JPH10264288A - Composite material for building material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve abrasion resistance, an anti-scratching property, and transparency beside weatherability, an anti-fouling property, and non- adhesiveness of a building composite material, and provide a sufficient hardness by forming on the base material surface a coat film consisting of a metallic oxide layer with minute particles of fluorine-contained polymer containing a specific functional group dispersed uniformly. SOLUTION: A coat film is formed on the base material surface, which has minute particles of an ethylenic polymer being polymerized with a 0.05-50 mol.% fluorine-contained ethylenic monomer having a specific functional group and a 50-99.95 mol.% fluorine-contained ethylenic polymer having no functional group dispersed in a metallic oxide layer. A specific functional group is selected from groups consisting of a hydroxyl group, a carboxyl group, carboxylic acid salt, a carboxylic ester group and epoxy group. For such a fluorine-contained ethylenic polymer having no functional group, tetrafluoroethylene is preferable, and an oxide of silicon, an oxide of aluminum, and an oxide of titanium are preferable for a metallic oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to weather resistance, heat resistance,
Excellent antifouling properties, non-adhesiveness, transparency (design), abrasion resistance, rust prevention, flame retardancy, weathering prevention, water and oil repellency, etc., and especially excellent adhesion and hardness to substrates The present invention relates to a composite material for building materials having a coating on the surface of a base material in which fine particles of a fluoropolymer are dispersed in a metal oxide layer.

[0002]

2. Description of the Related Art Conventionally, building materials such as architectural glass, various interior and exterior wall materials, roofing materials and interior and exterior materials, signs, traffic signals,
Civil engineering materials such as card rails, telephone poles and soundproof walls,
Because it is used by being exposed to the surroundings and the environment, its surface has weather resistance, dust, stain resistance against exhaust gas and rain streaks,
Transparency and design are required. In addition, heat resistance, non-adhesiveness against oil, burning and scale, and antifouling properties are used for various furniture, kitchen dwellings such as gas tables and range hoods, system kitchens, washbasins, toilets and bathrooms. Is required. In the present specification, all of the above products are referred to as "building materials", but the base material constituting these building materials is made of glass, metal, ceramic, synthetic resin, concrete, or the like, and the surface thereof is not subjected to any treatment. Although some have not,
Fluoropolymers with excellent heat resistance, chemical resistance, corrosion resistance, weather resistance, surface properties (non-adhesiveness, low friction, etc.), electrical insulation, etc., are used for composite materials used in building materials. And so on. However, due to its excellent non-adhesion, the fluoropolymer does not have sufficient adhesiveness to the surface of a substrate such as a metal. Therefore, (1) an adhesive is used, or (2) sandblast or It is necessary to perform etching by an electrochemical method, to provide irregularities on the surface, and to perform adhesion by an anchor effect.

However, in the method using an adhesive as in (1), since there is no heat-resistant, transparent and high-adhesive adhesive, unevenness on the surface of the base material as in (2) is required. In this method, the surface becomes extremely rough due to the formation of irregularities, and there is a problem of design that the color tone such as the transparency of the glass substrate and the metallic luster of the metal substrate cannot be utilized. Furthermore, even if a transparent adhesive is developed, the fluoropolymer constituting the coating on the surface of the building material is generally soft. Transparency and design are reduced due to scratches on the coating, and the inherent weather resistance, antifouling property, water repellency and non-adhesion of the fluoropolymer are reduced due to wear. Because it is softer, when applied to exterior building materials, dirt, dust, dirt, etc., are easily embedded in the coating, which makes it easier to get dirty,
Sometimes it is difficult to remove.

In an attempt to solve these problems, an inorganic filler such as glass or aluminum is added to a film made of a fluoropolymer to impart hardness, but the film becomes brittle. There is a problem that transparency and design properties are reduced.

In addition, various studies have been conducted to impart water repellency to glass for the purpose of repelling water droplets attached to a window glass or a side mirror of a car in rainy weather or the like to improve visibility. It can be used in the field of building materials.

For example, Japanese Patent Application Laid-Open Nos. H4-124047, H4-325446, and H5-248.
No. 85 describes that a silane compound containing a fluoroalkyl group (Rf group) is applied to a substrate such as glass. Also, JP-A-4-359086, JP-A-5-170486, and JP-A-5-213
No. 633 discloses that a fluoroalkyl group-containing silane compound or a metal alkoxide mixed with a fluoroalkyl group-containing silane compound is partially hydrolyzed and polycondensed (solified) with an acid or the like, applied on a glass substrate, and baked. To form a water-repellent oxide film (gelation).

However, the water-repellent glass obtained by these treatment methods has a problem that the water-repellent groups are easily distributed on the outermost surface of the coating, and the water-repellency is reduced by abrasion. Further, the fluoroalkyl group-containing silane compound and its condensate itself have insufficient heat resistance, and have a problem that they deteriorate when used for a long period of time and cannot maintain the water-repellent performance.
The properties required for building material composites cannot be satisfied.

On the other hand, by using fluororesin particles having no functional group as a water-repellent component and dispersing the fluororesin particles in a metal oxide layer obtained by a so-called sol-gel method, sufficient A water-repellent coating having high hardness and a water-repellent glass provided with the same are disclosed. For example, JP-A-5-51238, JP-A-6-32
9442, JP-A-6-340451, JP-A-7-1
No. 02207, JP-A-7-157335, etc., a sol solution obtained by hydrolyzing and dehydrating and condensing a metal alkoxide-based compound in a solvent such as alcohol is used to prepare polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer. Coating liquid is prepared by mixing fluorinated resin particles (powder or dispersion) having water repellency such as coalesced, fluorinated acrylic resin, applied, and baked (gelled),
It describes that a water-repellent film in which water-repellent particles are distributed in a sol-gel film is formed on a substrate such as glass.

However, these methods can be expected to improve the heat resistance, but have the following problems.

The dispersion stability of the fluorine-containing resin particles in the coating solution prepared by mixing the fluorine-containing resin particles with the sol solution is poor, the fluorine-containing resin particles are likely to settle, and the coated film becomes cloudy or transparent. Is significantly reduced.

Although the coating solution is apparently dispersed, the dispersion stability is insufficient as the coating film is concentrated in the coating and baking steps, so that the fluorine-containing resin particles aggregate and become cloudy or transparent. It becomes a bad film.

In the first place, since the interface affinity between the metal oxide and the fluororesin particles is low, the dispersibility of the fluororesin particles in the obtained coating is poor, the coating itself becomes brittle in strength, and the abrasion resistance is low. It becomes a bad film.

[0013] The interfacial adhesion between the metal oxide and the fluororesin particles in the obtained coating film is weak, and the fluororesin particles fall off in the abrasion resistance test, and the water repellency decreases.

That is, according to the conventional sol-gel method,
There is no coating suitable for a building material composite material that is sufficiently excellent not only in adhesiveness and transparency but also in abrasion resistance, heat resistance, water and oil repellency, and scratch resistance.

[0015]

In view of the above facts, an object of the present invention is to basically employ a sol-gel method.
By using a specific functional group-containing fluoropolymer,
An object of the present invention is to provide a composite material for building materials having a coating made of a metal oxide layer in which the fine particles are uniformly dispersed on the surface of a base material.

It is a further object of the present invention to provide a composite for building materials which is excellent in wear resistance, scratch resistance and transparency (design) in addition to weather resistance, stain resistance and non-adhesiveness and has sufficient hardness. To provide materials.

[0017]

SUMMARY OF THE INVENTION The present invention provides (a) a functional group containing at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylate, a carboxyester group and an epoxy group. 0.05 to 50 at least one kind of fluorine-containing ethylenic monomer
(B) at least one monomer of the above-mentioned fluorine-containing ethylenic monomer having no functional group and 50 to 99.95.
The present invention relates to a composite material for a building material having a coating on the surface of a base material, in which fine particles of a functional group-containing fluorine-containing ethylenic polymer (A) obtained by copolymerizing the metal oxide (A) and the metal oxide (B) are dispersed in a metal oxide (B) layer.

In this case, the functional group-containing fluorine-containing ethylenic monomer (a) is represented by the formula (1): CX ₂ = CX ¹ -R _f -Y (1) (where Y is -CH ₂ OH) , -COOH, a carboxylate salt, a carboxyester group or an epoxy group, X and X ¹ are the same or different and are a hydrogen atom or a fluorine atom,
R _f is a divalent fluorinated alkylene group having 1 to 40 carbon atoms,
A fluorine-containing oxyalkylene group having 1 to 40 carbon atoms, a fluorine-containing alkylene group containing an ether group having 1 to 40 carbon atoms or a fluorine-containing oxyalkylene group containing an ether bond having 1 to 40 carbon atoms) Preferably, it is a fluorine-containing ethylenic monomer containing various functional groups.

Further, the fluorine-containing ethylenic monomer (b) having no functional group is preferably tetrafluoroethylene.

Further, the fluorine-containing ethylenic monomer (b) having no functional group is a tetrafluoroethylene 85-85.
99.7 mol% and formula (2): CF ₂ ＝ CF—R _f ¹ (2) (where R _f ¹ is CF ₃ or OR _f ² (R _f ² is carbon number 1 to
5 perfluoroalkyl group)
It is preferably a mixed monomer of up to 15 mol%.

The fluorine-containing ethylenic monomer having no functional group (b) is preferably tetrafluoroethylene 40 to 40.
It is preferably a mixed monomer of 80 mol%, 20 to 60 mol% of ethylene, and 0 to 15 mol% of other copolymerizable monomers.

The metal oxide (B) is preferably a silicon oxide.

The metal oxide (B) is preferably an aluminum oxide.

The metal oxide (B) is preferably a titanium oxide.

Preferably, the substrate is a metal-based substrate.

Preferably, the substrate is a synthetic resin substrate.

Preferably, the synthetic resin substrate is transparent.

Preferably, the synthetic resin substrate is made of polycarbonate.

Preferably, the synthetic resin substrate is artificial marble.

Preferably, the substrate is a non-metallic inorganic substrate.

Preferably, the non-metallic inorganic substrate is made of glass.

Preferably, the non-metallic inorganic substrate is made of concrete.

Preferably, the non-metallic inorganic substrate is made of cement.

Further, the present invention relates to a building exterior member using the building material composite material.

The present invention also relates to a curtain wall using the building material composite.

Further, the present invention relates to a roof member using the above-mentioned composite material for building materials.

Further, the present invention relates to a roof tile using the above-mentioned composite material for building materials.

The present invention also relates to a roofing material using the composite material for building materials.

The present invention also relates to a window member using the building material composite material.

The present invention also relates to sashes using the building material composite.

The present invention also relates to a gutter using the composite material for building materials.

The present invention also relates to exteriors using the above-mentioned composite material for building materials.

[0043] The present invention also relates to a door opening using the composite material for building materials.

Further, the present invention relates to an outer fence using the above-mentioned composite material for building materials.

[0045] The present invention also relates to a member for building interior using the composite material for building material.

The present invention also relates to a wall material using the building material composite material.

The present invention also relates to a flooring made of the building material composite.

[0048] The present invention also relates to a ceiling made of the building material composite.

The present invention also relates to a building material using the building material composite material.

The present invention also relates to an interior door using the composite material for building materials.

Further, the present invention relates to a blind using the composite material for building materials.

[0052] The present invention also relates to a housing equipment using the composite material for building materials.

The present invention also relates to a bath-toiletries using the composite material for building materials.

The present invention also relates to a wash basin using the building material composite.

The present invention also relates to a toilet bowl using the composite material for building materials.

The present invention also relates to a bathtub using the above-mentioned composite material for building materials.

Further, the present invention relates to a member for kitchen using the composite material for building material.

The present invention also relates to a system kitchen using the building material composite.

The present invention also relates to a gas table using the building material composite.

The present invention also relates to a range hood using the building material composite.

The present invention also relates to an elevator using the building material composite.

The present invention also relates to an escalator using the composite material for building materials.

The present invention also relates to a building material for civil engineering using the composite material for building material.

The present invention also relates to a road construction member using the composite material for building material.

The present invention also relates to a road construction soundproofing wall using the building material composite material.

The present invention also relates to a sign for road construction using the composite material for building material.

The present invention also relates to a road construction guardrail using the building material composite material.

The present invention also relates to a traffic signal cover for road construction using the composite material for building material.

The present invention also relates to a road construction light cover using the composite material for building material.

The present invention also relates to a water and sewage facility member using the composite material for building materials.

The present invention also relates to a bridge member using the composite material for building material.

The present invention also relates to a railway facility member using the building material composite material.

The present invention also relates to a bolt for a railway facility using the composite material for building materials.

The present invention also relates to a signal cover for a railway facility using the composite material for building materials.

The present invention also relates to an overhead line for a railway facility using the composite material for building materials.

The present invention also relates to a railway tower for a railway facility using the composite material for building materials.

Further, the present invention relates to a member for an electric power facility using the composite material for building materials.

Further, the present invention relates to a glass for electric power facilities using the composite material for building materials.

The present invention also relates to a power pole for electric power facilities using the composite material for building materials.

The present invention also relates to an arm for electric power facilities using the composite material for building materials.

The present invention also relates to a chemical plant member using the building material composite.

[0082]

BEST MODE FOR CARRYING OUT THE INVENTION As a result of repeated studies to achieve the above object, the present inventors have improved weather resistance, stain resistance, non-adhesion, water repellency, abrasion resistance and scratch resistance. It has been found that coated films can be obtained and that they can be applied to building materials.

The composite material for a building material of the present invention comprises (a) a functional group-containing composite material having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylate, a carboxylester group and an epoxy group. At least one kind of fluorine-containing ethylenic monomer 0.05 to 3
0 mol% and (b) at least one kind of the above-mentioned fluorine-containing ethylenic monomer having no functional group in the range of 70 to 99.9.
A film formed by dispersing fine particles of a fluorine-containing ethylenic polymer (A) having a functional group obtained by copolymerizing 5 mol% with a metal oxide (B) layer serving as a matrix was formed on the substrate surface. Things.

The functional group-containing fluorine-containing polymer (A) used to obtain the composite material of the present invention has the above-mentioned functional group by using the functional group-containing fluorine-containing ethylenic monomer (a). It is important to copolymerize with the fluorinated ethylenic monomer (b) to introduce a functional group into the fluorinated polymer, whereby the adhesion of the conventional fluorinated polymer is insufficient or impossible. Dispersibility of the fluorinated polymer in the metal oxide that was the matrix, improved interfacial adhesion between the fluorinated polymer and the metal oxide, excellent transparency to the coating and the composite coated with the coating, It can provide durability (abrasion resistance, scratch resistance). That is, even a functional group-containing fluoropolymer has excellent heat resistance as compared with a copolymer obtained by copolymerizing a non-fluorinated functional group-containing monomer, and has a high temperature (for example, 200 to 4).
(Such as 00 ° C.) to suppress the thermal decomposition during processing, and to form a coating film having excellent transparency and design without coloring, foaming, pinholes and leveling defects. it can. Also, when the composite material is used at a high temperature, coating defects such as coloring, whitening, foaming and pinholes are less likely to occur.

The functional group-containing fluoropolymer (A) itself has not only heat resistance but also weather resistance, antifouling property, non-adhesive property, water and oil repellency, and water resistance of the fluoropolymer. It also has excellent properties such as chemical properties and low friction, and can be applied to building material composites without deteriorating these excellent properties.

Next, the functional group-containing fluorine-containing ethylenic copolymer (A) which is a material of the composite material of the present invention will be described.

The functional groups of the functional group-containing fluorine-containing ethylenic polymer (A) include a hydroxyl group, a carboxyl group,
At least one selected from a carboxylate, a carboxyester group, and an epoxy group, and the fluorine-containing polymer (A) gives good dispersibility in a matrix composed of the metal oxide (B) by the effect of the functional group; Further, it can provide good interfacial adhesion and affinity between the fluoropolymer (A) and the metal oxide. The type and combination of the functional groups are appropriately selected depending on the type, purpose and application of the metal oxide (B) as a matrix, but those having a hydroxyl group are most preferable in terms of heat resistance.

The functional group-containing fluorine-containing ethylenic polymer (A) which can be used in the present invention is, specifically, (a) a formula (1): CX ₂ = CX ¹ -R _f -Y (1) ( In the formula, Y is CH ₂ OH or COOH or a carboxylate or carboxyester group, X and X ¹ are the same or different and are each a hydrogen atom or a fluorine atom, and R _f is a divalent fluorine-containing carbon atom having 1 to 40 carbon atoms. An alkylene group or a divalent fluorinated alkylene group containing an ether bond having 1 to 40 carbon atoms).
(B) 50 to 99.95 mol% of at least one fluorine-containing ethylenic monomer copolymerizable with the functional group-containing fluorine-containing ethylenic monomer (a). And a functional group-containing fluorinated ethylenic polymer, which is excellent in heat resistance, stain resistance and water repellency.

The functional group-containing fluorinated ethylenic monomer (a) is specifically represented by the following formula (3): CF ₂ −CF—R _f ³ —Y (3) wherein Y is the formula (1) R _f ³ has 1 to 4 carbon atoms
0 divalent fluorinated alkylene group or OR _f ⁴ (R _f ⁴ is a divalent fluorinated alkylene group having 1 to 40 carbon atoms or a divalent fluorinated alkylene group containing an ether bond having 1 to 40 carbon atoms) ], Formula (4): CF ₂ = CFCF ₂ -OR _f ⁵ -Y (4) [wherein, Y is the same as Y in formula (1), and R _f ⁵ has 1 to 3 carbon atoms.
9 divalent fluorine-containing alkylene groups or 1 to 39 carbon atoms
Represents a divalent fluorine-containing alkylene group containing an ether bond of the formula], formula (5): CH ₂ ＣＦCFCF ₂ —R _f ⁶ —Y (5) wherein Y is the same as Y in the formula (1); R _f ⁶ has 1 to 3 carbon atoms
9, a divalent fluorine-containing alkylene group, or OR _f ⁷ (R _f ⁷
Represents a C1-C39 divalent fluorinated alkylene group or a C1-C39 divalent fluorinated alkylene group containing an ether bond) or a formula (6): CH ₂ ＣＨCH—R _f ⁸ -Y (6) [in the formula, Y is the same as Y in formula (1), R _f ⁸ is 1 to 4 carbon atoms
And a divalent fluorine-containing alkylene group of 0].

The functional group-containing fluorinated ethylenic monomers represented by the formulas (3) to (6) have relatively good copolymerizability with the fluorinated ethylenic monomer (b). Further, it is preferable because the heat resistance, non-adhesiveness and water repellency of the copolymer obtained by copolymerization are not significantly reduced.

Among them, the monomers represented by the formulas (3) and (5) from the viewpoint of copolymerizability with other fluorine-containing ethylenic monomers and heat resistance of the obtained copolymer. The monomer is preferable, and a monomer represented by the formula (2) is particularly preferable.

The functional group-containing fluorine-containing ethylenic monomer represented by the formula (3) is described in more detail.

[0093]

Embedded image

And the like.

As the functional group-containing fluorine-containing ethylenic monomer represented by the formula (4),

[0096]

Embedded image

Examples are shown.

As the functional group-containing fluorine-containing ethylenic monomer represented by the formula (5),

[0099]

Embedded image

And the like.

As the functional group-containing fluorine-containing ethylenic monomer represented by the formula (6),

[0102]

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And the like.

As other monomers,

[0105]

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And the like.

The ethylenic monomer copolymerizable with the functional group-containing fluorine-containing ethylenic monomer (a) can be appropriately selected from known monomers.
In order to impart antifouling properties, non-adhesiveness, water repellency, chemical resistance and low friction to the copolymer, the copolymer is selected from the fluorine-containing ethylenic monomers (b).

Specific fluorinated ethylenic monomer (b)
As formula (2): CF ₂ ＣＦCF—R _f ¹ (2) wherein R _f ¹ is CF ₃ or OR _f ² (R _f ² is carbon number 1 to
5), hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, vinylidene fluoride,
Perfluoro (alkyl vinyl ether) s, hexafluoroisobutene,

[0109]

Embedded image

(Wherein, X ² is both selected from a hydrogen atom, a fluorine atom, and a chlorine atom, and n is an integer of 1 to 5)
And so on.

Further, in addition to the functional group-containing fluorine-containing ethylenic monomer (a) and the above-mentioned fluorine-containing ethylenic monomer (b), it has weather resistance, heat resistance, antifouling property, non-adhesiveness and water repellency. An ethylenic monomer having no fluorine atom may be copolymerized as long as the amount does not decrease. In this case, the ethylenic monomer having no fluorine atom is selected from ethylenic monomers having 5 or less carbon atoms so as not to reduce weather resistance, heat resistance, antifouling property, non-adhesiveness, and water repellency. Preferably, ethylene, propylene, 1-butene, 2-butene and the like are mentioned.

In the coating of the present invention, the content of the functional group-containing fluorine-containing ethylenic monomer (a) in the functional group-containing fluorine-containing ethylenic polymer (A) depends on the type of the metal oxide (B), A composition ratio of the functional group-containing fluorine-containing ethylenic polymer (A) and the metal oxide (B), a solid content concentration,
Further, it can be appropriately selected depending on the purpose and application, but is preferably 0.05 to 50 mol%, more preferably 0.1 to 50 mol%.
It is 20 mol%, particularly preferably 0.1 to 10 mol%.

When the content of the functional group-containing fluorine-containing ethylenic monomer (a) is less than 0.05%, the dispersion in the coating becomes uneven and the coating becomes white. Also,
The interfacial adhesion between the metal oxide in the coating and the functional group-containing fluorine-containing ethylenic polymer (A) dispersed in the coating becomes insufficient, and the functional group-containing fluorine-containing ethylenic polymer (A) ) Falls off, deteriorating antifouling properties, non-adhesiveness and water repellency.

Conversely, when the content of the functional group-containing fluorine-containing ethylenic monomer (a) exceeds 50 mol%, the functional group-containing fluorine-containing ethylenic polymer (A) originally has Loses antifouling properties, non-adhesiveness, water repellency, and deteriorates heat resistance, and thermally decomposes during baking at high temperatures, resulting in coating failure such as coloring, foaming, pinholes, and deterioration of coating performance. Easy to cause.

Preferred examples of the functional group-containing fluorine-containing ethylenic polymer (A) used in the present invention are shown below.

(I) A polymer (I) comprising 0.05 to 50 mol% of a functional group-containing fluorine-containing ethylenic monomer (a) and 50 to 99.95 mol% of tetrafluoroethylene (reactive P
TFE).

This polymer is most excellent in heat resistance and chemical resistance, and further excellent in antifouling property, non-adhesiveness and low friction property.

(II) The functional group-containing fluorine-containing ethylenic monomer (a) is used in an amount of 0.05 to 50 mol% based on the total amount of the monomers.
And 85 to 99.7 mol% of tetrafluoroethylene with respect to the total amount of the monomer excluding the monomer (a) and the formula (2): CF ₂ = CF-R _f ¹ (2) [ R _f ¹ is ^{_{CF 3, OR f 2 (R}} f 2 is a perfluoroalkyl group having 1 to 5 carbon atoms) polymer of monomer 0.3 to 15 mole% represented by] selected from (II) . For example, a tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer having a functional group (reactive PFA) or a tetrafluoroethylene-hexafluoropropylene polymer having a functional group (reactive FEP).

This polymer has excellent heat resistance and chemical resistance.
Good antifouling property, non-adhesiveness and water repellency.

(III) A monomer containing the functional group-containing fluorine-containing ethylenic monomer (a) in an amount of 0.05 to 50 mol% based on the total amount of the monomer, and further excluding the monomer (a) To a total amount of 40 to 80 mol% of tetrafluoroethylene, 20 to 60 mol% of ethylene, and 0 to 15 mol% of the other copolymerizable monomer (ethylene-tetrafluoroethylene having a functional group). Ethylene polymer (III) (reactive ET
FE)).

This polymer is excellent in antifouling property and non-adhesiveness,
Furthermore, it has excellent transparency and mechanical properties.

The functional group-containing fluorine-containing ethylenic polymer given as a specific example thereof has a high melting point of 200 ° C. or more, and has a functional group-containing fluorine-containing ethylenic polymer (A).
When preparing a coating composed of the functional group-containing fluorine-containing ethylenic polymer (A) and the metal oxide (B), in which the fine particles are dispersed, the particles do not melt even when fired at a high temperature, and This is preferable because the form can be maintained.

The functional group-containing fluorinated ethylenic polymer (A) which can be used in the present invention comprises the above-mentioned functional group-containing fluorinated ethylenic monomer (a) and the ethylenic monomer (b). It can be obtained by copolymerization using a well-known polymerization method. Among them, a method based on radical copolymerization is mainly used. That is, the means for initiating the polymerization is not particularly limited as long as it proceeds radically, but is initiated by, for example, an organic or inorganic radical polymerization initiator, heat, light or ionizing radiation. As the type of polymerization, solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, or the like can be used. In addition, the molecular weight, the concentration of the monomer used for polymerization, the concentration of the polymerization initiator, the concentration of the chain transfer agent,
Controlled by temperature. The composition of the resulting copolymer is
It can be controlled by the composition of the charged monomers.

In the present invention, the metal oxide (B) capable of forming a matrix of the coating is, for example, a starting material such as a metal organic compound or a metal inorganic compound, and a solvent (C) in a coating composition described later. And those obtained by hydrolysis and polycondensation are preferred.

The metal oxide (B) thus obtained
Can be used depending on the purpose and application. For example, in the periodic table of the elements, Group Ia: Li, Na, Group Ib: Cu, Group IIa: Ca, Sr, Ba, Group IIb: Zn, Group IIIa : Y, Group IIIb: B, Al, Ga, Group IVa: Ti, Zr, Group IVb: Si, Ge, Group Va: V, Ta, Group Vb: P, Sb, Group VIa: W, Group lanthanide: La, An oxide of a metal (M) such as Nd or the like, and a divalent or higher metal having a functional group such as an alkyl group, a fluorine-containing alkyl group, an amino group, an epoxy group, or a hydroxyl group. An organic group (R) such as an alkylene group is a metal (M)
A metal oxide (R-MO) directly bonded to a metal can also be used. More specific metal oxides (B) include those described below.

The metal (M) can be variously selected depending on the purpose and application. However, the metal (M) is particularly preferably selected from Si, Al, Ti and Zr in that a transparent, high-hardness, and durable coating can be formed. .

In the present invention, the ratio (volume ratio) of the functional group-containing fluorine-containing ethylenic polymer (A) and the metal oxide (B) in the coating on the substrate surface is (A) / (B) is 1 ~ 85
/ 99-15, especially 5-75 from the viewpoint of transparency and film strength
/ 25 to 95 is preferred. If the amount of the polymer (A) is too large, the transparency of the film is lowered or the film becomes brittle. On the other hand, if the amount is too small, the inherent excellent performance of the fluororesin such as antifouling property, non-adhesiveness and water repellency cannot be exhibited.

Examples of the substrate on which the coating in the present invention can be formed include a metal-based substrate, a nonmetallic inorganic substrate, and a synthetic resin substrate.

The metal of the metal base material includes metals and alloys of two or more metals, and metal salts such as metal oxides, metal hydroxides, carbonates and sulfates.

Specific examples of the metal-based substrate include metals, metal compounds such as aluminum, iron, nickel, titanium, molybdenum, magnesium, manganese, copper, silver, lead, tin, chromium, beryllium, tungsten, and cobalt; And alloys composed of two or more kinds.

Specific examples of alloys include carbon steel, Ni steel,
Cr steel, Ni-Cr steel, Cr-Mo steel, stainless steel,
Alloy steel such as silicon steel, permalloy, Al-Cl, Al
-Mg, Al-Si, Al-Cu-Ni-Mg, Al-
Aluminum alloys such as Si-Cu-Ni-Mg, brass, bronze (bronze), copper alloys such as silicon bronze, silicon brass, nickel silver, nickel bronze, nickel manganese (D
Nickel), nickel-aluminum (Z nickel),
Nickel alloys such as nickel-silicon, monel metal, constantan, nichrome inconel, and Hastelloy are included.

Further, with respect to aluminum-based metals, pure aluminum, oxides of aluminum, Al-Cu-based metals,
Al-Si, Al-Mg and Al-Cu-Ni-
Casting or wrought aluminum alloys such as Mg-based, Al-Si-Cu-Ni-Mg-based alloys, high-strength aluminum alloys, and corrosion-resistant aluminum alloys can be used.

Further, iron-based metals include pure iron, iron oxide, carbon steel, Ni steel, Cr steel, Ni-Cr steel, Cr-M
o steel, Ni-Cr-Mo steel, stainless steel, silicon steel,
Permalloy, insensitive magnetic steel, magnet steel, cast irons and the like can be used.

For the purpose of preventing metal corrosion, etc.
Electroplating, hot-dip plating, chromizing,
Applying siliconizing, calorizing, sheradizing, thermal spraying, etc. to coat other metals, forming phosphate coating by phosphate treatment, forming metal oxide by anodic oxidation or heat oxidation Or can be adhered to substrates that have been subjected to electrochemical corrosion protection.

Further, for the purpose of further improving the adhesiveness, the surface of the metal substrate is subjected to a chemical conversion treatment with phosphate, sulfuric acid, chromic acid, oxalic acid, or the like, or is subjected to sand blasting, shot blasting, grit blasting, horning, Surface roughening treatment such as paper scratch, wire scratch, and hair line treatment may be performed, and coloring, printing, etching, etc. may be performed on the metal surface for the purpose of design.

Further, in the case of the above-mentioned aluminum or aluminum alloy base material, the surface thereof is subjected to anodic oxidation using caustic soda, oxalic acid, sulfuric acid and chromic acid for the purpose of corrosion prevention, surface hardening and improvement of adhesion. An oxide film formed by performing the process (alumite) or a material subjected to the above-described surface treatment can also be used.

Further, in the same manner as described above, a material having a surface plated with another metal, for example, a hot-dip galvanized steel sheet, an alloyed hot-dip galvanized steel sheet, an aluminum-plated steel sheet, a zinc-nickel-plated steel sheet, a zinc-aluminum steel sheet, etc.
Those coated with another metal by a thermal spraying method, those formed with an oxide film by a chromic acid-based or phosphoric acid-based chemical conversion treatment or heat treatment, and those subjected to an electrical anticorrosion method (for example, a carbanic steel plate) may be used.

Examples of the non-metallic inorganic substrate include glass, pottery, and porcelain.

The composition of the glass is not particularly limited, and examples thereof include quartz glass, lead glass, alkali glass, and alkali-free glass.

Examples of the synthetic resin base material include acrylic resin, polycarbonate, artificial marble, heat-resistant engineering plastic, thermosetting resin and the like.

As the base material of the composite material for building materials of the present invention, among the above-mentioned base materials, as the metal base material, aluminum,
Steel plates made of stainless steel, iron, titanium, etc., and galvanized or aluminum-plated steel plates, chemical conversion-treated steel plates that have been oxidized with chromic acid, phosphoric acid, etc., and anodized steel plates that have been anodized Is usually used.

Examples of the non-metallic inorganic base material include glass base materials such as crystallized glass, foamed glass, heat ray reflective glass, heat ray absorbing glass, and double-layer glass; ceramics such as tiles, large ceramic plates, ceramic panels, and bricks. Base material, natural stones such as granite and marble, high-strength concrete, glass fiber reinforced concrete (GRC), carbon fiber reinforced concrete (CFRC), lightweight cellular foamed concrete (ALC),
Concrete base materials such as composite ALC, cement base materials such as extrusion molded cement and composite molded cement, and other materials such as asbestos slate and enameled steel plate are generally used.

Further, as the synthetic resin substrate, polycarbonate, polyester resin, acrylic resin, vinyl chloride resin, artificial marble (mainly unsaturated polyester resin and acrylic resin), other vinyl chloride resin, acrylic resin or urethane resin Painted steel plates and the like are used.

[0144] Above all, non-metallic inorganic base materials such as glass, and synthetic resin base materials such as acrylic resin and polycarbonate are usually used for the parts requiring transparency.

The shape of the substrate in the present invention is as follows:
Sheets, films, tubes, pipes, plates, tubes, rods and other irregular shapes may be used, but are preferably the same shape as the final product or a shape close to the final product for processability.

The thickness of the metal oxide film varies depending on the type and site of the building material to be applied.
, Preferably 0.1 to 70 µm, particularly preferably 1 to 50 µm.

The coating in the present invention is a metal oxide coating prepared by a so-called sol-gel method, wherein the fine particles of the functional group-containing fluorine-containing ethylenic polymer (A) and the precursor of the metal oxide (B) are used. Metal oxide sol (B-1)
It can be formed by applying a coating composition comprising (a low molecular condensate before gelation) and a solvent (C) to a substrate.

As the solvent (C) that can be used in the coating composition, various solvents can be used. However, methanol and ethanol can be used because the metal oxide sol (B-1) can be prepared homogeneously. , Propanol, isopropanol, butanol, alcohols such as isobutanol,
In addition, those selected from water and the like for promoting hydrolysis are mainly used.

When a metal compound insoluble in the solvent (C) is used as a starting material for the metal oxide sol (B-1) (that is, a metal oxide film), ethylene glycol, propylene glycol, triethanolamine , Xylene or the like may be used. Formamide, dimethylformamide, dioxane, oxalic acid and the like may be used to prevent cracks in the coating.

In such a coating composition, the functional group-containing fluorine-containing ethylenic polymer (A) and the metal oxide sol (B
-1) The composition ratio of each component of the solvent (C) can be appropriately selected depending on the type and site of the building material, but the functional group-containing fluorine-containing ethylenic polymer (A) and the metal oxide sol (B-1) 1 to 85% by volume of the polymer (A), 15 to 99% by volume of the metal oxide sol (B-1), 5 to 75% by volume of the polymer (A), Sol (B-1) 25
More preferably, it is 95% by volume.

The total amount of the functional group-containing fluorine-containing ethylenic polymer (A) and the metal oxide (B) in the whole composition is 0.1 to 70% by weight, preferably 0.5 to 70% by weight.
50% by weight.

In the coating composition used in the present invention, the functional group-containing fluorine-containing ethylenic polymer (A) is preferably fine particles, and is dispersed in the form of fine particles in the coated metal oxide film. In particular, a coating excellent in abrasion resistance, stain resistance, non-adhesion, and water repellency can be provided.

The fine particles of the functional group-containing fluorine-containing ethylenic polymer (A) have an average particle diameter of 0.01 to 1.0 μm.
Degree, preferably 0.6 μm or less, and 0.4 μm or less in this range, particularly when transparency is required.
m or less, and most preferably 0.2 μm or less when the dispersion stability and storage stability of the coating composition and the transparency of the coating film are required.

The fine particles of the functional group-containing fluorine-containing ethylenic polymer (A) can be produced by various methods. However, since the particle diameter can be controlled finely and uniformly, it can be produced by an emulsion polymerization method. preferable. In this case, the aqueous dispersion of the functional group-containing fluorine-containing ethylenic polymer (A) obtained by the emulsion polymerization is directly mixed with the previously prepared solution of the metal oxide sol (B-1). Or functional group-containing fluorine-containing ethylenic polymer (A)
The coating composition can be obtained by performing hydrolysis and polycondensation of a metal compound as a starting material in a solvent containing an aqueous dispersion of the above.

The coating composition may contain additives such as a surfactant, a pigment, a dye, an ultraviolet absorber and a thickener.

In the present invention, the coating film formed on the substrate is a coating composition (sol solution) containing the fine particles of the functional group-containing fluorine-containing ethylenic polymer (A) and the metal oxide sol (B-1). ) Is applied to a substrate such as glass or metal and is fired (gelled) (i.e., a sol-gel method), whereby the polycondensation of the metal oxide sol (B-1) further proceeds, and is hard and high. A strong metal oxide (B) coating was formed, and the fluorine-containing copolymer (A) was formed into a metal oxide coating in which particles were uniformly dispersed.

In the metal oxide film of the present invention, since the fine particles of the functional group-containing fluorine-containing ethylenic polymer (A) are uniformly distributed to the inside of the film, even if the surface of the film is worn and scraped, In addition, the fluorocarbon resin exhibits excellent properties (such as antifouling property, non-adhesiveness, water repellency, etc.) to the inside of the coating and does not deteriorate.

In the calcination, the functional group-containing fluorinated ethylenic polymer (A) was dispersed in the metal oxide film in order to uniformly disperse the functional group-containing fluorinated ethylenic polymer (A) in the form of particles. It is preferable to carry out at a temperature below the melting point. However, those having high melt viscosity and not melting (for example, PT
When FE or the like is used as fine particles, firing can be performed at a temperature not lower than the melting point as long as the decomposition temperature of the functional group-containing fluorine-containing ethylenic polymer (A) is not exceeded.

Such a metal oxide film is obtained, for example, by subjecting at least one selected from the group consisting of metal alkoxides, metal acetyl acetates, metal carboxylate, metal nitrates, and metal chlorides to a hydrolysis reaction and a condensation reaction. The metal oxide sol (B-1) obtained and an aqueous dispersion containing the fine particles of the functional group-containing fluorine-containing ethylenic polymer (A) obtained by the emulsion polymerization method can be used, and (1) the metal oxidation Coating solution preparing step of preparing a coating liquid by mixing the sol (B-1) with the aqueous dispersion, (2) a coating film forming step of applying the coating liquid to a substrate to form a coating film, and (3) A) a coating form in which the coating film is baked to form a coating film in which fine particles of the functional group-containing fluorine-containing ethylenic polymer (A) are dispersed; Step can be more preparation of the reduced coating.

(Preparation of Metal Oxide Sol Solution) The metal oxide sol (B-1) may be a metal alkoxide, a metal acetyl acetate, a metal carboxylate, a metal nitrate, a metal chloride or a mixture thereof. It can be prepared by the above hydrolysis and polycondensation.

Of these, metal alkoxides are preferred because they are highly reactive and easily undergo a hydrolysis and polycondensation reaction to form a polymer (metal oxide) having a metal-oxygen bond.

When there is no suitable metal alkoxide, that is, when synthesis is difficult or when the metal alkoxide is insoluble in commonly used solvents such as water and alcohol (for example, copper alkoxide), metal acetyl is used. Carboxylates such as acetate and metal acetate, oxyacid salts and the like can be used.

In the absence of a suitable metal alkoxide or other organic metal compound, an inorganic metal compound such as a metal nitrate, a metal chloride, or a metal oxide can be used.

The metal alkoxide is a compound represented by M (OR) n (where M is a metal, R is alkyl, and n is a numerical value corresponding to the valence of the metal). The alkyl group R can be appropriately selected depending on the purpose and application of the film containing the corresponding metal oxide finally obtained, and whether the alkyl group R is soluble or not in a solvent, hydrolysis reactivity, polycondensation reactivity, or the like. Since it depends, it can be selected according to the purpose in consideration of these matters.

The metal alkoxide is specifically LiOC
H ₃ , NaOCH ₃ , Cu (OCH ₃ ) ₂ , Ca (OC
_{H 3) 2, Sr (OC} 2 H 5) 2, Ba (OC 2 H 5) 2, Zn
(OC ₂ H ₆ ) ₂ , Y (OC ₄ H ₉ ) ₃ , B (OCH ₃ ) ₃ , A
l (OCH ₃ ) ₃ , Al (OC ₂ H ₅ ) ₃ , Al (iso-OC
_{3 H 7) 3, Al (} OC 4 H 9) 3, Ga (OC 2 H 5) 3, T
i (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (iso-OC
_{3 H 7) 4, Ti (} OC 4 H 9) 4, Zr (OCH 3) 4, Zr
(OC ₂ H ₅ ) ₄ , Zr (OC ₃ H ₇ ) ₄ , Zr (OC ₄ H ₉ )
₄ , Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (iso
—OC ₃ H ₇ ) ₄ , Si (t-OC ₄ H ₉ ) ₄ , Ge (OC _{2
H 5) 4, Pb (OC} 4 H 9) 4, P (OCH 3) 3, Sb
(OC ₂ H ₅ ) ₃ , VO (OC ₂ H ₅ ) ₃ , Ta (OC ₃ H ₇ )
₅ , W (OC ₂ H ₅ ) ₆ , La (OC ₃ H ₇ ) ₃ , Nb (OC _{2
H 5) 3, La [Al} (iso-OC 3 H 7) 4] 3, Mg [A
_{l (iso-OC 3 H 7} ) 4] 2, Mg [Al (sec-OC
_{4 H 9) 4] 2,} Ni [Al (iso-OC 3 H 7) 4] 2, (C 3
H ₇ O) ₂ Zr [Al (OC ₃ H ₇ ) ₄ ] ₂ , Ba [Zr
₂ (OC ₂ H ₅ ) ₉ ] _{2 and the} like.

Examples of the metal alkoxide include not only a compound in which only an alkoxyl group is bonded to a metal, but also a compound in which part of an alkoxyl group is substituted with an alkyl group such as a methyl group or an ethyl group, or a compound in which a fluorine-containing alkyl group is substituted. Compounds substituted with an alkylene group having a functional group such as an amino group, an epoxy group, a hydroxyl group, and a mercapto group can also be used.

As specific examples of these,

[0168]

Embedded image

And the like.

Other examples of the organometallic compound include metal acetylacetonates such as Zr (COCH ₂ C
H ₃ ) ₄ , In (COCH ₂ COCH ₃ ) ₃ , Zn (COC
H ₂ COCH ₃ ) ₂ , metal carboxylate such as Pb
(CH ₃ COO) ₂ , Y (C ₁₇ H ₃₅ COO) ₃ , Ba (H
COO) _{2 and the} like.

Examples of the inorganic metal compound include metal nitrates such as Y (NO ₃ ) ₃ .6H ₂ O and Ni (NO ₃ ) _2.
3H ₂ O, metal oxychloride such as ZrOCl ₂ , Al
OCl, metal chlorides such as TiCl _{4 and the} like. Alternatively, a metal oxide such as fumed silica can be used to form a sol again, and the sol-gel method can be applied.

In preparing the metal oxide sol solution, first, a metal compound corresponding to the metal of the target metal oxide is selected from the above-mentioned compounds and dissolved in an alcohol-based solvent. In this case, it is desirable that the metal compound is uniformly dissolved in the solvent, and it is preferable to select a soluble metal compound.

By adding water and an acid or an alkali as a catalyst to the metal compound solution, hydrolysis and polycondensation occur, and particles of the metal oxide (B) are formed, and the metal oxide sol (B-1) Is obtained.

As the acid as the catalyst, for example, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid and the like are generally used, and as the alkali as the catalyst, ammonia which can be removed by volatilization after the treatment is preferably used.

The reaction temperature for preparing the metal oxide sol solution varies depending on the type of metal, the type of metal compound used, the target degree of polymerization of the sol, and the like, but is generally from room temperature to 100 ° C., preferably from room temperature. The solid content is preferably 0.5 to 50% by weight.

In some cases, hydrolysis and polycondensation are carried out gradually with water in the air without adding water or a catalyst.
It is also possible to prepare the metal oxide sol (B-1).

(Preparation of aqueous dispersion of functional group-containing fluorine-containing ethylenic polymer) Metal oxide sol (B-1)
Group-containing fluorine-containing ethylenic polymer (A) to be mixed with
Can be produced by various methods.

Specifically, (a) the powder of the functional group-containing fluorinated ethylenic polymer (A) obtained by the suspension polymerization method or the like is finely pulverized, and then the solution is added to the metal oxide sol (B-1) solution. , A method of adding a surfactant and the like and mixing uniformly (in this case, a coating solution is formed simultaneously with the dispersion), and (b) aqueous polymerization of the functional group-containing fluorine-containing ethylenic polymer simultaneously with the polymerization by the emulsion polymerization method. Producing a dispersion (in this case, directly the metal oxide sol (B-1)
Solution that can be mixed with a solution). From the viewpoint of productivity and quality (smaller particle size and uniform particle size),
An aqueous dispersion is prepared by an emulsion polymerization method, and a metal oxide sol (B-
1) It is preferable to mix with the solution. The aqueous dispersion of the fine particles of the functional group-containing fluorine-containing ethylenic polymer (A) to be mixed usually has a solid content of 1 to 70% by weight, and preferably 5 to 50% by weight.

(Preparation Step of Coating Solution) As a method for preparing a metal oxide sol (B-1) solution (coating solution) containing fine particles of the functional group-containing fluorine-containing ethylenic polymer (A), (C) A metal compound is hydrolyzed and polycondensed in an alcohol solution containing an aqueous dispersion containing fine particles of a group-containing fluorine-containing ethylenic polymer (A) to form a metal oxide sol (B-1). (D) mixing a metal oxide sol (B-1) solution previously prepared by hydrolysis and polycondensation with an aqueous dispersion containing fine particles of a functional group-containing fluorine-containing ethylenic polymer (A), Any of the methods for preparing a coating liquid can be employed.

The present inventors have found that the dispersion containing the fine particles of the functional group-containing fluorine-containing ethylenic polymer (A) can be made of an alcohol-based or other non-functional material due to the effect of the functional group of the polymer. They have found that they have high dispersion stability in aqueous solvents and do not cause sedimentation or coagulation of fine particles in the coating liquid preparation step by any of the above methods. Prior to coating, the target film thickness,
Depending on the type and shape of the base material, the solid content concentration of the coating liquid may be adjusted, or the viscosity of the coating liquid may be adjusted by adding a thickener.

(Coating Step) The coating material can be applied to the base material according to the type and site of the target building material. Since it is difficult to process when firing, the substrate is preferably in the shape of the final product.

As a coating method, known coating methods such as dipping, spin coating, spraying, brush coating, and roll coating can be employed.

(Firing Step) The coating film is fired to form a coating film in which fine particles of the functional group-containing fluorine-containing ethylenic polymer (A) are dispersed on the surface of the substrate. Usually, a drying step of removing water and a solvent is performed prior to firing. Drying is usually performed at room temperature to 100 ° C, preferably at room temperature to about 80 ° C.

The firing depends on the purpose, application, and type of the functional group-containing fluorine-containing ethylenic polymer (A).
0 ° C. or higher, functional group-containing fluorine-containing ethylenic polymer (A)
Below the decomposition temperature, preferably at least 150 ° C., and below the melting point of the functional group-containing fluorine-containing ethylenic polymer (A). If the reaction is carried out at a temperature of 100 ° C. or lower, the condensation polymerization (gelation) of the metal oxide does not proceed sufficiently, so that the crosslinking is insufficient.
High hardness and high strength coatings are difficult to obtain.

When the temperature exceeds the decomposition temperature of the functional group-containing fluorine-containing ethylenic polymer (A), excellent properties of the fluororesin such as water repellency as well as foaming and coloring are lost.

Further, the functional group-containing fluorine-containing ethylenic polymer (A) is dispersed in the form of particles in a coating comprising fine particles of the metal oxide (B) and the functional group-containing fluorine-containing ethylenic polymer (A). For this reason, the calcination is preferably performed at a temperature equal to or lower than the melting point of the functional group-containing fluorine-containing ethylenic polymer (A). However, when a material having a high melt viscosity and not melting (for example, PTFE or the like) is used as fine particles, the sintering is performed at a temperature higher than the melting point unless the decomposition temperature of the functional group-containing fluorine-containing ethylenic polymer (A) is exceeded. can do.

Thus, the composite material for building materials of the present invention can be manufactured.

The composite material for building materials is often required to be particularly antifouling, non-adhesive, and water-repellent. For this reason, fine particles of the functional group-containing fluorine-containing ethylenic polymer (A) are used as fine particles. It is preferable to use a water-repellent coating composition containing a fluoroethylenic polymer (A) having a contact angle with water of 80 ° or more, particularly 95 ° or more. Further, the metal oxide (B) and the functional group-containing fluorine-containing ethylenic polymer (A)
In order to maintain the shape of the water-repellent fine particles in the film made of the water-repellent fine particles, a fluorinated copolymer that does not thermally decompose or melt in the firing step at a high temperature is preferable, and specifically has a melting point of 150 ° C. or higher. , Preferably at least 200 ° C, particularly preferably at least 250 ° C.

Particularly, the functional group-containing fluorine-containing ethylenic polymer (A) which gives a film having excellent water repellency, specifically, the above-mentioned reactive PTFE, reactive PFA, reactive FEP, reactive ETFE, etc. Are preferred.

The functional group content in these functional group-containing fluorine-containing ethylenic polymer (A) is 0.1 to 10%.
Molar% is particularly preferred.

The composite material of the present invention obtained as described above comprises firstly a functional group-containing fluorine-containing ethylenic polymer (A)
Fine particles of metal oxide (B) with good interfacial adhesion
Secondly, a coating composed of fine particles (B) of a functional group-containing fluorine-containing ethylenic polymer (A) because the coating is uniformly dispersed in the coating composed of Has good weather resistance, antifouling properties, non-adhesiveness, water repellency, heat resistance, abrasion resistance, scratch resistance, etc., for example, architectural glass, building materials, kitchen housing, housing equipment, civil engineering For various building materials including various members in the field of (1).

[0192] Suitable building materials in which the composite material for building materials of the present invention can be used and the parts thereof are specifically listed below according to the field of the building materials. Therefore, the present invention also relates to building materials and various parts described below.

[0193] Tables 1 to 9 show the items classified and arranged for each item. In addition, what was described in the column of "metal oxide" in the table is a metal (M) which is preferable for constituting the metal oxide (B).

Architectural Glass In addition to architectural glass, polished architectural glass (window glass), stained glass window, windshield glass, glass having a function of adjusting light blocking ratio, and the like.

In these, the transparency, antifouling property and flame retardancy of the composite material for building materials of the present invention can be particularly effectively utilized.

Exterior wall material, roof material and interior / exterior material (made of metal) (a) In addition to metal exterior building materials for walls, metallic building materials, interior / exterior panels made of metal for construction, metal fences, metal tiles and metal And building boards.

(B) In addition to metal roofing materials, solar system built-in roofing materials and the like.

(C) In addition to metal doors, metal grids, metal shutters, metal fences, metal pouches (for construction), and the like.

(D) Metal blinds (for outdoor and outdoor use), sashes, shutters and the like.

(E) Metal ceiling boards, metal floor tiles, metal wall boards coated with a vinyl chloride decorative sheet on the surface, and the like.

(F) Other metal parking facilities for automobiles, general metal artworks, etc.

In these, the weather resistance, antifouling property and transparency (design) of the composite material for building materials of the present invention can be particularly effectively used.

Outer wall material, roof material, and interior / exterior material (made of nonmetallic inorganic material) (a) Concrete block to which segment-shaped or tiled or sliced natural stone is pasted, concrete-shaped pavement plate having segment-shaped or surface made of rubber material,
Concrete boards which may be reinforced, such as GRC (fiber reinforced concrete) wall materials.

(B) A cement extruded product such as a cement having a tile-like surface.

(C) Architectural stones such as artificial stones.

(D) Architectural tiles, raster glazed tiles,
Tiles such as floor tiles, ceramic tiles and ceramic border tiles.

(E) Non-metallic building exterior materials, building materials,
Architectural and wall cladding, such as architectural panels and architectural wall tiles.

(F) Roof materials such as ceramic roof materials with built-in solar system.

(G) Gravestones such as tombstones and tombstones.

(H) Stone, concrete or marble statues, figurines, statues, bustes and other art objects.

In these, the composite material for building materials of the present invention has weather resistance, antifouling property, waterproof property, transparency (design property), workability, adhesion, and (c) further has abrasion resistance.
In addition, the above (g) and (h) can be used particularly effectively for preventing weathering.

Outer wall material, roof material and interior / exterior agent (resin) (a) Floor plate, ceiling plate, etc.

(B) Grids, blinds and doors, including those for indoor use.

(C) Plastic panels for concrete.

(D) Architectural gaskets.

(E) Curtains, covers, sunshades, etc. with a film for preventing insects, blocking ultraviolet rays and heat rays and preventing scattering.

(F) Stone or a polyvinyl chloride flooring material with a stone pattern on the surface.

(G) Plastic roofing material with a built-in solar system.

(H) Combination-type polyvinyl chloride tiles having gaps and being drainable.

(I) A sash made of synthetic resin.

(J) Counters, furniture, thresholds, wall boards,
Backsplash, fir tree, veneer for fencing walls such as bathrooms and shower stalls.

(K) Assembling sets such as a washroom, a shower room, a toilet room, a toilet, a portable simple toilet, and a simple public toilet.

(L) Assembly set of sauna room, garage, etc.

In these, the weather resistance, antifouling property, transparency (design), water resistance, workability and adhesion of the composite material for building materials of the present invention can be particularly effectively utilized.

Outer wall material and roof material (wood) (a) Timber for production of household tools, veneer boards, architectural wood boards such as wooden panels, decorative boards and the like.

(B) Wooden fences, doors for indoor installation, wooden window frames, and the like.

(C) A wooden building material in which a rubber elastic material is attached to the back surface of a plywood.

(D) Wooden architectural assembly set.

Also in these, the weather resistance, antifouling property, transparency (design), water resistance, workability and adhesion of the composite material for building materials of the present invention can be particularly effectively utilized.

Furniture (a) Glass showcase, wagon, product display wagon, product display panel, product display stand, meal transport wagon, flower stand, etc.

(B) shelves, screens, desks, settees and shelves for storage cabinets, etc.

(C) Telephone box made of metal or various base materials.

Also in these, the antifouling property, transparency (design property), water resistance, and workability of the composite material for building materials of the present invention,
Abrasion resistance and scratch resistance can be particularly effectively utilized.

(A) Gas table, range hood, ventilation hood, etc.

(B) Metal ducts for central heating, ventilation equipment, air conditioning equipment, etc.

In these, the antifouling property, non-adhesiveness (to oil stains), workability and adhesion of the composite material for building materials of the present invention can be particularly effectively utilized.

Housing Equipment (a) System kitchen including kitchen range (oven), sink, etc.

(B) Electricity, gas and petroleum water heaters (including instantaneous water heaters).

(C) Wash basins such as wash basins for installation, vanities, household hair washer, vanities having a hair-washing function, wash basins for wash basins, wash basins with a top plate, and bay window-type wash basins.

(D) toilets such as flush toilets, compact toilets for vehicles, toilets for urinals, toilets with urine component measuring devices and infants, toilets with a hot water washing function, deodorizing devices and toilet seats, And a water tank for flush toilets.

(E) Bathrooms such as linings used in bathrooms including shower rooms, home saunas and commercial sauna baths, bathtubs such as simple bathtubs and bathtubs with bubble generators, handles attached to the bathtubs, soap storages, etc. furniture.

(F) Other escalators, elevators (including those for private houses) and the like.

In these, the antifouling property, design property (transparency) and workability of the composite material for building materials of the present invention, heat resistance of (a), (b) and (e) are further improved.
In the above (c) to (e), the wear resistance and the scratch resistance can be further utilized, and in the above (f), the slip property or rust prevention can be particularly effectively utilized.

Civil engineering (a) Signs including metal road signs such as signs for bus stops, signs for streets, and signs for guardrail attachment.

(B) Traffic lights such as issue-type traffic lights and mechanical traffic lights.

(C) Guardrails made of various base materials.

(D) Utility poles made of various base materials.

(E) Soundproof walls.

(F) Others A plastic concrete formwork for construction or construction.

In these, the weather resistance, antifouling property, scratch resistance, transparency (design), workability and adhesion of the composite material for building materials of the present invention, and the releasability of the above (f) are described. It can be used particularly effectively.

[0251]

[Table 1]

[0252]

[Table 2]

[0253]

[Table 3]

[0254]

[Table 4]

[0255]

[Table 5]

[0256]

[Table 6]

[0257]

[Table 7]

[0258]

[Table 8]

[0259]

[Table 9]

[0260]

EXAMPLES Next, the composite material of the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

Production Example 1 (Production of aqueous dispersion comprising PFA having a hydroxyl group) In a 3 liter glass-lined autoclave equipped with a stirrer, a valve, a pressure gauge and a thermometer, 1500 ml of pure water and perfluorooctane were added. 9.0 g of ammonium acid and 60 g of paraffin were added, and the atmosphere was sufficiently replaced with nitrogen gas. Then, the mixture was evacuated and charged with 20 ml of ethane gas.

Then, perfluoro- (1,1,9,9
-Tetrahydro-2,5-bistrifluoromethyl-
3,6-dioxa-8-nonenol) (formula (7))

[0263]

Embedded image

Then, 1.9 g of perfluoro (propyl vinyl ether) (PPVE) and 16.1 g of perfluoro (propyl vinyl ether) were injected by using nitrogen gas, and the temperature in the system was maintained at 70 ° C.

While stirring, tetrafluoroethylene gas (TFE) was injected so that the internal pressure became 8.5 kgf / cm ² G.

Next, a solution prepared by dissolving 0.15 g of ammonium persulfate in 5.0 g of water was injected under pressure using nitrogen to start the reaction.

Since the pressure decreases with the progress of the polymerization reaction, when the pressure decreases to 7.5 kgf / cm ² G, the pressure is increased again to 8.5 kgf / cm ² with tetrafluoroethylene gas, and the pressure reduction and pressure increase are repeated. .

While the supply of tetrafluoroethylene was continued, about 40% of tetrafluoroethylene gas was supplied from the start of polymerization.
Every time the g was consumed, 0.96 g of the fluorine-containing ethylenic monomer having a hydroxy group (the compound represented by the formula (7)) was injected 9 times in total (8.64 g in total). When about 400 g of tetrafluoroethylene had been consumed from the start of the polymerization, the supply was stopped and the autoclave was cooled to release unreacted monomers to obtain 1978 g of a bluish translucent aqueous dispersion.

The concentration of the polymer in the obtained aqueous dispersion was 21.1%, and the particle diameter measured by a dynamic light scattering method was 97 nm.

Further, a part of the obtained aqueous dispersion was subjected to freeze coagulation, and the precipitated polymer was washed.
Dry and isolate a white solid. The composition of the obtained copolymer was determined by ¹⁹ F-NMR analysis and IR analysis to be TFE / PP.
VE / (a fluorine-containing ethylenic monomer having a hydroxyl group represented by the formula (7)) = 99.2 / 0.3 /
It was 0.5 mol%.

The infrared spectrum was 3620-3400.
Characteristic absorption of -OH was observed at cm ^-1 .

According to DSC analysis, Tm = 313 ° C., DT
GA analysis revealed a 1% thermal decomposition temperature Td = 357 ° C. 2mm, length 8mm using a Koka type flow tester
Nozzle, preheat at 372 ° C for 5 minutes, load 7kgf
The melt flow rate was measured at 1.5 g / cm ² and found to be 1.5
g / 10 min.

Production Example 2 (P having a hydroxyl group)
Production of Aqueous Dispersion Consisting of FA) In the same autoclave as in Production Example 1, 1500 ml of pure water, 9.0 g of ammonium perfluorooctanoate, and 60 g of paraffin were placed, sufficiently purged with nitrogen gas, evacuated, and charged with 20 ml of ethane gas.

Next, perfluoro- (1,1,9,9
-Tetrahydro-2,5-bistrifluoromethyl-
3.6 g of 3,6-dioxa-8-nonenol (compound represented by the formula (7)) and 16.5 g of perfluoro (propyl vinyl ether (PPVE)) were injected using nitrogen gas, and the temperature in the system was increased to 70 ° C. Kept.

While stirring, tetrafluoroethylene (TFE) was injected so that the internal pressure became 8.5 kgf / cm ² G.

Next, a solution in which 0.15 g of ammonium persulfate was dissolved in 5.0 g of water was injected under pressure using nitrogen to start the reaction.

Since the pressure decreases with the progress of the polymerization reaction, when the pressure decreases to 7.5 kgf / cm ² G, the pressure is reduced again to 8.5 kgf / cm ² G with tetrafluoroethylene gas. Repeated.

Each time 40 g of tetrafluoroethylene gas is consumed from the start of polymerization while the supply of tetrafluoroethylene is continued, the fluorine-containing ethylenic monomer having a hydroxyl group (shown by the formula (7)) Compound)
The polymerization was continued by injecting 1.8 g of the mixture 9 times in total (16.2 g in total), and the amount of tetrafluoroethylene was 400
The feed was stopped at the time when the g had been consumed, the autoclave was cooled, and unreacted monomer was discharged. 1997 g of an aqueous dispersion were obtained. The concentration of the polymer in the obtained aqueous dispersion was 22.1%, and the particle size was 141 nm.

In the same manner as in Production Example 1, a part of the aqueous dispersion was taken and a white solid was isolated.

When the white solid obtained in the same manner was analyzed, TFE / PPVE / (a fluorine-containing monomer having a hydroxyl group represented by the formula (7)) = 98.2 / 0.7 /
1.1 mol% Tm = 314 ° C. 1% Thermal decomposition temperature Td = 366 ° C. Melt flow rate: 1.3 g / 10 min The infrared spectrum is −3620-3400 cm ⁻¹ .
Characteristic absorption of OH was observed.

Production Example 3 (P having a hydroxyl group)
Production of Aqueous Dispersion Consisting of FA) In the same autoclave as in Production Example 1, 1500 ml of pure water, 9.0 g of ammonium perfluorooctanoate, and 60 g of paraffin were placed, sufficiently purged with nitrogen gas, evacuated, and charged with 20 ml of ethane gas.

Next, perfluoro- (1,1,9,9
-Tetrahydro-2,5-bistrifluoromethyl-
3.6 g of 3,6-dioxa-8-nonenol (compound represented by the formula (7)) and 18.4 g of perfluoro (propyl vinyl ether (PPVE)) were injected by using nitrogen gas, and the temperature in the system was increased to 70 ° C. Kept.

While stirring, tetrafluoroethylene (TFE) was injected under pressure to an internal pressure of 8.5 kgf / cm ² G.

Next, a solution in which 0.15 g of ammonium persulfate was dissolved in 5.0 g of water was injected under pressure using nitrogen to start the reaction.

Since the pressure decreases with the progress of the polymerization reaction, when the pressure decreases to 7.5 kgf / cm ² G, the pressure is reduced to 8.5 kgf / cm ² G with tetrafluoroethylene gas, and the pressure is reduced and increased. Repeated.

Each time 40 g of tetrafluoroethylene gas is consumed from the start of polymerization while the supply of tetrafluoroethylene is continued, the above-mentioned fluorine-containing ethylenic monomer having a hydroxyl group (shown by the formula (7)) Compound)
Was injected 9 times in total (32.4 g in total), and the polymerization was continued.
The feed was stopped at the time when the g had been consumed, the autoclave was cooled, and unreacted monomer was discharged. 1988 g of an aqueous dispersion were obtained. The concentration of the polymer in the obtained aqueous dispersion was 22.3%, and the particle size was 85 nm.

In the same manner as in Production Example 1, a part of the aqueous dispersion was taken and a white solid was isolated.

When the white solid obtained in the same manner was analyzed, TFE / PPVE / (a fluorine-containing monomer having a hydroxyl group represented by the formula (7)) = 97.3 / 0.9 /
1.8 mol% Tm = 314 ° C. 1% Thermal decomposition temperature Td = 371 ° C. Melt flow rate: 1.1 g / 10 min The infrared spectrum is −3620 to 3400 cm ⁻¹ .
Characteristic absorption of OH was observed.

Production Example 4 (Synthesis of Aqueous Dispersion of PFA Having No Functional Group) In Production Example 1, paraffin, perfluoro- (1,
Except that 1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol) (compound of the formula (7)) was not used,
Emulsion polymerization was carried out in the same manner as in Production Example 1 to obtain 1922 g of an aqueous dispersion of PFA containing no functional group.

The concentration of the polymer in the aqueous dispersion was 21.6%, and the particle size was 156 nm.

A white solid was isolated and analyzed in the same manner as in Production Example 1.

TFE / PPVE = 99.3 / 0.7 mol% Tm = 317 ° C. 1% Thermal decomposition temperature Td = 479 ° C. Melt flow rate = 19.2 g / 10 min In the infrared spectrum, characteristic absorption of —OH was observed. Was not done.

Example 1 (1) Preparation of metal oxide sol 54 g of tetraethoxysilane, 46 g of triethoxymethylsilane and 200 g of ethanol were placed in a 500 ml beaker and stirred at room temperature for 1 hour. Next, 50 g of a 0.1N hydrochloric acid aqueous solution was added and stirred at 50 ° C. for 3 hours to obtain a silica sol solution.

(2) Preparation of coating liquid The dispersion of PFA obtained in Production Example 3 was 44.8.
87 g of the silica sol solution obtained in the above (1).
5 g was added and the mixture was stirred at room temperature for 1 hour to obtain a coating liquid.

(3) Coating The coating liquid obtained in the above (2) was coated on a Pyrex glass plate using a 10 mil applicator,
A wet coating was formed.

(4) Firing The wet coating film obtained in the above (3) was air-dried at room temperature.
After drying the water or ethanol on the glass substrate, it was baked at 250 ° C. for 60 minutes in the atmosphere to obtain a test plate having a coating of about 6 μm.

(5) Test The following test was performed on the coating liquid and the film obtained in Example 1.

Dispersion Stability of Coating Solution The coating solution obtained in the above (2) was allowed to stand at room temperature for 3 hours, and the dispersibility was observed. Was evaluated as “Δ” when the sample was cloudy, and “x” when the fluorocopolymer was partially settled or the entire solution was coagulated.

Transparency of Coating Film The haze value of the transparency of the coating film after firing obtained in the above (4) was measured by a haze meter.

Hardness of Coating A pencil hardness at room temperature was measured by a pencil scratch test according to JIS K5401.

Adhesion According to JIS K5400, 100 crosscuts were formed on the coating, and a cellophane adhesive tape was stuck on the crosscut surface. It was indicated by the remaining number of coatings / 100.

Non-adhesion test The measurement was performed at room temperature. FIG. 1 shows a schematic perspective view of a test piece used for the non-adhesion test. The test plate 1 was the test plate obtained in the above (4), the length a was 150 mm or more, and the dirt on the surface was wiped with acetone. First, an 18 mm wide adhesive tape 2 (JIS Z 1522) was
Cut off, place only the portion having a length a of 150 mm on the test plate 1, rub it with the eraser of JIS S 6050 from above the tape 2, and compress it to obtain the adhesive portion 3. A paper (not shown) was pasted on the remaining 150 mm portion to make it easy to handle. After the pressure bonding, the tape 20 was left for about 20 minutes, and the tape 20 was adapted to the test plate 1. The tape 2 was peeled off from the end of the test plate 1 to the position of the width b (25 mm).
Was attached to the lower grip of the tensile tester. The tip of the peeled tape 2 is folded back by 180 ° to the upper grip,
The tape 2 was attached so that it could be peeled straight. The force at which the tape 2 was peeled off from the test plate 1 was measured at a tensile speed of 20 mm / min using a testing machine. As the value, the average of the portion where the tape 2 was smoothly peeled was taken as the measured value.

The water repellency of the coating The contact angle with water of the coating was measured with a contact angle meter.

Abrasion Resistance Using a flannel cloth (cotton No. 300) under a load of 1.5 kg / 4 cm ² , the coating was rubbed 3,000 times, and the contact angle with water was measured in the same manner as described above.

Table 10 shows the results of the test.

Example 2 Using the aqueous dispersion of the fluorinated copolymer (A) obtained in Production Example 2, a coating liquid having the composition shown in Table 1 was prepared in the same manner as in Example 1.

Coating, baking and testing were performed in the same manner as in Example 1 except that the coating liquid was applied using a 6 mil applicator. Table 10 shows the results.

Example 3 The procedure of Example 2 was repeated except that the aqueous dispersion of the fluorinated copolymer (A) obtained in Production Example 1 was used to prepare a coating solution having the composition shown in Table 1. Preparation, application, baking and testing of a coating solution were performed. Table 10 shows the results.

Comparative Example 1 Example 1 was repeated except that the aqueous dispersion of the fluorine-containing copolymer having no functional group obtained in Production Example 4 was used to prepare a coating solution having the composition shown in Table 1. Preparation, application, baking, and testing of a coating solution were performed in the same manner as described above. Table 10 shows the results.

Comparative Example 2 Coating, sintering and evaluation were performed in the same manner as in Example 1 using only the silica sol solution to which the aqueous dispersion of the fluorine-containing copolymer was not added. Table 10 shows the results.

[0311]

[Table 10]

As is clear from the results in Table 10, the coating composition of the present invention has excellent dispersion stability, and the coating obtained from the composition is hard, transparent, non-tacky, water-repellent, and abrasion-resistant. It turns out that it is excellent.

Example 4 In place of the Pyrex glass plate in Example 1, a 1.5 mm-thick pure aluminum plate (A
Except for using 1050P), the coating liquid was adjusted, applied, and fired in the same manner as in Example 1 to form a coating on an aluminum plate. A transparent, well-designed film with a clear reflection of the underlying aluminum was obtained.

Using the above-mentioned coated plate, a test for the thickness, adhesion, non-adhesion and water repellency of the coating was carried out in the same manner as in Example 1. Further, a stain resistance and weather resistance test were conducted by the following methods.

Carbon contamination test (Preparation of carbon solution) Carbon powder (Mitsubishi Chemical Corporation)
MA100) was added to 90 g of ion-exchanged water,
The mixture was dispersed and mixed using glass beads to obtain a carbon dispersion.

(Coating of Carbon) The above-mentioned carbon dispersion was applied to the above-mentioned coated plate by spraying at about 50 g / m ^2, and 80 ° C.
For 2 hours to obtain a black test plate.

(Evaluation) The obtained black test plate was traced and washed with a brush while being exposed to running water. Then, the degree of contamination was visually observed and evaluated according to the following criteria. Table 11 shows the results.

：: Contamination can be removed by washing,
It almost returned to the painted plate before the contamination test.

Δ: Part of the contaminants could be removed by washing, but gray dirt was soaked on the entire surface of the coated plate, and the dirt could not be removed.

X: Black stains remained on the entire surface of the coated plate and could not be removed by washing with water.

Weathering test The above coated plate was put into an I-Super UV tester (manufactured by Iwasaki Electric Co., Ltd.), and an accelerated weathering test was conducted.
The adhesion angle to water of the coated plate after the time test was measured. Table 11 shows the results.

Comparative Example 3 The same aluminum plate as in Example 4 was subjected to sandblasting with 80 to 120 mesh, and then a primer (Polyflon TFE Enamel EK-195, manufactured by Daikin Industries, Ltd.)
9 DGN) by spray painting and 9 in an infrared drying oven.
After drying at 0 ° C., a primer layer was provided.

PFA powder paint (manufactured by Daikin Industries, Ltd., NEOFLON powder paint ACX-3) was formed on the primer layer.
After 1) was electrostatically coated, it was baked at 350 ° C. for 30 minutes to obtain a PFA powder coated plate on which a coating was formed. A gray-brown coating of the primer was obtained.

Further, the same test as in Example 4 was performed using the PFA powder coated plate. Table 11 shows the results.

Comparative Example 4 Zeffle GK, a varnish for a room temperature-curable fluororesin paint
510 (OH value 60, manufactured by Daikin Industries, Ltd.) 100
g, isocyanate curing agent Coronate HX, 10.5 g (manufactured by Nippon Polyurethane Co., Ltd.) and butyl acetate 120
g were mixed to prepare a clear coating paint adjusted to an OH / NCO ratio of 1: 1.

An aluminum plate subjected to sand blasting in the same manner as in Comparative Example 3 was spray-coated with the coating material for clear coating, and then baked at 120 ° C. for 30 minutes to obtain a coated plate. The same test as in Example 4 was performed using the coated plate. Table 11 shows the results.

Comparative Example 5 Acrydic A801, a varnish for an acrylic resin coating at room temperature, (OH value 100, manufactured by Dainippon Ink Co., Ltd.)
100 g, 17 g of isocyanate curing agent Coronate HX (same as Comparative Example 4) and 120 g of butyl acetate were mixed.
A paint was prepared in which the H / NCO ratio was adjusted to 1: 1. In the same manner as in Comparative Example 4, an aluminum plate was spray-coated and fired using this paint to obtain a coated plate on which a coating was formed.

The same test as in Example 4 was performed using the coated plate. Table 11 shows the results.

[0329]

[Table 11]

[0330]

The present inventors have proposed a coating composition obtained by introducing the above-mentioned specific functional group into a fluorine-containing copolymer and combining it with a metal oxide and a solvent, and a coating film obtained using the same. The following effects were found for

The fluororesin inherently has low affinity for water and solvents, and even in the dispersion of fluororesin fine particles containing an emulsifier, it becomes unstable and often coagulates by adding it to the solvent. By introducing a specific functional group as described above, the dispersion stability of the dispersion of the functional group-containing fluorine-containing ethylenic polymer (A) is improved, and an alcohol-based solvent such as used in the coating composition of the present invention. A stable composition without coagulation was obtained.

In the preparation of the metal oxide sol (B-1) solution and in the condensation polymerization process after hydrolysis, the functional group of the functional group-containing fluorine-containing ethylenic polymer (A) is Partially involved in the reaction with B-1), the dispersion stability of the metal oxide sol (B-1) and the functional group-containing fluorine-containing ethylenic polymer (A) was improved.

In the process of further proceeding the polycondensation of the metal oxide (B) in the firing step after coating, the same reaction as described above occurs, and the functional group-containing fluorinated ethylenic polymer (A) in the film is bonded to the film. Dispersibility with metal oxide (B) (gel), interfacial adhesion, and adhesion to a substrate were improved.

As described above, the coating comprising the functional group-containing fluorinated ethylenic polymer (A) and the metal oxide (B) can be applied not only to glass but also to various other materials such as metals, resins and ceramics. To provide a composite material suitable for a building material firmly bonded to various base materials.

As a result, the composite material for building materials of the present invention has a coating having excellent adhesion on its surface, and has not only water repellency and transparency, but also weather resistance, antifouling property, non-adhesiveness, It can provide properties such as heat resistance, chemical resistance, low friction, low refraction, and anti-reflection, and can add a great deal of added value to various building materials.

[Brief description of the drawings]

FIG. 1 is a schematic perspective view of a test piece subjected to a non-adhesion test in an example of the present invention.

[Explanation of symbols]

 1 Test plate 2 Adhesive tape 3 Adhesive part

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masahiro Kumegawa 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (72) Inventor Noritoshi Oka 1-1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin (72) Inventor Tetsuo Shimizu 1-1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industry Co., Ltd. Yodogawa Works

Claims (65)

[Claims] 1. A method for producing a functional group-containing fluorine-containing ethylenic monomer having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylate, a carboxyester group and an epoxy group. 0.05 to 50 mol% of at least one monomer and 50 to 99.95 mol% of at least one monomer of the fluorine-containing ethylenic monomer having no functional group (b) A composite material for a building material having a coating on the surface of a base material in which fine particles of a functional group-containing fluorine-containing ethylenic polymer (A) obtained by copolymerization are dispersed in a metal oxide (B) layer. 2. The functional group-containing fluorine-containing ethylenic monomer (a) is represented by the formula (1): CX ₂ ＣCX ¹ -R _f -Y (1) (where Y is -CH ₂ OH,- COOH, carboxylate, carboxyester group or epoxy group, X and X ¹ are the same or different, and are a hydrogen atom or a fluorine atom,
R _f is a divalent fluorinated alkylene group having 1 to 40 carbon atoms,
A fluorine-containing oxyalkylene group having 1 to 40 carbon atoms, a fluorine-containing alkylene group containing an ether group having 1 to 40 carbon atoms or a fluorine-containing oxyalkylene group containing an ether bond having 1 to 40 carbon atoms) The composite material for building materials according to claim 1, which is a kind of fluorine-containing ethylenic monomer containing a functional group. 3. The building material composite according to claim 1, wherein the fluorine-containing ethylenic monomer having no functional group (b) is tetrafluoroethylene. 4. The method according to claim 1, wherein the fluorine-containing ethylenic monomer (b) having no functional group is tetrafluoroethylene 85-9.
9.7 mol% and the formula (2): CF ₂ ＣＦCF—R _f ¹ (2) (where R _f ¹ is CF ₃ or OR _f ² (R _f ² is carbon number 1 to
5 perfluoroalkyl group)
The composite material for a building material according to claim 1 or 2, which is a mixed monomer of up to 15 mol%. 5. The fluorinated ethylenic monomer having no functional group (b) is a tetrafluoroethylene 40-80.
The composite material for building materials according to claim 1 or 2, which is a mixed monomer of mol%, 20 to 60 mol% of ethylene, and 0 to 15 mol% of other copolymerizable monomers. 6. The building material composite according to claim 1, wherein the metal oxide (B) is an oxide of silicon. 7. The composite material for building materials according to claim 1, wherein said metal oxide (B) is an oxide of aluminum. 8. The composite material for building materials according to claim 1, wherein said metal oxide (B) is an oxide of titanium. 9. The substrate according to claim 2, wherein the substrate is a metal-based substrate.
5. The composite material for building materials according to any one of 5. 10. The composite material for building materials according to claim 2, wherein said base material is a synthetic resin base material. 11. The composite material for building materials according to claim 10, wherein said synthetic resin base material is transparent. 12. The composite material for building materials according to claim 10, wherein said synthetic resin base is made of polycarbonate. 13. The building material composite according to claim 10, wherein the synthetic resin substrate is artificial marble. 14. The composite material for building materials according to claim 2, wherein said base material is a non-metallic inorganic base material. 15. The building material composite according to claim 14, wherein the nonmetallic inorganic base material is made of glass. 16. The composite material for building materials according to claim 14, wherein said non-metallic inorganic base material is made of concrete. 17. The building material composite according to claim 14, wherein the non-metallic inorganic base material is made of cement. 18. A building exterior member using the building material composite material according to claim 1. Description: 19. A curtain wall using the composite material for building materials according to claim 1. 20. A roofing member using the composite material for building materials according to claim 1. 21. A roofing tile using the composite material for building materials according to claim 1. 22. A roofing material using the composite material for building materials according to claim 1. 23. A window member using the composite material for building materials according to claim 1. 24. Sashes using the composite material for building materials according to claim 1. 25. A gutter using the composite material for building materials according to claim 1. 26. Exteriors using the composite material for building materials according to claim 1. Description: 27. An opening using the composite material for building materials according to claim 1. 28. An outer fence using the composite material for building materials according to claim 1. 29. A member for a building interior using the composite material for a building material according to claim 1. Description: 30. A wall material using the composite material for building materials according to claim 1. 31. A flooring comprising the composite material for building materials according to claim 1. 32. A ceiling made of the composite material for building materials according to claim 1. 33. A construction material using the composite material for building materials according to claim 1. Description: 34. An interior door using the composite material for building materials according to claim 1. 35. A blind using the composite material for building materials according to claim 1. 36. Housing equipment using the composite material for building materials according to claim 1. 37. Bath-toiletries using the composite material for building materials according to claim 1. 38. A washstand using the composite material for building materials according to claim 1. 39. A toilet using the composite material for building materials according to claim 1. 40. A bathtub using the composite material for building materials according to claim 1. 41. A kitchen member using the composite material for building materials according to claim 1. 42. A system kitchen using the composite material for building materials according to claim 1. 43. A gas table using the composite material for building materials according to claim 1. 44. A range hood using the composite material for building materials according to claim 1. 45. An elevator using the composite material for building materials according to claim 1. 46. An escalator using the composite material for building materials according to claim 1. 47. A construction material for civil engineering using the composite material for construction material according to claim 1. 48. A road construction member using the composite material for building materials according to claim 1. 49. A soundproof wall for road construction, comprising the building material composite material according to claim 1. Description: 50. A road construction sign using the composite material for building material according to claim 1. 51. A guardrail for road construction using the composite material for building materials according to claim 1. 52. A traffic signal cover for road construction, comprising the building material composite material according to claim 1. 53. A road construction light cover using the composite material for building material according to claim 1. Description: 54. A water and sewage facility member using the composite material for building materials according to claim 1. 55. A bridge member using the composite material for building materials according to claim 1. 56. A railway facility member using the composite material for building materials according to claim 1. 57. A bolt for a railway facility using the composite material for building materials according to claim 1. 58. A traffic signal cover for a railway facility using the composite material for building materials according to claim 1. 59. An overhead line for a railway facility using the composite material for building materials according to claim 1. 60. A steel tower for a railway facility using the composite material for building materials according to claim 1. 61. A member for an electric power facility using the composite material for a building material according to claim 1. Description: 62. A glass for an electric power facility using the composite material for building materials according to claim 1. 63. A utility pole for a power facility using the composite material for building materials according to claim 1. 64. An arm for a power facility using the composite material for building materials according to claim 1. 65. A member for a chemical plant using the composite material for building materials according to claim 1.