CN105960441B - It is used to form the coating composition of the film with impact resistance - Google Patents

Abstract

The problem to be solved in the present invention is to provide a kind of coating composition and coating film-forming methods, and article made of coating is carried out as the coating composition, wherein, the coating operability of the coating composition is excellent and the impact resistances such as the resistance to weathering of film obtained, chipping resistance and water resistance, finished appearance are excellent, and the film excellent to the adhesiveness of coated article can be formed on the coated articles such as the blade of wind-driven generator.The present invention provides a kind of coating composition, it contains (A) polyalcohol, (B) polyisocyanate compound and (C) curing catalysts, it is characterized in that, ingredient (A) contains the polyalcohol (A1) of the structural unit of the fatty acid source with 8 or more carbon atom number, and the curing catalysts (C) contain the imidazolium compounds at least one imidazole ring.

Description

It is used to form the coating composition of the film with impact resistance

Technical field

[cross reference to related applications]

This application claims the explanations based on the Japanese patent application proposed on January 24th, 2014 the 2014-011773rd The priority of book (content of the application is totally integrating in this specification by reference).

The present invention relates to a kind of for forming the coating composition with the film of impact resistance on coated article, film is made The article of film is formed at method and using the coating composition.

Background technique

In recent years, wind energy is attracted attention as one of renewable energy and by people, is added to be converted into electric energy To utilize, all construction have wind-driven generator in many places such as land and sea, environment at present, it is contemplated that also will increase from now on.

For the blade being mounted on wind-driven generator, is rotated and be exposed to sometimes very strong due to the blade itself In rain wind and sandstorm etc., therefore, be arranged under normal circumstances or use coated article (for example, the roof and exterior wall of household, Car body) on film compared to it is necessary to have significantly high impact resistances.As being set to being applied in above-mentioned harsh environment Object can also enumerate the wing etc. of aircraft and helicopter, with the impact resistance of the film under this harsh environment, for example resistance to weathering Property etc. evaluated as index.

In the past, for the blade of wind-driven generator, it is known to using coating composition, gel coating agent containing polyurethane etc. The case where fluoropolymer and polyester polymers are coated (Patent Documents 1 to 5).

But the film for being formed by these compositions, the impact resistances such as resistance to weathering, water resistance and insufficient. In addition, in the case where implementing coating under high humidity conditions or contain wetly in coating or in coated article, it some times happens that The problem of abnormal appearances such as blistering.

Existing technical literature

Patent document

Patent document 1: No. 2010/122157 handbook of International Publication bulletin

Patent document 2: No. 2005/030893 handbook of International Publication bulletin

Patent document 3: Japanese Unexamined Patent Publication 2002-20686 bulletin

Patent document 4: Japanese Unexamined Patent Application Publication 2013-544898 bulletin

Patent document 5: No. 2013/184424 handbook of International Publication bulletin

Summary of the invention

The technical problems to be solved by the invention

The present invention has been made in view of the above-described circumstances, and an object thereof is to provide a kind of coating compositions and the film side of being formed Method, and article made of coating is carried out as the coating composition, wherein aforementioned coating composition is to painting environments such as humidity Dependence is small and the impact resistances such as the resistance to weathering of film obtained, chipping resistance and water resistance, finished appearance are (on bodyguard Ga り) it is excellent, and it is capable of forming the film excellent to the adhesiveness of the coated articles such as the blade of wind-driven generator.

Means needed for solving the problems, such as

Under such situation, the inventors of the present invention are studied intensively, as a result, it has been found that: by containing specific polynary Alcohol, polyisocyanate compound coating composition in mix specific imidazolium compounds as curing catalysts, be able to solve Above-mentioned technical problem.

The present invention provides coating composition, coating film-forming methods and the article with film shown in following every scheme.

1st scheme: a kind of coating composition contains (A) polyalcohol, (B) polyisocyanate compound and (C) solidification Catalyst, which is characterized in that the polyalcohol (A) contains the structural unit of the fatty acid source with 8 or more carbon atom number Polyalcohol (A1), and the curing catalysts (C) contain the imidazolium compounds at least one imidazole ring.

2nd scheme: the coating composition as described in the 1st scheme, wherein the curing catalysts (C) are containing following Imidazolium compounds represented by logical formula (I),

In the logical formula (I), R₁Indicate hydrogen atom, the alkyl of carbon atom number 1~4, the naphthenic base of carbon atom number 3~8, carbon The aryl or acyl group of the hydroxy alkyl of atomicity 1~4, carbon atom number 6~10,

R₂And R₃Separately indicate hydrogen atom, the alkyl of carbon atom number 1~4, carbon atom number 1~4 hydroxy alkyl, Acyl group, alkoxy carbonyl group, carboxyl or halogen or R₂And R₃With R₂、R₃The carbon atom of upper bonding is formed together aromatic rings,

R₄Indicate hydrogen atom, the alkyl of carbon atom number 1~12, the alkenyl of carbon atom number 2~4, aralkyl, can substituted base Aryl or lower formula (II) shown in functional group,

In the logical formula (II), R₅Indicate that the alkyl of hydrogen atom or carbon atom number 1~4, p indicate 1~3 integer

3rd scheme: the coating composition as described in the 2nd scheme, wherein imidazoles represented by the logical formula (I) Closing object is selected from by 1- methylimidazole, DMIZ 1,2 dimethylimidazole, 1- (3- dimethylamino-propyl) imidazoles, 1- isobutyl group -2- methyl At least one of the group that imidazoles, 1- normal-butyl -2-methylimidazole and 1 benzyl 2 methyl imidazole are constituted.

4th scheme: the coating composition as described in any one of the 1st~3 scheme, wherein also containing described in conduct The bismuth compound of curing catalysts (C).

5th scheme: the coating composition as described in any one of the 1st~4 scheme, wherein

The polyalcohol (A1) be selected from by

(A1-1) carboxylate of the fatty acid of the hydroxyl of 8 or more carbon atom number and polyalcohol,

(A1-2) polymer of the unsaturated fatty acid of the hydroxyl of 8 or more carbon atom number,

Polyalcohol obtained from (A1-3) being restored to the polymer of the unsaturated fatty acid of 8 or more carbon atom number,

(A1-4) to the unsaturation of the unsaturated fatty acid (a1-4-1) of 8 or more carbon atom number and/or 8 or more carbon atom number The carboxylate (a1-4-2) of fatty acid and polyalcohol carries out polyalcohol obtained from hydroxyl modification

At least one of group constituted.

6th scheme: the coating composition as described in the 5th scheme, wherein the polyalcohol (A1) is selected from castor oil At least one of with rilanit special.

7th scheme: the coating composition as described in any one of the 1st~6 scheme also contains as described polynary Alcohol (A) is selected from by polycaprolactone glycol, polycaprolactonetriol, polycaprolactone tetraol, polycarbonate glycol and polyacrylate At least one of the group that polyalcohol is constituted polyalcohol (A2).

8th scheme: coating composition as described in scheme 7, wherein described relative to the ingredient (A) of 100 mass parts The combined amount of polyalcohol (A1) is 10 mass parts~70 mass parts, and the combined amount of the polyalcohol (A2) is in 30 mass parts~90 matter In the range of amount part.

9th scheme: the coating composition as described in any one of the 1st~8 scheme, wherein relative to 100 mass parts Ingredient (A), at least one imidazole ring imidazolium compounds combined amount be 0.005 mass parts~8 mass parts.

10th scheme: the coating composition as described in any one of the 1st~9 scheme also contains coloring components (D)。

11st scheme: the coating composition as described in any one of the 1st~10 scheme also contains hydrophobing agent (E) And/or fluororesin (F).

12nd scheme: a kind of coating film-forming methods, wherein by coating group described in any one of the 1st~11 scheme Conjunction object, which is painted on coated article, forms film.

13rd scheme: the coating film-forming methods as described in the 12nd scheme, wherein the coated article is plastics or metal Substrate, the gel coating material containing epoxy resin is layered in object made of on the substrate, by the bottom containing epoxy resin It paints object made of film is formed on the substrate or the gel coating material containing epoxy resin is layered in the substrate Above and on the gel coating material it is further formed object made of the primer coating film containing epoxy resin.

14th scheme: the coating film-forming methods as described in the 12nd or 13 scheme, wherein coated article is wind-driven generator Blade.

15th scheme: a kind of article is by applying coating composition described in any one of the 1st~11 scheme The article obtained on coated article.

The effect of invention

Using coating composition of the invention, it can be formed on blade surface of wind-driven generator etc. resistance to The impact resistances such as weathering, chipping resistance and excellent and excellent to the adhesiveness of the blade painting of water resistance, finished appearance Film.In addition, in the coating under conditions of thering is moisture to be mingled with (that is, the coating, substrate under high humility atmosphere contain moisture Coating etc.) in also there is excellent curability, and film is inhibited to blister, stable film physical property can be obtained.

In addition, reaching the method according to the embodiment of the present application in the present invention for resistance to weathering performance and evaluating.

Detailed description of the invention

Fig. 1 is the perspective view indicated in the embodiment of the present application for the breadboard of weathering test.

Specific embodiment

Coating composition

The present invention provides a kind of coating composition, contains (A) polyalcohol, (B) polyisocyanate compound and (C) solidification Catalyst, which is characterized in that the ingredient (A) contains the polynary of the structural unit of the fatty acid source with 8 or more carbon atom number Alcohol (A1), and the curing catalysts (C) are the imidazolium compounds at least one imidazole ring.

(A) polyalcohol

In the present invention, for (A) polyalcohol, as long as including the fatty acid source with 8 or more carbon atom number The polyalcohol (A1) of structural unit, just there is no particular limitation.

The polyalcohol (A1) of the structural unit of fatty acid source with 8 or more carbon atom number

In the present invention, so-called " polyalcohol (A1) of the structural unit of the fatty acid source with 8 or more carbon atom number ", Refer to the polyalcohol of the structural unit with fatty acid source, and indicates to constitute the structural unit of the fatty acid source of the polyalcohol In at least one unit carbon atom number 8 or more.

As ingredient (A1), for example, can enumerate:

(A1-1) carboxylate of the fatty acid of the hydroxyl of 8 or more carbon atom number and polyalcohol；

(A1-2) polymer of the unsaturated fatty acid of the hydroxyl of 8 or more carbon atom number；

(A1-3) polyalcohol obtained from being restored the polymer of the unsaturated fatty acid of 8 or more carbon atom number；

(A1-4) by the unsaturated fatty acid (a1-4-1) of 8 or more carbon atom number and/or the unsaturation of 8 or more carbon atom number The carboxylate (a1-4-2) of fatty acid and polyalcohol carries out polyalcohol obtained from hydroxyl modification etc..

The fatty acid of the hydroxyl of 8 or more the carbon atom number as constituent (A1-1), for example, carbon atom can be enumerated The fatty acid for the hydroxyl that number is 8~28, preferably 10~20；More specifically, ricinoleic acid, ricinelaidic acid etc. can be enumerated Saturated fatty acids of hydroxyls such as unsaturated fatty acid, 12- hydroxy stearic acid, the cerebronic acid of hydroxyl etc..Hydroxyl is contained for these The fatty acid of base, one or two kinds of combination of the above that can be used alone use.

As the polyalcohol of constituent (A1-1), glycerol, ethylene glycol, polyethylene glycol, propylene glycol, poly- the third two can be enumerated Alcohol, trimethylolpropane, pentaerythrite, sorbierite etc..For these polyalcohols, can be used alone one or two kinds of above group It closes and uses.

The fatty acid of hydroxyl as 8 or more carbon atom number and the carboxylate of polyalcohol can enumerate above-mentioned enumerate The carboxylate etc. of the fatty acid of the hydroxyl of 8 or more carbon atom number and the above-mentioned polyalcohol enumerated.

In addition, in a preferred embodiment of the invention, as the substance for containing ingredient (A1-1), castor-oil plant can be enumerated Oil, rilanit special etc..Castor oil is the vegetable oil using the seed of castor-oil plant as raw material, it is known that be ricinoleic acid, oleic acid etc. no The glyceride of the saturated fatty acids such as saturated fatty acid and palmitinic acid.Here, since ricinoleic acid is 8 or more carbon atom number containing hydroxyl Therefore castor oil or the rilanit special as its modifier are mixed in coating composition as ingredient (A) by the fatty acid of base Made of substance can contain ingredient (A1-1).For these ingredients (A1-1), can be used alone one or two kinds of combination of the above It uses.

The unsaturated fatty acid of the hydroxyl of 8 or more the carbon atom number as the ingredient (A1-2) for constituting polymer, for example, It is enumerated listed by the example that the unsaturated fatty acid of the hydroxyl of 8 or more the carbon atom number as constituent (A1-1) can be used Substance, can preferably enumerate ricinoleic acid, ricinelaidic acid etc..

As polymer, there is no particular limitation, can enumerate dimer, trimer, tetramer etc., preferably dimerization Object.Therefore, as ingredient (A1-2), the unsaturated fatty acid of the hydroxyl of above-mentioned 8 or more the carbon atom number enumerated can be enumerated Dimer, trimer, tetramer etc., preferably dimer.For these ingredients (A1-2), can be used alone one kind or two Kind combination of the above uses.

The polymer of unsaturated fatty acid as 8 or more the carbon atom number for constituting the raw material as ingredient (A1-3), The unsaturated fatty acid of 8 or more carbon atom number, for example, the unsaturation that carbon atom number is 8~28, preferably 10~20 can be enumerated Fatty acid；More specifically, can enumerate the unsaturated fatty acids of the hydroxyls such as ricinoleic acid, ricinelaidic 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, Eicosadienoic acid, two dodecadienoic acids, linolenic acid, pinolenic acid, eleostearic acid, Mead acid, eicosatrienoic acid, 18 carbon four The unsaturated fatty acid etc. of the not hydroxyl such as olefin(e) acid, arachidonic acid, eicosatetraenoic acid, adrenic acid.

The polymer of the unsaturated fatty acid of 8 or more the carbon atom number as the raw material as ingredient (A1-3), Ke Yiju Dimer, trimer, the tetramer of unsaturated fatty acid etc. of 8 or more carbon atom number, preferably dimer out.Therefore, as The polymer of the unsaturated fatty acid of 8 or more the carbon atom number of raw material as ingredient (A1-3) can enumerate above-mentioned enumerate Dimer, trimer, the tetramer of unsaturated fatty acid etc. of 8 or more carbon atom number, preferably dimer.For ingredient (A1- 3) for, can enumerate by the polymer of the unsaturated fatty acid of above-mentioned 8 or more carbon atom number using method known per se into Substance made of row reduction.As the typical example of ingredient (A1-3), for example, ricinoleic acid, oleic acid, linoleic acid, flax Acid, reduzate of dimeric dibasic acid of eleostearic acid etc..

In addition, constituting the polymer of the unsaturated fatty acid of 8 or more the carbon atom number of mentioned component (A1-3), it is able to use Market sale product.As market sale product, for example, the PRIPOL2033 etc. of CRODA company can be enumerated.

For these ingredients (A1-3), one or two kinds of combination of the above that can be used alone is used.

The unsaturated fatty acid (a1-4-1) of 8 or more the carbon atom number as the raw material as ingredient (A1-4), for example, can To enumerate the unsaturated fatty acid that carbon atom number is 8~28, preferably 10~20；More specifically, can enumerate ricinoleic acid, Unsaturated fatty acid, myristoleic acid, palmitoleic acid, palmitoleic acid, oleic acid, elaidic acid, the different oil of the hydroxyls such as ricinelaidic acid Acid, gadoleic acid, 20 carbon monoenoic acids, erucic acid, nervonic acid, linoleic acid, eicosadienoic acid, two dodecadienoic acids, linolenic acid, Pinolenic acid, eleostearic acid, Mead acid, eicosatrienoic acid, parinaric acid, arachidonic acid, eicosatetraenoic acid, adrenal gland The sour unsaturated fatty acid etc. for waiting not hydroxyl.As ingredient (a1-4-1), it is preferable to use the not hydroxyl of above-mentioned carbon atom number Unsaturated fatty acid.

As the polyalcohol of constituent (A1-4), glycerol, ethylene glycol, polyethylene glycol, propylene glycol, poly- the third two can be enumerated Alcohol, trimethylolpropane, pentaerythrite, sorbierite etc..For these polyalcohols, can be used alone one or two kinds of above group It closes and uses.

In addition, the unsaturated fatty acid and polyalcohol of the carbon atom number 8 or more as the raw material as ingredient (A1-4) Carboxylate (a1-4-2), for example, the unsaturated fatty acid of above-mentioned 8 or more carbon atom number and the esterification of above-mentioned polyalcohol can be enumerated Object etc.；More specifically, unsaturated fatty acid and polyalcohol that carbon atom number is 8~28, preferably 10~20 can be enumerated Carboxylate etc.；It is more specifically 8 or more it is preferable to use carbon atom number, is preferably carbon atom number 8~28, more excellent It is selected as the glyceride of the unsaturated fatty acid of carbon atom number 10~20.

The glyceride of the unsaturated fatty acid of above-mentioned 8 or more carbon atom number, for example, being included in grease.Therefore, as upper The insatiable hunger containing 8 or more carbon atom number can be used using ingredient (a1-4-2) in the raw material for stating ingredient (A1-4) With the grease of the glyceride of fatty acid.

The grease of glyceride as the unsaturated fatty acid containing above-mentioned 8 or more carbon atom number, for example, can preferably make With soybean oil, castor oil, palm oil, rapeseed oil etc..

The unsaturated fatty acid (a1-4-1) of 8 or more above-mentioned carbon atom number in ingredient (A1-4) and/or carbon atom number 8 with On unsaturated fatty acid and the hydroxyl modification of carboxylate (a1-4-2) of polyalcohol method known per se can be used to implement. Specifically, for example, can enumerate the unsaturated group in mentioned component (a1-4-1) and/or (a1-4-2) using peroxide It rolls into a ball after carrying out epoxidation, the method etc. for making the epoxides generated and monohydric alcohol or polyalcohol react.

As for making the unsaturated group in mentioned component (a1-4-1) and/or (a1-4-2) that epoxidised peroxide occur Compound, for example, Peracetic acid, hydrogen peroxide etc. can be enumerated.

As for making above-mentioned epoxides that the monohydric alcohol of hydroxyl modification occur, for example, can enumerate: methanol, ethyl alcohol, third The straight chain primary alcohols such as alcohol；The secondary alcohol such as isopropanol；The alcohol containing unsaturated group such as allyl alcohol；The branched-chain alcohos such as isobutanol, neopentyl alcohol；Hexamethylene The cyclic alcohols such as alcohol, benzylalcohol；The ethylene glycol monoalkyl ethers such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether；Diethyl The diethylene glycols monoalky lether such as glycol monomethyl ether；The propylene-glycol monoalky lethers such as propylene glycol monomethyl ether；Dipropylene glycol monomethyl ether etc. two Propylene-glycol monoalky lether etc..For these monohydric alcohols, one or two kinds of combination of the above that can be used alone is used.As for making The polyalcohol of hydroxyl modification occurs for above-mentioned epoxides, for example, can enumerate glycerol, ethylene glycol, polyethylene glycol, propylene glycol, gather Propylene glycol, butanediol, neopentyl glycol, trimethylolpropane, pentaerythrite, sorbierite etc..For these polyalcohols, can individually make It is used with one or two kinds of combination of the above.

In addition, market sale product can be used as mentioned component (A1-4).As market sale product, for example, can lift The Sovermol 750, Sovermol 760, Sovermol 805, Sovermol 815, Sovermol 819 of BASF AG out Deng.

For these ingredients (A1-4), one or two kinds of combination of the above that can be used alone is used.

In addition, can individually make for these ingredients (A1-1), ingredient (A1-2), ingredient (A1-3) and ingredient (A1-4) It is used with one or two kinds of combination of the above.

(A) polyalcohol can also contain the polyalcohol other than ingredient (A1) in the present invention.

In a preferred embodiment of the invention, it as the polyalcohol other than ingredient (A1), can be used from polycaprolactone It is selected in the group that glycol, polycaprolactonetriol, polycaprolactone tetraol, polycarbonate glycol, polyacrylate polyol are constituted At least one polyalcohol (A2).

Polyalcohol (A2)

For polycaprolactone polyol, for example, can by by 6-caprolactone using binary~quaternary polyalcohol as cause Agent carries out ring-opening polymerisation to obtain.As the polyalcohol more than binary, for example, ethylene glycol, glycerol, trihydroxy methyl can be enumerated Ethane, trimethylolpropane, diglycerol, double trimethylolpropane, 1,2,6- hexanetriol, pentaerythrite, three (2- ethoxys) are different Cyanurate makes dimethylolalkanoic acids and mono-epoxy compounds (for example, what HEXION Specialty Chemicals company manufactured The ethylene oxidic ester of " Cardura E10 ", the high branch chain saturated fatty acid of synthesis) react obtained polyol compound Deng.For these ingredients, the one or more that can be used alone are applied in combination.

In addition, market sale product can be used as above-mentioned polycaprolactone polyol.As market sale product, for example, can To enumerate: Daisel chemical industry Co., Ltd (Daicel Chemical Industries Ltd.) manufacture as " Placcel 205 ", " Placcel 205H ", " the Placcel L205AL ", " Placcel of 200 series of Placcel C205U”、“Placcel 208”、“Placcel 210”、“Placcel 210N”、“Placcel 210CP”、“Placcel 212”、“Placcel 212AL”、“Placcel 220”、“Placcel 220N”、“Placcel 220CPB”、“Placcel 220UA ", as " Placcel 303 " of the series of Placcel 300, " Placcel 305 ", " Placcel 308 ", " Placcel 309 ", " Placcel 312 ", " Placcel 320 ", " Placcel 320AL ", " Placcel 410 " etc.；Pottery " TONE301 ", " TONE305 " etc. of family name chemical company (Dow Chemical Company) manufacture.

From the viewpoint of resistance to weathering, in polycaprolactone polyol, preferably its hydroxyl value 100mgKOH/g~ In the range of 700mgKOH/g, more preferably in the range of 130mgKOH/g~600mgKOH/g, further particularly preferably exist In the range of 150mgKOH/g~500mgKOH/g, it is also preferable to its number-average molecular weight in the range of 200~1800 and There are more than two hydroxyls in a molecule.

Specifically, in polycaprolactone polyol, preferably polycaprolactonetriol, polycaprolactone tetraol.

For polycarbonate glycol, for example, can be obtained by making diol component react with carbonyl agent.As structure At the carbonyl agent of polycarbonate glycol, for example, ethylene carbonate, propylene carbonate, dimethyl carbonate, carbonic acid two can be enumerated Ethyl ester, dibutyl carbonate, diphenyl carbonate, diphenyl carbonate, phosgene etc..It, can as the diol component of polycarbonate glycol To enumerate aliphatic diol, alicyclic diol etc.；As specific example, 1,4-butanediol, 3- methyl-1,5- penta 2 can be enumerated The alicyclic diols such as the aliphatic diols such as alcohol, 1,6-HD, diethylene glycol, 1,4- cyclohexanediol, bis- (ethoxys) are to benzene two The aromatic diols such as the alkylene oxide adduct of the esterdiols such as formic acid esters class or bisphenol-A.

As above-mentioned polycarbonate glycol, market sale product can be used.As market sale product, for example, can enumerate: " the Placcel CD of Daisel chemical industry Co., Ltd (Daicel Chemical Industries Ltd.) manufacture CD205”、“Placcel CD CD205PL”、“Placcel CD CD205HL”、“Placcel CD CD210”、“Placcel CD CD210PL"；" Duranol T5652 ", " the Duranol T5651 ", " Duranol of Asahi Kasei Corporation's manufacture T5650J”、“Duranol 5650E”、“Duranol G4672”、“Duranol T4671”、“Duranol T4692”、 " Duranol T4691 " etc..

For these polycarbonate glycol, one or two kinds of combination of the above that can be used alone is used.

From the viewpoint of resistance to weathering, in polycarbonate glycol, preferably its hydroxyl value 110mgKOH/g~ Exist in the range of 700mgKOH/g, more preferably in the range of 130mgKOH/g~600mgKOH/g and then particularly preferably In the range of 150mgKOH/g~500mgKOH/g, preferably its number-average molecular weight is in the range of 200~1800.

As polyacrylate polyol, in general, can be using method known per se, such as in organic solvent molten The methods of liquid polymerization, by by the polymerism unsaturated monomer of hydroxyl and can be with the polymerism unsaturated monomer of the hydroxyl Other polymerism unsaturated monomers being copolymerized are copolymerized to manufacture.

The polymerism unsaturated monomer of hydroxyl is to be respectively provided with more than one hydroxyl and polymerism in a molecule The compound of unsaturated bond, specifically, for example, can enumerate: (methyl) acrylic acid 2- hydroxyl ethyl ester, (methyl) acrylic acid 2- hydroxyl Propyl ester, (methyl) acrylic acid 3- hydroxypropyl acrylate, (methyl) acrylic acid 4- hydroxy butyl ester, (methyl) acrylic acid 5- hydroxy pentane ester, (methyl) third (methyl) acrylic acid and the carbon atoms such as the own ester of olefin(e) acid 6- hydroxyl, (methyl) acrylic acid 7- hydroxyl heptyl ester, (methyl) acrylic acid 8- hydroxyl monooctyl ester The monoesters compound of the dihydric alcohol of number 2~8；Should (methyl) acrylic acid and carbon atom number 2~8 dihydric alcohol monoesters compound ε-oneself Lactone-modified body；N- methylol (methyl) acrylamide；With allyl alcohol and then molecular end is hydroxyl with polyoxyethylene (methyl) acrylate of alkene chain etc..In addition, in the present invention, aftermentioned 2- hydroxyl -4- (3- methacryloxy -2- hydroxyl Base propoxyl group) benzophenone etc. is included in the polymerism unsaturated monomer of ultraviolet-absorbing functional group can be with hydroxyl In other polymerism unsaturated monomers that polymerism unsaturated monomer is copolymerized, and not included in the polymerism of hydroxyl It is saturated in monomer.

In addition, as other polymerism unsaturated monomers that can be copolymerized with the polymerism unsaturated monomer of hydroxyl, For example, can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) propylene Isopropyl propionate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) propylene The just own ester of acid, (methyl) n-octyl, (methyl) acrylic acid 2- b hexyl, (methyl) nonyl acrylate, (methyl) propylene Sour tridecane base ester, (methyl) lauryl acrylate, (methyl) stearyl acrylate acyl ester, " acrylic acid isooctadecane ester (trade name Claim, Osaka Organic Chemical Industry Co., Ltd. manufacture) ", (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) alkyl acrylate or (methyl) such as (methyl) t-butylcyclohexyl ester, (methyl) acrylic acid cyclododecane base ester Acrylate base ester；(methyl) isobornyl acrylate etc. has the polymerism unsaturated monomer of isobornyl；(methyl) third Olefin(e) acid adamantane esters etc. have the polymerism unsaturated monomer of adamantyl；Styrene, α-methylstyrene, vinyltoluene Equal vinyl aromatic compounds；Vinyltrimethoxysilane, vinyltriethoxysilane, (the 2- methoxyl group of vinyl three Ethyoxyl) silane, γ-(methyl) acryloyloxypropyltrimethoxysilane, three ethoxy of γ-(methyl) acryloxypropyl Base silane etc. has the polymerism unsaturated monomer of alkoxysilane group；Perfluoro butyl ethyl (methyl) acrylate, perfluor are pungent Base ethyl (methyl) acrylate etc. perfluoroalkyls (methyl) acrylate；Fluoroolefin etc. has the polymerism of fluorinated alkyl not It is saturated monomer；Dimaleoyl imino etc. has the polymerism unsaturated monomer of optical polymerism functional group；N- vinylpyrrolidone, second The vinyl compounds such as alkene, butadiene, chlorobutadiene, vinyl propionate, vinylacetate；(methyl) acrylic acid, maleic acid, bar The carboxylic polymerism unsaturated monomer such as beans acid, β-acryloxypropionic acid；(methyl) acrylonitrile, (methyl) acrylamide, (first Base) acrylic acid N, N- dimethylamino ethyl ester, N, N- dimethylamino-propyl (methyl) acrylamide, (methyl) acrylic acid shrink sweet The nitrogenous polymerism unsaturated monomer such as the adduct of grease and amine compounds；(methyl) allyl acrylate, 1,6-HD The polymerism in a molecule with more than two polymerism unsaturated groups such as two (methyl) acrylate is unsaturated single Body；(methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl esters, (methyl) acrylic acid 3,4- epoxy group Cyclohexylmethyl, (methyl) acrylic acid 3,4- expoxycyclohexyl ethyl ester, (methyl) acrylic acid 3,4- expoxycyclohexyl propyl ester, The polymerism unsaturated monomer containing epoxy group such as allyl glycidyl ether；Molecular end is alkoxy with polyethylene glycol oxide (methyl) acrylate of chain；2- acrylamide -2- methyl propane sulfonic acid, acrylic sulfonic acid, styrene sulfonic acid sodium salt, methyl-prop Olefin(e) acid Sulfoethyl esters and its sodium salt, ammonium salt etc. have sulfonic polymerism unsaturated monomer；2- acryloyl-oxyethyl acid Phosphate, 2- methacryloxyethyl phosphate ester acid, 2- acryloxypropyl phosphate ester acid, 2- methacryl Oxygroup propyl 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- acryloxy -2- hydroxy propyloxy group) benzophenone, 2,2 '-dihydroxies Base -4- (3- methacryloxy -2- hydroxy propyloxy group) benzophenone, 2,2 '-dihydroxy -4- (3- acryloxy -2- hydroxyl Base propoxyl group) benzophenone, 2- (2 '-hydroxyls -5 '-methaciylyloxyethylphenyl) -2H- benzotriazole etc. have it is ultraviolet The polymerism unsaturated monomer of line absorption functional group；4- (methyl) acryloxy -1,2,2,6,6- pentamethvl, 4- (methyl) acryloxy -2,2,6,6- tetramethyl piperidine, 4- cyano -4- (methyl) Acryloyl amino -2,2,6,6- tetramethyl Phenylpiperidines, 1- (methyl) acryloyl group -4- (methyl) Acryloyl amino -2,2,6,6- tetramethyl piperidine, 1- (methyl) propylene Acyl group -4- cyano -4- (methyl) Acryloyl amino -2,2,6,6- tetramethyl piperidine, 4- crotons acyloxy -2,2,6,6- tetramethyl Phenylpiperidines, 4- crotonocyl amino -2,2,6,6- tetramethyl piperidine, 1- crotonocyl -4- crotons acyloxy -2,2,6,6- tetramethyl piperazine The UV stables polymerism unsaturated monomer such as pyridine；Methacrylaldehyde, Diacetone Acrylamide, diacetone methacrylamide, first Base acrylic acid acetoacetoxyethyl, formoxyl styrene, the vinyl alkyl ketone with 4~7 carbon atoms are (for example, second Enyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) etc. with carbonyl polymerism unsaturated monomer compound etc..It is right They can use individually or be used in combination.

For polyacrylate polyol, from low temperature under curability feature and obtained film water resistance Viewpoint is set out, it is usually preferred to in the range of 30mgKOH/g~300mgKOH/g, particularly preferably in 40mgKOH/g In the range of~250mgKOH/g, further particularly preferably with hydroxyl value in the range of 50mgKOH/g~200mgKOH/g.

Polyacrylate polyol, it is usually preferred to in the range of 3000~100000, particularly preferably have In the range of 3000~50000, further particularly preferably there is the weight average molecular weight in 4000~30000 ranges.

" weight average molecular weight ", " number-average molecular weight " in this specification be according to method described in JIS K 0124-2011, According to the chromatography for using gel permeation chromatography device to measure value calculated on the basis of the molecular weight of standard polystyren.Gel Permeation chromatography device uses " HLC8120GPC " (Japanese TOSOH Co., Ltd manufactures).Chromatographic column uses " TSKgel G-4000H (trade name is by × L ", " TSKgel G-3000H × L ", " TSKgel G-2500H × L ", " TSKgel G-2000H × L " The manufacture of Japanese TOSOH Co., Ltd) this 4 columns, mobile phase is tetrahydrofuran, measurement temperature is 40 DEG C, flow velocity is 1mL/ points Clock, detector measure under conditions of being RI.

As polyacrylate polyol, from the viewpoint of resistance to weathering, preferably as the polymerism insatiable hunger of hydroxyl Polyacrylate polyol and propylene made of being copolymerized with monomer with (methyl) acrylate with polycaprolactone skeleton Polyacrylate polyol made of sour hydroxy butyl ester (HBA) is copolymerized.

It for the use ratio of ingredient (A1) and ingredient (A2), is not particularly limited, but from finished appearance and resistance to weathering Property from the perspective of, relative to the ingredient (A) of 100 mass parts, the combined amount of preferred component (A1) is 10 mass parts~80 mass Part, more preferably 10 mass parts~70 mass parts.In addition, from the viewpoint of finished appearance and water resistance, relative to 100 mass The ingredient (A) of part, the combined amount of preferred component (A2) are 20 mass parts~90 mass parts, more preferably 30 mass parts~90 mass Part.These ingredients (A) can be used alone or be used in combination.

Polyalcohol (A3) other than ingredient (A1) and (A2)

(A) polyalcohol in the present invention may also comprise the polyalcohol (A3) other than ingredient (A1) and (A2).As ingredient (A3) polyalcohol is the polyol component for being not classified as (A1) and (A2), for example, can enumerate: in addition to (A1) and (A2) Polyalcohol, polyester polyol, Polyacetal polyols, polyester amide polyol or Polythioether polyols in addition, other hydroxyls Resin etc..

As the polyalcohol other than above-mentioned (A1) and (A2), can enumerate: as tool in a molecule, there are two hydroxyls The compound of base and the aliphatic diol illustrated in front, aromatic diol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol etc. are poly- Ether glycols；Glycerol, trimethylolethane, trimethylolpropane, diglycerol, triglycerin, 1,2,6- hexanetriol, pentaerythrite, The alcohol more than trivalents such as dipentaerythritol, three (2- ethoxy) isocyanuric acid ester, sorbierite, carbohydrate, mannitols；Make these trivalents Polyester polyols alcohols obtained from above alcohol and acid anhydrides etc. react etc..

As the resin of hydroxyl than that described above, for example, the polyether resin containing hydroxyl, polycarbonate can be enumerated The resins such as resin, polyurethane resin, epoxy resin, alkyd resin.They can be used individually or two or more combinations It uses.

As long as the polyalcohol (A3) other than ingredient (A) can be contained in the range of not damaging film performance.When mixed When closing polyalcohol (A3), using the resin solid content total amount of polyalcohol (A) as benchmark, preferably its mixed proportion is in 30 mass % Below.

(B) polyisocyanate compound

Polyisocyanate compound (B) is the compound in a molecule at least two isocyanate group, for example, It can enumerate: aliphatic polyisocyante, alicyclic polyisocyanates, aromatic-aliphatic polyisocyanates, aromatic series polyisocyanate cyanogen Acid esters, the derivative etc. of these polyisocyanates.

As above-mentioned aliphatic polyisocyante, for example, can enumerate: trimethylene diisocyanate, tetramethylene two Isocyanates, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2- trimethylene diisocyanate, 1,2- Aden Group diisocyanate, 2,3- tetramethylene diisocyanate, 1,3- tetramethylene diisocyanate, 2,4,4 or 2,2,4- trimethyl six Methylene diisocyanate, dimer acid diisocyanate, 2,6- diisocyanate methyl caproate (common name: two isocyanide of lysine Acid esters) etc. aliphatic diisocyanates；2,6- diisocyanate base caproic acid 2- isocyanatoethyl methacrylate, 1,6- diisocyanate base -3- are different Cyanic acid ylmethyl hexane, tri- isocyanate group octane of 1,4,8-, tri- isocyanate group hendecane of 1,6,11-, 1,8- diisocyanate base -4- Isocyanatometyl octane, tri- isocyanate group hexane of 1,3,6-, 2,5,7- trimethyl -1,8- diisocyanate base -5- isocyanate group Aliphatic triisocyanate such as methyloctane etc..

As aforementioned alicyclic polyisocyanates, for example, can enumerate: 1,3- cyclopentene diisocyanate, Isosorbide-5-Nitrae-hexamethylene Alkane diisocyanate, 1,3- cyclohexane diisocyanate, 3- isocyanatometyl -3,5,5- trimethylcyclohexylisocyanate (common name: isophorone diisocyanate), 4- methyl-1,3- cyclohexene diisocyanate (common name: hydrogenation TDI), 2- first Base -1,3- cyclohexene diisocyanate, 1,3- or bis- (isocyanatometyl) hexamethylene (common names: hydrogenated xylylene of 1,4- Diisocyanate) or mixtures thereof, di-2-ethylhexylphosphine oxide (4,1- hexamethylene diyl) diisocyanate (common name: hydrogenation MDI), drop ice The alicyclic diisocyanates such as piece alkane diisocyanate；Tri- isocyanate group hexamethylene of 1,3,5-, 1,3,5- trimethyl isocyanate group Hexamethylene, 2- (3- isocyanate group propyl) -2,5- two (isocyanatometyl)-bicyclic (2.2.1) heptane, 2- (3- isocyanate group Propyl) -2,6- two (isocyanatometyl)-bicyclic (2.2.1) heptane, two (isocyanate group of 3- (3- isocyanate group propyl) -2,5- Methyl)-bicyclic (2.2.1) heptane, 5- (2- isocyanatoethyl) -2- isocyanatometyl -3- (3- isocyanate group propyl)-bis- Ring (2.2.1) heptane, 6- (2- isocyanatoethyl) -2- isocyanatometyl -3- (3- isocyanate group propyl)-bicyclic (2.2.1) heptane, 5- (2- isocyanatoethyl) -2- isocyanatometyl -2- (3- isocyanate group propyl)-bicyclic (2.2.1) - The rouge such as heptane, 6- (2- isocyanatoethyl) -2- isocyanatometyl -2- (3- isocyanate group propyl)-bicyclic (2.2.1) heptane Ring race triisocyanate etc..

As aforementioned fragrance race polyisocyanates, for example, can enumerate: di-2-ethylhexylphosphine oxide (Isosorbide-5-Nitrae-phenylene) diisocyanate Or mixtures thereof (common name: MDI), 1,3- or Isosorbide-5-Nitrae-xylylene diisocyanate, ω, ω '-diisocyanate base-Isosorbide-5-Nitrae-two Ethylbenzene, 1,3- or bis- (1- isocyanate group -1- Methylethyl) benzene (common name: tetramethyl xylylene diisocyanate) of 1,4- or Its mixture, m-benzene diisocyanate, paraphenylene diisocyanate, 4,4 '-diphenyl diisocyanates, 1,5- naphthalene diisocyanate Ester, 2,4 toluene diisocyanate (common name: 2,4-TDI) or 2,6- toluene di-isocyanate(TDI) (common name: 2,6-TDI) or its The aromatic diisocyanates such as mixture, 4,4 '-toluidine diisocyanates, 4,4 '-diphenyl ether diisocyanates；1,3,5- tri- Toluene isocyanate, triphenylmenthane -4,4 ', 4 "-triisocyanates, tri- phenyl isocyanate of 1,3,5-, tri- isocyanic acid first of 2,4,6- The aromatic tri-isocyanates such as phenyl ester；4,4 '-diphenyl-methanes -2,2 ', the aromatic series tetraisocyanate such as 5,5 '-tetraisocyanates Deng.

In addition, the derivative as aforementioned polyisocyanates, for example, can enumerate the dimer of above-mentioned polyisocyanates, Trimer, biuret, allophanate, urea diketone, uretonimine, isocyanuric acid ester, oxadiazines triketone, polymethylene polyphenyl Polyisocyanates (thick MDI, polymeric MDI), thick TDI etc..

Above-mentioned polyisocyanates and its derivative can both use individually a kind of or or two or more make together With.In addition, in these polyisocyanates, preferred fat (cyclo) aliphatic diisocyanates, alicyclic diisocyanate and their derivative Object.

In addition, can be used as aforementioned polyisocyanates compound (B): by above-mentioned polyisocyanates and its derivative The prepolymer for reacting and being formed under the conditions of isocyanate group is excessive with the compound that can be reacted with the polyisocyanates. As the compound that can be reacted with the polyisocyanates, for example, the chemical combination with hydroxyl, amino isoreactivity hydrogen-based can be enumerated Object, specifically, it is, for example, possible to use polyalcohol, low molecular weight polyester resin, amine, water etc..

In addition, can be used as aforementioned polyisocyanates compound (B): the polymerism insatiable hunger containing isocyanate group With the polymer of monomer, alternatively, should polymerism unsaturated monomer containing isocyanate group in addition to this contains isocyanate group Polymerism unsaturated monomer other than polymerism unsaturated monomer copolymer.

It as above-mentioned polyisocyanate compound (B), can be used: the isocyanide with above-mentioned polyisocyanate compound The polyisocyanate compound for the sealing end that sealing end obtains occurs for perester radical.As sealer, for instance, it may be preferable to use: phenolate is closed Object；Lactam compound；Alcoholic compound；Oxime compound；Mercaptan compound；Dimethyl malenate；Diethyl malonate isoreactivity Methylene compound etc..Sealing end can by the polyisocyanate compound not blocked is mixed with sealer come It is easy to carry out.These polyisocyanate compounds can be used alone or be used in combination, can also will be uncapped Polyisocyanate compound be used together with the polyisocyanate compound of sealing end.

As polyisocyanate compound (B), especially from the viewpoint of water resistance, preferred hexa-methylene diisocyanate Isocyanuric acid ester, biuret, uretonimine, the trimethylolpropane of ester (HDI) and/or isophorone diisocyanate (IPDI) (TMP) adduct etc..

In addition, above-mentioned polyisocyanate compound (B) is flat preferably in a molecule from the viewpoint of resistance to weathering Equal isocyanate functional group's number is in the range of 1.9~6, more preferably in the range of 2.5~5, particularly preferably 2.6~6 In range.

From the viewpoint of finished appearance and resistance to weathering, for the mixed of polyisocyanate compound (B) and polyalcohol (A) Composition and division in a proportion example preferably sets the isocyanate group (NCO) that polyisocyanate compound (B) has and the hydroxyl that polyalcohol (A) has (OH) molar ratio, 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 at least part as (C) curing catalysts, using at least one imidazole ring Imidazolium compounds.

As curing catalysts, by the inclusion of the imidazolium compounds at least one imidazole ring, even if existing in moisture When be also capable of forming excellent impact resistance, particularly the excellent film of resistance to weathering.

As above-mentioned imidazolium compounds, for example, in aforementioned formula (I), R₁Indicate the alkane of hydrogen atom, carbon atom number 1~4 Base, the naphthenic base of carbon atom number 3~8, the hydroxy alkyl of carbon atom number 1~4, carbon atom number 6~10 aryl or acyl group；R₂With R₃Separately indicate hydrogen atom, the alkyl of carbon atom number 1~4, the hydroxy alkyl of carbon atom number 1~4, acyl group, alcoxyl carbonyl Base, carboxyl or halogen；R₄Preferably hydrogen atom, the alkyl of carbon atom number 1~12, the alkenyl of carbon atom number 2~4, aralkyl, can Aryl with substituent group or have lower formula (II) (in formula (II), R₅Indicate the alkyl of hydrogen atom or carbon atom number 1~4, p Indicate the group of functional group shown in 1~3 integer).

R contained by logical formula (I)₁、R₂、R₃、R₄And R₅With foregoing meaning.

As R₁、R₂、R₃And R₅In carbon atom number 1~4 alkyl, for example, the straight chain of carbon atom number 1~4 can be enumerated Alkyl or branched alkyl；More specifically, methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl etc. can be enumerated.

As R₁In carbon atom number 3~8 naphthenic base, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, ring can be enumerated Heptyl and cyclooctyl, the preferably naphthenic base of carbon atom number 5~7.

As R₁、R₂And R₃In carbon atom number 1~4 hydroxy alkyl, for example, can enumerate by 1~3 hydroxyl, preferably Group made of replacing for alkyl of 1 hydroxyl to the above-mentioned carbon atom number 1~4 enumerated etc..Specifically, for example, can To enumerate methylol, 2- ethoxy, 3- hydroxypropyl, 3- hydroxypropyl, 2- hydroxypropyl, 1- methyl -2- ethoxy, tri- hydroxypropyl of 3,3,3- Base, 4- hydroxyl butyl etc..

As R₁In carbon atom number 6~10 aryl, for example, phenyl, naphthalene can be enumerated.

As R₁、R₂And R₃In acyl group, for example, formoxyl, acetyl group, propiono, benzoyl, (first can be enumerated Base) carbon atom numbers 1~7 such as acryloyl group acyl group etc..

As R₂And R₃In alkoxy carbonyl group, methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropyl can be enumerated The unbranched alkoxy or branched alkoxy of the carbon atom numbers such as Epoxide carbonyl, butoxy carbonyl 1~4 are bonded with the carbon atom of carbonyl Made of structure.

As R₂And R₃In halogen, fluorine, chlorine, boron, iodine etc. can be included, can preferably enumerate chlorine etc..

Alternatively, it is also possible to being R₂And R₃It is bonded and is formed the substance of aromatic ring structure, specifically, R can be enumerated₂ And R₃Form the imidazoles being bonded by their substituent group and form benzimidazole etc..

As R₄In carbon atom number 1~12 alkyl, for example, the straight chained alkyl or branch of carbon atom number 1~4 can be enumerated Alkyl group, more specifically, can enumerate methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, n-pentyl, just oneself Base, n-heptyl, n-nonyl, decyl, undecyl, dodecyl etc..

As R₄In carbon atom number 2~4 alkenyl, vinyl, allyl, 3- cyclobutenyl, 2- cyclobutenyl can be enumerated Deng.

As R₄In aralkyl, for example, can enumerate with 1~3 (preferably have 1) above-mentioned carbon atom enumerated The alkyl etc. of the aryl of number 6~10, the above-mentioned carbon atom number 1~4 enumerated.More specifically, benzyl, 2- phenyl can be enumerated Ethyl, tri- phenylpropyl of 3,3,3-, 4,4,4- triphenyl butyl etc..

As R₄In the aryl with substituent group, in the aryl that the above-mentioned carbon atom number 6~10 enumerated can be enumerated Aryl and unsubstituted aryl with substituent group etc..As the substituent group of aryl, there is no particular limitation, can be halogen, hydroxyl Base, oxo group, alkyl, carbonyl, aryl can also have heterocycle via urethane bonds, carbonyl bond etc. in its end.As miscellaneous Ring can enumerate furans, thiophene, pyrroles, pyridine, thiazole, imidazoles, pyrimidine etc..In addition, the heterocycle also can have aforementioned substitution Base.

As imidazolium compounds represented by aforementioned formula (I), more specifically, can enumerate imidazoles, 1- methylimidazole, 2-methylimidazole, 2- butylimidazolium, 1- t-butyl imidazole, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2- bis- Ethyl imidazol(e), 1,4- diethyl imidazolium, 1,5- diethyl imidazolium, 2- undecyl imidazole, 2- heptadecyl imidazole, 1- isobutyl Base -2-methylimidazole, 1- normal-butyl -2-methylimidazole, 2- hydroxymethylimidazole, 4- methylol -2-methylimidazole, 1- (2- hydroxyl Ethyl)-imidazoles, 4- hydroxymethylimidazole, 2- cyclohexyl imidazoles, 2- phenylimidazole, 2- phenyl -4-methylimidazole, 2- ethyl miaow Azoles, 2 isopropyl imidazole, 2- phenyl -4- benzyl imidazole, 1 benzyl 2 methyl imidazole, 1- (3- dimethylaminopropyl) imidazoles, 1- aminoethyl -2-methylimidazole, 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- carboxylate, 4- imidazolyl carboxylic acid, 2- Butyl -4- formyl imidazoles, 4- butyl-hydroxy methylimidazole, the chloro- 5- formyl imidazoles of 2- butyl -4-, 4- formoxyl -1- first Base imidazoles, 5- formoxyl -1- methylimidazole, 4- formoxyl -1- trityl imidazole, 1- benzyl -2- formyl imidazoles, 1- benzyl Base -5- hydroxymethylimidazole, 1- benzyl -4- hydroxy imidazole, 2- methylol -1- benzyl imidazole, 1- vinyl imidazole, 1- allyl Imidazoles, 2- methyl-1-vinyl imidazole, 1- dodecyl-2-methylimidazole, 1- benzyl-2- phenylimidazole, 4- ethyl-5- (4- Imidazo-5-yl benzoyl) -1,3- glyoxalidine -2- ketone, benzimidazole, 1- tolimidazole etc. have in a molecule The compound etc. of one imidazole ring.

As particularly preferred imidazolium compounds, specifically, 1 benzyl 2 methyl imidazole, 1- cyanoethyl-can be enumerated 2-methylimidazole, 1- cyanoethyl -2-ethyl-4-methylimidazole, 1- cyanoethyl -2- undecyl imidazole, 1- cyanoethyl -2- isopropyl Base imidazoles, 1-cyanoethyl-2-phenylimidazole, 1- methylimidazole, DMIZ 1,2 dimethylimidazole, 1- (3- dimethylamino-propyl) imidazoles, 1- isobutyl-2-methyl imidazole, 1- normal-butyl-2-methylimidazole, 1- vinyl imidazole, 1- allyl imidazole, 2- methyl-1-second Alkenyl imidazoles, 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..Further, particularly preferred 1- methylimidazole, 1,2- methylimidazole, 1- (3- dimethylamino-propyl) imidazoles, 1- isobutyl-2-methyl imidazole, 1- normal-butyl -2-methylimidazole and 1- benzyl -2- methyl Imidazoles.

It can also be enumerated in addition to the foregoing as the imidazolium compounds at least one imidazole ring: 2,4- diaminos Base -6- [2 '-methylimidazolyls-(1) ']-ethyl-sym-triazine, 2,4- diamino -6- [2 '-ethyls -4-methylimidazole base - (1) ']-ethyl-sym-triazine, 2,4- diamino -6- [2 '-undecyl imidazole bases-(1) ']-ethyl-sym-triazine, 2- methyl Imidazoles isocyanuric acid adduct, 2- phenylimidazole isocyanuric acid adduct, 4,4 '-methylene-bis--(2- ethyl -5- methyl Imidazoles), 1,4- bis- [(1H- imidazoles -1- base) methyl] benzene, 1,1 '-N,N'-carbonyldiimidazoles, 1,1 '-oxalyl group diimidazoles, 1,1 '-(oxygen two Ethylidene) bis- (2- methyl-imidazoles), 1,1 '-(oxygen diisopropylidenes) bis- (2- methyl-imidazoles), 1,1 '-(oxygen diethylidenes) are double [2- ethyl -4 (5)-methyl-imidazoles], 1,1 '-(oxygroup diisopropylidenes) are bis- [2- ethyl -4 (5)-methyl-imidazoles]；Passing through will 2- phenyl -4,5- bishydroxymethyl imidazoles, 2- phenyl -4- methyl -5- hydroxymethylimidazole, 2- phenyl -4- benzyl -5- hydroxyl first The imidazolium compounds containing methylol such as base imidazoles is dehydrated, piptonychia aldehyde reaction and be condensed into, have two in a molecule A above compound of imidazole ring etc. is in a molecule with the compound etc. of more than two imidazole rings.

In the present invention, relative to 100 mass parts of ingredient (A) solid component, the combined amount of imidazolium compounds preferably exists In the range of 0.005 mass parts~8 mass parts.

In coating composition of the invention, may be used also other than above-mentioned imidazolium compounds as curing catalysts (C) With and with other curing catalysts.As other curing catalysts, for example, it is former to enumerate bismuth compound, organic acid, carbon Carboxylic metallic salt, tertiary amine of subnumber 1~20 etc..

They can be used individually or are used in combination.Especially from resistance to weathering, the viewpoint of environmental protection It sets out, particularly preferably and uses bismuth compound.

As aforementioned bismuth compound, for example, bismuth carboxylate can be enumerated.Specifically, for example, caproic acid bismuth (3 can be enumerated Valence), Bismuth Octoate (trivalent), 2 ethyl hexanoic acid bismuth (trivalent), oleo-bi (trivalent), bismuth neodecanoate (trivalent), versatic acid bismuth (bismuth Versalate) (trivalent), bismuth naphthenate (trivalent) etc..

In the present invention, when and use bismuth compound as curing catalysts (C) in the case where, relative to 100 mass parts Polyalcohol (A), in terms of solid component content, preferably the combined amount of bismuth compound 4 below the mass, more preferably in 0.005 matter In the range of amount part~4 mass parts.

In the present invention, as curing catalysts (C), it can be used alone above-mentioned imidazolium compounds, it can also be by the miaow Azole compounds are applied in combination with other curing catalysts.In the present invention, total relative to curing catalysts (C) to imidazolium compounds There is no particular limitation for the content of amount, for example, can properly set as 99 mass % or more, 95 mass % or more, 90 matter % or more, 80 mass % or more, 70 mass % or more, 60 mass % or more, 50 mass % are measured with first-class.

(D) coloring components

As the coloring components in coating composition of the invention, can will in paint field well known one or two Above coloring pigment, illuminating colour are used in mixed way.

As coloring pigment, for example, can enumerate titanium oxide, zinc white, carbon black, graphite, iron oxide, chrome vermillion, it is Prussian blue, Cobalt blue, azo pigment, phthalocyanine pigment, quinoline azone class pigment, isoindoline class pigment, intellectual circle's class pigment, class pigment, two Oxazines class pigment, diketopyrrolo-pyrrole class pigment etc..

As other coloring pigments, can enumerate as the sheet metals such as aluminium for representing embodiment powder or paste, pearl powder, Luminous pigments such as graphite, MIO etc..As the sheet metal powder, for example, aluminium flake, nickel sheet, copper sheet, stainless steel substrates, Huang can be enumerated Copper sheet and chromium piece etc.；In addition, as mica powder, for example, emerylite, coloring emerylite etc. can be enumerated.

These coloring components can directly make an addition in coating composition, can also be mixed with dispersing agent, dispersion resin Splitting or integrating is dissipated, is mixed in coating after gelatinization.Well known material and method can be used in dispersing agent, dispersion resin and dispersing method. These ingredients (D), can be used alone a kind of or two or more combinations of use.

(E) hydrophobing agent

Coating composition of the invention can contain hydrophobing agent.As hydrophobing agent, silicon class hydrophobing agent can be enumerated, fluorine class is dredged Wax class such as aqua, native paraffin, synthetic wax etc..

As silicon class hydrophobing agent, for example, the organopolysiloxanes such as dimethyl polysiloxane can be enumerated, to organic poly- silicon oxygen Modified organic silicon made of alkane is modified etc..As modified organic silicon, specifically, alkyl-modified poly- silicon oxygen can be enumerated Alkane, phenyl modified polysiloxanes, polyester-modified polysiloxanes, Siloxane-Oxyalkylene Copolymers etc., preferably polyester-modified polysiloxanes Deng.These one or two kinds of combination of the above that can be used alone use.

Specifically, for example, dimethyl polysiloxane, methyl phenyl silicone, polyether-modified dimethyl can be enumerated Polysiloxanes, polyester modification dimethyl polysiloxane, poly- methyl alkyl siloxane, polyester modification methylalkylpolysiloxanes, virtue Alkyl-modified methylalkylpolysiloxanes, contain polyester modification (first at the dimethyl polysiloxane containing polyether-modified acryloyl group Base) acryloyl group dimethyl polysiloxane etc., preferred polyester modification dimethyl polysiloxane.Furthermore it is possible to enumerate: siliceous The silicon resinoid or single as other unsaturations with that can be copolymerized with the monomer that polymerism unsaturated monomer independently forms The silicon resinoid of the copolymer of body；The alkylalkoxy silanes such as hexyl trimethoxysilane；With 17 fluorine decyl trimethoxy silicon Fluorine-containing silicon compound such as alkane etc. as effective component and be dissolved or dispersed in organic solvent, in aqueous medium made of substance etc.. But it is not limited to these.

As fluorine class hydrophobing agent, other than aftermentioned (F), fluororesin, for example, can enumerate perfluorocarboxylic acid etc. contains perfluor The compound etc. of alkyl.

It as native paraffin, can enumerate: the plant waxes such as candelila wax, Brazil wax, rice wax, haze tallow；Beeswax, wool The animals such as rouge, spermaceti system wax；The mineral system such as lignite wax, ceresine, pure white ceresine wax etc..

In addition, can be enumerated as synthetic wax: the Synthins such as f-t synthetic wax, polyethylene wax；Lignite wax derivative, The modified waxes such as the paraffin derivatives such as chlorinated paraffin, solid paraffin, microcrystallite wax derivative；12- hydroxy stearic acid, stearmide, neighbour Phthalate anhydride acid imide etc..One or two kinds of combination of the above can be used to them to use.

(F) fluororesin

Coating composition of the invention can contain fluororesin.As fluororesin, PTFE (polytetrafluoroethylene (PTFE)) can be enumerated Or it is the copolymers of the unsaturated monomers such as polyvinylidene fluoride resin, fluoroolefin and vinyl ethers, fluorine-containing acrylic resin, fluorine-containing Polyester resin etc..

As PTFE, for example, Teflon (registered trademark) (Dupont-Mitsui as market sale product can be enumerated Fluorochemicals Co., Ltd. manufacture) etc..As polyvinylidene fluoride resin, market sale product can be enumerated, for example, can 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 " (are name of product, Kynar series, ARKEMA Co., Ltd. above Manufacture) etc..

Well known method can be used to obtain in the copolymer of the unsaturated monomers such as aforementioned fluoroolefin and vinyl ethers.As Fluoroolefin, for example, tetrafluoroethene, chlorotrifluoroethylene, trifluoro-ethylene, vinylidene fluoride, hexafluoropropene, five fluorine third can be enumerated The fluoroolefin that the carbon atom numbers such as alkene are 2 or 3.Wherein, go out from the good angle of the alternating copolymerization of other unsaturated monomers Hair, preferably tetrafluoroethene, chlorotrifluoroethylene, more preferable chlorotrifluoroethylene.

As the unsaturated monomer that can be copolymerized with above-mentioned fluoroolefin, for example, vinyl ethers, allyl ether can be enumerated Class, isopropenyl ethers, vinyl esters of carboxylic acids class, allyl carboxylate class, carboxylic acid isopropenyl ethers, alpha-olefines, (methyl) Esters of acrylic acid, hydroxyalkyl vinyl esters, hydroxy alkyl allyl esters, (methyl) hydroxyalkyl acrylates class etc..

As vinyl ethers, for example, can enumerate: ethyl vinyl ether, butyl vinyl ether, cyclohexylvinyl The alkyl vinyls ethers such as ether, vinyl ethers, perfluor (alkyl vinyl ether), hydroxyalkyl vinyl ether class, second two Alcohol mono-vinyl ethers etc..

As hydroxyalkyl vinyl ether, for example, can 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 fourth Base vinyl ethers, 5- Hydroxy pentyl vinyl ethers, 6- hydroxyl hexylvinyl ether etc..

As ethylene glycol monovinyl ether, for example, diethylene glycol monovinyl base ether, triethylene glycol mono-vinyl can be enumerated Ether, tetraethylene glycol mono vinyl ether etc..

As allyl ether series, for example, can enumerate: the polyoxyethylenes base such as ethyl allyl ether, cyclohexyl allyl ether Ethers, hydroxy alkyl allyl ether series.

As hydroxy alkyl allyl ether, for example, can enumerate 2- hydroxyethyl allyl ether, 4- hydroxyl butyl allyl ether, Glycerine mono allyl ether etc..

As isopropenyl ethers, for example, the alkyl isopropenyl ethers such as methyl isopropyl alkene ether can be enumerated.

As vinyl esters of carboxylic acids class, for example, the VEOVA 10 of the fatty acid vinyl ester with branched alkyl can be enumerated (product name, the manufacture of SHELL Chemical Co., Ltd.), vinyl butyrate, vinylacetate, pivalic acid vinyl acetate, versatic acid second The fatty acid ethylenes esters such as enester.

As allyl carboxylate class, for example, the fatty allyl propionate class such as allyl propionate, allyl acetate can be enumerated.

As alpha-olefines, for example, ethylene, propylene, isobutene etc. can be enumerated.

As (methyl) acrylate, for example, (methyl) methyl acrylate, (methyl) ethyl acrylate, (first can be enumerated Base) butyl acrylate etc..

As hydroxyalkyl vinyl ester, for example, 2- hydroxyethyl vinyl ester, 4- hydroxyl butylethylene ester etc. can be enumerated.

As hydroxy alkyl allyl ester, for example, ethoxy allyl ester, hydroxyl butyl allyl ester etc. can be enumerated.

As (methyl) hydroxyalkyl acrylates, for example, (methyl) hydroxy-ethyl acrylate etc. can be enumerated.

As the market sale product of fluoroolefin and the copolymer of vinyl ethers, for example, can enumerate: Lumiflon series (manufacture of Asahi Glass company), Zeffle series (manufacture of Daikin Industrial Co., Ltd) etc..

Aforementioned fluorine-containing acrylic resin is, in a molecule with perfluoroalkyl and polymerism unsaturated group, Resin that polymerism unsaturated monomer with fluorine atom independently forms or that copolymerization formation is carried out with other unsaturated monomers. It as the above-mentioned polymerism unsaturated monomer with fluorine atom, can enumerate: perfluoropropene, (methyl) perfluoroethyl hexamethylene Ester, (methyl) perfluoroethyl nonyl ethyl ester, (methyl) perfluoroethyl decyl ethyl ester, (methyl) perfluoroethyl butyl second Ester, (methyl) perfluoroethyl methyl formate, (methyl) perfluoroethyl butyl methyl esters, (methyl) perfluoroethyl octyl first Ester, (methyl) perfluoroethyl decyl methyl esters, (methyl) perfluoroethyl methyl propyl ester, (methyl) perfluoroethyl propyl third Ester, (methyl) perfluoroethyl octyl propyl ester, (methyl) perfluoroethyl octyl pentyl ester, (methyl) perfluoroethyl octyl 11 Ester etc. has (methyl) perfluoroalkyl acrylate of perfluoroalkyl etc. of C1~20.As (methyl) third with perfluoroalkyl Olefin(e) acid esters, can be used product, for example, can enumerate " Viscoat 8F ", " Viscoat 8FM ", " Viscoat 3F ", " Viscoat 3FM " (being Osaka Organic Chemical Industry Co., Ltd.'s manufacture) etc..

As other unsaturated monomers that can be copolymerized with the above-mentioned polymerism unsaturated monomer with fluorine atom, as long as Workable unsaturated monomer in the manufacture of the polyacrylate polyol of aforementioned (A2), so that it may make without particular limitation With.

It for these ingredients (F), is added after solvent being dissolved in advance, foregoing polyols (A) etc. can also be scattered in Coating is carried out in resin solution.

To these ingredients (F), one or two kinds of combination of the above that can be used alone is used.

Other compositions

Coating composition of the invention, can be further containing following well known coating in the range of not damaging film performance With additive: the resin of the hydroxyl other than ingredient (A), with isocyanate group reactive compound (for example, Amino-compound etc.), ultraviolet absorbing agent is (for example, benzotriazole absorbent, triazines absorbent, salicyclic acid derivatives class Absorbent, benzophenone absorbent etc.), light stabilizer (for example, hindered amines etc.), extender pigment (talcum, clay, kaolinite Soil, barium monoxide, barium sulfate, barium carbonate, calcium carbonate, silica, alumina white etc.), resin particle, tackifier, defoaming agent, antirust Agent, chelating agent (acetylacetone,2,4-pentanedione etc.), plasticizer, solvent, pigment dispersing agent, surface conditioner, anti-settling agent etc..

Coating composition of the invention

In coating composition of the invention, when using ingredient (D), its mixed proportion can be properly set, relative to The ingredient (A) of 100 mass parts be generally set to 1 mass parts~500 mass parts in the range of, be preferably set to 2 mass parts~300 In the range of mass parts, more preferably it is set in the range of 3 mass parts~200 mass parts.

In coating composition of the invention, when using ingredient (E), its mixed proportion can be properly set, relative to The ingredient (A) of 100 mass parts be generally set to 0.1 mass parts~50 mass parts in the range of, be preferably set to 0.2 mass parts~ In the range of 30 mass parts.

In coating composition of the invention, when using ingredient (F), its mixed proportion can be properly set, relative to The ingredient (A) of 100 mass parts be generally set to 1 mass parts~50 mass parts in the range of, be preferably set to 2 mass parts~30 matter In the range of amount part.

The adjustment of coating composition

It for the form of coating composition of the invention, is not particularly limited, can be water paint, You Jirong Any form in dosage form coating and no-solvent type coating.In addition, in the present specification, so-called water paint is in contrast to having The term of solvent type coating is typically referred to by dispersing film formative resin, pigment etc. and/or being dissolved in water or with water Make coating made of in medium as main component (aqueous medium).It, should when coating composition of the invention is water paint The content of water in coating composition is suitble in the range of the 10 mass % of mass %~90, preferably in 20 matter of mass %~80 In the range of amount %, more preferably in the range of the 30 mass % of mass %~70.In addition, so-called above-mentioned organic solvent type coatings are Refer to as substantially not aqueous or solvent the coating for wholly or largely belonging to organic solvent of solvent.It is steady from coating storage From the perspective of qualitative, coating composition preferable organic solvent type coating or non-aqueous dispersion type coating of the invention.

As organic solvent, for example, the ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) can be enumerated；Acetic acid second The esters such as ester, butyl acetate, methyl benzoate, ethoxyl ethyl propionate, ethyl propionate, methyl propionate；Tetrahydrofuran, two dislike The ethers such as alkane, dimethoxy-ethane；Glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether vinegar The gylcol ethers such as acid esters, 3- Methoxy acetic acid butyl ester；Arene, fat hydrocarbon etc..It, can be without spy as organic solvent Not Xian Ding ground use, but from the viewpoint of influencing human body and environment, preferably without toluene, dimethylbenzene etc..

The purpose of being adjusted according to viscosity adjustment, coating, uses above-mentioned organic solvent come proper combination.

For the solid component of coating composition of the invention, from coating operability and organic solvent be discharged is cut down From the perspective of amount, preferably adjustment solid component content adjusts solid component content 35 more than 15 mass %, particularly preferably Coating is carried out in the range of the mass of quality %~90 %.

In the present specification, so-called solid component refers to the residue of removal volatile ingredient；As residue, at normal temperature Either solid-like is also possible to liquid.It, can be opposite by residue quality of the setting after dry for solid component quality Before dry the ratio of quality be solid component than and by solid component than being found out multiplied by the sample mass before drying.

As coating composition of the invention, based one-pack-type coating can be, be also possible to the multiple groups such as two-component-type coating Parting coating.From the viewpoint of storage stability and coating operability, in coating composition of the invention, preferably by containing more The two-component-type coating that the host agent of first alcohol (A) and the crosslinking agent for containing polyisocyanate compound (B) are constituted, is suitble to make With using after mixing before to two components, (C)~(F) can be suitably contained in any one of host agent or curing agent Ingredient, water or organic solvent equal solvent, pigment dispersing agent, anti-settling agent, defoaming agent, antioxidant, ultraviolet absorbing agent etc. are various Additive etc..When coating composition of the invention is based one-pack-type coating, it is preferable to use the polyisocyanate compound of sealing end.

Coating film-forming methods

The present invention provides a kind of coating film-forming methods that aforementioned coatings composition is coated on coated article and forms film.

As coated article, preferably it is laminated using the substrate of plastics or metal, by the gel coating material containing epoxy resin Object made of on the substrate, priming paint (primer) film containing epoxy resin is formed on the substrate made of object, Or the gel coating material containing epoxy resin is laminated in the substrate and is further formed on the gel coating material containing ring Object made of the primer coating film of oxygen resin.

< metal base >

As metal base, be not particularly limited as long as metal, for example, can enumerate magnesium, aluminium, zinc, titanium, iron, The gold such as at least two or more alloy in metals such as nickel, chromium, gold, silver, copper, tin, platinum, palladium, zirconium, tungsten itself and these metals Belong to material.As two or more metal materials, the alloyed zincs such as Zn-Al, Zn-Ni, Zn-Fe, stainless steel, plating can be enumerated There is the steel etc. of above-mentioned metal material.

< plastic basis material >

It as plastic basis material, can enumerate: the polyolefin resins such as polyvinyl resin, acrylic resin；Polycarbonate, poly- pair The polyester trees such as ethylene terephthalate, polybutylene terephthalate (PBT), poly terephthalic acid/ethylene isophthalate Rouge；Styrene butadiene block copolymer, 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, m xylylene adipamide Polyamides such as (meta-xylene adipamide)；Polymethyl methacrylate, methyl methacrylate-acrylic acid second The acrylic resins such as ester；The vinylidene resins such as Corvic, vinyl chloride-vinyl acetate；Unsaturated polyester resin, The tree such as phenolic resin, melamine resin, urea resin, polyphenylene oxide resin, acetal resin, polyurethane resin, epoxy resin The plastic materials such as rouge and various fibre reinforced plastics (FRP).Above-mentioned plastic basis material is also possible to the hydridization of two or more resins Resin.

So-called above-mentioned fibre reinforced plastics (FRP) refer to the modeling by making to improve its intensity in plastics containing reinforcing fiber Material.

As reinforcing fiber used in FRP, it is any known that glass fibre, aramid fiber, carbon fiber etc. can be used A variety of reinforcing fibers also can be used together in reinforcing fiber.Particularly, by containing glass fibre and carbon fiber, with plastic basis material sheet Body is compared, and specific strength, specific modulus are good.In order to obtain the FRP material that component is light and mechanical-physical character is excellent, preferably individually make With the reinforcing fiber or two or more reinforcing fibers is used, but from especially cheap and high intensity angle, is preferably contained There is glass fibre.It is preferred that the ratio that glass fibre occupies in reinforcing fiber is 10 mass of mass %~100 %.

As the matrix resin of FRP, (also referred to as basic resin is plastics as base material and after shaping as substrate Resin), it may be used at the resin enumerated in the project of above-mentioned plastic basis material, unsaturated polyester resin, phenolic resin etc..Especially Ground, from the viewpoint of the adhesion with reinforcing fiber, preferred epoxy.As epoxy resin, formed as long as being suitable for FRP Epoxy resin can arbitrarily use.Also curing agent can be used.As curing agent, for example, amine compounds, acid can be enumerated Acid anhydride compound, polyimide compound and imidazolium compounds etc..

As the forming method of FRP, well known method can be used, the sheet molding compound manufactured using mold can be enumerated (SMC) method of forming, resin infusion (RIMP) method of forming, prepreg/autoclave pressing.

For above-mentioned metal base or various plastic basis materials, by its molding component etc., their surface can be by Applied using tables such as lotion, the degreasing of solvent, phosphate treated, chromic acid salt treatment, composite oxides processing, washing, grindings Surface treatment, and face can also be formed with primary coat film (also contain and be formed by overlay film by gel coating material) on them.

< primary coat film >

So-called primary coat film, refers to and is formed by film, root under the film formed by coating composition of the invention The bottom-coating of primary coat film is used to form according to coatings such as the type of coated surface and states.By by Coating material composition of the invention Object, which is formed by between film, is arranged film, and adhesion and impact resistance between coated surface can be improved.Also, it is attached in order to improve Property, primary coat film be also possible to two layers or more of multilayer.As primary coat film, for example, the case where substrate is metal base Under, it can enumerate and be carried out by the way that primer base and/or the middle coating composition for applying coating will be known as in paint field Coating simultaneously solidifies it and the film that can obtain.In addition, can enumerate in the case where substrate is FRP substrate by quilt Referred to as the FRP product surface of gel coating material carries out coating and it is made to solidify overlay film obtained etc..

As the constituent for the bottom-coating for constituting above-mentioned primary coat film, specifically, for example it is preferable to use contain There are overlay film formative resin, crosslinking agent, coloring pigment, extender pigment, photoluminescent pigment, rust resisting pigment, conductive pigment etc. Coating composition, also, the bottom-coating composition can suitably contain ultraviolet absorbing agent, light stabilizer, curing catalysts, increasing Mould the coating additives such as agent, tackifiers, compatilizer, defoaming agent, viscous regulator, antirust agent, surface conditioner.

As the type of overlay film formative resin, for example, can enumerate polyol resin, acrylic resin, polyester resin, Alkyd resin, polyurethane resin, polyolefin resin, epoxy resin, phenolic resin, polyamide and their hydroxyl Resin etc..These resins may be used singly or two or more in combination.

Both can be crosslinked by mixed cross-linker, can not also mixed cross-linker to not handing over substantially Connection.Furthermore it is also possible to which the infiltration of crosslinking agent contained in film by upper layer is crosslinked.

As crosslinking agent, such as it is preferable to use: melamine resin, the amino resins such as urea resin, polyisocyanic acid Ester compounds, the polyisocyanate compound etc. of sealing end.As above-mentioned bottom-coating composition, organic solvent type painting can be used Any one of feed composition, water-based paint compositions, can also be solvent-free.

From the viewpoint of impact resistance and adhesion with coated surface, coating composition of the invention is preferably the bottom of with It applies and carries out coating on the coated article of film, the primary coat film is by the coating composition containing epoxy resin and/or containing epoxy resin Gel coating material is formed.Specifically, being preferably laminated in aforementioned substrates using by the gel coating material for containing epoxy resin Primer coating film containing epoxy resin is formed in object made of on the substrate or will contain epoxy resin by object made of upper Gel coating material be laminated on the substrate and be further formed priming paint containing epoxy resin on the gel coating material and apply Object made of film.

Here, so-called gel coating material is referred to and is formed Coating material composition used on the surface of FRP substrate using mold Object.It as the laminating method of gel coating material, can enumerate: the overlay film that can form outer plate surfaces being formed into resin coating in advance In model inner face to form overlay film, reinforcing fiber base is configured on the gel coating material, model is closed, is then poured into FRP resin simultaneously makes its solidification, is demoulded and makes the coating transfer in the method on the surface of FRP outside plate；In mold in advance So that fiber reinforced plastic materials (hereinafter sometimes referred to simply as FRP material) heated, formed, then obtained molding with Above-mentioned gel coating material is injected between mould inner wall, be removed from the molds after making the gel coating material solidification cladding at The method etc. of type object.

As the constituent of gel coating material, can be used composition that front is enumerated in primary coat film project at Point.In addition, forming resin as overlay film can also use other than the resin that front is enumerated in primary coat film project Polycarbonate resin, vinyl ester resin, unsaturated polyester resin, bimaleimide resin, carbamide resin etc. are all known Resin.These resins can combine more than one uses, still, from the viewpoint of adhesion, preferably as constituent A part contain epoxy resin；From the viewpoint of resistance to weathering, preferably polyalcohol and aromatic isocyanate etc. are being used Gel coating material containing epoxy resin in the urethane cures class composition of curing agent.

As epoxy resin contained in above-mentioned bottom-coating (also including gel coating material), there is no special limits It is fixed, various resins can be used.For example, can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A D-ring Oxygen resin, 9,9- bis- (3- methyl -4- hydroxy phenyl) fluorenes type epoxy resin, bisphenol-s epoxy resin, tert-butyl catechol type Bifunctional types' epoxy resin such as epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, nonyl The multivalence epoxy resin such as phenol novolak type epoxy resin, by these epoxy resin made of binary acid etc. is modified Epoxy ester resin, alicyclic epoxy resin, polyglycol type epoxy resins, acrylic resin containing epoxy group etc..

It as the coating process of the bottom-coating other than gel coating material, is not particularly limited, can use Coating process known per se, for example, can according to purposes of substrate etc. suitably selection roller, aerial spraying, airless spraying, Lithing spray gun (リ シ Application ガ Application), omnipotent spray gun, brush, roll coater etc..It can be according to the type etc. of bottom-coating used Implement drying condition by any method in heat drying, force drying or air drying.

< others coated article >

In addition, as coated article in addition to the foregoing, as long as being also possible in the range of adhesion meets: glass, The inorganic material such as cement, concrete, timber, fibrous material (paper, cloth etc.) etc..

The case where according to these coated articles, can suitably carry out ungrease treatment, surface treatment etc..

It in the method for the invention, can be for above-mentioned coated article using such as electrostatic spraying, aerial spraying, without gas blowout The methods of painting, roller, brush coating coating composition of the invention.At this point, for film thickness, from the viewpoint of resistance to weathering, It is preferably based on cured coating film to be set in the range of 30 μm~500 μm, more preferably be set in the range of 50 μm~300 μm.? In method of the invention, in general, after painting is filled to scheduled film thickness, by by film under such as room temperature (5 DEG C~35 DEG C) into Row dry solidification can get cured coating film.Relative humidity (being sometimes referred to simply as RH below) when coating is 70% hereinafter, preferably 60% or less.As the curing time of air drying, preferably 1 day or more, more preferably 3 days or more.Drying for film For solidification, it can also be heated；Temperature when as heating, for example, it is preferable to be 30 DEG C~100 DEG C, more preferably 35 DEG C ~90 DEG C.As heating time, for example, it is preferable to be 5 minutes~120 minutes, more preferably 10 minutes~100 minutes.

It as the purposes for the coated article for being coated with coating composition of the invention, is not particularly limited, particularly preferably For the article or its component being exposed in strong rain wind, sand and dust etc..For example, the blade of wind-driven generator, aircraft can be enumerated With the wing of helicopter, the car body of automobile and bicycle, the body of building machinery etc..

Embodiment

In the following, by enumerating embodiment, present invention be described in more detail.In addition, unless otherwise specified, " part " and " % " indicates " mass parts " and " quality % ".

<<preparation of coating composition>>

(embodiment 1)

50 parts of castor oil (note 1), 100 parts of TIPAQUE CR-95 (note 22), 37.5 parts of butyl acetates are mixed, and Dispersed using sand mill, obtains dispersion paste.In obtained dispersion paste, 50 parts of Placcel 410 (note is mixed 14), 0.5 part of DMIZ 1,2 dimethylimidazole, relative to hydroxyl be 1 equivalent Sumidur N3300 (note 34) and be added butyl acetate It is stirred so that solid content is 80%, thus to obtain the coating composition of number 1.For the painting of obtained number 1 Feed composition carries out the test of aftermentioned coating operational (storage period and sagging resistance).It shows the results of the evaluation in table 1.

(embodiment 2~77,83~87, comparative example 1~14)

It other than being set as forming shown in table 1~7, is operated in the same manner as in the above embodiment 1, obtains number 2 ~77,83~101 coating composition.For obtained aforementioned coating composition, the combined amount in table 1~7 be by The amount that solid component is indicated.For obtained coating composition carry out aftermentioned coating operability (storage period and it is anti-under Hang down property) test.It shows the results of the evaluation in table 1~7.

(embodiment 78)

By 50 parts of castor oil (note 1), 80 parts of TIPAQUE CR-95 (note 22), 20 parts of (notes of calcium carbonate (タ Application カ Le) 300 43), 37.5 parts of butyl acetates are mixed, and are dispersed using sand mill, and dispersion paste is obtained.It is pasted in obtained dispersion In agent, 50 parts of Placcel 410 (note 14), 0.5 part of 1,2- methylimidazole, the Sumidur relative to hydroxyl for 1 equivalent are mixed N3300 (note 34) and addition butyl acetate are stirred so that solid content is 80%, thus to obtain the coating group of number 78 Close object.

(embodiment 79)

By 50 parts of castor oil (note 1), 80 parts of TIPAQUE CR-95 (note 22), 20 parts of KAOLIN HA-90T (note 44), 37.5 parts of butyl acetates are mixed, and are dispersed using sand mill, and dispersion paste is obtained.In obtained dispersion paste In, mix 50 parts of Placcel 410 (note 14), 0.5 part of 1,2- methylimidazole, the Sumidur relative to hydroxyl for 1 equivalent N3300 (note 34) and be added butyl acetate be stirred so that solid content 80% must be made, thus to obtain the coating group of number 79 Close object.

(embodiment 80)

By 50 parts of castor oil (note 1), 80 parts of TIPAQUE CR-95 (note 22), 20 parts of BARIFINE BF-20 (note 45), 37.5 parts of butyl acetates are mixed, and are dispersed using sand mill, and dispersion paste is obtained.In obtained dispersion paste In, mix 50 parts of Placcel 410 (note 14), 0.5 part of 1,2- methylimidazole, the Sumidur relative to hydroxyl for 1 equivalent N3300 (note 34) and addition butyl acetate are stirred so that solid content is 80%, thus to obtain the coating group of number 80 Close object.

(embodiment 81)

By 50 parts of castor oil (note 1), 80 parts of TIPAQUE CR-95 (note 22), 20 parts of Sylophobic 200 (note 46), 37.5 parts of butyl acetates are mixed, and are dispersed using sand mill, and dispersion paste is obtained.In obtained dispersion paste In, mix 50 parts of Placcel 410 (note 14), 0.5 part of 1,2- methylimidazole, the Sumidur relative to hydroxyl for 1 equivalent N3300 (note 34) and addition butyl acetate are stirred so that solid content is 80%, thus to obtain the coating group of number 81 Close object.

(embodiment 82)

By 50 parts of castor oil (note 1), 80 parts of TIPAQUE CR-95 (note 22), 20 parts of Sylophobic 200 (note 46), 0.5 part of BYK-161,37.5 parts of butyl acetates are mixed, and are dispersed using sand mill, and dispersion paste is obtained.In gained To dispersion paste in, mix 50 parts of Placcel 410 (note 14), 0.5 part of 1,2- methylimidazole, be 1 to work as relative to hydroxyl The Sumidur N3300 (note 34) and addition butyl acetate of amount are stirred so that solid content is 80%, thus to obtain volume Numbers 82 coating composition.

(test example 1~71 and comparative test example 1~14)

The production method > of < breadboard

Aforementioned coating composition by airless spraying is coated on coated article shown in " coated article " column of table 1~7 so that It obtains dry film thickness and reaches 150 μm.Under conditions of by obtained film described in " dry solidification condition " column of table 1~7 into Row drying obtains breadboard.These breadboards are supplied to used in aftermentioned test.It shows the results of the evaluation in table 1~7.

In addition, in " dry solidification condition " column of table 1~7,

The expression of dry solidification condition 1 is dried over 7 days by placing at 20 DEG C, RH60%；

The expression of dry solidification condition 2 is dried over 7 days by placing at 20 DEG C, RH90%；

Dry solidification condition 3 is indicated by placing over 7 days at 20 DEG C, RH60% after heating 30 minutes at 80 DEG C It is dried.

Here, in " coated article " column of table 1~7, coated article 1~5 has used following objects.

Coated article 1:FRP

82 parts of Epikote (エ ピ コ ー ト) 828 are added, and (name of product, bisphenol A type epoxy resin, solid content are 100%, Japanese epoxy resin Co., Ltd. (Japan Epoxy Resins Co., Ltd.) manufacture), 6 parts of Seikacure-S (name of product, diaminodiphenylsulfone, solid content 100%, Wakayama Seika Kogyo Co., Ltd.'s manufacture), 5.0 parts of phenyl two Methylurea (50 μm of average grain diameter, solid content 100%), 7 parts of dicyandiamides (7 μm of average grain diameter), and mix up to uniform, Obtain the composition epoxy resin of matrix resin.

Using roll coater, which is equably coated on processing release paper to reach 30g/m²Painting Cloth amount forms resin layer.Glass fibre 125g/m is clamped by above-mentioned resin layer²Two faces, using roller in 100 DEG C, 2kg/ cm²Under conditions of carry out pressurized, heated, obtain prepreg.

16 above-mentioned prepregs are laminated in a manner of making machine direction alternating orthogonal, are heated to 130 by mold on one side DEG C, apply 10kg/cm on one side²Pressure 15 minutes, obtain fiberglass reinforced plastics (coated article 1).

Coated article 2:FRP+ gel coat

16 above-mentioned prepregs are laminated in a manner of making machine direction alternating orthogonal and are set in mold, and set half The gap of cured sheets and mold is 500 μm.The gel coating material of following compositions is injected between mold and prepreg, then Apply 10kg/cm while being heated to 130 DEG C²Pressure 15 minutes, obtain and be laminated with the glass fiber reinforcement of gel coat Plastics (coated article 2).

[gel coating material]

By 50 parts of castor oil, (name of product, Epikote are registered trademark, bisphenol type epoxy tree to 30 parts of Epikote 828 Rouge, the manufacture of Japanese epoxy resin Co., Ltd.), 50 parts of NN kaolin (name of product, clay, Zhu Yuan chemical industry Co., Ltd. Manufacture) it is mixed until after uniformly, 20 parts of methyl diphenylene diisocyanates are added, and then be mixed until uniformly.

Coated article 3:FRP+ priming paint

Use " Epomarine GX (name of product, two-component-type epoxy primer, Kansai Paint Co., Ltd (KANSAI PAINT CO., LTD.) manufacture) ", by air spray finishing, the glass fiber reinforcement shown in above-mentioned " coated article 1:FRP " The prime coat that 50 μm of thickness are formed on the plate of plastics, using the object being consequently formed as coated article 3.

Coated article 4:FRP+ gel coat+priming paint

On the fiber enhanced plastic plate for forming gel coat shown in above-mentioned " coated article 2:FRP+ gel coat ", use Epomarine GX (name of product, two-component-type epoxy primer, Kansai Paint Co., Ltd's manufacture) passes through air spray finishing shape At the prime coat of 50 μ m thicks, using the object being consequently formed as coated article 4.

Coated article 5:Al

Aluminium sheet

The size of breadboard

When for aftermentioned weathering test (hereinafter simply referred to as " RET "), for the blade shape for being shaped to aftermentioned Fig. 1 Above-mentioned 1~5 coated article, the coating composition for using apneumatic spraying method coating of the invention so that dry film thickness for 150 μm, Solidified under " the dry solidification condition " of table 1~7, using thus obtained object as breadboard.

When for test other than RET, above-mentioned 1~5 coated article is cut into the plate of 10cm × 20cm, is applied Coating composition of the invention is filled, is solidified under the conditions of " dry solidification " of table 1~7, thus obtained object is made For breadboard.

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

(note 1) castor oil: hydroxyl value 160mgKOH/g

(note 2) URIC Y-406: name of product, the compound modified castor oil of aliphatic category, hydroxyl value 165mgKOH/g, Yi Teng The manufacture of liquefaction Co., Ltd.

(note 3) POLYCASTOR#10: name of product, castor oil polymers, hydroxyl value 160mgKOH/g, her rattan liquefaction strain formula Commercial firm's manufacture

(note 4) Pripol 2033: name of product, dimer diol, the manufacture of hydroxyl value 207mgKOH/g, CRODA company

(note 5) Sovermol 750: name of product, the polyalcohol of vegetable oil source, hydroxyl value 315mgKOH/g, BASF AG Manufacture

(note 6) Sovermol 760: name of product, the polyalcohol of vegetable oil source, hydroxyl value 390mgKOH/g, BASF AG Manufacture

(note 7) Sovermol 815: name of product, the polyalcohol of vegetable oil source, hydroxyl value 215mgKOH/g, BASF AG Manufacture

(note 8) Sovermol 819: name of product, the polyalcohol of vegetable oil source, hydroxyl value 240mgKOH/g, BASF AG Manufacture

(note 9) Placcel 205: name of product, polycaprolactone glycol, number-average molecular weight 530, hydroxyl value 212mgKOH/ The manufacture of g, Daicel company

(note 10) Placcel 208: name of product, polycaprolactone glycol, number-average molecular weight 830, hydroxyl value 135mgKOH/g, The manufacture of Daicel company

(note 11) Placcel 303: name of product, polycaprolactonetriol, number-average molecular weight 300, hydroxyl value 540mgKOH/g, The manufacture of Daicel company

(note 12) Placcel 305: name of product, polycaprolactonetriol, number-average molecular weight 550, hydroxyl value 305mgKOH/g, The manufacture of Daicel company

(note 13) Placcel 309: name of product, polycaprolactonetriol, number average molecular weight are 900, hydroxyl value The manufacture of 187mgKOH/g, Daicel company

(note 14) Placcel 410: name of product, polycaprolactone tetraol, number-average molecular weight 1000, hydroxyl value 224mgKOH/ The manufacture of g, Daicel company

(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: polycarbonate glycol, Asahi Chemical Corp's manufacture, number-average molecular weight 800, hydroxyl value 140mgKOH/g

(note 17) Duranol T5650E: polycarbonate glycol, Asahi Chemical Corp's manufacture, number-average molecular weight 500, hydroxyl value 225mgKOH/g

The polyacrylate polyol of (note 18) number 1: with blender, thermometer, reflux cooler and dropwise addition dress In the reaction vessel set, 40 parts of butyl acetates, 40 parts of methoxypropyl acetates are packed into, are existed at 130 DEG C while being blown into nitrogen It is stirred, wherein by 5.0 parts of styrene, 54.0 parts of n-butyl acrylates, 15.0 parts of 2-Hydroxyethyl methacrylate, 25.0 Part Placcel FM-3X (name of product, Daicel company manufacture, 6-caprolactone modified methacrylic acid hydroxyl ethyl ester), 1.0 part third (product name, Wako Pure Chemicals Co., Ltd. manufacture, 2,2 '-azos are bis- (2- methylbutyronitrile), and polymerization causes by olefin(e) acid and V-59 Agent) mixture, be added dropwise with uniform speed by 3 hours, and then cure at the same temperature 2 hours.

Then, then by the mixture of 10 parts of butyl acetates and V-59 (0.5 part) by 1 hour it is added drop-wise in reaction vessel, Completion of dropwise addition post curing 1 hour, obtain the solution of the polyacrylate polyol of the number 1 of solid content 54%.It is obtained The hydroxyl value of resin solid content is 94.4mgKOH/g, weight average molecular weight 10000.

The polyacrylate polyol of (note 19) number 2: with blender, thermometer, reflux cooler and dropwise addition dress In the reaction vessel set, it is packed into 40 parts of butyl acetate, 40 parts of methoxypropyl acetate, is existed at 130 DEG C while being blown into nitrogen It is stirred, wherein by 5.0 parts of styrene, 15.0 parts of methyl methacrylates, 50.0 parts of n-butyl acrylates, 29.0 part third The mixture of olefin(e) acid 4- hydroxy butyl ester, 1.0 parts of acrylic acid and 5.0 parts of V-59 (initiator) with uniform speed by 3 hours into Row is added dropwise, and then cures at the same temperature 2 hours.

Then, then 10 parts of butyl acetates and the mixture of 0.5 part of V-59 (initiator) reaction was added drop-wise to by 1 hour to hold In device, completion of dropwise addition post curing 1 hour, the solution of the polyacrylate polyol of the number 2 of solid content 54% is obtained.Gained To resin solid content hydroxyl value be 113mgKOH/g, weight average molecular weight 10000.

(note 20) Desmophen 670: name of product, polyester polyol, 100 mass % of solid content, hydroxyl value 142mgKOH/g, number-average molecular weight about 2000.Sumitomo Bayer polyurethane Co., Ltd. (Sumika Bayer Urethane Co., Ltd. it) manufactures

(note 21) Nipporan 800: name of product, polyester polyol, number-average molecular weight 700, hydroxyl value 290mgKOH/g, Solid content 100%, Nippon Polyurethane Industry Co., Ltd. (Nippon Polyurethane Industry Co., Ltd.) system It makes.

(note 22) TIPAQUE CR-95: name of product, titanium white, Ishihara Sangyo Kaisha, Ltd.'s manufacture

(note 23) High Wax 200PF: name of product, polyethylene wax, Mitsui Chemicals, Inc's manufacture

(note 24) BYK-333: name of product, modified dimethyl siloxane, the manufacture of society, BYK-Chemie company

(note 25) Moresco white P-80: name of product, atoleine, Matsumura Oil Res Corp.'s manufacture

(note 26) 2-Ethylhexyl Alcohol

(note 27) Megafac F-562: name of product, the compound containing perfluoroalkyl, Dainippon Ink Chemicals's manufacture

(note 28) 60%Lumiflon LF200: product name, fluoroolefin-vinyl ether co-polymer of hydroxyl, hydroxyl Value 31, solid content 60%, Asahi Glass Co., Ltd's manufacture.

(note 29) 60%Lumiflon LF800: fluoroolefin-vinyl ether co-polymer of hydroxyl, hydroxyl value 23mgKOH/ G, solid content 60%, Asahi Glass Co., Ltd's manufacture,

The fluororesin of (note 30) number 1: by 600 parts of 3- ethoxyl ethyl propionates, 170 parts of ethyl alcohol, 60 parts of cyclohexyl. vinyls Base ether (CHVE), 90 parts of ethyl vinyl ethers (EVE), 400 parts of hydroxybutyl vinyl ethers (HBVE), 5.0 parts of potassium carbonate and 10 parts of Perbutyl PV (organic peroxide, NOF Corp's manufacture), be placed in autoclave carry out it is closed, After degassing operation, 680 parts of chlorotrifluoroethylene (CTFE) are packed into autoclave, polymerization 17 hours is carried out at 75 DEG C.Instead Ying Hou, by being filtered removal potassium carbonate, the 3- ethoxyl ethyl propionate for obtaining the fluororesin of number 1 by adjusting concentration is molten Liquid (non-volatile matter is 70 mass %).

The fluoropolymer-containing composition of obtained number 1 is the polymerized unit based on the CTFE/polymerization list based on CHVE Member/the polymerized unit based on the EVE/polymerized unit (mol%)=50/5/10/35 based on HBVE.In addition, the fluororesin of number 1 Hydroxyl value be 160mgKOH/g, number-average molecular weight 5000.

(note 31) 50%Zeffle GK-510: name of product, the manufacture of PTFE, great Jin (Daikin) Co., Ltd., hydroxyl value 60mgKOH/g,

(note 32) Dyneon TF9205: polytetrafluoroethylene powder, the manufacture of 3M company

(note 33) Kynar 711: name of product, Kynoar, the manufacture of ARKEMA Co., Ltd.

(note 34) Sumidur N3300: the isocyanuric acid ester of name of product, hexamethylene diisocyanate (is write a Chinese character in simplified form: HDI Isocyanuric acid ester), solid content 100%, NCO content=21.8%, Sumitomo Bayer polyurethane Co., Ltd. (Sumika Bayer Urethane Co., Ltd.) manufacture

(note 35) Desmodur Z4470BA: name of product, the isocyanuric acid ester body (letter of isophorone diisocyanate Write: IPDI isocyanuric acid ester), solid content 70%, NCO content=11.9%, the manufacture of Sumitomo Bayer polyurethane Co., Ltd.

(note 36) Duranate 24A-90E: the biuret body of name of product, hexamethylene diisocyanate (is write a Chinese character in simplified form: HDI Biuret), solid content 90%, NCO content=21.2%, Asahi Kasei Corporation's manufacture

(note 37) Desmodur XP2565: name of product, hexamethylene diisocyanate allophanate body (write a Chinese character in simplified form: HDI allophanate), solid content 80%, the manufacture of NCO content=12%, Bayer company

(note 38) Takenate D-160N: name of product, trimethylolpropane/hexamethylene diisocyanate adduct Body (is write a Chinese character in simplified form: TMP/HDI adduct), solid 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), solid content 75%, NCO content=10.6%, Mitsui Takeda Chemical Co., Ltd's manufacture

(note 40) Desmodur N3400: two ketoboidies of urea of name of product, hexamethylene diisocyanate (is write a Chinese character in simplified form: HDI urea Diketone), solid content 100%, NCO content 21.8%, the manufacture of Sumitomo Bayer polyurethane Co., Ltd.

(note 41) TLA-100: the isocyanuric acid ester body of name of product, hexamethylene diisocyanate (is write a Chinese character in simplified form: HDI isocyanide Urea acid esters), solid content 100%, NCO content=23.4%, Asahi Chemical Corp's manufacture

(note 42) Desmodur N3800: name of product, aliphatic polyisocyante polyurethane prepolymer, solid content 100 weight %, NCO content 11.0%, the manufacture of Sumitomo Bayer polyurethane Co., Ltd.

(note 43) Tankaru 300: name of product, calcium carbonate, the manufacture of Zhu Yuan chemical industry Co., Ltd.

(note 44) KAOLIN HA-90T: name of product, calcined kaolin, SHANXI JINYANG CALCINED KAOLIN manufacture

(note 45) BARIFINE BF-20: name of product, barium sulfate, Sakai Chemical Industry Co., Ltd.'s manufacture

(note 46) Sylophobic 200: name of product, silica, chemistry of silicones Co., Ltd., Fuji (Fuji Silysia Chemical Ltd.) manufacture

(note 47) BYK-161: name of product, pigment dispersing agent, the manufacture of BYK company

(note 48) BYK-410: name of product, tackifier, the manufacture of BYK company

(note 49) Desmophen NH-1220: name of product, amino-compound, Bayer MaterialScience company Manufacture

(note 50) HALS 292: name of product, light stabilizer, BASF AG's manufacture

(note 51) BYK-057: name of product, not siliceous polymer-like antifoams, the manufacture of BYK company

(note 52) BYK-066N: name of product, silicon class defoaming agent, the manufacture of BYK company

<<test method>>

(note 53) coating operability (curing rate)

[storage period]

Obtained each coating composition will uniformly be mixed in previous embodiment and comparative example made of whole components 20 It is placed at DEG C, measures the time until gelation, pressed and state evaluation criteria and evaluated.

S:30 minutes or more；

A:20 minutes more than or lower than 30 minutes；

B:10 minutes more than or lower than 20 minutes；

C: it is lower than 10 minutes.

[sagging resistance]

Dry film thickness is set to change and apply by airless spraying coating composition obtained in previous embodiment and comparative example On " coated article 2:FRP+ gel coat ", by each coated plate be maintained at relative to level in the case where 60 ° of angles 20 It is dried, solidifies under the conditions of DEG C-RH90%.Sagging dry film thickness limit occurs by visual assessment

S:250 μm or more；

A:200 μm more than or lower than 250 μm；

B:150 μm more than or lower than 200 μm；

C: it is lower than 150 μm.

(note 54) appearance

By each breadboard of visual observations, by following benchmark evaluations bubble trace, fold, blistering incidence.

S: absolutely not bubble trace, fold, blistering；

A: subtle bubble trace, fold, any phenomenon in blistering can marginally be observed；

B: bubble trace, fold, any phenomenon in blistering can been considerably be observed；

C: bubble trace, fold, any phenomenon in blistering can obviously be observed.

(note 55) resistance to weathering test: RET

By all each coating compositions as the aforementioned in simulation air vane (radius of curvature 9mm) up-front 23cm length It is coated and dried on coated article, prepares breadboard.

Same breadboard 3 is prepared, is installed on blade-carrying horizontal rotor.Rotor is rotated so that from turning The speed of sub- axis farthest reaches 160m/ seconds, the part nearest from armature spindle reach 120m/ seconds.

It is uniform with the test water droplet of diameter 1mm~2mm to will be equivalent to the water of 30mm/ hours~35mm/ hours precipitation Ground is sprayed to the coating surface of rotation.It stops rotating within every 30 minutes, passes through the up-front coating surface of visual observations breadboard, record Film was cut down from front end to the average time of 5cm or more.

S:5 hours or more；

A:4 hours more than or lower than 5 hours；

B:3 hours more than or lower than 4 hours；

C: it is lower than 3 hours.

(note 56) water resistance

For each breadboard, the test of washing was carried out after 30 days in the warm water for being impregnated in 40 DEG C by following benchmark evaluations The appearance of plate.

Appearance [after water resistant test]

S: relative to the film before test, appearance absolutely not changes；

A: relative to the film before test, it can slightly observe the phenomenon that gloss degenerates, blisters or changes colour, but be made Reach the level that there is no problem in the case where product；

B: relative to the film before test, the phenomenon that gloss degenerates, blisters or changes colour can be observed on a small quantity；

C: for the film before test, the phenomenon that gloss degenerates, blisters or changes colour can be obviously observed.

Claims (14)

1. a kind of coating composition contains (A) polyalcohol, (B) polyisocyanate compound and (C) curing catalysts, special Sign is that the polyalcohol (A) contains the polyalcohol (A1) of the structural unit of the fatty acid source with 8 or more carbon atom number, And the curing catalysts (C) contain the imidazolium compounds at least one imidazole ring；

Wherein, polyisocyanate compound (B) ingredient, it is single using isocyanuric acid ester and allophanate Solely using one such；

The polyalcohol (A1) be selected from by

(A1-1) carboxylate of the fatty acid of the hydroxyl of 8 or more carbon atom number and polyalcohol,

(A1-2) polymer of the unsaturated fatty acid of the hydroxyl of 8 or more carbon atom number,

Polyalcohol obtained from (A1-3) being restored to the polymer of the unsaturated fatty acid of 8 or more carbon atom number,

(A1-4) to the unsaturated fat of the unsaturated fatty acid (a1-4-1) of 8 or more carbon atom number and/or 8 or more carbon atom number The carboxylate (a1-4-2) of acid and polyalcohol carries out polyalcohol obtained from hydroxyl modification

At least one of group constituted.

2. coating composition as described in claim 1, wherein the curing catalysts (C) are represented containing general formula (I) Imidazolium compounds,

In the logical formula (I), R₁Indicate hydrogen atom, the alkyl of carbon atom number 1~4, the naphthenic base of carbon atom number 3~8, carbon atom The aryl or acyl group of the hydroxy alkyl of number 1~4, carbon atom number 6~10,

R₂And R₃Separately indicate hydrogen atom, the alkyl of carbon atom number 1~4, the hydroxy alkyl of carbon atom number 1~4, acyl group, Alkoxy carbonyl group, carboxyl or halogen or R₂And R₃With R₂、R₃The carbon atom of upper bonding is formed together aromatic rings,

R₄Indicate hydrogen atom, the alkyl of carbon atom number 1~12, the alkenyl of carbon atom number 2~4, aralkyl, can substituted base virtue Functional group shown in base or lower formula (II),

In the logical formula (II), R₅Indicate that the alkyl of hydrogen atom or carbon atom number 1~4, p indicate 1~3 integer.

3. coating composition as claimed in claim 2, wherein imidazolium compounds represented by the logical formula (I) be selected from by 1- methylimidazole, DMIZ 1,2 dimethylimidazole, 1- (3- dimethylamino-propyl) imidazoles, 1- isobutyl-2-methyl imidazole, the positive fourth of 1- At least one of the group that base -2-methylimidazole and 1 benzyl 2 methyl imidazole are constituted.

4. coating composition according to any one of claims 1 to 3 also contains as the curing catalysts (C) Bismuth compound.

5. coating composition as described in claim 1, wherein the polyalcohol (A1) is selected from castor oil and rilanit special At least one of.

6. coating composition according to any one of claims 1 to 3 also contains being selected from as the polyalcohol (A) It is made of polycaprolactone glycol, polycaprolactonetriol, polycaprolactone tetraol, polycarbonate glycol and polyacrylate polyol At least one of group polyalcohol (A2).

7. coating composition as claimed in claim 6, wherein relative to the polyalcohol (A) of 100 mass parts, the polyalcohol (A1) combined amount is 10 mass parts~70 mass parts, and the combined amount of the polyalcohol (A2) is in 30 mass parts~90 mass parts In range.

8. coating composition according to any one of claims 1 to 3, wherein relative to the polyalcohol (A) of 100 mass parts, The combined amount of imidazolium compounds at least one imidazole ring is 0.005 mass parts~8 mass parts.

9. coating composition according to any one of claims 1 to 3 also contains coloring components (D).

10. coating composition according to any one of claims 1 to 3 also contains hydrophobing agent (E) and/or fluororesin (F)。

11. a kind of coating film-forming methods, wherein by coating composition according to any one of claims 1 to 10 be painted on by Film is formed in coat.

12. coating film-forming methods as claimed in claim 11, wherein the coated article is the substrate of plastics or metal, will contain The gel coating material of epoxy resin is layered in object made of on the substrate, is formed in the primer coating film containing epoxy resin Object made of on the substrate or the gel coating material containing epoxy resin is layered on the substrate and described solidifying Object made of the primer coating film containing epoxy resin is further formed on glue coating material.

13. the coating film-forming methods as described in claim 11 or 12, wherein the coated article is the blade of wind-driven generator.

14. a kind of article is by the way that coating composition according to any one of claims 1 to 10 to be painted on coated article And the article obtained.