CN1286927C - Coating composition - Google Patents

Abstract

A coating composition characterized by containing an acrylic resin , an epoxy resin (B) having at least 2 epoxy groups in 1 molecule, and an amine curing agent (C) containing an aminosilane.

Description

coating composition

technical field

The present invention relates to corrosion resistance and aesthetics of steel structures such as power transmission and communication tower structures, transportation tanks, ships, bridges, tanks, etc., which can be formed in the next step of coating at room temperature and have excellent corrosion resistance and weather resistance. The coating composition of the coating film. The coating composition of the present invention has both functions of primer coating and top coating.

Background technique

Anti-corrosion coating is applied to steel structures such as tower structures for power transmission and communication, tanks for transportation, ships, bridges, and tanks to prevent corrosion and maintain aesthetics. When coating, usually after coating an epoxy resin primer with excellent corrosion resistance, various top coats with excellent weather resistance are often applied. However, in order to achieve the purpose of maintaining the above-mentioned performance, it is necessary to apply the primer coating multiple times, and then apply the middle coating, and at least three coating processes are required including the top coating. Especially when coating the steel structure that has already been built, not only must it work at a height without a foothold, but also because labor costs, scaffolding, etc. account for more than 80% of the coating cost, so coating is required in terms of safety and economy. As few times as possible, shorten the coating process.

As a countermeasure against the above problems, for example, JP-A-10-509195 discloses a coating material containing a special epoxy resin, polysiloxane, low-molecular-weight alkoxysilane, and bifunctional amine. However, this method is not only environmentally friendly, but also has uneven gloss. In addition, there is a problem that cracks may appear after long-term exposure of more than one year.

Contents of the invention

An object of the present invention is to provide a coating composition capable of greatly shortening the coating process and forming a coating film excellent in corrosion resistance and weather resistance in order to prevent corrosion and maintain the appearance of steel structures.

That is, the present invention provides a coating composition characterized by containing an acrylic resin (A), an epoxy resin (B) having at least two epoxy groups in one molecule, and an amine curing agent (C) containing an aminosilane.

According to a preferred first aspect of the present invention, there is provided a coating composition characterized in that it contains an acrylic resin (A), an epoxy resin (B) having at least two epoxy groups in one molecule, and an amine-cured resin obtained by containing an aminosilane. agent (C) and curing catalyst (E), and the compounding amount of the curing catalyst (E) is 0.01 to 10 parts by weight relative to 100 parts by weight of the total resin solid content.

The preferred second aspect of the present invention provides a coating composition characterized in that it contains an acrylic resin (A), an epoxy resin (B) having at least two epoxy groups in one molecule, and an amine-cured epoxy resin obtained by containing an aminosilane. In the coating composition of agent (C), the epoxy resin (B) is an epoxy resin (i) having at least 2 epoxy groups in one molecule covered with a dibasic acid (ii) and/or a carboxyl-containing phenol Class (iii) modified modified epoxy resins (B ₂ ).

The preferred third aspect of the present invention provides a coating composition, which is characterized in that it contains an acrylic resin (A), an epoxy resin (B) having at least two epoxy groups, and a ketimidated aminosilane. Ketoiminated amine curing agent (C ₁ ).

Specific Embodiments of the Invention

As the acrylic resin of the present invention, conventionally known ones can be used without particular limitation, but generally, an acrylic copolymer obtained by copolymerizing a polymerizable unsaturated monomer mixture with a radical polymerization initiator in the presence of an organic solvent is preferably used.

Examples of the polymerizable unsaturated monomer include methyl (meth)acrylate, ethyl methacrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (meth) tert-butyl acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, tert-butylcyclohexyl ( C1-24 alkyl or cycloalkyl esters of acrylic acid or methacrylic acid such as methacrylate, cycloundecyl (meth)acrylate, etc., methoxy methacrylate, methoxy Unsaturated monomers containing alkoxy groups with 1 to 24 carbons such as ethacrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate Hydroxyl-containing unsaturated monomers, carboxyl-containing unsaturated monomers such as acrylic acid and methacrylic acid, styrene, (meth)acrylamide, vinyl acetate, etc., can be used alone or in combination of two or more.

As the above-mentioned polymerizable unsaturated monomer, from the viewpoint of introducing a crosslinkable functional group that reacts with the amine curing agent (C) described later, and improving the corrosion resistance and weather resistance of the coating film, epoxy group-containing monomers can be used. unsaturated monomers and/or alkoxysilyl-containing unsaturated monomers.

As an epoxy-containing unsaturated monomer, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, β-methylglycidyl (methyl) ) acrylate, allyl glycidyl ether, etc., may be used alone or in combination of two or more.

As an unsaturated monomer containing an alkoxysilyl group, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, γ-( Meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, and the like may be used alone or in combination of two or more.

In addition, as the above-mentioned polymerizable unsaturated monomer, from the viewpoint of improving the weather resistance of the above-mentioned acrylic resin (A), an ultraviolet-absorbing unsaturated monomer and/or an ultraviolet-stable unsaturated monomer can be used.

The UV-absorbing unsaturated monomer is a monomer containing a polymerizable unsaturated group and a UV-absorbing site, and examples include benzotriazoles, triazines, phenylanilines, benzophenones, and oxalate phenyl Anilines, oxalic acid phenylanilines, cyanoacrylates, etc., for example, 2-[2'-hydroxy-5'-(methacryloyloxymethyl)phenyl]-2H-benzotriazole, 2-[2'-Hydroxy-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloxy Propyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyhexyl)phenyl]-2H-benzotriazole, 2-[2' -Hydroxy-3'-tert-butyl-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-tert-butyl-3 '-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5- Chloro-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[ 2'-Hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-cyano-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyl Oxyethyl)phenyl]-5-tert-butyl-2H-benzotriazole, 2-[2'-hydroxyl-5'-(methacryloyloxyethyl)phenyl]-5-nitro Base-2H-benzotriazole and so on. These may be used alone or in combination of two or more.

UV-stabilizing unsaturated monomers are monomers containing polymerizable unsaturated groups and UV-stabilizing moieties, specifically, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperene Pyridine, 4-(meth)acrylamide-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethyl Piperidine, 4-(meth)acrylamido-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4-(meth)acrylamido-2,2,6, 6-tetramethylpiperidine, 4-crotonyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonamido-2,2,6,6-tetramethylpiperidine, etc., These may be used alone or in combination of two or more.

As the above-mentioned polymerizable unsaturated monomer, when using an epoxy group-containing unsaturated monomer, it contains 0 to 70% by weight in the monomer mixture, preferably 1 to 20% by weight. When using an alkoxysilyl group-containing In the case of an unsaturated monomer, it is contained in the monomer mixture in an amount of 0 to 70% by weight, preferably in an amount of 1 to 30% by weight. In addition, as the polymerizable unsaturated monomer, when using a UV absorbing unsaturated monomer, it contains 0 to 20% by weight in the monomer mixture, preferably 0.1 to 10% by weight, and when using a UV stabilizing unsaturated monomer In the case of a monomer, it is contained in the monomer mixture at 0 to 20% by weight, preferably at 0.1 to 10% by weight.

The organic solvent used in the copolymerization is not particularly limited, and examples include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and ester solvents such as butyl acetate. Alcohol solvents such as isopropanol, mineral spirits, n-hexane, n-octane, 2,2,2-trimethylpentane, isooctane, n-nane, cyclohexane, methylcyclohexane, etc. Aliphatic hydrocarbons, etc. These may be used alone or in combination of two or more. There is no particular limitation on the polymerization initiator, and azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis(2-methylpropiononitrile) can be used ), 2,2-azobis (2,4-dimethylvaleronitrile) and other azo initiators or benzoyl peroxide, tert-butyl peroxy octanoate, diisobutyl peroxide peroxides, bis(2-ethylhexylperoxypivalate), decanoyl peroxide and other peroxides.

The weight average molecular weight of the acrylic resin (A) obtained above is 1,000-100,000, preferably 2,000-50,000. When it is less than 1,000, the weather resistance is insufficient, and when it exceeds 100,000, the compatibility between the epoxy resin (B), the organosilane compound (D) and the amine curing agent (C) is not sufficient, so it is not preferable.

The solubility parameter value (hereinafter abbreviated as [SP value]) of the acrylic resin (A) is 8-10, Preferably it is the range of 8-9.5. When it is less than 8, the compatibility with the epoxy resin (B) is insufficient, and when it exceeds 10, the compatibility with the organosilane compound (D) falls, and it is unpreferable. The SP value of the copolymer acrylic resin of the above-mentioned monomer mixture was calculated according to the following formula.

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

(In the above formula, SP1, SP2, ... SPn represent the SP value of the homopolymer of each monomer, fw1, fw2, ... fwn represent the ratio of each monomer relative to the total amount of monomer The SP value of the homopolymer of each monomer is described in J. Paint Technology, vol. 42 [541] 76-102 (1970) and the like.

The epoxy resin (B) in the present invention is a substance having at least two epoxy groups in one molecule, and the epoxy resin can include glycidyl ether type epoxy resins such as bisphenol A and bisphenol F, hydrogenated Bisphenol A type epoxy resins, glycidyl ester epoxy resins, cycloaliphatic epoxy resins, polyol type epoxy resins; these epoxy resins are modified by at least one selected from alkylphenols and fatty acids Modified epoxy resins formed by the modification of epoxy resins; alkylphenol or alkylphenol novolac resins reacted with epichlorohydrin to introduce epoxy groups into alkylphenol or alkylphenol novolac resins; dibasic acid-modified rings epoxy resin etc. (hereinafter referred to as epoxy resin (i)). The weight average molecular weight of the epoxy resin (B) is in the range of about 200 to about 3,000, preferably in the range of about 300 to about 1,000. When the weight-average molecular weight is less than 200, the corrosion resistance decreases, and when it exceeds 3,000, the compatibility with other resins becomes poor, which is not preferable.

[Epikote 828], [Epikote 830], [Epikote 834], [Epikote 806H] (manufactured by Japan Epoxy Resin Co., Ltd.), [DER- 331J] (Dow Chemical Co., Ltd.), [AER260] (Asahi Kasei Epoxy Co., Ltd.), [ST-3000], [ST-5080] (Tohto Chemical Co., Ltd.), [EpomikR#140P] (Mitsui Chemicals Co., Ltd.), Commercially available products such as [ERL-4221], [ERL-4229] (manufactured by UNION CARBIDE JAPAN K.K.), [Denacol EX-830] (manufactured by Nagase Chemical Industry Co., Ltd.), [HARIPOLE EP-450] (manufactured by HARIMA Chemical Co., Ltd.) Taste.

In the present invention, when the above-mentioned acrylic resin (A) contains a functional group capable of reacting with epoxy groups, an acrylic-modified epoxy resin produced by reacting at least a part of the above-mentioned acrylic resin (A) and the above-mentioned epoxy resin (B) can be used. (B ₁ ). A method for synthesizing an acrylic modified epoxy resin (B ₁ ), for example, as an acrylic resin (A), a monomer having a carboxyl group or an amino monomer is copolymerized to make at least part of the epoxy resin contained in the epoxy resin (B) Either all the groups are reacted, or the polymerizable unsaturated monomer forming the acrylic resin (A) with the epoxy resin (B) is graft-polymerized or copolymerized in the presence of a polymerization initiator. When described reaction is the reaction of epoxy group and carboxyl group, also can use the reaction catalyst that is used for this reaction purpose, as this reaction catalyst can enumerate as tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride Ethylammonium, tetrabutylphosphonium bromide, triphenylbenzylphosphonium chloride and other quaternary ammonium base catalysts, triethylamine, tributylamine and other amines.

As the epoxy resin (B) of the present invention, an epoxy resin having at least two epoxy groups in one molecule (i) modified by dibasic acid (ii) and/or carboxyl group-containing phenols (iii) can be used. Sexual modified epoxy resin (B ₂ ).

The dibasic acid (ii) is a substance that undergoes polyaddition reaction of the above-mentioned epoxy resin (i) to extend the bond of the epoxy resin. The epoxy resin (B ₂ ) obtained in this way has a high molecular weight, and improves the dry-to-touch property, impact resistance, etc. of the coating film.

Examples of the dibasic acid (ii) include phthalic anhydride, isophthalic acid, terephthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, and tetrahydrophthalic anhydride. , Hexahydrophthalic anhydride, dicarboxylic acid hydrogenated bisphenol A, hydrogenated cannabinic acid, hydrogenated naphthalene dicarboxylic acid, 1,4-dicyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid acid, tricyclosilane dicarboxylic acid, succinic acid, glutaric acid, fumaric acid, adipic acid, sebacic acid, maleic anhydride, cannabinoid, etc. These may be used alone or in combination of two or more.

The above carboxyl group-containing phenol (iii) introduces a phenolic hydroxyl group into the epoxy resin (i) to improve curability. Examples of the carboxyl group-containing phenol (iii) include salicylic acid, p-hydroxybenzoic acid, and 4-hydroxymethylbenzoic acid, and these may be used alone or in combination of two or more.

Modified epoxy resin (B ₂ ) can be obtained by using the above (i) component and (ii) and/or (iii) component with the epoxy group of (i) component and (ii) and/or (iii) The equivalent ratio of the epoxy groups of the components is mixed in the ratio range of 1:0.05 to 1:0.5, preferably 1:0.1 to 1:0.3. For example, the epoxy group/carboxyl group is reacted in the presence of a catalyst, and the heating reaction is usually 1 to 10 hours or so. As an epoxy group/carboxyl reaction catalyst, such as tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium chloride, tetrabutylphosphonium bromide, triphenylbenzylphosphonium chloride, etc. Quaternary ammonium base catalyst, triethylamine, tributylamine and other amines. The reaction temperature is suitably around 120-150°C.

In the present invention, the compounding ratio of the acrylic resin (A) and the epoxy resin (B) is 5 to 95% by weight, preferably 10 to 90% by weight, and (B) is 5 to 95% by weight relative to the total amount of solid components of these resins (A). 95% by weight, preferably 10 to 90% by weight. When the proportion of the acrylic resin (A) is less than 5% by weight, the coating film is likely to be split and the drying property after coating is lowered. On the other hand, if it exceeds 95% by weight, the corrosion resistance and weather resistance are lowered, which is not preferable. When the compounding ratio of the epoxy resin (B) is less than 5% by weight, the anti-corrosion property will decrease, and on the contrary, if it exceeds 95% by weight, the weather resistance will decrease, which is not preferable.

In the present invention, an organosiloxane compound (D) may be contained as necessary from the viewpoint of weather resistance. The organosiloxane compound (D) is suitably represented by the following formula (1)

(In formula (1), R ¹ and R ⁶ respectively represent a hydrogen atom, an alkyl group with 1 to 6 carbons, an aryl group or SiR ₃ (R is the same or different, and is a hydroxyl group, an alkyl group with 1 to 6 carbons, aryl or alkoxy), R ² and R ³ are the same or different, representing an alkyl or aryl group with 1 to 6 carbons, R ⁴ and R ⁵ are the same or different, representing an alkyl group with 1 to 6 carbons , aryl or alkoxy, m is in the range of 0 to 134, n is in the range of 0 to 134, m+n≥2)

The indicated weight average molecular weight is in the range of 400 to 30,000, preferably 1,000 to 10,000. In the above formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R are examples of alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, (iso) Propyl, pentyl, hexyl, cyclohexyl, etc., R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R are specific examples of aryl, such as phenyl, tolyl, etc. Specific examples of R ⁴ , R ⁵ and R being alkoxy include, for example, methoxy, ethoxy and the like. Specifically, [DC3074], [DC3037] (TORAYDOWCORNING SILICONE Co., Ltd), [KR-9218], [KR-212], [X-40-9220] (manufactured by Shin-Etsu Chemical Co., Ltd.), [TSR165] ( Commercial items such as TOSHIBA SILICONE Co., Ltd. These may be used alone or in combination of two or more, and their hydrolyzed/condensed products may also be used.

In order to align the alkoxysilyl group on the surface layer of the coating film and further improve the weather resistance, an alkylalkoxysilane and its hydrolyzate/condensate may be used in combination with the organosiloxane compound (D). Specific examples of alkylalkoxysilane include trimethoxymethylsilane, trimethoxyethylsilane, triethoxymethylsilane, trimethoxyisopropoxysilane, trimethoxyphenyl Silane, triethoxyphenylsilane, dimethoxydimethylsilane, dimethoxydiethoxysilane, methoxytrimethylsilane, methoxytriethylsilane, etc., which can be used alone It is also possible to use 2 or more types together.

When the organosiloxane compound (D) is used in the present invention, the total amount (A) of the resin solid content relative to the acrylic resin (A), epoxy resin (B) and organosiloxane compound (D) is 5 to 5 95% by weight, preferably 10 to 80% by weight, (B) is 5 to 95% by weight, preferably 10 to 80% by weight, and (D) is 0 to 90% by weight, preferably 10 to 80% by weight. When the blending ratio of the organosiloxane compound (D) exceeds 90% by weight, the anti-corrosion property will be lowered, which is not preferable.

The amine curing agent (C) used in the present invention is a curing agent that reacts with the epoxy group in the epoxy resin (B), and when the alkoxysilyl group is introduced into the coating composition, it can also act as a It is used as a reaction catalyst when water is hydrolyzed and condensed.

The amine catalyst (C) is an amine that may contain an aminosilane, and it is particularly preferable to use a polyfunctional amine. Examples of the polyfunctional amine include aliphatic or alicyclic polyamines, epoxy resin-added polyamines of the polyamines, etc. Compounds, polyamidoamines, aromatic amines, aliphatic or alicyclic mannich compounds, etc., may be used alone or in combination of two or more. Specifically, commercially available products such as [SUNMIDE J230N], [SUNMIDEI 518] (manufactured by Sanwa Chemical Industry Co., Ltd.), and [DAITOCURAR 1969] (manufactured by Daito Sangyo Co., Ltd.) can be used.

As the above-mentioned aminosilane, it is usually the following formula (2):

X-Si-(OY) ₃ (2)

(wherein, X is an alkyl group, aryl group, alkoxyalkyl group, cycloalkyl group that may contain _-NH2 and/or -NH-bonds, and Y is an alkyl group with 1 to 6 carbon atoms) , specifically N-β-(aminoethyl)aminopropyltrimethoxysilane, N-β-(aminoethyl)aminopropyltriethoxysilane, N-phenyl-γ-aminopropyl Trimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like may be used alone or in combination of two or more. As a commercial item, [KBM-603], [KBM-903] (made by Shin-Etsu Chemical Co., Ltd.) etc. are mentioned, for example.

The amine curing agent (C) is a substance containing the above-mentioned polyfunctional amine and aminosilane, or only one of them may be contained, preferably in combination, and its ratio is preferably 0.1 mol or more of aminosilane relative to 1 mol of the polyfunctional amine. When the proportion of aminosilane is less than 0.1 mol, the weather resistance is lowered, which is not preferable.

In the present invention, as the amine curing agent (C), a ketiminated amine curing agent (C ₁ ) containing a ketiminated aminosilane can be used.

The ketiminated amine curing agent (C ₁ ) used in the present invention is a curing agent that reacts with the epoxy group in the epoxy resin (B) if the protection of the amino group is removed, and then the alkane is introduced into the coating composition. In the case of an oxysilyl group, it can also be used as a reaction catalyst when moisture in the air is induced to undergo hydrolysis and condensation reactions.

The ketiminated amine curing agent (C ₁ ) used in the present invention may contain a ketiminated aminosilane, and a polyfunctional amine or a ketimized product of an aminosilane may be used. The above-mentioned ones can be used as the polyfunctional amine or aminosilane.

The above-mentioned ketoimidation of polyfunctional amines and aminosilanes essentially means that all the primary amino groups are blocked by carbonyl compounds to protect the amino groups. This carbonyl compound can enumerate as ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl tert-butyl ketone, diisobutyl ketone, cyclohexanone, and It can also be used in combination with aldehydes such as acetaldehyde and benzaldehyde to achieve partial aldimination.

The amine curing agent (C ₁ ) is a substance containing the ketimide of the above-mentioned polyfunctional amine aminosilane, and it may be only any one of them. When used in combination, it is preferably 0.1 mol relative to 1 mol of the polyfunctional amine aminosilane. above. When the proportion of aminosilane is less than 0.1 mol, the weather resistance is lowered, which is not preferable.

The compounding ratio of the amine curing agent (C): the ratio of (the number of equivalents of the active hydrogen of the amino group)/(the number of equivalents of the epoxy groups contained in the above-mentioned epoxy resin (B) and acrylic resin (A)) is 0.1～ 2.0, preferably in the range of 0.2 to 1.2, preferably from the viewpoints of curability of the coating film, corrosion resistance, weather resistance, and the like.

The compounding ratio of the amine curing agent (C ₁ ): (the number of equivalents of active hydrogen of the amino group released from the carbonyl compound)/(the number of equivalents of the epoxy groups contained in the above-mentioned epoxy resin (B) and acrylic resin (A) ) ratio is in the range of 0.1 to 2.0, preferably in the range of 0.2 to 1.2, which is preferred in terms of curability, corrosion resistance, weather resistance and the like of the coating film.

The coating composition of the present invention comprising the above-mentioned amine curing agent (C ₁ ) may be a one-component type or a two-component type, and the one-component type is preferable from the viewpoint of workability. In the case of a one-component type, it is preferable to further mix a dehydrating agent (F). Known dehydrating agents can be used as the dehydrating agent (F), and representative examples thereof are listed below.

①Powdered porous metal oxides or carbides; such as synthetic silica, activated alumina, zeolite, activated carbon, etc.,

② Calcium compounds composed of CaSO ₄ , CaSO4·1/2H ₂ O, CaO, etc.; such as calcined gypsum, soluble gypsum, quicklime, etc.,

③Metal alkoxides; such as isopropylaluminum, tert-butylaluminum, tetraisopropyl? , 2-zirconium propionate, zirconium n-butyrate, ethyl silicate, vinyltrimethoxysilane, etc.,

④ Organic alkoxy compounds; such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, isopropyl orthoacetate, dimethoxypropane, etc.

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

These dehydrating agents (F) can be used alone or in combination of two or more. The amount of the dehydrating agent (F) varies depending on the amount of water contained in the coating composition and the absorption and adsorption capacity of the dehydrating agent, or its reactivity with water. From the viewpoints of storage stability and coating film performance, it is generally The weight of the coating composition is based on 0.2 to 25% by weight, preferably in the range of 0.5 to 15% by weight.

In the present invention, in order to promote the formation of siloxane bonds, a curing catalyst (E) may be appropriately added as necessary. Examples of the curing catalyst (E) include tin octoate, dibutyltin bis(2-ethylhexanoate), dioctyltin bis(2-ethylhexanoate), dibutyltin diacetate, dioctyltin diethyl Organotin compounds such as tributyltin dilaurate, dibutyltin dilaurate, dibutyltin oxide, dioctyltin oxide, dibutyltin dioctoate, monobutyltin trioctanoate, dibutyltin fatty acid salt, etc.; tri(ethyl acetoacetate) aluminum , diisopropoxy monoethyl acetoacetate aluminum, tetraisopropyl octanoate and other metal chelate compounds or metal alkoxides; trimethyl borate, triethyl borate, tributyl borate, etc. Boric acid compounds, etc.

The compounding quantity of this curing catalyst (E) is 0.01-10 weight part with respect to 100 weight part of all resin solid content in a coating material, Preferably it exists in the range of 0.1-5 weight part.

The coating composition of the present invention is preferably mixed with a main ingredient containing the above-mentioned acrylic resin (A), epoxy resin (B), and curing catalyst (E) and, if necessary, an organosiloxane compound (D) before use. The aminosilane-containing amine curing agent (C) can be used as a room temperature curable two-component coating composition.

The coating composition of the present invention is preferably mixed with the main ingredient containing the above-mentioned acrylic resin (A) and modified epoxy resin (B ₁ ) and, if necessary, an organosiloxane compound (D) before use. The amine curing agent (C) can be used to prepare a room temperature curable two-component coating composition.

The coating composition of the present invention is preferably a room temperature curable one-component coating composition obtained by mixing the above-mentioned acrylic resin (A), epoxy resin (B) and ketimidized amine curing agent (C ₁ ). .

In the present invention, in order to improve the anti-pollution properties such as rain pollution prevention, the following formula (3)

Si(OR ⁷ ) ₄ (3)

(in the formula (3), R ⁷ is the same or different monovalent hydrocarbon groups having 1 to 10 carbon atoms) and/or its condensate (K). In formula (3), R ⁷ includes, for example, an alkyl group, an aryl group, and the like. As the alkyl group, any straight chain or branched chain can be used, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, iso- Pentyl, neopentyl, n-hexyl, isohexyl, n-octyl, etc. Among them, lower alkyl groups having 1 to 4 carbon atoms are preferred. The aryl group may be monocyclic or polycyclic, and examples thereof include phenyl, tolyl, xylyl, and naphthyl, among which phenyl is preferred.

Specific examples of the above organosilicates include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, dimethoxydiethyl Oxysilane, etc. These can be used 1 type or in combination of 2 or more types.

The condensate of the above-mentioned organosilicate is a branched or straight-chain condensate between the organosilicates represented by the above general formula, preferably with a degree of condensation of 2 to 100, and when the degree of condensation exceeds 100, it has excellent stain resistance. The effect is lowered and is not preferable. As the condensate of the organic silicate, a compound wherein R ⁷ is a lower alkyl group having 1 to 4 carbon atoms and a condensation degree of 2 to 100 is particularly preferable. Two or more different organosilicate condensates may be used in combination.

In addition, the modified organosilicate can be prepared by reacting a mercapto compound or a boric acid compound in the above-mentioned organosilicate and/or its condensate (K), or by adding the above-mentioned organosilicate and/or its The condensate (K) is modified by introducing an alkyl group having 8 or more carbon atoms.

The above organic silicate and/or its condensate (K) has a compounded solid content of 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the total resin solids in the paint. When the compounding amount is less than 0.1 parts by weight, the stain resistance of the coating film is poor, and when it exceeds 50 parts by weight, the coating film becomes hard, and defects such as cracks and gloss reduction may occur, which is not preferable.

In addition, in order to promote the hydrolysis of the organosilicate and/or its condensate (K), a boron compound or an organotin compound, an aluminum compound, an acidic phosphate, or the like may be added as necessary.

In the present invention, it is further preferable to add either one or both of the ultraviolet absorber (G) and the ultraviolet stabilizer (H) to the coating composition in order to provide weather resistance as necessary. Examples of the ultraviolet absorber (G) include benzotriazoles, triazines, phenylanilines, benzophenones, oxalic acid phenylanilines, and cyanoacrylates, and commercially available products include [ TINUVIN1130], [TINUVIN400] (manufactured by Chiba Special Chemicals Co., Ltd. above), [CYASORB UV-1164L] (manufactured by Mitsui Cytec Ltd.), [SANDUVOR3206] (manufactured by Clariant Japan K.K.). The ultraviolet stabilizer (H) is preferably a hindered amine (hindered amine), and commercially available products include [TINUVIN123], [TINUVIN144] (the above are made by Chiba Special Chemical Co., Ltd.), [SANOL LS-292] (manufactured by Sankyo Co., Ltd. ).

The coating composition of the present invention can be used as a cleaning coating, and can also be used as a glaze coating in combination with pigments such as coloring pigments, extender pigments, and antirust pigments. Examples of these pigments include titanium dioxide, carbon black, lamp black, zinc oxide, iron oxide, toluidine, volatile yellow, copper phthalocyanine blue, copper phthalocyanine green, carbazole violet, crystalline silica, palladium sulfate, silicon Magnesium acid, calcium silicate, mica, micaceous iron oxide, calcium carbonate, zinc powder, aluminum, aluminum silicate, gypsum, feldspar, etc. These can be used 1 type or in mixture of 2 or more types. The mixing ratio of the pigment is preferably a pigment volume concentration (PVC) of 10 to 40 vol%. The method for dispersing the pigment can be a conventionally known method without particular limitation, and examples include methods such as ball milling, sand milling, and the like.

The present invention can be combined with additives for coatings such as tackifier, anti-drip agent, leveling agent, defoamer, dispersant, organic solvent, etc. as necessary. Urethane resin, polyester resin, alcohol, etc. Main ingredient such as acid resin or amine curing agent (C).

As the organic solvent, hydrocarbons, esters, ketones, ethers, alcohols and the like can be used, and conventionally known ones can be used without particular limitation. When compounding paint and/or as a diluting solvent when coating, use an organic solvent containing more than 80% by weight of a hydrocarbon solvent selected from aliphatic hydrocarbon solvents and high-boiling aromatic hydrocarbon solvents. It is very suitable for the surface to be coated. The condition of the old coating film surface.

The coating composition of the present invention is mainly applied to the surface of a metal raw material that has been treated as a primer as necessary, such as a steel plate surface, or a galvanized surface, a stainless steel surface, an aluminum surface, or an old coated surface coated by these, etc. , It can also be coated with alkaline substrates such as concrete, cement, slate, slate tiles, raw material surfaces such as ceramic building materials, plastics, or old coating surfaces coated by these. There are no special restrictions on the coating method, such as spray coating, roller coating, brush coating, flow coating, etc. The coating film is not particularly limited, and the coating is usually 50-200 μm at a time, preferably within the range of 60-120 μm . The coating composition of the present invention can be cured at normal temperature, and its cured product can exhibit excellent performance, and can also be forced or heated.

Although the coating composition of the present invention can form a coating film with excellent corrosion resistance and weather resistance that has both the functions of the primer and the top coating in one coating process, it does not exclude the application of the primer and the top coating. Coating, on the surface to be coated as necessary, coat the coating composition of the present invention after carrying out anti-corrosion coating such as primers such as epoxy primer or organic system or inorganic system zinc-rich base (zinc-rich primer), Alternatively, a topcoat such as a urethane-based coating may be finished coated on a coating film formed from the coating composition of the present invention, or the coating composition of the present invention may be repeatedly coated.

Example

Examples are given below to describe the present invention in detail. "Parts" and "%" in the text mean "parts by weight" and "% by weight" without special explanation.

Preparation of Acrylic Resin (A)

Preparation Example 1

660 parts of toluene and 20 parts of [MOA] (trade name, manufactured by Nippon Chemical Co., Ltd., active ingredient is methyl orthoacetate, dehydrating agent) were charged into the flask, and the temperature was raised to 130° C. while stirring with nitrogen gas. Then, while keeping the temperature at 130°C, the following mixture was added dropwise over 3 hours,

Methyl methacrylate 600 parts

Methoxyethyl acrylate 100 parts

n-butyl acrylate 300 parts

tert-butylperoxy-2-ethylhexanoate 40 parts

Then it was incubated at 130° C. for 2 hours to prepare a substantially colorless and transparent slightly viscous acrylic resin solution (A-1) with 60% non-volatile content.

Preparation example 2

An acrylic resin solution (A-2) having a non-volatile content of 60% was prepared in the same manner as in Preparation Example 1 except that the following compounds were used for the mixture of vinyl monomer and polymerization initiator in Preparation Example 1.

Glycidyl methacrylate 100 parts

Methyl methacrylate 600 parts

Methoxyethyl acrylate 100 parts

n-butyl acrylate 200 parts

tert-butylperoxy-2-ethylhexanoate 40 parts

Preparation example 3

An acrylic resin solution (A-3) having a nonvolatile content of 60% was prepared in the same manner as in Preparation Example 1, except that the following compounds were used for the mixture of vinyl monomer and polymerization initiator in Preparation Example 1.

Glycidyl methacrylate 100 parts

Methyl methacrylate 500 parts

Methoxyethyl acrylate 100 parts

n-butyl acrylate 200 parts

KBM-503 (Note 1) 100 copies

tert-butylperoxy-2-ethylhexanoate 40 parts

Preparation of Acrylic Modified Epoxy Resin (B ₁ )

Preparation Example 4

532 parts of mineral spirits and 429 parts of [Epikote 828] (manufactured by Japan Epoxy Resin Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent 187) were heated to 140° C. under nitrogen flow, and the following ethylene was added dropwise over 3 hours. The mixture of the monomer and the polymerization initiator was matured for 2 hours after the dropwise addition. Then add 0.2 parts of tetraethylammonium bromide, react for about 2 hours, and when the oxygen value of the resin reaches 0.3 mgKOH/g, add 157 parts of mineral spirits to obtain an acrylic modified epoxy resin (B ₁ -1). The resin solution has a non-volatile content of 65% and an epoxy equivalent of 652.

Methacrylic acid 10 parts

Styrene 250 parts

Ethyl acrylate 200 parts

Isobutyl methacrylate 200 parts

2-Ethylhexyl acrylate 290 parts

KBM-503 (Note 1) 50 copies

tert-butylperoxy-2-ethylhexanoate 80 parts

(Note 1) Product name, manufactured by Shin-Etsu Chemical Co., Ltd., γ-methacryloxypropyltrimethoxysilane

Preparation Example 5

100 parts of toluene, 300 parts of [SUN THOTO ST-3000] and 108 parts of [HARIDIMER-200] are heated to 135°C under nitrogen flow, and the following mixture of ethylene monomer and polymerization initiator is added dropwise for 2 hours, and the addition is completed Post-ripen for 1 hour. Next, 0.6 part of tetrabutylammonium bromide was added and reacted for about 2 hours. Then add 12 parts of salicylic acid and react for about 1 hour. When the oxygen value of the resin is below 1 mgKOH/g, add 150 parts of toluene to obtain an acrylic modified epoxy resin (B ₁ -2). The resin solution has a non-volatile content of 70% and an epoxy equivalent of 763 (solid content).

Acrylic 3 parts

Cyclohexyl methacrylate 90 parts

Methyl methacrylate 54 parts

n-butyl acrylate 15 parts

2-Hydroxyethyl methacrylate 18 parts

tert-butylperoxy-2-ethylhexanoate 5 parts

Preparation of Modified Epoxy Resin (B ₂ )

Preparation example 6

[SUN THOTO ST-3000] (manufactured by Tohto Chemical Co., Ltd., hydrogenated bisphenol A type epoxy resin, epoxy equivalent 231) 430 parts, [HARIDIMER-200] (HARIMA CHEMICALSINC, cannabinoid acid) 320 parts, tetrabromide 0.8 parts of butyl ammonium was heated to 140°C under nitrogen flow, and reacted for about 2 hours. When the oxygen value of the resin was below 1 mgKOH/g, 250 parts of toluene was added to prepare modified epoxy resin (B ₂ -1). The resin solution has a non-volatile content of 75% and an epoxy equivalent of 1014 (solid content).

Preparation Example 7

[SUN THOTO ST-3000] 670 parts, 130 parts of adipic acid and 0.8 parts of tetrabutylammonium bromide are heated to 140°C under nitrogen flow, and react for about 3 hours. When the oxygen value of the resin is below 1mgKOH/g, add toluene 200 parts to prepare modified epoxy resin (B ₂ -2). The resin solution has a non-volatile content of 80% and an epoxy equivalent of 812 (solid content).

Preparation example 8

[SUN THOTO ST-3000] 518 parts, [HARIDIMER-200] 250 parts and tetrabutylammonium bromide 0.8 parts are heated to 140 ℃ under nitrogen flow, react for about 1 hour, then add 32 parts of salicylic acid, react for about 1 Hours, when the oxygen value of the resin is below 1 mgKOH/g, 200 parts of toluene are added to obtain a modified epoxy resin (B ₂ -3). The resin solution has a non-volatile content of 80% and an epoxy equivalent of 709 (solid content).

make paint

Embodiment 1～8 and comparative example 1～2

Mix the epoxy resin and pigment shown in Table 1 in the ball mill, and carry out dispersing treatment for 1 hour to make a pigment dispersion paste, adjust the main agent with the compounding composition shown in Table 1, and mix the curing agent to prepare each coating. The numbers in Table 1 represent solid components, and the marks are as follows:

A-4: [UMRS-2818]: Nippon Catalyst Co., Ltd., an acrylic resin containing cyclohexyl methacrylate and a UV-stabilizing monomer in the copolymerization component, solid content 60%

B-1: [Epikote 828EL]: manufactured by Japan Epoxy Resin Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent 187

B-2: [ST-3000]: Manufactured by Tohto Chemical Co., Ltd., trade name, hydrogenated bisphenol type epoxy resin, epoxy equivalent 231

B-3: [ST-5080]: manufactured by Tohto Chemical Co., Ltd., trade name, bisphenol type epoxy resin/hydrogenated bisphenol type epoxy resin, molecular weight 1200

D-1: [KR212]: Shin-Etsu Silicones Co., Ltd., phenylmethyl alkoxy silicone oligomer

C-1: [KBM-603]: Shin-Etsu Silicones, N-β(aminoethyl)γ-aminopropyltrimethoxysilane

C-2: [KBM-903]: Shin-Etsu Silicones Co., Ltd., γ-aminopropyltrimethoxysilane

C-3: [SUNMIDE390-70]: manufactured by Sanwa Chemical Industry Co., Ltd., modified polyamidated amine

E-1: [CAT-AC]: Shin-Etsu Silicones Co., Ltd., trade name: aluminum chelate catalyst, active ingredient 50%

E-2: [SCAT-8]: Sankyo Organic Synthesis Co., Ltd., trade name: dibutyltin acetate, active ingredient 100%

E-3: [Tetra isopropyl titanate]: manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name, active ingredient 100%

G-1: [TINUVIN1130]: Sankyo Co., Ltd., hindered amine UV stabilizer

H-1: [SANOL LS 292]: Chiba Special Chemicals, benzotriazole UV absorber

K-1: [Ethyl Silicate48]: Tama Chemical Co., Ltd., a condensate of ethyl silicate

Table 1 Example comparative example 1 2 3 4 5 6 7 8 1 2 acrylic 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 organosiloxane D-1 10 20 10 30 20 20 20 20 Hardener C-1 2.4 19 10 C-2 3.9 14.5 3.9 14.5 7.7 C-3 9.9 7.2 catalyst 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 talc 14 13 19 70 66 57 13 66 58 17 count 200.4 211.9 220.9 287.0 271.5 306.2 221.9 276.5 273.7 261.0 trait value pvc twenty one 20 twenty one 30 30 30 20 30 30 20 Coating Solids 78 77 80 88 88 68 74 86 79 63 Active Hydrogen/Epoxy 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

Mix the epoxy resins and pigments shown in Table 2 in the ball mill, and carry out dispersing treatment for 1 hour to make a pigment dispersion paste. Adjust the main agent with the compounding composition shown in Table 2, and mix the curing agent to prepare each coating. The numbers in Table 2 represent solid components, and the marks are as follows:

D-2: [DC-3074]: TORAY DOWCORNING SILICONE Co., Ltd., oligomer of phenylmethyl alkoxy silicone, molecular weight 1000

C-4: [SUNMIDE J-230N]: manufactured by Sanwa Chemical Industry Co., Ltd., polyoxypropylene triamine

Table 2 Example comparative example 9 10 11 12 13 14 15 3 4 acrylic 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 organosiloxane D-2 20 20 20 20 30 20 20 30 Hardener C-2 6.6 8.2 9.4 11.6 4.4 5.5 29 34 C-4 9.1 solvent Toluene 50 twenty three 51 28 60 28 60 59 33 pigment Titanium dioxide 80 80 80 80 80 80 80 80 80 talc 15 15 16 60 55 58 56 27 82 total 251.6 226.2 256.4 279.6 299.4 275.1 301.5 295.0 329.0 trait value pvc 20 20 20 30 30 30 30.11 20 30 Coating Solids 80 90 80 90 80 90 80.10 80 90 Active Hydrogen/Epoxy 1 1 1 1 1 1 1 1 1 Pilot projects dryness/time 3 4 2.5 3 4 4 4 8 12 warm and cold cycle ○ ○ ○ ○ ○ ○ ○ ○ x Corrosion resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ weather resistance ○ ○ ○ ○ ○ ○ ○ ○ ○

Examples 16-24 and Comparative Examples 5-8

Mix the epoxy resins and pigments shown in Table 3 in a ball mill, and carry out a dispersion treatment for 1 hour to make a pigment dispersion paste. Stir and mix the ingredients according to the compounding composition shown in Table 3 to prepare each coating composition. The numbers in Table 3 represent solid components, and the marks are as follows:

F-1: [Methyl orthoacetate]: Nippon Chemical Co., Ltd., dehydrating agent

C ₁ -1: Ketoimide from methyl butyl ketone of γ-aminopropyltriethoxysilane

C _1-2 : Ketoimide from methyl butyl ketone of 1,3-aminomethylcyclohexane

C-4: 1,3-Aminomethylcyclohexane

table 3 Example comparative example 16 17 18 19 20 twenty one twenty two twenty three twenty four 5 6 7 8 acrylic 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 organosiloxane D-1 20 30 30 10 20 95 70 20 Dehydrating agent F-1 11 10 11 10 11 10 10 10 11 10 10 11 10 Hardener 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 twenty three 3 pigment Titanium dioxide 80 80 80 80 80 80 80 80 80 80 80 80 80 talc 19 15 10 10 19 16 15 10 16 10 10 11 5 total 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 solid content (%) 77 77 74 77 77 77 77 77 77 77 77 77 70 Active Hydrogen/Epoxy 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

experiment method

(*1) Whitening property: On a steel plate degreased with acetone, spray each coating composition prepared from the formulations shown in Table 1 so that the dry film thickness reaches 70 μm, then cure at 20°C for 5 hours, and then after 10 hours , respectively immerse half of each coated panel in water for 1 hour, lift the coated panel after immersion in water, observe the state of the water-free part and the non-water-free part, evaluate according to the following standards, and the results are shown in Table 4.

○: There is no difference in color

△: There are some differences (the part without water is slightly white)

×: There is a big difference (the part without water is very white)

(*2): Corrosion resistance: On a steel plate degreased with acetone, each coating composition prepared from the formulations shown in Table 1 and Table 3 was sprayed to a dry film thickness of 70 μm, and then dried at room temperature (20°C) for 2 Weekly make each test board.

In order to expose each board to the raw material, cut a slit with a width of 1 mm, conduct a 192-hour salt spray test according to JIS K5400.9.1, observe the state of the coating film, and then evaluate according to the following criteria (○: no abnormality △: slightly rusted ×: visibly rusted). The results are shown in Table 4 and Table 6.

(*3) Weather resistance test: Each test panel was prepared in the same manner as in (*2) above for each coating composition prepared in Table 1 and Table 3, and was irradiated with a carbon arc lamp according to JIS K5400.9.8.1 The testing machine was tested for 300 hours. The glossiness of the coating film was observed before and after the accelerated weather resistance test, and then evaluated according to the following criteria (○: basically no change △: slightly decreased ×: significantly decreased). The results are shown in Table 4 and Table 6.

(*4) Outdoor staining property: On a zinc phosphate-treated steel plate (0.8 mm thick), each coating composition obtained in Examples 7 and 8 and Comparative Examples 1 and 2 was coated at one time so that the dry film thickness became 60 μm 2 times of spray coating, and then dried for 7 days under the environment of 20°C and 65RH to prepare each test panel.

Each test panel faces the sun, and the coated surface is tilted upward by 30°, and the test is carried out outdoor exposure for 3 months and 12 months. The contamination of the coated surface after the test is visually observed. In addition, the color difference before and after exposure is observed according to JIS Z8730, and ΔL (brightness) is calculated. Index difference) (○: basically no contamination △: contamination ×: significant contamination). The results are shown in Table 5.

(*5) Storage stability: Store 800 g of each coating composition prepared from the formulations shown in Table 3 in a 1-liter round can, and observe the state after placing it at 40°C for 1 month (○: basically no abnormality △: Viscosity greatly increased x: gelation). The results are shown in Table 6.

(*6) Repeated heat and cold test: For each coating composition prepared from the formulations shown in Table 2 and Table 3, each test panel was prepared in the same manner as in (*2) above, and immersed in warm water at 60°C for 6 hours , taking "drying at 180°C for 1 hour→drying at -20°C for 1 hour" as a cycle, carry out 20 cycles, and observe the state of the coating film according to the following standards (○: no abnormality in the coating film ×: cracks in the coating film , separation occurs). The results are shown in Table 2 and Table 6.

(*7) Dryness: On the steel plate degreased with acetone, spray the various coating compositions prepared from the formulations shown in Table 2 to make the dry film thickness reach 70 μm, and then cure it at room temperature to achieve semi-curing according to JIS K5400 The drying time was evaluated, and the structures are shown in Table 2.

(*8) Corrosion resistance: Each test panel was made of each coating composition prepared by blending shown in Table 2 in the same manner as in (*2) above, and a slit of 1 mm in width was made on it in order to expose the original material, according to JIS K5400.9.1 After the salt spray test for 1000 hours, the state of the coating film was observed, and then evaluated according to the following criteria (○: no abnormality △: slightly rusted ×: obviously rusted). The results are shown in Table 2 together.

(*9) Weather resistance: Test the coating compositions prepared from the formulations shown in Table 2, except that the weather resistance test time of the above (*3) was changed to 500 hours, and the results are shown in the table. 2.

Table 4 Example comparative example 1 2 3 4 5 6 7 8 1 2 Pilot projects Albinism 5h ○ ○ ○ ○ ○ ○ ○ ○ x △ 10h ○ ○ ○ ○ ○ ○ ○ ○ △ ○ anti-corrosion ○ ○ ○ ○ ○ ○ ○ ○ ○ x weather resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

table 5 Example comparative example 7 8 1 2 Outdoor Pollution 3 months polluted appearance ○ ○ △ △ ΔL 1.2 1.1 8.0 7.6 1 month polluted appearance ○ ○ x x ΔL 3.1 2.5 12.5 11.8

Table 6 Example comparative example 16 17 18 19 20 twenty one twenty two twenty three twenty four 5 6 7 8 Pilot projects storage stability ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ x ○ Corrosion resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ △ ○ ○ x weather resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ hot and cold trial and error ○ ○ ○ ○ ○ ○ ○ ○ ○ x x ○ ○

Claims (11)

1. 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, contain aminosilane and amine hardener (C) and organosilicone compounds (D), wherein this organosilicone compounds (D) is for following formula (1) expression:

In the formula (1), R ¹, R ⁶Represent respectively hydrogen atom, carbon number be 1～6 alkyl, aryl or-SiR ₃, R is identical or different herein, 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 ⁵Identical or different respectively, alkyl, aryl or the alkoxyl group of expression carbon number 1～6; M is 0～134, n in 0～134 scope, m+n 〉=2.

2, coating composition according to claim 1, wherein, when described acrylic resin (A) contains can be with the functional group of epoxy reaction the time acrylic modified epoxy resin (B that uses the reaction of this acrylic resin (A) and Resins, epoxy (B) to generate ₁) replace acrylic resin (A), Resins, epoxy (B) or acrylic resin (A) and Resins, epoxy (B).

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, the cooperation ratio of acrylic resin (A), Resins, epoxy (B) and organosilicone compounds (D) forms in the branch at their total resin admittedly, (A) be 10～80 weight %, (B) being 10～80 weight %, (D) is 10～80 weight %.

5. coating composition according to claim 1, wherein, the amine hardener (C of the ketoimineization that amine hardener (C) gets for the aminosilane that can contain ketoimineization ₁).

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

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

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

9. coating composition according to claim 1 wherein, contains the organosilicate shown in the following formula (3) and/or its condenses (K),

Si(OR ⁷) ₄ (3)

In the formula (3), R ⁷Identical or different, be the monovalence alkyl of carbon number 1～10.

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

11. coating process, the described coating composition of coating claim 1 on coated surface.