WO2017186714A1 - Method of forming wrinkle finish coating on a metal substrate - Google Patents

Method of forming wrinkle finish coating on a metal substrate Download PDF

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Publication number
WO2017186714A1
WO2017186714A1 PCT/EP2017/059790 EP2017059790W WO2017186714A1 WO 2017186714 A1 WO2017186714 A1 WO 2017186714A1 EP 2017059790 W EP2017059790 W EP 2017059790W WO 2017186714 A1 WO2017186714 A1 WO 2017186714A1
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WO
WIPO (PCT)
Prior art keywords
coating
μιτι
base paint
mass
wrinkle finish
Prior art date
Application number
PCT/EP2017/059790
Other languages
French (fr)
Inventor
Nagao Hori
Akiko OKUDA
Hitofusa Mitani
Yuichi KOJO
Taichiro Kohashi
Tetsuya SHIBAMOTO
Takahiro Tsujita
Original Assignee
Akzo Nobel Coatings International B.V.
Obayashi Corporation
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 Akzo Nobel Coatings International B.V., Obayashi Corporation filed Critical Akzo Nobel Coatings International B.V.
Publication of WO2017186714A1 publication Critical patent/WO2017186714A1/en

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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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/28—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for wrinkle, crackle, orange-peel, or similar decorative effects
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/061—Special surface effect
    • B05D5/062—Wrinkled, cracked or ancient-looking effect
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass

Definitions

  • the present invention relates to a method of forming wrinkle finish coating on a metal substrate at an installation site with the appearance similar to that of a wrinkle finish coating that is formed in the factory, and to a method of repairing a damaged wrinkle finish coating on a metal substrate at an installation site.
  • the wrinkle finish coating formed at the installation site may be a different pattern from the wrinkle finish coating that was formed at the factory. This makes it very difficult to form the wrinkle finish coating on the metal surface at the installation site, so that the repaired area and the pattern of the repaired area would have a similar appearance to the non-damaged area obtained at the factory.
  • Japanese patent application No. 2008-291 195 discloses a composition containing polyester resins, hexakis(alkoxymethyl)melamine resins, dehydrating agents, sulfonic acid compounds blocked by amine compounds, and particulate ingredients to stabilize the pattern, etc. as a paint composition that forms a wrinkle finish coating.
  • a paint composition that forms a wrinkle finish coating.
  • it is difficult to form a wrinkle finish coating at the installation site using this composition so that it looks similar to the wrinkle finish coating that was formed at the factory using this composition.
  • Japan patent application No. 2002-102791 describes a patterned film repair method of forming a specific wrinkle finish coating at an installation site, wherein a patterned coating is formed on an adhesive sheet under the same environment and conditions as the coating environment and conditions under which the original patterned film was formed.
  • a patterned coating is formed on an adhesive sheet under the same environment and conditions as the coating environment and conditions under which the original patterned film was formed.
  • the pattern-coated adhesive sheet must be cut to match the shape of the area to be repaired, adhesion must be done so that the boundary between the originally formed patterned coating and the pattern- coated adhesive sheet is not apparent, and the pattern-coated adhesive sheet must be adhered to follow the contours of curved surfaces, etc. without forming wrinkles, etc.
  • Japanese patent application No. H1 1 -290769 describes a design coating repair method that consists of disposing a base coating on a substrate, and then disposing a patterned coating on said base coating, wherein the paint for the base coating is applied to the repair area and, while said base coating is tacky before drying and curing, the patterned coating side of a pattern transfer sheet, on which a patterned coating is formed on the surface of a releasable sheet, is placed onto and pressed into said base coating, transferring said patterned coating on the base coating and forming a design coating in the repair area.
  • the adhesion surface area gets larger, the drying condition of the base coating becomes irregular and adhesion of the base coating becomes irregular, so that the pattern cannot be transferred well.
  • the objective of the present invention is to provide a method of forming wrinkle finish coating that can yield a wrinkle patter that is similar to that in the factory, despite fluctuations in film thickness, because a wrinkle finish coating is formed at the installation site that is similar to the wrinkle finish coating that is formed in the factory.
  • the present invention is intended to provide a method for forming wrinkle finish coating on a metal substrate whereby a wrinkle finish coating is formed at the installation site that is similar to the wrinkle finish coating that is formed in the factory, Also a method for repairing a damaged wrinkle finish coating on a metal substrate is provided. Using the provided method scratches, etc. that occur in a patterned coating like a wrinkle finish coating during transport and work can be easily repaired at the installation site.
  • the inventors discovered that the specific wrinkle finish coating formed in the factory can be easily reproduced at the installation site by using a paint composition A2 at the installation site in which a specific quantity of particulate silica with a specific average particle diameter is added to a base paint A1 , which was used to form the wrinkle finish coating in the factory.
  • the inventors also discovered that scratches, etc. that occur in a patterned coating like a wrinkle finish coating during transport and work can be easily repaired at the installation site, and completed the invention.
  • the present invention relates to a method of forming a wrinkle finish coating on a metal substrate at an installation site with the appearance similar to that of the wrinkle finish formed by applying a base paint A1 in a factory, in which method a coating composition A2 is obtained by adding 0.1-20 parts by mass of silica particulate with an average particle diameter of 0.1 ⁇ -40 ⁇ per 100 parts by mass of the solids in base paint A1 to the base paint A1 , the coating composition A2 is applied to the metal substrate at the installation site of said component that is the object of wrinkle finish coating, and then heat- cured.
  • the present invention also relates to a method of repairing a damaged wrinkle finish coating on a metal substrate, which coating has been obtained by curing a base paint A1 in a factory, said method comprising preparing a coating composition A2 from the base paint A1 by adding to it 0.1-20 parts by mass of silica particulate with an average particle diameter of 0.1 ⁇ -40 ⁇ per 100 parts by mass of the solids in the base paint A1 , applying the coating composition A2 to the damaged area of the metal substrate to be repaired at the installation site and heat-curing.
  • the wrinkle finish coating that was formed in advance in the factory easily can be reproduced even at the installation site using the method of forming wrinkle finish coating of the present invention. Scratches in the wrinkle finish coating also can be easily repaired. Furthermore, a coating having excellent soil resistance also can be obtained in a repaired area.
  • a wrinkle finish coating similar to a standard wrinkle finish coating that is formed in a factory by applying at least a base paint A1 is formed by applying a base paint composition A2 that contains particulate silica to a metal substrate, which can be an object component at the site to be installed, then heat curing the same.
  • a wrinkle finish can also be expressed as a crepe finish, and indicates a patterned surface condition of suppressed gloss.
  • the base paint A1 is a paint that can be used to form wrinkle finish coating in factory work, but when applied and heat cured at an installation site, the quantity of paint, the drying condition of the paint that has been applied, the curing speed, etc. fluctuate due to differences in application equipment, the application environment, such as temperature and humidity, and the heating equipment, etc. and if the standard application quantity is not met, or if the heating temperature is low, etc. it becomes difficult for the wrinkle pattern to be achieved, gloss increases, and differences appear with the wrinkle finish coating that was formed at the factory. Therefore, by using a paint composition A2 in which particulate silica is separately added to the base paint A1 , increased glossiness is controlled and it looks similar to the wrinkle finish coating formed at the factory. Further, the standard paint wrinkle finish coating that is formed at the factory or by a similar method to that at the factory is referred to in this Specification as the "wrinkle finish coating formed by applying base paint A1 at the factory.”
  • Particulate silica manufactured by either the wet method or the dry method can be used as the particulate silica in the present invention.
  • Particulate silica that has been surface-treated, such as by coating, can also be used.
  • the particulate silica used in the present invention can be used appropriately selected from among known particulate silica, but it is preferred that the average particle diameter of the particulate silica is 0.1-40 ⁇ , and more preferably 1-25 ⁇ . If the average particle diameter is less than 0.1 ⁇ , there are cases in which the matting effect of the particulate silica will not be obtained and the specific wrinkle finish coating formed in advance at the factory will not be able to be reproduced. Additionally, if the average particle diameter exceeds 40 ⁇ , there are cases when the coating appearance will be diminished.
  • the particulate silica referred to here can be an aggregate of multiple smaller (nanometer size) primary particles that clump together.
  • Average particle diameter also called median diameter or D50
  • the added quantity of particulate silica used in the present invention is 0.1-20 parts by mass per 100 parts by mass solids in the base paint A1 , preferably 0.2-18 parts by mass, and more preferably 0.5-15 parts by mass. If the added quantity is less than 0.1 parts by mass, there are cases in which the additive effects of particulate silica are not obtained and the wrinkle finish coating formed in advance at the factory will not be able to be reproduced. Additionally, if the added quantity exceeds 20 ⁇ , there are cases when the coating appearance will be diminished.
  • the method of adding particulate silica to the base paint A1 can be a normal addition method using a dispersion mixer, or the like. For example, particulate silica is gradually added and uniformly mixed while stirring the base paint A1 with a dispersion mixer. The residual quantity of base paint A1 used to form the wrinkle finish coating at the factory can be subdivided, and then particulate silica can be added to the subdivided base paint A1 at the installation site. Adding particulate silica to the base paint A1 at the installation site has the advantage of being able to adjust the quantity of particulate silica added in consideration of the installation site environment. Additionally, in cases where there are multiple worksites, there is the advantage that the quantity of particulate silica added can be adjusted for each worksite according to the respective site environments.
  • the base paint A1 of the present invention is a paint composition that contains a hydroxyl group-containing resin, a melamine resin, and a sulfonic acid compound that has been blocked with an amine, and may be a known base paint A1 that normally is used to form wrinkle finish coating at factories.
  • Examples thereof include wrinkle finish paint compositions disclosed in Japanese patent application 62-174276, Japanese patent application 62- 205173, Japanese patent application H01 -31875, Japanese patent application H05-39443, Japanese patent application H05-320578, Japanese patent application H10-195346, Japanese patent application H10-265732, Japanese patent application H1 1 -172163, Japanese patent application 2000-73007, Japanese patent application 2002-146280, Japanese patent application 2005- 66440, Japanese patent application 2008-195796, and Japanese patent application 2009-235287.
  • a specific example is a base paint A that contains (A) a hydroxyl group- containing polyester resin, (B) a hexakis(alkoxymethyl)melamine resin, and (C) a blocked sulfonic acid compound that has been blocked with a tertiary amine compound.
  • a preferred embodiment of a base paint A1 whereby good wrinkle finish pattern is formed and said pattern is stabilized is a base paint A1 that contains (A) a hydroxyl group-containing polyester resin, (B) a hexakis(alkoxymethyl)melamine resin, and (C) a blocked sulfonic acid compound that has been blocked with a tertiary amine compound, and (D) a particle and/or fiber.
  • a base paint A1 imbued with soil resistance is a base paint A1 that contains (A) a hydroxyl group-containing polyester resin, (B) a hexakis(alkoxymethyl)melamine resin, (C) a blocked sulfonic acid compound that has been blocked with a tertiary amine compound, (D) particles and/or fibers, (E) an organosilicate expressed by general formula (1 ) and an organosilicate expressed by general formula (2), a condensate of either one or both of the aforementioned two organosilicates, or a silicate compound that is a partial hydrolysate of said condensate, and (F) a dehydrating agent.
  • R 1 -Si-(OR 2 ) 3 (1 ) wherein, R 1 is phenyl group or an alkyl group having 1-18 carbons and R 2 is an alkyl group having 1-6 carbons.
  • the hydroxyl value of the hydroxyl group-containing polyester resin that is ingredient (A) is 5-200 mgKOH/g. If the hydroxyl value is less than 5 mgKOH/g, solvent resistance decreases because the crosslink density becomes too low when the coating is cured. If the hydroxyl value exceeds 200 mgKOH/g, workability decreases because the crosslink density becomes too high when the coating is cured. Additionally, it is preferred that the number average molecular weight of the hydroxyl group-containing polyester resin that is ingredient (A) is 500-20000.
  • the number average molecular weight is less than 500, workability decreases because the crosslink density becomes too high when the coating is cured, and if the number average molecular weight exceeds 20000, solvent resistance decreases because the crosslink density becomes too low when the coating is cured.
  • the hydroxyl group-containing polyester resin of ingredient (A) is obtained using known methods, such as the direct esterification, transesterification, and ring-opening polymerization.
  • the polybasic carboxylic acid include dibasic acids, such as phthalic acid, isophthalic acid, tetraphthalic acid, succinic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, hexahydrophthalic acid, and anhydrides thereof, and trivalent or higher polybasic carboxylic acids, such as trimellitic acid and pyromellitic acid, and anhydrides thereof.
  • examples of the polyhydric alcohol include diols, such as ethylene glycol, propylene glycol, diethylene glycol, butane diol, neopentyl glycol, 1 ,4-hexane diol, 1 ,6-hexane diol, and cyclohexane dimethanol, and trivalent or higher polyhydric alcohols, such as glycerin, trimethylol ethane, trimethylol propane, and pentaerythritol.
  • diols such as ethylene glycol, propylene glycol, diethylene glycol, butane diol, neopentyl glycol, 1 ,4-hexane diol, 1 ,6-hexane diol, and cyclohexane dimethanol
  • trivalent or higher polyhydric alcohols such as glycerin, trimethylol ethane, trimethylol propane, and pentaerythritol.
  • the hydroxyl group-containing polyester resin of ingredient (A) also can be obtained by polycondensation by transesterification of a lower alkylester of polybasic carboxylic acid and a polyhydric alcohol. Furthermore, the hydroxyl group-containing polyester resin of ingredient (A) also can be obtained by ring- opening polymerization of lactones, such as /3-propiolactone, ⁇ 5-valerolactone, and ⁇ -caprolactone.
  • the hexakis(alkoxymethyl)melamine resin of ingredient (B) in the aforementioned base paint A1 has the role reacting with the hydroxyl group in ingredient (A) to form a crosslinked structure, and the role of contributing the wrinkle pattern to the coating.
  • the hexakis(alkoxymethyl)melamine resin of ingredient (B) is a methylated melamine resin having 6 alkoxy groups.
  • Methylated melamine resins are compounds having 6 methylol groups in which formaldehyde has been added to 3 of the amino groups on melamine ring, and the hexakis(alkoxymethyl)melamine resin of ingredient (B) is a compound in which the aforementioned 6 methylol groups have been further alkoxylated.
  • Examples of the 6 terminal alkyl groups include methyl groups, isopropyl groups, and n-butyl groups, but methyl groups are most preferred.
  • Examples of commercially available hexakis(methylated) melamines include Cymel 300, Cymel 303 (trade names, manufactured by Japan SciTech Industries, Ltd.), and Nikalac MW-30 (trade name, manufactured by Sanwa Chemical Co., Ltd.), etc.
  • the mass ratio of ingredient (A) and ingredient (B) in the aforementioned base paint A1 is 60/40-90/10, as solids content. If the content of ingredient (A) is less in the mass ratio of ingredient (A) and ingredient (B) is less than 60/40, by solids content, there will not be enough flexible resin ingredient and sufficient workability will not be obtained, and if ingredient (A) is greater than 90/10, there will not be enough coating crosslinking ingredient and solvent resistance will decrease.
  • the blocked sulfonic acid compound that is blocked by a tertiary amine compound that is ingredient (C) is one in which sulfonic acid has been turned into a salt of the tertiary amine compound, whereby the catalytic action of the sulfonic acid is temporarily blocked.
  • sulfonic acid is a reaction catalyst for ingredient (A) and ingredient (B) that shortens the reaction time and increases the difference between surface curing and internal curing of the coating film, improving the wrinkle pattern, but the salt of the tertiary amine compound temporarily blocks this catalytic action.
  • the boiling point of the tertiary amine compound used in the blocked sulfonic acid compound that is ingredient (C) preferably is 50-300°C. If the boiling point of the tertiary amine compound is less than 50°C, the pattern stability of the wrinkle pattern in the coating decreases over time because volatility is high. If the boiling point exceeds 300°C, it becomes difficult for the wrinkle finish pattern to form because volatility is low.
  • Examples of the tertiary compound in ingredient (C) include triethylamine, tributylamine, triallylamine, N-methyldiallylamine, N-methylmorpholine, N,N,N',N'-tetramethyl-1 ,2-diaminoethane, N-methylpiperidine, piperidine, and 4- ethylpiperidine. Any one of these can be used alone, or they can be used in mixtures of two or more, but it is especially preferred to use triethylamine.
  • sulfonic acid used in ingredient (C) examples include para-toluene sulfonic acid, dodecylbenzene sulfonic acid, dinonylnaphthalene disulfonic acid, methane sulfonic acid, and dinonylnaphthalene sulfonic acid, and any one of these can be used alone, or they can be used in mixtures of two or more. It is especially preferred to use para-toluene sulfonic acid.
  • the molar ratio of tertiary amine compound to sulfonic acid is 0.2-0.9 when the sulfonic acid is blocked by the tertiary amine compound. If the molar ratio of tertiary amine compound to sulfonic acid is less than 0.2, a good wrinkle pattern cannot be formed because there is not enough tertiary amine, and if the molar ratio exceeds 0.9, the stability of the hydrophilizing agent decreases because there is too much tertiary amine.
  • the particles and/or fibers that are ingredient (D) in the above base paint A1 contribute to the good formation of the pattern of the wrinkle finish and to the stability of that pattern, and specifically at least one is used selected from (a) organic resin particles with an average particle diameter of 40 ⁇ or less, (b) inorganic glass particles with an average particle diameter of 100 ⁇ or less, and (c) inorganic fibers with an average length of 300 ⁇ or less. It is preferred that the average particle diameter of the (a) organic resin particles is 40 ⁇ or less. If the average particle diameter exceeds 40 ⁇ , the coating appearance deteriorates. The preferred lower limit of the average particle diameter of organic resin particles normally is not less than 1 ⁇ . Examples of commercially available organic resin particles include Techpolymer MBX-5, MBX-12, and MBX-30 (trade names, manufactured by Sekisui Plastics Co., Ltd.).
  • the average particle diameter of the (b) inorganic glass particles is 100 ⁇ or less. If the average particle diameter exceeds 100 ⁇ , the coating appearance deteriorates.
  • the preferred lower limit of the average particle diameter of inorganic glass particles normally is not less than 1 ⁇ . Examples of commercially available inorganic glass particles include Crystalite AA, W-S, and VX-S2 (trade names, manufactured by Tatsumori Ltd.), and Greendensic #600, #800, and #1200 (trade names, manufactured by Showa Denko Co., Ltd.).
  • the average length of the (c) inorganic fibers is 300 ⁇ or less. If the average length of the inorganic fibers exceeds 300 ⁇ , the coating appearance deteriorates.
  • the preferred lower limit of the average particle diameter of inorganic fibers normally is not less than 5 ⁇ .
  • the preferred average diameter of the inorganic fibers normally is 1-40 ⁇ . Examples of commercially available inorganic fibers include Surfa-Strand REV1 , REV4, and REV8 (trade names, manufactured by Nippon Glass Co., Ltd.), and EPG-200, EPG-200-10, EPG-100-31 , and EFH-150-31 (trade names, manufactured by Central Glass Co., Ltd.).
  • the silicate compound used as ingredient (E) in the above base paint A1 hydrophilizes the coating surface, improving the soil resistance thereof.
  • the organosilicates expressed by general formula (1 ) and general formula (2), condensates of either one or both of the aforementioned two organosilicates, and hydrolysates of said condensates can be used as the silicate compound of ingredient (E).
  • R 1 is phenyl group or an alkyl group having 1-18 carbons, where the number of carbons in the alkyl group preferably is 1-14, and particularly preferably 1-9. If the number of carbons in the organic group indicated by R 1 exceeds 18, when an organosilicate and/or a condensate thereof is used, the surface of the coating will not be hydrophilized because not enough surface orientation is yielded when the coating film forms, and good soil resistance is not obtained.
  • R 2 in general formula (1 ) and R 3 in general formula (2) are each an alkyl group having 1-6 carbons, and preferably is an alkyl group having 1-3 carbons. If an organosilicate and/or condensate thereof are used in which the number of carbons in the alkyl group indicated by R 2 or R 3 exceeds 6, the rate of hydrolysis will be slowed.
  • Specific examples of the above general formula (2) include tetrahydroxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilnae, and dimethoxydiethoxysilane. These can be used singly or in combinations of two or more.
  • Condensates of organosilicates can be branched or linear condensates obtained by condensing one or two or more of the organosilicates expressed by the aforementioned general formula (1 ) and general formula (2), and linear condensates with degree of condensation of 2-100 are preferred. It is undesirable for this degree of condensation to exceed 100, as the soil resistance effect becomes small and the workability of the coating is also decreased. It is particularly preferable that the degree of condensation is 2-50 in the organosilicate condensate used in the present invention.
  • organosilicate condensates examples include MKC Silicate MS51 , MS56, MS57, and MS58B15 (trade names, manufactured by Mitsubishi Chemical Corp.), and Ethylsilicate 40, Ethylsilicate 48 and EMS-485 (trade names, manufactured by Colcoat Co., Ltd.).
  • the content proportions of ingredients (C)-(F) in the resin composition in the above base paint A1 are preferably such that the content of ingredient (C) by solids content is 0.1-5 parts by mass, the content of ingredient (D) is 1-30 parts by mass by solids content, the content of ingredient (E) is 0.5-10 parts by mass by solids content, and the content of ingredient (F) is 0.1-10 parts by mass by solids content, each per 100 parts by mass of the total solids content of ingredient (A) and ingredient (B).
  • ingredient (C) is less than 0.1 parts by mass, sufficient curing is not achieved and solvent resistance decreases, and if it exceeds 5 parts by mass, excess tertiary amine compound decreases the stability of the hydrophilizing agent. If the content of ingredient (D) is less than 1 part by mass, a stable wrinkle finish patter cannot be formed, and if it exceeds 30 parts by mass, the workability is decreased.
  • ingredient (E) is less than 0.5 parts by mass, sufficient surface hydrophilizing cannot occur and good soil resistance is not obtained, and if it exceeds 10 parts by mass, water resistance decreases.
  • the above base paint A1 may also contain one or more of inorganic pigments, such as titanium dioxide, carbon black, iron oxide, and chrome yellow, organic pigments, such as cyanine green and cyanine blue, metal powder, such as aluminum powder or copper powder, extender pigments, such as barium sulfate, talc, and mica, additives, such as dispersing agents, leveling agents, antisettling agents, and foam breakers, and solvents.
  • inorganic pigments such as titanium dioxide, carbon black, iron oxide, and chrome yellow
  • organic pigments such as cyanine green and cyanine blue
  • metal powder such as aluminum powder or copper powder
  • extender pigments such as barium sulfate, talc, and mica
  • additives such as dispersing agents, leveling agents, antisettling agents, and foam breakers, and solvents.
  • the paint composition A2 in which particulate silica is separately added to the base paint A1 can be adjusted to an applicable viscosity using an organic solvent, and then applied by a common coating formation method, such as fine brushing, French polishing, brush application, roller application, and spray application.
  • the above paint composition A2 after application to a metal substrate, can be heat cured, e.g. with an infrared dryer, carbon dryer, far infrared dryer, near infrared dryer, or hot air dryer. Further, the dryer is not specifically limited as long as it able to raise the surface temperature.
  • the surface of the coating obtained by applying the above paint composition A2 it is preferred to heat the surface of the coating obtained by applying the above paint composition A2 to a temperature of 95-300°C. Not less than 100°C and not more than 250°C is even more preferable. There are cases where the coating appearance will deteriorate if the surface temperature of the coating is less than 95°C.
  • the described method is used on metal substrates, particularly on ferrous substrates.
  • the metal substrate is a steel sheet or a steel panel.
  • Production example 1 Production of ingredient (A) - hydroxyl group-containing polyester resin
  • a reactor vessel equipped with a reflux tube filled with a stainless steel filler and equipped with a Dean-Stark trap, a thermometer, and a stirring apparatus was charged 22.6 parts by mass isophthalic acid, 12.5 parts by mass adipic acid, 19.0 parts by weight neopentyl glycol, and 7.4 parts by mass trimethylolpropane and heated to 150°C, and then heated over 2 hours to 200°C, then heated over 1 hour to 230°C, and a dehydration condensation reaction was performed while adding 2.5 parts by mass xylene until the resin acid value reached 10, after which, the reaction temperature was decreased to 140°C and 36.0 parts by mass cyclohexanone were added to yield an apparently transparent, hydroxyl group-containing polyester resin solution.
  • Production example 3 Production of base paint A1 -1
  • 80 parts by mass solids content of the hydroxyl group-containing polyester resin shown in production example 1 80 parts by mass titanium oxide, and 30 parts by mass of a mixed solution (solution of a 50/50 by mass parts mixture of Solvesso #100 (manufactured by Esso Corp., trade name: aromatic petroleum naphtha) and cyclohexanone) were dispersed using a sand mill until the pigment particle diameter reached 10 ⁇ . Then, the various ingredients except for the solvent were admixed with the other ingredients listed in Table 1 at the solids content ratios shown therein to yield base paint A1 -1 . The viscosity of the resulting base paint A1 -1 was adjusted using the aforementioned mixed solvent to a No. 4 Ford cup viscosity of 120 ⁇ 10 seconds (25°C). Further, the additive amounts of the ingredients listed in Table 1 are in parts by mass (indicated as solids content).
  • Base paints A1 -2 and A1 -3 were obtained by the same method as in production example 3, using the ingredients listed in Table 1 .
  • the viscosities of the resulting base paints A1 -2 and A1 -3 were adjusted using the aforementioned mixed solvent to a No. 4 Ford cup viscosity of 120 ⁇ 10 seconds (25°C).
  • Embodiment 1 5 parts by mass of particulate silica A were gradually added and uniformly blended, while stirring 100 parts by mass of base paint (A1 -1 ) with a dispersion mixer, to make the paint composition A2 of embodiment 1 .
  • Embodiments 2-27, comparative examples 1-14 The base paints A1 and particulate silicas listed in Table 2 and Table 3 were variously uniformly blended by the same method as in embodiment 1 to make the paint compositions A2 of embodiments 2-27 and comparative examples 1- 14. Further, resin particles and inorganic glass particles were used in comparative examples 5 and 6, respectively, instead of particulate silica. Preparation of standard coating 1
  • An epoxy resin primer (Precolor Primer HP301 , trade name, manufactured by BASF Japan Ltd.) was applied by roll coater to a dried coating film thickness of 5 ⁇ onto a 0.27 mm-thick Galvalume steel sheet treated with a chromate film, and the paint was then baked under conditions of 40 seconds to a PMT (peak metal temperature) of 200°C.
  • base paint A1 -1 was applied by roll coater to a dried coating film thickness of 20 ⁇ and baked under conditions of 50 seconds to a PMT of 230°C to yield standard coating 1 .
  • Standard coating 2 was prepared by the same method as in the preparation of standard coating 1 , using base paint A1 -2.
  • Standard coating 3 was prepared by the same method as in the preparation of standard coating 1 , using base paint A1 -3.
  • silica A *1 5 0.2 7 15 19 5 5 5 0.2 7 15 (parts by mass)
  • Base paint A1 - 2 (parts by 100 100 100 100 100 100 100 100
  • Base paint A1 - 3 (parts by 100 100 100 100 100 100 100 100 100 100 100 mass (solids))
  • the particulate silicas below are aggregates in which several 10 nm primary grains are aggregated.
  • Particulate silica B SFP-20M (trade name, manufactured by Denka Co., Ltd., average particle diameter 0.3 ⁇ )
  • Particulate silica C #200 (trade name, manufactured by Maruto Testing Machine Co., average particle diameter 36 ⁇ ) *4 Particulate silica D: Syloid C803 (trade name, manufactured by Grace Japan Ltd., average particle diameter 3 ⁇ ) * 5 Particulate silica E: #250 (trade name, manufactured by Maruto Testing Machine Co., average particle diameter 22 ⁇ )
  • Particulate silica F gicaster (43-00-501 ) (trade name, manufactured by Corefront Corp., average particle diameter 0.05 ⁇ ) * 7 Particulate silica G: #100 (trade name, manufactured by Maruto Testing Machine Co., average particle diameter 50 ⁇ )
  • Inorganic glass particles EGB731 (trade name, manufactured by Potters Ballotini Co., Ltd., average particle diameter 20 ⁇ ) (Inorganic glass particles consist of individual particles and are not comprised of aggregates)
  • the coating films obtained with the paint composition A2 of the present invention was evaluated by the following method.
  • Coating appearance was visually evaluated according to the following criteria by comparing the wrinkle finish patterns of two test samples comprising an evaluation site 1 where the dried film thickness of the wrinkle coating on the test sample was 20 ⁇ 1 ⁇ and an evaluation site 2 where said dried film thickness was 5 ⁇ 1 ⁇ with the wrinkle finish pattern of a standard paint coating.

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Abstract

The present invention relates to a method of forming a wrinkle finish coating on a metal substrate at an installation site with the appearance similar to that of the wrinkle finish formed by applying a base paint A1 in a factory, in which method a coating composition A2 is obtained by adding 0.1–20 parts by mass of silica particulate with an average particle diameter of 0.1 µm–40 µm per 100 parts by mass of the solids in base paint A1 to the base paint A1, the coating composition A2 is applied to the metal substrate at the installation site of said component that is the object of wrinkle finish coating, and then heat-cured. Using this method, scratches, etc. that occur in a patterned coating like a wrinkle finish coating during transport and work can be easily repaired at an installation site.

Description

Method of forming wrinkle finish coating on a metal substrate
Technical field
The present invention relates to a method of forming wrinkle finish coating on a metal substrate at an installation site with the appearance similar to that of a wrinkle finish coating that is formed in the factory, and to a method of repairing a damaged wrinkle finish coating on a metal substrate at an installation site.
Background technology
It has become common in recent years to apply patterned coatings for the purpose of imparting a design to coated metal panels. Often such patterned coatings are formed by applying a coating that will manifest the pattern in advance to the panel at the factory, prior to work at an installation site. Therefore, there are instances in which scratches would occur during transportation to the installation site and during work, damaging the pattern on the coated surface. Therefore, the need arose to be able to repair such coatings whereby the specific wrinkle finish coating, which had already been formed at the factory, is easily reproduced at the installation site.
In this case, even if the repaired area were directly repaired by brushing, French polishing, or roll-application, etc. using the paint used to form the wrinkle finish coating at the factory, because the coating equipment and coating environment are different from those used in the factory work, the wrinkle finish coating formed at the installation site may be a different pattern from the wrinkle finish coating that was formed at the factory. This makes it very difficult to form the wrinkle finish coating on the metal surface at the installation site, so that the repaired area and the pattern of the repaired area would have a similar appearance to the non-damaged area obtained at the factory.
Japanese patent application No. 2008-291 195 discloses a composition containing polyester resins, hexakis(alkoxymethyl)melamine resins, dehydrating agents, sulfonic acid compounds blocked by amine compounds, and particulate ingredients to stabilize the pattern, etc. as a paint composition that forms a wrinkle finish coating. However, even when wrinkle finish coatings are formed at installation sites using this composition, because the coating equipment and coating environment at the installation site differ from those at the factory, there are problems in that it is difficult to form a wrinkle finish coating at the installation site using this composition so that it looks similar to the wrinkle finish coating that was formed at the factory using this composition. Also, when making repairs, when applying paint an oblique angle so that the boundary between normal areas and the repaired area is not apparent, it is difficult to realize the wrinkle finish in the thin film area of the obliquely applied paint.
Japan patent application No. 2002-102791 describes a patterned film repair method of forming a specific wrinkle finish coating at an installation site, wherein a patterned coating is formed on an adhesive sheet under the same environment and conditions as the coating environment and conditions under which the original patterned film was formed. However, there are cases in which, as the adhesion surface area gets larger, uniform adhesion is difficult without being affected by dirt and particles, etc. at the installation site. There are also problems in that the pattern-coated adhesive sheet must be cut to match the shape of the area to be repaired, adhesion must be done so that the boundary between the originally formed patterned coating and the pattern- coated adhesive sheet is not apparent, and the pattern-coated adhesive sheet must be adhered to follow the contours of curved surfaces, etc. without forming wrinkles, etc. Japanese patent application No. H1 1 -290769 describes a design coating repair method that consists of disposing a base coating on a substrate, and then disposing a patterned coating on said base coating, wherein the paint for the base coating is applied to the repair area and, while said base coating is tacky before drying and curing, the patterned coating side of a pattern transfer sheet, on which a patterned coating is formed on the surface of a releasable sheet, is placed onto and pressed into said base coating, transferring said patterned coating on the base coating and forming a design coating in the repair area. However, there are cases in this instance in which, as the adhesion surface area gets larger, the drying condition of the base coating becomes irregular and adhesion of the base coating becomes irregular, so that the pattern cannot be transferred well.
Summary of the invention
Problems to be solved by the invention
As described above, when a paint composition is used like that described in JP 2008-291 195, it is difficult to form the wrinkle finish coating on a metal substrate that is formed in the factory using the same paint composition at the installation site. One of the major causes is that it is difficult to obtain a similar film thickness distribution to that in the factory because the available application methods are limited on the installation site. For example, because the paint must be sprayed out in a mist form when spray coating, it is difficult to obtain as uniform a film thickness as in the factory, and as a result the wrinkle pattern formed in the factory cannot be formed in the thin film. In the case of brush or roller application, as well, the entire surface cannot be painted at once, making recoating necessary to enable coating without gaps. However, overlap areas develop, making it difficult to obtain as uniform a film thickness as in the factory. The objective of the present invention is to provide a method of forming wrinkle finish coating that can yield a wrinkle patter that is similar to that in the factory, despite fluctuations in film thickness, because a wrinkle finish coating is formed at the installation site that is similar to the wrinkle finish coating that is formed in the factory.
Addressing the aforementioned circumstances, the present invention is intended to provide a method for forming wrinkle finish coating on a metal substrate whereby a wrinkle finish coating is formed at the installation site that is similar to the wrinkle finish coating that is formed in the factory, Also a method for repairing a damaged wrinkle finish coating on a metal substrate is provided. Using the provided method scratches, etc. that occur in a patterned coating like a wrinkle finish coating during transport and work can be easily repaired at the installation site. Means of solving the problems
As the result of diligent research to solve the aforementioned problems, the inventors discovered that the specific wrinkle finish coating formed in the factory can be easily reproduced at the installation site by using a paint composition A2 at the installation site in which a specific quantity of particulate silica with a specific average particle diameter is added to a base paint A1 , which was used to form the wrinkle finish coating in the factory. The inventors also discovered that scratches, etc. that occur in a patterned coating like a wrinkle finish coating during transport and work can be easily repaired at the installation site, and completed the invention. Namely, the present invention relates to a method of forming a wrinkle finish coating on a metal substrate at an installation site with the appearance similar to that of the wrinkle finish formed by applying a base paint A1 in a factory, in which method a coating composition A2 is obtained by adding 0.1-20 parts by mass of silica particulate with an average particle diameter of 0.1 μιτι-40 μιτι per 100 parts by mass of the solids in base paint A1 to the base paint A1 , the coating composition A2 is applied to the metal substrate at the installation site of said component that is the object of wrinkle finish coating, and then heat- cured.
The present invention also relates to a method of repairing a damaged wrinkle finish coating on a metal substrate, which coating has been obtained by curing a base paint A1 in a factory, said method comprising preparing a coating composition A2 from the base paint A1 by adding to it 0.1-20 parts by mass of silica particulate with an average particle diameter of 0.1 μιτι-40 μιτι per 100 parts by mass of the solids in the base paint A1 , applying the coating composition A2 to the damaged area of the metal substrate to be repaired at the installation site and heat-curing.
Effect of the invention
The wrinkle finish coating that was formed in advance in the factory easily can be reproduced even at the installation site using the method of forming wrinkle finish coating of the present invention. Scratches in the wrinkle finish coating also can be easily repaired. Furthermore, a coating having excellent soil resistance also can be obtained in a repaired area.
Conditions of embodiment of the invention According to the present invention, a wrinkle finish coating similar to a standard wrinkle finish coating that is formed in a factory by applying at least a base paint A1 is formed by applying a base paint composition A2 that contains particulate silica to a metal substrate, which can be an object component at the site to be installed, then heat curing the same. Further, a wrinkle finish can also be expressed as a crepe finish, and indicates a patterned surface condition of suppressed gloss.
The base paint A1 is a paint that can be used to form wrinkle finish coating in factory work, but when applied and heat cured at an installation site, the quantity of paint, the drying condition of the paint that has been applied, the curing speed, etc. fluctuate due to differences in application equipment, the application environment, such as temperature and humidity, and the heating equipment, etc. and if the standard application quantity is not met, or if the heating temperature is low, etc. it becomes difficult for the wrinkle pattern to be achieved, gloss increases, and differences appear with the wrinkle finish coating that was formed at the factory. Therefore, by using a paint composition A2 in which particulate silica is separately added to the base paint A1 , increased glossiness is controlled and it looks similar to the wrinkle finish coating formed at the factory. Further, the standard paint wrinkle finish coating that is formed at the factory or by a similar method to that at the factory is referred to in this Specification as the "wrinkle finish coating formed by applying base paint A1 at the factory."
Particulate silica manufactured by either the wet method or the dry method can be used as the particulate silica in the present invention. Particulate silica that has been surface-treated, such as by coating, can also be used.
The particulate silica used in the present invention can be used appropriately selected from among known particulate silica, but it is preferred that the average particle diameter of the particulate silica is 0.1-40 μιτι, and more preferably 1-25 μιτι. If the average particle diameter is less than 0.1 μιτι, there are cases in which the matting effect of the particulate silica will not be obtained and the specific wrinkle finish coating formed in advance at the factory will not be able to be reproduced. Additionally, if the average particle diameter exceeds 40 μιτι, there are cases when the coating appearance will be diminished. The particulate silica referred to here can be an aggregate of multiple smaller (nanometer size) primary particles that clump together.
Average particle diameter, also called median diameter or D50, can be determined by any conventional method, preferably by image analysis. When a commercially available product is used, the average particle diameter is known from the manufacturer. The added quantity of particulate silica used in the present invention is 0.1-20 parts by mass per 100 parts by mass solids in the base paint A1 , preferably 0.2-18 parts by mass, and more preferably 0.5-15 parts by mass. If the added quantity is less than 0.1 parts by mass, there are cases in which the additive effects of particulate silica are not obtained and the wrinkle finish coating formed in advance at the factory will not be able to be reproduced. Additionally, if the added quantity exceeds 20 μιτι, there are cases when the coating appearance will be diminished.
The method of adding particulate silica to the base paint A1 can be a normal addition method using a dispersion mixer, or the like. For example, particulate silica is gradually added and uniformly mixed while stirring the base paint A1 with a dispersion mixer. The residual quantity of base paint A1 used to form the wrinkle finish coating at the factory can be subdivided, and then particulate silica can be added to the subdivided base paint A1 at the installation site. Adding particulate silica to the base paint A1 at the installation site has the advantage of being able to adjust the quantity of particulate silica added in consideration of the installation site environment. Additionally, in cases where there are multiple worksites, there is the advantage that the quantity of particulate silica added can be adjusted for each worksite according to the respective site environments.
The base paint A1 of the present invention is a paint composition that contains a hydroxyl group-containing resin, a melamine resin, and a sulfonic acid compound that has been blocked with an amine, and may be a known base paint A1 that normally is used to form wrinkle finish coating at factories. Examples thereof include wrinkle finish paint compositions disclosed in Japanese patent application 62-174276, Japanese patent application 62- 205173, Japanese patent application H01 -31875, Japanese patent application H05-39443, Japanese patent application H05-320578, Japanese patent application H10-195346, Japanese patent application H10-265732, Japanese patent application H1 1 -172163, Japanese patent application 2000-73007, Japanese patent application 2002-146280, Japanese patent application 2005- 66440, Japanese patent application 2008-195796, and Japanese patent application 2009-235287.
A specific example is a base paint A that contains (A) a hydroxyl group- containing polyester resin, (B) a hexakis(alkoxymethyl)melamine resin, and (C) a blocked sulfonic acid compound that has been blocked with a tertiary amine compound.
A preferred embodiment of a base paint A1 whereby good wrinkle finish pattern is formed and said pattern is stabilized is a base paint A1 that contains (A) a hydroxyl group-containing polyester resin, (B) a hexakis(alkoxymethyl)melamine resin, and (C) a blocked sulfonic acid compound that has been blocked with a tertiary amine compound, and (D) a particle and/or fiber.
Yet another preferred embodiment of a base paint A1 imbued with soil resistance is a base paint A1 that contains (A) a hydroxyl group-containing polyester resin, (B) a hexakis(alkoxymethyl)melamine resin, (C) a blocked sulfonic acid compound that has been blocked with a tertiary amine compound, (D) particles and/or fibers, (E) an organosilicate expressed by general formula (1 ) and an organosilicate expressed by general formula (2), a condensate of either one or both of the aforementioned two organosilicates, or a silicate compound that is a partial hydrolysate of said condensate, and (F) a dehydrating agent.
R1-Si-(OR2)3 (1 ) wherein, R1 is phenyl group or an alkyl group having 1-18 carbons and R2 is an alkyl group having 1-6 carbons.
Si-(OR3)4 (2) wherein, R3 is an alkyl group having 1-6 carbons.
It is preferred that the hydroxyl value of the hydroxyl group-containing polyester resin that is ingredient (A) is 5-200 mgKOH/g. If the hydroxyl value is less than 5 mgKOH/g, solvent resistance decreases because the crosslink density becomes too low when the coating is cured. If the hydroxyl value exceeds 200 mgKOH/g, workability decreases because the crosslink density becomes too high when the coating is cured. Additionally, it is preferred that the number average molecular weight of the hydroxyl group-containing polyester resin that is ingredient (A) is 500-20000. If the number average molecular weight is less than 500, workability decreases because the crosslink density becomes too high when the coating is cured, and if the number average molecular weight exceeds 20000, solvent resistance decreases because the crosslink density becomes too low when the coating is cured.
The hydroxyl group-containing polyester resin of ingredient (A) is obtained using known methods, such as the direct esterification, transesterification, and ring-opening polymerization. When synthesized by direct esterification by polycondensation of polybasic carboxylic acid and polyhydric alcohol, examples of the polybasic carboxylic acid include dibasic acids, such as phthalic acid, isophthalic acid, tetraphthalic acid, succinic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, hexahydrophthalic acid, and anhydrides thereof, and trivalent or higher polybasic carboxylic acids, such as trimellitic acid and pyromellitic acid, and anhydrides thereof. Additionally, examples of the polyhydric alcohol include diols, such as ethylene glycol, propylene glycol, diethylene glycol, butane diol, neopentyl glycol, 1 ,4-hexane diol, 1 ,6-hexane diol, and cyclohexane dimethanol, and trivalent or higher polyhydric alcohols, such as glycerin, trimethylol ethane, trimethylol propane, and pentaerythritol.
The hydroxyl group-containing polyester resin of ingredient (A) also can be obtained by polycondensation by transesterification of a lower alkylester of polybasic carboxylic acid and a polyhydric alcohol. Furthermore, the hydroxyl group-containing polyester resin of ingredient (A) also can be obtained by ring- opening polymerization of lactones, such as /3-propiolactone, <5-valerolactone, and ε-caprolactone.
The hexakis(alkoxymethyl)melamine resin of ingredient (B) in the aforementioned base paint A1 has the role reacting with the hydroxyl group in ingredient (A) to form a crosslinked structure, and the role of contributing the wrinkle pattern to the coating. The hexakis(alkoxymethyl)melamine resin of ingredient (B) is a methylated melamine resin having 6 alkoxy groups. Methylated melamine resins are compounds having 6 methylol groups in which formaldehyde has been added to 3 of the amino groups on melamine ring, and the hexakis(alkoxymethyl)melamine resin of ingredient (B) is a compound in which the aforementioned 6 methylol groups have been further alkoxylated. Examples of the 6 terminal alkyl groups (the alkyl groups in the hexakis(alkoxy) groups) include methyl groups, isopropyl groups, and n-butyl groups, but methyl groups are most preferred. Examples of commercially available hexakis(methylated) melamines include Cymel 300, Cymel 303 (trade names, manufactured by Japan SciTech Industries, Ltd.), and Nikalac MW-30 (trade name, manufactured by Sanwa Chemical Co., Ltd.), etc.
It is preferred that the mass ratio of ingredient (A) and ingredient (B) in the aforementioned base paint A1 is 60/40-90/10, as solids content. If the content of ingredient (A) is less in the mass ratio of ingredient (A) and ingredient (B) is less than 60/40, by solids content, there will not be enough flexible resin ingredient and sufficient workability will not be obtained, and if ingredient (A) is greater than 90/10, there will not be enough coating crosslinking ingredient and solvent resistance will decrease.
In the above base paint A1 , the blocked sulfonic acid compound that is blocked by a tertiary amine compound that is ingredient (C) is one in which sulfonic acid has been turned into a salt of the tertiary amine compound, whereby the catalytic action of the sulfonic acid is temporarily blocked. Namely, sulfonic acid is a reaction catalyst for ingredient (A) and ingredient (B) that shortens the reaction time and increases the difference between surface curing and internal curing of the coating film, improving the wrinkle pattern, but the salt of the tertiary amine compound temporarily blocks this catalytic action.
The boiling point of the tertiary amine compound used in the blocked sulfonic acid compound that is ingredient (C) preferably is 50-300°C. If the boiling point of the tertiary amine compound is less than 50°C, the pattern stability of the wrinkle pattern in the coating decreases over time because volatility is high. If the boiling point exceeds 300°C, it becomes difficult for the wrinkle finish pattern to form because volatility is low. Examples of the tertiary compound in ingredient (C) include triethylamine, tributylamine, triallylamine, N-methyldiallylamine, N-methylmorpholine, N,N,N',N'-tetramethyl-1 ,2-diaminoethane, N-methylpiperidine, piperidine, and 4- ethylpiperidine. Any one of these can be used alone, or they can be used in mixtures of two or more, but it is especially preferred to use triethylamine.
Examples of the sulfonic acid used in ingredient (C) include para-toluene sulfonic acid, dodecylbenzene sulfonic acid, dinonylnaphthalene disulfonic acid, methane sulfonic acid, and dinonylnaphthalene sulfonic acid, and any one of these can be used alone, or they can be used in mixtures of two or more. It is especially preferred to use para-toluene sulfonic acid.
When the above base paint A1 is imbued with soil resistance by containing ingredient (E) and ingredient (F), it is preferred that the molar ratio of tertiary amine compound to sulfonic acid is 0.2-0.9 when the sulfonic acid is blocked by the tertiary amine compound. If the molar ratio of tertiary amine compound to sulfonic acid is less than 0.2, a good wrinkle pattern cannot be formed because there is not enough tertiary amine, and if the molar ratio exceeds 0.9, the stability of the hydrophilizing agent decreases because there is too much tertiary amine.
The particles and/or fibers that are ingredient (D) in the above base paint A1 contribute to the good formation of the pattern of the wrinkle finish and to the stability of that pattern, and specifically at least one is used selected from (a) organic resin particles with an average particle diameter of 40 μιτι or less, (b) inorganic glass particles with an average particle diameter of 100 μιτι or less, and (c) inorganic fibers with an average length of 300 μιτι or less. It is preferred that the average particle diameter of the (a) organic resin particles is 40 μιτι or less. If the average particle diameter exceeds 40 μιτι, the coating appearance deteriorates. The preferred lower limit of the average particle diameter of organic resin particles normally is not less than 1 μιτι. Examples of commercially available organic resin particles include Techpolymer MBX-5, MBX-12, and MBX-30 (trade names, manufactured by Sekisui Plastics Co., Ltd.).
It is preferred that the average particle diameter of the (b) inorganic glass particles is 100 μιτι or less. If the average particle diameter exceeds 100 μιτι, the coating appearance deteriorates. The preferred lower limit of the average particle diameter of inorganic glass particles normally is not less than 1 μιτι. Examples of commercially available inorganic glass particles include Crystalite AA, W-S, and VX-S2 (trade names, manufactured by Tatsumori Ltd.), and Greendensic #600, #800, and #1200 (trade names, manufactured by Showa Denko Co., Ltd.).
It is preferred that the average length of the (c) inorganic fibers is 300 μιτι or less. If the average length of the inorganic fibers exceeds 300 μιτι, the coating appearance deteriorates. The preferred lower limit of the average particle diameter of inorganic fibers normally is not less than 5 μιτι. The preferred average diameter of the inorganic fibers normally is 1-40 μιτι. Examples of commercially available inorganic fibers include Surfa-Strand REV1 , REV4, and REV8 (trade names, manufactured by Nippon Glass Co., Ltd.), and EPG-200, EPG-200-10, EPG-100-31 , and EFH-150-31 (trade names, manufactured by Central Glass Co., Ltd.). The silicate compound used as ingredient (E) in the above base paint A1 hydrophilizes the coating surface, improving the soil resistance thereof. The organosilicates expressed by general formula (1 ) and general formula (2), condensates of either one or both of the aforementioned two organosilicates, and hydrolysates of said condensates can be used as the silicate compound of ingredient (E).
R1-Si-(OR2)3 (1 ) Si-(OR3)4 (2) In general formula (1 ), R1 is phenyl group or an alkyl group having 1-18 carbons, where the number of carbons in the alkyl group preferably is 1-14, and particularly preferably 1-9. If the number of carbons in the organic group indicated by R1 exceeds 18, when an organosilicate and/or a condensate thereof is used, the surface of the coating will not be hydrophilized because not enough surface orientation is yielded when the coating film forms, and good soil resistance is not obtained. Additionally, R2 in general formula (1 ) and R3 in general formula (2) are each an alkyl group having 1-6 carbons, and preferably is an alkyl group having 1-3 carbons. If an organosilicate and/or condensate thereof are used in which the number of carbons in the alkyl group indicated by R2 or R3 exceeds 6, the rate of hydrolysis will be slowed.
Specific examples of the above general formula (1 ) include trimethoxybutylsilane and trimethoxyethylsilane.
Specific examples of the above general formula (2) include tetrahydroxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilnae, and dimethoxydiethoxysilane. These can be used singly or in combinations of two or more.
Condensates of organosilicates can be branched or linear condensates obtained by condensing one or two or more of the organosilicates expressed by the aforementioned general formula (1 ) and general formula (2), and linear condensates with degree of condensation of 2-100 are preferred. It is undesirable for this degree of condensation to exceed 100, as the soil resistance effect becomes small and the workability of the coating is also decreased. It is particularly preferable that the degree of condensation is 2-50 in the organosilicate condensate used in the present invention. Examples of commercially available organosilicate condensates include MKC Silicate MS51 , MS56, MS57, and MS58B15 (trade names, manufactured by Mitsubishi Chemical Corp.), and Ethylsilicate 40, Ethylsilicate 48 and EMS-485 (trade names, manufactured by Colcoat Co., Ltd.). The content proportions of ingredients (C)-(F) in the resin composition in the above base paint A1 are preferably such that the content of ingredient (C) by solids content is 0.1-5 parts by mass, the content of ingredient (D) is 1-30 parts by mass by solids content, the content of ingredient (E) is 0.5-10 parts by mass by solids content, and the content of ingredient (F) is 0.1-10 parts by mass by solids content, each per 100 parts by mass of the total solids content of ingredient (A) and ingredient (B).
If the content of ingredient (C) is less than 0.1 parts by mass, sufficient curing is not achieved and solvent resistance decreases, and if it exceeds 5 parts by mass, excess tertiary amine compound decreases the stability of the hydrophilizing agent. If the content of ingredient (D) is less than 1 part by mass, a stable wrinkle finish patter cannot be formed, and if it exceeds 30 parts by mass, the workability is decreased.
If the content of ingredient (E) is less than 0.5 parts by mass, sufficient surface hydrophilizing cannot occur and good soil resistance is not obtained, and if it exceeds 10 parts by mass, water resistance decreases.
If the content of ingredient (F) is less than 0.1 parts by mass, dehydrating action is insufficient and stability of the hydrophilizing agent is insufficient, and if it exceeds 10 parts by mass, pattern stability is not obtained in the wrinkle finish. The above base paint A1 may also contain one or more of inorganic pigments, such as titanium dioxide, carbon black, iron oxide, and chrome yellow, organic pigments, such as cyanine green and cyanine blue, metal powder, such as aluminum powder or copper powder, extender pigments, such as barium sulfate, talc, and mica, additives, such as dispersing agents, leveling agents, antisettling agents, and foam breakers, and solvents.
The paint composition A2 in which particulate silica is separately added to the base paint A1 can be adjusted to an applicable viscosity using an organic solvent, and then applied by a common coating formation method, such as fine brushing, French polishing, brush application, roller application, and spray application.
The above paint composition A2, after application to a metal substrate, can be heat cured, e.g. with an infrared dryer, carbon dryer, far infrared dryer, near infrared dryer, or hot air dryer. Further, the dryer is not specifically limited as long as it able to raise the surface temperature.
It is preferred to heat the surface of the coating obtained by applying the above paint composition A2 to a temperature of 95-300°C. Not less than 100°C and not more than 250°C is even more preferable. There are cases where the coating appearance will deteriorate if the surface temperature of the coating is less than 95°C.
The described method is used on metal substrates, particularly on ferrous substrates. Preferably, the metal substrate is a steel sheet or a steel panel.
Production example 1 : Production of ingredient (A) - hydroxyl group-containing polyester resin
A reactor vessel equipped with a reflux tube filled with a stainless steel filler and equipped with a Dean-Stark trap, a thermometer, and a stirring apparatus was charged 22.6 parts by mass isophthalic acid, 12.5 parts by mass adipic acid, 19.0 parts by weight neopentyl glycol, and 7.4 parts by mass trimethylolpropane and heated to 150°C, and then heated over 2 hours to 200°C, then heated over 1 hour to 230°C, and a dehydration condensation reaction was performed while adding 2.5 parts by mass xylene until the resin acid value reached 10, after which, the reaction temperature was decreased to 140°C and 36.0 parts by mass cyclohexanone were added to yield an apparently transparent, hydroxyl group-containing polyester resin solution. The characteristics of the resulting hydroxyl group-containing polyester resin solution were Gardner viscosity Y at 25°C, with 60.3% by mass heat residue. Additionally, the number average molecular weight by GPC was 3,250 in terms of polystyrene molecular weight, and the hydroxyl value was 78 mgKOH/g. Production example 2: Production of ingredient (C) - sulfonic acid compound blocked by tertiary amine compound
72 parts by mass of an isopropanol solution of 50% by mass para-toluene sulfonic acid (PTSA) and 12.7 pars by mass triethylamine (TEA, boiling point 89.4°C) were blended in a reaction vessel, and then stirred to overall uniformity to yield a blocked sulfonic acid compound (TEA/PTSA molar ratio (theoretical) = 0.6).
Production example 3: Production of base paint A1 -1
80 parts by mass solids content of the hydroxyl group-containing polyester resin shown in production example 1 , 80 parts by mass titanium oxide, and 30 parts by mass of a mixed solution (solution of a 50/50 by mass parts mixture of Solvesso #100 (manufactured by Esso Corp., trade name: aromatic petroleum naphtha) and cyclohexanone) were dispersed using a sand mill until the pigment particle diameter reached 10 μιτι. Then, the various ingredients except for the solvent were admixed with the other ingredients listed in Table 1 at the solids content ratios shown therein to yield base paint A1 -1 . The viscosity of the resulting base paint A1 -1 was adjusted using the aforementioned mixed solvent to a No. 4 Ford cup viscosity of 120 ± 10 seconds (25°C). Further, the additive amounts of the ingredients listed in Table 1 are in parts by mass (indicated as solids content).
[0052]
Production of base paints A1 -2, A1 -3
Base paints A1 -2 and A1 -3 were obtained by the same method as in production example 3, using the ingredients listed in Table 1 . The viscosities of the resulting base paints A1 -2 and A1 -3 were adjusted using the aforementioned mixed solvent to a No. 4 Ford cup viscosity of 120 ± 10 seconds (25°C).
Embodiment 1 5 parts by mass of particulate silica A were gradually added and uniformly blended, while stirring 100 parts by mass of base paint (A1 -1 ) with a dispersion mixer, to make the paint composition A2 of embodiment 1 .
Embodiments 2-27, comparative examples 1-14 The base paints A1 and particulate silicas listed in Table 2 and Table 3 were variously uniformly blended by the same method as in embodiment 1 to make the paint compositions A2 of embodiments 2-27 and comparative examples 1- 14. Further, resin particles and inorganic glass particles were used in comparative examples 5 and 6, respectively, instead of particulate silica. Preparation of standard coating 1
An epoxy resin primer (Precolor Primer HP301 , trade name, manufactured by BASF Japan Ltd.) was applied by roll coater to a dried coating film thickness of 5 μιτι onto a 0.27 mm-thick Galvalume steel sheet treated with a chromate film, and the paint was then baked under conditions of 40 seconds to a PMT (peak metal temperature) of 200°C. Next, base paint A1 -1 was applied by roll coater to a dried coating film thickness of 20 μιτι and baked under conditions of 50 seconds to a PMT of 230°C to yield standard coating 1 .
Preparation of standard coating 2
Standard coating 2 was prepared by the same method as in the preparation of standard coating 1 , using base paint A1 -2.
Preparation of standard coating 3
Standard coating 3 was prepared by the same method as in the preparation of standard coating 1 , using base paint A1 -3.
Preparation of test pieces An epoxy resin primer Precolor Primer HP301 was applied by roll coater to a dried coating film thickness of 5 μιτι onto a 0.27 mm-thick Galvalume steel sheet treated with a chromate film, and then baked under conditions of 40 seconds to a PMT (peak metal temperature) of 200°C. Next, viscosities of the paint composition A2 in embodiments 1-27 and comparative examples 1-14 were adjusted using the aforementioned mixed solvent to a No. 4 Ford cup viscosity of 20 ± 5 seconds (25°C) using a mixed solution (solution of a 50/50 by mass parts mixture of Solvesso #100 (manufactured by Esso Corp., trade name: aromatic petroleum naphtha) and cyclohexanone), and then applied by air sprayer at an oblique angle to a dried coating film thickness of 0-25 μιτι and baked using a hot drying hearth under conditions of 50 seconds to the PMT temperatures listed in Table 2 and Table 3. The evaluation results are shown in Table 2 and Table 3.
Table 1
Figure imgf000019_0001
Table 2
Table 2 (1/2) Embodiment
1 2 3 4 5 6 7 8 9 10 1 1 12 13
Base paint A1 -1
(parts by mass 100 100 100 100 100 100 100 100 100
(solids))
Base paint A1 -2
(parts by mass 100 100 100 100 (solids))
Base paint A1 -3
(parts by mass
(solids))
Particulate
silica A *1 5 0.2 7 15 19 5 5 5 0.2 7 15 (parts by mass)
Particulate
5
silica B *2
Figure imgf000020_0001
Table 2 (2/2) Embodiment (cont.)
14 15 16 17 18 19 20 21 22 23 24 25 26 27
Base paint A1 - 1 (parts by
mass (solids))
Base paint A1 - 2 (parts by 100 100 100 100 100
mass (solids))
Base paint A1 - 3 (parts by 100 100 100 100 100 100 100 100 100 mass (solids))
Particulate
silica A *1 19 5 0.2 7 15 19
(parts by mass)
Particulate
silica B *2 5 5
(parts by mass)
Particulate
silica C *3 5 5
(parts by mass)
Particulate
silica D *4 5 5
(parts by mass)
Particulate 5 5
Figure imgf000021_0001
Table 3
Figure imgf000021_0002
mass)
Figure imgf000022_0001
s te
Notes for Table 1 -Table 3 are below. The particulate silicas below are aggregates in which several 10 nm primary grains are aggregated.
*1 Particulate silica A: Syloid C807 (trade name, manufactured by Grace Japan Ltd., average particle diameter 7 μιτι)
*2 Particulate silica B: SFP-20M (trade name, manufactured by Denka Co., Ltd., average particle diameter 0.3 μιτι)
*3 Particulate silica C: #200 (trade name, manufactured by Maruto Testing Machine Co., average particle diameter 36 μιτι) *4 Particulate silica D: Syloid C803 (trade name, manufactured by Grace Japan Ltd., average particle diameter 3 μιτι) *5 Particulate silica E: #250 (trade name, manufactured by Maruto Testing Machine Co., average particle diameter 22 μιτι)
*6 Particulate silica F: gicaster (43-00-501 ) (trade name, manufactured by Corefront Corp., average particle diameter 0.05 μιτι) *7 Particulate silica G: #100 (trade name, manufactured by Maruto Testing Machine Co., average particle diameter 50 μιτι)
*8 Resin particles: MBX-20 (trade name, manufactured by Sekisui Plastics Co., Ltd., average particle diameter 20 μιτι)
*9 Inorganic glass particles: EGB731 (trade name, manufactured by Potters Ballotini Co., Ltd., average particle diameter 20 μιτι) (Inorganic glass particles consist of individual particles and are not comprised of aggregates)
*10 Melamine resin: Cymel 303 (hexa(methoxymethyl)melamine, trade name, manufactured by Japan SciTech Industries, Ltd., solids content 100% by mass)
*1 1 Dehydrating agent: OFE (orthoformic acid ethyl ester, trade name, manufactured by Nippoh Chemicals Co., Ltd., solids content 98% by mass)
*12 Silicate compound: MKC Silicate MS56 (methylsilicate, trade name, manufactured by Mitsubishi Chemical Corp.)
*13 Organic resin particles: MBX-30 (crosslinked poly(methyl methacrylate), trade name, Sekisui Plastics Co., Ltd., average particle diameter 30 μιτι) *14 Inorganic fibers: Surfa-Strand REV4 (trade name, manufactured by Nippon Glass Co., Ltd., average diameter 13 μιτι, average length 70 μιτι)
Additionally, the coating films obtained with the paint composition A2 of the present invention was evaluated by the following method.
Coating appearance The coating appearance was visually evaluated according to the following criteria by comparing the wrinkle finish patterns of two test samples comprising an evaluation site 1 where the dried film thickness of the wrinkle coating on the test sample was 20 ± 1 μιτι and an evaluation site 2 where said dried film thickness was 5 ± 1 μιτι with the wrinkle finish pattern of a standard paint coating.
Θ : Very good (Visible difference from standard paint coating was minimal and not obvious)
O : Good (Visible difference from standard paint coating was noticeable, but not obvious)
Δ : Poor (Visible difference from standard paint coating was noticeable and obvious) x : Very poor (Visible difference from standard paint coating was greatly noticeable and very obvious)

Claims

Claims
1 . A method of forming a wrinkle finish coating on a metal substrate at an installation site with the appearance similar to that of a wrinkle finish formed by applying a base paint A1 in a factory, in which method a coating composition A2 is obtained by adding 0.1-20 parts by mass of silica particulate with an average particle diameter of 0.1 μιτι-40 μιτι per 100 parts by mass of the solids in base paint A1 to the base paint A1 , the coating composition A2 is applied to the metal substrate at the installation site of said component that is the object of wrinkle finish coating, and then heat-cured.
The method according to claim 1 , wherein the coating composition A2 applied by brush and/or by spray coater to the metal substrate at the installation site.
The method according to claim 1 or 2, wherein the base paint A1 contains (A) a hydroxyl group-containing polyester resin with a hydroxyl group value of 5-200 mgKOH/g and a number average molecular weight of 500- 20000, (B) a hexakis(alkoxymethyl)melamine resin, and (C) a blocked sulfonic acid compound that has been blocked with a tertiary amine compound with a boiling point of 50-300°C.
The method according to claim 3, comprising further (D) at least one selected from (a) organic resin particles with an average particle diameter of 40 μιτι or less, (b) inorganic glass particles with an average particle diameter of 100 μιτι or less, and (c) inorganic fibers with an average length of 300 μιτι or less. The method according to 4, wherein the base paint A1 further comprises
(E) a silicate compound, which is selected from an organosilicate expressed by general formula (1 )
R1-Si-(OR2)3 (1 )
wherein, R1 is phenyl group or an alkyl group having 1-18 carbons and R2 is an alkyl group having 1-6 carbons, an organosilicate expressed by general formula (2)
Si-(OR3)4 (2)
wherein, R3 is an alkyl group having 1-6 carbons,
a condensate of either one or both of the aforementioned two
organosilicates, or a silicate compound that is a partial hydrolysate of said condensate, and
(F) a dehydrating agent.
The method according to any one of claims 3-5, wherein the sulfonic acid compound (C) has been blocked with a tertiary amine compound in a molar ratio amine compound to sulfonic acid of 0.2-0.9
The method according to any one of claims 3 to 6, wherein the mass ratio of ingredient (A) and ingredient (B) is 60/40-90/10 by solids content.
A method of repairing a damaged wrinkle finish coating on a metal substrate, which coating has been obtained by curing a base paint A1 in a factory, said method comprising preparing a coating composition A2 from the base paint A1 by adding to it 0.1-20 parts by mass of silica particulate with an average particle diameter of 0.1 μιτι-40 μιτι per 100 parts by mass of the solids in the base paint A1 , applying the coating composition A2 to the damaged area of the metal substrate to be repaired at the installation site and heat-curing. The method according to claim 8, wherein the base paint A1 contains (A) a hydroxyl group-containing polyester resin with a hydroxyl group value of 5-200 mgKOH/g and a number average molecular weight of 500-20000, (B) a hexakis(alkoxymethyl)melamine resin, (C) a blocked sulfonic acid compound that has been blocked with a tertiary amine compound with a boiling point of 50-300°C.
The method according to claim 9, further comprising (D) at least one selected from (a) organic resin particles with an average particle diameter of 40 μιτι or less, (b) inorganic glass particles with an average particle diameter of 100 μιτι or less, and (c) inorganic fibers with an average length of 300 μιτι or less.
1 1 . The method according to claim 10, wherein the base paint A1 further
comprises (E) a silicate compound, which is selected from an
organosilicate expressed by general formula (1 )
R1-Si-(OR2)3 (1 )
wherein, R1 is phenyl group or an alkyl group having 1-18 carbons and R2 is an alkyl group having 1-6 carbons, an organosilicate expressed by general formula (2)
Si-(OR3)4 (2)
wherein, R3 is an alkyl group having 1-6 carbons,
a condensate of either one or both of the aforementioned two
organosilicates, or a silicate compound that is a partial hydrolysate of said condensate, and
(F) a dehydrating agent.
12. The method according to claim 1 1 , wherein the sulfonic acid compound (C) has been blocked with a tertiary amine compound in a molar ratio amine compound to sulfonic acid of 0.2-0.9.
13. The method according to claim 9 to 12, wherein the mass ratio of ingredient (A) and ingredient (B) is 60/40-90/10 by solids content.
14. The method according to any one of claims 1 -1 1 , wherein the metal substrate is a steel sheet or a steel panel.
PCT/EP2017/059790 2016-04-28 2017-04-25 Method of forming wrinkle finish coating on a metal substrate WO2017186714A1 (en)

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