CN105623500B - The weatherability coating composition of normal temperature cure - Google Patents

Abstract

The present invention provides the weatherability coating composition of normal temperature cure, is suitable for forming cured coating film excellent the long-term weatherability under harsh corrosion working conditions under conditions of air drying.The weatherability coating composition of normal temperature cure, the coating process of the coating coating composition, the weatherability coating composition of the normal temperature cure is the composition containing multicomponent system made of host agent ingredient (I) and curing agent component (II), host agent ingredient (I) contains polyamines (A), curing agent component (II) contains polyepoxide (B), it is characterized in that, contain organo-metallic compound (C) either in host agent ingredient (I) and curing agent component (II) or in two sides, organic siliconresin (D) containing hydrolyzable silyl group, and the ultraviolet absorbing agent with hydroxyl and/or the light stabilizer with hydroxyl (E).

Description

The weatherability coating composition of normal temperature cure

Technical field

The present invention relates to even if can also be with cured weatherability coating composition in room temperature.

Background technique

It is influenced to protect the steel structures such as bridge, factory, tank object not by extraneous corrosive environment, and assigns and maintain beauty The function of sight, constructs to corrosion-proof coating.In the corrosion-proof coating of the harsh steel structure object of such corrosive environment, It is general carry out such as combination have zinc rich paint, the bottom-coating of epoxy resin, epoxy resin middle painting coating and polyurethane Resin system, fluororesin system painting coating at least 3 times or more coating process.Therefore, shorten coating process, from safety, Economy etc. considers, is strongly required the coating that design takes into account anticorrosive property and weatherability.

From such requirement, a kind of coating composition is disclosed in patent document 1, it is intended that providing one Kind coating composition, the coating composition is beautiful for the anticorrosion and maintenance of steel structure object, in room temperature and even if 1 painting Anticorrosive property can also be formed and the film that has excellent weather resistance in dress process, and it includes can contain acrylic resin, in 1 molecule The amine hardener and curing catalysts of epoxy resin, amino silane at least with 2 epoxy groups.In addition, remembering in the publication The coating composition of load, which also records, can contain ultraviolet absorbing agent or light stabilizer.

In addition, disclosing a kind of weatherability coating composition in patent document 2, it includes containing hydrolyzable silyl group Fluororesin, the acrylic resin containing hydrolyzable silyl group and the organic siliconresin containing hydrolyzable silyl group.

By the coating for the coating composition that patent document 1 or 2 is recorded, the beauty of steel structure object can be suitably maintained It sees, in recent years, further expects the exploitation with the coating of long-term weatherability.

Existing technical literature

Patent document

Patent document 1: special open 2004-051943 bulletin

Patent document 2: International Publication 2012-128223 pamphlet

Summary of the invention

Problems to be solved by the invention

Even if the object of the present invention is to provide be suitable for being formed under conditions of air drying in harsh corrosive environment item Also there is the weatherability coating composition of the film of long-term weatherability under part.

Means for solving the problems

The inventors of the present invention concentrate on studies to above-mentioned project, as a result, it has been found that, by specific resin combination Middle application has the ultraviolet absorbing agent or light stabilizer of specific structure, improves the weatherability of film significantly, so far completes The present invention.

That is, the present invention relates to the weatherability coating composition of normal temperature cure, to contain host agent ingredient (I) and solidification The composition of multicomponent system made of agent ingredient (II), host agent ingredient (I) contain polyamines (A), and curing agent component (II) is containing poly- Epoxides (B), which is characterized in that containing organic in either host agent ingredient (I) and curing agent component (II) or two sides Metallic compound (C), the organic siliconresin (D) containing hydrolyzable silyl group and the ultraviolet absorbing agent with hydroxyl and/ Or the light stabilizer (E) with hydroxyl.

The effect of invention

Weatherability coating composition according to the present invention, even if can be formed in the condition of air drying in harsh corrosion Long-term weatherability also excellent cured coating film under environmental condition.

Specific embodiment

To each ingredient contained in weatherability coating composition of the invention, it is illustrated in the following order.

< polyamines (A) >

In the present invention, as polyamines, it is the compound in molecule at least two amino, can be preferably listed to contain The compound of (methyl) acryloyl group is principal component, with amino-containing polymerism unsaturated monomer and can be with the polymerism insatiable hunger Other polymerism unsaturated monomers with monomer copolymerization are the amino-containing acrylic resin of copolymer composition.

Its manufacturing method is not particularly limited, both can by by azo-compound or peroxide be used for initiator from Manufactured by conventional methods such as base polymerizations, or commercially available product also can be used etc..

As amino-containing polymerism unsaturated monomer, it can be mentioned, for example: N, N- dimethyl aminoethyl (methyl) propylene Acid esters, N, N- diethylamino ethyl (methyl) acrylate, N, N- dimethylaminopropyl (methyl) acrylate, the tertiary fourth of N- Base amino-ethyl (methyl) acrylate, N, N- dimethrlaminobutyl (methyl) acrylate, N, N- dimethylaminopropyl (methyl) acrylamide etc., these can be used alone or in combination of two kinds or more.

In the present invention, the long-term weatherability of the film formed under air drying, it is suitble to using tool There is the compound of tertiary amino as polyamines.

As other polymerism unsaturated monomers, can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) nonyl acrylate, (methyl) dodecylacrylate ((methyl) lauryl acrylate), (methyl) tridecyl acrylate, (methyl) stearyl acrylate base ester, (methyl) acrylic acid iso stearyl ester, (methyl) propylene Sour cyclohexyl, (methyl) acrylic methyl cyclohexyl, (methyl) t-butylcyclohexyl ester, (methyl) acrylic acid cyclododecane (methyl) such as base ester, (methyl) isobornyl acrylate, (methyl) adamantyl acrylate, (methyl) tricyclodecyl acrylates Acrylic acid alkyl or cycloalkyl ester etc. have (methyl) alkyl acrylate of alkyl；(methyl) benzyl acrylate, styrene, α- The polymerism unsaturated monomer containing aromatic rings such as methyl styrene, vinyltoluene；(methyl) acrylic acid 2- hydroxy methacrylate, (first Base) (methyl) propylene such as acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxybutyl The monoesters compound of 2 yuan of alcohol of acid and carbon number 2~8, should (methyl) acrylic acid and carbon number 2~8 dihydric alcohol monoesters compound ε- Caprolactone modification object, N- hydroxymethyl (methyl) acrylamide, allyl alcohol, with molecular end be hydroxyl polyoxyethylene chain The polymerism unsaturated monomer of the hydroxyls such as (methyl) acrylate；(methyl) dimethylaminoethyl acrylate methyl villaumite, (methyl) dimethylaminoethyl acrylate benzyl villaumite, (methyl) acrylic acid diethylamino ethyl-methyl villaumite, (methyl) Acrylic acid diethylamino Ethylbenzyl villaumite, (methyl) acrylic-amino propyl-dimethyl ammonium methyl villaumite, (methyl) propylene Sour ammonium benzyl villaumite, (methyl) acrylic-amino propyl diethyl ammonium methyl villaumite, (methyl) acrylic acid Aminopropyl diethyl ammonium benzyl villaumite, (methyl) acrylic acid trimethylammoniumethyl sulfuric acid, (methyl) acrylic acid triethyl group Ammonium methylsulfuric acid ester salt, (methyl) acrylic-amino propyl-dimethyl ammonium methylsulfuric acid ester salt, (methyl) acrylic-amino propyl Dimethyl ammonium ethyl sulfuric acid ester salt, (methyl) acrylic acid trimethylaminoethyl group p-methyl benzenesulfonic acid ester salt, (methyl) acrylic acid ammonia The polymerism unsaturated monomers containing quaternary ammonium group such as base propyl-dimethyl ethyl ammonium ethyl sulfuric acid ester salt；Vinyl trimethoxy silicon Alkane, vinyltriethoxysilane, vinyl three (2- methoxy ethoxy) silane, γ-(methyl) acryloxypropyl three Methoxy silane, γ-(methyl) acryloxypropyl triethoxysilane etc. have the polymerism of alkoxysilyl not It is saturated monomer；(methyl) perfluoroethyls such as (methyl) perfluoroethyl butyl ethyl ester, (methyl) perfluoroethyl octyl ethyl ester Arrcostab；Polymerism unsaturated monomer with the fluorination alkyl such as fluoroolefins；With the optical polymerisms function such as dimaleoyl imino The polymerism unsaturated monomer of group；N-vinyl pyrrolidone, ethylene, butadiene, chlorobutylene, vinyl propionate, vinyl acetate The vinyl compounds such as ester；The carboxylic polymerisms such as (methyl) acrylic acid, maleic acid, crotonic acid, P-carboxy ethyl acrylates Unsaturated monomer；The nitrogenous polymerism unsaturated monomers such as (methyl) acrylonitrile, (methyl) acrylamide；(methyl) acrylic acid shrinks Glyceryl ester, (methyl) propenoic acid beta-methylglycidyl ester, (methyl) acrylic acid 3,4- expoxycyclohexyl methyl esters, (first Base) acrylic acid 3,4- expoxycyclohexyl ethyl ester, (methyl) acrylic acid 3,4- expoxycyclohexyl propyl ester, allyl glycidol The polymerism unsaturated monomer containing epoxy group such as base ether；N- methoxy (methyl) acrylamide, N- butoxymethyl (first Base) acrylamide, (methyl) methoxyethyl acrylate, (methyl) methoxypropyl ester, (methyl) ethioxy (methyl) alkoxyalkyl acrylates such as ethyl ester, (methyl) ethioxy propyl ester, polyethylene glycol mono methoxy (methyl) The polymerism unsaturated monomers containing alkoxy such as the polyalkylene glycol monos such as acrylate alkoxy (methyl) acrylate；Propylene Aldehyde, Diacetone Acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formoxyl styrene, Vinyl alkyl ketone (such as ethenyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) with 4~7 carbon atoms etc. Polymerism unsaturated monomer containing carbonyl etc., these can be used alone or two or more is applied in combination.

It is a feature of the present invention that the usage amount of above-mentioned amino-containing polymerism unsaturated monomer, with the manufacture of polyamines (A) Used in whole polymerism unsaturated monomers on the basis of, in the range of 0.2~25 mass parts, more preferably 0.5~20 In the range of mass parts.

In amino-containing acrylic resin, other polymerism unsaturated monomers are suitble to using with carbon number be 4 or more Alkyl (methyl) acrylate on the basis of other polymerism unsaturated monomer quality for 50 mass % or more, preferably 50~ 95 mass %.This is from the intermiscibility with Weak solvent and the aftermentioned organic siliconresin (D) containing hydrolyzable silyl group and to pass through From the perspective of the Physical properties of coating film such as long-term weatherability, the water resistance of film obtained from air drying.

As (methyl) acrylate of the alkyl for being 4 or more with carbon number, such as (methyl) acrylic acid can be enumerated N-butyl, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) third Olefin(e) acid n-octyl, (methyl) lauryl acrylate, (methyl) stearyl acrylate base ester, " acrylic acid iso stearyl ester " (trade name, Osaka organic chemistry society system), (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid tridecane (methyl) acrylate containing straight-chain, branched or cyclic alkyl such as base ester, these can be used alone or two or more group It closes and uses.

Weak solvent in this specification is common term in this field, it is however generally that refer to the weak solvent of dissolving power, Not closely be defined, but in the classification according to the organic solvent of the law of labour safety and health, can regard as the 3rd kind it is organic Solvent.As its concrete example, can enumerate for example gasoline, kerosene, coal tar naphtha (containing solvent naphtha), petroleum ether, Petroleum based naphtha, benzin, turpentine oil, mineral spirits (comprising mineral oil diluent, benzin, white spirit and Mineral turpentine), these can be used singly or two or more kinds in combination, and can contain labour safety and hygiene with 5 mass % or less The 1st kind of organic solvent, the 2nd kind of organic solvent in method.

Be explained, the 1st kind of organic solvent can enumerate chloroform, carbon tetrachloride, 1,2- dichloroethanes, 1,2-dichloroethene, 1,1,2,2- tetrachloroethanes, trichloroethanes, carbon disulfide and the mixture being only made of these etc., the 2nd kind of organic solvent also by Referred to as so-called strong solvent, can enumerate: acetone, isobutanol, isopropanol, isoamyl alcohol, ethyl alcohol, ethylene glycol monoethyl ether, ethylene glycol The mono- n-butyl ether of single monoethyl ether acetate, ethylene glycol, glycol monoethyl ether, o-dichlorobenzene, dimethylbenzene, cresols, chlorobenzene, acetic acid are different Butyl ester, isopropyl acetate, isoamyl acetate, ethyl acetate, acetic acid-N-butyl, acetic acid-n-propyl, acetic acid-n-pentyl ester, acetic acid Methyl esters, cyclohexanol, cyclohexanone, 1,4- bis-Alkane, methylene chloride, N,N-dimethylformamide, styrene, tetrachloro-ethylene, tetrahydro Furans, 1,1,1- trichloroethanes, toluene, n-hexane, n-butyl alcohol, 2- butanol, methanol, methyl iso-butyl ketone (MIBK), methyl ethyl ketone, first Cyclohexanol, methyl cyclohexanone, methyl-normal-butyl ketone etc..

As above-mentioned Weak solvent, commercially available product also can be used, as its concrete example, can enumerate: " Swazol 1000 ", " Swazol 1500 " (more than, ball is apt to petroleum Co. Ltd. system), " Solvesso 150 ", " Solvesso 200 ", " HAWS ", " LAWS " (more than, society, shell Japan system), " エ ッ ソ Na Off サ No.6 ", " EXXSOL D30 " (trade name, Exxon Mobilization Learn society's system), " Pegasol3040 " (trade name, Exxon Mobil chemistry society system), " A Solvent ", " Cresol ", " イ プ ゾ ー Le 100 " (Idemitsu Kosen Co., Ltd.'s system), " Mineral spirit A ", " Ha イ ア ロ system 2S ", " Ha イ ア ロ system 2S " (more than, Nippon Petrochemicals Co., Ltd.'s system), " リ ニ ア レ Application 10 ", " リ ニ ア レ Application 12 " (more than, light petroleum out Chemical Co., Ltd. system), " リ カ ソ Le Block 900 ", " リ カ ソ Le Block 910B ", " リ カ ソ Le Block 1000 " (more than, Xin Benli Change Co. Ltd. system) etc., these substances may be used alone or in combination.

As the weight average molecular weight of amino-containing acrylic resin described above, from the water resistance, weather-proof for forming film Property, Weak solvent dissolubility etc. consider, preferably 1,000~150,000, preferably in the range of 5,000~50,000.

In the present specification, weight average molecular weight is on the basis of the weight average molecular weight of polystyrene, will use gel infiltration color The weight average molecular weight of spectrum (Tosoh (strain) society system, " HLC8120GPC ") measurement carries out the resulting value that converts.Chromatographic column uses “TSKgelG-4000H×L”、“TSKgel G-3000H×L”、“TSKgelG-2500H×L”、“TSKgel G-2000H×L” (being Tosoh (strain) society system, trade name) this 4, in mobile phase: tetrahydrofuran, measuring temperature: 40 DEG C, flow velocity: 1ml/ points Clock, detector: it is carried out under conditions of RI.

< polyepoxide (B) >

In the present invention, as polyepoxide (C), it is the compound in molecule at least two epoxy group, can enumerates Such as: ethylene glycol diglycidyl base ether, polyethylene glycol diglycidyl base ether, 1,6- hexane diol diglycidyl ether, Bisphenol A-epichlorohydrin type epoxy resin, bisphenol F-epichlorohydrin type epoxy resin, bis-phenol-epichlorohydrin type epoxy resin, glycerol-table chlorine Poly epihydric alcohol base ether, cresols diglycidyl ether, polybutadiene diglycidyl ether, the quinhydrones two of alcohol addition product shrink Glyceryl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexahydrophthalic acid two contract Water glyceryl ester, hydrogenated bisphenol A type diglycidyl ether, dihydroxy anthracene type epoxy resin, polypropylene glycol diglycidyl Ether, diphenyl sulfone diglycidyl ether, dihydroxy benaophenonel diglycidyl ether, bis-phenol diglycidyl ether, two Phenylmethane diglycidyl ether, bisphenol fluorene diglycidyl ether, double cresols fluorenes diglycidyl ethers, double phenoxy group second Alcohol fluorenes diglycidyl ether, 1,3- bis- (N, N- diglycidyl amino methyl) hexamethylenes, N, N- diglycidyl benzene Amine, N, N- diglycidyl toluidines etc..

< organo-metallic compound (C) >

It as the concrete example of organo-metallic compound (C), can enumerate: tin dilaurate dioctyl tin, two neodecanoic acid dioctyls Tin, the condensation product of bis- (2- ethylhexyl maleic acid) dioctyl tin, dioctyl tin oxide or Dibutyltin oxides and silicate, two Sad dibutyl tin, dibutyl tin dilaurate, distearyl acid dibutyl tin, dibutyltin diacetate, two fourth of diacetyl acetone Ji Xi, bis- (ethyl maleic acid) dibutyl tins, bis- (butyl maleic acid) dibutyl tins, bis- (2 ethyl hexanoic acid maleic acid) dibutyl Tin, bis- (oleyl maleic acid) dibutyl tins, stannous octoate, stearic acid tin, lauric acid di-n-butyl tin oxide, double isononyls- 3- mercaptopropionic acid dibutyl tin, double isononyl -3- mercaptopropionic acid dioctyl tins, double isononyl -3- mercaptopropionic acid octyl butyl tins, Double iso-octyl thioglycolic acid dibutyl tins, double iso-octyl thioglycolic acid dioctyl tins, double iso-octyl thioglycolic acid octyls The organo-tin compounds such as butyl tin, dioctyl acid tin, distearyl acid tin；Titanium alkoxides or the acetylacetone,2,4-pentanediones such as isopropyl titanate, butanol titanium The organic titanic compounds such as bis- (acetylacetone,2,4-pentanedione) titaniums of titanium, 2 ethyl hexanoic acid titanium, diisopropoxy；The acetic acid of iron (II) or iron (III) The organoiron compounds such as salt, acetylacetonate, 2 ethyl hexanoic acid salt；The aluminium-alcohol salts such as aluminium isopropoxide, aluminium butoxide or ethyl Acetone aluminium diisopropanol, aluminium tris(acetylacetonate), three (ethylacetoacetate) aluminium, the bis- (ethyls of monoacylphosphine acetic acid esters Acetic acid) organo-aluminum compounds such as aluminium, alkyl acetoacetates yl acetate；Manganese acetate (II), acetoacetate manganese (II), 2 ethyl hexanoic acid The organo-manganese compounds such as manganese (II)；Cobalt acetate (II), acetoacetate cobalt (II), benzoyl acetyl cobalt (II), 2 ethyl hexanoic acid The organic cobalt compounds such as cobalt (II), naphthoic acid cobalt；Propyl alcohol zirconium (IV), zirconium acetate (IV), acetoacetate zirconium (IV), 2 ethyl hexanoic acid The organic zirconates such as zirconium (IV)；Propyl alcohol nickel (II), nickel stearate (II), nickel acetate (II), acetoacetate nickel (II), 2- second The organo-nickel compounds such as base caproic acid nickel (II)；The organo-bismuths such as bismuth neodecanoate (III), bismuth acetate (III), 2 ethyl hexanoic acid bismuth (II) Compound；The organocopper compounds such as acetoacetate copper (II), butyl phthalic acid copper (II)；Zinc acetate (II), acetyl group The organic zinc compounds such as zinc acetate (II), 2 ethyl hexanoic acid zinc (II)；Barium acetate (II), acetoacetate barium (II), 2- ethyl Organic barium compounds such as caproic acid barium (II) etc., these can be used alone or two or more is applied in combination.

Organic siliconresin (D) > of < containing hydrolyzable silyl group

Organic siliconresin (D) containing hydrolyzable silyl group is in resin containing hydrolyzable silyl group and with poly- The resin of siloxane backbone.

In the present specification, hydrolyzable silyl group is to generate silanol group by hydrolysis, which is taken off Water is condensed and is formed the group of siloxanes key, as long as having the water-disintegrable atom for the monovalence for being bonded directly to silicon atom (to pass through React and generate the atom of silanol group with water) and be bonded directly to silicon atom monovalence hydrolization group (by anti-with water Answer and generate the group of silanol group) two or a party silicyl, be just not particularly limited.As above-mentioned water-disintegrable first The concrete example of silylation, it can be mentioned, for example: the halosilyl groups such as chlorosilyl, silyl bromide base；Methoxysilyl, Alkoxysilyls such as triethoxysilyl, isopropoxysilyl group, butoxy silicyl etc. and theirs is any Combination.

Organic siliconresin (D) containing hydrolyzable silyl group is, for example, by by following formula (1):

SiX_nY_4-nFormula (1)

(in formula, X indicates hydroxyl or alkoxy, and Y indicates 1 valency alkyl that can have substituent group, and n expression 1~4 is whole Number.)

2 or more organosilans indicate, identical or different are chemically bonded and the resin that generates, such as oligomeric Object.

In the organic siliconresin (D) containing hydrolyzable silyl group, organosilan that formula (1) indicates can with straight-chain or Branched is bonded.In addition, the organic siliconresin (D) containing hydrolyzable silyl group preferably has and silicon atom Direct Bonding Alkyl.

As the organosilan that formula (1) indicates, it can be mentioned, for example dimethyldimethoxysil,nes, dimethyl diethoxy Silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, vinyltrimethoxysilane, vinyl triethoxyl Silane, vinyltriacetoxy silane, gamma-amino propyl trimethoxy silicane, γ-glycidoxypropyl group trimethoxy silicon Alkane, γ-epoxy propoxy propyl triethoxysilane, β-(3,4- expoxycyclohexyl) ethyl trimethoxy silane, γ-(3, 4- expoxycyclohexyl) ethyl triethoxysilane, γ-(methyl) acryloyloxypropyltrimethoxysilane, phenyl front three Oxysilane, phenyl triacetoxysilane, γ mercaptopropyitrimethoxy silane, γ-r-chloropropyl trimethoxyl silane, β- Cyano ethyl triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyl tripropoxy silane, methyl Three butoxy silanes, ethyl trimethoxy silane, ethyl triethoxysilane, tetramethoxy-silicane, tetraethoxysilane, 4 third Oxysilane, four butoxy silanes, dimethyldichlorosilane, diphenyl dichlorosilane, aminomethyl phenyl dimethoxysilane, front three Methoxylsilane, trimethylethoxysilane, γ aminopropyltriethoxy silane, 4- ammobutyltriethoxysilane, P-aminophenyl trimethoxy silane, N- (2- amino-ethyl) -3- TSL 8330, aminoethylaminomethyl Phenethyl trimethoxy silane, 3- glycidoxypropyltrime,hoxysilane, 2- (3,4- expoxycyclohexyl) ethyl front three Oxysilane, 3- TSL 8330,3-aminopropyltriethoxysilane, 4- aminobutyl triethoxysilicane Alkane, N- (6- Aminohexyl) TSL 8330,3- r-chloropropyl trimethoxyl silane, 3- chloropropyl trichloro-silane, (to chloromethyl) phenyltrimethoxysila,e, 4- chlorphenyl trimethoxy silane, 3- methacryloxypropyl trimethoxy Silane, 3- methacryloxypropyl, 3- acryloyloxypropyltrimethoxysilane, styryl second Base trimethoxy silane, 3-mercaptopropyi trimethoxy silane, vinyl three (2- methoxy ethoxy) silane, trifluoro propyl three Methoxy silane etc. and their arbitrary combination.

From the viewpoint of with the intermiscibility of polyamines (A) and being formed by the weatherability of film, contain hydrolyzable silyl group Organic siliconresin (D) preferably there is methyl and/or phenyl with silicon atom Direct Bonding.

Especially from the viewpoint of being formed by the long-term weatherability of film by the present composition, host agent ingredient (I) It may include comprising the organic siliconresin containing hydrolyzable silyl group, curing agent component (II) containing phenyl non-containing the aqueous of phenyl The form of the organic siliconresin of solution property silicyl.

As the commercially available product of the organic siliconresin (D) containing hydrolyzable silyl group, it can be mentioned, for example: " SR2406 ", " SR2410 ", " SR2420 ", " SR2416 ", " SR2402 ", " AY42-161 ", " DC-3074 " and " DC-3037 " (more than, east Beautiful-DOW CORNING-silicone Co. Ltd. system), " FZ-3704 " and " FZ-3511 " (more than, Japan Unicar society system), " KC-89S ", “KR-500”、“X-40-9225”、“X-40-9246”、“X-40-9250”、“KR-217”、“KR-9218”、“KR-213”、“KR- 510”、“X-40-9227”、“X-40-9247”、“X-41-1053”、“X-41-1056”、“X-41-1805”、“X-41-1810”、 “X-40-2651”、“X-40-2308”、“X-40-9238”、“X-40-2239”、“X-40-2327”、“KR-400”、“X-40- 175 " and " X-40-9740 " (more than, Shin-Etsu Chemial Co., Ltd's system) etc..

Ultraviolet absorbing agent of the < with hydroxyl and/or the light stabilizer with hydroxyl (E) >

In the present invention, as the ultraviolet absorbing agent with hydroxyl, as long as with the ultraviolet light of hydroxyl in a molecule Absorbent is just not particularly limited, and it can be mentioned, for example hydroxy phenyl benzotriazole derivatives, hydroxyphenyltriazinuv derivatives etc..

As the ultraviolet absorbing agent with hydroxyl, specifically, it can be mentioned, for example: 2- (2 '-hydroxyls -3 ', 5 '-diamyls Base phenyl) benzotriazole, 2- (2,4- dihydroxy phenyl) -4,6- pairs-(2,4- 3,5-dimethylphenyl) -1,3,5- triazine and (2- second Base hexyl) reaction product of-ethyl glycolate, propionic acid 2- [4- [bis- ([1,1 '-biphenyl] -4- the base) -1,3,5- triazine -2- of 4,6- Base) -3- hydroxyphenoxy]-isooctyl acrylate, bis- [2- hydroxyl -4- the butoxy phenyl] -6- (2,4- dibutoxy phenyl)-of 2,4- 1,3,5- triazine, 2- (2- hydroxyl -5- tert-butyl-phenyl) -2H- benzotriazole, 2-hydroxy-4-n-octoxybenzophenone, 2- (2- hydroxyl -5- t-octyl phenyl) -2H- benzotriazole, salicylic acid 4- tert-butyl benzene base ester, 2- (two-uncle of 2- hydroxyl -3,5- penta Base phenyl)-benzotriazole etc..

As the light stabilizer with hydroxyl, as soon as long as it is not limited especially in molecule with the light stabilizer of hydroxyl System, it can be mentioned, for example the piperidine derivatives etc. that intramolecular has hydroxyl.

As the ultraviolet absorbing agent with hydroxyl, specifically, it can be mentioned, for example: 4- hydroxyl -1,2,2,6,6- five first Phenylpiperidines, 2- [[bis- (1,1- the dimethyl ethyl) -4- hydroxy phenyls of 3,5-] methyl] bis- [1,2,2,6,6- of -2- butylmalonic acid Pentamethyl -4- bipyridyl], the reaction product of dimethyl succinate and 4- hydroxyl -2,2,6,6- tetramethyl -1- piperidine ethanol, 2- ethylaminoethanol and hexamethylene and the chloro- 1,3,5- of peroxidating N- butyl -2,2,6,6- tetramethyl -4- piperidines amino -2,4,6- three The reactant of triazine.

< weatherability coating composition >

Weatherability coating composition of the invention contain polyamines (A), polyepoxide (B), organo-metallic compound (C), Organic siliconresin (D) containing hydrolyzable silyl group and the ultraviolet absorbing agent with hydroxyl and/or the light with hydroxyl are steady Agent (E) is determined, as the use ratio of these each ingredients, from the long-term weatherability side of the film obtained under conditions of air drying Face considers, on the basis of 100 mass parts of solid component of the organic siliconresin (D) containing hydrolyzable silyl group, it is expected that polyamines (A) 25~250 mass parts, preferably 50~100 mass parts, polyepoxide (B) are calculated as by solid component quality by solid component quality It is calculated as 1~50 mass parts, preferably 5~20 mass parts, organo-metallic compound (C) and is calculated as 0.1~25 matter by effective component quality Measure part, preferably 3~20 mass parts, the ultraviolet absorbing agent with hydroxyl and/or the light stabilizer (E) with hydroxyl by effectively at Component is calculated as in the range of 0.1~20 mass parts, preferably 1~10 mass parts.

In the present invention, contain polyamines (A) in host agent ingredient (I), polyepoxide is contained in curing agent component (B), whether the two is taken care of in storage stage respectively, about containing in any in host agent ingredient (I) and curing agent component (I) Have the ingredient other than it, both can suitably select, or the ingredient can also be allocated and host agent ingredient (I) and solidification Contain in the two of agent ingredient (I).

In addition, weatherability coating composition of the invention can contain: silane coupling agent；Pigment；Acrylic resin, fluorine tree The modifying resins such as rouge, alkyd resin, carbamate resins；Organic solvent；Reactive diluent；Adhere to imparting agent, anti-settling Additive for coatings such as shallow lake agent, dispersing agent, wetting agent, dehydrating agent etc..

As above-mentioned silane coupling agent, it can be mentioned, for example: γ-(2- amino-ethyl) TSL 8330, γ- Aminopropyltriethoxywerene werene, N- β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N- β (amino-ethyl) γ-ammonia The amino-containing silane coupling agents such as base hydroxypropyl methyl dimethoxysilane；γ-glycidoxypropyltrime,hoxysilane, γ- The silane coupling agent containing glycidyl such as epoxy propoxy propyl methyl dimethoxysilane；γ-mercaptopropyi trimethoxy The silane coupling agent containing sulfydryl such as silane；Vinyltriethoxysilane, vinyltrimethoxysilane, three (methoxy of vinyl Base oxethyl) silane coupling agent containing vinyl such as silane；γ-(methyl) acryloyloxypropyltrimethoxysilane, γ- (methyl) acryloxypropyl triethoxysilane, γ-(methyl) acryloxypropyl dimethoxymethylsilane etc. contain The silane coupling agent etc. of (methyl) acryloyl group.

When weatherability coating composition of the invention contains silane coupling agent, as the content of silane coupling agent, from raising From the perspective of adhesion, based on 100 mass parts of solid component quality of the organic siliconresin (D) containing hydrolyzable silyl group, Be suitable for 30 below the mass, the range of preferably 5~20 mass parts.

Weatherability coating composition of the invention is that host agent ingredient (I) contains polyamines, curing agent component (II) contains polycyclic The substance of oxide, for the use ratio of host agent ingredient (I) and curing agent component (II), from being formed by the long-term of film From the perspective of weatherability and curability, it is adapted to 1 mole of amino, is 0.5~5 mole, preferably 1~3 with epoxy group Mole mode be adjusted.

Weatherability coating composition of the invention is normal temperature cured type, and the cured coating film of formation can play excellent property Can, but may be force drying curing type or heat-curing type.

It as the purposes of weatherability coating composition of the invention, is not particularly limited, is suitable for bridge, power transmission steel tower, work The face of the heavy anticorrosive coating of the steel structures object such as factory, tank applies purposes.

< coating >

As the coated article for the weatherability coating composition for answering coating of the invention, it can enumerate and bases have been carried out according to expectation The metal material of reason, the substrate such as steel plate, zinc-plated, stainless steel, aluminium with alkalinity；Such as concrete, mortar, slabstone, stone Pan tile etc., ceramics are building materials, plastics etc. and the material for being formed on outmoded film.

Above-mentioned weatherability coating composition can the means well known to such as spraying, roller coating, brushing, flowing coating etc. carry out Coating.

In addition, before forming weatherability film using weatherability coating composition, it can the coating primary coat on coated article Coating or middle coating intermediate form anticorrosion film.

As above-mentioned bottom-coating, water system well known in the art or solvent-based bottom-coating can be enumerated.

It as the example of above-mentioned bottom-coating, can enumerate: epoxy coating, modified epoxy resin paint, epoxy resin It is GLASS FLAKE COATINGS, epoxy resin lining material, super thick membranous type epoxy coating, epoxy resin zinc rich paint, inorganic zinc-rich Paint, chlorinated rubber resin system coating, phthalic resin system coating, epoxy ester resin paint etc..

It as the example of above-mentioned middle coating intermediate, can enumerate: epoxy resin coating, polyurethane series coating, epoxy resin MIO The water system or solvent of coating, phenolic resin system MIO coating, chlorinated rubber resin system coating, phthalic resin system coating etc. The coating of system.

Weatherability coating composition of the invention can also easily solidify even if under conditions of air drying, even if To corrosion-proof coating constructed as can also form the long-term excellent film of weatherability under harsh environment.

In turn, since weatherability coating composition of the invention can form the weatherability film with long-term weatherability, Therefore, it can extend during until brushing again, and can be omitted coating process, it is possible to substantially inhibition and steel structure The related maintenance cost of the coating of the coated articles such as object.

[embodiment]

Hereinafter, further specifically describing the present invention by embodiment.But the present invention is not only defined in these realities Apply example.It is explained, " part " and " % " in following examples refers respectively to " mass parts " and " quality % ".

Embodiment 1~18 and comparative example 1~6

Coating composition is manufactured in a manner of becoming the proportion of table 1, for atmospheric exposure test.

[table 2]

Table 1 is continuous

(note) 50% polyamines solution: methyl methacrylate/acrylic acid N-butyl/n-BMA/methyl-prop Olefin(e) acid dimethylamino ethyl ester=38/26/26/10 copolymer mineral spirits solution, amine equivalent 3100, weight average molecular weight 20000, solid component 50%,

(note) polyepoxide (B-1): " グ リ シ エ ー Le PP-300P ", trade name, Sanyo's chemical conversion society's system, polyoxy the third two Alcohol diglycidyl ether, epoxide equivalent 256, effective component 100%,

(note) organo-metallic compound (C-1): dibutyl tin dilaurate,

(note) organic siliconresin (D-1): " DC3074 ": trade name, contains methyl and phenyl at eastern beautiful DOW CORNING silicone society system The organic siliconresin containing alkoxysilyl, effective component 100%,

(note) organic siliconresin (D-2): " SR2402 ": trade name, Dong Li DOW CORNING society system, methyl methoxy radical siloxane, Effective component 100%,

(note) light stabilizer (E-1)；4- hydroxyl -1,2,2,6,6- pentamethvl,

(note) light stabilizer (E-2): " ア デ カ ス タ Block LA-52 ", trade name, ADEKA society system, four (1,2,2,6,6- Pentamethyl -4- bipyridyl) butane -1,2,3,4- tetrabasic ester, effective component 100%,

(note) ultraviolet absorbing agent (E-3): " Tinuvin400 ", trade name, BASF society system, hydroxyphenyltriazinuv are derivative Object, effective component 85%,

(note) ultraviolet absorbing agent (E-4): " Tinuvin405 ", trade name, BASF society system, hydroxyphenyltriazinuv are derivative Object, effective component 100%,

Light stabilizer

(note) light stabilizer (E-5): " Tinuvin292 ", trade name, BASF society system, bis- (1,2,2,6,6- pentamethyl -4- Piperidyl) mixture of decylate and methyl 1,2,2,6,6- pentamethyl -4- piperidyl decylate, effective component 100%,

(*) weatherability

On the steel plate for having carried out degreasing with acetone by dry film thickness become 25 μm in a manner of each Coating material composition of atomized spray painting Object makes it dry 168 hours at 23 DEG C, and thus production test coated plate, promotes weatherability using the weather-proof instrument testing machine evaluation of xenon.It presses According to following benchmark by the gloss of the film after 2000 hours with do not carry out promote atmospheric exposure test initial stage film Gloss be compared.

◎: gloss hardly reduces.

Zero: gloss although several reductions, but as product, there is no problem.

△: gloss slightly reduces.

×: gloss reduces significantly.

Claims (5)

1. the weatherability coating composition of normal temperature cure, to be formed containing host agent ingredient (I) and curing agent component (II) Multicomponent system composition, which is characterized in that

Host agent ingredient (I) contains polyamines (A), and polyamines (A) is that can polymerize with amino-containing polymerism unsaturated monomer and with this Property unsaturated monomer copolymerization other polymerism unsaturated monomers be that copolymer composition, other polymerism unsaturated monomers contain It is (methyl) of the alkyl for being 4 or more with carbon number of 50 mass % or more on the basis of other polymerism unsaturated monomer quality The amino-containing acrylic resin of acrylate,

Curing agent component (II) contains polyepoxide (B), in either host agent ingredient (I) and curing agent component (II) or two Contain organo-metallic compound (C), the organic siliconresin (D) containing hydrolyzable silyl group and with the ultraviolet of hydroxyl in side Light absorbers and/or light stabilizer (E) with hydroxyl.

2. weatherability coating composition according to claim 1, wherein

Host agent ingredient (I) includes the organic siliconresin containing hydrolyzable silyl group containing phenyl, and curing agent component (II) includes The organic siliconresin containing hydrolyzable silyl group without phenyl.

3. weatherability coating composition according to claim 1 or 2, wherein

Also contain silane coupling agent.

4. coating process, which is characterized in that

In coated surface coating weatherability coating composition according to any one of claims 1 to 3.

5. coated article is obtained by method as claimed in claim 4.