JPH02240155A - Aqueous dispersion of fluoroolefin copolymer - Google Patents

Abstract

PURPOSE:To improve mechanical stability, pigment dispersibility, etc., by emulsion-polymerizing a (fluoro)olefin, a vinyl ester and/or a vinyl ether, a specified emulsifier and an ethylenically unsatd. acid in an aq. medium. CONSTITUTION:100 pts.wt. (hereinbelow described as pts.) mixture of 10-80wt.% fluoroolefin (e.g. chlorotrifluoroolefin), 5-30wt.% olefin (e.g. ethylene), 10-80wt.% vinyl ester, pref. vinyl acetate and/or vinyl verstate, and/or vinyl ether, pref. one having a 2-4C alkyl group, a polymerizable reactive emulsifier contg. a sulfone group and/or a sulfate group, and an ethylenically unsatd. acid in the same molecule, 0.1-3.0wt.% copolymerizable ethylenically unsatd. acid (e.g. crotonic acid) and, if necessary, a copolymerizable vinyl monomer are emulsion- polymerized in the presence of 1-10 pts. emulsifier and 0.5-3 pts. radical initiator in 50-500 pts.aq. medium.

Description

Detailed Description of the Invention (Industrial Icheon Field) The present invention has good mechanical stability, pigment dispersibility, and sedimentation stability of emulsion particles, and has excellent weather resistance, chemical resistance, film forming property, and adhesion. The present invention relates to an aqueous fluoroolefin copolymer dispersion having excellent properties.

(Prior Art) Fluoroolefin copolymers are known as binders that provide high weather resistance and high chemical resistance, and are already commercially available in the form of organic solvent solutions. However, since it contains a large amount of organic solvent, there are problems such as fire danger, toxicity, and air pollution, and it is also undesirable to release organic solvent from the viewpoint of resource conservation.

In contrast, aqueous dispersions of fluoroolefin polymers such as tetrafluoroethylene, vinylidene butylidene, and hexafluoropropylene have been proposed, but these require drying or baking at high temperatures; 57-
In the technology disclosed in Japanese Patent No. 38845, the intrinsic viscosity of vinylidene fluoride and hexafluoropropylene copolymer [
η] is set to a low molecular weight of 0.1 to 0.5, baking is required at a temperature of 180 to 230°C for 1 to 3 minutes. Therefore, it cannot be applied to applications such as outdoor paints and indoor paints that require a film to be formed at room temperature. Furthermore, fluoroolefin monomers are expensive, and it is unavoidable to have a cost disadvantage if the copolymer is made entirely of fluoroolefin. On the other hand, the applicant of the present application has developed a method for solving such problems by using a fluoroolefin containing 1O to 55 mol%, a fluoroolefin containing 1O to 7
We have already proposed that an aqueous copolymer dispersion consisting of 0 mol% alkyl vinyl ether and 5 to 80 mol% carboxylic acid vinyl ester has good low-temperature film forming properties and is economically advantageous (Unexamined Japanese Patent Publication No. Publication number 61-261367)
.

[Problem to be solved by the invention]

However, the above-mentioned aqueous dispersions are still not fully satisfactory in terms of mechanical stability, pigment dispersibility, adhesion, etc. The present inventors have made extensive efforts to solve these problems and obtain an aqueous fluoroolefin copolymer dispersion with excellent mechanical stability, pigment dispersibility, and adhesion. Vinyl ether is further copolymerized with an olefin such as ethylene as an internal plasticizing monomer, and an ethylenically unsaturated monomer having a sulfone or sulfate group such as nyl sulfonic acid or its salt and a relatively copolymer such as crotonic acid. By copolymerizing ethylenically unsaturated acids with good polymerizability,
The present invention was completed based on the discovery that it is possible to obtain an aqueous dispersion that has excellent mechanical stability and pigment dispersibility, and also forms films with good adhesion to various substrates, weather resistance, and chemical resistance. The purpose of the present invention is to have good mechanical stability and pigment dispersibility, form a film by heating at room temperature or relatively low temperature, have excellent adhesion to substrates, and have water resistance, weather resistance, and chemical resistance. An object of the present invention is to provide an aqueous decomposition product of a fluoroolefin copolymer that can form a film with good properties. [Means for Solving the Problems] In order to achieve the above object, the fluoroolefin copolymer aqueous dispersion of the present invention contains 10 to 80% by weight of fluoroolefins, 5 to 30% by weight of olefins, and 10 to 80% by weight of olefins. ~
A copolymerizable reactive emulsifier containing 80% by weight of vinyl ester and/or vinyl ether, 0.1 to 3.0% by weight of sulfone group and/or sulfate, and ethylenically unsaturated acid in the same molecule. , and 0.1 to 3.0% by weight of a copolymerizable ethylenically unsaturated acid.

The fluoroolefins used in the present invention include vinyl butylene, vinylidene butylene, chlorotrifluoroethylene, tetrafluoroethylene, l,1-dichloro-2,2-difluoroethylene, l-chloride-2.2-difluoroethylene, l-''RORO 1.2-difluoroethylene, hexafluorobrobylene, 1,l,3,3.3-pentafluoropropylene, 2,3.3,3-tetrafluorobrobylene, 3.3.3-} Refluorescent propylene, 1.
1. Fluoroolefins such as 2-trifluoropropylene, preferably 1 of tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene
A species or two or more species. The content of such fluoroolefins in the copolymer is from 10 to
It is 80% by weight, preferably 20 to 50% by weight. If this amount is less than 10% by weight, the fluorine content in the copolymer will be low, resulting in poor water resistance and weather resistance.
Furthermore, if the fluoroolefin content exceeds 80% by weight, the film-forming properties of the aqueous dispersion will be poor, making it impossible to obtain a good film or coating. As the olefin, ethylene is preferable, propylene,
Butene-1 can also be used depending on the case. The copolymerized amount of olefin is 5 to 30% by weight, preferably 10 to 25% by weight. If the olefin content is less than 5% by weight, the film-forming properties of the resulting aqueous dispersion or the flexibility of the film will decrease, and if it exceeds 30% by weight, the copolymer will be excessively plasticized and the durability of the aqueous dispersion film will deteriorate. Blocking performance, durability, etc. decrease. Vinyl esters include vinyl acetate, vinyl probionate, vinyl butyrate, vinyl pivalin, vinyl cabroate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pt-butyl benzoate, and vinyl salicylate. , monochlorovinyl acetate, etc., and preferably aliphatic, aromatic, or alicyclic carboxylic acid vinyl esters having 4 to 17 carbon atoms. Vinyl ethers include alkyl groups such as methyl, ethyl, n-propyl, isobrobyl, n-butyl, isobutyl, m-butyl, isoamyl, n-hexyl, n-octyl, 2-ethylhexyl, hydroxyethyl, hydroxybutyl, etc. It is a vinyl ether having an alkyl group containing a substituent, preferably having an alkyl group having 2 to 4 carbon atoms. The amount of carboxylic acid vinyl ester and/or alkyl vinyl ether is 10 to 80% by weight, preferably 10
~50% double star. If this amount is less than 10% by weight, the adhesion to the substrate will be poor, and if it exceeds 80% by weight, the fluorine and ethylene contents in the copolymer will be low, resulting in coating 15! Physical properties are poor. These vinyl esters and vinyl ethers, both heptanomers, have high reactivity towards fluoroolefins and can be used alone or in combination. As the copolymerizable reactive emulsifier containing a sulfonic group and/or a sulfate group and an ethylenically unsaturated group in the same molecule, vinyl sulfonic acid and/or its salts are preferred, and salts of alkylarylsuccinic acid, 2- Acrylamido-2-methylbrobanesulfonic acid and/or its salts can also be used. The amount of these reactive emulsifiers is 0
．． 1-3.0% by weight, preferably 0.5-2. It is 0% by weight. If this amount is less than 0.1% by weight, mechanical stability and pigment dispersibility will be insufficient, while if it exceeds 3.0% by weight, water resistance will decrease, which is not preferable. As the copolymerizable ethylenically unsaturated acid, crotonic acid is preferred, and itaconic acid and itaconic acid monoalkyl esters can also be used. The amount of these unsaturated acids is from 0.1 to 3.0% by weight, preferably from 0.5 to 2.0% by weight; Sufficient mechanical stability when the amount of Ht is less than %,
It is not preferable to improve the dispersibility and adhesion of the pigment, and if it exceeds 3.0% by weight, the water resistance and alkali resistance will deteriorate. The above-mentioned reactive emulsifier and ethylenically unsaturated acid are more preferably used in a total amount of l. O weight%~3
．． It is best to use it at 0% by weight, which improves mechanical stability and
It is possible to obtain an aqueous fluoroolefin copolymer dispersion that has good pigment stability and produces films or coatings with excellent adhesion and durability. Furthermore, vinyl monomers that can be copolymerized within a range that does not impair the effects of the present invention, such as vinyl chloride, vinyl halides such as vinylidene chloride, and acrylic esters (having 1 to 8 carbon atoms)
, methacrylic acid ester (having 1 to 8 carbon atoms), acrylamide, N-methylol acrylamide, glycidyl acrylate, hydroxy-containing acrylate, and other functional group-containing monomers may be copolymerized, but these are generally the main component monomers of the present invention. Since it does not have good emulsion copolymerizability with star bodies, it should be limited to the minimum amount necessary to obtain these specific effects, and it is usually not necessary to use it. The aqueous dispersion of the present invention is a polymer aqueous dispersion obtained by emulsion polymerization. In the emulsion polymerization at that time, the heptanomer mixture is emulsified with an emulsifier in water or an aqueous solution containing water as the main component and a small amount of organic solvent, and
by thermal or redox decomposition of the initiator (catalyst).
Conventional methods for carrying out polymerization are common. Examples of emulsifiers include anionic emulsifiers such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, higher fatty acid salts, alkyl sulfate ester salts, alkyl ether sulfate ester salts, phosphate ester salts, barfluoroalkyl fatty acid salts; alkylphenol ethylene oxide; Nonionic emulsifiers such as adducts, higher alcohol ethylene oxide adducts, ethylene oxide and brobylene oxide block copolymers, and polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, methyl cellulose, hydroxypropyl cellulose, and polyacrylic acid. Aqueous polymers such as soda and ethylene-maleic anhydride copolymers can be used as protective colloids. As the radical initiator, water-soluble catalysts such as potassium persulfate and ammonium persulfate, oil-soluble catalysts such as penzoyl peroxide and t-butylbarbenzoate alone, or water-soluble reducing agents such as sodium sulfite, Rongalite, and ascorbic acid are used. This is done by using a combination of In addition, a chain transfer agent, a crosslinking monomer, and a pH buffering agent can be optionally used in the polymerization system.

In normal emulsion polymerization, ゜ζ is the total amount of monomers 100
50 to 500 parts by weight of water and 1 to 1 part of emulsifier
Parts by weight of O and 0.5 to 3 parts by weight of catalyst are used, but the range is not limited. The aqueous fluoroolefin copolymer dispersion of the present invention preferably has a nonvolatile content of 20 to 65% by weight. Furthermore, the aqueous dispersion of the present invention may contain dispersants such as sodium tripolyphosphate, sodium hexametaphosphate, and sodium polyacrylate, wetting agents such as the nonionic emulsifier, and protective colloids, depending on performance such as workability and processing characteristics. Thickeners such as silicone oil, antifoaming agents such as mineral oil, plasticizers or coalescent agents such as dibutyl phthalate, dioctyl phthalate, butyl carbitol acetate, butyl cellosolve, titanium dioxide and/or used in conventional emulsion propellants. Filled pigments such as calcium carbonate, clay, and silica, preservatives, anti-pesky agents, PH adjusters, and acrylic, vinyl acetate, vinyl chloride, acrylic-styrene, ethylene-vinyl acetate, ethylene-vinyl acetate-vinyl chloride It is also possible to add polymer emulsions such as (Examples) The present invention will be further explained below with reference to Examples.

In the following explanation, all parts and percentages are by weight. Example 1 A solution having the following composition was placed in a pressure-resistant autoclave equipped with a stirrer. Ion exchange water・・・・・・・・・・・・・・・・・・
500 parts Neugen EA-120 (Daiichi Kogyo Seiyaku II product, polyoxyethylene alkylphenol ether) 12 parts Pluronik F68 (Asahi Denka Kogyo Co., Ltd.) Product, oxyethylene oxypropylene block copolymer) 1.1...
−・・・−・・・・・・・・・1・・・−・181 Emar O (Kao ■ product, sodium lauryl sulfate)・・・・・・
・・・－・・・・・・・・・・・・・・・・・・・・・
・・3 parts vinyl sulfonic acid soda・・・・・・・・・・・・
・・・−・・1・・6 parts crotonic acid ． ．． ．． ．． ．． ．． ．． ．． ．． ．． =． −． −． ---・
=． ．．・−・−=−・−−−−= 6 parts N a H C
O s-・・・・・・・・・・・・１．
−・・・・・・・・・・・・・・・・・・・・・・・・・
... 6 parts Then, 30 parts of the total 1300 parts of vinyl acetate, 5 parts of the 300 parts of chlorotrione ethylene, and 3 parts of the 6 parts of potassium persulfate were charged into an autoclave, and ethylene was introduced. After removing the air in the reaction system, ethylene was introduced and heated with stirring to raise the temperature to 80°C. At this time, the internal pressure of the autoclave was 50kg/c+1
I adjusted it so that Then, 80°C, 50kg/c
While maintaining the pressure of the vessel, add the remaining 270 parts of vinyl acetate,
and the remaining 295 parts of chlorotrifluoroethylene were added evenly over a period of 4 hours. At the same time, add the remaining 3 parts of potassium persulfate to ion-exchanged water. A solution of 100 parts was added dropwise evenly over a period of 5 hours. The aqueous dispersion thus obtained was diluted with water to adjust the solid content reduction to 50% to obtain an aqueous copolymer dispersion. The viscosity of this copolymer aqueous dispersion (BM type rotational viscometer 6Orpm) was 40c.
psSp}{was 4.0. The polymer solids in this copolymer aqueous dispersion were 15% ethylene and 44% vinyl acetate.
%, and 41% chlorotrifluoroethylene. Compositional analysis of the above copolymer was performed as follows. The fluorine content of the fluoroolefins was determined by the alizarin combination method, and the vinyl ether and vinyl carboxylate were determined by NMR and pyrolysis gas chromatography measurements. Also, from the whole (100%) fluoroolefins,
Vinyl ester and/or vinyl ether content (%)
The ethylene content (%) was calculated by subtracting the amount. The physical properties of the resulting aqueous copolymer dispersion, such as stability and pigment dispersibility, were measured and are shown in Table 1. Comparative Example 1 A ゜ζ copolymer aqueous dispersion was obtained in the same manner as in Example 1, except that no sodium vinylsulfonate was used. The physical properties of the resulting aqueous copolymer dispersion, such as stability and pigment dispersibility, were measured and are shown in Table 1. Comparative Example 2 A copolymer aqueous dispersion was obtained in the same manner as in Example 1, except that no crotonic acid was used.

Physical properties such as stability and pigment dispersibility of the obtained copolymer aqueous dispersion were measured and are shown in Table 1.

(Leaving space below) Table 1 (In Table 1, the judgment display is Good Q>@>△>×.) The test method for each physical property is as follows. (1) Amount of aggregate produced during polymerization After the completion of polymerization, the aqueous dispersion produced was filtered through an IOO mesh wire mesh, and the weight of the precipitate was measured.
Converted to (g) per 1,000 g of aqueous dispersion. (2) Mechanical stability: After diluting the aqueous dispersion with ion-exchanged water to a concentration of 5%, 300 g of it was used in a homomixer (1/
6HP) for 10 minutes at 5000 rpmS, and after standing for 24 hours, the presence or absence of a precipitate was determined visually.

(3) Dilution stability: Add ion-exchanged water to the dehydrated liquid to give a solid content concentration of 5%, stir well, and centrifuge the diluted sample at 2000 rpm for 15 minutes using a centrifuge. (4) Minimum film forming temperature:
Temperature/smell heat distribution plate type minimum IF! Measured by temperature measuring device (I
SO2 115). (5) #R material dispersibility: Copolymer water loss? & l 0 0 parts by weight, 2 parts by weight of water loss (Dainippon Ink & Chemicals ■Disburse Clar SD-
902) and stirred uniformly using a policeman.
, put it in a test tube and let it stand. Visually check for separation and aggregation of the compound. O Coating film physical properties test specimen preparation conditions: 200 g/cd of a coloring compound that was checked for corrosion resistance was applied to a 3 mm thick flexible board (5 cm x 15 cm) using a brush, and the temperature was 70°C x 10
Dry in the dryer for minutes. (6) Adhesion: The specimen prepared under the above conditions was cut with a knife to create 25 squares with a side of 2 mm. Perform a peel test using sellotape and visually judge the state of paint film peeling (paint film remaining). (Weather resistance: After subjecting the specimen prepared under the above conditions to a QUV weather meter (manufactured by Suga Test Instruments) for 500 hours, visual judgment was made for loss of gloss, cracks, etc. on the painted surface. (8) Water resistance 2 Under the above conditions After immersing the prepared specimen in water for 15 days, the painted surface was visually judged for whitening, swelling, pristalling, softening, gloss, etc.

(9) Alkali resistance 2 The specimen prepared under the above conditions was Ca(
OH)! After 15 days of immersion in a saturated, 2% NaOH aqueous solution, the painted surface was visually judged for whitening, swelling, blistering, softening, loss of gloss, etc.

No.! From the results shown in the table, it can be seen that the aqueous dispersion prepared without using any sodium vinyl sulfonate and the aqueous dispersion prepared without using crotonic acid have an increased amount of aggregate formation during polymerization, and the stability of the aqueous dispersion. It became clear that the properties and adhesion of the paint film decreased. Example 2 The same emulsifier and crotonic acid solution as in Example 1 was placed in an autoclave. Next, 25 parts out of the total amount of 250 parts of vinyl acetate, "VeoValO (a product of Shell Co., Ltd., a tertiary carboxylic acid vinyl ester represented by the following general formula, Rl l CH, skin CH-0-C-C-R, I1 O R , In the above formula, the total number of carbon atoms of Rl, Ryo and R is 8) 150
Of the club! 5 parts, total amount of chlorotrifluoroethylene 20
5 parts out of 0 parts and 4 parts of sodium hydrosulfite
Add ethylene and raise the temperature to 50'C. At this time, the autoclave internal pressure was set to 60 kg/cd at node U8. Then, while maintaining a pressure of 60}Cg/cj at 50°C, the remaining 225 parts of vinyl acetate, "VeoValO" 1
35 parts of chlorotrifluoroethylene and 195 parts of chlorotrifluoroethylene were added in 5 equal portions every hour. At the same time, a solution of 3 parts of hydrogen peroxide (30%) dissolved in 100 parts of ion-exchanged water was uniformly and continuously dropped over 6 hours. The aqueous dispersion thus obtained was diluted with water to adjust the solid content concentration to 50% to obtain an aqueous copolymer dispersion. The viscosity of this copolymer aqueous dispersion was 40 cps, pH 4,
It was O. The polymer solids in this copolymer aqueous dispersion were 20.4% ethylene and 2% chlorotrifluoroethylene.
5.5%, vinyl acetate 33.6%, 'VeoValO゜' 20.5%. The properties of this aqueous copolymer dispersion are shown in Table 2, and the physical properties of the coating film are shown in Table 3.
Comparative Example 3 An aqueous copolymer dispersion was produced in the same manner as in Example 2, except that the ethylene pressure was 170 kg/cal. The polymerized solid in this aqueous copolymer dispersion contains 35% ethylene.
0%, chlorotriphnoreoloethylene 206%, vinyl acetate 27.6%, and "VeoValO゜'!6.8%." The properties of this copolymer aqueous dispersion are shown in Table 2.
The illFJ characteristics are shown in Table 3. Comparative Example 4 The amount of heptanomer used was 400 parts of vinyl acetate, “■eoVa
An aqueous copolymer dispersion was produced in the same manner as in Example 2, except that 150 parts of chlorotrifluoroethylene, 50 parts of chlorotrifluoroethylene, and the ethylene pressure were changed to 15 kg/c.In this aqueous copolymer dispersion, The polymerized solid is ethylene 7.8
%, chlorotrifluoroethylene 7.7%, vinyl acetate 61.5%, and “VeoValO” 23.0%. The properties of this aqueous copolymer dispersion are shown in Table 2, and the physical properties of the coating film are shown in Table 3. Comparative Example 5 The amount of heptanomer used was changed to 20 parts of vinyl acetate, “VeoVal
Example 2 except that 20 parts of O'', 560 parts of chlorotrifluoroethylene, and the ethylene pressure were changed to 60 kg/cd.
An aqueous copolymer dispersion was prepared in the same manner as above. The polymerized solid in this copolymer aqueous dispersion is ethylene 12.
0%, chlorotrifluoroethylene 820%, vinyl acetate 3.1%, and "VeoValO" 2.9%. The properties of this aqueous copolymer dispersion are shown in Table 2, and the physical properties of the coating film are shown in Table 3. Table 2 Table 3 The test method was the same as in Table 1. Test methods not shown in Table 1 are as follows. (l [D Blocking resistance: Place a piece of kraft paper of 3 cm on each side on the painted surface,
After placing a kg weight on it and leaving it in a room at 23℃ and 65% humidity for 24 hours, the kraft paper was peeled off and judged based on the peel resistance of the kraft paper and the amount of residue left on the painted surface.

From the results shown in Tables 2 and 3, it is clear that the ethylene content is 3
If it is 5%, the blocking property will be poor, and if the amount of carboxylic acid vinyl ester increases, the water resistance, alkali resistance,
It was found that weather resistance decreased. Furthermore, as chlorotrifluoroethylene increased, a decrease in the decomposition of the material and the adhesion of the paint film was observed. Examples 3 to 8 The amounts of sodium vinyl sulfonate and crotonic acid (amount % of the amount per calculated yield of copolymer) were each 0.5.
% and 1.5% (Example 3), 10% and l, O%
(Example 4), l. , 5% and 0.5% (Example 5),
1.5% and 1. Emulsification was carried out in the same manner as in Example 1, except that the concentrations were changed to 5% (Example 6), 0.5% and 0.5% (Example 7), and 2.0% and 2.0% (Example 8). Polymerization was performed to obtain aqueous dispersions of each copolymer. The amount of aggregate produced during each polymerization was 0.2 g (Example 3), 0.2 g (Example 3), 0.2 g (Example 3),
1g (Example 4), 0.1>g (Example 5), 0.1
>g (Example 6), 0.4g (Example 7), and Ig (Example 8). The properties and coating film properties of each copolymer aqueous dispersion were as shown in Table 4. Comparative Examples 6 to 9 The charged amounts of vinyl sulfonic acid and crotonic acid (charged amount % per calculated yield of copolymer) were 0% and 1.0%, respectively.
5% (Comparative Example 6), 1. 5% and O% (Comparative Example 7
), 3.0% and 0% (Comparative Example 8), 0% and 3.0%
Emulsion polymerization was carried out in the same manner as in Example 1, except that (Comparative Example 9) was changed, and each copolymer aqueous dispersion was obtained. The amount of aggregate produced during each polymerization was 5 g (Comparative Example 6),
2g (Comparative Example 7), 2g (Comparative Example 8) and 4g (Comparative Example 9). The properties and coating film properties of each copolymer aqueous dispersion were as shown in Table 4. (Left below) Table 4 The test method was the same as in Table 1. From the results in Table 4, it was found that when only either sodium vinylsulfonate or crotonic acid was used, the amount of aggregates produced during polymerization increased and the stability of the aqueous dispersion was also poor.

Example 9 15 parts of Neogen R in a 21 stainless steel autoclave
(Dodecylbenzenesulfonic acid sodium, Daiichi Kogyo Seiyaku■
10 parts of Neugen EA-120 (polyoxyethylene nonylphenol ether, manufactured by Daiichi Kogyo Seiyaku), 5
An aqueous solution prepared by dissolving 100 parts of sodium nylsulfonate, 5 parts of crotonic acid, and 5 parts of ammonium carbonate in 650 parts of ion-exchanged water was added, and then 150 parts of vinyl pivalate was charged, and then 10 kg/ml of ethylene was added. c) Pressurized and degassed. After repeating the ethylene pressurization and degassing operations twice, 112 parts of ethyl vinyl ether and 233 parts of hexafluorobrobylene, which had been liquefied and collected in advance, were pressurized into the autoclave through a glass pressure-resistant tube under ethylene pressure.
Increase the pressure to 40kg/c with ethylene! j
I wrote one verse. The temperature of the autoclave was adjusted to 60°C, and a catalyst solution containing 5 parts of ammonium persulfate dissolved in 90 parts of ion-exchanged water was added dropwise over 6 hours, and the reaction was continued for an additional 2 hours. The pressure decreased as the polymerization progressed, but
No new ethylene supplementation was performed. After cooling to 30°C, the aqueous dispersion was taken out to obtain an aqueous copolymer dispersion. The solid content concentration of this copolymer aqueous dispersion was 40.1%,
At a viscosity of 950 cps. The polymerized solid was composed of 37% hexafluoropropylene, 15% ethylene, 21% ethyl vinyl ether, and 27% vinyl bivalate. The properties of this aqueous copolymer dispersion and the physical properties of the coating film were as shown in Table 5. Comparative Example 10 An aqueous copolymer dispersion was produced by polymerizing in the same manner as in Example 9, except that ethylene was not used and pressure was applied with nitrogen. The properties of this aqueous copolymer dispersion and the physical properties of the coating film were as shown in Table 5. Comparative Example 11 An aqueous copolymer dispersion was produced by polymerizing in the same manner as in Example 9, except that 6 parts of acrylic acid was used without using sodium vinylsulfonate and crotonic acid. The properties of this aqueous copolymer dispersion and the physical properties of the coating film were as shown in Table 5. The fifth was shown. [Effects of the Invention] The aqueous dispersion of the present invention has good sedimentation stability, mechanical stability, and dispersibility of emulsion particles, and can form a film by heating at room temperature or a relatively low temperature, and has excellent adhesion to substrates. It can produce a film with excellent water resistance, weather resistance, and chemical resistance. Due to these features, the aqueous dispersion of the present invention is suitable for applications such as exterior architectural paints, exterior building material coatings, coatings and fiber processing agents.

Claims (6)

[Claims] (1) 10 to 80% by weight of fluoroolefins and 5 to 80% by weight of fluoroolefins;
30% by weight of olefin, 10-80% by weight of vinyl ester and/or vinyl ether, 0.1-3.0% by weight
A copolymerizable reactive emulsifier containing sulfonic groups and/or sulfate groups and an ethylenically unsaturated acid in the same molecule in an amount of 0.1 to 3.0% by weight, and a copolymerizable ethylenically unsaturated acid in an amount of 0.1 to 3.0% by weight. An aqueous fluoroolefin copolymer dispersion characterized by being obtained by emulsion copolymerization of and. (2) The aqueous fluoroolefin copolymer dispersion according to claim (1), wherein the copolymerizable reactive emulsifier is sodium vinylsulfonate and/or sodium alkylsulfosuccinate. (3) The aqueous fluoroolefin copolymer dispersion according to claim (1) or (2), wherein the copolymerizable ethylenically unsaturated acid is crotonic acid. (4) Claim (1), (2) or (4) wherein the fluoroolefin is a chlorotrifluoroolefin.
3) The fluoroolefin copolymer aqueous dispersion described above. (5) The aqueous fluoroolefin copolymer dispersion according to claim (1), (2), (3) or (4), wherein the olefin is ethylene. (6) Claims (1) and (6) characterized in that the vinyl ester is vinyl acetate and/or vinyl versatate.
2), (3), (4), or the fluoroolefin copolymer aqueous dispersion described in (5).