WO2015111709A1 - Composition de revêtement permettant de former un film de revêtement présentant une résistance aux chocs - Google Patents

Composition de revêtement permettant de former un film de revêtement présentant une résistance aux chocs Download PDF

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Publication number
WO2015111709A1
WO2015111709A1 PCT/JP2015/051876 JP2015051876W WO2015111709A1 WO 2015111709 A1 WO2015111709 A1 WO 2015111709A1 JP 2015051876 W JP2015051876 W JP 2015051876W WO 2015111709 A1 WO2015111709 A1 WO 2015111709A1
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group
carbon atoms
coating composition
polyol
coating
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PCT/JP2015/051876
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English (en)
Japanese (ja)
Inventor
祐一 稲田
日高　貴弘
綾 境口
孝仁 山田
靖洋 富崎
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関西ペイント株式会社
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Priority to JP2015559136A priority Critical patent/JP6571007B2/ja
Priority to CN201580005331.7A priority patent/CN105960441B/zh
Publication of WO2015111709A1 publication Critical patent/WO2015111709A1/fr

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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
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy 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
    • C08G18/7806—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
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate 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
    • 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
    • C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C08G18/8025—Masked aliphatic or cycloaliphatic polyisocyanates
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03D—WIND MOTORS
    • F03D1/00—Wind motors with rotation axis substantially parallel to the air flow entering the rotor 
    • F03D1/06—Rotors
    • F03D1/065—Rotors characterised by their construction elements
    • F03D1/0675—Rotors characterised by their construction elements of the blades
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05B—INDEXING SCHEME RELATING TO WIND, SPRING, WEIGHT, INERTIA OR LIKE MOTORS, TO MACHINES OR ENGINES FOR LIQUIDS COVERED BY SUBCLASSES F03B, F03D AND F03G
    • F05B2240/00—Components
    • F05B2240/20—Rotors
    • F05B2240/30—Characteristics of rotor blades, i.e. of any element transforming dynamic fluid energy to or from rotational energy and being attached to a rotor
    • F05B2240/32—Characteristics of rotor blades, i.e. of any element transforming dynamic fluid energy to or from rotational energy and being attached to a rotor with roughened surface
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/70—Wind energy
    • Y02E10/72—Wind turbines with rotation axis in wind direction

Definitions

  • the present invention relates to a coating composition for forming a coating film having impact resistance on an object to be coated, a coating film preparation method, and an article on which a coating film is formed using the coating composition.
  • the object to be installed or used in a normal environment (for example, a house) It is necessary to have a significantly higher impact property than a coating film on a roof, an outer wall, or an automobile body.
  • a coating film on a roof, an outer wall, or an automobile body examples include aircraft and helicopter wings, etc., but the impact resistance of the coating film in such a severe environment is evaluated using, for example, rain erosion resistance as an index. Has been.
  • Patent Documents 1 to 5 it is known that the blades of wind power generators are coated with a fluorine-containing polymer and a polyester polymer with a coating composition, a gel coating agent containing polyurethane, etc.
  • the coating film formed from these compositions was not sufficient in impact resistance such as rain erosion resistance and water resistance.
  • appearance abnormality such as blistering occurs when the coating is performed under high humidity conditions or when moisture is contained in the paint or the object to be coated.
  • the present invention has been made in view of the above circumstances, and the object of the present invention is less dependent on the coating environment such as humidity, and the obtained coating film has impact resistance such as rain erosion resistance and chipping resistance. And providing a coating composition capable of forming a coating film excellent in water resistance and finish, and having excellent adhesion to an object to be coated such as a blade of a wind power generator, and a coating film forming method, and the coating composition It is to provide an article painted with an object.
  • the present invention provides a coating composition, a coating film forming method, and an article having a coating film shown in the following items:
  • a coating composition containing (A) a polyol, (B) a polyisocyanate compound and (C) a curing catalyst, wherein the polyol (A) comprises a polyol (A1) having a structural unit derived from a fatty acid having 8 or more carbon atoms.
  • Item 2. The coating composition according to item 1, wherein the curing catalyst (C) contains an imidazole compound represented by the following general formula (I).
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyl group.
  • R 2 and R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, an acyl group, an alkoxycarbonyl group, a carboxyl group, or a halogen atom.
  • R 4 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, having 2 to 4 carbon atoms
  • R 5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and p represents an integer of 1 to 3).
  • the imidazole compound represented by the general formula (I) is 1-methylimidazole, 1,2-dimethylimidazole, 1- (3-dimethylaminopropyl) imidazole, 1-isobutyl-2-methylimidazole, 1-n- Item 3.
  • Item 4. The coating composition according to any one of Items 1 to 3, further comprising a bismuth compound as the curing catalyst (C).
  • the polyol (A1) is (A1-1) Esterified product of a hydroxyl group-containing fatty acid having 8 or more carbon atoms and a polyhydric alcohol (A1-2) Multimer of hydroxyl group-containing unsaturated fatty acid having 8 or more carbon atoms (A1-3) An unsaturated compound having 8 or more carbon atoms Polyol (A1-4) obtained by reducing a polymer of saturated fatty acid (A1-4) unsaturated fatty acid (a1-4-1) having 8 or more carbon atoms and / or esterified product of unsaturated fatty acid having 8 or more carbon atoms and polyhydric alcohol (a1) Item 5.
  • the coating composition according to any one of Items 1 to 4, which is at least one selected from the group consisting of polyols modified with a hydroxyl group.
  • Item 6 The coating composition according to Item 5, wherein the polyol (A1) is at least one selected from castor oil and hydrogenated castor oil.
  • Item 7 As the polyol (A), Item 7.
  • Item 8 A term wherein the blending amount of the polyol (A1) is 10 to 70 parts by weight and the blending amount of the polyol (A2) is in the range of 30 to 90 parts by weight with respect to 100 parts by weight of the component (A). 8. The coating composition according to any one of 7 above.
  • Item 9 The coating composition according to any one of claims 1 to 8, wherein a blending amount of the imidazole compound having at least one imidazole ring is 0.005 to 8 parts by mass with respect to 100 parts by mass of the component (A). .
  • Item 10 The coating composition according to any one of Items 1 to 9, further comprising a coloring component (D).
  • Item 11 The coating composition according to any one of Items 1 to 10, further comprising a water repellent (E) and / or a fluorine resin (F).
  • Item 12. A method for forming a coating film, wherein a coating film is formed by applying the coating composition according to any one of Items 1 to 11 to an object to be coated.
  • the object to be coated is a plastic or metal base material, a base material on which a gel coat material containing an epoxy resin is laminated, a base material film containing an epoxy resin on the base material, or an epoxy resin on the base material.
  • stacks the gel coat material containing this and forms the primer coating film which contains an epoxy resin further on this gel coat material.
  • Item 14 The method for forming a coating film according to Item 12 or 13, wherein the article to be coated is a blade of a wind power generator.
  • Item 15 An article obtained by applying the coating composition according to any one of Items 1 to 11 to an object to be coated.
  • a coating film excellent in impact resistance such as rain erosion resistance and chipping resistance, water resistance, finish, and adhesion to the blade is applied to the blade of the wind power generator. It can be formed on the surface. In addition, it has excellent curability in coating under conditions where moisture is present (that is, coating in a high-humidity atmosphere or when the substrate contains moisture), and the occurrence of blistering of the coating film is suppressed and stable. The film properties can be obtained.
  • the rain erosion resistance can be evaluated according to the method described in the examples of the present application.
  • FIG. 1 is a perspective view of a test plate used in a rain erosion test in the present embodiment.
  • Coating composition is a coating composition comprising (A) a polyol, (B) a polyisocyanate compound, and (C) a curing catalyst, wherein the component (A) is a structural unit derived from a fatty acid having 8 or more carbon atoms.
  • a coating composition characterized by comprising a polyol (A1) having an imidazole and the curing catalyst (C) being an imidazole compound having at least one imidazole ring.
  • the (A) polyol is not particularly limited as long as it has a polyol (A1) having a structural unit derived from a fatty acid having 8 or more carbon atoms.
  • Polyol (A1) having a structural unit derived from a fatty acid having 8 or more carbon atoms is a polyol having a structural unit derived from fatty acid, and at least of the structural units derived from fatty acid constituting the polyol. One of them has 8 or more carbon atoms.
  • (A1-1) Esterified product of a hydroxyl group-containing fatty acid having 8 or more carbon atoms and a polyhydric alcohol (A1-2) Multimer of hydroxyl group-containing unsaturated fatty acid having 8 or more carbon atoms (A1-3)
  • An unsaturated compound having 8 or more carbon atoms Polyol (A1-4) obtained by reducing a polymer of saturated fatty acid (A1-4) unsaturated fatty acid (a1-4-1) having 8 or more carbon atoms and / or esterified product of unsaturated fatty acid having 8 or more carbon atoms and polyhydric alcohol (a1) -4-2) is a hydroxyl-modified polyol.
  • Examples of the hydroxyl group-containing fatty acid having 8 or more carbon atoms constituting the component (A1-1) include a hydroxyl group-containing fatty acid having 8 to 28 carbon atoms, preferably 10 to 20 carbon atoms, and more specifically, ricinoleic acid. And hydroxyl group-containing unsaturated fatty acids such as ricinaleic acid, and hydroxyl group-containing saturated fatty acids such as 12-hydroxystearic acid and cerebronic acid. These hydroxyl group-containing fatty acids can be used singly or in combination of two or more.
  • polyhydric alcohol constituting component (A1-1) examples include glycerin, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, trimethylolpropane, pentaerythritol, and sorbitol. These polyhydric alcohols can be used singly or in combination of two or more.
  • esterified product of a hydroxyl group-containing fatty acid having 8 or more carbon atoms and a polyhydric alcohol examples include esterified products of the hydroxyl group-containing fatty acid having 8 or more carbon atoms listed above and the polyhydric alcohol listed above.
  • examples of the component (A1-1) include castor oil and hydrogenated castor oil.
  • Castor oil is a vegetable oil derived from castor bean seeds, and is known to be a glyceride of unsaturated fatty acids such as ricinoleic acid and oleic acid and saturated fatty acids such as palmitic acid.
  • ricinoleic acid is a hydroxyl group-containing fatty acid having 8 or more carbon atoms
  • a composition in which castor oil or hydrogenated castor oil which is a modified product thereof is blended as a component (A) in the coating composition is component (A1-1). Will be included.
  • These components (A1-1) can be used singly or in combination of two or more.
  • Examples of the hydroxyl group-containing unsaturated fatty acid having 8 or more carbon atoms constituting the multimeric component (A1-2) include, for example, examples of the hydroxyl group-containing unsaturated fatty acid having 8 or more carbon atoms constituting the component (A1-1). Those listed can be used, and preferred examples include ricinoleic acid and ricinaleic acid.
  • the multimer is not particularly limited, and examples thereof include dimers, trimers, and tetramers, and dimers are preferable. Accordingly, examples of the component (A1-2) include dimers, trimers, tetramers and the like, preferably dimers, of the hydroxyl group-containing unsaturated fatty acids having 8 or more carbon atoms listed above. These components (A1-2) can be used singly or in combination of two or more.
  • the unsaturated fatty acid having 8 or more carbon atoms constituting the multimer of unsaturated fatty acid having 8 or more carbon atoms, which is a raw material for the component (A1-3), is, for example, an unsaturated fatty acid having 8 to 28 carbon atoms, preferably 10 to 20 carbon atoms.
  • fatty acid-containing unsaturated fatty acids such as ricinoleic acid and ricinaleic acid, myristoleic acid, palmitoleic acid, sapienoic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, elca Hydroxyl groups such as acid, nervonic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, eleostearic acid, mead acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, and adrenic acid And unsaturated fatty acids that do not have any.
  • unsaturated fatty acids such as ricinoleic acid and ricinaleic acid, myristoleic acid, palmitoleic acid, sapienoic acid,
  • Examples of the multimers of unsaturated fatty acids having 8 or more carbon atoms, which are raw materials for the component (A1-3), include dimers, trimers, and tetramers of unsaturated fatty acids having 8 or more carbon atoms, and dimers are preferred. Accordingly, the multimers of unsaturated fatty acids having 8 or more carbon atoms, which are the raw materials for component (A1-3), include dimers, trimers, tetramers, etc. of unsaturated fatty acids having 8 or more carbon atoms listed above, preferably dimers. Is mentioned.
  • Examples of the component (A1-3) include those obtained by reducing a multimer of unsaturated fatty acids having 8 or more carbon atoms by a method known per se. Representative examples of component (A1-3) include reduced products of dimer acid of ricinoleic acid, oleic acid, linoleic acid, linolenic acid, and eleostearic acid.
  • the multimer of unsaturated fatty acids having 8 or more carbon atoms constituting the multimer of unsaturated fatty acids having 8 or more carbon atoms in the component (A1-3) can be used.
  • Examples of commercially available products include PRIPOL 2033 manufactured by CRODA.
  • Examples of the unsaturated fatty acid (a1-4-1) having 8 or more carbon atoms, which is a raw material for the component (A1-4), include unsaturated fatty acids having 8 to 28 carbon atoms, preferably 10 to 20 carbon atoms, and more Specifically, hydroxyl-containing unsaturated fatty acids such as ricinoleic acid and ricinaleic acid, myristoleic acid, palmitoleic acid, sapienoic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid Unsaturated without hydroxyl groups such as acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, eleostearic acid, mead acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eico
  • polyhydric alcohol used as a raw material for the component (A1-4) examples include glycerin, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, trimethylolpropane, pentaerythritol, sorbitol and the like. These polyhydric alcohols can be used singly or in combination of two or more.
  • examples of the esterified product (a1-4-2) of an unsaturated fatty acid having 8 or more carbon atoms and a polyhydric alcohol used as a raw material for the component (A1-4) include the above unsaturated fatty acids having 8 or more carbon atoms.
  • esterified products of unsaturated fatty acids having 8 to 28 carbon atoms, preferably 10 to 20 carbon atoms and polyhydric alcohols preferably 10 to 20 carbon atoms and polyhydric alcohols.
  • glycerides of unsaturated fatty acids having 8 or more carbon atoms, preferably 8 to 28 carbon atoms, more preferably 10 to 20 carbon atoms can be suitably used.
  • the glycerides of unsaturated fatty acids having 8 or more carbon atoms are contained, for example, in fats and oils. Therefore, when the component (a1-4-2) is used as the raw material for the component (A1-4), fats and oils containing glycerides of unsaturated fatty acids having 8 or more carbon atoms can be used.
  • oils containing glycerides of unsaturated fatty acids having 8 or more carbon atoms for example, soybean oil, castor oil, palm oil, rapeseed oil and the like can be suitably used.
  • Hydroxyl modification can be performed by a method known per se. Specifically, for example, after epoxidizing the unsaturated group in the component (a1-4-1) and / or (a1-4-2) with a peroxide, the resulting epoxide and the monovalent or polyvalent Examples include a method of reacting with alcohol.
  • Examples of the peroxide for epoxidizing the unsaturated group in the component (a1-4-1) and / or (a1-4-2) include peracetic acid and hydrogen peroxide.
  • Examples of the monohydric alcohol for modifying the epoxide with a hydroxyl group include linear primary alcohols such as methanol, ethanol and propanol; secondary alcohols such as isopropanol; unsaturated group-containing alcohols such as allyl alcohol; isobutanol, Branched alcohols such as neopentyl alcohol; cyclic alcohols such as cyclohexanol and benzyl alcohol; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monopropyl ether; diethylene glycol mono such as diethylene glycol monomethyl ether Alkyl ethers; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether; Dipropylene Dipropylene glycol monoalkyl ethers such as glycol monomethyl ether.
  • linear primary alcohols such as methanol, ethanol and propanol
  • These monohydric alcohols can be used singly or in combination of two or more.
  • the polyhydric alcohol for modifying the epoxide with a hydroxyl group include glycerin, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butanediol, neopentyl glycol, trimethylolpropane, pentaerythritol, sorbitol and the like. These polyhydric alcohols can be used singly or in combination of two or more.
  • component (A1-4) commercially available products can be used.
  • commercially available products include BASF Corporation's Sovermol 750, Sovermol 760, Sovermol 805, Sovermol 815, Sovermol 819, and the like.
  • component (A1-1), component (A1-2), component (A1-3) and component (A1-4) can be used singly or in combination of two or more.
  • the (A) polyol may contain a polyol other than the component (A1).
  • the polyol other than the component (A1) is at least one polyol selected from the group consisting of polycaprolactone diol, polycaprolactone triol, polycaprolactone tetraol, polycarbonate carbonate diol, and polyacrylate polyol.
  • (A2) can be used.
  • the polycaprolactone polyol can be obtained, for example, by ring-opening polymerization of ⁇ -caprolactone using a dihydric to tetravalent polyhydric alcohol as an initiator.
  • a dihydric to tetravalent polyhydric alcohol examples include ethylene glycol, glycerin, trimethylolethane, trimethylolpropane, diglycerin, ditrimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, tris (2-hydroxy).
  • Examples thereof include polyhydric alcohol compounds obtained by reacting ethyl) isocyanuric acid, dimethylolalkanoic acid and a monoepoxy compound (for example, “Cardura E10” manufactured by HEXION Specialty Chemicals, a glycidyl ester of a synthetic highly branched saturated fatty acid). These can be used alone or in combination of two or more.
  • polycaprolactone polyol a commercially available product can be used as the polycaprolactone polyol.
  • commercially available products include, for example, “Placcel 205”, “Placcel 205H”, “Placcel L205AL”, “Placcel C205U”, “Placcel 208”, “Placcel 210”, which are Placel 200 series manufactured by Daicel Chemical Industries, Ltd.
  • the hydroxyl value is in the range of 100 to 700 mgKOH / g, more preferably 130 to 600 mgKOH / g, more particularly 150 to 500 mgKOH / g, and the number average molecular weight is 200 to Those having a range of 1,800 and having two or more hydroxyl groups in one molecule are preferable.
  • polycaprolactone polyols examples include polycaprolactone triol and polycaprolactone tetraol.
  • Polycarbonate diol can be obtained, for example, by reacting a diol component with a carbonylating agent.
  • the carbonylating agent constituting the polycarbonate diol include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate, diphenyl carbonate, phosgene and the like.
  • the diol component of the polycarbonate diol include aliphatic diols and alicyclic diols, and specific examples include 1,4-butanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol.
  • aliphatic diols such as diethylene glycol, alicyclic diols such as 1,4-cyclohexanediol, ester diols such as bis (hydroxyethyl) terephthalate, and aromatic diols such as alkylene oxide adducts of bisphenol A.
  • polycarbonate diol examples include “Placcel CD CD205”, “Placcel CD CD205PL”, “Placcel CD CD205HL”, “Placcel CD CD210”, “Placcel CD210PL” manufactured by Daicel Chemical Industries, Ltd., Asahi Kasei Corporation Examples thereof include “Duranol T5652”, “Duranol T5651”, “Duranol T5650J”, “Duranol 5650E”, “Duranol G4672”, “Duranol T4671”, “Duranol T4692”, “Duranol T4691”, and the like.
  • polycarbonate diols can be used singly or in combination of two or more.
  • the hydroxyl value is in the range of 110 to 700 mgKOH / g, further 130 to 600 mgKOH / g, more particularly 150 to 500 mgKOH / g, and the number average molecular weight is 200 to 1, Those within the range of 800 are preferred.
  • polyacrylate polyol usually, a hydroxyl group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer are used in a method known per se, for example, in an organic solvent. It can manufacture by making it copolymerize by methods, such as solution polymerization method of this.
  • the hydroxyl group-containing polymerizable unsaturated monomer is a compound having at least one hydroxyl group and one polymerizable unsaturated bond in one molecule, and specifically includes, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 7-hydroxyheptyl (meth) acrylate Monoesterified product of (meth) acrylic acid such as 8-hydroxyoctyl (meth) acrylate and a dihydric alcohol having 2 to 8 carbon atoms; and (meth) acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms ⁇ -caprolactone modified monoester product; N-hydroxyme Le (meth) acrylamide; allyl alcohol, furthermore, may be mentioned molecular ends having
  • the polymerizable unsaturated monomer having an ultraviolet absorbing functional group such as 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone described later is a hydroxyl group-containing polymerizable unsaturated monomer.
  • it is included in other polymerizable unsaturated monomers copolymerizable with a hydroxyl group-containing polymerizable unsaturated monomer.
  • polymerizable unsaturated monomers copolymerizable with a hydroxyl group-containing polymerizable unsaturated monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl ( (Meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, “isostearyl acrylate (trade name, manufactured by Osaka Organic Chemical Industry)”, cyclo
  • the polyacrylate polyol is generally in the range of 30 ⁇ 300 mgKOH / g, particularly 40 to 250 mgKOH / g, more particularly 50 to 200 mgKOH / g, from the viewpoint of curability at low temperature and water resistance of the resulting coating film. It preferably has a hydroxyl value.
  • the polyacrylate polyol generally has a weight average molecular weight in the range of 3,000 to 100,000, particularly 3,000 to 50,000, more preferably 4,000 to 30,000.
  • Weight average molecular weight and “number average molecular weight” in this specification are calculated based on the molecular weight of standard polystyrene from the chromatogram measured by gel permeation chromatograph according to the method described in JIS K 0124-2011. It is the value.
  • As the gel permeation chromatograph “HLC8120GPC” (manufactured by Tosoh Corporation) was used.
  • Mobile phase tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: under the conditions of RI.
  • polyacrylate polyol from the viewpoint of rain erosion resistance, as a hydroxyl group-containing polymerizable unsaturated monomer, a copolymer of (meth) acrylate having a polycaprolactone skeleton and a copolymer of hydroxybutyl acrylate (HBA) are used. preferable.
  • the use ratio of the component (A1) and the component (A2) is not particularly limited, but from the viewpoint of finish and rain erosion resistance, the amount of the component (A1) is based on 100 parts by mass of the component (A).
  • the amount is preferably 10 to 80 parts by mass, and more preferably 10 to 70 parts by mass.
  • the amount of component (A2) is preferably 20 to 90 parts by weight, and preferably 30 to 90 parts by weight with respect to 100 parts by weight of component (A). Is more preferable.
  • These components (A) can be used alone or in combination of two or more.
  • the (A) polyol may contain a polyol (A3) other than the components (A1) and (A2).
  • the polyol of the component (A3) is a polyol component not classified into (A1) and (A2), for example, a polyhydric alcohol other than (A1) and (A2), a polyester polyol, a polyacetal polyol, a polyesteramide polyol or Examples thereof include polythioether polyol and other hydroxyl group-containing resins.
  • Polyhydric alcohols other than the above (A1) and (A2) are compounds having two hydroxyl groups in one molecule, and aliphatic diols and aromatic diols exemplified above, polyethylene glycol, polypropylene glycol, polybutylene glycol.
  • Polyether diols such as glycerin, trimethylolethane, trimethylolpropane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, tris (2-hydroxyethyl) isocyanurate, sorbitol And trihydric or higher alcohols such as saccharides and mannitol; polyester polyols obtained by reacting these trihydric or higher alcohols with acid anhydrides and the like.
  • hydroxyl group-containing resin examples include resins having a hydroxyl group, such as polyether resin, polycarbonate resin, polyurethane resin, epoxy resin, and alkyd resin. These can be used alone or in combination of two or more.
  • the polyol (A3) other than the component (A) can be contained as long as the coating film performance is not impaired.
  • the blending ratio is preferably 30% by mass or less based on the total amount of resin solids of the polyol (A).
  • the polyisocyanate compound (B) is a compound having at least two isocyanate groups in one molecule, for example, an aliphatic polyisocyanate, an alicyclic polyisocyanate, an araliphatic polyisocyanate, Aromatic polyisocyanates, derivatives of the polyisocyanates and the like can be mentioned.
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3.
  • Aliphatic diisocyanates such as butylene diisocyanate, 2,4,4
  • Examples of the alicyclic polyisocyanate 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-methyl-1,3-cyclohexylene diisocyanate (common name: hydrogenated TDI), 2-methyl-1,3-cyclohexylene diisocyanate, 1,3- or 1,4-bis (isocyanato) Methyl) cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, methylenebis (4,1-cyclohexanediyl) diisocyanate (common name: hydrogenated MDI), norbornane diisocyanate such as norbornane diisocyanate 1,3,5-tri
  • aromatic polyisocyanate examples include methylene bis (1,4-phenylene) diisocyanate (common name: MDI), 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ⁇ , ⁇ ′-diisocyanato-1.
  • polyisocyanate derivatives examples include dimer, trimer, biuret, allophanate, uretdione, uretoimine, isocyanurate, oxadiazine trione, polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI). And Crude TDI.
  • polyisocyanates and derivatives thereof may be used alone or in combination of two or more.
  • polyisocyanates aliphatic diisocyanates, alicyclic diisocyanates, and derivatives thereof are preferred.
  • polyisocyanate compound (B) a prepolymer obtained by reacting the polyisocyanate and its derivative with a compound capable of reacting with the polyisocyanate under an excess of isocyanate groups may be used.
  • the compound capable of reacting with the polyisocyanate include compounds having an active hydrogen group such as a hydroxyl group and an amino group.
  • polyhydric alcohol, low molecular weight polyester resin, amine, water, etc. can be used.
  • the polyisocyanate compound (B) is a polymer of an isocyanate group-containing polymerizable unsaturated monomer, or a polymerizable unsaturated group other than the isocyanate group-containing polymerizable unsaturated monomer and the isocyanate group-containing polymerizable unsaturated monomer.
  • a copolymer with a monomer may be used.
  • polyisocyanate compound (B) a blocked polyisocyanate compound in which the isocyanate group of the polyisocyanate compound is blocked may be used.
  • the blocking agent for example, phenol compounds; lactam compounds; alcohol compounds; oxime compounds; mercaptan compounds; dimethyl malonate; active methylene compounds such as diethyl malonate can be preferably used. Blocking can be easily performed by mixing an unblocked polyisocyanate compound and a blocking agent. These polyisocyanate compounds can be used alone or in combination of two or more thereof, and an unblocked polyisocyanate compound and a blocked polyisocyanate compound can be used in combination.
  • polyisocyanate compound (B) hexamethylene diisocyanate (HDI) and / or isophorone diisocyanate (IPDI) isocyanurate, biuret, allophanate, trimethylolpropane (TMP) adduct and the like are particularly preferable from the viewpoint of water resistance.
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • TMP trimethylolpropane
  • the polyisocyanate compound (B) has an average number of isocyanate functional groups in one molecule of 1.9 to 6, more preferably 2.5 to 5, particularly 2.6 to 6, from the viewpoint of rain erosion resistance. It is preferable to be within the range.
  • (C) Curing catalyst The present invention is characterized in that an imidazole compound having at least one imidazole ring is used as at least part of the (C) curing catalyst.
  • an imidazole compound having at least one imidazole ring as a curing catalyst, a coating film excellent in impact resistance, particularly rain erosion resistance can be formed even in the presence of moisture.
  • Examples of the imidazole compound include, in the general formula (I), R 1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a hydroxyalkyl having 1 to 4 carbon atoms.
  • R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, an acyl group Group, an alkoxycarbonyl group, a carboxyl group, or halogen, and R 4 has a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an arylalkyl group, or a substituent.
  • R 5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and p represents an integer of 1 to 3).
  • R 1 , R 2 , R 3 , R 4 and R 5 contained in the general formula (I) have the same meaning as described above.
  • Examples of the alkyl group having 1 to 4 carbon atoms in R 1 , R 2 , R 3 and R 5 include linear or branched alkyl groups having 1 to 4 carbon atoms, and more specifically, And methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group and the like.
  • Examples of the cycloalkyl group having 3 to 8 carbon atoms in R 1 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, and a cycloalkyl group having 5 to 7 carbon atoms is preferable. .
  • the alkyl group having 1 to 4 carbon atoms in R 1 , R 2 and R 3 is substituted with 1 to 3, preferably 1 hydroxyl group.
  • 1 hydroxyl group preferably 1 hydroxyl group.
  • Examples of the aryl group having 6 to 10 carbon atoms in R 1 include a phenyl group and a naphthyl group.
  • acyl group in R 1 , R 2 and R 3 examples include an acyl group having 1 to 7 carbon atoms such as formyl group, acetyl group, propionyl group, benzoyl group and (meth) acryloyl group.
  • Examples of the alkoxycarbonyl group in R 2 and R 3 include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, etc. Examples include a structure in which a chain or branched alkoxy group is bonded.
  • halogen in R 2 and R 3 examples include fluorine, chlorine, boron, iodine and the like, preferably chlorine and the like.
  • R 2 and R 3 may be bonded to form an aromatic ring structure. Specifically, R 2 and R 3 together with imidazole to which these substituents are bonded form benzimidazole, etc. Is mentioned.
  • Examples of the alkyl group having 1 to 12 carbon atoms in R 4 include a linear or branched alkyl group having 1 to 4 carbon atoms, and more specifically, a methyl group, an ethyl group, and n-propyl group.
  • Examples of the alkenyl group having 2 to 4 carbon atoms for R 4 include a vinyl group, an allyl group, a 3-butenyl group, and a 2-butenyl group.
  • Examples of the arylalkyl group for R 4 include the above-exemplified alkyl groups having 1 to 3 carbon atoms, preferably 1 to 3 carbon atoms having 6 to 10 carbon atoms exemplified above, and the like. be able to. More specifically, benzyl group, 2-phenylethyl group, 3,3,3-triphenylpropyl group, 4,4,4-triphenylbutyl group and the like can be mentioned.
  • Examples of the aryl group which may have a substituent in R 4 include the aryl groups having 6 to 10 carbon atoms exemplified above and those having a substituent and unsubstituted groups.
  • the substituent for the aryl group is not particularly limited, but may have a halogen, a hydroxyl group, an oxo group, an alkyl group, a carbonyl group, and further a heterocyclic ring via a urethane bond, a carbonyl bond, or the like.
  • Examples of the heterocyclic ring include furan, thiophene, pyrrole, pyridine, thiazole, imidazole, and pyrimidine. Moreover, this heterocyclic ring may have the said substituent.
  • examples of the imidazole compound represented by the general formula (I) include imidazole, 1-methylimidazole, 2-methylimidazole, 2-n-butylimidazole, 1-tert-butylimidazole, 1,2- Dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-diethylimidazole, 1,4-diethylimidazole, 1,5-diethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-isobutyl-2 -Methylimidazole, 1-n-butyl-2-methylimidazole, 2-hydroxymethylimidazole, 4-hydroxymethyl-2-methylimidazole, 1- (2-hydroxyethyl) -imidazole, 4-hydroxymethylimidazole, 2- Cyclohexyl Dazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethylimi
  • imidazole compounds are specifically 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl.
  • Imidazole 1-cyanoethyl-2-isopropylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-methylimidazole, 1,2-dimethylimidazole, 1- (3-dimethylaminopropyl) imidazole, 1-isobutyl-2-methyl Imidazole, 1-n-butyl-2-methylimidazole, 1-vinylimidazole, 1-allylimidazole, 2-methyl-1-vinylimidazole, 1,2-diethylimidazole, 1,4-diethylimidazole, 1,5- Diethyl Imidazole, 1-dodecyl-2-methylimidazole, 1-tert-butyl-imidazole, 1-benzyl-2-phenylimidazole, and the like.
  • 1-methylimidazole 1,2-dimethylimidazole, 1- (3-dimethylaminopropyl) imidazole, 1-isobutyl-2-methylimidazole, 1-n-butyl-2-methylimidazole and 1-benzyl- 2-methylimidazole is preferred.
  • Examples of the imidazole compound having at least one imidazole ring include 2,4-diamino-6- [2′-methylimidazolyl- (1) ′]-ethyl-s-triazine, 2,4-diamino- 6- [2'-ethyl-4-methylimidazolyl- (1) ']-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1)']-ethyl-s -Triazine, 2-methylimidazolium isocyanuric acid adduct, 2-phenylimidazolium isocyanuric acid adduct, 4,4'-methylene-bis- (2-ethyl-5-methylimidazole), 1,4-bis [( 1H-imidazol-1-yl) methyl] benzene, 1,1′-carbonyldiimidazole, 1,1′-oxalyld
  • the blending amount of the imidazole compound is desirably within the range of 0.005 to 8 parts by mass with respect to 100 parts by mass of the component (A) solid content.
  • curing catalyst (C) in addition to the imidazole compound, other curing catalysts can be used in combination.
  • other curing catalysts include bismuth compounds, organic acids, carboxylic acid metal salts having 1 to 20 carbon atoms, and tertiary amines.
  • bismuth compound examples include bismuth carboxylate. Specifically, for example, bismuth hexanoate (trivalent), bismuth octoate (trivalent), bismuth 2-ethylhexanoate (trivalent), bismuth oleate (trivalent), bismuth neodecanoate (trivalent), Examples thereof include bismuth versatic acid (trivalent) and bismuth naphthenate (trivalent).
  • the blending amount of the bismuth compound is 4 parts by mass or less, 0.005 to 0.005 to 100 parts by mass of the polyol (A) in solid content. A range of 4 parts by mass is more desirable.
  • the imidazole compound may be used alone, or the imidazole compound and another curing catalyst may be used in combination.
  • the content of the imidazole compound with respect to the total amount of the curing catalyst (C) is not particularly limited, but for example, 99% by mass or more, 95% by mass or more, 90% by mass or more, 80% by mass or more, 70% by mass or more. , 60% by mass or more, 50% by mass or more.
  • coloring component As the coloring component in the coating composition of the present invention, a known color pigment or coloring dye in the coating material field can be used alone or in combination.
  • coloring pigments include titanium oxide, zinc white, carbon black, graphite, iron oxide, molybdenum red, Prussian blue, cobalt blue, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, selenium pigments, Examples include perylene pigments, dioxazine pigments, and diketopyrrolopyrrole pigments.
  • color pigment examples include metal flake powder such as aluminum, paste, pearl powder, graphite, MIO and other bright pigments.
  • metal flake powder examples include aluminum flakes, nickel flakes, copper flakes, stainless steel flakes, brass flakes and chrome flakes.
  • mica powders examples include pearl mica and colored pearl mica.
  • coloring components may be directly added to the coating composition, or may be mixed with a dispersing agent and a dispersing resin to be dispersed and pasted into a coating composition.
  • a dispersing agent and a dispersing resin to be dispersed and pasted into a coating composition.
  • Known dispersants, dispersion resins, and dispersion methods can be used.
  • These components (D) can be used individually by 1 type or in combination of 2 or more types.
  • the coating composition of this invention can contain a water repellent agent.
  • the water repellent include silicon water repellents, fluorine water repellents, waxes such as natural wax and synthetic wax.
  • Examples of the silicon-based water repellent include organopolysiloxanes such as dimethylpolysiloxane, and modified silicon obtained by modifying organopolysiloxane.
  • Specific examples of the modified silicon include alkyl-modified polysiloxane, phenyl-modified polysiloxane, polyester-modified polysiloxane, and polyether-modified polysiloxane, and polyester-modified polysiloxane is preferable. These can be used alone or in combination of two or more.
  • dimethylpolysiloxane, methylphenylpolysiloxane, polyether-modified dimethylpolysiloxane, polyester-modified dimethylpolysiloxane, polymethylalkylsiloxane, polyester-modified methylalkylpolysiloxane, aralkyl-modified methylalkylpolysiloxane, polyether-modified Examples include acrylic group-containing dimethylpolysiloxane and polyester-modified (meth) acryloyl group-containing dimethylpolysiloxane, and polyester-modified dimethylpolysiloxane is preferred.
  • silicon-containing polymerizable unsaturated monomers alone or copolymers with other unsaturated monomers copolymerizable with such monomers alkyl alkoxysilanes such as hexyltrimethoxysilane; heptadecafluorodecyltrimethoxy Examples include, but are not limited to, those containing a fluorine-containing silicon compound such as silane as an active ingredient and dissolved or dispersed in an organic solvent or an aqueous medium.
  • the fluorine-based water repellent is other than the fluorine resin described later (F), and examples thereof include perfluoroalkyl group-containing compounds such as perfluorocarboxylic acid.
  • natural waxes include plant waxes such as candelilla wax, carnauba wax, rice wax, and wax; animal waxes such as beeswax, lanolin, and whale wax; mineral waxes such as montan wax, ozokerite, and ceresin. .
  • Synthetic waxes include synthetic hydrocarbons such as Fischer-Tropsch wax and polyethylene wax; modified waxes such as montan wax derivatives, paraffin wax derivatives such as chlorinated paraffin and solid paraffin, and microcrystalline wax derivatives; 12-hydroxystearin Examples include acid, stearic acid amide, and phthalic anhydride imide. These can be used alone or in combination of two or more.
  • the coating composition of the present invention can contain a fluorine resin.
  • the fluorine resin include PTFE (polytetrafluoroethylene) and polyvinylidene fluoride resins, copolymers of fluoroolefins and unsaturated monomers such as vinyl ether, fluorine-containing acrylic resins, and fluorine-containing polyester resins.
  • PTFE As a commercial item, for example, Teflon (registered trademark) (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) and the like can be mentioned.
  • the polyvinylidene fluoride resin include commercially available products, such as “Kayner 710”, “Kayner 711”, “Kayner 720”, “Kayner 721”, “Kayner 740”, “Kayner 760”, and “Kayner 761”.
  • the copolymer of fluoroolefin and unsaturated monomer such as vinyl ether can be obtained by a known method.
  • the fluoroolefin include C2 or C3 fluoroolefins such as tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, hexafluoropropylene, and pentafluoropropylene. Of these, tetrafluoroethylene and chlorotrifluoroethylene are preferred, and chlorotrifluoroethylene is more preferred because of the good alternating copolymerization with other unsaturated monomers.
  • Examples of the unsaturated monomer copolymerizable with the fluoroolefin include vinyl ethers, allyl ethers, isopropenyl ethers, carboxylic acid vinyl esters, carboxylic acid allyl esters, carboxylic acid isopropenyl ethers, and ⁇ -olefins. , (Meth) acrylic acid esters, hydroxyalkyl vinyl esters, hydroxyalkyl allyl esters, (meth) acrylic acid hydroxyalkyl esters, and the like.
  • vinyl ethers examples include alkyl vinyl ethers such as ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, fluoroalkyl vinyl ether, and perfluoro (alkyl vinyl ether), hydroxyalkyl vinyl ethers, ethylene glycol monovinyl ethers, and the like.
  • hydroxyalkyl vinyl ether examples include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl.
  • Examples include vinyl ether, 5-hydroxypentyl vinyl ether, and 6-hydroxyhexyl vinyl ether.
  • ethylene glycol monovinyl ether examples include diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, and tetraethylene glycol monovinyl ether.
  • allyl ethers examples include alkyl allyl ethers such as ethyl allyl ether and cyclohexyl allyl ether, and hydroxyalkyl allyl ethers.
  • hydroxyalkyl allyl ether examples include 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, and the like.
  • isopropenyl ethers examples include alkyl isopropenyl ethers such as methyl isopropenyl ether.
  • carboxylic acid vinyl esters examples include Veova 10 (trade name, manufactured by Shell Chemical Co., Ltd.) which is a fatty acid vinyl ester having a branched alkyl group, vinyl butyrate, vinyl acetate, vinyl pivalate A And fatty acid vinyl esters.
  • carboxylic acid allyl esters examples include fatty acid allyl esters such as allyl propionate and allyl acetate.
  • ⁇ -olefins examples include ethylene, propylene, isobutylene and the like.
  • (meth) acrylic acid esters examples include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, and the like.
  • hydroxyalkyl vinyl ester examples include 2-hydroxyethyl vinyl ester and 4-hydroxybutyl vinyl ester.
  • hydroxyalkyl allyl ester examples include hydroxyethyl allyl ester and hydroxybutyl allyl ester.
  • (meth) acrylic acid hydroxyalkyl esters examples include hydroxyethyl (meth) acrylate and the like.
  • Examples of commercially available copolymers of fluoroolefin and vinyl ether include Lumiflon series (Asahi Glass Co., Ltd.), Zaffle series (Daikin Kogyo Co., Ltd.), and the like.
  • the fluorine-containing acrylic resin is a resin obtained by copolymerizing a polymerizable unsaturated monomer having a fluorine atom having a perfluoroalkyl group and a polymerizable unsaturated group in one molecule alone or with other unsaturated monomers.
  • the polymerizable unsaturated monomer having a fluorine atom include hexafluoropropene, perfluorocyclohexyl (meth) acrylate, perfluorononylethyl (meth) acrylate, perfluorodecylethyl (meth) acrylate, and perfluorobutylethyl (meth).
  • the other unsaturated monomer copolymerizable with the polymerizable unsaturated monomer having a fluorine atom can be used without particular limitation as long as it can be used in the production of the polyacrylate polyol of (A2). .
  • components (F) may be added after previously dissolved in a solvent, or may be dispersed in a resin solution such as the polyol (A) to form a paint.
  • the coating composition of the present invention further has a hydroxyl group-containing resin other than the component (A), a compound having reactivity with an isocyanate group (for example, an amino compound, etc.), ultraviolet absorption, and the like within a range not impairing the coating film performance.
  • a hydroxyl group-containing resin other than the component (A) a compound having reactivity with an isocyanate group (for example, an amino compound, etc.), ultraviolet absorption, and the like within a range not impairing the coating film performance.
  • Agents for example, benzotriazole absorbers, triazine absorbers, salicylic acid derivative absorbers, benzophenone absorbers, etc.
  • light stabilizers for example, hindered amines, etc.
  • extenders talc, clay, kaolin, barita, sulfuric acid, etc.
  • resin particles thickeners, antifoaming agents, rust inhibitors, chelating agents (acetylacetone, etc.) plasticizers, solvents, pigment dispersants, surface conditioners, sedimentation
  • Known additives for paints such as inhibitors can be included.
  • the blending ratio thereof is usually 1 to 500 parts by mass, preferably 2 to 100 parts by mass with respect to 100 parts by mass of the component (A).
  • the amount can be appropriately set in the range of 300 parts by mass, more preferably 3 to 200 parts by mass.
  • the blending ratio is usually 0.1 to 50 parts by mass, preferably 0.2 to 30 parts by mass with respect to 100 parts by mass of the component (A). It can set suitably in the range of a part.
  • the blending ratio thereof is usually in the range of 1 to 50 parts by mass, preferably 2 to 30 parts by mass with respect to 100 parts by mass of the component (A). It can be set appropriately.
  • the form of the paint composition of the present invention is not particularly limited, and may be any form of a water-based paint, an organic solvent-type paint, and a solventless paint.
  • the water-based paint is a term contrasted with an organic solvent-type paint, and generally, water or a medium containing water as a main component (aqueous medium), a film-forming resin, a pigment, and the like. Means a paint in which is dispersed and / or dissolved.
  • the coating composition of the present invention is a water-based coating
  • the water content in the coating composition is in the range of 10 to 90% by mass, preferably 20 to 80% by mass, more preferably 30 to 70% by mass.
  • the organic solvent-type paint is a paint that does not substantially contain water as a solvent or in which all or most of the solvent is an organic solvent.
  • the coating composition of the present invention is preferably an organic solvent type coating or a non-aqueous dispersion type coating from the viewpoint of the storage stability of the coating.
  • organic solvent examples 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. Although it does not specifically limit as an organic solvent and it can be used, From a viewpoint of the influence on a human body or an environment, it is preferable that toluene, xylene, etc. are not included.
  • the above organic solvents can be used in appropriate combination according to the purpose such as adjustment of viscosity and adjustment of coating property.
  • the solid content of the coating composition of the present invention is such that the solid content is adjusted to 15% by mass or more, particularly preferably 35 to 90% by mass. It is preferable from the viewpoint of reduction.
  • the solid content means a residue excluding volatile components, 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 after drying to the mass before drying as the solid content rate, and multiplying the solid content rate by the sample mass before drying.
  • the paint composition of the present invention may be a one-component paint or a multi-component paint such as a two-component paint.
  • a two-pack type coating comprising a main agent containing polyol (A) and a crosslinking agent containing polyisocyanate compound (B) is preferred.
  • a mixture such as components (C) to (F)
  • solvents such as water or organic solvents, pigment dispersants, anti-settling agents, antifoaming agents, antioxidants, ultraviolet absorbers, etc.
  • Various additives and the like can be appropriately included in either the main agent or the curing agent.
  • the coating composition of the present invention is a one-pack type coating, it is preferable to use a blocked polyisocyanate compound.
  • the present invention provides a coating film forming method for forming a coating film by coating the coating composition on an object to be coated.
  • the object to be coated includes a plastic or metal base material, a base material on which a gel coat material containing an epoxy resin is laminated, a base material film on which the primer coating containing an epoxy resin is formed, or an epoxy material on the base material. What laminated
  • stacked the gel coat material containing resin and formed the primer coating film which contains an epoxy resin further on this gel coat material can be used conveniently.
  • the metal substrate is not particularly limited as long as it is a metal, for example, a metal itself such as magnesium, aluminum, zinc, titanium, iron, nickel, chromium, gold, silver, copper, tin, platinum, palladium, zirconium, tungsten, and the like.
  • metal materials such as alloys of at least two kinds of these metals.
  • the two or more kinds of metal materials include alloyed zinc such as Zn—Al, Zn—Ni, and Zn—Fe, stainless steel, and steel plated with the above metal materials.
  • plastic substrates include polyolefin resins such as polyethylene resins and polypropylene resins; polyester resins such as polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and polyethylene terephthalate / isophthalate; styrene-butadiene block copolymers, styrene-acrylonitrile, acrylonitrile-butadiene -Styrene resins such as styrene (ABS), polystyrene, acrylonitrile-styrene-acrylate, polyamide resins such as nylon 6, nylon 6,6, nylon 6,10, metaxylylene adipamide, polymethyl methacrylate, methyl methacrylate Acrylic resins such as ethyl acrylate; polyvinyl chloride resins, vinylidene chloride resins such as vinyl chloride-vinyl acetate, and unsaturated poly Ester resins, phenol resins,
  • the above-mentioned fiber reinforced plastic means a material whose strength is improved by including a reinforced fiber in the plastic.
  • any known reinforcing fiber such as glass fiber, aramid fiber, and carbon fiber can be used, and a plurality of types of reinforcing fibers can be used in combination.
  • glass fibers and carbon fibers specific strength and specific elastic modulus are superior to those of the plastic substrate itself.
  • glass fiber is included. It is preferable that It is preferable that the ratio of glass fiber to be reinforced in the reinforcing fiber is 10 to 100% by mass.
  • the FRP matrix resin (also referred to as a base resin, which is a plastic that becomes a base material and that becomes a base material after molding) includes the resins, unsaturated polyester resins, and phenols mentioned above in the section on plastic base materials. Resin or the like is used.
  • an epoxy resin is suitable from the viewpoint of adhesion to reinforcing fibers, and any arbitrary epoxy resin can be applied as long as it is suitable for FRP molding.
  • a curing agent may be used, and examples of the curing agent include amine compounds, acid anhydride compounds, polyimide compounds, and imidazole compounds.
  • a known method can be used, and examples thereof include a sheet molding compound (SMC) molding method manufactured using a mold, a resin infusion (RIMP) molding method, a prepreg / autoclave press method, and the like. It is done.
  • SMC sheet molding compound
  • RIMP resin infusion
  • Surfaces such as the above metal substrates or various plastic substrates and parts molded therefrom are subjected to surface treatment such as degreasing, phosphate treatment, chromate treatment, complex oxide treatment, cleaning, polishing, etc. using detergents and solvents. Further, an undercoat coating film (including a coating film formed of a gel coating material) may be formed thereon.
  • surface treatment such as degreasing, phosphate treatment, chromate treatment, complex oxide treatment, cleaning, polishing, etc. using detergents and solvents.
  • an undercoat coating film including a coating film formed of a gel coating material
  • the undercoat coating is a coating formed under the coating formed by the coating composition of the present invention, and the undercoating for forming the undercoat can be applied to the type or state of the surface to be coated. Painted accordingly.
  • the undercoat coating film may be a multilayer of two or more layers in order to improve adhesion.
  • the undercoat film for example, when the substrate is a metal substrate, a coating composition which can be obtained by applying and curing a coating composition called a primer coating and / or an intermediate coating known in the coating field. A membrane is mentioned.
  • a base material is a FRP base material
  • the film etc. which are obtained by coating and hardening on the surface of FRP products called a gel coat material are mentioned.
  • the constituents of the undercoat paint constituting the undercoat coating film include, for example, a film-forming resin, a crosslinking agent, a color pigment, an extender pigment, a glitter pigment, a rust preventive pigment, a conductive pigment, and the like.
  • the undercoating composition can be used as an ultraviolet absorber, a light stabilizer, a curing catalyst, a plasticizer, an adhesion-imparting agent, a compatibilizer, an antifoaming agent, a viscosity modifier, Paint additives such as a rusting agent and a surface conditioner can be appropriately contained.
  • the film-forming resin examples include polyols, acrylic resins, polyester resins, alkyd resins, urethane resins, polyolefin resins, epoxy resins, phenol resins, polyamide resins, and hydroxyl group-containing resins. Or two or more types can be used in combination.
  • crosslinked may be crosslinked by blending a crosslinking agent, or it may be substantially uncrosslinked without blending a crosslinking agent. Moreover, you may make it bridge
  • crosslinking agent for example, amino resins such as melamine resins and urea resins, polyisocyanate compounds, blocked polyisocyanate compounds and the like can be suitably used.
  • the undercoat coating composition either an organic solvent-type coating composition or an aqueous coating composition may be used, or a solvent-free coating composition may be used.
  • the coating composition of the present invention is preferably formed of a coating composition containing an epoxy resin and / or a gel coating material containing an epoxy resin from the viewpoint of impact resistance and adhesion to a coated surface. It is preferable to apply on an article having an undercoat film. Specifically, a laminate in which a gel coat material containing an epoxy resin is laminated on the substrate, a primer coat film containing an epoxy resin formed on the substrate, or a gel coat material containing an epoxy resin is laminated on the substrate. A gel coating material on which a primer coating film containing an epoxy resin is further formed can be suitably used.
  • the gel coat material refers to a coating composition for forming on the surface of the FRP substrate using a mold.
  • a film is formed by previously coating the inner surface of the mold with a film-forming resin that can be the surface of the outer plate, a reinforcing fiber base material is placed on the gel coat material, and the mold is closed.
  • FRP resin is injected, cured, demolded, and the coating is transferred to the surface of the FRP outer plate, or a fiber reinforced plastic material (hereinafter abbreviated as FRP material) in the mold.
  • FRP material fiber reinforced plastic material
  • Examples include a method of heating and molding, then injecting the gel coat material between the obtained molded product and the inner wall of the mold, curing the gel coat material, and then removing the coated molded product from the mold. .
  • the constituent component of the gel coat material those mentioned in the previous section of the undercoat film can be used.
  • the film forming resin in addition to the resins mentioned in the previous section of the undercoat film, any known resin such as polycarbonate resin, vinyl ester resin, unsaturated polyester resin, bismaleimide resin, polyurea resin can be used. .
  • These resins can be used in combination of one or more, but from the viewpoint of adhesion, it is preferable to include an epoxy resin as a part of the constituent components, and from the viewpoint of rain erosion resistance, polyols and aromatic isocyanates, etc.
  • a gel coat material in which an epoxy resin is included in a urethane curable composition using a curing agent is preferred.
  • the epoxy resin contained in the undercoat paint is not particularly limited, and various types can be used.
  • bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, biscresol fluorene type epoxy resin, bisphenol S type epoxy resin, t-butylcatechol type epoxy resin, phenol novolac Type epoxy resin, cresol novolac type epoxy resin, polyvalent epoxy resin such as nonylphenol novolac type epoxy resin, epoxy ester resin modified with dibasic acid etc., alicyclic epoxy resin, polyglycol type epoxy resin, epoxy Examples thereof include a group-containing acrylic resin.
  • the method of applying the undercoat paint other than the gel coat material is not particularly limited, and can be performed using a known coating means, for example, roller, air spray, airless spray, lysing gun, universal gun, brush, roll coater. It can be appropriately selected depending on the use of the base material.
  • the drying conditions can be performed by any of heat drying, forced drying or room temperature drying depending on the type of the undercoat used.
  • the object to be coated other than the above may be an inorganic material such as glass, cement or concrete; wood; fiber material (paper, cloth, etc.), etc., as long as the adhesion is satisfied.
  • ⁇ Degreasing treatment or surface treatment can be appropriately performed according to these objects to be coated.
  • the coating composition of the present invention can be applied to the object to be coated by a method such as electrostatic coating, air spray, airless spray, roller, or brush.
  • the film thickness is preferably in the range of 30 to 500 ⁇ m, more preferably in the range of 50 to 300 ⁇ m, based on the cured coating film, from the viewpoint of rain erosion resistance.
  • a cured coating film can be usually obtained by coating the coating film so as to have a predetermined film thickness and then drying and curing the coating film at room temperature (5 to 35 ° C.), for example.
  • the relative humidity during coating (hereinafter sometimes abbreviated as RH) is preferably 70% or less and 60% or less.
  • the curing time for room temperature drying is preferably 1 day or longer, more preferably 3 days or longer.
  • the coating film may be dried and cured by heating.
  • the temperature at the time of heating is, for example, preferably 30 to 100 ° C., more preferably 35 to 90 ° C.
  • the heating time is preferably, for example, 5 to 120 minutes, more preferably 10 to 100 minutes.
  • the use of the object to be coated with the coating composition of the present invention is not particularly limited, and an article or a part thereof exposed to strong rain wind or sand is particularly preferable.
  • Examples include wind power generator blades, aircraft and helicopter wings, automobiles and bicycles, construction machine bodies, and the like.
  • Part and % indicate “part by mass” and “% by mass” unless otherwise specified.
  • Example 1 50 parts of castor oil (Note 1), 100 parts of TIPAQUE CR-95 (Note 22) and 37.5 parts of butyl acetate were mixed and dispersed with a sand mill to obtain a dispersion paste. 50 parts of Plaxel 410 (Note 14), 0.5 part of 1,2-dimethylimidazole and 1 equivalent of Sumidule N3300 (Note 34) to the hydroxyl group are mixed with the obtained dispersion paste to obtain a solid content of 80%. As shown in FIG. 1 was obtained. The obtained coating composition No. For No. 1, the test of coating workability (pot life and sagging resistance) described later was conducted. Table 1 shows the evaluation results.
  • Examples 2 to 77, 83 to 87, Comparative Examples 1 to 14 Except for the compositions shown in Tables 1 to 7, the coating composition No. 2 to 77 and 83 to 101 were obtained. In the obtained coating composition, the blending amounts in Tables 1 to 7 are indicated by solid content. About the obtained coating composition, the test of postscript coating workability (pot life and sagging resistance) was done. Tables 1 to 7 show the evaluation results.
  • Example 78 50 parts of castor oil (Note 1), 80 parts of TIPAQUE CR-95 (Note 22), 20 parts of Tankar 300 (Note 43) and 37.5 parts of butyl acetate were mixed and dispersed with a sand mill to obtain a dispersed paste. 50 parts of Plaxel 410 (Note 14), 0.5 part of 1,2-dimethylimidazole and 1 equivalent of Sumidule N3300 (Note 34) to the hydroxyl group are mixed with the obtained dispersion paste to obtain a solid content of 80%. As shown in FIG. 78 was obtained.
  • Example 79 Castor oil (Note 1) 50 parts, TIPAQUE CR-95 (Note 22) 80 parts, KAOLIN HA-90T (Note 44) 20 parts, butyl acetate 37.5 parts are mixed and dispersed with a sand mill to obtain a dispersion paste It was. 50 parts of Plaxel 410 (Note 14), 0.5 part of 1,2-dimethylimidazole and 1 equivalent of Sumidule N3300 (Note 34) to the hydroxyl group are mixed with the obtained dispersion paste to obtain a solid content of 80%. As shown in FIG. 79 was obtained.
  • Example 80 50 parts of castor oil (Note 1), 80 parts of TIPAQUE CR-95 (Note 22), 20 parts of BARIFINE BF-20 (Note 45), 37.5 parts of butyl acetate are mixed and dispersed with a sand mill to obtain a dispersion paste It was. 50 parts of Plaxel 410 (Note 14), 0.5 part of 1,2-dimethylimidazole and 1 equivalent of Sumidule N3300 (Note 34) to the hydroxyl group are mixed with the obtained dispersion paste to obtain a solid content of 80%. As shown in FIG. 80 was obtained.
  • Example 81 Mix 50 parts of castor oil (Note 1), 80 parts of TIPAQUE CR-95 (Note 22), 20 parts of Silo Hovic 200 (Note 46) and 37.5 parts of butyl acetate, and disperse with a sand mill to obtain a dispersed paste It was. 50 parts of Plaxel 410 (Note 14), 0.5 part of 1,2-dimethylimidazole and 1 equivalent of Sumidule N3300 (Note 34) to the hydroxyl group are mixed with the obtained dispersion paste to obtain a solid content of 80%. As shown in FIG. 81 was obtained.
  • Example 82 50 parts castor oil (Note 1), TIPAQUE CR-95 (Note 22) 80 parts, 20 parts of silo hovic 200 (46), 0.5 part of BYK-161, 37.5 parts of butyl acetate are mixed and dispersed in a sand mill The dispersion paste was obtained. 50 parts of Plaxel 410 (Note 14), 0.5 part of 1,2-dimethylimidazole and 1 equivalent of Sumidule N3300 (Note 34) to the hydroxyl group are mixed with the obtained dispersion paste to obtain a solid content of 80%. As shown in FIG. 82 was obtained.
  • Test Examples 1 to 71 and Comparative Test Examples 1 to 14 ⁇ Method for producing test plate>
  • the coating composition was applied to the coating materials shown in the column “Coating material” in Tables 1 to 7 by airless spraying so as to have a dry film thickness of 150 ⁇ m.
  • the obtained coating film was dried under the conditions described in the “Drying / Curing Conditions” column of Tables 1 to 7 to obtain test plates. These test plates were subjected to the test described later. Tables 1 to 7 show the evaluation results.
  • Drying / curing condition 1 is to dry by leaving at 20 ° C. and RH 60% for 7 days.
  • Drying / curing condition 2 is drying by leaving at 20 ° C. and RH 90% for 7 days.
  • Drying / curing condition 3 indicates that drying is performed by heating at 80 ° C. for 30 minutes and then leaving at 20 ° C. and RH 60% for 7 days.
  • FRP Epicoat 828 product name, manufactured by Japan Epoxy Resin Co., Ltd., bisphenol A type epoxy resin, solid content 100%
  • Seika Cure-S product name, manufactured by Wakayama Seika Co., Ltd., diaminodiphenyl sulfone, solid content 100
  • phenyldimethylurea average particle size 50 ⁇ m, solid content 100%
  • dicyandiamide average particle size 7 ⁇ m
  • This epoxy resin composition was uniformly applied by a roll coater so that the amount applied was 30 g / m 2 on the release paper to form a resin layer. Both sides of glass fiber 125 g / m 2 were sandwiched between the resin layers, and heated with a roller under conditions of 100 ° C. and 2 kg / cm 2 to obtain a prepreg.
  • Coating object 2 FRP + gel coat Sixteen prepregs were laminated so that the fiber directions were alternately perpendicular to each other and placed in a mold, and the gap between the prepreg and the mold was set to 500 ⁇ m. After injecting a gel coat material having the following composition between the mold and the prepreg, a glass fiber reinforced plastic (coated object 2) having a gel coat layer laminated thereon is heated to 130 ° C. and applied with a pressure of 10 kg / cm 2 for 15 minutes. Obtained.
  • Coating object 3 FRP + primer Using the “Epomarine GX product name, two-component epoxy primer, manufactured by Kansai Paint Co., Ltd.” on the glass fiber reinforced plastic plate shown in the above “Coating object 1: FRP” method The material to be coated 3 was obtained by forming a primer layer having a thickness of 50 ⁇ m.
  • Object 4 FRP + gel coat + primer A primer having a thickness of 50 ⁇ m by an air spray method using (Epomarin GX product name, two-pack type epoxy primer, manufactured by Kansai Paint Co., Ltd.) on a fiber-reinforced plastic plate coated with the gel shown in “Coating object 2: FRP + gel coat”. What formed the layer was set as the to-be-coated article 4.
  • test plate When it is used for a later-described rain erosion test (hereinafter abbreviated as “RET”), an airless spray is used for the above-described objects 1 to 5 formed into the blade shape shown in FIG. Then, the coating composition of the present invention was applied so as to have a dry film thickness of 150 ⁇ m and cured under the “drying / curing conditions” in Tables 1 to 7 as test plates.
  • RET rain erosion test
  • the above-mentioned 1 to 5 coated objects are cut into 10 cm ⁇ 20 cm flat plates and coated with the coating composition of the present invention under the “drying / curing” conditions shown in Tables 1 to 7.
  • the cured product was used as a test plate.
  • Castor oil hydroxyl value 160 mgKOH / g
  • URIC Y-406 Product name, aliphatic compound-modified castor oil hydroxyl value 165 mgKOH / g, manufactured by Ito Oil Co., Ltd.
  • Duranol T5650J Polycarbonate diol, manufactured by Asahi Kasei Chemicals, number average molecular weight 800, hydroxyl value 140 mgKOH / g
  • Duranol T5650E Polycarbonate diol, manufactured by Asahi Kasei Chemicals Corporation, number average molecular weight 500, hydroxyl value 225 mgKOH / g
  • Polyacrylate polyol no. 1 A reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a dropping device was charged with 40 parts of butyl acetate and 40 parts of methoxypropyl acetate, and stirred at 130 ° C.
  • Styrene 5.0 parts n-Butyl acrylate 54.0 parts 2-hydroxyethyl methacrylate 15.0 parts
  • PLACCEL FM-3X product name, ⁇ -caprolactone-modified hydroxyethyl methacrylate, manufactured by Daicel
  • PLACCEL FM-3X product name, ⁇ -caprolactone-modified hydroxyethyl methacrylate, manufactured by Daicel
  • PLACCEL FM-3X product name, ⁇ -caprolactone-modified hydroxyethyl methacrylate, manufactured by Daicel
  • acrylic acid 1.0 part of acrylic acid
  • And V-59 trade name, manufactured by Wako Pure Chemical Industries, Ltd., 2,2′-azobis (2-methylbutyronitrile, polymerization initiator
  • NIPPOLAN 800 Product name, polyester polyol, number average molecular weight 700, hydroxyl value 290 mgKOH / g, solid content 100%, manufactured by Nippon Polyurethane Industry Co., Ltd.
  • TIPAQUE CR-95 Product name, titanium white, manufactured by Ishihara Sangyo Co., Ltd.
  • fluororesin No. No. 1 had a hydroxyl value of 160 mgKOH / g and a number average molecular weight of 5,000.
  • Zaffle GK-510 Product name, PTFE, manufactured by Daikin, hydroxyl value 60 mgKOH / g
  • Dinion TF9205 Polytetrafluoroethylene powder, manufactured by 3M
  • Kyner 711 Product name, polyvinylidene fluoride, manufactured by Arkema
  • KAOLIN HA-90T Product name, calcined kaolin, manufactured by SHANXI JINYANG CALCINED KAOLIN
  • BARIFINE BF-20 Product name, barium sulfate, manufactured by Sakai Chemical Industry Co., Ltd.
  • Silo Hovic 200 Product name, silica, manufactured by Fuji Silysia Chemical Ltd.
  • BYK-161 Product name, pigment Dispersant, BYK (Note 48)
  • BYK-410 Product name, thickener, BYK Note 49)
  • Desmophen NH-1220 Product name, amino compound, manufactured by Bayer MaterialScience (Note 50)
  • HALS 292 Product name, light stabilizer, manufactured by BASF (Note 51)
  • BYK-057 Product name, silicon-free polymer -Based antifoaming agent, manufactured by BYK (Note 52)
  • BYK-066N Product name, silicone-based antifoaming agent, manufactured by BYK
  • Test water droplets having a diameter of 1 to 2 mm were sprayed with water corresponding to precipitation of 30 to 35 mm / hour evenly on the rotating coating surface. The rotation was stopped every 30 minutes, and the coated surface of the front edge of the test plate was visually observed, and the average time during which the coating was scraped 5 cm or more from the tip was recorded. S: More than 5 hours A: 4 hours or more and less than 5 hours B: 3 hours or more and less than 4 hours C: Less than 3 hours.

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Abstract

Le problème à résoudre par la présente invention concerne une composition de revêtement et un procédé de formation de film de revêtement permettant de former, sur un objet à revêtir, un film de revêtement présentant une exceptionnelle usinabilité du revêtement, le film de revêtement ainsi obtenu présentant une exceptionnelle résistance aux chocs telle qu'un résistance à l'érosion par la pluie et une résistance à l'écaillage, une résistance à l'eau et des propriétés de finition, et une exceptionnelle adhésivité à un objet à revêtir tel qu'une pale d'une éolienne électrique ou analogue ; et concerne un objet revêtu par cette composition de revêtement. La présente invention concerne une composition de revêtement contenant (A) un polyol, (B) un composé polyisocyanate, et (C) un catalyseur de durcissement, la composition de revêtement étant caractérisée en ce que le constituant (A) contient un polyol (A1) comprenant un motif structurel dérivé d'un acide gras en C8 ou plus, et le catalyseur de durcissement (C) contient un composé imidazole comprenant au moins un cycle imidazole.
PCT/JP2015/051876 2014-01-24 2015-01-23 Composition de revêtement permettant de former un film de revêtement présentant une résistance aux chocs WO2015111709A1 (fr)

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CN201580005331.7A CN105960441B (zh) 2014-01-24 2015-01-23 用于形成具有耐冲击性的涂膜的涂料组合物

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JP2017193705A (ja) * 2016-04-15 2017-10-26 関西ペイント株式会社 塗料組成物及び塗膜形成方法
JP2019534342A (ja) * 2016-09-06 2019-11-28 アクゾ ノーベル コーティングス インターナショナル ビー ヴィ 熱硬化性組成物、塗装仕上げ方法、および塗装品を製造するための方法
KR20200018979A (ko) * 2018-08-13 2020-02-21 주식회사 케이씨씨 Smc 소재용 도료 키트
WO2024147294A1 (fr) * 2023-01-06 2024-07-11 旭化成株式会社 Composition de polyisocyanate, composition de matériau de revêtement et film de revêtement

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