WO2007126107A1 - 複層塗膜形成方法 - Google Patents
複層塗膜形成方法 Download PDFInfo
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- WO2007126107A1 WO2007126107A1 PCT/JP2007/059346 JP2007059346W WO2007126107A1 WO 2007126107 A1 WO2007126107 A1 WO 2007126107A1 JP 2007059346 W JP2007059346 W JP 2007059346W WO 2007126107 A1 WO2007126107 A1 WO 2007126107A1
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- coating film
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- colored
- polyester resin
- acid
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- 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
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- 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
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
- B05D7/572—Three layers or more the last layer being a clear coat all layers being cured or baked together
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
- C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
- C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- 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
- C09D5/002—Priming paints
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- 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
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/4423—Polyesters, esterified polyepoxides
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- 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
- B05D2202/00—Metallic substrate
- B05D2202/10—Metallic substrate based on Fe
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- 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
- B05D2508/00—Polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
- B05D7/577—Three layers or more the last layer being a clear coat some layers being coated "wet-on-wet", the others not
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- 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
- C08K3/011—Crosslinking or vulcanising agents, e.g. accelerators
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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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
Definitions
- a water-based first colored paint, a water-based second colored paint, and a clear paint are sequentially applied on an object to be coated, and the resulting three-layered multi-layer coating film is heated and cured simultaneously.
- the object of the present invention is to provide smoothness, sharpness, chipping resistance, water resistance by 3 C 1 B method. It is providing the method of forming the multilayer coating film excellent in property.
- the present inventors as a water-based first colored paint, in the coating process of a multilayer coating film by 3 C 1 B method, Polyester resin (X) containing a cyclohexane ring with a specific content, isocyanate group-containing compound (a), oxazoline group-containing compound (b), carpositimide group-containing compound (c), hydrazide group-containing compound (d ) And at least one curing agent (Y) selected from the group consisting of semi-carbazide group-containing compounds (e), it has excellent smoothness, sharpness, chipping resistance, water resistance, etc.
- the present inventors have found that a multilayer coating film can be formed and have completed the present invention.
- the present invention provides the following steps (1) to (4):
- step (3) A step of applying a clear paint (C) on the second colored coating film formed in step (2) to form a clear coating film
- the present invention provides a method characterized by being at least one compound selected from the group consisting of a hydrazide group-containing compound (d) and a semicarbazide group-containing compound (e).
- a multilayer coating film excellent in smoothness, sharpness, chipping resistance and water resistance is formed on an object by 3 C 1 B method. be able to.
- a benzene ring and a cyclohexane ring are contained in a molecule on the article to be coated, and the total content thereof is 1. o to 2.2 mo 1 / kg
- the polyester resin (X) used as the base resin in the first aqueous colored paint (A) contains a benzene ring and a hexane ring in the molecule, and the total content of these rings is 1 0 to 2.2 mo 1 / kg (resin solid content), preferably 1.2 to 2.0 mo 1 / kg (resin solid content), more preferably 1.4 to 1.9 mol lkg ( ⁇ (Solid fat content).
- the polyester resin (X) is generally 10 to 95 parts by mass, particularly 20 to 70 parts by mass, more particularly 2 based on 100 parts by mass of the resin solid content in the aqueous first colored paint (A). It is preferable to use it in a proportion of 0 to 70 parts by mass.
- the solid content of the resin in the paint is the total quality of the polyester resin (X), the curing agent (Y), and other base resin additionally used as necessary and the modifying resin added as appropriate. Amount.
- the “total content of benzene ring and cyclohexane ring” is the total number of moles of benzene ring and cyclohexane ring contained in 1 kg (solid content) of polyester resin, Divide the total number of moles (Wm) of the benzene ring and the hexane ring included in the monomer used for resin synthesis by the mass of the generated resin excluding condensed water (W r: kg) (ie, WmZW r) can be calculated.
- Polyester resin (X) is, for example, a polybasic acid component and a polyhydric alcohol component, at least one of which contains a benzene ring and Z or a cyclohexane ring, and, if necessary, a monobasic acid such as benzoic acid and Z Alternatively, it can be produced by subjecting monoalcohol to an esterification reaction or an ester exchange reaction.
- the polybasic acid component is a compound having at least two carboxyl groups in one molecule.
- phthalic acid isophthalic acid, terephthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic acid , Hexahydrophthalic acid, maleic acid, fumaric acid, itaconic acid, trimellitic acid, pyromellitic acid, and other polybasic acids; anhydrides of these polybasic acids; lower alkyls of these polybasic acids Examples include esterified products, and these can be used alone or in combination of two or more.
- examples of the polybasic acid component having a benzene ring include phthalic acid, Polybasic acids such as isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid; anhydrides of these polybasic acids; and lower alkyl esterified products of these polybasic acids.
- Polybasic acids having a cyclohexane ring examples include cyclohexan-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexahydrophthalanoreic acid, hexahydroisophthalanolic acid, hexahydrodrothephthalenolic acid, hexahydrotritriolenoic acid.
- polybasic acids such as merit acid and methylhexaphthalophthalic acid; anhydrides of these polybasic acids; and lower alkyl esterified products of these polybasic acids.
- the polyhydric alcohol component is a compound having at least two hydroxyl groups in one molecule.
- ethylene glycol 1,2-propylene glycol, 1,2-butylene glycol, 2,3-butylene glycol Nole, 1,2-Hexanediol, 1,2-Dihydroxycyclohexane, 3-Ethoxypropane-1,2-diol, 3-Phenoxypropane-1,2-diol, etc.
- examples of the polyhydric alcohol component having a benzene ring include bisphenol A and bisphenol F
- examples of the polyhydric alcohol component having a cyclohexane ring include 1,3-dihydroxycyclohexane.
- examples include hexane, 1,3-cyclohexanedimethanol, 1,4-dihydroxycyclohexane, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F.
- the esterification reaction or transesterification reaction of the polybasic acid component and the polyhydric alcohol component can be carried out by a method known per se, for example, the polybasic acid component and the polyhydric alcohol component are about 180 to about It can be carried out by polycondensation at a temperature of 2500 ° C.
- the polyester resin (X) is obtained by obtaining a polyester resin having a hydroxyl group and a no- or carboxyl group from the polybasic acid component and the polyhydric alcohol component, and then adding a hydroxyl group and a no- or carboxyl group to the hydroxyl group of the polyester resin. It can also be obtained by reacting a functional group having reactivity with a carboxyl group and a compound having a benzene ring and / or a cyclohexane ring.
- Such compounds include: Examples thereof include monobasic acids having a benzene ring such as benzoic acid and z or cyclohexane ring; acrylic resins having a benzene ring and Z or cyclohexane ring and an isocyanate group.
- a hydroxyl group and / or carboxyl group into a polyester resin skeleton is, for example, a polyhydric alcohol component having three or more hydroxyl groups in one molecule together with a dibasic acid and a dihydric alcohol in an esterification reaction.
- Z or a polybasic acid component having three or more carboxyl groups can be used in combination.
- maleic acid, maleic anhydride, phthalic anhydride, trimellitic anhydride, etc. are added to the hydroxyl group of the polyester resin.
- Carboxyl groups can also be introduced into the resin by reacting polybasic acids.
- the polyester resin may be modified with a fatty acid, a monoepoxy compound (for example, “Cardiula E 10”, a glycidyl ester of a synthetic hyperbranched fatty acid, a product name manufactured by HEXION Specialty Chemicals), etc. You can also.
- a monoepoxy compound for example, “Cardiula E 10”, a glycidyl ester of a synthetic hyperbranched fatty acid, a product name manufactured by HEXION Specialty Chemicals
- fatty acid examples include coconut oil fatty acid, cottonseed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, tung oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid Dehydrated castor oil fatty acid, safflower oil fatty acid and the like.
- Polyester resin (X) is generally an acid within the range of 5-8 OmgKOHZg, especially 10-70 mgKOH / g, more particularly 15-5 OmgKOHZg, from the viewpoints of storage stability of the paint and water resistance of the resulting coating film. In addition, from the viewpoint of the water resistance of the resulting coating film, it is generally 60-20 OmgK0HZg, especially 80-185 mgKOH / g, more particularly 100-; 17 Hydroxyl group within the range of OmgKOHZg It is preferable to have a valence. Polyester resin (X) is generally 500 to 4,000, particularly 600 to 3,000, and more particularly 700 to 2 from the viewpoint of smoothness, sharpness, and chipping resistance of the resulting coating film.
- the number average molecular weight is preferably within the range of 1,000,000, and from the standpoint of chipping resistance, it is generally from 1 to 20 to 20 ° C, preferably from 1 to 50 to 10 ° C, more preferably from 1 It is preferred to have a glass transition temperature in the range of 30-5 ° C.
- the number average molecular weight and the weight average molecular weight are the number average molecular weight and the weight average molecular weight measured by gel permeation chromatography (“HLC8120GPC” manufactured by Tosohichi Co., Ltd.), and the molecular weight of standard polystyrene. This is a value converted based on the standard.
- TKg el G—4000HXL As columns, “TSKg el G—4000HXL”, “TSKg e 1 G—3000HXL”, “TSKg el G—2500HXL”, “TSK ge 1 G—2000HXL”
- the product can be measured under the conditions of mobile phase: tetrahydrofuran, measurement temperature: 40 ° C, flow rate: lmL / min, detector: RI.
- the polyester resin (X) preferably neutralizes carboxyl groups present in the molecule.
- the neutralizing agent used in this case include ammonia; methylamine, ethylamine, propylamine, isopropylamine, butylamine, 2-ethenorehexenoleamine, hexylamine, dimethylamine, jetylamine, dipropylamine, diisopropylamine.
- a suitable range is usually 0.1 to 2.0 equivalents, preferably 0.3 to 1.2 equivalents, relative to the carboxyl group in (X).
- an isocyanate group-containing compound (a), an oxazoline group-containing compound (b), a carpositimide group-containing compound (c :), a hydrazide group At least one compound selected from the group consisting of the containing compound (d) and the semicarbazide group-containing compound (e) is used.
- the curing agent (Y) is preferably an isocyanate group-containing compound (a).
- the curing agent (Y) is generally 1 to 60 parts by weight, particularly 10 to 50 parts by weight, more particularly 20 to 40 parts by weight, based on 100 parts by weight of the resin solid content in the aqueous first colored paint (A). It is suitable to use in the ratio.
- the polyester resin (X) is a polyester resin having a hydroxyl group
- the polyester resin (X) is usually 60 to 20 Omg.
- the isocyanate group-containing compound (a) has an equivalent ratio of hydroxyl group of the isocyanate group to the polyester resin (X) (NCOZOH) of usually 0.5 to 2.0, particularly 0.8 to 1.5. It is preferable to use at a ratio that falls within the range.
- the isocyanate group-containing compound (a) is a compound having at least two isocyanate groups in one molecule, and includes, for example, an aliphatic polyisocyanate, an alicyclic polyol. Examples include lyisocyanate, araliphatic polyisocyanate, aromatic polyisocyanate, and derivatives of the polyisocyanate. '
- aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentadiene diisocyanate, 2,3-butylene diisocyanate, 1, 3-Petylenediisocyanate, 2, 4, 4— or 2, 2, 4 1 Trimethylhexamethylene diisocyanate, 2, 6-Diisocyanatomethyl caproate and other aliphatic diisocyanates; Lysine ester triisocyanates, 1 , 4,8-triisocyanatooctane, 1,6,11-triisocyanatotundecane, 1,8-diisocyanatoto 4-monoisocyanatometho- / leoctane, 1,3,6_triisocyanatohexane, 2, 5, Aliphatic triisocyanates such as 7-trimethyl-1,8-diisocyanato 5-isocyanatomethyloct
- alicyclic polyisocyanates examples include 1,3-cyclopentenediocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, and 3-isocyanatomethylolene.
- 3,5,5-trimethylenocyclohexyl isocyanate (common name: isophorone diisocyanate), methyl-2,4-cyclohexane diisocyanate, methylolene 2,6-cyclohexanediisocyanate, 1 , 3—or 1,4-bis (isocyanatomethyl) cyclohexane (common name: hydrogenated xylylene diisocyanate) or mixtures thereof, alicyclic diisocyanates such as norpolnandi socyanate; 1, 3, 5-tri Isocyanato oral hexane, 1, 3, 5-trimethylisocyanato oral hexane, 2- (3-Sociana Propyl) one 2, 5-di (isocyanatomethyl) Bishikuro (2.2.1) heptane, 2- (3-isocyanatopropyl) -2, 6-di (Isoshianatome Til) monobicyclo (2.
- araliphatic polyisocyanate examples include 1, 3— or 1,4 monoxylylene diisocyanate or a mixture thereof, ⁇ , ⁇ , diisocyanate 1, 4, 4-jetylbenzene, 1, 3_ or 1,4-bis (1-isocyanato 1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or araliphatic diisocyanates such as mixtures thereof; 1, 3, 5-triisocyanato Examples thereof include aromatic aliphatic triisocyanates such as methylbenzene.
- aromatic polyisocyanate examples include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, and 1,5-naphthalene diisocyanate. 2, 4'- or 4,4'-diphenylmethane diisocyanate or mixtures thereof, 2, 4- or 2,6-tolylene diisocyanate or mixtures thereof, 4, 4 'monotoluidine diisocyanate, 4, 4 , —Aromatic diisocyanates such as diphenyl ether diisocyanate; Triphenylmethane 1, 4, 4,, '' One triisocyanate, 1, 3, 5—Triisocyanatobenzene, 2, 4, 6- aromatic isotopes such as triisocyanatotoluene 4,4'-diphenylmethane-1,2,2,5,5'-aromatic tetraisocyanate such as tetrisocyanate.
- polyisocyanate derivative examples include dimer, trimer, biuret, allophanate, uretidine, uretoimine, isocyanurate, oxadiazine trione, polymethylene polyphenylene polyisocyanate of the above polyisocyanate compound. (Crude MD I, polymeric MD I), and crude TDI.
- polyisocyanates and their derivatives may be used alone or in combination of two or more.
- aliphatic diisocyanates, alicyclic diisocyanates and derivatives thereof may be used alone or
- a hydrophilized polyisocyanate compound (a ′) obtained by modifying the polyisocyanate compound to be hydrophilic is particularly preferable from the viewpoint of smoothness of the resulting coating film.
- hydrophilic polyisocyanate compound (a ′) examples include an anionic property obtained by reacting an active hydrogen group of an active hydrogen group-containing compound having an anionic group with an isocyanate group of a polyisocyanate compound.
- Hydrophilic polyisocyanate compound (a ') examples include an anionic property obtained by reacting an active hydrogen group of an active hydrogen group-containing compound having an anionic group with an isocyanate group of a polyisocyanate compound.
- nonionic hydrophilized polyisocyanate compounds obtained by reacting hydrophilic polyether alcohols such as polyoxyethylene monoalcohol with polyisocyanate compounds.
- hydrophilic polyether alcohols such as polyoxyethylene monoalcohol
- ayu-on hydrophilized polyisocyanate compound (a′-1) is particularly suitable because of excellent smoothness of the formed coating film.
- the active hydrogen group-containing compound having an anionic group has an anionic group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a betaine structure-containing group, and for example, a compound having an active hydrogen group such as a hydroxyl group or an amino group that can react with the nate group is included.
- a polyisocyanate compound By reacting the compound with a polyisocyanate compound, hydrophilicity can be imparted to the polyisocyanate compound. it can.
- the active hydrogen group-containing compound having an anionic group is not particularly limited, and examples thereof include a compound having one anionic group and at least two active hydrogen groups. More specifically, examples of the active hydrogen group-containing compound having a carboxyl group include 2,2-dimethylolacetic acid, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid.
- Dimethylol heptanoic acid dimethylol nonanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylol dihydroxylcarboxylic acid such as monovaleric acid; 1 monocarboxyl 1,5-pentylenediamine, dihydroxybenzoic acid 3, diaminocarboxylic acids such as 3,5-diaminobenzoic acid, lysine and arginine; and half ester compounds of polyoxypropylene triol with maleic anhydride and phthalic anhydride.
- Examples of the active hydrogen group-containing compound having a sulfonic acid group include N, N-bis (2-hydroxyxetyl) -1,2-aminoethanesulfonic acid, 1,3-phenylenediamine-4,6-disulfonic acid, Aminobutane sulfonic acid, 3, 6-diamino 2-Toluene sulfonic acid, 2, 4-Diamino 5-Toluene sulfonic acid, 2-(Cyclohexyloleamino) Monoethane sulfonic acid, 3 1 (Cyclohexyloleamino) 1 Propane sulfone An acid etc. are mentioned.
- Examples of the active hydrogen group-containing compound having a phosphate group include 2,3-dihydroxypropylphenyl phosphate.
- Examples of the active hydrogen group-containing compound having a betaine structure-containing group include a sulfobetaine group-containing compound obtained by a reaction between a tertiary amine such as N-methyljetanolamine and 1,3-propane sultone. Can be mentioned. These active hydrogen group-containing compounds having an anionic group may be converted to an alkylene oxide modified product by adding an alkylene oxide such as ethylene oxide or propylene oxide.
- active hydrogen group-containing compounds having a terionic group can be used alone or in combination of two or more.
- the ionic hydrophilized polyisocyanate compound (a, 1 1) contains, among others, an active hydrogen group having a sulfonic acid group and Z or a phosphate group. It is particularly preferable to use an anionic hydrophilic polyisocyanate compound obtained by reacting an active hydrogen group of a compound with a isocyanate group of a polyisocyanate compound.
- hydrophilized modified polyisocyanate compound (a ′) as the polyisocyanate compound that can be hydrophilized, the same polyisocyanate compounds as described above can be used. Range isocyanate
- HMD I hexamethylene diisocyanate
- IPDI isophorone diisocyanate
- IPDI isophorone diisocyanate
- the oxazoline group-containing compound (b) can be used as the curing agent ( ⁇ ), and the oxazoline group-containing compound
- (b) is preferably a polymer compound (b-1) having at least two oxazoline groups in the side chain, or a simple compound (b-2) having at least two oxazoline groups in one molecule. It is mentioned as a thing. Where the oxazoline group has the formula
- R 2 , R 3 and R 4 independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
- a polymeric compound (b-1) having at least two oxazoline groups in the side chain is prepared by converting a polymerizable unsaturated monomer (b-la) having an oxazoline group to other polymerizable compounds, if necessary. It can be obtained by polymerizing with an unsaturated monomer (b-lb) in the presence of a radical polymerization initiator.
- the monomer (b-1a) is a compound having one or more oxazoline groups and polymerizable unsaturated bonds in one molecule, for example, 2-vinyl_2-oxazoline, 2-Buhl 4-Methyl-1-2-Oxazoline, 2-Buhl 5-Methyl-I 2-Oxazoline, 2 _Isopropenolyl 2-Oxazoline, 2 _Isopropenyl 1-Methanolet 2-Oxazoline, 2-Isoprobenil 5 -Ethyl-2-azosazoline. .
- the monomer (b-1b) is a compound having at least one polymerizable unsaturated bond in one molecule other than the monomer (b-1a).
- radical polymerization initiator that can be used in the (co) polymerization of the unsaturated monomer
- those known per se can be used.
- benzoyl peroxide, di-tert-butyl hydro- gen can be used.
- the content of the monomer (b-1a) is usually 1 to: L 0 0 based on the total mass with the monomer (b-1b). It can be in the range of mass%, preferably 10 to 60 mass ° / 0 , more preferably 20 to 50 mass%.
- the polymeric compound (b-1) is usually 5 0 0 to 1 0 0, 0 0 0, particularly 1, 0 0 0 to 5 0, 0 0 0, more particularly 3, 0 0 0 to 3 0, It is preferred to have a number average molecular weight in the range of 0 to 0.
- Polymerization of monomer (b—la) and monomer (b—lb) is itself
- the polymerization can be carried out by a known method such as solution polymerization or emulsion polymerization, and the resulting polymer compound (b-1) can be either water-soluble or water-dispersible.
- monomeric compounds (b-2) include, for example, 2, 2'-bis (2-xoxazoline), 2,2'-methylene-bis (2-oxazoline), 2, 2'- Ethylene bis bis (2-oxazoline), 2, 2'-trimethylene bis bis (2-oxazoline), 2, 2'-tetramethylene bis bis (2-oxazoline), 2, 2 'hexamethylene bis 1, 2- (oxazoline), 2, 2'-octamethylene bis (2-oxazoline), 2, 2'-ethylene bis (4, A 'dimethyl-2-oxazoline), 2, 2' 1-p-phenylene-bis-bis (2-oxazoline), 2, 2 '1-m-phenylene-bis-bis (2-oxazoline), 2, 2'-m-phenylene-bis-bis (4, A 'monodimethyl-2-oxazoline), bis (2-oxazolinylcyclohexane) sulfide, bis (2-Oxazoliny
- a polymer compound (b-1) having at least two oxazoline groups in the side chain and a simple compound (b-2) having at least two oxazoline groups in one molecule may be used in combination. ,.
- the amount of the oxazoline group-containing compound (b) used as the curing agent (Y) is from the viewpoint of low-temperature curability, etc., with respect to 1 mol of carboxyl group in the polyester resin (X).
- the ratio in which the oxazoline group is usually in the range of 0.2 to 1.0 mol, particularly 0.5 to 1.0 mol is preferable.
- a strong rubodiimide group-containing resin (c) can also be used as the curing agent ( ⁇ ).
- Trees containing calposiimide groups The fat (C) can be obtained, for example, by reacting the isocyanate groups of the polyisocyanate compound with each other by deoxidizing carbon, and as commercially available products, for example, “carbodilite V-02”, “carbohydrate” V—02—L 2 ”,“ Carbodilite V—04 ”,“ Carbodilite E—01 ”,“ Carbodilite E-02 ”(all manufactured by Nisshinbo Co., Ltd.) can be used.
- a polyester resin (X) having a carboxyl group can be used. It is preferable that the acid value derived from the carboxyl group of the polyester resin (X) is usually in the range of 5 to 8 OmgK0H / g, particularly 10 to 7 Omg KOH / g, more particularly 30 to 7 OmgKOHZg.
- the semicarbazide group-containing compound ( e ) includes a compound having at least two, preferably 2 to 10 semicarbazide groups represented by 1 NH—CO—NH—NH 2 in one molecule.
- semicarbazide groups represented by 1 NH—CO—NH—NH 2 in one molecule.
- Active hydrogen compounds containing a hydrophilic group such as polyfunctional semicarbazide obtained by excessively reacting drazine or the hydrazides exemplified above, such polyisocyanate compounds, polyethers, polyols, polyethylene glycol monoalkyl ethers, etc.
- hydrazide group-containing compound (d) or semicarbazide group-containing compound (e) can generally be used in combination with a polyester resin (X) having a carbo group.
- the water-based first colored paint (A) used in the step (1) according to the present invention includes, in addition to the polyester resin (X), a water-soluble or water-dispersible polyurethane resin, acrylic resin, alkyd resin, polyester resin, silicone Resin, fluororesin, epoxy resin and other modifying resins can be included, and in particular from the viewpoint of finish and chipping resistance, it is desirable to include polyurethane resin and acrylic resin.
- the water-based first colored paint (A) includes, as an auxiliary crosslinking agent, a melamine resin, a block polyisocyanate compound, a hydroxyl group and a block in one molecule.
- a urethane-modified polyester resin in which a isocyanate group coexists can be contained.
- the melamine resin examples include a partial or completely methylolated melamine resin obtained by a reaction between melamine and aldehyde, and examples of the aldehyde include formaldehyde and paraformaldehyde.
- the methylol group of the methylolated melamine resin can be partially or completely etherified with alcohol.
- alcohols used for etherification include methyl alcohol, ethyl alcohol, n
- examples thereof include —propyl alcoholenole, i-propinoreanoreconole, n -butinoreanolecoleore, i-petitenoreanolol, 2-ethyloctanol, 2-ethylhexanol and the like.
- melamine resin examples include, for example, Cymel 300, Cymel 3 2 3, Cymel 3 2 5, Cymel 3 2 7, Cymenole 3 500, Cymel 3 70, Cymel manufactured by Nippon Cytec Industries, Ltd. 3 8 0, Cymel 3 8 5, Cymel 2 1 2, Cymel 2 5 1, Cymel 2 5 4, My Coat 7 7 6 (all are trade names); Resin, Monsantone clay 7 3 5, Resin 7 4 0 Resimin 7 4 1, Resimin 7 4
- sulfonic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, and salts of these acids and amines may be used as catalysts. it can.
- the block polyisocyanate compound is formed by using the isocyanate group of the polyisocyanate compound exemplified in the description of the isocyanate group-containing compound (a) as a probe.
- a compound blocked with an oxidant, and the reaction between the polyisocyanate compound and the blocking agent can be carried out by a method known per se.
- the blocking agent temporarily blocks a free isocyanate group, and the block polyisocyanate compound blocked with the block agent is, for example, 10 °. c or higher, preferably 1 15 ° C or higher, more preferably 1 30 ° C or higher, whereby the blocking agent is dissociated and the isocyanate group is regenerated to easily react with a hydroxyl group or the like. Will be able to.
- block rocks examples include phenol, cresol monole, xylenore, nitrophenol, ethenolevenole, hydroxydiphenyl, butylphenol, isopropylphenol, noninolephenol, octylphenol, hydroxy Phenolic compounds such as methyl benzoate; ⁇ -force prolactam, ⁇ -valerolatatum, ⁇ -petitolactam, lactams such as 6-propiolactam; methanolol, ethanol, propyl alcohol, butyl alcohol, amyl alcohol, Aliphatic alcohols such as lauryl alcohol; ethylene glycol mono-monomethino ethenore, ethylene glycol mono-mono chineno ethenore, ethylene glycol monobutino reeenore, diethylene glycone Ethenoles such as Lemonomethinoreethenole, Jetylene Glyconolemonoethylenole,
- a hydroxycarboxylic acid having at least one hydroxyl group and at least one carboxyl group in one molecule can be used, and as the hydroxycarboxylic acid, Examples thereof include hydroxybivalic acid and dimethylpropionic acid.
- a carboxyl group which is a hydrophilic group, is introduced into the compound by the carboxyl group in the hydroxycarboxylic acid. It can be suitably used as a good block polyisocyanate compound.
- the urethane-modified polyester resin in which a hydroxyl group and a block isocyanate group coexist in one molecule is a self-crosslinking resin, for example, a hydroxyl group-containing polyester resin It can be synthesized by subjecting a partial block polyisocyanate compound to a urethanation reaction with a part of the hydroxyl group therein.
- the aqueous first colored paint (A) can contain a polyol compound.
- these polyol compounds the smoothness of the formed coating film is excellent, and among these, the number average molecular weight is usually 100 to 2,000, particularly 200 to 1,800, more particularly 300 to 1,600, and more particularly 400-1. , 000 is preferred.
- the polyol compound is a compound having at least two hydroxyl groups in one molecule, and examples thereof include polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, and hydrogenated polybutadiene polyol. These can be used alone or in combination of two or more.
- polyether polyol examples include polyethylene glycol, polypropylene glycolol, poly (ethylene / propylene) glycolanol, polytetramethylene glycol, poly (ethylene / tetramethylene) glycol, and the like.
- the polyester polyol has a total content of benzene ring and ring hexane ring of less than 1.
- Omo 1 / kg (resin solid content), preferably in the range of 0.1 to 0.9 molZk g (resin solid content). It is preferred that the polyester polyol has an acid value of usually less than 5 mg KOHZg, particularly in the range of 0.1 mgKOHZg.
- the polyester polyol is preferably linear. Examples of the polyester polyol include those obtained by esterifying a polyhydric alcohol component and a polybasic acid component, and obtained by ring-opening reaction of a rataton compound using a polyhydric alcohol component as an initiator.
- polyhydric alcohol component and the polybasic acid component examples include those exemplified in the description of the polyester resin (X). These polyhydric alcohol components and polybasic acid components can be used alone or in combination of two or more.
- latonone compound examples include ⁇ -force prolatathone and poly] 3-methyl-1- ⁇ -valerolataton; TL.
- polycarbonate polyol examples include a reaction product of a polyhydric alcohol and phosgene, and a ring-opening polymer of a cyclic carbonate (such as an alkylene carbonate).
- a polyhydric alcohol examples include 3-methyl-1,5-pentanediol and 1,6-hexanediol.
- the cyclic carbonate examples include ethylene carbonate, trimethylene carbonate, and tetramethylene carbonate. Etc.
- the polycarbonate polyol may have an ester bond as well as a carbonate bond in the molecule.
- the polyol compound is generally 1 to 8 on the basis of 100 parts by mass of the resin solid content in the aqueous first colored paint ( ⁇ ). It is preferably used in a proportion of 0 parts by mass, especially 5 to 50 parts by mass, more particularly 10 to 25 parts by mass.
- the water-based first colored paint ( ⁇ ) can further contain a pigment.
- the facial material include coloring pigments, extender pigments, and luster pigments. These pigments can be used alone or in combination of two or more.
- the amount of the pigment is generally 1 to 200 based on 100 parts by mass of the resin solid content in the water-based first colored paint ( ⁇ ). It can be in the range of 20 parts by mass, preferably 20 to 150 parts by mass, more preferably 50 to 120 parts by mass.
- coloring pigment examples include titanium dioxide, zinc oxide, carbon black, lead sulfate, lead acid strength, zinc phosphate, anoleminum phosphate, zinc molybdate, Calcium molybdate, bituminous, ultramarine, cobalt blue, copper phthalocyanine blue, indanthrone blue, yellow lead, synthetic yellow iron oxide, transparent brown (yellow), bismuth vanadate, titanium yellow, zinc yellow (zinc yellow), monoazo yellow, isind Linon Yellow, Metal Complex Azo Yellow, Quinophthalone Yellow, Benzimid Dazolon Yellow, Bengal, Red Tan, Monoazoled, Kinatari Donreddo, Azo Lake (Mn Salt), Kinatari Don Magenta, Ansansu Kano Orange, Giantsla Kinoni Lane Quinacridone magenta, perylene red, diketopyrrolopyrrole chromium vermilion, chlorinated phthalocyanine green, brominated phthalocyanine green, pyrazolone ole Di,
- the amount of the colored pigment is usually 1 to 100 parts by weight based on 100 parts by mass of the resin solid content in the aqueous first colored paint (A). It can be in the range of 120 parts by weight, preferably 10 to 100 parts by weight, and more preferably 15 to 90 parts by weight.
- Examples of the extender pigment include clay, kaolin, barium sulfate, norium carbonate, calcium carbonate, talc, silica, and alumina white. Among them, it is possible to use barium sulfate and no or talc. preferable.
- the amount of the extender pigment is usually 1 to 100 parts by weight based on 100 parts by mass of the resin solid content in the aqueous first colored paint (A). It can be in the range of 100 parts by mass, preferably 5 to 60 parts by mass, and more preferably 8 to 40 parts by mass.
- the bright pigment examples include non-leafing type or leafing type aluminum (including vapor-deposited aluminum), copper, zinc, brass, nickel, Examples include aluminum oxide, mica, aluminum oxide coated with titanium oxide or iron oxide, mica coated with titanium oxide or iron oxide, glass flakes, hologram material, etc., each of which can be used alone or in combination of two or more. Can be used.
- the blending amount of the glittering pigment is usually based on 100 parts by mass of the resin solid content in the water-based first colored paint (A). It can be in the range of 1 to 50 parts by mass, preferably 2 to 30 parts by mass, and more preferably 3 to 20 parts by mass.
- the aqueous first colored paint (A) preferably further contains a curing catalyst.
- the curing catalyst include tin octylate, dibutyltin di (2-ethylhexanoate), dioctyltin di (2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, Dioctyltin oxide, dibutyltin fatty acid salt, lead 2-ethylethylhexanoate, zinc octylate, zinc naphthenate, zinc fatty acid, cobalt naphthenate, calcium octylate, copper naphthenate, tetra (2-ethyl) Xylyl) organometallic compounds such as titanate; tertiary amines; phosphoric acid compounds, etc., which can be used alone or in combination of two or more.
- the blending amount of the curing catalyst is usually 0.00 on the basis of 100 parts by mass of the resin solid content in the aqueous first colored paint (A).
- 0 0:! Can be in the range of ⁇ 5 parts by weight, preferably in the range of 0.1 to 0.5 parts by weight, more preferably in the range of 0.05 to 0.3 parts by weight.
- the water-based first colored paint (A) can be used as usual, such as a dispersant, an anti-settling agent, an organic solvent, an antifoaming agent, a thickener, an antifungal agent, an ultraviolet absorber, and a surface conditioner You may mix
- the water-based first colored paint (A) is either a one-component paint or a multi-component paint.
- W 200 but from the viewpoint of storage stability, a two-component paint comprising a main component (A1) containing a polyester resin (X) and a curing agent (A2) containing a curing agent (Y) It is preferable to do this.
- the main agent (A1) further contains a pigment, a curing catalyst and a solvent
- the curing agent (A2) further contains a solvent.
- the curing agent (A2) When the isocyanate group-containing compound (a) is used as the curing agent (Y), the curing agent (A2), a surfactant, in particular a cationic surfactant, and a Z or nonionic surfactant, It is particularly preferable to contain an anionic surfactant.
- the water-based first colored paint (A) can be applied on the substrate by a method known per se, for example, air spray, airless spray, rotary atomizer, etc. May be performed.
- the coating film thickness can be usually in the range of 10 to 10 ⁇ , preferably 10 to 50 ⁇ , and more preferably 15 to 35 ⁇ m as a cured film thickness.
- the water-based first colored paint (A) according to the present invention is applied so that the cured film has a thickness of 30 ⁇ from the viewpoint of smoothness and sharpness of the obtained coating film, and at 80 ° C. for 10 minutes.
- gel fraction of the coating film after heating is generally 1 to 95 wt%, it is preferable that preferably 15-92 mass 0/0, more preferably coating be in the range of 30 to 90 wt% .
- the article to be coated with the water-based first colored paint (A) is not particularly limited, and examples thereof include those made of materials such as metals and plastics.
- aqueous second colored paint (B) is applied onto the coating film of the aqueous first colored paint (A) (hereinafter referred to as the first colored paint film) formed in the step (1) described above.
- the coating film of the aqueous first colored paint (A) has a solid content ratio of the paint film by means of, for example, preheating or air blowing.
- normal 7 0: 1 0 0 mass 0/0, especially 8 0: L 0 0 mass 0/0, more especially 9 0: is preferably adjusted such that the L 0 0 the range of weight percent.
- the preheating is usually about 50 to about 110 in a drying furnace. (: Preferably, it can be performed by heating directly or indirectly at a temperature of about 60 to about 90 ° C. for about 1 to 30 minutes. Also, the air blow is usually performed on a workpiece. This can be done by blowing air heated to room temperature or at a temperature of about 25 ° C to about 80 ° C.
- the solid content of the coating film can be measured by the following method: First, at the same time that the water-based first colored paint (A) is applied on the object to be coated, the mass (WJ is measured in advance). The water-based first colored paint (A) is also applied onto the aluminum foil that has been applied, and the aluminum foil that has been preheated after painting is collected immediately before the water-based second colored paint (B) is applied. , measuring the mass (W 2). Next, the recovered aluminum foil and dried for 60 minutes at 1 1 0 ° C and was allowed to cool to room temperature in a desiccator, of the aluminum foil by weight (W 3) The solid content is determined according to the following formula.
- Solid content (mass%) ⁇ (W 3 — / (W 2 — ⁇ X 1 0 0
- the gel fraction of the coating film can be measured by the following method:
- the water-based first colored paint (A) is applied on the object to be coated, and at the same time, the water-based first colored paint (A) is also applied on the polypropylene plate. Collect the propylene plate just before the water-based second colored paint (B) is applied. Then, to recover the first colored coating on ⁇ Po polypropylene plate, measuring the mass (w a). Thereafter, the coating film was placed in a 300-mesh stainless steel mesh container, extracted for 5 hours in an equal-mass mixed solvent of acetone and methanol heated to 64 ° C, and heated at 110 ° C for 6 hours. The coating film mass (W b ) after drying for 0 minute is measured, and the insoluble coating film residual ratio (mass%) obtained according to the following formula is calculated, which is defined as the gel fraction.
- Water-based second colored paint (B) applied on the first colored coating film includes, for example, cross-linked carboxyl groups, hydroxyl groups, etc.
- Base resin such as talyl resin, polyester resin, alkyd resin, urethane resin, and epoxy resin having a functional functional group, and a cross-linking agent such as polyisocyanate compound, melamine resin, and urea resin that may be blocked. It is possible to use a resin component obtained by dissolving or dispersing a resin component in water together with pigments and other additives.
- the pigment it is possible to use the color pigment, the glitter pigment, the extender pigment, etc. exemplified in the description of the aqueous first colored paint (A), and the glitter pigment is used as at least a part of the pigment component. Thus, it is possible to form a metallic or pearly coating film having a dense feeling.
- the water-based second colored paint (B) can be applied by a method known per se, for example, air spray, airless spray, rotary atomizer, etc. Good.
- the coating thickness is usually 5 to 40 ⁇ , preferably 10 in terms of cured film thickness.
- the coating film of the water-based second colored paint ( ⁇ ) applied is, for example, 1 at a temperature of about 50 to about 110 ° C, preferably about 60 to about 90 ° C by preheating, air blowing, or the like.
- ⁇ 6 0 Step (3) that can be dried by heating for about a minute:
- a clear paint (C) is further applied on the coating film of the water-based second colored paint (B) (hereinafter referred to as the second colored paint film) formed by the step (2).
- a base resin such as an acrylic resin, a polyester resin, an alkyd resin, a urethane resin, an epoxy resin, or a fluororesin having a crosslinkable functional group such as a hydroxyl group, a carboxyl group, an epoxy group, or a silanol group, and melamine Resin, urea resin, polyisocyanate compound which may be blocked, 'carboxyl group-containing compound or resin, epoxy group-containing compound or organic solvent-based thermosetting paint containing resin or other cross-linking agent, Examples include aqueous thermosetting paints and thermosetting powder paints.
- thermosetting paints containing hydroxyl group-containing resins and melamine resins thermosetting paints containing carboxyl group-containing resins and epoxy group-containing resins, and polyisocyanate compounds that may be blocked with hydroxyl group-containing resins.
- the thermosetting coating material containing is suitable.
- a one-component paint or a two-component paint such as a two-component urethane resin paint may be used.
- the clear paint (C) can contain coloring pigments, glittering pigments, dyes, etc. to the extent that it does not impair the transparency, if necessary. Further, it is an extender, an ultraviolet absorber, an antifoaming agent. Further, paint additives such as thickeners, antifungal agents, and surface conditioners can be appropriately added.
- Talia paint (C) is applied to the coating surface of the water-based second colored paint (B) by a method known per se, for example, airless spray, air spray, rotary atomizer. Electrostatic application may be performed during painting.
- the coating film thickness can usually be in the range of 10 to 60 ⁇ , preferably 25 to 50 m in terms of cured film thickness.
- the multi-layer coating film composed of three layers of the first colored coating film, the second colored coating film and the clear coating film formed in the steps (1) to (3) described above is an ordinary coating film baking means.
- it can be cured at the same time by heating for about 20 to about 40 minutes at a temperature of about 80 to about 170 ° C, preferably about 120 to about 160 ° C.
- a multilayer coating film excellent in smoothness, sharpness, chipping resistance, and water resistance can be formed.
- trimellitic anhydride molecular weight 192
- 2- (dimethylamino) ethanol was added in an equivalent amount to the acid group.
- deionized water was gradually added and dispersed in water to obtain a polyester resin solution (X-1) having a solid content of 45% and a pH of 7.2.
- the resulting polyester resin has a total content of benzene ring and cyclohexane ring of 1.62mo 1 / kg (resin solid content), acid value of 35mgKH / g, hydroxyl group value of 130mgKOHZg, number average molecular weight was 1,440 and the glass transition temperature was -15 ° C.
- the total content of benzene ring and cyclohexane ring of the obtained polyester resin was calculated by the following calculation.
- polyester resin solutions (X-2) to (X-14) having a solid content concentration of 45% and a pH of 7.2.
- the total concentration, acid value, hydroxyl value, number average molecular weight, and glass transition temperature of the benzene ring and cyclohexane ring of each obtained polyester resin were determined according to Production Example 1 and the obtained polyester resin solution (X-1). It is also shown in Table 1 below.
- a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and dripping device was charged with 130 parts deionized water and Aqualon KH-10 (Note 2) 0.52 part, and stirred and mixed in a nitrogen stream. The temperature was raised to 80 ° C. Subsequently, 1% of the total amount of the following monomer emulsion (1) and 5.3 parts of a 6% ammonium persulfate aqueous solution were introduced into the reaction vessel and maintained at 80 ° C. for 15 minutes. Thereafter, the remaining monomer emulsion 1 was dropped into a reaction vessel maintained at the same temperature over 3 hours, and aged for 1 hour after completion of the dropping.
- AQUALON KH-10 Polyoxyethylene alkyl ether sulfate ester stellan molybdenum salt: Product name, active ingredient 97%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
- Monomer emulsion (1) 42 parts of deionized water, Aqualon KH-10 0.72 parts, 2.1 parts of aryl methacrylate, 2.8 parts of styrene, 1 part of methyl methacrylate
- a monomer emulsion (1) was obtained by mixing and stirring 6 ⁇ 1 part, 28 parts of ethyl acrylate and 21 parts of n-butyl acrylate.
- Monomer emulsion (2) Deionized water 18 parts, AQUALON KH—10 0.31 parts, ammonium persulfate 0.03 parts, methacrylic acid 5.1 parts, 2-hydroxyethyl oleate, 5.1 parts, styrene 3 parts Then, 6 parts of methyl methacrylate, 1.8 parts of ethyl acrylate and 9 parts of n-butyl acrylate were mixed and stirred to obtain a monomer emulsion (2). Manufacturing of bright pigment concentrate
- the acid value due to the phosphate group of this resin was 83 mg KOH / g, the hydroxyl value derived from 4-hydroxybutyl acrylate was 29 mg KOHZg, and the weight average molecular weight was 10 and 0 0 0 .
- Phosphoric acid group-containing polymerizable monomer Put 57.5 parts of monoptyl phosphoric acid and 1 part of isobutanol in a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and dripping device. After raising the temperature to 0 ° C., 42.5 parts of glycidyl methacrylate was added dropwise over 2 hours, and the mixture was further aged and stirred for 1 hour. Thereafter, 59 parts of isopropanol was added to obtain a phosphate group-containing polymerizable monomer solution having a solid concentration of 50%. The acid value due to the phosphate group was 285 mg K0HZg.
- each water-based 1st coloring paint shown in Table 2 is solid content mass ratio of each component.
- the pigment component add 44.4 parts of polyester resin in each water-based first colored paint (20 parts of solid content of the moon) and 20 parts of deionized water to the amount of pigment shown in the table. After adjusting to pH 8.0 with 2- (dimethylamino) ethanol, disperse with a paint shaker for 30 minutes to form a pigment dispersion paste, and stir and mix with other ingredients. Further, deionized water and 2- (dimethylamino) ethanol are added. By addition, each aqueous first colored paint was obtained by adjusting to a viscosity of 40 seconds at 20 ° C. using pH 8.0 and Ford Cup No. 4.
- the pigments (P-1) to (P-3) and the curing agents (Y-1) to (Y19) in Table 2 below are as follows.
- Pigment (P-1) JR-806 (product name, rutile type titanium dioxide, manufactured by Tika)
- Pigment (P-3) Carbon MA-100 (Mitsubishi Chemical Corporation, trade name, carbon black)
- Curing agent (Y-1) sulfonic acid-modified polyisocyanate compound obtained in Production Example 18 Solution (a '-1-1), solid content 80%, N CO content 1 6.0%
- Curing agent (Y-2) Takenate WD-220 (Mitsui Chemicals Polyurethane, trade name, nonion modified isocyanate, solid content 100%, NCO content 17.4%)
- Curing agent (Y-3) Dice module N 3400 (manufactured by Sumika Bayer Urethane Co., Ltd., polyisocyanate, trade name, uretdione of hexamethylene diisocyanate, solid content 100%, NCO content 21.8%)
- Curing agent (Y-4) Epochros WS-500 (Nippon Shokubai Co., Ltd., trade name, oxazoline group-containing compound, solid content 40%, oxazoline group content 4.5 mmol / g resin solid content)
- Curing agent (Y-6) Adipic acid dihydrazide (10% aqueous solution, hydrazide group content 1 1. 48 mm o 1 Z g resin solids)
- Curing agent (Y-8) Cymel 325 (Nippon Cytec Industries, trade name, melamine resin, solid content 80%)
- test plates were prepared and evaluated. (Preparation of test article)
- Electron GT-10 (trade name, cationic electrodeposition paint) made of cold rolled steel sheet with Palbond # 3020 (Nippon Parr Rising Co., Ltd., zinc phosphate treatment agent) with a dry film thickness of 20 ⁇ Electrodeposition coating was carried out, and the coating was made by heating at 1700C for 30 minutes and curing.
- Example 1
- the above-mentioned production is performed on the above-mentioned test object, the above-described aluminum foil for measuring the solid content of the coated film and the polypropylene plate for measuring the gel fraction
- the aqueous first colored paint (A-1) obtained in Example 19 was applied using a rotary atomizing coater so that the cured film thickness was 30 ⁇ .
- the solid content and gel fraction of the first colored coating film were measured. Table 3 shows the measurement results.
- the water-based second colored paint (B-1) obtained in Production Example 46 was applied to the first colored coating film using a rotary atomizing bell-type coating machine to obtain a cured film thickness of 15 ⁇ . And pre-heated at 80 ° C for 3 minutes.
- the second colored coating film Magiclon KI NO- 1 210 (Acryl resin-based solvent-type clear coating, manufactured by Kansai Paint Co., Ltd., trade name, sometimes referred to as “Talia paint (C-1)”) is 40 m in thickness.
- the coating was allowed to stand for 7 minutes and then heated at 140 ° C. for 30 minutes to simultaneously cure the first colored coating, the second colored coating, and the clear coating to prepare a test plate. Examples 2 to 23, comparative example:! ⁇ Four
- Example 1 except that the water-based first colored paints (A-2) to (A-27) shown in Table 3 were used instead of the water-based first colored paint (A-1) obtained in Production Example 19.
- Each test plate was produced in the same manner as in Example 1.
- the test plates obtained in Examples 1 to 23 and Comparative Examples 1 to 4 were evaluated by the following test methods. Table 3 shows the evaluation results.
- the Long Wave (LW) value is an index of the amplitude of the surface roughness at a wavelength of about 1.2 to 12 mm, and the smaller the measured value, the higher the smoothness of the coated surface.
- Vividness Evaluated using the Short Wave (SW) value measured by the above Wave S can.
- the Short Wave (SW) value is an index of the amplitude of the surface roughness at a wavelength of about 0.3 to 1.2 mm, and the smaller the measured value, the higher the clearness of the coated surface.
- a test plate is installed on the specimen holder of the stepping stone testing machine JA-4400 (Chibbing test equipment) manufactured by Suga Test Instruments Co., Ltd. at 0.30 2 MP at 120 ° C. a (4 kgf Z cm 2 ) of compressed air of 50 g of granite No. 7 granite meteorite was sprayed onto the coating surface, and the degree of scratches on the coating film was visually observed. It was evaluated with.
- A The size of the scratch is extremely small, and the electrodeposition surface and the base steel plate are not exposed.
- ⁇ The size of the scratch is small, and the electrodeposition surface and the base steel plate are not exposed.
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
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Priority Applications (4)
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US12/226,564 US8247035B2 (en) | 2006-04-25 | 2007-04-24 | Method for forming multilayer coating film |
CN2007800151404A CN101432082B (zh) | 2006-04-25 | 2007-04-24 | 形成多层涂膜的方法 |
JP2008513320A JP4825871B2 (ja) | 2006-04-25 | 2007-04-24 | 複層塗膜形成方法 |
GB0819764A GB2450835B (en) | 2006-04-25 | 2007-04-24 | Method for forming multilayer coating film |
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JP2006-121115 | 2006-04-25 | ||
JP2006121115 | 2006-04-25 | ||
JP2006-178833 | 2006-06-28 | ||
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US (1) | US8247035B2 (ja) |
JP (1) | JP4825871B2 (ja) |
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WO (1) | WO2007126107A1 (ja) |
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- 2007-04-24 CN CN2007800151404A patent/CN101432082B/zh not_active Expired - Fee Related
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WO2010038713A1 (en) * | 2008-09-30 | 2010-04-08 | Toyota Jidosha Kabushiki Kaisha | Coating method and coated article obtained by the same |
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JP7016607B2 (ja) | 2016-07-21 | 2022-02-07 | 大日本塗料株式会社 | ウレタン樹脂塗料組成物及びコンクリート基材の保護方法 |
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US11014122B2 (en) | 2017-04-25 | 2021-05-25 | Basf Coatings Gmbh | Method for forming multilayer coating film |
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JPWO2019159453A1 (ja) * | 2018-02-13 | 2021-02-25 | 東洋製罐グループホールディングス株式会社 | 水性塗料組成物 |
JP7322870B2 (ja) | 2018-02-13 | 2023-08-08 | 東洋製罐グループホールディングス株式会社 | 水性塗料組成物 |
WO2020059739A1 (ja) | 2018-09-21 | 2020-03-26 | 旭化成株式会社 | 複層塗膜積層体及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
GB2450835B (en) | 2011-03-02 |
GB0819764D0 (en) | 2008-12-03 |
US20090117396A1 (en) | 2009-05-07 |
GB2450835A (en) | 2009-01-07 |
US8247035B2 (en) | 2012-08-21 |
JPWO2007126107A1 (ja) | 2009-09-17 |
CN101432082B (zh) | 2011-10-05 |
CN101432082A (zh) | 2009-05-13 |
JP4825871B2 (ja) | 2011-11-30 |
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