WO2008050778A1 - Procédé de revêtement d'un article en plastique moulé - Google Patents
Procédé de revêtement d'un article en plastique moulé Download PDFInfo
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- WO2008050778A1 WO2008050778A1 PCT/JP2007/070674 JP2007070674W WO2008050778A1 WO 2008050778 A1 WO2008050778 A1 WO 2008050778A1 JP 2007070674 W JP2007070674 W JP 2007070674W WO 2008050778 A1 WO2008050778 A1 WO 2008050778A1
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Classifications
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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
- B05D7/02—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 to macromolecular substances, e.g. rubber
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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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- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
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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
- B05D2503/00—Polyurethanes
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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
- B05D2507/00—Polyolefins
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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
- B05D2520/00—Water-based dispersions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
Definitions
- the present invention relates to a method for coating a plastic molded product that can form a coating film excellent in adhesion, water resistance, durability and the like to a plastic molded product even by low-temperature baking.
- plastic molded products have been widely used as interior and exterior parts for automobile bodies.
- a method for coating the plastic molded product for example, a water-based primer, a water-based base paint, and a clear paint are sequentially applied, and then heated, and a three-layer coating film is simultaneously baked and cured.
- Known for example, Japanese Patent Laid-Open No. 10-2 9 6 1 71, Japanese Patent Laid-Open No. 2 0 0 4-3 3 1 9 1 1, Japanese Patent Laid-Open No. 2 0 0 5-9 0 5 See).
- the object of the present invention is that the above-mentioned problems do not occur, and even if low-temperature baking at 100 ° C or lower is performed in a three-coat one-bake method, adhesion to plastic molded products, water resistance, durability
- the object is to provide a method for coating a plastic molded product capable of forming a coating film having excellent properties.
- the above object is achieved by coating the plastic molded article with the water-based primer (I), coating the water-based base coat paint (II) on the coated surface, and further applying the water-based base coat paint (II) onto the uncured coated surface.
- a coating method comprising applying a clear coat paint (III) to a film and simultaneously baking and curing the three-layer coating film formed,
- the water-based primer (I) is composed of the water-based polyolefin resin (A) and the water-based acrylic resin (B). B) is contained in a proportion of 90 to 10% by weight,
- Water-based base coat paint (II) is water-based polyurethane resin (C), water-based acrylic resin and hydroxyl-containing water-based polyester resin (D), and melamine resin (E) based on the total solid content of these three resins.
- the resin (C) is contained in such a ratio that the resin (C) is ") to 50% by weight, the resin (D) is 10 to 96% by weight, and the resin (E) is 3 to 40% by weight,
- the melamine resin (E) is a butyl methyl mixed etherified melamine resin and has a weight average molecular weight in the range of 1 500 to 3000;
- the coating method of the present invention in a method of coating a three-layer coating film of a water-based primer, a water-based base coating material and a clear coating material by a three-coating one-bake method, Even if it is dry, it is possible to obtain sufficient dryness and curability, and it is a plastic molded product with a multilayer coating film that has excellent adhesion to plastic molded products, water resistance, durability, and Ricoh adhesive properties. It can be formed on the surface.
- plastic molded products to be painted in the method of the present invention include automobile outer plate parts such as bumpers, boilers, grills, and fenders; plastic molded items used for outer plate parts of home appliances, etc.
- the material include polyolefins obtained by (co) polymerizing one or more olefins having 2 to 10 carbon atoms such as ethylene, propylene, butylene, and hexene.
- the method of the present invention can also be applied to plastic molded articles made of materials such as a polystrength, ABS resin, urethane resin, and polyamide.
- these plastic molded products can be appropriately subjected to pretreatment such as degreasing and rinsing in accordance with a method known per se before coating.
- the water-based primer (I) is applied to the plastic molded article, and then the water-based base coat paint (II) is applied onto the coated surface, and the clear coat paint (III) is applied onto the uncured coated surface.
- the coating method consists of simultaneously baking and curing the three layers of the coating film.
- the water-based primer (I) used in the present invention is a water-based paint comprising a water-based polyolefin resin (A) and a water-based acrylic resin (B) as film-forming components, and has a total solid content of both resins.
- the resin (a) is 1 0-9 0 weight 0/0, preferably 4 0-8 0% by weight, more preferably 4 0-6 0% by weight
- the resin (B) is 1 0-90% by weight, preferably one of 20 to 60 weight 0 / o, more preferably in a proportion such that 40 to 60% by weight, these two resins in an aqueous medium It can be prepared by dissolving or dispersing in. If the content of the resins (A) and (B) is outside the above range, the coating film performance becomes insufficient, which is not preferable.
- Aqueous polyolefin resin (A) is 1 0-9 0 weight 0/0, preferably 4 0-8 0% by weight, more preferably 4
- a resin having an olefin polymer as the main skeleton and introducing a hydrophilic group such as a carboxyl group into the molecule can be used.
- an olefin polymer modified with a polymerizable unsaturated dicarboxylic acid or its anhydride is included.
- a polymerizable unsaturated dicarboxylic acid or its anhydride is added to an olefin polymer by a known method. Examples thereof include those obtained by regraft polymerization.
- Examples of the olefin-based polymer before modification include, for example, a polymer obtained by (co) polymerizing at least one olefin-based monomer selected from ethylene and propylene, or these olefin-based monomers and other Examples thereof include copolymers obtained by copolymerizing with monomers (for example, butadiene, isoprene, styrene, acrylonitrile, etc.). Specific examples include polypropylene, ethylene-propylene copolymer, ethylene-propylene-butadiene copolymer, and the like. These olefinic polymers generally have a weight average molecular weight within the range of 30000 to 150,000, particularly 50000 to 120,000, and more particularly 60000 to 110,000.
- the polymerizable unsaturated dicarboxylic acid or anhydride thereof used for modifying the olefin polymer is a compound having one polymerizable unsaturated bond and at least two carboxyl groups or acid anhydride groups in one molecule. Examples thereof include maleic acid or its anhydrous product, itaconic acid or its anhydride, citraconic acid or its anhydride, and these can be used alone or in combination of two or more.
- Graph of polymerizable unsaturated dicarboxylic acid or anhydride thereof to olefin polymer The polymerization reaction can be carried out by a method known per se.
- the ratio of the polymerizable unsaturated dicarboxylic acid or its anhydride is such that the acid value of the resulting modified polyolefin resin is usually 10 to 60 mg KOHZg, particularly 20 to 50 mg KOHZg, more particularly 20 to 4 Omg KOHZg. It is preferable that it is within the range.
- the olefin polymer may be chlorinated, and this chlorination can be performed before or after the graph polymerization.
- chlorination degree chlorine content
- based on the Orefin based polymer before grayed RAFT polymerization generally 0-30 wt%, 1 5 to 25 weight especially 0/0, more particularly 15 to 22 wt% Within the range of is preferable.
- the olefin-based polymer may be further acrylic-modified as required.
- the polymerizable unsaturated monomer that can be used for the acrylic modification include methyl (meth) acrylate, ethyl (meth). Acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl Alkyl esters of (meth) acrylic acid such as (meth) acrylic acid; (meth) acrylic acid, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylic acid, (meth) acrylamide, (meth) acrylonitrile Acrylic monomers such as Furthermore styrene and the like, these may be used alone or in combination on two or more kinds.
- (meth) acryl means acryl or methacryl
- ⁇ (meth) acrylate means acrylate or methacrylate.
- the acrylic modification method include, for example, a reactive property with respect to the force lpoxyl group in the olefin-based polymer. For example, (meth) glycidyl acrylate is reacted with the olefin-based polymer to form a polymerizable unsaturated group. And then polymerizing the polymerizable unsaturated group with one or more other polymerizable unsaturated monomers.
- the above polymerizable unsaturated mono is 30% by weight or less based on the solid content weight of the resulting polyolefin resin, preferably from the viewpoint of compatibility with other components and adhesion of the formed coating film. 25% by weight, still more preferably in the range of 0.1 to 20 weight 0 / o.
- a surfactant can be used in combination with neutralization with these amine compounds for water-solubilization or water-dispersion.
- aqueous acrylic resin (B) examples include a hydrophilic group-containing polymerizable unsaturated monomer such as a carboxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers, at least a part of which is an acrylic monomer.
- a water-soluble acryl resin having a weight average molecular weight of 5000 to 100000, preferably 1 000 0 to 90000, more preferably 20000 to 80000, particularly a carboxyl group-containing acryl resin, and a weight average
- acrylic resin emulsions having a molecular weight of 50000 or more, preferably 75000 or more, more preferably 100000 or more, particularly carboxyl group-containing acryl resin emulsion.
- carboxy group-containing polymerizable unsaturated monomer examples include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and half monoalkyl esterified products of dicarboxylic acid among them.
- Other hydrophilic group-containing polymerizable unsaturated monomers include, for example, polyethylene group Polyalkylene chain-containing polymerizable unsaturated monomers such as recall (meth) acrylate, polypropylene glycol (meth) acrylate, and the like.
- Examples of the other polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-, i-propyl (meth) acrylate, n-, i-one, t-butyl ( Carbon number of (meth) acrylic acid such as (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, etc.
- the copolymerization of the above monomer mixture can be carried out by a method known per se, for example, by a solution polymerization method when a water-soluble acrylic resin is desired, or by emulsion weighting when an acrylic resin emulsion is desired. This can be done legally.
- the aqueous acrylic resin (B) is an acrylic resin emulsion obtained by emulsion polymerization, it is a multilayer structure particle emulsion obtained by emulsion polymerization of the monomer mixture in multiple stages in the presence of water and an emulsifier. There may be.
- the carboxyl group of the aqueous acrylic resin (B) can be neutralized with a basic substance as necessary.
- the basic substance is preferably a water-soluble substance, such as ammonia, methylamine, ethylamine, propylamine, ptylamine, dimethylamine, trimethylamine, triethylamine, ethylenediamine, morpholine, methylethanolamine, dimethylethanolamine.
- Min diethanolamine, triethanolamine, diisopropanolamine , 2-amino-2-methylpropanol, etc., and these can be used alone or in combination of two or more.
- the aqueous primer (I) used in the present invention includes, as necessary, an aqueous resin other than the resin (A) and the resin (B), a cross-linking agent, a color pigment, an extender pigment, a conductive pigment, a curing agent.
- a cross-linking agent such as a catalyst, a rheology control agent, an antifoaming agent and an organic solvent can be appropriately selected and blended.
- the water-based primer (I) usually has a solid content of 30% by weight or more, preferably 35 to 45% by weight during coating. / 0 and, preferably, the viscosity is adjusted to 20-40 seconds Ford Cup # 4 within the range of 20 ° C, and then plastic molding, for example, spray coating, airless spray coating, brush It can be painted by methods such as painting and immersion.
- the coating film thickness of the water-based primer (I) is usually preferably in the range of 5 to 30 m, particularly F to 25 m, more particularly 10 to 2 OjUm, based on the cured coating film.
- the coating film of the water-based primer (I) can be forcibly dried at a temperature of about 60 to about 100 ° C., particularly about 70 to about 90 ° C. for about 1 to 5 minutes.
- the aqueous base paint (II) used in the present invention comprises an aqueous polyurethane resin (C), an aqueous acrylic resin and / or aqueous polyester resin (D) containing a hydroxyl group, and a melamine resin (E).
- the an aqueous coating composition comprising as film-forming component, based on the total solid content of these three resins, the resin (C) is 1-50 wt 0/0, preferably 3-30 wt%, more preferably is 5-20 by weight 0 / o resin (D) is 1 0-96% by weight, preferably 30 to 80 wt%, more good Mashiku 40 to 75 weight 0/0, and the resin (E) is 3
- the content is 40% by weight, preferably 10 to 30% by weight, and more preferably 15 to 30% by weight.
- the aqueous base coat paint (II) can be prepared by dissolving or dispersing a colored component such as a colored pigment, a bright pigment, and a dye together with these resin components in an aqueous medium.
- a hydrophilic polyurethane resin that can be dissolved or dispersed in water can be preferably used.
- aliphatic and Z or alicyclic diisocyanate (ii) number average A diol having a molecular weight of 500 to 5000, (ii ⁇ ) a low molecular weight polyhydroxyl compound and (iV) dimethylol alkanoic acid is usually 1 to 0.5 to 10.95, particularly 1 to 0.6 to 10.
- aliphatic diisocyanate and alicyclic diisocyanate ( ⁇ ) in particular, an aliphatic diisocyanate having 2 to 12 carbon atoms, such as hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, Lysine diisocyanate; alicyclic diisocyanate having 4 to 18 carbon atoms, such as 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate , Methylcyclohexylene di-sociane, isopropylidene dicyclohexyl-1,4'-di-sociate; modified products of these di-socianes (such as carpositimide, uretdione, uretoimine).
- aliphatic diisocyanate having 2 to 12 carbon atoms such as hexamethylene diisocyanate, 2,2,4
- the diol (ii) having a number average molecular weight of 500 to 5000, preferably 1 000 to 3000 includes, for example, alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) and heterocyclic ether (tetrahydrofuran, etc.) ) Is polymerized or (block or random) copolymerized Specifically, polyethylene diol, polypropylene glycol, polyethylene monopropylene (block or random) glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, polyoctamethylene ether Glycols, etc .; Dicarponic acid (adipic acid, succinic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid, phthalic acid, etc.) and glycol (ethylene glycol, propylene glycol, 1,4-butanediol, 1, 6 Polyester diol obtained by polycondensation of hexanediol, 3-methyl
- the low molecular weight polyhydroxyl compound ( ⁇ ii) includes compounds having a number average molecular weight of less than 500 having at least two hydroxyl groups in one molecule. And its alkylene oxide low molar adducts (molecular weight less than 500); trihydric alcohols such as glycerin, trimethylolethane, trimethylolpropane and the like, and their alkylene oxide low molar adducts (molecular weight less than 500); And a mixture of at least two of these.
- These low-molecular-weight polyhydroxyl compounds (iii) are generally used in an amount of 0.3% to 20% by weight, preferably 0.3 to 15% by weight, more preferably 0% to the diol (i ⁇ ). It can be used at a ratio in the range of 5 to 10% by weight.
- dimethylol alkanoic acid (i V) is an alkane having two hydroxyl groups and one carboxyl group in one molecule, and examples thereof include dimethylol acetic acid, dimethylol propionic acid, and dimethylol butyric acid. These di
- the amount of methylol alkanoic acid used is such that the content as a carboxyl group (one COOH) is 0.5 to 5% by weight, preferably 1 in the urethane prepolymer obtained by reacting the components (i) to (iV). An amount in the range of ⁇ 3% by weight is suitable.
- the aqueous polyurethane resin (C) obtained by reacting the components ( ⁇ ) to (i V) described above by a one-shot method or a multi-stage method according to a known method is used to facilitate water-solubilization or water-dispersion. It is preferable to neutralize a part or all of the carboxyl groups introduced by the dimethylolalkanoic acid contained in the resin with an amine compound.
- Examples of the amine compound used in this case include tertiary amines such as triethylamine, triptylamin, dimethylethanolamine, and triethanolamine; secondary amines such as jetylamine, dibutylamine, diethanolamine, and morpholine; propylamine, ethanol First-class amin such as ammin.
- the amount of amine used is usually in the range of 0.5 to 1 equivalent, particularly 0.7 to 1 equivalent, relative to 1 equivalent of the carboxyl group of dimethylolalkanoic acid.
- the aqueous polyurethane resin (C) has a neutralized carboxyl group, and can further have a hydroxyl group derived from the low molecular weight polyhydroxyl compound (ii).
- Aqueous polyurethane resins (C) generally have an acid value in the range of 10-60 mg KOHZg, especially 20-5 OmgKOH / g, more particularly 20-4 Omg KOHZg and generally 10-60 mg KOHZg, especially 20-50 mg KOHZ g In particular, it preferably has a hydroxyl value in the range of 20 to 4 Omg KOHZg.
- aqueous polyurethane resin C
- a single coating film of the resin is immersed in water adjusted to pH 4.0 with acetic acid (temperature 80 ° C) for 2 hours and dried at 1300 ° C for 1 hour. After drying, the tensile strength and elongation decrease rate of the coating film after being left in a humid-heat oven at 70 ° C and 95% humidity for 200 hours is within 25% compared to before these tests, especially 20 It is preferable to use a coating film that is within% and that the coating film after drying shows little or no visual whitening phenomenon.
- Aqueous acryl resin containing hydroxyl group and Z or aqueous polyester resin (D) As the aqueous acryl resin containing hydroxyl group and / or aqueous polyester resin (D), either one or both can be used.
- the aqueous acryl resin containing a hydroxyl group is a monomer mixture comprising a hydrophilic group-containing polymerizable unsaturated monomer such as a hydroxyl group-containing polymerizable unsaturated monomer, a carboxyl group-containing polymerizable unsaturated monomer, and other polymerizable unsaturated monomers.
- a water-soluble acryl resin having a weight average molecular weight of 5000-100000, preferably 100000-90000, more preferably 20000-80000, a weight average molecular weight of 50000 or more, preferably 75000 or more, more preferably obtained by copolymerization. Examples include acrylic resin emulsions of 100000 or more.
- hydroxyl group-containing polymerizable unsaturated monomer examples include acrylic acid such as 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, or the like. And hydroxyalkyl esters of methacrylic acid; polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and the like. These may be used alone or in combination of two or more.
- Hydrophilic group-containing polymerizable unsaturated monomers such as the above-mentioned force-loxyl group-containing polymerizable unsaturated monomers and other polymerizable unsaturated monomers are appropriately selected from those exemplified for the aqueous acryl-based resin (B). Can be used.
- copolymerization of these monomer mixtures can be carried out by a method known per se, for example, by a solution polymerization method when a water-soluble acrylic resin is desired, or by an emulsion polymerization method when an acrylic resin emulsion is desired. Can be done.
- the force loxyl group of the aqueous acrylic resin can be neutralized with the above-mentioned basic substance, if necessary.
- Aqueous acrylic resins containing hydroxyl groups are generally in the range of 10 to 100 mg KOHZg, especially 15 to 80 mg KOHZg, more particularly 20 to 60 mg KOHZg. It is preferable that it has an acid value of 10 to 250 mg KOHZg, particularly 20 to 200 mg KOHZg, more particularly 30 to 15 Omg KOHZg.
- the aqueous polyester resin containing a hydroxyl group is usually prepared by an esterification reaction using a polyhydric alcohol and a polybasic acid, and if necessary, a monobasic acid, an oil component (including this fatty acid) and the like. And those obtained by neutralizing oil-free or oil-modified polyester resins.
- the polyester resin generally has a weight average molecular weight in the range of about 3000 to 100000, preferably 4000 to 70000, more preferably 5000 to 30000.
- polyhydric alcohol examples include ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, 2,2-dimethylpropanediol, glycerin, ⁇ methylolpropane, pentaerythritol
- examples thereof include ethylene oxide adducts and propylene oxide adducts of phenol compounds, and these can be used alone or in combination of two or more.
- polybasic acids examples include phthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, adipic acid, sebacic acid, limimellitic acid, pyromellitic acid, and their anhydrides. These may be used alone or in combination of two or more.
- monobasic acids include benzoic acid and t-butylbenzoic acid.
- oil components include, for example, castor oil, dehydrated castor oil, safflower oil, soybean oil, linseed oil, Examples include tall oil, coconut oil, and fatty acids thereof, and these can be used alone or in combination of two or more.
- introduction of a carboxyl group may be carried out by using a polybasic acid such as trimellitic acid or pyromellitic acid having 3 or more carboxyl groups in one molecule as a part of the polybasic acid component.
- the dicarboxylic acid can be added by half ester addition.
- it can be easily carried out by using a polyhydric alcohol such as glycerin or trimethylolpropane having 3 or more hydroxyl groups in one molecule as a part of the polyhydric alcohol component.
- polyester resin containing a hydroxyl group in particular, from the viewpoint of stabilizing the coating by improving the coating performance and finish properties such as water resistance of the formed coating, and further improving the compatibility of other ingredients.
- polyester polyols obtained by reacting monoepoxide compounds having long-chain hydrocarbon groups are further reacted with polybasic acids and / or polyisocyanate compounds having a functionality of 3 or more.
- the polyester resin obtained by this is suitable.
- Examples of the tribasic or higher polybasic acid include, for example, anhydrous trimellitic anhydride, ethylene glycol bis (anhydro trimellitate), 1,3-propanediol bis (anhydro trimellitate), and pyromellitic anhydride.
- Examples of polyisocyanate compounds include diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, burette type adducts of these diisocyanates, and isocyanurate ring adducts. Etc. can be used.
- the carboxyl group of the polyester resin can be neutralized using the above basic substance.
- Aqueous polyester resins containing hydroxyl groups are generally 10-1 OOmg KOH Zg, especially 20-8 Omg KOHZg, more particularly 2 O-5 O mg KOH g, acid values in the range and generally 10-300 mg KOH / g, In particular, it preferably has a hydroxyl value within the range of 30 to 200 mg KOH / g, more particularly 50 to 20 Omg KOH g.
- the melamine resin (E) has a weight average molecular weight of 1 500 to 3000, preferably 1 500 to 2500, more preferably 1 500 to 2.
- a butyl methyl mixed etherified melamine resin in the range of 000.
- the molar ratio of the butyl ether group and the methyl ether group is usually within the range of 46-9Z1, particularly 5 / 5-9 / 1.
- the water-based base coat paint (II) used in the present invention includes, in addition to the above-mentioned tree (C), resin (D) and resin (E), as a coloring component, a coloring pigment, a bright pigment, a dye, etc. Can be contained.
- Color pigments include, for example, titanium oxide, carbon black, yellow lead, ocher, yellow iron oxide, Hansa Yellow, pigment yellow, chrome orange, chrome vermillion, permanent orange, amber, permanent red, brilliant carmine, fast violets ⁇ ⁇ ⁇ ⁇ , Methyl violet lake, ultramarine, bitumen, cobalt blue, phthalocyanine bimbling, pigment green, naphthol green, etc.
- brilliant materials include, for example, aluminum powder, evaporated aluminum, aluminum oxide bronze powder, copper powder, Examples include, but are not limited to, metallic materials such as tin powder and mica-like iron oxide; mica flakes coated with titanium oxide and iron oxide, and light-interfering pigments such as mica flakes. These pigments can be used alone or in combination of two or more, and can be solid color paints, metallic paints or light interference paints.
- an aqueous resin other than the resin (C), the resin (D) and the resin (E), a curing catalyst, a reo-mouth control agent, an antifoaming agent, Paint additives such as organic solvents can be appropriately selected and blended.
- the water-based base coat paint (II) is applied to the surface of the water-based primer (I) that has already been applied to plastic molded products by methods such as air spray coating, airless spray coating, electrostatic coating, and immersion coating. Can be painted on.
- the coating film thickness is usually in the range of 10 to 40 jUm, particularly 12 to 25 jUm, based on the cured coating film.
- the coating film of the water-based base coat paint (II) was cross-linked three-dimensionally by heating for about 5 to 40 minutes at a temperature of about 60 to about 140 ° C, preferably about 80 to about 120 ° C. A cured coating film can be formed.
- the clear paint (III) used in the present invention is a hydroxyl group-containing resin.
- Clearcoat paint (III) usually consists of a base resin component mainly composed of a hydroxyl group-containing resin (F) and a crosslinker component mainly composed of a crosslinker (G), which are mixed immediately before coating. It is desirable to be a two-component type for use in Hydroxyl-containing resin (F)
- hydroxyl group-containing resin (F) examples include hydroxyl group-containing resins such as acrylic resins, polyester resins, alkyd resins, fluororesins, urethane resins, and silicon-containing resins. Particularly, hydroxyl group-containing acrylic resins are suitable. It is.
- the hydroxyl group-containing resin (F) usually has a hydroxyl group value in the range of 10 to 12 Omg KOHZg, particularly 25 to 10 Omg KOH / g, more particularly 40 to 8 Omg KOHZg.
- Isocyanate crosslinker (G2 Isocyanate cross-linking agent (G) is a polyisocyanate monobasic compound having a uretdione structure and a dimer or more of a diisocyanate trimer in a solid content weight ratio of 10 90 to 50 Z50, preferably 1 5 85 to 40/60, more preferably Is included within the range of 15/85 to 35Z65.
- the finally formed multilayer coating film becomes insufficient in curability. Since performance becomes insufficient, it is not preferable.
- polyisocyanate compound having a urezine structure a uretdione form of hexamethylene diisocyanate produced by a method known per se is suitable.
- a compound having a trimer or more of diisocyanate for example, diisocyanate isocyanurate, biuret, and allophanate such as hexamethylene diisocyanate and sophorone disocyanate can be used. .
- Isocyanate crosslinking agent (G) is generally 1 OOOm Pa 'sZ25 ° C or less, especially 90 OmP a ⁇ s / 25 ° C or less, from the viewpoints of curability of the multilayer coating and high solid differentiation of the clear coat paint. In particular, it is desirable to have a viscosity of 800 mPa ⁇ sZ25 ° C or less.
- the proportion of the hydroxyl group-containing resin (F) and isocyanate cross-linking agent (G) used is usually 0 to 2.0 equivalents of isocyanate group in the cross-linking agent (G) with respect to 1 equivalent of hydroxyl group in the resin (F). It is desirable to select a ratio of 0.8 to 1.8 equivalents, more particularly 0.8 to 1.6 equivalents.
- the viscosity within the range of 14 to 20 seconds Novode Cup # 4 20 ° C at the time of painting, for example, air spray painting, airless spray painting, electrostatic painting It can be applied to the uncured surface of the water-based base coat paint (II) by methods such as dip coating.
- the coating thickness is usually 15 to 80 jU m, particularly 25 to 50 jU m, based on the cured coating.
- the water-based primer (I), the water-based base coat paint (II) and the clear coat paint (III) are applied by wet-on-wet as described above, and then about 40 to about 110 ° C., particularly By heating at a baking temperature of about 80 to about 100 ° C. for about 10 to about 40 minutes, the three-layer coating can be crosslinked and cured almost simultaneously.
- the following monomer emulsion (2) was added dropwise over 2 hours, and after aging for 1 hour, 1. Cooled to 30 ° C while gradually adding 89 parts of 50/0 dimethylethanolamine aqueous solution to the reaction vessel.
- the acrylic resin emulsion (D-1) with an average particle size of 100 nm, an acid value of 30.7 mg KOHZg, and a hydroxyl group value of 22.1 mg KOHZg was filtered while passing through a 100 mesh nylon cloth. (Solid content 25.2%) was obtained.
- N ewcol 562S F Nippon Emulsifier Co., Ltd., trade name, ammonium polyoxyethylene alkylbenzenesulfonate, active ingredient 60%.
- Monomer emulsion (1) 94.3 parts of deionized water, 17 parts of methyl methacrylate, 80 parts of n-butyl acrylate, 3 parts of aryl methacrylate and 1.2 parts of New CO I 562S F Mixing and stirring were performed to obtain a monomer emulsion (1).
- Monomer emulsion (2) 39 parts of deionized water, 15.4 parts of methyl methacrylate, 2.9 parts of n-butyl acrylate, 5.9 parts of hydroxyethyl acrylate, 5.1 parts of methacrylic acid and N ewco I 562S F 0.5 part was mixed and stirred to obtain a monomer emulsion (2).
- aqueous polyolefin resin (A) in solid weight 60 parts by weight of aqueous polyolefin resin (A) in solid weight, 40 parts in weight of aqueous acrylic resin (B), “JR-806” (trade name, titanium white, manufactured by Tika) 80 parts And 21 parts of “VU LCAN XC-72” (CABOT, trade name, conductive bonbon black pigment) were mixed and dispersed according to a conventional method, and deionized water so that the solid content was 35%.
- the aqueous primer paint (I) was obtained by diluting with water.
- Preparation Example 1 In Preparation Example 1, Preparation Example 1 except that the amount of melamine resin (E) was changed to 50 parts (40 parts by weight of solid content) and the amount of aqueous urethane resin (C) was changed to 0 parts. In the same manner, an aqueous base coat paint (II-4) was obtained.
- Acrylic resin 25 parts of styrene, 20 parts of n-butyl methacrylate, 30 parts of n-butyl acrylate, hydroxyethyl methacrylate ⁇
- Example 2 After spray-coating the water-based primer (I) produced as described above on polypropylene (degreased) molded into a bumper to a dry film thickness of approximately 1 OjUrn, preheat at 80 ° C for 3 minutes. Next, an aqueous base coat coating (11-1) was electrostatically coated thereon so that the dry film thickness was about 15 im, preheated at 80 ° C for 3 minutes, and then on the uncured coating surface. The clear coat paint (IM-1) was electrostatically coated to a dry film thickness of about 3 Oj «m, and dried by heating at 90 ° C for 30 minutes to produce a coated product.
- Example 2 Example 2
- Example 1 a coated product was produced in the same manner as in Example 1 except that the aqueous base coat paint (II-2) was used instead of the aqueous base coat paint (11-1). Comparative Example 1
- Example 1 a coated product was produced in the same manner as in Example 1 except that the aqueous base coat paint (II 1 3) was used instead of the aqueous base coat paint (II 1 1). Comparative Example 2
- Example 1 A coated product was produced in the same manner as in Example 1 except that the clear coat paint (III-2) was used instead of the clear coat paint (III-1). Comparative Example 3 In Example 1, a coated product was produced in the same manner as in Example 1 except that the aqueous base coat paint (II 1 4) was used instead of the aqueous base coat paint (II 1 1). Each coated product prepared as described above was subjected to the following performance test. The results are shown in Table 1.
- X is 50 or less.
- X indicates the occurrence of blistering.
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- Application Of Or Painting With Fluid Materials (AREA)
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Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/311,887 US20110293948A1 (en) | 2006-10-18 | 2007-10-17 | Method for coating molded articles |
CN2007800385074A CN101528362B (zh) | 2006-10-18 | 2007-10-17 | 塑料成型品的涂装方法 |
EP20070830408 EP2087944B1 (en) | 2006-10-18 | 2007-10-17 | Method for coating plastic molded article |
JP2008541002A JP5442994B2 (ja) | 2006-10-18 | 2007-10-17 | プラスチック成形品の塗装方法 |
Applications Claiming Priority (2)
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JP2006284107 | 2006-10-18 | ||
JP2006-284107 | 2006-10-18 |
Publications (1)
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WO2008050778A1 true WO2008050778A1 (fr) | 2008-05-02 |
Family
ID=39324575
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2007/070674 WO2008050778A1 (fr) | 2006-10-18 | 2007-10-17 | Procédé de revêtement d'un article en plastique moulé |
Country Status (5)
Country | Link |
---|---|
US (1) | US20110293948A1 (ja) |
EP (1) | EP2087944B1 (ja) |
JP (1) | JP5442994B2 (ja) |
CN (1) | CN101528362B (ja) |
WO (1) | WO2008050778A1 (ja) |
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JP2010075839A (ja) * | 2008-09-25 | 2010-04-08 | Honda Motor Co Ltd | 塗装物の生産方法及び塗装物生産設備 |
WO2013125705A1 (ja) | 2012-02-24 | 2013-08-29 | 関西ペイント株式会社 | 複層塗膜形成方法、及び塗装物品 |
WO2013129136A1 (ja) * | 2012-03-01 | 2013-09-06 | 本田技研工業株式会社 | 複層塗膜形成方法 |
US9475957B2 (en) | 2012-04-04 | 2016-10-25 | Kansai Paint Co., Ltd. | Aqueous paint composition and method of manufacturing painted article |
JP2019210308A (ja) * | 2018-05-31 | 2019-12-12 | 三菱ケミカル株式会社 | 水性塗料組成物 |
WO2020153057A1 (ja) * | 2019-01-21 | 2020-07-30 | 関西ペイント株式会社 | 複層塗膜形成方法 |
JP2020527189A (ja) * | 2017-07-18 | 2020-09-03 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングBASF Coatings GmbH | 低温硬化1kベースコート及びその1kベースコートを有する基材をコーティングする方法 |
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- 2007-10-17 JP JP2008541002A patent/JP5442994B2/ja not_active Expired - Fee Related
- 2007-10-17 US US12/311,887 patent/US20110293948A1/en not_active Abandoned
- 2007-10-17 WO PCT/JP2007/070674 patent/WO2008050778A1/ja active Application Filing
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Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2010075839A (ja) * | 2008-09-25 | 2010-04-08 | Honda Motor Co Ltd | 塗装物の生産方法及び塗装物生産設備 |
WO2013125705A1 (ja) | 2012-02-24 | 2013-08-29 | 関西ペイント株式会社 | 複層塗膜形成方法、及び塗装物品 |
US9427779B2 (en) | 2012-02-24 | 2016-08-30 | Kansai Paint Co., Ltd. | Multilayer film-forming method and coated article |
WO2013129136A1 (ja) * | 2012-03-01 | 2013-09-06 | 本田技研工業株式会社 | 複層塗膜形成方法 |
CN104136135A (zh) * | 2012-03-01 | 2014-11-05 | 本田技研工业株式会社 | 多层涂膜形成方法 |
JPWO2013129136A1 (ja) * | 2012-03-01 | 2015-07-30 | 本田技研工業株式会社 | 複層塗膜形成方法 |
US9475957B2 (en) | 2012-04-04 | 2016-10-25 | Kansai Paint Co., Ltd. | Aqueous paint composition and method of manufacturing painted article |
JP2020527189A (ja) * | 2017-07-18 | 2020-09-03 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングBASF Coatings GmbH | 低温硬化1kベースコート及びその1kベースコートを有する基材をコーティングする方法 |
JP7204731B2 (ja) | 2017-07-18 | 2023-01-16 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング | 低温硬化1kベースコート及びその1kベースコートを有する基材をコーティングする方法 |
JP2019210308A (ja) * | 2018-05-31 | 2019-12-12 | 三菱ケミカル株式会社 | 水性塗料組成物 |
JP7206637B2 (ja) | 2018-05-31 | 2023-01-18 | 三菱ケミカル株式会社 | 水性塗料組成物 |
WO2020153057A1 (ja) * | 2019-01-21 | 2020-07-30 | 関西ペイント株式会社 | 複層塗膜形成方法 |
JPWO2020153057A1 (ja) * | 2019-01-21 | 2021-10-14 | 関西ペイント株式会社 | 複層塗膜形成方法 |
JP7083046B2 (ja) | 2019-01-21 | 2022-06-09 | 関西ペイント株式会社 | 複層塗膜形成方法 |
US11958074B2 (en) | 2019-01-21 | 2024-04-16 | Kansai Paint Co., Ltd | Method for forming a multilayer coating film |
Also Published As
Publication number | Publication date |
---|---|
CN101528362B (zh) | 2013-05-08 |
JPWO2008050778A1 (ja) | 2010-02-25 |
EP2087944A1 (en) | 2009-08-12 |
EP2087944B1 (en) | 2012-12-12 |
JP5442994B2 (ja) | 2014-03-19 |
CN101528362A (zh) | 2009-09-09 |
US20110293948A1 (en) | 2011-12-01 |
EP2087944A4 (en) | 2011-08-03 |
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