JPH10272718A - Antifouling composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifouling composite material obtained by rigidly adhering a film having excellent antifouling, heat resistance, water repellence, wear resistance, flaw resistance and transparency, and high hardness to a base material. SOLUTION: A film in which fine particles of a functional group-containing fluoroethylenic polymer obtained by copolymerizing 0.05 to 50 mol.% of functional group-containing fluoroethylenic monomer having at least one type of hydroxy group, carboxyl group, carboxylate and carboxyester group and 50 to 99.95 mol.% of fluoroethylenic monomer having no functional group are dispersed in a metal oxide layer is provided on a surface of a base material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention is particularly excellent in antifouling properties, and further excellent in heat resistance, transparency (design), non-adhesion and water / oil repellency, as well as adhesion to substrates and hardness. In addition, the present invention relates to an antifouling composite material having a coating film in which fine particles of a fluoropolymer are dispersed in a metal oxide layer on the surface of a substrate.

[0002]

2. Description of the Related Art For exterior building materials such as outer walls and roofs, interior building materials such as inner walls, ceilings and floors, and architectural building materials such as exteriors, cooking equipment or tableware that processes and heats food due to adhesion of dust and fumes. Due to the adhesion of food oil or office equipment that uses toner, such as electrostatic copying machines, toner and fingerprints, and household appliances such as ventilation fans due to dust, cigarette dust and oil adhesion Since the function and aesthetic appearance of the device are impaired, it is required to use an antifouling material in a portion where such adhesion is possible.

[0003] In response to such demands, for example, conventionally, for example, building materials such as architectural glass, various inner and outer wall materials, roofing materials and interior and exterior materials, signs, traffic lights, card rails, telephone poles and soundproof walls, etc. Civil engineering materials are exposed to the environment and surroundings, so their surfaces have weather resistance, dust, antifouling properties against exhaust gas and rain streaks, transparency,
Designability is required. In addition, household equipment such as various furniture, kitchen housing such as gas table and range hood, system kitchen, wash basin, toilet and bathroom,
There is a demand for heat resistance, non-adhesion to oil, burning and scale, and antifouling properties. 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. There are some that do not, but in response to the above request, composite materials used for building materials have been added to heat resistance, chemical resistance, corrosion resistance, weather resistance, surface characteristics (non-adhesive, low friction, etc.), electrical insulation, etc. Excellent fluoropolymers have been applied to the surface of various building materials. 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 Etching by electrochemical method,
It is necessary to provide unevenness on the surface and perform bonding 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, there is an uneven surface on the substrate as in (2). 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 coating made of a fluoropolymer to impart hardness, but the coating 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 fields requiring non-stickiness.

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 film, and the non-adhesiveness and the water repellency are reduced by abrasion. Further, the fluoroalkyl group-containing silane compound and the condensate itself have a problem in that they have insufficient heat resistance and deteriorate over time and cannot maintain non-adhesiveness or water repellency.

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 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 are agglomerated 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.

The interfacial adhesion between the metal oxide and the fluororesin particles in the obtained coating film is weak, the fluororesin particles fall off in the abrasion resistance test, and the non-adhesion and water repellency decrease.

That is, according to the conventional sol-gel method,
No antifouling film having excellent transparency and excellent abrasion resistance, heat resistance, water / oil repellency and scratch resistance has not been obtained.

[0016]

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 an antifouling composite material having a coating made of a metal oxide layer in which the fine particles are uniformly dispersed on the surface of a substrate.

Further objects of the present invention are, in particular, abrasion resistance,
An object of the present invention is to provide an antifouling composite material having excellent scratch resistance and transparency (design), and having sufficient hardness.

[0018]

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 an antifouling composite 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 with a metal oxide (B) are dispersed in a metal oxide (B) layer. .

Further, in the present invention, the functional group-containing fluorinated ethylenic monomer (a) is represented by the formula (1): CX ₂ = CX ¹ -R _f -Y (1) (wherein Y is -CH ₂ OH, —COOH, a carboxylate, 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) The present invention relates to the above-mentioned antifouling composite material, which is a kind of functional group-containing fluorine-containing ethylenic monomer.

[0020] The present invention also relates to the antifouling composite material, wherein the fluorine-containing ethylenic monomer (b) having no functional group is tetrafluoroethylene.

In the present invention, the fluorine-containing ethylenic monomer (b) having no functional group is composed of 85 to 99.7 mol% of tetrafluoroethylene and a compound represented by the following 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 1)
5 perfluoroalkyl group)
The present invention relates to the above antifouling composite material, which is a mixed monomer of up to 15 mol%.

The present invention also relates to a fluorine-containing ethylenic monomer (b) having no functional group, comprising 40 to 80 mol% of tetrafluoroethylene, 20 to 60 mol% of ethylene and another copolymerizable monomer. The present invention relates to the antifouling composite material, which is a monomer mixture with 0 to 15 mol% of a monomer.

The present invention also relates to the antifouling composite material, wherein the metal oxide (B) is an oxide of silicon.

The present invention also relates to the antifouling composite material, wherein the metal oxide (B) is an oxide of aluminum.

The present invention also relates to the antifouling composite material, wherein the metal oxide (B) is an oxide of titanium.

Further, the present invention relates to the antifouling composite material, wherein the base material is a metal base material.

[0027] The present invention also relates to the antifouling composite material, wherein the base material is a non-metallic inorganic base material.

Examples of the non-metallic inorganic substrate include glass, concrete, cement, tile and ceramic plate.

Further, the present invention relates to the antifouling composite material, wherein the substrate is a synthetic resin substrate.

[0030]

DETAILED DESCRIPTION OF THE INVENTION As a result of repeated studies to achieve the above objects, the present inventors have been able to obtain a coating having antifouling properties and improved water repellency, abrasion resistance and scratch resistance. Further, they have found that they have excellent adhesion to various substrates.

The antifouling composite material of the present invention comprises (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 30 mol% of at least one monomer of the fluorine-containing ethylenic monomer and (b) at least one monomer 70 of the fluorine-containing ethylenic monomer having no functional group To 99.95 mol% of a fluorine-containing ethylenic polymer (A) having a functional group obtained by copolymerization in a metal oxide (B) layer serving as a matrix. It is formed in.

The functional group-containing fluoropolymer (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 antifouling property, chemical resistance, non-adhesion, low friction property and weather resistance of the fluoropolymer. It also has excellent properties such as water-repellency and oil-repellency, and can be provided without deteriorating these excellent properties.

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

The functional group of the functional group-containing fluorine-containing ethylenic polymer (A) includes 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) that can be used in the present invention is, specifically, (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 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 and water repellency of the copolymer obtained by copolymerization are not significantly reduced.

Among them, the monomers represented by the formulas (3) and (5) are preferred in view of their copolymerizability with other fluorine-containing ethylenic monomers and the 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.

[0041]

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And the like.

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

[0044]

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And the like.

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

[0047]

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And the like.

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

[0050]

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And the like.

As other monomers,

[0053]

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And the like.

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

Specific examples of the fluorine-containing ethylenic monomer include tetrafluoroethylene, formula (2): CF ₂ ＣＦCF—R _f ¹ —Y (2) wherein R _f ¹ is CF ₃ or OR _f ² (R _f ² has 1 to 1 carbon atoms)
5), hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, perfluoro (alkyl vinyl ether) s, hexafluoroisobutene,

[0057]

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), a fluorine atom is added as long as the non-adhesion, heat resistance and water repellency are not reduced. An ethylenic monomer having no ethylenic monomer may be copolymerized. In that case, the ethylenic monomer having no fluorine atom is preferably selected from ethylenic monomers having 5 or less carbon atoms in order not to reduce non-adhesion, heat resistance and water repellency. Examples include ethylene, propylene, 1-butene, 2-butene and the like.

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%.

If the content of the functional group-containing fluorinated 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) ) May fall off, reducing non-adhesiveness and water repellency.

On the other hand, 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 Non-adhesive, water repellency is lost, heat resistance is reduced,
When baked at a high temperature, it is thermally decomposed, and is liable to cause coloring, foaming, defective coating such as pinholes, and a decrease in water repellency.

Preferred examples of the functional group-containing fluorine-containing ethylenic polymer (A) for imparting non-tackiness used in the present invention are shown below together with other characteristics.

(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 low friction.

(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 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 properties and further excellent in transparency and mechanical properties.

Further, the functional group-containing fluorine-containing ethylenic polymer given as a specific example has a high melting point of 200 ° C. or more and the 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 fluorine-containing ethylenic polymer (A) which can be used in the present invention comprises the above-mentioned functional group-containing fluorine-containing 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 the 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, a metal selected from Si, Al, Ti or Zr is particularly preferable because it is transparent, has high hardness and can form a coating having high durability. .

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. Conversely, if the amount is too small, the excellent performance inherent in the fluororesin, such as water repellency, non-adhesiveness, and antifouling properties, is reduced.

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

The metal of the metal-based substrate includes metals and alloys of two or more metals, and metal salts such as metal oxides, metal hydroxides, carbonates and sulfates. Among them, metals, metal oxides, and alloys are more preferable in terms of adhesiveness.

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, as the iron-based metal, 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 obtained by plating the surface 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 nonmetallic inorganic base material include glass, concrete, cement, tile, porcelain plate, porcelain, 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 substrate include acrylic resin, polycarbonate, artificial marble, heat-resistant engineering plastic, and thermosetting resin.

As the base material of the antifouling composite material 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.

The non-metallic inorganic base materials include glass base materials such as crystallized glass, foamed glass, heat-reflective glass, heat-absorbing glass, and multi-layer glass; and ceramic-based materials 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 base material, polycarbonate, polyester resin, acrylic resin, vinyl chloride resin, artificial marble (based mainly on unsaturated polyesters and acrylics), other vinyl chloride resins, acrylic resins or urethanes Painted steel plates coated with resin are used.

Of these, glass, which is a nonmetallic inorganic base material, and acrylic resin, polycarbonate, or the like, which is a synthetic resin base material, are usually used in portions where transparency is required.

In the present invention, the shape of the substrate 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 location of the equipment or equipment to be applied.
0 μm, preferably 0.01 to 70 μm,
Particularly preferably, it is 0.02 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 to prepare the metal oxide sol (B-1) 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, a functional group-containing fluorine-containing ethylenic polymer (A), a 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 cooking appliance, but the functional group-containing fluorine-containing ethylenic polymer (A) and the metal oxide sol (B-
1 to 85% by volume of the polymer (A) based on the total amount of 1),
The metal oxide sol (B-1) is 15 to 99% by volume, the polymer (A) is 5 to 75% by volume, and the metal oxide sol (B-
1) More preferably, the content is 25 to 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 metal oxide film after application. Especially antifouling properties, abrasion resistance,
A coating excellent in water repellency can be provided.

The average particle size of the fine particles of the functional group-containing fluorine-containing ethylenic polymer (A) is 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 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, the fine particles of the functional group-containing fluorine-containing ethylenic polymer (A) are evenly distributed to the inside of the film. The fluororesin exhibits excellent antifouling properties, water repellency and the like to the inside of the coating, and does not deteriorate its properties.

The calcination is preferably carried out at a temperature equal to or lower than the melting point of the functional group-containing fluorinated ethylenic polymer (A) in order to uniformly disperse the particles in the metal oxide film. However, when a material having a high melt viscosity and not melting (for example, PTFE) is used as fine particles, firing can be performed at a temperature higher 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 hydrolysis and condensation reactions. 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 Object (B-
1) a coating liquid preparation step of preparing a coating liquid by mixing a sol and 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 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.

(Preparation of Metal Oxide Sol Solution) The metal oxide sol is prepared by hydrolyzing the corresponding metal alkoxide, metal acetyl acetate, metal carboxylate, metal nitrate, metal chloride or two or more of these. It can be prepared by 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, etc.), metal acetyl is used. Carboxylates such as acetate and metal acetate, oxyacid salts and the like can be used.

When there is no 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 valency 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 a 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,

[0116]

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.

The inorganic metal compounds 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 to form metal oxide particles, and the metal oxide sol (B-1) solution is available.

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 to be used, the target degree of polymerization of the sol, and the like, but is generally room temperature to 100 ° C., preferably room temperature. The solid content is preferably 0.5 to 50% by weight.

In some cases, hydrolysis and polycondensation are gradually carried out 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 Functional Group-Containing Fluorinated Ethylene Polymer Aqueous Dispersion) 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) The metal compound is hydrolyzed and polycondensed in an alcohol solution containing an aqueous dispersion containing fine particles of the 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 reported 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.

(Applying Step) The above-mentioned base material is applied according to the type and site of the equipment which requires antifouling property. 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 calcination depends on the purpose, application and the 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 fluorine resin 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 antifouling composite material of the present invention can be produced.

The antifouling composite material often requires further water repellency. Therefore, the fine particles of the functional group-containing fluorinated ethylenic polymer (A) are used as fine particles of the functional group-containing fluorinated ethylenic polymer (A). It is preferable to use a coating composition having water repellency, including those having a water contact angle of 80 ° or more, particularly 95 ° or more. Further, in order to maintain the shape of the water-repellent fine particles in the coating made of the metal oxide (B) and the water-repellent fine particles of the functional group-containing fluorine-containing ethylenic polymer (A), a high-temperature baking step is required. A fluorine-containing copolymer which does not thermally decompose or melt is preferred, and more specifically, one having a melting point of 150 ° C. or higher, preferably 200 ° C. or higher, particularly preferably 250 ° C. or higher is used.

Particularly, the functional group-containing fluorine-containing ethylenic polymer (A) which gives a film excellent in antifouling property and water repellency includes:
Specifically, the above-mentioned reactive PTFE, reactive PF
A, reactive FEP, and reactive ETFE are preferred.

The content of the functional group in the 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 can firstly maintain excellent antifouling properties for a long period of time.
Secondly, the fine particles of the functional group-containing fluorine-containing ethylenic polymer (A) are uniformly dispersed in the coating made of the metal oxide (B) with good interfacial adhesion, and the coating has sufficient hardness, transparency and Third, because of the adhesiveness, the coating comprising the fine particles (B) of the functional group-containing fluorine-containing ethylenic polymer (A) has good heat resistance, weather resistance, abrasion resistance, scratch resistance, and non-tackiness. Since it has water repellency, antibacterial property, etc., it can be used for various devices, instruments, building materials and the like.

[0140] Preferable equipment and instruments, building materials and parts thereof to which the antifouling composite material of the present invention can be used are specifically listed below according to their fields, but are not limited thereto.

[1] Cooking Equipment and Cooking Utensils (Including Tableware) Cooking equipment and utensils often use adhesive oils and foodstuffs, and are particularly required to have antifouling properties. Hereinafter, representative examples thereof will be given, but the present invention is not limited thereto.

Jar and Pot (a) The inner surface and inner lid of an electric pot including an electric water heater and the like.

In these, the antifouling property (to scale), hot water resistance and antibacterial property of the antifouling composite material of the present invention can be particularly effectively utilized.

(B) Gas and electric rice cookers, and inner surfaces and inner lids of rice cookers having a rice washing mechanism.

In these, the antifouling property (against rice grains and scorching) and the heat resistance of the antifouling composite material of the present invention can be particularly effectively utilized. Can reduce performance deterioration due to abrasion, scratching, etc.

Cooking equipment (a) Frying pans, bats, manual mixers for cooking and household use, surfaces such as caskets, knives, bread moulders, bread reverse sheets, bread splitting rounders and the like, and inner surfaces such as balls and rice bins, In the case of a mixer, its wings.

In these, the antifouling property (to combustible and sticky dirt) and heat resistance of the antifouling composite material of the present invention can be particularly effectively utilized. In addition, performance degradation due to abrasion or damage by a metal spatula or the like can be improved.

(B) Household electric food crusher, electric food crusher, kitchen electric meat grinder, kitchen electric blender, electric food processor such as kitchen electric mixer, etc., inner surface and blades.

In these, the antifouling property (for vegetables and meat juices) of the antifouling composite material of the present invention can be particularly effectively utilized.

Gas table (a) Top plate, side surface, surface of gas stove such as gas stove with a built-in gas cylinder, and the surface of their juice tray cover.

In these, the antifouling property (with respect to oil stains), heat resistance, and transparency (designability with respect to color, pattern, etc.) of the antifouling composite material of the present invention can be particularly effectively utilized. In addition, it is possible to improve the performance deterioration due to abrasion and damage when polished with a scourer or the like.

Microwave ovens including toasters, ranges, etc. (a) Ovens such as commercial ovens, electric ovens (including commercial ones), electric ovens with a refrigerator for commercial use, commercial cooking ovens, commercial cooking ovens, etc. Kitchen ovens), commercial baking ovens, automatic ovens for home use such as baking ovens, toasters, electric oven toasters such as bread toasters, and commercial microwave ovens.
The inner surface (metal part) of a microwave oven such as a microwave oven and a pan for a microwave oven.

In these, the antifouling property (to oil and scorch) and heat resistance of the antifouling composite material of the present invention can be particularly effectively utilized, and further, wear and scratches caused by a spatula or scourer can be used. Can be improved.

(B) The inner surfaces of the doors of the microwave ovens described in (a) above.

In these, the antifouling property, heat resistance and transparency of the antifouling composite material of the present invention, and in the case of a microwave oven, the energy ray resistance can be particularly effectively utilized.

Pots and Pots (a) Pots such as glass pots, enamel pots, aluminum pots, electric frying pans, electric tempura pots, electric pressure pots and electric pressure stew pots, and inner surfaces of pots and the like.

In these, the antifouling properties of the antifouling composite material of the present invention (burning and sticking dirt, oil in the case of the above-mentioned frying pan and tempura pan) and heat resistance are particularly effectively utilized. Can be further improved, and wear and damage caused by a spatula or scourer can be improved.

(B) Pots and pot lids mentioned in (a) above.

In these, in addition to the above-mentioned properties (a) of the antifouling composite material of the present invention, transparency can be particularly effectively utilized.

Garbage disposal machine The inside of a cooking waste (waste) treatment machine such as a household cooking waste disposal machine and a food waste composting device.

In these, the antifouling property of the antifouling composite material of the present invention can be particularly effectively utilized.

Other heating cooking equipment (a) Heating surface of hot plate, lid, etc.

In these, the antifouling properties of the antifouling composite material of the present invention (to combustible and sticky dirt),
The heat resistance and the transparency of the lid can be particularly effectively utilized, and the deterioration in performance and the deterioration of appearance due to abrasion with a metal spatula or scratches can be improved.

(B) A cooking surface of an electromagnetic cooker such as an electromagnetic range and a stove.

In these, the antifouling property, heat resistance and transparency possessed by the antifouling composite material of the present invention can be particularly effectively utilized, and abrasion and scratches caused by scouring can be improved.

(C) An inner surface of an electric steamer such as a commercial food steamer, a door inner wall and a lid.

In these, the antifouling property, heat resistance and steam resistance of the antifouling composite material of the present invention can be particularly effectively utilized, and wear and scratches caused by scouring can be improved.

(D) The inner surface and lid of a boiled noodle bowl for business use.

In these, the antifouling property, heat resistance and hot water resistance of the antifouling composite material of the present invention can be utilized particularly effectively, and abrasion and damage due to scouring can be improved.

(E) The inner surface, inner surface (metal portion), inner surface of door, bread for cooking range, etc. of a commercial cooking and cooking appliance.

[0171] In these, the antifouling property (for scorching and sticking dirt) and heat resistance of the antifouling composite material of the present invention can be particularly effectively utilized, and abrasion and scratching due to scouring can be improved. .

(F) Inner surfaces of commercial tableware, dishwashers and the like.

In these, the antifouling property and hot water resistance of the antifouling composite material of the present invention can be particularly effectively utilized.

(G) The inner surface of the commercial storage and the inner surface of the door.

In these, the antifouling property, transparency and heat resistance of the antifouling composite material of the present invention can be particularly effectively utilized.

Other cooking appliances to which the antifouling composite material of the present invention can be preferably applied include the following.

[0177] Examples of the above range (b) include porridge cookers and rice warmers.

[0178] As those in the range of the above (a), various cooking utensils (for thin slices, etc.), cooking utensils, cooking machinery and appliances, cooking devices (for foods, etc.), cooking iron plates, cooking appliances and equipment, barbecue utensils , Food processing machinery / equipment (e.g., with a pressurizing device), chocolate manufacturing machine and associated temperature control equipment for raw material processing.

Examples of the range (b) include a synthetic cooker, a vegetable slicer, a food slicer, a peeler, a rhinoceros cutter, a food cutter, a meat chopper, a meat slicer, a meat tenderizer, a cutter mixer, a mixer, and a food mixer. , Bren,
Apple cooking machine, continuous egg breaking machine, tofu cutting food molding machine, breading machine, vegetable washing machine, etc.

The above range includes a low range,
Table stove, electric range, gas range, gas table, electric table, etc.

Examples of the above-mentioned range include a gas salamander, an electric salamander, a convection oven, and a boiler.

Examples of the above range include a wok, a one-handed pan, a two-handed pan, a gas fryer, a tempura fryer, an oil filter unit, a buckwheat pan, and a rotating pan.

Examples of the above range include a gyoza, an electromagnetic low range, a gas evaporator, and a steam evaporator.

[2] OA-Related Equipment In addition to the parts that use toner, OA-related equipment has many parts that are particularly susceptible to dirt caused by cigarette smoke, dust, fingerprints, dust, and the like. Hereinafter, representative examples thereof will be given, but the present invention is not limited thereto.

(1) Electronic copiers, facsimile machines, word processors, printers, and other devices having a printing function It is preferable to use toner or as a material for a portion to which toner can adhere. For example:

Fixing Roll (a) Monochrome Substrate: Made of Aluminum or SUS The use of the composite material of the present invention composed of the above-described substrate provides anti-fouling properties
It is possible to obtain a fixing roll with excellent durability and heat resistance,
Since the functional group-containing fluoropolymer itself has excellent adhesiveness, it is not necessary to provide a primer, and the processability is excellent.

(B) Color / monochrome substrate: A metal coated with silicon rubber or urethane rubber, and coated with release silicone oil. ,
It is possible to obtain a fixing roll having excellent release properties, elasticity, and abrasion resistance of paper, and since the functional group-containing fluoropolymer has excellent adhesiveness, it is not necessary to provide a primer layer. Excellent workability.

Pressure roll (for both color and monochrome) Substrate: a metal coated with silicon rubber or urethane rubber.
A pressure roll with excellent elasticity and wear resistance can be obtained.
In addition, the functional group-containing fluoropolymer itself does not need to be provided with a primer layer, and is excellent in adhesiveness, so that the processability is good.

Charging roll (for both color and monochrome) Base material: urethane rubber When the composite material of the present invention comprising the above base material is used, antifouling properties and
It is possible to obtain a charged roll with excellent controllability of conductivity, uniformity of resistance value, releasability of paper and abrasion resistance.Because the functional group-containing fluoropolymer itself has excellent adhesiveness, a primer layer is required. It is not necessary to provide them, and the manufacturing processability is good.

Transfer Roll (Common for Color and Monochrome) Substrate: Made of Urethane Rubber The use of the composite material of the present invention composed of the above-mentioned substrate provides anti-fouling properties.
A transfer roll with excellent controllability of conductivity, uniformity of resistance value, releasability of paper, abrasion resistance and elasticity can be obtained, and a primer layer because the functional group-containing fluoropolymer has excellent adhesiveness Need not be provided, and the manufacturing processability is good.

Transfer Belt (Common for Color / Monochrome) Substrate: Made of Polyimide When the composite material of the present invention composed of the above substrate is used, the antifouling property
It is possible to obtain a transfer belt with excellent controllability of conductivity, uniformity of resistance value and abrasion resistance.Because the functional group-containing fluoropolymer itself has excellent adhesiveness, there is no need to provide a primer layer. Excellent workability.

Separating claw and fixing bearing (surface) Base material: made of heat-resistant resin (eg, polyphenylene sulfide (PPS), polyamide imide, polyether imide, polyoxymethylene (POM), polyether ether ketone (PEEK), etc.) The use of the composite material of the present invention comprising the above substrate, antifouling properties,
Separating claws with excellent abrasion resistance and paper feedability, which do not scratch the roll, and fixing bearings with low friction, abrasion resistance and heat resistance can be obtained, and the functional group-containing fluoropolymer adheres to the adhesive. Since it has excellent properties, it does not require a primer layer and has excellent processability.

Discharge Roller and Discharge Guide Substrate: Resin (for example, PPS, polyamide imide, polyether imide, POM or PEEK, etc.) When the composite material of the present invention comprising the above substrate is used, the antifouling property is improved. ,
A discharge roller and a discharge guide having excellent abrasion resistance can be obtained. Since the functional group-containing fluoropolymer has excellent adhesiveness, it does not require a primer layer and has excellent processability.

Further, the composite material of the present invention can be used for the following parts for OA-related equipment by utilizing its good transparency.

CRT, liquid crystal panel and plasma display (front) Base material: glass Fluoropolymer containing functional group: reactive PFA or FE
P or reactive ETFE Application form: paint When this composite material is used, it is possible to obtain a cathode ray tube, a liquid crystal panel and a plasma display having excellent transparency, antifouling property against dust and fingerprints, and it is necessary to provide a primer layer. It is excellent in manufacturing processability.

Contact Glass (Surface) Substrate: Glass When the composite material of the present invention comprising the above substrate is used, transparency,
It is possible to obtain a contact glass with excellent antifouling properties against dust and fingerprints, correction liquid, ink, etc., and it is not necessary to provide a primer layer because the functional group-containing fluoropolymer has excellent adhesiveness Excellent in processability.

[3] Building Materials For building materials, there are material facilities that are required to have antifouling properties. Hereinafter, examples of each building material will be described while referring to the effects achieved in addition to the antifouling property.

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

In these, the transparency, non-adhesion and flame retardancy of the composite material 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, architectural metal interior / exterior panels, 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, etc.

(E) Metal ceiling boards, metal floor tiles, metal wall boards coated with vinyl chloride decorative sheets on their surfaces, and the like.

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

In these, the weather resistance, non-adhesiveness, and transparency (design) of the composite material of the present invention can be particularly effectively used.

Outer wall material, roof material and interior / exterior material (made of non-metallic inorganic material) (a) Concrete block to which segmented or tiled or sliced natural stone is pasted, concrete pavement plate having segmented 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) Building 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) Roofing materials such as ceramic roofing 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 of the present invention has weather resistance, non-adhesiveness, waterproofness, transparency (design), workability, adhesiveness, and (c) further has abrasion resistance, and With respect to (g) and (h), the weathering prevention property can be used particularly effectively.

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 materials with 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 washrooms, shower rooms, toilet rooms, toilets, portable simple toilets, and simple public toilets.

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

In these, the weather resistance, non-adhesion, transparency (design), water resistance, workability, and adhesion of the composite material of the present invention can be particularly effectively utilized.

Exterior wall material and roof material (wood) (a) Wood for construction of household tools, veneer board, wood panel for construction such as wood panel, decorative board, etc.

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

(C) A wooden building material obtained by attaching a rubber elastic material to the back surface of a plywood.

(D) Wooden architectural assembly set.

Also in these, the weather resistance, non-adhesion, transparency (design), water resistance,
Workability and adhesion 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.

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

Also in these, the non-adhesiveness, transparency (design), water resistance, and workability of the composite material of the present invention, and the above (c), the adhesiveness of paper, anti-adhesion property, adhesiveness, and abrasion resistance are further examined. It can be used particularly effectively.

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

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

In these, the non-adhesiveness, workability and adhesion of the composite material of the present invention can be particularly effectively utilized.

Housing equipment (a) A system kitchen including a 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 window-type wash basins.

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

In these, the non-adhesiveness, design (transparency), workability, abrasion resistance and antibacterial properties of the composite material of the present invention can be effectively utilized.

(E) Lining used in bathrooms including shower stalls, home saunas and commercial sauna baths, bathtubs such as simple bathtubs and bathtubs with bubble generators, handles attached to bathtubs, bathrooms such as soap storage furniture.

(F) Other escalators, elevators (including those for private houses), etc.

In these, the non-adhesiveness, design (transparency), workability, and heat resistance of the composite material for building materials of the present invention are further improved with respect to (a), (b) and (e).
The wear resistance of (c) to (e) can be more effectively utilized, and the lubricity or rust prevention of (f) can be utilized more effectively.

Civil engineering (a) Signs such as signs for bus stops, signs for streets, and signs for mounting guardrails.

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

(C) Guardrails made of various base materials.

(D) Electric poles made of various base materials.

(E) Soundproof walls.

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

In these, the weather resistance, non-adhesiveness, transparency, workability, and adhesion of the composite material of the present invention, and the releasability of (f) can be particularly effectively utilized.

[4] Automobile Related Equipment (Including Motorcycles, etc.) It is possible to prevent dirt, mud, dust, oil, etc. from contaminating exterior members such as a vehicle body and a window glass by air. The same effect can be obtained for the interior as in the above-mentioned house. In addition, similar effects are obtained for parts such as wheels, mirrors, and lights.

Vehicle body Applicable parts: Body surface, bumper, spoiler Base material: acrylic painted surface, steel plate, PP, urethane resin, polyester functional group-containing fluoropolymer: reactive PTFE, reactive P
FA or FEP, reactive ETFE Application form: paint Effect: antifouling property against dust and soot, transparency, design, and scratch resistance.

Automobile window Applicable parts: windshield, side glass, rear glass, window glass for train vehicles Base material: glass Fluorine-containing polymer containing functional groups: reactive PTFE, reactive P
FA or FEP, reactive ETFE Application form: paint Effect: anti-fouling property against dust, smoke, fingerprint, water repellency,
Transparency, wiper wear.

Lights (headlights, tail lamps,
Applicable places: cover surface, light bulb surface Base material: polycarbonate, glass Functional group-containing fluoropolymer: reactive PTFE, reactive P
FA or FEP, reactive ETFE Application form: paint Effect: antifouling property against dust and smoke, water repellency, transparency, scratch resistance.

Automotive interior materials Applicable places: dashboard, front panel, rear panel, trunk Base material: urethane resin, PP functional group-containing fluoropolymer: reactive PTFE, reactive P
FA or FEP, reactive ETFE Application form: paint Effect: antifouling property against cigarette smoke, dust, fingerprint, transparency, and design.

Mirrors Applicable parts: Rearview mirror, rearview mirror Base material: Glass Fluoropolymer containing functional group: Reactive PTFE, Reactive P
FA or FEP, reactive ETFE Application form: paint Effect: antifouling property, water repellency, and transparency against dust and smoke.

Wheel Applicable part: Surface Base material: Aluminum, cast iron, PP, ABS, PA, PC, PP
E, alloys Functional group-containing fluoropolymer: reactive PTFE, reactive P
FA or FEP, reactive ETFE Application form: paint Effect: antifouling property against dust and mud, scratch resistance against stones, etc., transparency, and design.

[5] Home Appliances In addition to the home appliances used in the kitchen housing equipment described above,
It can be used for parts and parts where contamination of various home appliances becomes a problem. Representative examples are given below.

Air conditioner (including cooling and heating) Applicable places: Indoor unit outlet, outdoor unit exterior, aluminum fin, propeller Base material: PP, aluminum, galvanium steel sheet, galvanized steel sheet Functional group-containing fluoropolymer: reactive PTFE, reactive P
FA or FEP, reactive ETFE Application form: paint Effect: antifouling property against dust, smoke, tobacco tar,
Wipeability, transparency, design, workability.

Ventilation fan Applicable parts: blade, frame, cover Base material: PP, aluminum, galvanium steel sheet, galvanized steel sheet Functional group-containing fluoropolymer: reactive PTFE, reactive P
FA or FEP, reactive ETFE Application form: paint Effect: antifouling property against oil stains, stickiness, transparency, design, abrasion resistance against scouring, etc., scratch resistance.

Light bulbs (or their umbrellas) Applicable places: Surfaces of light bulbs, covers, surfaces of umbrellas Base materials: glass, PP functional group-containing fluoropolymers: reactive PTFE, reactive P
FA or FEP, reactive ETFE Application form: paint Effect: antifouling property against dust and soot, transparency, scratch resistance.

Refrigerator Applicable places: exterior surface, interior surface Base material: PP, aluminum, SUS, galvanium steel sheet, galvanized steel sheet Functional group-containing fluoropolymer: reactive PTFE, reactive P
FA or FEP, reactive ETFE Application form: paint Effect: antifouling property against foods and seasonings, wiping property against sticking, transparency, design property, workability.

[6] Others Insulators, pantographs Applicable places: Surface Base material: Porcelain Functional polymer-containing fluoropolymer: Reactive PTFE, Reactive P
FA or FEP, reactive ETFE Application form: paint Effect: antifouling property against dust and heavy smoke, scratch resistance, workability.

Bolt Applicable part: Surface Base material: Iron, SUS Fluorine-containing polymer containing functional group: Reactive PTFE, Reactive P
FA or FEP, reactive ETFE Application form: paint Effect: antifouling property, rustproofing property, impact resistance, workability

[0270]

EXAMPLES Next, the antifouling 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 (P having a hydroxyl group)
Production of aqueous dispersion composed of FA) Pure water 1500 m in a 3 liter glass-lined autoclave equipped with a stirrer, a valve, a pressure gauge, and a thermometer
l, 9.0 g of ammonium perfluorooctanoate and 60 g of paraffin were added, and after sufficiently replacing with nitrogen gas,
It was evacuated and charged with 20 ml of ethane gas.

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

[0273]

Embedded image

Then, 1.9 g of perfluoro (propyl vinyl ether) (PPVE) and 16.1 g of perfluoro (propyl vinyl ether) were injected under pressure 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 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 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.

Then, 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 above-mentioned 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 to 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.

Then, 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 press-injected to an internal pressure of 8.5 kgf / cm ² G.

Then, 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 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 polymer concentration 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 / 0.7mo
1% Tm = 317 ° C. 1% Thermal decomposition temperature Td = 479 ° C. Melt flow rate = 19.2 g / 10 min In the infrared spectrum, no characteristic absorption of —OH was observed.

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 applied on a Pyrex glass plate using a 10 mil applicator,
A wet coating was formed.

(4) Firing The wet coating film obtained in (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 baked coating film obtained in the above (4) was measured by a haze meter.

The hardness of the coating 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 film, and a cellophane adhesive tape was attached to 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 allowed to stand 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 a position of a width b (25 mm), and the test plate 1 was attached to a lower grip of a tensile tester. The peeled end of the tape 2 was folded back by 180 ° and attached to the upper grip so that the tape 2 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 film The contact angle with water of the coating film was measured.

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.

The results of the test are shown in Table 1.

Example 2 Using the aqueous dispersion of the fluorinated copolymer (A) obtained in Production Example 2, a coating solution 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 this coating solution was applied using a 6 mil applicator. Table 1 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 1 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 1 shows the results.

Comparative Example 2 Using only a silica sol solution to which no aqueous dispersion of a fluorinated copolymer was added, coating, firing and evaluation were performed in the same manner as in Example 1. Table 1 shows the results.

[0321]

[Table 1]

As is clear from the results in Table 1, 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 film 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 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 2 shows the results.

：: Contamination can be removed by washing,
It almost returned to the painted plate before the contamination test. Δ: Part of the contamination could be removed by washing, but gray stains adhered so as to permeate the entire surface of the coated plate, and the stains could not be removed. ×: Black stains remained on the entire surface of the coated plate and could not be removed by washing with water.

Weathering test The coated plate was placed in an I-Super UV tester (manufactured by Iwasaki Electric Co., Ltd.), and an accelerated weathering test was carried out.
The adhesion angle to water of the coated plate after the time test was measured. Table 2 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.

On the primer layer, a PFA powder paint (manufactured by Daikin Industries, Ltd., NEOFLON powder paint ACX-3)
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.

The same test as in Example 4 was conducted using the PFA powder coated plate. Table 2 shows the results.

Comparative Example 4 Zeffle GK which is 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 sandblasting in the same manner as in Comparative Example 3 was spray-coated with the above-mentioned paint 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 2 shows the results.

Comparative Example 5 Acrydic A801 (a varnish for cold-setting acrylic resin paint, OH value 100, manufactured by Dainippon Ink and Chemicals, Inc.)
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.

A test similar to that of Example 4 was performed using the coated plate. Table 2 shows the results.

[0337]

[Table 2]

[0338]

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 in the dispersion of fine particles of a fluororesin containing an emulsifier, it is often unstable and coagulated 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 during the polycondensation reaction after the hydrolysis, the functional group of the functional group-containing fluorine-containing ethylenic polymer (A) was changed to the metal oxide sol (B-1). 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 promoting 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 fluorine-containing ethylenic polymer (A) in the coating 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 give a composite material firmly adhered to various substrates.

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

[Description of Signs] 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 (16)

[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) An antifouling composite 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 antifouling composite material according to claim 1, which is a kind of fluorine-containing ethylenic monomer containing a functional group. 3. The antifouling composite material according to claim 1, wherein the fluorine-containing ethylenic monomer (b) having no functional group 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 antifouling composite 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 antifouling composite material 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 another copolymerizable monomer. 6. The antifouling composite according to claim 1, wherein the metal oxide (B) is an oxide of silicon. 7. The antifouling composite according to claim 1, wherein the metal oxide (B) is an oxide of aluminum. 8. The antifouling composite according to claim 1, wherein the metal oxide (B) is an oxide of titanium. 9. The method according to claim 1, wherein the base material is a metal base material.
5. The antifouling composite material according to any one of 5. 10. The antifouling composite according to claim 1, wherein the substrate is a nonmetallic inorganic substrate. 11. The substrate according to claim 1, wherein the substrate is a glass substrate.
0 antifouling composite material. 12. The antifouling composite material according to claim 10, wherein the base material is made of concrete. 13. The method according to claim 1, wherein the substrate is made of cement.
0 antifouling composite material. 14. The substrate according to claim 10, wherein the substrate is a tile.
The antifouling composite material according to the above. 15. The antifouling composite material according to claim 10, wherein the base material is a ceramic plate. 16. The antifouling composite according to claim 1, wherein the substrate is a synthetic resin substrate.