CN100365081C - Coating composition - Google Patents

Abstract

A paint composition is provided to improve anticorrosion and weatherability in steel structures with significantly reducing application process, as compared to that of the conventional anticorrosive paint. The paint composition comprises: an acryl resin(A); an epoxy resin(B) having at least two epoxy groups in one molecule; and an amine type curing agent(C) which may include amino silane. The paint composition may further comprise an acryl-modified epoxy resin(B1) by reacting the acryl resin(A) with the epoxy resin(B), provided that the acryl resin comprises a functional group that may react with an epoxy group.

Description

Coating composition

The application is dividing an application of application number 03138648.2, May 29 2003 applying date, denomination of invention " coating composition ".

Technical field

The present invention relates to for make send electricity with communicate by letter with tower structure, conveying is with steel design protection against corrosion such as jar, boats and ships, bridge, tank and keep attractive in appearance, can form non-corrosibility and the good coating composition of filming of weathering resistance once going on foot painting process at normal temperatures.Coating composition of the present invention has priming paint and two kinds of functions of last coating concurrently.

Background technology

Send electricity with and communicate by letter with tower structure, carry with steel design such as jar, boats and ships, bridge, tanks, in order to prevent to corrode and to keep attractive in appearance and carry out protection against corrosion and be coated with.In when coating, after being coated with the good epoxy resin priming paint of Corrosion Protection, also be coated with the good various coatings of going up of weathering resistance mostly usually.Yet, in order to reach the purpose that keeps above-mentioned performance, be necessary repeatedly barrier coating coating, add again and be coated with middle coating intermediate, but also comprise coating, the painting process of needs more than at least 3 times.Particularly when the steel construction that coating has been built well, not only the working aloft at standpoint will do not had, and because labour cost, scaffolding etc. account for more than 8 one-tenths of coating expense, so on security and economy, all require the coating number of times to lack as far as possible, the shortening painting process.

As the countermeasure of the problems referred to above, for example open the coating that discloses in the flat 10-509195 communique with the amine that contains special Resins, epoxy, polysiloxane, low-molecular-weight organoalkoxysilane and 2 functional groups the spy.But this method not only aspect the protection environment and also gloss also inhomogeneous, in addition, also exist long-term exposure more than 1 year the problem of crackle can occur.

Summary of the invention

The object of the present invention is to provide in order to make the steel design protection against corrosion and to keep attractive in appearance, painting process is significantly shortened, can form the good coating composition of filming of non-corrosibility and weathering resistance.

Promptly the invention provides coating composition, it is characterized in that containing the Resins, epoxy (B) that has 2 epoxy group(ing) in acrylic resin (A), 1 molecule at least and contain aminosilane and amine hardener (C).

The preferred first kind of mode of the present invention, coating composition is provided, it is characterized in that containing the Resins, epoxy (B) that has 2 epoxy group(ing) in acrylic resin (A), 1 molecule at least, contain aminosilane and amine hardener (C) and curing catalysts (E), and the use level of this curing catalysts (E) to form branch 100 weight parts admittedly with respect to all resins be 0.01～10 weight part.

The preferred second way of the present invention, coating composition is provided, it is characterized in that containing the Resins, epoxy (B) that has 2 epoxy group(ing) in acrylic resin (A), 1 molecule at least and contain aminosilane and the coating composition of amine hardener (C) in, this Resins, epoxy (B) is the Resins, epoxy (i) that has 2 epoxy group(ing) in 1 molecule at least by two basic acids (ii) and/or the (iii) modified epoxy (B of modification of the phenols that contains carboxyl ₂).

Preferred the third mode of the present invention provides coating composition, it is characterized in that containing acrylic resin (A), at least have the Resins, epoxy (B) of 2 epoxy group(ing) and contain ketoimineization aminosilane and must the amine hardener (C of ketoimineization ₁).

The embodiment of invention

Can use over knownly as acrylic resin of the present invention, not have particular restriction, preferably use in the presence of organic solvent usually, polymerizability unsaturated monomer mixture is by the acrylic copolymer of radical polymerization initiator copolymerization gained.

As above-mentioned polymerizability unsaturated monomer, can enumerate as (methyl) methyl acrylate, methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, 2-ethylhexyl (methyl) acrylate, (methyl) vinylformic acid Lauryl Ester, (methyl) vinylformic acid cyclohexyl ester, methylcyclohexyl (methyl) acrylate, tert-butylcyclohexyl (methyl) acrylate, the alkyl ester or the cycloalkyl ester of the carbon number 1～24 of vinylformic acid such as (methyl) vinylformic acid ring undecyl ester or methacrylic acid, the methoxymethyl acrylate, methoxy ethyl acrylate etc. contains the unsaturated monomer of the alkoxyl group of carbon number 1～24, hydroxyethyl (methyl) acrylate, hydroxypropyl (methyl) acrylate, the unsaturated monomer of hydroxyls such as hydroxyl butyl (methyl) acrylate, vinylformic acid, carboxylic unsaturated monomer such as methacrylic acid, vinylbenzene, (methyl) acrylamide, vinyl acetate between to for plastic base esters etc., they can use separately also and can share more than 2 kinds.

As above-mentioned polymerizability unsaturated monomer, from importing the bridging property functional group that reacts with amine hardener described later (C), improve the non-corrosibility and the weathering resistance aspect of filming and consider, can use unsaturated monomer that contains epoxy group(ing) and/or the unsaturated monomer that contains alkoxysilane group.

As containing the epoxy group(ing) unsaturated monomer, can enumerate as glycidyl (methyl) acrylate, 3,4-epoxy group(ing) cyclohexyl (methyl) acrylate, Beta-methyl glycidyl (methyl) acrylate, allyl glycidyl ether etc., they can use separately also and can share more than 2 kinds.

As the unsaturated monomer that contains alkoxysilane group, can enumerate as vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, γ-(methyl) acryloxy propyl trimethoxy silicane, γ-(methyl) acryloxy propyl-triethoxysilicane etc., they can use separately also and can share more than 2 kinds.

Also have,, consider, can use ultraviolet-absorbing unsaturated monomer and/or UV stable unsaturated monomer from the weathering resistance aspect that improves aforesaid propylene acid resin (A) as above-mentioned polymerizability unsaturated monomer.

The ultraviolet-absorbing unsaturated monomer is the monomer that contains the position of polymerizability unsaturated group and ultraviolet absorption ability, can enumerate benzotriazole category, triazines, the phenylaniline class, benzo benzophenone class oxalic acid phenylaniline class, oxalic acid phenylaniline class, cyanoacrylate etc., concrete example such as 2-[2 '-hydroxyl-5 '-(methacryloxy methyl) phenyl]-the 2H-benzotriazole, 2-[2 '-hydroxyl-5 '-(methacryloxyethyl) phenyl]-the 2H-benzotriazole, 2-[2 '-hydroxyl-5 '-(methacryloxypropyl) phenyl]-the 2H-benzotriazole, 2-[2 '-hydroxyl-5 '-(methacryloxy hexyl) phenyl]-the 2H-benzotriazole, 2-[2 '-hydroxyl-the 3 '-tertiary butyl-5 '-(methacryloxyethyl) phenyl]-the 2H-benzotriazole, 2-[2 '-hydroxyl-the 5 '-tertiary butyl-3 '-(methacryloxyethyl) phenyl]-the 2H-benzotriazole, 2-[2 '-hydroxyl-5 '-(methacryloxyethyl) phenyl]-5-chloro-2H-benzotriazole, 2-[2 '-hydroxyl-5 '-(methacryloxyethyl) phenyl]-5-methoxyl group-2 H-benzotriazole, 2-[2 '-hydroxyl-5 '-(methacryloxyethyl) phenyl]-5-cyano group-2H-benzotriazole, 2-[2 '-hydroxyl-5 '-(methacryloxyethyl) phenyl]-the 5-tertiary butyl-2H-benzotriazole, 2-[2 '-hydroxyl-5 '-(methacryloxyethyl) phenyl]-5-nitro-2H-benzotriazole etc.They can use separately also and can share more than 2 kinds.

The UV stable unsaturated monomer is the monomer that contains the position of polymerizability unsaturated group and UV stable ability, concrete example such as 4-(methyl) acryloxy-2,2,6, the 6-tetramethyl piperidine, 4-(methyl) acrylamido-2,2,6, the 6-tetramethyl piperidine, 4-(methyl) acryloxy-1,2,2,6,6-pentamethyl-piperidines, 4-(methyl) acrylamido-1,2,2,6,6-pentamethyl-piperidines, 4-cyano group-4-(methyl) acrylamido-2,2,6, the 6-tetramethyl piperidine, 4-crotons acyloxy-2,2,6, the 6-tetramethyl piperidine, 4-crotonoyl amido-2,2,6,6-tetramethyl piperidine etc., they can use separately also and can share more than 2 kinds.

As above-mentioned polymerizability unsaturated monomer, when use contains the unsaturated monomer of epoxy group(ing), in monomer mixture, contain 0～70 weight %, preferably contain 1～20 weight %, when use contains the unsaturated monomer of alkoxysilane group, in monomer mixture, contain 0～70 weight %, preferably contain 1～30 weight %.In addition, as the polymerizability unsaturated monomer, when use contains the ultraviolet-absorbing unsaturated monomer, in monomer mixture, contain 0～20 weight %, preferably contain 0.1～10 weight %, when use contains the UV stable unsaturated monomer, in monomer mixture, contain 0～20 weight %, preferably contain 0.1～10 weight %.

Organic solvent during as copolymerization does not have particular restriction, can enumerate as aromatic hydrocarbon solvents such as toluene, dimethylbenzene, ketones solvent such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), esters solvents such as N-BUTYL ACETATE, alcoholic solvents such as Virahol, mineral turpentine, normal hexane, octane, 2,2, the such fat hydrocarbon of 2-trimethylpentane, octane-iso, positive third of the twelve Earthly Branches alkane, hexanaphthene, methylcyclohexane etc.They can use separately also and can share more than 2 kinds.Polymerization starter there is not particular restriction; can use azo two isobutyl acyl cyanides, 2; 2-azo two (2-methylbutyryl nitrile), 2; 2-azo two (2-methyl-prop acyl cyanide), 2; peroxides such as 2-azo two azo-initiators such as (2,4-dimethyl-penten acyl cyanide) or benzoyl superoxide, t-butylperoxy octanoate, diisobutyl superoxide, two (2-ethylhexyl peroxy pivalate), decanoyl superoxide.

The weight-average molecular weight of the above-mentioned acrylic resin that makes (A) is 1,000～100,000, preferred 2,000～50,000.It is not enough to be lower than 1,000 o'clock weathering resistance, and it is insufficient to surpass the intermiscibility that Resins, epoxy (B), organic-silylation contain thing (D) and amine hardener (C) at 100,000 o'clock, so not preferred.

The solubility parameter value of acrylic resin (A) (being designated hereinafter simply as [SP value]) is 8～10, preferred 8～9.5 scope.Be lower than 8 o'clock insufficient with the intermiscibility of Resins, epoxy (B), surpass 10 o'clock not preferred with the intermiscibility decline of organic silane compound (D).The SP value of the multipolymer acrylic resin of above-mentioned monomer mixture is calculated according to following formula and is obtained.

SP value=SP1 * fw1+SP2 * fw2+......+SPn * fwn

(in the following formula, SP1, SP2 ... SPn represents the SP value of each monomeric homopolymer, fw1, fw2 ... fwn represents the weight fraction of each monomer with respect to the monomer total amount) the SP value of each monomeric homopolymer is documented in J.Paint Technology, vol.42[541] in 76～102 (1970) etc.

Resins, epoxy among the present invention (B) is the material that has 2 epoxy group(ing) in 1 molecule at least, this Resins, epoxy can be enumerated as Racemic glycidol ether type epoxies such as dihydroxyphenyl propane, Bisphenol F, the hydrogenation bisphenol A type epoxy resin, the glycidyl ester epoxy resin, cycloaliphatic epoxy resin, how pure type Resins, epoxy; The modified epoxy that these Resins, epoxy form by a kind of modifier modification selecting from alkylphenol and lipid acid at least; Alkylphenol or alkylphenol varnish type resin and Epicholorohydrin reaction have imported the alkylphenol or the alkylphenol varnish type resin of epoxy group(ing); (hereinafter referred to as Resins, epoxy (i)) such as two basic acid modified epoxies.The weight-average molecular weight of Resins, epoxy (B) is in about scope of 200～about 3,000, preferably in about scope of 300～about 1,000.Weight-average molecular weight is lower than 200 o'clock non-corrosibilities and descends, and is bad and not preferred with the intermiscibility of other resin above 3,000 o'clock.

Above-mentioned Resins, epoxy (i) as Resins, epoxy (B) specifically can use [Epikote 828], [Epikote 830], [Epikote 834], [Epikote 806H] (japan epoxy resin corporate system), [DER-331J] (Dow Chemical Company's system), [AER260] (Epoxy of Asahi Chemical Industry corporate system), [ST-3000], [ST-5080] (Dongdu changes into corporate system), [EpomikR#140P] (Mitsui Chemicals corporate system), [ERL-4221], [ERL-4229] (UNION CARBIDE JAPAN K.K. system), [Denacol EX-830] (long rapids industrial's system that changes into), the commercially available product of [HARIPOLE EP-450] (HARIMA chemical company system) etc.

Among the present invention, aforesaid propylene acid resin (A) contains can be with the functional group of epoxy reaction the time, the acrylic modified epoxy resin (B that can use at least a portion reaction of this acrylic resin (A) and above-mentioned Resins, epoxy (B) to generate ₁).Acrylic modified epoxy resin (B ₁) synthetic method, for example as acrylic resin (A), make monomer or amino monomer copolymerization with carboxyl, make in the Resins, epoxy (B) contained to small part epoxy group(ing) or total overall reaction, perhaps in the presence of polymerization starter, will form the graft polymerization of polymerizability unsaturated monomer or the copolymerization of acrylic resin (A) with Resins, epoxy (B).When described reaction is the reaction of epoxy group(ing) and carboxyl, also can use the catalysts that is used for this reaction purpose, can enumerate as quaternary ammonium hydroxide catalyzer such as tetraethylammonium bromide, Tetrabutylammonium bromide, etamon chloride, Xiuization 4-butyl-phosphonium, chlorinated triphenyl base Bian Ji Phosphonium, amines such as triethylamine, tributylamine as this catalysts.

As Resins, epoxy of the present invention (B), can use the Resins, epoxy (i) that has 2 epoxy group(ing) in 1 molecule at least (ii) and/or the (iii) modified epoxy (B of modification of the phenols that contains carboxyl by two basic acids ₂).

Two basic acids are (ii) for making the material of above-mentioned Resins, epoxy (i) polyaddition reaction, prolongation Huan oxygen tree Zhi Key.Resins, epoxy (the B that makes thus ₂) polymer quantizes, and makes raisings such as the touch dry of filming, shock-resistance.

As this two basic acid (ii), can enumerate Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acids, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, dicarboxylic acid Hydrogenated Bisphenol A, hydrogenation cannabinoid acid, hydrogenation naphthalene dicarboxylic acids, 1,4-bicyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, three cyclosilane dicarboxylic acid, succsinic acid, pentanedioic acid, fumaric acid, hexanodioic acid, sebacic acid, maleic anhydride, cannabinoid acid etc.They can use separately also and can share more than 2 kinds.

The above-mentioned phenol of carboxyl that contains is (iii) for importing the material that the phenol hydroxyl improves solidified nature in Resins, epoxy (i).(iii) can enumerate as Whitfield's ointment, P-hydroxybenzoic acid, 4-hydroxymethyl phenylformic acid etc. as this phenol that contains carboxyl, they can use separately also and can share more than 2 kinds.

Make modified epoxy (B ₂), can by with above-mentioned (i) composition and (ii) with and/or (iii) composition with the epoxy group(ing) of (i) composition and (ii) with and/or (iii) the equivalence ratio of the epoxy group(ing) of composition at 1: 0.05～1: 0.5, preferably mixed in 1: 0.1～1: 0.3 proportional range, for example epoxy group(ing)/carboxyl reaction is in the presence of catalyzer, and reacting by heating is about 1～10 hour usually.As epoxy group(ing)/carboxyl reaction catalyzer, can enumerate as quaternary ammonium hydroxide catalyzer such as tetraethylammonium bromide, Tetrabutylammonium bromide, etamon chloride, Xiuization 4-butyl-phosphonium, chlorinated triphenyl base Bian Ji Phosphonium, amines such as triethylamine, tributylamine.Temperature of reaction suits about 120～150 ℃.

Among the present invention, it is 5～95 weight % that the cooperation ratio of acrylic resin (A) and Resins, epoxy (B) forms a deciliter metering (A) admittedly with respect to these resins, and preferred 10～90 weight % (B) are 5～95 weight %, preferred 10～90 weight %.The cooperation ratio of acrylic resin (A) is lower than 5 weight %, films and isolates easily, and drying property after the coating descends, and surpasses 95 weight % on the other hand, and non-corrosibility, weathering resistance descend and not preferred.Resins, epoxy (B) cooperation ratio is lower than 5 weight %, and non-corrosibility descends, and surpasses 95 weight % on the contrary, and weathering resistance descends and not preferred.

Among the present invention, consider, can contain organosilicone compounds (D) according to necessity from the weathering resistance aspect.This organosilicone compounds (D) is suitable to following formula (1)

(in the formula (1), R ¹, R ⁶Represent that respectively hydrogen atom, carbon number are 1～6 alkyl, aryl or SiR ₃(R is identical or different, is alkyl, aryl or the alkoxyl group of hydroxyl, carbon number 1～6), R ², R ³Identical or different respectively, the alkyl or aryl of expression carbon number 1～6, R ⁴, R ⁵Respectively identical or different, alkyl, aryl or the alkoxyl group of expression carbon number 1～6, m be 0～134, n in 0～134 scope, m+n 〉=2) weight-average molecular weight of expression is 400～30,000, preferably 1,000～10, in 000 the scope.In the above-mentioned formula (1), R ¹, R ², R ³, R ⁴, R ⁵, R ⁶With R be the examples of alkyl groups of carbon number 1～6, for example can enumerate methyl, ethyl, (different) propyl group, amyl group, hexyl, cyclohexyl etc., R ¹, R ², R ³, R ⁴, R ⁵, R ⁶With R be the concrete example of aryl, for example can enumerate phenyl, tolyl etc.R ⁴, R ⁵With R be the concrete example of alkoxyl group, for example can enumerate methoxyl group, oxyethyl group etc.Specifically can use [DC3074], [DC3037] (TORAYDOWCORNING SILICONE Co., Ltd), [KR-9218], [KR-212], [X-40-9220] (chemical industrial company of SHIN-ETSU HANTOTAI system), [TSR165] (the SILICONE Co. of Toshiba, Ltd) commercially available product of Denging.They can use separately also and can share more than 2 kinds, also can use their hydrolytic condensate.

On the top layer of filming, make the alkoxysilane group orientation, in order further to improve weathering resistance, can with alkylalkoxy silane with and hydrolytic condensate and organosilicone compounds (D) share.Concrete example as alkylalkoxy silane, can enumerate trimethoxymethylsila,e, trimethoxy ethylsilane, triethoxy methyl silicane, trimethoxy isopropoxy silane, trimethoxy-benzene base silane, triethoxyphenylsilan, dimethoxy dimethylsilane, dimethoxy diethoxy silane, methoxytrimethylsilane, methoxyl group triethyl silicane etc., they can use separately also and can share more than 2 kinds.

When using organosilicone compounds (D) among the present invention, admittedly the total amount (A) that forms branch with respect to the resin of acrylic resin (A), Resins, epoxy (B) and organosilicone compounds (D) is 5～95 weight %, preferred 10～80 weight %, (B) being 5～95 weight %, preferred 10～80 weight %, (D) is 0～90 weight %, preferred 10～80 weight %.The cooperation ratio of organosilicone compounds (D) makes non-corrosibility descend and not preferred when surpassing 90 weight %.

The amine hardener that uses among the present invention (C) for Resins, epoxy (B) in the solidifying agent of epoxy reaction, and when in coating composition, importing alkoxysilane group, can also as cause that airborne moisture is hydrolyzed, catalysts use during condensation reaction.

This amine catalyst (C) is for containing the amine of aminosilane; especially the multi-functional amine of preferred use; the Resins, epoxy that can enumerate polyamines as aliphatics or ester ring type, this polyamines as this multi-functional amine adds with the uncommon compound of thing, multiamide amine, aromatic amine, aliphatics or the slow Buddhist nun of ester ring type etc., and they can use separately also and can share more than 2 kinds.Specifically can use the commercially available product of [SUNMIDE J230N], [SUNMIDE I518] (three and chemical industrial company's system), [DAITOCURAR1969] (mostly industry corporate system) etc.

As above-mentioned aminosilane, be generally following formula (2)

X-Si-(OY) ₃ (2)

(in the formula, X is for can contain-NH ₂And/or-alkyl of NH-Key, aryl, alkoxyalkyl, cycloalkyl, Y is the alkyl of carbon number 1～6) shown in material, specifically can enumerate N-β-(aminoethyl) aminopropyl trimethoxysilane, N-β-(aminoethyl) aminopropyl triethoxysilane, N-phenyl-γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanyiyangjiguiwan etc., they can use separately also and can share more than 2 kinds.Commercially available product can be enumerated as [KBM-603], [KBM-903] (chemical company of SHIN-ETSU HANTOTAI system) etc.

Amine hardener (C) is for containing the material of above-mentioned multi-functional amine and aminosilane, also can only contain wherein a kind ofly, preferably share, and its ratio is preferably with respect to this multi-functional amine 1mol, and aminosilane is more than 0.1mol.The ratio of aminosilane makes weathering resistance descend and not preferred when being lower than 0.1mol.

Among the present invention,, can use the aminosilane that contains ketoimineization and the amine hardener (C of the ketoimineization that gets as amine hardener (C) ₁).

Amine hardener (the C of the ketoimineization of using among the present invention ₁), if remove amino protection, for Resins, epoxy (B) in the solidifying agent of epoxy reaction, and then when in coating composition, importing alkoxysilane group, can also as cause that airborne moisture is hydrolyzed, catalysts use during condensation reaction.

Amine hardener (the C of the ketoimineization of using among the present invention ₁) be the material that can contain the aminosilane of ketoimineization, can use the ketoimine thing of multi-functional amine or aminosilane.Can use above-mentioned material as this multi-functional amine or aminosilane.

The ketoimineization of above-mentioned multi-functional amine and aminosilane, essence are all sealed by carbonyl compound for primary amine groups wherein becomes the amino material of protection.This carbonyl compound can be enumerated as ketones such as acetone, methyl ethyl ketone, methyl isopropyl Ketone, methyl iso-butyl ketone (MIBK), methyl tertbutyl ketone, diisobutyl ketone, pimelinketone, and can share with aldehydes such as acetaldehyde, phenyl aldehydes and make the part aldimineization.

Amine hardener (C ₁) for containing the material of ketoimine thing of above-mentioned multi-functional aminate aminosilane, also can be only for wherein any one, when share preferably with respect to this multi-functional amine 1mol aminosilane more than 0.1mol.The ratio of aminosilane makes weathering resistance descend and not preferred when being lower than 0.1mol.

The cooperation ratio of amine hardener (C): the ratio of (equivalents of amino active hydrogen)/(equivalents of contained epoxy group(ing) in above-mentioned Resins, epoxy (B) and the acrylic resin (A)) is 0.1～2.0, preferably in 0.2～1.2 scope, consider from aspects such as the solidified nature of filming, non-corrosibility, weathering resistancies and preferred.

Amine hardener (C ₁) the cooperation ratio: the ratio of (carbonyl compound is from the equivalents of the active hydrogen of the amino that takes off)/(equivalents of contained epoxy group(ing) in above-mentioned Resins, epoxy (B) and the acrylic resin (A)) is for being 0.1～2.0, preferably in 0.2～1.2 scope, consider preferred from aspects such as the solidified nature of filming, non-corrosibility, weathering resistancies.

Cooperate above-mentioned amine hardener (C ₁) coating composition of the present invention that constitutes, can be that 1 liquid type also can be 2 liquid types, consider suitable 1 liquid type from operability.Preferably also cooperate dewatering agent (F) when being 1 liquid type.(F) can use known dewatering agent as this dewatering agent, below enumerates its typical example.

1. porous metal oxide of Powdered richness or carbide; For example synthetic silica, activated alumina, zeolite, gac etc.,

2. has CaSO ₄, CaSO4.1/2n ₂The calcium cpd class that O, CaO etc. form; For example calcined gypsum, soluble plasters, unslaked lime etc.,

3. metal alkoxide class; For example sec.-propyl aluminium, tertiary butyl aluminium, tetra isopropyl?, 2-propionic acid zirconium, butanic acid zirconium, tetraethyl silicate, vinyltrimethoxy silane etc.,

4. organic alkoxy compounds; For example original acid A ester, ethyl orthoformate, ortho-acetic acid methyl esters, ethyl orthoacetate, ortho-acetic acid isopropyl ester, Propanal dimethyl acetal etc.,

5. monofunctional isocyanates class; AdditiveTI (SUMITOMO Bayel UrethaneCo., Ltd.) etc.,

These dewatering agents (F) can share separately or more than 2 kinds.The usage quantity of this dewatering agent (F) is because of absorption, the adsorptive power or different with the reactivity of water of amount of moisture contained in the coating composition and dewatering agent, consider from viewpoints such as storage stability and film performances, generally the weight with coating composition is that benchmark is at 0.2～25 weight %, preferably in the scope of 0.5～15 weight %.

Among the present invention,, can suit to add curing catalysts (E) according to necessity in order to promote the formation of Gui Yang Wan Key.This curing catalysts (E) can be enumerated as organo-tin compounds such as stannous octoate, dibutyl tin two (2-ethylhexoate), dioctyl tin two (2-ethylhexoate), dibutyl tin diacetin, dioctyl tin diacetin, dibutyl tin two lauric acid salt, dibutyltin oxide, di-n-octyltin oxide, dibutyl tin diocatanoate, Monobutyltin three octylates, dibutyl tin soaps; Metal-chelate and the compounds or the metal alkoxide of three (methyl aceto acetate) aluminium, diisopropoxy list ethyl acetoacetic acid salt aluminium, tetra isopropyl octylate etc.; Boronic acid compounds such as trimethyl borate, triethyl borate, tributyl borate etc.

The use level of this curing catalysts (E) is 0.01～10 weight part for to form branch 100 weight parts admittedly with respect to all resins in the coating, preferably in the scope of 0.1～5 weight part.

Coating composition of the present invention is preferably containing aforesaid propylene acid resin (A), Resins, epoxy (B) and curing catalysts (E) and then is containing according to necessity in the host of organic silane compound (D), and the mixed amine hardener (C) that contains aminosilane can make 2 liquid type coating compositions of ambient cure before using.

Coating composition of the present invention is preferably containing aforesaid propylene acid resin (A) and modified epoxy (B ₁) and then contain according to necessity in the host of organic silane compound (D), the mixed amine hardener (C) that contains aminosilane can make 2 liquid type coating compositions of ambient cure before using.

Coating composition of the present invention will be preferably by containing the amine hardener (C of aforesaid propylene acid resin (A), Resins, epoxy (B) and ketoimineization ₁) mix the 1 liquid type coating composition that makes ambient cure.

Among the present invention, in order to improve stain resistances such as preventing the rain pollution, according to necessary and then in coating composition, add following formula (3)

Si(OR ⁷) ₄ (3)

(in the formula (3), R ⁷1 valency alkyl for identical or different carbon number 1～10) organosilicate shown in and/or its condenses (K).In the formula (3), R ⁷For example can enumerate alkyl, aryl etc.As alkyl, any kind of straight chain or side chain can, can enumerate as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, isohexyl, n-octyl etc., wherein preferred carbon number is 1～4 low alkyl group.As aryl, monocycle or polycyclic all can, can enumerate as phenyl, tolyl, xylyl, naphthyl etc. wherein preferred phenyl.

As the concrete example of above-mentioned organosilicate, can enumerate as tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, tetraphenoxy-silicane alkane, dimethoxy diethoxy silane etc.They can be used in combination more than a kind or 2 kinds.

As the condenses of above-mentioned organosilicate, chain or straight chain shape condenses between the organosilicate of representing for above-mentioned general formula, preferred condensation degree 2～100, the effect that condensation degree surpasses 100 o'clock stain resistances reduces and not preferred.As the condenses of this organosilicate, preferred especially R ⁷For the low alkyl group of carbon number 1～4, condensation degree at 2～100 compound.Organosilicate condensess different more than 2 kinds also can mix use.

In addition, can be by in above-mentioned organosilicate and/or its condenses (K), make the reaction of sulfhydryl compound or boronic acid compounds make the modified organic silicon hydrochlorate, also can import the alkyl of carbon number more than 8 and carry out modification by in above-mentioned organosilicate and/or its condenses (K).

Above-mentioned organosilicate and/or its condenses (K) form branch 100 weight parts admittedly with respect to all resins in the coating and cooperate solid formation to be divided into 0.1～50 weight part, preferred 1～20 weight part.The stain resistance of filming when this use level is lower than 0.1 weight part is bad, and the hardening of filming when surpassing 50 weight parts degradation defective under crackle, the glossiness might occur and not preferred.

In addition, in order to promote the hydrolysis of above-mentioned organosilicate and/or its condenses (K), can add boron compound or or organo-tin compound, aluminium compounds, acid phosphoric acid ester etc. according to necessity.

Among the present invention, in order to provide weathering resistance as required, and then preferably in coating composition, add any a kind or 2 kinds of UV light absorber (G) and ultra-violet stabilizer (H).Can enumerate benzotriazole category, triazines, phenylaniline class, benzo benzophenone class, oxalic acid phenylaniline class, cyanoacrylate as UV light absorber (G), can enumerate [TINUVIN1130], [TINUVIN400] (above is the special chemical corporate system of Chiba) as commercially available product, [CYASORB UV-1164L] (being Mitsui Cytec Ltd. system), [SANDUVOR3206] (being Clariant Japan K.K. system).The preferred hindered amines (hindered amine) of ultra-violet stabilizer (H), commercially available product can be enumerated [TINUVIN123], [TINUVIN144] (above is the special chemical corporate system of Chiba), [SANOL LS-292] (Sankyo Co., Ltd's system).

Coating composition of the present invention can be used as cleaning coating and uses, and also can cooperate pigment class such as tinting pigment, pigment extender, rust-stabilising pigment to use as glaze lacquer coating in addition.These pigment class can be enumerated titanium dioxide, carbon black, dim, zinc oxide, ferric oxide, Tolylamine, volatilization Huang, copper phthalocyanine indigo plant, copper phthalocyanine green, carbazole violet, crystallinity silicon oxide, palladous sulfate, Magnesium Silicate q-agent, Calucium Silicate powder, mica, mica shape ferric oxide, lime carbonate, zinc powder, aluminium, pure aluminium silicate, gypsum, feldspar etc.They can mix use more than a kind or 2 kinds.The cooperation ratio preferred pigments volumetric concentration (PVC) of pigment is 10～40vol%.The dispersing of pigments method known method of can adopting does not over have particular restriction, can enumerate as using dispersive methods such as ball milling, sand milling.

The present invention and then can cooperate coating additives such as tackifier, anti-drip agent, levelling agent, defoamer, dispersion agent, organic solvent according to necessity can be with the host or amine hardener (C) cooperation of carbamate resins, vibrin, Synolac etc. as share resin.

As organic solvent, can use hydro carbons, ester class, ketone, ethers, alcohols etc., can there be particular restriction ground to use known material in the past.Diluting solvent during when cooperating coating and/or as coating uses the organic solvent that contains the above varsol of selecting of 80 weight % from fat hydrocarbon solvent and high boiling aromatic hydrocarbon kind solvent, is well suited for applied and is the situation of old coating film face.

Coating composition of the present invention, the main raw material metal face of having handled according to necessary barrier coating, for example steel plate face or zinc surfacing, surface stainless steel, aluminium face, by the coated surfaces such as the face that is coated with that wear of these coatings, can be coated with also that concrete, cement, slabstone, slates etc. have the starting material face such as base material, Tao Ye class building materials, plastics of alkalescence or by the coated surface that wears of these coatings etc.Coating process does not have particular restriction, can be coated with as spraying, roller coat, bristle, method such as flow coat, filming of coating do not have particular restriction, finishes coating 50～200 μ m common 1 time, preferably in the scope of 60～120 μ m.Coating composition of the present invention can solidify at normal temperature, and its cured article can be brought into play good performance, also can carry out forced drying or heat drying.

Coating composition of the present invention, though by 1 painting process, can form the non-corrosibilityization and good the filming of weathering resistance that have priming paint and two kinds of functions of last coating concurrently, single barrier coating coating and last coating do not got rid of, carry out protection against corrosion coating back coating coating composition of the present invention according to necessity priming paints such as (zinc-rich primer) at the bottom of the rich zinc-base of coating epoxies priming paint or organic system or inorganic system on the coated surface, perhaps form by coating composition of the present invention film on the amino formate etc. coating finish coating, perhaps also can be coated with coating composition of the present invention repeatedly.

Embodiment

The present invention will be described in detail below to enumerate embodiment." part " in the literary composition and " % " do not have specific explanation to represent " weight part " and " weight % " respectively.

Preparation acrylic resin (A)

Preparation example 1

Pack in flask 20 parts of 660 parts of toluene, [MOA] (effective constituent is the ortho-acetic acid methyl esters, dewatering agent for trade(brand)name, the precious KCC of order system), logical nitrogen limit, limit is warmed up to 130 ℃ under stirring.Limit insulation is at 130 ℃ then, and the limit is with dripping following mixture in 3 hours,

600 parts of methyl methacrylates

100 parts of methoxy ethyl acrylate

300 parts of n-butylacrylate

40 parts of t-butylperoxy-2-ethylhexanoate

Be incubated then 130 ℃ of maturations 2 hours, make the acrylic resin soln (A-1) of the water white substantially slightly viscosity of non-volatile component 60%.

Preparation example 2

The vinyl monomer in preparation example 1 and the mixture of polymerization starter be with the following compound, and other and preparation example 1 are same, makes the acrylic resin soln (A-2) of nonvolatile component 60%.

100 parts of glycidyl methacrylates

600 parts of methyl methacrylates

100 parts of methoxy ethyl acrylate

200 parts of n-butylacrylate

40 parts of t-butylperoxy-2-ethylhexanoate

Preparation example 3

The vinyl monomer in preparation example 1 and the mixture of polymerization starter be with the following compound, and other and preparation example 1 are same, makes the acrylic resin soln (A-3) of nonvolatile component 60%.

100 parts of glycidyl methacrylates

500 parts of methyl methacrylates

100 parts of methoxy ethyl acrylate

200 parts of n-butylacrylate

100 parts of KBM-503 (annotating 1)

40 parts of t-butylperoxy-2-ethylhexanoate

Acrylic modified epoxy resin (B ₁) preparation

Preparation example 4

532 parts of mineral turpentine and [Epikote 828] (japan epoxy resin corporate system, bisphenol A type epoxy resin, epoxy equivalent (weight) 187) 429 parts are heated to 140 ℃ under nitrogen gas stream, drip the following vinyl monomer and the mixture of polymerization starter with 3 hours, drip and finish after ripen 2 hours.Then add 0.2 part of tetraethylammonium bromide, reacted about 2 hours, when the resin oxygen number is 0.3mgKOH/g, add 157 parts of mineral turpentine, make acrylic modified epoxy resin (B1-1).This resin solution nonvolatile component 65%, epoxy equivalent (weight) 652.

10 parts of methacrylic acids

250 parts of vinylbenzene

200 parts of ethyl propenoates

200 parts of Propenoic acid, 2-methyl, isobutyl esters

290 parts of 2-ethylhexyl acrylate

50 parts of KBM-503 (annotating 1)

80 parts of t-butylperoxy-2-ethylhexanoate

(annotating 1) trade(brand)name, chemical industrial company of SHIN-ETSU HANTOTAI system, γ-methacryloxypropyl trimethoxy silane

Preparation example 5

300 parts of 100 parts of toluene, [SUN THOTO ST-3000] and [HARIDIMER-200] 108 parts are heated to 135 ℃ under nitrogen gas stream, drip the following vinyl monomer and the mixture of polymerization starter with 2 hours, drip the end after ripen 1 hour.Then add 0.6 part of Tetrabutylammonium bromide, reacted about 2 hours.Adding 12 parts of Whitfield's ointments again, reacted about 1 hour, is 1mgKOH/g when following to the resin oxygen number, adds 150 parts of toluene, makes acrylic modified epoxy resin (B1-2).This resin solution nonvolatile component 70%, epoxy equivalent (weight) 763 (dividing) Gu form.

3 parts in vinylformic acid

90 parts of cyclohexyl methacrylates

54 parts of methyl methacrylates

15 parts of n-butyl acrylates

18 parts of 2-hydroxyethyl meth acrylates

5 parts of t-butylperoxy-2-ethylhexanoate

Modified epoxy (B ₂) preparation

Preparation example 6

[SUN THOTO ST-3000] (Dongdu changes into corporate system, the hydrogenation bisphenol A type epoxy resin, epoxy equivalent (weight) 231) 430 parts, [HARIDIMER-200] (HARIMA CHEMICALSINC, cannabinoid acid) 320 parts and Tetrabutylammonium bromide are heated to 140 ℃ for 0.8 part under nitrogen gas stream, reacted about 2 hours, to the resin oxygen number is 1mgKOH/g when following, adds 250 parts of toluene, makes modified epoxy (B ₂-1).This resin solution nonvolatile component 75%, epoxy equivalent (weight) 1014 (dividing) Gu form.

Preparation example 7

[SUN THOTO ST-3000] 670 parts, 130 parts of hexanodioic acids and Tetrabutylammonium bromide are heated to 140 ℃ for 0.8 part under nitrogen gas stream, reacted about 3 hours, and be 1mgKOH/g when following to the resin oxygen number, add 200 parts of toluene, make modified epoxy (B ₂-2).This resin solution nonvolatile component 80%, epoxy equivalent (weight) 812 (dividing) Gu form.

Preparation example 8

250 parts of [SUN THOTO ST-3000] 518 parts, [HARIDIMER-200] and Tetrabutylammonium bromide are heated to 140 ℃ for 0.8 part under nitrogen gas stream, reacted about 1 hour, add 32 parts of Whitfield's ointments again, reacted about 1 hour, to the resin oxygen number is that 1mgKOH/g is when following, add 200 parts of toluene, make modified epoxy (B ₂-3).This resin solution nonvolatile component 80%, epoxy equivalent (weight) 709 (dividing) Gu form.

Make coating

Embodiment 1～8 and comparative example 1～2

Cooperate Resins, epoxy and the pigment that cooperates shown in the table 1 in ball milling, carry out 1 hour dispersion treatment, make pigment dispersion paste, adjust host with cooperating shown in the table 1 to form, mixed solidifying agent makes each coating.The numeral of table 1 forms branch admittedly, and mark is as follows respectively:

A-4:[UMRS-2818]: Japanese catalyst Co. system, in copolymer composition, contain the monomeric acrylic resin of cyclohexyl methacrylate and UV stable, divide 60% Gu form

B-1:[Epikote 828EL]: japan epoxy resin corporate system, bisphenol A type epoxy resin, epoxy equivalent (weight) 187

B-2:[ST-3000]: Dongdu changes into corporate system, trade(brand)name, hydrogenation bisphenol-type epoxy resin, epoxy equivalent (weight) 231

B-3:[ST-5080]: Dongdu changes into corporate system, trade(brand)name, bisphenol-type epoxy resin/hydrogenation bisphenol-type epoxy resin, molecular weight 1200

D-1:[KR212]: Shin-Etsu Silicones corporate system, phenyl methyl alkoxyl group silicone oligopolymer

C-1:[KBM-603]: Shin-Etsu Silicone s corporate system, N-β (aminoethyl) γ-An Bingjisanjiayangjiguiwan

C-2:[KBM-903]: Shin-Etsu Silicones corporate system, γ-An Bingjisanjiayangjiguiwan

C-3:[SUNMIDE390-70]: three and chemical industrial company's system, modified polyamide amine

E-1:[CAT-AC]: Shin-Etsu Silicones corporate system, trade(brand)name: aluminium chelating catalyst, effective constituent 50%

E-2:[SCAT-8]: the synthetic Co., Ltd. of three total machines system, trade(brand)name: acetate dibutylester tin, effective constituent 100%

E-3:[Tetra isopropyl titanate]: Mitsubishi Gas Chemical Co., Ltd's system, trade(brand)name, effective constituent 100%

G-1:[TINUVIN1130]: Sankyo Co., Ltd's system, hindered amines ultra-violet stabilizer

H-1:[SANOL LS 292]: Chiba is becomed privileged length of schooling, benzotriazole category UV light absorber

K-1:[Ethyl Silicate48]: the chemical company's system of rubbing, the condenses of tetraethyl silicate more

Table 1

			Embodiment								Comparative example
													1	2	3	4	5	6	7	8	1	2
			Vinylformic acid		A-1	80					80
A-2		70															70		60
					A-3			60															100
A-4														30
					B 1-1					50											50
Epoxy		B-1											10			40								20
			B-2		10			30		10	30
		B-3													30			20
			Organo-siloxane		D-1	10	20	10	30	20		20									20			20
Solidifying agent		C-1											2.4			19							10
			C-2		3.9			14.5		3.9	14.5	7.7
		C-3													9.9			7.2
			Catalyzer		E-1	1			5																1
E-2		2													1		2	1
					E-3			3			3
Additive		G-1													1									1
			H-1			1						1
		K-1																	10	5
			Solvent		Toluene	2	12	6	12	9	58	12									9			25	52
Pigment		Titanium dioxide											80	80	80	80	80	80	80	80		80	80
			Carbon black	1	1	1	1	1	1	1	1	1									1
		Talcum											14	13	19	70	66	57	13	66		58	17
			Meter			200.4	211.9	220.9	287.0	271.5	306.2	221.9									276.5			273.7	261.0
Character value	PVC												21	20	21	30	30	30	20	30		30	20
			The coating solids component		78	77	80	88	88	68	74	86									79			63
	Active hydrogen/epoxy group(ing)												0.6	0.8	1	1.2	1	0.8	0.8	1		0.8	0.8

Embodiment 9～15 and comparative example 3～4

Cooperate Resins, epoxy and the pigment that cooperates shown in the table 2 in ball milling, carry out 1 hour dispersion treatment, make pigment dispersion paste, adjust host with cooperating shown in the table 2 to form, mixed solidifying agent makes each coating.The numeral of table 2 forms branch admittedly, and mark is as follows respectively:

D-2:[DC-3074]: TORAY DOWCORNING SILICONE Co., Ltd system, the oligopolymer of phenyl methyl alkoxyl group silicone, molecular weight 1000

C-4:[SUNMIDE J-230N]: three and chemical industrial company's system, the polyoxypropylene triamine

Table 2

			Embodiment							Comparative example
												9	10	11	12	13	14	15	3	4
			Vinylformic acid		A-3	20	20	20		40											50	20
Modified epoxy		B 2-1										60						50
			B 2-2		60
		B 2-3												60
			B 1-2				80	30	80
		B-2																	60	70
			Organo-siloxane		D-2	20	20	20	20	30	20											20	30
Solidifying agent		C-2										6.6	8.2	9.4	11.6	4.4		5.5	29	34
			C-4						9.1
		Solvent										Toluene	50	23	51	28	60	28	60	59		33
Pigment				Titanium dioxide	80	80	80	80	80	80	80										80		80
		Talcum	15									15	16	60	55	58	56	27	82
				Close Meter			251.6	226.2	256.4	279.6	299.4									275.1	301.5	295.0	329.0
Character value	PVC		20									20	20	30	30	30	30.11	20	30
				The coating solids component		80	90	80	90	80	90									80.10	80	90
	Active hydrogen/epoxy group(ing)		1									1	1	1	1	1	1	1	1
				Test subject	Drying property/time		3	4	2.5	3	4									4	4	8	12
The cold circulation of temperature		○	○									○	○	○	○	○	○	×
					Non-corrosibility		○	○	○	○	○								○	○	○	○
Weathering resistance		○	○									○	○	○	○	○	○	○

Embodiment 16～24 and comparative example 5～8

In ball milling, cooperate Resins, epoxy and the pigment that cooperates shown in the table 3, carry out 1 hour dispersion treatment, make pigment dispersion paste, stir mixed each composition, make each coating composition according to cooperating shown in the table 3 to form.The numeral of table 3 forms branch admittedly, and mark is as follows respectively:

F-1:[ortho-acetic acid methyl esters]: Nippoh Chemicals Co., Ltd's system, dewatering agent

C ₁-1: the methyl butyl ketone by γ-An Bingjisanyiyangjiguiwan makes the ketoimine thing

C ₁-2: by 1, the methyl butyl ketone of 3-aminomethyl hexanaphthene makes the ketoimine thing

C-4:1,3-aminomethyl hexanaphthene

Table 3

		Embodiment									Comparative example
															16	17	18	19	20	21	22	23	24	5	6	7	8
		Vinylformic acid	A-1								60
A-3	60															80	70	40				40	5		40	100
			B 1-1		90				60
A-4																				50
			Epoxy	B-2	40	10	20	30	40	10	20	30	40														30	40
Organo-siloxane	D-1																	20	30	30	10	20	95	70	20
			Dewatering agent	F-1	11	10	11	10	11	10	10	10	11	10													10	11	10
Solidifying agent	C 1-1	20															7	16	12	11	6		5	6		3
			C 1-2		11	11	7					12
	C-4																								6
			Additive	G-1	1	1			1	1			1															1
H-1	1	1															1	1			1			1
				Solvent	Toluene	15	4	5	3	27	19	18	7	26												45	50	23	3
Pigment	Titanium dioxide	80	80												80	80	80	80	80	80	80	80	80	80	80
				Talcum	19	15	10	10	19	16	15	10	16	10												10	11	5
	Close Meter		247												222	217	217	255	239	234	213	247	250	256	233				201
PVC(％)				20	20	20	20	20	20	20	20	20	20	20												20	20
		Coating forms branch (%) admittedly													77	77	74	77	77	77	77	77	77	77	77			77	70
Active hydrogen/epoxy group(ing)				0.6	0.8	0.5	0.8	0.6	0.6	0.8	0.3	0.8	0.5	0.3												0.8	0.1

Test method

(* 1) albefaction: on steel plate with the acetone degreasing, spraying is by cooperating each coating composition that makes shown in the table 1, make dry film thickness reach 70 μ m, then 20 ℃ of healths 5 hours, after 10 hours, respectively half area of each coated plate is immersed in the water 1 hour, immersion water is lifted coated plate after finishing, observation there is not water portion and there is not the state of water portion, and according to following standard evaluation, the result is as shown in table 4.

Zero: color does not have difference

△: some differences (there be not water portion slightly in vain) are arranged

*: big-difference (do not have water portion very white) is arranged very

(* 2): non-corrosibility: on the steel plate with the acetone degreasing, spraying makes dry film thickness reach 70 μ m by cooperating each coating composition that makes shown in table 1 and the table 3, makes each test board in dry 2 weeks of room temperature (20 ℃) then.

In order to make each plate expose starting material, cut the seam of wide 1mm, carry out 192 hours salt spray testing according to JIS K5400.9.1 after, observe being coated with membrane stage, then according to following standard evaluation (zero: do not have unusual △: slightly rust *: obviously send out rust).The results are shown in table 4 and table 6.

(* 3) atmospheric exposure test:, carry out 300 hours test with irradiation carbon arc lamp trier according to JIS K5400.9.8.1 to by cooperating each coating composition and above-mentioned (* 2) that make to make each test board equally shown in table 1 and the table 3.The reflecting feel that observation is filmed is carrying out difference before and after the accelerated weathering test, then according to following standard evaluation (zero: do not change △ substantially: slightly descend *: obviously descend).The results are shown in table 4 and table 6.

(* 4) outdoor contaminative: on the steel plate (0.8mm is thick) that zinc phosphate is handled, once be coated with each coating composition by embodiment 7,8 and comparative example 1,2 gained, make dry film thickness reach such 2 times spraying coatings of 60 μ m, under 20 ℃, the environment of 65RH, made each test board then in dry 7 days.

With each test board on the sunny side, be coated with towards tilting 30 °, carry out test outdoor exposure 3 months and 12 months, be coated with the pollution of face after the visual observations test, aberration before and after observe exposing according to JIS Z8730 in addition, calculate Δ L (lightness index poor) (zero: do not pollute △ substantially: pollute *: pollute significantly).The results are shown in table 5.

(* 5) storage stability: will each the coating composition 800g make is airtight to be kept in 1 liter the round can by cooperating shown in the table 3,40 ℃ place 1 month after observation state (zero: basic no abnormal △: viscosity significantly increases *: gelation).The results are shown in table 6.

(* 6) cold and hot repetition test: to each coating composition that makes by cooperation shown in table 2 and the table 3, make each test board equally with above-mentioned (* 2), submergence is after 6 hours in 60 ℃ warm water, with " 1 hour →-20 ℃ dryings of 180 ℃ of dryings 1 hour " as 1 circulation, carry out 20 circulations, according to following standard observe the state of filming (zero: the no abnormality seen of filming *: filming crackle occurs, occurs separating).The results are shown in table 2 and table 6.

(* 7) drying property: on steel plate with the acetone degreasing, spraying makes dry film thickness reach 70 μ m, then in the room temperature health by cooperating each coating composition that makes shown in the table 2, the semicure exsiccant time that reaches according to JIS K5400 regulation is estimated, and structure is shown in table 2 in the lump.

(* 8) non-corrosibility: use equally by cooperating each coating composition that makes to make each test board shown in the table 2 with above-mentioned (* 2), carve the seam of wide 1mm thereon in order to expose former material, carry out 1000 hours salt spray testing according to JIS K5400.9.1 after, observation is coated with membrane stage, then according to following standard evaluation (zero: do not have unusual △: slightly rust *: obviously send out rust).The result is shown in table 2 in the lump.

(* 9) weathering resistance: to by cooperating each coating composition make to test shown in the table 2, other is identical except that the atmospheric exposure test time with above-mentioned (* 3) changed into 500 hours, and the result is shown in table 2 in the lump.

Table 4

		Embodiment								Comparative example
												1	2	3	4	5	6	7	8	1	2
		Test subject	Albefaction 5h	○	○	○	○	○	○	○	○											×	△
10h	○											○	○	○	○	○	○	○	△	○
			Protection against corrosion	○	○	○	○	○	○	○	○										○	×
Weathering resistance	○											○	○	○	○	○	○	○	○	○

Table 5

			Embodiment		Comparative example
							7	8	1	2
			Contaminative outside the room	3 months	Pollute outward appearance	○					○	△	△
ΔL	1.2	1.1					8.0	7.6
					1 month	Pollute outward appearance			○	○	×	×
ΔL	3.1	2.5		12.5			11.8

Table 6

		Embodiment									Comparative example
															16	17	18	19	20	21	22	23	24	5	6	7	8
		Test subject	Storage stability	○	○	○	○	○	○	○	○	○	○	○														×	○
Non-corrosibility	○														○	○	○	○	○	○	○	○	△	○	○	×
			Weathering resistance	○	○	○	○	○	○	○	○	○	○	○													○	○
Cold and hot repetition test	○														○	○	○	○	○	○	○	○	×	×	○	○

Claims (9)

1. coating composition is characterized in that containing Resins, epoxy (B) that has 2 epoxy group(ing) in acrylic resin (A), 1 molecule at least and the amine hardener (C) that contains aminosilane;

Wherein, acrylic resin (A) is to be obtained by copolymerization by the unsaturated monomer that contains alkoxysilane group that contains 1～30 weight % in polymerizability unsaturated monomer mixture.

2. coating composition according to claim 1, wherein, in the mixture of acrylic resin (A) and Resins, epoxy (B), acrylic resin (A) contain can with the functional group of epoxy reaction, also contain the acrylic modified epoxy resin (B that at least a portion reaction of acrylic resin with the functional group who gets with epoxy reaction and Resins, epoxy (B) generates ₁).

3. coating composition according to claim 1, wherein, Resins, epoxy (B) is the Resins, epoxy (i) that has 2 epoxy group(ing) in 1 molecule at least by two basic acids (ii) and/or the (iii) modified epoxy (B of modification of the phenols that contains carboxyl ₂).

4. coating composition according to claim 1, wherein, amine hardener (C) is for containing amine hardener (C aminosilane, ketoimineization of ketoimineization ₁).

5. coating composition according to claim 4 wherein contains dewatering agent (F).

6. coating composition according to claim 1 wherein contains curing catalysts (E).

7. coating composition according to claim 6, wherein, curing catalysts (E) forms branch 100 weight parts admittedly with respect to all resins and contains 0.01～10 weight part.

8. coating composition according to claim 1 wherein contains UV light absorber (G) and/or ultra-violet stabilizer (H).

9. coating process is coated with the described coating composition of claim 1 on coated surface.