JPH09165551A - Resin composition for coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition containing a fluororesin having a functional group, a multimer of a tetra-valent hydrolyzable silane compound and a silane compound having a specific structure in each specific amount, giving a coated membrane capable of preventing the generation of a filth caused by rain streaks, and excellent in preservation stability. SOLUTION: This resin composition contains (A) a fluororesin having a functional group, (B) a multimer of a tetra-valent hydrolyzable silane compound (preferably a tetraalkoxysilane), and (C) a monomer of a silane compound of the formula: R<1> m Si(OR<2> )4-m [R<1> , R<2> are each a monovalent organic group; (m) is an integer of 0 to 3], and the amount of the component (B) is 0.1-100 pts.wt. based on 100 pts.wt. component (A), and that of the component (C) is equimolar or more amount based on the functional group of the component (A). Also, it is preferable to contain (D) 0.1-100 pts.wt. curing agent capable of curing the component (A) and (E) 0.1-100 pts.wt. alcohol.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for coatings, which provides a coating film or the like for preventing the generation of stains on rain lines and has excellent storage stability.

[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 for the purpose of protecting the surface and imparting design and functionality. There are various developments of paints for that purpose.

Recently, fluororesin paints have been widely used as paints having excellent weather resistance. This fluororesin paint exhibits remarkable weather resistance as compared with various synthetic resin paints which have been widely used before. However, the antifouling property against dirt on the surface is almost the same as that of other synthetic resin paints.
The improvement is desired.

[0004]

In order to solve the stain on the surface of a coated article, a coating composition containing a polyfluorinated carbon chain and a polymer having a hydrophilic group has been proposed (JP-A-1-198653). ), This coating composition is confirmed to have an effect of preventing the generation of spot-like stains caused by rainwater, but streak-like stains (hereinafter referred to as streak-like stains) generated in a portion where rainwater gathers and flows, such as under an outdoor article such as a window frame of a building. It was not enough to prevent rain streaks.

Further, there has been proposed a coating composition containing a condensate of an organosilicate (WO94 / 06).
870), this coating composition had poor storage stability, and it was difficult to apply it to the field of using a one-pack type baking coating such as factory line coating.

[0006]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned problems and comprises a functional group-containing fluororesin (a), a tetrafunctional hydrolyzable silane compound multimer (b), and a general formula. A large amount of a silane compound monomer (c) represented by R ¹ _m Si (OR ² ) _4-m (wherein R ¹ and R ² are monovalent organic groups, m is an integer of 0 to 3), and The ratio of the body (b) is 100 for the functional group-containing fluororesin (a).
The resin composition for coating is 0.1 to 100 parts by weight with respect to parts by weight and the ratio of the monomer (c) is equimolar or more to the functional groups of the functional group-containing fluororesin (a).

It is very good to apply the composition of the present invention to a place where rain streak stains are likely to occur on an outdoor article, or to use the article coated with the composition of the present invention at a place where rain streak stains are likely to occur. Can prevent the generation of rain streaks stains for a long time.

The functional group-containing fluororesin (a) (hereinafter simply referred to as "resin (a)") is not particularly limited, and a wide range of fluororesins can be used, and a fluoroolefin known as a fluororesin for coating and a copolymer with the fluoroolefin are known. A resin obtained by copolymerizing possible monomers is preferable in terms of solubility in a solvent, weather resistance of a coating film, workability of coating, and the like.

Examples of the fluoroolefin 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, carboxylic acid vinyl ester, allyl ether, carboxylic acid allyl ester, isopropenyl ether, carboxylic acid isopropenyl ester, methallyl ether, carboxylic acid methallyl ester, One or more kinds of monomers selected from α-olefin, acrylic acid ester, methacrylic acid ester and the like can be mentioned.

Examples of vinyl ethers include alkyl vinyl ethers such as ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, fluoroalkyl vinyl ether, and perfluoro (alkyl vinyl ether).

Examples of the carboxylic acid vinyl ester include fatty acid vinyl ester such as Veova-10 (trade name of Shell Chemical Co.) having a branched alkyl group, vinyl butyrate, vinyl acetate, vinyl pivalate, vinyl versatate and the like.

Examples of the allyl ether include alkyl allyl ethers such as ethyl allyl ether and cyclohexyl allyl ether. Examples of the carboxylic acid allyl ester include 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. If the copolymerization ratio of the fluoroolefin is too high, the solubility in a solvent will decrease, which is not preferable.
Therefore, as the resin (a), a copolymer having a proportion of fluoroolefin-based polymerized units in the copolymer of 30 to 70 mol%, particularly 40 to 60 mol%, is preferable.

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, carboxylic acid vinyl ester, allyl ether, and carboxylic acid allyl ester are preferable because they have excellent copolymerizability with fluoroolefins. Alkyl vinyl ether, fatty acid vinyl ester, alkyl allyl ether and fatty acid allyl ester having a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms are more preferable.

Since the resin (a) has a functional group capable of undergoing a crosslinking reaction with the curing agent (d) described below in addition to the above-mentioned copolymerization component, a stronger coating film can be obtained. As this functional group, an active hydrogen-containing group 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 or a carboxyl group, is preferable. In addition to the active hydrogen-containing group, an epoxy group, a halogen,
Functional groups such as double bonds are also preferred. It is preferably an active hydrogen-containing group, and particularly preferably a hydroxyl group.

As a method of introducing such a functional group, a monomer having a functional group other than a double bond involved in polymerization, for example, hydroxybutyl vinyl ether, hydroxybutyl allyl ether, ethylene glycol monoallyl ether, cyclohexanediol mono is used. Vinyl ether,
There is a method of copolymerizing acrylic acid, methacrylic acid, crotonic acid, undecenoic acid, glycidyl vinyl ether, glycidyl allyl ether and the like.

A method of introducing a functional group by modifying the copolymer, for example, a copolymer having a hydroxyl group or an epoxy group is reacted with a polybasic acid anhydride such as succinic anhydride to form a carboxyl group. There is a method of modifying the copolymer to have, a method of similarly reacting an isocyanate alkyl methacrylate or the like to a copolymer having a double bond, and the like. The content of the copolymerized unit having a functional group is preferably 5 to 20 mol% in the copolymer.

Examples of such resin (a) include Lumiflon (trade name, manufactured by Asahi Glass Co., Ltd.), Cefralcoat (produced by Central Glass Co., Ltd.), Zaflon (manufactured by Toagosei Chemical Industry Co., Ltd.), Zeffle (manufactured by Daikin Industry Co., Ltd.), Fluoronate (Dainippon Ink and Chemicals Co., Ltd.). Commercially available products such as manufactured products) and Floren (made by Japan Synthetic Rubber).

The curing agent (d) is not particularly limited as long as it can crosslink the resin (a). From the viewpoint of forming a one-component coating material, one that does not undergo a crosslinking reaction with the resin (a) at room temperature is preferable. Specific examples of preferable curing agent (d) include aminoplast-based curing agents and blocked isocyanate-based curing agents.

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

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 methylol ureas include alkylated methylol ureas such as methylated methylol urea and ethylated methylol urea. When an aminoplast-based curing agent is used, the crosslinking reaction can be promoted by adding an acidic catalyst.

As the blocked isocyanate curing agent, there is a blocked product of a polyvalent isocyanate compound.
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.

Polyvalent isocyanate compounds, specifically ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, hexamethylene triisocyanate, lysine diisocyanate, and other aliphatic polyisocyanate compounds, isophorone diisocyanate, dicyclohexylmethane diisocyanate, diisocyanate Alicyclic polyvalent isocyanate compounds such as methylcyclohexane and non-yellowing aromatic isocyanate compounds such as m-xylene diisocyanate and p-xylene diisocyanate are used.

Examples of modified products and multimers of polyvalent isocyanate compounds include urethane modified products, urea modified products, isocyanurate modified products, burette modified products, allophanate modified products, and carbodiimide modified products. In particular, a modified isocyanurate which is a trimer, a modified urethane which is a reaction product with a polyhydric alcohol such as trimethylolpropane, and the like are preferable.

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

When a block 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, etc. 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 (b) is 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. Preferably, it is a group obtained by removing a hydrogen atom from a hydroxyl group of a monohydric alcohol such as an alkoxy group and an alkoxyalkoxy group. Particularly, an alkoxy group is preferable, and the number of carbon atoms is preferably 4 or less, particularly preferably 1 or 2.

The polymer (b) has a degree of polymerization which does not form a gel product in the coating resin composition. The multimer (b) is a compound that is soluble in a solvent and has a degree of multimerization or a liquid compound. Here, the degree of multimerization means the number of condensed molecules of the tetrafunctional hydrolyzable silane compound.

Multimers include those having a linear, branched, cyclic, or network structure. Usually, those having a linear structure or those having a linear structure are branched, cyclic, or It is considered to be a mixture containing those having a network structure.
As the multimer (b) 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 (b) include a polymer of tetraalkoxysilane. If this is shown as having a linear structure, the general formula R ³ O (Si (OR
³ ) ₂ O) _n R ³

In the general formula, n represents the degree of multimerization of the multimer. The normally available multimers are mixtures of multimers with different n, and the degree of multimerization is represented by n averaged. The average degree of multimerization n can be calculated from the “silica content” described below. Preferred n is 2 or more, and particularly preferably 4 or more.

If n is 1, the effect of preventing the generation of the target rain streaks is not sufficient. The larger the value of n, the greater the effect of preventing the generation of the desired rain streak stains, and the smaller the variation in the degree of the effect due to changes in the baking conditions. Particularly those having n of 20 or more are suitable for printing. However, when n is too large, the viscosity of the multimer (b) becomes too large, and the storage stability of the multimer (b) decreases, which is not preferable.

In the general formula, R ³ is exemplified by an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group and butyl group. From the viewpoint of the hydrolyzability and condensability of the alkoxy group, a tetramethoxysilane multimer in which R ³ is a methyl group or a tetraethoxysilane multimer in which R ³ 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. A plurality of R ³ 's may be different in one molecule.

Commercially available products of the multimer (b) include MKC silicates MS51, MS56 and MSEP manufactured by Mitsubishi Kasei.
2. Colcoat-made methyl silicate 51, ethyl silicate 40, 40T, 48, Matsumoto Kyosho Organix SI series, Tama Chemical's ethyl silicate 40,
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". “Silica content” refers to the weight ratio of silica (SiO ₂ ) produced from the compound, and is obtained by measuring the amount of silica produced by completely hydrolyzing and calcining the compound.

Further, "silica content" indicates the ratio of silica produced from one molecule of the compound to one molecule of the compound, and the formula [silica content (% by weight) = degree of multimerization × (SiO 2
₂ molecular weight) × 100 / (molecular weight of the compound)].

In the present invention, the general formula R ¹ _m Si (OR
² ) _4-m (wherein R ¹ and R ² are monovalent organic groups, m
Is an integer of 0 to 3), and it is important to incorporate the monomer (c) of the silane compound. By using such a monomer (c), gelation of the paint during storage can be suppressed and a one-pack paint can be achieved.

R in the general formula R ¹ _m Si (OR ² ) _4-m
¹ and R ² are each independently a monovalent organic group such as an alkyl group, a vinyl group or an allyl group. Preferably R
¹ and R ² are alkyl groups. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group is preferable. Further, the monomer (c) may be composed of only compounds having the same m in the general formula, or may be a mixture of compounds having different m.

The OR ² of the monomer (c) is preferably the same as the OR ³ of the multimer (b) from the viewpoint of improving storage stability. Also, if the hydrolysable groups OR ² and multimers (b) are different, OR ² is to be selected which show comparable or higher reactivity and hydrolyzable groups multimers (b), the storage It is preferable from the viewpoint of improving stability. As R ² , a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

When m is 4, the effect of improving storage stability is not recognized, and the effect of preventing the generation of rain streaks may be impaired. It is preferable that m is 1 or 2, and particularly m
No. 1 is preferable because it has an excellent balance of storage stability and the effect of preventing the generation of rain streaks. Preferable specific examples of the silane compound (c) include methyltrimethoxysilane and dimethyldimethoxysilane.

The silane compound (c) is mixed in an equimolar amount or more with respect to the functional group of the resin (a). When the amount of the silane compound (c) is smaller than the amount of the functional groups of the resin (a), the effect of improving the storage stability does not appear significantly. It is preferable to add 1.1 times or more moles of the functional group of the resin (a). Further, if the silane compound (C) is excessively blended, the effect of preventing rain streak stains may be impaired or the coating film may become brittle, which is not preferable. The upper limit is not particularly limited, but the silane compound (c) per 100 parts by weight of the resin (a)
Is preferably 100 parts by weight or less.

Further, in the composition of the present invention, the storage stability can be further improved by using the alcohol (e) together. The alcohol (e) is not particularly limited, and lower alcohols such as ethanol, propanol and butanol can be used. Further, alcohol (e) has a boiling point,
Considering the evaporation rate and the like, it is preferable to select a suitable one for coating workability. Further, for the purpose of improving storage stability, lower alcohols are preferable because their effects are greater than the amount added. In addition, the addition amount of resin (a) 1
It is 0.1 to 100 parts by weight per 00 parts by weight. Preferably, it is 1 to 100 parts by weight.

The composition of the present invention can be used together with the solvent (f) which dissolves the resin (a), the polymer (b), the silane compound (c) and the curing agent (d). For example, ketones such as methyl ethyl ketone and methyl isobutyl ketone,
Butyl acetate, esters such as ethyl acetate, xylene,
Aromatic solvents such as toluene, as well as aliphatic solvents, ether solvents and petroleum solvents are exemplified. Two or more of these solvents may be used in combination. The composition of the present invention may be prepared by dispersing the resin (a), the polymer (b), the silane compound (c) and the curing agent (d) in an organic solvent or an aqueous medium.

The resin (a), the curing agent (d) and the multimer (b) 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 is 0.1 to 100 parts by weight of the polymer (b). 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. A particularly preferable ratio is 1 to 50 parts by weight of the curing agent (d) and 1 to 50 parts by weight of the multimer (b) with respect to 100 parts by weight of the resin (a).

When the resin (a) is a hydroxyl group-containing fluororesin, the content ratio of the blocked isocyanate curing agent should be 0.8 mol or more per 1 mol of the hydroxyl group-containing fluororesin. Is preferred. If it is less than 0.8 mol, the curing of the coating composition will be insufficient and the solvent resistance etc. may be reduced, such being undesirable. Particularly, when the amount is 1.1 mol or more, the effect of preventing the generation of rain streaks is increased, 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 properties. Therefore, the upper limit is preferably 2.0 or less, more preferably 1.2 to 1. 6
It is.

When the multimer (b) is a tetramethoxysilane multimer or a tetraethoxysilane multimer, the content of each 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 rain streak stains is low, and if it exceeds 50 parts by weight, curing failure of the coating film is likely to occur, which is not preferable.

It is considered that the polymer (b) undergoes hydrolysis 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 with respect to 100 parts by weight of the polymer (b).
-20 parts by weight, preferably 1-10 parts by weight.

In addition to the above-mentioned 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.

Examples of the material of the article having a portion where rain streaks are liable to stain 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 a surface treatment such as a primer or an undercoat. For substrates with poor adhesion when applied directly,
It is preferable to apply after performing surface treatment such as sanding or undercoating.

The composition of the present invention is applied to, for example, the following outdoor articles where rain streaks are likely to stain.
As a result, it is possible to prevent the generation of rain streaks for an extremely long period of time.

Cars, trains, helicopters, ships, bicycles, snowmobiles, ropeways, lifts, hovercraft,
Transportation equipment such as motorcycles, sashes, shutters,
Water tanks, doors, balconies, building exterior panels, roofing materials, stairs, skylights, concrete fences and other building materials,
Building exterior walls, guardrails, pedestrian bridges, sound barriers, signs, highway side walls, railway viaducts, road components such as bridges, tanks, pipes, towers, plant facilities such as chimneys, vinyl greenhouses, greenhouses, silos, agricultural sheets, etc. Agricultural equipment,
Communication equipment such as power poles, power transmission towers, and parabolic antennas,
Electric wiring boxes, lighting equipment, air conditioners outdoor units, electric machines such as washing machines, and their covers, monuments, tombstones, paving materials, windshields, waterproof sheets, building curing sheets, etc.

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.

[0058]

EXAMPLES Examples 1 to 11 below are examples and Examples 12 to 14 are comparative examples.

Example 1 Hydroxyl group-containing fluororesin (chlorotrifluoroethylene / cyclohexyl vinyl ether / ethyl vinyl ether / hydroxybutyl vinyl ether = 50/15/25/10 mol% copolymer) xylene solution (solid content 60% by weight) %, Hydroxyl value 50: hereinafter referred to as fluororesin solution 1) to 167 parts by weight of tetramethoxysilane polymer (average degree of polymerization 40, silica content 56% by weight: hereinafter referred to as polymer 1) 10 parts by weight, 21.4 parts by weight of dimethyldimethoxysilane (hereinafter referred to as silane compound 1), titanium oxide (CR-9 manufactured by Ishihara Sangyo)
0) 43 parts by weight and 0.5 parts by weight of aluminum monoacetylacetonate bis (ethylacetoacetate) were added and uniformly mixed. Further, butyl acetate was added to adjust the fluororesin concentration to 35% by weight to obtain a coating composition 1.

The composition 1 for coating composition was evaluated for storage stability, and the composition 1 was coated on an aluminum plate.
Table 1 shows the evaluation results of the coating film dried at 60 ° C. for 30 minutes.

"Examples 2 to 14" Tables 1 and 2 show the results of the same tests as in Example 1 except that the polymer, silane compound, curing agent and alcohol were changed. The polymer 2 is a tetraethoxysilane polymer (silica content: 48% by weight), the silane compound 2 is methyltrimethoxysilane, and the curing agent 1 is a blocked isocyanate (Coronate 2507 manufactured by Nippon Polyurethane).

The storage stability was evaluated by storing the coating composition in a thermostatic chamber at 50 ° C. and observing the state after 2 weeks.
The case where there was no change even after a lapse of weeks was marked with ◎.

In the outdoor exposure test, the coating test piece was folded in half and exposed to the outdoors (Kawasaki City) with the coating surface outside so that the upper part was at an angle of 30 degrees from the horizontal and the lower part was vertical. The appearance was observed after a lapse of months. Those with no rain streak stains were marked with O, and those with rain streak stains were marked with X.

Solvent resistance was measured by xylene rubbing test 200.
A sample whose appearance did not change with time was marked with a circle. For impact resistance, one that does not change due to DuPont impact (1 kg × 50 cm) is ○
And

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

Since the article coated with the coating resin composition of the present invention does not cause rain streak stains, it has the effect of maintaining aesthetics when used as an exterior article for construction, an outer panel of an automobile or the like. Excel. Further, the composition of the present invention is excellent in storage stability, so that it can be made into a one-component paint, and can be applied to a wide range of fields such as factory line painting.

Claims (5)

[Claims] 1. A functional group-containing fluororesin (a), a tetrafunctional hydrolyzable silane compound multimer (b), and a general formula R ¹ _m.
A monomer (c) of a silane compound represented by Si (OR ² ) _4-m (wherein R ¹ and R ² are monovalent organic groups, m is an integer of 0 to 3), and a multimer (b ) Is a functional group-containing fluororesin (a) 10
0.1 to 100 parts by weight relative to 0 parts by weight, and the proportion of the monomer (c) is at least equimolar to the functional groups of the functional group-containing fluororesin (a). 2. The composition according to claim 1, wherein the tetrafunctional hydrolyzable silane compound is a tetraalkoxysilane. 3. A curing agent (d) capable of crosslinking the functional group-containing fluororesin (a) in an amount of 0.1 to 100 parts by weight based on 100 parts by weight of the functional group-containing fluororesin (a). 1
Or the composition of 2. 4. The composition according to claim 1, which contains the alcohol (e) in an amount of 0.1 to 100 parts by weight based on 100 parts by weight of the functional group-containing fluororesin (a). 5. The functional group-containing fluororesin (a) is a hydroxyl group-containing fluororesin, and the curing agent (d) is an isocyanate-based curing agent or an aminoplast-based curing agent.
Or the composition of 3.