JPH09194538A - Aqueous dispersion of fluororesin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the aqueous dispersion of a fluororesin comprising the structural units of a fluoroolefin, etc., in a specific ratio, excellent in storage stability, mechanical stability and workability, giving coating films excellent in water resistance, stain resistance and weather resistance, and useful for coatings, etc. SOLUTION: A fluororesin comprising (A) 10-70mol.% of structural units based on a fluoroolefin such as chlorotrifluoroethylene or tetrafluoroethylene, (B) 0.1-20mol.% of structural units based on an organic silicon compound having an olefinic unsaturated bond and an alkoxysilyl group, such as a vinyltrialkoxysilane, (C) 0.1-20mol.% of structural units based on an unsaturated carboxylic acid of the formula: CH2 =CH-(CH2 )n -COOH [(N) is 3-15] such as 10-undecylenoic acid, and (D) 30-85mol.% of one or more other copolymerizable compounds such as an alkylvinylether is dispersed in an aqueous medium. The total content of the components A-D is 100mol.%.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aqueous fluororesin dispersion for paints.

[0002]

2. Description of the Related Art Conventionally, a polymer containing a fluoroolefin has been widely applied to the field of coatings because of its excellent weather resistance.
For example, a copolymer produced from a fluoroolefin, a fatty acid vinyl ester such as vinyl acetate, and other monomers (Japanese Patent Publication No. 4-40365) is soluble in various solvents and is a room temperature curable coating mainly for the construction field. Is used as. However, since these paints contain a large amount of organic solvents, there is concern about fire risk, harmfulness to human bodies, air pollution, and the like, and non-organic solvent-based paints, particularly water-based solvent paints, have been demanded.

In order to meet this demand, various fluororesin aqueous dispersions capable of forming a film at room temperature have been studied. Generally, the dispersions are produced by an emulsion polymerization method, in which a large amount of emulsifier is used. Since this emulsifier remains in the finally formed coating film to increase the water absorption, there is a problem that it is inferior in water resistance and stain resistance as compared with the conventional solvent-based coating film.

On the other hand, in an attempt to improve the water resistance and stain resistance of the coating film by introducing a cross-linking structure into the coating film, an aqueous fluororesin dispersion using a monomer containing an alkoxysilyl group which is a self-crosslinking group. Liquids have been studied (Japanese Patent Laid-Open No. 4-
202484, JP-A-5-25421). But,
It is difficult for them to satisfy the contradictory properties of the stability of the alkoxysilyl group, which is the cross-linking site, in the emulsion and the cross-linking property after coating film formation. There is a problem in stability, and those having good storage stability tend to be inferior in initial water resistance because of slow crosslinking speed. In addition, there is a use form in which a catalyst for promoting a crosslinking reaction is added immediately before coating to a composition having a slow crosslinking rate, but this is practically no different from a two-pack type coating composition and there is a problem that workability is poor.

[0005]

The present invention is intended to solve the problems of the prior art. That is, it is a one-liquid cross-linking type, and it is a fluororesin aqueous dispersion for water-based paints that is practically satisfying the storage stability of the emulsion, the workability during use, and is excellent in the initial water resistance, stain resistance, and weather resistance of the coating film. Is provided.

[0006]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have studied a fluoroolefin and a monomer to be copolymerized therewith, and further a polymerization method thereof. As a result, an olefinic unsaturated bond and an alkoxysilyl group were identified. A fluororesin aqueous dispersion produced by selecting a copolymerization monomer so that it simultaneously contains an organosilicon compound and an unsaturated carboxylic acid, and does not separately add an emulsifier or emulsion-polymerizes a smaller amount than usual. However, it is said that it is excellent in practical storage stability, and the coating film obtained from the dispersion is a one-pack type, and is superior in workability, initial water resistance and stain resistance of the coating film as compared with conventional water-based paints. This has led to the present invention.

That is, the present invention is a fluororesin aqueous dispersion in which a fluororesin is dispersed in an aqueous medium, wherein the fluororesin is a structural unit 10 based on fluoroolefin (A).
˜70 mol%, 0.1 to 20 mol% of a structural unit based on the organosilicon compound (B) having both an olefinic unsaturated bond and an alkoxysilyl group, and a general formula CH ₂ ═CH— (C
H ₂ ) _n —COOH (n is an integer of 3 to 15) represented by an unsaturated carboxylic acid (C), which is a structural unit 0.
1 to 20 mol%, and 30 to 85 mol% of a structural unit based on the other copolymerizable compound (D),
(A), (B), (C) and (D) are 100 mol% in total, which is a fluororesin aqueous dispersion, and (A)
10-70 mol%, (B) 0.1-20 mol%, (C)
0.1 to 20 mol% and (D) 30 to 85 mol%, and the sum of (A), (B), (C) and (D) is 1
It is a method for producing a fluororesin dispersion, which comprises emulsion-polymerizing a monomer composition in an amount of 00 mol% in an aqueous medium.

The fluoroolefin (A) in the present invention is a component necessary for imparting weather resistance to the polymer, and has a polymerizable double bond containing at least one fluorine atom in the molecule. It is a compound that has. Examples thereof include fluoroolefins having 2 to 6 carbon atoms such as chlorotrifluoroethylene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, hexafluoropropylene and hexafluoroisobutene. , And chlorotrifluoroethylene are most preferred. Further, the fluoroolefins can be used alone or in combination of two or more kinds, and in that case, it is preferable to contain chlorotrifluoroethylene.

The ratio of the fluoroolefin (A) is preferably 10 to 70 mol% in all monomers,
-60 mol% is more preferred. When the ratio is less than 10 mol%, the weather resistance is insufficient, and when it is more than 70 mol%, the film-forming property is deteriorated, which is not preferable.

The organosilicon compound (B) having both the olefinic unsaturated bond and the alkoxysilyl group in the present invention is a component which becomes a crosslinking site in the polymer. That is, the state of the alkoxysilyl group is stable in the emulsion, but it is presumed that the alkoxysilyl group hydrolyzes into a silanol group during film formation, contributing to the crosslinking reaction. It is considered that they react with each other to form intermolecular crosslinks by a siloxane bond. It is presumed that the coating film obtained due to the crosslinked structure has improved water resistance, stain resistance, and solvent resistance.

Component (B) is an organosilicon compound having both an olefinically unsaturated bond and an alkoxysilyl group,
The group having an olefinically unsaturated bond is not particularly limited, but examples thereof include a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group. The alkoxysilyl group is not particularly limited, but at least one hydrogen bonded to the Si atom of a silyl group or an alkylsilyl group is a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group. Group, tert-
Examples thereof include those substituted with a butoxy group. Non-limiting examples of these compounds are vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (n-propoxy) silane, vinyltriisopropoxysilane,
Vinyltributoxysilane, vinyltris (methoxyethoxy) silane, vinylmethyldiethoxysilane, vinylmethyldiisopropoxysilane, vinylmethyldi-n
-Propoxysilane, vinyldimethylethoxysilane,
Vinyldimethylisopropoxysilane, vinyldimethyl-n-propoxysilane, vinylmethoxydiethoxysilane, vinylmethoxydiisopropoxysilane, vinylmethoxydi-n-propoxysilane, vinylethoxydimethoxysilane, vinylethoxydiisopropoxysilane, vinylethoxy Di-n-propoxysilane, vinyl-n-propoxydimethoxysilane, vinyl-n-propoxydiethoxysilane, vinyl-n-propoxydiisopropoxysilane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane , 3- (N-allyl-N-methacryloyl) aminopropyltrimethoxysilane, N, N-bis [3- (trimethoxysilyl) propyl] methacrylamide, N, N-bis [3- (methyldimethoxysilyl) ) Propyl] methacrylamide, 3
-Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltris (trimethylsiloxy) silane and the like. These may be used alone or in combination of two or more. In addition, vinyltrialkoxysilanes having the same or different three alkoxy groups selected from the alkoxy groups having 1 to 4 carbon atoms among the above are particularly preferable because they have excellent copolymerizability with other monomers. Therefore, it is desirable to contain these when combining two or more kinds.

The proportion of the organosilicon compound (B) having both an olefinic unsaturated bond and an alkoxysilyl group in all monomers is 0.1 to 20 mol%, preferably 0.1 to 5 mol%, 0.1 to 3 mol% is more preferable. If the proportion is less than 0.1 mol%, the crosslinking will not be sufficient and the coating film will be inferior in water resistance and stain resistance, and if it exceeds 20 mol%, the storage stability of the dispersion will be poor, such being undesirable.

An unsaturated carboxylic acid represented by the general formula CH ₂ ═CH— (CH ₂ ) _n —COOH (n is an integer of 3 to 15) or a carboxyl group introduced by the same according to the present invention. Is
It is a component that plays a role of stabilizing the aqueous dispersion of the fluororesin of the present invention and acting as a catalyst for the crosslinking reaction of alkoxysilyl groups. The stabilizing action of (C) means that the unsaturated carboxylic acid of (C) has the same action as the emulsifier, that is, it acts as a reactive emulsifier, so that the amount of the non-reactive emulsifier used can be reduced. . In general, non-reactive emulsifiers have the problem of bleeding from the coating film and depositing on the surface to absorb water and contaminants when the compatibility with the resin is poor, and compatibility with them. Even if it is good, water resistance is imparted to the resin itself, which may deteriorate the water resistance of the coating film. Therefore, it is speculated that the use of the component (C) of the present invention results in the effect of improving the water resistance and stain resistance of the coating film.

On the other hand, regarding the catalytic action for the crosslinking reaction, the carboxyl group introduced by the unsaturated carboxylic acid (C) functions as an acid catalyst for the alkoxysilyl group. Generally, to a dispersion liquid having an alkoxysilyl group as a crosslinking site, a crosslinking catalyst such as di-n-dibutyltin dilaurate (IV) or an organic acid may be added immediately before use in order to obtain a sufficient crosslinking rate. is necessary. However, in the fluororesin aqueous dispersion of the present invention, it is not always necessary to add such a catalyst, and it is possible to prepare a one-component cross-linking type coating exhibiting a sufficient cross-linking rate.
Therefore, the conventional fluororesin water-based cross-linking paint had to be used as a two-pack type paint, whereas the dispersion of the present invention can be made into a one-pack cross-linking paint, which is excellent in workability, Since the resin itself has a catalytic function, the crosslinked structure of the coating film is quickly formed, and as a result, the initial water resistance and stain resistance of the coating film are improved.

In the present invention, the carboxyl group introduced by (C) does not act on the alkoxysilyl group existing inside because it exists on the surface of the emulsion particles in the state of the aqueous dispersion, but coating by water volatilization is performed. It is considered that when the film is formed, it diffuses uniformly and catalyzes the alkoxysilyl group. Therefore, it is assumed that the long-term storage stability of the dispersion is sufficiently secured, and that the coating film is excellent in initial water resistance and stain resistance because it rapidly catalyzes the crosslinking reaction by evaporation of water accompanying the formation of the coating film. To be done.

To illustrate the unsaturated carboxylic acid (C) according to the present invention, 5-hexenoic acid, 6-heptenoic acid,
7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-
Undecylenic acid, 11-dodecylene acid, 17-octadecylene acid and the like can be mentioned. These may be used in combination of two or more. If n is less than 3, the monomer has a high water solubility and thus does not contribute to the improvement of stability of the dispersion during the production of the dispersion, while if it exceeds 15, the polymerization reactivity becomes poor. . Where 10 of these
-Undecylenic acid is preferred because it has particularly good polymerizability during the production of the dispersion and the storage stability of the produced dispersion.

The content of (C) in all monomers is 0.1 to 20 mol%, preferably 0.1 to 5 mol%.
1-2 mol% is more preferable. If it is less than 0.1 mol%, the stabilizing action of the dispersion is insufficient, and the amount of non-reactive emulsifier used to compensate for it is increased, which lowers the water resistance of the coating film, which is not preferable. . 20 mol%
If the amount is larger than the above range, the alkali resistance of the coating film decreases, which is not preferable.

The other copolymerizable compound (D) in the present invention is not particularly limited, but examples thereof include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl pivalate, vinyl caproate and caprylic acid. Carbon number 1 such as vinyl, vinyl caprate, vinyl laurate, vinyl cyclohexanecarboxylate, vinyl pivalate, vinyl versatate (veova 9, veova 10)
Alkyl vinyl ethers having a branched or cyclic alkyl group having 1 to 6 carbon atoms, such as fatty acid vinyl esters derived from fatty acids which may have a branch of 8 to 8, ethyl vinyl ether, propyl vinyl ether, cyclohexyl vinyl ether, Carboxylic allyl esters such as allyl acetate, allyl propionate, allyl butyrate, allyl isobutyrate, allyl caproate, allyl caprylate, allyl laurate, allyl cyclohexanecarboxylate, methyl allyl ether, ethyl allyl ether, butyl allyl ether, etc. Allyl ethers, hydroxybutyl allyl ether, ethylene glycol monoallyl ether, propylene glycol monoallyl ether, triethylene glycol monoallyl ether, glycerin monoary Hydroxyl group-containing allyl ethers such as ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, hydroxymethyl vinyl ether and other hydroxyl group-containing vinyl ethers, α-olefins such as ethylene, propylene, 1-butene, 1-octene, polyethylene oxide chains, polypropylene Unsaturated esters or unsaturated ethers having hydrophilic side chains such as oxide chains, halogenated olefins such as vinyl chloride and vinylidene chloride, styrene, α-methylstyrene,
Aromatic vinyl compounds such as vinyltoluene, (meth) acryloyl compounds such as ethyl (meth) acrylate, unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride or the like Derivatives, unsaturated carboxylic acids other than (C) such as (meth) acrylic acid, crotonic acid, vinylacetic acid, and maleic acid, and dicarboxylic acids, and unsaturated carboxylic acids such as sodium 10-undecylenate are used as alkaline substances. And sulfonic acid-containing monomers. Among these, fatty acid vinyl esters and alkyl vinyl ethers can be mentioned as preferable ones because they are particularly excellent in polymerizability and film-forming property when forming a coating film from a dispersion liquid.

The ratio of (D) is 30 to 85 in all monomers.
The content is preferably mol%, and more preferably 35 to 70 mol%. When the ratio is less than 30 mol%, the film-forming property is poor, and when it is more than 85 mol%, the weather resistance is poor, which is not preferable.

The fluororesin aqueous dispersion of the present invention comprises a fluoroolefin, an organosilicon compound having both an olefinically unsaturated bond and an alkoxysilyl group, a general formula: CH ₂ ═CH— (CH ₂ ) _n —COOH (n is 3 It is obtained by emulsion-polymerizing the unsaturated carboxylic acid represented by the formula (1) to 15) and other copolymerizable compounds. As the medium in this case, an aqueous medium, that is, water or a mixed liquid of water and an organic solvent can be used. Here, as the organic solvent, alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, dihydric alcohols such as ethylene glycol and diethylene glycol, methyl cellosolve, ethyl cellosolve, isopropyl. Examples thereof include ether alcohols such as cellosolve, aromatic or aliphatic hydrocarbons such as xylene, and esters such as butyl acetate and ethyl acetate. These organic solvents can be used alone or as a mixed liquid of two or more kinds. The organic solvent used at this time is preferably 20% by weight or less of the total amount of the solvent to form a uniform medium.

For the purpose of ensuring the action of the unsaturated carboxylic acid (C) as a reactive emulsifier in the present invention and further improving the storage stability of the alkoxysilyl group in the dispersion, The pH of the medium and the resulting dispersion is preferably 5-9, more preferably 6-9. Therefore, it is preferable to use various pH adjusting agents here for the purpose of pH adjustment. Examples of the pH adjusting agent used include inorganic salts such as sodium carbonate, potassium carbonate, sodium hydrogen orthophosphate, sodium thiosulfate and sodium tetraborate, and organic bases such as triethylamine, triethanolamine, ammonia and dimethylethanolamine. To be done. The addition amount of the pH adjusting agent is usually 10
It is about 0.05 to 5 parts by weight per 0 parts by weight. These can be added at the time of polymerization or after the polymerization and can be used together.

The initiation of emulsion polymerization is carried out by adding a polymerization initiator. As such a polymerization initiator, a water-soluble initiator is preferably used in terms of polymerization stability and workability. Examples of the polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide, and a redox initiator composed of a combination of these with a reducing agent such as sodium sulfite. The amount of the polymerization initiator added is 0.0001 to 5 parts by weight with respect to 100 parts by weight of the total amount of monomers,
0.001 to 3 parts by weight is preferable.

The optimum temperature for the emulsion polymerization initiation temperature is selected mainly depending on the kind of the polymerization initiator, but it is 0 to 100 ° C., preferably 30 to 70 ° C., from the viewpoint of workability and polymerization reaction stability.
Is adopted.

In the present invention, various dispersion stabilizers may be used for the purpose of improving the stability of the emulsified state during polymerization. Here, as the dispersion stabilizer, known surfactants such as anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants, and water-soluble polymers such as polyvinyl alcohol and methyl cellulose are used. However, nonionic surfactants are preferred because they have excellent compatibility with the polymer. More preferably, it is a nonionic surfactant having an HLB value of 10 to 18, which represents the balance between hydrophilicity and hydrophobicity. You may use these dispersion stabilizers individually or in combination of 2 or more types. Further, if the addition amount of these dispersion stabilizers is large, the water resistance and weather resistance of the coating film are poor, so it is preferable to add 10 parts by weight or less to 100 parts by weight of the total amount of monomers. It is more preferably 5 parts by weight or less.

The fluororesin aqueous dispersion of the present invention can be used as a paint as it is, but when it is made into a paint, various additives conventionally used in the field of paints,
That is, plasticizers, organic solvents, film-forming aids, dispersants, wetting agents, pigments, viscosity modifiers, leveling agents, antifreeze agents, preservatives, defoamers, stabilizers such as UV absorbers and antioxidants. You may mix 1 type (s) or 2 or more types.

Further, it is possible to add an alkyl silicate represented by the following general formula to the fluororesin aqueous dispersion of the present invention.

[0027]

Embedded image

(In the formula, X is an alkyl group having 1 to 8 carbon atoms,
n is 0 or an integer of 11 or less. Here, the alkyl silicate is tetraalkoxysilane or a condensate thereof, and specific examples thereof include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, and tetra-n-butoxysilane. 2-Methoxyethoxysilane, tetra-2-ethylhexyloxysilane, or partial hydrolysates thereof can be mentioned.

These alkyl silicates can be added in a form of being dissolved or dispersed in water or various organic solvents, and a mixed solvent of two or more kinds, but they are generally used for emulsion paints. A method in which the agent is dissolved and added is preferably used.

[0030]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The numbers of parts in the following examples are parts by weight unless otherwise specified.

[Synthesis Example 1] Vinyl butyrate 125.
7 parts, Veova 9 (vinyl ester produced by Shell Chemical) 81.
2 parts, vinyl pivalate 39.5 parts, vinyltriethoxysilane 25.1 parts, undecylenic acid 40.6 parts, ion-exchanged water 570 parts, ammonium persulfate 2.58 parts, sodium carbonate decahydrate 1.14 parts , Newcol50
4 (11.4 parts of nonionic emulsifier manufactured by Nippon Emulsifier) was charged. Then, the operation of cooling the autoclave with ice water, pressurizing the autoclave with nitrogen gas to 5 kg / cm ² and then degassing was repeated 3 times, and then about 10 mmHg
To remove dissolved air. Furthermore, after introducing 257.0 parts of chlorotrifluoroethylene into the autoclave, the reaction was carried out at 50 ° C. for 24 hours to obtain a solid content of 48.6.
% Fluororesin aqueous dispersion was obtained.

[Synthesis Examples 2 to 9] Polymerization was carried out in the same manner as in Synthesis Example 1 with the monomer composition shown in Table 1 or Table 2,
The fluororesin aqueous dispersions shown in Table 1 or Table 2 were obtained.

[0033]

[Table 1]

[0034]

[Table 2]

Explanation of Abbreviations in Tables 1 and 2 CTFE: Chlorotrifluoroethylene TFE: Tetrafluoroethylene VBu: Vinyl butyrate V-9: Veova 9 (Vinyl ester manufactured by Shell Chemical) VAc: Vinyl acetate VPv: Vinyl pivalate V -10: Veova 10 (Vinyl ester manufactured by Shell Chemical Industry) VTES: Vinyltriethoxysilane ECAE: ε-caprolactam modified allyl ether Pr: Propylene PKA: PKA-5003 (Allylated polyether manufactured by NOF Corporation) UA: 10-Undecylenic acid APS : Ammonium persulfate KPS: Potassium persulfate Na ₂ CO ₃ · 10H ₂ O: Sodium carbonate decahydrate Newcol 504: Nonionic emulsifier (manufactured by Nippon Emulsifier, HLB = 16.0) Newcol 566: Nonionic emulsifier ( HLB = 14.0 manufactured by Nippon Emulsifier) [Examples and Comparative Examples] The fluororesin aqueous dispersions obtained in Synthesis Examples 1 to 9 had a solid content of 45% by concentration with an evaporator and / or dilution with water. I adjusted it so that. Further, butyl carbitol acetate was added as a film-forming aid to 10 parts of 100 parts of the solid content of the fluororesin aqueous dispersion, and 28% ammonia solution was added so that the pH of the dispersion became 7, respectively. Paints (Paints 1-9) were prepared. The test of the items shown in Table 3 or Table 4 for the obtained water-based paints and coating films of about 0.2 mm obtained by applying each water-based paint to an aluminum plate with an applicator and drying at room temperature for 3 days Was carried out and the result was shown.

[0036]

[Table 3]

[0037]

[Table 4]

Evaluation of storage stability of coating material The dispersion state of the aqueous coating material was visually observed after storage at 50 ° C. for 4 weeks.・ Evaluation of mechanical stability of paints Water-based paints are manufactured by Disper (TK, TK, TK
-Homodisperse) was stirred at 3000 rpm for 5 minutes, and the presence or absence of aggregates in the paint was visually observed.

○: No agglomeration ×: Agglomerate generation ・ Evaluation of initial water resistance of coating film After immersing the coating film in water at room temperature for 96 hours, the appearance change was observed and the appearance change such as swelling was visually observed. It was judged.

○: No change in appearance such as swelling △: Partial change in appearance such as swelling ×: There is change in appearance such as swelling ・ Evaluation of stain resistance of coating film: 10% dispersion of carbon / water on the coating film Dripping at 20 ℃
It was dried under saturated vapor pressure for 1 day and at 40 ° C. for 2 days, and the degree of carbon remaining after the dropping portion was wiped off with gauze was visually observed.

○: Almost no trace of carbon remains to be thin. X: Thick trace of carbon remains to be not wiped off.-Weather resistance evaluation of coating film: The gloss of the coating film is untreated and it is 4000 hours by a sunshine weatherometer. It was measured after the treatment, and the gloss retention was determined by the following formula to evaluate the weather resistance.

[0042]

[0043]

EFFECT OF THE INVENTION The paint prepared from the fluororesin aqueous dispersion of the present invention is a one-part curable paint having good workability, but has excellent storage stability and mechanical stability, and was obtained. The coating film has a remarkable effect of being excellent in water resistance, stain resistance and weather resistance in the initial stage.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09D 127/12 PFG C09D 127/12 PFG 131/02 PFR 131/02 PFR 133/02 PFW 133/02 PFW 143/04 143/04 (72) Inventor Politics Hasegawa 2805 Imafuku Nakadai, Kawagoe City, Saitama Central Glass Co., Ltd. Chemical Research Laboratory (72) Inventor Kentaro Tsutsumi 2805, Imafuku Nakadai, Kawagoe City, Saitama Prefecture Central Glass Chemical Laboratory Co., Ltd.

Claims (7)

[Claims] 1. A fluorine resin in which a fluororesin is dispersed in an aqueous medium.
A base resin aqueous dispersion, wherein the fluororesin is fluoro
Structural unit based on reffin (A) 10 to 70 mol%,
Has both a reffinic unsaturated bond and an alkoxysilyl group
Structural unit based on organosilicon compound (B)
Mol%, general formula CH_Two= CH- (CH_Two) _n-COOH
 (N is an integer of 3 to 15)
0.1 to 20 mol% of a structural unit based on rubic acid (C),
And structures based on other copolymerizable compounds (D)
The unit consists of 30 to 85 mol% and comprises (A), (B),
Fluorine in which the total of (C) and (D) is 100 mol%
Aqueous resin dispersion. 2. The fluororesin aqueous dispersion according to claim 1, wherein the fluoroolefin (A) is chlorotrifluoroethylene and / or tetrafluoroethylene. 3. An organosilicon compound (B) having both an olefinically unsaturated bond and an alkoxysilyl group has a carbon number of 1
The fluororesin aqueous dispersion according to claim 1 or 2, which is a vinyltrialkoxysilane having three same or different alkoxy groups each selected from the alkoxy groups of 4 to 4. 4. The general formula CH ₂ ═CH— (CH ₂ ) _n —C.
The fluororesin aqueous dispersion according to claim 1, wherein the unsaturated carboxylic acid (C) represented by OOH (n is an integer of 3 to 15) is 10-undecylenic acid. 5. The other copolymerizable compound (D) is
Fatty acid vinyl ester derived from fatty acid which may have a branch having 1 to 8 carbon atoms and / or 1 to 1 carbon atoms
The fluororesin aqueous dispersion according to claims 1 to 4, which is an alkyl vinyl ether having 6 branches or an alicyclic alkyl group. 6. The fluororesin aqueous dispersion according to claim 1, which has a pH of 5-9. 7. (A) 10 to 70 mol%, (B) 0.1
~ 20 mol%, (C) 0.1-20 mol% and (D)
30-85 mol%, characterized in that the monomer composition in which the total of (A), (B), (C) and (D) is 100 mol% is emulsion polymerized in an aqueous medium. Claim 1
5. The method for producing a fluororesin dispersion according to any one of 5 to 6.