WO2019064958A1 - 複層塗膜形成方法 - Google Patents
複層塗膜形成方法 Download PDFInfo
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- WO2019064958A1 WO2019064958A1 PCT/JP2018/029958 JP2018029958W WO2019064958A1 WO 2019064958 A1 WO2019064958 A1 WO 2019064958A1 JP 2018029958 W JP2018029958 W JP 2018029958W WO 2019064958 A1 WO2019064958 A1 WO 2019064958A1
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- coating film
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- 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
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/325—Polyamines containing secondary or tertiary amino 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
- C08G18/4241—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols from dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
- C08G18/6233—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols the monomers or polymers being esterified with carboxylic acids or lactones
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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
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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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
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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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
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
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- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- 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
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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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- 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
- B05D2201/00—Polymeric substrate or laminate
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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
- B05D2350/00—Pretreatment of the substrate
- B05D2350/10—Phosphatation
Definitions
- the present invention relates to a multilayer coating film forming method which can form a coating film excellent in low temperature curability and excellent in hardness and finish appearance.
- the mixed layer of the intermediate coating film and the base coating film is likely to occur, so that the smoothness and the image sharpness of the obtained coating film are reduced, and the curing accompanying the transfer of the curing agent between the coating films
- problems such as a decrease in chipping resistance and a decrease in water resistance which are presumably due to a change in balance.
- a polyester resin (X) containing a benzene ring and a cyclohexane ring in a specific content in a molecule as an aqueous first colored paint in the coating step of a multilayer coating film by the 3C1B system and isocyanate
- At least one curing agent selected from the group consisting of group-containing compound (a), oxazoline group-containing compound (b), carbodiimide group-containing compound (c), hydrazide group-containing compound (d) and semicarbazide group-containing compound (e) It has been proposed to form a multilayer coating film excellent in smoothness, sharpness, chipping resistance, water resistance and the like by using a paint comprising (Y).
- Patent Document 2 in a 3-coat 1-bake system, an aqueous middle coat paint, an aqueous base paint and a clear paint are sequentially coated on a substrate to be coated, and the resulting multilayer coat film is simultaneously heated and cured.
- the base coat resin (A), the curing agent (B) and the diester compound (C) are contained as an aqueous intermediate coating, and the curing agent (B) is a polyisocyanate compound (B1) and / or a polycarbodiimide compound (B2)
- Certain multilayer coating formation methods have been proposed.
- An object of the present invention is to provide a method capable of forming a multilayer coating film excellent in low temperature curability and excellent in hardness and finish appearance.
- a step of applying an aqueous two-component first colored paint (X) to form an uncured first colored coating film (2)
- the aqueous one-component second colored paint (Y) is applied on the uncured first colored coating obtained in the step (1) to form an uncured second colored coating Process, (3) applying a two-component clear paint (Z) on the uncured second colored coating film obtained in the step (2) to form an uncured clear coating film; And the like) by heating the uncured first colored coating film formed in the steps (1) to (3), the uncured second colored coating film, and the uncured clear coating film.
- the aqueous one-pack second colored paint (Y) contains a hydroxyl group-containing acrylic resin (Y1), a hydroxyl group-containing polyester resin (Y2), and a block polyisocyanate compound and / or a melamine resin (Y3),
- the hydroxyl group-containing acrylic resin (Y1) contains a core-shell type water dispersible hydroxyl group-containing acrylic resin (Y11),
- the core / shell type water dispersible hydroxyl group-containing acrylic resin (Y11) is Has a core-shell type structure, and The content ratio of each monomer in the total amount of the monomer components constituting the core portion and the shell portion is based on the total mass of the monomer components constituting the core portion and the shell portion.
- the present invention relates to a method for forming a multilayer coating film, wherein the hydroxyl group-containing polyester resin (Y2) contains a polyester resin (Y21) having a hydroxyl value of 100 to 200 mg KOH / g and an acid value of 10 to 30 mg KOH / g.
- a multilayer coating film excellent in curability even at a baking temperature of 100 ° C. or less and excellent in hardness and finished appearance can be formed.
- Process (1) According to the method for forming a multilayer coating film of the present invention, first, the aqueous two-component first colored paint (X) is coated on a substrate to form an uncured first colored coating film.
- a to-be-coated-article there is no restriction
- raw materials such as a metal and a plastic
- metal and / or plastic automobile bodies, or parts thereof, particularly steel plates for automobile bodies may be subjected to chemical conversion treatment as necessary, as commonly practiced, and It is also possible to apply electrodeposition coating beforehand.
- a primer can be coated on the plastic surface as required.
- the aqueous two-pack type first colored paint (X) to be coated on the object to be coated usually contains a hydroxyl group-containing resin (X1), a polyisocyanate compound (X2) and a pigment (X3).
- the hydroxyl group-containing resin (X1) is a resin having at least one hydroxyl group in one molecule. From the viewpoint of water resistance and the like of the obtained coating film, the hydroxyl value of the hydroxyl group-containing resin (X1) is preferably about 5 to 300 mg KOH / g, more preferably about 15 to 200 mg KOH / g, and further preferably about 20 to 180 mg KOH / g. preferable.
- the hydroxyl group-containing resin (X1) may have an acid group in the molecule.
- the acid group may, for example, be a carboxyl group, a sulfonic acid group or a phosphoric acid group. Among these, a carboxyl group is preferable.
- the hydroxyl group-containing resin (X1) can be solubilized or dispersed in water.
- the acid value of the hydroxyl group-containing resin (X1) is such as the storage stability of the aqueous two-component first colored paint (X), the water resistance of the obtained coating film, etc. From the viewpoint, about 3 to 100 mg KOH / g is preferable, about 5 to 80 mg KOH / g is more preferable, and about 10 to 70 mg KOH / g is more preferable.
- a hydroxyl group-containing resin (X1) having an acid value of 10 mg KOH / g or less is used, the hydroxyl group-containing resin (X1) and an emulsifier are mixed instead of neutralization using the above-mentioned basic compound.
- the hydroxyl group-containing resin (X1) can be forcibly dispersed in water by applying mechanical shear force and stirring.
- hydroxyl group-containing resin (X1) examples include polyester resins, acrylic resins, polyether resins, polycarbonate resins, polyurethane resins, epoxy resins, alkyd resins, and modified resins thereof. These can be used alone or in combination of two or more. In particular, it is desirable that the hydroxyl group-containing resin (X1) contains the acrylic modified polyester resin (X11) from the viewpoint of improving the chipping resistance.
- the acryl-modified polyester resin (X11) has a main chain that is a polyester portion made of a polyester resin, and is modified with an acryl portion made of an acrylic (co) polymer.
- the polyester portion is a trunk polymer
- the acrylic portion is a branch polymer
- the acrylic portion is bonded to the polyester portion via a graft point.
- the method for producing the acrylic modified polyester resin (X11) is not particularly limited, and can be synthesized by a conventional method. Specific examples thereof include a method of polymerizing a mixture of an unsaturated group-containing polyester resin and an unsaturated monomer, and a method by an esterification reaction of a polyester resin and an acrylic resin.
- the ratio of the acryl part to the polyester part of the acryl-modified polyester resin (X11) is 5 to 20 parts of the acryl part to the acryl-modified polyester resin (X11) (total amount of the acryl part and the polyester part) 40% by mass, particularly 5 to 30% by mass, more particularly 5 to 25% by mass, 60 to 95% by mass of polyester part, particularly, 70 to 95% by mass, more particularly 75 to 95% by mass Is preferred.
- the acrylic modified polyester resin (X11) has a hydroxyl value of 20 to 200 mg KOH / g, particularly 30 to 150 mg KOH / g, more particularly 30 to 150 mg KOH / g. preferable.
- the hydroxyl value of the acrylic part is preferably in the range of 0 to 70 mg KOH / g, particularly 0 to 50 mg KOH / g, more particularly 0 to 30 mg KOH / g.
- the hydroxyl value of the polyester part is preferably in the range of 20 to 200 mg KOH / g, particularly 30 to 150 mg KOH / g, more particularly 30 to 120 mg KOH / g.
- the acrylic modified polyester resin (X11) has an acid value of 10 to 100 mg KOH / g, particularly 15 to 80 mg KOH / g, more particularly 15 to 60 mg KOH / g from the viewpoint of water dispersibility. preferable.
- the acid value of the acrylic part is preferably in the range of 50 to 500 mg KOH / g, particularly 80 to 400 mg KOH / g, more particularly 100 to 300 mg KOH / g.
- the acid value of the polyester portion is preferably in the range of 0 to 20 mg KOH / g, particularly 0 to 15 mg KOH / g, more particularly 0 to 10 mg KOH / g.
- the number average molecular weight of the acryl modified polyester resin (X11) is in the range of 1000 to 100000, particularly 2000 to 50000, more particularly 2000 to 20000, from the viewpoint of coating film appearance, coating film physical properties and chipping resistance. Is preferred.
- the average molecular weight is determined by the retention time (retention capacity) measured using gel permeation chromatograph (GPC) by the retention time (retention capacity) of standard polystyrene of known molecular weight measured under the same conditions. It is a value obtained by converting into the molecular weight of polystyrene.
- GPC gel permeation chromatograph
- G2000HXL trade names, all manufactured by Tosoh Corporation
- a differential refractometer is used as a detector
- mobile phase tetrahydrofuran
- measurement temperature 40 ° C.
- flow rate 1 mL / min. It can be measured below.
- the polyisocyanate compound (X2) is a compound having at least two unblocked isocyanate groups in one molecule, and for example, aliphatic polyisocyanate, alicyclic polyisocyanate, araliphatic polyisocyanate, aromatic Group polyisocyanate, derivatives of the polyisocyanate, and the like.
- aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, and the like.
- Aliphatic diisocyanates such as -butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethyl caproate; lysine ester triisocyanate, 1,4,8-triisocyanate Isocyanato octane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyl octane, 1,3,6-triisocyanatohexane, 2,5 , And the like aliphatic triisocyanate such as 7-trimethyl-1,8-diisocyanato-5-isocyanatomethyl octane.
- alicyclic polyisocyanate examples include, for example, 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (common name) : Isophorone diisocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane (conventional name: hydrogenated xylylene diisocyanate) or Mixtures thereof, cycloaliphatic diisocyanates such as norbornane diisocyanate; 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2- (3- (3-) Socianatopropy
- araliphatic polyisocyanate examples include, for example, 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ⁇ , ⁇ ′-diisocyanato-1,4-diethylbenzene, 1,3- or 1,4-bis Aromatic aliphatic diisocyanates such as (1-isocyanato-1-methylethyl) benzene (common name: tetramethyl xylylene diisocyanate) or mixtures thereof; Araliphatic triisocyanates such as 1,3,5-triisocyanatomethylbenzene etc. Can be mentioned.
- aromatic polyisocyanate examples include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4′- or 4,4′-diphenylmethane diisocyanate or the like Mixtures, aromatic diisocyanates such as 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, 4,4'-toluidine diisocyanate, 4,4'-diphenylether diisocyanate; triphenylmethane-4,4 ', 4' Aromatic triisocyanates such as '-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene; 4,4'-diphenylmethane-2,2', 5,5'- Tetri And aromatic tetraisocyanates such as cyanate and the like.
- the derivatives of the polyisocyanate include, for example, dimers, trimers, biurets, allophanates, uretones, uretimines, isocyanurates, oxadiazinetriones, polymethylene polyphenyl polyisocyanates (crude MDI, polymeric MDI, etc.) of the polyisocyanate compounds described above. And crude TDI.
- polyisocyanates and their derivatives may be used alone or in combination of two or more.
- aliphatic diisocyanates, alicyclic diisocyanates and their derivatives are preferably used alone or in combination of two or more.
- a polyisocyanate compound (X2) it is preferable to use a water dispersible polyisocyanate compound from a viewpoint of the smoothness etc. of the coating film obtained.
- a water dispersible polyisocyanate compound any polyisocyanate compound which can be stably dispersed in an aqueous medium can be used without limitation, but among them, a hydrophilicized polyisocyanate compound modified to be hydrophilic (X21)
- a polyisocyanate compound or the like to which water dispersibility is imparted by mixing the polyisocyanate compound (X2) and the surfactant in advance can be suitably used.
- hydrophilized polyisocyanate compound (X21) for example, an anionic hydrophilized polyisocyanate compound 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 ( X 211), nonionic hydrophilicized polyisocyanate compounds (X212) obtained by reacting a hydrophilic polyether alcohol such as polyoxyethylene monoalcohol with a polyisocyanate compound, and the like, and these may be used alone or in combination of two or more It can be used in combination.
- a hydrophilic polyether alcohol such as polyoxyethylene monoalcohol
- the active hydrogen group-containing compound having an anionic group examples include groups having an anionic group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a betaine structure-containing group and capable of reacting with an isocyanate group, for example, A compound having an active hydrogen group such as a hydroxyl group or an amino group is included, and by reacting the compound with a polyisocyanate compound, the polyisocyanate compound can be rendered hydrophilic.
- the anionic hydrophilized polyisocyanate compound (X211) one having a sulfonic acid group is particularly preferable.
- the aqueous two-pack type first colored paint (X) contains the hydroxyl group-containing resin (X1) and the polyisocyanate compound (X2) in the polyisocyanate compound (X2) relative to one equivalent of hydroxyl group in the hydroxyl group-containing resin (X1). It is preferable from the viewpoint of low-temperature curability that the resin has an isocyanate group content of 1.1 to 2.0 equivalents, particularly 1.1 to 1.7 equivalents.
- the pigment (X3) for example, titanium oxide, zinc flower, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, graphene pigment, perylene pigment Colored pigments such as pigments, dioxazine pigments, diketopyrrolopyrrole pigments; clay pigments such as clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, alumina white, etc .; aluminum (including vapor-deposited aluminum), copper And zinc, brass, nickel, aluminum oxide, mica, aluminum oxide coated with titanium oxide or iron oxide, mica coated with titanium oxide or iron oxide, glass flake, etc. Alone or in combination of two or more It is possible to use Te.
- the compounding amount of the pigment (X3) is generally 1 to 10 parts by weight based on 100 parts by mass of the total solid content of the hydroxyl group-containing resin (X1) and the polyisocyanate compound (X2) in the aqueous two-pack type first colored paint (X). It is suitable to be in the range of 200 parts by mass, preferably 20 to 150 parts by mass, and more preferably 50 to 120 parts by mass.
- the aqueous two-component first colored paint (X) is, if necessary, a curing agent other than the polyisocyanate compound (X2) such as melamine resin, a curing catalyst, a thickener, a UV absorber, a light stabilizer, an antifoaming agent
- a curing agent other than the polyisocyanate compound (X2) such as melamine resin, a curing catalyst, a thickener, a UV absorber, a light stabilizer, an antifoaming agent
- Additives for paints such as an agent, a plasticizer, an organic solvent, a surface control agent, and an anti-settling agent, can be suitably contained.
- the solid content concentration of the aqueous two-pack type first colored paint (X) is usually preferably 30 to 80% by mass, more preferably 40 to 70% by mass, and 45 to 60% by mass Is more preferred.
- An aqueous two-pack type first colored paint (X) is generally a two-pack type comprising a main agent containing a hydroxyl group-containing resin (X1) and a pigment (X3), and a curing agent containing a polyisocyanate compound (X2) It is preferable to use a paint.
- the aqueous two-component first colored paint (X) can be coated on a substrate by a method known per se, for example, air spray coating, airless spray coating, rotary atomization coating, curtain coating coating, etc. At the time of coating, electrostatic application may be performed. Among these, methods such as air spray coating and rotary atomization coating are preferable.
- the coating amount is preferably 10 to 50 ⁇ m, preferably 10 to 40 ⁇ m, as a cured film thickness.
- Process (2) In the method for forming a multilayer coating film of the present invention, next, an aqueous one-component second colored paint (Y) is applied on the uncured first colored coating film obtained in step (1), Form a cured second colored coating.
- the aqueous one-component second colored paint (Y) contains a hydroxyl group-containing acrylic resin (Y1), a hydroxyl group-containing polyester resin (Y2), and a block polyisocyanate compound and / or a melamine resin (Y3).
- the hydroxyl group-containing acrylic resin (Y1) contains a core-shell type water dispersible hydroxyl group-containing acrylic resin (Y11), and the core-shell type water dispersible hydroxyl group-containing acrylic resin (Y11) has a core-shell type structure
- the content ratio of each monomer in the total amount of the monomer components constituting the core portion and the shell portion of the core-shell type structure is based on the total mass of the monomer components constituting the core portion and the shell portion, 40 to 85 mass% of a polymerizable unsaturated monomer (a-1) having a glass transition temperature of -20 ° C.
- Examples of the polymerizable unsaturated monomer (a-1) having a homopolymer having a glass transition temperature of ⁇ 20 ° C. or less include linear or branched alkyl acrylates having 2 to 18 carbon atoms, and having hydroxyl group-containing polymerizability Monomers having functional groups such as unsaturated monomers are excluded.
- Examples of the monomer include ethyl acrylate (glass transition temperature (Tg) of homopolymer: -22 ° C.), n-butyl acrylate (-54 ° C.), isobutyl acrylate (-22 ° C.), n-hexyl acrylate (-57) C., n-octyl acrylate (-63.degree. C.), 2-ethylhexyl acrylate (-53.degree. C.), lauryl acrylate (-65.degree. C.) and the like. These monomers can be used alone or in combination of two or more.
- the Tg of the homopolymer of each monomer is the value according to Polymer Hand Book (Second Edition, edited by J. Brandup. E. H. Immergut) III-139-179. Also, when the Tg of the homopolymer of the monomer is not clear, a static glass transition temperature is used, and a sample is placed in a measuring cup using, for example, a differential scanning calorimeter "DSC-220U" (manufactured by Seiko Instruments Inc.). After completely removing the solvent by suction, measure the change in heat value in the range of -20 ° C to + 200 ° C at a heating rate of 3 ° C / min, and change the first baseline change point on the low temperature side to a static glass transition It was the temperature.
- DSC-220U differential scanning calorimeter
- the hydroxyl group-containing polymerizable unsaturated monomer (a-2) can improve the stability of the obtained core-shell type water-dispersible acrylic resin (Y11) in an aqueous medium.
- the hydroxyl group-containing polymerizable unsaturated monomer (a-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) ⁇ -caprolactone modified of monoester of (meth) acrylic acid such as acrylate with dihydric alcohol having 2 to 8 carbon atoms, monoester of the (meth) acrylic acid and dihydric alcohol of 2 to 8 carbon atoms It is possible to use N-hydroxymethyl (meth) acrylamide, allyl alcohol, (meth) acrylate having a polyoxyethylene chain whose molecular terminal is a hydroxyl group, and the like.
- the carboxyl group-containing polymerizable unsaturated monomer (a-3) can improve the stability of the obtained core-shell type water-dispersible hydroxyl group-containing acrylic resin (Y11) in an aqueous medium.
- Examples of the carboxyl group-containing polymerizable unsaturated monomer (a-3) include (meth) acrylic acid, maleic acid, crotonic acid, ⁇ -carboxyethyl acrylate and the like. These monomers can be used alone or in combination of two or more.
- the polymerizable unsaturated monomers (a-4) other than the above-mentioned polymerizable unsaturated monomers (a-1) to (a-3) are appropriately selected according to the characteristics desired for the water-dispersible hydroxyl group-containing acrylic resin (Y1). Can be used. Specific examples of the polymerizable unsaturated monomer (a-4) are listed below. These can be used alone or in combination of two or more.
- Examples of the polymerizable unsaturated monomer (a-4) include methyl (meth) acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl (meth) acrylate and hexyl Methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, tricyclodecanyl (meth) acrylate And alkyl or cycloalkyl (meth) acrylates; and isobornyl groups such as isobornyl (
- Nitrogen-containing compounds such as (meth) acrylonitrile, (meth) acrylamide, methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, 2- (methacryloyloxy) ethyl trimethyl ammonium chloride, an adduct of glycidyl (meth) acrylate and an amine compound, etc.
- Polymerizable unsaturated monomer Polymerizable unsaturated monomer having at least two polymerizable unsaturated groups in one molecule, such as allyl (meth) acrylate and 1,6-hexanediol di (meth) acrylate; Glycidyl (meth) acrylate , ⁇ Epoxy groups such as methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate and allyl glycidyl ether Containing polymerizable unsaturated monomer; (meth) acrylate having a polyoxyethylene chain whose molecular terminal is an alkoxy group; 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth)
- the content ratio of the polymerizable unsaturated monomer (a-4) other than the polymerizable unsaturated monomers (a-1) to (a-3) are the smoothness, the image sharpness and the water resistance of the formed coating film From the viewpoint of the above, it is preferable to be within the following range based on the total mass of these monomer components.
- a-1 having a homopolymer having a glass transition temperature of ⁇ 20 ° C. or less
- the hydroxyl group-containing polymerizable unsaturated monomer (a-2) 0.1 to 15% by mass, preferably 0.5 to 15% by mass
- Carboxyl group-containing polymerizable unsaturated monomer (a-3) 0.1 to 10% by mass, preferably 0.5 to 5% by mass
- the core-shell type water-dispersible hydroxyl group-containing acrylic resin (Y11) is preferably further crosslinked in the core portion, and the polymerizable unsaturated group is preferably 1 based on the total mass of the monomer components constituting the core portion. It is desirable to contain 0.1 to 10% by mass, preferably 0.1 to 5% by mass, of a polymerizable unsaturated monomer having at least two in the molecule.
- the above-mentioned core-shell type water-dispersible hydroxyl group-containing acrylic resin (Y11) can generally have an average particle diameter within the range of about 10 to 1,000 nm, particularly about 20 to 500 nm.
- the average particle size of the core-shell type water-dispersible hydroxyl group-containing acrylic resin (Y11) is diluted with deionized water by a conventional method using a dynamic light scattering particle size distribution analyzer. And at 20 ° C.
- a dynamic light scattering particle size distribution measuring apparatus for example, "Submicron particle analyzer N5" (trade name, manufactured by Beckman Coulter, Inc.) can be used.
- the core-shell type water-dispersible hydroxyl group-containing acrylic resin (Y11) is neutralized with an acidifying agent such as a carboxyl group which the water-dispersible acrylic resin has, in order to improve the mechanical stability of the particles. It is desirable to do.
- the neutralizing agent is not particularly limited as long as it can neutralize an acid group, and examples thereof include sodium hydroxide, potassium hydroxide, trimethylamine, 2- (dimethylamino) ethanol, 2-amino-2-methyl- Examples include 1-propanol, triethylamine, aqueous ammonia and the like. These neutralizing agents are preferably used in such an amount that the pH of the aqueous dispersion of the water-dispersible acrylic resin after neutralization is about 6.5 to 9.0.
- the ratio of the core portion to the shell portion is solid, from the viewpoint of improving the smoothness, the image sharpness, the brightness and the water resistance of the formed film.
- the core / shell ratio is preferably about 50/50 to 95/5, more preferably about 70/30 to 95/5, in terms of the mass ratio by mass.
- the core-shell type water-dispersible hydroxyl group-containing acrylic resin (Y11) is usually obtained by emulsion-polymerizing a monomer mixture constituting the core portion to obtain an emulsion of the core portion copolymer, and then the shell portion is formed in this emulsion.
- the emulsion polymerization can be carried out by a conventionally known method, for example, by emulsion polymerization of a monomer mixture using a polymerization initiator in the presence of a surfactant.
- the core-shell type water-dispersible hydroxyl group-containing acrylic resin (Y11) obtained as described above has an acid value of 0.1 to 100 mg KOH / g from the viewpoint of the storage stability of the paint and the water resistance of the obtained coating film.
- the hydroxyl value is preferably about 2 to 50 mg KOH / g, more preferably about 0.1 to 100 mg KOH / g, and still more preferably about 2 to 50 mg KOH / g.
- the glass transition temperature is preferably about ⁇ 50 to 0 ° C., and more preferably about ⁇ 30 to ⁇ 5 ° C., from the viewpoint of penetration of the curing agent component from the upper layer and the lower layer film.
- the above-mentioned hydroxyl group-containing polyester resin (Y2) is obtained by the reaction of an acid component and an alcohol component, and has a hydroxyl value of 100 to 200 mg KOH / g, preferably 105 to 195 mg KOH / g, and an acid value of 10 to 30 mg KOH / g, preferably It contains 10 to 25 mg KOH / g of polyester resin (Y21).
- the hydroxyl group-containing polyester resin (Y21) particularly contains an alicyclic polyvalent carboxylic acid (including an acid anhydride) (b-1) as an acid component of the raw material, and the content thereof is based on the total amount of the acid component
- the diol component (b-2) is at least 30 mol% and has a branched alkylene group and at least 5 carbon atoms as an alcohol component of the raw material, and its content is at least 40 based on the total amount of alcohol components. It is desirable from the viewpoint of securing the coating film hardness that it is mol%.
- the alicyclic polyvalent carboxylic acid (including the acid anhydride) (b-1) includes at least one alicyclic structure (preferably a four- to six-membered ring structure) and at least two carboxyls in one molecule.
- Group-containing compounds and acid anhydrides of the compounds specifically, for example, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid anhydride, 1,3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic anhydride, 3-methyl-1,2-cyclohexanedicarboxylic acid, 3-methyl-1,2-dicarboxylic acid Cyclohexanedicarboxylic acid anhydride, 4-methyl-1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexane
- the other acid component that can be used in combination with the above-mentioned alicyclic polyvalent carboxylic acid (including acid anhydride) (b-1) is not particularly limited, and one usually used in the production of polyester resin It is likewise possible to use, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, octadecanedioic acid, citric acid, maleic acid
- Polyvalent carboxylic acids such as fumaric acid, itaconic acid, and anhydrides thereof (including acid anhydrides); phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic anhydride , Aromatic polyvalent carboxylic acids (including acid anhydrides) such as pyromellitic acid, pyromellitic anhydride,
- polyhydric alcohols having at least two hydroxyl groups in one molecule can be suitably used.
- Examples of the diol (b-2) having a branched alkylene group and having at least 5 carbon atoms include 3-methyl-1,2-butanediol, 2,2-diethyl-1,3 and the like among the above-mentioned dihydric alcohols.
- the synthesis method of the hydroxyl group-containing polyester resin (Y21) is not particularly limited, and can be performed according to a usual method.
- the acid component and the alcohol component can be synthesized by heating in a nitrogen stream at about 150 to about 250 ° C. for about 5 to 10 hours to carry out an esterification reaction of a hydroxyl group and a carboxyl group.
- the acid component and the alcohol component When the acid component and the alcohol component are subjected to an esterification reaction, they may be added at once or in several portions. In addition, after a hydroxyl group-containing polyester resin is first synthesized, acid anhydride may be reacted to perform half-esterification.
- the hydroxyl group-containing polyester resin (Y21) generally has a number average molecular weight within the range of 300 to 50000, particularly 500 to 20000, and more particularly 800 to 10000, from the viewpoint of the smoothness and coating film performance of the obtained coating It is suitable.
- the hydroxyl group-containing polyester resin (Y21) is preferably neutralized with a neutralizing agent in order to facilitate mixing and dispersion in water.
- block polyisocyanate compound and / or the melamine resin (Y3) either one or both of a block polyisocyanate compound and a melamine resin can be used.
- the blocked polyisocyanate compound is a compound obtained by blocking an isocyanate group of a polyisocyanate compound having at least two isocyanate groups in one molecule with a blocking agent.
- polyisocyanate compounds examples include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, derivatives of these polyisocyanates, and the like, as described above for the polyisocyanate compounds (X2). Those listed are listed.
- the above blocking agents block free isocyanate groups, and for example, phenolic compounds, lactams, ether compounds, glycolic acid esters, lactic acid esters, alcohol compounds, oxime compounds, active methylene compounds, A mercaptan type compound, an amide type compound, an imide type compound, an amine type compound, a urea type compound, a carbamic acid ester type compound, an imine type compound, an azole type compound, etc. are mentioned.
- An especially preferred blocked polyisocyanate compound is an active methylene blocked polyisocyanate compound (Y31) having a hydrophilic group.
- the active methylene block polyisocyanate compound having a hydrophilic group in particular, a part of the isocyanate group in the polyisocyanate compound is reacted with an active hydrogen-containing compound having a hydrophilic group to introduce a hydrophilic group, and further, in the polyisocyanate compound
- a block polyisocyanate compound (Y311) obtained by reacting an active methylene compound with an isocyanate group can be suitably used, and the block polyisocyanate compound (Y311) is further obtained by reacting a secondary alcohol having 6 or more carbon atoms. Can be suitably used.
- the active hydrogen-containing compound having a hydrophilic group examples include an active hydrogen-containing compound having a nonionic hydrophilic group, an active hydrogen-containing compound having an anionic hydrophilic group, an active hydrogen-containing compound having a cationic hydrophilic group, and the like. These can be used alone or in combination of two or more. Among them, it is preferable to use an active hydrogen-containing compound having a nonionic hydrophilic group, since the reaction of blocking the isocyanate group in the polyisocyanate compound with the active methylene compound is hardly inhibited.
- an active hydrogen-containing compound having a nonionic hydrophilic group for example, an active hydrogen-containing compound having a polyoxyalkylene group can be suitably used.
- a polyoxyalkylene group a polyoxyethylene group, a polyoxypropylene group etc. are mentioned, for example, These can be used individually or in combination of 2 or more types.
- an active hydrogen-containing compound having a polyoxyethylene group is preferable from the viewpoint of storage stability of the present paint.
- the active hydrogen-containing compound having a nonionic hydrophilic group has a number average molecular weight in the range of 200 to 2,000 from the viewpoint of the storage stability of the present paint and the water resistance of the multilayer coating film formed. Is preferred.
- the lower limit of the number average molecular weight is more preferably 300, and still more preferably 400, from the viewpoint of the storage stability of the present paint.
- the upper limit is more preferably 1,500, and even more preferably 1,200, from the viewpoint of water resistance of the multilayer coating film to be formed.
- the active hydrogen-containing compound having a nonionic hydrophilic group for example, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether and polyethylene glycol are preferable, and polyethylene glycol monomethyl ether is more preferable.
- polyethylene glycol monomethyl ether for example, “UNIOX M-400”, “UNIOX M-550”, “UNIOX M-1000”, “UNIOX M-2000”, etc. manufactured by NOF Corporation Can be mentioned.
- the reaction of a part of the isocyanate groups in the polyisocyanate compound with the active hydrogen-containing compound having a hydrophilic group can be carried out at 0 to 150 ° C., and a solvent may be used.
- a solvent an aprotic solvent is preferable, and in particular, an ester, an ether, an N-alkylamide, a ketone and the like are preferable.
- the active hydrogen containing compound which did not react with the isocyanate group in a polyisocyanate compound can be removed after completion
- the reaction ratio of the polyisocyanate compound and the active hydrogen-containing compound having a hydrophilic group is poly in view of storage stability and curability of the paint, and smoothness, sharpness and adhesion of the multilayer coating film formed.
- the number of moles of active hydrogen in the active hydrogen-containing compound is in the range of 0.03 to 0.6 mol, and further in the range of 0.04 to 0.4 mol based on 1 mol of the isocyanate group in the isocyanate compound. Is preferred.
- Active methylene compounds include, for example, dimethyl malonate, diethyl malonate, di n-propyl malonate, diisopropyl malonate, di n-butyl malonate, diisobutyl malonate, di sec-butyl malonate, di t- malonate Butyl, di-n-pentyl malonate, di-n-hexyl malonate, di (2-ethylhexyl) malonate, methyl isopropyl malonate, ethyl isopropyl malonate, n-butyl malonate, n-butyl ethyl malonate, malon Malonic acid diesters such as methyl isobutyl acid, ethyl isobutyl malonate, methyl sec-butyl malonate, sec-butyl ethyl malonate, diphenyl malonate and dibenzyl malonate, methyl
- the active methylene compound is dimethyl malonate, diethyl malonate, diisopropyl malonate, methyl acetoacetate, ethyl acetoacetate, methyl isobutyryl acetate and It is preferable that it is at least one compound selected from the group consisting of ethyl isobutyryl acetate, and in particular, the smoothness and sharpness of the multilayer coating film formed, the reactivity of the block polyisocyanate compound obtained, and the present paint It is more preferable that it is diisopropyl malonate from the viewpoint of storage stability of
- a reaction catalyst can be used for the blocking reaction of the isocyanate group by an active methylene compound as needed.
- the reaction catalyst include metal hydroxides, metal alkoxides, metal carboxylates, metal acetylacetonates, hydroxides of onium salts, onium carboxylates, metal salts of active methylene compounds, onium salts of active methylene compounds, aminosilanes Basic compounds such as amines and phosphines are preferred.
- As the above onium salt ammonium salt, phosphonium salt and sulfonium salt are preferable.
- the amount of the reaction catalyst to be used is usually preferably in the range of 10 to 10,000 ppm, and more preferably in the range of 20 to 5,000 ppm, based on the total solid mass of the polyisocyanate compound and the active methylene compound. Is more preferred.
- the blocking reaction of the isocyanate group with the active methylene compound can be carried out at 0 to 150 ° C., and a solvent may be used.
- a solvent an aprotic solvent is preferable, and in particular, an ester, ether, N-alkylamide, ketone and the like are preferable. If the reaction proceeds as intended, the basic component which is a catalyst may be neutralized to stop the reaction by adding an acid component.
- the amount of the active methylene compound to be used is not particularly limited, but 0.1 to 3 moles, preferably 0.2 based on 1 mole of the isocyanate group in the polyisocyanate compound. It is preferable to use up to 2 moles.
- the active methylene compound which has not reacted with the isocyanate group in the polyisocyanate compound can be removed after completion of the blocking reaction.
- the isocyanate group in the polyisocyanate compound is reacted with the active methylene compound to obtain a block polyisocyanate compound (Y311).
- the block polyisocyanate compound (Y311) can further be reacted with a secondary alcohol having 6 or more carbon atoms.
- Examples of the secondary alcohol having 6 or more carbon atoms include 4-methyl-2-pentanol, 5-methyl-2-hexanol, 6-methyl-2-heptanol, 7-methyl-2-octanol and the like. These can be used alone or in combination of two or more.
- part or all of the alcohol derived from active methylene in the block polyisocyanate compound (Y311) is removed by distillation outside the system by heating and reduced pressure or the like. This is a preferred method of promoting the reaction to obtain the product.
- the above production method is carried out at a temperature of 20 to 150 ° C., preferably 75 to 95 ° C., optionally under reduced pressure, for 5 minutes to 20 hours, preferably 10 minutes to 10 hours. It is appropriate to remove some or all of the alcohol.
- the blend ratio of the block polyisocyanate compound (Y311) and the secondary alcohol is preferably in the range of 5 to 500 parts by mass based on 100 parts by mass of the solid content of the block polyisocyanate compound (Y311). And more preferably in the range of 10 to 200 parts by mass.
- the number average molecular weight of the active methylene block polyisocyanate compound (Y31) having a hydrophilic group obtained as described above is the compatibility with other paint components, smoothness of the multilayer coating film formed, sharpness, water resistance And from the viewpoint of chipping resistance etc., it is preferably in the range of 600 to 30,000, and more preferably in the range of 900 to 10,000.
- Examples of the melamine resin include methylolmelamines such as dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine and hexamethylolmelamine; alkyl ether compounds of methylolmelamine and alcohol; condensate of methylolmelamine and alcohol Etherified products of
- examples of the alcohol include C1-10 alkanols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol and 2-ethylhexyl alcohol.
- melamine resin for example, a melamine resin having an average of at least three methylolated methylol groups per triazine core; a hydrophilic imino group-containing alkyletherified melamine resin having a weight average molecular weight of about 500 to 1000, etc. It can be used suitably.
- sulfonic acids such as para-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, etc .
- curing salts of the sulfonic acid and amine and phosphoric acid ester compounds as a curing catalyst
- Neutralizing salts with amines can be used.
- the blending ratio of the hydroxyl group-containing acrylic resin (Y1), the hydroxyl group-containing polyester resin (Y2), and the block polyisocyanate compound and / or the melamine resin (Y3) in the aqueous one-component second colored paint (Y) is the total of these Based on 100 parts by mass, it can be in the following range.
- the aqueous one-pack second colored paint (Y) contains, in addition to the above (Y1) to (Y3), a modifying resin such as a water-soluble or water-dispersible acrylic resin, polyurethane resin or alkyd resin. Can.
- the aqueous one-pack second colored paint (Y) may further contain a pigment such as a color pigment, an extender pigment, or a bright pigment. Among them, it is preferable to contain a color pigment and / or a luster pigment as at least one of the above pigments.
- color pigments examples include titanium oxide, zinc flower, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigments, and phthalocyanines as exemplified in the description of the aqueous two-pack type first colored paint (X).
- pigments such as system pigments, quinacridone pigments, isoindoline pigments, srene pigments, perylene pigments, dioxazine pigments, diketopyrrolopyrrole pigments and the like.
- the content of the color pigment is based on 100 parts by mass of the resin solids in the aqueous one-pack second colored paint (Y) It is preferably in the range of usually 1 to 150 parts by mass, in particular 3 to 130 parts by mass, and more particularly 5 to 110 parts by mass.
- the luster pigment examples include aluminum (including vapor-deposited aluminum), copper, zinc, brass, nickel, aluminum oxide, mica, aluminum oxide coated with titanium oxide and iron oxide, titanium oxide and iron oxide and the like And mica pigments, glass flakes, hologram pigments and the like.
- aluminum, aluminum oxide, mica, aluminum oxide coated with titanium oxide or iron oxide, and mica coated with titanium oxide or iron oxide are preferably used.
- the bright pigments may be used alone or in combination of two or more.
- the content of the bright pigment is 100 parts by mass of resin solid content in the aqueous one-pack second colored paint (Y).
- it is preferably in the range of usually 1 to 50 parts by mass, particularly 2 to 30 parts by mass, and more particularly 3 to 20 parts by mass.
- the aqueous one-component second colored paint (Y) is, if necessary, an organic solvent, a curing catalyst, a thickener, a UV absorber, a light stabilizer, an antifoamer, a plasticizer, a surface conditioner, and an antisettling agent.
- Conventional paint additives such as agents can be used alone or in combination of two or more.
- the aqueous one-pack second colored paint (Y) can be coated by a method known per se, for example, air spray, airless spray, rotary atomizer, etc. It is also good.
- the coating film thickness can be in the range of usually 5 to 50 ⁇ m, preferably 5 to 40 ⁇ m, and more preferably 5 to 30 ⁇ m, as a cured film thickness.
- Process (3) In the multilayer coating film forming method of the present invention, the two-component clear paint (Z) is applied on the uncured second colored coating film obtained in the above step (2) to form an uncured clear coating film. Do.
- the second colored coating film is preheated (preheating) under heating conditions such that the coating film does not substantially cure before applying the two-component clear paint (Z) ), Air blow, etc. are preferable.
- the temperature for preheating is preferably in the range of usually about 40 to about 80 ° C., particularly about 50 to about 80 ° C., and more particularly about 60 to about 80 ° C.
- the preheating time is usually about 30 seconds to about 15 minutes, preferably about 1 to about 10 minutes, and more preferably about 2 to about 5 minutes.
- the air blowing can be carried out by spraying the air heated to normal temperature or a temperature of 25 ° C. to about 80 ° C. for about 30 seconds to about 15 minutes onto the coated surface of the object to be coated.
- the second colored coating film usually has a solid content of 70 to 100% by mass of the coating film by performing the above-mentioned preheating, air blowing, etc. as necessary before applying the two-component clear paint (Z).
- the two-component clear paint (Z) contains a hydroxyl group-containing acrylic resin (Z1) and a polyisocyanate compound (Z2).
- the hydroxyl group-containing acrylic resin (Z1) can be usually produced by copolymerizing a hydroxyl group-containing unsaturated monomer and another unsaturated monomer copolymerizable with the monomer according to a conventional method.
- the hydroxyl group-containing unsaturated monomer is a compound having at least one hydroxyl group and at least one polymerizable unsaturated bond in one molecule, and examples thereof include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, Monoesters of (meth) acrylic acid such as 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and a dihydric alcohol having 2 to 8 carbon atoms; (meth) acrylic acid and 2 to carbon atoms ⁇ -caprolactone modified product of monoester compound with dihydric alcohol of 8; allyl alcohol; (meth) acrylate having a polyoxyethylene chain whose molecular terminal is a hydroxyl group.
- Examples of other unsaturated monomers copolymerizable with the above-mentioned hydroxyl group-containing unsaturated monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n -Butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate Lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, "isostearyl acrylate” (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), cycl
- Carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, maleic acid, crotonic acid, ⁇ -carboxyethyl acrylate (Meth) acrylonitrile, (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, adduct of glycidyl (meth) acrylate with amines, etc.
- Nitrogen-containing unsaturated monomers glycidyl (meth) acrylate, ⁇ -methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxy Epoxy group-containing unsaturated monomers such as cyclohexylpropyl (meth) acrylate and allyl glycidyl ether; (meth) acrylates having a polyoxyethylene chain whose molecular terminal is an alkoxy group; 2-acrylamido-2-methylpropane sulfonic acid, allyl sulfone Unsaturated monomers having a sulfonic acid group such as acid, styrene sulfonic acid sodium salt, sulfoethyl methacrylate and its sodium salt and ammonium salt; 2-acryloyloxyethyl
- the synthesis of the hydroxyl group-containing acrylic resin (Z1) can be carried out using a general unsaturated monomer polymerization method, but in view of versatility and cost, it is carried out by a solution type radical polymerization method in an organic solvent Is the most suitable.
- the hydroxyl group-containing acrylic resin (Z1) is, for example, an aromatic solvent such as xylene or toluene; a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone; an ester solvent such as ethyl acetate, butyl acetate, isobutyl acetate or 3-methoxybutyl acetate
- the hydroxyl group-containing acrylic resin (Z1) has a hydroxyl value of 80 to 200 mg KOH / g, particularly 90 to 170 mg KOH / g, and particularly 100, from the viewpoint of finished appearance such as smoothness and sharpness and coating film performance such as weatherability.
- the acid value is preferably in the range of ⁇ 140 mg KOH / g, and the acid value is preferably in the range of 1 to 40 mg KOH / g, particularly 3 to 30 mg KOH / g, and more particularly 5 to 20 mg KOH / g.
- the hydroxyl group-containing acrylic resin (Z1) has a weight average molecular weight of 4000 to 20000, particularly 6000 to 16000, and more particularly 8000 to 12000, from the viewpoint of finished appearance such as smoothness and sharpness and coating film performance such as weatherability. It is preferable to be within the range of
- the polyisocyanate compound (Z2) is a compound having at least two isocyanate groups in one molecule, and examples thereof include aliphatic polyisocyanate, alicyclic polyisocyanate, araliphatic polyisocyanate, and aromatic polyisocyanate, There can be mentioned derivatives of polyisocyanate and the like, which can be appropriately selected and used from the polyisocyanate compounds listed in the description of the above-mentioned polyisocyanate compound (X2), and may be used alone, or two kinds. The above may be used in combination.
- aliphatic diisocyanates and derivatives of aliphatic diisocyanates can be suitably used from the viewpoints of the smoothness and the sharpness and the weather resistance of the obtained coating film.
- the two-component clear paint (Z) is a hydroxyl group-containing acrylic resin (Z1) and a polyisocyanate compound (Z2), and an isocyanate in the polyisocyanate compound (Z2) relative to one equivalent of hydroxyl groups in the hydroxyl group-containing acrylic resin (Z1). It is preferable from the viewpoint of low temperature curability that the group is contained in a proportion of 1.1 to 2.0 equivalents, particularly 1.1 to 1.8 equivalents.
- a color pigment, a bright pigment, a dye, etc. can be contained to the extent that the transparency is not impaired, and further, an extender pigment, an ultraviolet absorber, A light stabilizer, an antifoamer, a thickener, a rust inhibitor, a surface control agent, etc. can be contained suitably.
- the two-component clear paint (Z) is preferably a two-component paint comprising a main agent containing a hydroxyl group-containing acrylic resin (Z1) and a curing agent containing a polyisocyanate compound (Z2).
- the two-component clear paint (Z) can be applied to the second colored coating film surface by a method known per se, such as air spray coating, airless spray coating, rotary atomization coating, etc. At this time, electrostatic application may be performed.
- the clear coating (Z) can be applied to have a cured film thickness of usually 10 to 80 ⁇ m, preferably 15 to 60 ⁇ m, more preferably 20 to 50 ⁇ m.
- Process (4) In the method for forming a multilayer coating film of the present invention, the uncured first colored coating film, the uncured second colored coating film, and the uncured clear coating formed in the steps (1) to (3) described above The film is simultaneously cured by heating.
- the curing of the first colored coating film, the second colored coating film and the clear coating film can be carried out by a conventional coating film baking means such as hot air heating, infrared heating, high frequency heating and the like.
- the heating temperature can be in the range of usually about 60 to about 120 ° C., preferably about 70 to about 100 ° C., and more preferably about 80 to about 100 ° C.
- the heating time is not particularly limited, but generally about 10 to 60 minutes, preferably about 15 to 40 minutes. This heating makes it possible to simultaneously cure a multilayer coating film consisting of three layers of the first colored coating film, the second colored coating film and the clear coating film.
- Production Example 2 In Production Example 1, 43 parts of “Bayjodur XP-2655” and 43 parts of “Bibijule 3100” (trade name, manufactured by Sumika Kobesutorurethane Co., Ltd., polyisocyanate compound) (NC0 / OH ratio is 1.55) An aqueous first colored paint (X-2) was obtained in the same manner as in Production Example 1 except for using the above.
- the reaction solution was cooled to 85 ° C., neutralized with dimethylethanolamine, deionized water was added, and dispersed in water to obtain an aqueous dispersion (X1-1) of an acrylic modified polyester resin having a solid content of 35%.
- the obtained acrylic modified polyester resin had an acid value of 35 mg KOH / g, a hydroxyl value of 110 mg KOH / g, and a number average molecular weight of 2,300.
- Pigment dispersion paste (P-1) 20 parts by weight of solid content mass of water dispersion (X1-1) (Note 1) of the above acrylic modified polyester resin in a stirring and mixing vessel, "JR-806" ( Trade name, manufactured by Tayca, 60 parts of rutile titanium dioxide, 30 parts of "BLANC FIXE micro” (trade name, manufactured by Sachtleben chemie, barium sulfate, particle diameter of 0.7 ⁇ m), "Mitsubishi carbon black MA-100” The product was mixed with 0.6 parts of carbon black (trade name, manufactured by Mitsubishi Chemical Corporation) and 30 parts of deionized water, mixed uniformly, and further adjusted to pH 8.0 by adding 2- (dimethylamino) ethanol.
- the obtained mixed solution is placed in a wide-mouthed glass bottle, glass beads with a diameter of about 1.3 mm ⁇ are added as a dispersion medium, sealed, and dispersed for 4 hours with a paint shaker to obtain a pigment dispersion (P-1) Obtained.
- Hydroxyl group-containing acrylic resin water dispersion (X1-2) A water-dispersed body fluid of a core-shell type hydroxyl group-containing acrylic resin having a hydroxyl value of 65 mg KOH / g, an acid value of 13 mg KOH / g and a solid content concentration of 30%.
- the remaining monomer emulsion (1) was dropped into the reaction vessel maintained at the same temperature over 3 hours, and aging was performed for 1 hour after the dropping was completed. Thereafter, the following monomer emulsion (2) was added dropwise over 1 hour, and after aging for 1 hour, it was cooled to 30 ° C. while gradually adding 40 parts of a 5% aqueous 2- (dimethylamino) ethanol solution to the reaction vessel. Average particle diameter 195 nm (Diluted with deionized water and measured at 20 ° C.
- Monomer emulsion (1) 54 parts of deionized water, 6.9 parts of "ADEKAREASOAP SR-1025", 49 parts of 2-ethylhexyl acrylate, 23 parts of ethyl acrylate, 13 parts of methyl methacrylate, 2-hydroxyether methacrylate4. 5 parts and 0.2 parts of allyl methacrylate were mixed and stirred to obtain a monomer emulsion (1).
- Monomer emulsion (2) 12 parts of deionized water, 0.8 parts of "ADEKAREASOAP SR-1025", 0.2 parts of ammonium persulfate, 3.1 parts of methyl methacrylate, 5 parts of ethyl acrylate, 2-hydroxyethyl methacrylate One part and 1.2 parts of methacrylic acid were mixed and stirred to obtain a monomer emulsion (2).
- Production Examples 4 to 8 A water dispersible hydroxyl group-containing acrylic resin dispersion (Y1-2) is operated in the same manner as in Production Example 3 except that the monomer compositions in the monomer emulsions (1) and (2) are changed as shown in Table 1 below. To obtain (Y1-6).
- Production Example 15 of Aqueous Second Colored Paint 120 parts of the water-dispersible hydroxyl group-containing acrylic resin dispersion (Y1-1) obtained in Production Example 3 (36 parts of resin solid content), 71.4 parts of the hydroxyl group-containing polyester resin solution (Y2-1) obtained in Production Example 9 (Solid resin content 27 parts), “UX-3945” (trade name, manufactured by Sanyo Chemical Industries, Ltd., aqueous polyurethane resin) 26.3 parts (solid resin content 10 parts), bright pigment concentrated liquid (P-2) (Note 4) 63 parts, 16.6 parts (10 parts of resin solid content) of the block polyisocyanate compound solution (Y3-1) obtained in Production Example 13, melamine resin ("Cymel 327", trade name, manufactured by Ornex) 11.
- Bright pigment concentrated solution (P-2): 20 parts of aluminum pigment paste (trade name "GX-180A", manufactured by Asahi Kasei Metals Co., Ltd., metal content 74%) in a stirring and mixing vessel, 2- 35 parts of ethyl-1-hexanol, 8 parts of a phosphoric acid group-containing resin solution (Note 5) and 0.2 parts of 2- (dimethylamino) ethanol were uniformly mixed to obtain a bright pigment dispersion.
- Phosphate group-containing resin solution A mixture of 27.5 parts of methoxypropanol and 27.5 parts of isobutanol in a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, a nitrogen introducing pipe, and a dropping device. The solvent was charged and heated to 110 ° C.
- the acid value by the phosphoric acid group of the phosphoric acid group-containing resin was 83 mg KOH / g, the hydroxyl value was 29 mg KOH / g, and the weight average molecular weight was 10,000.
- Phosphoric acid group-containing polymerizable monomer 57.5 parts of monobutyl phosphoric acid and 41 parts of isobutanol are put into a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, a nitrogen introducing pipe and a dropping device, After the temperature was raised to 90 ° C., 42.5 parts of glycidyl methacrylate was dropped over 2 hours. Then, after aging for 1 hour with stirring, 59 parts of isopropanol was added to obtain a phosphoric acid group-containing polymerizable monomer solution having a solid concentration of 50%. The acid value by the phosphate group of the obtained monomer was 285 mg KOH / g.
- Production Examples 16 to 25 Aqueous second colored paints (Y-2) to (Y-11) were obtained in the same manner as in Production Example 15 except that the formulation was changed as shown in Table 3 in Production Example 15.
- a polymerization initiator solution in which 0.5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (polymerization initiator) was dissolved in 3 parts of Swazole 1000 (hydrocarbon solvent) for 1 hour It dripped over. Then, after aging for 2 hours while bubbling nitrogen gas at 155 ° C., the solution is cooled to 100 ° C. and diluted with 29 parts of butyl acetate to obtain a hydroxyl group-containing acrylic resin (Z1-1) solution having a solid content of 60%. Obtained.
- the obtained hydroxyl group-containing acrylic resin (Z1-1) had a hydroxyl value of 129 mg KOH / g, an acid value of 19 mg KOH / g, and a weight average molecular weight of about 12000.
- Production Example 27 In Production Example 26, a composition comprising 30 parts of styrene, 37.5 parts of n-butyl acrylate, 30 parts of 2-hydroxypropyl acrylate, 2.5 parts of acrylic acid, and 4 parts of diterchathia mill peroxide (polymerization initiator) Monomer having a composition comprising 30 parts of styrene, 40.5 parts of n-butyl acrylate, 27 parts of 2-hydroxyethyl acrylate, 2.5 parts of acrylic acid, and 4 parts of diterchatrial mill peroxide (polymerization initiator)
- a solution of hydroxyl group-containing acrylic resin (Z1-2) having a solid content of 60% was obtained by manufacturing in the same manner as in Production Example 26 except that the mixture was changed to a mixture.
- the obtained hydroxyl group-containing acrylic resin (Z1-2) had a hydroxyl value of 129 mg KOH / g, an acid value of 19 mg KOH / g, and a weight average molecular weight of about 12000
- Benzotriazole-based UV absorber 100 parts of active ingredient
- 2.0 parts of "TINUVIN 292" trade name, B.A.S.F., a hindered amine light stabilizer, 100% of active ingredient
- “Swazol 1000” trade name, manufactured by Cosmo Oil Co., Ltd., hydrocarbon-based solvent
- Ford cup No. 1 at 20 ° C. was added.
- a clear paint (Z-1) having a viscosity of 25 seconds according to No. 4 was obtained.
- Production Example 29 A production example 28 is the same as production example 28 except that the hydroxyl group-containing acrylic resin (Z1-2) solution obtained in production example 27 is used instead of the hydroxyl group-containing acrylic resin (Z1-1) solution obtained in production example 26.
- the clear paint (Z-2) was obtained.
- Production Example 30 Production Example 28 except that “Desmodur N 3900” is 45 parts of “Duranate TLA-100” (trade name, manufactured by Asahi Kasei Chemicals Corporation, polyisocyanate compound) (NC0 / OH ratio is 1.6). A clear paint (Z-3) was obtained in the same manner as in.
- test article (2) air spray coating is performed on the polypropylene plate (greased) with the primer Soflex 3100 (trade name: Kansai Paint Co., Ltd., polyolefin-containing conductive organic solvent type paint) to a dry film thickness of 10 ⁇ m, The composition was heated and cured at 80 ° C. for 30 minutes to obtain a test article (2).
- primer Soflex 3100 trade name: Kansai Paint Co., Ltd., polyolefin-containing conductive organic solvent type paint
- the dry first film thickness of the aqueous first colored paint (X-1) obtained in the above-mentioned Production Example 1 is set to 20 ⁇ m in a dry film thickness using the rotary atomization type electrostatic coating machine on the test object (1) for test.
- the aqueous second colored paint (Y-1) obtained in Production Example 15 on the uncured first colored coating film after electrostatic deposition and standing for 2 minutes. It electrostatically coated so that it might be set to 10 micrometers by dry film thickness using the machine, and after standing for 2 minutes, preheating was performed at 80 degreeC for 3 minutes.
- the clear paint (Z-1) obtained in Production Example 28 was electrostatically coated on the base paint film to a dry film thickness of 35 ⁇ m and left for 7 minutes.
- the test coated plate was produced by heating and curing the three-layer coating film by heating at 95 ° C. for 20 minutes (keep time).
- Example 2 to 17 and Comparative Examples 1 to 2 A test coated plate was produced in the same manner as in Example 1 except that the substrate, the aqueous first colored paint, the aqueous second colored paint and the clear paint in Example 1 were combined as shown in Table 4 below.
- Pencil hardness According to JIS K 5600-5-4, place the pencil lead at an angle of about 45 ° to the test coated plate surface, press the test coated plate surface strongly to the extent that the core does not break, and uniform speed forward Moved about 10 mm. The hardness symbol of the hardest pencil whose coating did not break was taken as pencil hardness.
- the Wc value is an index of the surface roughness amplitude at a wavelength of about 1 to 3 mm, and the smaller the measured value, the higher the smoothness of the coated surface.
- Sharpness Evaluated using Wa value measured by Wave Scan DOI.
- the Wa value is an index of the amplitude of the surface roughness of a wavelength of about 0.1 to 0.3 mm, and the smaller the measured value, the higher the sharpness of the painted surface.
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Abstract
Description
(1) 水性2液型第1着色塗料(X)を塗装して未硬化の第1着色塗膜を形成する工程、
(2) 工程(1)で得られた前記未硬化の第1着色塗膜の上に水性1液型第2着色塗料(Y)を塗装して、未硬化の第2着色塗膜を形成する工程、
(3) 工程(2)で得られた前記未硬化の第2着色塗膜の上に2液型クリヤ塗料(Z)を塗装して、未硬化のクリヤ塗膜を形成する工程、ならびに
(4) 工程(1)~(3)で形成された前記未硬化の第1着色塗膜、前記未硬化の第2着色塗膜及び前記未硬化のクリヤ塗膜を加熱することによって、これらの塗膜を同時に硬化させる工程、
を順次行なうことを含む、複層塗膜形成方法であって、
前記水性1液型第2着色塗料(Y)が、水酸基含有アクリル樹脂(Y1)、水酸基含有ポリエステル樹脂(Y2)、ならびに、ブロックポリイソシアネート化合物及び/又はメラミン樹脂(Y3)を含有し、
前記水酸基含有アクリル樹脂(Y1)が、コア・シェル型水分散性水酸基含有アクリル樹脂(Y11)を含み、
前記コア・シェル型水分散性水酸基含有アクリル樹脂(Y11)は、
コア・シェル型構造を有し、かつ、
コア部とシェル部を構成するモノマー成分の合計量における各モノマーの含有割合が、コア部とシェル部とを構成するモノマー成分の合計質量を基準として、
ホモポリマーのガラス転移温度が-20℃以下である重合性不飽和モノマー(a-1) 40~85質量%、
水酸基含有重合性不飽和モノマー(a-2) 0.1~15質量%、
カルボキシル基含有重合性不飽和モノマー(a-3) 0.1~10質量%、及び、
前記重合性不飽和モノマー(a-1)~(a-3)以外の重合性不飽和モノマー(a-4) 0~59.8質量%、
であり、
前記水酸基含有ポリエステル樹脂(Y2)が水酸基価100~200mgKOH/g、酸価10~30mgKOH/gのポリエステル樹脂(Y21)を含む、複層塗膜形成方法に関する。
工程(1):
本発明の複層塗膜形成方法によれば、まず、被塗物上に、水性2液型第1着色塗料(X)を塗装して未硬化の第1着色塗膜を形成する。
本発明の複層塗膜形成方法では、次に、工程(1)で得られた未硬化の第1着色塗膜の上に水性1液型第2着色塗料(Y)を塗装して、未硬化の第2着色塗膜を形成する。
ホモポリマーのガラス転移温度が-20℃以下である重合性不飽和モノマー(a-1):40~85質量%、好ましくは45~80質量%、
水酸基含有重合性不飽和モノマー(a-2):0.1~15質量%、好ましくは0.5~15質量%、
カルボキシル基含有重合性不飽和モノマー(a-3):0.1~10質量%、好ましくは0.5~5質量%、
重合性不飽和モノマー(a-1)~(a-3)以外の重合性不飽和モノマー(a-4):0~59.8質量%、好ましくは0~54質量%。
水酸基含有アクリル樹脂(Y1):20~70質量部、好ましくは25~65質量部、
水酸基含有ポリエステル樹脂(Y2):20~70質量部、好ましくは25~65質量部、
ブロックポリイソシアネート化合物及び/又はメラミン樹脂(Y3):10~30質量部、好ましくは10~25質量部。
水性1液型第2着色塗料(Y)は、上記(Y1)~(Y3)の他に、水溶性もしくは水分散性のアクリル樹脂、ポリウレタン樹脂、アルキド樹脂等の改質用樹脂を含有することができる。
本発明の複層塗膜形成方法では、上記工程(2)で得られた未硬化の第2着色塗膜上に2液型クリヤ塗料(Z)を塗装して未硬化のクリヤ塗膜を形成する。
本発明の複層塗膜形成方法では、以上に述べた工程(1)~(3)で形成された未硬化の第1着色塗膜、未硬化の第2着色塗膜及び未硬化のクリヤ塗膜を加熱することによって同時に硬化させる。
製造例1
顔料分散ペースト(P-1)(注2)を固形分で110.6部、アクリル変性ポリエステル樹脂の水分散体(X1-1)(注1)を固形分で10部、水酸基含有アクリル樹脂水分散体(X1-2)(注3)を固形分で15部、「ユーコートUX-310」(商品名、三洋化成工業社製、ポリカーボネート系水性ポリウレタン樹脂)を固形分で20部、2-(ジメチルアミノ)エタノール及び脱イオン水を加えてpH調整し、さらに「バイヒジュールXP-2655」(商品名、住化コベストロウレタン社製、ポリイソシアネート化合物)35部(NC0/OH比が1.55)を均一に混合し、固形分51%、20℃におけるフォードカップNo.4による粘度20秒の水性第1着色塗料(X-1)を得た。
製造例1において、「バイヒジュールXP-2655」35部を「バイビジュール3100」(商品名、住化コベストロウレタン社製、ポリイソシアネート化合物)の量を43部(NC0/OH比が1.55)とする以外は製造例1と同様にして、水性第1着色塗料(X-2)を得た。
製造例3
温度計、サーモスタット、撹拌器、還流冷却器、窒素導入管及び滴下装置を備えた反応容器に脱イオン水120部、「アデカリアソープSR-1025」(商品名、ADEKA製、乳化剤、有効成分25%)0.52部を仕込み、窒素気流中で撹拌混合し、80℃に昇温した。次いで下記のモノマー乳化物(1)のうちの全量の1%量と6%過硫酸アンモニウム水溶液2.2部とを反応容器内に導入し80℃で15分間保持した。その後、残りのモノマー乳化物(1)を3時間かけて、同温度に保持した反応容器内に滴下し、滴下終了後1時間熟成を行なった。その後、下記のモノマー乳化物(2)を1時間かけて滴下し、1時間熟成した後、5%2-(ジメチルアミノ)エタノール水溶液40部を反応容器に徐々に加えながら30℃まで冷却し、平均粒子径195nm(サブミクロン粒度分布測定装置「COULTER N4型」(ベックマン・コールター社製)を用いて、脱イオン水で希釈し20℃で測定した。)、固形分濃度30%の水分散性水酸基含有アクリル樹脂分散液(Y1-1)を得た。得られた水分散性アクリル樹脂は、水酸基価が24mgKOH/g、酸価が8mgKOH/gであった。
モノマー乳化物(1)及び(2)におけるモノマー組成を下記表1に示すように変更する以外は、製造例3と同様に操作して、水分散性水酸基含有アクリル樹脂分散液(Y1-2)~(Y1-6)を得た。
製造例9~12
加熱装置、攪拌装置、温度計、還流冷却器及び精留塔を備えた4つ口フラスコに、下記表1に示すモル比の酸成分及びアルコール成分を仕込み、160℃まで昇温させた後、160℃から230℃まで3時間かけて、生成する縮合水を精留塔を用いて溜去しながら昇温させ、その後230℃で2時間反応させた。
製造例13
温度計、サーモスタット、撹拌装置、還流冷却器、窒素導入管、滴下装置及び除去溶媒簡易トラップを備えた反応容器に、「スミジュールN-3300」」(商品名、住化バイエルウレタン社製、ヘキサメチレンジイソシアネート由来のイソシアヌレート構造含有ポリイソシアネート、固形分約100%、イソシアネート基含有率21.8%)360部、「ユニオックスM-550」(日油社製、ポリエチレングリコールモノメチルエーテル、平均分子量 約550)60部及び2,6-ジ-tert-ブチル-4-メチルフェノール0.2部を仕込み、よく混合して、窒素気流下で130℃で3時間加熱した。次いで、酢酸エチル110部及びマロン酸ジイソプロピル252部を仕込み、窒素気流下で攪拌しながら、ナトリウムメトキシドの28%メタノール溶液3部を加え、65℃で8時間攪拌した。得られた樹脂溶液中のイソシアネート量は0.12モル/Kgであった。これに4-メチル-2-ペンタノール683部を加え、系の温度を80~85℃に保ちながら減圧条件下で3時間かけて溶剤を留去し、ブロックポリイソシアネート化合物溶液(Y3-1)1010部を得た。除去溶媒簡易トラップには、イソプロパノールが95部含まれていた。得られたブロックポリイソシアネート化合物溶液(Y3-1)の固形分濃度は約60%であった。
温度計、サーモスタット、撹拌装置、還流冷却器、窒素導入管、滴下装置及び除去溶媒簡易トラップを備えた反応容器に、「スミジュールN-3300」360部、「ユニオックスM-400」(日油社製、ポリエチレングリコールモノメチルエーテル、平均分子量 約400)50部、「PEG#600」(日油社製、ポリエチレングリコール、平均分子量 約600)5部及び2,6-ジ-tert-ブチル-4-メチルフェノール0.2部を仕込み、よく混合して、窒素気流下で130℃で3時間加熱した。次いで、酢酸エチル110部及びマロン酸ジイソプロピル247部を仕込み、窒素気流下で攪拌しながら、ナトリウムメトキシドの28%メタノール溶液3部を加え、65℃で8時間攪拌した。得られた樹脂溶液中のイソシアネート量は0.11モル/Kgであった。これに4-メチル-2-ペンタノール670部を加え、系の温度を80~85℃に保ちながら減圧条件下で3時間かけて溶剤を留去し、ブロックポリイソシアネート化合物溶液(Y3-2)1010部を得た。除去溶媒簡易トラップには、イソプロパノールが92部含まれていた。得られたブロックポリイソシアネート化合物溶液(Y3-2)の固形分濃度は約60%であった。
製造例15
製造例3で得た水分散性水酸基含有アクリル樹脂分散液(Y1-1)120部(樹脂固形分36部)、製造例9で得た水酸基含有ポリエステル樹脂溶液(Y2-1)71.4部(樹脂固形分27部)、「UX-3945」(商品名、三洋化成社製、水性ポリウレタン樹脂)26.3部(樹脂固形分10部)、光輝性顔料濃厚液(P-2)(注4)63部、製造例13で得たブロックポリイソシアネート化合物溶液(Y3-1)16.6部(樹脂固形分10部)、メラミン樹脂(「サイメル327」、商品名、オルネクス社製)11.1部(樹脂固形分10部)を均一に混合し、更に、「プライマルASE-60」(商品名、ロームアンドハース社製、増粘剤)、2-(ジメチルアミノ)エタノール及び脱イオン水を加えて、pH8.0、塗料固形分25%、20℃におけるフォードカップNo.4による粘度が40秒の水性第2着色塗料(Y-1)を得た。
製造例15において、配合組成を表3に示すとおりとする以外は、製造例15と同様にして水性第2着色塗料(Y-2)~(Y-11)を得た。
製造例26
撹拌装置、温度計、冷却管、窒素ガス導入口を備えた四ツ口フラスコにエトキシエチルプロピオネート31部を仕込み、窒素ガス通気下で155℃に昇温した。155℃に達した後、窒素ガスの通気を止め、スチレン30部、n-ブチルアクリレート37.5部、2-ヒドロキシプロピルアクリレート30部、アクリル酸2.5部及びジターシャリアミルパーオキサイド(重合開始剤)4部からなる組成配合のモノマー混合物を4時間かけて滴下した。30分後、2,2´-アゾビス(2,4-ジメチルバレロニトリル)(重合開始剤)0.5部をスワゾール1000(炭化水素系溶剤) 3部に溶解させた重合開始剤溶液を1時間かけて滴下した。ついで、155℃で窒素ガスを通気しながら2時間熟成させた後、100℃まで冷却し、酢酸ブチル29部で希釈することにより、固形分60%の水酸基含有アクリル樹脂(Z1-1)溶液を得た。得られた水酸基含有アクリル樹脂(Z1-1)は、水酸基価129mgKOH/g、酸価19mgKOH/g、重量平均分子量約12000であった。
製造例26において、スチレン30部、n-ブチルアクリレート37.5部、2-ヒドロキシプロピルアクリレート30部、アクリル酸2.5部及びジターシャリアミルパーオキサイド(重合開始剤)4部からなる組成配合のモノマー混合物を、スチレン30部、n-ブチルアクリレート40.5部、2-ヒドロキシエチルアクリレート27部、アクリル酸2.5部及びジターシャリアミルパーオキサイド(重合開始剤)4部からなる組成配合のモノマー混合物に変更する以外は、製造例26と同様にして製造することにより、固形分60%の水酸基含有アクリル樹脂(Z1-2)溶液を得た。得られた水酸基含有アクリル樹脂(Z1-2)は、水酸基価129mgKOH/g、酸価19mgKOH/g、重量平均分子量約12000であった。
製造例28
製造例26で得た水酸基含有アクリル樹脂(Z1-1)溶液100部(固形分60部)、「デスモジュールN3900」(商品名、住化コベストロウレタン社製、ポリイソシアネート化合物)45 部(NC0/OH比が1.6)、「BYK-300」(商品名、ビックケミー社製、表面調整剤、有効成分52%)0.2部、「TINUVIN900」(商品名、B.A.S.F.社製、ベンゾトリアゾール系紫外線吸収剤、有効成分100%)2.0部及び「TINUVIN292」(商品名、B.A.S.F.社製、ヒンダードアミン系光安定剤、有効成分100%)1.0部を均一に混合し、さらに、「スワゾール1000」(商品名、コスモ石油社製、炭化水素系溶剤)を加えて、20℃におけるフォードカップNo.4による粘度が25秒のクリヤ塗料(Z-1)を得た。
製造例28において、製造例26で得た水酸基含有アクリル樹脂(Z1-1)溶液の代わりに製造例27で得た水酸基含有アクリル樹脂(Z1-2)溶液を用いる以外は、製造例28と同様にしてクリヤ塗料(Z-2)を得た。
製造例28において、「デスモジュールN3900」を「デュラネートTLA-100」(商品名、旭化成ケミカルズ社製、ポリイソシアネート化合物)45部(NC0/OH比が1.6)とする以外は、製造例28と同様にしてクリヤ塗料(Z-3)を得た。
リン酸亜鉛化成処理を施した冷延鋼板に、「エレクロンGT-10」(商品名、関西ペイント社製、カチオン電着塗料)を乾燥膜厚20μmとなるように電着塗装し、170℃で30分間加熱して硬化させて、試験用被塗物(1)とした。
実施例1
上記試験用被塗物(1)に、上記製造例1で得た水性第1着色塗料(X-1)を、回転霧化型の静電塗装機を用いて、乾燥膜厚で20μmとなるように静電塗装し、2分間静置後、該未硬化の第1着色塗膜上に製造例15で得た水性第2着色塗料(Y-1)を、回転霧化型の静電塗装機を用いて、乾燥膜厚で10μmとなるように静電塗装し、2分間静置後、80℃で3分間プレヒートを行なった。
実施例1において、被塗物、水性第1着色塗料、水性第2着色塗料及びクリヤ塗料を下記表4に示す組合せとする以外は、実施例1と同様にして試験塗板を作製した。
上記実施例1~17及び比較例1~2で得られた各試験板について、下記の試験方法により評価を行なった。評価結果を併せて下記表4に示す。
鉛筆硬度:JIS K 5600-5-4に準じて、試験塗板面に対し約45°の角度に鉛筆の芯を当て、芯が折れない程度に強く試験塗板面に押し付けながら前方に均一な速さで約10mm動かした。塗膜が破れなかった最も硬い鉛筆の硬度記号を鉛筆硬度とした。
Claims (4)
- 被塗物上に、
(1) 水性2液型第1着色塗料(X)を塗装して未硬化の第1着色塗膜を形成する工程、
(2) 工程(1)で得られた前記未硬化の第1着色塗膜の上に水性1液型第2着色塗料(Y)を塗装して、未硬化の第2着色塗膜を形成する工程、
(3) 工程(2)で得られた前記未硬化の第2着色塗膜の上に2液型クリヤ塗料(Z)を塗装して、未硬化のクリヤ塗膜を形成する工程、ならびに
(4) 工程(1)~(3)で形成された前記未硬化の第1着色塗膜、前記未硬化の第2着色塗膜及び前記未硬化のクリヤ塗膜を加熱することによって、これらの塗膜を同時に硬化させる工程、
を順次行なうことを含む、複層塗膜形成方法であって、
前記水性1液型第2着色塗料(Y)が、水酸基含有アクリル樹脂(Y1)、水酸基含有ポリエステル樹脂(Y2)、ならびに、ブロックポリイソシアネート化合物及び/又はメラミン樹脂(Y3)を含有し、
前記水酸基含有アクリル樹脂(Y1)が、コア・シェル型水分散性水酸基含有アクリル樹脂(Y11)を含み、
前記コア・シェル型水分散性水酸基含有アクリル樹脂(Y11)は、コア・シェル型構造を有し、かつ、前記コア・シェル型構造のコア部とシェル部を構成するモノマー成分の合計量における各モノマーの含有割合が、コア部とシェル部とを構成するモノマー成分の合計質量を基準として、
ホモポリマーのガラス転移温度が-20℃以下である重合性不飽和モノマー(a-1) 40~85質量%、
水酸基含有重合性不飽和モノマー(a-2) 0.1~15質量%、
カルボキシル基含有重合性不飽和モノマー(a-3) 0.1~10質量%、及び、
前記重合性不飽和モノマー(a-1)~(a-3)以外の重合性不飽和モノマー(a-4) 0~59.8質量%、
であり、
前記水酸基含有ポリエステル樹脂(Y2)が水酸基価100~200mgKOH/g、酸価10~30mgKOH/gのポリエステル樹脂(Y21)を含む、
複層塗膜形成方法。 - 前記水酸基含有ポリエステル樹脂(Y21)が、原料の酸成分として脂環族多価カルボン酸(酸無水物を含む)(b-1)を含み、前記脂環族多価カルボン酸(酸無水物を含む)(b-1)の含有量が酸成分の合計量を基準として少なくとも30モル%であり、且つ原料のアルコール成分として分岐アルキレン基を有し炭素原子数が少なくとも5であるジオール(b-2)を含み、前記分岐アルキレン基を有し炭素原子数が少なくとも5であるジオール(b-2)の含有量がアルコール成分の合計量を基準として少なくとも40モル%である、請求項1に記載の複層塗膜形成方法。
- 前記水性2液型第1着色塗料(X)が、水酸基含有樹脂(X1)及びポリイソシアネート化合物(X2)を、水酸基含有樹脂(X1)中の水酸基1当量に対し、ポリイソシアネート化合物(X2)中のイソシアネート基が1.1~2.0当量となる割合で含有する、請求項1記載の複層塗膜形成方法。
- 前記2液型クリヤ塗料(Z)が、水酸基含有アクリル樹脂(Z1)及びポリイソシアネート化合物(Z2)を、水酸基含有アクリル樹脂(Z1)中の水酸基1当量に対し、ポリイソシアネート化合物(Z2)中のイソシアネート基が1.1~2.0当量となる割合で含有する、請求項1又は2に記載の複層塗膜形成方法。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007126107A1 (ja) | 2006-04-25 | 2007-11-08 | Kansai Paint Co., Ltd. | 複層塗膜形成方法 |
JP2011530393A (ja) | 2008-08-12 | 2011-12-22 | 関西ペイント株式会社 | 複層塗膜形成方法 |
WO2012137864A1 (ja) * | 2011-04-06 | 2012-10-11 | 関西ペイント株式会社 | 複層塗膜形成方法 |
WO2014054593A1 (ja) * | 2012-10-01 | 2014-04-10 | 関西ペイント株式会社 | 複層塗膜形成方法 |
JP2016155945A (ja) * | 2015-02-25 | 2016-09-01 | 関西ペイント株式会社 | 光輝性塗料組成物及び複層塗膜形成方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002177872A (ja) * | 2000-12-18 | 2002-06-25 | Nippon Paint Co Ltd | 塗膜形成方法およびそれから得られる塗膜 |
WO2005075587A1 (ja) * | 2004-02-06 | 2005-08-18 | Nippon Paint Co., Ltd. | 水性中塗り塗料組成物及び複層塗膜の形成方法 |
CN102959019B (zh) * | 2010-07-02 | 2015-05-13 | 关西涂料株式会社 | 形成多层涂膜的方法 |
WO2012137884A1 (ja) * | 2011-04-08 | 2012-10-11 | 関西ペイント株式会社 | 複層塗膜形成方法、及び塗装物品 |
EP2818252B1 (en) * | 2012-02-24 | 2020-05-27 | Kansai Paint Co., Ltd. | Multilayer film-forming method and coated article |
CN104321395B (zh) * | 2012-04-03 | 2018-03-20 | 关西涂料株式会社 | 水性涂料组合物和形成涂膜的方法 |
US20150111026A1 (en) * | 2012-05-24 | 2015-04-23 | Kansai Paint Co., Ltd. | Water-Based Coating Composition, Method for Forming Multi-layer Coating Film, and Article Having Multi-layer Coating Film |
JP6165152B2 (ja) * | 2012-09-20 | 2017-07-19 | 関西ペイント株式会社 | 複層塗膜形成方法 |
JP6275447B2 (ja) * | 2013-02-06 | 2018-02-07 | 関西ペイント株式会社 | 塗料組成物及び複層塗膜形成方法 |
BR112017024749B1 (pt) * | 2015-05-22 | 2022-05-03 | Basf Coatings Gmbh | Tinta base aquosa de dois componentes, método para produzir um revestimento sobre um substrato, revestimento, e, uso de um revestimento |
-
2018
- 2018-08-09 CN CN201880060707.8A patent/CN111093841A/zh active Pending
- 2018-08-09 JP JP2019544390A patent/JP7106558B2/ja active Active
- 2018-08-09 US US16/650,687 patent/US20210205844A1/en not_active Abandoned
- 2018-08-09 CA CA3076799A patent/CA3076799A1/en active Pending
- 2018-08-09 WO PCT/JP2018/029958 patent/WO2019064958A1/ja unknown
- 2018-08-09 EP EP18860828.5A patent/EP3689476A4/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007126107A1 (ja) | 2006-04-25 | 2007-11-08 | Kansai Paint Co., Ltd. | 複層塗膜形成方法 |
JP2011530393A (ja) | 2008-08-12 | 2011-12-22 | 関西ペイント株式会社 | 複層塗膜形成方法 |
WO2012137864A1 (ja) * | 2011-04-06 | 2012-10-11 | 関西ペイント株式会社 | 複層塗膜形成方法 |
WO2014054593A1 (ja) * | 2012-10-01 | 2014-04-10 | 関西ペイント株式会社 | 複層塗膜形成方法 |
JP2016155945A (ja) * | 2015-02-25 | 2016-09-01 | 関西ペイント株式会社 | 光輝性塗料組成物及び複層塗膜形成方法 |
Non-Patent Citations (2)
Title |
---|
"Polymer Handbook", vol. III, pages: 139 - 179 |
See also references of EP3689476A4 |
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JP7106558B2 (ja) | 2022-07-26 |
JPWO2019064958A1 (ja) | 2020-09-10 |
EP3689476A1 (en) | 2020-08-05 |
EP3689476A4 (en) | 2021-06-30 |
US20210205844A1 (en) | 2021-07-08 |
CN111093841A (zh) | 2020-05-01 |
CA3076799A1 (en) | 2019-04-04 |
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