JPH10110078A - Water-base fluroresin dispersion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-base coating material which forms a weather- resistant high-gloss coating film hardly stained outdoors by compounding a water-base fluroresin dispersion with a tetrafunctional silicate compd. SOLUTION: A water-base fluororesin dispersion (A) in an amount of 100 pts.wt. (solid basis) is compounded with 1-50 pts.wt. tetrafunctional silicate compd. (B1 ) represented by formula I (wherein R is a 1-8C org. group excluding the case when all the R groups are a 1C group) or its condensate (B2 ) and optionally 0-25 pts.wt. trifunctional silicate compd. (C) represented by formula II (wherein R<1> is a 1-8C org. group; and R<2> is H or a 1-8C org. group). This water-base dispersion contains 0.1-10wt.% (based on the sum of ingredients B and C) emulsifier having an HLB of 5-15. A condensate of ingredient B1 and ingredient C is used as a silicate component. Ingredient A includes fluoroolefin polymers and copolymers and their blends. A 2-4C fluoroolefin is suitable. Tetraethoxyilane is a pref. example of ingredient B1 . Ingredient C contributes to the external appearance and in-water stability of the resultant coating film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing resin aqueous coating composition which is excellent in non-staining adhesion and weather resistance and can form a high gloss coating film.

[0002]

2. Description of the Related Art Attempts to improve non-staining adhesion and weather resistance by adding a silicate compound to a paint have been already known.

For example, JP-A-6-506632 and WO95 / 02462 disclose coating compositions in which a tetrafunctional silicate compound is blended in an organic coating.

[0004] These publications disclose that a tetrafunctional silicate compound is applied to a water-based paint, and there are examples in which the compound is added to an acrylic emulsion paint.
There is no disclosure of an example of addition to a fluorine-containing resin aqueous paint. Also, there is no description of an emulsion of a tetrafunctional silicate compound, and no description is given of a method of adding a silicate compound in the form of an emulsion. Further, it does not describe a co-condensate of a tetrafunctional silicate compound and a trifunctional silicate compound.

JP-A-7-109435 discloses an outdoor article having a silicon atom concentration of 5% by weight or more and an octane contact angle of 102 ° or more in water to which a 1-3-functional silicate compound is added. ing. However, no reference is made to water-based paints. Further, it does not describe a co-condensate of a tetrafunctional silicate compound and a trifunctional silicate compound.

JP-A-8-120221 discloses that a silicate compound having three or less functions is added to a water-based paint. However, it does not describe the addition of a tetrafunctional silicate compound, nor does it describe a co-condensate of a tetrafunctional silicate compound and a trifunctional silicate compound.

[0007]

SUMMARY OF THE INVENTION The present invention provides an aqueous dispersion of a fluorine-containing resin, which is blended with an additive for forming a coating and a tetrafunctional silicate compound having a hydrolyzable silyl group in the molecule. An aqueous dispersion composition of a fluorine-containing resin, which is capable of providing a coating composition capable of forming a coating film having extremely low outdoor adhesion, excellent weather resistance, and a high gloss coating film. It is an object of the present invention to provide a water-based coating composition, and a coated article obtained by coating the same.

[0008]

The present invention basically comprises an aqueous dispersion of a fluorine-containing resin and a silicate component having a tetrafunctional silicate compound or a condensate or co-condensate thereof as an essential component.

That is, according to the present invention, a solid content of 100 parts (parts by weight; the same applies hereinafter) of a fluorine-containing resin aqueous dispersion is represented by the formula (I):

[0010]

Embedded image

(Wherein, R is the same or different, and each is an organic group having 1 to 8 carbon atoms, provided that at least one organic group has 2 to 8 carbon atoms) A-1) and / or a condensate thereof (A-
2) (hereinafter also referred to as "(A)")
To 50 parts of a fluororesin aqueous dispersion composition.
The silicate component is represented by the formula (II):

[0012]

Embedded image

[0013] (In the formula, R ¹ represents an organic group having 1 to 8 carbon atoms, R ²
Is a hydrogen atom or an organic group having 1 to 8 carbon atoms)
The functional silicate compound (B) may be contained in an amount of 25 parts or less based on 100 parts of the solid content of the fluororesin aqueous dispersion.

In the present invention, the silicate component is a co-condensate (C) of a tetrafunctional silicate compound (A) and a trifunctional silicate compound (B), and the solid content of the fluororesin aqueous dispersion is 100 parts by weight. 1 to 50 parts by weight of the composition.

The aqueous fluororesin dispersion composition comprises:
An emulsifier having an HLB value of 5 to 15 is added to a silicate component of 0.1%.
-10% (% by weight; the same applies hereinafter).

The emulsifier may be blended after previously mixing with the silicate component, or may be added together with the silicate component to water so as to have a silicate component concentration of 1 to 70% to form an aqueous composition. You may.

Further, the present invention relates to a coating composition comprising the aqueous fluororesin dispersion composition and a coating additive, and a coated article obtained by coating the coating composition.

[0018]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, an aqueous dispersion of a fluorine-containing resin is used. It is also possible to add a silicate compound to the resin aqueous dispersion other than the fluorine-containing resin,
When a severe test such as an accelerated weathering test or a thermal cycle is performed on a material other than a fluorine-containing resin, cracks and cracks occur on the coating film surface.

The fluorine-containing resin includes a fluoroolefin polymer, a copolymer of a fluoroolefin and a monomer copolymerizable with the fluoroolefin, and a blend resin of the polymer and a resin containing no fluorine atom. , A composite resin.

Examples of the fluoroolefin include vinyl fluoride, vinylidene fluoride (VdF),
C2-C4 such as tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), and trifluoroethylene
A degree of fluoroolefin is used.

The monomers copolymerizable with the fluoroolefin include, for example, ethylene; α-olefins such as propylene and isobutylene; ethyl vinyl ether (EVE) and 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; alkenyls such as polyoxyethylene allyl ether, ethyl allyl ether, hydroxyethyl allyl ether, allyl alcohol, allyl ether; vinyl acetate, vinyl lactate, butyric acid Vinyl, vinyl pivalate, vinyl benzoate, VEOVA
9, VEOVA10 (both are product names of Shell Chemical Company)
And vinyl esters such as itaconic anhydride, succinic anhydride, crotonic acid and the like.

The fluoroolefin polymers include VdF / TFE copolymer, VdF / HFP copolymer, VdF / CTFE copolymer, and VdF / TFE / CT.
VdF copolymers such as FE copolymers and VdF / TFE / HFP copolymers; and TFE / HFP copolymers.

The copolymer of a fluoroolefin and a monomer copolymerizable with the fluoroolefin includes CT
Examples thereof include a copolymer of FE and vinyl ethers.

Examples of blend resins or composite resins of these polymers and resins containing no fluorine include:
Examples thereof include a fluorine-based composite resin obtained by seed-polymerizing a monomer having an α, β unsaturated group in an aqueous medium in the presence of VdF-based copolymer particles.

The solid concentration of the aqueous fluororesin dispersion is from about 20 to 70%, preferably from about 30 to 60%, from the viewpoint of stability during coating. The average particle size of the particles is about 50 to 300 nm, preferably about 100 to 200 nm, from the viewpoint of the stability of the aqueous dispersion. The pH of the aqueous dispersion is usually in the range of 5-10.

The silicate compound (A-1) of the formula (I) used in the present invention is tetrafunctional and has 1 to 8 carbon atoms in the organic group R. However, at least one organic group must have 2 to 8 carbon atoms. When all the organic groups have 1 carbon atom, they hydrolyze when incorporated into the aqueous fluororesin dispersion and aggregate the system, which is not preferable. In the case of containing an organic group having 9 or more carbon atoms, the hydrolysis rate becomes extremely slow, so that the surface of the formed coating film cannot have a hydrophilizing effect and cannot have a contamination adhesion preventing effect.

Specific examples of the organic group R include, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-pentyl, i-pentyl, neopentyl, n-hexyl, n-octyl One or two or more of a linear or branched alkyl group having 1 to 8 carbon atoms such as phenyl and 2-ethylhexyl; an aryl group having 6 to 8 carbon atoms such as phenyl; a vinyl group; an allyl group. . Among them, ethyl, n-propyl, i-propyl and n-propyl are used in view of the balance between the stability of the paint and the surface hydrophilicity.
Butyl and t-butyl are particularly preferred.

Specific examples of the tetrafunctional silicate compound (A-1) include, for example, tetraethoxysilane, tetrapropoxysilane, tetra-n-butoxysilane, tetraphenoxysilane, dimethoxydiethoxysilane and the like.
Species or two or more species are mentioned, and in particular, tetraethoxysilane, tetra-n-propoxysilane, and tetra-n-butoxysilane are preferable from the viewpoint of the balance between the stability of the paint and the hydrophilicity.

Condensate of tetrafunctional silicate compound (A-
2) the degree of condensation is from 2 to 100 from the viewpoint of coating film appearance,
Particularly, those having 2 to 20 are preferable. The condensate (A-
2) also includes compounds in which some of the side chains have been replaced with different alcohols. For example, in the condensate of tetramethoxysilane (which itself is not included in the condensate (A-2) of the present invention), a part of the methyl group in the side chain is substituted with an alcohol having 3 to 8 carbon atoms. Is raised. As a specific example, methyl silicate 51 (manufactured by Colcoat Co., Ltd.), which is a condensate of tetramethoxysilane, and an alcohol such as n-propanol, n-butanol or 2-ethylhexanol are converted into a base such as triethylamine or an acid such as sulfuric acid. A substituted product obtained by heating to 60 to 150 ° C. and distilling off generated methanol can be exemplified.

This tetrafunctional silicate compound (A) is used to render the resulting coating film hydrophilic and non-staining.
1 to 5 based on 100 parts of the solid content of the aqueous fluororesin dispersion
0 parts, preferably 5 to 30 parts are blended. If the amount is too small, the non-staining property is inferior. If the amount is too large, the formed coating film is inferior in gloss and cracks may occur.

Next, as described above, the trifunctional silicate compound (B) represented by the formula (II) which may be blended as an optional component is an organic group having 1 to 8 carbon atoms in which R ¹ is the same or different. Wherein R ² is a hydrogen atom or an organic group having 1 to 8 carbon atoms.

Examples of the organic group R ¹ include those exemplified as the organic group R, and among them, an alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of high reactivity with a tetrafunctional silicate compound.

As the organic group R ² , in addition to those exemplified above as the organic group R, γ-methacryloyloxypropyl,
and γ-hydroxypropyl. Among them, an alkyl group having 2 to 8 carbon atoms and γ-methacryloyloxypropyl are preferred from the viewpoint of good stability in the presence of water.

Specific examples of the trifunctional silicate compound (B) include, for example, methyltrimethoxysilane, methyltriethoxysilane, octyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane,
γ-methacryloyloxypropyltrimethoxysilane,
One or more of γ-hydroxypropyltrimethoxysilane and the like can be mentioned, and γ-hydroxypropyltrimethoxysilane is preferable in that it has an effect of particularly improving the appearance of the obtained coating film.

The trifunctional silicate compound (B) is an optional component that is blended especially to improve the appearance of the coating film and the stability in water.
0 to 25 parts, preferably 1 to 25 parts, particularly preferably 1 to 15 parts are added to parts. If the amount is too large, the surface of the coating film will not be sufficiently hydrophilized, and the non-staining adhesion will be reduced.

In the present invention, a co-condensate (C) of a tetrafunctional silicate compound (A) and a trifunctional silicate compound (B) can be used as the silicate component. The co-condensate (C) is obtained by reacting the silicate compounds (A) and (B) in water in the presence of an acid such as hydrochloric acid or sulfuric acid. For example, tetraethoxysilane and .gamma.-methacryloyloxypropyltrimethoxysilane are removed from water in the presence of hydrochloric acid in an amount of about 0-60.
It is obtained by stirring at a temperature of about 0.5 to 3 hours. The co-condensate (C) can be regarded as one mode when the silicate compounds (A) and (B) are used in combination, and therefore, the ratio of the co-condensation of the silicate compounds (A) and (B) is expressed in terms of weight ratio. 1 to 50/1 to 25, preferably 5
30/1 to 15. Further, any of the silicate compounds (A) and (B) may be co-condensed in two or more kinds.

Preferred cocondensates (C) are, for example, tetraethoxysilane / γ-methacryloyloxypropyltrimethoxysilane cocondensate, tetraethoxysilane / n-methyltrimethoxysilane cocondensate, tetraethoxysilane / n One or more of -propyltrimethoxysilane cocondensate, tetraethoxysilane / n-octyltriethoxysilane cocondensate, tetrapropoxysilane / γ-methacryloyloxypropyltrimethoxysilane cocondensate, and the like. Co-condensation of tetraethoxysilane / γ-methacryloyloxypropyltrimethoxysilane, tetraethoxysilane / methyltrimethoxysilane, tetraethoxysilane / n-propyltrimethoxysilane, especially from the viewpoint of stability in water and appearance of coating film Are preferred.

The compounding amount of the co-condensate (C) is 1 to 50 parts, preferably 5 to 30 parts, per 100 parts of solids of the aqueous fluororesin dispersion.

In the present invention, an emulsifier having an HLB value of 5 to 15 is added to the fluororesin aqueous dispersion composition, which is preferable in terms of improving the mixing property between the silicate compound and the fluororesin aqueous dispersion composition.

The emulsifiers useful in the present invention include nonionic emulsifiers, such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters,
Examples thereof include polyoxyethylene alkylphenyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, and glycerin esters.

Preferred emulsifiers have an HLB value in the range of 5 to 5.
When the HLB value is out of this range, the silicate compound is not rapidly emulsified, and even if emulsified, the emulsified state cannot be maintained for a long period of time. More preferably, the HLB value ranges from 7 to
13 sorbitan alkyl esters and polyoxyethylene sorbitan alkyl esters.

Further, in addition to the nonionic emulsifier, a known anionic emulsifier, amphoteric emulsifier, cationic emulsifier and the like can be used in combination. Examples of anionic emulsifiers include fatty acid salts such as sodium stearate; alkyl aryl sulfonates such as sodium dodecylbenzenesulfonate and sodium alkylnaphthalene sulfonate; alkyl sulfates such as sodium lauryl sulfate;
N-acyl amino acid salts such as sodium lauroyl sarcosine; dialkyl sulfosuccinates; alkyl phosphates; and polyoxyethylene lauryl ether sulfate. Examples of the cationic emulsifier include alkylamine acetate, alkylammonium halide and the like. Examples of the amphoteric emulsifier include dimethyl alkyl betaine, alkyl glycine, amido betaine type, imidazoline type and the like. When an emulsifier other than the nonionic emulsifier is used in combination, the amount of the emulsifier other than the nonionic emulsifier is preferably 10% or less of the amount of the nonionic emulsifier. If it exceeds 10%, the water resistance of the coating film during film formation decreases.

The emulsifier is 0.1 to 10 of the silicate component.
%, Preferably 0.5 to 2%. If the amount of the emulsifier is too small, it will be difficult to form an emulsion, and if the amount is too large, the water resistance of the coating film will decrease.

The emulsifier may be added to the composition of the aqueous dispersion of the fluorine-containing resin and the silicate component. It is preferable to do so from the viewpoint of improving the appearance of the coating film.

In particular, it is preferable to mix in the form of the following aqueous silicate compound composition (D).

Such an aqueous silicate compound composition (D)
(A) the tetrafunctional silicate compound (A) and the 3
A mixture of the functional silicate compound (B) or the co-condensate (C), (b) an emulsifier having an HLB value of 5 to 15 and (c) water, wherein the amount of the emulsifier is 0.1% of the component (a).
-10%, and the concentration of the component (a) is 1-70%
Is an aqueous composition.

In the component (a), the ratio between the silicate compounds (A) and (B) is 1 to 50/1 to 2 by weight.
5, and particularly preferably from 5 to 30/1 to 15, from the viewpoints of paint stability, hydrophilicity and coating film appearance. The type and amount of the emulsifier are the same as described above.

The concentration of the silicate component as the component (a) is 1 to 70%. If it is less than 1%, the amount of water increases at the time of addition to the paint, and the stability of the resulting water-based paint is impaired.
On the other hand, if it exceeds 70%, the emulsion does not emulsify, or the stability of the obtained aqueous composition becomes extremely poor even if it can be emulsified. Also,
When a silicate mixture is used as the silicate component, the concentration is preferably in the range of 20 to 60%. 2
If it is less than 0%, the coating workability tends to be poor.
%, The stable period of the aqueous composition tends to be short.

The aqueous silicate compound composition comprises (a)
The component (b) can be prepared by simply mixing and stirring the component in water (c). However, when the component is strongly stirred with a homogenizer or the like and forcedly emulsified to form an emulsion, the dispersibility in the aqueous fluororesin dispersion and the stability of the paint are reduced. It will be excellent.

When mixing and stirring, it is preferable to add an organic solvent to the mixed system from the viewpoint of paint stability. Preferred organic solvents include, for example, diethyl adipate,
Texanol, propylene glycol methyl ether acetate and the like. The addition amount is preferably 1 to 100 parts based on the silicate compound.

The aqueous silicate compound composition (D) is a novel composition.

The same kind of aqueous composition is disclosed in the above publications.
For example, Japanese Patent Publication No. Hei 3-13195 discloses an emulsion in which an alkylalkoxysilane is dispersed together with an emulsifier, and an emulsion obtained by emulsifying a mixture or co-condensate of a tetrafunctional silicate compound and a trifunctional silicate compound having high condensability with an emulsifier. Is not disclosed.

The aqueous silicate compound composition (D) has excellent properties such as stability against hydrolysis in water, hydrophilicity, and excellent compatibility with the resin. In addition to a coating composition capable of forming a coating film having excellent non-staining adhesion in combination with a dispersion, it can be combined with another resin. Other resins include, for example, acrylic resin, acrylic silicon resin, urethane resin and the like.

In addition, it is also useful as a hydrophilizing agent for the surface of fibers or resins.

The present invention further relates to an aqueous fluororesin coating composition comprising the above-mentioned aqueous fluororesin dispersion composition and an additive for coating.

As the additives for paints, additives which are usually used in the field of paints can be used. For example, pigments, pigment dispersants, film-forming auxiliaries, wetting agents, thickeners, ultraviolet absorbers, antioxidants , An antifreezing agent, an antifoaming agent, a fungicide, a pH adjuster and the like. The type and amount of the coating additive may be appropriately selected in consideration of the respective functions, so as not to impair the intended effects of the present invention.

The water-based coating composition of the present invention provides a coating film having excellent non-staining adhesion, and is suitable for coating exterior materials such as inorganic base materials, sizing boards for houses and buildings.

The present invention also relates to a coated article obtained by applying the above-mentioned aqueous fluororesin coating composition. The articles to be coated include those described above. The resulting coated articles have excellent non-staining adhesion.

As a coating method, a normal coating method may be used.
For example, a spray, bar coater, dipping, curtain coater and the like can be mentioned.

[0060]

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

Example 1 Zeffle SE310 (vinylidene fluoride resin / acrylic resin composite resin aqueous emulsion, pH = 7, solid content concentration 51%) manufactured by Daikin Industries, Ltd. was used as a base emulsion.

10.0 parts of water, SN502 as a dispersant
7 (manufactured by Sannobuco) 5.3 parts, FS01 as defoamer
0.3 parts of 3B (manufactured by Dow Corning), 4.0 parts of ethylene glycol, 0.1 part of 28% aqueous ammonia, and Taipaque CR97 (manufactured by Ishihara Sangyo Co., Ltd.) as titanium oxide 7
0.0 parts was dispersed in water by a sand mill to prepare a pigment paste. Next, 28.2 parts in 68.2 parts of Zeffle SE310
0.6 parts of 8% aqueous ammonia was added, and then 24.1 parts of pigment paste, 5.1 parts of diethyl adipate, and FS013B (manufactured by Dow Corning) 0.1 as an antifoaming agent.
And 1.9 parts of a 10% aqueous solution of ADEKANOL UH420 (manufactured by Asahi Denka Kogyo KK) as a thickener, and 400 rpm
The mixture was stirred at m for 1 hour to obtain a white paint. This white paint is SE31
Called 0W. For 100g of this SE310W,
7 g of ethyl silicate 40 (manufactured by Colcoat), which is a tetramer condensate of tetraethoxysilane, was added and stirred for 15 minutes to obtain a coating composition. This coating composition was measured for the following items.

Paint stability: The paint composition was cured at 24 ° C. for 24 hours.
The mixture was allowed to stand for a time, and the change in the viscosity of the paint and the presence or absence of aggregates were confirmed. The paint condition was classified as follows. ：: no change △: thickened ×: aggregated

Mitsuzawa: The coating composition was prepared according to JIS H400
10 on an AM712 chemical conversion treated aluminum plate
It was applied with a mil doctor blade. After drying at room temperature for 3 days, the gloss of the coating film was measured using a gloss meter (manufactured by Suga Test Instruments Co., Ltd.).

Water contact angle: The coated plate used for the gloss measurement was washed with running water, air-dried, and the static contact angle of water was measured with a contact angle meter (manufactured by Kyowa Kagaku Co., Ltd.). Also, on the roof of the research building in the Daikin Industries Yodogawa Works in Settsu, Osaka,
After one week of actual exposure at an angle of inclination, the coated plate was washed with running water, and the water resistant contact angle was measured in the same manner.

Actual exposure stain: The pigment value of the coated plate used for the gloss measurement was measured for L value by using DP300 manufactured by Minolta Co., Ltd., and was used as an initial value. The coated plate was subjected to actual exposure for 2 months on the research building rooftop of the Daikin Industries Yodogawa Works in Settsu City, Osaka Prefecture, at a 30 ° southern slope, and the L value was measured again. Classified as follows. A: ΔL ≦ 3 B: 3 ≦ ΔL ≦ 5 C: 5 ≦ ΔL ≦ 10 D: 10 ≦ ΔL

Accelerated weather resistance: The coated plate used for the gloss measurement was subjected to an accelerated weather resistance test for 1000 hours with an I-Super UV tester manufactured by Iwasaki Electric Co., Ltd., and the gloss was measured. The gloss retention GR relative to the initial gloss was measured. Was determined by the following equation. GR (%) = (gloss after 1000 hours / initial gloss) ×
The 100 results were classified as follows. ：: GR ≧ 80% Δ: 80%> GR. ≧ 50% ×: 50%> GR.

Further, cracks in appearance, presence / absence of blisters, dirt, etc. were visually confirmed.

Table 1 shows the above results.

Synthesis Example 1 In a 100 ml beaker, while stirring with a stirrer, 8 g of a 5% hydrochloric acid aqueous solution was added at room temperature 25 ° C. to a mixed solution of 30 g of tetraethoxysilane and 10 g of γ-methacryloyloxypropyltrimethoxysilane (MPTS). . Soon,
It generates white heat and becomes cloudy.
Stirred for minutes. Immediately thereafter, 60 ml of water was added to terminate the reaction. The obtained substance was converted to an aqueous GPC column PW4000.
H (manufactured by Tosoh Corporation) as a developing solution, and a flow rate of 1 ml /
As a result, the weight average molecular weight Mw was about 1000 as a result of measuring the molecular weight in terms of styrene using the detector RI with the min. From the ratio of Si to C in elemental analysis, it was confirmed that it was a cocondensate in which 3 units of tetraethoxysilane and 1 unit of MPTS were condensed. This co-condensate is called EM-1.

Synthesis Example 2 A co-condensate was obtained in the same manner as in Synthesis Example 1 except that the silicate compound was changed to 30 g of tetraethoxysilane and 10 g of methyltriethoxysilane. As a result of analysis, it was confirmed that this cocondensate was a cocondensate in which 2 units of tetraethoxysilane and 1 unit of methyltriethoxysilane were condensed. EM-
No. 2.

Synthesis Example 3 A cocondensate was obtained in the same manner as in Synthesis Example 1 except that the silicate compound was changed to 20 g of tetraethoxysilane and 20 g of octyltriethoxysilane. As a result of analysis, this co-condensate was found to be 3.5% of tetraethoxysilane.
It was confirmed that the unit was a co-condensate in which 0.5 unit of methyltriethoxysilane was condensed. This co-condensate is called EM-3.

Example 2 A coating composition was obtained in the same manner as in Example 1 except that the silicate compound added to SE310W was changed to a mixture of 5 g of ethyl silicate 40 and 2 g of MPTS. This composition was evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 3 A coating composition was obtained in the same manner as in Example 1 except that the silicate compound added to SE310W was changed to 7 g of EM-1. Example 1 for this composition
Was evaluated in the same way as Table 1 shows the results.

Example 4 Example 1 was repeated except that Lumiflon FE3000 (chlorotrifluoroethylene / vinyl ether copolymer resin aqueous emulsion, pH = 8, solid content concentration 50%) manufactured by Asahi Glass Co., Ltd. was used as the base emulsion. In the same manner as in the above, a coating composition containing a silicate emulsion was obtained. This composition was evaluated in the same manner as in Example 1. Table 1 shows the results
Shown in

Comparative Examples 1 to 3 A silicate emulsion-containing coating composition was obtained in the same manner as in Example 1, except that SE310W in Example 1 was replaced with a commercially available water-based emulsion type coating. The aqueous emulsion type paint used was as follows.

Aqueous acrylic paint: Tile rack (manufactured by Nippon Paint Co., Ltd.) Acrylic urethane aqueous paint: Audefresh U100
(Nippon Paint Co., Ltd.) Acrylic silicone water-based paint: Component Silicon (Esk Chemical Co., Ltd.)

This composition was evaluated in the same manner as in Example 1. Table 1 shows the results.

In Table 1, EtSi40 is ethyl silicate 40 (a tetraethoxysilane condensate manufactured by Colcoat), MPTS is γ-methacryloyloxypropyltrimethoxysilane, and EM-1 is a cocondensate prepared in Synthesis Example 1. Is shown.

[0080]

[Table 1]

According to the results shown in Table 1, in the case of resin paints other than the fluorine-containing resin, in addition to the phenomenon of resin deterioration such as reduction in gloss and chalking, which are generally pointed out after the accelerated weathering test, cracking of the coating film occurs. I understand.

Examples 5 to 12 and Comparative Examples 4 to 7 A coating composition was prepared in the same manner as in Example 1 except that the silicate compound added to SE310W was changed to the silicate compound shown in Table 2 and the amount added. I got it. This composition was evaluated in the same manner as in Example 1. Table 2 shows the results. However, in Comparative Example 4, methyl silicate 5
In the system to which No. 1 was added, the subsequent items could not be measured because the paint agglomerated immediately after the addition of the silicate.

The abbreviations of the silicate compounds in Table 2 indicate the following compounds.

MeSi51: methyl silicate 51 (condensate of tetramethoxysilane manufactured by Colcoat) EtSi28: ethyl silicate 28 (tetraethoxysilane monomer manufactured by Colcoat) EtSt40: ethylsilicate 40 (tetraethoxysilane manufactured by Colcoat) Condensation product) PrSi: (Tetrapropoxysilane monomer manufactured by Colcoat) LSi: 100% lauryl group-substituted product of MeSi51 manufactured by Colcoat BuSi: M manufactured by Colcoat manufactured by the following synthesis method
100% butyl group substitution of methyl group of eSi51 In a 200 ml four-necked flask equipped with a stirrer, a reflux tube and a thermometer, 50 g of methyl silicate 51 (tetramer of tetramethoxysilane) manufactured by Colcoat Co., Ltd. (0.1 mol) ) Was added thereto, and 74 g (1.0 mol) of n-butyl alcohol was added thereto. Further, after adding 10 g of triethylamine, the mixture was refluxed at 80 to 120 ° C for 2 hours. Then 1
Volatile components were distilled off under reduced pressure at 00 ° C. to obtain 32 g of a product. N
From MR, it was confirmed that the methyl group was almost completely substituted with an n-butyl group. EHSi: Colcoat M obtained by the following synthesis method
70% ethyl hexyl substitution of eSi51 100 g (0.78 mol) in place of n-butyl alcohol
The reaction was carried out in the same manner as in the above BuSi synthesis method except that 2-ethylhexyl alcohol of 1) was used to obtain 120 g of a product. From NMR, it was confirmed that the substitution rate by the 2-ethylhexyl group was 70%.

[0085]

[Table 2]

From the results, when the number of carbon atoms in the side chain of the silicate compound is less than 2 (Comparative Example 4), aggregation occurs due to hydrolysis at the time of addition to the paint, and when the number of carbon atoms exceeds 8, the paint (Comparative Example 5). It is understood that the surface of the film is not hydrophilized, and the adhesion of contamination is not reduced. When the amount of the silicate compound is small (Comparative Example 6), the surface of the coating film is not hydrophilized and the adhesion of contamination is not reduced. When the amount is too large (Comparative Example 7), the coating film becomes brittle and cracks may occur. I understand.

Examples 13 to 20 and Comparative Examples 8 to 10 A coating composition was prepared in the same manner as in Example 1 except that the silicate compound added to SE310W was changed to the silicate compound shown in Table 3 and the amount added. I got it. This composition was evaluated in the same manner as in Example 1. Table 3 shows the results.

The abbreviations of the silicate compounds in Table 3 indicate the following compounds.

EtSi40: Ethylsilicate 40 (condensate of tetraethoxysilane manufactured by Colcoat Co., Ltd. MPTS: γ-methacryloyloxypropyltrimethoxysilane MTrES: methyltriethoxysilane OtrES: octyltriethoxysilane EM-1: Synthesis Example 1 Co-condensate prepared EM-2: Co-condensate prepared in Synthesis Example 2 EM-3: Co-condensate prepared in Synthesis Example 3

[0090]

[Table 3]

From these results, it is found that silicate (B) is used in combination with silicate compound (A) (Examples 13 to 17).
It can be seen that the gloss of the coating film is improved while maintaining the non-staining property. In addition, when the silicate compound (B) is used in combination with the silicate compound (B), the amount of the silicate compound (B) is too large (Comparative Example 9). Use of a co-condensate of the silicate compound (A) and the silicate compound (B) (Example 1)
8 to 19), it is understood that the gloss of the coating film is further improved as compared with the combined use of the silicate compound (A) and the silicate compound (B).

Example 21 In a 10 ml glass test tube, 1.5 g of ethyl silicate 40 (manufactured by Colcoat Co., Ltd.), a condensate of tetraethoxysilane, 0.5 g of γ-methacryloyloxypropyltrimethoxysilane, and an organic solvent And 2.06 g of polyoxyethylene sorbitan ester-based nonionic emulsifier SL10 (manufactured by Nippon Chemical Co., Ltd., HLB value 8.6) was dissolved in this mixture. To this mixture was added 6.0 g of a 0.1% aqueous solution of sodium hydrogencarbonate (pH = 7.8, 20 ° C.), and the mixture was stirred with a touch mixer for 3 minutes to obtain an emulsion. The initial emulsified state of this silicate emulsion and the stability of the emulsion after one week and two weeks after the emulsion were examined. The results were classified as follows and are shown in Table 4.

Initial emulsifiability: A: Emulsified uniformly B: Almost emulsified C: Not emulsified D: Aggregated

Stability with time: confirmed after 2 weeks and 4 weeks ○: redispersible △: increase in viscosity ×: agglomerated

Next, a silicate emulsion was added to SE310W in such an amount that the silicate compound of the silicate emulsion became 20% of the resin in SE310W, and the mixture was stirred for 15 minutes to obtain a coating composition. This coating composition was evaluated in the same manner as in Example 1. Table 4 shows the results.

Examples 22 to 25 and Comparative Examples 11 to 17 The same procedures as in Example 21 were carried out except that the silicate compound, the organic solvent and the emulsifier in Example 21 were changed as shown in Table 1. 25 and the silicate emulsions of Comparative Examples 11 to 17 were prepared and evaluated in the same manner as in Example 21. Then, these were added to SE310W in Example 21.
And the obtained coating composition was evaluated in the same manner as in Example 1. Table 4 shows the results.

The silicate compounds used in Table 4
Abbreviations of the organic solvent and the nonionic emulsifier are as follows.

(Silicate compound) MeSi39: methyl silicate 30 (tetramethoxysilane monomer manufactured by Colcoat) EtSi40: ethylsilicate 40 (condensate of tetraethoxysilane manufactured by Colcoat) EHSi: 70% ethylhexyl substitution of MeSi51 Compound LSi: 100% lauryl group-substituted product of MeSi51 MPTS: γ-methacryloyloxypropyltrimethoxysilane

(Organic solvent) ADE: diethyl adipate CS12: 2,2,4-trimethyl-produced by Chisso Corporation
1,3-pentanediol monoisobutyrate PMA: propylene glycol methyl ether acetate (manufactured by Dow Corning)

(Emulsifier) SL10: Polyoxyethylene sorbitan ester (HLB value: 8.6) manufactured by Nikko Chemical Co., Ltd. 106: Rheodol TW-O106 (manufactured by Kao Corporation)
Polyoxyethylene sorbitan ester (HLB value 1
0.0) 430: Reodol 430 (manufactured by Kao Corporation), polyoxyethylene sorbite tetraoleate (HLB value 1)
0.5) OP10: Polyoxyethylene alkyl phenyl ether type (HLB value 13.1) manufactured by Nikko Chemical Co., Ltd. OP50: Polyoxyethylene alkyl phenyl ether type (HLB value 4.5) manufactured by Nikko Chemical Co., Ltd. MYO2: Nikko Chemical Co., Ltd. polyoxyethylene alkyl ester type (HLB value: 15.5) Mixed system: Kao Corporation's Reodol TWO-106, Reodol MS50 60/40 (weight ratio) mixed emulsifier (HLB) Value 5.7)

[0101]

[Table 4]

[0102]

[Table 5]

From the results shown in Table 4, the HLB range of the emulsifier is 5
It is understood that a stable silicate emulsion can be obtained in the range of ~ 15. When the amount of the emulsifier exceeds 10% based on the silicate compound (Comparative Example 12), it is not preferable because the water resistance of the coating film becomes poor and blisters are generated during the accelerated weather resistance test. Also, it can be seen that the gloss is improved by adding the silicate compound in the form of an emulsion to the paint.

[0104]

According to the present invention, a fluorine-containing resin aqueous dispersion composition which is excellent in non-staining adhesion and weather resistance and has a long-term liquid stability which gives a glossy coating film, and using the same. An aqueous coating composition can be provided.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Katsuhiko Imoto 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (72) Inventor Nagato Dai 1-1 1-1 Nishiichitsuya, Settsu-shi, Osaka Daikin Industries Inside Yodogawa Works

Claims (7)

[Claims] 1. The solid content of an aqueous dispersion of a fluorine-containing resin is 100.
The silicate component is represented by the formula (I): (Wherein, R is the same or different, and all have 1 to 1 carbon atoms)
8 organic groups. However, the number of carbon atoms of at least one organic group is 2 to 8), and the tetrafunctional silicate compound (A-1) and / or its condensate (A-2) is 1 to
50 parts by weight, and formula (II): (Wherein, R ¹ is the same or different and each has 1 carbon atom
To 8 organic groups, and R ² is a hydrogen atom or an organic group having 1 to 8 carbon atoms).
A fluorine-containing resin aqueous dispersion composition containing 25 parts by weight. 2. The solid content of the aqueous fluororesin dispersion is 100.
A tetrafunctional silicate compound (A-1) represented by the formula (I) according to claim 1 and / or a condensate thereof (A-2) and a trifunctional compound represented by the formula (II), based on parts by weight. A fluororesin aqueous dispersion composition comprising 1 to 50 parts by weight of a cocondensate (C) with a silicate compound (B). 3. An emulsifier having an HLB value of 5 to 15 is compounded in an amount of 0.1 to 10% by weight of the silicate component.
Or the aqueous dispersion composition according to 2. 4. The aqueous dispersion composition according to claim 3, which is obtained by mixing the emulsifier and the silicate component in advance, and then adding the mixture to the fluororesin aqueous dispersion. 5. The aqueous dispersion according to claim 3, wherein the emulsifier and the silicate component are added to the fluororesin aqueous dispersion in the form of an aqueous composition having a concentration of the silicate component of 1 to 70% by weight. Composition. 6. A fluororesin aqueous coating composition comprising the fluororesin aqueous dispersion composition according to claim 1 and a coating additive. 7. A coated article obtained by applying the fluorine-containing resin aqueous coating composition according to claim 6.