JPH07109435A - Outdoor article - Google Patents

Abstract

PURPOSE:To obtain an outdoor article having a coating surface on which rain uniformly flows to wash out dusts and which prevents the deposition of dusts and the occurrence of stained streaks due to rain by providing the article with a specified coating surface. CONSTITUTION:An outdoor article is provided with a coating surface having an angle of contact with octane of at least 102 degree in water. A surface treatment containing preferably a hydrolyzate of a mono- to tri-functional hydrolyzable silane compound (e.g. 3-glycidoxypropylmethyldimethoxysilane), a silicon compound comprising an alkali silicate or colloidal silica, and a film-forming component comprising a synthetic resin (e.g. a fluoroolefin polymer) is applied to the surface of an outdoor article preferably in a thickness of 0.01-50mum, forming an objective coating film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an article used outdoors (hereinafter referred to as "outdoor article"), and more particularly to an article having a coating surface having an octane contact angle of 102 degrees or more in water.

[0002]

2. Description of the Related Art Conventionally, products such as metals, inorganic materials, plastics, wood, paper, leather and fibers have been coated with a surface coating for the purpose of protecting them, giving them design and functionality. It is being appreciated.

Recently, as a paint having excellent weather resistance, a paint giving a hydrophobic synthetic resin coating film such as a fluororesin paint has been widely used. This fluororesin paint shows much better weather resistance than previous synthetic resin paints, but the surface stains are similar to those of other synthetic resin paints, and improvement is expected as a high-performance product. It is rare.

Particularly, in outdoor articles having a hydrophobic synthetic resin coating film, stains on spots due to rainwater are likely to occur on the surface of the hydrophobic synthetic resin coating film exposed to rain. Furthermore, streak-like stains (hereinafter referred to as rain streak stains) are likely to occur in a portion where rainwater gathers and flows, such as under a window frame of a building.

Although this rain streak stain can be easily removed by washing, repeated washing is not only complicated but also
Cleaning work is not easy for large outdoor articles such as buildings. Therefore, a coated outdoor article having a surface with less generation of rain streaks is desired.

[0006] Conventionally, a coating composition containing a polyfluorinated carbon chain and a polymer having a hydrophilic group has been proposed in an attempt to solve the problem of stains on the surface of a coated article (JP-A-1-198653). ). However, although the effect of improving stains on spots due to rainwater is recognized on the coated surface with this coating composition, it is not sufficient in terms of preventing the generation of rain streak stains.

[0007]

SUMMARY OF THE INVENTION The present invention provides an outdoor article having a coating surface for preventing the generation of rain streak stains.

[0008]

The present invention has been made to solve the above-mentioned problems, and is an outdoor article having a coating film surface having an octane contact angle of 102 degrees or more in water.

In the present invention, a method of forming a coating film surface having an octane contact angle of 102 degrees or more in water on an outdoor article includes a silicon compound (A) and a synthetic resin film-forming component (B) on the surface of the outdoor article. And a silicon compound (A) or a silicon compound (A) and a synthetic resin film on the coating film surface of an outdoor article having a hydrophobic synthetic resin coating film surface. There is a method of forming a thin film by applying a surface treatment agent containing the component (B).

The present inventor believes that the action of preventing the formation of rain streaks by the thin film formed of the surface treatment agent is basically due to the hydrophilicity and oil repellency of the thin film surface. The oily soil in rainwater adheres to the hydrophobic surface along the stream of rainwater and remains as streaky soil on drying. On the other hand, since the oily stain does not spread on the hydrophilic and oil-repellent surface, the contact area between the surface and the oily stain becomes narrow. Therefore, the adhesion of the oily stain to the surface is low, and the oily stain easily flows down with the flow of rainwater.

The degree of hydrophobicity-hydrophilicity of the surface can be measured by measuring the octane contact angle in water. The larger the octane contact angle in water, the more hydrophilic the surface and the higher the oil repellency. The present inventor has found that the octane contact angle in water is preferably 102 degrees or more in order to sufficiently prevent the generation of rain streaks. The surface treatment agent in the present invention can make the octane contact angle in water of the thin film formed thereby to be 102 degrees or more. The contact angle is preferably 110 degrees or more, more preferably 115 degrees or more, and most preferably 120 degrees or more.

The silicon compound (A) is a compound selected from hydrolysates of 1 to 3 functional hydrolyzable silane compounds, silicic acid alkali salts, colloidal silica and the like. These may be used alone or as a mixture of two or more kinds.

The 1 to 3 functional hydrolyzable silane compound is
It is a silane compound in which 1 to 3 hydrolyzable groups are bonded to a silicon atom. Although the hydrolyzable groups may be different, they are usually the same hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, an alkoxyalkoxy group, an acyloxy group, an aryloxy group, an aminoxy group, an amide group, a ketoxime group, an isocyanate group and a halogen atom. Particularly, a group obtained by removing a hydrogen atom from a hydroxyl group of a monohydric alcohol such as an alkoxy group or an alkoxyalkoxy group is preferable. The most preferable hydrolyzable group is an alkoxy group, and the number of carbon atoms thereof is 4 or less, particularly preferably 1 or 2.

In the 1 to 3 functional, preferably 2 to 3 functional hydrolyzable silane compound, the organic group other than the hydrolyzable group may be an alkyl group, an alkyl group having a functional group, an aryl group or other silicon atom. There are organic groups that have a carbon atom attached to them. In particular, when there is one organic group having a functional group, and another organic group is present, it is usually preferable that it is an organic group having no functional group such as an alkyl group.
Examples of the functional group in the organic group having a functional group include an amino group, an epoxy group, a mercapto group, and an isocyanate group.

Specifically, methyltrimethoxysilane,
Methyldiethoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-isocyanate propyltrimethoxysilane, methylsilyltriisocyanate, vinylsilyltriisocyanate, diethoxysilyldiisocyanate, dimethyldichlorosilane, trimethylchlorosilane, chloromethyldimethylsilane,
Methyltrichlorosilane, chloromethyldimethylvinylsilane, diphenylchloromethylsilane, 3-chloropropyltrimethoxysilane, hexamethylsilazane, cyclic silazane, polysilazane, N, N-bis (trimethylsilyl) trifluoroacetamide, N-trimethylsilylacetamide, N- Trimethylsilylphenylurea, bistrimethylsilylurea, dimethyltrimethylsilylamine, trimethylsilylimidazole, trimethylsilyldimethylamine, methyltriacetoxysilane, 1,3-bis (3-aminopropyl) -1,1,
3,3-Tetramethyldisiloxane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, CH ₃ Si
_{[ON = C (CH 3)} (C 2 H 5)] 3 , and the like.

Commercially available products are T manufactured by Toshiba Silicone Co., Ltd.
SL8000 series, TSL8100 series, TS
L8300 series, TSL9306, TSL88 series, XC95 series, XC96 series, XC99
Series, CRB-110 (silicon-based ceramic paint) manufactured by Nittaku Giken Co., Ltd., KBM1000 series manufactured by Shin-Etsu Chemical Co., KBE1000 series, KBC100 series,
KBM 400, 500, 600, 700, 800, 90
0 series, X-12 series, KBP503 series, AZ series of Japan Unicar Co., A series, silane coupling agent A series of Union Carbide and the like.

Examples of alkali silicate salts include sodium silicate, potassium silicate, calcium silicate, magnesium silicate, aluminum silicate, zirconium silicate and the like. A double salt obtained by treating an alkali silicate salt with hydrofluoric acid or hydrochloric acid can also be used. A double salt obtained by treating aluminum silicate or the like with hydrofluoric acid in the presence of calcium hydroxide or the like is preferable because of its large polarity.

Colloidal silica is fine particles of SiO ₂ or a dispersion thereof, and is TT600 of Nippon Aerosil, Snowtex 30 of Nissan Chemical Co., Ltd., and Cataloid 2 of Nippon Shokubai.
0HL, SI-30 and the like.

The surface treatment agent in the present invention is preferably one in which the silicon compound (A) is dissolved or dispersed in a medium. In particular, a uniform solution is preferable for forming a uniform and thin thin film (formed by surface treatment). In addition, an aqueous medium is preferable for reasons such as work stability and environmental conservation, but a non-aqueous medium may be used. As the aqueous medium, basically only water or a mixed medium of water and a water-soluble organic solvent is preferable. Even when the medium is only water, when the hydrolysis for producing the hydrolyzate of the silicon compound (A) is carried out in an aqueous medium, by-products by-produced by hydrolysis such as alcohol are mixed. It becomes a medium. As the medium in the present invention, a medium containing such a by-product medium can be used.

As the water-soluble organic solvent, water-soluble alcohols such as ethanol, isopropanol, n-butanol, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether and diacetone alcohol are preferable, and one or more kinds thereof are used. it can. This organic solvent has a boiling point of 200 ° C. or less, especially 1
A water-soluble organic solvent having a temperature of 10 ° C. or lower is preferable. Those having a too high boiling point are not preferable because they tend to remain in the thin film formed by the surface treatment. Further, for the purpose of accelerating the evaporation of water, a solvent which is azeotropic with water, such as acetone, ethanol, isopropanol, etc., can be used.

As the non-aqueous medium, alcohols such as ethanol, isopropanol and n-butanol,
Ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as butyl acetate and ethyl acetate, aromatic solvents such as xylene and toluene, aliphatic solvents,
An ether solvent, a petroleum solvent, etc. can be used. As such a non-aqueous medium, polar solvents such as alcohols, ketones and esters are preferable. Among the non-aqueous media, alcohols and the like may be used by incorporating a small amount of water for hydrolysis. These non-aqueous media may be used alone or in combination of two or more.

The content of the silicon compound (A) in the surface treatment agent is preferably 0.01 to 100 parts by weight, particularly 0.1 to 10 parts by weight, based on 100 parts by weight of the medium.
If the amount of the silicon compound (A) is too small, a large amount of the treating agent must be used in order to achieve the effect of the surface treating agent, which is not preferable because the coating property is deteriorated. On the other hand, if the amount is too large, the thin film formed becomes too thick and becomes brittle or cracked, which is not preferable. In addition, a silicon compound (A)
Has the effect of improving storage stability when diluted with a non-aqueous medium.

As the non-aqueous medium, those mentioned above can be used without limitation, and alcohols are particularly preferable. Two
When two or more kinds of non-aqueous media are mixed and used, at least one of them is preferably an alcohol. The amount of alcohol used is equivalent to or more than the silicon compound (A),
In particular, it is preferably double equivalent or more.

The thickness of the thin film formed by the surface treatment agent is preferably 0.01 to 50 μm, more preferably 0.1 to 30 μm. Further, a thin film formed by a surface treatment agent which does not use the following synthetic resin film-forming component (B) or which is used in a very small amount is liable to become brittle, so 0.1 to 10 μm
Is preferred.

The synthetic resin film-forming component (B) is added to the surface treatment agent in a proportion of 0.01 to 100 parts by weight, preferably 0.1 to 10 parts by weight, based on 1 part by weight of the silicon compound (A). By blending, the film forming property of the surface treatment agent becomes good, and a tough thin film is formed. Further, the adhesion with the hydrophobic synthetic resin coating film is also improved.

As the synthetic resin film-forming component (B), various resins used as paints such as fluororesin, acrylic resin, acrylic silicone resin, polyester resin, alkyd resin and epoxy resin can be used. Two or more kinds of these resins can be used. As this resin, a so-called fluororesin for paints, which is particularly used for paints, is preferable from the viewpoint of weather resistance. In particular, when the hydrophobic synthetic resin coating film on the outdoor article is a fluororesin coating film, it is preferable from the viewpoint of adhesion with the coating film.

As the fluororesin for paint, a resin composed of one or more polymers of fluoroolefin or a copolymer obtained by copolymerizing fluoroolefin with another copolymerizable monomer is dissolved in a solvent. From the viewpoints of properties, weather resistance of the surface treatment agent coating film, coating workability of the surface treatment agent, film-forming property of the surface treatment agent, and the like. In addition, various solvent-soluble fluororesins for paints such as fluororesins for paints composed of vinylidene fluoride polymers or copolymers can be used. Hereinafter, the fluororesin for coating material made of a fluoroolefin copolymer will be mainly described.

Examples of fluoroolefins include fluoroolefins having 2 or 3 carbon atoms such as tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, hexafluoropropylene and pentafluoropropylene. Particularly, tetrafluoroethylene and chlorotrifluoroethylene are preferable. As the fluoroolefin-based copolymer,
It may be a copolymer of two or more fluoroolefins such as a vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer. However, a copolymer obtained by copolymerizing a fluoroolefin and a copolymerizable monomer other than the fluoroolefin is more preferable.

As the monomer copolymerizable with the fluoroolefin, vinyl ether, vinyl ester, allyl ether, allyl ester, isopropenyl ether, isopropenyl ester, methallyl ether, methallyl ester, α-olefin, acrylic ester,
There are monomers such as methacrylic acid esters. Two or more kinds of these monomers can be used in combination.

The vinyl ether is preferably an alkyl vinyl ether such as ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, (fluoroalkyl) vinyl ether, perfluoro (alkyl vinyl ether). Examples of the vinyl ester include "Veova-10" (trade name of Shell Chemical Co.) having a branched alkyl group, vinyl pivalate,
Fatty acid vinyl esters such as vinyl versatate, vinyl butyrate and vinyl acetate are preferred.

The allyl ether is preferably an alkyl allyl ether such as ethyl allyl ether or cyclohexyl allyl ether, and the allyl ester is preferably a fatty acid allyl ester such as allyl propionate or allyl acetate. The isopropenyl ether is preferably an alkyl isopropenyl ether such as methyl isopropenyl ether, and the α-olefin is preferably ethylene, propylene or isobutylene.

If the copolymerization ratio of the fluoroolefin is too low, the sufficiently excellent function as the weather-resistant synthetic resin film-forming component (B) cannot be exhibited. Further, if the copolymerization ratio of the fluoroolefin becomes too large, the solubility in a solvent will decrease, which is not preferable. Therefore,
A fluororesin in which the fluoroolefin is copolymerized in a proportion of 30 to 70 mol%, particularly 40 to 60 mol% based on all the monomers is preferable.

Among the above-mentioned monomers copolymerized with the fluoroolefin, vinyl ether, vinyl ester, allyl ether and allyl ester are particularly preferable because of excellent copolymerizability with the fluoroolefin.
Further, an alkyl vinyl ether having a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms, a fatty acid vinyl ester, an alkyl allyl ether and a fatty acid allyl ester are preferable.

The fluororesin for paints may have a functional group which is crosslinked by reacting with a curing agent, in addition to the above-mentioned copolymer components. A stronger coating film can be obtained by reacting the fluororesin having this functional group with a curing agent to crosslink it. Examples of this functional group include an active hydrogen-containing group capable of reacting with an isocyanate curing agent or an aminoplast curing agent, such as a hydroxyl group, an amino group, an amide group or a carboxyl group. Other than that, functional groups such as epoxy group, halogen, and double bond are also exemplified.

As a method of introducing such a functional group, a monomer having a functional group, for example, hydroxybutyl vinyl ether, hydroxybutyl allyl ether, ethylene glycol monoallyl ether, cyclohexanediol monovinyl ether, acrylic acid, methacrylic acid, Crotonic acid, undecenoic acid, glycidyl vinyl ether,
There is a method of copolymerizing glycidyl allyl ether or the like.

A method of introducing a functional group by modifying the copolymer, for example, a method of introducing a carboxylic acid group by reacting a hydroxyl group or an epoxy group with a polybasic acid anhydride such as succinic anhydride. Alternatively, a method of reacting an isocyanate alkyl methacrylate or the like to introduce a double bond can be applied.

The copolymerized unit having a functional group is preferably 5 to 20 mol% based on all copolymerized units in the copolymer.

As the fluororesin as the synthetic resin film forming component (B), even if it has a functional group, it is not always necessary to use it in combination with a component that crosslinks the functional group, that is, a curing agent. Curing agents, particularly curing agents such as polyvalent isocyanate compounds, include alcohols, water, silicon compounds (A)
Since it easily reacts with other components in surface treatment agents such as
It is often difficult to preliminarily mix and use it in the surface treatment agent. On the other hand, even a fluororesin having a functional group exerts a sufficient effect as the synthetic resin film-forming component (B) without using a curing agent together. Further, since a fluororesin having a functional group such as a hydroxyl group or a carboxyl group has high solubility in a polar solvent such as alcohols, use of a fluororesin having a functional group for this reason even if a curing agent is not used. Is preferred.

Examples of such a fluororesin include Lumiflon (Asahi Glass), Sepral Coat (Central Glass), Zaflon (Toa Gosei), Zeffle (Daikin Industries), Fluoronate (Dainippon Ink Kogyo), Floren (Japan Synthetic Rubber) and Kainer. Commercially available products such as (Atochem) can be used.

As the hydrophobic synthetic resin coating film that the outdoor article has, as will be described later, a coating film formed by coating a fluororesin paint is most preferable. The above-mentioned fluororesin can be used as the fluororesin for the fluororesin paint. In that case, a fluororesin having a functional group is usually used together with a curing agent. A curing agent, a compounding agent, and the like for the fluororesin coating material that forms the hydrophobic synthetic resin coating film will be described below together with the description regarding the fluororesin as the synthetic resin film-forming component (B). Therefore, the following description of the curing agent and the like does not mean that it is essential as the synthetic resin film-forming component (B).

The curing agent is not particularly limited as long as it can react with the functional group of the fluororesin to crosslink the fluororesin. Examples of the curing agent used for the fluorine resin having a hydroxyl group include aminoplast type curing agents, isocyanate type curing agents, polybasic acid type curing agents, polyvalent amine type curing agents, and the like.

As the aminoplast-based curing agent, methylolmelamines, methylolguanamines, methylolureas and the like can be used. As the methylolmelamines, methylolmelamine etherified with a lower alcohol such as butylated methylolmelamine, methylated methylolmelamine, and epoxy-modified methylolmelamine can be used. As the methylol ureas, alkylated methylol ureas such as methylated methylol urea and ethylated methylol urea can be used. When an aminoplast-based curing agent is used, an acidic catalyst is usually used to accelerate the crosslinking reaction.

As the isocyanate-based curing agent, there are polyvalent isocyanate compounds and blocked products thereof. The polyvalent isocyanate compound is a compound having two or more isocyanate groups, and may be a compound having two or more isocyanate groups which is a modified product or a multimer thereof.

Examples of the polyvalent isocyanate compound include aliphatic polyvalent isocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, hexamethylene triisocyanate and lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, diisocyanate methyl. Alicyclic polyvalent isocyanate compounds such as cyclohexane and non-yellowing aromatic polyvalent isocyanate compounds such as xylylene diisocyanate are used.

Examples of the modified or multimeric compound of the polyvalent isocyanate compound include what are called urethane modified products, urea modified products, isocyanurate modified products, burette modified products, allophanate modified products, and carbodiimide modified products. is there. Particularly preferred are isocyanurate modified products which are trimers and urethane modified products which are reaction products with polyhydric alcohols such as trimethylolpropane.

A coating composition using an isocyanate type curing agent having a free isocyanate group can be cured at room temperature. In particular, it is an almost indispensable curing agent for painting by field construction. An isocyanate-based curing agent having a blocked isocyanate group is usually a heat-curable coating composition like other curing agents. When an isocyanate-based curing agent is used, a urethanization catalyst such as dibutyltin dilaurate is usually used.

When a curing agent is required in the fluororesin paint for forming the hydrophobic synthetic resin coating film, the mixing amount of the curing agent is 0.1 to 100 parts by weight of the fluororesin resin.
The proportion is preferably 100 parts by weight, particularly 1 to 50 parts by weight.

When the surface treating agent in the present invention is alkaline as described above, the silicone oligomer and the silyl isocyanate in the silicon compound (A) accelerate the condensation, so that the storage stability of the surface treating agent tends to deteriorate. Therefore, the pH is preferably 7 or less. Particularly, from the viewpoint of storage stability, it is preferable to set the pH to about 3 to 4. Therefore, it is preferable to use an acid catalyst for hydrolysis as described above. In addition, pH with acid catalyst
It is preferable to use a buffering agent together in order to stabilize As the buffering agent, weak acids such as acetic acid and carbonic acid or salts thereof are preferable. The buffer itself may also have an effect as a hydrolysis catalyst. The total amount of these acid catalysts or buffers (D) is 0.001 to 100 parts by weight of the medium.
It is preferable to use 100 parts by weight, particularly 0.01 to 10 parts by weight.

When an aqueous medium is used in the present invention, it is preferable to use a surfactant together. By adding a surfactant, cissing can be suppressed when a surface treatment agent is applied on the hydrophobic synthetic resin coating film, and a uniform thin film can be formed. The amount of the surfactant blended depends on the type of surfactant,
It is appropriately selected depending on the kind of the hydrophobic synthetic resin coating film. However, it is usually 0.001 with respect to 100 parts by weight of the aqueous medium.
The ratio of -100 parts by weight, preferably 0.01-10 parts by weight is used. In particular, as a result, the surface tension of the surface treatment agent should be 30 dyn / cm or less, especially 20 dyn.
It is preferable to adjust the type and the amount so that the amount becomes / cm or less.

The type of surfactant is not particularly limited,
Nonionic ones are preferred. A fluorine-based surfactant having a high surface-active effect even in a small amount is particularly preferable. As the fluorine-based surfactant, for example, a perfluoroalkyl group-containing alkyl ether-based, alkyl ester-based, polyoxyethylene alkylamine-based, polyoxyethylene alkylamide-based fluorine-based surfactant and the like are preferable.

In the present invention, it is considered that the silicone oligomer and silylisocyanate in the silicon compound (A) are further hydrolyzed or condensed near the surface of the thin film formed by the surface treatment agent on the surface of the hydrophobic synthetic resin coating film. . A catalyst that accelerates this reaction can be added to the surface treatment agent. Such catalysts include metal compound catalysts such as metal chelates, metal esters and metal alkoxides. Examples of the metal component of this catalyst include aluminum, titanium, silicon, tin and zinc. Specifically, there are metal compound catalysts such as aluminum monoacetylacetonate bis (ethylacetoacetate) and aluminum tris (acetylacetonate). The amount used is appropriately 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, relative to 100 parts by weight of the silicon compound (A).
Parts by weight.

The surface treating agent in the present invention may contain a pigment, a light stabilizer, an ultraviolet absorber, a matting agent, a leveling agent and the like in addition to the above components. However, the thin film formed by the surface treatment agent is preferably a transparent thin film. Therefore, it is preferable not to normally use a component such as a pigment that hinders transparency. Of course, even additives such as pigments that may impair transparency can be used within the range that does not impair transparency.

Examples of the color pigment include inorganic pigments such as transparent red iron oxide, carbon black, and titanium oxide, which have good weather resistance, and organic pigments such as phthalocyanine blue, phthalocyanine green, quinacridone red, indanthrene orange, and isoindolinone yellow. Alternatively, a dye or the like may be used. The coloring pigment or dye may be contained in an amount of 3 parts by weight or less based on 100 parts by weight of the silicon compound (A) or 100 parts by weight of the total of the silicon compound (A) and the synthetic resin film forming component (B). Is preferably mixed and dispersed. When a color pigment is used, any transparent colored thin film can be formed.

Examples of the light stabilizer include hindered amine light stabilizers, and specific examples thereof include MARX.
LA62 (made by Adeka Argus Chemical Co., Ltd.) and MARXLA6
7 (manufactured by Adeka Argus Chemical Co., Ltd.) and the like. In addition, tinuvin 292, tinuvin 144, CGL-12
3, TINUVIN 440 (above, manufactured by Ciba Geigy) and the like. The amount used is 100 parts by weight of the silicon compound (A) or the silicon compound (A) and the synthetic resin film-forming component (B).
It is preferable to add 5 parts by weight with respect to 100 parts by weight in total. When these light stabilizers are added, it is usually preferable to add them after dissolving them in a solvent such as toluene.

Examples of the ultraviolet absorber include benzotriazole-based ones, and Tinuvin 328 and Tinuvin 1130 (all manufactured by Ciba-Geigy) are typical examples.
The addition amount is 100 parts by weight of the silicon compound (A) or 100 in total of the silicon compound (A) and the synthetic resin film forming component (B).
It is a range not exceeding 10 parts by weight with respect to parts by weight.

The surface treating agent in the present invention can easily form a uniform thin film by using a usual coating method. The coating method is not particularly limited, and brush coating, roller coating, tampo coating, spray coating, spin coating, flow coating and the like can be used. Further, after application, a thin film is formed only by drying at room temperature, but forced drying may be performed depending on the case.

The surface treating agent in the present invention is used for suppressing the generation of rain streaks on the surface of a coating film made of a hydrophobic synthetic resin applied to outdoor articles. Rain streaks stains are likely to occur on the hydrophobic surface, and are less likely to occur on the thin film surface formed by this surface treatment agent. Therefore, the surface treatment agent in the present invention is applied to a portion of the outdoor article coated with the hydrophobic synthetic resin, which is exposed to rain and a portion where rainwater flows down. Of course, it may be applied to the peripheral portion at the same time.

As the synthetic resin forming the hydrophobic synthetic resin coating film, there are various hydrophobic resins used as coating materials such as fluororesin, acrylic resin, acrylic silicone resin, polyester resin, alkyd resin and epoxy resin.
Two or more kinds of these resins can be mixed and used. As the hydrophobic synthetic resin coating film, a coating film formed of a fluororesin coating material having high hydrophobicity and easily causing rain streak stains has a high necessity of applying the present invention. In a synthetic resin coating film made of a coating material other than a fluororesin coating material, the coating film is likely to deteriorate, and thus the thin film formed by the surface treatment agent is easily peeled off, and the effect of the surface treatment is easily lost. On the other hand, the fluororesin coating film is less likely to be deteriorated as described above and exhibits a sufficient effect which is not the object of the present invention.

As the fluororesin coating material, the fluororesin used in the above-mentioned synthetic resin film-forming component (B) can be used. Since the surface of the hydrophobic synthetic resin coating film becomes a tougher coating film,
It is preferable to use a fluororesin coating containing a fluororesin having a functional group and a curing agent as basic components. In addition, other types of fluororesin paint may be used.

The material of the base material constituting the outdoor article is not limited. For example, inorganic materials such as concrete, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), CFRC (carbon fiber reinforced concrete), stone, slate, glass, acrylic resin, polycarbonate resin, vinyl chloride resin, polyethylene resin, etc. Synthetic organic material such as resin and rubber, natural organic material such as wood, aluminum, copper, brass, titanium, iron, stainless steel, zinc steel plate, metal material such as steel plate,
Furthermore, FRP (glass fiber reinforced synthetic resin), CFRP
There are organic-inorganic composite materials such as (carbon fiber reinforced synthetic resin).

The outdoor article according to the present invention is an outdoor article having a portion where rain streak stain is likely to occur.
For example, transportation equipment such as automobiles, trains, helicopters, ships, bicycles, snow vehicles, ropeways, lifts, fevercrafts, motorcycles, sashes, shutters, water storage tanks, doors, balconies, exterior panel panels for construction, roofing materials. , Stairs, skylights, building materials such as concrete fences, outer walls of buildings such as buildings and houses, guardrails, pedestrian bridges,
Soundproof walls, signs, highway side walls, railway viaducts, road components such as bridges, tanks, pipes, towers, plant facilities such as chimneys, greenhouses such as greenhouses, greenhouses, silos, agricultural sheets, utility poles, power transmission towers. , Communication equipment such as parabolic antenna, electric wiring box, lighting equipment, air conditioner outdoor unit, electric machine such as washing machine, and their covers, monuments, tombstones, paving materials, windshield sheets, tarpaulins,
Includes a building curing sheet.

Particularly, the present invention is preferably applied to the coated surface of the outer surface of fixed buildings such as buildings and houses and fixed structures such as steel towers and bridges. Most of such fixed structures have a surface on which rainwater flows down, and if the surface is a highly hydrophobic coated surface, rain streak stains are likely to occur. Moreover, many of these fixed structures are large, and repeated cleaning is complicated and requires high cost. Most preferably, the invention applies to such fixed structures.

[0063]

【Example】

[Example 1] A solvent-soluble fluororesin Lumiflon 200 (manufactured by Asahi Glass Co., Ltd., hydroxyl value: 52) was used as a fluoroolefin polymer, and Coronate HX (manufactured by Nippon Polyurethane Co.) was used as an isocyanate curing agent. The solid content of the curing agent is 18.5 parts by weight based on 100 parts by weight of the fluoroolefin polymer solid content, and the silane coupling agent (3-
Glycidoxypropylmethyldimethoxysilane) to 0.
8 parts by weight, 80% xylene solution of benzotriazole-based UV absorber Tinuvin 1130 (manufactured by Ciba Geigy) 3
Parts by weight, 1.5 parts by weight of a hindered amine light stabilizer CGL123 (manufactured by Ciba Geigy), 42 parts by weight of titanium oxide (manufactured by Ciba Geigy), and 3 parts by weight of Airwasil T600 (fine silica manufactured by Nippon Aerosilyl Co., Ltd.),
A composition for coloring paint was prepared. The obtained composition was diluted with Solvesso # 150, a mixed solvent of cyclohexanone and xylene (weight ratio 1: 1: 5) as an aromatic solvent to obtain a colored paint.

In addition, trimethoxysilane having a polyoxyethylene chain (Toshiba XC96-60
20 parts by weight of 1) was decomposed and condensed with hydrochloric acid in advance. Paint this on an aluminum plate and fold the plate in half with the coated side up,
Make the bottom part vertical so that the angle is in degrees,
Exposed outdoors. The state of the coating film surface was observed for two months.

[Example 2] X manufactured by Toshiba Corporation in Example 1
C96-601 is a silicon-based ceramic coating (Nichiban Giken C
RB-110) was used and evaluated in the same manner.

[Example 3] X manufactured by Toshiba Corporation in Example 1
Evaluation was made in the same manner except that C96-601 was changed to polysilazane.

[Comparative Example 1] X manufactured by Toshiba Corporation in Example 1
Evaluation was made in the same manner except that C96-601 was not added.

[Test Method] 1. Octane contact angle in water: The plate having the coating film surface is left still in water so that the coating film surface faces downward, and to this surface,
Attach 0.25 ml of octane with a U-shaped injection needle,
The contact angle was measured.

2. Silicon concentration: The silicon concentration in the coating film surface was measured by ESCA.

3. Gloss: According to JIS K5400, the specular glossiness at an incident angle of 60 ° and a light receiving angle of 60 ° was measured.

4. Weather resistance: The one having a light retention rate of 80% or more at 3000 hours by the sunshine weather meter was defined as "◯".

5. Rain streak stain: The stain streak was visually determined according to the following criteria. "No": No lines are observed when approaching within 10 m, "Reduction": No lines are observed at 10 m or more, but is found within 10 m, "Yes": 10
Approved above m.

Table 1 shows the results of Examples 1 to 3 and Comparative Example 1 described above.

[0074]

[Table 1]

[0075]

EFFECT OF THE INVENTION The outdoor article having the specific coating film surface of the present invention has reduced adhesion of dirt, and since the coating film surface has affinity with rain, the rain flow surface becomes uniform, Dust is washed out by rain, and the dusting property and the generation of rain streaks are further reduced than before.

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Claims (6)

[Claims] 1. An outdoor article having a coating film surface having an octane contact angle of 102 degrees or more in water. 2. The coating film is a thin film formed by applying a surface treatment agent containing a silicon compound (A) and a synthetic resin film-forming component (B) onto the surface of an outdoor article. Outdoor goods. 3. A coating film comprising a silicon compound (A) or a silicon compound (A) and a synthetic resin film-forming component (B) on the surface of the coating film of an outdoor article having a hydrophobic synthetic resin coating film surface. The outdoor article according to claim 1, which is a thin film formed by applying a surface treatment agent. 4. The coating film comprises a thin film formed from a silicon compound (A) and a synthetic resin film forming component (B), and the silicon atom concentration in the thin film is 5% by weight or more. The outdoor article according to any one of items. 5. The outdoor article according to any one of claims 1 to 4, wherein the silicon compound (A) is a hydrolyzate of a 1 to 3 functional hydrolyzable silane compound, an alkali silicate salt or colloidal silica. 6. The outdoor article according to claim 3, wherein the hydrophobic synthetic resin coating film is a fluororesin coating film.