WO2014119781A1 - 複層塗膜形成方法 - Google Patents
複層塗膜形成方法 Download PDFInfo
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- WO2014119781A1 WO2014119781A1 PCT/JP2014/052425 JP2014052425W WO2014119781A1 WO 2014119781 A1 WO2014119781 A1 WO 2014119781A1 JP 2014052425 W JP2014052425 W JP 2014052425W WO 2014119781 A1 WO2014119781 A1 WO 2014119781A1
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- coating film
- water
- resin
- aqueous base
- uncured
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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
- C09D7/43—Thickening agents
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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
-
- 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
- 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
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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
- 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
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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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
- B05D2451/00—Type of carrier, type of coating (Multilayers)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Definitions
- the present invention relates to a method for forming a multilayer coating film, in particular, a multilayer in which three layers are heated and cured at a time after applying a first aqueous base paint, a second aqueous base paint and a clear paint by so-called wet-on-wet coating.
- the present invention relates to a coating film forming method.
- the coating of automobile bodies and the like is an electrodeposition coating, a first base coating (sometimes referred to as “water-based intermediate coating”), and a second base coating (“colored base coating”). And a clear coating film are sequentially laminated on a steel plate to be coated.
- a method of baking and curing each time each constituent coating film is formed there are a method of baking and curing each time each constituent coating film is formed, and a method of simultaneously curing a plurality of laminated coating films.
- the heat curing step can be omitted and energy saving of the coating can be realized.
- a first base coating film, a second base coating film, and a clear coating film are sequentially formed on a wet-on-wet basis, followed by baking and curing. Paint is in progress.
- the conventional 3-coat 1-bake coating particularly when using a water-based paint, after applying the first base paint composition, it is dried at, for example, 60 to 100 ° C. for 2 to 20 minutes. A process is required.
- the obtained multilayer coating film is required to have a good coating film appearance that is not inferior to conventional coating methods.
- Patent Document 1 discloses an intermediate coating film with a water-based intermediate coating composition, a metallic base coating film with a water-based metallic base coating composition, and a clear coating composition with a clear coating composition.
- the aqueous intermediate coating composition and / or the aqueous metallic base coating composition contains a polycarbodiimide compound and a carboxyl group-containing aqueous resin. A film forming method is described (claim 1).
- Patent Document 2 JP 2004-358462 (Patent Document 2) describes the formation of a multilayer coating film in which an aqueous intermediate coating composition, an aqueous base coating composition and a clear coating composition are applied wet-on-wet and then baked and cured simultaneously.
- the aqueous intermediate coating composition has a glass transition temperature of ⁇ 50 to 20 ° C., an acrylic resin emulsion having a solid content acid value of 2 to 60 mgKOH / g and a solid content hydroxyl value of 10 to 120 mgKOH / g, a solid content acid value of 5
- a method for forming a multilayer coating film comprising a urethane resin emulsion having ⁇ 50 mg KOH / g and a curing agent is described (claim 1). It is described that this method can effectively prevent a mixed phase between the intermediate coating film and the base coating film to form a multilayer coating film having excellent surface smoothness.
- preheating is performed at 80 ° C. for 5 minutes (paragraph [0117]).
- JP 2009-262002 A discloses a multilayer coating film in which an aqueous intermediate coating composition, an aqueous base coating composition and a clear coating composition are applied wet-on-wet and then baked and cured simultaneously.
- the aqueous intermediate coating composition is an acrylic resin emulsion having a solid content hydroxyl value of 50 to 120 and a solid content acid value of 20 to 60 mgKOH / g;
- a method for forming a multilayer coating film comprising a fully alkyl etherified melamine resin that is 4; and a carbodiimide compound is described (claim 1). It is described that this method can prevent a mixed layer between the intermediate coating film and the base coating film in the 3-coat 1-bake method.
- preheating is performed at 80 ° C. for 5 minutes (paragraph [0162]).
- Patent Document 4 discloses that an aqueous intermediate coating composition containing an acrylic resin emulsion and a curing agent is mixed with an aqueous dispersion of a dimer acid derivative in an aqueous intermediate coating composition. It is described that a pseudo crystalline state is formed to make the coating film hydrophobic, thereby preventing migration of a solvent containing water from the aqueous base paint. Even in this method, it is difficult to completely omit the preheating step, and mixed layers and sagging are observed.
- the present invention makes it a subject to solve the problem of the said prior art. More specifically, the present invention relates to wet-on-wet coating in which the first aqueous base coating is applied to provide an uncured first aqueous base coating, and then the second aqueous base coating is applied without curing.
- the present invention it is an object to provide a blend of the first water-based base paint and the second water-based base paint that does not cause problems such as mixed layers.
- the present invention A step (1) of applying a first water-based base coating to the surface of an object to obtain an uncured first water-based base coating; a second water-based base on the uncured first water-based base coating A step (2) of applying a coating material to form an uncured second aqueous base coating film, and applying a clear coating material on the uncured second aqueous base coating film to form an uncured clear coating film Step (3) and the uncured first aqueous base coating film, uncured second aqueous base coating film and uncured clear coating film obtained in the above steps (1) to (3) at a time
- a method for forming a multilayer coating film comprising a step (4) of forming a multilayer coating film by heating and curing,
- the first aqueous base paint contains a hydrophilic associative viscosity agent; and
- the second aqueous base paint contains an acrylic emulsion resin (A), a water-soluble acrylic resin (B) and a water-soluble polyester resin (C) as a coating film-forming
- the present invention also includes the following embodiments:
- the hydrophilic associative viscosity agent contained in the first aqueous base paint is a polyamide-type viscosity agent;
- the acrylic emulsion resin (A) contained in the second aqueous base paint contains a single-layer acrylic emulsion resin (a) and a core-shell acrylic emulsion resin (b);
- the second aqueous base paint is applied in the step (2), the uncured first aqueous base paint film has a coating viscosity at 20 ° C. of 45 to 100 Pa ⁇ s at a shear rate of 0.01 / s. Being There is no heat drying step between the step (1) and the step (2).
- the present inventors applied the first aqueous base paint to obtain an uncured first aqueous base coating film, and then applied the second aqueous base paint without going through a preliminary drying step (preheating step).
- a method that does not cause defects such as sagging or mixed layers has been studied.
- the viscosity of the first aqueous base coating without preheating is 50 to 100 Pa ⁇ s (shear rate 0.01 / s), whereas when preheating is performed, the first aqueous base coating The viscosity of the coating film exceeds 10,000 Pa ⁇ s (shear rate 0.01 / s).
- the viscosity of the first aqueous base coating film obtained without preheating is about 150 Pa ⁇ s (shear rate 0.01 / s)
- the viscosity of the first aqueous base coating film and the second aqueous base coating composition The correlation with the sauce after applying the object was examined, but no relationship was found.
- the viscosity of the first aqueous base coating film after the application of the second aqueous base paint was measured by a special method and correlated with the sagging.
- the sagging decreases as the viscosity of the first aqueous base coating film increases, and when the viscosity at a shear rate of 0.01 / s at 20 ° C. is less than 45 Pa ⁇ s, Many found that the sagging drastically decreased when it exceeded 45 Pa ⁇ s.
- the present invention has been made on the basis of this finding, and in order to increase the viscosity of the first aqueous base coating film at the time of applying the second aqueous base coating material, a hydrophilic associative viscosity agent is added to the first aqueous base coating material.
- a hydrophilic associative viscosity agent is added to the first aqueous base coating material.
- the blending design for preventing the outflow of moisture to the first water-based base coating was achieved.
- the blended design of the first water-based base paint and the second water-based base paint of the present invention is applied to a so-called wet-on-wet coating method, there is no preheating step (that is, a preliminary drying step).
- a preheating step that is, a preliminary drying step.
- defects such as sagging and mixed layers do not occur, and it has become possible to omit the normally essential preheating step from the water-based multi-layer coating coating step. Therefore, not only energy in the preheating process is unnecessary, but also the time and process of the coating process can be shortened.
- the first aqueous base paint of the present invention usually comprises an acrylic emulsion resin and a curing agent, and in the present invention further comprises a hydrophilic associative viscosity agent.
- the first aqueous base paint may further contain a pigment and optional additives.
- the acrylic resin constituting the acrylic emulsion resin has a glass transition temperature (Tg) of preferably ⁇ 20 ° C. to 60 ° C., more preferably ⁇ 10 ° C. to 50 ° C., and 0 ° C. to 40 ° C. More preferably.
- Tg glass transition temperature
- the Tg of the acrylic emulsion resin can be calculated based on the known Tg and composition ratio of the constituent monomer or homopolymer.
- the solid acid value of the acrylic resin constituting the acrylic emulsion resin is 2 to 60 mgKOH / g, and preferably 5 to 50 mgKOH / g. If the solid acid value of the resin is less than 2 mgKOH / g, the storage stability, mechanical stability, stability against freezing, etc. of the acrylic emulsion resin and the first aqueous base paint using the same will decrease. In the curing reaction with the curing agent, sufficient curability cannot be ensured, and various strengths, chipping resistance, and water resistance of the coating film are lowered. On the other hand, when the solid content acid value of the resin exceeds 60 mgKOH / g, the polymerization stability of the resin is lowered or the water resistance of the obtained coating film is lowered.
- the solid content acid value of the acrylic resin can be adjusted by selecting the type and blending amount of each monomer component so that the solid content acid value of the resin falls within the above range. As described in detail below, it is important to use a carboxyl group-containing monomer among the acid group-containing ethylenically unsaturated monomers (ii), and among the monomers (ii), the carboxyl group-containing monomer is 50% by mass or more. It is preferable that it is contained, and 80% by mass or more is more preferable.
- the hydroxyl value of the solid content of the acrylic resin constituting the acrylic emulsion resin is 10 to 120 mgKOH / g, preferably 20 to 100 mgKOH / g.
- the solid content hydroxyl value is less than 10 mgKOH / g, sufficient curability cannot be ensured in the curing reaction with the curing agent, the mechanical properties of the coating film are low, chipping resistance is lowered, water resistance and solvent resistance are reduced. The nature is also reduced.
- the solid content hydroxyl value exceeds 120 mgKOH / g, the water resistance of the obtained coating film decreases, the compatibility with the curing agent is low, the coating film is distorted, and the curing reaction is uneven. As a result, various strengths of the coating film, particularly chipping resistance, solvent resistance and water resistance, are lowered.
- the solid content acid value and solid content hydroxyl value of the acrylic resin can be calculated based on the solid content acid value and solid content hydroxyl value of the monomer mixture used.
- the acrylic emulsion resin contained in the first aqueous base paint used in the method for forming a multilayer coating film of the present invention comprises (meth) acrylic acid alkyl ester (i), acid group-containing ethylenically unsaturated monomer (ii), and hydroxyl group
- the monomer mixture containing the ethylenically unsaturated monomer (iii) can be obtained by emulsion polymerization.
- the compounds (i) to (iii) exemplified below as components of the monomer mixture may be used alone or in combination of two or more.
- (Meth) acrylic acid alkyl ester (i) is used to constitute the main skeleton of the acrylic emulsion resin.
- Specific examples of (meth) acrylic acid alkyl ester (i) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic.
- methyl (meth) acrylate represents methyl acrylate and methyl methacrylate.
- the acid group-containing ethylenically unsaturated monomer (ii) improves various properties such as storage stability, mechanical stability and stability against freezing of the resulting acrylic emulsion resin, and cures melamine resin and the like during coating film formation. Used to accelerate the curing reaction with the agent.
- the acid group is preferably selected from a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like.
- a particularly preferred acid group is a carboxyl group from the viewpoints of the above-mentioned various stability improvements and curing reaction promoting functions.
- Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, maleic anhydride and fumaric acid.
- Examples of the sulfonic acid group-containing ethylenically unsaturated monomer include p-vinylbenzenesulfonic acid, p-acrylamidepropanesulfonic acid, t-butylacrylamidesulfonic acid and the like.
- Examples of the phosphoric acid group-containing ethylenically unsaturated monomer include 2-hydroxyethyl acrylate phosphoric acid monoester, 2-hydroxypropyl methacrylate phosphoric acid monoester light ester PM (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.
- the hydroxyl group-containing ethylenically unsaturated monomer (iii) imparts hydrophilicity based on hydroxyl groups to the acrylic emulsion resin, improves workability and stability against freezing when used as a paint, and is suitable as a curing agent. It is used for imparting curing reactivity with a melamine resin or an isocyanate curing agent that can be used.
- hydroxyl group-containing ethylenically unsaturated monomer (iii) examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, N-methylolacrylamide, allyl alcohol, and ⁇ -caprolactone-modified acrylic monomer.
- ⁇ -caprolactone-modified acrylic monomer examples include Plaxel FA-1, Plaxel FA-2, Plaxel FA-3, Plaxel FA-4, Plaxel FA-5, Plaxel FM-1 and Plaxel FM manufactured by Daicel Chemical Industries, Ltd. -2, Plaxel FM-3, Plaxel FM-4, Plaxel FM-5 and the like.
- the monomer mixture used for the preparation of the acrylic emulsion resin is at least selected from the group consisting of styrene monomers, (meth) acrylonitrile and (meth) acrylamide as optional components.
- styrene monomers include ⁇ -methylstyrene in addition to styrene.
- the monomer mixture may contain a crosslinking monomer such as a carbonyl group-containing ethylenically unsaturated monomer, a hydrolyzable polymerizable silyl group-containing monomer, and various polyfunctional vinyl monomers.
- a crosslinking monomer such as a carbonyl group-containing ethylenically unsaturated monomer, a hydrolyzable polymerizable silyl group-containing monomer, and various polyfunctional vinyl monomers.
- Examples of the carbonyl group-containing ethylenically unsaturated monomer include acrolein, diacetone (meth) acrylamide, acetoacetoxyethyl (meth) acrylate, formylstyrene, alkyl vinyl ketone having 4 to 7 carbon atoms (for example, methyl vinyl ketone, And monomers containing keto groups such as ethyl vinyl ketone and butyl vinyl ketone. Of these, diacetone (meth) acrylamide is preferred.
- hydrolyzable polymerizable silyl group-containing monomer examples include ⁇ - (meth) acryloxypropylmethyldimethoxysilane, ⁇ - (meth) acryloxypropylmethyldiethoxysilane, ⁇ - (meth) acryloxypropyltriethoxysilane, and the like. And a monomer containing an alkoxysilyl group.
- a polyfunctional vinyl monomer is a compound having two or more radically polymerizable ethylenically unsaturated groups in the molecule, such as divinylbenzene, ethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, allyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexane di (meth) acrylate, neopentylglycol di (meth) acrylate, pentaerythritol di ( Examples include divinyl compounds such as (meth) acrylate, and pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
- divinylbenzene ethylene glycol di (meth
- the acrylic emulsion resin used in the method for forming a multilayer coating film of the present invention can be prepared by emulsion polymerization of a monomer mixture containing the above (i) to (iii).
- Emulsion polymerization emulsion copolymerization
- Emulsion copolymerization can be carried out by heating the monomer mixture in an aqueous solution under stirring in the presence of a radical polymerization initiator and an emulsifier.
- the reaction temperature is preferably 30 to 100 ° C. and the reaction time is preferably 1 to 10 hours, for example.
- the reaction temperature can be adjusted by batch addition of monomer mixture or monomer pre-emulsified liquid or temporary dropping to a reaction vessel charged with water and an emulsifier.
- radical polymerization initiator known initiators usually used in emulsion polymerization of acrylic resins can be used.
- a water-soluble free radical polymerization initiator for example, persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, or azo series such as 4,4′-azobis-4-cyanovaleric acid
- persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, or azo series such as 4,4′-azobis-4-cyanovaleric acid
- a so-called redox initiator which is a combination of an oxidizing agent such as potassium persulfate, sodium persulfate, ammonium persulfate or hydrogen peroxide and a reducing agent such as sodium bisulfite, sodium thiosulfate, Rongalite or ascorbic acid, is used as an aqueous solution. It is preferable to use as.
- the emulsifier is selected from an amphiphilic compound having a hydrocarbon group having 6 or more carbon atoms and a hydrophilic moiety such as a carboxylate, sulfonate, or sulfate partial ester in the same molecule.
- Anionic or nonionic emulsifiers are used.
- anionic emulsifiers include alkali metal salts or ammonium salts of sulfuric acid half esters of alkylphenols or higher alcohols; alkali metal salts or ammonium salts of alkyl or allyl sulfonates; polyoxyethylene alkylphenyl ethers, polyoxyethylenes Examples thereof include alkali metal salts or ammonium salts of alkyl ether or sulfuric acid half ester of polyoxyethylene allyl ether.
- nonionic emulsifiers include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, and polyoxyethylene allyl ether.
- the molecule has a radically polymerizable unsaturated double bond, that is, acrylic, methacrylic, propenyl, allyl, allyl ether, maleic acid, etc.
- Various anionic and nonionic reactive emulsifiers having the above-mentioned groups are also used singly or in combination of two or more.
- an auxiliary agent for adjusting the molecular weight such as a mercaptan compound, a lower alcohol or ⁇ -methylstyrene dimer may be used as necessary. It is often preferable to use these auxiliaries (chain transfer agents) from the viewpoint of promoting emulsion polymerization and from the viewpoint of promoting the smooth and uniform formation of a coating film and improving the adhesion to an object to be coated. .
- Emulsion polymerization can be performed by any one of the usual one-step continuous monomer uniform dropping method, core-shell polymerization method which is a multi-stage monomer feed method, and power feed polymerization method which continuously changes the monomer composition fed during the polymerization. Legal can also be used.
- a single-layer acrylic emulsion resin can be obtained when the normal single-stage continuous monomer uniform dropping method is used, and a core-shell polymerization method that is a multi-stage monomer feed method is used.
- a shell type acrylic emulsion resin can be obtained.
- the acrylic emulsion resin used in the present invention is prepared.
- the weight average molecular weight of the acrylic resin constituting the acrylic emulsion resin is not particularly limited, but is generally preferably about 50,000 to 1,000,000, and preferably about 100,000 to 800,000. More preferred.
- the weight average molecular weight can be measured by GPC (gel permeation chromatography) and can be calculated by a conversion value based on a polystyrene standard.
- the dispersion stability of the acrylic emulsion resin may be improved by adding a basic compound to the acrylic emulsion resin thus obtained and neutralizing a part or all of the carboxylic acid.
- a basic compound such as ammonia, various amines, alkali metals and the like can be used.
- the first aqueous base paint of the present invention preferably contains a curing agent.
- the curing agent can be used without any particular limitation as long as it causes a curing reaction with the acrylic emulsion resin and can be blended in the first aqueous base paint.
- Examples of the curing agent include melamine resin, blocked isocyanate resin, oxazoline compound, carbodiimide compound, and the like. These may be used alone or in combination of two or more.
- the melamine resin is not particularly limited, and those usually used as a curing agent can be used.
- the melamine resin for example, an alkyl etherified melamine resin obtained by alkyl etherification is preferable, and a melamine resin substituted with a methoxy group and / or a butoxy group is more preferable.
- melamine resins those having a methoxy group alone, Cymel 325, Cymel 327, Cymel 370, Mycoat 723; those having both a methoxy group and a butoxy group, Cymel 202, Cymel 204, Cymel 211, Cymel 232, Cymel 235, Cymel 236, Cymel 238, Cymel 251, Cymel 254, Cymel 266, Cymel 267, Cymel 285 (all trade names, manufactured by Nihon Cytec Industries, Inc.); Examples include My Coat 506 (trade name, manufactured by Mitsui Cytec Co., Ltd.), Uban 20N60, Uban 20SE (both trade names, manufactured by Mitsui Chemicals). These may be used alone or in combination of two or more. Among these, Cymel 211, Cymel 251, Cymel 285, Cymel 325, Cymel 327, and My Coat 723 are more preferable.
- Block isocyanate resin is a polyisocyanate compound blocked with a suitable blocking agent.
- the polyisocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups in one molecule.
- aliphatic diisocyanates such as hexamethylene diisocyanate (HMDI) and trimethylhexamethylene diisocyanate (TMDI); Alicyclic diisocyanates such as isophorone diisocyanate (IPDI); aromatic-aliphatic diisocyanates such as xylylene diisocyanate (XDI); aromatic diisocyanates such as tolylene diisocyanate (TDI) and 4,4-diphenylmethane diisocyanate (MDI) Hydrogenated diisocyanates such as dimer acid diisocyanate (DDI), hydrogenated TDI (HTDI), hydrogenated XDI (H6XDI), hydrogenated MDI (H12MDI) Sulfonates
- the blocking agent for blocking the polyisocyanate compound is not particularly limited.
- oximes such as methyl ethyl ketoxime, acetoxime, and cyclohexanone oxime; phenols such as m-cresol and xylenol; butanol, 2-ethylhexanol, cyclohexanol, Alcohols such as ethylene glycol monoethyl ether; lactams such as ⁇ -caprolactam; diketones such as diethyl malonate and acetoacetate; mercaptans such as thiophenol; ureas such as thiouric acid; imidazoles; carbamic acids and the like Can be mentioned.
- oximes, phenols, alcohols, lactams and diketones are preferred.
- the oxazoline-based compound is preferably a compound having two or more 2-oxazoline groups, and examples thereof include the following oxazolines and oxazoline group-containing polymers. These 1 type (s) or 2 or more types can be used in combination.
- the oxazoline-based compound can be obtained by using a method in which amide alcohol is heated in the presence of a catalyst for dehydration cyclization, a method in which amide alcohol is synthesized from nitrile, or a method in which amide alcohol is synthesized from carboxylic acid. .
- oxazolines examples include 2,2′-bis- (2-oxazoline), 2,2′-methylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (2-oxazoline), 2,2'-trimethylene-bis- (2-oxazoline), 2,2'-tetramethylene-bis- (2-oxazoline), 2,2'-hexamethylene-bis- (2-oxazoline), 2,2 '-Octamethylene-bis- (2-oxazoline), 2,2'-ethylene-bis- (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis- (2-oxazoline) ), 2,2′-m-phenylene-bis- (2-oxazoline), 2,2′-m-phenylene-bis- (4,4′-dimethyl-2-oxazoline), bis- (2-oxazoline) Nilcyclohe Sun) sulfide, bis - (such as 2-oxazolidone sulfon
- the oxazoline group-containing polymer is obtained by polymerizing an addition polymerizable oxazoline and, if necessary, at least one other polymerizable monomer.
- the addition polymerizable oxazoline include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Examples include 2-isopropenyl-4-methyl-2-oxazoline and 2-isopropenyl-5-ethyl-2-oxazoline. These 1 type (s) or 2 or more types are used in combination as appropriate. Of these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.
- the amount of addition polymerizable oxazoline used is not particularly limited, but is preferably 1% by mass or more in the oxazoline group-containing polymer. If the amount is less than 1% by mass, the degree of curing tends to be insufficient, and the durability and water resistance of the resulting coating film tend to be impaired.
- the other polymerizable monomer is not particularly limited as long as it is a monomer that can be copolymerized with an addition-polymerizable oxazoline and does not react with the oxazoline group.
- methyl (meth) acrylate, (meth) (Meth) acrylates such as butyl acrylate and 2-ethylhexyl (meth) acrylate; unsaturated nitriles such as (meth) acrylonitrile; unsaturated amides such as (meth) acrylamide and N-methylol (meth) acrylamide
- Vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; ⁇ -olefins such as ethylene and propylene; halogenated ⁇ and ⁇ such as vinyl chloride, vinylidene chloride and vinyl fluoride -Unsaturated monomers: ⁇ such as styrene and
- the oxazoline group-containing polymer can be produced by addition polymerization oxazoline and, if necessary, at least one other polymerizable monomer by a conventionally known polymerization method such as suspension polymerization, solution polymerization, emulsion polymerization and the like.
- a conventionally known polymerization method such as suspension polymerization, solution polymerization, emulsion polymerization and the like.
- Examples of the supply form of the oxazoline group-containing compound include organic solvent solutions, aqueous solutions, non-aqueous dispersions, and emulsions, but are not particularly limited to these forms.
- carbodiimide compounds those produced by various methods can be used, but basically those obtained by synthesizing isocyanate-terminated polycarbodiimides by condensation reactions involving decarbonization of organic diisocyanates should be mentioned. Can do. More specifically, in the production of a polycarbodiimide compound, a polycarbodiimide compound containing at least two isocyanate groups in one molecule, and a polyol having a hydroxyl group at the molecular end, the molar amount of the isocyanate group of the polycarbodiimide compound.
- Hydrophilization obtained by the step of reacting at a ratio exceeding the molar amount of hydroxyl group of the polyol and the step of reacting the reaction product obtained in the step with a hydrophilizing agent having active hydrogen and a hydrophilic moiety can be mentioned as a preferable one.
- the carbodiimide compound containing at least two isocyanate groups in one molecule is not particularly limited, but is preferably a carbodiimide compound having isocyanate groups at both ends from the viewpoint of reactivity.
- a method for producing a carbodiimide compound having isocyanate groups at both ends is well known by those skilled in the art. For example, a condensation reaction involving decarbonization of an organic diisocyanate can be used.
- hydrophilic associative viscosity agent is a viscosity agent that has a hydrogen bond between the viscosity agents or between the base resins and utilizes the bonding force (interaction).
- examples of such a hydrophilic associative viscosity agent include polyamide-type viscosity agents, and commercially available ones include BYK-430, BYK-431 (both trade names, manufactured by BYK Chemie), Disparon AQ.
- Disparon AQ-600 Disparon AQ-607 (all trade names, manufactured by Enomoto Kasei Co., Ltd.), Tixol W-300, Tixol W-400LP (all trade names, manufactured by Kyoeisha Chemical Co., Ltd.), and the like.
- the first water-based base paint used in the present invention may contain a viscosity agent other than the hydrophilic associative viscosity agent.
- the other viscosity agent include a hydrophobic associative viscosity agent and an alkali thickening viscosity agent that use the interaction between hydrophobic groups (parts) in the molecule to develop viscosity.
- hydrophobic associative viscosity agent examples include polyvinyl alcohol, polyethylene oxide, and commercially available products (hereinafter referred to as trade names), such as Adecanol UH-420, Adecanol UH-462, Adecanol UH-472, UH- 540, Adecanol UH-814N (all manufactured by Asahi Denka Kogyo Co., Ltd.), Primal RH-1020 (manufactured by Rohm & Haas), Kuraray Poval (manufactured by Kuraray Co., Ltd.) and the like.
- trade names such as Adecanol UH-420, Adecanol UH-462, Adecanol UH-472, UH- 540, Adecanol UH-814N (all manufactured by Asahi Denka Kogyo Co., Ltd.), Primal RH-1020 (manufactured by Rohm & Haas), Kuraray Poval (manu
- alkali thickening viscosity agent examples include viscose, methylcellulose, ethylcellulose, hydroxyethylcellulose, and commercially available products (hereinafter referred to as trade names), Tyroze MH and Tyroze H (both manufactured by Hoechst).
- Cellulose-based materials such as sodium acrylate, polyvinyl alcohol, carboxymethyl cellulose, and commercially available products (hereinafter referred to as trade names) include Primal ASE-60, Primal TT-615, Primal RM-5 (any Rohm & Haas Co.) and Euker Polyphore (Union Carbide).
- the content of the hydrophilic associative viscosity agent and the other viscosity agent in the first aqueous base paint used in the present invention is the resin solid content of the first aqueous base paint (the solid content of all resins contained in the first aqueous base paint). ) To 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass. If it is less than 0.01% by mass, the effect of viscosity control cannot be obtained, and sagging may occur during application. If it exceeds 20% by mass, the appearance and various performances of the resulting coating film may be deteriorated. There is.
- the solids content ratio of the hydrophilic associative viscosity agent and other viscosity agents contained in the first aqueous base paint used in the present invention is 100/0 to 50/50 for the hydrophilic associative viscosity agent / other viscosity agents. It is preferable that the ratio is 100/0 to 80/20. If the ratio of the hydrophilic associative viscosity agent / other viscosity agent exceeds 50/50, there is a risk of sagging at the time of application and deterioration of the final appearance of the multilayer coating film. is there.
- the first aqueous base paint used in the present invention may contain, for example, an additional resin component, a pigment dispersion paste, and other additives in addition to the acrylic emulsion resin, the curing agent, and the hydrophilic associative viscosity agent.
- the additional resin component is not particularly limited, and examples thereof include a polyester resin, an acrylic resin, a carbonate resin, and an epoxy resin.
- the pigment dispersion paste is obtained by previously dispersing a pigment and a pigment dispersant in a small amount of an aqueous medium.
- the pigment dispersant is a resin having a structure including a pigment affinity part and a hydrophilic part. Examples of the pigment affinity portion and the hydrophilic portion include nonionic, cationic and anionic functional groups.
- the pigment dispersant may have two or more of the above functional groups in one molecule.
- nonionic functional group examples include a hydroxyl group, an amide group, and a polyoxyalkylene group.
- cationic functional group include an amino group, an imino group, and a hydrazino group.
- anionic functional group examples include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.
- Such pigment dispersants can be produced by methods well known to those skilled in the art.
- the pigment dispersant is preferably one that can efficiently disperse the pigment with a small amount of the pigment dispersant.
- the pigment dispersant for example, commercially available ones (hereinafter referred to as trade names) can also be used. Specifically, anionic and nonionic dispersants Disperbyk 190, Disperbyk 181, Disperbyk 182, Disperbyk 184 (all manufactured by Big Chemie), EFKAPOLYMER 4550 (manufactured by EFKA), Solsperse 27000 (manufactured by Abyssia) which is a nonionic dispersant, Solsperse 41000 which is an anionic dispersant, Solsperse 53955 (all of which are manufactured by Abyssia), etc. Can be mentioned.
- the number average molecular weight of the pigment dispersant is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 50,000. If it is less than 1,000, the dispersion stability may not be sufficient, and if it exceeds 100,000, the viscosity may be too high and handling may be difficult.
- the pigment dispersion paste can be obtained by mixing and dispersing a pigment dispersant and a pigment according to a known method.
- the ratio of the pigment dispersant in producing the pigment dispersion paste is preferably 1 to 20% by mass with respect to the solid content of the pigment dispersion paste. If it is less than 1% by mass, it is difficult to disperse the pigment stably, and if it exceeds 20% by mass, the physical properties of the resulting coating film may be inferior. Preferably, it is 5 to 15% by mass.
- the pigment is not particularly limited as long as it is a pigment used in ordinary water-based paints, but is preferably a colored pigment from the viewpoint of improving weather resistance and ensuring concealability.
- titanium dioxide is more preferable because it is excellent in color concealment and is inexpensive.
- pigments other than titanium dioxide include azo chelate pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, indigo pigments, perinone pigments, perylene pigments, dioxane pigments, quinacridone pigments, and isoindolinone.
- Organic pigments such as pigments, diketopyrrolopyrrole pigments, benzimidazolone pigments, and metal complex pigments; inorganic pigments such as yellow lead, yellow iron oxide, Bengala, and carbon black. These pigments may be used in combination with extender pigments such as calcium carbonate, barium sulfate, clay, and talc.
- the pigment preferably has a pigment weight content (PWC) of 10 to 60% by mass with respect to the total mass of the solid content of the resin and the total mass of the pigment contained in the first aqueous base paint. If it is less than 10% by mass, the concealability may be lowered. When it exceeds 60 mass%, viscosity increase at the time of hardening will be caused, flow property may fall and a coating-film external appearance may fall.
- PWC pigment weight content
- additives include additives usually added in addition to the above components, such as UV absorbers, antioxidants, antifoaming agents, surface conditioners, pinhole inhibitors. These compounding amounts are within the range known to those skilled in the art.
- the first water-based base paint is prepared by mixing the above-mentioned acrylic emulsion resin, curing agent and hydrophilic associative viscosity agent, and other components as required.
- the content of the acrylic emulsion resin, the curing agent and the hydrophilic associative viscosity agent is 1 to 60% by mass, more preferably 10 to 50% by mass, in terms of resin solids mass ratio.
- the curing agent is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and the hydrophilic associative viscosity agent 0.01 to 20% by mass, more preferably 0.1 to 10% by mass.
- acrylic emulsion resin exceeds 60 mass%, there exists a possibility that the external appearance of the coating film obtained may fall.
- acrylic emulsion resin is less than 1 mass%, there exists a possibility that coating workability
- curing agent exceeds 80 mass%, there exists a possibility that the chipping resistance of the coating film obtained may fall.
- curing agent is less than 5 mass%, there exists a possibility that the water resistance of the coating film obtained may fall.
- the hydrophilic associative viscosity agent exceeds 20% by mass, the appearance of the coating film may be deteriorated or the water resistance may be deteriorated.
- the hydrophilic associative viscosity agent is less than 0.01% by mass, there is a possibility that sagging or a mixed layer may occur when the second aqueous base paint is applied.
- Additional resin components, pigment dispersion pastes and other additives that can be used as needed can be mixed in appropriate amounts.
- the additional resin component is preferably blended at a ratio of 50% by mass or less based on the solid content of all the resins contained in the first aqueous base paint. When it exceeds 50 mass%, it is difficult to increase the solid content concentration in the coating material, which is not preferable.
- the order of adding these components is not particularly limited.
- the form of the first water-based base paint of the present invention is not particularly limited as long as it is aqueous, and examples thereof include water-soluble, water-dispersed, and emulsion forms.
- a second water-based base paint As the second water-based base paint used in the method for forming a multilayer coating film of the present invention, a second water-based base paint usually used in the application of automobile bodies can be used.
- a second aqueous base paint for example, a coating film forming resin, a curing agent, a bright pigment, a pigment such as a color pigment or an extender pigment, various additives, etc. in a state of being dispersed or dissolved in an aqueous medium. The inclusion can be mentioned.
- a coating film forming resin for example, a coating film forming resin, a curing agent, a bright pigment, a pigment such as a color pigment or an extender pigment, various additives, etc. in a state of being dispersed or dissolved in an aqueous medium.
- the film-forming resin an acrylic emulsion resin (A), a water-soluble acrylic resin (B) and a water-soluble polyester resin (C) are included.
- Acrylic emulsion resin (A) As the acrylic emulsion resin (A), the acrylic emulsion resin described in the first aqueous base paint can be used. However, the acrylic emulsion resin (A) preferably contains a single-layer acrylic emulsion resin (a) and a core-shell acrylic emulsion resin (b). In the second aqueous base paint, the water retention of the single layer acrylic emulsion resin (a) is lower than that of the core / shell type acrylic emulsion resin (b), and the proportion of the single layer acrylic emulsion resin (a) is increased. The amount of water transferred to the first aqueous base coating film increases, and sagging or mixed layers in the first aqueous base coating film may occur.
- the ratio of the core / shell type acrylic emulsion resin (b) When the ratio of the core / shell type acrylic emulsion resin (b) is increased, the coating viscosity of the second water-based base coating material becomes too high, resulting in a problem that the smoothness is impaired.
- the blending ratio of the core / shell type acrylic emulsion resin (b) and the single layer type acrylic emulsion resin (a) becomes important, and the single layer type acrylic emulsion resin (a) It is preferable that the percentage of the ratio (a) / (A) of the resin solid mass of the resin and the resin solid mass of the acrylic emulsion resin (A) is 30 to 60%.
- Water-soluble acrylic resin (B) The water-soluble acrylic resin (B) can be prepared by copolymerizing a hydroxyl group-containing monomer and another monomer.
- hydroxyl group-containing monomers examples include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and these hydroxyl group-containing (meth) acrylates.
- a reaction product of ⁇ caprolactone and an esterified product of a polyhydric alcohol such as polyethylene glycol mono (meth) acrylate and acrylic acid or methacrylic acid.
- a reaction product obtained by ring-opening polymerization of ⁇ -caprolactone to a monoester product of the above polyhydric alcohol and acrylic acid or methacrylic acid can also be used.
- These hydroxyl group-containing monomers (a) may be used alone or in combination of two or more.
- “(meth) acrylate” means “acrylate or methacrylate”.
- Examples of other monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and fumaric acid, and ethyl maleate, butyl maleate, ethyl itaconate, and butyl itaconate.
- carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and fumaric acid, and ethyl maleate, butyl maleate, ethyl itaconate, and butyl itaconate.
- Dicarboxylic acid monoester monomers methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n, i or t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate (Meth) acrylic acid alkyl ester monomers such as: (meth) acrylic acid cyclopentyl, (meth) acrylic acid cyclohexyl, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, adamantyl (meth) Alicyclic group-containing monomers such as acrylate; (meth) acrylic acid aminoalkyl ester monomers such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and butylaminoethyl (meth) acrylate; aminoeth
- Amide group-containing monomers vinyl cyanide monomers such as (meth) acrylonitrile and ⁇ -chloroacrylonitrile; saturated aliphatic carbo such as vinyl acetate and vinyl propionate Examples thereof include vinyl ester monomers; styrene monomers such as styrene, ⁇ -methylstyrene and vinyltoluene; These other monomers may be used individually by 1 type, and may use 2 or more types together.
- acrylic acid methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, and the like are preferably used. .
- a method for polymerizing the hydroxyl group-containing monomer and other monomers methods commonly used by those skilled in the art can be used.
- the polymerization method for example, a bulk polymerization method using a radical polymerization initiator, a solution polymerization method, a bulk-suspension two-stage polymerization method in which suspension polymerization is performed after bulk polymerization, or the like can be used.
- the solution polymerization method can be particularly preferably used.
- the solution polymerization method include a method in which the monomer mixture is heated in the presence of a radical polymerization initiator at a temperature of, for example, 80 to 200 ° C. with stirring.
- the water-soluble acrylic resin (B) preferably has a number average molecular weight of 1,000 to 15,000, more preferably 1,000 to 8,000, and 1,000 to 5,000. Is more preferable. When the number average molecular weight is less than 1,000, the coating film properties of the resulting multilayer coating film may be inferior. On the other hand, when the number average molecular weight exceeds 15,000, the viscosity of the resin component becomes high, and a large amount of solvent may be required in preparation of the coating material.
- the water-soluble acrylic resin (B) preferably has a solid content hydroxyl value of 50 to 250 mgKOH / g, more preferably 60 to 200 mgKOH / g, and still more preferably 80 to 180 mgKOH / g.
- the solid content hydroxyl value is less than 50 mgKOH / g, the reactivity with the curing agent is lowered, the coating film properties of the resulting multilayer coating film may be inferior, and the coating film adhesion may be inferior.
- the solid content hydroxyl value exceeds 250 mgKOH / g, the resulting multilayer coating film may have poor water resistance.
- the water-soluble acrylic resin (B) preferably has a solid content acid value of 2 to 50 mgKOH / g, and more preferably 5 to 20 mgKOH / g.
- the solid content acid value is less than 2 mgKOH / g, the coating film properties of the resulting multilayer coating film may be inferior.
- the solid content acid value exceeds 50 mgKOH / g, the resulting multilayer coating film may have poor water resistance.
- water-soluble acrylic resin (B) may be used.
- trade names “Acridic” series for example, Acridick A-837, Acridick A-871, Acridick A-1370, etc.
- Harima Kasei's brand name “Hariacron” series for example, Hariacron D-1703, Hariacron N-2043-60MEX, etc.
- Mitsubishi Rayon's brand name “Dianar” series Hitachi Kasei Kogyo's brand name “Hitaroid” ", And Mitsui Chemicals' brand name” Olestar "series.
- the second water-based base paint in the present invention contains a water-soluble polyester resin (C).
- a water-soluble polyester resin (C) By including the water-soluble polyester resin (C) in the second aqueous base paint, there is an advantage that the coating workability is improved and the appearance of the obtained coating film is improved.
- the water-soluble polyester resin (C) contained in the second aqueous base paint one having two or more hydroxyl groups in one molecule, generally called polyester polyol, is preferably used.
- Such a water-soluble polyester resin can be prepared by polycondensation (ester reaction) of a polyhydric alcohol and a polybasic acid or an anhydride thereof.
- polyhydric alcohol examples include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, , 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, hydrogenated bisphenol A, hydroxyalkylated bisphenol A, 1,4-cyclohexanedimethanol, 2,2-dimethyl-3-hydroxypropyl- 2,2-dimethyl-3-hydroxypropionate, 2,2,4-trimethyl-1,3-pentanediol, N, N-bis- (2-hydroxyethyl) dimethylhydantoin, polytetramethylene ether glycol , Polycaprolactone polyol, glycerin, sorbitol, trimethylol ethane,
- Polybasic acid or its anhydride includes phthalic acid, phthalic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, methyltetrahydrophthalic acid, methyltetrahydrophthalic anhydride, hymic anhydride , Trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, isophthalic acid, terephthalic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, Examples thereof include succinic anhydride, lactic acid, dodecenyl succinic acid, dodecenyl succinic anhydride, cyclohexane-1,4-dicarboxylic acid, and endo acid anhydride.
- a water-soluble polyester resin modified with lactone, fat or fatty acid, melamine resin, urethane resin or the like can also be used.
- water-soluble polyester resins modified with oils or fats include castor oil, dehydrated castor oil, coconut oil, corn oil, cottonseed oil, linseed oil, camellia oil, poppy oil, safflower oil, soybean oil, tung oil, etc.
- the polyester resin is modified using fats and oils or fatty acids extracted from these fats and oils.
- the water-soluble polyester resin (C) has a number average molecular weight of 500 to 6,000, more preferably 1,000 to 4,000, in terms of polystyrene as measured by GPC.
- the number average molecular weight is less than 500, the adhesion of the resulting coating film may be inferior.
- the number average molecular weight exceeds 6,000, the conformability to an object to be coated may be inferior at the time of application.
- the water-soluble polyester resin (C) preferably has a solid content hydroxyl value of 80 to 350 mgKOH / g, more preferably 80 to 300 mgKOH / g, and even more preferably 150 to 250 mgKOH / g.
- the solid content hydroxyl value is less than 80 mgKOH / g, the reactivity with the curing agent is lowered, the coating film properties of the resulting multilayer coating film may be inferior, and the coating film adhesion may be inferior.
- the solid content hydroxyl value exceeds 350 mgKOH / g, the resulting multilayer coating film may have poor water resistance.
- the percentage of the mass ratio (A) / (A + B + C) needs to be 40 to 60%.
- an acrylic emulsion resin has a high molecular weight and agglomerates abruptly when the resin solid content becomes high. Therefore, it has a property that water can be discharged more easily than a water-soluble resin.
- the water-soluble resin ratio in the second water-based base paint that is, by reducing the ratio of the acrylic emulsion resin (A)
- the water-holding power of the second water-based base paint is increased, and the first lower layer is the lower layer when applied. Suppresses the amount of water transferred to the aqueous base coating film.
- the ratio of the acrylic emulsion resin (A) is lowered, the resulting coating film viscosity is lowered and the design property (for example, the orientation of the aluminum pigment in the second aqueous base coating film) is lowered (backed).
- the blending ratio of the acrylic emulsion resin (A) and the water-soluble resin that is, the water-soluble acrylic resin (B) and the water-soluble polyester resin (C) becomes important.
- the ratio is the ratio between the resin solid mass of the acrylic emulsion resin (A) and the total resin solid content of the acrylic emulsion resin (A), the water-soluble acrylic resin (B), and the water-soluble polyester resin (C). Expressed as a percentage of (A) / (A + B + C), it is 40-60%. The percentage of this ratio is preferably 50-60%, more preferably 55-60%. When it is less than 40%, the coating viscosity of the second aqueous base coating film is lowered and the designability (aluminum pigment orientation) is lowered. On the other hand, when it exceeds 60%, the water holding power of the second water-based base paint is weak, and when the second water-based base paint is applied, water migrates to the first water-based base coating film and causes defects such as sagging and mixed layers.
- the pigment second aqueous base paint preferably contains a pigment.
- pigments generally used in the paint field can be used.
- examples include non-colored or colored metallic luster materials such as metals or alloys and mixtures thereof, luster pigments such as interference mica pigments, white mica pigments, and graphite pigments. Each of these pigments may be used alone or in combination of two or more.
- the pigment mass concentration (PWC) contained in the second aqueous base paint is generally 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, further 1 to 30% by mass. preferable.
- PWC pigment mass concentration
- the second water-based base paint in the present invention may contain additives other than the above as necessary.
- Additives include, for example, organic solvents, curing catalysts (organometallic catalysts), anti-sagging / anti-settling agents, surface preparation agents, anti-coloring agents, dispersants, antifoaming / waxing agents, viscosity modifiers (increase) (Viscous agent), leveling agent, delustering agent, ultraviolet absorber, antioxidant, plasticizer, film-forming aid and the like.
- organic solvent examples include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, Solvesso 100, Solvesso 150, Solvesso 200 (all manufactured by Exxon Chemical), toluene, xylene, methoxybutyl acetate, cellosolve acetate, butyl cellosolve acetate, methyl acetate, acetic acid
- examples include ethyl, butyl acetate, petroleum ether, and petroleum naphtha.
- the content of the organic solvent is not particularly limited, it is more preferably used in an amount taking into consideration environmental protection and environmental load in recent years.
- anti-sagging / sedimentation agent for example, “DISPARON 6700” (trade name, aliphatic bis-amide thixotropic agent, manufactured by Enomoto Kasei Co., Ltd.) can be preferably used.
- color separation preventing agent for example, “DISPARON 2100” (trade name, silicon-added aliphatic polyvalent carboxylic acid, manufactured by Enomoto Kasei Co., Ltd.) can be preferably used.
- defoaming and anti-bacterial agent for example, “DISPARON 1950” (trade name, special vinyl polymer, manufactured by Enomoto Kasei Co., Ltd.) can be preferably used.
- the surface conditioner examples include polyether-modified siloxane, polyester-modified polymethylalkylsiloxane, polyether-modified polydimethylsiloxane, and acrylic group-containing polyether-modified polydimethylsiloxane. By using such a surface conditioner, the surface tension of the paint can be adjusted to a suitable range.
- the second water-based base paint can be prepared by the same method as the first water-based base paint.
- the form of the second water-based base paint is not particularly limited as long as it is water-based.
- Clear paint As the clear paint used in the method for forming a multilayer coating film of the present invention, those usually used as a clear paint for automobile bodies can be used.
- a clear coating material include those containing a film-forming resin and, if necessary, a curing agent and other additives in a state of being dispersed or dissolved in a medium.
- the film forming resin include acrylic resin, polyester resin, epoxy resin, and urethane resin. These can be used in combination with a curing agent such as an amino resin and / or an isocyanate resin.
- an acrylic resin and / or a polyester resin and an amino resin it is preferable to use a combination of an acrylic resin and / or a polyester resin and an amino resin, or an acrylic resin and / or a polyester resin having a carboxylic acid / epoxy curing system.
- the paint form of the clear paint may be any of organic solvent type, aqueous type (water-soluble, water-dispersible, emulsion), non-aqueous dispersion type, and powder type. Further, the clear coating material may contain a curing catalyst, a surface conditioner, a viscosity control agent, an ultraviolet absorber, a light stabilizer and the like as necessary.
- the multilayer coating film forming method of the present invention comprises the following steps: A step (1) of applying a first aqueous base paint to the surface of the object to form an uncured first aqueous base coating film; A step (2) of applying a second aqueous base coating material on the obtained uncured first aqueous base coating film to form an uncured second aqueous base coating film; On the obtained uncured second aqueous base coating film, a clear coating is applied to form an uncured clear coating film, and the uncured product obtained in steps (1) to (3). Step (4) of forming a multilayer coating film by heating and curing the cured first aqueous base coating film, the uncured second aqueous base coating film and the uncured clear coating film at a time. Is a way of wrapping.
- the object to be coated used in the method for forming a multilayer coating film of the present invention is not particularly limited.
- the object to be coated may have a cured electrodeposition coating film formed on the surface.
- the cured electrodeposition coating film is formed by electrodeposition-coating an electrodeposition coating material on an object to be coated, followed by heat curing.
- the electrodeposition paint is not particularly limited, and a known cationic electrodeposition paint or anion electrodeposition paint can be used. Electrodeposition coating and baking can be performed by the methods and conditions usually used for electrodeposition coating of automobile bodies.
- a first aqueous base paint is applied to the surface of an object to form an uncured first aqueous base coating film.
- the first water-based base paint is, for example, an air electrostatic spray commonly called “react gun”, commonly called “micro-microbell ( ⁇ bell)”, “microbell ( ⁇ bell)”, “metallic bell (metabell)”, etc. It can apply
- the coating amount is adjusted so that the film thickness of the coated film after curing is 5 to 40 ⁇ m, preferably 10 to 30 ⁇ m. If the film thickness is less than 5 ⁇ m, the appearance and chipping resistance of the resulting coating film may be reduced, and if it exceeds 40 ⁇ m, problems such as sagging during coating and pinholes during baking hardening may occur.
- the following second aqueous base paint is applied without heating and curing the uncured first aqueous base paint film obtained by applying the first aqueous base paint.
- an uncured second aqueous base coating film is formed.
- wet-on-wet coating is performed without preheating between the formation of the uncured first aqueous base coating film and the application of the second aqueous base coating material.
- a preheating step is generally performed in which the uncured first aqueous base coating film is preliminarily dried by heating before the second aqueous base coating is applied.
- the reason why the preheating process has been performed is that water remaining in the uncured first aqueous base coating film causes bumping in the process of baking the multilayer coating film, and it is easy to generate cracks.
- the second aqueous base coating is applied onto the aqueous base coating, the uncured first aqueous base coating and the uncured second aqueous base coating are mixed to form a mixed layer, and the resulting multilayer This is because the appearance of the coating film deteriorates.
- a preheating step for example, a step of drying at a temperature of about 80 ° C. for 1 to 10 minutes has been performed.
- the second aqueous base paint can be wet-on-wet-coated without performing a preheating step.
- “without performing the preheating step” means, for example, a mode in which the second aqueous base paint is applied within 0 to 30 minutes after the first aqueous base paint is applied at room temperature (for example, 10 to 30 ° C.). Is mentioned.
- Such performance in the present invention is that when the second aqueous base paint is applied onto the uncured first aqueous base paint film, the water contained in the second aqueous base paint is uncured in the first aqueous base paint. This is probably because the transition to the film is suppressed, and the viscosity of the uncured first aqueous base coating film is controlled by the hydrophilic associative viscosity agent, and the effect of preventing sagging and mixed layers is exhibited.
- the second aqueous base coating is applied on the uncured first aqueous base coating obtained as described above to form an uncured second aqueous base coating.
- the second water-based base paint is, for example, an air electrostatic spray called “react gun”, commonly called “micro-microbell ( ⁇ bell)”, “microbell ( ⁇ bell)”, “metallic bell (metabell)”, etc. It can apply
- the coating amount of the second water-based base paint is usually adjusted so that the film thickness after curing of the coating film is 5 to 30 ⁇ m. If the film thickness after curing is less than 5 ⁇ m, the masking of the underlayer may be insufficient or color unevenness may occur. If it exceeds 30 ⁇ m, sagging may occur during coating and pinholes may occur during heat curing. There is a risk of doing so.
- the coating viscosity at 20 ° C. of the uncured first aqueous base coating film, which is the lower layer, after applying the second aqueous base coating is At a speed of 0.01 / s, the pressure is preferably 45 to 100 Pa ⁇ s, and more preferably 60 to 90 Pa ⁇ s.
- the coating film viscosity can be measured as follows. (1) A first aqueous base paint is applied onto the cured electrodeposition coating film formed on the substrate, and then set at 25 ° C. for 6 minutes to apply the second aqueous base paint. (2) Then, after setting at 25 ° C.
- the aluminum foil is placed on the second aqueous base coating film and peeled off to transfer only the second aqueous base coating film to the aluminum foil.
- (3) The remaining first aqueous base coating film is collected with a spatula, and the viscosity is measured with a viscometer (MCR-301) manufactured by Anton Paar at a shear rate of 0.01 / s.
- a clear coating is applied on the obtained uncured second aqueous base coating to form an uncured clear coating.
- the clear paint can be applied using an application method according to the form of the paint.
- the coating amount of the clear coating is usually adjusted so that the film thickness after drying and curing of the coating film is 10 to 70 ⁇ m. If the film thickness after curing is less than 10 ⁇ m, the appearance of the multi-layer coating film such as gloss may be deteriorated. On the other hand, when the film thickness exceeds 70 ⁇ m, the sharpness may be deteriorated, or problems such as unevenness and sagging may occur during application. It is preferable that after the uncured second aqueous base coating film is formed, for example, preheating at 40 to 100 ° C. for 2 to 10 minutes can give a better finished appearance.
- the obtained uncured first aqueous base coating film, uncured second aqueous base coating film and uncured clear coating film are simultaneously heat-cured.
- Heating is usually performed at a temperature of 110 to 180 ° C, preferably 120 to 160 ° C.
- a cured coating film having a high degree of crosslinking can be obtained. If the heating temperature is less than 110 ° C, curing tends to be insufficient, and if it exceeds 180 ° C, the resulting coating film may be hard and brittle.
- the heating time can be appropriately set according to the above temperature, and for example, when the temperature is 120 to 160 ° C., it is 10 to 60 minutes.
- the multilayer coating film obtained by the multilayer coating film forming method of the present invention after applying the first aqueous base coating material, even if the second aqueous base coating material is applied wet-on-wet without preheating,
- a multilayer coating film having high smoothness and good coating film appearance can be obtained. Therefore, it is not necessary to perform a preheating process after applying the first water-based base paint, energy saving and CO 2 emission reduction in the application process can be achieved, and there are also advantages in coating equipment cost and coating line space. .
- Production Example 1 Production of Acrylic Emulsion Resin
- New Coal 293 Japanese emulsifier
- the mixture was emulsified using a homogenizer, and the monomer pre-emulsion was dropped into the reaction vessel over 3 hours with stirring.
- an aqueous solution prepared by dissolving 1 part of APS (ammonium persulfate) as a polymerization initiator in 50 parts of water is uniformly dropped into the reaction vessel until the end of the dropping of the monomer pre-emulsified solution. did.
- the reaction was further continued at 80 ° C. for 1 hour, and then cooled. After cooling, an aqueous solution in which 2 parts of dimethylaminoethanol was dissolved in 20 parts of water was added to obtain an acrylic emulsion resin having a solid content concentration of 40.6% by mass.
- the resulting acrylic emulsion resin had a solid content acid value of 20 mg KOH / g, a solid content hydroxyl value of 60 mg KOH / g, and a Tg of 30 ° C. (solid content concentration: measured according to JIS K 5601-1-2 heating residue measurement method).
- Production Example 4 Preparation of first aqueous base paint (1) 206.6 parts of pigment dispersion paste obtained from Production Example 2 above, 45.0 parts of acrylic emulsion resin obtained from Production Example 1 above, Production Example 3 above After mixing 62.4 parts of the obtained polyester resin aqueous dispersion and 78.7 parts of Cymel 211 (melamine resin manufactured by Nippon Cytec Industries, Inc., non-volatile content 80%) as a curing agent, BYK-430 (Bic Chemie) as a viscosity agent.
- Cymel 211 melamine resin manufactured by Nippon Cytec Industries, Inc., non-volatile content 80%
- Production Example 5 Preparation of the first water-based base paints (2) to (9)
- the hydrophilic associative viscosity agent BYK-430 used as the viscosity agent was changed to that shown in Table 1 and the mass% shown in Table 1.
- the first water-based base paints (7) to (9) use a hydrophobic associative viscosity agent instead of a hydrophilic associative viscosity agent.
- surface is the mass% with respect to the coating-resin solid content of a 1st water base paint.
- * 1 Hydrophilic associative viscosity agent manufactured by Big Chemie
- 2 Hydrophilic associative viscosity agent manufactured by Enomoto Kasei Co., Ltd.
- 3 Hydrophobic associative viscosity agent manufactured by ADEKA
- 4 Hydrophobic associative viscosity agent manufactured by Elementis
- 5 Big Chemie Hydrophobic associative viscosity agent
- This core-shell type acrylic emulsion resin (b) has a core Tg of 104 ° C., a shell Tg of 40 ° C., a non-volatile content of 49.2%, a pH of 6.0, a viscosity of 550 mPa ⁇ s (using a B-type viscometer, Rotor No.
- An initiator solution consisting of 10 parts of propylene glycol methyl ether and 1 part of tertiary butyl peroxy 2-ethylhexanoate was dropped into the reaction vessel in parallel over 3 hours. After completion of the dropping, aging was performed at the same temperature for 0.5 hours. Further, an initiator solution consisting of 5 parts of tripropylene glycol methyl ether and 0.3 part of tertiary butyl peroxy 2-ethylhexanoate was dropped into the reaction vessel over 0.5 hours. After completion of the dropping, aging was performed at the same temperature for 2 hours. After removing 16.1 parts of the solvent at 110 ° C.
- the obtained water-soluble acrylic resin (B) had a nonvolatile content of 30%, a solid content acid value of 40 mgKOH / g, a hydroxyl value of 50 mgKOH / g, and a viscosity of 140 Pa ⁇ s (E-type viscometer 1 rpm / 25 ° C.). It was.
- the pressure inside the system was gradually reduced, the pressure was reduced to 5 mmHg over 20 minutes, and the pressure was further reduced to a vacuum of 0.3 mmHg or less, and a polycondensation reaction was performed at 260 ° C. for 40 minutes.
- the mixture was cooled to 220 ° C. in a nitrogen atmosphere, 23 parts of trimellitic anhydride was added, and a reaction was performed at 220 ° C. for 30 minutes to obtain a polyester resin.
- 40 parts of butyl cellosolve and 2.7 parts of triethylamine were added, followed by stirring at 80 ° C. for 1 hour for dissolution.
- Production Example 10 Preparation of Second Water-Based Base Paint (1) As acrylic emulsion resin (A), 50 parts (resin solid content 25%) of single-layer acrylic emulsion resin (a) obtained in Production Example 6 above. The core-shell type acrylic emulsion resin (b) obtained in Production Example 7 is mixed with 60 parts (resin solid content: 49.2%), and the water-soluble acrylic resin (B) 79 obtained in Production Example 8 is further mixed.
- acrylic emulsion resin (A) 50 parts (resin solid content 25%) of single-layer acrylic emulsion resin (a) obtained in Production Example 6 above.
- the core-shell type acrylic emulsion resin (b) obtained in Production Example 7 is mixed with 60 parts (resin solid content: 49.2%), and the water-soluble acrylic resin (B) 79 obtained in Production Example 8 is further mixed.
- Production Example 11 Preparation of second aqueous base paints (2) to (8) Table 2 shows the blending ratio of acrylic emulsion resin (A), water-soluble acrylic resin (B), water-soluble polyester resin (C) and other components. Second water-based base paints (2) to (8) were prepared in the same manner as in Production Example 10 except that the above changes were made.
- Example 1 Formation of multi-layer coating film A zinc phosphate-treated dull steel plate was electrodeposited with Powernics 110 (cation paint electrodeposited by Nippon Paint Co., Ltd.) so that the dry coating film was 20 ⁇ m, and was heated at 160 ° C. for 30 minutes. The cured electrodeposition coating film was formed by cooling after heat curing.
- Powernics 110 cation paint electrodeposited by Nippon Paint Co., Ltd.
- the first aqueous base coating (1) obtained in Production Example 4 was applied to the substrate on which the cured electrodeposition coating was formed by air spray coating at room temperature to a thickness of 20 ⁇ m, and the uncured first aqueous base coating was coated. Obtained. Thereafter, the second aqueous base paint (1) obtained in Production Example 10 was applied by 10 ⁇ m by air spray coating without being put in a preheat oven, and preheated at 80 ° C. for 3 minutes. Furthermore, after applying 35 ⁇ m of Macflow O-1800W-2 Clear (Nippon Paint Co., Ltd. acid epoxy curing clear paint) as a clear paint to the coated plate by air spray coating, heat curing at 140 ° C. for 30 minutes is performed. A test piece having a multilayer coating film was obtained.
- Macflow O-1800W-2 Clear Nippon Paint Co., Ltd. acid epoxy curing clear paint
- the first aqueous base paint (1), the second aqueous base paint (1) and the clear paint were diluted under the following conditions and used for application.
- SW value and LW value Regarding the finished appearance of the obtained multilayer coating film, LW (measurement wavelength: 1,300 to 12,000 ⁇ m), SW (measurement wavelength: 300 to 1,200 ⁇ m) using a wave scan DOI (manufactured by BYK Gardner). Evaluation was carried out by measuring. These numerical values indicate that the smaller the numerical value, the better the smoothness.
- a test plate was prepared in the same manner as the above multi-layer coating except that a coating plate having an electrodeposition coating with a hole of 5 mm in diameter was used as a sacrificial substrate. was measured. These numerical values indicate that the smaller the numerical value, the better the sagging property.
- Example 2 to 7 and Comparative Examples 1 to 5 A test piece having a multilayer coating film was prepared in the same manner as in Example 1 except that the materials shown in Table 3 were used instead of the first water-based base paint (1) and the second water-based base paint (2) in Example 1. Obtained. The viscosity (Pa ⁇ s), sagging property, design property and smoothness of the uncured first aqueous base coating film in the step (2) were also measured, and the results are shown in Table 3.
- the first water-based base paint used in the examples contains a hydrophilic associative viscosity agent, even if the second water-based base paint is applied without preheating after the application, the obtained multilayer coating film has a smooth surface.
- the coating film appearance was excellent without mixing the first aqueous base coating film and the second aqueous base coating film.
- Comparative Examples 1 to 3 are examples in which a hydrophobic associative viscosity agent is used, and the sagging property, the design property, and the appearance (smoothness, especially the SW value) are not good.
- the hydrophobic associative viscosity agent when the second aqueous base coating is applied, the water contained in the second aqueous base coating is transferred to the first aqueous base coating and the viscosity of the first aqueous base coating is reduced. It is considered that the above evaluation has decreased.
- Comparative Examples 4 and 5 correspond to an example in which the content of the acrylic emulsion resin (A) is large (Comparative Example 4) and an example in which the content of the acrylic emulsion resin (A) is small (Comparative Example 5), both of which are sagging and designable. And either the appearance is bad.
- the composition of the first water-based base paint and the second water-based base paint is controlled, and after the first water-based base paint is applied, the second water-based base paint is applied wet-on-wet without preheating. Even so, there is an advantage that a multilayer coating film having high designability and smoothness and a good coating film appearance can be obtained. Therefore, it is not necessary to perform a preheating process after the application of the first water-based base paint, energy saving and CO 2 emission reduction can be achieved in the painting process, and there are also advantages in coating equipment cost and painting line space.
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Abstract
Description
本発明は、複層塗膜形成方法、特に、いわゆるウェット・オン・ウェット塗装で第1水性ベース塗料、第2水性ベース塗料およびクリヤー塗料を塗布した後、3層を一度に加熱硬化する複層塗膜形成方法に関する。
被塗物表面に対して、第1水性ベース塗料を塗布して未硬化の第1水性ベース塗膜を得る工程(1)、前記未硬化の第1水性ベース塗膜上に、第2水性ベース塗料を塗布して未硬化の第2水性ベース塗膜を形成する工程(2)、前記未硬化の第2水性ベース塗膜上に、クリヤー塗料を塗布して未硬化のクリヤー塗膜を形成する工程(3)、および、前記工程(1)~(3)で得られた未硬化の第1水性ベース塗膜、未硬化の第2水性ベース塗膜および未硬化のクリヤー塗膜を、一度に加熱硬化して複層塗膜を形成する工程(4)を含む複層塗膜形成方法であって、
前記第1水性ベース塗料が親水会合型粘性剤を含んでおり、かつ、
前記第2水性ベース塗料が、塗膜形成樹脂としてアクリルエマルション樹脂(A)、水溶性アクリル樹脂(B)および水溶性ポリエステル樹脂(C)を含み、アクリルエマルション樹脂(A)の樹脂固形分質量と、アクリルエマルション樹脂(A)、水溶性アクリル樹脂(B)および水溶性ポリエステル樹脂(C)の合計樹脂固形分合計質量との比率(A)/(A+B+C)の百分率が40~60%である、
ことを特徴とする、複層塗膜形成方法、を提供するものであり、これにより上記課題が解決される。
前記第1水性ベース塗料に含まれる親水会合型粘性剤がポリアマイド型粘性剤であること、
前記第2水性ベース塗料に含まれるアクリルエマルション樹脂(A)が、単層型アクリルエマルション樹脂(a)およびコア・シェル型アクリルエマルション樹脂(b)を含んでいること、
前記工程(2)において前記第2水性ベース塗料を塗布した際の前記未硬化の第1水性ベース塗膜の20℃での塗膜粘度が剪断速度0.01/sにおいて、45~100Pa・sであること、
前記工程(1)と前記工程(2)との間に、加熱乾燥工程がないこと。
本発明の第1水性ベース塗料は、通常、アクリルエマルション樹脂および硬化剤を含み、本発明では親水会合型粘性剤を更に含む。この第1水性ベース塗料にはさらに、顔料および必要に応じた添加剤を含んでもよい。
アクリルエマルション樹脂を構成するアクリル樹脂のガラス転移温度(Tg)は-20℃~60℃であるのが好ましく、-10℃~50℃であるのがより好ましく、0℃~40℃であるのがさらに好ましい。樹脂のTgが-20℃未満では塗膜の機械的強度が不足し、耐チッピング性が低下する。一方、樹脂のTgが60℃を超えると、塗膜が硬くて脆くなるため、耐衝撃性に欠け、耐チッピング性が低下する。上記アクリルエマルション樹脂のTgは、構成するモノマーまたはホモポリマーの既知のTgおよび組成比に基づいて算出することができる。
本発明の第1水性ベース塗料は硬化剤を含むことが好ましい。この硬化剤は、上記アクリルエマルション樹脂と硬化反応を生じ、第1水性ベース塗料中に配合することができるものであれば、特に限定されずに用いることができる。硬化剤として、例えば、メラミン樹脂、ブロックイソシアネート樹脂、オキサゾリン系化合物あるいはカルボジイミド系化合物などが挙げられる。これらは1種で用いてもよく、2種以上を併用してもよい。
親水会合型粘性剤は、粘性剤同士、あるいは基体樹脂との間に水素結合を有し、その結合力(相互作用)を利用した粘性剤である。このような親水会合型粘性剤としては、例えば、ポリアマイド型の粘性剤が挙げられ、市販されているものとしては、BYK-430、BYK-431(いずれも商品名、ビックケミー社製)、ディスパロンAQ-580、ディスパロンAQ-600、ディスパロンAQ-607(いずれも商品名、楠本化成社製)、チクゾールW-300、チクゾールW-400LP(いずれも商品名、共栄社化学製)などを挙げることができる。
アクリルエマルション樹脂、硬化剤および親水会合型粘性剤の含有量は、樹脂固形分質量比で、アクリルエマルション樹脂1~60質量%、より好ましくは10~50質量%、
硬化剤5~80質量%、より好ましくは10~70質量%、および親水会合型粘性剤0.01~20質量%、より好ましくは0.1~10質量%、であるのが好ましい。
アクリルエマルション樹脂が60質量%を超える場合は、得られる塗膜の外観が低下するおそれがある。また、アクリルエマルション樹脂が1質量%未満である場合は、塗装作業性が低下するおそれがある。
硬化剤が80質量%を超える場合は、得られる塗膜の耐チッピング性が低下するおそれがある。また、硬化剤が5質量%未満である場合は、得られる塗膜の耐水性が低下するおそれがある。
親水会合型粘性剤が20質量%を超える場合は、塗膜の外観が低下、あるいは耐水性が低下するおそれがある。また、親水会合型粘性剤が0.01質量%未満である場合は、第2水性ベース塗料を塗布した際に、タレや混層が生じるおそれがある。
本発明の複層塗膜形成方法で用いる第2水性ベース塗料として、自動車車体の塗布において通常用いられる第2水性ベース塗料を用いることができる。このような第2水性ベース塗料として、例えば、水性媒体中に分散または溶解された状態で、塗膜形成樹脂、硬化剤、光輝性顔料、着色顔料や体質顔料などの顔料、各種添加剤などを含むものを挙げることができる。塗膜形成樹脂としては、アクリルエマルション樹脂(A)、水溶性アクリル樹脂(B)および水溶性ポリエステル樹脂(C)を含む。
アクリルエマルション樹脂(A)は、第1水性ベース塗料で説明したアクリルエマルション樹脂を用いることができる。但し、アクリルエマルション樹脂(A)は、単層型アクリルエマルション樹脂(a)とコア・シェル型アクリルエマルション樹脂(b)とを含むものが好ましい。第2水性ベース塗料では、コア・シェル型アクリルエマルション樹脂(b)に比べて単層型アクリルエマルション樹脂(a)の水保持性が低く、単層型アクリルエマルション樹脂(a)の割合を上げると、第1水性ベース塗膜への水の移行量が多くなり、第1水性ベース塗膜でのタレや混層が生じるおそれがある。コア・シェル型アクリルエマルション樹脂(b)の割合を上げると、第2水性ベース塗料の塗膜粘度が高くなりすぎ、平滑性が損なわれるという不具合も生じる。水保持性と平滑性を両立させるためには、コア・シェル型アクリルエマルション樹脂(b)と単層型アクリルエマルション樹脂(a)の配合比率が重要になり、単層型アクリルエマルション樹脂(a)の樹脂固形分質量と、アクリルエマルション樹脂(A)の樹脂固形分質量の比率(a)/(A)の百分率が30~60%であるのが好ましい。
水溶性アクリル樹脂(B)は、水酸基含有モノマーおよび他のモノマーを共重合することによって調製することができる。
本発明における第2水性ベース塗料には水溶性ポリエステル樹脂(C)が含まれる。第2水性ベース塗料に水溶性ポリエステル樹脂(C)が含まれることによって、塗装作業性が向上し、得られる塗膜の外観が向上するという利点がある。第2水性ベース塗料に含まれる水溶性ポリエステル樹脂(C)として、一般にポリエステルポリオールと呼ばれる、1分子中に2個以上の水酸基を有するものが好適に用いられる。このような水溶性ポリエステル樹脂は、多価アルコールと多塩基酸またはその無水物とを重縮合(エステル反応)して調製することができる。
第2水性ベース塗料は顔料を含むのが好ましい。顔料としては、塗料分野において一般的に用いられる顔料を用いることができ、例えば、上記第1水性ベース塗料で挙げた顔料の他、アルミニウム、銅、亜鉛、鉄、ニッケル、スズ、酸化アルミニウム等の金属または合金等の無着色あるいは着色された金属製光輝材およびその混合物、干渉マイカ顔料、ホワイトマイカ顔料、グラファイト顔料等の光輝性顔料等が挙げられる。これらの顔料は、それぞれ1種のみが用いられてもよいし、2種以上を併用してもよい。
本発明の複層塗膜形成方法で用いるクリヤー塗料としては、自動車車体用クリヤー塗料として通常用いられているものを用いることができる。このようなクリヤー塗料として、例えば、媒体中に分散または溶解された状態で、塗膜形成樹脂、そして必要に応じた硬化剤およびその他の添加剤を含むものを挙げることができる。塗膜形成樹脂としては、例えば、アクリル樹脂、ポリエステル樹脂、エポキシ樹脂、ウレタン樹脂などが挙げられる。これらはアミノ樹脂および/またはイソシアネート樹脂などの硬化剤と組み合わせて用いることができる。透明性または耐酸エッチング性などの点から、アクリル樹脂および/もしくはポリエステル樹脂とアミノ樹脂との組み合わせ、または、カルボン酸・エポキシ硬化系を有するアクリル樹脂および/もしくはポリエステル樹脂などを用いることが好ましい。
本発明の複層塗膜形成方法は、下記工程:
被塗物表面に対して、第1水性ベース塗料を塗布して、未硬化の第1水性ベース塗膜を形成する工程(1)、
得られた未硬化の第1水性ベース塗膜の上に、第2水性ベース塗料を塗布して未硬化の第2水性ベース塗膜を形成する工程(2)、
得られた未硬化の第2水性ベース塗膜上に、クリヤー塗料を塗布して未硬化のクリヤー塗膜を形成する工程(3)、および、工程(1)~(3)で得られた未硬化の第1水性ベース塗膜、未硬化の第2水性ベース塗膜および未硬化のクリヤー塗膜を、一度に加熱硬化して複層塗膜を形成する工程(4)
を包む方法である。
(1)基材の上に形成した硬化電着塗膜上に、第1水性ベース塗料を塗布した後、25℃で6分間セッティングし、第2水性ベース塗料を塗布する。
(2)その後同じく25℃で3分間セッティングした後、アルミ箔を第2水性ベース塗膜の上に載せて、それを剥がすことによって第2水性ベース塗膜のみをアルミ箔に移行させて取り除く。
(3)残った第1水性ベース塗膜をスパチュラでかき集めて、それをアントン・パール(Anton Paar)社製粘度計(MCR-301)にて剪断速度0.01/sで粘度を測定する。
攪拌機、温度計、滴下ロート、還流冷却器および窒素導入管などを備えた通常のアクリル系樹脂エマルション製造用の反応容器に、水445部およびニューコール293(日本乳化剤社製)5部を仕込み、攪拌しながら75℃に昇温した。メタクリル酸メチル145部、スチレン50部、アクリル酸エチル220部、メタクリル酸2-ヒドロキシエチル70部およびメタクリル酸15部を含むモノマー混合物、水240部およびニューコール293(日本乳化剤社製)30部の混合物を、ホモジナイザーを用いて乳化し、そのモノマープレ乳化液を上記反応容器中に3時間にわたって攪拌しながら滴下した。モノマープレ乳化液の滴下と併行して、重合開始剤としてAPS(過硫酸アンモニウム)1部を水50部に溶解した水溶液を、上記反応容器中に上記モノマープレ乳化液の滴下終了時まで均等に滴下した。モノマープレ乳化液の滴下終了後、さらに80℃で1時間反応を継続し、その後、冷却した。冷却後、ジメチルアミノエタノール2部を水20部に溶解した水溶液を投入し、固形分濃度40.6質量%のアクリルエマルション樹脂を得た。
分散剤であるDisperbyk 190(ビックケミー社製ノニオン・アニオン系分散剤)4.5部、消泡剤であるBYK-011(ビックケミー社製消泡剤)0.5部、イオン交換水22.9部、二酸化チタン72.1部を予備混合した後、ペイントコンディショナー中でガラスビーズ媒体を加え、室温で粒度5μm以下となるまで混合分散し、顔料分散ペーストを得た。
攪拌機、温度計、環流冷却器および窒素導入管などを備えた通常のポリエステル系樹脂製造用反応容器に、イソフタル酸19部、ヘキサヒドロフタル酸無水物36部、トリメチロールプロパン7部、ネオペンチルグリコール12部、1,6-ヘキサンジオール26部、触媒としてジブチル錫オキサイド0.1部を仕込み、150℃から230℃まで3時間かけて昇温し、230℃で5時間程度保持した。
上記製造例2より得られた顔料分散ペースト206.6部、上記製造例1より得られたアクリルエマルション樹脂45.0部、上記製造例3より得られたポリエステル樹脂水分散体62.4部、および硬化剤としてサイメル211(日本サイテックインダストリーズ社製メラミン樹脂、不揮発分80%)78.7部を混合した後、粘性剤としてBYK-430(ビックケミー社製親水会合型粘性剤、不揮発分30%)6.7部(第1水性ベース塗料の樹脂固形分に対して2質量%に相当)を混合撹拌し、第1水性ベース塗料(1)を得た。
粘性剤として用いた親水会合型粘性剤BYK-430を、表1に記載するものおよび表1に記載する質量%に変更する以外は、製造例4と同様に第1水性ベース塗料(2)~(9)を調製した。なお、第1水性ベース塗料(7)~(9)は、親水会合型粘性剤でなく、疎水会合型粘性剤を用いたものである。
*1:ビックケミー社製親水会合型粘性剤
*2:楠本化成社製親水会合型粘性剤
*3:ADEKA社製疎水会合型粘性剤
*4:エレメンティス社製疎水会合型粘性剤
*5:ビックケミー社製疎水会合型粘性剤
反応容器に脱イオン水126.5部を加え、窒素気流中で混合撹拌しながら80℃に昇温した。次いで、アクリル酸メチル27.61部、アクリル酸エチル53.04部、スチレン4.00部、メタクリル酸2-ヒドロキシエチル9.28部、メタクリル酸3.07部およびメタクリル酸アリル3.00部のモノマー混合物100部、アクアロンHS-10(ポリオキシエチレンアルキルプロペニルフェニルエーテル硫酸エステル、第一工業製薬社製)0.7部、アデカリアソープNE-20(α-[1-[(アリルオキシ)メチル]-2-(ノニルフェノキシ)エチル]-ω-ヒドロキシオキシエチレン、旭電化社製)0.5部、および脱イオン水80部からなるモノマー乳化物と、過硫酸アンモニウム0.3部、および脱イオン水10部からなる開始剤溶液とを2時間にわたり並行して反応容器に滴下した。滴下終了後、2時間同温度で熟成を行った。次いで、40℃まで冷却し、400メッシュフィルターで濾過した後、脱イオン水70部およびジメチルアミノエタノール0.32部を加えpH6.5に調整し、平均粒子径150nm、不揮発分25%、固形分酸価20mgKOH/g、水酸基価40mgKOH/gの単層型アクリルエマルション樹脂(a)を得た。
撹拌機、還流冷却器、滴下ロート、窒素導入管、温度センサーを備えた2Lのセパラブルフラスコに、イオン交換水651部を仕込んだ後、窒素ガスを吹込みながら、撹拌下、70℃に昇温した。次いで滴下ロートから、予め調製しておいたメチルメタクリレート300部、スチレン194部、メタアクリル酸6部(以上の単量体から得られるコアの計算Tg:104℃)、15%水溶液のポリオキシエチレンノニルフェニルエーテル硫酸アンモニウム塩(「ハイテノールN-08」;第一工業製薬社製)33部、25%水溶液のポリオキシエチレンノニルフェニルエーテル(「ノニポール200」;三洋化成社製)40部と脱イオン水102部からなるプレエマルション(1)を第一段目の単量体成分として1時間30分にわたって滴下した。このとき、同時に、5%過硫酸アンモニウム水溶液30部を1時間30分にわたって滴下した。滴下終了後、40分熟成を行い、続けて予め調製しておいた2-エチルヘキシルアクリレート116部、メチルメタクリレート206部、スチレン150部、アクリル酸28部(以上の単量体から得られるシェルのTg:40℃)、15%水溶液のハイテノールN-08を33部、25%水溶液のノニポール200を40部と脱イオン水102部からなるプレエマルション(2)を最終段目の単量体成分として1時間30分にわたって滴下した。このとき、同時に、5%過硫酸アンモニウム水溶液30部を1時間30分にわたって滴下した。滴下終了後、1時間熟成を行った。冷却して、25%アンモニア水を4.6部添加して中和を行い、コア・シェル型アクリルエマルション樹脂(b)を得た。このコア・シェル型アクリルエマルション樹脂(b)は、コアのTgが104℃、シェルのTgが40℃、不揮発分49.2%、pH6.0、粘度550mPa・s(B型粘度計を用い、ローターNo.2、30回/分、25℃で測定;以下同じ)、動的光散乱式粒径測定装置LB-500(堀場製作所社製)によって、20℃で測定したところ、平均粒子径140nmであった。
反応容器にトリプロピレングリコールメチルエーテル23.89部およびプロピレングリコールメチルエーテル16.11部を加え、窒素気流中で混合撹拌しながら105℃に昇温した。次いで、メタクリル酸メチル13.1部、アクリル酸エチル68.4部、メタクリル酸2-ヒドロキシエチル11.6部およびメタクリル酸6.9部を含むモノマー混合物を作成し、そのモノマー混合物100部、トリプロピレングリコールメチルエーテル10部およびターシャルブチルパーオキシ2-エチルヘキサノエート1部からなる開始剤溶液を3時間にわたり並行して反応容器に滴下した。滴下終了後、0.5時間同温度で熟成を行った。さらに、トリプロピレングリコールメチルエーテル5部およびターシャルブチルパーオキシ2-エチルヘキサノエート0.3部からなる開始剤溶液を0.5時間にわたり反応容器に滴下した。滴下終了後、2時間同温度で熟成を行った。脱溶剤装置により、減圧下(70torr)110℃で溶剤を16.1部留去した後、脱イオン水204部およびジメチルアミノエタノール7.1部を加えて水溶性アクリル樹脂(B)を得た。得られた水溶性アクリル樹脂(B)の不揮発分は30%であり、固形分酸価40mgKOH/g、水酸基価50mgKOH/g、粘度は140Pa・s(E型粘度計1rpm/25℃)であった。
攪拌機、コンデンサー、温度計を具備した反応容器にジメチルテレフタル酸372部、ジメチルイソフタル酸380部、2-メチル-1,3-プロパンジオール576部、1,5-ペンタンジオール222部、テトラブチルチタネート0.41部を仕込み、160℃から230℃まで昇温しつつ4時間かけてエステル交換反応を行った。次いで系内を徐々に減圧していき、20分かけて5mmHgまで減圧し、さらに0.3mmHg以下の真空下まで減圧して、260℃にて40分間重縮合反応を行った。窒素雰囲気下、220℃まで冷却し、無水トリメリット酸を23部投入し、220℃で30分間反応を行ってポリエステル樹脂を得た。このポリエステル樹脂100部に、ブチルセロソルブ40部、トリエチルアミン2.7部を投入した後、80℃で1時間攪拌を行って溶解させた。次いで、イオン交換水193部をゆるやかに添加し、不揮発分30%の水溶性ポリエステル樹脂(C)を得た。平均粒子径を測定するために、専用セルにイオン交換水だけを入れ、水溶性ポリエステル樹脂(C)を1滴添加しかき混ぜ、樹脂固形分濃度0.1質量%に調整して動的光散乱式粒径測定装置LB-500(堀場製作所社製)によって、20℃で測定したところ、35nmであった。
アクリルエマルション樹脂(A)として、先の製造例6で得られた単層型アクリルエマルション樹脂(a)を50部(樹脂固形分25%)と製造例7で得られたコア・シェル型アクリルエマルション樹脂(b)を60部(樹脂固形分49.2%)とを混合し、さらに製造例8で得られた水溶性アクリル樹脂(B)79部(樹脂固形分30%)、製造例9で得られた水溶性ポリエステル樹脂(C)14部(樹脂固形分30%)、メラミン樹脂としてサイメル204(三井サイテック社製混合アルキル化型メラミン樹脂、固形分80%)を38部、プライムポールPX-1000(三洋化成工業社製2官能ポリエーテルポリオール)10部、光輝性顔料としてアルペーストMH8801(旭化成社製アルミニウム顔料)21部(固形分65%、PWC12%)、リン酸基含有アクリル樹脂5部、ラウリルアシッドフォスフェート0.3部を添加し、さらに、2-エチルヘキサノール30部、アデカノールUH-814N3.3部(ADEKA社製増粘剤、固形分30%)を均一分散することにより第2水性ベース塗料(1)を得た。
アクリルエマルション樹脂(A)、水溶性アクリル樹脂(B)、水溶性ポリエステル樹脂(C)およびその他の成分の配合割合を表2のとおりに変更する以外は、製造例10と同様に第2水性ベース塗料(2)~(8)を作成した。
複層塗膜の形成
リン酸亜鉛処理したダル鋼板に、パワーニクス110(日本ペイント社製カチオン電着塗料)を、乾燥塗膜が20μmとなるように電着塗装し、160℃で30分間の加熱硬化後冷却して、硬化電着塗膜を形成した。
希釈溶媒:イオン交換水
40秒/NO.4フォードカップ/20℃
希釈溶媒:イオン交換水
45秒/NO.4フォードカップ/20℃
希釈溶媒:EEP(エトキシエチルプロピオネート)/S-150(エクソン社製芳香族系炭化水素溶剤)=1/1(質量比)の混合溶剤
30秒/NO.4フォードカップ/20℃
得られた複層塗膜の意匠性(フリップフロップ性)について、X-Rite MA68II(エックスライト社製)を用いて、15°(正面)、110°(シェード)のL値を測定した。これらの数値は、数値が大きい程意匠性(フリップフロップ性)が良好である事を示す。
得られた複層塗膜の仕上がり外観について、ウエーブスキャン DOI(BYK Gardner社製)を用いて、LW(測定波長:1,300~12,000μm)、SW(測定波長:300~1,200μm)を測定することにより評価を行った。これらの数値は、数値が小さい程平滑性が良好である事を示す。
基板として、直径5mmの穴を開けた電着塗膜を有する塗板を用いたこと以外は上記複層塗膜の作成と同様にして試験板を作成し、加熱硬化後の穴下部タレ長さを測定した。これらの数値は、数値が小さい程タレ性が良好である事を示す。
基材の上に形成した硬化電着塗膜上に、第1水性ベース塗料を塗布した後、25℃で6分間セッティングし、第2水性ベース塗料を塗布した。その後同じく25℃で3分間セッティングした後、アルミ箔を第2水性ベース塗膜の上に載せて、それを剥がすことによって第2水性ベース塗膜のみをアルミ箔に移行させて取り除く。残った第1水性ベース塗膜をスパチュラでかき集めて、それをアントン・パール(Anton Paar)社製粘度計(MCR-301)にて剪断速度0.01/sで、20℃における粘度を測定した。
実施例1において第1水性ベース塗料(1)および第2水性ベース塗料(2)の代わりに、表3に示すものを用いる以外は、実施例1と同様に複層塗膜を有する試験片を得た。工程(2)の際の未硬化の第1水性ベース塗膜の粘度(Pa・s)、タレ性、意匠性および平滑性も測定し、結果を表3に示す。
Claims (5)
- 被塗物表面に対して、第1水性ベース塗料を塗布して未硬化の第1水性ベース塗膜を得る工程(1)、前記未硬化の第1水性ベース塗膜上に、第2水性ベース塗料を塗布して未硬化の第2水性ベース塗膜を形成する工程(2)、前記未硬化の第2水性ベース塗膜上に、クリヤー塗料を塗布して未硬化のクリヤー塗膜を形成する工程(3)、および、前記工程(1)~(3)で得られた未硬化の第1水性ベース塗膜、未硬化の第2水性ベース塗膜および未硬化のクリヤー塗膜を、一度に加熱硬化して複層塗膜を形成する工程(4)を含む複層塗膜形成方法であって、
前記第1水性ベース塗料が親水会合型粘性剤を含んでおり、かつ、
前記第2水性ベース塗料が、塗膜形成樹脂としてアクリルエマルション樹脂(A)、水溶性アクリル樹脂(B)および水溶性ポリエステル樹脂(C)を含み、アクリルエマルション樹脂(A)の樹脂固形分質量と、アクリルエマルション樹脂(A)、水溶性アクリル樹脂(B)および水溶性ポリエステル樹脂(C)の樹脂固形分合計質量との比率(A)/(A+B+C)の百分率が40~60%である、
ことを特徴とする、複層塗膜形成方法。 - 前記第1水性ベース塗料に含まれる親水会合型粘性剤がポリアマイド型粘性剤である請求項1に記載の複層塗膜形成方法。
- 前記第2水性ベース塗料に含まれるアクリルエマルション樹脂(A)が、単層型アクリルエマルション樹脂(a)およびコア・シェル型アクリルエマルション樹脂(b)を含んでいる請求項1または2に記載の複層塗膜形成方法。
- 前記工程(2)において前記第2水性ベース塗料を塗布した際の前記未硬化の第1水性ベース塗膜の20℃での塗膜粘度が剪断速度0.01/sにおいて、45~100Pa・sである請求項1~3のいずれか1つに記載の複層塗膜形成方法。
- 前記工程(1)と前記工程(2)との間に、加熱乾燥工程がない、請求項1~4のいずれか1つに記載の複層塗膜形成方法。
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Also Published As
Publication number | Publication date |
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MX351244B (es) | 2017-10-05 |
CA2899829C (en) | 2019-01-22 |
EP2952265A4 (en) | 2016-10-12 |
CA2899829A1 (en) | 2014-08-07 |
CN105377450A (zh) | 2016-03-02 |
MX2015010028A (es) | 2016-03-04 |
JP2014147918A (ja) | 2014-08-21 |
US10214654B2 (en) | 2019-02-26 |
JP5688571B2 (ja) | 2015-03-25 |
EP2952265A1 (en) | 2015-12-09 |
CN105377450B (zh) | 2017-12-08 |
EP2952265B1 (en) | 2018-08-08 |
US20150368484A1 (en) | 2015-12-24 |
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