CN105960441A - Coating composition for forming coating film having impact resistance - Google Patents

Coating composition for forming coating film having impact resistance Download PDF

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Publication number
CN105960441A
CN105960441A CN201580005331.7A CN201580005331A CN105960441A CN 105960441 A CN105960441 A CN 105960441A CN 201580005331 A CN201580005331 A CN 201580005331A CN 105960441 A CN105960441 A CN 105960441A
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China
Prior art keywords
coating composition
acid
polyhydric alcohol
carbon number
coating
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Granted
Application number
CN201580005331.7A
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Chinese (zh)
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CN105960441B (en
Inventor
稻田祐
稻田祐一
日高贵弘
境口绫
山田孝仁
富崎靖洋
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Combustion & Propulsion (AREA)
  • Laminated Bodies (AREA)
  • Wind Motors (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The problem to be solved by the present invention is: to provide a coating composition and coating film formation method capable of forming, on an object to be coated, a coating film having exceptional coating workability, the resulting coating film having exceptional impact resistance such as rain erosion resistance and chipping resistance, water resistance, and finish properties, and exceptional adhesiveness to an object to be coated such as a blade of a wind power generator or the like; and to provide an object coated by this coating composition. The present invention provides a coating composition containing (A) a polyol, (B) a polyisocyanate compound, and (C) a curing catalyst, wherein the coating composition is characterized in that component (A) contains a polyol (A1) having a structural unit derived from a C 8 or higher fatty acid, and the curing catalyst (C) contains an imidazole compound having at least one imidazole ring.

Description

For forming the coating composition of the film with resistance to impact
Technical field
[Cross-Reference to Related Applications]
This application claims based on the Japanese patent application proposed on January 24th, 2,014 (disclosure of which is totally integrating this specification by quoting to the description of No. 2014-011773 In) priority.
The present invention relates to a kind of coating for forming the film with resistance to impact on coated article Compositions, film creating method and use this coating composition formed film article.
Background technology
In recent years, wind energy is attracted attention by people as one of regenerative resource, in order to by it Be converted to electric energy be used, all build in a lot of place, the environment such as land and sea at present It is provided with wind-driven generator, it is contemplated that the most also can increase.
For the blade being arranged on wind-driven generator, owing to this blade itself rotates and sometimes It is exposed in the strongest rain wind and sandstorm etc., therefore, and arranges under normal circumstances or make Coated article (such as, the roof of household and exterior wall, car body) on film compare, Need that there is significantly high resistance to impact.As the coated article being arranged in above-mentioned harsh and unforgiving environments, The wing etc. of aircraft and helicopter can also be enumerated, with the resistance to punching of the film under this harsh and unforgiving environments Hitting property, the most resistance to weathering etc. are evaluated as index.
In the past, for the blade of wind-driven generator, it is known to use coating composition, containing poly-ammonia Situation (the patent that fluoropolymer and polyester polymers are coated with by the gel coating agent etc. of ester Document 1～5).
But, for the film formed by these compositionss, the resistance to impact such as resistance to weathering, Resistance to water is the most insufficient.It addition, implement application under high humidity conditions or in coating or quilt Containing in the case of wetly in coat, it some times happens that the problem of the abnormal appearances such as foaming.
Prior art literature
Patent documentation
Patent documentation 1: No. 2010/122157 handbook of International Publication publication
Patent documentation 2: No. 2005/030893 handbook of International Publication publication
Patent documentation 3: Japanese Unexamined Patent Publication 2002-20686 publication
Patent documentation 4: Japanese Unexamined Patent Application Publication 2013-544898 publication
Patent documentation 5: No. 2013/184424 handbook of International Publication publication
Summary of the invention
Invent technical problem to be solved
The present invention completes in view of the foregoing, its object is to provide a kind of Coating material composition Thing and coating film-forming methods, and the article of application are carried out by this coating composition, wherein, Aforementioned coating composition is little to the dependency of the painting environments such as humidity and the resistance to rain of film that obtained Resistance to impact and resistance to water, the finished appearance (Ga り on bodyguard) such as erosion property, chipping resistance Excellent, and the painting that the cohesive that can form the coated articles such as the blade to wind-driven generator is excellent Film.
Means needed for solution problem
Under such situation, the present inventor etc. is studied intensively, found that: by Containing specific polyhydric alcohol, polyisocyanate compound coating composition in mix specific miaow Azole compounds is as curing catalysts, it is possible to solve above-mentioned technical problem.
The present invention provides coating composition, coating film-forming methods and the tool shown in following every scheme There are the article of film.
1st scheme: a kind of coating composition, it contains (A) polyhydric alcohol, (B) polyisocyanate Cyanate esters and (C) curing catalysts, it is characterised in that described polyhydric alcohol (A) contains There is the polyhydric alcohol (A1) of the construction unit of the fatty acid source with carbon number more than 8, and And described curing catalysts (C) is containing the imidazolium compounds with at least one imidazole ring.
2nd scheme: the coating composition as described in the 1st scheme, wherein, described solidification Catalyst (C) contains the imidazolium compounds represented by general formula (I),
In described logical formula (I), R1Represent that hydrogen atom, the alkyl of carbon number 1～4, carbon are former The cycloalkyl of subnumber 3～8, the hydroxy alkyl of carbon number 1～4, carbon number 6～10 Aryl or acyl group,
R2And R3Separately represent hydrogen atom, the alkyl of carbon number 1～4, carbon atom Hydroxy alkyl, acyl group, alkoxy carbonyl group, carboxyl or the halogen of several 1～4, or R2And R3With R2、R3The carbon atom of upper bonding forms aromatic rings together,
R4Represent hydrogen atom, the alkyl of carbon number 1～12, the thiazolinyl of carbon number 2～4, Aralkyl, can the aryl of substituted base or the functional group shown in lower formula (II),
In described logical formula (II), R5Represent hydrogen atom or the alkyl of carbon number 1～4, p table Show the integer of 1～3
3rd scheme: the coating composition as described in the 2nd scheme, wherein, described formula (I) imidazolium compounds represented by is choosing free 1-Methylimidazole., DMIZ 1,2 dimethylimidazole, 1-(3- Dimethylamino-propyl) imidazoles, 1-isobutyl-2-methyl imidazole, 1-normal-butyl-2-methylimidazole and At least one in the group that 1 benzyl 2 methyl imidazole is constituted.
4th scheme: the coating composition as according to any one of the 1st～3 scheme, wherein, Possibly together with the bismuth compound as described curing catalysts (C).
5th scheme: the coating composition as according to any one of the 1st～4 scheme, wherein,
Described polyhydric alcohol (A1) is that choosing is free
(A1-1) fatty acid of the hydroxyl of carbon number more than 8 and polyhydric alcohol carboxylate,
(A1-2) unsaturated fatty acid of the hydroxyl of carbon number more than 8 polymer,
(A1-3) polymer of the unsaturated fatty acid of carbon number more than 8 is reduced and The polyhydric alcohol that obtains,
(A1-4) unsaturated fatty acid (a1-4-1) and/or carbon to carbon number more than 8 are former The carboxylate (a1-4-2) of the unsaturated fatty acid of subnumber more than 8 and polyhydric alcohol carries out hydroxyl and changes Property and the polyhydric alcohol that obtains
At least one in the group constituted.
6th scheme: the coating composition as described in the 5th scheme, wherein, described polynary Alcohol (A1) is at least one in Oleum Ricini and castor oil hydrogenated.
7th scheme: the coating composition as according to any one of the 1st～6 scheme, it is also Containing as the free polycaprolactone glycol of choosing of described polyhydric alcohol (A), polycaprolactonetriol, In the group that polycaprolactone tetraol, PCDL and polyacrylate polyol are constituted extremely Few a kind of polyhydric alcohol (A2).
8th scheme: the coating composition as described in scheme 7, wherein, relative to 100 matter The composition (A) of amount part, the combined amount of described polyhydric alcohol (A1) is 10 mass parts～70 matter Amount part, the combined amount of described polyhydric alcohol (A2) is in the range of 30 mass parts～90 mass parts.
9th scheme: the coating composition as according to any one of the 1st～8 scheme, wherein, Relative to the composition (A) of 100 mass parts, there is the imidazolium compounds of at least one imidazole ring Combined amount be 0.005 mass parts～8 mass parts.
10th scheme: the coating composition as according to any one of the 1st～9 scheme, its Possibly together with coloring components (D).
11st scheme: the coating composition as according to any one of the 1st～10 scheme, its Possibly together with water-repelling agent (E) and/or fluororesin (F).
12nd scheme: a kind of coating film-forming methods, wherein, will appoint in the 1st～11 scheme One described coating composition is painted on coated article formation film.
13rd scheme: the coating film-forming methods as described in the 12nd scheme, wherein, described Coated article is plastics or the base material of metal, the gel coating material containing epoxy resin is layered in institute State the object on base material, by containing epoxy resin primer coating film formed on the substrate and Become object or by the gel coating material stacking containing epoxy resin on the substrate and The object of the primer coating film containing epoxy resin is formed further on described gel coating material.
14th scheme: the coating film-forming methods as described in the 12nd or 13 scheme, wherein, Coated article is the blade of wind-driven generator.
15th scheme: a kind of article, it is by by institute any one of the 1st～11 scheme The coating composition stated is painted on the article obtained on coated article.
The effect of invention
In the case of the coating composition using the present invention, it is possible at the blade of wind-driven generator Surfaces etc. are upper to be formed outside the resistances to impact such as resistance to weathering, chipping resistance and resistance to water, finished product See excellent and excellent to the cohesive of blade film.It addition, at the bar having moisture to be mingled with (that is, the application under high humility atmosphere, substrate contain the painting in the case of moisture in application under part Dress etc.) in also there is excellent curable, and suppress film to bubble, it is possible to obtain stably Film physical property.
Additionally, in the present invention, enough according to the side described in the embodiment of the present application for resistance to weathering performance Method is evaluated.
Accompanying drawing explanation
Fig. 1 is the axonometric chart representing the bread board tested in the embodiment of the present application for weathering.
Detailed description of the invention
Coating composition
The present invention provides a kind of coating composition, and it contains (A) polyhydric alcohol, (B) many isocyanides Ester compound and (C) curing catalysts, it is characterised in that this composition (A) is containing having The polyhydric alcohol (A1) of the construction unit of the fatty acid source of carbon number more than 8, and this solidification Catalyst (C) is the imidazolium compounds with at least one imidazole ring.
(A) polyhydric alcohol
In the present invention, for (A) polyhydric alcohol, as long as comprising, there is carbon number 8 The polyhydric alcohol (A1) of the construction unit of above fatty acid source, just there is no particular limitation.
There is the polyhydric alcohol (A1) of the construction unit of the fatty acid source of carbon number more than 8
In the present invention, so-called " have the construction unit of the fatty acid source of carbon number more than 8 Polyhydric alcohol (A1) ", refer to the polyhydric alcohol with the construction unit of fatty acid source, and table Show the carbon atom of at least 1 unit in the construction unit of the fatty acid source constituting this polyhydric alcohol Number is more than 8.
As composition (A1), for example, it is possible to enumerate:
(A1-1) fatty acid of the hydroxyl of carbon number more than 8 and the carboxylate of polyhydric alcohol；
(A1-2) polymer of the unsaturated fatty acid of the hydroxyl of carbon number more than 8；
(A1-3) carry out reducing by the polymer of the unsaturated fatty acid of carbon number more than 8 and The polyhydric alcohol obtained；
(A1-4) by former to unsaturated fatty acid (a1-4-1) and/or the carbon of carbon number more than 8 The carboxylate (a1-4-2) of the unsaturated fatty acid of subnumber more than 8 and polyhydric alcohol carries out hydroxyl and changes Property and the polyhydric alcohol etc. that obtains.
As the fatty acid of hydroxyl of the carbon number more than 8 of constituent (A1-1), example As, carbon number can be enumerated and be 8～28, be preferably the fatty acid of the hydroxyl of 10～20； More specifically, can enumerate the hydroxyl such as castor oil acid, ricinelaidic acid unsaturated fatty acid, The satisfied fatty acid etc. of the hydroxyls such as 12-hydroxy stearic acid, cerebronic acid.For these hydroxyls Fatty acid, the one or two kinds of that can be used alone combination of the above uses.
As the polyhydric alcohol of constituent (A1-1), glycerol, ethylene glycol, poly-second can be enumerated Glycol, propylene glycol, polypropylene glycol, trimethylolpropane, tetramethylolmethane, sorbitol etc..Right In these polyhydric alcohol, the one or two kinds of that can be used alone combination of the above uses.
As the carboxylate of fatty acid and polyhydric alcohol of the hydroxyl of carbon number more than 8, permissible Enumerate the above-mentioned carbon number more than 8 enumerated hydroxyl fatty acid with above-mentioned enumerate polynary The carboxylate etc. of alcohol.
It addition, in a preferred embodiment of the invention, as the thing containing composition (A1-1) Matter, can enumerate Oleum Ricini, castor oil hydrogenated etc..Oleum Ricini is using the seed of Semen Ricini as former The vegetable oil of material, it is known that be that the unsaturated fatty acid such as castor oil acid, oleic acid and Palmic acid etc. are saturated The glyceride of fatty acid.Here, it is the hydroxyl of carbon number more than 8 due to castor oil acid Fatty acid, therefore, using Oleum Ricini or as the castor oil hydrogenated of its modifier as composition (A) The material being mixed in coating composition can contain composition (A1-1).For these compositions (A1-1) one or two kinds of that, can be used alone combination of the above uses.
As constitute polymeric composition (A1-2) carbon number more than 8 hydroxyl not Satisfied fatty acid, it is, for example possible to use as constituent (A1-1) carbon number 8 with On hydroxyl unsaturated fatty acid example listed by the material enumerated, it may be preferred to enumerate castor Oleum Sesami acid, ricinelaidic acid etc..
As polymer, there is no particular limitation, can enumerate dimer, trimer, four gather Thing etc., preferably dimer.Accordingly, as composition (A1-2), above-mentioned enumerating can be enumerated The dimer of unsaturated fatty acid of hydroxyl of carbon number more than 8, trimer, four gather Thing etc., preferably dimer.For these compositions (A1-2), the one that can be used alone or It is used in combination.
Unsaturated lipid as the carbon number more than 8 constituting the raw material being used as composition (A1-3) Polymeric, the unsaturated fatty acid of carbon number more than 8 of fat acid, for example, it is possible to enumerate Carbon number is 8～28, is preferably the unsaturated fatty acid of 10～20；More specifically, may be used With enumerate the unsaturated fatty acid of the hydroxyl such as castor oil acid, ricinelaidic acid, myristoleic acid, Palmitoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, 20 carbon one alkene Acid, erucic acid, nervonic acid, linoleic acid, eicosadienoic acid, two dodecadienoic acids, Caulis et Folium Lini Acid, pinolenic acid, eleostearic acid, Mead acid, eicosatrienoic acid, parinaric acid, Semen arachidis hypogaeae The unsaturated fatty acid etc. of the not hydroxyl such as tetraenoic acid, eicosatetraenoic acid, Adrenic acid..
Unsaturated fatty acid as the carbon number more than 8 of the raw material as composition (A1-3) Polymer, the dimer of the unsaturated fatty acid of carbon number more than 8, trimerization can be enumerated Thing, tetramer etc., preferably dimer.Accordingly, as the raw material as composition (A1-3) The polymer of unsaturated fatty acid of carbon number more than 8, the above-mentioned carbon enumerated can be enumerated The dimer of the unsaturated fatty acid of atomic number more than 8, trimer, tetramer etc., be preferably Dimer.For composition (A1-3), can enumerate above-mentioned carbon number more than 8 The polymer of unsaturated fatty acid uses method known per se to carry out the material reduced.Make For the typical example of composition (A1-3), such as can enumerate castor oil acid, oleic acid, linoleic acid, Linolenic acid, the reduzate etc. of dimeric dibasic acid of eleostearic acid.
It addition, constitute the unsaturated fatty acid of the carbon number more than 8 of mentioned component (A1-3) Polymer, it is possible to use market sale product.As market sale product, for example, it is possible to enumerate The PRIPOL2033 etc. of CRODA company.
For these compositions (A1-3), the one or two kinds of that can be used alone combination of the above uses.
Unsaturated fatty acid as the carbon number more than 8 of the raw material as composition (A1-4) (a1-4-1), for example, it is possible to enumerate carbon number and be 8～28, be preferably 10～20 not Satisfied fatty acid；More specifically, the hydroxyl such as castor oil acid, ricinelaidic acid can be enumerated Unsaturated fatty acid, myristoleic acid, palmitoleic acid, palmitoleic acid, oleic acid, elaidic acid, Vaccenic acid, gadoleic acid, 20 carbon monoenoic acids, erucic acid, nervonic acid, linoleic acid, 20 carbon two The acid of olefin(e) acid, two dodecadienoic acids, linolenic acid, pinolenic acid, eleostearic acid, Mead, 20 carbon Trienic acid, parinaric acid, arachidonic acid, eicosatetraenoic acid, Adrenic acid. etc. are no The unsaturated fatty acid etc. of hydroxyl.As composition (a1-4-1), above-mentioned carbon is preferably used former The unsaturated fatty acid of the not hydroxyl of subnumber.
As the polyhydric alcohol of constituent (A1-4), glycerol, ethylene glycol, poly-second can be enumerated Glycol, propylene glycol, polypropylene glycol, trimethylolpropane, tetramethylolmethane, sorbitol etc..Right In these polyhydric alcohol, the one or two kinds of that can be used alone combination of the above uses.
It addition, the unsaturation of the carbon number more than 8 as the raw material as composition (A1-4) Fatty acid and the carboxylate (a1-4-2) of polyhydric alcohol, for example, it is possible to enumerate above-mentioned carbon number 8 Above unsaturated fatty acid and the carboxylate etc. of above-mentioned polyhydric alcohol；More specifically, Ke Yiju Go out carbon number to be 8～28, be preferably the unsaturated fatty acid of 10～20 and the esterification of polyhydric alcohol Thing etc.；More specifically, it may be preferred to use carbon number to be more than 8, be preferably carbon The glyceride of atomic number 8～28, the more preferably unsaturated fatty acid of carbon number 10～20.
The glyceride of the unsaturated fatty acid of above-mentioned carbon number more than 8, such as, is included in oil In fat.Accordingly, as the raw material of mentioned component (A1-4), using composition (a1-4-2) In the case of, it is possible to use the glyceride of the unsaturated fatty acid containing carbon number more than 8 Oils and fats.
As the oils and fats of the glyceride of the unsaturated fatty acid containing above-mentioned carbon number more than 8, For example, it is possible to soybean oil, Oleum Ricini, Petiolus Trachycarpi oil, Oleum Brassicae campestris etc. are preferably used.
The unsaturated fatty acid (a1-4-1) of the above-mentioned carbon number more than 8 in composition (A1-4) And/or the carboxylate (a1-4-2) of the unsaturated fatty acid of carbon number more than 8 and polyhydric alcohol Hydroxyl modification can use method known per se to implement.Specifically, for example, it is possible to enumerate Peroxide is used to be entered by the unsaturated group in mentioned component (a1-4-1) and/or (a1-4-2) After row epoxidation, make the method that the epoxide of generation reacts with monohydric alcohol or polyhydric alcohol Deng.
As being used for making the unsaturated group in mentioned component (a1-4-1) and/or (a1-4-2) send out Raw epoxidised peroxide, for example, it is possible to enumerate peracetic acid, hydrogen peroxide etc..
As the monohydric alcohol for making above-mentioned epoxide generation hydroxyl modification, for example, it is possible to lift Go out: the straight chain primary alcohols such as methanol, ethanol, propanol；The secondary alcohol such as isopropanol；1-propenol-3s etc. are containing insatiable hunger Alcohol with group；The branched-chain alcoho such as isobutanol, neopentyl alcohol；The cyclic alcohol such as Hexalin, benzylalcohol；Second The ethylene glycol monoalkyl ethers such as glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether；Two The diethylene glycol monoalky lethers such as glycol monoethyl ether；The propylene-glycol monoalky lethers such as propylene glycol monomethyl ether； The dipropylene glycol monoalkylether etc. such as dipropylene glycol monomethyl ether.For these monohydric alcohols, can individually make Use by one or two kinds of combination of the above.As being used for making above-mentioned epoxide generation hydroxyl change Property polyhydric alcohol, for example, it is possible to enumerate glycerol, ethylene glycol, Polyethylene Glycol, propylene glycol, poly- Propylene glycol, butanediol, neopentyl glycol, trimethylolpropane, tetramethylolmethane, sorbitol etc.. For these polyhydric alcohol, the one or two kinds of that can be used alone combination of the above uses.
It addition, as mentioned component (A1-4), it is possible to use market sale product.As market Sales item, for example, it is possible to enumerate the Sovermol 750 of BASF AG, Sovermol 760, Sovermol 805, Sovermol 815, Sovermol 819 etc..
For these compositions (A1-4), the one or two kinds of that can be used alone combination of the above uses.
It addition, for these compositions (A1-1), composition (A1-2), composition (A1-3) and Composition (A1-4), can be used alone one or two kinds of combination of the above and uses.
In the present invention, (A) polyhydric alcohol can also be containing the polyhydric alcohol in addition to composition (A1).
In a preferred embodiment of the invention, as the polyhydric alcohol beyond composition (A1), can To use from polycaprolactone glycol, polycaprolactonetriol, polycaprolactone tetraol, Merlon two At least one polyhydric alcohol (A2) selected in the group that alcohol, polyacrylate polyol are constituted.
Polyhydric alcohol (A2)
For polycaprolactone polyol, such as, can by by 6-caprolactone with binary～quaternary Polyhydric alcohol carries out ring-opening polymerisation as initiator and obtains.As polyhydric alcohol more than this binary, For example, it is possible to enumerate ethylene glycol, glycerol, trimethylolethane, trimethylolpropane, double sweet Oil, double trimethylolpropane, 1,2,6-hexanetriol, tetramethylolmethane, three (2-ethoxy) isocyanide urea Acid, make dimethylolalkanoic acids and mono-epoxy compounds (such as, HEXION Specialty " Cardura E10 ", the shrink of synthesis height chain saturated fatty acid that Chemicals company manufactures are sweet Grease) react obtained polyol compound etc..For these compositions, can individually make It is applied in combination with one or more.
It addition, as above-mentioned polycaprolactone polyol, it is possible to use market sale product.As city Field sales item, for example, it is possible to enumerate: Daisel chemical industry Co., Ltd (Daicel Chemical Industries Ltd.) " Placcel 205 " as Placcel 200 the series, " Placcel that manufacture 205H”、“Placcel L205AL”、“Placcel C205U”、“Placcel 208”、“Placcel 210”、“Placcel 210N”、“Placcel 210CP”、“Placcel 212”、“Placcel 212AL”、 " Placcel 220 ", " Placcel 220N ", " Placcel 220CPB ", " Placcel 220UA ", As Placcel 300 series " Placcel 303 ", " Placcel 305 ", " Placcel 308 ", “Placcel 309”、“Placcel 312”、“Placcel 320”、“Placcel 320AL”、“Placcel 410 " etc.；" TONE301 " that Dow Chemical (Dow Chemical Company) manufactures, " TONE305 " etc..
From the viewpoint of resistance to weathering, in polycaprolactone polyol, preferably its hydroxyl value exists In the range of 100mgKOH/g～700mgKOH/g, more preferably at 130mgKOH/g～ In the range of 600mgKOH/g, further particularly preferably at 150mgKOH/g～ In the range of 500mgKOH/g, it is also preferable to its number-average molecular weight is 200～1800 In the range of and there is in a molecule plural hydroxyl.
Specifically, in polycaprolactone polyol, preferably polycaprolactonetriol, polycaprolactone four Alcohol.
For PCDL, such as, can be anti-by making diol component and carbonyl agent occur Should obtain.As the carbonyl agent of composition PCDL, for example, it is possible to enumerate carbonic acid Ethyl, propylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, carbonic acid Diphenyl ester, diphenyl carbonate, phosgene etc..As the diol component of PCDL, can To enumerate aliphatic diol, alicyclic diol etc.；As instantiation, Isosorbide-5-Nitrae-fourth can be enumerated Glycol, 3-methyl isophthalic acid, aliphatic diol, the 1,4-such as 5-pentanediol, 1,6-HD, diethylene glycol Esterdiol class or the bisphenol-As such as the alicyclic diols such as cyclohexanediol, double (ethoxy) terephthalate The aromatic diol such as alkylene oxide adduct.
As above-mentioned PCDL, it is possible to use market sale product.As market sale product, For example, it is possible to enumerate: Daisel chemical industry Co., Ltd (Daicel Chemical Industries Ltd.) " Placcel CD CD205 ", " Placcel CD CD205PL ", " the Placcel CD manufactured CD205HL”、“Placcel CD CD210”、“Placcel CD CD210PL”；Asahi Chemical Industry's strain Formula commercial firm manufacture " Duranol T5652 ", " Duranol T5651 ", " Duranol T5650J ", “Duranol 5650E”、“Duranol G4672”、“Duranol T4671”、“Duranol T4692 ", " Duranol T4691 " etc..
For these PCDLs, the one or two kinds of that can be used alone combination of the above uses.
From the viewpoint of resistance to weathering, in PCDL, preferably its hydroxyl value exists In the range of 110mgKOH/g～700mgKOH/g, more preferably at 130mgKOH/g～ In the range of 600mgKOH/g and then particularly preferably at 150mgKOH/g～500mgKOH/g In the range of, preferably its number-average molecular weight is in the range of 200～1800.
As polyacrylate polyol, generally, method known per se, such as can be used The methods such as solution polymerization process in organic solvent, by by the polymerism unsaturation list of hydroxyl Body and other polymerisms can being copolymerized with the polymerism unsaturated monomer of this hydroxyl are unsaturated Monomer carries out copolymerization and manufactures.
The polymerism unsaturated monomer of hydroxyl be respectively provided with in a molecule more than one Hydroxyl and the compound of polymerism unsaturated bond, specifically, for example, it is possible to enumerate: (first Base) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 3- Hydroxypropyl acrylate, (methyl) acrylic acid 4-hydroxy butyl ester, (methyl) acrylic acid 5-hydroxy pentane ester, (first Base) the own ester of acrylic acid 6-hydroxyl, (methyl) acrylic acid 7-hydroxyl heptyl ester, (methyl) acrylic acid 8- The monoesters compound of the dihydroxylic alcohols of (methyl) acrylic acid such as hydroxyl monooctyl ester and carbon number 2～8；Should (first Base) the 6-caprolactone modification body of monoesters compound of dihydroxylic alcohols of acrylic acid and carbon number 2～8； N-methylol (methyl) acrylamide；There is 1-propenol-3 and then molecular end is the tool of hydroxyl There is (methyl) acrylate etc. of polyethylene oxide chain.Additionally, in the present invention, described later 2-hydroxyl-4-(3-methacryloxy-2-hydroxy propyloxy group) benzophenone etc. has ultraviolet and inhales The polymerism unsaturated monomer of Shou Xing functional group is included in can be with the polymerism unsaturation list of hydroxyl In other polymerism unsaturated monomers that body is copolymerized, and not it is included in the polymerization of hydroxyl In property unsaturated monomer.
It addition, be polymerized as other can being copolymerized with the polymerism unsaturated monomer of hydroxyl Property unsaturated monomer, for example, it is possible to enumerate: (methyl) acrylic acid methyl ester., (methyl) third Olefin(e) acid ethyl ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) N-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (first Base) the most own ester of acrylic acid, (methyl) n-octyl, (methyl) acrylic acid 2-second oneself Ester, (methyl) acrylic acid nonyl ester, (methyl) tridecyl acrylate, (methyl) third Olefin(e) acid lauryl, (methyl) stearyl acrylate acyl ester, " acrylic acid isooctadecane ester (trade name Claim, Osaka Organic Chemical Industry Co., Ltd. manufacture) ", (methyl) cyclohexyl acrylate, (first Base) acrylic methyl cyclohexyl, (methyl) t-butylcyclohexyl ester, (methyl) third (methyl) alkyl acrylate or (methyl) the acrylate bases such as olefin(e) acid cyclo-dodecyl ester Ester；(methyl) isobornyl acrylate etc. has the polymerism unsaturated monomer of isobornyl； (methyl) acrylic acid adamantane esters etc. has the polymerism unsaturated monomer of adamantyl；Benzene The vinyl aromatic compounds such as ethylene, α-methyl styrene, vinyltoluene；Vinyl three Methoxy silane, VTES, vinyl three (2-methoxy ethoxy) silicon Alkane, γ-(methyl) acryloxypropyl trimethoxy silane, γ-(methyl) acryloxy Propyl-triethoxysilicanes etc. have the polymerism unsaturated monomer of alkoxysilane group；Perfluor fourth The perfluor alkane such as base ethyl (methyl) acrylate, perfluorooctylethyl group (methyl) acrylate Base (methyl) acrylate；Fluoroolefins etc. have the polymerism unsaturated monomer of fluorinated alkyl； Dimaleoyl iminos etc. have the polymerism unsaturated monomer of optical polymerism functional group；N-ethylene pyrrole The ethylene such as pyrrolidone, ethylene, butadiene, chlorobutadiene, propionate, vinylacetate Based compound；(methyl) acrylic acid, maleic acid .beta.-methylacrylic acid, β-acryloxypropionic acid etc. contain The polymerism unsaturated monomer of carboxyl；(methyl) acrylonitrile, (methyl) acrylamide, (first Base) acrylic acid N, N-dimethylamino ethyl ester, N, N-dimethylamino-propyl (methyl) acryloyl The polymerism that the adduct of amine, (methyl) glycidyl acrylate and amines etc. are nitrogenous Unsaturated monomer；(methyl) allyl acrylate, 1,6-HD two (methyl) acrylic acid The polymerism that ester etc. have plural polymerism unsaturated group in a molecule is unsaturated Monomer；(methyl) glycidyl acrylate, (methyl) propenoic acid beta-methyl glycidyl Ester, (methyl) acrylic acid 3,4-expoxycyclohexyl methyl ester, (methyl) acrylic acid 3,4-ring Epoxide cyclohexyl ethyl ester, (methyl) acrylic acid 3,4-expoxycyclohexyl propyl ester, pi-allyl contract The polymerism unsaturated monomer containing epoxy radicals such as water glycerin ether；Molecular end is having of alkoxyl (methyl) acrylate of polyethylene oxide chain；2-acrylamide-2-methyl propane sulfonic acid, third Olefin sulfonic acid, styrene sulfonic acid sodium salt, sulfoethyl methacrylate and sodium salt, ammonium salt etc. There is sulfonic polymerism unsaturated monomer；2-acryloyl-oxyethyl phosphate ester acid, 2- Methacryloxyethyl phosphate ester acid, 2-acryloxypropyl phosphate ester acid, 2- Methacryloxypropyl phosphate ester acid etc. has the polymerism unsaturated monomer of phosphate； 2-hydroxyl-4-(3-methacryloxy-2-hydroxy propyloxy group) benzophenone, 2-hydroxyl-4-(3-third Alkene acyloxy-2-hydroxy propyloxy group) benzophenone, 2,2 '-dihydroxy-4-(3-methacryloxy -2-hydroxy propyloxy group) benzophenone, 2,2 '-dihydroxy-4-(3-acryloxy-2-hydroxy propyloxy group) The tool such as benzophenone, 2-(2 '-hydroxyl-5 '-methaciylyloxyethylphenyl)-2H-benzotriazole There is the polymerism unsaturated monomer of ultraviolet-absorbing functional group；4-(methyl) acryloxy -1,2,2,6,6-pentamethvl, 4-(methyl) acryloxy-2,2,6,6-tetramethyl piperidine, 4- Cyano group-4-(methyl) Acryloyl amino-2,2,6,6-tetramethyl piperidine, 1-(methyl) acryloyl Base-4-(methyl) Acryloyl amino-2,2,6,6-tetramethyl piperidine, 1-(methyl) acryloyl group -4-cyano group-4-(methyl) Acryloyl amino-2,2,6,6-tetramethyl piperidine, 4-crotonocyl epoxide -2,2,6,6-tetramethyl piperidine, 4-crotonocyl amino-2,2,6,6-tetramethyl piperidine, 1-crotonocyl-4- The UV stable polymerism unsaturated monomers such as crotonocyl epoxide-2,2,6,6-tetramethyl piperidine；Third Olefine aldehydr, N-[2-(2-methyl-4-oxopentyl), diacetone methacrylamide, methacrylic acid acetoacetyl Epoxide ethyl ester, formoxyl styrene, there is the vinyl alkyl ketone of 4～7 carbon atoms (such as, Ethenyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) etc. there is the polymerism of carbonyl Unsaturated monomer compound etc..They can individually be used or be used in combination.
For polyacrylate polyol, curable feature from low temperature and being obtained From the viewpoint of the resistance to water of film, it is usually preferred to have at 30mgKOH/g～ In the range of 300mgKOH/g, particularly preferably have at 40mgKOH/g～250mgKOH/g In the range of, the most particularly preferably there is the scope at 50mgKOH/g～200mgKOH/g Interior hydroxyl value.
Polyacrylate polyol, it is usually preferred to have in the range of 3000～100000, special The most preferably have in the range of 3000～50000, the most particularly preferably have 4000～ Weight average molecular weight in the range of 30000.
" weight average molecular weight ", " number-average molecular weight " in this specification is according to JIS K Method described in 0124-2011, according to the chromatograph using gel permeation chromatography device to measure with standard Value calculated on the basis of the molecular weight of polystyrene.Gel permeation chromatography device uses " HLC8120GPC " (TOSOH Co., Ltd of Japan manufactures).Chromatographic column uses " TSKgel G-4000H×L”、“TSKgel G-3000H×L”、“TSKgel G-2500H×L”、“TSKgel G-2000H × L " (trade name is TOSOH Co., Ltd of Japan and manufactures) these 4 posts, Flowing mutually for oxolane, measure temperature be 40 DEG C, flow velocity be 1mL/ minute, detector is Measure under conditions of RI.
As polyacrylate polyol, from the viewpoint of resistance to weathering, preferably as containing hydroxyl The polymerism unsaturated monomer of base and (methyl) acrylate with polycaprolactone skeleton are carried out The polyacrylate polyol of copolymerization and hy-droxybutyl (HBA) carry out copolymerization and The polyacrylate polyol become.
For composition (A1) and the use ratio of composition (A2), it is not particularly limited, but From the viewpoint of finished appearance and resistance to weathering, relative to the composition (A) of 100 mass parts, The combined amount of preferred component (A1) is 10 mass parts～80 mass parts, more preferably 10 mass Part～70 mass parts.It addition, from the viewpoint of finished appearance and resistance to water, relative to 100 The composition (A) of mass parts, the combined amount of preferred component (A2) is 20 mass parts～90 matter Amount part, more preferably 30 mass parts～90 mass parts.These compositions (A) can be used alone or Person is used in combination.
Polyhydric alcohol (A3) in addition to composition (A1) and (A2)
(A) polyhydric alcohol in the present invention, it is possible to include in addition to composition (A1) and (A2) Polyhydric alcohol (A3).As the polyhydric alcohol of composition (A3), it is to be not classified as (A1) (A2) polyol component, for example, it is possible to enumerate: except (A1) and (A2) with Outer polyhydric alcohol, PEPA, Polyacetal polyols, polyester amide polyol or polythiaether Polyhydric alcohol, the resin etc. of other hydroxyls.
As the polyhydric alcohol in addition to above-mentioned (A1) and (A2), can enumerate: as one Individual molecule has the compound of two hydroxyls and at the aliphatic diol of foregoing illustrative, aromatic series The PTMEG classes such as glycol, Polyethylene Glycol, polypropylene glycol, polytetramethylene glycol；Glycerol, three hydroxyl first Base ethane, trimethylolpropane, diglycerol, triglycerin, 1,2,6-hexanetriol, tetramethylolmethane, Bis(pentaerythritol), three (2-ethoxy) isocyanuric acid ester, sorbitol, saccharide, mannitol etc. 3 Alcohol more than valency；The polyester that the alcohol making more than these trivalents reacts with anhydride etc. and obtains is many Unit's alcohols etc..
As the resin of hydroxyl than that described above, for example, it is possible to enumerate gathering containing hydroxyl The resins such as ether resin, polycarbonate resin, polyurethane resin, epoxy resin, alkyd resin. They can individually be used or be used in combination.
As long as not damaging in the range of film performance, can be containing in addition to composition (A) Polyhydric alcohol (A3).As polyols blend (A3), the resin with polyhydric alcohol (A) is solid Body composition total amount is as benchmark, and preferably its mixed proportion is below 30 mass %.
(B) polyisocyanate compound
Polyisocyanate compound (B) is to have at least two isocyanates in a molecule The compound of base, for example, it is possible to enumerate: aliphatic polyisocyante, alicyclic polyisocyanic acid Ester, aromatic-aliphatic polyisocyanates, aromatic polyisocyanate, these polyisocyanates Derivant etc..
As above-mentioned aliphatic polyisocyante, for example, it is possible to enumerate: trimethylene two isocyanide Acid esters, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene two isocyanide Acid esters, 1,2-trimethylene diisocyanate, 1,2-tetramethylene diisocyanate, 2,3-butylidene two Isocyanates, 1,3-tetramethylene diisocyanate, 2,4,4 or 2,2,4-tri-methyl hexamethylene two are different Cyanate, dimer acid diisocyanate, 2,6-diisocyanate methyl caproate (common name: rely Propylhomoserin diisocyanate) etc. aliphatic diisocyanate；2,6-bis-isocyanate group caproic acid 2-isocyanide Acidic group ethyl ester, 1,6-bis-isocyanate group-3-isocyanatometyl hexane, 1,4,8-tri-isocyanate group are pungent Alkane, 1,6,11-tri-isocyanate group hendecane, 1,8-bis-isocyanate group-4-isocyanatometyl octane, 1,3,6-tri-isocyanate group hexane, 2,5,7-trimethyl-1,8-two isocyanate group-5-isocyanatometyl The aliphatic triisocyanates etc. such as octane.
As aforementioned alicyclic polyisocyanates, for example, it is possible to enumerate: 1,3-cyclopentenes two is different Cyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate group Methyl-3,5,5-trimethylcyclohexylisocyanate (common name: isophorone diisocyanate), 4-methyl isophthalic acid, 3-cyclohexene diisocyanate (common name: hydrogenation TDI), 2-methyl isophthalic acid, 3-hexamethylene Double (isocyanatometyl) hexamethylene (common name: hydrogenation of benzene of alkene diisocyanate, 1,3-or 1,4- Dimethyl diisocyanate) or its mixture, di-2-ethylhexylphosphine oxide (4,1-hexamethylene diyl) two Carbimide .s The alicyclic diisocyanates such as ester (common name: hydrogenation MDI), norbornene alkyl diisocyanate； 1,3,5-tri-isocyanate group hexamethylene, 1,3,5-trimethyl isocyanate group hexamethylene, 2-(3-Carbimide. Base propyl group)-2,5-two (isocyanatometyl)-dicyclo (2.2.1) heptane, 2-(3-isocyanate group third Base)-2,6-two (isocyanatometyl)-dicyclo (2.2.1) heptane, 3-(3-isocyanate group propyl group)-2,5- Two (isocyanatometyl)-dicyclo (2.2.1) heptane, 5-(2-isocyanatoethyl)-2-isocyanate group first Base-3-(3-isocyanate group propyl group)-dicyclo (2.2.1) heptane, 6-(2-isocyanatoethyl)-2-Carbimide. Ylmethyl-3-(3-isocyanate group propyl group)-dicyclo (2.2.1) heptane, 5-(2-isocyanatoethyl)-2- Isocyanatometyl-2-(3-isocyanate group propyl group)-dicyclo (2.2.1)-heptane, 6-(2-isocyanate group second Base)-2-isocyanatometyl-2-(3-isocyanate group propyl group)-dicyclo (2.2.1) heptane etc. alicyclic three Isocyanates etc..
As aforementioned fragrance race polyisocyanates, for example, it is possible to enumerate: di-2-ethylhexylphosphine oxide (Isosorbide-5-Nitrae-Asia Phenyl) diisocyanate (common name: MDI), 1,3-or 1,4-xylylene diisocyanate Or its mixture, ω, ω '-two isocyanate groups-Isosorbide-5-Nitrae-diethylbenzene, 1,3-or Isosorbide-5-Nitrae-bis-(1-isocyanate groups -1-Methylethyl) benzene (common name: tetramethyl xylylene diisocyanate) or its mixture, M-benzene diisocyanate, PPDI, 4,4 '-diphenyl diisocyanate, 1,5-naphthalene two Isocyanates, 2,4 toluene diisocyanate (common name: 2,4-TDI) or 2,6-toluene two are different Cyanate (common name: 2,6-TDI) or its mixture, 4,4 '-toluidine diisocyanate, 4,4 '- The aromatic diisocyanates such as diphenyl ether diisocyanate；1,3,5-tri-TI, triphen Methane-4,4 ', 4 "-triisocyanate, 1,3,5-tri-carbanil, 2,4,6-tri-TI Deng aromatic tri-isocyanates；4,4 '-diphenyl-methane-2,2 ', the aromatic series four such as 5,5 '-tetraisocyanate Isocyanates etc..
It addition, as the derivant of aforementioned polyisocyanates, for example, it is possible to enumerate above-mentioned polyisocyanate The dimer of cyanate, trimer, biuret, allophanate, urea diketone, uretonimine, Isocyanuric acid ester, diazine triketone, poly methylene poly phenyl poly isocyanate are (thick MDI, poly- Close MDI), thick TDI etc..
Above-mentioned polyisocyanates and derivant thereof, both can individually use one or can also Two or more it is used together.It addition, in these polyisocyanates, preferred aliphat two isocyanide Acid esters, alicyclic diisocyanate and their derivant.
It addition, as aforementioned polyisocyanates compound (B), it is possible to use: by above-mentioned many Isocyanates and derivant thereof and the compound that can react with this polyisocyanates are at NCO The prepolymer reacted under conditions of excess and formed.As reacting with this polyisocyanates Compound, for example, it is possible to enumerate, there is hydroxyl, the compound of amino isoreactivity hydrogen-based, tool For body, it is, for example possible to use polyhydric alcohol, low molecular weight polyester resin, amine, water etc..
It addition, as aforementioned polyisocyanates compound (B), it is possible to use: containing isocyanide The polymer of the polymerism unsaturated monomer of perester radical, or, should gathering containing NCO Close property unsaturated monomer with in addition to this polymerism unsaturated monomer containing NCO The copolymer of polymerism unsaturated monomer.
As above-mentioned polyisocyanate compound (B), it is possible to use: make above-mentioned polyisocyanic acid There is to block the polyisocyanates chemical combination of the end-blocking obtained in the NCO that ester compounds has Thing.As sealer, for instance, it may be preferable to use: phenolic compounds；Lactam compound；Alcohol Compound；Oxime compound；Mercaptan compound；Dimethyl malenate；Diethyl malonates etc. are lived Property methylene compound etc..The polyisocyanates chemical combination that can pass through to block of end-blocking Thing carries out mixing with sealer and easily carries out.These polyisocyanate compounds can individually make With or be used in combination, it is also possible to by unblocked polyisocyanate compound and envelope The polyisocyanate compound of end is used together.
As polyisocyanate compound (B), particularly from the viewpoint of resistance to water, excellent Select hexamethylene diisocyanate (HDI) and/or isophorone diisocyanate (IPDI) Isocyanuric acid ester, biuret, uretonimine, trimethylolpropane (TMP) adduct etc..
It addition, from the viewpoint of resistance to weathering, above-mentioned polyisocyanate compound (B) is excellent The average isocyanate ester functional group number being selected in a molecule in the range of 1.9～6, more preferably In the range of 2.5～5, particularly preferably in the range of 2.6～6.
From the viewpoint of finished appearance and resistance to weathering, for polyisocyanate compound (B) With the mixed proportion of polyhydric alcohol (A), preferably set what polyisocyanate compound (B) had The mol ratio of the hydroxyl (OH) that NCO (NCO) and polyhydric alcohol (A) have, i.e. NCO/OH=0.5/1.0～1.5/1.0, more preferably in the range of 0.7/1.0～1.3/1.0.
(C) curing catalysts
It is a feature of the present invention that as (C) curing catalysts is at least some of, uses There is the imidazolium compounds of at least one imidazole ring.
As curing catalysts, by comprising the imidazolium compounds with at least one imidazole ring, Even if it is excellent also to be able to form excellent impact resistance, the most resistance to weathering in the presence of dampness Film.
As above-mentioned imidazolium compounds, such as, in aforementioned formula (I), R1Expression hydrogen atom, The alkyl of carbon number 1～4, the cycloalkyl of carbon number 3～8, the hydroxyl of carbon number 1～4 Base alkyl, the aryl of carbon number 6～10 or acyl group；R2And R3Separately represent that hydrogen is former Son, the alkyl of carbon number 1～4, the hydroxy alkyl of carbon number 1～4, acyl group, alcoxyl Carbonyl, carboxyl or halogen；R4It is preferably hydrogen atom, the alkyl of carbon number 1～12, carbon former The thiazolinyl of subnumber 2～4, aralkyl, can have the aryl of substituent group or there is lower formula (II) (in formula (II), R5Representing hydrogen atom or the alkyl of carbon number 1～4, p represents 1～3 The group of the functional group shown in integer).
Logical R contained by formula (I)1、R2、R3、R4And R5There is foregoing implication.
As R1、R2、R3And R5In the alkyl of carbon number 1～4, for example, it is possible to lift Go out straight chained alkyl or the branched alkyl of carbon number 1～4；More specifically, can enumerate methyl, Ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group etc..
As R1In the cycloalkyl of carbon number 3～8, can enumerate cyclopropyl, cyclobutyl, Cyclopenta, cyclohexyl, suberyl and ring octyl group, the preferably cycloalkyl of carbon number 5～7.
As R1、R2And R3In the hydroxy alkyl of carbon number 1～4, for example, it is possible to lift Go out by 1～3 hydroxyl, be preferably 1 hydroxyl alkane to the above-mentioned carbon number 1～4 enumerated Base carries out the group etc. replaced.Specifically, for example, it is possible to enumerate methylol, 2-hydroxyl Ethyl, 3-hydroxypropyl, 3-hydroxypropyl, 2-hydroxypropyl, 1-methyl-2-ethoxy, 3,3,3-tri-hydroxyl Propyl group, 4-hydroxyl butyl etc..
As R1In the aryl of carbon number 6～10, for example, it is possible to enumerate phenyl, naphthyl.
As R1、R2And R3In acyl group, for example, it is possible to enumerate formoxyl, acetyl group, The acyl group etc. of the carbon numbers 1～7 such as propiono, benzoyl, (methyl) acryloyl group.
As R2And R3In alkoxy carbonyl group, can enumerate methoxycarbonyl, ethoxy carbonyl, The straight chain alcoxyl of the carbon numbers 1～4 such as positive propoxy carbonyl, isopropoxy carbonyl, butoxy carbonyl Base or branched alkoxy carry out the structure being bonded with the carbon atom of carbonyl.
As R2And R3In halogen, fluorine, chlorine, boron, iodine etc. can be included, it may be preferred to Enumerate chlorine etc..
Alternatively, it is also possible to be R2And R3Carry out being bonded and forming the material of aromatic ring structure, tool For body, R can be enumerated2And R3Formed by their substituent group carry out the imidazoles that is bonded and Form benzimidazole etc..
As R4In the alkyl of carbon number 1～12, for example, it is possible to enumerate carbon number 1～ The straight chained alkyl of 4 or branched alkyl, more specifically, can enumerate methyl, ethyl, positive third Base, isopropyl, normal-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-nonyl, Decyl, undecyl, dodecyl etc..
As R4In the thiazolinyl of carbon number 2～4, can enumerate vinyl, pi-allyl, 3-cyclobutenyl, crotyl etc..
As R4In aralkyl, there is 1～3 (preferably have 1 for example, it is possible to enumerate Individual) aryl of the above-mentioned carbon number 6～10 enumerated, the above-mentioned carbon number 1～4 enumerated Alkyl etc..More specifically, can enumerate benzyl, 2-phenylethyl, 3,3,3-tri-phenylpropyl, 4,4,4-triphenyl butyl etc..
As R4In the aryl of had substituent group, the above-mentioned carbon number enumerated can be enumerated The aryl of 6～10 has the aryl of substituent group and unsubstituted aryl etc..Taking as aryl For base, there is no particular limitation, can be halogen, hydroxyl, oxo group, alkyl, carbonyl, virtue Base can also have heterocycle in its end via urethane bonds, carbonyl bond etc..As heterocycle, Furan, thiophene, pyrroles, pyridine, thiazole, imidazoles, pyrimidine etc. can be enumerated.It addition, should Heterocycle can also have foregoing substituents.
As the imidazolium compounds represented by aforementioned formula (I), more specifically, can enumerate Imidazoles, 1-Methylimidazole., 2-methylimidazole, 2-butylimidazolium, 1-t-butyl imidazole, 1,2- Methylimidazole, 2-ethyl-4-methylimidazole, 1,2-diethyl imidazolium, 1,4-diethyl imidazolium, 1,5-diethyl imidazolium, 2-undecyl imidazole, 2-heptadecyl imidazole, 1-isobutyl group-2-methyl Imidazoles, 1-normal-butyl-2-methylimidazole, 2-hydroxymethylimidazole, 4-methylol-2-methylimidazole, 1-(2-ethoxy)-imidazoles, 4-hydroxymethylimidazole, 2-cyclohexyl imidazoles, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl imidazol(e), 2 isopropyl imidazole, 2-phenyl-4-benzyl imidazole, 1 benzyl 2 methyl imidazole, 1-(3-dimethylaminopropyl) imidazoles, 1-aminoethyl-2-methyl Imidazoles, 2-phenyl-4,5-bishydroxymethyl imidazoles, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, Methylimidazole .-4-carboxylate, ethyl imidazol(e)-4-carboxylic acid Ester, 4-imidazolyl carboxylic acid, 2-butyl-4-formyl imidazoles, 4-butyl-hydroxy Methylimidazole., 2-fourth Base-4-chloro-5-formyl imidazoles, 4-formoxyl-1-Methylimidazole., 5-formoxyl-1-Methylimidazole., 4-formoxyl-1-trityl imidazole, 1-benzyl-2-formyl imidazoles, 1-benzyl-5-hydroxymethyl Imidazoles, 1-benzyl-4-hydroxy imidazole, 2-methylol-1-benzyl imidazole, 1-vinyl imidazole, 1- Allyl imidazole, 2-methyl isophthalic acid-vinyl imidazole, 1-dodecyl-2-methylimidazole, 1-benzyl -2-phenylimidazole, 4-ethyl-5-(4-imidazo-5-yl benzoyl)-1,3-glyoxalidine-2-ketone, benzene And imidazoles, 1-tolimidazole etc. have the compound etc. of an imidazole ring in a molecule.
As particularly preferred imidazolium compounds, specifically, 1-benzyl-2-methyl can be enumerated Imidazoles, 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl -2-undecyl imidazole, 1-cyanoethyl-2 isopropyl imidazole, 1-cyanoethyl-2-phenylimidazole, 1- Methylimidazole., DMIZ 1,2 dimethylimidazole, 1-(3-dimethylamino-propyl) imidazoles, 1-isobutyl group-2-first Base imidazoles, 1-normal-butyl-2-methylimidazole, 1-vinyl imidazole, 1-allyl imidazole, 2-methyl -1-vinyl imidazole, 1,2-diethyl imidazolium, 1,4-diethyl imidazolium, 1,5-diethyl imidazolium, 1-dodecyl-2-methylimidazole, 1-t-butyl imidazole, 1-benzyl-2-phenylimidazole etc..Enter one Step ground, particularly preferred 1-Methylimidazole., 1,2-methylimidazole, 1-(3-dimethylamino-propyl) miaow Azoles, 1-isobutyl-2-methyl imidazole, 1-normal-butyl-2-methylimidazole and 1 benzyl 2 methyl imidazole.
As there is the imidazolium compounds of at least one imidazole ring, in addition to the foregoing, it is also possible to Enumerate: 2,4-diaminourea-6-[2 '-methylimidazolyl-(1) ']-ethyl-sym-triazine, 2,4-diaminourea -6-[2 '-ethyl-4-methylimidazole base-(1) ']-ethyl-sym-triazine, 2,4-diaminourea-6-[2 '-hendecane Base imidazole radicals-(1) ']-ethyl-sym-triazine, 2-methylimidazole isocyanuric acid adduct, 2-phenyl Imidazoles isocyanuric acid adduct, 4,4 '-methylene-bis--(2-ethyl-5-Methylimidazole .), 1,4-are double [(1H-imidazoles-1-base) methyl] benzene, 1,1 '-N,N'-carbonyldiimidazole, 1,1 '-oxalyl group diimidazole, 1,1 '-(oxygen Diethylidene) double (2-methyl-imidazoles), 1,1 '-(oxygen diisopropylidene) double (2-methyl-imidazoles), 1,1 '-(oxygen diethylidene) double [2-ethyl-4 (5)-methyl-imidazoles], 1,1 '-(epoxide diisopropylidene) Double [2-ethyl-4 (5)-methyl-imidazoles]；By by 2-phenyl-4,5-bishydroxymethyl imidazoles, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole etc. are containing hydroxyl first The imidazolium compounds of base carries out being dehydrated, piptonychia aldehyde reaction and be condensed into, have in a molecule The compound etc. having plural imidazole ring has plural imidazole ring in a molecule Compound etc..
In the present invention, relative to composition (A) solid constituent 100 mass parts, imidazoles chemical combination The combined amount of thing is preferably in the range of 0.005 mass parts～8 mass parts.
In the coating composition of the present invention, as curing catalysts (C), except above-mentioned miaow Beyond azole compounds, it is also possible to and with other curing catalysts.Solidification as other is catalyzed Agent, for example, it is possible to enumerate bismuth compound, organic acid, the carboxylic acid metal of carbon number 1～20 Salt, tertiary amine etc..
They can individually be used or be used in combination.Particularly from resistance to weathering Property, from the viewpoint of environmental protection, particularly preferably and use bismuth compound.
As aforementioned bismuth compound, for example, it is possible to enumerate bismuth carboxylate.Specifically, such as, Can enumerate caproic acid bismuth (trivalent), Bismuth Octoate (trivalent), 2 ethyl hexanoic acid bismuth (trivalent), Bismuth trioleate. (trivalent), bismuth neodecanoate (trivalent), versatic acid bismuth (bismuth versalate) (3 Valency), bismuth naphthenate (trivalent) etc..
In the present invention, when and with bismuth compound as curing catalysts (C) in the case of, Relative to the polyhydric alcohol (A) of 100 mass parts, in terms of solid component content, preferably bismuth chemical combination The combined amount of thing is below 4 mass parts, more preferably in 0.005 mass parts～the scope of 4 mass parts In.
In the present invention, as curing catalysts (C), can be used alone above-mentioned imidazoles Compound, it is also possible to this imidazolium compounds is applied in combination with other curing catalysts.In the present invention In, imidazolium compounds is the most particularly limited relative to the content of curing catalysts (C) total amount Fixed, for example, it is possible to be set as more than more than 99 mass %, 95 mass %, 90 matter aptly Amount more than %, 80 mass % more than, more than 70 mass %, more than 60 mass %, 50 mass % With first-class.
(D) coloring components
As the coloring components in the coating composition of the present invention, can be by public in paint field One or more coloring pigment, the illuminating colour known are used in mixed way.
As coloring pigment, for example, it is possible to enumerate titanium oxide, zinc white, white carbon black, graphite, oxygen Change ferrum, chrome vermillion, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinoline Azone class Pigment, isoindoline class pigment, intellectual circle's class pigment, class pigment, diazines pigment, two Ketone pyrrolopyrrole class pigment etc..
As other coloring pigments, can enumerate as sheet metal powder such as the aluminum representing embodiment Or the luminous pigment etc. such as paste, Margarita powder, graphite, MIO.As this sheet metal powder, example As, aluminium flake, nickel sheet, copper sheet, stainless steel substrates, latten(-tin) and chromium sheet etc. can be enumerated；It addition, As mica powder, for example, it is possible to enumerate emerylite, coloring emerylite etc..
These coloring components can directly make an addition in coating composition, it is also possible to dispersant, Dispersion resin carries out mixing, disperses, be mixed in coating after gelatinizing.Dispersant, dispersion resin Known material and method can be used with process for dispersing.These compositions (D), can individually make With a kind of or use two or more combination.
(E) water-repelling agent
The coating composition of the present invention can contain water-repelling agent.As water-repelling agent, silicon can be enumerated The wax classes etc. such as class water-repelling agent, fluorine class water-repelling agent, native paraffin, synthetic wax.
As silicon class water-repelling agent, for example, it is possible to enumerate organic poly-silica such as dimethyl polysiloxane Alkane, the modified organic silicon etc. that organopolysiloxane is modified.As modified organic silicon, Specifically, can enumerate alkyl-modified polysiloxanes, phenyl modified polysiloxanes, polyester change Property polysiloxanes, Siloxane-Oxyalkylene Copolymers etc., preferably polyester-modified polysiloxanes etc..These The one or two kinds of that can be used alone combination of the above uses.
Specifically, for example, it is possible to enumerate dimethyl polysiloxane, methyl phenyl silicone, Polyether-modified dimethyl polysiloxane, polyester modification dimethyl polysiloxane, poly-methyl alkyl silicon Oxygen alkane, polyester modification methylalkylpolysiloxanes, aralkyl modified methylalkylpolysiloxanes, Dimethyl polysiloxane containing polyether-modified acryloyl group, containing polyester modification (methyl) third The dimethyl polysiloxane etc. of enoyl-, preferably polyester modification dimethyl polysiloxane.It addition, Can enumerate: silicon resinoid that siliceous polymerism unsaturated monomer independently forms or as with The silicon resinoid of the copolymer of other unsaturated monomers can being copolymerized with this monomer；Hexyl three The alkylalkoxy silanes such as methoxy silane；With fluorine silicon such as 17 fluorine decyl trimethoxy silanes Compounds etc. are as effective ingredient and are dissolved or dispersed in organic solvent, aqueous medium Material etc..But it is not limited to these.
As fluorine class water-repelling agent, in addition to aftermentioned (F), fluororesin, for example, it is possible to enumerate The compound etc. containing perfluoroalkyl such as perfluorocarboxylic acid.
As native paraffin, can enumerate: candelilla wax, Brazil wax, rice wax, haze tallow etc. Department of botany's wax；The animal system waxes such as Cera Flava, lanoline, spermaceti；Lignite wax, ceresine, pure white The mineral system waxes etc. such as wax.
It addition, as synthetic wax, can enumerate: the synthesis hydrocarbon such as f-t synthetic wax, Tissuemat E Class；The paraffin derivatives such as lignite wax derivant, chlorinated paraffin, hard paraffin, microwax are derivative The modified waxes such as thing；12-hydroxy stearic acid, stearmide, phthalic anhydride acid imide etc..Right They can be used alone or in combination of two or more.
(F) fluororesin
The coating composition of the present invention, can contain fluororesin.As fluororesin, can enumerate The insatiable hungers such as PTFE (politef) or polyvinylidene fluoride resin, fluoroolefin and vinyl ethers With the copolymer of monomer, fluorine-containing acrylic resin, fluorine-containing polyester resin etc..
As PTFE, for example, it is possible to enumerate the Teflon (registered trade mark) as market sale product (Dupont-Mitsui Fluorochemicals Co., Ltd. manufacture) etc..As Kynoar tree Fat, can enumerate market sale product, for example, it is possible to enumerate " Kynar 710 ", " Kynar 711 ", “Kynar 720”、“Kynar 721”、“Kynar 740”、“Kynar 760”、“Kynar 761”、 “Kynar 761A”、“Kynar HSV900”、“Kynar 460”、“Kynar 461”、“Kynar 301F ", " Kynar 900HD ", " Kynar 1000HD " (be name of product, Kynar above Series, ARKEMA Co., Ltd. manufactures) etc..
The copolymer of the unsaturated monomers such as aforementioned fluoroolefin and vinyl ethers can use known side Method obtains.As fluoroolefin, for example, it is possible to enumerate tetrafluoroethene, CTFE, The carbon numbers such as trifluoro-ethylene, vinylidene fluoride, hexafluoropropene, pentafluoropropene are 2 or 3 Fluoroolefin.Wherein, from the angle good with the alternating copolymerization of other unsaturated monomers, Preferably tetrafluoroethene, CTFE, more preferably CTFE.
As can be with the unsaturated monomer of above-mentioned fluoroolefin copolymerization, for example, it is possible to enumerate ethylene Base ethers, allyl ether series, isopropenyl ethers, vinyl esters of carboxylic acids class, allyl carboxylate Class, carboxylic acid isopropenyl ethers, alpha-olefines, (methyl) esters of acrylic acid, hydroxy alkyl Vinyl esters, hydroxy alkyl allyl esters, (methyl) hydroxyalkyl acrylates class etc..
As vinyl ethers, for example, it is possible to enumerate: ethyl vinyl ether, butyl vinyl The alkyl such as ether, cyclohexyl vinyl ether, vinyl ethers, perfluor (alkyl vinyl ether) Vinyl ethers, hydroxyalkyl vinyl ether class, ethylene glycol monovinyl ether class etc..
As hydroxyalkyl vinyl ether, for example, it is possible to enumerate: 2-hydroxyethyl vinylethers, 3-hydroxypropyl vinyl ethers, 2-hydroxypropyl vinyl ethers, 2-hydroxy-2-methyl propyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methyl butyl vinyl ether, 5-Hydroxy pentyl ethylene Base ether, 6-hydroxyl hexyl vinyl ethers etc..
As ethylene glycol monovinyl ether, for example, it is possible to enumerate diethylene glycol monovinyl base ether, Triethylene glycol mono vinyl ether, TEG mono vinyl ether etc..
As allyl ether series, for example, it is possible to enumerate: ethyl allyl ether, cyclohexyl allyl The polyoxyethylene base ethers such as base ether, hydroxy alkyl allyl ether series.
As hydroxy alkyl allyl ether, for example, it is possible to enumerate 2-hydroxyethyl allyl ether, 4- Hydroxyl butyl allyl ether, glycerol mono allyl ether etc..
As isopropenyl ethers, for example, it is possible to enumerate the alkyl isopropyls such as methyl isopropyl alkene ether Thiazolinyl ethers.
As vinyl esters of carboxylic acids class, for example, it is possible to enumerate the fatty acid second with branched alkyl The VEOVA 10 (trade name, SHELL KCC manufactures) of alkene ester, butanoic acid second The fatty acid ethylene esters such as alkene ester, vinylacetate, pivalic acid vinyl acetate, tertiary ethylene carbonate.
As allyl carboxylate class, for example, it is possible to enumerate allyl propionate, allyl acetate etc. Fatty acid allyl esters.
As alpha-olefines, for example, it is possible to enumerate ethylene, propylene, isobutene. etc..
As (methyl) acrylate, for example, it is possible to enumerate (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) butyl acrylate etc..
As hydroxyalkyl vinyl ester, for example, it is possible to enumerate 2-hydroxyethyl vinyl ester, 4-hydroxyl fourth Base vinyl acetate etc..
As hydroxy alkyl allyl ester, for example, it is possible to enumerate ethoxy allyl ester, hydroxyl butyl alkene Propyl ester etc..
As (methyl) hydroxyalkyl acrylates, for example, it is possible to enumerate (methyl) propylene Acid hydroxyl ethyl ester etc..
As the market sale product of fluoroolefin Yu the copolymer of vinyl ethers, for example, it is possible to lift Go out: Lumiflon series (manufacture of Asahi Glass company), Zeffle series (Daikin industry strain Formula commercial firm manufactures) etc..
Aforementioned fluorine-containing acrylic resin is to have perfluoroalkyl and polymerism in a molecule Unsaturated group, the polymerism unsaturated monomer with fluorine atom independently forms or and its His unsaturated monomer carries out the resin of copolymerization formation.There is the polymerism of fluorine atom not as above-mentioned Saturated monomer, can enumerate: perfluoropropene, (methyl) perfluoroethyl cyclohexyl, (first Base) perfluoroethyl nonyl ethyl ester, (methyl) perfluoroethyl decyl ethyl ester, (methyl) Perfluoroethyl butyl ethyl ester, (methyl) perfluoroethyl methyl formate, (methyl) propylene Acid perfluoro butyl methyl ester, (methyl) perfluoroethyl octyl group methyl ester, (methyl) acrylic acid are complete Fluorine decyl methyl ester, (methyl) perfluoroethyl methyl propyl ester, (methyl) perfluoroethyl third Base propyl ester, (methyl) perfluoroethyl octyl group propyl ester, (methyl) perfluoroethyl octyl group penta Ester, (methyl) perfluoroethyl octyl group 11 ester etc. have (the first of the perfluoroalkyl of C1～20 Base) perfluoroalkyl acrylate etc..As having (methyl) esters of acrylic acid of perfluoroalkyl, Goods can be used, for example, it is possible to enumerate " Viscoat 8F ", " Viscoat 8FM ", " Viscoat 3F ", " Viscoat 3FM " (be Osaka Organic Chemical Industry Co., Ltd. manufacture) etc..
As can be unsaturated with other of the above-mentioned polymerism unsaturated monomer copolymerization with fluorine atom Monomer, as long as in the manufacture of the polyacrylate polyol of aforementioned (A2) spendable not Saturated monomer, it is possible to use without particular limitation.
For these compositions (F), add after solvent can be dissolved in advance, it is also possible to be scattered in The resin solutions such as foregoing polyols (A) carry out coating.
To these compositions (F), the one or two kinds of that can be used alone combination of the above uses.
Other compositions
The coating composition of the present invention, can contain in the range of film performance further not damaging Following known additive for coatings: the resin of hydroxyl in addition to composition (A), tool There are the compound (such as, amino-compound etc.) of reactivity with NCO, ultraviolet Absorbent (such as, benzotriazole absorbent, triazines absorbent, salicyclic acid derivatives class Absorbent, benzophenone absorbent etc.), light stabilizer (such as, hindered amines etc.), Extender pigment (Talcum, clay, Kaolin, Barium monoxide, barium sulfate, brium carbonate, calcium carbonate, Silicon dioxide, alumina white etc.), resin particle, viscosifier, defoamer, antirust agent, chelating Agent (acetylacetone,2,4-pentanedione etc.), plasticizer, solvent, pigment dispersing agent, surface conditioner, anti-settling Agent etc..
The coating composition of the present invention
In the coating composition of the present invention, when using composition (D), can set aptly Its mixed proportion, relative to the composition (A) of 100 mass parts be generally set to 1 mass parts～ In the range of 500 mass parts, it is preferably set in the range of 2 mass parts～300 mass parts, more It is preferably set in the range of 3 mass parts～200 mass parts.
In the coating composition of the present invention, when using composition (E), can set aptly Its mixed proportion, relative to the composition (A) of 100 mass parts be generally set to 0.1 mass parts～ In the range of 50 mass parts, it is preferably set in the range of 0.2 mass parts～30 mass parts.
In the coating composition of the present invention, when using composition (F), can be set it aptly Mixed proportion, is generally set to 1 mass parts～50 relative to the composition (A) of 100 mass parts In the range of mass parts, it is preferably set in the range of 2 mass parts～30 mass parts.
The adjustment of coating composition
For the form of the coating composition of the present invention, it is not particularly limited, Ke Yishi Any one form in water paint, organic solvent type coatings and no-solvent type coating.Additionally, In this manual, so-called water paint is the term ining contrast to organic solvent type coatings, generally Refer to by making the dispersions such as film formative resin, pigment and/or being dissolved in water or using water as master Want the coating in the medium (aqueous medium) of composition.When the coating composition of the present invention is During water paint, the content of the water in this coating composition is suitable in 10 mass %～90 mass % In the range of, preferably in the range of 20 mass %～80 mass %, more preferably in 30 mass In the range of %～70 mass %.It addition, so-called above-mentioned organic solvent type coatings refers to as molten Agent is the most aqueous or the coating wholly or largely belonging to organic solvent of solvent.From From the viewpoint of coating storage stability, the preferred organic solvent type of coating composition of the present invention is coated with Material or non-aqueous dispersion type coating.
As organic solvent, for example, it is possible to enumerate acetone, methyl ethyl ketone, methyl-isobutyl The ketones such as ketone；Ethyl acetate, butyl acetate, essence of Niobe, ethoxyl ethyl propionate, third The esters such as acetoacetic ester, methyl propionate；The ethers such as oxolane, dioxane, dimethoxy-ethane； Glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetic acid The gylcol ethers such as ester, 3-Methoxy acetic acid butyl ester；Arene, fat hydrocarbon etc..As Organic solvent, can be not particularly limited to use, but go out from the viewpoint affecting human body and environment Send out, preferably without toluene, dimethylbenzene etc..
Can adjust according to viscosity, the purpose such as coating adjustment is carried out proper combination and is used above-mentioned organic Solvent.
For the solid constituent of the coating composition of the present invention, from application operability and reduction institute Discharge organic solvent amount from the viewpoint of, preferably adjust solid component content 15 mass % with Upper, particularly preferably adjustment solid component content is carried out in the range of 35 mass %～90 mass % Application.
In this manual, so-called solid constituent refers to remove the residue of volatile ingredient；As Residue, the most both can be solid, shaped can also be aqueous.For solid constituent quality, Can be by setting dried residue quality relative to the ratio of quality before being dried as solid constituent Solid constituent is also obtained by ratio than the sample mass being multiplied by before being dried.
As the coating composition of the present invention, can be based one-pack-type coating, it is also possible to be double groups The multicomponent type coating such as typing coating.From the viewpoint of storage stability and application operability, In the coating composition of the present invention, preferably by the host containing polyhydric alcohol (A) with containing many isocyanides The two-component-type coating that the cross-linking agent of ester compound (B) is constituted, is suitable for using Use after two components being mixed before, can any one in host or firming agent be fitted Preferably containing (C)～(F) composition, water or organic solvent equal solvent, pigment dispersing agent, prevent The various additives etc. such as heavy agent, defoamer, antioxidant, UV absorbent.Work as the present invention Coating composition when being based one-pack-type coating, the polyisocyanate compound of end-blocking is preferably used.
Coating film-forming methods
The present invention provides a kind of and aforementioned coatings compositions is coated on coated article and forms the painting of film Film forming method.
As coated article, preferably use plastics or the base material of metal, by coagulating containing epoxy resin Glue coating material folds object on the substrate, by the priming paint containing epoxy resin (primer) film forms object on the substrate or by coagulating containing epoxy resin Glue coating material is laminated on this base material and is formed further containing asphalt mixtures modified by epoxy resin on this gel coating material The object of the primer coating film of fat.
＜ metal base ＞
As metal base, as long as metal just has no particular limits, for example, it is possible to enumerate Magnesium, aluminum, zinc, titanium, ferrum, nickel, chromium, gold, silver, copper, stannum, platinum, palladium, zirconium, tungsten etc. The metal materials such as the alloy more than at least two in metal itself and these metals.As two Kind above metal material, can enumerate alloyed zincs such as Zn-Al, Zn-Ni, Zn-Fe, no Rust steel, it is plated with the steel etc. of above-mentioned metal material.
＜ plastic basis material ＞
As plastic basis material, can enumerate: the polyolefin tree such as polyvinyl resin, acrylic resin Fat；Merlon, polyethylene terephthalate, polybutylene terephthalate (PBT), poly- The polyester resin such as terephthalic acid/isophthalic acid glycol ester；Styrene butadiene block copolymerization Body, styrene-acrylonitrile, acrylonitrile-butadiene-styrene (ABS) (ABS), polystyrene, third The phenylethylene resin series such as alkene nitrile-cinnamic acrylic ester；Nylon 6, nylon 6,6, nylon 6,10, The polyamides such as m xylylene adipamide (meta-xylene adipamide)；Poly-methyl-prop The acrylic resins such as e pioic acid methyl ester, methyl methacrylate-ethyl acrylate；Corvic, The vinylidene resins such as vinyl chloride-vinyl acetate；Unsaturated polyester resin, phenolic resin, Melmac, urea resin, polyphenylene oxide resin, acetal resin, polyurethane resin, The plastic materials such as the resins such as epoxy resin and various fibre reinforced plastics (FRP).Above-mentioned plastics Base material can also be the hybrid resin of two or more resins.
So-called above-mentioned fibre reinforced plastics (FRP) refer to by making in plastics containing reinforcing fiber Improve the plastics of its intensity.
As the reinforcing fiber used in FRP, it is possible to use glass fibre, aramid fiber, carbon The reinforcing fiber that fiber etc. are any known, it is also possible to and use multiple reinforcing fiber.Especially, logical Crossing containing glass fibre and carbon fiber, compared with plastic basis material itself, specific strength, specific modulus are good Good.In order to obtain, component is light and the FRP material of mechanical-physical good properties, is preferably used alone This reinforcing fiber or use two or more reinforcing fibers, but from cheap especially and intensity is high Angle is set out, and preferably comprises glass fibre.The ratio that preferably glass fibre occupies in reinforcing fiber Rate is 10 mass %～100 mass %.
As FRP matrix resin (also referred to as basic resin, be the plastics as mother metal and As the resin of base material after molding), it is usable in the project of above-mentioned plastic basis material the tree enumerated Fat, unsaturated polyester resin, phenolic resin etc..Especially, from the tack with reinforcing fiber From the viewpoint of, preferred epoxy.As epoxy resin, as long as be suitable to FRP molding Epoxy resin just can arbitrarily use.Firming agent can also be used.As firming agent, such as, Amines, anhydride compound, polyimide compound and imidazolium compounds etc. can be enumerated.
As the forming method of FRP, known method can be used, use mould system can be enumerated Sheet molding compound (SMC) method of forming made, resin infusion (RIMP) method of forming, prepreg / autoclave pressing.
For above-mentioned metal base or various plastic basis material, by parts of its molding etc. for, it Surface can be applied in employing lotion, the defat of solvent, phosphate treated, chromate Process, the surface such as composite oxides process, wash, grinding processes, and on them and also Could be formed with primary coat film (also containing the overlay film formed by gel coating material).
＜ primary coat film ＞
So-called primary coat film, refers to institute under the film formed by the coating composition of the present invention The film formed, according to applications such as the kind of coated surface and states for forming the end of primary coat film It is coated with coating.By arranging film between the film formed by the coating composition of the present invention, can With the tack between raising and coated surface and resistance to impact.Further, in order to improve tack, the end It is coated with the multilamellar that film can also be more than two-layer.As primary coat film, such as, base material be gold In the case of belonging to base material, can enumerate by paint field being known as primer base And/or the coating composition of middle painting coating carries out application and makes it solidify and the film that is obtained in that. It addition, in the case of base material is FRP base material, can enumerate by being referred to as gel coating The FRP product surface of material carries out application and makes it solidify obtained overlay film etc..
As the constituent of the bottom-coating constituting above-mentioned primary coat film, specifically, such as, Can be preferably used containing overlay film formative resin, cross-linking agent, coloring pigment, extender pigment, The coating composition of photoluminescent pigment, rust resisting pigment, conductive pigment etc., and, this primary coat Coating composition can suitably contain UV absorbent, light stabilizer, curing catalysts, plasticising Agent, tackifiers, compatilizer, defoamer, viscous regulator, antirust agent, surface conditioner etc. Coating additive.
As the kind of overlay film formative resin, for example, it is possible to enumerate polyol resin, propylene Acid resin, polyester resin, alkyd resin, polyurethane resin, vistanex, epoxy resin, Phenolic resin, polyamide and the resin etc. of their hydroxyl.Permissible to these resins It is used alone or is used in combination.
Both can be cross-linked by mixed cross-linker, it is also possible to not mixed cross-linker thus in reality Do not crosslink in matter.Furthermore it is also possible to by cross-linking agent contained in the film on upper strata Infiltration cross-links.
As cross-linking agent, for example, it is possible to be preferably used: melmac, urea resin etc. Amino resins, polyisocyanate compound, the polyisocyanate compound etc. of end-blocking.As upper State bottom-coating compositions, it is possible to use organic solvent type coatings compositions, aqueous coating composition Any one in thing, it is also possible to solvent-free.
From resistance to impact and with the tack of coated surface from the viewpoint of, the Coating material composition of the present invention Thing preferably carries out application on the coated article with primary coat film, and this primary coat film is by containing asphalt mixtures modified by epoxy resin The coating composition of fat and/or the gel coating material containing epoxy resin are formed.Specifically, may be used The thing that gel coating material containing epoxy resin be laminated in aforementioned substrates in is preferably used Part, the primer coating film containing epoxy resin is formed at the object on this base material or will contain The gel coating material of epoxy resin is laminated on this base material and at this gel coating material enterprising one Step forms the object of the primer coating film containing epoxy resin.
Here, so-called gel coating material, refer to use mould to become on the surface of FRP base material Coating composition used by type.As the laminating method of gel coating material, can enumerate: pre- First the overlay film that can form outer plate surfaces is formed resin-coated in model inner face to form overlay film, will Reinforcing fiber base is configured on this gel coating material, closes closed model, is then poured into FRP and uses Resin also makes it solidify, and carries out the demoulding and makes this coating transfer in the method on the surface of FRP outside plate； Fiber reinforced plastic materials (hereinafter sometimes referred to simply as FRP material) is made to carry out in mould in advance Heating, molding, then inject above-mentioned gel between obtained article shaped and mould inner wall and be coated with Cloth material, is removed from the molds the side of the article shaped of cladding after making the solidification of this gel coating material Method etc..
Constituent as gel coating material, it is possible to use above in primary coat film project The constituent enumerated.It addition, form resin as overlay film, except above at primary coat film Beyond the resin enumerated in project, it is also possible to use polycarbonate resin, vinyl ester resin, All known resins such as unsaturated polyester resin, bimaleimide resin, carbamide resin. These resins can combine more than one and use, but, from the viewpoint of tack, preferably A part as constituent contains epoxy resin；From the viewpoint of resistance to weathering, preferably The urethane cures based composition using the firming agent such as polyhydric alcohol and aromatic isocyanate contains There is the gel coating material of epoxy resin.
As epoxy resin contained in above-mentioned bottom-coating (also including gel coating material), It is not particularly limited, it is possible to use various resins.For example, it is possible to enumerate: bisphenol A-type Epoxy resin, bisphenol f type epoxy resin, bisphenol-A D-ring epoxy resins, 9,9-bis-(3-methyl -4-hydroxy phenyl) fluorenes type epoxy resin, bisphenol-s epoxy resin, tert-butyl catechol type ring Bifunctional type's epoxy resin such as epoxy resins, phenol novolak type epoxy resin, cresol novolac are clear The multivalence epoxy resin such as paint shaped epoxy resin, nonyl phenol phenolic resin varnish type epoxy resin, by this A little epoxy resin use epoxy ester resin, the ester ring type asphalt mixtures modified by epoxy resin that binary acid etc. are modified Fat, polyglycol type epoxy resins, acrylic resin etc. containing epoxy radicals.
As the coating process of the bottom-coating in addition to gel coating material, the most especially Limit, coating process known per se can be used, for example, it is possible to according to the purposes etc. of base material Suitably select roller, aerial spraying, airless spraying, Lithing spray gun (リ シ Application ガ Application), ten thousand Can spray gun, brush, roll coater etc..Can pass through to add according to the kind of bottom-coating used etc. Any one method in heated drying, force drying or normal temperature drying implements drying condition.
Other coated article ＞ of ＜
It addition, as coated article in addition to the foregoing, as long as in the scope that tack meets, Can also be: the inorganic material such as glass, cement, concrete, timber, fibrous material (paper, Cloth etc.) etc..
According to the situation of these coated articles, ungrease treatment, surface process etc. can be carried out aptly.
In the method for the invention, such as electrostatic spraying, sky can be used for above-mentioned coated article The coating composition of the method application present invention such as gas blowout painting, airless spraying, roller, brush.Now, For thickness, from the viewpoint of resistance to weathering, it is preferably based on cured coating film and is set in In the range of 30 μm～500 μm, more preferably it is set in the range of 50 μm～300 μm.? In the method for the present invention, generally, be coated be filled to predetermined thickness after, by by film such as It is dried solidification under room temperature (5 DEG C～35 DEG C), cured coating film can be obtained.Relative during application Humidity (being sometimes referred to simply as RH below) is less than 70%, preferably less than 60%.As often The hardening time that temperature is dried, preferably more than 1 day, more preferably more than 3 days.For film Dry solidification for, it is also possible to heat；As temperature during heating, for example, it is preferable to It is 30 DEG C～100 DEG C, more preferably 35 DEG C～90 DEG C.As heat time heating time, for example, it is preferable to It is 5 minutes～120 minutes, more preferably 10 minutes～100 minutes.
As the purposes of the coated article of the coating composition being coated with the present invention, the most particularly Limit, be particularly preferably exposed to the article in strong rain wind, sand and dust etc. or its parts.Example As, the wing of the blade of wind-driven generator, aircraft and helicopter, automobile and voluntarily can be enumerated The car body of car, the body etc. of building machinery.
Embodiment
Below, by enumerating the embodiment further description present invention.Additionally, as long as no Special instruction, " part " and " % " all represents " mass parts " and " quality % ".
<<preparation of coating composition>>
(embodiment 1)
By 50 parts of Oleum Ricini (note 1), 100 parts of TIPAQUE CR-95 (note 22), 37.5 Part butyl acetate mixes, and uses sand mill to disperse, it is thus achieved that dispersion paste.Institute In the dispersion paste obtained, mix 50 parts of Placcel 410 (note 14), 0.5 part 1,2-diformazan Base imidazoles, relative to the Sumidur N3300 (note 34) that hydroxyl is 1 equivalent and add acetic acid Butyl ester is stirred so that solids content is 80%, is derived from the coating composition of numbering 1. For the coating composition of obtained numbering 1 carry out application operability described later (storage period and Sagging resistance) test.Evaluation result is shown in Table 1.
(embodiment 2～77,83～87, comparative example 1～14)
In addition to being set as the composition shown in table 1～7, carry out in the same manner as above-described embodiment 1 Operation, it is thus achieved that numbering 2～the coating composition of 77,83～101.To obtained above-mentioned coating For compositions, the combined amount in table 1～7 is the amount being indicated by solid constituent.For Obtained coating composition carries out application operability described later (storage period and sagging resistance) Test.Evaluation result is shown in table 1～7.
(embodiment 78)
By 50 parts of Oleum Ricini (note 1), 80 parts of TIPAQUE CR-95 (note 22), 20 parts Calcium carbonate (タ Application カ Le) 300 (notes 43), 37.5 parts of butyl acetates mix, and adopt Disperse with sand mill, it is thus achieved that dispersion paste.In obtained dispersion paste, mix 50 Part Placcel 410 (note 14), 0.5 part of DMIZ 1,2 dimethylimidazole, it is 1 equivalent relative to hydroxyl Sumidur N3300 (note 34) and add butyl acetate and be stirred so that solids content It is 80%, is derived from the coating composition of numbering 78.
(embodiment 79)
By 50 parts of Oleum Ricini (note 1), 80 parts of TIPAQUE CR-95 (note 22), 20 parts KAOLIN HA-90T (note 44), 37.5 parts of butyl acetates mix, and use husky mill Machine disperses, it is thus achieved that dispersion paste.In obtained dispersion paste, mix 50 parts of Placcel 410 (notes 14), 0.5 part of DMIZ 1,2 dimethylimidazole, relative to the Sumidur that hydroxyl is 1 equivalent N3300 (note 34) and add butyl acetate be stirred with must make solids content for 80%, by This obtains the coating composition of numbering 79.
(embodiment 80)
By 50 parts of Oleum Ricini (note 1), 80 parts of TIPAQUE CR-95 (note 22), 20 parts BARIFINE BF-20 (note 45), 37.5 parts of butyl acetates mix, and use husky mill Machine disperses, it is thus achieved that dispersion paste.In obtained dispersion paste, mix 50 parts of Placcel 410 (notes 14), 0.5 part of DMIZ 1,2 dimethylimidazole, relative to the Sumidur that hydroxyl is 1 equivalent N3300 (note 34) and addition butyl acetate are stirred so that solids content is 80%, by This obtains the coating composition of numbering 80.
(embodiment 81)
By 50 parts of Oleum Ricini (note 1), 80 parts of TIPAQUE CR-95 (note 22), 20 parts Sylophobic 200 (note 46), 37.5 parts of butyl acetates mix, and use sand mill Disperse, it is thus achieved that dispersion paste.In obtained dispersion paste, mix 50 parts of Placcel 410 (notes 14), 0.5 part of DMIZ 1,2 dimethylimidazole, relative to the Sumidur that hydroxyl is 1 equivalent N3300 (note 34) and addition butyl acetate are stirred so that solids content is 80%, by This obtains the coating composition of numbering 81.
(embodiment 82)
By 50 parts of Oleum Ricini (note 1), 80 parts of TIPAQUE CR-95 (note 22), 20 parts Sylophobic 200 (note 46), 0.5 part of BYK-161,37.5 parts of butyl acetates mix, And use sand mill to disperse, it is thus achieved that dispersion paste.In obtained dispersion paste, mixed Close 50 parts of Placcel 410 (note 14), 0.5 part of DMIZ 1,2 dimethylimidazole, relative to hydroxyl be Sumidur N3300 (note 34) and the addition butyl acetate of 1 equivalent are stirred so that consolidating Body burden is 80%, is derived from the coating composition of numbering 82.
(test example 1～71 and comparative test example 1～14)
Manufacture method ＞ of ＜ bread board
Aforementioned coating composition is coated on by airless spraying " coated article " hurdle institute of table 1～7 The coated article shown is so that dry film thickness reaches 150 μm.By obtained film at table 1～7 " dry solidification condition " hurdle described under conditions of be dried, it is thus achieved that bread board.By these Bread board is supplied to used by test described later.Evaluation result is shown in table 1～7.
Additionally, in " dry solidification condition " hurdle of table 1～7,
Dry solidification condition 1 represent by 20 DEG C, place under RH60% and do over 7 days Dry；
Dry solidification condition 2 represent by 20 DEG C, place under RH90% and do over 7 days Dry；
Dry solidification condition 3 be represent by heat at 80 DEG C after 30 minutes 20 DEG C, Place under RH60% and be dried over 7 days.
Here, in " coated article " hurdle of table 1～7, coated article 1～5 employs following object.
Coated article 1:FRP
Add 82 parts of Epikote (エ ピ U ト) 828 (name of product, bisphenol type epoxies Resin, solids content is 100%, Japan epoxy resin Co., Ltd. (Japan Epoxy Resins Co., Ltd.) manufacture), 6 parts of Seikacure-S (name of product, DADPS, solids Content 100%, Wakayama Seika Kogyo Co., Ltd. manufactures), 5.0 parts of phenyl dimethyl urea (flat All particle diameter 50 μm, solids content 100%), 7 parts of dicyandiamides (mean diameter 7 μm), and Carry out mixing until uniformly, it is thus achieved that the composition epoxy resin of matrix resin.
Use roll coater, this composition epoxy resin is coated on processing release paper equably with Reach 30g/m2Coating weight, formed resin bed.By above-mentioned resin bed clamping glass fiber 125g/m2Two faces, use roller at 100 DEG C, 2kg/cm2Under conditions of carry out pressurized, heated, Obtain prepreg.
In the way of making machine direction alternating orthogonal, 16 above-mentioned prepregs of stacking, pass through Mould is heated to 130 DEG C, applies 10kg/cm2Pressure 15 minutes, it is thus achieved that glass fibre Reinforced plastics (coated article 1).
Coated article 2:FRP+ gel coat
16 above-mentioned prepregs of stacking being arranged in the way of making machine direction alternating orthogonal In mould, and set the prepreg gap with mould as 500 μm.At mould and prepreg Between inject the gel coating material of following composition, be then heated to 130 DEG C and apply 10kg/cm2Pressure 15 minutes, it is thus achieved that be laminated with the fiberglass reinforced plastics of gel coat (coated article 2).
[gel coating material]
By 50 parts of Oleum Ricini, (name of product, Epikote is registrar to 30 parts of Epikote 828 Mark, bisphenol A type epoxy resin, Japan epoxy resin Co., Ltd. manufacture), 50 parts of NN height Ridge soil (Zhu Yuan chemical industry Co., Ltd. manufactures for name of product, clay) mix and blend until After Jun Yun, add 20 parts of methyl diphenylene diisocyanates, and then mix and blend is until uniformly.
Coated article 3:FRP+ priming paint
Use " Epomarine GX (name of product, two-component-type epoxy primer, Northwest coating strain Formula commercial firm (KANSAI PAINT CO., LTD.) manufactures) ", by air spray finishing, Thickness is formed on the plate of the fiberglass reinforced plastics shown in above-mentioned " coated article 1:FRP " The prime coat of 50 μm, using the object that is consequently formed as coated article 3.
Coated article 4:FRP+ gel coat+priming paint
Increase at the fiber forming the gel coat shown in above-mentioned " coated article 2:FRP+ gel coat " On strong plastic plate, (name of product, two-component-type epoxy primer close to use Epomarine GX Western coating Co., Ltd. manufactures) prime coat of 50 μ m thick is formed by air spray finishing, general The object being consequently formed is as coated article 4.
Coated article 5:Al
Aluminium sheet
The size of bread board
When for weathering described later test (hereinafter simply referred to as " RET "), after being shaped to State Fig. 1 blade shape above-mentioned 1～5 coated article, use the apneumatic spraying method application present invention Coating composition so that dry film thickness is 150 μm, at " the dry solidification bar of table 1～7 Part " under solidify, using thus obtained object as bread board.
When being used for the test in addition to RET, the coated article of above-mentioned 1～5 is cut into The flat board of 10cm × 20cm, the coating composition of the application present invention, " being dried at table 1～7 Solidification " under the conditions of solidify, using thus obtained object as bread board.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
(note 1) Oleum Ricini: hydroxyl value 160mgKOH/g
(note 2) URIC Y-406: name of product, the compound modified Oleum Ricini of aliphatic category, Hydroxyl value 165mgKOH/g, Itoh Oil Mfg manufactures
(note 3) POLYCASTOR#10: name of product, castor oil polymers, hydroxyl value 160mgKOH/g, Itoh Oil Mfg manufactures
(note 4) Pripol 2033: name of product, dimer diol, hydroxyl value 207mgKOH/g, CRODA company manufactures
(note 5) Sovermol 750: name of product, the polyhydric alcohol of vegetable oil source, hydroxyl value 315mgKOH/g, BASF AG manufactures
(note 6) Sovermol 760: name of product, the polyhydric alcohol of vegetable oil source, hydroxyl value 390mgKOH/g, BASF AG manufactures
(note 7) Sovermol 815: name of product, the polyhydric alcohol of vegetable oil source, hydroxyl value 215mgKOH/g, BASF AG manufactures
(note 8) Sovermol 819: name of product, the polyhydric alcohol of vegetable oil source, hydroxyl value 240mgKOH/g, BASF AG manufactures
(note 9) Placcel 205: name of product, polycaprolactone glycol, number-average molecular weight 530, Hydroxyl value is that 212mgKOH/g, Daicel company manufactures
(note 10) Placcel 208: name of product, polycaprolactone glycol, number-average molecular weight 830, Hydroxyl value 135mgKOH/g, Daicel company manufactures
(note 11) Placcel 303: name of product, polycaprolactonetriol, number-average molecular weight 300, Hydroxyl value 540mgKOH/g, Daicel company manufactures
(note 12) Placcel 305: name of product, polycaprolactonetriol, number-average molecular weight 550, Hydroxyl value 305mgKOH/g, Daicel company manufactures
(note 13) Placcel 309: name of product, polycaprolactonetriol, number mean molecule quantity Being 900, hydroxyl value 187mgKOH/g, Daicel company manufactures
(note 14) Placcel 410: name of product, polycaprolactone tetraol, number-average molecular weight 1000, Hydroxyl value 224mgKOH/g, Daicel company manufactures
(note 15) Capa 4801: name of product, polycaprolactone tetraol, number-average molecular weight 8000, Hydroxyl value 28mgKOH/g, Solvay Chemicals, Inc. manufacture
(note 16) Duranol T5650J: PCDL, Asahi Chemical Corp Manufacture, number-average molecular weight 800, hydroxyl value 140mgKOH/g
(note 17) Duranol T5650E: PCDL, Asahi Chemical Corp Manufacture, number-average molecular weight 500, hydroxyl value 225mgKOH/g
The polyacrylate polyol of (note 18) numbering 1: have blender, thermometer, In the reaction vessel of reflux cooler and Dropping feeder, load 40 parts of butyl acetates, 40 portions of vinegar Acid methoxyl group propyl ester, is blown into nitrogen and is stirred at 130 DEG C, wherein, by 5.0 Part styrene, 54.0 parts of n-butyl acrylates, 15.0 parts of HEMAs, 25.0 (name of product, Daicel company manufactures part Placcel FM-3X, 6-caprolactone modified methyl third Olefin(e) acid hydroxyl ethyl ester), 1.0 parts of acrylic acid and V-59 (trade name, and light pure medicine strain formula Commercial firm manufactures, 2,2 '-azo double (2-methylbutyronitrile), polymerization initiator) mixture, with uniformly Speed dripped through 3 hours, and then ripening 2 hours at the same temperature.
Then, then by the mixture of 10 parts of butyl acetates and V-59 (0.5 part) through 1 hour It is added drop-wise in reaction vessel, completion of dropwise addition post curing 1 hour, it is thus achieved that the volume of solids content 54% The solution of the polyacrylate polyol of number 1.The hydroxyl value of obtained resin solid content is 94.4mgKOH/g, weight average molecular weight are 10000.
The polyacrylate polyol of (note 19) numbering 2: have blender, thermometer, In the reaction vessel of reflux cooler and Dropping feeder, load butyl acetate 40 parts, acetic acid methoxy Base propyl ester 40 parts, is blown into nitrogen and is stirred at 130 DEG C, wherein, by 5.0 Part styrene, 15.0 parts of methyl methacrylates, 50.0 parts of n-butyl acrylates, 29.0 part third Olefin(e) acid 4-hydroxy butyl ester, 1.0 parts of acrylic acid and the mixture of 5.0 parts of V-59 (initiator) Drip through 3 hours with uniform speed, and then ripening 2 hours at the same temperature.
Then, then by the mixture of 10 parts of butyl acetates and 0.5 part of V-59 (initiator) pass through Within 1 hour, it is added drop-wise in reaction vessel, completion of dropwise addition post curing 1 hour, it is thus achieved that solids content 54% The solution of polyacrylate polyol of numbering 2.The hydroxyl value of obtained resin solid content It is 10000 for 113mgKOH/g, weight average molecular weight.
(note 20) Desmophen 670: name of product, PEPA, solids content 100 Quality %, hydroxyl value 142mgKOH/g, number-average molecular weight about 2000.Sumitomo Bayer polyurethane strain Formula commercial firm (Sumika Bayer Urethane Co., Ltd.) manufactures
(note 21) Nipporan 800: name of product, PEPA, number-average molecular weight 700, Hydroxyl value 290mgKOH/g, solids content 100%, Nippon Polyurethane Industry Co., Ltd. (Nippon Polyurethane Industry Co., Ltd.) manufacture.
(note 22) TIPAQUE CR-95: name of product, titanium white, Ishihara Sangyo Kaisha, Ltd. Manufacture
(note 23) High Wax 200PF: name of product, Tissuemat E, Mitsui Chemicals strain formula Commercial firm manufactures
(note 24) BYK-333: name of product, modified dimethyl siloxane, BYK-Chemie Society of company manufactures
(note 25) Moresco white P-80: name of product, liquid paraffin, Co., Ltd. MORESCO manufactures
(note 26) 2-Ethylhexyl Alcohol
(note 27) Megafac F-562: name of product, the compound containing perfluoroalkyl, DIC Co., Ltd. manufactures
(note 28) 60%Lumiflon LF200: trade name, the fluoroolefin of hydroxyl- Vinyl ether co-polymer, hydroxyl value 31, solids content is 60%, and Asahi Glass Co., Ltd manufactures.
Fluoroolefin-vinyl ethers the copolymerization of (note 29) 60%Lumiflon LF800: hydroxyl Thing, hydroxyl value 23mgKOH/g, solids content 60%, Asahi Glass Co., Ltd manufactures,
The fluororesin of (note 30) numbering 1: by 600 parts of 3-ethoxyl ethyl propionates, 170 parts Ethanol, 60 parts of cyclohexyl vinyl ether (CHVE), 90 parts of ethyl vinyl ethers (EVE), 400 parts of hydroxybutyl vinyl ether (HBVE), 5.0 parts of potassium carbonate and 10 parts of Perbutyl PV (organic peroxide, NOF Corp manufactures), enters in being placed in autoclave After airtight, the degassing operation of row, 680 parts of CTFEs (CTFE) are loaded autoclaves In, carry out being polymerized 17 hours at 75 DEG C.After reaction, remove potassium carbonate by carrying out filtering, (non-volatile by adjusting the 3-ethoxyl ethyl propionate solution of the fluororesin that concentration obtains numbering 1 Material is 70 mass %).
The composition of the fluoropolymer of obtained numbering 1 is, polymerized unit based on CTFE/ Polymerized unit based on CHVE/polymerized unit based on EVE/polymerized unit based on HBVE (mol%)=50/5/10/35.It addition, the hydroxyl value of the fluororesin of numbering 1 be 160mgKOH/g, Number-average molecular weight is 5000.
(note 31) 50%Zeffle GK-510: name of product, PTFE, great Jin (Daikin) Co., Ltd. manufactures, hydroxyl value 60mgKOH/g,
(note 32) Dyneon TF9205: polytetrafluoroethylene powder, 3M company manufactures
(note 33) Kynar 711: name of product, Kynoar, ARKEMA strain formula meeting Society manufactures
(note 34) Sumidur N3300: name of product, hexamethylene diisocyanate different Cyanurate (is write a Chinese character in simplified form: HDI isocyanuric acid ester), solids content 100%, NCO content=21.8%, Sumitomo Bayer polyurethane Co., Ltd. (Sumika Bayer Urethane Co., Ltd.) manufactures
(note 35) Desmodur Z4470BA: name of product, isophorone diisocyanate Isocyanuric acid ester body (writing a Chinese character in simplified form: IPDI isocyanuric acid ester), solids content 70%, NCO Content=11.9%, Sumitomo Bayer polyurethane Co., Ltd. manufactures
(note 36) Duranate 24A-90E: name of product, hexamethylene diisocyanate Biuret body (is write a Chinese character in simplified form: HDI biuret), solids content 90%, NCO content=21.2%, Asahi Kasei Corporation manufactures
(note 37) Desmodur XP2565: name of product, hexamethylene diisocyanate Allophanate body (is write a Chinese character in simplified form: HDI allophanate), solids content 80%, NCO content =12%, Bayer company manufactures
(note 38) Takenate D-160N: name of product, trimethylolpropane/hexa-methylene Diisocyanate adduct body (is write a Chinese character in simplified form: TMP/HDI adduct), solids content 75%, NCO content=12.8%, Mitsui Takeda Chemical Co., Ltd (Mitsui Takeda Chemicals, Inc.) manufacture
(note 39) Takenate D-140NF: name of product, trimethylolpropane/isophorone Diisocyanate adduct body (is write a Chinese character in simplified form: TMP/IPDI adduct), solids content 75%, NCO content=10.6%, Mitsui Takeda Chemical Co., Ltd manufactures
(note 40) Desmodur N3400: name of product, the urea of hexamethylene diisocyanate Two ketoboidies (are write a Chinese character in simplified form: HDI urea diketone), solids content 100%, NCO content 21.8%, Sumitomo Bayer polyurethane Co., Ltd. manufactures
(note 41) TLA-100: name of product, the isocyanuric acid of hexamethylene diisocyanate Ester body (is write a Chinese character in simplified form: HDI isocyanuric acid ester), solids content 100%, NCO content=23.4%, Asahi Chemical Corp manufactures
(note 42) Desmodur N3800: name of product, aliphatic polyisocyante polyurethane Prepolymer, solids content 100 weight %, NCO content 11.0%, Sumitomo Bayer polyurethane strain Formula commercial firm manufactures
(note 43) Tankaru 300: name of product, calcium carbonate, bamboo former chemical industry strain formula meeting Society manufactures
(note 44) KAOLIN HA-90T: name of product, calcined kaolin, SHANXI JINYANG CALCINED KAOLIN manufactures
(note 45) BARIFINE BF-20: name of product, barium sulfate, chemical industry strain Formula commercial firm manufactures
(note 46) Sylophobic 200: name of product, silicon dioxide, Fuji's chemistry of silicones strain formula Commercial firm (Fuji Silysia Chemical Ltd.) manufactures
(note 47) BYK-161: name of product, pigment dispersing agent, BYK company manufactures
(note 48) BYK-410: name of product, viscosifier, BYK company manufactures
(note 49) Desmophen NH-1220: name of product, amino-compound, Bayer MaterialScience company manufactures
(note 50) HALS 292: name of product, light stabilizer, BASF AG manufactures
(note 51) BYK-057: name of product, the most siliceous polymer-like antifoams, BYK Company manufactures
(note 52) BYK-066N: name of product, silicon class defoamer, BYK company manufactures
<<test method>>
(note 53) application operability (curing rate)
[storage period]
Each painting obtained by uniformly mixing in the previous embodiment of whole composition and comparative example Feed composition is placed at 20 DEG C, measures the time till gelation, presses and states metewand and enter Row is evaluated.
More than S:30 minute；
A:20 minute less than 30 minutes；
B:10 minute less than 20 minutes；
C: less than 10 minutes.
[sagging resistance]
Make to be dried by airless spraying by the coating composition obtained in previous embodiment and comparative example Thickness changes and is painted on " coated article 2:FRP+ gel coat ", is maintained at by each coated plate It is to be dried under the conditions of 20 DEG C-RH90% in the case of 60 ° of angles, solidify relative to level. Sagging dry film thickness limit is there is by visual assessment
More than S:250 μm；
A:200 μm is less than 250 μm；
B:150 μm is less than 200 μm；
C: less than 150 μm.
(note 54) outward appearance
By each bread board of visual observations, by following benchmark evaluation bubble trace, fold, the sending out of foaming Raw rate.
S: entirely without bubble trace, fold, foaming；
A: can marginally observe the arbitrary phenomenon in trickle bubble trace, fold, foaming；
B: can been considerably observe the arbitrary phenomenon in bubble trace, fold, foaming；
C: can substantially observe the arbitrary phenomenon in bubble trace, fold, foaming.
(note 55) resistance to weathering is tested: RET
By all each coating compositions as the aforementioned in simulation air vane (radius of curvature is 9mm) It is coated on the coated article of the 23cm length of leading edge, is dried, prepare bread board.
Prepare same bread board 3, be installed on blade-carrying horizontal rotor.By rotor Carry out rotating so that speed from armature spindle farthest reaches 160m/ second, nearest from armature spindle Part reaches the 120m/ second.
Will be equivalent to the water of precipitation of 30mm/ hour～35mm/ hour with diameter 1mm～ The test water droplet of 2mm is sprayed to the coating surface rotated equably.Within every 30 minutes, stop the rotation, By the coating surface of visual observations bread board leading edge, record film is cut down to 5cm from front end Above average time.
More than S:5 hour；
A:4 hour less than 5 hours；
B:3 hour less than 4 hours；
C: less than 3 hours.
(note 56) resistance to water
For each bread board, by following benchmark evaluation in impregnated in the warm water of 40 DEG C after 30 days Carried out the outward appearance of the bread board of washing.
Outward appearance [after water resistant test]
S: relative to the film before test, outward appearance is entirely without change；
A: relative to the film before test, can slightly observe that gloss is degenerated, bubbled or variable color Phenomenon, but in the case of making product, reach no problem level；
B: relative to the film before test, can observe that gloss is degenerated, bubbled or variable color on a small quantity Phenomenon；
C: relative to test before film for, can substantially observe gloss degenerate, bubble or The phenomenon of variable color.

Claims (15)

1. a coating composition, it contains (A) polyhydric alcohol, the esterification of (B) polyisocyanic acid Compound and (C) curing catalysts, it is characterised in that described polyhydric alcohol (A) is containing having carbon The polyhydric alcohol (A1) of the construction unit of the fatty acid source of atomic number more than 8, and described solid Change catalyst (C) containing the imidazolium compounds with at least one imidazole ring.
2. coating composition as claimed in claim 1, wherein, described curing catalysts (C) Containing the imidazolium compounds represented by general formula (I),
In described logical formula (I), R1Represent that hydrogen atom, the alkyl of carbon number 1～4, carbon are former The cycloalkyl of subnumber 3～8, the hydroxy alkyl of carbon number 1～4, carbon number 6～10 Aryl or acyl group,
R2And R3Separately represent hydrogen atom, the alkyl of carbon number 1～4, carbon atom Hydroxy alkyl, acyl group, alkoxy carbonyl group, carboxyl or the halogen of several 1～4, or R2And R3With R2、R3The carbon atom of upper bonding forms aromatic rings together,
R4Represent hydrogen atom, the alkyl of carbon number 1～12, the thiazolinyl of carbon number 2～4, Aralkyl, can the aryl of substituted base or the functional group shown in lower formula (II),
In described logical formula (II), R5Represent hydrogen atom or the alkyl of carbon number 1～4, p table Show the integer of 1～3.
3. coating composition as claimed in claim 2, wherein, described logical formula (I) institute table The imidazolium compounds shown is choosing free 1-Methylimidazole., DMIZ 1,2 dimethylimidazole, 1-(3-diformazan ammonia Base propyl group) imidazoles, 1-isobutyl-2-methyl imidazole, 1-normal-butyl-2-methylimidazole and 1-benzyl At least one in the group that-2-methylimidazole is constituted.
4. the coating composition as according to any one of claims 1 to 3, it is possibly together with conduct The bismuth compound of described curing catalysts (C).
5. the coating composition as according to any one of Claims 1 to 4, wherein,
Described polyhydric alcohol (A1) is that choosing is free
(A1-1) fatty acid of the hydroxyl of carbon number more than 8 and polyhydric alcohol carboxylate,
(A1-2) unsaturated fatty acid of the hydroxyl of carbon number more than 8 polymer,
(A1-3) polymer of the unsaturated fatty acid of carbon number more than 8 is reduced and The polyhydric alcohol that obtains,
(A1-4) unsaturated fatty acid (a1-4-1) and/or carbon to carbon number more than 8 are former The carboxylate (a1-4-2) of the unsaturated fatty acid of subnumber more than 8 and polyhydric alcohol carries out hydroxyl and changes Property and the polyhydric alcohol that obtains
At least one in the group constituted.
6. coating composition as claimed in claim 5, wherein, described polyhydric alcohol (A1) It is at least one in Oleum Ricini and castor oil hydrogenated.
7. the coating composition as according to any one of claim 1～6, it is possibly together with conduct The free polycaprolactone glycol of choosing of described polyhydric alcohol (A), polycaprolactonetriol, polycaprolactone At least one in the group that tetrol, PCDL and polyacrylate polyol are constituted is many Unit's alcohol (A2).
8. coating composition as claimed in claim 7, wherein, relative to 100 mass parts Composition (A), the combined amount of described polyhydric alcohol (A1) is 10 mass parts～70 mass parts, The combined amount of described polyhydric alcohol (A2) is in the range of 30 mass parts～90 mass parts.
9. the coating composition as according to any one of claim 1～8, wherein, relative to The composition (A) of 100 mass parts, has the combined amount of the imidazolium compounds of at least one imidazole ring It is 0.005 mass parts～8 mass parts.
10. the coating composition as according to any one of claim 1～9, it is possibly together with coloring Composition (D).
11. coating compositions as according to any one of claim 1～10, it is possibly together with dredging Water preparation (E) and/or fluororesin (F).
12. 1 kinds of coating film-forming methods, wherein, according to any one of claim 1～11 Coating composition be painted on coated article formation film.
13. coating film-forming methods as claimed in claim 12, wherein, described coated article is to mould Material or the base material of metal, by the gel coating material stacking containing epoxy resin on the substrate and The object that becomes, the primer coating film containing epoxy resin is formed object on the substrate, Or the gel coating material stacking containing epoxy resin on the substrate and is coated with at described gel The object of the primer coating film containing epoxy resin is formed further on cloth material.
14. coating film-forming methods as described in claim 12 or 13, wherein, described are coated with Thing is the blade of wind-driven generator.
15. 1 kinds of article, it is by by the coating according to any one of claim 1～11 Compositions is painted on the article obtained on coated article.
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