JP6497695B2 - Room temperature curable weatherable paint composition - Google Patents

Description

  The present invention relates to a weather-resistant coating composition that can be cured at room temperature.

  Anti-corrosion coating is applied to protect steel structures such as bridges, plants, and tanks from the corrosive environment of the outside world, and to provide a function of maintaining aesthetics. For such anticorrosive coating of steel structures with severe corrosive environments, for example, zinc rich paint, epoxy resin-based undercoating paint, epoxy resin-based intermediate coating, polyurethane resin-based and fluororesin-based topcoating are used. In general, at least three or more combined coating steps are performed. For this reason, it has been strongly demanded to shorten the coating process and to design a paint having both corrosion resistance and weather resistance from the viewpoints of safety and economy.

  In view of these demands, Patent Document 1 provides a coating composition that can form a coating film excellent in corrosion resistance and weather resistance at room temperature and in a single coating process in order to prevent corrosion and maintain the beauty of steel structures. A coating composition is disclosed that includes an acrylic resin, an epoxy resin having at least two epoxy groups in a molecule, an amine curing agent that can include aminosilane, and a curing catalyst. The document also describes that the coating composition described can contain an ultraviolet absorber and a light stabilizer.

  Patent Document 2 discloses a weather-resistant coating composition containing a hydrolyzable silyl group-containing fluororesin, a hydrolyzable silyl group-containing acrylic resin, and a hydrolyzable silyl group-containing silicone resin.

  Although the aesthetic appearance of the steel structure can be appropriately maintained by applying the coating composition described in Patent Document 1 or 2, in recent years, the development of a coating having longer weather resistance is expected. .

Japanese Patent Laid-Open No. 2004-051943 International Publication 2012-128223 Pamphlet

  An object of the present invention is to provide a weather-resistant coating composition suitable for forming a coating film having long-term weather resistance even under severe corrosive environment conditions even under conditions of room temperature drying.

  As a result of intensive studies on the above-described problems, the inventors of the present invention can significantly improve the weather resistance of the coating film by applying an ultraviolet absorber or a light stabilizer having a specific structure to a specific resin composition. And reached the present invention.

That is, the present invention
A multi-component composition comprising a main component (I) and a curing agent component (II), wherein the main component (I) includes a polyamine (A) and the curing agent component (II) is a polyepoxide (B). And the content of the silane coupling agent is more than 0 and 30 parts by mass or less based on 100 parts by mass of the hydrolyzable silicone resin (D) solid content, and the main component (I) And / or curing agent component (II), organometallic compound (C), hydrolyzable silyl group-containing silicone resin (D), and UV absorber having hydroxyl group and / or light stabilization having hydroxyl group The present invention relates to a room temperature curable weather-resistant coating composition for steel structures characterized by containing an agent (E).

  According to the weather-resistant coating composition of the present invention, a cured coating film excellent in long-term weather resistance can be formed even under severe corrosive environment conditions even under conditions of room temperature drying.

  Each component contained in the weather-resistant coating composition of the present invention will be described below in order.

<Polyamine (A)>
In the present invention, the polyamine is a compound having at least two amino groups in the molecule, preferably a (meth) acryloyl group-containing compound as a main component, an amino group-containing polymerizable unsaturated monomer and the polymerizable unsaturated monomer. An amino group-containing acrylic resin having another polymerizable unsaturated monomer copolymerizable with the monomer as a copolymerization component can be mentioned.

  The production method is not particularly limited, and it may be produced by a conventional method such as a radical polymerization method using an azo compound or a peroxide as an initiator, or a commercially available product may be used.

  Examples of the amino group-containing polymerizable unsaturated monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N- Examples include t-butylaminoethyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, and these may be used alone or in combination of two or more. .

  In the present invention, the use of a compound having a tertiary amino group as a polyamine is suitable from the viewpoint of long-term weather resistance of a coating film formed by drying at room temperature.

  Other polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl ( (Meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate ( Lauryl (meth) acrylate), tridecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate , T-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, alkyl such as tricyclodecanyl (meth) acrylate or alkyl such as cycloalkyl (meth) acrylate Alkyl (meth) acrylate having a group; aromatic ring-containing polymerizable unsaturated monomer such as benzyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Monoesterified product of (meth) acrylic acid such as acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and dihydric alcohol having 2 to 8 carbon atoms, (meth) acrylic acid Ε-caprolactone modified product of monoesterified product of C2-C8 dihydric alcohol, N-hydroxymethyl (meth) acrylamide, allyl alcohol, polyoxyethylene chain whose molecular terminal is a hydroxyl group (meth) Hydroxyl group-containing polymerizable unsaturated monomers such as acrylate; (meth) acrylic acid dimethylaminoethyl methyl chloride salt, (meth) acrylic acid dimethylaminoethyl benzyl chloride salt, (meth) acrylic acid diethylaminoethyl methyl chloride salt, (meth) acrylic Diethylaminoethyl benzyl chloride salt, aminopropyldimethylammonium methyl chloride (meth) acrylate, aminopropyldimethylammonium benzyl ammonium chloride (meth) acrylate, aminopropyldiethyl (meth) acrylate Ammonium methyl chloride salt, (meth) acrylic acid aminopropyl diethylammonium benzyl chloride salt, (meth) acrylic acid trimethylammonium methyl sulfate salt, (meth) acrylic acid triethylammonium methyl sulfate salt, (meth) acrylic acid aminopropyldimethylammonium methyl salt Quaternary ammonium group content such as sulfate salt, (meth) acrylic acid aminopropyldimethylammonium ethyl sulfate salt, (meth) acrylic acid trimethylaminoethyl p-toluenesulfonate salt, (meth) acrylic acid aminopropyldimethylethylammonium ethyl sulfate salt Polymerizable unsaturated monomer: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane Polymerizable unsaturated monomers having an alkoxysilyl group such as γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane; perfluorobutylethyl (meth) acrylate, perfluorooctylethyl Perfluoroalkyl (meth) acrylate such as (meth) acrylate; Polymerizable unsaturated monomer having a fluorinated alkyl group such as fluoroolefin; Polymerizable unsaturated monomer having a photopolymerizable functional group such as maleimide group; N-vinyl Vinyl compounds such as pyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate and vinyl acetate; carboxyl group-containing polymerizable unsaturated monomers such as (meth) acrylic acid, maleic acid, crotonic acid and β-carboxyethyl acrylate; Nitrogen-containing polymerizable unsaturated monomers such as acrylonitrile and (meth) acrylamide; glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 3,4-epoxycyclohexylethyl Epoxy group-containing polymerizable unsaturated monomers such as (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether; N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, methoxy Alkoxyalkyl (meth) acrylates such as ethyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate, polyester Alkoxy group-containing polymerizable unsaturated monomers such as polyalkylene glycol monoalkoxy (meth) acrylates such as tylene glycol monomethoxy (meth) acrylate; acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrene, 4 Examples thereof include carbonyl group-containing polymerizable unsaturated monomers such as vinyl alkyl ketones having ˜7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), and these may be used alone or in combination of two or more. Can be used.

  In the present invention, the amount of the amino group-containing polymerizable unsaturated monomer used is in the range of 0.2 to 25 parts by mass based on the total polymerizable unsaturated monomer used in the production of the polyamine (A). It is more preferable that it is in the range of 0.5 to 20 parts by mass.

  In the amino group-containing acrylic resin, the other polymerizable unsaturated monomer is a (meth) acrylate having an alkyl group having 4 or more carbon atoms based on the mass of the other polymerizable unsaturated monomer, preferably 50% by mass or more. It is suitable to use ~ 95% by mass. This is from the viewpoints of compatibility with a weak solvent and a hydrolyzable silyl group-containing silicone resin (D) described later, and coating film properties such as long-term weather resistance and water resistance of the coating film obtained by drying at room temperature.

  Examples of the (meth) acrylate having an alkyl group having 4 or more carbon atoms include n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n -Octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, "isostearyl acrylate" (trade name, manufactured by Osaka Organic Chemical Co., Ltd.), cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tridecyl (meth) ) A linear, branched or cyclic alkyl group-containing (meth) acrylate such as acrylate can be mentioned, and these can be used alone or in combination of two or more.

The weak solvent in this specification is a term often used in the field, and generally means a solvent having a weak dissolving power and is not strictly defined. In the classification of the organic solvent, the organic solvent can be a third type organic solvent.
Specific examples thereof include gasoline, kerosene, coal tar naphtha (including solvent naphtha), petroleum ether, petroleum naphtha, petroleum benzine, turpentine oil, mineral spirit (mineral thinner, petrolium spirit, white spirit and mineral turpentine. These may be used singly or in combination of two or more, and contain 5% by mass or less of the first type organic solvent and the second type organic solvent in the Industrial Safety and Health Act. It may be.

  The first type organic solvent is chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,2-dichloroethylene, 1,1,2,2-tetrachloroethane, trichloroethane, carbon disulfide, and The second type organic solvent is a so-called strong solvent, such as acetone, isobutyl alcohol, isopropyl alcohol, isopentyl alcohol, ethyl alcohol, ethylene glycol monoethyl ether, ethylene. Glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether, ethylene glycol monomethyl ether, ortho-dichlorobenzene, xylene, cresol, chlorobenzene, isobutyl acetate, isopropyl acetate, isopentyl acetate, ethyl acetate, acetic acid n-butyl, acetic acid-n-propyl, acetic acid-n-pentyl, methyl acetate, cyclohexanol, cyclohexanone, 1,4-dioxane, dichloromethane, N, N-dimethylformamide, styrene, tetrachloroethylene, tetrahydrofuran, 1,1,1 -Trichloroethane, toluene, n-hexane, 1-butanol, 2-butanol, methanol, methyl isobutyl ketone, methyl ethyl ketone, methyl cyclohexanol, methyl cyclohexanone, methyl-n-butyl ketone and the like can be mentioned.

  Commercially available products may be used as the weak solvent, and specific examples thereof include “Swazole 1000”, “Swazol 1500” (manufactured by Maruzen Petroleum Co., Ltd.), “Solvesso 150”, “Solvesso 200”, “ “HAWS”, “LAWS” (above, manufactured by Shell Japan), “Essonaphtha No. 6”, “Exor D30” (trade name, manufactured by ExxonMobil Chemical), “Pegasol 3040” (trade name, manufactured by ExxonMobil Chemical) ), “A Solvent”, “Clensol”, “Ipsol 100” (manufactured by Idemitsu Kosan Co., Ltd.), “Mineral Spirit A”, “High Alom 2S”, “High Alom 2S” (above, Shin Nippon Petrochemical Co., Ltd.), “Linearene 10”, “Linearene 12” (above, manufactured by Idemitsu Petrochemical Co., Ltd.), “Rikasolve 900”, “Rikaso” Bed 910B "," Rikasorubu 1000 "(or, New Japan Chemical Co., Ltd.) and the like can be illustrated, may be used alone or in combination.

  The weight average molecular weight of the amino group-containing acrylic resin described above is 1,000 to 150,000, preferably 5,000 to 50,000. It is preferable from the viewpoint of weak solvent solubility.

  In the present specification, the weight average molecular weight is a value obtained by converting a weight average molecular weight measured with a gel permeation chromatograph (“HLC8120GPC” manufactured by Tosoh Corporation) based on the weight average molecular weight of polystyrene. Columns are “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, “TSKgel G-2000H × L” (both manufactured by Tosoh Corporation, trade name). Four were used, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: RI.

<Polyepoxide (B)>
In the present invention, the polyepoxide (C) is a compound having at least two epoxy groups in the molecule. For example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A・ Epichlorohydrin type epoxy resin, bisphenol F / epichlorohydrin type epoxy resin, biphenol / epichlorohydrin type epoxy resin, glycerin / epichlorohydrin adduct polyglycidyl ether, resorcinol diglycidyl ether, polybutadiene di Glycidyl ether, hydroquinone diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexahydrophthal Acid diglycidyl ester, hydrogenated bisphenol A type diglycidyl ether, dihydroxyanthracene type epoxy resin, polypropylene glycol diglycidyl ether, diphenylsulfone diglycidyl ether, dihydroxybenzophenone diglycidyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol full Orange glycidyl ether, biscresol fluorenediglycidyl ether, bisphenoxyethanol fluorenediglycidyl ether, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidylaniline, N, N-diglycidyltoluidine Etc.

<Organic metal compound (C)>
Specific examples of the organometallic compound (C) include dioctyltin dilaurate, dioctyltin dineodecanoate, dioctyltin bis (2-ethylhexyl maleate), dioctyltin oxide or dibutyltin oxide and silicate. Dibutyltin dioctanoate, dibutyltin dilaurate, dibutyltin distearate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin bis (ethyl maleate), dibutyltin bis (butyl maleate) , Dibutyltin bis (2-ethylhexyl maleate), dibutyltin bis (oleyl maleate), stannous octoate, tin stearate, di-n-butyltin laurate oxide, dibutyltin bisisononyl-3-mercaptopropione -Dioctyltin bisisononyl-3- Lukaptopropionate, octylbutyltin bisisononyl-3-mercaptopropionate, dibutyltin bisisooctylthiogluconate, dioctyltin bisisooctylthiogluconate, octylbutyltin bisisooctylthioglu Organotin compounds such as cholate, tin dioctylate and tin distearate; titanium alkoxide such as titanium isopropoxide and titanium butoxide, titanium acetylacetonate, titanium-2-ethylhexanate, titanium diisopropoxybis (acetylacetate) Organic titanium compounds such as iron (II) or (III), organic iron compounds such as acetate, acetylacetonate and 2-ethylhexanate; aluminum alkoxides such as aluminum isopropoxide and aluminum butoxide, and ethyl acetate Organoaluminum compounds such as cetoacetonate aluminum diisopropoxide, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum monoacetylacetonate bis (ethylacetoacetate), alkylacetylacetonate; Organic manganese compounds such as manganese (II) acetate, manganese (II) acetyl acetate, manganese (II) -2-ethylhexanate; cobalt (II) acetate, cobalt (II) acetyl acetate, cobalt (II) benzoylacetonate, Organic cobalt compounds such as cobalt (II) -2-ethylhexanate and cobalt naphthanate; zirconium (IV) propoxide, zirconium (IV) acetate, zirconium (IV) acetyl acetate, Organozirconium compounds such as ruthenium (IV) -2-ethylhexanate; nickel (II) propoxide, nickel (II) stearate, nickel (II) acetate, nickel (II) acetyl acetate, nickel (II) -2- Organic nickel compounds such as ethyl hexanate; organic bismuth compounds such as bismuth (III) neodecanate, bismuth (III) acetate, bismuth (II) -2-ethylhexanate; copper (II) acetyl acetate, copper (II) butyl phthalate Organic copper compounds such as: zinc (II) acetate, zinc (II) acetyl acetate, organic zinc compounds such as zinc (II) -2-ethylhexanate; barium (II) acetate, barium (II) acetyl acetate, barium ( II) Organic barium compounds such as 2-ethylhexanate These may be used alone or in combination of two or more.

<Hydrolyzable silyl group-containing silicone resin (D)>
The hydrolyzable silyl group-containing silicone resin (D) is a resin containing a hydrolyzable silyl group and having a polysiloxane skeleton in the resin.

  In this specification, the hydrolyzable silyl group is a group that forms a silanol group by hydrolysis, and the silanol group undergoes dehydration condensation to form a siloxane bond, and is a monovalent hydrolyzable that is directly bonded to a silicon atom. Silyl having both or one of atoms (atom that generates silanol group by reacting with water) and monovalent hydrolyzable group (group that generates silanol group by reacting with water) directly bonded to silicon atom There is no particular limitation as long as it is a group. Specific examples of the hydrolyzable silyl group include, for example, halogenated silyl groups such as chlorosilyl group and bromosilyl group, alkoxysilyl groups such as methoxysilyl group, ethoxysilyl group, propoxysilyl group, butoxysilyl group, and the like. Any combination of these is mentioned.

The hydrolyzable silyl group-containing silicone resin (D) is, for example, the following formula (1):
SiX _n Y _4-n formula (1)
(Wherein X represents a hydroxyl group or an alkoxy group, Y represents a monovalent hydrocarbon group which may have a substituent, and n represents an integer of 1 to 4)
A resin formed by chemical bonding of two or more of the same or different organosilanes, for example, an oligomer.

  In the hydrolyzable silyl group-containing silicone resin (D), the organosilane represented by the formula (1) can be bonded linearly or branched. The hydrolyzable silyl group-containing silicone resin (D) preferably has a hydrocarbon group that is directly bonded to a silicon atom.

  Examples of the organosilane represented by the formula (1) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ- Aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) ) Ethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxy Sisilane, β-cyanoethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane , Tetrabutoxysilane, dimethyldichlorosilane, diphenyldichlorosilane, methylphenyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, γ-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, p-aminophenyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, aminoethylaminomethylphenethyltrimethoxysilane, 3-glyci Doxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, N- (6 -Aminohexyl) aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrichlorosilane, (p-chloromethyl) phenyltrimethoxysilane, 4-chlorophenyltrimethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, styrylethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltris (2-methoxy Ethoxy) silane, trifluoropropyl trimethoxy silane, as well as any combination thereof.

  The hydrolyzable silyl group-containing silicone resin (D) has a methyl group and / or a phenyl group directly bonded to a silicon atom from the viewpoint of compatibility with the polyamine (A) and the weather resistance of the formed coating film. It is preferable.

  In particular, from the viewpoint of long-term weather resistance of the coating film formed from the composition of the present invention, the main component (I) contains a phenyl group-containing hydrolyzable silyl group-containing silicone resin, and the curing agent component (II) has a non-phenyl group. The aspect containing the containing hydrolyzable silyl group containing silicone resin is good.

  Examples of commercially available hydrolyzable silyl group-containing silicone resins (D) include “SR2406”, “SR2410”, “SR2420”, “SR2416”, “SR2402”, “AY42-161”, and “DC-3074”. And “DC-3037” (manufactured by Toray Dow Corning Silicone Co., Ltd.), “FZ-3704” and “FZ-3511” (manufactured by Nihon Unicar), “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 "(manufactured by Shin-Etsu Chemical Co., Ltd.).

<Ultraviolet absorber having a hydroxyl group and / or light stabilizer having a hydroxyl group (E)>
In the present invention, the ultraviolet absorber having a hydroxyl group is not particularly limited as long as it is an ultraviolet absorber having a hydroxyl group in one molecule, and examples thereof include a hydroxyphenylbenzotriazole derivative and a hydroxyphenyltriazine derivative.

  Specific examples of the ultraviolet absorber having a hydroxyl group include 2- (2′-hydroxy-3 ′, 5′-dipentylphenyl) benzotriazole and 2- (2,4-dihydroxyphenyl) -4,6-bis. Reaction product of (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester, propionic acid, 2- [4- [4,6-bis ([1, 1'-biphenyl] -4-yl) -1,3,5-triazin-2-yl) -3-hydroxypenoxy]-, isooctyl ester, 2,4-bis [2-hydroxy-4-butoxyphenyl ] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2-hydroxy-4-n- Octoxy Nzophenone, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole, salicylic acid, 4-t-butylphenyl ester, 2- (2-hydroxy-3,5-di-t-amylphenyl) -A benzotriazole etc. are mentioned.

  The light stabilizer having a hydroxyl group is not particularly limited as long as it is a light stabilizer having a hydroxyl group in one molecule, and examples thereof include piperidine derivatives having a hydroxyl group in the molecule.

  Specific examples of the ultraviolet absorber having a hydroxyl group include 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 2-[[3,5-bis (1,1-dimethylethyl)- 4-Hydroxyphenyl] methyl] -2-butylpropanedioic acid bis [1,2,2,6,6-pentamethyl-4-piperidinyl], dimethyl succinate and 4-hydroxy-2,2,6,6-tetra Reaction product of methyl-1-piperidineethanol, 2-aminoethanol, cyclohexane and peroxide N-butyl-2,2,6,6-tetramethyl-4-piperidineamino-2,4,6-trichloro-1, A reaction product of 3,5-triazine is exemplified.

<Weather-resistant paint composition>
The weather-resistant coating composition of the present invention comprises a polyamine (A), a polyepoxide (B), an organometallic compound (C), a hydrolyzable silyl group-containing silicone resin (D), a hydroxyl group-containing ultraviolet absorber and / or a hydroxyl group. Comprising the light stabilizer (E), and the proportion of each component used is as follows:
Based on 100 parts by mass of hydrolyzable silyl group-containing silicone resin (D) solid content,
The polyamine (A) has a solid content of 25 to 250 parts by mass, preferably 50 to 100 parts by mass, and the polyepoxide (B) has a solids content of 1 to 50 parts by mass, preferably 5 to 20 parts by mass,
The organometallic compound (C) is 0.1 to 25 parts by mass, preferably 3 to 20 parts by mass of the active ingredient, and the UV absorber having a hydroxyl group and / or the light stabilizer (E) having a hydroxyl group is the active ingredient. In the range of 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass, it is desirable from the viewpoint of the long-term weather resistance of the coating film obtained under normal temperature drying conditions.

  In the present invention, the polyamine (A) is contained in the main agent component (I) and the polyepoxide (B) is contained in the curing agent component, and both are separately stored in the storage stage, but the other components are the main agent components. Either (I) or the curing agent component (I) can be selected as appropriate, or the component is divided and included in both the main component (I) and the curing agent component (I). It is also possible.

  In addition, the weather-resistant coating composition of the present invention includes a silane coupling agent; a pigment; a modifying resin such as an acrylic resin, a fluororesin, an alkyd resin, and a urethane resin; an organic solvent; a reactive diluent; Additives for paints such as an inhibitor, a dispersant, a wetting agent, and a dehydrating agent can be included.

  Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β. (Aminoethyl) amino group-containing silane coupling agents such as γ-aminopropylmethyldimethoxysilane; glycidyl group-containing silane coupling agents such as γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropylmethyldimethoxysilane; Mercapto group-containing silane coupling agents such as γ-mercaptopropyltrimethoxysilane; Vinyl group-containing silane coupling agents such as vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (methoxyethoxy) silane; γ- (meth) acryloyloxy The Pills trimethoxysilane, .gamma. (meth) acryloyloxy propyl triethoxysilane, .gamma. (meth) acryloyloxy propyl, such as dimethoxymethyl silane (meth) acryloyl group-containing silane coupling agent and the like.

  When the weather resistant coating composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is 30 masses based on 100 mass parts of hydrolyzable silyl group-containing silicone resin (D) solid content mass. Or less, preferably within the range of 5 to 20 parts by mass. This is from the viewpoint of improving adhesion.

  The weather-resistant coating composition of the present invention is one in which the main agent component (I) comprises a polyamine and the curing agent component (II) comprises a polyepoxide, and the use ratio of the main agent component (I) and the curing agent component (II). Is suitable from the viewpoint of long-term weather resistance and curability of the coating film to be formed such that the epoxy group is adjusted to 0.5 to 5 mol, preferably 1 to 3 mol, relative to 1 mol of the amino group. ing.

  The weather-resistant coating composition of the present invention is a room temperature curing type, and the formed cured coating film can exhibit excellent performance, but may be a forced drying curing type or a heat curing type.

  Although it does not restrict | limit especially as a use of the weather-resistant coating material composition of this invention, It is suitable for the top coating use of heavy anticorrosion coating of steel structures, such as a bridge, a power transmission tower, a plant, and a tank.

<Paint>
As an object to be coated with the weather-resistant coating composition of the present invention, a base material, for example, steel plate, galvanized, stainless steel, aluminum, etc., which has been subjected to a ground treatment as desired, has an alkaline base material such as concrete, mortar. , Slate, slate roof tiles, ceramic building materials, plastics, etc., and those having an old coating film formed thereon.

  The weather-resistant coating composition can be applied by known means such as spray coating, roller coating, brush coating, and flow coating.

  Moreover, before forming a weather-resistant coating film with a weather-resistant coating composition, an anti-corrosion coating film may be formed by applying an undercoating paint or an intermediate coating composition to an object to be coated.

  Examples of the undercoat paint include water-based or solvent-based undercoat paints known in the art.

  Examples of the above-mentioned undercoat paints include epoxy resin paints, modified epoxy resin paints, epoxy resin glass flake paints, epoxy resin coating materials, ultra-thick film epoxy resin paints, epoxy resin zinc rich paints, inorganic zinc rich paints, and chlorinated rubber resins. Paints, phthalic acid resin paints, epoxy ester resin paints, and the like.

  Examples of the intermediate coating include water-based or solvent-based paints such as epoxy resin paints, polyurethane paints, epoxy resin MIO paints, phenol resin MIO paints, chlorinated rubber resin paints, and phthalic acid resin paints. .

  The weather-resistant coating composition of the present invention can be easily cured even under conditions of room temperature drying, and forms a coating film having excellent weather resistance over a long period of time even in a severe environment where anticorrosion coating is applied. Can do.

  Furthermore, since the weather-resistant coating composition of the present invention can form a weather-resistant coating film having long-term weather resistance, the period until repainting can be lengthened, and the coating process can be omitted. Therefore, the maintenance cost related to the coating of the object such as a steel structure can be greatly reduced.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples. In the following examples, “part” and “%” mean “part by mass” and “% by mass”, respectively.

Examples 1-18 and Comparative Examples 1-6
The coating composition was manufactured so that it might become a mixture ratio of Table 1, and it used for the weather resistance test.

(Note) 50% polyamine solution: methyl methacrylate / n-butyl acrylate / n-butyl methacrylate / dimethylaminoethyl methacrylate = 38/26/26/10 copolymer mineral spirit solution, amine equivalent 3100, weight average molecular weight 20000, 50% solids,
(Note) Polyepoxide (B-1): “Glicier PP-300P”, trade name, manufactured by Sanyo Kasei Co., Ltd., polyoxypropylene glycol diglycidyl ether, epoxy equivalent 256, active ingredient 100%,
(Note) Organometallic compound (C-1): dibutyltin dilaurate,
(Note) Silicone resin (D-1): “DC3074”: trade name, manufactured by Toray Dow Corning Silicone, alkoxysilyl group-containing silicone resin containing methyl group and phenyl group, active ingredient 100%,
(Note) Silicone resin (D-2): “SR2402”: trade name, manufactured by Toray Dow Corning, methylmethoxysiloxane, active ingredient 100%,
(Note) Light stabilizer (E-1); 4-hydroxy-1,2,2,6,6-pentamethylpiperidine,
(Note) Light stabilizer (E-2): “ADEKA STAB LA-52”, trade name, manufactured by ADEKA Corporation, tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl) butane-1,2 , 3,4-tetracarboxylate, 100% active ingredient,
(Note) Ultraviolet absorber (E-3): “Tinvin 400”, trade name, manufactured by BASF, hydroxyphenyltriazine derivative, active ingredient 85%,
(Note) Ultraviolet absorber (E-4): “Tinuvin 405”, trade name, manufactured by BASF, hydroxyphenyltriazine derivative, active ingredient 100%,
Light stabilizer (Note) Light stabilizer (E-5): “Tinvin 292”, trade name, manufactured by BASF, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1 , 2,2,6,6-pentamethyl-4-piperidyl sebacate, 100% active ingredient,
(*) Weather resistance Each coating composition was spray-coated on a steel sheet degreased with acetone to a dry film thickness of 25 μm, and dried at 23 ° C. for 168 hours to prepare a test coated plate. The accelerated weather resistance was evaluated using a meter tester. The gloss of the coating after 2000 hours was compared with the gloss of the initial coating without the accelerated weather resistance test according to the following criteria.
A: Gloss was hardly lowered,
○: The gloss is slightly reduced, but there is no problem as a product.
Δ: Gloss slightly decreased,
X: The gloss was remarkably lowered.

Claims (4)

A multi-component composition comprising a main component (I) and a curing agent component (II), wherein the main component (I) includes a polyamine (A) and the curing agent component (II) is a polyepoxide (B). And the content of the silane coupling agent is more than 0 and 30 parts by mass or less based on 100 parts by mass of the hydrolyzable silicone resin (D) solid content, and the main component (I) And / or curing agent component (II), organometallic compound (C), hydrolyzable silyl group-containing silicone resin (D), and UV absorber having hydroxyl group and / or light stabilization having hydroxyl group A room-temperature curable weather-resistant coating composition for steel structures, which contains an agent (E). The weather resistance according to claim 1, wherein the main component (I) includes a phenyl group-containing hydrolyzable silyl group-containing silicone resin, and the curing agent component (II) includes a phenyl group-free hydrolyzable silyl group-containing silicone resin. Paint composition. A coating method comprising coating the weather-resistant coating composition according to claim 1 or 2 onto a surface to be coated of a steel structure . A coated article obtained by the method according to claim 3.