JP2014058613A - Weather-resistant coating composition, and method for forming coated article having weather-resistant coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a weather-resistant coating composition excellent in thick-film coating property, from which a coating film having excellent long-term weather resistance can be formed.SOLUTION: The weather-resistant coating composition is a multi-component composition comprising a main agent (I) and a curing agent (II). The main agent (I) includes an acrylic resin (A) having both of fluorine and a hydrolyzable silyl group, and a hydrolyzable silyl group-containing silicone resin (B). The curing agent (II) includes a catalyst that promotes polycondensation of a hydrolyzable silyl group. The resin (A) includes, on the basis of the whole monomer units, a fluorine-containing polymerizable unsaturated compound (a) by 1 to 80 mass%, a hydrolyzable silyl group-containing polymerizable unsaturated compound (a) by 1 to 50 mass%, and a (meth)acryloyl group-containing compound (a) by 1 to 90 mass%.

Description

  The present invention relates to a weather-resistant coating composition and a method for forming a coated article having a weather-resistant coating film.

  Anti-corrosion coating is applied to protect steel structures such as bridges, plants and tanks, metal products such as steel plates and steel pipes from the corrosive environment of the outside world, and to provide a function of maintaining aesthetics. For anticorrosion coating of steel structures, for example, at least three or more coating processes combining zinc rich paint, epoxy resin-based undercoating, intermediate coating, and polyurethane resin-based or fluororesin-based overcoating are performed. It is common that In particular, when painting on existing steel structures, work is done at high places, so labor costs and scaffolding costs often account for more than 80% of the painting cost, and the number of paintings should be minimized. Shortening the painting process has been strongly demanded from the viewpoints of safety and economy.

  For example, 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 aesthetics of a steel structure. To this end, 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 cured coating film obtained by the coating composition described in Patent Document 1 is formed by a single coating finish, and has excellent corrosion resistance and weather resistance. You can maintain the beauty of things.

  On the other hand, in recent years, even in heavy anticorrosion coatings, there are increasing cases in which fluororesin-based paints are used as top coats in order to reduce long-term maintenance costs.

  For example, Patent Document 2 discloses a hydrolyzable silyl compound that aims to provide an anticorrosion method for a weather-resistant steel with a reduced number of processes that retains rust resistance and weather resistance for a long period of time and enables arbitrary coloring. A colored organic-inorganic composite topcoat containing a fluororesin having a group, organosilane or a partially hydrolyzed condensate thereof, a pollution-free rust preventive pigment, and a colorant, and a corrosion-resistant method for weathering steel using the topcoat Have been described.

  By the way, in recent years, there has been a strong demand for environmental harmony and the health of residents, and as a safety issue, paints with less danger are demanded in consideration of the Fire Service Law, Industrial Safety and Health Law, PL Law, etc. ing.

  In recent years, the number of newly installed structures has decreased, and the market for repainting existing structures has expanded, and there is a need for paints that are less prone to coating defects during repainting, for example, blemishes. Therefore, development of paints containing a solvent having a good coating environment and excellent recognizability and not too high solubility, that is, so-called weak solvent paints, has been actively conducted.

  For example, Patent Document 3 includes a predetermined hydroxyl group-containing fluororesin, polyisocyanate, weak solvent, and a predetermined hydroxyl group-containing acrylic resin, and the fluorine atom content in the coating resin solid content is 2 to 25% by mass and the hydroxyl value is A weak solvent type fluororesin-based coating composition that is 20 to 60 mg KOH / g is disclosed.

JP 2004-51943 A JP 2003-170529 A JP 2006-152080 A

  However, the coating compositions described in Patent Documents 1 to 3 have insufficient thick film paintability that can affect long-term weather resistance of steel structures and the like.

  Accordingly, an object of the present invention is to provide a weather-resistant coating composition that can form a coating film that is excellent in thick film paintability and excellent in long-term weather resistance.

  As a result of intensive studies, the present inventors have found that an acrylic resin (A) containing both fluorine and a hydrolyzable silyl group, and a curing comprising a main agent (I) containing a hydrolyzable silyl group-containing silicone resin (B) and a catalyst. A weather-resistant coating composition composed of the agent (II) was found.

  The weather-resistant coating composition of the present invention has good storage stability of the main agent (I) and the curing agent (II), and the composition obtained by mixing both is excellent in curability and thick film coatability. And the coating film excellent in long-term weather resistance can be formed.

  The weather-resistant coating composition of the present invention comprises an acrylic resin (A) containing both fluorine and a hydrolyzable silyl group, a main agent (I) containing a hydrolyzable silyl group-containing silicone resin (B), and a hydrolyzable silyl group. It is comprised from the hardening | curing agent (II) containing the catalyst which accelerates | stimulates polycondensation.

<< Acrylic resin containing both fluorine and hydrolyzable silyl group (A) >>
The acrylic resin (A) containing both fluorine and a hydrolyzable silyl group is an acrylic copolymer having fluorine, a hydrolyzable silyl group, and a group derived from a (meth) acryloyl group in the resin. is there.

  In the present specification, the “hydrolyzable silyl group” is a group that forms a silanol group by hydrolysis, which undergoes dehydration condensation to form a siloxane bond, and is a monovalent bond directly bonded to a silicon atom. Either or both of hydrolyzable atoms (atoms that generate silanol groups by reacting with water) and monovalent hydrolyzable groups directly bonded to silicon atoms (groups that generate silanol groups by reacting with water) As long as it is a silyl group having, there is no particular limitation. 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.

  In the present specification, “(meth) acryloyl” group means acryloyl group and methacryloyl group, or acryloyl group or methacryloyl group, and “(meth) acrylic acid” means acrylic acid and methacrylic acid, or acrylic. It means acid or methacrylic acid.

Examples of the acrylic resin (A) include those other than the fluorine-containing polymerizable unsaturated compound (a ₁ ), the hydrolyzable silyl group-containing polymerizable unsaturated compound (a ₂ ), and (a ₁ ) and (a ₂ ). (meth) include those containing a monomer unit of an acryloyl group-containing compound (a _3).

Examples of the fluorine-containing polymerizable unsaturated compound (a ₁ ) include hexafluoroisopropyl (meth) acrylate, perfluorooctylmethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate; trifluoromethyl (meth) acrylate, 2, 2,2-trifluoroethyl (meth) acrylate, 1,1,1,3,3,3-hexafluoro-2-propyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, perfluoropropylmethyl (meth) ) Acrylate, perfluorobutylmethyl (meth) acrylate, perfluoropentylmethyl (meth) acrylate, perfluorohexylmethyl (meth) acrylate, perfluoroheptylmethyl (meth) acrylate, perfluorooctylmethyl (Meth) acrylate, perfluorononylmethyl (meth) acrylate, perfluorodecylmethyl (meth) acrylate, perfluoroundecylmethyl (meth) acrylate, perfluorododecylmethyl (methyl) acrylate, perfluorotridecylmethyl (meth) Acrylate, perfluorotetradecylmethyl (meth) acrylate, polyperfluorotetradecylmethyl (meth) acrylate, 2- (trifluoromethyl) ethyl (meth) acrylate, 2- (perfluoroethyl) ethyl (meth) acrylate, 2 -(Perfluoropropyl) ethyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluoropentyl) ethyl (meth) acrylate, 2- (perfluorohe Xyl) ethyl (meth) acrylate, 2- (perfluoroheptyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorononyl) ethyl (meth) acrylate, (perfluoro Fluoroalkyl (meth) acrylates such as fluorine-containing alkyl (meth) acrylates such as tridecyl) ethyl (meth) acrylate and 2- (perfluorotetradecyl) ethyl (meth) acrylate; fluoroalkyl trifluorovinyl ether, perfluoroalkyl Fluorovinyl ethers such as trifluorovinyl ether: as well as any combination thereof.

Examples of the hydrolyzable silyl group-containing polymerizable unsaturated compound (a ₂ ) include vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltris ( Vinylalkoxysilanes such as methoxyethoxy) silane; Vinylchlorosilanes such as vinyltrichlorosilane, divinyldichlorosilane, vinylmethyldichlorosilane; γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane , Β- (meth) acryloxyethyltrimethoxysilane, β- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxy (Meth) acryloxyalkoxy such as propylmethyldiethoxysilane, γ- (meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxybutylphenyldimethoxysilane, γ- (meth) acryloxypropyldiethylmethoxysilane Silane and the like; and any combination thereof.

  In the present specification, the (meth) acryloxy group means an acryloxy group and a methacryloxy group, or an acryloxy group or a methacryloxy group.

As the (meth) acryloyl group-containing compound (a ₃ ), methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 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, cyclohexyl (meth) acrylate, isobornyl (meth) Linear, branched or cyclic alkyl group-containing (meth) acrylates such as acrylate and tridecyl (meth) acrylate; N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and methoxy Alkoxyalkyl (meth) acrylates such as ethyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxyethyl (meth) acrylate, and ethoxypropyl (meth) acrylate; polyalkylene glycol monoalkoxy such as polyethylene glycol monomethoxy (meth) acrylate Alkoxy group-containing (meth) acrylates such as (meth) acrylate; Epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate; acrylic acid, methacrylic acid, hydroxyalkyl ( Carboxyl group-containing (meth) acrylates such as half esterified products of (meth) acrylates and acid anhydrides; sulfos such as 2-acrylamido-2-methylpropanesulfonic acid Acid group-containing (meth) acrylate; Acid phosphooxyethyl (meth) acrylate, phosphoric acid group-containing (meth) acrylate such as mono-[(2-hydroxyethyl) (meth) acrylic acid] ester; N, N -Dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, Nt-butylaminoethyl (meth) acrylate, N, N-dimethylamino Amino group-containing (meth) acrylates such as butyl (meth) acrylate; (meth) acryloyloxyethyltrimethylammonium chloride, quaternary ammonium base-containing (meth) acrylates such as dimethylaminoethylmethyl chloride methacrylate; 2-hydroxyethyl ( Meta) Relate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, and the above hydroxyalkyl (meth) acrylate such as ε-caprolactone Examples thereof include a compound obtained by ring-opening polymerization of a lactone, a hydroxyl group-containing (meth) acrylate such as a monoesterified product of a polyhydric alcohol such as polyethylene glycol mono (meth) acrylate and acrylic acid or methacrylic acid; and combinations thereof.

In another embodiment of the weather-resistant coating composition of the present invention, the acrylic resin (A) containing both fluorine and a hydrolyzable silyl group comprises a fluorine-containing polymerizable unsaturated compound (a ₁ ), hydrolyzable silyl It includes monomer units of a group-containing polymerizable unsaturated compound (a ₂ ), a (meth) acryloyl group-containing compound (a ₃ ), and other polymerizable unsaturated compounds (a ₄ ).

Other polymerizable unsaturated compounds (a ₄ ) include, for example, aromatic vinyl compounds such as styrene and vinyltoluene; cyclohexyl vinyl ether, nonyl vinyl ether, 2-ethylhexyl vinyl ether, hexyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, t -Vinyl ethers such as butyl vinyl ether; Allyl ethers such as ethyl allyl ether and hexyl allyl ether; Carboxylic acid vinyl esters such as "Beova-9" and "Beova-10" (both manufactured by Shell Chemical Co., Ltd.); Examples include olefins such as propylene and isobutylene.

  In the present invention, the acrylic resin (A) containing both fluorine and a hydrolyzable silyl group does not contain a fluorine-containing olefin unit based on the solid content mass of the resin (A).

  Examples of the fluorine-containing olefin include vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, bromotrifluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, and hexafluoropropylene.

  The acrylic resin (A) containing both fluorine and a hydrolyzable silyl group can be produced by any known method, for example, a radical polymerization method using an azo compound, a peroxide or the like as an initiator, It is also commercially available.

Acrylic resin (A) is a monomer unit of fluorine-containing polymerizable unsaturated compound (a ₁ ), hydrolyzable silyl group-containing polymerizable unsaturated compound (a ₂ ), and (meth) acryloyl group-containing compound (a ₃ ). In the embodiment including the acrylic resin (A) based on the total monomer units,
About 1 to 80% by mass, preferably about 2 to 60% by mass of the fluorine-containing polymerizable unsaturated compound (a ₁ ) as a monomer unit, and the hydrolyzable silyl group-containing polymerizable unsaturated compound (a ₂ ) About 1 to 50% by mass as a monomer unit, preferably about 3 to 35% by mass, and about 1 to 90% by mass, preferably about 5 to 80% by mass, of (meth) acryloyl group-containing compound (a ₃ ) as a monomer unit. Including. This is from the viewpoint of the storage stability of the weather-resistant coating composition, the curability of the formed coating film and the physical properties of the coating film.

  The acrylic resin (A) containing both fluorine and a hydrolyzable silyl group preferably has solubility in a weak solvent.

  “Weak solvent” is a well-known term in the art, and generally means a solvent having a weak dissolving power. The weak solvents include those listed as the third type organic solvents in the classification of organic solvents according to the Industrial Safety and Health Act. Examples of Class 3 organic solvents 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 Are included).

  The weak solvent is a commercially available product. For example, “Swazole 1000” and “Swazole 1500” (manufactured by Maruzen Petroleum Co., Ltd.), “Solvesso 150”, “Solvesso 200”, “ “HAWS” and “LAWS” (manufactured by Shell Japan Co., Ltd.), “Essonaphtha No. 6” and “Exor D30” (trade name, manufactured by ExxonMobil Chemical Co., Ltd.), “Pegasol 3040” (trade name, manufactured by ExxonMobil Chemical Co., Ltd.) ), “A Solvent”, “Clensol” and “Ipsol 100” (manufactured by Idemitsu Kosan Co., Ltd.), “Mineral Spirit A”, “High Alom 2S” and “High Alom 2S” (above, Shin Nippon Petrochemical Co., Ltd.), “Linearene 10” and “Linearene 12” (made by Idemitsu Petrochemical Co., Ltd.), “Ricasolve 900” "Rikasorubu 910B" and "Rikasorubu 1000" (or more, New Japan Chemical Co., Ltd.), and the like.

  The acrylic resin (A) containing both fluorine and hydrolyzable silyl groups can be produced by polymerizing the above monomers in the presence of the weak solvent and / or other organic solvents. it can.

  Examples of the other organic solvents include known solvents, for example, hydrocarbon solvents such as n-butane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane, cyclobutane; and aromatic solvents such as toluene and xylene. Solvents; ketone solvents such as methyl isobutyl ketone; ether solvents such as n-butyl ether, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol; ethyl acetate, acetic acid Esters such as n-butyl, isobutyl acetate, ethylene glycol monomethyl ether acetate, butyl carbitol acetate; methyl ethyl ketone, methyl isobutyl ketone, diisobutyl keto Ketone solvents and the like; ethanol, isopropanol, n- butanol, sec- butanol, alcohol solvents such as isobutanol; and combinations thereof.

  The weight average molecular weight of the non-volatile component of the acrylic resin (A) containing both fluorine and hydrolyzable silyl groups is not particularly limited, but from the viewpoint of curability, weather resistance and thick film coatability, It is in the range of 1,000 to about 100,000, and preferably in the range of about 2,000 to about 80,000.

  In this specification, the weight average molecular weight is the retention time (retention capacity) of a standard polystyrene having a known molecular weight measured under the same conditions as the retention time (retention capacity) measured using a gel permeation chromatograph (GPC). Is a value obtained by converting to a molecular weight of polystyrene.

  The weight average molecular weight is, for example, using “HLC8120GPC” (trade name, manufactured by Tosoh Corporation) as a gel permeation chromatograph apparatus, and “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel” as columns. G-2500HXL ”and“ TSKgel G-2000HXL ”(trade names, both manufactured by Tosoh Corporation) were used, a differential refractometer was used as a detector, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C. The flow rate can be measured under the condition of 1 mL / min.

≪Hydrolysable silyl group-containing silicone resin (B) ≫
The hydrolyzable silyl group-containing silicone resin (B) is a component that is blended from the viewpoint of thick film paintability of the weather-resistant coating composition, and contains a hydrolyzable silyl group and a polysiloxane skeleton in the resin. It is resin which has.

The hydrolyzable silyl group-containing silicone resin (B) 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 3)
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 (B), the organosilane represented by the formula (1) can be bonded linearly or branched. The hydrolyzable silyl group-containing silicone resin (B) 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-acinopropyltriethoxysilane, 4-acinobutyltriethoxysilane, 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 (B) is compatible with the acrylic resin (A) containing both fluorine and hydrolyzable silyl groups, thick film paintability of the resulting weather-resistant coating composition, and formed. From the viewpoint of the bending resistance of the coating film, it preferably has a methyl group and / or a phenyl group directly bonded to a silicon atom.

  The weight average molecular weight of the non-volatile component of the hydrolyzable silyl group-containing silicone resin (B) is not particularly limited, but is compatible with fluorine and the hydrolyzable silyl group-containing acrylic resin (A) and weather resistance. From the viewpoint of high solidification of the coating material, thick film paintability, and bending resistance of the formed coating film, it is generally in the range of about 400 to about 30,000, preferably about 400 to about 20,000.

  Examples of commercially available hydrolyzable silyl group-containing silicone resins (B) 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.).

≪Hydrolysable silyl group-containing acrylic resin (C) ≫
In one embodiment of the weather resistant coating composition of the present invention, the weather resistant coating composition further includes a hydrolyzable silyl group-containing acrylic resin (C).

  In the present invention, the hydrolyzable silyl group-containing acrylic resin (C) is an acrylic copolymer having a hydrolyzable silyl group and a group derived from a (meth) acryloyl group in the resin.

  The hydrolyzable silyl group-containing acrylic resin (C) contains both fluorine and hydrolyzable silyl groups in that it does not contain fluorine, based on the solid content mass of the hydrolyzable silyl group-containing acrylic resin (C). It differs from the acrylic resin (A) contained.

Examples of the hydrolyzable silyl group-containing acrylic resin (C) include a hydrolyzable silyl group-containing polymerizable unsaturated compound (c ₁ ) and a (meth) acryloyl group-containing compound (c ₂ ) other than (c ₁ ). And those containing a monomer unit.

As the hydrolyzable silyl group-containing polymerizable unsaturated compound (c ₁ ), the hydrolyzable silyl group-containing polymerizable unsaturated compound (a) in the “acrylic resin (A) containing both fluorine and hydrolyzable silyl group” (a) ₂ ).

As the (meth) acryloyl group-containing compound (c ₂ ), the same compounds as the (meth) acryloyl group-containing compound (a ₃ ) in “Acrylic resin (A) having both fluorine and hydrolyzable silyl groups” and these compounds Any combination is mentioned.

In the embodiment in which the hydrolyzable silyl group-containing acrylic resin (C) includes monomer units of the hydrolyzable silyl group-containing polymerizable unsaturated compound (b ₁ ) and the (meth) acryloyl group-containing compound (b ₂ ), The hydrolyzable silyl group-containing acrylic resin (C) is preferably from about 1 to about 1 by using the hydrolyzable silyl group-containing polymerizable unsaturated compound (c ₁ ) as a monomer unit based on the total monomer units. More preferably from about 2 to about 30% by weight, more preferably from about 3 to about 20% by weight, and preferably from about 50 to about 99% by weight of the (meth) acryloyl group-containing compound (c ₂ ) as a monomer unit. %, More preferably about 70 to about 98% by mass, and still more preferably about 80 to about 97% by mass. This is from the viewpoint of the storage stability of the weather-resistant coating composition, the curability of the formed coating film and the physical properties of the coating film.

  The hydrolyzable silyl group-containing acrylic resin (C) can be produced by any known method, for example, a radical polymerization method using an azo compound, a peroxide, or the like as an initiator, and is commercially available. Yes.

The hydrolyzable silyl group-containing acrylic resin (C) preferably contains a methacryloyl group-containing compound (c ₂₁ ) as the (meth) acryloyl group-containing compound (c ₂ ) from the viewpoint of the weather resistance of the coating film to be formed. .

In an embodiment in which the (meth) acryloyl group-containing compound (c ₂ ) is a methacryloyl group-containing compound (c ₂₁ ), the hydrolyzable silyl group-containing acrylic resin (C) is a hydrolyzable silyl group-containing acrylic resin (C). From the viewpoint of the weather resistance of the coating film to be formed, the unit of the methacryloyl group-containing compound (c ₂₁ ) is preferably about 50% by mass or more, and more preferably 70% by mass or more based on the solid content mass of Desirable from.

The methacryloyl group-containing compound (c ₂₁ ) contains a methacryloyl group among the compounds exemplified by the hydrolyzable silyl group-containing polymerizable unsaturated compound (c ₁ ) and the (meth) acryloyl group-containing compound (c ₂ ). For example, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, β-methacryloxyethyltrimethoxysilane, β-methacryloxyethyltriethoxysilane, γ-methacryloxypropyl Methacryloxy such as methyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyldipropoxysilane, γ-methacryloxybutylphenyldimethoxysilane, γ-methacryloxypropyldiethylmethoxysilane Coxysilane; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, isobol Linear, branched or cyclic alkyl group-containing methacrylates such as nyl methacrylate and tridecyl methacrylate; alkoxyalkyl methacrylates such as methoxyethyl methacrylate, methoxypropyl methacrylate, ethoxyethyl methacrylate and ethoxypropyl methacrylate; 2-hydroxyethyl methacrylate and hydroxypropyl Meta Hydroxyalkyl methacrylates such as relate, 2,3-dihydroxybutyl methacrylate and 4-hydroxybutyl methacrylate; phosphate group-containing methacrylates such as acid phosphooxyethyl methacrylate and phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester; And carboxyl group-containing methacrylates such as methacrylic acid; and combinations thereof.

In the embodiment in which the hydrolyzable silyl group-containing acrylic resin (C) includes monomer units of the hydrolyzable silyl group-containing polymerizable unsaturated compound (c ₁ ) and the (meth) acryloyl group-containing compound (c ₂ ), The (meth) acryloyl group-containing compound (c ₂ ) preferably contains a linear, branched or cyclic alkyl ester (c ₂₂ ) of (meth) acrylic acid having about 4 to 18 carbon atoms. The solubility of the hydrolyzable silyl group-containing acrylic resin (C) in a weak solvent is improved, and the acrylic resin (A) having both fluorine and hydrolyzable silyl groups and the hydrolyzable silyl group-containing silicone resin (B) This is because the compatibility is improved and the weather resistance of the formed coating film is improved.

Examples of (meth) acrylic acid linear, branched or cyclic alkyl ester (c ₂₂ ) having about 4 to 18 carbon atoms include n-butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl. (Meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tridecyl (meth) acrylate And combinations thereof.

Further, the (meth) acryloyl group-containing compound (c ₂ ) includes a hydroxyalkyl ester of (meth) acrylic acid. Examples of hydroxyalkyl esters of (meth) acrylic acid include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like (Meth) acrylic acid hydroxyalkyl ester, a compound obtained by ring-opening polymerization of a lactone such as ε-caprolactone to the hydroxyalkyl ester, and a polyhydric alcohol such as polyethylene glycol mono (meth) acrylate and (meth) acrylic acid Examples thereof include monoesterified products and the like, and combinations thereof, and 2-hydroxyethyl methacrylate is preferable. 2-hydroxyethyl (meth) acrylate is preferable from the viewpoint of increasing the gloss of the coating film to be formed.

  In the embodiment in which the hydrolyzable silyl group-containing acrylic resin (C) includes a hydroxyalkyl ester of (meth) acrylic acid, the hydrolyzable silyl group-containing acrylic resin (C) is based on the total monomer unit ( Preferably, it contains about 0.1-40% by weight, and more preferably 1-20% by weight, of a hydroxyalkyl ester of meth) acrylic acid. This is from the viewpoint of the gloss of the formed coating film and the solubility in a weak solvent.

In another embodiment of the weather resistant coating composition of the present invention, the hydrolyzable silyl group-containing acrylic resin (C) comprises a hydrolyzable silyl group-containing polymerizable unsaturated compound (c ₁ ) and a (meth) acryloyl group. It contains monomer units of the containing compound (c ₂ ) and other polymerizable unsaturated compounds (c ₃ ).

Other polymerizable unsaturated compounds (b ₃ ) are appropriately selected from those listed as other polymerizable unsaturated compounds (a ₄ ) in the acrylic resin (A) containing both fluorine and hydrolyzable silyl groups. Can be used in

  The weight average molecular weight of the non-volatile component of the hydrolyzable silyl group-containing acrylic resin (C) is not particularly limited, but from the viewpoint of curability, weather resistance and thick film coatability, about 1,000 to about 1,000 It is in the range of 100,000, preferably in the range of about 2,000 to about 80,000.

≪Fluororesin (D) ≫
In this invention, a fluororesin (D) is mix | blended as needed for the purpose of improving sclerosis | hardenability and a weather resistance, and is resin which has a fluorine-containing olefin unit in a molecule | numerator.

  The fluororesin (D) preferably contains about 1% by mass or more, more preferably about 5% by mass or more, more preferably about 5% by mass or more of fluorine-containing olefin units based on the solid content mass of the fluororesin (D). It contains about 10% by weight or more, and more preferably about 15% by weight or more.

  As long as a fluororesin (D) has a fluorine-containing olefin unit, a structure is not specifically limited, What was manufactured by arbitrary methods is mentioned, and is marketed.

  Commercially available fluororesins include, for example, Lumiflon series (Asahi Glass Co., Ltd.), Cefral Coat Series (Central Glass Co., Ltd.), Zaffle Series (Daikin Kogyo Co., Ltd.), Cotax (Toray Industries, Inc.), Fluonate Series ( Dainippon Ink & Chemicals, Inc., trade name), ZAFLON series (product of Toagosei Co., trade name), Zaffle series (product of Daikin Industries, trade name), and the like.

  The fluororesin (D) preferably has a hydroxyl group. In this case, the preferable range of the solid content hydroxyl value is 0.01 to 100 mgKOH / g, preferably 0.1 to 80 mgKOH / g.

For example, the fluororesin (D) includes a fluorine-containing olefin (d ₁ ), a fluorine-containing polymerizable unsaturated compound (d ₂ ) other than the desired (d ₁ ), and a desired hydroxyl group-containing polymerizable unsaturated compound (d ₃ ). , And optionally other polymerizable unsaturated compound (d ₄ ) monomer units.

Examples of the fluorine-containing olefin (d ₁ ) include vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, bromotrifluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, and hexafluoropropylene.

The fluorine-containing polymerizable unsaturated compound (d ₂ ) is appropriately selected from those listed as fluorine-containing polymerizable unsaturated compounds (a1) of acrylic resins containing both fluorine and hydrolyzable silyl groups. Can do.

Examples of the hydroxyl group-containing polymerizable unsaturated compound (d ₃ ) include hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2, Hydroxyalkyl (meth) acrylates such as 3-dihydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, compounds obtained by ring-opening polymerization of lactones such as ε-caprolactone to the above hydroxyalkyl (meth) acrylate, and polyethylene glycol And hydroxyl group-containing (meth) acrylates such as monoesterified products of polyhydric alcohols such as mono (meth) acrylate and acrylic acid or methacrylic acid.

Moreover, as other polymerizable unsaturated compound (d ₄ ) as desired, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 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, cyclohexyl (meth) Linear, branched or cyclic alkyl group-containing (meth) acrylates such as acrylate, isobornyl (meth) acrylate, tridecyl (meth) acrylate; N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylic Alkoxyalkyl (meth) acrylates such as amide, methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate; polyalkylenes such as polyethylene glycol monomethoxy (meth) acrylate Alkoxy group-containing (meth) acrylates such as glycol monoalkoxy (meth) acrylate; Epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate; Styrene, vinyltoluene and the like Aromatic vinyl compounds; carboxyl group-containing (meth) acrylates such as acrylic acid, methacrylic acid, half-esterified products of hydroxyalkyl (meth) acrylates and acid anhydrides Sulfonic acid group-containing (meth) acrylate such as 2-acrylamido-2-methylpropanesulfonic acid; acid phosphooxyethyl (meth) acrylate, mono-[(2-hydroxyethyl) (meth) acrylic acid] Phosphoric acid group-containing (meth) acrylates such as esters; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, Nt -Amino group-containing (meth) acrylates such as butylaminoethyl (meth) acrylate and N, N-dimethylaminobutyl (meth) acrylate; (meth) acryloyloxyethyltrimethylammonium chloride, dimethylaminoethylmethyl methacrylate methacrylate and the like 4th grade Ammoni A vinyl base such as vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltris (methoxyethoxy) silane; Vinylchlorosilanes such as vinyltrichlorosilane, divinyldichlorosilane, and vinylmethyldichlorosilane; γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, β- (meth) acryloxyethyltri Methoxysilane, β- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxy Hydrolysis of (meth) acryloxyalkoxysilane such as lan, γ- (meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxybutylphenyldimethoxysilane, γ- (meth) acryloxypropyldiethylmethoxysilane Decomposable silyl group-containing polymerizable unsaturated compounds; cyclohexyl vinyl ether, nonyl vinyl ether, 2-ethylhexyl vinyl ether, hexyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether and other vinyl ethers; ethyl allyl ether, hexyl allyl ether, etc. Allyl ethers; carboxylic acid vinyl esters such as “Beova-9” and “Beova-10” (both manufactured by Shell Chemical Co., Ltd.); Olefins such as ethylene, propylene, and isobutylene Emissions, etc., as well as any combination thereof.

  In the weather resistant coating composition of the present invention, the fluororesin (D) preferably has solubility in a weak solvent.

  Although the weight average molecular weight of the non-volatile component of the fluororesin (D) is not particularly limited, an acrylic resin (A) containing both fluorine and a hydrolyzable silyl group and a hydrolyzable silyl group-containing silicone resin ( From the viewpoint of compatibility with B), long-term weather resistance, and solubility in weak solvents, it is generally in the range of about 2,000 to about 200,000, and preferably about 3,000 to about 60,000. In the range of 000.

≪Weather-resistant paint composition≫
The weather resistant coating composition of the present invention comprises an acrylic resin (A) containing both fluorine and hydrolyzable silyl groups and a hydrolyzable silyl group-containing silicone resin (B) based on their total solid mass, The acrylic resin (A) containing both fluorine and hydrolyzable silyl groups is about 1 to about 90% by mass, preferably about 3 to about 80% by mass, and the hydrolyzable silyl group-containing silicone resin is about 1 to about 50% by weight, preferably about 3 to about 40% by weight.

  The weather resistant coating composition of the present invention comprises an acrylic resin (A) containing both fluorine and hydrolyzable silyl groups, a hydrolyzable silyl group-containing silicone resin (B), and a hydrolyzable silyl group-containing acrylic resin (C). In embodiments comprising from about 1 to about 90% by weight, preferably from about 5 to about 80% by weight of acrylic resin (A) containing both fluorine and hydrolyzable silyl groups, based on their total solids weight. The hydrolyzable silyl group-containing silicone resin (B) is about 1 to about 50% by mass, preferably about 5 to about 40% by mass, the hydrolyzable silyl group-containing acrylic resin (C) is about 1 to 90% by mass, Preferably it contains about 5-55 mass%.

  In the embodiment in which the weather-resistant coating composition of the present invention contains a fluororesin (D), the acrylic resin (A) and hydrolyzation in which the content of the fluororesin (D) contains both fluorine and hydrolyzable silyl groups. 1 to 90% by mass, preferably 5 to 75% by mass, based on the total solid mass of the functional silyl group-containing silicone resin (B).

  In this specification, “solid” means the ratio of non-volatile components excluding volatile components such as water and organic solvent in the sample, and about 2 g of the sample is dried at 105 ° C. for 3 hours and dried. It can be determined from the mass before and after. Moreover, in this specification, "solid content mass" means the mass of the said non-volatile component in a sample.

  In one embodiment of the weather-resistant coating composition of the present invention, an organosilicate is further included in order to impart low contamination to the formed coating film.

The organosilicate is a compound other than the hydrolyzable silyl group-containing silicone resin (B), and has, for example, the following formula (2) having no hydrocarbon group directly bonded to a silicon atom:
Si (-OR ¹ ) ₄ formula (2)
(Wherein R ¹ is the same or different monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group)
And the partial hydrolysis and condensate thereof.

In Formula (2), R ¹ is preferably an alkyl group having 1 to 4 carbon atoms.

  Examples of organosilicates include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-isopropoxysilane, tetra-n-butoxysilane, tetra-isobutoxysilane, tetra-t-butoxysilane, and the like Any combination thereof, as well as their partial hydrolysis and condensates.

  As commercially available products of organosilicates, for example, “ethyl silicate 45”, “ethyl silicate 40” and “ethyl silicate 48” (above, manufactured by Colcoat), “silicate 45” and “silicate 40” (above, Tama Chemical Industries, Ltd.) And TES40WN (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.).

  In an embodiment in which the weather-resistant coating composition of the present invention includes an organosilicate, the weather-resistant coating composition has a solid content based on 100 parts by mass of the total solid content of resin contained in the weather-resistant coating composition. Preferably, it comprises from about 1 to about 30 parts by weight, and more preferably from about 5 to about 20 parts by weight. This is from the viewpoint of crack resistance of the formed coating film.

  In one embodiment of the weather resistant coating composition of the present invention, the weather resistant coating composition comprises a conventionally known pigment. Examples of the pigment include coloring pigments such as titanium oxide, bengara, cyanine color pigments, carbon black and zircon powder; silica, barita powder, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, white carbon, Examples thereof include extender pigments such as diatomaceous earth, talc, magnesium carbonate, alumina white, gloss white, and tancal, and combinations thereof.

  In an embodiment where the weatherable coating composition includes a pigment, the weatherable coating composition is preferably a solids mass, preferably based on 100 parts by weight of resin total solids mass contained in the weatherable coating composition. About 50 to about 100 parts by weight, and more preferably about 60 to about 90 parts by weight. This is from the viewpoint of thick film coatability and weather resistance of the formed coating film.

  The weather-resistant coating composition of the present invention is a two-component coating composition comprising a main agent and a curing agent.

  The two-component coating composition includes a main resin containing a fluorine resin (A) containing both fluorine and a hydrolyzable silyl group hydroxyl group and a hydrolyzable silyl group-containing silicone resin (B), a curing agent containing a catalyst, This is a two-component coating composition.

  Since the main agent and curing agent are mixed immediately before coating and the coating viscosity can be adjusted with a solvent if desired, coating can be performed even in low-temperature environments and early after coating, with thick film hardening, weather resistance, and finish. An excellent coating film can be obtained.

  In the embodiment of the weather-resistant coating composition of the present invention, in order to improve the room temperature curability of the coating film and to form a coating film excellent in weather resistance at an early stage, the curing agent constituting the weather-resistant coating composition, A catalyst that promotes polycondensation of hydrolyzable silyl groups is included.

  Examples of the catalyst include those conventionally known, and examples of the catalyst include diacetyltin diacetate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, diacetyltin dioctoate, tin octylate, and dibutyltin diacetate. , Organotin compounds such as dibutyltin dioctoate; aluminum trimethoxide, aluminum tris (acetylacetonate), aluminum tri-n-butoxide, aluminum tris (acetoacetate ethyl), aluminum diisopropoxy (acetoacetate ethyl), aluminum acetyl Organoaluminum compounds such as acetonate; titanium tetra (monoethyl ethoxide), titanium tetra (monoethyl ethoxide), titanium tetra (monobutyl ethoxy) ), Organic titanium compounds such as titanium tetrakis (acetylacetonate) and tetranormal butyl titanate; zirconium tetra (monomethyl ethoxide), zirconium tetra (monoethyl ethoxide), zirconium tetra (monobutyl ethoxide), zirconium normal propylate Organic zirconium compounds such as zirconium normal butyrate and zirconium tetrakis (acetylacetonate); organic zinc compounds such as zinc naphthenate; organic cobalt compounds such as cobalt octylate and cobalt naphthenate; trimethylamine, triethylamine, 2- (dimethylamino) ) Ethyl methacrylate, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diaza Aliphatic amines such as cyclo [4.3.0] -5-nonene, 1-methylpiperidine, 1-methylpyrrolidine, pyridine, 4-dimethylaminopyridine, 4- (1-piperidyl) pyridine, N-methylimidazole, Amine catalysts such as N, N-dimethylaniline; lead, tin, zinc, and iron complexes of carboxylic acids; trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, triphenyl borate, triborate borate ( 4-chlorophenyl), boric acid compounds such as boric acid esters such as trihexafluoroisopropyl borate, and combinations thereof.

  The amount of the catalyst is, for example, from about 0.01 to about 20 parts by mass, and more preferably from about 0.01 to about 20 parts by mass, based on 100 parts by mass of the total solid content of resin contained in the weather resistant coating composition. It is preferable from 0.1 to about 10 mass parts from a viewpoint of sclerosis | hardenability and pot life.

  In one embodiment of the weather resistant coating composition of the present invention, the weather resistant coating composition is of a high solid type. In this embodiment, the solid content of the weather-resistant coating composition or main ingredient in the storage stage (sealed state) is, for example, in the range of about 60 to about 85% by mass, particularly about 65 to about 80% by mass.

  In one embodiment of the weather-resistant coating composition of the present invention, the weather-resistant coating composition is a weak solvent type coating composition. In this embodiment, the ratio of the weak solvent contained in the paint or the main agent in the storage stage (sealed can state) is in the range of about 80% by mass or more, particularly about 80 to about 100% by mass, based on the total amount of organic solvent. Preferably there is. Since the weather-resistant coating composition is a weak solvent type coating composition, it is possible to suppress the occurrence of wrinkles and the like when the weather-resistant coating composition is applied onto a base, for example, an old coating film, and Excellent paint workability. In addition, as a weak solvent, the 1 or several solvent selected from the group of the above-mentioned 3rd type organic solvent is mentioned.

  In an embodiment in which the weather-resistant coating composition is a weak solvent-type coating composition, the weather-resistant coating composition is a first organic solvent in the Industrial Safety and Health Act based on the total amount of organic solvents in addition to the weak solvent. And the second organic solvent may be contained in an amount of preferably about 20% by mass or less, and more preferably about 5% by mass or less.

  Examples of the first type organic solvent include chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,2-dichloroethylene, 1,1,2,2-tetrachloroethane, trichloroethane, carbon disulfide, And any combination thereof.

  The second type organic solvent is a so-called strong solvent, for example, 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, -n-butyl acetate, -n-propyl acetate, acetic acid -n- Pentyl, methyl acetate, cyclohexanol, cyclohexanone, 1,4-dioxane, dichloromethane, N, N-dimethylformamide, styrene, tetrachloroethylene, te Lahydrofuran, 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 Any combination can be mentioned.

  In some embodiments of the weather-resistant coating composition of the present invention, the main agent (I) and / or the curing agent (II) is a silane coupling agent; an antirust pigment; a curing agent component; an acrylic resin, an epoxy resin, an alkyd. Resin for modification, such as resin and urethane resin; Organic solvent; Reactive diluent; Additive for paint such as adhesion imparting agent, anti-settling agent, dispersant, wetting agent, dehydrating agent, and the like.

  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 (Meth) acryloyl group-containing silane coupling agents such as pyrtrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropyldimethoxymethylsilane; γ-isocyanatopropyltriethoxysilane, γ -Isocyanato group-containing silane coupling agents such as isocyanatepropyltrimethoxysilane.

  In the embodiment in which the weather-resistant coating composition contains a silane coupling agent, the weather-resistant coating composition preferably contains the silane coupling agent based on 100 parts by mass of the total solid content of resin contained in the weather-resistant coating composition. In the range of about 1.0 to about 30 parts by weight, and more preferably about 1.5 to about 20 parts by weight. This is from the viewpoint of improving adhesion.

  In one embodiment of the weather resistant coating composition of the present invention, the weather resistant coating composition is a room temperature curing type, and the formed cured coating film can exhibit excellent performance. In another embodiment of the weather-resistant coating composition of the present invention, the weather-resistant coating composition is a dry-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, The top coating use of heavy anticorrosion coating of steel structures, such as a bridge, a power transmission tower, a plant, a tank, is mentioned.

≪Method for producing coated article having weather-resistant coating film≫
As an object to be coated with a weather-resistant coating composition, a metal material subjected to a ground treatment as desired, for example, a steel plate, galvanized, stainless steel, aluminum, etc., an alkaline substrate such as concrete, mortar, slate, Examples include slate roof tiles, ceramic building materials, plastics, etc., and those on which an old coating film is formed.

  A coated article having a weather-resistant coating film can be produced, for example, by applying the weather-resistant coating composition to the article to be coated to form a weather-resistant coating film.

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

  In one embodiment of the method for producing a coated article having a weather-resistant coating, before forming the weather-resistant coating with the weather-resistant coating composition, an undercoating coating is applied to the article to be coated, and the anti-corrosion coating Form.

  Examples of the undercoat paint include 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.

  The undercoat paint is applied by one or more coatings, and the thickness thereof is a dry film thickness, preferably about 10 to about 2,500 μm, more preferably about 30 to about 600 μm, and more preferably about It is in the range of 60 to about 120 μm.

  Since the weather-resistant coating composition of the present invention has thick film coatability, the intermediate coating can be omitted, and the intermediate coating and the top coating can be combined. When the weather-resistant coating composition of the present invention also serves as an intermediate coating and a top coating, the weather-resistant coating composition is applied by a single coating or multiple coatings, and the film thickness of the coating film is about a dry film thickness. It can range from 50 to about 150 μm, in particular from about 50 to about 100 μm.

  In yet another embodiment of the method for producing a coated article having a weather resistant coating, an intermediate coating is formed by an intermediate coating on the anticorrosion coating by the undercoating before the weather resistant coating composition is applied. To do.

  Examples of the intermediate coating include epoxy resin coatings, polyurethane coatings, epoxy resin MIO coatings, phenol resin MIO coatings, chlorinated rubber resin coatings, and phthalic acid resin coatings. In this embodiment, the primer coating is applied such that the dry film thickness is preferably about 30 to about 1,200 μm, more preferably about 30 to about 600 μm, and even more preferably about 60 to about 120 μm, and intermediate coating The paint is applied such that the dry film thickness is preferably about 30 to about 80 μm, more preferably about 30 to about 60 μm, and the weather resistant paint composition is preferably about 20 to about 60 μm in dry film thickness, More preferably, the coating can be performed so as to have a thickness of about 20 to about 50 μm.

  Each of the undercoat paint, intermediate coat paint and weather resistant paint composition can be applied once or multiple times.

  In still another embodiment of a method for producing a coated article having a weather-resistant coating film, a phthalic acid resin-based, urethane resin-based, acrylic silicon resin-based, fluorine resin-based top coating, alkyd resin-based, acrylic-modified epoxy resin-based, The above weather-resistant coating composition is applied as an overtop coat on a coating that serves both as an undercoat and a topcoat of a silicon-modified epoxy resin.

  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.

  Further, since the weather-resistant coating composition of the present coating is excellent in thick film coating properties, it can be applied not only as a top coating but also as a middle top coating that serves as both an intermediate coating and a top coating.

  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.

≪Manufacture of paint composition≫
[Examples 1-41 and Comparative Examples 1-3]
According to the composition of Table 1, each material was added to the container and stirred to adjust the solid content to about 75%. 1-44 were produced.

  In Table 1, the numbers in parentheses, that is, acrylic resin (A) containing both fluorine and hydrolyzable silyl groups, hydrolyzable silyl group-containing silicone resin (B), hydrolyzable silyl group-containing acrylic resin The amounts of (C) and the fluororesin (D) mean the solid mass, and the numbers without parentheses, that is, the amounts of silicone oligomer, organosilicate, catalyst and silane coupling agent are the amounts actually added. means.

≪Creation of test coating board≫
A. Examples where the weather resistant coating composition is a top coat:
On a steel plate degreased with acetone, a weak solvent soluble thick film type modified epoxy resin-based rust preventive paint ("ESCO NB Safety" (trade name, manufactured by Kansai Paint Co., Ltd., main agent / amine curing agent = 17/1), dried film Spray-coated to a thickness of 60 μm, dried at 23 ° C. for 24 hours, and then weakly solvent-soluble isocyanate-cured polyurethane coating (“Serect Mild Intermediate Coating” (trade name, manufactured by Kansai Paint Co., Ltd. / Isocyanate curing agent mass ratio 10/1) is spray-coated so that the dry film thickness is 30 μm, dried at 23 ° C. for 24 hours, and then coating composition Nos. 1 to 44 are obtained with a dry film thickness of 25 μm. Test plate (A) Nos. 1 to 44 were produced by spray coating so that the sample was dried and dried at 23 ° C. for 168 hours.

B. An example of a weather-resistant coating composition that serves as an intermediate coat and top coat. On a steel plate degreased with acetone, a weak solvent soluble thick film type modified epoxy resin-based rust preventive paint ("ESCO NB Mild H" (trade name, Kansai Paint) Co., Ltd., main agent / amine curing agent = 9/1) was spray-coated so that the dry film thickness was 120 μm, dried at 23 ° C. for 24 hours, and then coating compositions No. 1 to 44 were dried films Test plates (B) Nos. 1 to 44 were manufactured by spray coating so as to have a thickness of 55 μm, and drying at 23 ° C. for 168 hours.

≪Performance evaluation≫
Coating composition No. 1-44 were evaluated. The results are shown in Table 1 below.

<< Acrylic resin containing both fluorine and hydrolyzable silyl group (A) >>
[A1]
Hexafluoroisopropyl methacrylate / cyclohexyl methacrylate / n-butyl acrylate / γ-methacryloxypropyltrimethoxysilane = 37/43/10/10 copolymer solution, weight average molecular weight: 29,000, solid content: 64%, Solvent: Mineral Spirit [A2]
Hexafluoroisopropyl methacrylate / cyclohexyl methacrylate / γ-methacryloxypropyltrimethoxysilane = 40/45/15 copolymer solution, weight average molecular weight: 38,000, solid content: 64%, solvent: mineral spirit [A3]
Hexafluoroisopropyl methacrylate / cyclohexyl methacrylate / tert-butyl acrylate / γ-methacryloxypropyltrimethoxysilane = 28/32/35/5 copolymer solution, weight average molecular weight: 25,000, solid content: 64%, Solvent: mineral spirit.

≪Hydrolysable silyl group-containing silicone resin (B) ≫
[B1]
Hydrolyzable silyl group-containing phenylmethylalkoxysilicone oligomer, weight average molecular weight: 1,200, solid content: 100%
[B2]
Hydrolyzable silyl group-containing phenylmethylalkoxysilicone oligomer, weight average molecular weight: 6,000, solid content: 100%
[B3]
Hydrolyzable silyl group-containing dimethylalkoxysilicone oligomer, weight average molecular weight: 2,500, solid content: 100%
≪Hydrolysable silyl group-containing acrylic resin (C) ≫
[C1]
Solution of copolymer of isobornyl acrylate / cyclohexyl methacrylate / isobutyl methacrylate / 2-ethylhexyl methacrylate / γ-methacryloxypropyltrimethoxysilane = 20/30/20/20/10, weight average molecular weight: 20,000, solid Min: 60%, Solvent: Mineral Spirit “C2”
Solution of copolymer of isobornyl acrylate / cyclohexyl methacrylate / isobutyl methacrylate / 2-ethylhexyl methacrylate / γ-methacryloxypropyltrimethoxysilane = 5/40/20/30/5, weight average molecular weight: 25,000 , Solid content: 60%, Solvent: Mineral spirit [C3]
Solution of copolymer of isobornyl acrylate / cyclohexyl methacrylate / 2-ethylhexyl methacrylate / γ-methacryloxypropylmethyldiethoxysilane = 30/50/10/10, weight average molecular weight: 30,000, solid content: 60% 、 Solvent: Mineral Spirit [C4]
Solution of copolymer of isobornyl acrylate / cyclohexyl methacrylate / 2-ethylhexyl methacrylate / γ-methacryloxypropyltriethoxysilane = 50/25/15/10, weight average molecular weight: 28,000, solid content: 60%, Solvent: Mineral Spirit [C5]
Solution of copolymer of isobornyl acrylate / cyclohexyl methacrylate / 2-ethylhexyl methacrylate / γ-methacryloxypropylmethyldimethoxysilane = 10/55/20/15, weight average molecular weight: 24,000, solid content: 60%, Solvent: Mineral Spirit [C6]
Solution of copolymer of isobornyl acrylate / isobutyl methacrylate / 2-ethylhexyl methacrylate / γ-methacryloxypropyltrimethoxysilane = 20/35/35/10, weight average molecular weight: 31,000, solid content: 60%, Solvent: Mineral Spirit [C7]
Solution of copolymer of isobornyl acrylate / 2-hydroxyethyl methacrylate / isobutyl methacrylate / 2-ethylhexyl methacrylate / γ-methacryloxypropyltrimethoxysilane = 20/5/30/35/10, weight average molecular weight: 30, 000, solid content: 60%, solvent: mineral spirit [C8]
Solution of copolymer of isobornyl acrylate / cyclohexyl methacrylate / 2-hydroxyethyl methacrylate / isobutyl methacrylate / 2-ethylhexyl methacrylate / γ-methacryloxypropyltrimethoxysilane = 20/20/10/5/35/10, weight Average molecular weight: 35,000, solid content: 60%, solvent: mineral spirit [C9]
Isobornyl acrylate / methyl methacrylate / 2-hydroxyethyl methacrylate / isobutyl methacrylate / 2-ethylhexyl methacrylate / γ-methacryloxypropyltrimethoxysilane = 20/10/15/15/35/5 copolymer solution, weight Average molecular weight: 40,000, solid content: 60%, solvent: mineral spirit [C10]
Solution of cyclohexyl methacrylate / t-butyl methacrylate / 2-hydroxyethyl methacrylate / isobutyl methacrylate / 2-ethylhexyl methacrylate / γ-methacryloxypropyltrimethoxysilane = 25/10/15/15/30/5 copolymer, weight Average molecular weight: 22,000, solid content: 60%, solvent: mineral spirit [C11]
Solution of copolymer of cyclohexyl methacrylate / t-butyl methacrylate / isobutyl methacrylate / 2-ethylhexyl methacrylate / γ-methacryloxypropyltrimethoxysilane = 35/15/15/25/10, weight average molecular weight: 33,000, solid Min: 60%, Solvent: Mineral Spirit [C12]
Solution of copolymer of cyclohexyl methacrylate / isobutyl methacrylate / 2-ethylhexyl methacrylate / γ-methacryloxypropyltrimethoxysilane = 45/15/30/10, weight average molecular weight: 29,000, solid content: 60%, solvent: Mineral spirit.

≪Fluororesin (D) ≫
[D1]
Chlorotrifluoroethylene / cyclohexyl acrylate / vinyltrimethoxysilane = 48/46/6 copolymer solution, weight average molecular weight 40000, solid content 64%, solvent: mineral spirit [D2]
Chlorotrifluoroethylene / cyclohexyl acrylate / n-butyl acrylate / hydroxyethyl acrylate = 37/44/10/9 copolymer solution, hydroxyl value: 44 mgKOH / g, weight average molecular weight: 28,000, solid content: 64% 、 Solvent: Mineral Spirit << Catalyst >>
[E1]
Catalyst, “SCAT-8”, trade name, dibutyltin acetate << organosilicate >>
[F1]
“Ethyl silicate 48”, trade name, manufactured by Tama Chemical Co., Ltd., tetraethoxysilane condensate << other ingredients >>
[F2]
Titanium dioxide, “TRONOX CR-826”, trade name, manufactured by TRONOX PIGMENTS [F3]
Thickener, “Disparon 6820-10M”, trade name, Enomoto Kasei Co., Ltd., Amide [F4]
Silane coupling agent, 3-glycidoxypropyltriethoxysilane.

[Weatherability]
The accelerated weather resistance of the test plate (A) and the test plate (B) was evaluated using a xenon weather meter tester. The gloss of the coating after 5000 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. B: Gloss was slightly lowered, but there was no problem as a product. Δ: Gloss was remarkably lowered. X: Gloss was remarkably lowered.

[Flexibility]
Coating composition No. Each of the test plates (C) No. 1 to 44 was spray-coated on a steel plate degreased with acetone so as to have a dry film thickness of 25 μm and dried at 23 ° C. for 168 hours. 1-44 were manufactured and the bending resistance of each test plate (C) was evaluated.
According to JIS K 5600-5-1: 1999, part 5: mechanical properties of the coating film, section 1: bending resistance (cylindrical mandrel method), the mandrel diameter is 10 mm. Evaluation was performed according to the following criteria using a test apparatus.
◎: No change was observed in the coating film on the bent surface ○: No crack was observed in the coating film on the bent surface, but there was a slight change in the coating film △: Part of the coating film on the bending portion Cracking was observed x: Cracking was observed on the entire coating film at the bent portion.

[Anti-corrosion]
A test plate (A) and a test plate (B) were subjected to a salt spray test for 500 hours by making an X-shaped scratch with a width of 1 mm so as to reach the metal substrate with a cutter knife. Were evaluated according to the following criteria.
○: No abnormality was observed at the place where the scratch was made with the cutter knife. △: Slight rust was observed around the place where the scratch was made with the cutter knife. X: Around the place where the damage was made with the cutter knife. Significant rust was observed.

[Thick film paintability]
On the steel plate degreased vertically with acetone, the coating composition No. 1 to 44 were coated using a sag tester shown in JIS K 5400-6.4, dried at 23 ° C. for 24 hours, and then measured for the upper limit of the dry film thickness of the part where the coating film did not flow. It was evaluated with.
A: The upper limit was 60 μm or more. O: The upper limit was 55 μm or more and less than 60 μm. Δ: The upper limit was 50 μm or more and less than 55 μm. X: The upper limit was less than 50 μm.

[Repairability]
On a steel plate degreased with acetone, a weak solvent soluble thick film type modified epoxy resin-based rust preventive paint ("ESCO NB Safety" (trade name, manufactured by Kansai Paint Co., Ltd., main agent / amine curing agent = 17/1), dried film Spray-coated to a thickness of 60 μm and dried at 23 ° C. for 24 hours. On top of this, a weak solvent-soluble isocyanate-cured polyurethane coating (“Serect Mild Intermediate Coating” (trade name, manufactured by Kansai Paint Co., Ltd., main agent / Isocyanate curing agent mass ratio 10/1) was spray-coated so that the dry film thickness was 30 μm, dried at 23 ° C. for 24 hours, and then coating composition Nos. 1 to 44 were dried film thickness. Was spray-coated so as to be 25 μm, and was dried for 168 hours at 23 ° C. Next, the same coating composition No. 1 to 44 was applied as a top coating film for repairing to the above. Test plate (D) Nos. 1 to 44 were produced by spray coating to a thickness of 5 μm and drying for 168 hours at 23 ° C. The test plates (D) No. 1 to 44 were immersed in water for 168 hours. Immediately after pulling up from the water, the adhesion was tested in accordance with JIS K5600 “Part 5: Mechanical properties of coating film” and “Section 6: Adhesion (cross-cut method)” and evaluated according to the following criteria.
◎: The topcoat film for repair did not peel ○: The topcoat film for repair was slightly peeled △: The topcoat film for repair was remarkably peeled x: The topcoat film for repair was remarkably peeled

Claims (7)

A multi-component composition comprising a main agent (I) and a curing agent (II),
The main agent (I) includes an acrylic resin (A) containing both fluorine and a hydrolyzable silyl group and a hydrolyzable silyl group-containing silicone resin (B), and the curing agent (II) is a compound of hydrolyzable silyl groups. Including a catalyst that promotes condensation,
Acrylic resin (A) containing both fluorine and hydrolyzable silyl groups is based on the total monomer units,
₁ to 80% by mass of the fluorine-containing polymerizable unsaturated compound (a ₁ ) as a monomer unit, 1 to 50% by mass of the hydrolyzable silyl group-containing polymerizable unsaturated compound (a ₂ ) as a monomer unit, A weather-resistant coating composition comprising 1 to 90% by mass of a (meth) acryloyl group-containing compound (a ₃ ) as a monomer unit.   The composition according to claim 1, further comprising a hydrolyzable silyl group-containing acrylic resin (C) (excluding those containing fluorine).   The composition of Claim 1 or 2 which further contains the fluororesin (D) which has a fluorine-containing olefin unit in a molecule | numerator.   The composition according to any one of claims 1 to 3, wherein the hydrolyzable silyl group-containing silicone resin (B) is an oligomer having a methyl group and / or a phenyl group directly bonded to a silicon atom. A method for producing a coated article having a weather resistant coating,
Applying the composition according to any one of claims 1 to 4 to an object to be coated to form a weather-resistant coating film;
Including methods.   The method according to claim 5, further comprising the step of applying an undercoat to the article to form an anticorrosion coating before the step of forming the weather resistant coating.   Applying an intermediate coating on the anticorrosion coating to form an intermediate coating after the step of forming the anticorrosion coating and before the step of forming the weather resistant coating. Item 7. The method according to Item 6.