JPH0812921A - Resin composition for paint - Google Patents

Abstract

(57) [Summary] [Structure] A functional group-containing fluororesin (a), a curing agent (b) capable of cross-linking the functional group-containing fluororesin (a), and a tetrafunctional hydrolyzable silane compound multimer (c). A coating resin composition containing the same. [Effect] It is possible to prevent the generation of streak-like stains generated in a portion where rainwater gathers and flows under the window frame of a building.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating resin composition and an outdoor article coated with the resin composition.

[0002]

2. Description of the Related Art Conventionally, metals, inorganics, plastics,
Products such as wood, paper, leather and textiles have surface protection,
Surface coating such as painting is performed for the purpose of imparting designability and functionality, and various paints have been developed.

Recently, fluororesin paints have been widely used as paints having excellent weather resistance. This fluororesin paint exhibits marked weather resistance as compared with various synthetic resin paints that have been widely used for a long time. However, the antifouling property against stains on the surface is similar to that of other synthetic resin paints, and therefore, to use it as a high-performance product,
The improvement is desired.

[0004]

In the past, coating compositions containing a polyfluorinated carbon chain and a polymer having a hydrophilic group have been proposed in an attempt to solve the stain on the surface of a coated article (for example, a special method). See Kaihei 1-18653). However, the coating composition of this proposal has an effect of preventing the generation of stains on spots due to rainwater, but streaks are generated in a portion where rainwater gathers and flows, such as an outdoor article, for example, under a window frame of a building. It was not sufficient to prevent such stains (hereinafter referred to as rain streak stains).

[0005]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned problems and comprises a functional group-containing fluororesin (a) and a curing agent (b) capable of crosslinking the functional group-containing fluororesin (a). And a resin composition for paints, which comprises a multimer (c) of a tetrafunctional hydrolyzable silane compound.

By coating the composition of the present invention on a portion of an outdoor article where rain streak stains are likely to occur, it is possible to prevent generation of rain streak stains very well for a long period of time.

As the functional group-containing fluororesin (a) (hereinafter simply referred to as resin (a)), a wide range of fluororesins can be used without limitation, and fluoroolefins known as fluororesins for coating materials and copolymers therewith are known. The resin (a) obtained by copolymerizing possible monomers is preferable in terms of solubility in a solvent, weather resistance of a coating film, coating workability, and the like.

Examples of fluoroolefins include fluoroolefins having 2 or 3 carbon atoms such as tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, hexafluoropropylene and pentafluoropropylene.

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,
At least one monomer selected from methacrylic acid esters and the like can be mentioned.

Here, as the vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, fluoroalkyl vinyl ether,
An alkyl vinyl ether such as perfluoro (alkyl vinyl ether) is exemplified. Examples of the vinyl ester include fatty acid vinyl ester such as Veova-10 (trade name, manufactured by Shell Chemical Co.) having a branched alkyl group, vinyl butyrate, vinyl acetate, vinyl pivalate and vinyl versatate.

Examples of the allyl ether include alkyl allyl ethers such as ethyl allyl ether and cyclohexyl allyl ether. As an allyl ester,
Examples are fatty acid allyl esters such as allyl propionate and allyl acetate. Examples of the isopropenyl ether include alkyl isopropenyl ether such as methyl isopropenyl ether. Examples of the α-olefin include ethylene, propylene and isobutylene.

If the copolymerization ratio of the fluoroolefin is too low, the weather resistance of the weather resistant coating will not be sufficiently excellent. Further, if the copolymerization ratio of the fluoroolefin becomes too large, the solubility in a solvent will decrease, which is not preferable. Therefore, as the resin (a), the proportion of fluoroolefin is 30 to 70 mol%, particularly 40
It is preferable that the resin is copolymerized at a ratio of -60 mol%.

It is preferable that the resin (a) is copolymerized with the above compound in addition to the fluoroolefin from the viewpoint of solubility in a solvent. In particular, vinyl ether, vinyl ester, allyl ether, and allyl ester are preferable from the viewpoint of excellent copolymerizability with 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,
Fatty acid allyl esters are preferred.

Since the resin (a) has a functional group capable of undergoing a crosslinking reaction with the curing agent (b) in addition to the above-mentioned copolymerization component, a stronger coating film can be obtained. As this functional group,
Examples thereof include active hydrogen-containing groups capable of reacting with an isocyanate-based curing agent or an aminoplast-based curing agent, such as a hydroxyl group, an amino group, an amide group and a carboxyl group. Other than that, functional groups such as epoxy group, halogen, and double bond are also exemplified.

As a method for 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.

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

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

Examples of such resin (a) include Lumiflon (Asahi Glass), Cefraralcoat (Central Glass), Zaflon (Toa Gosei), Zeffle (Daikin Industries), Fluoronate (Dainippon Ink Kogyo), Floren (Nippon Synthetic Rubber). ), Kainer (Atochem) and the like which are commercially available can be used.

The curing agent (b) is not particularly limited as long as it can crosslink the resin (a). As a specific example,
Examples thereof include aminoplast-based curing agents, isocyanate-based curing agents, polybasic acid-based curing agents, polyvalent amine-based curing agents, and the like.

By cross-linking the curing agent (b) with the resin (a), a cured coating film having excellent physical properties is formed, and at the same time, a multimer (c) of a tetrafunctional hydrolyzable silane compound (hereinafter simply referred to as a large amount). It is considered that the reaction between the body (c) and the resin (a) is suppressed, the polymer (c) is oriented on the surface of the coating film, and the effect of preventing the generation of rain streaks becomes remarkable.

In the above-mentioned JP-A-1-198653, a composition comprising an alcohol solution of a hydrolyzate of a hydrolyzable silane compound and a hydroxyl group-containing fluororesin for the purpose of improving scratch resistance and bending resistance. Are known. However, it is not preferable to apply such a composition to the present invention for the following reasons. That is, since the alcohol in this composition reacts with the curing agent (b), particularly the isocyanate curing agent, a good cured coating film cannot be obtained.

When the functional group of the resin (a) has an active hydrogen-containing group as the curing reactive site, examples of the curing agent (b) include aminoplast-based curing agents and isocyanates used in ordinary acrylic paints and the like. At least one selected from a system curing agent, a polybasic acid or an acid anhydride thereof can be used.

As the aminoplast type curing agent, methylol melamines, methylol guanamines, methylol ureas and the like can be used. Examples of the methylol melamines include methylol melamine etherified with a lower alcohol such as butylated methylol melamine and methylated methylol melamine, and epoxy modified methylol melamine. Examples of the methylolureas include alkylated methylolureas such as methylated methylolurea and ethylated methylolurea. When an aminoplast-based curing agent is used, the crosslinking reaction can be promoted by adding an acidic catalyst.

Examples of the isocyanate type curing agent include polyvalent isocyanate compounds and blocked products thereof. A polyvalent isocyanate compound is a compound having two or more isocyanate groups, and is composed of a modified product or a multimer thereof.
It may be a compound having the above isocyanate group. Polyvalent isocyanate compounds, specifically ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, hexamethylene triisocyanate, aliphatic polyisocyanate compounds such as lysine diisocyanate,
Aliphatic polyisocyanate compounds such as isophorone diisocyanate, dicyclohexylmethane diisocyanate and diisocyanate methylcyclohexane, and m-
A non-yellowing aromatic isocyanate compound such as xylene diisocyanate or p-xylene diisocyanate is 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, carbodiimide modified products and the like. 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.

Examples of preferred polyvalent isocyanate compounds include non-yellowing isocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, and their blocked and polymerized products.

When a non-blocked polyvalent isocyanate compound is used, the resin (a) can be crosslinked at room temperature, which facilitates on-site construction and is advantageous when performing repair coating. When a polyvalent isocyanate compound is used, the crosslinking reaction can be promoted by adding a known catalyst such as dibutyltin dilaurate.

As the polybasic acid, long-chain aliphatic dicarboxylic acids, aromatic polyvalent carboxylic acids and the like are useful, and their acid anhydrides are also useful.

The tetrafunctional hydrolyzable silane compound is a compound in which four hydrolyzable groups are directly bonded to a silicon atom.
The polymer (c) is a compound obtained by condensation of this compound.

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. Preferred is 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. Particularly preferred is an alkoxy group, which has 4 or less carbon atoms, particularly 1 to
Two is preferable.

The multimer (c) has a degree of multimerization that does not form a gel-like product in the resin composition for coating material. Here, the degree of multimerization means the number of condensed molecules of a tetrafunctional hydrolyzable silane compound. Linear, branched, cyclic,
Some have a network structure, usually considered to be a linear structure or a mixture of linear structures containing branched, cyclic, or network structures. . As the multimer (c) used in the present invention, those having these structures may be used alone or as a mixture of those having these structures.

Examples of preferable polymer (c) include a polymer of tetraalkoxysilane. If this is shown as having a linear structure, the general formula RO (Si (OR)
₂ O) _n R.

In the general formula, n represents the degree of multimerization. The normally available multimers are mixtures of multimers with different n, and the degree of multimerization is represented by n averaged. Preferable n is 2 to 10, and 2 to 8 is particularly preferable. n is 1
Those having a large n do not have sufficient effect of preventing the generation of stains on rain streaks, and those having a large n have an excessively large viscosity, which makes it difficult to prepare and coat a resin composition for coating, which is not preferable.

In the general formula, R is exemplified by lower alkyl groups such as methyl group, ethyl group, propyl group and butyl group. From the aspect of hydrolyzability and condensation of the alkoxy group,
A tetramethoxysilane multimer in which R is a methyl group or a tetraethoxysilane multimer in which R is an ethyl group is preferable. A methyl group is particularly preferable in that it exhibits an effect even in a small amount and has an effect of preventing the generation of rain streak stains without deteriorating other coating film characteristics. Plural Rs may be different in one molecule.

Commercially available products of the multimer (c) are MKC silicates MS51, MS56 and MSEP manufactured by Mitsubishi Kasei.
2. Methyl silicate 51 manufactured by Colcoat, ethyl silicate 40, 40T, 48, ORGATICS SI series manufactured by Matsumoto Trading, ethyl silicate 40 manufactured by Tama Chemical Co.,
45 and the like.

The degree of multimerization of a tetrafunctional hydrolyzable silane compound such as tetraalkoxysilane and its multimers may be represented by "silica content". The “silica content” means the weight ratio of silica (SiO ₂ ) produced from the compound, and can be obtained by measuring the amount of silica produced by completely hydrolyzing the compound and calcining. Further, the "silica content" indicates the ratio of silica generated from one molecule of the compound to one molecule of the compound, and the formula [silica content (% by weight) = degree of multimerization × (molecular weight of SiO ₂ ) × 100]
/ (Molecular weight of the compound)].

By setting the silica content of the tetramethoxysilane polymer to be 40% by weight or more and the silica content of the other polymers to be 35% by weight or more, it is possible to prevent the generation of rain streaks stains for a long period of time. .

The composition of the present invention can be used with a solvent (d) which dissolves the resin (a), the curing agent (b) and the multimer (c). For example, alcohols such as ethanol and isopropanol, 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, and aliphatic solvents and ethers. Examples include solvents and petroleum-based solvents. Two or more of these solvents may be used in combination. The composition of the present invention may be one in which the resin (a), the curing agent (b) and the multimer (c) are dispersed in an organic solvent or an aqueous medium.

Of course, when the curing agent (b) is a polyvalent isocyanate compound, the use of a solvent which reacts with the polyvalent isocyanate compound such as alcohols and water must be avoided. This is because the polyvalent isocyanate compound is not sufficiently used for the original cross-linking of the resin (a), and the cross-linking of the resin (a) is insufficient, resulting in poor curing.

The resin (a), the curing agent (b) and the polymer (c) in the composition of the present invention are contained in an amount of 0.1 to 100 parts by weight based on 100 parts by weight of the resin (a). The ratio of 0.1 to 100 parts by weight of the polymer (c) is preferable. If the content of the curing agent is less than 0.1 parts by weight, the solvent resistance and hardness will be insufficient, and if the content of the curing agent exceeds 100 parts by weight, the workability and impact resistance will decrease, such being undesirable. Particularly preferred ratios are 1 to 50 parts by weight of the curing agent (b) and 1 to 50 parts of the polymer (c) with respect to 100 parts by weight of the resin (a).
The ratio is parts by weight.

When the resin (a) is a hydroxyl group-containing fluororesin, the isocyanate-based curing agent should be used such that the isocyanate group content is 0.8 mol or more per 1 mol of the hydroxyl group-containing fluororesin. preferable.
If it is less than 0.8 mol, the curing of the coating composition will be insufficient and the solvent resistance etc. may be deteriorated, which is not preferable.
In particular, when the amount is 1.1 mol or more, the effect of preventing rain streak stains increases, which is preferable. The upper limit is not particularly limited, but unreacted isocyanate groups may remain in the coating film, which may adversely affect weather resistance and other performances. Therefore, the preferable upper limit is about 2.0, and more preferably 1.2 to 10. 1.
It is 6.

When the polymer (c) is a polymer of tetramethoxysilane or a polymer of tetraethoxysilane, the content ratio is 5 to 100 parts by weight of the resin (a).
The proportion is preferably 50 parts by weight. Content ratio is 5
If it is less than 50 parts by weight, the desired effect of preventing the generation of stains on rain streaks is low, and if it exceeds 50 parts by weight, poor curing of the coating film is likely to occur, which is not preferable.

The polymer (c) is more preferably blended in an amount not less than the incompatibility point with respect to the resin (a). Here, the incompatible point means that the resin (a) and the multimer (c) are mixed with the solvent (d).
The method of applying the solution dissolved in to a glass plate and checking the presence or absence of white turbidity of the coating film when dried at 20 ° C. can confirm white turbidity “minimum condensate (c) to resin (a) weight”. ) Weight ”.

Since the multimer (c) is blended at a point of incompatibility or higher, the resin (a) and the multimer (c) undergo phase separation after coating, and the resin of the present invention formed on the surface of an outdoor article. It is considered that the polymer (c) is hydrolyzed in the vicinity of the coating film surface of the composition, so that the surface becomes hydrophilic and the generation of rain streak-like stains can be more effectively prevented. This incompatibility point has different values depending on the type of resin (a), the type of polymer (c) and the degree of condensation.

The inventor of the present invention basically has the effect of preventing the generation of rain streak stains by the coating film formed from the coating resin composition of the present invention because the coating film surface is hydrophilic and oil repellent. I believe. 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 coating resin composition of the present invention described above is one in which the coating film formed thereby can have an octane contact angle in water of 102 degrees or more.

The present inventor has also found that there is a correlation between the advancing tension of the surface and the susceptibility to the formation of rain streaks as well as the octane contact angle in water. That is, it was found that when the forward tension of the surface is smaller than 0 dyn / cm, rain streak stain is likely to occur, and when it is higher than this, rain streak stain is less likely to occur.

Although this action is not always clear, when the advancing tension of the surface is smaller than 0 dyn / cm, the rainwater tends to gather when it runs down, that is, because it flows like a streak, a streak appears at the trace of the rainwater. It is considered that when the surface tension is larger than 0 dyn / cm, rainwater-like stains are unlikely to occur because rainwater tends not to collect when the rainwater flows down. Therefore, in order to prevent the generation of rain streaks on the surface of painted outdoor articles,
The forward tension of the surface of the thin film formed by the surface treatment agent is 0d.
It is preferably yn / cm or more. A thin film having such a forward tension has an extremely excellent effect of preventing the generation of rain streaks.

The forward tension of the surface means the tension per unit peripheral length at the time when the sample comes into contact with the water surface when the sample having the thin film formed by the surface treatment agent is immersed in distilled water. When the sample is pulled up from distilled water, it is distinguished from the receding tension which is the tension per unit circumferential length at the time when the sample leaves the water surface.

This advancing tension can be measured using a dynamic contact angle measuring device. Further, since it is difficult to directly measure the advancing tension, the weight change amount (dyn) of the weight change of the sample is measured while the sample is immersed in distilled water at 25 ° C. at a constant rate.
Until the sample comes into contact with the water surface, and the weight change amount at the time when the sample comes into contact with the water surface is determined to obtain the unit perimeter length (c
It is a value determined by dividing by m). In addition, the present inventors adopted the value obtained by measuring at the immersion speed of 20 mm / min as the forward tension.

The composition of the present invention comprises a base composition (A) consisting of a solution containing a resin (a) and a curing agent composition (B) consisting of a solution containing a curing agent (b) and a multimer (c). It is preferable that the base resin composition (A) and the curing agent composition (B) are mixed with each other to prepare the resin composition for coating material of the present invention. This composition does not require a baking treatment and is excellent in on-site workability. As the curing agent (b) in this case, the above-mentioned non-blocked isocyanate curing agent or the like is used.

The compounding amounts of the curing agent (b) and the multimer (c) in the curing agent composition (B) and the compounding amount of the resin (a) in the main agent composition (A) are the same as the main agent composition (A). When the curing agent composition (B) is mixed with the curing agent composition (B), it is preferable to mix them in the respective compositions so as to have the above-mentioned mixing ratio.

It is considered that the polymer (c) is hydrolyzed near the surface of the coating film of the composition of the present invention formed on the surface of the outdoor article. A catalyst that accelerates this hydrolysis may be used. As such a catalyst, a metal chelate, a metal ester, a metal compound catalyst such as a metal alkoxide is used, and as the metal, aluminum, titanium, silicon, tin,
Examples include zinc. Specific examples include aluminum monoacetylacetonate bis (ethylacetoacetate) and aluminum tris (acetylacetonate). The amount used is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the polymer (c).

In addition to the above components, the composition of the present invention is used for improving the adhesion of a curing catalyst, a pigment, an ultraviolet absorber, a light stabilizer, a leveling agent, a matting agent, a surfactant, an anti-sagging agent or a coating film. The silane coupling agent and the like may be included. Further, other paint resins such as acrylic resin, polyester resin, epoxy resin, and silicone resin may be used in combination within a range that does not hinder the generation of rain streaks.

A silane coupling agent, which is a silane compound in which a hydrolyzable group and an organic group other than the hydrolyzable group are bonded to a silicon atom, is applied to the coating film together with the polymer (c) for preventing the generation of rain streaks. It is preferable to use them together for improving the adhesion.

In the present invention, the silane coupling agent means a silane compound having the above-mentioned hydrolyzable group and other organic group. Organic groups other than hydrolyzable groups are bonded to silicon atoms at terminal carbon atoms. The organic group may be a hydrocarbon group having no functional group, but it is preferable that at least one organic group has a functional group. An alkoxy group is particularly preferable as the hydrolyzable group bonded to the silicon atom, and an isocyanate group is also preferable. Particularly, a silane compound having 2 to 3 alkoxy groups is preferable.

In the above silane coupling agent, the organic group other than the hydrolyzable group has one organic group having a functional group, and when there is another organic group, it is usually a functional group such as an alkyl group. It is usually an organic group having no. 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. Particularly, a silane coupling agent having an amino group or an epoxy group is preferable because the adhesion is improved even if the addition amount is small. The amount of the silane coupling agent is appropriately 1 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the polymer (c).

The silane coupling agent can be used not only by blending it with the coating resin composition but also by pretreating the surface of the outdoor article as a primer. In this case, the silane coupling agent may be applied directly, or may be dissolved in an appropriate solvent such as alcohol or water and applied. A surface treatment is then applied over this primer.

Other than the silane coupling agent, other compounds capable of exhibiting the same effect can be used. Examples of the silane coupling agent and other adhesion improvers include the following compounds.

Methyltrimethoxysilane, dimethylvinylmethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane,
Vinyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, methylsilyltriisocyanate, vinylsilyltriisocyanate, diethoxysilyldiisocyanate, dimethyldichlorosilane, trimethyl Chlorosilane, chloromethyldimethylsilane, methyltrichlorosilane, chloromethyldimethylvinylsilane, hexamethylsilazane, cyclic silazane, N, N-bis (trimethylsilyl) trifluoroacetamide, N-trimethylsilylacetamide, N-trimethylsilylphenylurea, bistrimethylsilylurea, Dimethyl trimethyl silyl amine, trimethyl silyl imidazole, trimethyl silyl dimethyl Amine, methyl triacetoxy silane, 1,3-bis (.gamma.-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.

Commercially available products are T manufactured by Toshiba Silicone Co., Ltd.
SL8000 series, TSL8100 series, TS
L8300 series, TSL9306, TSL88 series, XC95 series, XC99 series, Shin-Etsu Chemical's KBM1000 series, KBE1000 series, KBC100 series, KBM400, 500, 6
00,700,800,900 series, X-12 series, KBP503 series, AZ manufactured by Nippon Unicar Co., Ltd.
Examples include series, A series, and Union Carbide silane coupling agent A series.

Preferred silane coupling agents are γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -γ-aminopropyltriethoxysilane. , N- (2-aminoethyl)
-Γ-aminopropyltrimethoxysilane, N- (2-
Amino group-containing silane coupling agents such as aminoethyl) -γ-aminopropylmethyldimethoxysilane, and 3-glycidoxypropyltrimethoxysilane, 3
-Glycidoxypropylmethyldimethoxysilane, 3-
Glycidoxypropylmethyldiethoxysilane, 2-
An epoxy group-containing silane coupling agent such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

Examples of the material of the article having a portion where rain streaks are easily generated include concrete, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), CFRC (carbon fiber reinforced concrete), stone, slate, Inorganic materials such as glass, acrylic resins, polycarbonate resins, vinyl chloride resins, polyethylene resins and other organic materials such as rubber, aluminum,
Examples of the material include metal materials such as copper, brass, titanium, iron, stainless steel, zinc steel plate and steel plate, wood, and organic-inorganic composite materials such as FRP (glass fiber reinforced synthetic resin) and CFRP (carbon fiber reinforced synthetic resin).

The composition of the present invention may be applied directly to a substrate made of any of these materials, or may be applied after surface treatment with a primer or the like or after undercoating.
It is preferable to apply a surface treatment such as sanding or an undercoating treatment to a substrate which has insufficient adhesion when directly coated.

The composition of the present invention is applied to, for example, the following outdoor articles where rain streak stains are likely to occur.
As a result, it is possible to prevent the generation of rain streaks for an extremely long period of time. As an outdoor article, for example, a car, a train, a helicopter, a ship, a bicycle, a snowmobile, a ropeway, a lift, a fovercraft, a transportation device such as a motorcycle, a sash, a shutter, a water tank, a door, a balcony, an exterior for construction. Construction materials such as board panels, roofing materials, stairs, skylights, concrete walls, building exterior walls, guardrails, pedestrian bridges, soundproof walls, signs, highway side walls, railway viaducts, road materials such as bridges, tanks, pipes, towers, Plant equipment such as chimneys, greenhouses, greenhouses, silos, agricultural equipment such as agricultural sheets, telephone poles, power transmission towers, communication equipment such as parabolic antennas, electrical wiring boxes, lighting equipment, air conditioners outdoor equipment, washing machines, etc. Electric appliances and their covers, monuments, tombstones, paving materials, windshields, tarpaulins, curing sheets for construction, etc. And the like.

The composition of the present invention can be applied by any ordinary coating method such as brush coating, roller coating, spray coating and flow coater without any particular limitation.

[0067]

【Example】

Example 1 Fluorine resin having hydroxyl group (chlorotrifluoroethylene / cyclohexyl vinyl ether / ethyl vinyl ether / hydroxybutyl vinyl ether =
100 parts by weight of a 50/15/25/10 mol% copolymer) in xylene solution (solid content: 60% by weight, hydroxyl value: 50) was added to ethyl silicate 40 [polymer of tetraethoxysilane manufactured by Colcoat Co., Ltd. Degree about 5, silica content 40
%)] Was added, and the amount of which became 30 parts by weight was coated on a glass plate and dried at 20 ° C. The coating film obtained was cloudy. The incompatible point was when 24 parts by weight was added.

100 parts by weight of the above-mentioned fluorine resin having a hydroxyl group, 18.5 parts by weight of Coronate HX (isocyanate-based curing agent from Japan Polyurethane: hexamethylene diisocyanate cyclic trimer) as a curing agent, and 25 parts by weight of titanium oxide as a pigment. Parts, 0.5 parts by weight of dibutyltin dilaurate (a solution diluted 1000 times with xylene, hereinafter referred to as dibutyltin dilaurate solution) as a curing catalyst, and 30 parts by weight of ethyl silicate 40 are added and uniformly mixed to obtain a fluororesin coating material. It was

The obtained coating material was applied onto a 15 cm × 40 cm zinc phosphate treated aluminum plate and dried at room temperature for 1 week to obtain a coated article. The aluminum plate was bent in half and exposed outdoors with the coated surface outside so that the upper part was at an angle of 30 degrees from the horizontal and the lower part was vertical. The coated article was free from rain streaks even after 5 months of exposure.

[Example 2] 10 parts by weight of ethyl silicate 40 was added to 100 parts by weight of the xylene solution of the fluorine-containing fluororesin used in Example 1, and the mixture was coated on a glass plate.
The coating film dried at 20 ° C. was transparent.

Next, to 100 parts by weight of the xylene solution of the fluorine-containing fluororesin used in Example 1, 18.5 parts by weight of Coronate HX as a curing agent, 25 parts by weight of titanium oxide as a pigment, and a dibutyltin dilaurate solution as a curing catalyst. 0.5 parts by weight and 10 parts by weight of ethyl silicate 40 were added and uniformly mixed to obtain a fluororesin coating material.

A coated article similar to that of Example 1 was obtained using the obtained coating material, and exposed outdoors as in Example 1. The coated article exhibited rain streaks even after 3 months of exposure. However, rain streaks were slightly observed after 5 months of exposure.

Example 3 100 parts by weight of a xylene solution of the fluororesin having a hydroxyl group used in Example 1 was mixed with methyl silicate 51 [a tetramethoxysilane polymer produced by Colcoat (average degree of polymerization: about 4, silica content). 51% by weight)]
The coating film obtained by adding 10 parts by weight to a glass plate and drying at 20 ° C. was cloudy. The incompatible point was when 6 parts by weight was added.

Next, 100 parts by weight of the xylene solution of the fluorine-containing fluororesin used in Example 1, 18.5 parts by weight of Coronate HX as a curing agent, 25 parts by weight of titanium oxide as a pigment, and a dibutyltin dilaurate solution as a curing catalyst. 0.5 parts by weight and 12 parts by weight of methyl silicate 51 were added and uniformly mixed to obtain a fluororesin coating material.

A coated article similar to that of Example 1 was obtained using the obtained coating material, and exposed outdoors as in Example 1, and the coated article exhibited rain streak stain even after 5 months of exposure. There was no The forward tension of the surface of this coated article is 2.1.
It was 5 dyn / cm.

Example 4 100 parts by weight of the xylene solution of the fluorine-containing fluororesin used in Example 1, 18.5 parts by weight of Coronate HX as an isocyanate-based curing agent, 25 parts by weight of titanium oxide as a pigment, and a curing catalyst were used. 0.5 parts by weight of dibutyltin dilaurate solution, 12 parts by weight of methyl silicate 51, and 0.1 parts by weight of aluminum monoacetylacetonate bis (ethylacetoacetate) were added and uniformly mixed to obtain a fluororesin coating material.

A coated article similar to that of Example 1 was obtained using the obtained coating material and exposed to the outdoors in the same manner as in Example 1. The coated article exhibited rain streak stain even after 5 months of exposure. There was no The forward tension of the surface of this coated article is 13.2d.
It was yn / cm.

After this coating film was dried at room temperature for 7 days, a xylene rubbing test (a test of rubbing the surface of the coating film while applying a load of 1 kg / cm ² of gauze impregnated with xylene) was conducted. The coating film did not change after 200 times.

"Examples 5 to 6, Comparative Example 1" Paints were prepared with the compositions shown in Table 1 and evaluated in the same manner as in Example 1. The results after 5 months of exposure are shown in Table 1. Further, the advancing tension on the surface of the coated article of Comparative Example 1 was -4.3 dyn / cm.

Example 7 In place of methyl silicate 51, ethyl silicate 48 [multimer of tetraethoxysilane manufactured by Colcoat (average degree of multimerization of about 8, silica content 48)
The same evaluation as in Example 3 was carried out except that 10 parts by weight of [) were added, and no rain streak stain was generated even after 5 months of exposure.

"Examples 8 to 9" Paints were prepared with the compositions shown in Table 2 and evaluated in the same manner as in Example 1. The results after 5 months of exposure are shown in Table 2.

"Comparative Example 2" In the same manner as in Example 4 except that 50 parts of HAS-1 (alcohol solution of tetraethoxysilane partially hydrolyzed condensate produced by Colcoat Co.) was used in place of methyl silicate 51 in Example 4. A coating film was formed. This coating film was dried at room temperature for 7 days and then subjected to a xylene rubbing test. As a result, the coating film dissolved in 20 times.

"Comparative Example 3" In Example 4, instead of the methyl silicate 51, ethyl silicate 28 (tetraethoxysilane monomer manufactured by Colcoat Co., silica content about 28.
The same evaluation as in Example 4 was carried out except that 50 parts by weight (8% by weight) was used, and after 1 month of exposure, rain streak stain was observed.

[Example 10] 100 parts by weight of a xylene solution of the fluorine-containing fluororesin used in Example 1, 25 parts by weight of titanium oxide, 75 parts by weight of xylene, 60 parts of butyl acetate.
Parts by weight, 8 parts of n-butanol, 30 parts by weight of butyrolized melamine (Uban 20SE60 manufactured by Mitsui Toatsu Co., solid content 60% by weight), curing catalyst (Nacure 5 manufactured by Kusumoto Kasei Co., Ltd.)
225) A composition comprising 0.5 parts by weight and 5 parts by weight of ethyl silicate 48 is coated on an aluminum plate and heated at 140 ° C.
It was dried and cured in 30 minutes.

When this test piece was exposed outdoors in the same manner as in Example 1, no rain streak stain was observed even after 5 months.

[Example 11] 100 parts by weight of a xylene solution of the fluorine-containing fluororesin used in Example 1, 25 parts by weight of titanium oxide, 75 parts by weight of xylene, 60 parts of butyl acetate.
20 parts by weight, blocked isocyanate (C-2507 manufactured by Nippon Polyurethane Industry Co., methyl ethyl ketoxime block of hexamethylene diisocyanate cyclic trimer, solid content 80% by weight), 0.5 parts by weight of dibutyltin dilaurate solution and 48 parts of ethyl silicate. The composition consisting of 10 parts of is coated on an aluminum plate,
It was dried and cured in 0 minutes.

When this test piece was exposed outdoors in the same manner as in Example 1, no rain streak stain was observed even after 5 months.

Reference Example 1 Twenty-five parts by weight of titanium oxide CR-95 (manufactured by Ishihara Sangyo) as a pigment and 100 parts by weight of a xylene solution of the fluororesin having a hydroxyl group used in Example 1 and a silane containing a terminal epoxy group are used. 0.5 parts by weight of 3-glycidoxypropylmethyldimethoxysilane as a coupling agent, 2 parts by weight of Tinuvin 1 as an ultraviolet absorber
130 (manufactured by Ciba Geigy), 0.1 part by weight of CGL123 (manufactured by Ciba Geigy) as a hindered amine light stabilizer, 2 parts by weight of Aerosil T600 (manufactured by Nippon Aerosil) as a fine silica of a matting agent, and promotes generation of hydroxyl groups by hydrolysis. As a catalyst to be used, 0.2 part by weight of aluminum monoacetylacetonate bis (ethylacetoacetate) was mixed to prepare a main component composition of a two-pack type coating composition.

A curing agent composition comprising 18 parts by weight of a hexamethylene diisocyanate trimer, 20 parts by weight of methyl silicate 51, and 35 parts by weight of a diluent solvent of toluene / butyl acetate (mixing ratio = 4/3). Was prepared.

Reference Example 2 In the curing agent composition of Reference Example 1, 50 parts by weight of ethyl silicate 40 was used instead of 20 parts by weight of methyl silicate 51.

Reference Example 3 In the curing agent composition of Reference Example 1, 20 parts by weight of methylolmelamine was used instead of 18 parts by weight of the trimer of hexamethylene diisocyanate.

Reference Example 4 In the curing agent composition of Reference Example 1, 25 parts by weight of hexamethylene diisocyanate trimer blocked with methyl ethyl ketoxime was used instead of 18 parts by weight of hexamethylene diisocyanate trimer. .

"Comparative Reference Example 1" In Reference Example 1, methyl silicate 51 was added to the main agent composition instead of being added to the curing agent composition.

"Comparative Reference Example 2" In Reference Example 2, ethyl silicate 40 was added to the base composition instead of being added to the curing agent composition.

The results of Reference Examples 1 to 4 and Comparative Reference Examples 1 and 2 are shown in Table 3 below. In addition, the storage stability in the table is 100 g of the main ingredient composition and the hardening agent composition of the paint, respectively, after putting them in a closed container at 50 ° C. for 30 days, and then returning the composition to room temperature to make the composition cloudy and solidified. Existence was checked.

[Example 12] A coated article similar to that of Example 1 was obtained using a coating material obtained by mixing 100 parts by weight and 35 parts by weight of the main agent composition and the curing agent composition of Reference Example 1, respectively. When exposed outdoors in the same manner as in Example 1, this coated article was free from rain streaks even after 5 months of exposure.

[Example 13] Coating similar to that of Example 1 was performed using a coating material obtained by mixing 100 parts by weight and 35 parts by weight of the main agent composition of Reference Example 1 and the curing agent composition of Reference Example 2, respectively. When an article was obtained and exposed to the outdoors in the same manner as in Example 1, the coated article did not show rain streaks even after 5 months of exposure.

[Example 14] Coating similar to that of Example 1 was performed using a coating material obtained by mixing 100 parts by weight and 35 parts by weight of the main agent composition of Reference Example 1 and the curing agent composition of Reference Example 3, respectively. When an article was obtained and exposed to the outdoors in the same manner as in Example 1, the coated article did not show rain streaks even after 5 months of exposure.

[Example 15] Coating similar to that of Example 1 using a coating material obtained by mixing 100 parts by weight and 35 parts by weight of the main agent composition of Reference Example 1 and the curing agent composition of Reference Example 4, respectively. When an article was obtained and exposed to the outdoors in the same manner as in Example 1, the coated article did not show rain streaks even after 5 months of exposure.

[Example 16] To 100 parts by weight of the fluororesin in the fluororesin coating material obtained in Example 1, 0.1 parts by weight of p-toluenesulfonate was added and uniformly mixed, and then coated on an aluminum plate. It was dried and cured at room temperature for 1 week. The advancing tension of the surface of this coated article was 1.21 dyn / cm, and the outdoor-exposed article did not show rain streaks even after 5 months of exposure.

[0101]

[Table 1]

[0102]

[Table 2]

[0103]

[Table 3]

[0104]

Since the article coated with the composition for a fluorine-containing coating of the present invention does not cause stains on rain lines, it has an effect of maintaining aesthetics when it is used as an outdoor article such as a building exterior material or an automobile outer panel. Is excellent.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese Patent Application No. 6-78732 (32) Priority date Hei 6 (1994) April 18 (33) Country of priority claim Japan (JP) (31) Priority Claim Number Japanese Patent Application No. 6-88939 (32) Priority Date No. 6 (1994) April 26 (33) Country of priority claim Japan (JP) (31) No. of priority application Japanese Patent Application No. 6-88940 (32) Priority Hihei 6 (1994) April 26 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 6-92206 (32) Priority Day Hei 6 (1994) April 28 (33) ) Country of priority claim Japan (JP) (72) Inventor Bunji Uchino 3-474-3 Tsukoshikoshi, Sachi-ku, Kawasaki-shi, Kanagawa Asahi Glass Co., Ltd. Tamagawa branch room

Claims (9)

[Claims] 1. A coating resin containing a functional group-containing fluororesin (a), a curing agent (b) capable of cross-linking the functional group-containing fluororesin (a), and a tetrafunctional hydrolyzable silane compound multimer (c). Composition. 2. A resin composition for coatings, a main agent composition (A) comprising a solution containing a functional group-containing fluororesin (a), and a curing agent comprising a solution containing a curing agent (b) and a multimer (c). The composition according to claim 1, which is obtained by preparing the composition (B) in advance and then mixing the base composition (A) and the curing agent composition (B). 3. The composition according to claim 1, wherein the tetrafunctional hydrolyzable silane compound is tetraalkoxysilane. 4. The composition according to claim 3, wherein the tetraalkoxysilane is tetramethoxysilane or tetraethoxysilane. 5. The composition according to claim 1, wherein the content of silica defined in the specification of the multimer (c) is 35% by weight or more. 6. A functional group is contained in a proportion of 0.1 to 100 parts by weight of a curing agent (b) and 0.1 to 100 parts by weight of a multimer (c) with respect to 100 parts by weight of a functional group-containing fluororesin (a). The composition according to claim 1, which comprises a fluororesin (a), a curing agent (b) and a multimer (c). 7. The functional group-containing fluororesin (a) according to claim 1, wherein the multimer (c) is contained in an amount not less than the incompatible point with respect to the functional group-containing fluororesin (a) defined in the specification. Composition. 8. The composition according to claim 1, wherein the functional group-containing fluororesin (a) is a hydroxyl group-containing fluororesin, and the curing agent (b) is an isocyanate curing agent or an aminoplast curing agent. 9. An outdoor article coated with the composition of claim 1.