WO2014181593A1 - アルミニウムホイール用のプライマー塗料組成物 - Google Patents
アルミニウムホイール用のプライマー塗料組成物 Download PDFInfo
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- WO2014181593A1 WO2014181593A1 PCT/JP2014/058126 JP2014058126W WO2014181593A1 WO 2014181593 A1 WO2014181593 A1 WO 2014181593A1 JP 2014058126 W JP2014058126 W JP 2014058126W WO 2014181593 A1 WO2014181593 A1 WO 2014181593A1
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- aluminum wheel
- copolymer resin
- polymerizable unsaturated
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- OJYIBEYSBXIQOP-UHFFFAOYSA-N CC(C)(c(cc1)ccc1OC)c(cc1)ccc1OC Chemical compound CC(C)(c(cc1)ccc1OC)c(cc1)ccc1OC OJYIBEYSBXIQOP-UHFFFAOYSA-N 0.000 description 2
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60B—VEHICLE WHEELS; CASTORS; AXLES FOR WHEELS OR CASTORS; INCREASING WHEEL ADHESION
- B60B3/00—Disc wheels, i.e. wheels with load-supporting disc body
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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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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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
- C09D125/00—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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
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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
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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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
- C09D133/24—Homopolymers or copolymers of amides or imides
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60B—VEHICLE WHEELS; CASTORS; AXLES FOR WHEELS OR CASTORS; INCREASING WHEEL ADHESION
- B60B2360/00—Materials; Physical forms thereof
- B60B2360/10—Metallic materials
- B60B2360/104—Aluminum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60B—VEHICLE WHEELS; CASTORS; AXLES FOR WHEELS OR CASTORS; INCREASING WHEEL ADHESION
- B60B2900/00—Purpose of invention
- B60B2900/10—Reduction of
- B60B2900/141—Corrosions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60B—VEHICLE WHEELS; CASTORS; AXLES FOR WHEELS OR CASTORS; INCREASING WHEEL ADHESION
- B60B2900/00—Purpose of invention
- B60B2900/30—Increase in
- B60B2900/321—Lifetime
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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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/326—Magnesium phosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Definitions
- the present invention relates to a primer coating composition for an aluminum wheel that can form a coating film having excellent coating stability and excellent corrosion resistance, edge corrosion resistance and yarn rust resistance.
- Aluminum and aluminum alloy members are widely used in automotive parts such as aluminum wheels because they are easy to machine, such as cutting and polishing, have excellent corrosion resistance, and are lightweight and improve fuel efficiency.
- a primer coating is applied on the aluminum wheel, and the coating film is required to have anticorrosion, edge anticorrosion and yarn rust resistance.
- Recent aluminum wheels have increased the number of complex designs that can give a sense of quality, so there are many sharp edges in the cutting process. Accordingly, various devised paints have been developed to cover and protect the edge portion.
- a primer coating composition containing 100 parts by weight of a self-crosslinking acrylic resin, 10 to 20 parts by weight of ultrafine silica, 3 to 10 parts by weight of an epoxy resin, and 5 to 20 parts by weight of a silane coupling agent is disclosed ( Patent Document 1).
- a specific anticorrosion paint composition (primer paint) on an aluminum wheel
- a clear paint composition is then applied, wherein the anticorrosion paint composition is a specific acrylic paint.
- the coating material contains a resin, a specific epoxy resin, and optionally powdered silica (Patent Document 2).
- the aluminum wheel may be used in severe corrosive environments such as salt damage running in a cold district where snow melting salt is poured, and in the coating film by the primer paint disclosed in Patent Document 1 or Patent Document 2, Any of anticorrosion, edge anticorrosion and yarn rust resistance was insufficient.
- An object of the present invention is to find a primer coating composition for an aluminum wheel capable of forming a coating film having excellent coating stability and excellent corrosion resistance, edge corrosion resistance and yarn rust resistance.
- primer paint composition for aluminum wheels may be simply abbreviated as “primer paint composition”.
- the present invention “1. 5-35% by mass of a nitrogen-containing radically polymerizable unsaturated monomer (a1) represented by the following formula (1) with respect to the total amount of constituent monomers, carboxyl group-containing radically polymerizable Copolymer resin (A) obtained by reacting a mixture of 1 to 10% by weight of unsaturated monomer (a2) and 55 to 94% by weight of other radical polymerizable unsaturated monomer (a3)
- 1 to 30 parts by mass of fumed silica (B) and 0.1 to 10 parts of phosphoric acid compound (C) containing magnesium with respect to 100 parts by mass in total of the solid content of the copolymer resin (A).
- Primer paint composition for aluminum wheels including parts by mass,
- R 1 represents a hydrogen atom or CH 3
- R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- the primer coating composition for an aluminum wheel according to 1, comprising 0.1 to 10 parts by mass of metal ion-exchanged silica (D) with respect to 100 parts by mass in total of the solid content of the copolymer resin (A), 3.
- the primer coating composition for an aluminum wheel according to 1 or 2 comprising 1 to 20 parts by mass of the epoxy compound (E) with respect to 100 parts by mass of the total solid content of the copolymer resin (A), 4).
- An uncured or cured coating film is formed on the aluminum wheel which may be surface-treated with the primer coating composition for an aluminum wheel according to any one of 1 to 5, and the uncured or cured coating is formed.
- the present invention relates to a coating film forming method characterized in that at least one top coat film is formed on a film.
- the primer coating composition of the present invention has good coating stability.
- An aluminum wheel obtained by applying the primer coating composition has excellent performance in anticorrosion, edge anticorrosion and yarn rust resistance.
- the present invention relates to a primer coating composition for an aluminum wheel comprising a specific copolymer resin (A), fumed silica (B) and a phosphoric acid compound (C) containing magnesium. Furthermore, a metal ion exchange silica (D), an epoxy resin (E), a silane coupling agent (F), a dehydrating agent (G), etc. can be mix
- the copolymer resin (A) used in the primer coating composition of the present invention comprises 5 to 35% by mass of a nitrogen-containing radically polymerizable unsaturated monomer (a1) represented by the following formula (1), a carboxyl group. It is a resin obtained by reacting a mixture of 1 to 10% by mass of the containing radical polymerizable unsaturated monomer (a2) and 55 to 94% by mass of the other radical polymerizable unsaturated monomer (a3). .
- the radical polymerizable unsaturated monomer means a monomer having one or more (for example, 1 to 4) polymerizable unsaturated groups.
- the polymerizable unsaturated group means an unsaturated group capable of radical polymerization. Examples of the polymerizable unsaturated group include a vinyl group, a (meth) acryloyl group, a (meth) acrylamide group, a vinyl ether group, and an allyl group.
- the alkyl group having 1 to 6 carbon atoms represented by R 2 is, for example, 1 to 6 carbon atoms, preferably 1 carbon atom.
- 4 to 4 alkyl groups on a straight chain or branched chain and specifically include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group. , T-butyl group, n-pentyl group, n-hexyl group and the like.
- nitrogen-containing radically polymerizable unsaturated monomer (a1) a monomer represented by the following formula (1) can be used without particular limitation, and examples thereof include N-methylol (meth) acrylamide, N -Methoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, Ni-propoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, Ni-butoxymethyl (meth) acrylamide, N- Examples include pentyloxymethyl (meth) acrylamide and N-hexyloxymethyl (meth) acrylamide.
- the nitrogen-containing radically polymerizable unsaturated monomer (a1) can be used alone or in combination of two or more as appropriate.
- Carboxyl group-containing radical polymerizable unsaturated monomer (a2) examples include a radical polymerizable unsaturated monomer having one or more, preferably 1 or 2, carboxyl groups.
- the carboxyl group-containing radically polymerizable unsaturated monomer (a2) can be used without any particular limitation.
- acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, and these Examples include carboxyl group-containing radically polymerizable unsaturated monomers such as anhydrides and half-esterified products.
- the carboxyl group-containing radically polymerizable unsaturated monomer (a2) can be used alone or in combination of two or more appropriately.
- radical polymerizable unsaturated monomer (a3) can be used without any particular limitation, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) Hydroxyl group-containing radically polymerizable unsaturated monomers such as hydroxybutyl acrylate, 2-hydroxychloropropyl (meth) acrylate and trade name “Placcel F” series (lactone-modified (meth) acrylic acid ester) manufactured by Daicel Chemical Industries, Ltd.
- the other radical polymerizable unsaturated monomer (a3) includes a hydroxyl group-containing radical polymerizable unsaturated monomer, an alkyl ester or cycloalkyl ester radical having 1 to 18 carbon atoms of acrylic acid or methacrylic acid. What contains at least 1 sort (s) of a polymerizable unsaturated monomer and an aromatic radically polymerizable unsaturated monomer is preferable.
- the carboxyl group-containing radical polymerizable unsaturated monomer (a2) is 1 to 10% by mass, preferably 2 to 8% by mass
- the unsaturated monomer (c) is 55 to 94% by mass, preferably 60 to 90% by mass.
- the blending ratio of these monomers is preferably in the above range from the viewpoints of curability, edge corrosion resistance, and yarn rust resistance.
- the copolymer resin (A) comprises a nitrogen-containing radical polymerizable unsaturated monomer (a1), a carboxyl group-containing radical polymerizable unsaturated monomer (a2), and other radical polymerizable unsaturated monomers (a3).
- an organic solvent maintained at about 50 ° C. to about 300 ° C., preferably about 60 ° C. to 250 ° C. in the presence of an inert gas such as nitrogen, for example, for about 1 hour to about 24 hours. It can be obtained by carrying out a radical polymerization reaction preferably for about 2 hours to about 10 hours.
- Examples of the organic solvent used in the radical polymerization reaction include alcohols such as n-propanol, isopropanol, n-butanol, t-butyl alcohol and isobutyl alcohol, ethylene glycol monobutyl ether, methyl carbitol, 2-methoxyethanol, 2 -Ethoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, Ethers such as propylene glycol monomethyl ether; aromatics such as xylene and toluene; acetone, methyl ethyl ketone, 2-pentanone, 2-hexanone, Ketones such as vasobutyl ketone, isophorone and cyclohexanone; esters such as methyl acetate, ethyl
- Examples of the polymerization initiator used in the radical polymerization reaction include benzoyl peroxide, di-t-butyl hydroperoxide, t-butyl hydroperoxide, cumyl peroxide, cumene hydroperoxide, t-butyl peroxybenzoate, and lauryl peroxide.
- Examples thereof include oxide, acetyl peroxide, azobisdimethylvaleronitrile, and azobisisobutyronitrile.
- the weight average molecular weight of the copolymer resin (A) is preferably in the range of 10,000 to 80,000, particularly 16,000 to 70,000, and the acid value is 10 to 40 mgKOH / g, particularly 12 to 35 mgKOH / g.
- the range is preferable, and the hydroxyl value is 0 to 120 mgKOH / g, particularly 55 to 105 mgKOH / g. It is desirable for improvement in coating film performance and paint stability to be within the above range.
- the glass transition temperature (Note 1) of the copolymer resin (A) is preferably in the range of 0 to 70 ° C, particularly 10 to 40 ° C.
- the copolymer resin (A) in the primer coating composition of the present invention can be used alone or in combination of two or more kinds of copolymer resins.
- Glass transition temperature of copolymer resin (A) Glass transition temperature (° C.) is a static glass transition temperature.
- DSC-50Q type trade name, manufactured by Shimadzu Corporation
- the sample is placed in a measuring cup using a vacuum, and the solvent is completely removed by vacuum suction. After that, the change in calorie is measured in the range of -100 ° C to 100 ° C at a rate of temperature rise of 3 ° C / min.
- the change point of the base line was defined as the glass transition temperature.
- the weight average molecular weight or number average molecular weight in the present invention is a value calculated based on the molecular weight of standard polystyrene from the chromatogram measured by gel permeation chromatograph according to the method described in JIS K 0124-83.
- As the gel permeation chromatograph “HLC8120GPC” (manufactured by Tosoh Corporation) was used.
- Mobile phase Tetrahydrofuran
- measurement temperature 40 ° C.
- flow rate 1 ml / min
- detector under the conditions of RI.
- Fumed silica (B) The fumed silica (B) used in the primer coating composition of the present invention is dry silica synthesized by vapor phase reaction in a high-temperature hydrogen flame by vaporizing silicon chloride. Fumed silica (B) is an amorphous glassy, spherical silica with no pores. The average primary particle size of such fumed silica (B) is 5 to 100 nm, preferably 20 to 50 nm. The average primary particle diameter of fumed silica (B) can be measured by observing it with an electron microscope. The specific surface area of the fumed silica (B) is in the range of 100 to 1,000 m 2 / g, preferably 200 to 500 m 2 / g.
- fumed silica examples include, for example, AEROSIL® 130, AEROSIL® 200, AEROSIL® R202, AEROSIL® 300, AEROSIL® 300CF, AEROSIL® 380PE, AEROSIL® R805, AEROSIL® R811, AEROSIL® R812, AEROSIL® R971, AEROSIL® R971, Product name manufactured by Nippon Aerosil Co., Ltd.).
- the blending ratio of fumed silica (B) in the primer coating composition of the present invention is 1 to 30 parts by weight, preferably 10 to 28 parts per 100 parts by weight of the total solid content of the copolymer resin (A). Part by mass, more preferably 15 to 25 parts by mass.
- the above range is desirable in order to obtain a coating film having excellent coating stability and edge corrosion resistance and yarn rust resistance.
- Phosphoric acid compound containing magnesium is a metal salt of a phosphoric acid compound such as phosphoric acid, phosphorous acid, or tripolyphosphoric acid, and is a compound containing at least magnesium as a metal element.
- a phosphoric acid compound such as phosphoric acid, phosphorous acid, or tripolyphosphoric acid
- Magnesium ions and phosphate ions released from the phosphate-based compound (C) containing magnesium effectively act to improve edge corrosion resistance and yarn rust resistance.
- the phosphoric acid compound (C) containing magnesium include, for example, magnesium phosphate, magnesium phosphate / ammonium eutectoid, magnesium monohydrogen phosphate, magnesium dihydrogen phosphate, magnesium phosphate.
- Examples include treated products, treated products of magnesium phosphate-containing metal phosphates such as magnesium triphosphate treated with magnesium dihydrogen phosphate, and silica-modified compounds of magnesium phosphate such as silica-modified magnesium phosphate.
- Examples of commercially available phosphoric acid compound (C) containing magnesium include K-White G105 (trade name, manufactured by Teika), LF Bowsei CRF-15 (trade name, manufactured by Kikuchi Color), and the like.
- the mixing ratio of the phosphoric acid compound (C) containing magnesium in the primer coating composition of the present invention is 0.1 to 10 mass with respect to 100 mass parts in total of the solid content of the copolymer resin (A). Parts, preferably 0.2 to 5 parts by mass, more preferably 0.3 to 3 parts by mass. The above range is desirable in order to obtain a coating film having excellent coating stability and edge corrosion resistance and yarn rust resistance.
- Metal ion exchange silica (D) is a metal ion exchange silica whose metal is at least one of calcium and magnesium, and examples thereof include calcium ion exchange silica and magnesium ion exchange silica. These metal ion exchange silicas (D) can be modified with phosphoric acid as necessary to obtain phosphoric acid modified metal ion exchange silica.
- the calcium ion exchange silica is a silica fine particle in which calcium ions are introduced into a fine porous silica carrier by ion exchange.
- Commercially available products of calcium ion exchanged silica include SHIELDEX (registered trademark) C303, SHIELDEXAC-3, SHIELDEXC-5 (all of which are manufactured by WR Grace & Co.), Silo Mask 52 (manufactured by Fuji Silysia). ) And the like.
- the magnesium ion exchanged silica is a silica fine particle in which magnesium ions are introduced into a fine porous silica carrier by ion exchange.
- Examples of commercially available magnesium ion exchanged silica include Silo Mask 52M (manufactured by Fuji Silysia) and Novinox ACE-110 (manufactured by SNCZ, France).
- the metal ion exchange silica (D) in the primer coating composition of the present invention preferably has an average particle size of 0.5 to 15 ⁇ m, particularly 1 to 10 ⁇ m.
- the average particle diameter of a metal ion exchange silica (D) can be measured with an electron microscope. Calcium ions or magnesium ions released from the metal ion-exchanged silica (D) are involved in various salt forming actions, and contribute to improvement of edge corrosion resistance and yarn rust resistance.
- the blend ratio of the metal ion exchange silica (D) is 100 parts by mass in total of the solid content of the copolymer resin (A). On the other hand, it is in the range of 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass, and more preferably 0.3 to 3 parts by mass. The above range is desirable in order to obtain a coating film having excellent coating stability and edge corrosion resistance and yarn rust resistance.
- Epoxy compound (E) The epoxy compound (E) used in the present invention is suitable to have a weight average molecular weight in the range of 300 to 4,000, preferably 500 to 2,500, particularly by reaction of a polyphenol compound and epihalohydrin.
- the resulting epoxy resin (e1) is preferred.
- Examples of the polyphenol compound used for forming the epoxy resin (e1) include bis (4-hydroxyphenyl) -2,2-propane [bisphenol A] and bis (4-hydroxyphenyl) methane [bisphenol F].
- Bis (4-hydroxycyclohexyl) methane [hydrogenated bisphenol F] 2,2-bis (4-hydroxycyclohexyl) propane [hydrogenated bisphenol A]
- 4,4′-dihydroxybenzophenone bis (4-hydroxyphenyl) -1,1-ethane, bis (4-hydroxyphenyl) -1,1-isobutane, bis (4-hydroxy-3-tert-butyl-phenyl) -2,2-propane, bis (2-hydroxynaphthyl) methane Tetra (4-hydroxyphenyl) -1,1,2,2-ethane 4,4'-dihydroxydiphenyl sulfone, phenol novolak, and the like cresol novolak.
- epoxy resin (e1) obtained by the reaction of the polyphenol compound and epichlorohydrin
- a resin represented by the following formula (2) derived from bisphenol A is particularly preferable.
- Examples of such commercially available epoxy resin (e1) include those sold by Mitsubishi Chemical Corporation under the product names jER828EL, jER1001, jER1002, jER1003, jER1004, and jER1007.
- a phosphoric acid-modified epoxy resin (e2) obtained by adding a phosphoric acid compound to the epoxy resin (e1) can also be used.
- the phosphoric acid-modified epoxy resin (e2) can improve coating film performance such as yarn rust resistance as compared with the epoxy compound (e1).
- Examples of the phosphoric acid compound include phosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphorous acid, and the like.
- the phosphoric acid-modified epoxy resin (e2) is obtained by adding a phosphoric acid compound to the epoxy resin (e1) and, for example, in the presence of a catalyst such as imidazoles and phosphonium salts, a reaction temperature of 70 to 150 ° C., preferably Can be obtained by reacting at 110 to 130 ° C. for a reaction time of 1 to 8 hours, preferably 3 to 6 hours.
- the phosphoric acid-modified epoxy resin (e2) thus obtained preferably has a weight average molecular weight in the range of 300 to 2,000, preferably 500 to 1,800 for corrosion resistance.
- phosphoric acid-modified epoxy resins are, for example, XU-8096.007, XU-71899.00, XQ-82908.00, XQ-82919.00, DER620-PP50, DER621-EB50, DER621-PP50. (Above, product names manufactured by Dow Chemical Japan Co., Ltd.), Epototo ZX1300, ZX1300-1 (above, product names manufactured by Toto Kasei Co., Ltd.) and the like.
- the blending ratio of the epoxy compound (E) is 1 to 100 parts by mass with respect to 100 parts by mass in total of the solid content of the copolymer resin (A). 20 parts by mass, preferably 2 to 15 parts by mass, more preferably 4 to 12 parts by mass.
- the above range is desirable in order to obtain a coating film having excellent paint stability and edge corrosion resistance and yarn rust resistance.
- Silane coupling agent (F) examples include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -amino).
- silane coupling agents include KBM-402, KBM-403, KBM-502, KBM-503, KBM-603, KBE-903, KBM-603, KBE-602, KBE-603 ( As mentioned above, Shin-Etsu Silicone Co., Ltd., a brand name) etc. can be used.
- the blending ratio of the silane coupling agent (F) is 1 to 20 with respect to 100 parts by mass in total of the solid content of the copolymer resin (A). Part by mass, preferably 2 to 15 parts by mass, more preferably 5 to 12 parts by mass. The above range is desirable in order to obtain a coating film having excellent paint stability and edge corrosion resistance and yarn rust resistance.
- Dehydrating agent (G) The primer coating composition of the present invention has good coating stability, but by adding a dehydrating agent (G), edge corrosion resistance, yarn rust resistance, and coating stability can be improved.
- a dehydrating agent (G) examples include methyl orthoacetate and methyl orthoformate.
- the blending ratio of the dehydrating agent (G) is preferably 1 to 30 parts by mass, preferably 100 parts by mass in total of the solid content of the copolymer resin (A). Is preferably from 10 to 25 parts by weight, more preferably from 15 to 23 parts by weight, from the viewpoint of improving the stability of the paint.
- Primer paint composition The primer paint composition of the present invention comprises the above copolymer resin (A), fumed silica (B), and a phosphoric acid compound (C) containing magnesium, and, if necessary, metal ion exchange. It is obtained by mixing silica (D), epoxy compound (E), silane coupling agent (F), dehydrating agent (G) and the like and dissolving or dispersing them in an organic solvent.
- organic solvent examples include ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, and methyl amyl ketone; methanol, ethanol, 2-propanol, n-propanol, iso-propanol, 2-methyl-1- Alcohols such as propanol, n-butyl alcohol, 2-methoxyethanol, n-octyl alcohol, 2-ethyl-1-hexanol; tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, diethylene glycol monoethyl ether, di Ethers such as propylene glycol monobutyl ether; esters such as methyl acetate, ethyl acetate, butyl acetate, carbitol acetate, 3-methoxybutyl acetate; dimethylformamide, dimethylacetate,
- a hydroxyl group-containing acrylic resin (a nitrogen-containing radical polymerizable unsaturated monomer (a1) is not blended in the monomer mixture)
- Acrylic resin different from coalesced resin (A)) other resins (for example, polyester resin, epoxy resin, polyurethane resin), dye, coloring pigment, extender pigment, metallic pigment, plasticizer, anti-settling agent, curing catalyst, ultraviolet ray Absorbers, antioxidants, surface conditioners, sagging inhibitors, thickeners, antifoaming agents, lubricants, crosslinkable polymer particles (microgels) and the like can be blended.
- the hydroxyl group-containing acrylic resin has a weight average molecular weight of 1,000 to 20,000, particularly 5,000 to 15,000, an acid value of 1 to 50 mgKOH / g, particularly 5 to 30 mgKOH / g, and a hydroxyl value. Is in the range of 0 to 350 mg KOH / g, especially 55 to 110 mg KOH / g, and the glass transition temperature (Note 1) is in the range of 10 to 50 ° C., particularly 25 to 40 ° C. It is desirable for improvement in coating film performance and paint stability to be within the above range.
- the primer paint composition thus obtained is applied to aluminum wheels used in passenger cars, motorcycles, trucks, wagon cars, and the like.
- the aluminum wheel is made of an alloy containing aluminum as a main component and containing magnesium, silicon, and the like, and is subjected to a surface treatment such as chromate treatment (chromium chromate, chromium phosphate, etc.) or non-chromium treatment (zirconium phosphate, zirconium oxide, etc.). Is preferable for edge corrosion resistance and yarn rust resistance.
- the primer coating composition is preferably applied by airless spray, air spray, electrostatic method, or the like.
- the coating viscosity is preferably 5 to 15 seconds / Ford Cup # 4/20 ° C.
- the coating thickness is 5 to 25 ⁇ m, preferably 10 to 23 ⁇ m, based on the cured coating film.
- the obtained coating film can be allowed to stand at room temperature or heat-dried at 100 ° C. or less, and heat-cured at 100 to 180 ° C., preferably 110 to 150 ° C., if necessary.
- the coating film obtained by applying and curing the primer coating composition of the present invention preferably has a glass transition temperature (coating film Tg) (Note 2) in the range of 50 to 80 ° C., preferably 55 to 75 ° C.
- a glass transition temperature of the cured coating film is in the above range, an aluminum wheel excellent in yarn rust resistance and edge corrosion resistance can be obtained.
- Glass transition temperature (coating film Tg) obtained by measuring with a dynamic viscoelasticity measuring device using a sample of a coating film prepared in a strip shape.
- thermosetting acrylic resin paints are suitable. Specifically, a thermosetting paint obtained by dissolving or dispersing an acrylic resin, a crosslinking agent and a pigment (optional component) in an organic solvent is preferable.
- Such a top coat is preferably applied by airless spray, air spray, electrostatic method or the like.
- the viscosity during coating is preferably 10 to 30 seconds / Ford Cup # 4/20 ° C.
- the coating film thickness is preferably about 10 to 50 ⁇ m, particularly 15 to 35 ⁇ m based on the cured coating film. Then, if necessary, it is left at room temperature or dried at 100 ° C. or lower, and then baked at a temperature of 100 to 180 ° C., preferably 110 to 150 ° C., for about 5 to 60 minutes, preferably about 10 to 40 minutes.
- a cured coating film can be formed by drying.
- Copolymer resin No. 1 The glass transition temperature of No. 1 (see Note 1) was 11.3 ° C., the acid value was 15.6 mg KOH / g, and the weight average molecular weight was 60,000.
- Production Example 6 Production Example of Magnesium Ion Exchange Silica 10 parts by mass of Silicia 710 (manufactured by Fuji Silysia Chemical Co., Ltd., trade name, fine silica particles, oil absorption of about 105 ml in a 5% by mass magnesium chloride aqueous solution of 10,000 parts by mass / 100 g) was stirred and mixed for 5 hours, and then filtered to take out the solid content. The solid content was thoroughly washed with water and dried to obtain magnesium ion-exchanged silica.
- Silicia 710 manufactured by Fuji Silysia Chemical Co., Ltd., trade name, fine silica particles, oil absorption of about 105 ml in a 5% by mass magnesium chloride aqueous solution of 10,000 parts by mass / 100 g
- Production Example 7 Production Example of Phosphoric Acid Modified Epoxy Resin Solution To 115 parts of 85% phosphoric acid, 280 parts of butyl glycidyl ether was added and reacted at 50-60 ° C. for 3 hours to obtain a phosphate ester compound.
- Adeka Resin EP-4100 manufactured by Asahi Denka Kogyo Co., Ltd., trade name, bisphenol A type epoxy resin, epoxy equivalent 190
- 58 parts of bisphenol A and 1 part of dimethylbenzylamine were mixed and reacted at 150 ° C. for 8 hours.
- an epoxy compound having an epoxy equivalent of 500 was obtained.
- Production Example 8 Production of Hydroxyl-Containing Acrylic Resin A Solution
- the following “mixture” was added for 4 hours.
- a 60% by mass hydroxyl group-containing acrylic resin A solution was produced.
- the hydroxyl group-containing acrylic resin B had a glass transition temperature (see Note 1) of 28.7 ° C., an acid value of 15.6 mgKOH / g, a hydroxyl value of 301.8 mgKOH / g, and a weight average molecular weight of 15,000.
- a stirrer stirrring blade having a diameter of 7 cm, 700 rpm
- Examples 2 to 23 Primer paint No. 2 to No. Production Example No. 23
- the primer paint No. 23 was prepared in the same manner as in Example 1 except that the contents of Table 2 were used. 2 to No. 23 was obtained.
- AEROSIL 380PE manufactured by Nippon Aerosil Co., Ltd., trade name, fumed silica (B), specific surface area 380 m 2 / g (Note 4)
- AEROSIL 130 manufactured by Nippon Aerosil Co., Ltd., trade name, fumed silica (B), specific surface area 130 m 2 / g (Note 5)
- K-White G105 manufactured by Teika Co., Ltd., trade name, magnesium-containing phosphate compound (C) (magnesium oxide treated with tripolyaluminum dihydrogen phosphate) (Note 6)
- LF bow CRF-15 manufactured by Kikuchi Color Co., Ltd., trade name, magnesium-containing phosphate compound (C) (Note 7)
- K-White 140E manufactured by Teica, trade name, aluminum dihydrogen tripolyphosphate (Note 8)
- Silo mask 52M manufactured by Fuji Silysia, trade name, magnesium ion exchanged silica (D) (average particle
- Anticorrosion A cast test liquid prepared according to JIS Z 2371 (2000) is sprayed at 50 ⁇ 2 ° C. for 120 hours on a sample in which a cut wound having a length of 10 cm is made with a cutter knife on the surface of an aluminum wheel coated article. After 24 hours, the degree of corrosion around the cut was evaluated: S: No abnormalities such as swelling and rust on the coating film A: Swelling or rust of less than 1 mm is seen from the cut part B: Swelling or rust of 1 mm or more and less than 2 mm is seen from the cut part C: Cut part Bulge or rust exceeding 2 mm is observed.
- Edge corrosion resistance Using the aluminum wheel coated article, a salt spray resistance test was conducted for 168 hours in accordance with JIS Z-2371, and the rust at the edge of the aluminum wheel was evaluated according to the following criteria: S: Number of generated rust is 0 / whole aluminum wheel A: Number of generated rust is 1 to 3 / whole aluminum wheel B: Number of generated rust is 4 to 10 / whole aluminum wheel C: Rust is generated The number of generation is 11 or more / the whole aluminum wheel.
- Yarn rust resistance Cut scratches were made on the surface of the aluminum wheel coated article, and a salt spray resistance test was conducted for 24 hours in accordance with JIS Z 2371. Then, it kept for 480 hours in the wet state (humidity 85%, 40 degreeC), and measured the rust width from a cut part. Rust and blister width from the cut part were evaluated according to the following criteria: S: The maximum width of rust or swelling is less than 2 mm on one side from the cut part, A: The maximum width of rust or swelling is 2 mm or more and less than 3 mm on one side from the cut part. B: The maximum width of rust or blisters is 3 mm or more and less than 4 mm on one side from the cut part, C: The maximum width of rust or swelling is 4 mm or more on one side from the cut part.
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Abstract
Description
本出願は、2013年5月8日に出願された、日本国特許出願第2013-098611号明細書(その開示全体が参照により本明細書中に援用される)に基づく優先権を主張する。
本発明は、塗料安定性に優れ、かつ防食性、エッジ防食性及び耐糸錆び性に優れた塗膜を形成できるアルミニウムホイール用のプライマー塗料組成物に関する。
「1.構成する単量体の合計に対して、下記の式(1)で表される窒素含有ラジカル重合性不飽和単量体(a1)を5~35質量%、カルボキシル基含有ラジカル重合性不飽和単量体(a2)を1~10質量%及びその他のラジカル重合性不飽和単量体(a3)を55~94質量%の混合物を反応させることによって得られる共重合体樹脂(A)、並びに共重合体樹脂(A)の固形分合計100質量部に対して、ヒュームドシリカ(B)を1~30質量部、マグネシウムを含有するリン酸系化合物(C)を0.1~10質量部含む、アルミニウムホイール用のプライマー塗料組成物、
2.共重合体樹脂(A)の固形分合計100質量部に対して、金属イオン交換シリカ(D)を0.1~10質量部含有する1項に記載のアルミニウムホイール用のプライマー塗料組成物、
3.共重合体樹脂(A)の固形分合計100質量部に対して、エポキシ化合物(E)を1~20質量部含有する1項又は2項に記載のアルミニウムホイール用のプライマー塗料組成物、
4.共重合体樹脂(A)の固形分合計100質量部に対して、シランカップリング剤(F)を1~20質量部含有する1~3項のいずれか1項に記載のアルミニウムホイール用のプライマー塗料組成物、
5.共重合体樹脂(A)の固形分合計100質量部に対して、脱水剤(G)を1~30質量部含有する1~4項のいずれか1項に記載のアルミニウムホイール用のプライマー塗料組成物、
6.表面処理されていてもよいアルミニウムホイール上に、1~5項のいずれか1項に記載のアルミニウムホイール用のプライマー塗料組成物による、未硬化又は硬化塗膜を形成し、該未硬化又は硬化塗膜上に、少なくとも1層の上塗塗膜を形成することを特徴とする塗膜形成方法」に関する。
本発明のプライマー塗料組成物に用いる共重合体樹脂(A)は、下記の式(1)で表される窒素含有ラジカル重合性不飽和単量体(a1)を5~35質量%、カルボキシル基含有ラジカル重合性不飽和単量体(a2)を1~10質量%及びその他のラジカル重合性不飽和単量体(a3)を55~94質量%の混合物を反応させることによって得られる樹脂である。
本発明において、ラジカル重合性不飽和単量体とは、1個以上(例えば、1~4個)の重合性不飽和基を有する単量体を示す。重合性不飽和基とは、ラジカル重合しうる不飽和基を意味する。かかる重合性不飽和基としては、例えば、ビニル基、(メタ)アクリロイル基、(メタ)アクリルアミド基、ビニルエーテル基、アリル基等が挙げられる。
窒素含有ラジカル重合性不飽和単量体(a1)を示す式(1)において、R2で示される炭素数1~6のアルキル基としては、例えば、炭素数1~6、好ましくは炭素数1~4の直鎖又は分枝鎖上のアルキル基等を挙げることができ、具体的には、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、t-ブチル基、n-ペンチル基、n-ヘキシル基等が含まれる。
カルボキシル基含有ラジカル重合性不飽和単量体(a2)としては、カルボキシル基を1個以上、好ましくは1又は2個有するラジカル重合性不飽和単量体等を挙げることができる。カルボキシル基含有ラジカル重合性不飽和単量体(a2)としては、特に限定されることなく使用でき、例えば、アクリル酸、メタアクリル酸、マレイン酸、クロトン酸、イタコン酸、フマル酸、及びこれらの無水物やハーフエステル化物などのカルボキシル基含有ラジカル重合性不飽和単量体が挙げられる。カルボキシル基含有ラジカル重合性不飽和単量体(a2)は、適宜に、単独もしくは2種以上組み合わせ使用することができる。
その他のラジカル重合性不飽和単量体(a3)としては、特に限定されることなく使用でき、例えば、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸ヒドロキシブチル、(メタ)アクリル酸2-ヒドロキシクロロプロピルおよびダイセル化学(株)製の商品名「プラクセルF」シリーズ(ラクトン変性(メタ)アクリル酸エステル)などの水酸基含有ラジカル重合性不飽和単量体;(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸オクチル、(メタ)アクリル酸ノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸トリデシル、(メタ)アクリル酸セチル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸ベンジル、(メタ)アクリル酸フェノキシエチル、(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸エチルカルビトール、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸i-ブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸ネオペンチル、(メタ)アクリル酸エチルヘキシル、(メタ)アクリル酸イソデシル、(メタ)アクリル酸イソステアリル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸トリシクロデシニル等のアクリル酸又はメタクリル酸の炭素数1~18のアルキルエステル又はシクロアルキルエステルラジカル重合性不飽和単量体;(メタ)アクリル酸アミノエチル、(メタ)アクリル酸ジメチルアミノエチル、(メタ)アクリル酸ブチルアミノエチル等のカルボン酸アミノアルキルエステルラジカル重合性不飽和単量体;(メタ)アクリル酸テトラヒドロフルフリルおよび(メタ)アクリル酸モルホリノエチル;(メタ)アクリル酸グリシジル、アリルグリシジルエーテル、グリシジルビニルエーテルなどのエポキシ基含有ラジカル重合性不飽和単量体;(メタ)アクリル酸トリメトキシシリルプロピル、(メタ)アクリル酸トリエトキシシリルプロピル、(メタ)アクリル酸メチルジメトキシシリルプロピルおよびビニルトリメトキシシランなどのアルコキシシリル基含有ラジカル重合性不飽和単量体;エチレン、プロピレンおよびイソブチレンなどのα-オレフィン;塩化ビニル、塩化ビニリデン、フッ化ビニルおよびフッ化ビニリデンなどの部分ハロゲン化オレフィン;酢酸アリル、酪酸アリル等のアリル化合物;クロトン酸エチル、クロトン酸プロピル等のクロトン酸エステル類;エチルビニルエーテル、シクロヘキシルビニルエーテル等のビニルエーテル類;酢酸ビニル、プロピオン酸ビニル、バーサチック酸ビニルなどのカルボン酸ビニル類;スチレン、α-メチルスチレン、ビニルトルエンなどの芳香族系ラジカル重合性不飽和単量体;アクリロニトリル、アクリルアミド、メタクリルアミド等が例示される。これらのその他のラジカル重合性不飽和単量体(a3)は、適宜に、単独でもしくは2種以上組み合わせて使用することができる。
55~105mgKOH/gである。上記の範囲内であることが、塗膜性能や塗料安定性の向上に望ましい。
本発明のプライマー塗料組成物に使用されるヒュームドシリカ(B)は、ケイ素塩化物を気化し、高温の水素炎中において気相反応によって合成される乾式シリカである。ヒュームドシリカ(B)は、アモルファスのガラス状で、かつ球状で細孔のないシリカである。このようなヒュームドシリカ(B)の平均一次粒径は、5~100nm、好ましくは20~50nmである。ヒュームドシリカ(B)の平均一次粒径は、電子顕微鏡を観察することによって測定できる。また、ヒュームドシリカ(B)の比表面積は、100~1,000m2/g、好ましくは200~500m2/gの範囲である。
マグネシウムを含有するリン酸系化合物(C)は、例えば、リン酸、亜リン酸、トリポリリン酸等のリン酸化合物の金属塩であり、金属元素として少なくともマグネシウムを含有する化合物である。マグネシウムを含有するリン酸系化合物(C)から放出されるマグネシウムイオン、リン酸イオンが、エッジ防食性や耐糸錆び性の向上に効果的に作用する。
金属イオン交換シリカ(D)は、金属がカルシウム及マグネシウムのうちの少なくとも1種である金属イオン交換シリカであり、例えば、カルシウムイオン交換シリカ、マグネシウムイオン交換シリカを挙げることができる。これらの金属イオン交換シリカ(D)は、必要に応じてリン酸で変性して、リン酸変性金属イオン交換シリカとすることもできる。
本発明で使用するエポキシ化合物(E)は、その重量平均分子量は300~4,000、好ましくは500~2,500の範囲を有するものが適しており、特に、ポリフェノール化合物とエピハロヒドリンとの反応によって得られるエポキシ樹脂(e1)が好ましい。
シランカップリング剤(F)は、例えば、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルメチルジメトキシシラン、N-(β-アミノエチル)-γ-アミノプロピルトリメトキシシラン、N-(β-アミノエチル)-γ-アミノプロピルメチルジメトキシシラン、N-(β-アミノエチル)-γ-アミノプロピルトリエトキシシラン、γ-ウレイドプロピルトリエトキシシラン、N-(β-(N-ビニルベンジルアミノエチル)-γ-アミノプロピルトリメトキシシラン、γ-アニリノプロピルトリメトキシシラン等のアミノ基含有シランカップリング剤;γ-グリシドキシプロピルメチルジメトキシシシラン、γ-グリシドキシプロピルトリエトキシキシシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン等のエポキシ基含有シランカップリング剤;β-カルボキシルエチルフェニルビス(2-メトキシエトキシ)シラン、N-β-(N-カルボキシメチルアミノエチル)-γ-アミノプロピルトリメトキシシラン等のカルボキシ含有シランカップリング剤、などが挙げられる。これらのシランカップリング剤は、単独で用いてもよく2種以上併用してもよい。
本発明のプライマー塗料組成物は、塗料安定性が良好であるが、さらに、脱水剤(G)を添加することによって、エッジ防食性、耐糸錆び性、塗料安定性を向上できる。脱水剤(G)としては、オルト酢酸メチル、オルト蟻酸メチルが挙げられる。
本発明のプライマー塗料組成物は、上記共重合体樹脂(A)、ヒュームドシリカ(B)及びマグネシウムを含有するリン酸系化合物(C)並びに、必要に応じて、金属イオン交換シリカ(D)、エポキシ化合物(E)、シランカップリング剤(F)及び脱水剤(G)などを混合し有機溶剤に溶解もしくは分散せしめることによって得られる。
(注2)ガラス転移温度(塗膜Tg):塗膜を短冊状に調製したものを試料とし、動的粘弾性測定装置を用いて測定して求めた。
反応容器中に、混合溶剤(キシレン/n-ブチルアルコール=80/20)30.0部を仕込み80℃に保持した中へ、以下の「混合物」を4時間掛けて滴下し、次いでアゾビスメチルバレロニトリル0.5部を添加し、80℃で3時間保持して反応を行い、さらに混合溶剤(キシレン/n-ブチルアルコール=80/20)で調整して、固形分60質量%の共重合体樹脂No.1溶液を製造した。
N-ブトキシメチルアクリルアミド 20部
アクリル酸 2部
スチレン 30部
アクリル酸エチル 48部
アゾビスメチルバレロニトリル 5部。
表1の配合内容とする以外は、製造例1と同様にして、共重合体樹脂No.2溶液~No.13溶液を得た。
5質量%の塩化マグネシウム水溶液10,000質量部中に、10質量部のサイリシア710(富士シリシア化学(株)製、商品名、シリカ微粒子、吸油量約105ml/100g)を5時間攪拌して混合した後、ろ過して固形分を取り出し、固形分をよく水洗し乾燥して、マグネシウムイオン交換シリカを得た。
85%リン酸115部に、ブチルグリシジルエーテル280部を加え、50~60℃で3時間反応させて、リン酸エステル化合物を得た。
反応容器中に、混合溶剤(キシレン/酢酸ブチル=80/20)30.0部を仕込み80℃に保持した中へ、以下の「混合物」を4時間掛けて滴下し、次いでアゾビスメチルバレロニトリル0.5部を添加し、80℃で3時間保持して反応を行い、さらに混合溶剤(キシレン/酢酸ブチル=80/20)で調整して、固形分60質量%の水酸基含有アクリル樹脂A溶液を製造した。
mgKOH/g、水酸基価103.5mgKOH/g、重量平均分子量15,000であった。
アクリル酸 2部
スチレン 30部
メタクリル酸メチル 20部
アクリル酸n-ブチル 20部
メタクリル酸2-ヒドロキシエチル 24部
アゾビスメチルバレロニトリル 7部。
反応容器中に、混合溶剤(キシレン/酢酸ブチル=80/20)30.0部を仕込み80℃に保持した中へ、以下の「混合物」を4時間掛けて滴下し、次いでアゾビスメチルバレロニトリル0.5部を添加し、80℃で3時間保持して反応を行い、さらに混合溶剤(キシレン/酢酸ブチル=80/20)で調整して、固形分60質量%の水酸基含有アクリル樹脂B溶液を製造した。
アクリル酸 2部
スチレン 8部
アクリル酸n-ブチル 20部
メタクリル酸2-ヒドロキシエチル 70部
アゾビスメチルバレロニトリル 7部。
実施例1 プライマー塗料No.1溶液の製造例
製造例1で得た共重合体樹脂No.1溶液を100部(固形分)、AEROSIL 380PE(注3)を20部、及びK-WhiteG105(注5)1.0部からなる混合物に、混合溶剤(キシレン/酢酸ブチル=50/50)を加えて、撹拌機(直径7cmの撹拌羽根、700rpm)で1時間撹拌し、固形分が50質量%のプライマー塗料No.1を得た。
表2の配合内容とする以外は、実施例1と同様にして、プライマー塗料No.2~No.23を得た。
(注4)AEROSIL 130:日本アエロジル社製、商品名、ヒュームドシリカ(B)、比表面積130m2/g
(注5)K-WhiteG105:テイカ社製、商品名、マグネシウムを含有するリン酸系化合物(C)(トリポリリン酸二水素アルミニウムの酸化マグネシウム処理物)
(注6)LFボウセイCRF-15:キクチカラー社製、商品名、マグネシウムを含有するリン酸系化合物(C)
(注7)K-White140E:テイカ社製、商品名、トリポリリン酸二水素アルミニウム
(注8)サイロマスク52M:富士シリシア社製、商品名、マグネシウムイオン交換シリカ(D)(平均粒子径 2.30~3.30μm)
(注9)SHIELDEX C303:W.R.Grace & Co.社製、商品名、カルシウムイオン交換シリカ(D)(平均粒子径3μm)
(注10)jER1001:三菱化学社製、商品名、エポキシ樹脂、エポキシ当量475、エポキシ化合物(E)(前述の式(2)で表されるエポキシ樹脂に該当)
(注11)KBM-403:信越化学社製、商品名、シランカップリング剤(F)。(3-グリシドキシプロピルトリメトキシシラン)
比較例1~14 プライマー塗料No.24~No.37の製造
表3の配合内容とする以外は、実施例1と同様にして、プライマー塗料No.24~No.37を得た。
ノンクロム化成処理を施したアルミニウムホイールに、各プライマー塗料を乾燥膜厚25μmになるようにスプレー塗装した。次いで、室温で5分間セッティングした。その上に、マジクロンEN-2クリヤー(関西ペイント株式会社製、商品名、アクリル樹脂系有機溶剤型のクリヤ塗料)を乾燥膜厚が25μmになるように塗装した後に、140℃で20分間加熱して、試験用のアルミニウムホイール塗装物品を得た。
アルミニウムホイール塗装物品の塗膜表面にカッターナイフにより10cm長さのカット傷を入れた試料に、JIS Z 2371(2000)に基づいて、調整されたキャス試験液を50±2℃で120時間噴霧を行い、24時間放置後、カット部の周辺における腐食の度合いを評価した:
S:塗膜のフクレおよび錆等の異常がない
A:カット部から1mm未満のフクレ又は錆がみられる
B:カット部から1mm以上で、かつ2mm未満のフクレ又は錆がみられる
C:カット部から2mmを超えるフクレ又は錆がみられる。
アルミニウムホイール塗装物品を用いて、JIS Z-2371に準じて168時間耐塩水噴霧試験を行い、アルミニウムホイールのエッジ部における錆を以下の基準で評価した:
S:錆の発生個数が、0個/アルミニウムホイール全体
A:錆の発生個数が、1~3個/アルミニウムホイール全体
B:錆の発生個数が、4~10個/アルミニウムホイール全体
C:錆の発生個数が、11個以上/アルミニウムホイール全体。
アルミニウムホイール塗装物品の表面にカット傷を入れ、JIS Z 2371に準じて24時間耐塩水噴霧試験を行った。その後、湿潤状態(湿度85%、40℃)に480時間保ち、カット部からの錆び幅を測定した。カット部からの錆、フクレ幅を以下の基準で評価した:
S:錆又はフクレの最大幅がカット部から片側2mm未満、
A:錆又はフクレの最大幅がカット部から片側2mm以上、3mm未満、
B:錆又はフクレの最大幅がカット部から片側3mm以上、4mm未満、
C:錆又はフクレの最大幅がカット部から片側4mm以上。
各々のプライマー塗料を35℃にて35日間容器中に密閉して貯蔵した。その後の状態を以下の基準で判断した:
S:貯蔵前と変化なく良好である
A:やや粘度上昇がみられるが、1分間程度の撹拌でもとの状態に戻る
B:粘度上昇又はやや層分離がみられる
C:層分離がみられる
Claims (6)
- 構成する単量体の合計に対して、下記の式(1)で表される窒素含有ラジカル重合性不飽和単量体(a1)を5~35質量%、カルボキシル基含有ラジカル重合性不飽和単量体(a2)を1~10質量%及びその他のラジカル重合性不飽和単量体(a3)を55~94質量%の混合物を反応させることによって得られる共重合体樹脂(A)、並びに共重合体樹脂(A)の固形分合計100質量部に対して、ヒュームドシリカ(B)を1~30質量部、マグネシウムを含有するリン酸系化合物(C)を0.1~10質量部含む、アルミニウムホイール用のプライマー塗料組成物。
- 共重合体樹脂(A)の固形分合計100質量部に対して、金属イオン交換シリカ(D)を0.1~10質量部含有する請求項1に記載のアルミニウムホイール用のプライマー塗料組成物。
- 共重合体樹脂(A)の固形分合計100質量部に対して、エポキシ化合物(E)を1~20質量部含有する請求項1又は2に記載のアルミニウムホイール用のプライマー塗料組成物。
- 共重合体樹脂(A)の固形分合計100質量部に対して、シランカップリング剤(F)を1~20質量部含有する請求項1~3のいずれか1項に記載のアルミニウムホイール用のプライマー塗料組成物。
- 共重合体樹脂(A)の固形分合計100質量部に対して、脱水剤(G)を1~30質量部含有する請求項1~4のいずれか1項に記載のアルミニウムホイール用のプライマー塗料組成物。
- 表面処理されていてもよいアルミニウムホイール上に、請求項1~5のいずれか1項に記載のアルミニウムホイール用のプライマー塗料組成物による未硬化又は硬化塗膜を形成し、該未硬化又は硬化塗膜上に、少なくとも1層の上塗塗膜を形成することを特徴とする塗膜形成方法。
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