WO2017056911A1 - 塗料組成物 - Google Patents
塗料組成物 Download PDFInfo
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- WO2017056911A1 WO2017056911A1 PCT/JP2016/076522 JP2016076522W WO2017056911A1 WO 2017056911 A1 WO2017056911 A1 WO 2017056911A1 JP 2016076522 W JP2016076522 W JP 2016076522W WO 2017056911 A1 WO2017056911 A1 WO 2017056911A1
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- polymerizable unsaturated
- meth
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- coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
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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
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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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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Definitions
- the present invention relates to a coating composition having excellent storage stability and excellent scratch resistance of the resulting coating film.
- a paint to be applied to an object such as an automobile body is required to have excellent coating film performance such as scratch resistance and excellent coating film appearance. It is known that there are scratches due to car washing and scratches due to coins, keys, etc., and the scratching mechanism is different, but it is desirable that both scratches be resistant. . On the other hand, since coating becomes difficult when thickening or sedimentation occurs during storage of the paint, the paint is also required to have storage stability.
- Patent Document 1 discloses that (A) a hydroxyl value of 110 to 700 mgKOH / g and a number average molecular weight of 200 to 1,800 are in the range of 3 or more hydroxyl groups in one molecule.
- a coating composition containing a polyol compound having (B) a polyisocyanate compound and (C) a resin-coated silica particle dispersion, wherein the resin-coated silica particle dispersion (C) is (c1) a polymerizable unsaturated group (C2) a resin-coated silica particle dispersion obtained by reacting (c2) a polymerizable unsaturated monomer with a mass ratio of (c1) :( c2) 20: 80 to 90:10, and The content of the resin-coated silica particle dispersion (C) is based on the total solid content of the polyol compound (A), the polyisocyanate compound (B), and the resin-coated silica particle dispersion (C). Characterized in
- Patent Document 2 discloses a coating composition comprising silica particles (A) whose surfaces are modified with a specific hydrolyzable silane compound (a) and a binder component (B). ing.
- the coating composition is excellent in car wash scratch resistance, there are cases where the resistance to scratches caused by coins and keys and storage stability are not sufficient.
- Patent Document 3 includes (A) (a) 25 to 50% by mass of a hydroxyl group-containing polymerizable unsaturated monomer, and (b) 5 to 30% by mass of a polymerizable unsaturated monomer having 6 to 20 carbon atoms and an alicyclic hydrocarbon group.
- Isocyanurate 3 based on the total amount of hydroxyl group-containing acrylic resin and (B) polyisocyanate compound, which is a copolymer of monomer components comprising 20% to 70% by mass of (c) other polymerizable unsaturated monomers
- Polyisocyanate comprising an aliphatic diisocyanate having a monomer content of 30 to 70% by mass, a uretdione dimer content of 3 to 30% by mass, and other trimer or higher polymer content of 0 to 67% by mass.
- a coating composition containing a compound and (C) polysiloxane-modified silica particles having an average primary particle diameter of 1 to 40 nm is disclosed.
- the coating composition is excellent in car wash scratch resistance, there are cases where the resistance to scratches caused by coins and keys and storage stability are not sufficient.
- Patent Document 4 includes (I) (a) colloidal silica modified with a hydrolyzable alkoxysilyl group-containing unsaturated monomer and homogeneously dispersed in an organic solvent, (b) a specific polysiloxane macromonomer, Contains (c) a hydroxyl group-containing unsaturated monomer, and if necessary, (d) a colloidal silica-containing acrylic resin obtained by copolymerizing other unsaturated monomers, and (II) a curing agent as essential components.
- Disclosed is a coating composition characterized by: However, although the coating composition is excellent in car wash scratch resistance, there are cases where the resistance to scratches caused by coins and keys and storage stability are not sufficient.
- Patent Document 5 discloses composite fine particles in which an organic polymer is integrated with inorganic fine particles and containing an ethylenically unsaturated group.
- the inorganic fine particles are used in the paint, the car wash scuff resistance is excellent, but there are cases where the resistance to scratches by coins and keys and the storage stability are not sufficient.
- Patent Document 6 discloses composite fine particles in which an organic polymer is fixed on the surface of inorganic fine particles, and the organic polymer includes organic polymer composite inorganic fine particles containing a perfluoroalkyl group and / or a silicone group.
- the inorganic fine particles when used in a paint, they have excellent resistance to scratches caused by pencils, but there are cases where the car wash scratch resistance and storage stability are not sufficient.
- An object of the present invention is to provide a coating composition having excellent storage stability and excellent scratch resistance of the resulting coating film.
- the present invention is a coating composition containing a hydroxyl group-containing resin (A), a curing agent (B), and an acrylic resin-coated silica particle (C) dispersion, wherein the acrylic resin-coated silica particle (C) dispersion is ,
- a reaction product of silica particles having a polymerizable unsaturated group (c1) and polymerizable unsaturated monomer (c2) in a mass ratio of (c1) :( c2) 20: 80 to 90:10.
- the polymerizable unsaturated monomer (c2) is used as at least a part of its components to have the following formula (I) (Wherein R 1 represents a hydrogen atom or a methyl group, Z represents a structure containing the following formula (II), X represents a hydrogen atom or a (meth) acryloyl group, an alkyl group, a hydroxyl group, an amino group, (an alicyclic ring) Formula) A group selected from an epoxy group, a carboxyl group, a mercapto group, a vinyl group, an isocyanate group, and an aryl group.
- R 1 represents a hydrogen atom or a methyl group
- Z represents a structure containing the following formula (II)
- X represents a hydrogen atom or a (meth) acryloyl group, an alkyl group, a hydroxyl group, an amino group, (an alicyclic ring) Formula
- the present invention relates to a coating composition
- a coating composition comprising a polymerizable unsaturated monomer (c2-1) represented by the formula (1) and having a molecular weight of 400 to 6000 for the resin covering the silica particles.
- the coating composition of the present invention it is possible to form a coating film having excellent storage stability, scratch resistance due to car washing, and scratch resistance due to coins and keys.
- the coating composition of the present invention (hereinafter sometimes referred to as “the present coating”) is a coating containing a dispersion containing a hydroxyl group-containing resin (A), a curing agent (B), and acrylic resin-coated silica particles (C).
- the hydroxyl group-containing resin (A) is not particularly limited as long as it contains a hydroxyl group, and a known thermosetting resin can be used.
- a hydroxyl group-containing acrylic resin is preferable.
- the hydroxyl group-containing acrylic resin can be produced by copolymerizing a hydroxyl group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer.
- the hydroxyl group-containing polymerizable unsaturated monomer is a compound having at least one hydroxyl group and one polymerizable unsaturated group in one molecule.
- the hydroxyl group-containing polymerizable unsaturated monomer is preferably a monoester product of acrylic acid or methacrylic acid and a dihydric alcohol having 2 to 10 carbon atoms, such as 2-hydroxyethyl (meth).
- Examples thereof include (meth) acrylate and 4-methylolcyclohexyl (meth) acrylate.
- caprolactone-modified hydroxyl group-containing (meth) acrylates examples include “Placcel FM” (trade name, manufactured by Daicel Chemical Industries), and the like.
- Examples of commercially available 4-methylolcyclohexyl acrylate include “CHDMMA”. (Trade name, manufactured by Nippon Kasei Co., Ltd.).
- the hydroxyl group-containing polymerizable unsaturated monomer is particularly a polymerizable unsaturated monomer having a hydroxyl group-containing hydrocarbon group having 3 to 20 carbon atoms from the viewpoint of scratch resistance of the formed coating film, specifically, 2-Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-methylol cyclohexyl acrylate and the like are preferably used.
- the hydroxyl group based on the hydroxyl group-containing polymerizable unsaturated monomer functions as a crosslinkable functional group of the resulting copolymer resin.
- the other copolymerizable polymerizable unsaturated monomer is a compound having one or more polymerizable unsaturated groups in one molecule other than the hydroxyl group-containing polymerizable unsaturated monomer, and specific examples thereof are as follows. Listed in (1) to (11).
- Aromatic polymerizable unsaturated monomers for example, styrene, ⁇ -methylstyrene, vinyltoluene and the like.
- a polymerizable unsaturated monomer having a branched hydrocarbon structure having 8 or more carbon atoms for example, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl ( And (meth) acrylate.
- Examples of commercially available products include “isostearyl acrylate” (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.).
- C8-22 linear alkyl ester of (meth) acrylic acid for example, lauryl (meth) acrylate, stearyl (meth) acrylate, etc.
- Epoxy group-containing polymerizable unsaturated monomer for example, glycidyl (meth) acrylate.
- Nitrogen-containing polymerizable unsaturated monomers for example, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, vinylpyridine, vinylimidazole and the like.
- Unsaturated group-containing nitrile compound For example, (meth) acrylonitrile and the like.
- Acidic functional group-containing polymerizable unsaturated monomer for example, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride and other carboxyl group-containing unsaturated monomers; vinyl sulfonic acid, sulfoethyl (meth) Sulfonic acid group-containing unsaturated monomers such as acrylates; 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3-chloropropyl acid phosphate, 2- Acid phosphate ester unsaturated monomers such as (meth) acryloyloxyethylphenyl phosphoric acid.
- Alkoxysilyl group-containing polymerizable unsaturated monomer for example, vinyltrimethoxysilane, vinyltriethoxysilane, acryloxyethyltrimethoxysilane, methacryloxyethyltrimethoxysilane, acryloxypropyltrimethoxysilane, methacryloxypropyltri Examples include methoxysilane, acryloxypropyltriethoxysilane, methacryloxypropyltriethoxysilane, and vinyltris ( ⁇ -methoxyethoxy) silane.
- the said other copolymerizable polymerizable unsaturated monomer can be used individually or in combination of 2 or more types.
- a hydroxyl group-containing acrylic resin can be obtained by copolymerizing the polymerizable unsaturated monomer mixture comprising the hydroxyl group-containing polymerizable unsaturated monomer and the other polymerizable unsaturated monomer.
- the use ratio of the hydroxyl group-containing polymerizable unsaturated monomer is from 15 to 50% by mass, preferably from 20 to 45% by mass, based on the total mass of the copolymerizable monomer components, from the viewpoint of scratch resistance and finish. Is appropriate.
- the monomer (1) As other polymerizable unsaturated monomer, it is desirable to use the monomer (1) from the viewpoints of finish (particularly gloss), water resistance and weather resistance, and the use ratio is based on the total mass of the copolymerization monomer components. Thus, it is appropriate that the amount is about 3 to 40% by mass, preferably about 5 to 30% by mass. In addition, it is desirable to use the monomer (2) as the other polymerizable unsaturated monomer from the viewpoint of finish and water resistance, and the proportion of use is 3 to 40 based on the total mass of the copolymerization monomer component. It is appropriate that the amount is about 5% by mass, preferably about 5 to 30% by mass.
- the monomer (3) is desirable to use as the other polymerizable unsaturated monomer from the viewpoint of the wettability to the object to be coated and the finish, and the use ratio is based on the total mass of the copolymerization monomer component.
- it is appropriate to be about 3 to 45% by mass, preferably about 8 to 40% by mass.
- the monomer (1), monomer (2), and monomer (3) The total mass of is suitably about 35 to 85% by mass, preferably about 40 to 80% by mass, based on the total mass of the copolymerizable monomer components.
- acidic functional group-containing polymerizable unsaturated monomers such as carboxyl group-containing unsaturated monomers, sulfonic acid group-containing unsaturated monomers, and acidic phosphate ester-based unsaturated monomers are obtained hydroxyl groups. It can act as an internal catalyst when the contained resin undergoes a crosslinking reaction with the polyisocyanate compound, and the amount used is within the range of about 0.1 to 5% by mass based on the total amount of the monomer mixture constituting the resin. Is preferable, and can be used within a range of about 0.5 to 3% by mass.
- the copolymerization method for copolymerizing the monomer mixture to obtain a hydroxyl group-containing acrylic resin is not particularly limited, and a known copolymerization method can be used. In particular, it is preferable to use a solution polymerization method in which polymerization is performed in an organic solvent in the presence of a polymerization initiator.
- organic solvent used in the solution polymerization method examples include aromatic solvents such as toluene, xylene, and high-boiling aromatic hydrocarbons; ethyl acetate, butyl acetate, 3-methoxybutyl acetate, ethylene glycol ethyl ether acetate Ester solvents such as propylene glycol methyl ether acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and methyl amyl ketone; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl Glycol ether solvents such as ether; propyl propionate, butyl propionate, ethoxyethyl propionate, etc. It is possible.
- Examples of commercially available high-boiling aromatic hydrocarbons include “Swazole 1000
- organic solvents can be used alone or in combination of two or more.
- the organic solvent when the hydroxyl group-containing acrylic resin has a high hydroxyl value, it is preferable to use an ester solvent or a ketone solvent having a high boiling point from the viewpoint of the solubility of the resin. Furthermore, a high boiling point aromatic solvent can be used in combination.
- Examples of the polymerization initiator that can be used for copolymerization of the hydroxyl group-containing acrylic resin include 2,2′-azobisisobutyronitrile, benzoyl peroxide, 2,2-di (t-amylperoxy) butane, and di- Known radical polymerization initiators such as t-butyl peroxide, di-t-amyl peroxide, t-butyl peroctoate, and 2,2′-azobis (2-methylbutyronitrile) can be exemplified.
- the hydroxyl group-containing acrylic resin may be composed of one kind of copolymer, but may be composed of two or more kinds of copolymers.
- the hydroxyl value of the hydroxyl group-containing acrylic resin is preferably in the range of 10 to 200 mgKOH / g, more preferably 50 to 200 mgKOH / g, and even more preferably 80 to 200 mgKOH / g, from the viewpoint of both scratch resistance and water resistance. It is.
- the weight average molecular weight of the hydroxyl group-containing acrylic resin is preferably in the range of 5,000 to 30,000, more preferably 5,000 to 20,000, and still more preferably from the viewpoint of acid resistance and finish. It is in the range of 10,000 to 20,000.
- a weight average molecular weight is the value computed on the basis of the molecular weight of standard polystyrene from the chromatogram measured by the gel permeation chromatograph.
- the gel permeation chromatograph “HLC8120GPC” (manufactured by Tosoh Corporation) was used.
- the columns four columns of “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL”, “TSKgel G-2000HXL” (both manufactured by Tosoh Corporation, trade name) were used.
- the glass transition temperature of the hydroxyl group-containing acrylic resin is preferably in the range of ⁇ 30 ° C. to 30 ° C., particularly in the range of ⁇ 20 ° C. to 20 ° C., from the viewpoint of coating film hardness and finish.
- Curing agent (B) As the curing agent, polyisocyanate compounds (including blocked ones) and amino resins such as melamine resins, guanamine resins and urea resins can be used.
- a polyisocyanate compound and / or a melamine resin is preferable from the viewpoint of obtaining a coating film excellent in weather resistance, scratch resistance, coating film hardness, adhesion, and the like.
- a polyisocyanate compound is a compound having two or more isocyanate groups in one molecule.
- the polyisocyanate compound include aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; cyclic aliphatic diisocyanates such as hydrogenated xylylene diisocyanate or isophorone diisocyanate; tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate.
- Organic diisocyanates such as aromatic diisocyanates themselves, or adducts of these organic diisocyanates with polyhydric alcohols, low molecular weight polyester resins or water, or cyclized polymers of the respective organic diisocyanates as described above,
- isocyanate and biuret bodies there are isocyanate and biuret bodies.
- These polyisocyanate compounds are blocked with a blocking agent. It can also be used ones. When using a blocked isocyanate compound, it is preferable to use a dissociation catalyst in combination.
- Examples of typical commercially available isocyanate compounds include Vernock D-750, -800, DN-950, -970 or 15-455 (above, trade name, manufactured by DIC Corporation), Sumijour N3300, or N3390. (Above, trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.), Duranate 24A-100, TPA-100, TLA-100, P301-75E "(above, trade name, manufactured by Asahi Kasei Chemicals Corporation).
- Examples of the polyisocyanate compound having a blocked isocyanate group include those obtained by blocking the above-mentioned polyisocyanate compound having a free isocyanate group with a known blocking agent such as oxime, phenol, alcohol, lactam, malonic ester, mercaptan, and the like. It is done. Examples of these typical commercial products include Barnock D-550 (trade name, manufactured by DIC Corporation) or Duranate SBN-70 (trade name, manufactured by Asahi Kasei Corporation).
- a melamine resin obtained by etherifying a methylol group of methylolated melamine with a monohydric alcohol having 1 to 8 carbon atoms can be preferably used.
- the etherified melamine resin may be one in which all methylol groups of the methylolated melamine are etherified, or may be partially etherified to leave a methylol group or imino group.
- etherified melamine resin examples include alkyl etherified melamines such as methyl etherified melamine, ethyl etherified melamine, and butyl etherified melamine. Only one type of etherified melamine resin may be used, or two or more types may be used in combination.
- melamine resins examples include butylated melamine resins (manufactured by Mitsui Chemicals, Inc .; Uban 20SE-60, Uban 225, manufactured by DIC Corporation; Super Becamine G840, Super Becamine G821, etc.), methylated melamine, and the like.
- Resin (Nippon Cytec Industries Co., Ltd .; Cymel 303, Sumitomo Chemical Co., Ltd .; Sumimar M-100, Sumimar M-40S, etc.), methyl etherified melamine resin (Nippon Cytec Industries Co., Ltd .; Cymel 303, Cymel 325, Cymel 327, Cymel 350, Cymel 370, Sumitomo Chemical Sumimar M55, etc.), methylated, butylated mixed etherified melamine resin (Nippon Cytec Industries, Ltd .; Cymel 253, Cymel 202, Cymel 2) 8, melmel resin such as Cymel 254, Cymel 272, Cymel 1130, manufactured by Sumitomo Chemical Co., Ltd .; Sumimar M66B, etc.), methylated, isobutylated mixed etherified melamine resin (Nippon Cytec Industries Cymel XV805, etc.) can be used. .
- the blending ratio of the curing agent may be appropriately blended so that the coating film is cured and has sufficient performance, but from the viewpoint of curability of the resulting coating film, the ratio of the hydroxyl group-containing resin / curing agent is 80 by mass ratio. A range of / 20 to 50/50 is preferred.
- the blending ratio thereof is generally such that the equivalent ratio (NCO / OH) between the isocyanate group of the polyisocyanate compound and the hydroxyl group of the hydroxyl group-containing resin in the coating composition of the present invention is 0.00.
- a range of 5 to 2.0, particularly 0.7 to 1.5 is preferred.
- the resin containing the specific polymerizable unsaturated monomer (c2-1) described later and having a molecular weight of 400 to 6000 covering the silica particles is used.
- Silica particles having a polymerizable unsaturated group (c1) For the silica particles (c1) having a polymerizable unsaturated group, for example, silica particles (d), an organic solvent (e), and a monomer (f) having a polymerizable unsaturated group and a hydrolyzable silyl group are mixed and heated. Silica particles (c1-i) having a polymerizable unsaturated group that can be obtained by the above method can be used, and a tertiary amine (g) is further added to the silica particles (c1-i) having a polymerizable unsaturated group. Polymerizable unsaturated group-containing silica particles (c1-ii) obtained by addition can also be used. From the viewpoint of the storability of the paint and the scratch resistance of the resulting coating film, it is preferable to use (c1-ii) as the silica particles (c1) having a polymerizable unsaturated group.
- Silica particles (d) may be subjected to surface modification with a polymerizable unsaturated group by forming a covalent bond by a reaction with a monomer (f) having a polymerizable unsaturated group and a hydrolyzable silyl group described later. Any silica particles can be used. Examples of such silica particles (d) include dry silica, wet silica, silica gel, calcium ion exchanged silica fine particles, colloidal silica, etc., and in particular, have a hydroxyl group and / or an alkoxy group on the particle surface, Colloidal silica that is silica fine particles dispersed in a dispersion medium is preferred.
- the dispersion medium examples include water; alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, isobutanol, and n-butanol; polyhydric alcohol solvents such as ethylene glycol; ethylene glycol monoethyl ether, ethylene glycol Examples include polyhydric alcohol derivatives such as monobutyl ether and propylene glycol monomethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol.
- a lower alcohol solvent having 3 or less carbon atoms and a lower polyhydric alcohol derivative are preferable. This is because it is easy to remove in the solvent removal step in the production of the polymerizable unsaturated group-containing silica particles (c1-i).
- colloidal silica examples include methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, PGM-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL (all manufactured by Nissan Chemical Industries, Ltd.) and the like can be mentioned.
- the average primary particle diameter of the silica particles (d) is preferably 5 to 100 nm, more preferably 5 to 50 nm. If the average primary particle size is less than 5 nm, the effect of improving the mechanical properties and the like may be reduced when the dispersion is used in a mixture with other organic materials. When the average primary particle diameter exceeds 100 nm, transparency may be impaired.
- “average primary particle size” means the median diameter (d50) of the volume-based particle size distribution, and the volume-based particle size distribution is measured by a laser diffraction / scattering method.
- the volume-based particle size distribution of the dispersion was measured using a laser diffraction / scattering particle size distribution measuring apparatus “Microtrack NT3300” (trade name, manufactured by Nikkiso Co., Ltd.). At that time, the sample concentration was adjusted to be within a predetermined transmittance range set in the apparatus.
- Organic solvent (e) is preferably a hydrophilic organic solvent.
- hydrophilic organic solvent include alcohol organic solvents such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; dioxane, tetrahydrofuran, and the like.
- Ether glycol organic solvents ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono tert-butyl ether , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono n-propyl ether, die Lenglycol monoisopropyl ether, diethylene glycol mono n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono tert-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol monoisopropyl ether, dipropylene Glycol ether organic solvents such
- alcohols and / or glycol ethers are preferable from the viewpoints of storage stability and scratch resistance.
- Ethers are preferred.
- alcohols having 2 to 8 carbon atoms, preferably 3 to 5 carbon atoms and glycol ethers having 3 to 5 carbon atoms, preferably 3 to 4 carbon atoms are preferable from the viewpoints of storage stability and scratch resistance.
- Monomers (f) having a polymerizable unsaturated group and a hydrolyzable silyl group include, for example, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 2- (meth) Acryloyloxyethyltrimethoxysilane, 2- (meth) acryloyloxyethyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 2- (meth) acryloyloxyethylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltri Polymerizable defects obtained by reaction of functional groups other than hydrolyzable silyl groups of ethoxysilane, allyltrimethoxysilane, allyltriethoxy
- the polymerizable unsaturated group-containing silica particles (c1-i) are prepared by heating and mixing the silica particles (d), the organic solvent (e), and the monomer (f) having a polymerizable unsaturated group and a hydrolyzable silyl group. Obtained by.
- silica particles (d) dispersed in a dispersion medium, an organic solvent (e), and a monomer (f) having a polymerizable unsaturated group and a hydrolyzable silyl group are mixed, and from this mixture,
- the organic solvent (e) and the dispersion medium of silica particles (d) are used under normal pressure or reduced pressure. It can be produced by carrying out a dehydration condensation reaction under heating while boiling or distilling and replacing the dispersion medium with the organic solvent (e).
- the non-volatile content of the dispersion during the reaction is preferably in the range of about 5 to about 50% by mass.
- the nonvolatile content concentration is less than about 5% by mass, that is, when the solvent exceeds about 95% by mass, the reaction time between the silica particles (d) and the monomer (f) having a polymerizable unsaturated group and hydrolyzable silyl group is long. The manufacturing efficiency may be reduced.
- the non-volatile content concentration exceeds about 50% by mass, the product may be gelled.
- the silicon atom on the surface of the silica particle (d) and the silicon atom of the monomer (f) having a polymerizable unsaturated group and a hydrolyzable silyl group are bonded through an oxygen atom to form a siloxane bond.
- the silica particles (c1-i) having a polymerizable unsaturated group in which the silica particles (d) and the monomer (f) having a polymerizable unsaturated group and a hydrolyzable silyl group are chemically bonded to each other.
- a dispersion can be obtained.
- the blending ratio of the monomer (f) having a polymerizable unsaturated group and a hydrolyzable silyl group in obtaining the silica particle (c1-i) having a polymerizable unsaturated group is based on 100 parts by mass of the silica particles (d).
- the amount is preferably about 0.2 parts by weight to about 95 parts by weight, more preferably about 0.5 parts by weight to about 50 parts by weight, and still more preferably about 1.0 parts by weight to about 20 parts by weight.
- the silica particles (c1-i) having a polymerizable unsaturated group to be produced are dispersed. It may be inferior in stability in the medium.
- the proportion of the monomer (f) having a polymerizable unsaturated group and a hydrolyzable silyl group is more than about 95 parts by mass, the polymerizable unsaturated group and the hydrolyzable silyl group are reduced in the reaction with the silica particles (d). The monomer (f) it has may remain unreacted.
- an alkoxysilane having an alkyl group having 1 or more carbon atoms is converted into a polymerizable unsaturated group and a hydrolyzable silyl group. You may make it react with a silica particle (d) with the monomer (f) which has this. By reacting an alkoxysilane having an alkyl group having 1 or more carbon atoms, the water resistance of the resulting coating film may be improved.
- alkoxysilane having an alkyl group having 1 or more carbon atoms examples include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, and dodecyltrimethoxy.
- Silane etc. are mentioned,
- the compound (for example, methyltriethoxysilane etc.) which substituted the methoxy group in these illustrated compounds by the ethoxy group is also mentioned.
- silica particles (c1) having a polymerizable unsaturated group from the viewpoints of storage stability, scratch resistance, etc., the polymerizable unsaturated groups obtained from the above components (d), (e) and (f) It is preferable to use a polymerizable unsaturated group-containing silica particle (c1-ii) dispersion obtained by adding a tertiary amine (g) to the group-containing silica particle (c1-i) dispersion.
- the tertiary amine (g) is particularly preferably a tertiary amine (g) having a molecular weight of 120 to 380, preferably 130 to 350, more preferably 150 to 300, and a terminal having an alkyl group and / or an aryl group. Can be used without limitation.
- the tertiary amine (g) at least one of the alkyl groups of the tertiary amine (g) has 3 or more carbon atoms, preferably 4 to 12, more preferably 5 from the viewpoints of storage properties and scratch resistance. It is preferably an alkyl group of ⁇ 10.
- it is particularly preferable that at least one of the alkyl groups of the tertiary amine (g) is a linear alkyl group.
- tertiary amine examples include: Linear tertiary amines such as tripropylamine, tributylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine; Branched tertiary amines such as branched tritridecylamines such as triisopropylamine, triisobutylamine, tri-2-ethylhexylamine; Tertiary amines having mixed hydrocarbon groups such as dimethyloctylamine, dimethyldodecylamine, dimethyloctadecylamine, hexyldiethylamine, octyldiethylamine, diethyldodecylamine; Alicyclic tertiary amines such as dimethylcyclohexylamine and tricyclohexylamine; Tertiary amines
- a conventionally known method can be used as a method for adding the tertiary amine (g) to the polymerizable unsaturated group-containing silica particle (c1-i) dispersion.
- the amount of the tertiary amine (g) used is that of the polymerizable unsaturated group-containing silica particles (i) from the viewpoints of storage stability and scratch resistance of the coating film obtained when blended with a paint. 0.1 to 5.0 parts by mass, preferably 1.5 to 3.0 parts by mass, and more preferably 1.7 to 2.5 parts by mass based on 100 parts by mass of the solid content.
- a polymerizable unsaturated group-containing silica particle (c1-ii) dispersion can be obtained.
- Polymerizable unsaturated monomer (c2) contains a specific polymerizable unsaturated monomer (c2-1) as at least a part of its components.
- Monomer (c2-1) has the following formula (I) (In the formula, R 1 represents a hydrogen atom or a methyl group, Z represents a structure containing the following formula (II), and X represents a hydrogen atom or a (meth) acryloyl group, an alkyl group, a hydroxyl group, an amino group, and an aryl group. Indicates the selected group.)
- R 2 represents a phenyl group or an alkyl group having 1 to 6 carbon atoms which may be the same or different from each other
- R 3 represents an alkylene group having 1 to 6 carbon atoms. Is shown.
- It is a polymerizable unsaturated monomer shown by.
- X is selected from a hydrogen atom or (meth) acryloyl group, alkyl group, hydroxyl group, amino group, (alicyclic) epoxy group, carboxyl group, mercapto group, vinyl group, isocyanate group, and aryl group.
- a group selected from a (meth) acryloyl group and an alkyl group more preferably a group selected from a (meth) acryloyl group and an alkyl group having 1 to 10 carbon atoms.
- m represents an integer of 5.5 to 160, preferably 12 to 106, more preferably an integer of 23 to 64.
- R 2 represents a phenyl group or an alkyl group having 1 to 6 carbon atoms which may be the same or different from each other, preferably an alkyl group having 1 to 3 carbon atoms, more preferably It is a methyl group.
- R 3 represents an alkylene group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group.
- the proportion of the monomer (c2-1) in the polymerizable unsaturated monomer (c2) is 0.01 to 15% by mass, preferably 0.05 to 5% by mass, more preferably based on the total amount of the polymerizable unsaturated monomer.
- the content is preferably 0.1 to 3% by mass.
- the monomer (c2-2) is a compound having one or more polymerizable unsaturated groups in one molecule, and is a monomer other than (c2-1). Specific examples are listed below.
- the hydroxyl-containing polymerizable unsaturated monomer is a compound having one or more hydroxyl groups and polymerizable unsaturated groups in one molecule, and the hydroxyl-containing polymerizable unsaturated monomer.
- a monoesterified product of acrylic acid or methacrylic acid and a dihydric alcohol having 2 to 10 carbon atoms is preferable, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meta ) Acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and other hydroxyalkyl (meth) acrylates.
- examples of the hydroxyl group-containing polymerizable unsaturated monomer (c2-2) include ring-opening polymerization adducts of the hydroxyalkyl (meth) acrylate and lactones such as ⁇ -caprolactone.
- lactones such as ⁇ -caprolactone.
- Plaxel FA-1 “Plaxel FA-2”, “Plaxel FA-3”, “Plaxel FA-4”, “Plaxel FA-5”, “Plaxel FM-1”, “ “Placcel FM-2”, “Placcel FM-3”, “Placcel FM-4”, “Placcel FM-5” (all of which are trade names, manufactured by Daicel Chemical Industries, Ltd.).
- polymerizable unsaturated monomer having an alicyclic hydrocarbon group examples include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meta ) Acrylate, adamantyl (meth) acrylate, 3,5-dimethyladamantyl (meth) acrylate, 3-tetracyclododecyl methacrylate, 4-methylcyclohexylmethyl (meth) acrylate, 4-ethylcyclohexylmethyl (meth) acrylate, 4- Methoxycyclohexylmethyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclododecyl (meth) acrylate, tetrahydrofurfuryl
- Acid group-containing polymerizable unsaturated monomer a compound having one or more acid groups and one unsaturated bond in a molecule, for example, (meth) acrylic acid, crotonic acid, itaconic acid, malein Carboxyl group-containing polymerizable unsaturated monomers such as acid and maleic anhydride; sulfonic acid group-containing polymerizable unsaturated monomers such as vinyl sulfonic acid and sulfoethyl (meth) acrylate; 2- (meth) acryloyloxyethyl acid phosphate; Acid phosphate ester polymerizable unsaturated monomers such as 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3-chloropropyl acid phosphate, 2-methacryloyloxyethylphenyl phosphate, and the like.
- Alkoxysilyl group-containing polymerizable unsaturated monomer for example, vinyltrimethoxysilane, vinyltriethoxysilane, acryloxyethyltrimethoxysilane, methacryloxyethyltrimethoxysilane, acryloxypropyltrimethoxysilane, methacryloxypropyltri Methoxysilane, acryloxypropyltriethoxysilane, methacryloxypropyltriethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane, etc.
- Aromatic polymerizable unsaturated monomers for example, styrene, ⁇ -methylstyrene, vinyltoluene and the like.
- Glycidyl group-containing polymerizable unsaturated monomer A compound having one glycidyl group and one unsaturated bond in one molecule, specifically glycidyl acrylate, glycidyl methacrylate, and the like.
- Nitrogen-containing polymerizable unsaturated monomers for example, (meth) acrylamide, dimethylacrylamide, N, N-dimethylpropylacrylamide, N-butoxymethylacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, diacetoneacrylamide, N, N-dimethylaminoethyl (meth) acrylate, vinylpyridine, vinylimidazole and the like.
- Other vinyl compounds For example, vinyl acetate, vinyl propionate, vinyl chloride, versatic acid vinyl ester “Veoba 9”, “Veoba 10” (trade name, manufactured by Japan Chemtech Co., Ltd.) and the like.
- Unsaturated bond-containing nitrile compound For example, acrylonitrile, methacrylonitrile and the like.
- the polymerizable unsaturated monomer (c2-2) can be used alone or in combination of two or more.
- the polymerizable unsaturated group means an unsaturated group capable of radical polymerization.
- examples of the polymerizable unsaturated group include a vinyl group and a (meth) acryloyl group.
- (meth) acrylate” means “acrylate or methacrylate”.
- (Meth) acrylic acid” means “acrylic acid or methacrylic acid”.
- (Meth) acryloyl” means “acryloyl or methacryloyl”.
- “(Meth) acrylamide” means “acrylamide or methacrylamide”.
- the polymerizable unsaturated monomer (c2-2) preferably contains (1) the hydroxyl group-containing polymerizable unsaturated monomer as at least a part thereof.
- a hydroxyl group-containing polymerizable unsaturated monomer having a hydroxyl group-containing hydrocarbon group having 4 or more carbon atoms, particularly 4-hydroxybutyl (meth) acrylate is preferred.
- the polymerizable unsaturated monomer (c2-2) contains the above-mentioned (1) hydroxyl group-containing polymerizable unsaturated monomer as at least a part thereof, the amount is based on the polymerizable unsaturated monomer (c2-2). 10 to 50% by mass, preferably 20 to 45% by mass, more preferably 25 to 40% by mass.
- the polymerizable unsaturated monomer (c2-2) is at least a part of the above (2) fat. It is preferable to contain a polymerizable unsaturated monomer having a cyclic hydrocarbon group.
- the polymerizable unsaturated monomer (c2-2) contains the polymerizable unsaturated monomer having the above (2) alicyclic hydrocarbon group as at least a part thereof, the amount of the polymerizable unsaturated monomer (c2) -2) based on 5 to 60% by mass, preferably 10 to 55% by mass, more preferably 20 to 50% by mass.
- the polymerizable unsaturated monomer (c2-2) is at least a part of the above (6) fragrance. It is preferable to contain a group-type polymerizable unsaturated monomer. Especially, it is preferable to contain styrene from a viewpoint of acid resistance and stain resistance.
- the polymerizable unsaturated monomer (c2-2) contains the above-mentioned (6) aromatic polymerizable unsaturated monomer as at least a part thereof, the amount of the polymerizable unsaturated monomer (c2-2) The standard is 5 to 40% by mass, preferably 10 to 30% by mass, and more preferably 15 to 25% by mass.
- the acrylic resin-coated silica particle (C) dispersion comprises a silica particle (c1) having a polymerizable unsaturated group, a polymerizable unsaturated monomer (c2), and a solvent. It can obtain by making it superpose
- the polymerization method is not particularly limited, and a known polymerization method can be used. In particular, polymerization is performed in an organic solvent in the presence of a catalyst, a polymerization initiator, and the like as appropriate. A solution polymerization method can be preferably used.
- organic solvent used in the solution polymerization method examples include benzene, toluene, xylene, ethylbenzene, “Swazole 1000”, “Swazole 1500” (trade name, manufactured by Maruzen Petrochemical Co., Ltd., high boiling point petroleum solvent), and the like.
- Hydrocarbon solvents such as aromatic compounds, pentane, hexane, heptane, octane, cyclohexane, cycloheptane, mineral spirits; halogenated hydrocarbons such as trichloroethylene, tetrachloroethylene; ethyl acetate, n-butyl acetate, isobutyl acetate Ester solvents such as ethyl propionate, methyl cellosolve acetate, butyl carbitol acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, ethyl 3-ethoxypropionate; Ketone solvents such as ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone; methanol, ethanol, isopropanol, n-butanol, sec-butanol, iso
- the polymerization initiator that can be used in the above polymerization is not particularly limited.
- the amount of the radical polymerization initiator used is 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable unsaturated monomer (c2). If the radical polymerization initiator is less than 0.1 part by mass, the proportion of the unreacted polymerizable unsaturated monomer (c2) that does not react with the silica particles (c1) having a polymerizable unsaturated group may increase. . If the radical polymerization initiator is more than 20 parts by mass, the particles may be aggregated by polymerization of the acrylic resin-coated silica particles.
- the acrylic resin-coated silica particles include unreacted polymerizable unsaturated monomer (c2), or silica particles (c1) having a polymerizable unsaturated group reacted with the polymerizable unsaturated monomer (c2). May contain a polymer that has not reacted.
- the mixing ratio of the above-mentioned polymerizable unsaturated group-containing silica particle (c1) dispersion and polymerizable unsaturated monomer (c2) is (c1) in terms of the solid content mass ratio from the viewpoint of the appearance of the coating film to be formed.
- (C2) 20: 80 to 90:10, preferably 30:70 to 80:20, more preferably 40:60 to 60:40.
- the silica particle (c1) having a polymerizable unsaturated group and the polymerizable unsaturated monomer (c2) Is preferably in the range of about 10% to about 90% by weight, particularly about 20% to about 70% by weight.
- the total mass concentration is less than about 10 mass%, the reaction time may be long and the production efficiency may be reduced.
- the total mass concentration is higher than about 90% by mass, the viscosity of the reaction system becomes high and stirring may become difficult.
- the reaction is preferably performed while stirring by substituting the gas phase in the reaction vessel with an inert gas from the viewpoint of suppressing polymerization reaction inhibition by oxygen and improving the reaction rate.
- the reaction temperature and reaction time can be appropriately selected depending on the type of the polymerizable unsaturated monomer (c2) and the like, but the reaction temperature is preferably in the range of about 0 ° C. to about 250 ° C., and the reaction time is 1 It is preferably within the range of 72 hours.
- the reaction can usually be performed under normal pressure, but can also be performed under pressure or reduced pressure.
- the polymerization rate of the polymerizable unsaturated monomer (c2) is preferably about 90% or more and about 95% or more. If the polymerization rate of the polymerizable unsaturated monomer (c2) is less than about 90%, the coating performance such as scratch resistance may be inferior, and unreacted when the resulting acrylic resin-coated silica particle (C) dispersion is used. Odor due to the polymerizable unsaturated monomer (c2) may become a problem. The amount of unreacted polymerizable unsaturated monomer (c2) can be reduced by extending the reaction time.
- the amount of the unreacted polymerizable unsaturated monomer (c2) is small, it can be reduced by adding a radical polymerization initiator and further carrying out the polymerization reaction. Moreover, the obtained acrylic resin-coated silica particle (C) dispersion may be substituted with another solvent such as water, if desired.
- the molecular weight of the resin coating the silica particles is 400 to 6000, preferably 1000 to 5500, more preferably 3000 to 5000.
- the hydroxyl value of the resin covering the silica particles in the acrylic resin-coated silica particle (C) dispersion obtained by the above production method is 50 to 200 mgKOH / percent from the viewpoint of scratch resistance of the formed coating film. g, particularly 70 to 200 mg KOH / g, more preferably 100 to 200 mg KOH / g.
- the glass transition temperature Tg of the resin coating the silica particles in the acrylic resin-coated silica particle (C) dispersion obtained by the above production method is ⁇ 40 from the viewpoint of the scratch resistance of the coating film to be formed. It is preferably in the range of ⁇ 40 ° C., more preferably in the range of ⁇ 30 to 30 ° C.
- W1, W2,... Wn are mass fractions of the respective monomers
- T1, T2... Tn are glass transition temperatures Tg (K) of the homopolymers of the respective monomers.
- the glass transition temperature of the homopolymer of each monomer is POLYMER HANDBOOK Fourth Edition, J. MoI. Brandrup, E .; h. Immergut, E .; A.
- the glass transition temperature of a monomer not described in the literature which is a value according to Grulk ed. (1999), was synthesized such that a homopolymer of the monomer had a weight average molecular weight of about 50,000, and its glass transition temperature.
- the content of the acrylic resin-coated silica particles (C) dispersion in this paint is 0.1 to 25% by mass, preferably 0.5, based on the total solid content of the hydroxyl group-containing resin (A) and the curing agent (B). It is suitable to be in the range of ⁇ 20% by mass, more preferably in the range of 1 ⁇ 15% by mass.
- the paint further comprises a curing catalyst, a pigment, an ultraviolet absorber (for example, a benzotriazole absorber, a triazine absorber, a salicylic acid derivative absorber, a benzophenone absorber, etc.), a light stabilizer (for example, a hinder).
- an ultraviolet absorber for example, a benzotriazole absorber, a triazine absorber, a salicylic acid derivative absorber, a benzophenone absorber, etc.
- a light stabilizer for example, a hinder
- Dopiperidines, etc. thickeners, antifoaming agents, plasticizers, organic solvents, surface conditioners, anti-settling agents and other usual paint additives, etc., either alone or in combination of two or more. Can do.
- the curing catalyst examples include tin octylate, dibutyltin di (2-ethylhexanoate), dioctyltin di (2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, and dioctyl.
- organometallic catalysts such as tin oxide and lead 2-ethylhexanoate, and tertiary amines. These can be used alone or in combination of two or more.
- the amount of the curing catalyst is 0.05 to 10 parts by mass based on 100 parts by mass of the total resin solid content of the hydroxyl group-containing resin (A) and the curing agent (B). It is preferably within the range, more preferably within the range of 0.1 to 5 parts by mass, and even more preferably within the range of 0.2 to 3 parts by mass.
- the blending amount of the ultraviolet absorber is 0.1 to 10 mass based on 100 mass parts of the total resin solid content of the hydroxyl group-containing resin (A) and the curing agent (B). Is preferably in the range of 0.2 to 5 parts by mass, and more preferably in the range of 0.3 to 2 parts by mass.
- the blending amount of the light stabilizer is 0.1 to 10 mass based on 100 mass parts of the total resin solid content of the hydroxyl group-containing resin (A) and the curing agent (B). Is preferably in the range of 0.2 to 5 parts by mass, and more preferably in the range of 0.3 to 2 parts by mass.
- This paint may be a one-component paint or a multi-component paint such as a two-component paint.
- a polyisocyanate compound that is not blocked as a curing agent from the viewpoint of storage stability, a two-component paint containing a main agent containing a hydroxyl group-containing resin and a curing agent is used. It is preferable to use a mixture of both.
- the form of the paint is not particularly limited, but an organic solvent solution type or a non-aqueous dispersion type is preferable.
- the organic solvent include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, methyl benzoate, ethyl ethoxypropionate, ethyl propionate, and methyl propionate; tetrahydrofuran, dioxane, Ethers such as dimethoxyethane; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; aromatic hydrocarbons and aliphatic hydrocarbons Etc. These can be used in appropriate combination depending on the purpose such as adjustment of viscosity and adjustment of coating property.
- the solid content of the paint is not particularly limited.
- the viscosity is adjusted appropriately using a solvent such as the above organic solvent so that the viscosity according to 4 is in the range of 15 to 60 seconds.
- the solid content means a residue excluding a volatile component, and the residue may be solid or liquid at room temperature.
- the solid content mass can be calculated by taking the ratio of the amount of the remaining substance when dried to the mass before drying as the solid content rate, and multiplying the solid content rate by the sample mass before drying.
- the material to which the present paint is applied is not particularly limited.
- the vehicle body of various vehicles such as a motor vehicle, a two-wheeled vehicle, and a container formed of these, may be sufficient.
- an undercoat film such as various electrodeposition paints may be formed on the metal substrate or the vehicle body, and the undercoat film and the intermediate coat film are formed. It may be an undercoating film, an intermediate coating film, and a base coating film, and an undercoating film, an intermediate coating film, a base coating film, and a clear coating film are formed. It may be.
- the coating method of the paint is not particularly limited, and examples thereof include air spray coating, airless spray coating, rotary atomization coating, curtain coat coating, and the like, and a wet coating film is formed by these methods. Can do. In these coating methods, electrostatic application may be performed as necessary. Of these, air spray coating or rotary atomization coating is particularly preferred.
- the coating amount of the paint is preferably about 10 to 50 ⁇ m as a cured film thickness.
- the viscosity of the coating is adjusted to a viscosity range suitable for the coating, usually Ford Cup No.
- a solvent such as an organic solvent so that a viscosity range of about 15 to 60 seconds at 20 ° C. is obtained.
- Curing of the wet coating film formed by applying the coating material to the object to be coated is performed by heating, and the heating can be performed by a known heating means, such as a hot air furnace, an electric furnace, an infrared induction heating furnace, etc. Any drying oven can be used.
- the heating temperature is in the range of 60 to 180 ° C., preferably 90 to 150 ° C.
- the heating time is not particularly limited, but is preferably within the range of 10 to 60 minutes, preferably 15 to 30 minutes. Since this coating material can obtain a cured coating film excellent in both scratch resistance and coating film appearance, it can be suitably used as a top-coated top clear coat coating composition.
- This paint can be particularly suitably used as an automobile paint.
- Multi-layer coating film forming method As a multi-layer coating film forming method in which this paint is applied as a top-top clear coat paint, at least one colored base coat paint and at least one clear coat paint are sequentially applied to an object to be coated. It is a method of forming a multilayer coating film by doing, Comprising: The multilayer coating-film formation method including apply
- a solvent-type or water-based base coat paint is applied on an object to which electrodeposition coating and / or intermediate coating has been applied, and the coating film is not cured, as needed.
- preheating was performed at 40 to 90 ° C. for about 3 to 30 minutes, and this unpainted base coat film was applied as a clear coat paint.
- a method for forming a multi-layer coating film of a 2-coat 1-bake method in which the base coat and the clear coat are cured together.
- the present paint can be suitably used as a top clear coat paint in a top coat of a 3-coat 2-bake method or a 3-coat 1-bake method.
- a conventionally known normal thermosetting base coat paint can be used.
- a base resin such as an acrylic resin, a polyester resin, an alkyd resin, a urethane resin type, or the like.
- a curing agent such as an amino resin, a polyisocyanate compound, or a block polyisocyanate compound is used in combination with a reactive functional group contained in the base resin as appropriate, and a paint is further used that contains a coloring pigment or a glitter pigment. be able to.
- the base coat paint for example, an aqueous paint, an organic solvent-based paint, and a powder paint can be used.
- a conventionally known normal thermosetting clear coat paint can be used as the clear coat paint other than the uppermost layer.
- silica particles having polymerizable unsaturated group (c1) A separable flask equipped with a reflux condenser, a thermometer and a stirrer was charged with PGM-ST (trade name, manufactured by Nissan Chemical Industries, Ltd., silica average primary particle size: 15 nm). Silica concentration: 30% by mass, dispersion medium: propylene glycol monomethyl ether) After adding 333 parts (solid content 100 parts) and 10 parts deionized water, KBM-503 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., ⁇ - 10 parts of methacryloyloxypropyltrimethoxysilane) was added and the dehydration condensation reaction was carried out with stirring at 80 ° C. for 2 hours.
- PGM-ST trade name, manufactured by Nissan Chemical Industries, Ltd., silica average primary particle size: 15 nm.
- Silica concentration 30% by mass
- dispersion medium propylene glycol monomethyl ether
- Production and production example 2 of acrylic resin-coated silica particle (C) dispersion A separable flask equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen gas inlet was charged with 135 parts of propylene glycol monomethyl ether and heated to 100 ° C. under nitrogen gas flow.
- Production Examples 3 to 16 Acrylic resin-coated silica particles (C-2) to (C-15) dispersions were obtained in the same manner as in Production Example 2, except that the formulation shown in Table 1 was used.
- the component (c2-1) in the table is as follows.
- “X-22-164B” trade name, manufactured by Shin-Etsu Silicone Co., Ltd.
- “X-22-164E” trade name, manufactured by Shin-Etsu Silicone
- “X-22-2404” trade name, manufactured by Shin-Etsu Silicone Co., Ltd.
- Example 1 Acrylic resin-coated silica particle (C-1) dispersion 25 parts (solid content 10 parts), hydroxyl group-containing acrylic resin (A-1) 138 parts (solid content 83 parts) obtained in Production Example 1, and Sumidur N3300 ( The product name, manufactured by Sumitomo Bayer Urethane Co., Ltd., 17 parts (solid content 17 parts) of isocyanurate cycloaddition product of hexamethylene diisocyanate, solid content 100%) is blended so that the solid content of the paint is 40%. The mixture was diluted with ethyl ethoxypropionate and stirred to obtain a coating composition No. 1 was obtained.
- Example 2 Comparative Examples 1 to 6
- the acrylic resin-coated silica particle dispersion (C-1) was replaced with resin-coated silica particle dispersions (C-2) to (C-15) as shown in Table 2, respectively.
- the coating composition No. 2-15 were obtained.
- test plate Each coating composition No. A viscosity of 1 to 15 was added to Ford Cup #No. 4 was adjusted to a viscosity of 25 seconds at 20 ° C., and a test plate was prepared as follows for each.
- Electron GT-10 (trade name, thermosetting epoxy resin-based cationic electrodeposition paint manufactured by Kansai Paint Co., Ltd.) has a thickness of 20 ⁇ m on a 0.8 mm-thick dull steel sheet subjected to zinc phosphate conversion treatment. Electrodeposited and heated at 170 ° C. for 30 minutes to cure, and then Amirac TP-65-2 (trade name, polyester / melamine resin-based automotive intermediate coating) manufactured by Kansai Paint Co., Ltd.
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Abstract
Description
水酸基含有樹脂(A)としては水酸基を含有していれば特に限定されず、熱硬化性樹脂として公知のものを使用することができる。
例えば、アルキド樹脂、ポリエステル樹脂、アクリル樹脂、セルロース樹脂等が挙げられるが、塗膜の耐候性や耐擦傷性の点から、水酸基含有アクリル樹脂が好ましい。
上記水酸基含有アクリル樹脂は、水酸基含有重合性不飽和モノマー及び該水酸基含有重合性不飽和モノマーと共重合可能なその他の重合性不飽和モノマーを、共重合せしめることによって製造することができる。
水酸基含有重合性不飽和モノマーは、1分子中に水酸基と重合性不飽和基とをそれぞれ1個以上有する化合物である。
水酸基含有重合性不飽和モノマーに基づく水酸基は、得られる共重合体樹脂の架橋性官能基として機能する。
(2)炭素原子数3~20の脂環式炭化水素基含有重合性不飽和モノマー:例えば、イソボルニル(メタ)アクリレート、トリシクロデカニル(メタ)アクリレート、アダマンチル(メタ)アクリレート、3,5-ジメチルアダマンチル(メタ)アクリレート、3-テトラシクロドデシル(メタ)アクリレート等の炭素原子数10~20の有橋脂環式炭化水素基含有重合性不飽和モノマー、シクロヘキシル(メタ)アクリレート、4-メチルシクロヘキシルメチル(メタ)アクリレート、4-エチルシクロヘキシルメチル(メタ)アクリレート、4-メトキシシクロヘキシルメチル(メタ)アクリレート、t-ブチルシクロヘキシル(メタ)アクリレート、シクロオクチル(メタ)アクリレート、シクロドデシル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート等の炭素原子数3~12の脂環式炭化水素基を有する重合性不飽和モノマー。
(4)(メタ)アクリル酸の炭素数1~7の直鎖状又は分岐状アルキルエステル:メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート等。
(6)エポキシ基含有重合性不飽和モノマー:例えば、グリシジル(メタ)アクリレート等。
(7)窒素含有重合性不飽和モノマー:例えば、(メタ)アクリルアミド、N,N-ジメチルアミノエチル(メタ)アクリレート、ビニルピリジン、ビニルイミダゾール等。
(8)その他のビニル化合物:例えば、酢酸ビニル、プロピオン酸ビニル、塩化ビニル、塩化ビニリデン、ジビニルエーテル、バーサティック酸ビニルエステルである「ベオバ9」、「ベオバ10」(商品名、ジャパンエポキシレジン社製)等。
(9)不飽和基含有ニトリル化合物:例えば、(メタ)アクリロニトリル等。
上記その他の共重合可能な重合性不飽和モノマーは、単独で又は2種以上を組み合わせて用いることができる。
水酸基含有重合性不飽和モノマーの使用割合は、耐擦傷性及び仕上り性の点から、共重合モノマー成分の全質量に基づいて、15~50質量%、好ましくは20~45質量%であることが適当である。
また、その他の重合性不飽和モノマーとして、仕上り性及び耐水性の点から、モノマー(2)を使用することが望ましく、その使用割合は、共重合モノマー成分の全質量に基づいて、3~40質量%程度、好ましくは5~30質量%程度であることが適当である。
また、その他の重合性不飽和モノマーとして、被塗物へのヌレ性及び仕上り性の点から、モノマー(3)を使用することが望ましく、その使用割合は、共重合モノマー成分の全質量に基づいて、3~45質量%程度、好ましくは8~40質量%程度であることが適当である。
また、上記共重合モノマー成分の全質量に基づいて、塗膜の耐酸性と耐擦傷性とのいずれにも極めて優れる樹脂を得る観点から、モノマー(1)、モノマー(2)及びモノマー(3)の合計質量は、共重合モノマー成分の全質量に基づいて、35~85質量%程度、好ましくは40~80質量%程度の範囲内であることが適当である。
水酸基含有アクリル樹脂の水酸基価は、耐擦傷性及び耐水性の両立の観点から、好ましくは10~200mgKOH/g、さらに好ましくは50~200mgKOH/g、さらに特に好ましくは80~200mgKOH/gの範囲内である。
水酸基含有アクリル樹脂の重量平均分子量は、耐酸性と仕上り性の観点から、好ましくは、5,000~30,000の範囲内であり、さらに好ましくは5,000~20,000、さらに特に好ましくは10,000~20,000の範囲内である。
水酸基含有アクリル樹脂のガラス転移温度は、塗膜硬度及び仕上り性の点から、-30℃~30℃、特に-20℃~20℃の範囲内であることが好ましい。
硬化剤としては、ポリイソシアネート化合物(ブロックしたものも含む)や、メラミン樹脂、グアナミン樹脂及び尿素樹脂等のアミノ樹脂を用いることができる。耐候性、耐擦傷性、塗膜硬度、付着性等により優れた塗膜を得る観点から、ポリイソシアネート化合物及び/又はメラミン樹脂が好ましい。
ポリイソシアネート化合物としては、例えば、ヘキサメチレンジイソシアネートもしくはトリメチルヘキサメチレンジイソシアネートの如き脂肪族ジイソシアネート類;水素添加キシリレンジイソシアネートもしくはイソホロンジイソシアネートの如き環状脂肪族ジイソシアネート類;トリレンジイソシアネートもしくは4,4′-ジフェニルメタンジイソシアネートの如き芳香族ジイソシアネート類などの有機ジイソシアネートそれ自体、又はこれらの各有機ジイソシアネートと多価アルコール、低分子量ポリエステル樹脂もしくは水等との付加物、あるいは上記した如き各有機ジイソシアネート同志の環化重合体、更にはイソシアネート・ビウレット体等が挙げられるが、これらのポリイソシアネート化合物をブロック化剤でブロックしたものも用いることができる。ブロックイソシアネート化合物を用いる場合には解離触媒を併用することが好ましい。
ブロックされたイソシアネート基を有するポリイソシアネート化合物としては、上記、フリーのイソシアネート基を有するポリイソシアネート化合物をオキシム、フェノール、アルコール、ラクタム、マロン酸エステル、メルカプタン等の公知のブロック剤でブロックしたものが挙げられる。これらの代表的な市販品の例としては、バーノックD-550(商品名、DIC株式会社製)又はデュラネートSBN-70(商品名、旭化成株式会社製)等が挙げられる。
アクリル樹脂被覆シリカ粒子(C)分散体は、重合性不飽和基を有するシリカ粒子(c1)と重合性不飽和モノマー(c2)との、(c1):(c2)=20:80~90:10の質量比での反応物である、アクリル樹脂被覆シリカ粒子分散体であって、かつ該重合性不飽和モノマー(c2)がその成分の少なくとも一部として、後述する特定の重合性不飽和モノマー(c2-1)を含み、かつシリカ粒子を被覆する樹脂の分子量が400~6000のものである。
重合性不飽和基を有するシリカ粒子(c1)は、例えばシリカ粒子(d)、有機溶剤(e)、ならびに重合性不飽和基及び加水分解性シリル基を有するモノマー(f)を混合加熱することによって得ることができる重合性不飽和基を有するシリカ粒子(c1-i)を用いることもできるし、該重合性不飽和基を有するシリカ粒子(c1-i)にさらに3級アミン(g)を添加して得られる重合性不飽和基含有シリカ粒子(c1-ii)を用いることもできる。塗料の貯蔵性の観点及び得られる塗膜の耐擦り傷性の観点等から、重合性不飽和基を有するシリカ粒子(c1)としては(c1-ii)を用いることが好ましい。
シリカ粒子(d)は、後述する重合性不飽和基及び加水分解性シリル基を有するモノマー(f)との反応により共有結合を形成することによって、重合性不飽和基による表面修飾を行うことが可能なシリカ粒子であれば、何れでも使用することができる。このようなシリカ粒子(d)としては、乾式シリカ、湿式シリカ、シリカゲル、カルシウムイオン交換シリカ微粒子、コロイダルシリカ等を挙げることができるが、特に、水酸基及び/又はアルコキシ基を粒子表面に有し、分散媒に分散されたシリカ微粒子であるコロイダルシリカが好ましい。
本明細書において、「平均一次粒子径」は、体積基準粒度分布のメジアン径(d50)を意味し、体積基準の粒度分布は、レーザー回折/散乱法によって測定される。本発明において、本分散体の体積基準の粒度分布は、レーザー回折/散乱式粒度分布測定装置「マイクロトラックNT3300」(商品名、日機装社製)を使用して測定した。その際、サンプル濃度は装置に設定された所定の透過率の範囲となるように調整した。
有機溶剤(e)は、親水性有機溶剤であることが好ましく、該親水性有機溶剤としては、例えば、メタノール、エタノール、イソプロパノール、n-ブタノール、イソブタノール等のアルコール系有機溶剤;ジオキサン、テトラヒドロフラン等のエーテル系有機溶剤;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノn-プロピルエーテル、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノn-ブチルエーテル、エチレングリコールモノイソブチルエーテル、エチレングリコールモノtert-ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノn-プロピルエーテル、ジエチレングリコールモノイソプロピルエーテル、ジエチレングリコールモノn-ブチルエーテル、ジエチレングリコールモノイソブチルエーテル、ジエチレングリコールモノtert-ブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノn-プロピルエーテル、プロピレングリコールモノイソプロピルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノn-プロピルエーテル、ジプロピレングリコールモノイソプロピルエーテル等のグリコールエーテル系有機溶剤;酢酸エチル、酢酸ブチル、酢酸イソブチル、3-メトキシブチルアセテート等のエステル系有機溶剤等が挙げられ、これらは単独で、または2種以上組み合わせて使用することができる。
なかでも、貯蔵性及び耐擦り傷性等の観点から、沸点が64~132℃、好ましくは沸点が82~118℃のアルコール類及び沸点が120~208℃、好ましくは沸点が120~192℃のグリコールエーテル類が好ましい。
なかでも、貯蔵性及び耐擦り傷性等の観点から、炭素数2~8、好ましくは3~5のアルコール類及び炭素数3~5、好ましくは3~4のグリコールエーテル類が好ましい。
重合性不飽和基及び加水分解性シリル基を有するモノマー(f)は、例えば、3-(メタ)アクリロイルオキシプロピルトリメトキシシラン、3-(メタ)アクリロイルオキシプロピルトリエトキシシラン、2-(メタ)アクリロイルオキシエチルトリメトキシシラン、2-(メタ)アクリロイルオキシエチルトリエトキシシラン、3-(メタ)アクリロイルオキシプロピルメチルジメトキシシラン、2-(メタ)アクリロイルオキシエチルメチルジメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、アリルトリメトキシシラン、アリルトリエトキシシラン、各種シランカップリング剤の有する加水分解性シリル基以外の官能基と不飽和化合物の不飽和基以外の官能基との反応により得られる重合性不飽和基及び加水分解性シリル基を有するモノマー等を挙げることができる。
より詳細には、分散媒に分散したシリカ粒子(d)と、有機溶剤(e)と、重合性不飽和基及び加水分解性シリル基を有するモノマー(f)とを混合し、この混合物から、有機溶剤(e)及びシリカ粒子(d)の分散媒(重合性不飽和基及び加水分解性シリル基を有するモノマーを加水分解して生じた低級アルコールを含む。)を常圧又は減圧下で共沸留出させ、分散媒を上記有機溶剤(e)に置換しながら、又は置換した後に、加熱下で脱水縮合反応させることにより製造することができる。
重合性不飽和基及び加水分解性シリル基を有するモノマー(f)の割合が約0.2質量部未満であると、生成する重合性不飽和基を有するシリカ粒子(c1-i)が、分散媒中で安定性に劣る場合がある。重合性不飽和基及び加水分解性シリル基を有するモノマー(f)の割合が約95質量部よりも多いと、シリカ粒子(d)との反応において重合性不飽和基及び加水分解性シリル基を有するモノマー(f)が未反応のまま残存する場合がある。
3級アミン(g)は、分子量が120~380、好ましくは130~350、さらに好ましくは150~300でありかつ末端がアルキル基及び/又はアリール基である3級アミン(g)であれば特に制限なく用いることができる。
3級アミン(g)としては、貯蔵性及び耐擦り傷性等の観点から、3級アミン(g)の有するアルキル基のうち少なくとも1つが炭素数3以上、好ましくは4~12、さらに好ましくは5~10のアルキル基であることが好適である。
なかでも、貯蔵性及び耐擦り傷性等の観点から、特に3級アミン(g)の有するアルキル基のうち少なくとも1つが直鎖状のアルキル基であることが好ましい。
トリプロピルアミン、トリブチルアミン、トリ-n-ペンチルアミン、トリ-n-ヘキシルアミン、トリ-n-ヘプチルアミン、トリ-n-オクチルアミン等の直鎖3級アミン;
トリイソプロピルアミン、トリイソブチルアミン、トリ-2-エチルヘキシルアミン等の分岐トリトリデシルアミン等の分岐3級アミン;
ジメチルオクチルアミン、ジメチルドデシルアミン、ジメチルオクタデシルアミン、ヘキシルジエチルアミン、オクチルジエチルアミン、ジエチルドデシルアミン等の混合炭化水素基を有する三級アミン;
ジメチルシクロヘキシルアミン、トリシクロヘキシルアミン等の脂環3級アミン;
ジメチルベンジルアミン、トリベンジルアミン等の芳香環置換基を持つ3級アミン;
等が挙げられる。これらのうちの1種または2種以上を組み合わせて用いてもよい。
上記3級アミン(g)の使用量としては、貯蔵安定性、及び、塗料に配合した際に得られる塗膜の耐擦り傷性等の観点から、重合性不飽和基含有シリカ粒子(i)の固形分100質量部を基準として0.1~5.0質量部、好ましくは1.5~3.0質量部、さらに好ましくは1.7~2.5質量部であることが好適である。
かくして重合性不飽和基含有シリカ粒子(c1-ii)分散液を得ることができる。
重合性不飽和モノマー(c2)はその成分の少なくとも一部として、特定の重合性不飽和モノマー(c2-1)を含む。
モノマー(c2-1)は、下記式(I)
で示される重合性不飽和モノマーである。
また上記式(II)において、R2は互いに同一でも異なっていても良いフェニル基又は炭素数1~6のアルキル基を示すが、好ましくは炭素数1~3のアルキル基であり、さらに好ましくはメチル基である。
さらにまた上記式(II)において、R3は炭素数1~6のアルキレン基を示すが、好ましくは炭素数1~3のアルキレン基であり、さらに好ましくはメチレン基である。
重合性不飽和モノマー(c2)におけるモノマー(c2-1)の占める割合は、重合性不飽和モノマー全量を基準として0.01~15質量%、好ましくは0.05~5質量%、さらに好ましくは0.1~3質量%であることが好適である。
モノマー(c2-2)は、1分子中に1個以上の重合性不飽和基を有する化合物であり、(c2-1)以外のモノマーである。その具体例を以下に列挙する。
(6)芳香族系重合性不飽和モノマー:例えば、スチレン、α-メチルスチレン、ビニルトルエン等。
(7)グリシジル基含有重合性不飽和モノマー:1分子中にグリシジル基と不飽和結合とをそれぞれ1個有する化合物で、具体的にはグリシジルアクリレート、グリシジルメタクリレート等。
(9)その他のビニル化合物:例えば、酢酸ビニル、プロピオン酸ビニル、塩化ビニル、バーサティック酸ビニルエステルである「ベオバ9」、「ベオバ10」(商品名、ジャパンケムテック社製)等。
(10)不飽和結合含有ニトリル系化合物:例えば、アクリロニトリル、メタクリロニトリル等。
なお、本明細書において、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)アクリロイル基等が挙げられる。
また、本明細書において、「(メタ)アクリレート」は「アクリレート又はメタクリレート」を意味する。「(メタ)アクリル酸」は、「アクリル酸又はメタクリル酸」を意味する。また、「(メタ)アクリロイル」は、「アクリロイル又はメタクリロイル」を意味する。また、「(メタ)アクリルアミド」は、「アクリルアミド又はメタクリルアミド」を意味する。
また、形成される塗膜の耐擦り傷性、耐酸性、耐汚染性及び塗膜外観の観点から、重合性不飽和モノマー(c2-2)としては、少なくともその一部として、上記(2)脂環式炭化水素基を有する重合性不飽和モノマーを含有することが好ましい。なかでも、耐酸性および耐汚染性の観点から、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレートを含有することが好ましい。重合性不飽和モノマー(c2-2)が、少なくともその一部として上記(2)脂環式炭化水素基を有する重合性不飽和モノマーを含有する場合、その量は、重合性不飽和モノマー(c2-2)を基準として5~60質量%、好ましくは10~55質量%、さらに好ましくは20~50質量%であることが好適である。
アクリル樹脂被覆シリカ粒子(C)分散体は重合性不飽和基を有するシリカ粒子(c1)と、重合性不飽和モノマー(c2)とを、溶媒の存在下で重合反応させることにより得ることができる。該重合方法としては特に限定されるものではなく、それ自体既知の重合方法を用いることができるが、なかでも、有機溶剤中にて、適宜、触媒、重合開始剤等の存在下で重合を行う溶液重合法を好適に使用することができる。
また、上記製造方法によって得られたアクリル樹脂被覆シリカ粒子(C)分散体においてシリカ粒子を被覆している樹脂の水酸基価は、形成される塗膜の耐擦り傷性の観点から、50~200mgKOH/g、特に70~200mgKOH/g、さらに特に100~200mgKOH/gの範囲内であることが好ましい。
また、上記製造方法によって得られたアクリル樹脂被覆シリカ粒子(C)分散体においてシリカ粒子を被覆している樹脂のガラス転移温度Tgは、形成される塗膜の耐擦り傷性の観点から、-40~40℃の範囲内であることが好ましく、-30~30℃の範囲内であることがさらに好ましい。
1/Tg(K)=W1/T1+W2/T2+・・・Wn/Tn
Tg(℃)=Tg(K)-273
式中、W1、W2、・・・Wnは各モノマーの質量分率であり、T1、T2・・・Tnは各モノマーのホモポリマーのガラス転移温度Tg(K)である。
なお、各モノマーのホモポリマーのガラス転移温度は、POLYMER HANDBOOK Fourth Edition,J.Brandrup,E.h.Immergut,E.A.Grulke編(1999年)による値であり、該文献に記載されていないモノマーのガラス転移温度は、該モノマーのホモポリマーを重量平均分子量が5万程度になるようにして合成し、そのガラス転移温度をセイコー電子工業DSC220U(示差走査型熱量計)により測定した値である。測定は試料50mgを専用のサンプル皿に所定量秤取し、130℃で3時間乾燥させた後、不活性気体中で、-50℃から10℃/分のスピードで150℃まで昇温し、得られた熱量変化カーブの変曲点の温度を読み取ることにより行った。
本塗料は、さらに、硬化触媒、顔料、紫外線吸収剤(例えばベンゾトリアゾール系吸収剤、トリアジン系吸収剤、サリチル酸誘導体系吸収剤、ベンゾフェノン系吸収剤等)、光安定剤(例えば、ヒンダードピペリジン類等)、増粘剤、消泡剤、可塑剤、有機溶剤、表面調整剤、沈降防止剤等の通常の塗料用添加剤等を、それぞれ単独でもしくは2種以上組合せて含有させることができる。
有機溶剤としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類;酢酸エチル、酢酸ブチル、安息香酸メチル、エトキシプロピオン酸エチル、プロピオン酸エチル、プロピオン酸メチル等のエステル類;テトラヒドロフラン、ジオキサン、ジメトキシエタン等のエーテル類;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、3-メトキシブチルアセテート等のグリコールエーテル類;芳香族炭化水素類、脂肪族炭化水素類等が挙げられる。
これらは、粘度の調整、塗布性の調整等の目的に応じて適宜組合せて使用することができる。
本明細書において固形分とは、揮発成分を除いた残存物を意味するものであり、残存物は常温で固形状であっても液状であっても差し支えない。固形分質量は、乾燥させた時の残存物質量の乾燥前質量に対する割合を固形分率とし、固形分率を乾燥前の試料質量に乗じることで算出することができる。
本塗料を適用される被塗物としては、特に限定されるものではない。例えば、冷延鋼板、亜鉛メッキ鋼板、亜鉛合金メッキ鋼板、ステンレス鋼板、錫メッキ鋼板等の鋼板、アルミニウム板、アルミニウム合金板等の金属基材;各種プラスチック素材等を挙げることができる。またこれらにより形成された自動車、二輪車、コンテナ等の各種車両の車体であってもよい。
本塗料の塗装方法としては、特に限定されないが、例えば、エアスプレー塗装、エアレススプレー塗装、回転霧化塗装、カーテンコート塗装等の塗装方法が挙げられ、これらの方法によりウエット塗膜を形成することができる。これらの塗装方法では、必要に応じて、静電印加してもよい。これらのうちでは、エアスプレー塗装又は回転霧化塗装が特に好ましい。
また、エアスプレー塗装、エアレススプレー塗装及び回転霧化塗装を行う場合には、本塗料の粘度を、該塗装に適した粘度範囲、通常、フォードカップNo.4粘度計において、20℃で15~60秒程度の粘度範囲となるように、有機溶剤等の溶媒を用いて、適宜、調整しておくことが好ましい。
本塗料は、耐擦り傷性及び塗膜外観のいずれにも優れる硬化塗膜を得ることができることから、上塗りトップクリヤコート塗料組成物として好適に用いることができる。本塗料は、自動車用塗料として特に好適に用いることができる。
本塗料が上塗りトップクリヤコート塗料として塗装される複層塗膜形成方法としては、被塗物に順次、少なくとも1層の着色ベースコート塗料及び少なくとも1層のクリヤコート塗料を塗装することにより複層塗膜を形成する方法であって、最上層のクリヤコート塗料として本発明の塗料組成物を塗装することを含む複層塗膜形成方法を挙げることができる。
また、ベースコート塗料としては、例えば、水性塗料、有機溶剤系塗料、粉体塗料を用いることができる。
複層塗膜形成方法において、クリヤコートを2層以上塗装する場合、最上層以外のクリヤコート塗料としては、従来から公知の通常の熱硬化型クリヤコート塗料を使用することができる。
製造例1
撹拌装置、温度計、冷却管、窒素ガス導入口を備えた四ツ口フラスコに、3-エトキシプロピオン酸エチル 31部を仕込み、窒素ガス通気下で155℃に昇温した。155℃に達した後、窒素ガスの通気を止め、下記に示すモノマーと重合開始剤からなる組成配合のモノマー混合物を4時間かけて滴下した。
2-ヒドロキシプロピルアクリレート 24.0部、
スチレン 20.0部、
イソボルニルアクリレート 20.8部、
2-エチルヘキシルアクリレート 34.2部、
アクリル酸 1.0部、及び
ジ-tert-アミルパーオキサイド 4.0部、
ついで、155℃で窒素ガスを通気しながら2時間熟成させた後、100℃まで冷却し、酢酸ブチル32.5部で希釈することにより、固形分60%の水酸基含有アクリル樹脂(A-1)溶液を得た。また、この共重合体の重量平均分子量は13,000、水酸基価は103mgKOH/g、ガラス転移温度は-11.0℃であった。
還流冷却器、温度計及び攪拌機を取り付けたセパラブルフラスコに、PGM-ST(商品名、日産化学工業社製、シリカ平均一次粒子径;15nm、シリカ濃度;30質量%、分散媒;プロピレングリコールモノメチルエーテル) 333部(固形分100部)及び脱イオン水 10部を入れた後、KBM-503(商品名、信越化学工業社製、γ-メタクリロイルオキシプロピルトリメトキシシラン) 10部を添加し、80℃で2時間攪拌しながら脱水縮合反応を行い、その後、フッ化テトラ-n-ブチルアンモニウム 0.03部を加えて更に1時間攪拌しながら反応させた。反応終了後、プロピレングリコールモノメチルエーテル 30部を添加し、次いで減圧状態で揮発成分を留出させて、表面が修飾されたシリカ粒子の固形分40%の重合性不飽和基含有シリカ粒子分散液を得た。該重合性不飽和基含有シリカ粒子分散液250部(固形分100部)にトリオクチルアミン1.9部を混合して撹拌し、固形分40%の重合性不飽和基含有シリカ粒子(c1)分散液を得た。
製造例2
還流冷却器、温度計、攪拌機及び窒素ガス導入口を取り付けたセパラブルフラスコに、プロピレングリコールモノメチルエーテル 135部を仕込み、窒素ガス通気下で100℃まで昇温した。100℃に達した後、上記重合性不飽和基含有シリカ粒子(c1)分散液 250部(固形分100部)と「X-22-164AS」(商品名、信越シリコーン社製、式(I)のR1基:メチル基、式(I)のX基:メタクリル基、式(II)のR2基:メチル基、式(II)のm:12) 2部、スチレン 20部、4-ヒドロキシブチルアクリレート 35.5部、イソボルニルアクリレート 41.5部、アクリル酸 1部、2,2アゾビス(2-メチルブチロニトリル)(商品名V-59、和光純薬工業製) 2.5部の混合物を、2時間かけて滴下した。次いで、100℃で1時間熟成させた後、V-59 0.83部及びプロピレングリコールモノメチルエーテル 20部の混合溶液を、0.5時間かけて滴下し、更に2時間熟成させた。不揮発分から求めた重合率は99%であった。その後、エトキシエチルプロピオネートを加え、減圧状態で共沸留出することにより溶剤を置換し、実測された不揮発分が40%であるアクリル樹脂被覆シリカ粒子(C-1)分散体を得た。
表1に示す配合とする以外は製造例2と同様にして、アクリル樹脂被覆シリカ粒子(C-2)~(C-15)分散体を得た。
「X-22-164B」:商品名、信越シリコーン社製、式(I)のR1基:メチル基、式(I)のX基:メタクリル基、式(II)のR2基:メチル基、式(II)のR3基:アルキレン基、式(II)のm:44、
「X-22-164E」:商品名、信越シリコーン社製、式(I)のR1基:メチル基、式(I)のX基:メタクリル基、式(II)のR2基:メチル基、式(II)のR3基:アルキレン基、式(II)のm:105、
「X-22-2404」:商品名、信越シリコーン社製、式(I)のR1基:メチル基、式(I)のX基:アルキル基、式(II)のR2基:メチル基、式(II)のR3基:アルキレン基、式(II)のm:6、
「KF-2012」:商品名、信越シリコーン社製、式(I)のR1基:メチル基、式(I)のX基:アルキル基、式(II)のR2基:メチル基、式(II)のR3基:アルキレン基、式(II)のm:62、
「X-22-164」:商品名、信越シリコーン社製、式(I)のR1基:メチル基、式(I)のX基:メタクリル基、式(II)のR2基:メチル基、式(II)のR3基:アルキレン基、式(II)のm:5、
「X-22-2426」:商品名、信越シリコーン社製、式(I)のR1基:メチル基、式(I)のX基:アルキル基、式(II)のR2基:メチル基、式(II)のR3基:アルキレン基、式(II)のm:162。
実施例1
アクリル樹脂被覆シリカ粒子(C-1)分散体 25部(固形分10部)、製造例1で得た水酸基含有アクリル樹脂(A-1) 138部(固形分83部)、及び スミジュール N3300(商品名、住友バイエルウレタン社製、ヘキサメチレンジイソシアネートのイソシアヌレート環付加物、固形分含有率100%)17部(固形分17部)を配合し、塗料固形分が40%になるように3-エトキシプロピオン酸エチルで希釈攪拌して、塗料組成物 No.1を得た。
実施例1において、アクリル樹脂被覆シリカ粒子分散体(C-1)を、表2に示すようにそれぞれ樹脂被覆シリカ粒子分散体(C-2)~(C-15)に替えたこと以外は実施例1と同様に行い、塗料組成物 No.2~15を得た。
上記各塗料組成物No.1~15の粘度を、酢酸ブチルを添加してフォードカップ#No.4を用いて20℃で25秒の粘度に調整し、それぞれについて以下の様にして試験板を作製した。
リン酸亜鉛化成処理を施した厚さ0.8mmのダル鋼板上に、エレクロンGT-10(関西ペイント社製、商品名、熱硬化性エポキシ樹脂系カチオン電着塗料)を膜厚が20μmになるように電着塗装し、170℃で30分間加熱し硬化させ、その上にアミラックTP-65-2(関西ペイント社製、商品名、ポリエステル・メラミン樹脂系自動車中塗り塗料)を膜厚35μmとなるようにエアスプレー塗装し、140℃で30分間加熱硬化させた。該塗膜上に溶剤ベースコートネオアミラック US-300(C)No202(関西ペイント社製、アクリル・メラミン樹脂系自動車用上塗ベースコート塗料、黒塗色)を膜厚15μmとなるように塗装し、室温で5分間放置してから、140℃で30分間加熱硬化させた。その後、該硬化塗膜上に上記実施例及び比較例にて製造・粘度調整した各塗料組成物を膜厚35μmとなるように塗装し、室温で10分間放置してから、140℃で20分間加熱し硬化させることにより試験板を得た。得られたそれぞれの試験板を常温で7日間静置してから下記塗膜性能試験を行なった。
塗料組成物の貯蔵安定性
前記実施例で得られた塗料組成物(1)~(15)について、フォードカップNo.4で測定した製造直後の粘度(秒)と、40℃で1週間静置した後の粘度(秒)の変化率によって評価した。○、△が合格、×が不合格である。
変化率(%)=40℃1週間後の粘度(秒)/製造直後の粘度(秒)×100
○:5%以内
△:5~10%未満
×:10%以上
上記で得られた各試験板を、20℃雰囲気下で洗車試験機(Amtec社製、Car-wash Lab Apparatus)の試験台に固定し、試験板の上にSikron SH200(商品名、粒径24μmのシリカ微粒子、Quarzwerke社製)を水1リットルに対して1.5g混合させた試験液を噴霧しながら、洗車ブラシを127rpmで回転させて試験台を10往復させた。その後、水洗および乾燥を行い、試験前後の20°光沢を光沢計(Byk-Gardner社製、装置名:Micro Tri Gross)を用いて測定し、下式より光沢保持率を算出した。 ○が合格、△、×が不合格である。
試験後の光沢/初期光沢×100
○:70%以上
△:50~70%未満
×:50%未満
上記で得られた各試験板について学振型摩擦試験機(スガ試験株式会社、FR-2S)を用いて9Nの摩擦力で15往復させる。その際に使用するサンドペーパーは#2400である。試験後、塗膜表面をエアスプレーした後に試験前後の20°光沢を光沢計(Byk-Gardner社製、装置名:Micro Tri Gross)を用いて測定し、下式より光沢保持率を算出した。 ○が合格、△、×が不合格である。
試験後の光沢/初期光沢×100
○:65%以上
△:40~65%未満
×:40%未満
Claims (5)
- 水酸基含有樹脂(A)、硬化剤(B)、及びアクリル樹脂被覆シリカ粒子(C)分散体を含有する塗料組成物であって、アクリル樹脂被覆シリカ粒子(C)分散体が、重合性不飽和基を有するシリカ粒子(c1)と重合性不飽和モノマー(c2)との、(c1):(c2)=20:80~90:10の質量比での反応物である、アクリル樹脂被覆シリカ粒子分散体であり、かつ該重合性不飽和モノマー(c2)がその成分の少なくとも一部として、下記式(I)
で示される重合性不飽和モノマー(c2-1)を含み、さらにシリカ粒子を被覆する樹脂の分子量が400~6000である、塗料組成物。 - 式(II)中のR2がメチル基である、請求項1に記載の塗料組成物。
- アクリル樹脂被覆シリカ粒子(C)分散体の含有量が、水酸基含有樹脂(A)及び硬化剤(B)の合計固形分を基準として1~15質量%の範囲内である、請求項1又は2に記載の塗料組成物。
- 請求項1乃至3のいずれか一項に記載の塗料組成物を塗装して得られる塗膜を含む、物品。
- 被塗物に順次、少なくとも1層の着色ベースコート塗料及び少なくとも1層のクリヤコート塗料を塗装することにより、複層塗膜を形成する方法であって、最上層のクリヤコート塗料として請求項1乃至3のいずれか一項に記載の塗料組成物を塗装することを含む、複層塗膜形成方法。
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JPWO2020203063A1 (ja) * | 2019-03-29 | 2020-10-08 | ||
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WO2022097418A1 (ja) * | 2020-11-09 | 2022-05-12 | 関西ペイント株式会社 | 塗料組成物及び複層塗膜形成方法 |
JP7071606B1 (ja) * | 2021-03-08 | 2022-05-19 | 関西ペイント株式会社 | アクリル樹脂変性シリカ粒子、塗料組成物及び複層塗膜形成方法 |
WO2022190464A1 (ja) * | 2021-03-08 | 2022-09-15 | 関西ペイント株式会社 | アクリル樹脂変性シリカ粒子、塗料組成物及び複層塗膜形成方法 |
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JP6869184B2 (ja) | 2021-05-12 |
KR20180063047A (ko) | 2018-06-11 |
US10472537B2 (en) | 2019-11-12 |
KR102577481B1 (ko) | 2023-09-12 |
CA2999405A1 (en) | 2017-04-06 |
CA2999405C (en) | 2023-07-04 |
ES2800063T3 (es) | 2020-12-23 |
JPWO2017056911A1 (ja) | 2018-07-19 |
CN108026411B (zh) | 2020-11-27 |
EP3357984A4 (en) | 2019-06-26 |
CN108026411A (zh) | 2018-05-11 |
US20180265730A1 (en) | 2018-09-20 |
EP3357984B1 (en) | 2020-04-29 |
EP3357984A1 (en) | 2018-08-08 |
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