WO2007144950A1 - 被覆鋼板 - Google Patents
被覆鋼板 Download PDFInfo
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- WO2007144950A1 WO2007144950A1 PCT/JP2006/312052 JP2006312052W WO2007144950A1 WO 2007144950 A1 WO2007144950 A1 WO 2007144950A1 JP 2006312052 W JP2006312052 W JP 2006312052W WO 2007144950 A1 WO2007144950 A1 WO 2007144950A1
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- WIPO (PCT)
- Prior art keywords
- steel sheet
- coating
- compound
- film
- resin
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
-
- 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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/08—Copolymers of ethene
- C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09D123/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0869—Acids or derivatives thereof
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
Definitions
- the present invention relates to a coated steel sheet.
- JP-A-2000-273659 discloses a reaction product of a monovalent metal, an ionomer neutralized with a divalent metal, a polyolefin resin neutralized with an amine, and an epoxy compound.
- a coated steel sheet treated with a metal surface antifouling treatment agent containing silica, an epoxy compound, a silane coupling agent, and thiosulfate ion is described.
- Such a treated steel sheet has improved alkali resistance and paint adhesion compared with the coated steel sheet disclosed in Japanese Patent Application Laid-Open No. 11 71536, as the silane coupling agent is added afterwards.
- the adhesion to the metal material is insufficient.
- JP-A-2003-155451 describes a coated steel sheet treated with an aqueous coating agent containing a water-dispersible resin, silica particles, and an organic titanate compound.
- an aqueous coating agent containing a water-dispersible resin, silica particles, and an organic titanate compound.
- the physical properties of the coating such as adhesion to the base material and resistance to press oil may be insufficient, and a coated steel sheet with further improved performance is required.
- Japanese Patent Application Laid-Open No. 2005-281863 describes a coated steel sheet in which a film containing a crosslinked resin matrix and an inorganic antifungal agent is formed.
- the present invention has an object of providing a coated steel sheet having improved properties such as adhesion to a base material and resistance to press oil.
- the present invention is a coated steel sheet coated with a composite coating, wherein the composite coating has an average particle size of 20 to 100 nm and has an silanol group and Z or alkoxysilyl group.
- 0.5 to 3 g / m 2 is a coated steel sheet.
- the silicon oxide particles (B) are 5 to 100% by mass with respect to the resin particles (A), and the content of titanium atoms is 0.05 to It is preferably 3% by mass.
- the composite film further includes at least one selected from the group consisting of a phosphate compound, a thiocarbonyl compound, niobium oxide, and a guanidine compound.
- a film in which the compound (D) is complexed is preferred.
- the coated steel sheet of the present invention has an average particle diameter of 20 to:! OOnm, silanol group and Z or alkoxysilyl group ethylene monounsaturated carboxylic acid copolymer resin particles (A), average particle diameter force to 50 nm It has a film in which the silicon oxide particles (B) and the organic titanium compound (C) are combined.
- the film in which the above (A) to (C) are combined has excellent properties such as corrosion resistance, solvent resistance, alkali resistance, and coating adhesion.
- the use of resin particles (A) having an average particle diameter of 20 to 100 nm increases the uniformity and denseness of the film, so that remarkable improvements in substrate adhesion and press oil resistance are observed. .
- the resin particles (A) include, for example, a copolymer resin of ethylene and an unsaturated carboxylic acid such as acrylic acid, methacrylic acid or maleic anhydride, and an alkali metal such as sodium hydroxide or potassium hydroxide.
- examples thereof include resin particles obtained by allowing a silane compound to act on a water-dispersed resin solution neutralized with hydroxide, ammonia water or organic amines and dispersed in water.
- resin particles obtained by allowing a silane compound or the like to act on a water-dispersed resin solution of an ethylene-methacrylic acid copolymer resin neutralized with a base can be made into fine particles and form a high-performance film. It is preferable in that it can.
- the ethylene-methacrylic acid copolymer resin is preferably one containing a methacrylic acid content of 10 to 30% by mass. If necessary, it may contain other monomers, but the amount used is preferably 10% by mass or less.
- the ethylene-methacrylic acid copolymer resin can be produced by a known method such as polymerization using a high-pressure low-density polyethylene production apparatus.
- the resin particles (A) have a silanol group and / or an alkoxysilyl group. By having the above functional group, it can react with the silicon oxide particles (B) and the organic titanium compound (C) to form a composite film, improving the adhesion to the substrate, resistance to press oil, etc. The ability to do good S.
- the alkoxysilyl group in the alkoxysilyl group is not particularly limited, and examples thereof include a trimethoxysilyl group, a dimethoxysilyl group, a methoxysilyl group, a triethoxysilyl group, a diethoxysilyl group, and an ethoxysilyl group.
- the functional group can be obtained by reacting a silane compound or the like with an aqueous dispersion of the ethylenically unsaturated carboxylic acid copolymer resin.
- the silane compound is preferably an epoxy group-containing silane compound.
- the epoxy group-containing silane compound examples include 3-glycidoxydoxypropyltriethoxysilane, 3-glycidoxypropylmethyljetoxysilane, 2- (3,4_epoxycyclohexenole) Examples include ethynoletrimethoxysilane. These may be used alone or in combination of two or more.
- the blending amount it is preferable to react the epoxy group-containing silane compound in an amount of 0.:! To 30 mass% with respect to the solid content of the aqueous dispersion resin liquid. More preferably, it is in the range of 1 to 10% by mass. This arrangement If the total amount is less than 0.1% by mass, the alkali resistance, solvent resistance, paint adhesion, etc.
- the reaction with the silane compound may be carried out in combination with an epoxy compound.
- an epoxy compound When an epoxy compound is used in combination, the affinity with an organic resin is increased, and therefore, when a top coat is applied to the composite film, it may be advantageous for improving the adhesion of the film.
- the epoxy compound include sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, glyceryl polyglycidyl ether, diglyceryl polyglycidyl ether, propylene glycol glycol diglycidyl ether, triglycidinoretris (2-hydroxy ester). Til) isocyanurate, bisphenolanol A glycidyl ether, hydrogenated bisphenol A diglycidyl ether, and the like. These may be used alone or in combination of two or more.
- the resin particles (A) have an average particle diameter of 20 to:! OOnm.
- the average particle size can be measured with a particle size measurement device using a dynamic light scattering method, such as FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).
- the above average particle size value is obtained by diluting an aqueous dispersion of resin particles (A) with ion-exchanged water to a concentration suitable for measurement by the above apparatus, and measuring at a liquid temperature of 25 ° C. It is. If the average particle size by the above method is less than 20 nm, problems such as poor workability and corrosion resistance occur due to high viscosity and excessive hydrophilicity. When the average particle size exceeds SlOOnm, there arises a problem that, in terms of film performance, adhesion to the substrate, press oil resistance, and the like deteriorate.
- the resin particles (A) have an average particle size in the above range by adjusting the neutralizer species, water dispersion conditions, silane compound species, silane compound reaction conditions, epoxy compound species, epoxy compound reaction conditions, and the like. Can fit inside.
- the neutralizing agent species the use of an alkali metal, which is preferably used to reduce the average particle size, is preferably used in combination with an alkali metal.
- water dispersion conditions it is preferable to carry out for a long time at a high temperature immediately before boiling and at a high stirring speed.
- the target particle size can be obtained by taking 4 hours or more at a rotation speed of 500 revolutions / minute or more.
- a silane compound and an epoxy compound It is preferable to carry out the reaction under heating, which is preferably water-insoluble and preferably has a low molecular weight.
- the above-mentioned oxide silicon particles (B) preferably have an average particle size of about 5 to 50 nm, and can be appropriately selected and used, such as colloidal silica or fumed silica.
- colloidal silica or fumed silica include Snowtex N, Snowtex C (Nissan Chemical Industry), Adelite AT-20N, AT-2 OA (Asahi Denka Kogyo), Cataloid S-20L, Cataloid SA (Catalytic Chemical Industry), etc. . These may be used alone or in combination of two or more.
- organic titanium compound (C) examples include dipropoxybis (triethanolaminato) titanium, dipropoxybis (diethanolaminato) titanium, dibutoxybis (triethanolaminato) titanium.
- examples thereof include titanium bis (monoammonium oxalate) and isopropyl tri (N-amidoethylaminoethyl) titanate. These may be used alone or in combination of two or more.
- the composite film is in a state where the resin particles (A), the silicon oxide particles (B), and the organic titanium compound (C) are bonded to each other. That is, the functional group on the surface of the resin particle, the functional group on the surface of the silicon oxide particle, and the functional group of the organotitanium compound (C) form a bond and are combined.
- the above bond is mainly due to the Si—OR group and / or Si—OH group of the resin particle (A), the Si—OH group on the surface of the silicon oxide particle (B), and the Ti ⁇ group of the organic titanium compound (C). And / or a bond formed by reaction of a Ti_OH group, which is considered to be a Si_O_Si bond, a Si_0_Ti_O_Si bond, or the like.
- These bonds provide an advantageous effect that organic resin particles and inorganic particles form chemically strong bonds.
- the particle diameters of the resin particles (A) and the silicon oxide particles (B) are within a specific range, the interparticle bonds are formed at a high density in the composite film.
- the composite coating may be a composite of at least one compound (D) selected from the group consisting of a phosphate compound, a thiocarbonyl compound, niobium oxide and a guanidine compound. This means that two or more phosphoric acid compounds, guanidine compounds, thiocarbonyl compounds and niobium oxides may be blended, or four of them may be blended.
- the composite film in addition to the essential components of the resin particles (A), the silicon oxide particles (B) and the organic titanium compound (C), a phosphoric acid compound, a thiocarbonyl compound, niobium oxide, and This means that at least one selected from the group consisting of guanidine compounds is compounded.
- the phosphoric acid compounds include phosphoric acids such as onoletrinic acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid, triammonium phosphate, diammonium hydrogen phosphate, trisodium phosphate, and hydrogen phosphate.
- phosphoric acids such as onoletrinic acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid, triammonium phosphate, diammonium hydrogen phosphate, trisodium phosphate, and hydrogen phosphate.
- phosphates such as disodium. These may be used alone or in combination of two or more.
- phosphate ions can passivate by forming a phosphate layer on the surface of the metal substrate, thereby improving the antifungal property.
- the thiocarbonyihu compound, niobium oxide, and guanidine compound are particularly effective in preventing white tint such as galvanized steel sheets, like the chromium compounds conventionally used for imparting corrosion resistance.
- the thiocarbonyl compound is represented by the following general formula (1).
- X and Y are the same or different and represent H, OH, SH or NH, or substituted
- It may have OH, SH or NH as a group, and 101, 1 NH-, 1 S-,
- — Represents a hydrocarbon group having 1 to 15 carbon atoms that may contain —CO— or —CS—, and X and Y may combine to form a ring.
- the thiocarbonyl compound represented by the general formula (1) is a thiocarbonyl group represented by the following formula (I):
- a thiocarbonyl group having a nitrogen atom or an oxygen atom represented by the following formula (II) is preferred.
- a compound that can form a thiocarbonyl group-containing compound in an aqueous solution or in the presence of an acid or an alkali can also be used.
- the thiocarbonyl compound include the following formula ( ⁇ ⁇ )
- Thiourea and derivatives thereof for example, methylthiourea, dimethylthiourea, trimethylthiourea, ethylthiourea, jetylthiourea, 1,3-dibutylthiourea, phenylthiourea, diphenylthiourea, 1, Examples include 3-bis (dimethylaminopropyl) 2-thiourea, ethylenethiourea, propylenethiourea and the like.
- carbothioic acids and salts thereof such as thioacetic acid, thiobenzoic acid, dithioacetic acid, sodium methyldithiocarbamate, sodium dimethyldithiocarbamate, triethylamamine dimethyldithiocarbamate, Sodium tildithiocarbamate, pentamethylenedithiocarbamate piperidine salt, pipecolyldithiocarbamate Examples include pipecoline salt and potassium o-ethylxanthate.
- thiocarbonyl compounds may be used alone or in combination of two or more.
- the niobium oxide is preferably niobium oxide colloidal particles.
- a film in which niobium oxide colloidal particles are combined can be formed, and the corrosion resistance can be further improved. Since the niobium oxide colloidal particles have a smaller average particle diameter and a more stable coating containing niobium oxide is formed, it is possible to stably impart antifungal properties to the object to be treated. More preferable.
- niobium oxide colloidal particles are particles in which oxides of niobium are dispersed in water in the form of fine particles.
- niobium oxide is not formed strictly, and an intermediate state between niobium hydroxide and niobium oxide is used. It may be in an amorphous state.
- niobium oxide sol produced by a known method can be used as the niobium oxide particles to be added to the aqueous coating used for forming the composite film.
- the niobium oxide sol is not particularly limited. For example, it is manufactured by a known method described in JP-A-6-321543, JP-A-8-143314, JP-A-8-325018, or the like. Etc. Also, niobium oxide sol commercially available from Taki Chemical Co., Ltd. can be used.
- the niobium oxide colloidal particles preferably have an average particle size of lOOnm or less.
- the average particle size is preferably 2 to 50 nm, more preferably force S, and more preferably 2 to 20 nm.
- the smaller the average particle size the more stable and dense a film containing niobium oxide is formed, and thus it is possible to stably impart antifungal properties to the object to be processed, and more preferable.
- the average particle size of the niobium oxide colloidal particles can be measured using a particle size measuring device using a dynamic light scattering method, such as FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).
- the guanidine compound is represented by the following formula (2).
- X 'and Y' are the same or different, and ⁇ , ⁇ , a phenyl group, or methylphenol
- Nyl group (tolyl group) power or ⁇ , ⁇ , phenyl group or methyl as a substituent
- guanidine compound examples include guanidine, aminoguanidine, guanylthiourine, 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide, 1,3-diphenylguanidine, and the like. It can.
- the above guanidine compounds may be used alone or in combination of two or more.
- the silicon oxide particles (B) are preferably 5 to 100% by mass with respect to the resin particles (A). If it is less than 5% by mass, the hardness and corrosion resistance of the film formed on the surface of the steel material may be lowered. If it exceeds 100% by mass, the film-forming property and water resistance may be lowered. More preferably, it is 10-50 mass%.
- the composite film preferably has a titanium atom content of 0.05 to 3% by mass with respect to 100% by mass of the total amount of the film. If it is less than 0.05% by mass, the components in the formed film are not sufficiently combined, and the film performance may be deteriorated. If it exceeds 3% by mass, the hydrophilicity of the film may become too high and the film performance may deteriorate, or the bath stability of the aqueous coating agent used may decrease. More preferably, it is 0.2 to 2% by mass.
- the content of the phosphate group is preferably 0.01 to 5% by mass in 100% by mass of the film. If it is less than 01% by mass, the corrosion resistance is insufficient, and if it exceeds 5% by mass, the aqueous dispersion resin used may gel and become unapplicable. More preferably, it is 0.05 to 3% by mass.
- the content of the thiocarbonyl compound is preferably 0.01 to 5% by mass in 100% by mass of the film.
- the amount is less than 01% by mass, the corrosion resistance becomes insufficient.
- the amount exceeds 5% by mass the corrosion resistance becomes saturated and becomes uneconomical. It may become impossible. More preferably, it is 0.05 to 5% by mass.
- the content of the niobium oxide is preferably 0.01 to 5% by mass in terms of Nb 2 O in 100% by mass of the film.
- the content of the guanidine compound is preferably 0.01 to 5% by mass in 100% by mass of the film.
- the corrosion resistance is insufficient. If the amount exceeds 5% by mass, the corrosion resistance becomes saturated and uneconomical. There is. More preferably, it is 0.05 to 3% by mass.
- the composite film may contain other components in addition to the above (A) to (D).
- a lubricant for example, conventionally known lubricants such as fluorine-based, hydrocarbon-based, fatty acid amide-based, ester-based, alcohol-based, metal stalagmite-based, and inorganic-based lubricants can be used.
- the pigment include titanium oxide (TiO), zinc oxide (ZnO), calcium carbonate (CaCO), barium sulfate (BaSO),
- Noremina Al O
- kaolin clay carbon black
- iron oxide FeO, Fe O
- the composite film can be formed by treating the surface of the base material with a coating material for steel material containing components necessary for forming the film.
- the steel coating material is preferably water-based.
- the aqueous coating material for steel materials for example, an aqueous dispersion of the neutralized product of the ethylene monounsaturated carboxylic acid copolymer, a silane compound, and an epoxy compound used as necessary Resin particles (A), silicon oxide particles (B), organotitanium compounds (C) obtained by reacting with the above, and phosphoric acid compounds, thiocarbonyl compounds, niobium oxides used as necessary And those containing at least one selected from the group consisting of guanidine compounds.
- the aqueous coating agent for steel materials is not particularly limited as long as these components are blended, and for example, it can be produced as follows (1).
- (1) The aqueous dispersion of the neutralized product of the above-mentioned ethylenically unsaturated carboxylic acid copolymer resin is appropriately heated while stirring, and the reaction is carried out by adding a silane compound and an epoxy compound to be used if necessary.
- An aqueous composition is prepared by blending the resulting resin particles (A) with the silicon oxide particles (B) and the organic titanium compound (C), and if necessary, a phosphoric acid compound, a thiocarbonyl compound, At least one compound (D) selected from the group consisting of niobium oxide and guanidine compounds is added.
- a solvent or a leveling agent may be used.
- the solvent is not particularly limited as long as it is generally used in paints, and examples thereof include alcohol-based, ketone-based, ester-based, ether-based hydrophilic solvents and silicone-based leveling agents. it can.
- Formation of the composite film using the above-described aqueous coating material for steel can be performed by applying the above-mentioned aqueous coating material for steel material to the surface of the steel material.
- the above-described aqueous coating agent for steel is applied to the article to be degreased as necessary.
- the coating method is not particularly limited, and commonly used roll coating, air spray, airless spray, immersion, etc. can be appropriately employed.
- the heating temperature of the object to be coated is 50 to 250 ° C, preferably 100 to 220 ° C.
- the drying time for heat drying after coating is preferably 1 second to 5 minutes.
- the composite film has a film amount of 0.5 to 3 gZm2.
- the amount of the film is less than 0.5 gZm 2 , there arises a problem that the corrosion resistance is lowered.
- the amount of the film exceeds 3 gZm 2 , there arises a problem that the adhesion of the substrate is lowered.
- the coated steel sheet of the present invention can also be used by forming a coating film by applying a top coating onto the composite film.
- the top coat include paints made of acrylic resin, acrylic modified alkyd resin, epoxy resin, urethane resin, melamine resin, phthalic acid resin, amino resin, polyester resin, vinyl chloride resin, and the like.
- the film thickness of the coating film of the top coating is appropriately determined depending on the use of the antifouling metal product, the type of the top coating used, and the like, and is not particularly limited. Usually, it is about 5 to 300 / m, more preferably about 10 to 200 / m.
- the top coat can be formed by applying a top coat onto a film formed by the above-described aqueous coating material for steel, heating, drying and curing.
- the drying temperature and time is a force that can be adjusted as appropriate according to the type of top coat to be applied, the film thickness of the coating film, etc. Normally, the drying time is preferably 50 to 250 ° C. Is preferably 5 minutes to 1 hour.
- a method for applying the top coating material a conventionally known method can be used depending on the coating form.
- Examples of the steel material in the present invention include a zinc-plated steel sheet, a zinc-nickenore-plated steel sheet, a zinc-iron-plated steel sheet, a zinc-chrome-plated steel sheet, a zinc-aluminum-plated steel sheet, and a zinc-titanium-plated steel Steel sheets, zinc-magnesium plated steel sheets, zinc-manganese plated steel sheets, zinc-aluminum-magnesium-plated steel sheets, zinc-aluminum-magnesium silicon-plated steel sheets such as silicon-plated steel sheets, and small amounts of different metals in these plating layers Cobalt, molybdenum, tungsten, nickel, titanium, chromium, aluminum, manganese, iron, magnesium, lead, bismuth, antimony, tin, copper, cadmium, arsenic, etc.
- the present invention can be applied to multi-layer plating in combination with the above plating and other types of plating such as iron plating, iron plating, nickel plating, and cobalt plating. Furthermore, it can be applied to aluminum or aluminum alloy plating.
- the plating method is not particularly limited, and may be any known method such as an electric plating method, a melting plating method, a vapor deposition plating method, a dispersion plating method, or a vacuum plating method.
- a coated steel sheet in which a coating film is formed by applying the above aqueous coating material for steel material to the surface of the steel material is provided with corrosion resistance, substrate adhesion, solvent resistance, alkali resistance, and press oil resistance. Furthermore, what forms a coating film by apply
- coating a top-coat paint has a favorable coating adhesiveness with the film and top coat film formed in the steel plate.
- a coated steel sheet having an organic-inorganic composite film excellent in substrate adhesion and press oil resistance without impairing corrosion resistance, solvent resistance, alkali resistance, and coating adhesion. can get.
- Ethylene-methacrylic acid copolymer resin (20% methacrylic acid content) in the reaction vessel, 3.7% sodium hydroxide, 6.3 for the resin. /. 25% ammonia water (concentration 25%) and deionized water were added and stirred at 95 ° C. for 6 hours to obtain an aqueous dispersion resin solution having a solid content of 20%.
- an aqueous dispersion resin solution having a solid content of 20%.
- 0.6% pentaerythritol polyglycidyl ether and 1.2% ⁇ -glycidoxypropyltriethoxysilane was added to this water-dispersed resin solution, the mixture was reacted at 85 ° C for 2 hours.
- An aqueous dispersion of resin particles (A_2) having a silanol group and Z or ethoxysilyl group having a solid content of 21% was obtained.
- the average particle size of the resin particles (A-2) measured in the same manner as described above was 84 nm.
- ethylene-methacrylic acid copolymer resin (methacrylic acid content 20%), ammonia water equivalent to 15.8% (concentration 25%) and deionized water, and 95 ° C
- the mixture was stirred for 2 hours to obtain an aqueous dispersion resin liquid having a solid content of 20%.
- an aqueous dispersion resin liquid having a solid content of 20%.
- An aqueous dispersion of resin particles (A-5) having a silanol group and / or methoxysilyl group having a solid content of 21% was obtained.
- the average particle size of the resin particles (A-5) measured in the same manner as above was 145 ⁇ m.
- a 2% aqueous solution of sodium lauryl sulfate was added to the reaction vessel and maintained at 80 ° C., and ammonium persulfate was charged to 0.3% with respect to the aqueous solution.
- the unsaturated monomer mixture composed of styrene, methyl methacrylate, 2-ethylhexyl acrylate, methacrylic acid and ⁇ -methacryloxypropyl trimethoxysilane in a mass ratio of 30: 34: 30: 2: 4.
- the dripping was started and the whole amount was charged evenly over 2 hours.
- the aqueous dispersion of the resin particles (A-1) is mixed with an aqueous dispersion of silicon oxide having an average particle diameter of 15 nm, dipropylbis (triethanolaminato) titanium, hydrogen ammonium phosphate, and thiourea.
- an aqueous composition having a solid content of 18% was prepared.
- Electrogalvanized steel sheet with a thickness of 0.8 mm (zinc adhesion amount: 20 g / m 2 ), 2% aqueous solution using alkaline degreasing agent (SurfCleaner 155, Nippon Paint Co., Ltd.) at 60 ° C 2 It was sprayed for minutes to degrease, washed with water and dried in warm air. After cooling, the above aqueous coating agent is applied to this degreased plate with a bar coater so that the dry film amount is lg / m 2 , and the steel plate temperature is reached using a hot air drying furnace with an atmospheric temperature of 500 ° C. A test plate was made by baking to a temperature of 180 ° C.
- alkaline degreasing agent SudfCleaner 155, Nippon Paint Co., Ltd.
- the end face part and back face part of the test plate were tape-sealed, and 5% saline was sprayed at 35 ° C., and the area ratio of white birch after 120 hours was evaluated according to the following evaluation criteria.
- ⁇ 10% or more and less than 30%
- absorbent cotton impregnated with ethanol is loaded 10 times with a load of 0.5 kgf / cm 2 (reciprocating), and absorbent cotton impregnated with kerosene is loaded 50 times with a load of 0.5 kgfZcm 2 (reciprocating).
- the film state after rubbing was evaluated according to the following evaluation criteria.
- Test plate made 10 days after adjustment with test plate made immediately after adjustment of water-based coating agent Alkaline degreasing agent (Surf Cleaner 53, manufactured by Nippon Paint Co., Ltd.) at 55 ° C for 30 minutes with stirring
- Alkaline degreasing agent Sudf Cleaner 53, manufactured by Nippon Paint Co., Ltd.
- the coating state after the test plate was immersed in press oil (G6318SK, Nippon Tool Oil Co., Ltd.) at room temperature for 24 hours was evaluated according to the following evaluation criteria.
- test plate was prepared and evaluated in the same manner as in Example 1 except that the formulation of the aqueous coating agent was changed as described in Table 1. The results are shown in Table 1.
- the coated steel sheet of the present invention has excellent properties in terms of physical properties such as corrosion resistance, substrate adhesion, solvent resistance, alkali resistance, press oil resistance, and coating adhesion. It became clear that it had.
- coated steel sheet of the present invention can be suitably used for automobiles, home appliances, building material products, and the like.
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020087029527A KR101298801B1 (ko) | 2006-06-15 | 2006-06-15 | 피복 강판 |
EP06757350A EP2037003B1 (en) | 2006-06-15 | 2006-06-15 | Coated steel sheet |
JP2008521062A JP4922295B2 (ja) | 2006-06-15 | 2006-06-15 | 被覆鋼板 |
BRPI0621823-7A BRPI0621823A2 (pt) | 2006-06-15 | 2006-06-15 | chapa de aço revestida |
US12/303,195 US8349446B2 (en) | 2006-06-15 | 2006-06-15 | Coated steel sheet |
PCT/JP2006/312052 WO2007144950A1 (ja) | 2006-06-15 | 2006-06-15 | 被覆鋼板 |
CN2006800549756A CN101466870B (zh) | 2006-06-15 | 2006-06-15 | 被覆钢板 |
TW095122590A TWI397609B (zh) | 2006-06-15 | 2006-06-23 | Coated steel plate |
MYPI20064063A MY149905A (en) | 2006-06-15 | 2006-08-30 | Coated steel sheet |
HK09111780.2A HK1135149A1 (en) | 2006-06-15 | 2009-12-15 | Coated steel sheet |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2006/312052 WO2007144950A1 (ja) | 2006-06-15 | 2006-06-15 | 被覆鋼板 |
Publications (1)
Publication Number | Publication Date |
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WO2007144950A1 true WO2007144950A1 (ja) | 2007-12-21 |
Family
ID=38831474
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2006/312052 WO2007144950A1 (ja) | 2006-06-15 | 2006-06-15 | 被覆鋼板 |
Country Status (10)
Country | Link |
---|---|
US (1) | US8349446B2 (ja) |
EP (1) | EP2037003B1 (ja) |
JP (1) | JP4922295B2 (ja) |
KR (1) | KR101298801B1 (ja) |
CN (1) | CN101466870B (ja) |
BR (1) | BRPI0621823A2 (ja) |
HK (1) | HK1135149A1 (ja) |
MY (1) | MY149905A (ja) |
TW (1) | TWI397609B (ja) |
WO (1) | WO2007144950A1 (ja) |
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WO2014125589A1 (ja) * | 2013-02-14 | 2014-08-21 | 千代田ケミカル株式会社 | 密着性向上剤 |
WO2015152187A1 (ja) * | 2014-04-04 | 2015-10-08 | 日本ペイント・サーフケミカルズ株式会社 | 亜鉛めっき鋼材用の金属表面処理剤、被覆方法及び被覆鋼材 |
JP2016520671A (ja) * | 2013-03-20 | 2016-07-14 | イ,ビョンソク | エチレン−(メタ)アクリル酸重合体の水分散性樹脂を利用した環境にやさしい紙コーティング剤の製造方法及びその用途 |
JP2020007606A (ja) * | 2018-07-06 | 2020-01-16 | 日本製鉄株式会社 | 表面処理鋼板及び表面処理鋼板の製造方法 |
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MX350444B (es) | 2012-12-19 | 2017-09-06 | Mabe S A De C V * | Recubrimiento de facil limpieza aplicado en superficies metalicas de acero inoxidable empleadas en la fabricacion de electrodomesticos. |
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JP6206373B2 (ja) * | 2014-10-17 | 2017-10-04 | 信越化学工業株式会社 | 有機ケイ素化合物の製造方法及び金属表面処理剤 |
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JP2020529500A (ja) * | 2017-07-31 | 2020-10-08 | クラレ・アメリカ・インコーポレイテッド | 接着特性が向上したアイオノマー中間層 |
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KR102382699B1 (ko) * | 2019-12-20 | 2022-04-04 | 주식회사 포스코 | 전기강판 접착 코팅 조성물, 전기강판 적층체 및 이의 제조 방법 |
EP4186952A1 (en) * | 2021-11-25 | 2023-05-31 | Henkel AG & Co. KGaA | Extrusion single layer coatings |
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Also Published As
Publication number | Publication date |
---|---|
HK1135149A1 (en) | 2010-05-28 |
US8349446B2 (en) | 2013-01-08 |
EP2037003B1 (en) | 2012-04-25 |
BRPI0621823A2 (pt) | 2011-12-20 |
MY149905A (en) | 2013-10-31 |
TW200801236A (en) | 2008-01-01 |
KR101298801B1 (ko) | 2013-08-22 |
TWI397609B (zh) | 2013-06-01 |
EP2037003A1 (en) | 2009-03-18 |
CN101466870A (zh) | 2009-06-24 |
US20100233470A1 (en) | 2010-09-16 |
KR20090018622A (ko) | 2009-02-20 |
JP4922295B2 (ja) | 2012-04-25 |
EP2037003A4 (en) | 2010-07-28 |
CN101466870B (zh) | 2011-01-26 |
JPWO2007144950A1 (ja) | 2009-10-29 |
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