JPH06256614A - Fluorine resin aqueous dispersion and aqueous coating composition containing the aqueous dispersion - Google Patents

Abstract

(57) [Summary] [Purpose] In particular, it is intended to provide a fluororesin aqueous dispersion which is excellent in long-term storage stability and has ultra-high weather resistance and excellent stain resistance. ,
Then, the present invention provides an aqueous coating composition containing an extremely practical fluororesin aqueous dispersion. [Structure] Characteristically, it has no reactive polar group,
A specific reactive nonion having a structure having a polymerizable unsaturated double bond and having a function of randomly copolymerizing without interfering with the polymerization of monomers containing fluoroolefins. A fluororesin aqueous dispersion obtained by polymerizing an emulsifier and a monomer containing the fluoroolefin; and an aqueous coating composition containing the aqueous dispersion.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is novel and useful,
TECHNICAL FIELD The present invention relates to an aqueous fluororesin dispersion and an aqueous coating composition containing the same. More specifically, the present invention is a specific, so-called reactive nonionic emulsifier, obtained by polymerizing with a fluoroolefin, etc., of course, ultra-high weather resistance and stain resistance, etc., of course,
The present invention relates to a fluororesin aqueous dispersion excellent in long-term storage stability and an aqueous coating composition containing the same.

[0002]

2. Description of the Related Art Conventionally, the purpose of coating the surface of various kinds of alkaline inorganic hardened materials such as metal or cement and various kinds of plastics with a paint is to improve the weather resistance of the base material,
This is done to improve so-called durability such as chemical resistance and water resistance, and for protection and beauty.

In recent years, in particular, coating materials that are exposed outdoors such as building exterior materials and industrial materials are required to have excellent durability and long-term maintenance-free properties.

Fluoroolefin copolymers are known as binders having high weather resistance and high chemical resistance, and are commercially available in the form of an organic solvent solution. However, since it contains a large amount of organic solvents, there are problems such as fire risk, harmfulness, and air pollution, and an aqueous fluoroolefin-based binder is required.

So far, tetrafluoroethylene,
Aqueous dispersions of various fluoroolefin polymers have been proposed, such as vinylidene fluoride or hexafluoropropylene.

However, these fluoroolefins
Polymer aqueous dispersions require baking at a high temperature in the film forming process. For example, in the invention described in JP-A-57-38845, vinylidene fluoride and In the case of a hexafluoropropylene copolymer, baking at a temperature of 180 to 230 ° C is required.

Such high temperature baking is, of course, impossible in the field of normally dry paint (normal temperature dry type paint) of painting on site, and it is also a so-called factory where heat drying is the main component. Even in line painting, it is undeniably economically disadvantageous.

On the other hand, in the invention described in JP-A-61-261367, as a method for solving such a problem, fluoroolefin, alkyl vinyl ether,
Disclosed is an emulsion polymer-based coating composition composed of a carboxylic acid vinyl ester. According to such an invention, the film-forming property is significantly improved.

Further, the invention described in JP-A-61-261367 discloses a resin composition for coatings based on an emulsion copolymer composed of a fluoroolefin, an alkyl vinyl ether and a vinyl carboxylic acid ester. However, although it is applicable to the protection of inorganic building materials, it is insufficient in terms of long-term storage stability and pigment dispersibility, and mechanical and chemical stability. It is something.

Further, according to the invention described in JP-A-2-225550, it is disclosed that an aqueous dispersion having good storage stability can be obtained by copolymerizing macromonomers having a hydrophilic group. ing. However, the reality is that it has not yet reached a practical storage stability.

[0011]

As described above, as long as the conventional technique is followed, in particular, it is excellent in long-term storage stability and, in addition, has super high weather resistance and excellent stain resistance. It is difficult and difficult to obtain a fluororesin aqueous dispersion (hereinafter, also referred to as an aqueous dispersion) in the form of an aqueous solution and an aqueous coating composition containing the fluororesin aqueous dispersion. You can see that.

However, the present inventors have earnestly started research based on the existence of various drawbacks in the conventional technique and the demands of the industry as described above.

[0013] Therefore, the problem to be solved by the present invention depends on one and the fluororesin aqueous dispersion excellent in long-term storage stability, and the aqueous dispersion and the pigments are essential components. An object is to provide an aqueous coating composition.

[0014]

Therefore, the present inventors have
In view of the advantages and disadvantages of the conventional technology, as a result of earnest and repeated studies, a specific reactive emulsifier and fluoroolefin are emulsion-polymerized to be an essential raw material component, and further, if necessary, other monomers. It was found that the fluororesin aqueous dispersion obtained by emulsion polymerization of the above-mentioned compounds can satisfy the above-mentioned problems brilliantly, and the present invention has been completed here.

That is, the present invention is a nonionic emulsifier having at least one ethylenically unsaturated bond (hereinafter, referred to as
Abbreviated as reactive nonionic emulsifier. ), The fluororesin aqueous dispersion obtained by emulsion-polymerizing the fluoroolefin as an essential component and other monomers,
In addition, a pigment is added to the aqueous dispersion,
An aqueous coating composition, which is intended to provide an aqueous coating composition, and further comprises, if necessary, a pigment and a thickener and / or an organic solvent in the aqueous dispersion. It is an attempt to provide something.

The above-mentioned reactive nonionic emulsifiers as used herein mean a stable emulsified state at all stages of the polymerization reaction of the fluororesin aqueous dispersion of the present invention, that is, before, during or after the polymerization. For maintaining, without causing decomposition in an aqueous medium, and without causing the ethylenically unsaturated double bond to inhibit the polymerization of the monomers containing the fluoroolefins, to be randomly copolymerized, Can be defined as an emulsifier which does not retain various reactive polar groups such as a carboxylic acid group, a sulfonic acid group or a phosphoric acid group.

When a so-called ionic reactive emulsifier having a reactive polar group, such as anionic or cationic, is used alone, the stability of the aqueous dispersion is apt to be influenced by pH. However, it is disadvantageous because it forms a salt by neutralization or neutralization, which adversely affects the physical properties of the coating film such as water resistance.

Even with nonionic emulsifiers, since the dispersion particles themselves are fluorine-based polymers that form the surface of relatively low energy particles, they are compared to ordinary polymers such as acrylic emulsions. It is highly water and oil repellent and does not strongly adsorb emulsifiers.

Therefore, there is a limit to the ability of the emulsifier to be adsorbed and stabilized on the dispersion particles only by the intermolecular force or the electric force. Therefore, the force due to the chemical bond is absolutely necessary. Is becoming.

For the above reasons, the reactive nonionic emulsifier is an essential component for improving the stabilization of the aqueous dispersion. As the reactive nonionic emulsifiers, only typical ones will be exemplified.

[0021]

[Chemical 19]

[Wherein R ₁ and R ₂ in the formula may be the same or different and each has 6 carbon atoms]
To 24 hydrocarbon groups having at least one, preferably 1 or 2 polymerizable unsaturated bonds, and R ₃ is an alkyl group having 1 to 4 carbon atoms. Or, it represents a proton, A represents an ethylene oxide bond and / or a propylene oxide bond, m is an integer of 1 or 2, and n is an integer of 5 or more. ]

[0023]

[Chemical 20]

[Wherein R ₁ has 6 to 2 carbon atoms]
4 represents a saturated or unsaturated hydrocarbon group, R ₂ represents an alkenyl group having 2 to 4 carbon atoms when R ₁ is a saturated hydrocarbon group, and R ₁
Is an unsaturated hydrocarbon group, it represents an alkyl group having 1 to 4 carbon atoms, A represents an ethylene oxide bond and / or a propylene oxide bond, and m is an integer of 1 or 2. And then
In addition, n is an integer of 5 or more. ]

[0025]

[Chemical 21]

[Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, and R ₂ has 1 to 4 carbon atoms] Represents an alkyl group or a proton, A represents an ethylene oxide bond and / or propylene oxide bond, m represents an integer of 1 or 2, and n represents an integer of 5 or more. . ]

[0027]

[Chemical formula 22]

[Wherein R ₁ represents a hydrocarbon group having 6 to 24 carbon atoms and having at least one polymerizable unsaturated bond, and R ₂ represents a proton or a methyl group. R ₃ represents an alkyl group having 1 to 4 carbon atoms, A represents an ethylene oxide bond and / or a propylene oxide bond, and n is an integer of 5 or more. ]

[0029]

[Chemical formula 23]

[Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, and R ₂ represents a proton or a methyl group] R ₃ represents an alkyl group having 1 to 4 carbon atoms, A represents an ethylene oxide bond and / or a propylene oxide bond, and n is an integer of 5 or more. ]

[0031]

[Chemical formula 24]

[Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, and R ₂ and R ₃ are the same, respectively. Or may be different, the carbon number is 1 to
4 represents an alkyl group or a proton, and A
And B each represent an ethylene oxide bond and / or a propylene oxide bond, which may be the same or different, and m and n may be the same or different, respectively. At least one of them is an integer of 5 or more, and the other is 0 or an integer of 1 or more. ]

[0033]

[Chemical 25]

[Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, and R ₂ and R ₃ are the same, respectively] Or may be different, the carbon number is 1 to
4 represents an alkyl group or a proton, and A
And B respectively represent an ethylene oxide bond and / or a propylene oxide bond, which may be the same or different, and m and n
May be the same or different, respectively,
At least one of them is an integer of 5 or more, and the other is 0 or an integer of 1 or more. ]

[0035]

[Chemical formula 26]

[However, R ₁ and R ₂ in the formula may be the same or different and each has 6 carbon atoms.
~ 24 represents an alkyl group or a proton, at least one of which is an alkyl group, and A and B may be the same or different, an ethylene oxide bond and / or Or a propylene oxide bond, and m and n may be the same or different, but at least one of them is an integer of 5 or more, and the other is 0 or 1. It is assumed that the above is an integer, and r is an integer of 1 to 4. 〕and

[0037]

Embedded image R ₁ COO (A) _n R ₂ [wherein R ₁ represents a hydrocarbon group having 6 to 24 carbon atoms and having at least one polymerizable unsaturated bond, R ₂ represents an alkyl group having 1 to 4 carbon atoms or a proton, A represents an ethylene oxide bond and / or a propylene oxide bond, and m and n are the same or different. However, at least one of them is an integer of 5 or more, and the other is 0 or an integer of 1 or more. ] As long as it has a chemical structural formula as shown by, and is not particularly limited as long as it corresponds to the above description, the hydrophilic segment has a polymerizable group through an ether bond. Of the vinyl ether type bonded to an unsaturated double bond, for example,

[0038]

Embedded image CH ₂ ═CHO (CH ₂ ) _m (OCH ₂ CH ₂ ) _n —OH ...
... [X] [wherein, m and n in the formula may be the same or different, each is an integer of 1 or more, m is an integer of 1 to 20, and n is It shall be an integer of 1 or more. When used in an aqueous medium, a compound such as the above] easily hydrolyzes under a certain condition, and therefore the use of such a compound must be avoided.

Also, other compounds, that is, for example,

[0040]

Embedded image CH ₂ ═CHCH ₂ O (CH ₂ ) _m (OCH ₂ CH ₂ ) _n —O
H ......... [XI] [wherein, m and n in the formula may be the same or different, each is an integer of 1 or more, and m is an integer of 1 to 20, n is an integer of 1 or more. ] Even a compound such as
If it is incorporated into polymer particles, it exerts a particle stabilizing ability, but since it lacks the ability to emulsify monomers before polymerization sufficiently, it is necessary to avoid use in practice. .

The amount of the reactive nonionic emulsifiers to be used may be 0.1% by weight or more based on the total amount of the monomers, and is limited unless the performance of the obtained aqueous dispersion is reduced. However, it is more effective in the range of 0.1 to 5% by weight.

The above are the reactive nonionic emulsifiers used as an essential raw material component for preparing the aqueous dispersion of the present invention. In addition to these, as shown below,
Combination with various non-reactive emulsifiers is also possible.

Examples of emulsifiers that can be used in combination include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, other anionic reactive emulsifiers, fluorine-based surfactants, substances having surface activity such as acrylic oligomers. Of these, nonionic and anionic emulsifiers are preferable because they generate less aggregates during polymerization.

Typical nonionic emulsifiers are polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers, ethylene oxide-propylene oxide block copolymers, and the like, and anionic emulsifiers are alkyl (benzene) sulfones. There are alkali metal salts, ammonium salts and amine salts of acids, alkyl sulfates, polyoxyethylene alkylphenyl sulphates and the like.

Further, instead of the above-mentioned anionic emulsifier or in combination, a water-soluble oligomer composed of polycarboxylic acid or sulfonate can be used. Furthermore, a water-soluble polymer substance such as polyvinyl alcohol or hydroxyethyl cellulose can be used as a protective colloid. The amount of the above-mentioned emulsifier or the like used is preferably 10% by weight or less based on the total amount of the monomers, from the viewpoint of physical properties of the coating film obtained.

Next, another essential raw material component,
The fluoroolefin will be described.
As the fluoroolefins used herein, only typical ones are exemplified, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, 1,1,3,3,3-pentafluoropropylene, 1,1,3,3-tetrafluoropropylene,
1,1,2-trifluoropropylene or 3,3,3
-Including fluoroolefins in a pure sense, such as trifluoropropylene,

Further, chlorotrifluoroethylene,
Bromotrifluoroethylene, 1-chloro-1,2-difluoroethylene or 1,1-dichloro-2,2-difluoroethylene such as those having a halogen atom other than a fluorine atom are also included in a broad sense. Fluoroolefins and the like.

Among these, the use of hexafluoropropylene, chlorotrifluoroethylene or vinylidene fluoride is particularly preferable from the viewpoint of reaction control during polymerization.

When the fluoroolefin is used in an amount of about 10 to 80% by weight based on all the monomers and introduced into the intended fluororesin, the weather resistance is particularly satisfactory. You get what you can.

On the other hand, various other main monomers which can be copolymerized with the fluoroolefin can be considered, and the kind and amount thereof are high in weather resistance,
It should be appropriately selected and used in consideration of various film performances such as chemical resistance, water resistance, alkali resistance, heat resistance and flexibility, and among them, particularly typical ones. The following is only an example.

(1) Various unsaturated carboxylic acids, such as crotonic acid, itaconic acid, citraconic anhydride or itaconic anhydride, or various esters thereof; (2) Polymerizable, such as citraconic acid or itaconic acid A variety of such unsaturated bond-containing polyhydroxyalkyl esters, such as dihydroxyalkyl esters of unsaturated double bond-containing polycarboxylic acids;

(3) Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isoamyl vinyl ether, n-hexyl vinyl ether,
various alkyl vinyl ethers such as n-octyl vinyl ether or 2-ethylhexyl vinyl ether;

Various cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether or methyl cyclohexyl vinyl ether; or various aromatic vinyl ethers such as benzyl vinyl ether or phenethyl vinyl ether;

Various (per) fluoroalkyl vinyl ethers such as perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, perfluorooctyl vinyl ether or perfluorocyclohexyl vinyl ether; or various kinds such as 4-hydroxybutyl vinyl ether. Various vinyl ethers such as hydroxyalkyl vinyl ethers;

(4) Vinyl acetate, vinyl propionate, n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl neononanoate, vinyl neodecanoate, vinyl 2-ethylhexanoate, vinyl laurate or stearin. Vinyl acetate, pt-
Various vinyl carboxylates such as vinyl butyl benzoate, vinyl salicylate, vinyl monochloroacetate or vinyl cyclohexanecarboxylate;

(5) Various halogenated olefins such as vinyl chloride or vinylidene chloride; or ethylene, propylene, n-butylene, isobutylene, n-
Various olefins such as pentene; or (6) butadiene, hexadiene, octadiene, decadiene, tetradecadiene, 2-methyloctadiene, decatriene or diallylphthalate,
Various monomers having two or more polymerizable unsaturated double bonds in the molecule; or various hydrolyzable compounds such as vinyltrimethoxysilane, vinyltriethoxysilane or vinyltris (2-methoxyethoxy) silane Various crosslinkable monomers such as silyl group-containing monomers and the like.

Of the various copolymerizable monomers as listed above, vinyl ethers and / or carboxylic acid vinyl esters, and further olefins,
It is suitable to use within the range of 5 to 90% by weight, preferably within the range of 5 to 20% by weight.

Further, among various copolymerizable monomers, vinyl ethers are easily hydrolyzed depending on the conditions when used in an aqueous medium. It is even more desirable to use other copolymerizable monomers except vinyl ethers.

The polymerization initiators may be any of those commonly used in emulsion polymerization,
Although there is no particular limitation, to exemplify only typical ones among them, various water-soluble inorganic peroxides such as hydrogen peroxide; ammonium persulfate,
Various persulfates such as potassium persulfate or sodium persulfate; Various organic peroxides such as cumene hydroperoxide or benzoyl peroxide;

There are various azo initiators such as azobisisobutyronitrile or azobiscyanovaleric acid (azobisisovaleronitrile), and these may be used alone or in combination of two or more kinds. Of course.

The amount of the polymerization initiators used is preferably 0.1 to 2% by weight based on the total amount of the monomers. In addition,
It goes without saying that a method known as a so-called redox polymerization method by using these polymerization initiators in combination with a metal ion and a reducing agent may be used.

In the present invention, the monomers are added in the presence of water, preferably in the presence of ion-exchanged water, or in the presence of the ion-exchanged water and an emulsifier optionally used. As is, or
Depending on the emulsified state, it is added to the reaction vessel all at once or in divided portions, or it is continuously added dropwise to the reaction vessel, and in the presence of the above-mentioned polymerization initiators, 0 to 100 is added.
℃, preferably at a temperature of 30 ~ 90 ℃, 3 ~ 100
Kg / cm ^2, preferably, it may be Seshimere polymerization Te than in 6~50Kg / cm ² becomes pressure.

In this case, the ratio of the total amount of monomers to water should be set so that the final solid content is in the range of 20 to 60% by weight. Further, in emulsion polymerization, a seed polymerization method may be used in which emulsion particles are allowed to exist in the aqueous phase in advance and polymerization is performed in order to grow or control the particle diameter.

The particle diameter of the fluororesin aqueous dispersion thus obtained is generally 0.05 to 3 μm (μ
m), while the glass transition temperature (Tg) of the polymer itself in the aqueous resin dispersion is generally in the range of -20 to + 60 ° C.

If necessary, the fluororesin aqueous dispersion of the present invention may be mixed with a pigment, a thickener and an organic solvent to prepare a coating composition.

The amount of the pigments used is preferably 200% by weight or less based on the solid content of the above-mentioned aqueous resin dispersion. When it is used in an amount of more than 200% by weight, the coating film obtained is inevitably porous and the long-term durability such as water resistance is deteriorated, which is not preferable.

As only specific examples of the pigments, titanium oxide, mica, talc,
Various inorganic pigments such as clay, precipitated barium sulfate, silica powder, calcium carbonate, iron oxide, zinc oxide, aluminum powder or carbon; phthalocyanine blue,
It is also possible to use various organic pigments and the like, and further to use so-called dispersed pigments in a form in which the various pigments as listed above are dispersed in water with an emulsifier or a dispersant. It is appropriately selected and used according to each purpose.

Next, organic solvents are added for the purpose of lowering the minimum film-forming temperature and further strengthening the film-forming state. Of these, only typical ones are used. To give an example, n-pentane or n
Various saturated hydrocarbons such as hexane; various aromatic hydrocarbons such as toluene or xylene; various esters such as ethyl acetate or butyl acetate;
Various alcohols such as ethyl alcohol, butyl alcohol, 2-ethylhexanol, benzyl alcohol or 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate;

Various ketones such as acetone, methyl ethyl ketone, methyl amyl ketone or methyl isobutyl ketone; various phthalate plasticizers such as dibutyl phthalate or dioctyl phthalate; dimethyl glycol phthalate, dimethyl glycol adipate or dimethyl glycol sebacate Various glycol plasticizers such as;

Various ethylene glycol derivatives such as methyl cellosolve, cellosolve, butyl cellosolve, cellosolve acetate or butyl cellosolve acetate; various diethylene glycol derivatives such as carbitol, carbitol acetate, butyl carbitol or butyl carbitol acetate, etc. Yes, it is used in an amount of less than 20% by weight, based on the aqueous dispersion, depending on the ability to reduce the minimum film-forming temperature. 20% by weight
The use of an amount exceeding the above range should not be used because it may significantly deteriorate the physical properties of the coating film.

Examples of the thickeners include water-soluble oligomers composed of the above-mentioned polycarboxylic acids or sulfonates, carboxylic acid polymer thickeners, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose or hydroxyethyl cellulose. Like,
Various water-soluble polymer substances and urethane-based thickeners can be used.

The thickeners may be used in an amount such that the desired viscosity can be obtained. However, in consideration of the water resistance of the coating film, 5% by weight or less based on the aqueous dispersion. Is desirable.

Further, various other additives, for example,
Dispersants, wetting agents, thixotropic agents, ultraviolet absorbers,
The use of antioxidants, water repellents, antifreezing agents, antiseptic / antifungal agents or antifoaming agents should be appropriately selected and used while considering the performance of the resulting coating film. Good.

Thus, each of the fluororesin aqueous dispersions having excellent physical properties such as ultrahigh weather resistance of the fluororesin and excellent long-term storage stability, and a highly practical fluororesin aqueous dispersion, and An aqueous coating composition containing the fluororesin aqueous dispersion and pigments as essential components can be obtained.

Next, the coating method or coating means will be described. First of all, as the base materials, concrete skeleton,
There is no particular limitation as long as it is a general construction base material such as a metal plate or the like, so-called various kinds of alkaline inorganic hardened materials such as wall materials or roof materials, and for example, brush coating, roller coating, Various coating means such as spray coating, roll coater coating or showering coating may be appropriately selected according to the situation.

At that time, it is desirable that the composition for construction at a construction site, that is, a so-called normal temperature type, has a minimum film forming temperature of 0 ° C. or lower.
The coating method may be a known and commonly used method such as brush coating, roller coating or spray coating.

As a drying condition after coating, a temperature of 0 ° C. or higher, preferably 20 ° C. or higher is suitable, and if drying is carried out at such a temperature for 7 days, it is completely possible. The coating film is hardened.

On the other hand, it can be applied to the so-called factory line coating for roof materials such as roof tiles, wall materials, etc., and according to the generally used forced heating drying method,
It is preferable to appropriately select and use a coating material having a minimum film-forming temperature of about 60 ° C. or less, preferably 50 ° C. or less, depending on each drying condition, as a coating method. Well-known and conventional methods such as roll coater coating, roller coating, spray coating or showering coating may be used.

The water-based coating composition may be directly coated on the base material by one coat or overcoating, or an acrylic or acrylic-styrene copolymer system. , An acrylic-urethane combination system, a silicon-acrylic combination system, an epoxy system, a urethane system, a silicon system, or the like, which is generally used as a top coat, and a coating material containing a binder having good alkali resistance. The coating composition may be applied to improve the weather resistance of the overall coating system.

In any of the coating systems described above, the dry thick film of the aqueous coating composition is as follows:
5 μm or more is suitable. This is because if the thickness is less than 5 μm, the long-term durability of the coating tends to be insufficient.

[0081]

EXAMPLES Next, the present invention will be described more specifically by way of Examples and Comparative Examples. In the following, all parts and% are based on weight unless otherwise specified.

Example 1 720 parts of ion-exchanged water, 16 parts of sodium dodecylbenzenesulfonate, and the following chemical structural formula were placed in a 2-liter stainless steel autoclave.

[0083]

Embedded image CH ₃ (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ CO
O (CH ₂ CH ₂ O) ₂₀ H ........ [XII] was charged with 1 part of polyoxyethylene oleic acid ester (hereinafter abbreviated as emulsifier A) and 3 parts of ammonium hydrogen carbonate. After dissolution, the inside of the autoclave was degassed with nitrogen. 8 parts of crotonic acid, 472 parts of vinyl neononanoate and 320 parts of liquefied and collected vinylidene fluoride were placed in a pressure-resistant dropping tank, and further ethylene was introduced under pressure to the autoclave at 15 atm.

The autoclave was heated to 80 ° C., and while stirring, a polymerization initiator solution prepared by dissolving 5.6 parts of ammonium persulfate in 80 parts of ion-exchanged water and monomers placed in a pressure-resistant dropping tank were added. Was added dropwise over 3 hours, and the temperature was maintained for 3 hours to complete the reaction. The product obtained here has a nonvolatile content of 50% and a pH of
Was an emulsion polymer of 1.6.

After cooling to room temperature, the pH of the reaction mixture was adjusted to 7.5 with 14% aqueous ammonia, and finally the nonvolatile content was adjusted to 45% with ion-exchanged water to obtain a Tg of At 0 ° C, softening point is 70 ° C, and particle size is 0.09μ
m aqueous resin dispersion I was obtained.

Examples 2 to 5 and Comparative Examples 1 to 5 Example 1 except that the kinds and amounts of the monomers and emulsifiers shown in Table 1 were changed.
In the same manner as in Examples 2, 3, 4, and 5, respectively.
Of aqueous resin dispersions II, III, IV and V, and of Comparative Examples 1, 2, 3, 4 and 5 aqueous resin dispersions VI, VII, VIII, IX and X. The characteristic values of these various aqueous resin dispersions are summarized in the same table. The characteristic values for storage stability are summarized in Table 2.

[0087]

[Table 1]

<< Footnote of Table 1 >> VF ……………… abbreviation of “vinylidene fluoride” HFP ………… abbreviation of “hexafluoropropylene” CTFE ………… abbreviation of “chlorotrifluoroethylene”

<< Footnotes in Table 1 >> DBSN ......... Abbreviation of "sodium dodecylbenzene sulfonate"

<< Footnote in Table 1 >> The correspondence between the symbols in "reactive nonionic emulsifiers" and chemical structural formulas is as follows.

A ... As mentioned above

B ...

[Chemical 31]

C ...

[Chemical 32]

D ...

[Chemical 33]

[0095]

[Table 2]

[0096]

[Table 3]

[0097]

[Table 4]

[0098]

[Table 5]

<< Footnote in Table 1 >>

[0100]

Embedded image E ... CH ₂ ═CHCH ₂ O (CH ₂ ) ₄ (OCH
₂ CH ₂ ) _n OH (number average molecular weight = about 800)

[0101]

Embedded image F ... CH ₂ ═CHO (CH ₂ ) ₄ (OCH ₂ CH
₂ ) _n OH (number average molecular weight = about 700)

<< Footnote in Table 1 >> a ... Polyoxyethylene nonylphenyl ether (20 mol of ethylene oxide adduct)

B ... Polyoxyethylene nonyl phenyl ether (30 mol of ethylene oxide adduct)

[0104]

[Table 6]

[0105]

[Table 7]

[0106]

[Table 8]

[0107]

[Table 9]

<< Footnote in Table 1 >> Storage stability (normal temperature) ..... Visual determination of sedimentation state of particles in the aqueous resin dispersion after standing at room temperature for 1 year

<< Footnote in Table 1 >> Storage stability (50.degree. C.) ... Visual determination of the sedimentation state of particles in the aqueous resin dispersion after standing in a constant temperature bath at 50.degree. C. for 2 months

[0110]

[Table 10]

[0111]

INDUSTRIAL APPLICABILITY As described above, the fluororesin aqueous dispersion of the present invention has extremely high practicality in that not only weather resistance but also storage stability can be maintained over a long period of time. In addition, it is also characterized by stain resistance.
Such extremely highly practical, by using the fluororesin aqueous dispersion of the present invention, it is possible to obtain an aqueous coating composition excellent in long-term storage stability, and also excellent in ultra-high weather resistance and stain resistance. I can.

Claims (5)

[Claims] 1. A general formula: [However, R ₁ and R ₂ in the formula may be the same or different and each is a hydrocarbon group having 6 to 24 carbon atoms, and at least one, preferably 1
Alternatively, R ₃ represents a hydrocarbon group having two polymerizable unsaturated bonds, R ₃ represents an alkyl group having 1 to 4 carbon atoms or a proton, and A represents an ethylene oxide bond and / or a propylene oxide bond. And m is an integer of 1 or 2,
In addition, n is an integer of 5 or more. ] [Chemical 2] [Wherein R ₁ represents a saturated or unsaturated hydrocarbon group having 6 to 24 carbon atoms, and R ₂ represents
When R ₁ is a saturated hydrocarbon group, it has 2 to 4 carbon atoms.
Represents an alkenyl group, and when R ₁ is an unsaturated hydrocarbon group, represents an alkyl group having 1 to 4 carbon atoms, and A represents an ethylene oxide bond and / or a propylene oxide bond. age,
m is an integer of 1 or 2, and n is 5
It shall be an integer greater than or equal to the above. ] [Chemical 3] [Wherein R ₁ represents a hydrocarbon group having 6 to 24 carbon atoms and having at least one polymerizable unsaturated bond, and R ₂ represents an alkyl group having 1 to 4 carbon atoms or A represents a proton, A represents an ethylene oxide bond and / or a propylene oxide bond, and m represents an integer of 1 or 2.
In addition, n is an integer of 5 or more. ] [Chemical 4] [Wherein R ₁ in the formula represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, R ₂ represents a proton or a methyl group, and R _{2 3} represents an alkyl group having 1 to 4 carbon atoms, A represents an ethylene oxide bond and / or a propylene oxide bond, and
n is an integer of 5 or more. ] [Chemical 5] [Wherein R ₁ in the formula represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, R ₂ represents a proton or a methyl group, and R _{2 3} represents an alkyl group having 1 to 4 carbon atoms, A represents an ethylene oxide bond and / or a propylene oxide bond, and
n is an integer of 5 or more. ] [Chemical 6] [Wherein R ₁ in the formula represents a hydrocarbon group having 6 to 24 carbon atoms and having at least one polymerizable unsaturated bond, and R ₂ and R ₃ are the same, respectively. May represent different alkyl groups having 1 to 4 carbon atoms or protons, and A and B are
Each represents an ethylene oxide bond and / or a propylene oxide bond, which may be the same or different, and m and n may be the same or different, but at least one of them Is an integer of 5 or more, and the other is an integer of 0 or 1 or more. ] [Chemical 7] [Wherein R ₁ in the formula represents a hydrocarbon group having 6 to 24 carbon atoms and having at least one polymerizable unsaturated bond, and R ₂ and R ₃ are the same, respectively. May represent different alkyl groups having 1 to 4 carbon atoms or protons, and A and B are
Each of them represents an ethylene oxide bond and / or a propylene oxide bond, which may be the same or different, and m and n may be the same or different. At least one is an integer of 5 or more, and the other is 0 or an integer of 1 or more. ] [Chemical 8] [Wherein, R ₁ and R ₂ in the formula each represent an alkyl group or a proton having 6 to 24 carbon atoms, which may be the same or different, and at least one of them represents Alkyl group, A
And B respectively represent an ethylene oxide bond and / or a propylene oxide bond, which may be the same or different, and m and n
May be the same or different, respectively,
At least one of them is an integer of 5 or more, and the other is 0 or an integer of 1 or more,
r is an integer of 1 to 4. And R ₁ COO (A) _n R ₂ [wherein R ₁ represents a hydrocarbon group having 6 to 24 carbon atoms and having at least one polymerizable unsaturated bond] R ₂ represents an alkyl group having 1 to 4 carbon atoms or a proton, A represents an ethylene oxide bond and / or a propylene oxide bond, and m and n are the same. May differ, but at least one of them is an integer of 5 or more, and the other is 0 or an integer of 1 or more. ] A fluororesin aqueous dispersion obtained by copolymerizing at least one compound selected from the group consisting of: and a fluoroolefin as an essential raw material component. 2. A general formula: [However, R ₁ and R ₂ in the formula may be the same or different and each is a hydrocarbon group having 6 to 24 carbon atoms, and at least one, preferably 1
Alternatively, R ₃ represents a hydrocarbon group having two polymerizable unsaturated bonds, R ₃ represents an alkyl group having 1 to 4 carbon atoms or a proton, and A represents an ethylene oxide bond and / or a propylene oxide bond. And m is an integer of 1 or 2,
In addition, n is an integer of 5 or more. ] [Chemical 11] [Wherein R ₁ represents a saturated or unsaturated hydrocarbon group having 6 to 24 carbon atoms, and R ₂ represents
When R ₁ is a saturated hydrocarbon group, it has 2 to 4 carbon atoms.
Represents an alkenyl group, and when R ₁ is an unsaturated hydrocarbon group, represents an alkyl group having 1 to 4 carbon atoms, and A represents an ethylene oxide bond and / or a propylene oxide bond. age,
m is an integer of 1 or 2, and n is 5
It shall be an integer greater than or equal to the above. ] [Chemical formula 12] [Wherein R ₁ represents a hydrocarbon group having 6 to 24 carbon atoms and having at least one polymerizable unsaturated bond, and R ₂ represents an alkyl group having 1 to 4 carbon atoms or A represents a proton, A represents an ethylene oxide bond and / or a propylene oxide bond, and m represents an integer of 1 or 2.
In addition, n is an integer of 5 or more. ] [Chemical 13] [Wherein R ₁ in the formula represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, R ₂ represents a proton or a methyl group, and R _{2 3} represents an alkyl group having 1 to 4 carbon atoms, A represents an ethylene oxide bond and / or a propylene oxide bond, and
n is an integer of 5 or more. ] [Chemical 14] [Wherein R ₁ in the formula represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, R ₂ represents a proton or a methyl group, and R _{2 3} represents an alkyl group having 1 to 4 carbon atoms, A represents an ethylene oxide bond and / or a propylene oxide bond, and
n is an integer of 5 or more. ] [Chemical 15] [Wherein R ₁ in the formula represents a hydrocarbon group having 6 to 24 carbon atoms and having at least one polymerizable unsaturated bond, and R ₂ and R ₃ are the same, respectively. May represent different alkyl groups having 1 to 4 carbon atoms or protons, and A and B are
Each represents an ethylene oxide bond and / or a propylene oxide bond, which may be the same or different, and m and n may be the same or different, but at least one of them Is an integer of 5 or more, and the other is an integer of 0 or 1 or more. ] [Chemical 16] [Wherein R ₁ in the formula represents a hydrocarbon group having 6 to 24 carbon atoms and having at least one polymerizable unsaturated bond, and R ₂ and R ₃ are the same, respectively. May represent different alkyl groups having 1 to 4 carbon atoms or protons, and A and B are
Each of them represents an ethylene oxide bond and / or a propylene oxide bond, which may be the same or different, and m and n may be the same or different. At least one is an integer of 5 or more, and the other is 0 or an integer of 1 or more. ] [Chemical 17] [Wherein, R ₁ and R ₂ in the formula each represent an alkyl group or a proton having 6 to 24 carbon atoms, which may be the same or different, and at least one of them represents Alkyl group, A
And B respectively represent an ethylene oxide bond and / or a propylene oxide bond, which may be the same or different, and m and n
May be the same or different, respectively,
At least one of them is an integer of 5 or more, and the other is 0 or an integer of 1 or more,
r is an integer of 1 to 4. And R ₁ COO (A) _n R ₂ [wherein R ₁ represents a hydrocarbon group having 6 to 24 carbon atoms and having at least one polymerizable unsaturated bond] R ₂ represents an alkyl group having 1 to 4 carbon atoms or a proton, A represents an ethylene oxide bond and / or a propylene oxide bond, and m and n are the same. May differ, but at least one of them is an integer of 5 or more, and the other is 0 or an integer of 1 or more. ] A fluororesin aqueous solution obtained by copolymerizing at least one compound selected from the group consisting of the following compounds, a fluoroolefin, and other copolymerizable monomers as essential raw material components Dispersion. 3. An aqueous coating composition obtained by mixing the fluororesin aqueous dispersion according to claim 1 with pigments. 4. An aqueous coating composition obtained by mixing the fluororesin aqueous dispersion according to claim 1 with pigments and thickeners. 5. An aqueous coating composition obtained by mixing the fluororesin aqueous dispersion according to claim 1 with pigments, thickeners and organic solvents.