JP3489403B2 - Fluorinated resin aqueous dispersion composition and painted object - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fluororesin aqueous dispersion composition useful as an aqueous paint excellent in non-staining adhesion, weather resistance and flexibility, and a coated article having a coating film obtained from the composition. .

[0002]

2. Description of the Related Art It has been proposed to use an aqueous dispersion composition containing an aqueous dispersion of a fluororesin as a raw material for an aqueous paint because it gives a coating film non-staining adhesion and weather resistance.

For example, Japanese Patent Application Laid-Open No. 8-259892 discloses a coating composition in which a tetrafunctional silicate is mixed with an aqueous coating. JP-A-8-120211, an aqueous dispersion composition containing trifunctional following organosilicate the fluororesin aqueous dispersion is disclosed, in Japanese Patent Laid-open flat 8-120210, containing An aqueous dispersion composition in which colloidal silica is mixed with a fluororesin aqueous dispersion is disclosed.

Aqueous paints containing a tetrafunctional silicate (Japanese Patent Laid-Open No. 8-259892) are not stable in practical use and have a short pot life. The composition using the fluororesin aqueous dispersion (JP-A-8-120211, JP-A-8-120210) has a practical level of stability, non-fouling adhesion, weather resistance and flexibility, Further improvement is desired.

[0005]

DISCLOSURE OF THE INVENTION The present invention enhances the stability of a fluororesin aqueous dispersion composition, and further investigates non-contamination adhesion, weather resistance and flexibility of a coating film formed using the same. However, they have found that when a water-soluble silicate is added, these properties are improved.

An aqueous resin composition containing lithium silicate, which is one of water-soluble silicates, for the purpose of improving the permeability and adhesion of an inorganic base material is disclosed in JP-A-2-308887. However, the present invention relates to a vinyl copolymer which is a non-fluorine-based resin, and does not mention the weather resistance which is a property unique to a fluorine-containing resin.

[0007]

That is, the present invention relates to a fluororesin aqueous dispersion composition containing a fluororesin aqueous dispersion and a water-soluble silicate.

The present invention also relates to a fluororesin aqueous dispersion composition further containing at least one water-soluble silicate curing agent.

The fluorine-containing resin is preferably a fluorine-containing resin having at least one functional group selected from the group consisting of hydrolyzable silyl group, hydroxyl group, epoxy group and carboxyl group.

The present invention further relates to a coated article having a coating film obtained from the above aqueous dispersion composition.

In the present invention, the fluororesin aqueous dispersion is an aqueous dispersion in which the fluororesin particles are stably dispersed in water, and the fluororesin aqueous dispersion itself is a known one (eg, JP-A-8-12021
No. 0, JP-A-8-120211, JP-A-4-7784.
No. 7-258499, etc.).

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The fluororesin particles for forming the fluororesin aqueous dispersion used in the present invention include a fluoroolefin polymer (1), a fluoroolefin and a monomer copolymerizable with the fluoroolefin. Examples of the particles include a copolymer (2) with and a composite resin (3) of these polymers and a non-fluorine-based resin.

Examples of fluoroolefins include vinyl fluoride, vinylidene fluoride (VdF), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE) and hexafluoropropylene (HF).
P), C2-C4 full olefins, such as trifluoroethylene.

Examples of the fluoroolefin polymer (1) include homopolymers of these fluoroolefins and copolymers of two or more kinds of fluoroolefins. Specifically, homopolymers such as VdF, TFE and CTFE, VdF / TFE copolymers, VdF / HFP copolymers, VdF / CTFE copolymers, VdF / TFE / C
TFE copolymer, VdF / TFE / HFP copolymer, T
Examples thereof include FE / HFP copolymer.

The aqueous dispersion of fluoroolefin polymer (1) particles can be produced by a conventional emulsion polymerization. For example, it can be obtained by emulsion polymerization of the above-mentioned fluoroolefin by a conventional method in the presence of an emulsifier of 5% (% by weight or less, the same unless otherwise specified), preferably 1% or less, with respect to water.

The water used at this time is preferably deionized water. Further, the emulsifier is preferably a fluorine-based surfactant. Furthermore, a reactive fluorine-based emulsifier can also be used. Further, a trace amount of a non-fluorine type nonionic emulsifier can be used together.

The fluorinated emulsifier in the present invention means one kind or a mixture of two or more kinds containing a fluorine atom in the structure and having surface activity. For example, X (C
F ₂ ) nCOOH (n is an integer of 6 to 20, X is F, H)
And the metal salt, ammonium salt, amine salt or quaternary ammonium salt thereof; Y (CH ₂ CF ₂ ) mC
Examples thereof include acids represented by OOH (m is an integer of 6 to 13 and Y is F or Cl) and metal salts, ammonium salts, amine salts or quaternary ammonium salts thereof. Further, the reactive emulsifiers exemplified in JP-A-8-67795 can be used alone or in combination with the above-mentioned fluorine-based emulsifiers. Further, the non-fluorinated nonionic emulsifier described in JP-A-7-90153 can be used in combination.

Next, a copolymer (2) of the fluoroolefin and a monomer copolymerizable with the fluoroolefin.
Will be described.

Examples of the monomer copolymerizable with the fluoroolefin include ethylene; α-olefins such as propylene and isobutylene; ethyl vinyl ether (EVE), cyclohexyl vinyl ether (CHV).
E), hydroxybutyl vinyl ether (HBVE),
Vinyl ethers such as butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether and polyoxyethylene vinyl ether; allyl ethers such as polyoxyethylene allyl ether, ethyl allyl ether and hydroxyethyl allyl ether; allyl alcohols such as allyl alcohol, diallyl alcohol and eugenol ; Vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pivalate, vinyl benzoate, VEOVA9, VE
Examples thereof include vinyl esters such as OVA10 (product name of Shell Chemical Co.); allyl esters such as allyl acetoacetate; ethylenically unsaturated carboxylic acids such as itaconic anhydride, succinic anhydride and crotonic acid. In particular, ethylene, α-olefins, vinyl ethers, vinyl esters, allyl ethers and allyl esters are preferably used.

The copolymer (2) of fluoroolefin and a monomer copolymerizable with the fluoroolefin is T
FE / propylene copolymer, TFE / ethylene copolymer, TFE / various vinyl ester copolymer, TFE / various vinyl ether copolymer, HFP / various vinyl ether copolymer, HFP / various vinyl ester copolymer, C
Examples include TFE / various vinyl ether copolymers,
Furthermore, terpolymers containing 30 mol% or less of a monomer copolymerizable with the fluoroolefin as a modifying monomer in these copolymers are exemplified.

The copolymer of these fluoroolefins and the monomer copolymerizable with the fluoroolefins preferably contains 20 to 80 mol% of the fluoroolefin monomer.

When the content of the fluoroolefin monomer is less than 20 mol%, the weather resistance is not sufficiently exhibited, and when it exceeds 80 mol%, the appearance is deteriorated when the coating is formed into a coating film, which is not preferable.

The aqueous dispersion of the fluoroolefin copolymer (2) particles can be produced, for example, by an emulsion polymerization method similar to the method for producing the aqueous dispersion of the fluoroolefin polymer (1) particles.

The copolymer of the fluoroolefin and the monomer copolymerizable with the fluoroolefin has at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, a carboxyl group and a hydrolyzable silyl group. Preferably. Further, among them, the compatibility with the water-soluble silicate and the inorganic additive is improved, and as a result, the hardness of the coating film and the transparency of the clear coating film can be improved. It is more preferable to have a silyl group. Preferred monomers for introducing such a functional group include hydroxyl group-containing monomers such as HBVE-containing vinyl ethers; allyl alcohol,
Hydroxy group-containing allyl compounds such as hydroxyethyl allyl ether; hydroxy group (meth) acrylic esters such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, etc. Examples are glycidyl group-containing monomers for introducing epoxy groups such as allyl glycidyl ether and glycidyl (meth) acrylate, and carboxyl group-containing monomers are acrylic acid, methacrylic acid, succinic acid, and itacone. Acids, crotonic acid, fumaric acid, maleic acid and the like, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ as the monomer containing a hydrolyzable silyl group
Examples thereof include alkoxysilyl group-containing monomers such as methacryloxypropylmethyldiethoxysilane, γmethacryloxypropylmethyldimethoxysilane, and vinyltrimethoxysilane.

Next, one of the fluorine-containing resins that can be used in the present invention
The composite resin (3), which is one of the two, will be described.

Examples of the composite resin of the polymer (1) or copolymer (2) and a resin containing no fluorine atom include the fluoroolefin polymer (1) or the fluoroolefin and the fluoroolefin. Fluorine-based composite resin obtained by seed polymerization of a monomer having a radically polymerizable unsaturated bond in an aqueous medium in the presence of particles of the copolymerizable monomer copolymer (2) Is exemplified.

Examples of the radically polymerizable monomer having an unsaturated bond include an alkyl acrylate having an alkyl group having 1 to 18 carbon atoms and an alkyl group having 1 carbon atom.
To methacrylic acid alkyl ester, a monomer having an ethylenically unsaturated unit copolymerizable therewith, and the like.

Examples of the acrylic alkyl ester whose alkyl group has 1 to 18 carbon atoms include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-acrylic acid acrylate.
Examples thereof include ethylhexyl and lauryl acrylate.

Examples of the methacrylic acid alkyl ester having an alkyl group having 1 to 18 carbon atoms include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-propyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate and methacrylic acid. Lauryl etc. can be mentioned.

For the purpose of improving solvent resistance and water resistance,
It is also possible to copolymerize a polyfunctional monomer such as ethylene glycol dimethacrylate or propylene glycol dimethacrylate.

Examples of the monomer having an ethylenically unsaturated unit copolymerizable with the above-mentioned acrylic ester and / or methacrylic ester include ethylene; α-olefins such as propylene and isobutylene; ethyl vinyl ether (EVE), cyclohexyl. Vinyl ether (CHVE), hydroxybutyl vinyl ether (HB
VE), butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether, polyoxyethylene vinyl ether and other vinyl ethers; polyoxyethylene allyl ether, ethyl allyl ether, hydroxyethyl allyl ether and other allyl ethers; allyl alcohol, diallyl alcohol, eugenol, etc. Allyl alcohols; Allyl esters such as allyl acetoacetate; Vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pivalate, vinyl benzoate, VEOVA9, VEO
Vinyl esters such as VA10 (product name of Shell Chemical Co.); ethylenically unsaturated carboxylic acids such as itaconic anhydride, succinic anhydride, crotonic acid; aromatics such as styrene, α-methylstyrene, p-tert-butylstyrene Examples thereof include vinyl compounds; acrylonitrile and the like.

Of the polymer (1) or the copolymer (2) to be the seed particles, the VdF-based fluoroolefin polymer (1) is preferable because it has good compatibility with the acrylic monomer at the time of seed polymerization. , And more preferably Vd
Polymer (1) containing 50 mol% or more of F units is preferable.

In the present invention, the composite resin (3) preferably contains the polymer (1) or the copolymer (2) in an amount of 20 to 90 mol% based on the whole composite resin.

When the content of the fluoroolefin monomer is less than 20 mol%, the weather resistance is not sufficiently exhibited, and when it exceeds 90 mol%, the appearance is deteriorated when it is formed into a coating film to form a coating film, which is not preferable.

In the present invention, the composite resin (3)
In the process of seed polymerization, a monomer containing at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, a carboxyl group and a hydrolyzable silyl group is used for the whole composite resin. On the other hand, it is preferable to introduce 0.1 to 30 mol% of the functional group. Preferred hydroxyl group-containing monomers include hydroxyl group-containing vinyl ethers such as HBVE; allyl alcohol, hydroxyethyl allyl ether and other hydroxyl group-containing allyl compounds; hydroxyethyl (meth) acrylate, hydroxypropyl (meth)
Examples include hydroxyl group-containing (meth) acrylates such as acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate,
Further, as the glycidyl group-containing monomer for introducing the epoxy group, allyl glycidyl ether, glycidyl (meth) acrylate, etc., as the carboxyl group-containing monomer, (meth) acrylic acid, etc., a hydrolyzable silyl group As the monomer containing, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, alkoxysilyl such as vinyltrimethoxysilane. Group-containing monomers may be mentioned.

The seed polymerization of ethylenically unsaturated monomers is
It can be carried out under the same conditions as in ordinary emulsion polymerization. For example, a surfactant, a polymerization initiator, a chain transfer agent, and in some cases, a chelating agent, a pH adjusting agent and a solvent may be added to an aqueous medium containing particles of the fluoropolymer (1) or (2). Add and carry out reaction at a temperature of about 20 to 80 ° C. for about 0.5 to 6 hours.

When the ethylenically unsaturated monomer is emulsion polymerized in the presence of the fluoropolymer particles, swelling of the monomer into the fluoropolymer particles first occurs, and at this point, the ethylenically unsaturated monomer is uniformly dissolved in the acrylic monomer. It is considered that the fluoropolymer becomes an aqueous dispersion and then the acrylic monomer is polymerized by the addition of the initiator, resulting in the formation of compatible particles in which the molecular chains are entangled.

As the surfactant, anionic, nonionic or a combination of anionic and nonionic surfactants are used, and in some cases amphoteric surfactants can also be used.

Nonionic surfactants include higher alcohol sulfuric acid esters, alkyl sulfonic acid sodium salts,
Alkylbenzene sulfonic acid sodium salt, succinic acid dialkyl ester sulfonic acid sodium salt, alkyl diphenyl ether disulfonic acid sodium salt and the like are used. Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl phenyl esters, sorbitan alkyl esters, glycerin esters and their derivatives. Are exemplified. Examples of the amphoteric surfactant include lauryl betaine.

It is also possible to use a so-called reactive emulsifier which is copolymerizable with the ethylenically unsaturated monomer. Examples of commercially available reactive emulsifiers include Bremmer PE-350, Bremmer PME-400, Bremmer 70PEP350B (above, NOF Corporation), N.
K ester M-40G, NK ester M-90G, NK
Ester M-230G (above, manufactured by Shin-Nakamura Chemical Co., Ltd.),
RMA450M (Nippon Emulsifier Co., Ltd.), Aqualon H
S10, Aqualon HS20, Aqualon HS102
5, AQUARON RN10, AQUARON RN20, AQUARON RN30, AQUARON RN50, AQUARON RN2
025 (above, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), NK ester AMP-60G, NK ester CB-1, NK ester SA, NK ester A-SA (above, Shin-Nakamura Chemical Co., Ltd.)
(Made by Sanyo Chemical Industry Co., Ltd.), Latemur WX (made by Kao Corporation), and the like.

The amount of the surfactant used is usually about 0.05 to 5.0 parts by weight per 100 parts by weight of the ethylenically unsaturated monomer.

The initiator is not particularly limited as long as it generates a radical that can be subjected to a free radical reaction in an aqueous medium between 20 and 90 ° C., and depending on the case, it may be used in combination with a reducing agent. It is possible. The water-soluble initiator is usually persulfate, hydrogen peroxide, 2,2-azobis (2-amidinopropane) hydrochloride (AJBA), and the reducing agent is sodium pyrobisulfite, sodium hydrogen sulfite, L-ascorbin. Sodium acid etc. can be mentioned. Examples of oil-soluble initiators include diisopropyl peroxydicarbonate (IPP), benzoyl peroxide, dibutyl peroxide, azobisisobutyronitrile (A
IBN) and the like.

The amount of the initiator used is usually about 0.05 to 2.0 parts by weight per 100 parts by weight of the ethylenically unsaturated monomer.

The polymerization temperature is 20 to 90 ° C., preferably 3
The range of 0 to 80 ° C is preferable.

As the chain transfer agent, halogenated hydrocarbons (eg chloroform, carbon tetrachloride etc.), mercaptans (eg n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan) etc. are used. The amount of the chain transfer agent used is usually about 0 to 5.0 parts by weight per 100 parts by weight of the ethylenically unsaturated monomer.

As a solvent, a small amount of methyl ethyl ketone, acetone, trichlorotrifluoroethane, in the range that does not impair workability, disaster prevention safety, environmental safety and manufacturing safety,
Methyl isobutyl ketone, cyclohexanone, ethyl acetate and the like may be used. The addition of a solvent may improve the monomer swellability on the seed polymer particles.

The seed polymerization is carried out by a known method, for example, a method in which all of the monomers are charged in a batch in the reaction system in the presence of seed particles, a part of the monomers is charged and reacted, and the rest is continuously or divided. It can be carried out by a method of continuously charging the whole amount of the monomer.

The aqueous dispersion of the fluorine-containing copolymer used in this seed polymerization has an average particle size of 2 after seed polymerization.
In order to suppress the particle diameter to 00 nm or less, it is preferable to include polymer particles having an average particle diameter of 180 nm or less in a concentration range of 30 to 50%, and further, include polymer particles having an average particle diameter of 150 nm or less in a concentration range of 35 to 60%. More preferred are those containing. If the resin particle size after seed polymerization exceeds 200 nm, the sedimentation stability of the aqueous dispersion becomes poor, and the minimum film forming temperature of the aqueous dispersion increases even with the same resin composition.

The present invention is a composition in which a water-soluble silicate is added to the above fluororesin aqueous dispersion. By blending a water-soluble silicate, a coating film excellent in non-staining adhesion and improvement in coating film hardness can be provided.

Examples of the water-soluble silicate that can be used in the present invention include those represented by the formula (I): M ₂ O.XSiO ₂ (I) (wherein M is an alkali metal or —N (CH ₂ OH) ₄ ,
_{-N (CH 2 CH 2 OH)} 4, -N (CH 2 CH 2 OH) 2 or _{-C (NH 2) 2 NH,} X is a water soluble silicate represented by 0.5-5) and the like . The water-soluble silicate may or may not have water of crystallization.

More specifically, as an aqueous solution of the water-soluble silicate represented by the formula (I), an alkali metal silicate composed of an alkali metal belonging to Group 1A of the periodic table and silicic acid, a tertiary ammonium can be used. And an aqueous solution of a quaternary ammonium silicate consisting of quaternary ammonium and silicic acid, and a guanidine silicate consisting of guanidine and silicic acid. Alkali metal silicates include sodium silicate, potassium silicate, lithium silicate, cesium silicate, and the like, and tertiary ammonium silicates include triethanolamine silicate and quaternary ammonium silicates. Examples thereof include tetramethanol ammonium silicate and tetraethanol ammonium silicate.

A modified water-soluble silicate obtained by reacting one or more fluorides such as calcium, magnesium, zinc and zirconium with these water-soluble silicates, or the above water-soluble silicates Used alone or a modified water-soluble silicate obtained by reacting one or two or more of metals belonging to Group 2A of the periodic table or oxides and / or hydroxides of zinc, zirconium, vanadium, cesium, etc. And can be used together.

Among the water-soluble silicates, lithium silicate,
Alkali metal silicates such as sodium silicate are preferably used. Especially in lithium silicate, SiO
₂ / Li ₂ O molar ratio is 3.0 to 25.0, and further 3.0
Those of .about.4.8 are preferably used. When the molar ratio is less than 3.0, the water resistance of the resulting coating film may be reduced, and when it is more than 25.0, workability and storage stability during preparation of the aqueous dispersion composition may be reduced. is there.
In the case of sodium silicate, the weight ratio of SiO ₂ / Na ₂ O is preferably in the range of 1.5 to 4.0, and more preferably 3.0.
The range of -4.0 is preferable. If the weight ratio is less than 1.5, the water resistance of the coating film may decrease,
When it is larger than 4.0, workability and storage stability during preparation of the aqueous dispersion composition may be deteriorated. And above all,
Lithium silicate is more preferable from the viewpoints of the hydrophilic effect of the coating film with a small amount of addition, the sustainability of the effect after warm water immersion, the transparency of the clear coating film, and the like.

The weight ratio of the fluororesin to the water-soluble silicate in the fluororesin aqueous dispersion composition is 99.9 /.
0.1 / 10/90 is preferable, and 99 / is more preferable.
It is in the range of 1 to 50/50. When the ratio of water-soluble silicate is less than 99.9 / 0.1, the non-contaminating adhesion of the surface of the coating film may be insufficient. With the progress of the above, defects such as cracks are likely to occur in the coating film due to lack of flexibility.
99.9 / 0.1-80 for applications where gloss is especially required
/ 20 is preferable. In this application, when it exceeds 80/20, the gloss tends to be lowered, and in the clear paint, the transparency is impaired.

The present invention relates to a composition obtained by adding at least one curing agent for the water-soluble silicate to the composition comprising the fluororesin dispersion and the water-soluble silicate. Soluble silicate reacts cured in an organic coating by adding a curing agent, as a result of being multi Goka through a strong bond, be further improved Erareru film hardness, water resistance You can

Examples of the water-soluble silicate curing agent that can be used in the present invention include, but are not limited to, the following compounds.

(I) Metals or transition metals belonging to Groups 2, 13 and 14 of the periodic table: eg Mg, Al, Ga, P
b, Fe, Co, Ni, Zn, Zr, etc.

(Ii) Metal oxides of the above (i): for example, aluminum oxide, magnesium oxide, zinc oxide,
Zirconium oxide etc.

(Iii) Metal hydroxide of (i) above: For example, aluminum hydroxide, magnesium hydroxide, iron hydroxide and the like.

(Iv) Metal chlorides such as calcium chloride, magnesium chloride and aluminum chloride.

(V) Fluorosilicate, for example, sodium fluorosilicate, ammonium fluorosilicate, zinc fluorosilicate, lead fluorosilicate, magnesium fluorosilicate and the like.

(Vi) Water-insoluble silicates such as calcium silicate, aluminum silicate, magnesium silicate and zirconium silicate.

(Vii) Sulfates such as aluminum sulfate, magnesium sulfate and calcium sulfate.

(Viii) Carbonates such as aluminum carbonate, magnesium carbonate and calcium carbonate.

(Ix) Sulfites such as calcium sulfite, aluminum sulfite, magnesium sulfite and barium sulfite.

(X) Thiosulfate For example, calcium thiosulfate, barium thiosulfate, etc.

(Xi) Phosphates such as aluminum phosphate, ammonium phosphate, calcium phosphate, iron phosphate, zinc phosphate and the like.

(Xii) heavy phosphate such as formula (III) M _i Oj.xP ₂ O ₅ (III) (wherein M is a metal such as aluminum, magnesium, zinc, calcium, iron, copper, barium or titanium) , I is 1
Or 2, j is an integer of 1 to 3 and is determined by the valence of M, and x is 0.25 to 4).

As a concrete example, for example, aluminum,
Orthophosphates such as magnesium, zinc, titanium, manganese, pyrophosphates, polyphosphates, metaphosphates or ultraphosphates, or primary phosphates such as aluminium, calcium, magnesium, manganese, zinc, iron; One or more phosphate mixtures of these primary or secondary phosphates are neutralized with hydroxides or salts and / or complex oxides of metals belonging to groups 2-4 and 13 of the periodic table. Examples thereof include condensed phosphates obtained by drying or calcining after the treatment. Examples of the hydroxide of a metal belonging to Groups 2 to 4 and 13 of the periodic table used to obtain the neutralized condensed phosphate include calcium hydroxide, barium hydroxide, aluminum hydroxide and titanium hydroxide. And so on. Examples of the salts include metal halides such as aluminum chloride, aluminum fluoride, calcium sulfate, magnesium carbonate, calcium carbonate and aluminum nitrate, sulfates, carbonates and nitrates. The metal complex oxides include metal compounds such as metal oxides, hydroxides and carbonates of Group 2 of the periodic table and metal oxides such as silicon, titanium and zirconium,
Approximately 50 parts of a mixture with metal compounds such as hydroxides and carbonates
What was baked at 0-1200 degreeC can be used.

(Xiii) Borate salts such as sodium borate, potassium borate, lithium borate and manganese borate.

(Ivx) inorganic acid For example, phosphoric acid, boric acid, etc.

(Xv) Organic acid For example, fumaric acid, trifluoroacetic acid, etc.

These curing agents may be used alone or in combination of two or more kinds. Further, it may be added to the aqueous dispersion in the form of a modified silicate obtained by previously reacting a water-soluble silicate with a part of a curing agent. When zinc oxide or the like is used, these curing agents may be heat-treated at 1000 ° C. or lower before use.

Particularly preferable curing agents include, for example, the above (ii), (iii), from the viewpoint of high reactivity at low temperature.
(V), (vi), (ix), (x), (xii), and the like, specifically, zinc oxide, magnesium oxide, aluminum oxide, aluminum hydroxide, potassium silicofluoride, ammonium silicofluoride, silicofluoride. Examples thereof include calcium acid salt, calcium sulfite, calcium thiosulfate, aluminum polyphosphate, aluminum metaphosphate and aluminum pyrophosphate.

Since the above curing agent is generally substantially insoluble or slightly soluble in water, in order to obtain an aqueous dispersion composition, a method of directly adding it in the form of a curing agent powder; an organic solvent having a high boiling point, If so, a method in which a known dispersant such as a surfactant or a water-soluble resin is used and the curing agent is added in the form of an aqueous dispersion liquid dispersed in water can be adopted. Specific examples of the latter curing agent aqueous dispersion include, for example, a particle diameter of 5 to 200 n using water as a dispersion medium.
Alumina sol, which is a colloidal solution of alumina hydrate particles of m, is known as commercially available products such as Alumina sol-100, Alumina sol-200, and Alumina sol-520 manufactured by Nissan Chemical Industries, Ltd.

In order to obtain a uniform dispersion composition, the average particle size of the curing agent is preferably in the range of 0.01 to 3 μm. Further, when the clear coating film is used, the average particle diameter of the curing agent is preferably 0.01 to 0.1 μm, and when the matte coating film is used, the average particle diameter of the curing agent is preferably 1 to 3 μm. .

The addition amount of the curing agent is preferably 100 parts by weight or less, particularly 10 to 100 parts by weight, based on 100 parts by weight of the water-soluble silicate. If it exceeds 100 parts by weight, problems such as an excessively high curing rate and a decrease in flexibility of the formed coating film may occur.

When a curing agent is used, the water-soluble silicate is lithium silicate or sodium silicate from the viewpoint of high reactivity, and sodium silicate (SiO ₂ content 30% by weight) from the viewpoint of particularly large coating hardness. Or more) is preferable.

In the present invention, the aqueous dispersion composition comprises
Further, it is preferable to add organosilicate and / or colloidal silica as an inorganic compounding agent from the viewpoint of obtaining a coating film with high hardness. Further, colloidal silica is preferable from the viewpoint of not affecting the storage stability of the aqueous dispersion.

Examples of such organosilicate compounds include those represented by the formula (II): R ¹ _a Si (OR ² ) _4-a (II) (wherein R ¹ is a non-hydrolyzable group or a hydrogen atom, and R ² is an alkyl group). , An aryl group, an alkenyl group or a hydrogen atom,
a is 0, 1 or 2) or 1
Examples thereof include two or more condensates.

In the above formula (II), the non-hydrolyzable group R
¹ is, for example, an alkyl group such as methyl, ethyl, propyl, butyl, hexyl, octyl or lauryl;
Aryl groups such as phenyl, tolyl, mesityl; alkenyl groups such as vinyl and allyl; haloalkyl groups such as γ-chloropropyl; γ-aminopropyl, γ- (2-
Aminopropyl groups such as aminoethyl) aminopropyl; epoxyalkyl groups such as γ-glycidoxypropyl, β- (3,4-epoxycyclohexyl) ethyl;
Examples thereof include methacryloyloxyalkyl groups such as γ-mercaptoalkyl and γ-methacryloyloxypropyl; and hydroxyalkyl groups such as γ-hydroxypropyl. Of these, a substituent having 8 or less carbon atoms is preferable because the reactivity decreases when the number of carbon atoms in the substituent is large. Also R
^{Also in 2} , an alkyl group having 4 or less carbon atoms is preferable from the viewpoint of reactivity.

Specific examples of the above (II) include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, Phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3, Examples thereof include 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-hydroxypropyltrimethoxysilane and the like.

The compound of formula (II) or the condensate can be added alone or in combination of two or more kinds.

Examples of the colloidal silica that can be used in the present invention include those produced by demetallizing a water-soluble silicate (ion exchange method, acid decomposition method, peptization method). What is usually supplied as an aqueous dispersion having a diameter of 4 to 150 nm, preferably 5 to 50 nm can be used as it is.

The colloidal silica may be acidic or basic when dispersed in water. As the acidic colloidal silica, for example, non-stabilized silica (pH 2 to 4) commercially available as Snowtex-O and Snowtex-OL (all manufactured by Nissan Kagaku Co., Ltd.) can be used. As the basic colloidal silica, silica (pH 8.4 to 10) stabilized by adding a trace amount of alkali metal ion, ammonium ion or amine.
There are, for example, Snowtex 20, Snowtex C, Snowtex N (above, Nissan Chemical Co., Ltd.), Ludox HS40, Ludox HS30, Ludox T.
Examples include commercially available products such as M, Ludox AS, Ludox AM (above, manufactured by DuPont), Nalcok (Nalco Chemical), and Mitten (Monsanto Chemical).

The blending amount of these inorganic compounding agents is preferably 0 to 50 parts by weight with respect to 100 parts by weight of the fluororesin. If the amount is more than 50 parts by weight, the flexibility of the coating film is lowered, and cracks may occur with the passage of time.

In the aqueous dispersion composition of the present invention, pigments such as inorganic pigments, calcined pigments, organic pigments, etc., viscosity modifiers, pigment dispersants, defoamers, antifreezing agents, film forming aids, etc. are used according to the purpose. UV absorbers, antioxidants, etc. can be added.

Specifically, the fluororesin aqueous dispersion 100
0 to 50 parts by weight of a film-forming aid such as an aliphatic ester, a condensation derivative of ethylene glycol, propylene glycol, a ketone-based solvent, etc., is used, and further a benzophenone-based, benzotriazole-based, oxalic anilide-based is used. , 0 to 5 parts by weight of an ultraviolet absorber such as a cyanoacrylate-based or triazine-based ultraviolet absorber, and 0 to 2 parts by weight of a viscosity modifier may be added. Examples of the method for preparing the aqueous dispersion composition of the present invention include the following methods.

An aqueous dispersion composition was prepared by adding a film forming aid and, if necessary, an aqueous dispersion pigment to the fluororesin aqueous dispersion with stirring at room temperature, and immediately thereafter adding a water-soluble silicate. To prepare.

When a curing agent is used in the present invention, the addition method is (1) a fluorine-containing resin aqueous dispersion composition containing a water-soluble silicate and the curing agent as described above in the form of powder or aqueous dispersion. In order to form a uniform composition by adding in the form of (2) a fluororesin aqueous dispersion composition containing (2) a water-soluble silicate, a hardener having a predetermined shape is added and mixed immediately before coating. A method of using as a so-called two-component type coating material, (3) a coating material containing a curing agent is applied onto a coating film coated with an aqueous dispersion of a fluororesin containing a water-soluble silicate to form a curing agent. Contacting method, (4) a method of applying a fluororesin aqueous dispersion composition containing a water-soluble silicate on a coating film coated with a coating material containing a curing agent, (5) water-soluble silicate and curing On top of the coating film containing the agent as an essential component, a curing agent, and if necessary A method of applying a fluororesin aqueous dispersion containing soluble silicate salts.
As a specific example of the method (5), for example, a coating method in which a fluororesin aqueous dispersion containing a curing agent such as phosphoric acid is applied onto an undercoat of an inorganic zinc-rich paint composed of a water-soluble silicate and zinc dust. Can be given.

If necessary, an organosilicate,
An inorganic compounding agent such as colloidal silica may be added with stirring. Organosilicate is added in the form of an aqueous dispersion using a known emulsifier as necessary, or in the form as it is, and as the colloidal silica, a commercially available product is added as it is or diluted with water. Also, one or more of these may be added at the same time. Further, if necessary, an ultraviolet absorber, an antioxidant, etc. are added in a form of being dissolved in an organic solvent such as a film forming aid, and mixed by stirring.

The composition thus obtained has properties applicable as a paint, for example, a spray, a flow coater,
Apply it on the base material by dipping or the like, and
A coated article can be obtained by drying at a temperature of up to 00 ° C. As the base material, in addition to ceramic building materials and boards, inorganic base materials such as concrete and slate are preferably used. It can also be applied to synthetic resin base materials such as acrylic resin, styrene resin, polycarbonate, and vinyl chloride resin. The invention also relates to the coated article thus obtained.

Next, preferred combinations of the respective components in the aqueous dispersion composition of the present invention will be exemplified, but the present invention is not limited to such combinations. "Parts" are parts by weight.

(1) (A) Fluorine-containing resin aqueous dispersion 199.8 to 160 parts Fluorine-containing resin: VdF copolymer / acrylic composite resin Concentration: 50% (B) Water-soluble silicate 0.1-20 part type: lithium silicate (SiO ₂ / Li ₂ O molar ratio: 3.5) (E) other additives 0 to 40 parts type: Narumakusukezai (effect) useful as clear coatings in this combination A transparent coating film with excellent stain resistance can be obtained. In addition, a high gloss enamel coating film can be obtained by further adding an aqueous dispersion pigment.

(2) (A) Fluorine-containing resin aqueous dispersion 199.8 to 100 parts Fluorine-containing resin: VdF / acrylic composite resin Concentration: 50% (B) Water-soluble silicate 0.1 to 50 parts Type: lithium silicate (SiO ₂ / Li ₂ O molar ratio: 3.5) (D) an inorganic compounding agents 1 to 150 parts type: colloidal silica (neutral to basic colloidal silica: concentration 30%) (E) other Additive 0-40 parts Type: film forming aid, thickener (effect) With this combination, a matte coating film having excellent stain resistance and a low coating film hardness and a low appearance can be obtained.

(3) Composition in which the inorganic compound (D) of (2) is changed to organosilicate: organosilicate: tetrafunctional ethyl silicate condensate or trifunctional ethyl silicate condensate (effect) A matte coating with excellent stain resistance and a low coating hardness and a soft appearance can be obtained.

(4) (A) Fluorine-containing resin aqueous dispersion liquid 199.8 to 20 parts Fluorine-containing resin: VdF / acrylic composite resin (1 to 30 mol% of a monomer having a hydrolyzable silyl group in the resin) including) concentration: 50% (B) water-soluble silicate from 0.1 to 90 parts type: lithium silicate (SiO ₂ / Li ₂ O molar ratio: 4.7) (D) an inorganic compounding agents 0-150 parts Type: colloidal silica (neutral to basic colloidal silica: concentration 30%) (E) Other additives 0 to 40 parts Type: film forming aid, thickener (effect) In this combination, the stain resistance is improved. Excellent, high coating hardness, transparent in clear coating, and high gloss coating when combined with aqueous dispersion pigment.

(5) (A) Fluorine-containing resin aqueous dispersion liquid 199.8 to 100 parts Fluorine-containing resin: VdF / acrylic resin concentration: 50% (B) Water-soluble silicate 0.1 to 50 parts Type: silica Lithium oxide (SiO2 / Li2O molar ratio: 3.5) (C) Curing agent 1-150 parts Type: Alumina sol (E) Other additives 0-40 parts Type: Film-forming aid, thickener (effect) In the combination, a matte coating having excellent stain resistance and a high coating hardness and a calm appearance can be obtained.

(6) (A) Fluorine-containing resin aqueous dispersion liquid 199.8 to 100 parts Fluorine-containing resin: VdF / acrylic resin concentration: 50% (B) Water-soluble silicate 0.1 to 50 parts Type: silica Sodium acidate (JIS K 1408 No. 3 water glass) (C) Hardener 0.01 to 50 parts Type: Zinc oxide (E) Other additives 0 to 40 parts Type: Film-forming aid, thickener (effect) ) With this combination, a matte coating film having excellent stain resistance and a calm appearance with high coating hardness can be obtained.

(7) (A) Fluorine-containing resin aqueous dispersion liquid 199.8 to 100 parts Fluorine-containing resin: VdF / acrylic resin concentration: 50% (B) Water-soluble silicate 0.1 to 50 parts Type: silica Sodium acidate (JIS K 1408 No. 3 water glass) (C) Curing agent 0.01 to 50 parts Type: potassium silicofluoride (D) Inorganic compounding agent 0 to 150 parts Type: Colloidal silica (neutral to basic colloidal silica) 30%) (E) Other additives 0 to 40 parts Type: film forming aid, thickener (effect) In this combination, excellent stain resistance, and matte appearance with a calm appearance due to high coating film hardness A coating film is obtained.

(8) (A) Fluorine-containing resin aqueous dispersion liquid 199.8 to 50 parts Fluorine-containing resin: VdF / acrylic resin concentration: 50% (B) Water-soluble silicate 0.1 to 50 parts Type: silica Sodium acidate (JIS K 1408 No. 3 water glass) (C) Curing agent 0.01 to 50 parts Type: aluminum pyrophosphate (E) Other additives 0 to 40 parts Type: film forming aid, thickener ( (Effect) With this combination, a matte coating film having excellent stain resistance and having a high coating hardness and a calm appearance can be obtained.

[0102]

EXAMPLES The present invention will now be specifically described with reference to synthetic examples and examples, but the present invention is not limited to such synthetic examples and examples.

Synthesis Example 1 Cyclohexyl vinyl ether (CHVE) 8.8 was placed in a 200 ml stainless steel autoclave equipped with a stirrer.
g, hydroxybutyl vinyl ether (HBVE) 8.
8 g, macromonomer having hydrophilic site (PKA50
03, manufactured by NOF CORPORATION, 4.0 g, ethyl vinyl ether (EVE) 10.0 g, ion-exchanged water 66.0 g,
Ammonium perfluorooctanoate (emulsifier) 0.3
5 g, potassium carbonate 0.35 g, sodium hydrogen sulfite 0.02 g, ammonium persulfate (initiator) 0.08 g
Was charged, cooled with ice and nitrogen gas of 3.5 kg / cm ²
Depressurize after pressurizing. This pressure degassing is 2
After repeated times, degassed to 10 mmHg to remove dissolved oxygen, and then chlorotrifluoroethylene (CTFE)
Charge 33.5g, react at 30 ℃ for 12 hours,
An aqueous dispersion of Synthesis Example 1 containing fluorine-containing copolymer (1) particles was obtained. The content ratio (functional group concentration) of the hydroxyl group-containing monomer in this resin is 26.8 mol% as a calculated value. The resulting aqueous dispersion has a solid content concentration of 48% and an average particle size of 1
It was 89 nm.

The solid content concentration was 1 in a vacuum dryer at 150 ° C.
After drying for an hour, the weight after drying was expressed as a percentage of the weight of the aqueous dispersion before drying.

The average particle size was measured by a laser light scattering particle size measuring device (ELS-3000 manufactured by Otsuka Electronics Co., Ltd.).

The functional group concentration was calculated from the composition of the obtained polymer.

Synthesis Example 2 (Synthesis of VdF Copolymer Aqueous Dispersion) In a pressure resistant reactor equipped with a stirrer and having an inner volume of 1 liter, 500 ml of deionized water, 0.5 g of ammonium perfluorooctanoate, a nonionic emulsifier (MYS40, Nikko Chemicals Co., Ltd. 0.
After charging 05 g and repeating nitrogen pressure deaeration to remove dissolved oxygen, a mixed monomer of vinylidene fluoride (VdF) / tetrafluoroethylene (TFE) / chlorotrifluoroethylene (CTFE) in a molar ratio of 74/14/12 The pressure was increased to 10 kgf / cm ² at 60 ° C. Next, 0.2 g of ammonium persulfate was charged, and VdF / TF was adjusted so that the pressure inside the tank was constant at 10 kgf / cm ^2.
A mixed monomer having a molar ratio of E / CTFE of 74/14/12 was continuously supplied and the reaction was carried out for 40 hours. Then, the inside of the tank was returned to room temperature and normal pressure to terminate the reaction. This aqueous dispersion was adjusted to pH 6.5 with 5% sodium hydrogen carbonate. The solid content concentration of the obtained aqueous dispersion of the fluorinated copolymer (2) was 42.
%, And the average particle size was 126 nm.

(Seed Polymerization of Acrylic Monomer) 100 g of the obtained aqueous dispersion of the fluorinated copolymer (2) was charged into a four-necked flask having an inner volume of 200 ml equipped with a stirring blade, a cooling tube and a thermometer, To this, 1.5 g of a reactive emulsifier (JS2, manufactured by Sanyo Chemical Industry Co., Ltd.) was added. The mixture was heated in a water bath with stirring, and when the bath temperature reached 75 ° C., 17.6 g of methyl methacrylate (MMA), 0.2 g of butyl acrylate, 0.2 g of acrylic acid, methoxy polyethylene glycol methacrylate (RMA450M, An emulsion obtained by emulsifying a 1.7 g mixture of Nippon Emulsifier Co., Ltd. with 10 g of a 1% aqueous solution of reactive emulsifier JS2 was added dropwise over 1 hour. Immediately after, 1m of a 10% solution of potassium persulfate
1 was added to start the reaction. After 3 hours from the start of the reaction, the temperature inside the tank was raised to 85 ° C., the temperature was maintained for 1 hour, then cooled, the pH was adjusted to 7 with aqueous ammonia, and the mixture was filtered through a 300-mesh wire net. An aqueous dispersion of a cationized resin (3) was obtained. The solid content concentration of this aqueous dispersion was 44.8%, and the average particle size was 163 nm.

Synthesis Examples 3 to 6 Aqueous dispersions of Synthesis Examples 3 to 6 were prepared in the same manner as in Synthesis Example 2 except that the acrylic monomer for seed polymerization was changed as shown in Table 1. The properties are shown in Table 1.

The abbreviations in Table 1 indicate the following compounds, respectively.

VdF: Vinylidene fluoride TFE: Tetrafluoroethylene CTFE: Chlorotrifluoroethylene CHVE: Cyclohexyl vinyl ether HBVE: Hydroxybutyl vinyl ether EVE: Ethyl vinyl ether PKA5003: Macromonomer (polyoxyethylene allyl ether) MMA: Methacryl Methyl acid BA: Butyl acrylate HEMA: Hydroxyethyl methacrylate GMA: Glycidyl methacrylate MPTS: γ Methacryloyloxypropyltrimethoxysilane AAc: Acrylic acid

[0112]

[Table 1]

Example 1 The aqueous dispersion obtained in Synthesis Example 1 was adjusted to pH 9 with aqueous ammonia.
After adjusting to 100 g of the resin solid content, 15 g of diethyl adipate as a film forming aid, 2 g of a 10% aqueous solution of Adecanol UH420 (manufactured by Asahi Denka Co., Ltd.) as a viscosity adjusting agent, and Foremaster FH013B as a defoaming agent. 0.1 g (manufactured by Dow Corning) was added and mixed by stirring with a disperser to prepare a clear paint. To this clear paint, 5 g of lithium silicate (SiO ₂ / Li ₂ O molar ratio of 4.5. Lithium silicate 45, manufactured by Nissan Kagaku Co., Ltd.) was added and mixed by stirring with a disperser to prepare an aqueous dispersion composition of the present invention. I got it. The following evaluation was performed on this composition. The results are shown in Table 2.

(1) Evaluation of clear coating film (transparency, contact angle) Transparency: The composition obtained was spread on a glass plate with a doctor blade of 6 mil and dried at room temperature for 24 hours, and then 50
The light transmittance of 0 nm was measured. The result of light transmittance is
X: 60> light transmittance, Δ: 80> light transmittance ≧ 60,
◯: Evaluation was made on the basis of light transmittance ≧ 80.

Contact angle: The static contact angle of water (initial stage) of the coating film obtained in the transparency test was measured by a contact angle meter manufactured by Kyowa Chemical Co., Ltd. The coating film was immersed in warm water at 50 ° C for 3 days and then at room temperature for 3 days.
The contact angle (after immersion in warm water) was similarly measured for the one dried for a time.

(2) Evaluation of characteristics of white coating film: 10.0 g of water, 1.8 g of DISROLL H14N (manufactured by Nippon Emulsifier Co., Ltd.) as a dispersant, and FS013 as an antifoaming agent.
0.3 g of B (manufactured by Dow Corning), 1.0 g of ethylene glycol, 0.1 g of 28% ammonia water, Taipaque CR97 (manufactured by Ishihara Sangyo Co., Ltd.) as titanium oxide 70.
0 g was dispersed by a sand mill to prepare a pigment paste.
Next, 24.1 g of the pigment paste was added to 43.5 g of the aqueous dispersion composition of the present invention, and the mixture was stirred with a disperser to obtain a white paint. 6 this white paint on the chemical conversion treated aluminum plate
Extend with a mill applicator and dry at room temperature for 24 hours,
After drying at 50 ° C. for 24 hours, a test coated plate was obtained. The following tests were conducted on this test coated plate. The results are shown in Table 2.

Gloss: 60 ° reflectance was measured using a gloss meter (manufactured by Suga Test Instruments Co., Ltd.).

Pencil hardness: According to JIS K 5400,
The pencil hardness was measured.

Flexibility: The test coated plate thus obtained was subjected to a 90 ° bending test at 20 ° C., and the presence or absence of cracks was visually inspected. Those with no abnormalities were marked with ◯, and those with abnormalities such as cracks were marked with x.

Accelerated weathering resistance: The coated plate under test is covered with Eye Super UV
The gloss was measured in a tester (manufactured by Iwasaki Electric Co., Ltd.) for 1000 hours after the accelerated weather resistance test, and the gloss retention rate was calculated from the following formula.

Gloss retention rate (%) = (Gloss after test / Initial gloss) × 100 Actual stain: The test coated plate is exposed at Daikin Kogyo Yodogawa Works, Settsu City, Osaka Prefecture, at 30 ° on the south side for 3 months. The color difference (brightness difference) ΔL with the coated plate before exposure was measured.

Examples 2 to 8 In Example 1, the fluororesin aqueous dispersion composition is shown in Table 2.
An aqueous dispersion composition of the present invention was obtained in the same manner as in Example 1 except that the composition shown in FIG. The characteristics of these compositions were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Examples 9 to 13 The aqueous dispersion of the fluorinated copolymer (2) obtained in Synthesis Example 2 was mixed with the additives and lithium silicate in the same proportion as in Example 1 while stirring, as shown in Table 2. Then, a coating composition was obtained. Immediately before use, the curing agent shown in Table 2 was added to this composition, stirred, and applied to a substrate. The characteristics of this composition were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Example 14 A zinc rich paint for undercoating was prepared by adding 85 parts by weight of zinc powder to 15 parts by weight of an aqueous solution of sodium silicate (concentration: 40% by weight). It was spread on a degreased mild steel plate (JIS G 3141) and dried at room temperature for 2 days. Then, the white paint prepared in Example 13 was applied and dried at room temperature for 7 days.

The obtained coating has a gloss of 43 and a pencil hardness of 5
H, weather resistance 89%, ΔL0.50, further 3%
No abnormality was found in the appearance even after immersion in saline for 10 days.

Example 15 A zinc-rich paint for undercoating was prepared by adding 85 parts by weight of zinc dust to 15 parts by weight of an aqueous solution of sodium silicate (concentration: 40% by weight). It was spread on a degreased mild steel plate (JIS G 3141) and dried at room temperature for 2 days. Then, the white paint prepared in Example 1 (however, 10% by weight of 80% phosphoric acid was mixed in place of sodium silicate) was applied and dried at room temperature for 7 days.

The obtained coating has a gloss of 70 and a pencil hardness of H.
B, weather resistance is 91%, ΔL is 3.83, and further 3
No abnormality was found in the appearance even after being dipped in 10% saline for 10 days.

Comparative Example 1 An aqueous dispersion composition was prepared in the same manner as in Example 2 except that lithium silicate was not added, and the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 2 An aqueous solution was prepared in the same manner as in Example 2 except that 30 g of Snowtex C-20 (basic colloidal silica manufactured by Nissan Chemical Industries Ltd.) was added without adding lithium silicate. A dispersion composition was prepared and evaluated for properties in the same manner as in Example 1. The results are shown in Table 2.

The inorganic compounding agents in Table 2 are the following compounds.

Ethyl silicate 40: Ethyl silicate pentamer MPTS manufactured by Colcoat: γ Methacryloyloxypropyltrimethoxysilane Snowtex C-20: Basic colloidal silica K bond manufactured by Nissan Kagaku: Teika Co., Ltd. Biphosphate Alumina Sol-100 manufactured by Nissan Chemical Industries, Ltd .: aqueous colloid of aluminum hydrate manufactured by Nissan Chemical Industries, Ltd.

[0132]

[Table 2]

[0133]

The fluororesin aqueous dispersion composition of the present invention can provide a coating film excellent in non-staining adhesion, weather resistance and flexibility. Therefore, as a water-based paint, stains such as rain streaks are hardly noticeable, and it is useful as a paint for building exterior.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroo Mitsuhata 1-1 Nishiichitsuya, Settsu-shi, Osaka Daikin Industry Co., Ltd. Yodogawa Seisakusho Co., Ltd. (56) Reference JP-A-7-53911 (JP, A) Kaihei 7-109435 (JP, A) JP 6-56942 (JP, A) JP 50-128741 (JP, A) JP 59-30865 (JP, A) (58) Fields investigated ( Int.Cl. ⁷ , DB name) C09D 1/00-10/00 C09D 101/00-201/10 C08C 19/00-19/44 C08F 6/00-246/00 C08F 251/00-283/00 C08F 283/02-289/00 C08F 291/00-297/08

Claims (4)

(57) [Claims] 1. A fluoroolefin polymer or full
Copolymerizable with oro-olefin and the fluoro-olefin
Radical polymerizability in the presence of particles of copolymers with monomers
A monomer having an unsaturated bond and having no fluorine atom
A fluororesin aqueous dispersion composition comprising a fluororesin aqueous dispersion obtained by seed polymerization and a water-soluble silicate. 2. The aqueous dispersion composition according to claim 1, further comprising at least one curing agent for water-soluble silicate. 3. The fluororesin having a functional group of at least one selected from the group consisting of a hydrolyzable silyl group, a hydroxyl group, an epoxy group and a carboxyl group. Aqueous dispersion composition of. 4. A coated article having a coating film obtained from the fluororesin aqueous dispersion composition according to claim 1.