed to an acrylic coating agent (Body Pen Clear manufactured by Soft 99 Corporation).
(1) Color tone evaluation The color tone of the cured product 4 and the coated product 4 was visually confirmed. The color tone was all "mochi". Furthermore, about the coating process goods 4, CIELAB was measured by the spectrophotometer (Konica Minolta make, CM-2600d). CIELAB was as shown in Table 1.

(2) Evaluation of visual angle color distinction For the cured product 4 and the coated product 4, when the line of sight is placed at a position shifted by 60 ° from the vertical direction with respect to this test product placed horizontally (tested at an included angle of 30 ° The presence or absence of the color tone change of the test product of when it looked at goods was evaluated. Almost no change in color tone was found in any of the cured product 4 and the coated product 4, and it was judged as "o."

(3) Evaluation of 60 degree mirror gloss (Gs 60 °) For the cured product 4 and the test item 4, 60 degree mirror gloss (Gs 60 °) is a gloss meter according to JIS Z8741 (Gloss Meter U manufactured by Toyo Seiki Seisakusho Co., Ltd.) Was measured at an incident angle of 60 degrees. The glossiness was, as shown in Table 1, before coating (36.7%) and after coating (48.7%), both being 50% or less.

(4) Wear Resistance A wear resistance test was conducted on the coated product 4 under the same conditions as in Example 1. The number of exposures to substrate exposure was 60.

Comparative Example 1
A coloring treatment and a hardening treatment were performed under the same conditions as in Example 1 without the sand blasting treatment and the electrolytic polishing treatment, to prepare a hardening treatment product 5. Moreover, the coating process was not performed.

(1) Color tone evaluation The color tone of the cured product 5 was visually confirmed. The color tone was "mochi". Furthermore, CIELAB was measured by a spectrocolorimeter (manufactured by Konica Minolta, CM-2600 d). CIELAB was as shown in Table 1.

(2) Evaluation of visual angle color distinction When the line of sight of the cured product 5 is shifted by 60 ° from the vertical direction with respect to the test product placed horizontally (when the test product is viewed at a depression angle of 30 °) The presence or absence of the color tone change of the test product of was evaluated. The color tone change of the cured product 5 was hardly found to be “o”.

(3) Evaluation of 60 degree specular gloss (Gs 60 °) For the cured product 5, 60 degree specular gloss (Gs 60 °) is measured using a gloss meter (Glossmeter U manufactured by Toyo Seiki Seisakusho Co., Ltd.) according to JIS Z8741. It was measured at an incident angle of 60 degrees. The glossiness was before coating (5.0%) as shown in Table 1.

(4) Wear resistance The cured product 5 was subjected to a wear resistance test under the same conditions as in Example 1. The number of exposures to substrate exposure was 30 times.

Comparative Example 2
The electropolished treatment, the color developing treatment and the curing treatment were performed under the same conditions as in Example 3 without sandblasting treatment, and a cured product 6 was produced. Moreover, the coating process was not performed.

(1) Color tone evaluation The color tone of the cured product 6 was visually confirmed. The color tone was "mochi". Furthermore, CIELAB was measured by a spectrocolorimeter (manufactured by Konica Minolta, CM-2600 d). CIELAB was as shown in Table 1.

(2) Evaluation of visual angle color distinction When the line of sight of the cured product 6 is shifted by 60 ° from the vertical direction with respect to the test product placed horizontally (when the test product is viewed at a depression angle of 30 °) The presence or absence of the color tone change of the test product of was evaluated. In the case of the cured product 6, the color tone was different on the upper surface side and the lower surface side, and it was determined to be "x".

(3) 60 degree specular gloss (Gs 60 °) evaluation For the cured product 6, the 60 degree specular gloss (Gs 60 °) is measured using a gloss meter (Gloss Meter U manufactured by Toyo Seiki Seisakusho) in accordance with JIS Z8741. It was measured at an incident angle of 60 degrees. The glossiness was before coating (100%) as shown in Table 1.

(4) Wear resistance The cured product 6 was subjected to a wear resistance test under the same conditions as in Example 1. The number of exposures to substrate exposure was 30 times.

Comparative Example 3
The electropolished treatment, the coloring treatment, the curing treatment, and the coating treatment were performed under the same conditions as in Example 3 without sandblasting treatment, and cured treatment products 7 and coating treatment products 7 were produced.

(1) Color tone evaluation The color tone of the cured product 7 and the coated product 7 was visually confirmed. The color tone was all "mochi". Furthermore, about the coating process goods 7, CIELAB was measured by the spectrophotometer (Konica Minolta make, CM-2600d). CIELAB was as shown in Table 1.

(2) Evaluation of visual angle color distinction For the cured product 7 and the coated product 7, when the line of sight is shifted by 60 ° from the vertical direction with respect to the test product placed horizontally (test product with a dip angle of 30 ° The presence or absence of the color tone change of the test product was evaluated. The color tone of each of the cured product 7 and the coated product 7 was different on the upper surface side and the lower surface side, and was determined as “x”.

(3) 60 degree specular gloss (Gs 60 °) evaluation For the cured product 7 and the coated product 7, the 60 degree specular gloss (Gs 60 °) is a gloss meter according to JIS Z8741 (Gross Meter U manufactured by Toyo Seiki Seisakusho Co., Ltd. Was measured at an incident angle of 60 degrees. The glossiness was, as shown in Table 1, before coating (100%) and after coating (65.6%), both exceeding 50%.

(4) Wear resistance A wear resistance test was conducted on the coated article 7 under the same conditions as in Example 1. The number of exposures to substrate exposure was 40 times.

Comparative Example 4
The electropolished treatment, the color forming treatment, the curing treatment and the coating treatment were performed under the same conditions as in Example 4 without sandblasting treatment, to produce a cured treatment product 8 and a coating treated product 8.

(1) Color tone evaluation The color tone of the cured product 8 and the coated product 8 was visually confirmed. The color tone was all "mochi". Furthermore, the CIELAB of the coated article 8 was measured by a spectrophotometer (CM-2600 d, manufactured by Konica Minolta). CIELAB was as shown in Table 1.

(2) Evaluation of visual angle color distinction When the cured product 8 and the coated product 8 are placed at a position shifted 60 ° from the vertical direction with respect to the test product placed in a horizontal line (the test product with a dip angle of 30 °) The presence or absence of the color tone change of the test product was evaluated. The color tone of each of the cured product 8 and the coated product 8 was different between the upper surface side and the lower surface side, and was determined to be “x”.

(3) Evaluation of 60 degree mirror gloss (Gs 60 °) For the cured product 8 and the coated product 8, the 60 degree mirror gloss (Gs 60 °) is a gloss meter according to JIS Z8741 (Gross Meter U manufactured by Toyo Seiki Seisakusho Co., Ltd. Was measured at an incident angle of 60 degrees. The glossiness was, as shown in Table 1, before coating (100%) and after coating (94.1%), both exceeding 50%.

(4) Wear Resistance A wear resistance test was conducted on the coated article 8 under the same conditions as in Example 1. The number of exposures to substrate exposure was 60.

<Summary>
(1) The colored stainless steel processed product subjected to the sandblasting treatment of the present invention is excellent in visual angle color distinction even after the coating treatment. In addition, the 60 ° specular gloss (Gs 60 °) is also 50% or less (Examples 1 and 2).
(2) The colored stainless steel processed product according to the present invention using sandblasting and electrolytic polishing in combination has a 60 degree specular gloss (Gs 60 °) of 36.7%, and the colored stainless steel processed product subjected only to sandblasting (12 Glossiness is higher than .0%. By using the electrolytic polishing treatment in combination, the 60 ° specular gloss (Gs 60 °) can be increased. However, even after the coating process, the 60 ° specular gloss (Gs 60 °) is 50% or less. Moreover, it is excellent in visual angle color tone identification property also after a coating process (Examples 3 and 4).
(3) The colored stainless steel products coated with the transparent coating film of the present invention are all excellent in visual angle color distinction. Moreover, abrasion resistance is also improved by the coating process (Examples 1-4, Comparative Examples 1-4).

  According to the present invention, it is possible to provide a colored stainless steel processed article excellent in corrosion resistance, abrasion resistance and scratch resistance, which is excellent in visual angle color discrimination and has advanced industrial color tone and which uses a chemical coloring technology.

Claims (6)

  A machined product of chemically colored stainless steel in which a rough surface formed by grinding is coated with a transparent coating film, wherein the 60 ° specular gloss [Gs (60 °)] of the rough surface coated with the transparent coating film is 5 Chemical processed stainless steel processed product characterized by being 50 to 50.   The chemically processed stainless steel processed article according to claim 1, wherein the grinding process is sandblasting.   The chemically processed stainless steel processed article according to claim 1, wherein the grinding process is a grinding process using a combination of sand blasting and electrolytic polishing.   The chemically colored stainless steel product according to any one of claims 1 to 3, wherein the transparent coating film is a film formed by applying an inorganic or organic coating composition. Sand blasting process of forming an irregular surface on the surface of the stainless steel product by spraying a mixture of abrasive and compressed air on the surface of the stainless steel product;
A color forming process step of forming a colored film on the surface of a processed stainless steel product by immersing the sandblasted processed stainless steel product in a coloring processing solution comprising a mixed solution of chromic acid and sulfuric acid.
A hardening treatment step of immersing the color processed stainless steel processed product in a hardening treatment solution comprising a mixed solution of chromic acid and phosphoric acid to harden the color forming film formed in the color forming treatment step;
A coating treatment step of applying an inorganic or organic coating composition to the surface of a hardened stainless steel product,
A method for producing a chemically colored stainless steel processed product, characterized by comprising: Sand blasting process of forming an irregular surface on the surface of the stainless steel product by spraying a mixture of abrasive and compressed air on the surface of the stainless steel product;
Electropolishing treatment step of electropolishing the sandblasted stainless steel product surface The electrolytically polished stainless steel product is immersed in a coloring treatment solution consisting of a mixed solution of chromic acid and sulfuric acid to color the stainless steel product surface Color forming process to form a film,
A hardening treatment step of immersing the color processed stainless steel processed product in a hardening treatment solution comprising a mixed solution of chromic acid and phosphoric acid to harden the color forming film formed in the color forming treatment step;
A coating treatment step of applying an inorganic or organic coating composition to the surface of a hardened stainless steel product,
A method for producing a chemically colored stainless steel processed product, characterized by comprising: