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WO2015087920A1 - Composition de revêtement - Google Patents

Composition de revêtement Download PDF

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Publication number
WO2015087920A1
WO2015087920A1 PCT/JP2014/082703 JP2014082703W WO2015087920A1 WO 2015087920 A1 WO2015087920 A1 WO 2015087920A1 JP 2014082703 W JP2014082703 W JP 2014082703W WO 2015087920 A1 WO2015087920 A1 WO 2015087920A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydroxyl group
acid
group
meth
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2014/082703
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English (en)
Japanese (ja)
Inventor
森田　鋭昭
裕二 鵜澤
山田　祐輝
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kansai Paint Co Ltd
Original Assignee
Kansai Paint Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kansai Paint Co Ltd filed Critical Kansai Paint Co Ltd
Priority to JP2015552487A priority Critical patent/JPWO2015087920A1/ja
Publication of WO2015087920A1 publication Critical patent/WO2015087920A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
    • C08G18/2027—Heterocyclic amines; Salts thereof containing one heterocyclic ring having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00

Definitions

  • the present invention relates to a coating composition that is excellent in curability at a low temperature and in a short time, can achieve both pot life (pot life), and can obtain a cured coating film that is excellent in finished appearance.
  • after electrodeposition coating usually an intermediate coating and a top coating are applied in order, and conventionally, after an intermediate coating and a top coating are applied, baking is performed each time.
  • the top coat was painted, the development of a reduction in the baking process in which the intermediate coating film and the top coating film were baked at one time was being developed. It is becoming.
  • a hydroxyl group / isocyanate group cross-linking coating material in which a hydroxyl group-containing resin is cured using a polyisocyanate compound as a cross-linking agent is considered to be promising. It has been studied so far.
  • Patent Document 1 as a coating composition excellent in low-temperature curability, a pyrazole block polyisocyanate compound containing two or more tertiary isocyanate groups blocked with a pyrazole compound in one molecule, a specific hydroxyl value and a weight are disclosed.
  • a coating composition comprising a hydroxyl group-containing resin having an average molecular weight as an essential component is disclosed.
  • this coating composition has insufficient curability under short-time conditions.
  • Patent Document 2 discloses, as a coating composition excellent in low-temperature curability, a resin component containing a polyester polyol and an acrylic polyol having a specific hydroxyl value, a crosslinking agent that may contain melamine as an essential component of blocked isocyanate, A one-component low-temperature curing colored enamel paint containing a blocked isocyanate dissociation catalyst comprising at least a dicarboxylate salt of dibutyltin and a pigment is disclosed.
  • this coating composition has insufficient curability under low temperature baking conditions.
  • Patent Document 3 contains a polyol (A1), a polyether polyol (B), and a solvent (C), and the paint resin composition mainly characterized in that the polyol (A1) has a ring structure; ) A curable coating composition containing a polyisocyanate compound, and a curable coating composition characterized in that the curable coating composition further contains a metal organic compound and an acidic substance.
  • this coating composition is excellent in low-temperature short-time curability in an embodiment containing the metal organic compound and the acidic substance, but has an insufficient pot life and an insufficient finished appearance of the resulting coating film. There was a case.
  • JP 2005-225907 A Japanese Patent Laid-Open No. 10-101996 JP 2002-97412 A
  • An object of the present invention is to provide a coating composition capable of obtaining a cured coating film which is excellent in curability and pot life (pot life) in a low temperature and in a short time, and also excellent in finished appearance.
  • the present invention (A) a hydroxyl group-containing acrylic resin having a hydroxyl value of 50 to 200 mg KOH / g, (B) a polyisocyanate compound, (C) an organometallic catalyst comprising a zinc compound and an amidine compound, and (D) at least selected from ⁇ -diketones, ⁇ -keto acid esters, malonic acid esters, ketones having a hydroxyl group at the ⁇ -position, aldehydes having a hydroxyl group at the ⁇ -position, and esters having a hydroxyl group at the ⁇ -position Contains one blocking agent, Provided is a coating composition characterized in that the amount of the blocking agent (D) is in the range of 0.7 to 25% by mass based on the total amount of the hydroxyl group-containing acrylic resin (A) and the polyisocyanate compound (B). To do.
  • the coating composition of the present invention contains an organometallic catalyst composed of a zinc compound and an amidine compound as a catalyst for a crosslinking reaction between a hydroxyl group-containing resin and a polyisocyanate compound, it is curable at a low temperature and in a short time. Is excellent.
  • the blocking agent selected from specific compounds such as ⁇ -diketone has a particularly high blocking effect especially on organometallic catalysts composed of zinc compounds and amidine compounds, it is extremely excellent in pot life.
  • a coating composition can be obtained.
  • the organometallic catalyst forms a complex structure in which the amidine compound is coordinated with the zinc compound, and this amidine compound becomes a steric hindrance, so that the structure in which the amidine compound is coordinated. This is considered to be because the catalytic activity of the urethanization reaction originally possessed by the zinc compound (zinc ion) can be suppressed.
  • the amidine compound dissociates at a relatively low temperature, the coordinated amidine compound is detached when the low dissociation temperature is reached, the metal compound is regenerated, and the urethane inherent in the metal compound (metal ion) It is considered that a coating composition having excellent curability at a low temperature in a short time can be obtained by the action of the catalytic activity of the conversion reaction.
  • blocking agents selected from specific compounds such as ⁇ -diketones have a particularly high blocking effect on organometallic catalysts composed of zinc compounds and amidine compounds, so that they are extremely effective in pot life. Are better.
  • the secondary hydroxyl group has a slower reaction rate than a primary hydroxyl group usually used as a hydroxyl group, and a urethane using a metal compound as a catalyst. It is considered that a cured coating film having an excellent finished appearance can be obtained because the rate of the oxidization reaction can be controlled to such an extent that the finish can be sufficiently ensured.
  • the coating composition of the present invention it is possible to obtain a cured coating film that is extremely excellent in curability and pot life (pot life) in a low temperature and in a short time, and further excellent in finished appearance. Can be provided.
  • the coating composition of the present invention (hereinafter sometimes referred to as “the present coating”) will be described in detail.
  • the coating composition of the present invention has a hydroxyl group-containing acrylic resin having a specific hydroxyl value (hereinafter, the hydroxyl group-containing acrylic resin having a specific hydroxyl value defined in the present invention may be referred to as a hydroxyl group-containing acrylic resin (A)).
  • an organometallic catalyst comprising a polyisocyanate compound (B), a zinc compound and an amidine compound (hereinafter sometimes referred to as an organometallic catalyst (C)), and at least one selected from a specific compound such as ⁇ -diketone
  • This coating composition contains a blocking agent (hereinafter sometimes referred to as a blocking agent (D)).
  • the hydroxyl group-containing acrylic resin (A) has a hydroxyl value of 50 to 200 mgKOH / g.
  • the hydroxyl value of the hydroxyl group-containing acrylic resin (A) is preferably 70 to 190 mgKOH / g, more preferably 90 to 180 mgKOH / g.
  • the hydroxyl value (mgKOH / g) is expressed in mg of potassium hydroxide when the amount of hydroxyl group contained in 1 g (solid content) of the sample is converted into potassium hydroxide.
  • the molecular weight of potassium hydroxide is 56.1.
  • the hydroxyl group-containing acrylic resin (A) is not particularly limited as long as the hydroxyl value falls within the above range.
  • the hydroxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers hydroxyl group-containing polymerizable monomers
  • the hydroxyl group-containing polymerizable unsaturated monomer include a secondary hydroxyl group-containing polymerizable unsaturated monomer (a) and a hydroxyl group (excluding the secondary hydroxyl group) -containing polymerizable unsaturated monomer described later.
  • polymerizable unsaturated monomers polymerizable unsaturated monomers other than hydroxyl-containing polymerizable unsaturated monomers
  • other polymerizable unsaturated monomers polymerization other than secondary hydroxyl-containing polymerizable unsaturated monomers described later
  • unsaturated monomers those other than “(2) polymerizable unsaturated monomer containing a hydroxyl group (excluding secondary hydroxyl group)” can be mentioned.
  • the 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 hydroxyl group-containing acrylic resin (A) comprises (a) a secondary hydroxyl group-containing polymerizable unsaturated monomer and (b) other polymerizable unsaturated monomer (a secondary hydroxyl group-containing polymerizable unsaturated monomer).
  • a secondary hydroxyl group-containing polymerizable unsaturated monomer can be produced by copolymerizing a monomer component comprising a polymerizable unsaturated monomer other than
  • the hydroxyl group-containing acrylic resin (A) obtained by such a method has a secondary hydroxyl group.
  • those having secondary hydroxyl groups as described above may be referred to as secondary hydroxyl group-containing acrylic resins (A ′).
  • the secondary hydroxyl group-containing polymerizable unsaturated monomer (a) is a compound having one secondary hydroxyl group and one polymerizable unsaturated bond in one molecule.
  • Examples of the secondary hydroxyl group-containing polymerizable unsaturated monomer (a) include 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate from the viewpoint of the finished appearance of the coating film and the pot life of the coating composition.
  • the monomer (a) can be used alone or in combination of two or more.
  • (meth) acrylate means “acrylate or methacrylate”.
  • (Meth) acrylic acid means “acrylic acid or methacrylic acid”.
  • (Meth) acryloyl means “acryloyl or methacryloyl”.
  • the other polymerizable unsaturated monomer (b) is a monomer other than the above-mentioned secondary hydroxyl group-containing polymerizable unsaturated monomer (a), and specifically has one polymerizable unsaturated bond in one molecule.
  • a compound Specific examples of the unsaturated monomer (b) are listed in the following (1) to (8).
  • Acid group-containing polymerizable unsaturated monomer is a compound having one acid group and one polymerizable unsaturated bond in each molecule.
  • the monomer include carboxyl group-containing monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and maleic anhydride; sulfonic acid group-containing monomers such as vinyl sulfonic acid and sulfoethyl (meth) acrylate; 2 -Acidic phosphoric acid such as (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3-chloropropyl acid phosphate, 2-methacryloyloxyethylphenyl phosphate Examples include ester monomers.
  • the acid value of the acrylic resin (A) is about 0.5 to 30 mgKOH / g, particularly about 1 to 20 mgKOH / g.
  • Hydroxyl (excluding secondary hydroxyl group) -containing polymerizable unsaturated monomer A compound having one hydroxyl group (excluding secondary hydroxyl group) and one polymerizable unsaturated bond in one molecule.
  • the monomer include (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate, and a dihydric alcohol having 2 to 10 carbon atoms.
  • monoesterified products excluding those having secondary hydroxyl groups
  • hydroxyl group-containing monomers modified by ring-opening polymerization reaction of ⁇ -caprolactone excluding those having secondary hydroxyl groups
  • hydroxyl group-containing monomer modified by ring-opening polymerization reaction of ⁇ -caprolactone a commercially available product can be used.
  • the commercially available product include “Placcel FA-1,” “Placcel FA-2,” “ Plaxel FA-3, Plaxel FA-4, Plaxel FA-5, Plaxel FM-1, Plaxel FM-2, Plaxel FM-3, Plaxel FM-4, Plaxel FM-5 "(all of which are trade names manufactured by Daicel Chemical Industries, Ltd.).
  • Esterified product of acrylic acid or methacrylic acid and monohydric alcohol having 1 to 20 carbon atoms Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl acrylate, n- Butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, iso Stearyl acrylate (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cycl
  • an alicyclic hydrocarbon group having 6 to 20 carbon atoms is selected from the viewpoint of improving the finished appearance and achieving both coating film hardness.
  • the polymerizable unsaturated monomer (b1) to be contained can be used.
  • Representative examples of the alicyclic hydrocarbon group having 6 to 20 carbon atoms include cyclohexyl group, cyclooctyl group, cyclododecyl group, isobornyl group, adamantyl group, and tricyclodecanyl group.
  • the unsaturated monomer (b1) include, for example, cyclohexyl (meth) acrylate, 4-methylcyclohexylmethyl (meth) acrylate, 4-ethylcyclohexylmethyl (meth) acrylate, 4-methoxycyclohexylmethyl (meth) acrylate, Cycloalkyl (meth) acrylates such as tert-butylcyclohexyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclododecyl (meth) acrylate; isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, adamantyl (meth) Examples include bridged alicyclic hydrocarbon group-containing polymerizable unsaturated monomers such as acrylate, 3,5-dimethyladamantyl (meth) acrylate, and 3-tetracyclododecyl (me)
  • the blending ratio thereof is in the range of 10 to 60% by mass, particularly 15 to 50% by mass, more particularly 20 to 45% by mass, based on the total amount of the monomer components. Is preferred.
  • Alkoxysilyl group-containing polymerizable unsaturated monomer Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, acryloxyethyltrimethoxysilane, methacryloxyethyltrimethoxysilane, acryloxypropyltrimethoxysilane, methacryloxy Examples thereof include propyltrimethoxysilane, acryloxypropyltriethoxysilane, methacryloxypropyltriethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane and the like.
  • preferred alkoxysilyl group-containing polymerizable unsaturated monomers include vinyltrimethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, and the like.
  • an alkoxysilyl group-containing polymerizable unsaturated monomer as a constituent component, in addition to the crosslinking bond between a hydroxyl group and an isocyanate group, a condensation reaction between alkoxylyl groups and a crosslinking bond between the alkoxysilyl group and the hydroxyl group are generated. Therefore, curability can be improved.
  • the blending ratio thereof is preferably in the range of 1 to 20% by mass, particularly 1 to 10% by mass, based on the total amount of monomer components.
  • Aromatic vinyl monomers Specific examples include styrene, ⁇ -methylstyrene, vinyltoluene and the like.
  • the glass transition temperature of the resulting resin is increased, and a hydrophobic coating film having a high refractive index can be obtained. The effect of improving the finished appearance can be obtained.
  • the blending ratio is preferably 3 to 40% by mass, particularly 5 to 30% by mass, based on the total amount of monomer components.
  • the glycidyl group-containing polymerizable unsaturated monomer is a compound having one glycidyl group and one polymerizable unsaturated bond in one molecule, specifically, glycidyl acrylate. And glycidyl methacrylate.
  • Polymerizable unsaturated bond-containing nitrogen atom-containing compounds such as acrylamide, methacrylamide, dimethylacrylamide, N, N-dimethylpropylacrylamide, N-butoxymethylacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, diacetone
  • vinyl compounds examples include vinyl acetate, vinyl propionate, vinyl chloride, and vinyl versatate.
  • examples of the versatic acid vinyl ester include “Veoba 9” and “Veoba 10” (trade names, manufactured by Japan Epoxy Resin Co., Ltd.), which are commercially available products.
  • the monomers represented by the above (1) to (8) may be used alone or in combination of two or more.
  • the weight average molecular weight of the acrylic resin (A) is preferably about 2000 to 50000, particularly about 5000 to 30000, from the viewpoint of the finished appearance and curability of the coating film.
  • the weight average molecular weight is a value calculated based on the molecular weight of standard polystyrene from the chromatogram measured by gel permeation chromatography.
  • gel permeation chromatograph “HLC8120GPC” (manufactured by Tosoh Corporation) was used.
  • TKgel G-4000HXL Tetrahydrofuran
  • TKgel G-3000HXL TSKgel G-2500HXL
  • TSKgel G-2000HXL both manufactured by Tosoh Corporation
  • the glass transition temperature of the acrylic resin (A) is preferably about ⁇ 10 to 30 ° C., more preferably about ⁇ 5 to 20 ° C. from the viewpoint of the curability of the coating film and the finished appearance.
  • W1, W2,... represent the respective mass fractions of the monomers used for copolymerization
  • T1, T2,... represent the Tg (K) of the homopolymer of each monomer.
  • the hydroxyl group-containing acrylic resin (A) is a copolymer of monomer components comprising (a) a secondary hydroxyl group-containing polymerizable unsaturated monomer and (b) other polymerizable unsaturated monomer, a secondary hydroxyl group-containing polymerizable unsaturated monomer
  • the blending ratio of the monomer (a) and the other polymerizable unsaturated monomer (b) is, for example, about 20 to 50% by mass of the secondary hydroxyl group-containing polymerizable unsaturated monomer (a) with respect to the total monomer amount, preferably Is about 25 to 45% by mass, and the other unsaturated monomer (b) is about 50 to 80% by mass, preferably about 55 to 75% by mass.
  • the amount of the secondary unsaturated hydroxyl group-containing polymerizable unsaturated monomer (a) is less than 20% by mass, the curability and the finished appearance of the cured coating film may be inadequate. The finished appearance of the film may be insufficient.
  • the secondary hydroxyl group-containing polymerizable unsaturated monomer (a) out of the total hydroxyl group-containing polymerizable unsaturated monomer content in the secondary hydroxyl group-containing acrylic resin (A ′). is preferably contained in an amount of 50 to 100% by mass, more preferably 80 to 100% by mass.
  • the acid value of the hydroxyl group-containing acrylic resin (A) is preferably about 0.5 to 30 mgKOH / g, particularly about 1 to 20 mgKOH / g, from the viewpoint of curability of the coating composition.
  • a secondary hydroxyl group-containing acrylic resin (A ′) can be obtained by copolymerizing the monomer mixture comprising the polymerizable unsaturated monomers (a) and (b).
  • the copolymerization method for obtaining the secondary hydroxyl group-containing acrylic resin (A ′) by copolymerizing the monomer mixture is not particularly limited, and a known copolymerization method can be used. However, a solution polymerization method in which polymerization is performed in an organic solvent in the presence of a polymerization initiator can be preferably used.
  • organic solvent used in the solution polymerization method examples include aromatic solvents such as toluene, xylene, and Swazol 1000 (trade name, high-boiling petroleum solvent) manufactured by Cosmo Oil; ethyl acetate, butyl acetate, 3 -Ester solvents such as methoxybutyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, propyl propionate, butyl propionate, ethoxyethyl pro Pionate can be mentioned.
  • aromatic solvents such as toluene, xylene, and Swazol 1000 (trade name, high-boiling petroleum solvent) manufactured by Cosmo Oil
  • ethyl acetate, butyl acetate, 3 -Ester solvents such as methoxybutyl
  • organic solvents can be used singly or in combination of two or more, but it is preferable to use a high boiling ester solvent or ketone solvent from the viewpoint of the solubility of the acrylic resin.
  • aromatic solvents having higher boiling points can be suitably used in combination.
  • Examples of the polymerization initiator that can be used in the copolymerization of the hydroxyl group-containing acrylic resin (A) include 2,2′-azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, and di-t-amyl. Mention may be made of radical polymerization initiators known per se, such as peroxide, t-butyl peroctoate, 2,2′-azobis (2-methylbutyronitrile).
  • the hydroxyl group-containing acrylic resin (A) can be used alone or in combination of two or more.
  • resins other than the hydroxyl group-containing acrylic resin (A) can be used together as necessary.
  • an acrylic resin other than the acrylic resin (A) a polyester resin, a polyether resin, a polyurethane resin, and the like can be mentioned.
  • Preferred examples thereof include a hydroxyl group-containing polyester resin and a hydroxyl group-containing polyurethane resin. it can.
  • the hydroxyl group-containing polyester resin can be produced by a conventional method, for example, by an esterification reaction between a polybasic acid and a polyhydric alcohol.
  • the polybasic acid is a compound having two or more carboxyl groups in one molecule.
  • phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic acid, hexa Examples include hydrophthalic acid, maleic acid, fumaric acid, itaconic acid, trimellitic acid, pyromellitic acid and their anhydrides.
  • the polyhydric alcohol contains two or more hydroxyl groups in one molecule.
  • trivalent or higher polyol components such as trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, and the like, and 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylol And hydroxycarboxylic acids such as pentanoic acid, 2,2-dimethylolhexanoic acid and 2,2-dimethyloloctanoic acid.
  • ⁇ -olefin epoxides such as propylene oxide and butylene oxide
  • monoepoxy compounds such as Cardura E10 (product name, glycidyl ester of synthetic hyperbranched saturated fatty acid) such as Cardura E10 are reacted with acids, and these are reacted.
  • a compound may be introduced into the polyester resin.
  • a carboxyl group into a polyester resin for example, it can also be introduced by adding an acid anhydride to a hydroxyl group-containing polyester and half-esterifying it.
  • the hydroxyl value of the hydroxyl group-containing polyester resin is preferably in the range of 100 to 250 mgKOH / g, more preferably 120 to 220 mgKOH / g.
  • the weight average molecular weight of the hydroxyl group-containing polyester resin is preferably 2500 to 40000, more preferably 5000 to 30000.
  • hydroxyl group-containing polyurethane resin examples include a hydroxyl group-containing polyurethane resin obtained by reacting a polyol and a polyisocyanate.
  • polyol examples include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, and hexamethylene glycol, and trihydric alcohols such as trimethylolpropane, glycerin, and pentaerythritol. Can do.
  • examples of the high molecular weight material include polyether polyol, polyester polyol, acrylic polyol, and epoxy polyol.
  • polyether polyol examples include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
  • polyester polyol examples include alcohols such as the aforementioned dihydric alcohols, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol, and dibasic acids such as adipic acid, azelaic acid, and sebacic acid.
  • Lactone-based ring-opening polymer polyol such as polycaprolactone, polycarbonate diol, and the like.
  • carboxyl group-containing polyols such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid can be used.
  • polyisocyanate to be reacted with the above polyol examples include aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, lysine diisocyanate; and burette type addition of these polyisocyanates.
  • Isocyanurate cycloadduct Isocyanurate cycloadduct; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or -2,6-) diisocyanate, 1,3- (or 1,4-) Alicyclic diisocyanates such as di (isocyanatomethyl) cyclohexane, 1,4-cyclohexane diisocyanate, 1,3-cyclopentane diisocyanate, 1,2-cyclohexane diisocyanate And burette type adducts, isocyanurate cycloadducts of these polyisocyanates; xylylene diisocyanate, metaxylylene diisocyanate, tetramethyl xylylene diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5
  • the hydroxyl value of the hydroxyl group-containing polyurethane resin is preferably 100 to 250 mgKOH / g, more preferably 120 to 220 mgKOH / g.
  • the weight average molecular weight of the hydroxyl group-containing polyurethane resin is preferably 2500 to 40,000, more preferably 5000 to 30000.
  • the glass transition temperature of the hydroxyl group-containing polyurethane resin is preferably in the range of ⁇ 40 ° C. to 85 ° C., more preferably in the range of ⁇ 30 ° C. to 80 ° C.
  • the resin other than the hydroxyl group-containing acrylic resin (A) contains a hydroxyl group.
  • the amount is preferably 100% by mass or less, more preferably 10 to 50% by mass, based on the total solid content of the acrylic resin (A).
  • Polyisocyanate compound (B) is a curing agent for the present coating composition, and is a compound having two or more isocyanate groups in one molecule.
  • Examples of the polyisocyanate compound (B) include those known for polyurethane production, such as aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. Can do.
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2- Fats such as butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,2,4-trimethyl-hexamethylene-1,6-diisocyanate, 2,6-diisocyanatomethyl caproate, lysine diisocyanate Lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, , It may be mentioned 3,6-tri diisocyanatohexane, aliphatic triiso
  • alicyclic polyisocyanate examples include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (common name: Isophorone diisocyanate), 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane ( Common name: hydrogenated xylylene diisocyanate) or mixtures thereof, alicyclic diisocyanates such as norbornane diisocyanate, for example, 1,3,5-triisocyanatocyclohexane, 1,3 5-trimethylisocyanatocyclohexane, 2-
  • araliphatic polyisocyanate examples include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ⁇ , ⁇ ′-diisocyanato-1,4-diethylbenzene, 1,3- or 1,4-bis ( 1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or a mixture thereof, for example, an araliphatic triisocyanate such as 1,3,5-triisocyanatomethylbenzene Etc.
  • aromatic polyisocyanate examples include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4′- or 4,4′-diphenylmethane diisocyanate, or a mixture thereof.
  • aromatic diisocyanates such as 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate, for example, triphenylmethane-4,4 ′, 4
  • Aromatic triisocyanates such as '' '-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, such as 4,4'-diphenylmethane-2,2', 5 , 5'-Tetra And aromatic tetraisocyanates such as isocyanate.
  • polyisocyanate derivative examples include dimer, trimer, biuret, allophanate, carbodiimide, uretdione, uretoimine, isocyanurate, oxadiazine trione, polymethylene polyphenyl polyisocyanate (crude MDI, polymeric). MDI) and crude TDI.
  • HMDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • derivatives thereof can be particularly suitably used because of industrial availability.
  • the above polyisocyanate compounds can be used alone or in combination of two or more.
  • the viscosity at 25 ° C. is preferably 200 to 4000 mPa ⁇ s, more preferably 250 to 3500 mPa ⁇ s, and still more preferably 300 to 3000 mPa ⁇ s. If it is less than 200 mPa ⁇ s, the curability of the coating composition of the present invention may be lowered. Moreover, when it exceeds 4000 mPa ⁇ s, the finished appearance of the obtained coating film may be deteriorated.
  • polyisocyanate compound (B) a compound containing a dimer or higher dimer of the diisocyanate compound can be suitably used from the viewpoints of low-temperature short-time curability and finished appearance.
  • the content of the isocyanurate trimer is 30 to 70 masses based on the total amount of the polyisocyanate compound. %, Especially 40 to 70% by weight, more particularly 50 to 70% by weight, the content of uretdione dimer is 3 to 30% by weight, particularly 5 to 25% by weight, more particularly 8 to 20% by weight, and other 3 A polymer having a content of a multimer equal to or higher than a monomer in the range of 0 to 67% by mass, particularly 5 to 55% by mass, and more particularly 10 to 42% by mass can be preferably used.
  • the isocyanurate trimer is a polyisocyanate having an isocyanurate group consisting of three molecules of a diisocyanate monomer
  • the uretdione dimer is a polyisocyanate having a uretdione group consisting of two molecules of a diisocyanate monomer.
  • the polyisocyanate compound preferably contains no unreacted diisocyanate monomer, and the residual diisocyanate monomer concentration is preferably 1% by mass or less, more preferably 0.5% by mass or less.
  • Organometallic catalyst (C) The organometallic catalyst (C) is a catalyst composed of a zinc compound (C1) and an amidine compound (C2).
  • the catalyst composed of the zinc compound (C1) and the amidine compound (C2) forms a complex structure, and the amidine compound serves as a blocking agent.
  • the catalytic ability of the zinc compound which is excellent in low-temperature curability, becomes active, making it possible to achieve both low-temperature curability of the coating composition and maintaining pot life to some extent. I think that is due to becoming.
  • Examples of the zinc compound (C1) include a carboxylic acid zinc salt compound and an acetylacetone zinc complex.
  • a carboxylic acid zinc salt compound can be preferably used.
  • the zinc carboxylate compound include compounds represented by the following formula (1): (RCO 2 ) n Zn (1) (Wherein R represents an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 1 to 30 carbon atoms, or an alkylaryl group, and n is an integer having a value of 1 or more and 4 or less) More specifically, examples include zinc 2-ethylhexanoate, zinc acetate, zinc octylate, zinc naphthenate, zinc octoate, zinc stearate, zinc neodecanoate, and zinc oleate.
  • R represents an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 1 to 30 carbon atoms, or an alkylaryl group, and n is an integer having a value of 1 or more and 4 or less
  • examples include zinc 2-ethylhexanoate, zinc acetate, zinc octylate, zinc naphthenate, zinc o
  • Zinc octylate can be used particularly suitably because of its excellent catalytic activity and easy industrial availability.
  • the amidine compound (C2) is an organic compound having a structure represented by R 1 —C ( ⁇ NR 2 ) —NR 3 R 4 .
  • This structure has a structure in which a carbon (C) atom has one nitrogen atom as a double bond and one nitrogen atom as a single bond.
  • R 1 is a hydrogen atom, an optionally substituted organic group bonded to a carbon atom, or an amine group, and specifically, an optionally substituted hydrocarbyl group or an etherified hydroxyl group. Can be mentioned.
  • R 2 and R 3 are independently of each other an organic group bonded to a hydrogen atom or a carbon atom, or a heterocyclic ring having a structure bonded to each other (having one or more heteroatoms, or one or more heterocycles). Having a bonded double ring with atoms).
  • R 4 is a hydrogen atom, an optionally substituted organic group bonded to a carbon atom, an optionally etherified hydroxyl group, or preferably an optionally substituted hydrocarbyl group having 8 or more carbon atoms. be able to.
  • R 1 or R 4 is an organic group
  • they can be, for example, those having 1 to 40 carbon atoms or polymer groups having a molecular weight of, for example, 500 to 50,000.
  • R 1 , R 2 , R 3 , and R 4 can each independently contain an alcoholic hydroxyl group as a substituent.
  • R 2 -R 3 forms a 5- to 7-membered ring containing two nitrogen atoms in the amidine structure
  • one of R 1 -R 3 or R 1 -R 4 is Amidine compounds having a structure in which a 5- to 9-membered ring is formed by one nitrogen atom and a plurality of carbon atoms in the amidine structure are also included in the amidine compound (C2).
  • amidine compounds having such a structure include 1,5-diazabicyclo (4.3.0) on-5-ene and 1,8-diazabicyclo (5.4.0) undec-7-.
  • 1,4-diazabicyclo (3.3.0) oct-4-ene 2-methyl-1,5-diazabicyclo (4.3.0) on-5-ene, 2,7,8-trimethyl- 1,5-diazabicyclo (4.3.0) on-5-ene, 2-butyl-1,5-diazabicyclo (4.3.0) on-5-ene, 1,9-diazabicyclo (6.5. 0) Tridec-8-ene and the like.
  • amidine compound a heterocyclic compound having a structure in which R 2 and R 3 in the structural formula R 1 —C ( ⁇ NR 2 ) —NR 3 R 4 (1) are bonded, such as imidazoline, imidazole , Tetrahydropyrimidine, dihydropyrimidine, and pyrimidine.
  • Imidazole derivatives are generally represented by the following structural formula.
  • R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, alkyl group or substituted alkyl group, hydroxyalkyl group, allyl group, aralkyl group, cycloalkyl group, heterocyclic ring, Ether group, thioether group, halogen, -N (R) 2 , polyethylene polyamines, nitro groups, keto groups, ester groups, carbonamido groups, and alkyl substituents of these functional groups.
  • imidazole compound examples include N- (2-hydroxyethyl) imidazole, N- (3-aminopropyl) imidazole, 4- (hydroxymethyl) imidazole, 1- (tert-butoxycarbonyl) imidazole, imidazole- 4-propionic acid, 4-carboxyimidazole, 1-butylimidazole, 1-methylimidazole, 2-methyl-4-imidazolecarboxylic acid, 4-formylimidazole, 1- (ethoxycarbonyl) imidazole, propylene oxide and imidazole and 2- Reaction product with methylimidazole, 1-trimethylsilylimidazole, 4- (hydroxymethyl) imidazole hydrochloride, copolymer of 1-chloro-2,3-epoxypropane and imidazole, 1 (p-toluenesulfonyl) Midazole, 1,1-carbonylbisimidazole, 1- (2-cyanoethyl)
  • the organometallic catalyst (C) is a zinc complex, and the complex heats, for example, 1 mol of zinc carboxylate and 2 mol of amidine compound in a solvent such as methanol. Can be manufactured.
  • a zinc complex can be prepared by holding at about 50 ° C. for about 2 hours until a transparent solution is obtained. The clear solution is filtered and dried.
  • the molar ratio of the amidine compound (C2) to the zinc compound (C1) (the value of the number of moles of (C2) / the number of moles of (C1)) is 1.3 to 8.0, particularly 1.6 to 5 0.0, more preferably in the range of 1.8 to 4.0.
  • any of the low-temperature short-time curability, pot life, and finished appearance may be insufficient.
  • the amount of the component (C) is 0.05 to 5% by mass, particularly 0.1% with respect to the total amount of the component (A) and the component (B) from the viewpoints of low-temperature short-time curability, pot life and finished appearance. It is preferably in the range of ⁇ 4% by mass, more preferably in the range of 0.3 ⁇ 3% by mass.
  • the low-temperature short-time curability may be insufficient.
  • the finished external appearance of the coating film obtained may become inadequate.
  • the organometallic catalyst (C) can be used after being dissolved in a solvent.
  • the solvent is not particularly limited, for example, alcohols such as ethylene glycol, diethylene glycol, dipropylene glycol, propylene glycol, butanediol, hydrocarbons such as toluene, xylene, mineral terpenes, mineral spirits, ethyl acetate, Esters such as butyl acetate, methyl glycol acetate and cellosolve acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, glycol ethers such as ethyl 3-ethoxypropionate and 3-methoxybutyl acetate, N, N-dimethylformamide And solvents such as organic solvents of amides such as N, N-dimethylacetamide.
  • a catalyst other than the organometallic catalyst (C) can be used as a catalyst, if necessary, in addition to the organometallic catalyst (C).
  • the catalyst other than the organometallic catalyst (C) is not particularly limited as long as it is a conventionally known organic metal as a polyurethane production catalyst.
  • stannous diacetate, stannous dioctoate examples thereof include organic tin catalysts such as stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, and dioctyltin dilaurate. Of these, stannous dioctate and dibutyltin dilaurate are preferred.
  • Blocking agent (D) is ⁇ -diketone, ⁇ -keto acid ester, malonic acid ester, ketone having hydroxyl group at ⁇ -position, aldehyde having hydroxyl group at ⁇ -position, and ester having hydroxyl group at ⁇ -position At least one compound selected from the group consisting of
  • ⁇ -diketones acetylacetone, benzoylacetone, dibenzoylmethane, ⁇ -keto acid esters: methyl acetoacetate, ethyl acetoacetate, ethyl benzoylacetate, malonic acid esters: ethyl malonate, ⁇
  • ⁇ -diketones are preferable, and acetylacetone is particularly preferable because it has a particularly high pot life extending effect and an excellent effect of low-temperature curability.
  • the amount of the blocking agent (D) is 0.7 to 25% by mass, preferably 1.0 to 20% by mass, more preferably 2.0 to 2.0% by mass based on the total solid content of the components (A) and (B). 15% by mass.
  • the pot life extending effect may be insufficient, 25 mass If it exceeds 50%, the pot life extending effect will reach its peak, and the resulting coating film may have insufficient curability.
  • the isocyanate group in the polyisocyanate compound (B) and a hydroxyl group-containing composition are obtained from the viewpoints of low-temperature short-time curability, the finished appearance of the resulting coating film, and the water resistance and acid resistance of the cured coating film.
  • the equivalent ratio (NCO / OH) with the hydroxyl group in the acrylic resin (A) is preferably 0.8 to 1.8, more preferably 0.8 to 1.2, and even more preferably 0.80 to 1.15. Is within the range.
  • Rheology control agent (E) In addition to the four components (A), (B), (C), and (D) described above, the present coating composition has a rheology control agent (for the purpose of imparting thixotropic properties to the coating composition). E) can be suitably blended.
  • the coating composition containing such a rheology control agent (E) is sufficiently sprayed and easily sprayed when a high shear stress is applied to the coating composition, for example, during spray coating.
  • a high shear stress is applied to the coating composition
  • almost no shear stress is applied to the coating composition, for example, after being applied to the surface to be coated
  • the apparent viscosity can be increased.
  • rheology control agent (E) examples include, for example, polymer fine particles, ultrafine barium sulfate, silica fine powder, bentonite flow modifier, polyamide flow modifier, mono primary amine and diisocyanate. Polyurea compounds such as the reaction product of can be used.
  • polymer fine particles, polyurea compounds, bentonite-based flow regulators and ultrafine barium sulfate are preferred, and polymer fine particles and polyurea compounds are particularly preferred.
  • soot polymer fine particles either those synthesized in an organic solvent system or those synthesized in an aqueous system (emulsion polymerization, suspension polymerization, etc.) can be used.
  • Polymer fine particles synthesized in organic solvent system (E-1) polymer fine particles synthesized in an organic solvent system may be referred to as “polymer fine particles (E-1) synthesized in an organic solvent system” or “polymer fine particles (E-1)”.
  • Examples of the polymer fine particles (E-1) synthesized in the organic solvent system include a non-aqueous dispersion type acrylic resin (E-1 ′), specifically, a polymer dispersion stabilizer and Examples thereof include a non-aqueous dispersion type acrylic resin obtained by dispersing and polymerizing at least one unsaturated monomer in the presence of an organic solvent.
  • the polymer dispersion stabilizer used in the production of the non-aqueous dispersion type acrylic resin (E-1 ′) is generally a polymer obtained by copolymerizing a long-chain unsaturated monomer with another unsaturated monomer as required. .
  • the long-chain unsaturated monomer used in the polymer can be appropriately selected according to the performance required for the coating film, but can be preferably used from the viewpoints of copolymerizability, solubility in organic solvents, and the like. The following can be exemplified.
  • n-butyl (meth) acrylate isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) C4-C18 alkyl or cycloalkyl esters of (meth) acrylic acid such as acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate; methoxybutyl (meth) acrylate, methoxyethyl (meth) ) Alkoxyalkyl esters of (meth) acrylic acid such as acrylate and ethoxybutyl (meth) acrylate; Esters of aromatic alcohol such as benzyl (meth) acrylate with (meth)
  • Adducts with monoepoxy compounds include vinyl aromatic compounds such as styrene, ⁇ -methylstyrene, vinyltoluene, p-chlorostyrene, pt-butylstyrene; itaconic acid, itaconic anhydride, crotonic acid, maleic acid, anhydrous ⁇ , ⁇ -Unsaturated carboxylic acids other than (meth) acrylic acid such as maleic acid, fumaric acid and citraconic acid, and monoalcohols having 4 to 18 carbon atoms such as butyl alcohol, pentyl alcohol, heptyl alcohol, octyl alcohol and stearyl alcohol Mono- or diesters with “Biscoat 8F”, “ “Scort 8FM”, “Biscoat 3F", “Biscoat 3FM” (both manufactured by Osaka Organic Chemical Co., Ltd., trade name, (meth) acrylates having a fluorine atom in the side chain), perfluorocyclo
  • Polymerization for producing the polymer dispersion stabilizer can be usually performed using a radical polymerization initiator.
  • radical polymerization initiators include azo initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile); benzoyl peroxide, lauryl peroxide, and peroxide initiators such as t-butyl peroctoate and t-butyl peroxy-2-ethylhexanoate.
  • These polymerization initiators are generally 0 per 100 parts by mass of the monomer used for polymerization. .About 2 to 10 parts by mass, preferably 0.5 to 5 parts by mass.
  • the reaction temperature during the polymerization is usually about 60 to 160 ° C., and the reaction time during the polymerization is usually about 1 to 15 hours.
  • the molecular weight of the copolymer used as the dispersion stabilizer is usually in the range of about 5,000 to 100,000, preferably about 5,000 to 50,000 in terms of weight average molecular weight. If the molecular weight is less than 5,000, the dispersed particles may not be sufficiently stabilized and aggregation and sedimentation may occur. If the molecular weight exceeds 100,000, the viscosity may increase and handling may be difficult.
  • Polymer dispersion stabilizers can be used alone or in combination of two or more. Further, if necessary, other dispersion stabilizers such as butyl etherified melamine-formaldehyde resin, alkyd resin and the like can be used in combination.
  • At least one unsaturated monomer is polymerized in an organic solvent in the presence of the polymer dispersion stabilizer, and the non-aqueous polymer particles insoluble in the organic solvent are obtained.
  • the organic solvent used in the polymerization includes organic solvents that do not substantially dissolve the polymer particles produced by the polymerization, but are good solvents for the polymer dispersion stabilizer and the unsaturated monomer. Is done.
  • organic solvents include aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; methyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, octyl alcohol, and the like.
  • Alcohols such as cellosolve, butyl cellosolve, diethylene glycol monobutyl ether; ketones such as methyl isobutyl ketone, diisobutyl ketone, methyl ethyl ketone, methyl hexyl ketone, ethyl butyl ketone; ethyl acetate, isobutyl acetate, amyl acetate, 2-ethylhexyl acetate Ester etc. can be mentioned. These organic solvents can be used alone or in combination of two or more.
  • organic solvent in particular, those mainly composed of aliphatic hydrocarbons and suitably combined with aromatic hydrocarbons, alcohols, ethers, ketones or esters can be suitably used.
  • an unsaturated monomer having excellent polymerizability and having a carbon number smaller than that of the monomer used as the monomer component of the polymer dispersion stabilizer is dispersed. This is preferable because it is easily formed as polymer particles.
  • Examples of such unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate.
  • Carbon number of (meth) acrylic acid such as 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, etc.
  • alkyl or cycloalkyl esters alkoxyalkyl esters of (meth) acrylic acid such as methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxybutyl (meth) acrylate; Esters of aromatic alcohols such as ru (meth) acrylate with (meth) acrylic acid; glycidyl (meth) acrylate and mono-C 2-18 such as acetic acid, propionic acid, oleic acid, pt-butylbenzoic acid Adducts with carboxylic acid compounds; Adducts with (meth) acrylic acid and monoepoxy compounds such as “Kardura E10”; styrene, ⁇ -methylstyrene, vinyltoluene, p-chlorostyrene, pt-butyl Vinyl aromatic compounds such as styrene; itaconic acid, itaconic anhydride, cro
  • the monomer component forming the polymer particles can stably form the particle component by using a polymer component having a carbon number smaller than that of the monomer component of the polymer dispersion stabilizer.
  • a polymer component having a carbon number smaller than that of the monomer component of the polymer dispersion stabilizer From the viewpoint, (meth) acrylic acid esters having 8 or less carbon atoms, preferably 4 or less, vinyl aromatic compounds, (meth) acrylonitrile, and the like can be suitably used. These unsaturated monomers can be used alone or in combination of two or more.
  • radical polymerization initiators include, for example, azo-based initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile); benzoyl peroxide, lauryl And peroxide initiators such as peroxide, t-butylperoctoate, t-butylperoxy-2-ethylhexanoate, and the like.
  • azo-based initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile
  • benzoyl peroxide lauryl And peroxide initiators such as peroxide, t-butylperoctoate, t-butylperoxy-2-ethylhexanoate, and the like.
  • These polymerization initiators are generally 100 parts by mass of monomers used for polymerization. It can be used in the range of about 0.2 to 10 parts by mass, preferably
  • the polymer dispersion stabilizer used in the polymerization is usually used in an amount of about 3 to 240 parts by weight, preferably about 5 to 82 parts by weight of the unsaturated monomer with respect to 100 parts by weight of the polymer dispersion stabilizer. is there. Further, the total concentration of the polymer dispersion stabilizer and the unsaturated monomer in the organic solvent is usually about 30 to 70% by mass, preferably about 30 to 60% by mass.
  • the polymerization can be carried out by a method known per se, the reaction temperature during the polymerization is usually about 60 to 160 ° C., and the reaction time during the polymerization is usually about 1 to 15 hours.
  • the liquid phase is a solution of a polymer dispersion stabilizer in an organic solvent
  • the solid phase is a polymer particle obtained by polymerizing an unsaturated monomer.
  • a stable non-aqueous dispersion of resin can be obtained.
  • the particle size of the polymer particles is usually in the range of about 0.1 to 1.0 ⁇ m. When the particle size is smaller than 0.1 ⁇ m, the viscosity of the non-aqueous dispersion may be increased. When the particle size is larger than 1.0 ⁇ m, the polymer particles may swell or aggregate during storage.
  • the storage stability and mechanical properties of the non-aqueous dispersion are improved by combining the polymer dispersion stabilizer and the polymer particles in the non-aqueous dispersion. Can do. Even when they are combined, there is almost no change in the dispersed state in appearance, and there is almost no change in the particle size of the polymer particles.
  • Examples of the method for bonding the polymer dispersion stabilizer and the polymer particles include a hydroxyl group, an acid group, an acid anhydride group, an epoxy group, a methylol group, an isocyanate group, an amide in the stage of preparing the polymer dispersion stabilizer in advance.
  • a monomer having a functional group such as a group, an isocyanate group, an amide group or an amino group.
  • a monomer having a functional group such as a group, an isocyanate group, an amide group or an amino group.
  • these combinations include an isocyanate group and a hydroxyl group, an isocyanate group and a methylol group, an epoxy group and an acid (anhydrous) group, an epoxy group and an amino group, an isocyanate group and an amide group, and an acid (anhydrous) group and a hydroxyl group.
  • Examples of the monomer having such a functional group include (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, and citraconic acid.
  • Saturated carboxylic acids include glycidyl group-containing compounds such as glycidyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-alkoxymethyl (meth) acrylamide, diacetone
  • Carboxylic acid amide compounds such as acrylamide and N-methylol (meth) acrylamide; containing sulfonic acid amide groups such as p-styrenesulfonamide, N-methyl-p-styrenesulfonamide, and N, N-dimethyl-p-styrenesulfonamide Compound; (me
  • polymer dispersion stabilizer As another method for bonding the polymer dispersion stabilizer and the polymer particles, it can be carried out by polymerizing an unsaturated monomer in the presence of a polymer dispersion stabilizer having a polymerizable double bond.
  • a polymerizable double bond is introduced into the polymer dispersion stabilizer by using an acid group-containing monomer such as carboxylic acid, phosphoric acid or sulfonic acid as a copolymerization component of the resin, and glycidyl (meth) in this acid group.
  • the reaction can be carried out by reacting a glycidyl group-containing unsaturated monomer such as acrylate or allyl glycidyl ether.
  • it can also be carried out by allowing a polymer dispersion stabilizer to contain a glycidyl group and reacting it with an acid group-containing unsaturated monomer.
  • a hydroxyl group-containing unsaturated monomer is polymerized alone or as a mixture with other unsaturated monomers in the presence of a hydroxyl group-containing polymer dispersion stabilizer and an organic solvent, and a non-aqueous dispersion containing a hydroxyl group in both.
  • the reaction can be carried out by blending a polyisocyanate compound or the like and reacting at room temperature for several hours to several days at about 60 to 100 ° C. for about 1 to 5 hours.
  • Any polyisocyanate compound may be used as long as it has two or more isocyanate groups in the molecule.
  • aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, or hydrides thereof.
  • An aliphatic diisocyanate such as hexamethylene diisocyanate, lysine diisocyanate, dimer acid (dimer of tall oil fatty acid) diisocyanate; and an alicyclic diisocyanate such as isophorone diisocyanate.
  • polymer dispersion stabilizers containing acid groups and combinations of polymer particles and polyepoxides polymer dispersion stabilizers containing epoxy groups and combinations of polymer particles and polycarboxylic acids, epoxy groups
  • a polymer dispersion stabilizer containing an isocyanate group and a combination of polymer particles and a polysulfide compound can also be used.
  • polyepoxides include bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, epoxy group-containing acrylic resins, and the like.
  • polycarboxylic acids include adipic acid, sebacic acid, azelaic acid, isophthalic acid, and the like;
  • polysulfide include pentamethylene disulfide, hexamethylene disulfide, and poly (ethylene disulfide).
  • the polymer dispersion stabilizer and the polymer particles can be chemically bonded. At this time, various functional groups and polymerizable double bonds are bonded to the polymer dispersion stabilizer and / or polymerizable. It is sufficient that the amount introduced into the particles is an amount that averages at least 0.1 per molecule of the dispersion stabilizer and / or particles.
  • the non-aqueous dispersion thus obtained has excellent storage stability because the polymer dispersion stabilizer and polymer particles are chemically bonded, and the formed coating film is chemically and mechanically formed. Can exhibit excellent properties.
  • the amount of the component (E-1) includes the coating workability (sag resistance) of the resulting coating composition and the coating obtained.
  • the solid content is 0.1 to 10% by mass, preferably, based on the total solid content of the hydroxyl group-containing acrylic resin (A) and polyisocyanate compound (B). It is suitable to be in the range of 0.3 to 9% by mass.
  • the amount of the non-aqueous dispersion acrylic resin (E-1 ′) Is a solid of hydroxyl group-containing acrylic resin (A) and polyisocyanate compound (B) from the viewpoint of finished appearance such as coating workability (sag resistance) of the obtained coating composition and smoothness of the coated surface of the obtained coating film.
  • the solid content is suitably in the range of 1 to 10% by mass, preferably 2 to 8% by mass, based on the total amount.
  • Polymer fine particles synthesized in water examples include the following polymer fine particles.
  • polymer fine particles synthesized in an aqueous system may be referred to as “polymer fine particles synthesized in an aqueous system (E-2)” or “polymer fine particles (E-2)”.
  • the polymer fine particle (E-2) comprises an allyl group-containing reactivity of a monomer (e-2-1) containing at least two unsaturated groups in the molecule and another unsaturated monomer (e-2-2).
  • Examples of the monomer (e-2-1) containing at least two unsaturated groups in the molecule include unsaturated monocarboxylic acid esters of polyhydric alcohols, unsaturated alcohol esters of polybasic acids, An aromatic compound substituted with an unsaturated group can be used.
  • ethylene glycol diacrylate ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1, 4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetra Methacrylate, glycerol dimetac Rate, glycerol diacrylate, glycerol allyloxy dimethacrylate, 1,1,1-trishydroxy
  • the other unsaturated monomer (e-2-2) is the remaining component constituting the fine particle polymer, the hydroxyl group-containing polymerizable unsaturated monomer exemplified as the raw material of the hydroxyl group-containing acrylic resin (A), and other polymerizations.
  • the polymerizable unsaturated monomers polymerizable unsaturated monomers other than the hydroxyl group-containing polymerizable unsaturated monomer
  • those other than the above (e-2-1) can be used in the same manner.
  • Diene compounds such as butadiene and isoprene can also be used. These monomers can be used alone or in combination of two or more.
  • the proportion of the monomers (e-2-1) and (e-2-2) used in the copolymerization is not strictly limited and can be changed according to the physical properties desired for the polymer fine particles.
  • the monomer (e-2-1) is 1 to 60% by mass, preferably 1 to 50% by mass, based on the total amount of the monomers (e-2-1) and (e-2-2). More preferably, the amount of the monomer (e-2-2) may be in the range of 40 to 99% by mass, preferably 50 to 99% by mass, and more preferably 60 to 99% by mass. .
  • the copolymerization of the monomers (e-2-1) and (e-2-2) can be carried out by emulsion polymerization known per se using a polymerization initiator in the presence of a reactive emulsifier containing an allyl group.
  • a reactive emulsifier containing an allyl group emulsion polymerization known per se using a polymerization initiator in the presence of a reactive emulsifier containing an allyl group.
  • the allyl group-containing reactive emulsifier any anionic, cationic or nonionic reactive emulsifier can be used as long as it is an allyl group-containing reactive emulsifier.
  • a contained reactive emulsifier can be preferably used.
  • anionic allyl group-containing reactive emulsifier examples include ammonium salts of sulfonic acid compounds having an allyl group.
  • an anionic emulsifier having a polyoxyethylene alkyl ether sulfate ester salt as a basic structure and a radically polymerizable allyl group introduced as a part of the hydrophobic group can be used.
  • emulsifiers examples include Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.), Latemul S-180A (Kao Corp.), SR-1025 (Asahi Denka Kogyo Co., Ltd.) and the like.
  • the amount of the reactive emulsifier is in the range of 0.1 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the monomers (e-2-1) and (e-2-2). Is suitable.
  • anionic surfactants examples include fatty acids, alkyl sulfate esters, alkylbenzene sulfonates, and alkyl phosphates.
  • Nonionic surfactants include, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene derivatives, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl amines, alkyl alkanolamides, and the like.
  • Examples of the zwitterionic surfactant include alkylbedine.
  • the concentration of the emulsifier used in combination as necessary is 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the total amount of the monomers (e-2-1) and (e-2-2). It is suitable to be within the range.
  • polymerization initiator for example, peroxides represented by ammonium persulfate, potassium persulfate, ammonium peroxide and the like, these peroxides, and reducing agents such as sodium bisulfite, sodium thiosulfate, Rongalite, and ascorbic acid And so-called redox initiators in combination with azo compounds such as 4,4′-azobis (4-cyanobutanoic acid).
  • azo compounds particularly water-soluble azoamide compounds, can be preferably used. Water-soluble azoamide compounds are known (see JP-A-61-218618 and JP-A-61-63643). As specific examples of commercially available products, the VA series (trade name, Wako Pure Chemical Industries, Ltd.) Product).
  • the amount of the polymerization initiator is usually in the range of 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the total amount of the monomers (e-2-1) and (e-2-2). It is.
  • the concentration of all unsaturated monomers in the emulsion polymerization reaction is usually in the range of 0.1 to 50% by mass, preferably 0.5 to 30% by mass.
  • reaction temperature during emulsion polymerization varies depending on the polymerization initiator used, it can usually be 60 to 90 ° C. and the reaction time can usually be 5 to 10 hours.
  • the polymer fine particles (E-2) have a hydroxyl value in the range of 0 to 70 mgKOH / g, preferably 0 to 60 mgKOH / g, more preferably 0 to 50 mgKOH / g, from the viewpoint of the water resistance of the resulting coating film. Can have.
  • the polymer fine particles (E-2) have an acid value in the range of 0 to 90 mgKOH / g, preferably 0 to 70 mgKOH / g, more preferably 0 to 50 mgKOH / g, from the viewpoint of water dispersibility and the like. be able to.
  • the polymer fine particles (E-2) can have a particle diameter in the range of 10 to 500 nm, preferably 20 to 250 nm, more preferably 30 to 150 nm.
  • the particle size was measured using a COULTER N4 type sub-micron particle analyzer (manufactured by Nikka Machine Co., Ltd.).
  • the polymer fine particles (E-2) can be neutralized with a basic compound as necessary.
  • basic compounds used for neutralization include ammonia; primary monoamines such as ethylamine, propylamine, butylamine, benzylamine, monoethanolamine, neopentanolamine, 2-aminopropanol, and 3-aminopropanol; diethylamine Secondary monoamines such as, diethanolamine, di-n- or diisopropanolamine, N-methylethanolamine, N-ethylethanolamine; N, N-dimethylethanolamine, trimethylamine, triethylamine, triisopropylamine, methyldiethanolamine, etc.
  • Tertiary monoamines such as diethylenetriamine, hydroxyethylaminoethylamine, ethylaminoethylamine, methylaminopropylamine, etc. Can. These can be used alone or in combination of two or more.
  • the amount of the basic compound used for neutralization is suitably 0.1 to 1.0 equivalent, particularly 0.2 to 0.8 equivalent, based on the acid groups in the polymer fine particles (E-2). Yes.
  • the polymer fine particle (E-2) is obtained as an emulsion in which fine particles are dispersed in water.
  • the solvent is obtained by substituting the organic solvent with water as a dispersion medium as necessary. It can be used as a system paint.
  • the amount of the polymer fine particles (E-2) depends on the coating workability (sag resistance) of the resulting coating composition and the obtained coating composition.
  • the solid content is 0.1 to 5% by mass, preferably with respect to the total solid content of the hydroxyl group-containing acrylic resin (A) and polyisocyanate compound (B). Is suitably in the range of 0.2 to 3% by weight.
  • Polyurea compound (E-3) Specific examples of the polyurea compound (E-3) include the following polyurea compounds.
  • a solid particulate polyurea compound comprising a reaction product of an isocyanurate trimer obtained from a diisocyanate compound having 3 to 20 carbon atoms and an amine compound having one or more primary amino groups (Japanese Patent Publication No. 7-81099).
  • the isocyanurate trimer is preferably made from a diisocyanate having 3 to 20, preferably 5 to 14, more preferably 8 to 12 carbon atoms, particularly preferably hexamethylene diisocyanate.
  • diisocyanates examples include methylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, ⁇ , ⁇ ° dipropyl ether diisocyanate, thiodipropyl diisocyanate, cyclohexyl-1,4-diisocyanate, dicyclohexylmethane-4, 4 ° -diisocyanate, 1,5-dimethyl-2,4-bis (isocyanatomethyl) -benzene, 1,5-dimethyl-2,4-bis ( ⁇ -isocyanatoethyl) -benzene, 1,3,5-trimethyl- 2,4-bis (isocyanatomethyl) benzene, 1,3,5-triethyl-2,4-bis (isocyanatomethyl) benzene, a compound sold under the trademark Desmodur TT from Bayer.
  • Ring diisocyanate dicyclohexylmethane-dimethyl-4,4'-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and diphenylmethane-4,4'-diisocyanate.
  • heterocyclic trimers of two or three different diisocyanates may be used.
  • a mixture of the above heterocyclic triisocyanates can also be used.
  • Suitable primary amines that are secondary components used to make polyurea compounds include benzylamine, ethylamine, n-propylamine, sec-propylamine, n-butylamine, sec-butylamine, tert-butylamine N-pentylamine, ⁇ -methylbutylamine, ⁇ -ethylpropylamine, ⁇ -ethylbutylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, aniline and hexamethylenediamine.
  • These primary amines generally contain up to 55 carbon atoms, preferably 1 to 24, more preferably 1 to 12 carbon atoms.
  • Amines having one or more primary amino groups and one or more ether and / or hydroxyl groups can also be used.
  • Mixtures of the above amines can also be used.
  • one of the heterocyclic triisocyanate or the primary amine can be used in excess of the stoichiometric amount.
  • the ratio of the number of amino groups of the primary amine to the number of heterocyclic triisocyanate groups can be 0.7 to 1.5, preferably 0.9 to 1.1.
  • the reaction between the heterocyclic triisocyanate and the primary amine can generally be carried out by any method selected by mixing reaction components and raising the temperature as necessary. This reaction is preferably carried out at a temperature of 10 ° C. to 150 ° C., more preferably at a temperature of 20 ° C. to 80 ° C.
  • the reaction components can be mixed in any selected manner, but it is desirable to add the heterocyclic triisocyanate to the primary amine, and it may be divided into several stages if necessary.
  • this reaction is carried out in the presence of a solvent such as an aliphatic hydrocarbon such as acetone, methyl isobutyl ketone, 1-methoxy-propanol-2, benzene, toluene, xylene, or petroleum ether.
  • a solvent such as an aliphatic hydrocarbon such as acetone, methyl isobutyl ketone, 1-methoxy-propanol-2, benzene, toluene, xylene, or petroleum ether.
  • the blending amount of the component (E-3) is 100 parts by weight in total of the hydroxyl group-containing acrylic resin (A) and the polyisocyanate compound (B).
  • the range of 1 to 20 parts by weight, particularly 2 to 10 parts by weight is suitable.
  • This coating material is a coating composition containing a hydroxyl group-containing acrylic resin (A), a polyisocyanate compound (B), an organometallic catalyst (C) and a blocking agent (D) as essential components, and is usually an organic solvent. If necessary, pigments, pigment dispersants, leveling agents, the aforementioned rheology control agents (E), UV absorbers, light stabilizers, plasticizers, etc. An agent can be contained.
  • the pigment it can be used without particular limitation, for example, titanium oxide, zinc white, carbon black, cadmium red, molybdenum red, chromium yellow, chromium oxide, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, Colored pigments such as isoindoline pigments, selenium pigments, perylene pigments; body pigments such as talc, clay, kaolin, barita, barium sulfate, barium carbonate, calcium carbonate, silica, alumina white; aluminum powder, mica powder, titanium oxide Examples thereof include metallic pigments such as coated mica powder.
  • the pigment content varies depending on the type, but is usually about 0 to 200% by mass, preferably about 1 to 100% by mass, based on the total solid content of the components (A) and (B).
  • the content of the color pigment varies depending on the kind thereof, it is usually about 0 to 150% by mass, preferably about 1 to 100% by mass with respect to the total solid content of the component (A) and the component (B).
  • ultraviolet absorber conventionally known ones can be used, and examples thereof include ultraviolet absorbers such as benzotriazole absorbers, triazine absorbers, salicylic acid derivative absorbers, and benzophenone absorbers.
  • the content of the ultraviolet absorber in the coating composition is usually in the range of 0 to 10% by weight, particularly 0.2 to 5% by weight, more particularly 0.3 to 2% by weight, based on the total solid content of the resin. It is preferable from the viewpoint of weather resistance and yellowing resistance.
  • light stabilizer conventionally known light stabilizers can be used, and examples thereof include hindered amine light stabilizers.
  • the content of the light stabilizer in the coating composition is usually in the range of 0 to 10% by mass, particularly 0.2 to 5% by mass, more particularly 0.3 to 2% by mass, based on the total amount of resin solids. It is preferable from the viewpoint of weather resistance and yellowing resistance.
  • the coating composition of the present invention is a two-component paint in which a hydroxyl group-containing acrylic resin (A), an organometallic catalyst (C), a blocking agent (D), and a polyisocyanate compound (B) are separated. It is preferable to mix the two immediately before use.
  • the coating material to which the present coating is applied is not particularly limited.
  • steel sheets such as cold-rolled steel sheets, galvanized steel sheets, zinc alloy-plated steel sheets, stainless steel sheets, and tin-plated steel sheets
  • Metal substrates such as aluminum plates and aluminum alloy plates; various plastic materials are preferred.
  • it may be a vehicle body such as an automobile, a two-wheeled vehicle, a container or the like formed of the metal base material or a plastic material.
  • the object to be coated may be one in which surface treatment such as phosphate treatment, chromate treatment, complex oxide treatment is performed on the metal substrate or the metal surface of the vehicle body.
  • primer coatings are formed on plastic substrates such as bumpers such as the above metal substrates, vehicle bodies, etc., with various undercoating and / or intermediate coatings. It may be what was done.
  • the coating method of this paint is not particularly limited, and for example, a wet coating film can be formed by a coating method such as air spray coating, airless spray coating, rotary atomization coating, curtain coat coating, or the like. In these coating methods, electrostatic application may be performed as necessary. Of these, air spray coating is particularly preferred. In general, the coating amount of the paint is preferably about 10 to 50 ⁇ m as a cured film thickness.
  • the viscosity of this 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.
  • the drying oven can be applied.
  • the heating and holding temperature (keep temperature) is excellent in curability at a low temperature, and is therefore preferably in the range of 60 to 120 ° C., particularly 70 to 110 ° C., and more particularly 80 to 100 ° C.
  • the heat holding time (keep time) is within the range of 5 to 15 minutes, particularly 5 to 12 minutes, more particularly 5 to 10 minutes, because the coating composition of the present invention has excellent curability in a short time. It is suitable to be.
  • This paint has excellent curability and pot life (pot life) at low temperatures and in a short time, and also can provide a cured coating film with excellent finished appearance. It can be preferably used.
  • This paint can be particularly suitably used as an automobile paint.
  • Organometallic catalysts (C-7) to (C-9) are catalysts for comparative examples.
  • (* 1) to (* 6) in Table 2 are as follows.
  • Nikka octix zinc (* 1) trade name, zinc octylate, zinc content 8%, manufactured by Nippon Chemical Industry Co., Ltd.
  • Zinc naphthenate (* 2): Zinc content 10.1%, Tokyo Chemical Industry Co., Ltd. Acetylacetone zinc (* 3): Zinc content 25%, Showa Chemical Co., Ltd. Nikka Octix Tin (* 4): Trade name, Tin octylate, tin content 28%, manufactured by Nippon Kagaku Sangyo Co., Ltd. K-KAT348 (* 5): Trade name, bismuth octylate, bismuth content 25%, King Industries DBU (* 6): 1,8- Diazabicyclo [5.4.0] undec-7-ene
  • Production and production example 12 of non-aqueous dispersion type acrylic resin A four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet was charged with 93 parts of heptane and 98 parts of the following 55% polymer dispersion stabilizer solution (* 7) and heated to reflux. A mixture of polymerization initiators was dropped over 3 hours, and further aged for 2 hours to obtain a non-aqueous dispersion type acrylic resin.
  • the obtained non-aqueous dispersion type acrylic resin (C-1) has a milky white stable low mass concentration of 53%, Gardner viscosity B, average particle size (measured by electron microscope) 0.2 to 0.3 ⁇ m ⁇ . It was a dispersion of a viscosity polymer. Even when left at room temperature for 3 months, no precipitates or coarse particles were observed.
  • the obtained polymer dispersion stabilizer solution had a mass solid content concentration of 55%, a Gardner viscosity G, and a weight average molecular weight of 16000.
  • Production and production example 13 of polymer fine particles synthesized in water A four-necked flask equipped with a stirrer, a thermometer, a condenser tube and a mantle heater was added to 355 parts of deionized water and Latemuru S-120A (sulfosuccinic acid-based anionic reactive emulsifier, manufactured by Kao Corporation, solid content 50 %) 4 parts were charged and the temperature was raised to 90 ° C. with stirring. To this was added 1.25 parts of VA-086 (water-soluble azoamide polymerization initiator, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], manufactured by Wako Pure Chemical Industries, Ltd.).
  • VA-086 water-soluble azoamide polymerization initiator, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], manufactured by Wako Pure Chemical Industries, Ltd.
  • aqueous dispersion is dried on a stainless steel vat at 60 ° C. in an electric hot air drier to remove water to form a solid, and then dispersed again in ethylene glycol monomethyl ether heated to 60 ° C.
  • a dispersion of polymer fine particles having a mass solid content concentration of 20% was obtained.
  • Polyurea compound production example 14 As the polyurea compound, a diurea compound which is a reaction product of 2 mol of benzylamine and 1 mol of hexamethylene diisocyanate was used.
  • the polyisocyanate compounds (B-1) and (B-2) in Table 3 have the following meanings, respectively.
  • Polyisocyanate compound (B-1) Polyisocyanate compound composed of hexamethylene diisocyanate, the composition ratio of the multimer is 53% for the isocyanurate trimer and 47% for the other multimer of the trimer or higher. Solid content 100%, NCO content 21.8%, viscosity is 3000 mPa ⁇ s at 25 ° C. *
  • Polyisocyanate compound (B-2) N3200, trade name, manufactured by Bayer, hexamethylene diisocyanate burette, solid content 100%, NCO content 23.0%, viscosity is 2500 mPa ⁇ s at 25 ° C.
  • Nonaqueous dispersion described in the column of “Rheology control agent (E)” in Table 3 represents the nonaqueous dispersion type acrylic resin obtained in Production Example 12
  • Mated fine particles indicate those obtained in Production Example 13
  • Polyurea indicates the diurea compound described in Production Example 14.
  • NCO reaction rate FT-IR equipment “FT / IR-420” (manufactured by JASCO), immediately after paint blending and viscosity adjustment, by liquid film method, and after heat curing (keep at 100 ° C. for 7 minutes) was evaluated by measuring the surface of the test plate by the ATR method.
  • the isocyanate peak (1690 cm ⁇ 1 ) intensity and the isocyanurate peak (2271 cm ⁇ 1 ) intensity were calculated, and the ratio of these was calculated to determine the NCO reaction rate.
  • NCO reaction rate (%) 100-NCO residual rate (%)
  • NCO residual ratio (%) (Isocyanate peak intensity after heat curing / isosinurate peak intensity) / (Isocyanate peak intensity immediately after blending of paint / isosinurate peak intensity) ⁇ 100 Pot life (pot life): As described above, the viscosity of each coating composition prepared and adjusted for viscosity at 20 ° C. at the beginning, after 4 hours and after 6 hours was measured according to Ford Cup #No. 4 was measured. In addition, what was gelatinized was described as the gel in Table 3 below.
  • 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 as above, cured by heating at 170 ° C.
  • Knoop hardness After leaving each test plate in a constant temperature room at 20 ° C. for 24 hours, “Tucon hardness” was measured with a TUKON (American Chain & “Cable Company”, micro hardness tester).
  • Knoop Hardness Number which is also called TU-CON hardness, represents the hardness of the coating film that is read from the size of the diamond-shaped indentation that is formed by pushing a square pyramid diamond indenter into the test surface of the material with a constant test load. The larger the value, the higher the hardness.
  • BYK “Wave-Scan” which is an apparatus that optically scans the light / dark pattern of the light on the coating film surface of each test plate and analyzes the contrast (strength) of reflected light, has a wavelength region of 600- A long wavelength value measured at 1000 ⁇ m and a short wavelength value measured at a wavelength region of 100 to 600 ⁇ m were determined, and each was evaluated as a parameter of the finished skin. These are the dispersion values of the measured light intensity. The smaller the value, the better the finished skin (smoothness of the painted surface). The test results are shown in Table 3 below together with the paint formulation.

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Abstract

La présente invention a pour objet une composition de revêtement ayant une aptitude au durcissement à basse température sur une courte durée et une excellente durée de vie en pot (durée d'emploi), ladite composition permettant également d'obtenir un film de revêtement durci ayant un excellent aspect fini. La composition de revêtement selon la présente invention contient une résine acrylique contenant des groupes hydroxyle ayant un indice d'hydroxyle particulier, un composé polyisocyanate, un catalyseur organométallique comportant un composé du zinc et un composé amidine, et au moins un type d'agent de blocage choisi parmi des composés particuliers tels que des composés β-dicéto et autres.
PCT/JP2014/082703 2013-12-12 2014-12-10 Composition de revêtement Ceased WO2015087920A1 (fr)

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JP2012111935A (ja) * 2010-11-22 2012-06-14 Rohm & Haas Co ビス（イソシアナトメチル）シクロヘキサンからのイソシアヌラート組成物および第三級アミン触媒を含むポリウレタンコーティング組成物
WO2012123166A1 (fr) * 2011-03-14 2012-09-20 Basf Coatings Gmbh Compositions de revêtement à base de polyuréthanne, procédé de revêtement en plusieurs étapes reposant sur l'utilisation desdites compositions, utilisation de ces compositions de revêtement en tant que vernis transparent et peinture pigmentée, et utilisation dudit procédé de revêtement pour la peinture dans la réparation automobile et/ou pour l'application d'un revêtement sur des substrats en plastique et/ou des véhicules utilitaires
WO2012126796A1 (fr) * 2011-03-18 2012-09-27 Basf Coatings Gmbh Composition d'agent de revêtement catalysée par un complexe de zinc-imidazole-carboxylate
WO2013047208A1 (fr) * 2011-09-30 2013-04-04 関西ペイント株式会社 Composition de revêtement et article enduit

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