JPH10243881A - Composite material for cooking appliance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite material for cooking appliance which is excellent in heat resistance, adhesion-proofness, and water repellency, and for which a film of a high hardness being excellent in abrasion resistance, scratch resistance, transparency and water repellency, is firmly bonded on a base material. SOLUTION: This composite material for cooking appliance is equipped with a film wherein particles of a functional group-containing fluoroethylene polymer A which is obtained by copolymerizing a functional group-containing fluoroethylene monomer having at least one kind of a hydroxy group, a carboxyl group, a carboxylic acid salt and a carboxyester group, and a fluorine-containing ethylene monomer having no functional group, are dispersed in a metallic oxide B layer, on the surface of a base material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to heat-resistant, non-adhesive, transparent (design), stain-resistant and water- and oil-repellent materials.
Also, the present invention relates to a composite material for a cooking appliance having a coating on the surface of a substrate, in which fine particles of a fluoropolymer having excellent adhesion and hardness to a substrate are dispersed in a metal oxide layer.

[0002]

2. Description of the Related Art It is desired that cooking equipment typified by a hot plate and a rice cooker can be cooked at a higher temperature in order to reduce cooking time and to pursue the taste of food obtained by cooking. ing. In addition, it is desired that such equipment be easy to remove dirt such as oil and burns so that it can be easily cleared after cooking.
It is also required that the surface is not scratched or worn by a spatula or a scallops due to long-term use. Further, it is also desired that the design be good because it affects the appearance of the article.

In response to such demands, composite materials used for cooking appliances have excellent heat resistance, chemical resistance, corrosion resistance, weather resistance, surface characteristics (non-adhesiveness, low frictional properties, etc.), electrical insulation and the like. BACKGROUND ART Fluoropolymers have been applied to heating surfaces of cooking appliances such as rice cookers and hot plates. However, fluoropolymers do not have sufficient adhesion to metal surfaces due to their excellent non-adhesiveness, and (1) use an adhesive or
(2) It is necessary to perform etching by sandblasting or an electrochemical method on the surface of the base material, to provide irregularities on the surface, and to perform adhesion by an anchor effect.

However, in the method using an adhesive as in (1), since there is no heat-resistant, transparent and high-adhesive adhesive, 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, since the fluoropolymer constituting the surface coating such as the cooking surface is soft, it is washed during use for a long time or with a spatula or scourer. During this time, the surface coating is scratched and the transparency and design are reduced, and the inherent water repellency and non-adhesion of the fluoropolymer are reduced due to wear.

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 the field of cooking appliances.

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

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

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

That is, according to the conventional sol-gel method,
A film excellent in transparency and excellent in abrasion resistance, heat resistance, water and 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 a cooking appliance composite material having a coating made of a metal oxide layer in which the fine particles are uniformly dispersed on the surface of a base material.

Further objects of the present invention are, in particular, abrasion resistance,
An object of the present invention is to provide a composite material for a cooking appliance 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
Mol% and (b) at least one monomer of the above-mentioned fluorine-containing ethylenic monomer having no functional group in the range of 50 to 99.95 mol%. The present invention relates to a composite material for a cooking appliance having, on a substrate surface, a coating film in which fine particles of a polymer (A) 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 composite material for a cooking appliance, which is a kind of fluorine-containing ethylenic monomer containing a functional group.

Further, the present invention relates to the composite material for a cooking appliance, 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 composite material for a cooking appliance, wherein the composite material is a monomer mixture with about 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 composite material for a cooking appliance, which is a monomer mixture with a monomer of 0 to 15 mol%.

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

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

Further, the present invention relates to the composite material for a cooking appliance, wherein the metal oxide (B) is an oxide of titanium.

Further, the present invention relates to the composite material for a cooking appliance, wherein the base material is a metal base material.

[0027] The present invention also relates to the cooking appliance composite, wherein the substrate is a glass substrate.

The present invention also relates to the cooking appliance composite, wherein the substrate is a synthetic resin substrate.

The present invention also relates to the cooking appliance composite, wherein the substrate is a ceramic.

Further, the present invention relates to a cooking appliance using the composite material for a cooking appliance.

The present invention also relates to a cooking device using the composite material for cooking appliances.

[0032] The present invention also relates to a hot plate using the composite material for cooking appliances.

[0033] The present invention also relates to a hot plate using the cooking appliance composite for a metal heating surface.

[0034] The present invention also relates to a hot plate using the cooking appliance composite for a glass lid.

Further, the present invention relates to a microwave oven using the composite material for cooking appliances.

Further, the present invention relates to a microwave oven using the above-mentioned composite material for cooking appliances on a metal inner surface.

The present invention also relates to a microwave oven using the cooking appliance composite for a cooking plate.

The present invention also relates to a microwave oven using the cooking appliance composite for a glass door.

Further, the present invention relates to a heating pan using the composite material for cooking appliances.

[0040] The present invention also relates to a heating pot using the cooking appliance composite material for a metal heating surface.

Further, the present invention relates to a heating pot using the above-mentioned composite material for cooking appliances in a glass lid.

The present invention also relates to a frying pan using the composite material for cooking appliances.

Further, the present invention relates to a frying pan using the above-mentioned composite material for cooking appliances on a metal heating surface.

The present invention also relates to a fryer using the composite material for cooking appliances.

Further, the present invention relates to a fryer using the above-mentioned composite material for cooking equipment on a metal inner surface.

The present invention also relates to a fryer using the above-mentioned composite material for cooking appliances on a glass inner surface.

[0047] The present invention also relates to a rice cooker using the composite material for cooking appliances.

The present invention also relates to a rice cooker using the above-mentioned composite material for cooking appliances on a metal inner surface.

The present invention also relates to a rice cooker using the above-mentioned composite material for cooking appliances in a metal inner lid.

[0050] The present invention also relates to a jar using the composite material for cooking appliances.

The present invention also relates to a jar using the cooking appliance composite material on a metal inner surface.

[0052] The present invention also relates to a jar using the cooking appliance composite material for a metal inner lid.

Further, the present invention relates to a tableware or a container using the composite material for cooking appliances.

[0054] The present invention also relates to a metal tableware or a container using the composite material for cooking appliances.

Further, the present invention relates to a glass tableware or container using the composite material for cooking appliances.

The present invention also relates to a cooking appliance for food processing using the composite material for a cooking appliance.

The present invention also relates to a food mixing cooking appliance using the cooking appliance composite.

The present invention also relates to a cooking appliance for cutting food products using the composite material for cooking appliance.

The present invention also relates to a bakery using the composite material for cooking appliances.

[0060]

BEST MODE FOR CARRYING OUT THE INVENTION As a result of repeated studies to achieve the above object, the present inventors have been able to obtain a film having non-adhesiveness, water repellency, and improved abrasion resistance and scratch resistance. And found that they could be applied to cooking appliances.

The composite material for a cooking appliance of the present invention comprises (a) a functional group having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylate, a carboxylester group and an epoxy group. At least one monomer of the fluorine-containing ethylenic monomer containing 0.05
(B) at least one kind of the above-mentioned fluorine-containing ethylenic monomer having no functional group and 70 to 99.95 mol% of a functional group-containing functional group. This is a film in which fine particles of a fluoroethylenic polymer (A) are dispersed in a metal oxide (B) layer serving as a matrix, and formed on the surface of the substrate.

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

Further, the functional group-containing fluoropolymer (A) itself has not only heat resistance but also chemical resistance, non-adhesion, antifouling property, 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 composite material of the present invention, will be described first.

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

The functional group-containing fluorine-containing ethylenic polymer (A) which can be used in the present invention is specifically (a-
1) Formula (1): CX ₂ = CX ¹ -R _f -Y (1) (wherein, Y is CH ₂ OH or COOH or a carboxylate or carboxyester group, and X and X ¹ are the same or different. Also represents a hydrogen atom or a fluorine atom, and R _f represents a divalent fluorinated alkylene group having 1 to 40 carbon atoms or a divalent fluorinated alkylene group having an ether bond having 1 to 40 carbon atoms) At least one functional group-containing fluorine-containing ethylenic monomer;
(B-1) the functional group-containing fluorinated ethylenic monomer (a
-1) a functional group-containing fluorine-containing ethylenic polymer obtained by copolymerizing 50 to 99.95 mol% of at least one fluorine-containing ethylenic monomer copolymerizable with -1). Excellent in aqueous terms.

The functional group-containing fluorine-containing ethylenic monomer (a
-1) is specifically represented by the formula (3): CF ₂ CF—R _f ³ —Y (3) wherein Y is the same as Y in the formula (1), and R _f ³ has 1 to 1 carbon atoms. 4
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 point that the functional group-containing fluorine-containing ethylenic monomer represented by the formulas (3) to (6) has relatively good copolymerizability with the fluorine-containing ethylenic monomer (b-1). And again
It is preferable because the heat resistance, non-adhesiveness and water repellency of the copolymer obtained by copolymerization are not significantly reduced.

Among them, the monomers represented by the formulas (3) and (5) are preferable 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 below.

[0071]

Embedded image

And the like.

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

[0074]

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And the like.

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

[0077]

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And the like.

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

[0080]

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Examples are shown.

Other monomers include

[0083]

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And the like.

The functional group-containing fluorine-containing ethylenic monomer (a
The ethylenic monomer copolymerizable with -1) can be appropriately selected from known monomers, but the copolymer has heat resistance, non-adhesion, water repellency, chemical resistance, and low friction. Is selected from the fluorine-containing ethylenic monomers (b-1).

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

[0087]

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, the functional group-containing fluorinated ethylenic monomer (a-1) and the fluorinated ethylenic monomer (b-1)
In addition, an ethylenic monomer having no fluorine atom may be copolymerized as long as heat resistance, non-adhesion and water repellency are not reduced. 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 heat resistance, non-adhesion, and water repellency. Has ethylene, propylene, 1-
Butene and 2-butene.

In the coating of the present invention, the content of the functional group in the functional group-containing fluorinated ethylenic polymer (A) depends on the type of the metal oxide (B) and the functional group-containing fluorinated ethylenic polymer (A). ) And metal oxide (B),
The solid content, which can be appropriately selected depending on the purpose and application, is preferably 0.05 to 50 mol%, more preferably 0.1 to 20 mol%, particularly preferably 0.1 to 1 mol%.
0 mol%.

If the content of the functional group is less than 0.05%, the dispersion in the coating becomes uneven, and the coating becomes white. In addition, 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 due to friction or the like. (A) falls off and reduces non-adhesiveness and water repellency.

Conversely, when the content of the functional group is 50 mol%
If it exceeds, the original non-adhesiveness and water repellency of the functional group-containing fluorine-containing ethylenic polymer (A) have been lost or the heat resistance has been reduced, and when it is fired at a high temperature, it is thermally decomposed, It is easy to cause coating defects such as coloring, foaming and pinholes, and a decrease in water repellency.

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

(I) Polymer (I) comprising 0.05 to 50 mol% of a functional group-containing fluorine-containing ethylenic monomer (a-1) and 50 to 99.95 mol% of tetrafluoroethylene (reactive PTFE) ).

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

(II) The functional group-containing fluorine-containing ethylenic monomer (a-1) is contained in an amount of 0.05 to 50 mol% based on the total amount of the monomer. 85 to 99.7 mol% of tetrafluoroethylene and the above formula (2): CF ₂ = CF-R _f ¹ (2) [R _f ¹ is CF ₃ , OR _f ² ( R _f ² is a polymer of the monomer 0.3 to 15 mole% represented by] selected from a perfluoroalkyl group) having 1 to 5 carbon atoms (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 non-tackiness and water repellency.

(III) The functional group-containing fluorine-containing ethylenic monomer (a-1) is used in an amount of 0.05 to 50% based on the total amount of the monomer.
Mol%, and based on the total amount of the monomers except for the monomer (a-1), 40 to 80 mol% of tetrafluoroethylene, 20 to 60 mol% of ethylene, and other copolymerizable monomers. 0 to 15 mol% of a polymer (ethylene-tetrafluoroethylene polymer (III) having a functional group (reactive ETFE)).

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

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

The functional group-containing fluorinated ethylenic polymer (A) which can be used in the present invention comprises the functional group-containing fluorinated ethylenic monomer (a-1) and the ethylenic monomer (b) -1) can be obtained by copolymerization using a known polymerization method. Among them, a method based on radical copolymerization is mainly used. That is, in order to start the polymerization, the means is not particularly limited as long as it proceeds radically, for example, organic, inorganic radical polymerization initiator,
Initiated by heat, light or ionizing radiation. As the type of polymerization, solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, or the like can be used. The molecular weight is controlled by the concentration of the monomer used for the polymerization, the concentration of the polymerization initiator, the concentration of the chain transfer agent, and the temperature. The composition of the resulting copolymer can be controlled by the composition of the charged monomers.

In the present invention, the metal oxide (B) capable of forming a coating matrix is, for example, starting from an organic metal compound or an inorganic metal compound and using 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 and Zr is particularly preferable because it is transparent, has high hardness, and can form a film 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 fluororesin such as water repellency, non-adhesion and antifouling properties cannot be exhibited.

In the present invention, the substrate on which the film can be formed includes a metal-based substrate, a ceramic-based substrate, and a resin-based substrate.

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

Specific examples of the metal-based material 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, as for aluminum-based metals, pure aluminum, oxides of aluminum, Al-Cu-based metals,
Al-Si, Al-Mg and Al-Cu-Ni-
Casting or wrought aluminum alloys such as Mg-based, Al-Si-Cu-Ni-Mg-based alloys, high-strength aluminum alloys, and corrosion-resistant aluminum alloys can be used.

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

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

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

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

Examples of the ceramic base include glass, pottery, and porcelain.

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

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

The base material of the composite material for a cooking appliance of the present invention may be a cold rolled steel plate, a plated steel plate, for example, a Zn-plated steel plate or a Zn-plated steel plate.
Alloy plated steel sheet, Al plated steel sheet or Al alloy plated steel sheet, Cr plated steel sheet (TFS), Ni plated steel sheet,
Aluminum plates, titanium plates, stainless plates, etc., such as Cu-plated steel plates and galvanium steel plates, are usually used.

In addition, glass as a ceramic base material and acrylic resin or polycarbonate as a resin base material are usually used in portions where transparency is required.

The thickness of the metal oxide film varies depending on the type and location of the cooking appliance to be applied, but is 0.01 to 100.
μm, preferably 0.01 to 50 μm, and particularly preferably 0.02 to 20 μm.

The coating according to 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, the functional group-containing fluorine-containing ethylenic polymer (A) and the metal oxide sol (B
-1) The composition ratio of each component of the solvent (C) can be appropriately selected depending on the type and site of the 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 coated metal oxide film. In particular, a coating excellent in abrasion resistance, non-adhesion, and 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.

Incidentally, additives such as a surfactant, a pigment, a dye and a thickener may be added to the coating composition.

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

In the metal oxide film of the present invention, since the fine particles of the functional group-containing fluorine-containing ethylenic polymer (A) are uniformly distributed inside the film, even if the surface of the film is abraded and scraped, In addition, the excellent properties (non-adhesiveness, water repellency, etc.) of the fluororesin are exhibited up to the inside of the coating, and this property is not reduced.

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) 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 alkoxide, metal acetyl acetate, metal carboxylate, metal nitrate and metal chloride to a hydrolysis and condensation reaction. The metal oxide sol (B-1) obtained and an aqueous dispersion containing the fine particles of the functional group-containing fluorine-containing ethylenic polymer (A) obtained by the emulsion polymerization method can be used, and (1) the metal oxidation Object (B)
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) baking the coating film. Then, it can be obtained by a method for producing a film through a film forming step of forming a 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.

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

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

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

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

The metal alkoxides are specifically LiOCH ₃ , NaOCH ₃ , Cu (OCH ₃ ) ₂ , Ca (OCH 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 , Al (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, Ti (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 (i _{so-OC 3 H 7) 4} ] 3, Mg [Al (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, and 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,

[0143]

Embedded image

And the like.

Other organic metal compounds 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, 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, an acid or an alkali as a catalyst to the metal compound solution, hydrolysis and polycondensation occur to form metal oxide (B) particles, and the metal oxide sol (B-1) Is obtained.

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

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

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

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

The present inventors have 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) Depending on the type and site of the cooking appliance to be applied, the coating can be applied to the base material. Since it is difficult to process when firing, the substrate is preferably in the shape of the final product.

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

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

The 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 composite material for a cooking appliance of the present invention can be manufactured.

The composite material for cooking appliances is particularly non-adhesive,
Water repellency is often required, and as a result, the fine particle of the functional group-containing fluorine-containing ethylenic polymer (A) has a contact angle with water of 80 ° or more of the functional group-containing fluorine-containing ethylenic polymer (A) itself, In particular, it is preferable to use a water-repellent coating composition containing a composition having a degree of 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.

In particular, the functional group-containing fluorine-containing ethylenic polymer (A) which gives a film having excellent water repellency includes the above-mentioned reactive PTFE, reactive PFA, reactive FEP, reactive ETFE and the like. 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 comprises firstly a functional group-containing fluorine-containing ethylenic polymer (A)
Fine particles of metal oxide (B) with good interfacial adhesion
Secondly, a coating composed of fine particles (B) of a functional group-containing fluorine-containing ethylenic polymer (A) because the coating is uniformly dispersed in the coating composed of Has good non-adhesiveness, heat resistance, abrasion resistance, scratch resistance, antifouling property, water repellency, antibacterial property, etc., so that it can be used for various cooking appliances.

[0167] Suitable cooking appliances to which the composite material for cooking appliances of the present invention can be used and the parts thereof are specifically listed below according to the field of cooking appliances. Therefore, the present invention also relates to a cooking appliance and various parts described later.

[0168] Tables 1 to 7 show the items classified and arranged for each item.

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 composite material for cooking appliances of the present invention can be particularly effectively utilized.

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

In these, the non-adhesive (against rice grains and scorch) antifouling property and heat resistance of the composite material for a cooking appliance of the present invention can be utilized particularly effectively.
Further, it is possible to improve performance deterioration due to abrasion, scratching, and the like of the coating during cleaning with a scourer or the like.

Cooking equipment (a) Surfaces of frying pan, bat, manual mixer for cooking / home use, sirs, kitchen knives, bread molder, reverse sheet for bread, split rounding machine for bread, etc., and inner surfaces of balls and rice bins, etc. In the case of a mixer, its wings.

In these, the non-adhesiveness (to combustible and sticky dirt), antifouling property and heat resistance of the composite material for cooking appliances 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) Inner surfaces and blades of electric food processors such as household electric food grinders, electric food crushers, kitchen electric meat grinders, electric kitchen blenders, and electric kitchen mixers.

In these, the non-adhesiveness (to vegetables and meat juices) and antifouling properties of the composite material for cooking appliances 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 non-adhesiveness (with respect to oil stains), heat resistance and transparency (design with respect to colors, patterns, etc.) of the composite material for cooking appliances 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.

Oven ranges including toasters, ranges, etc. (a) Ovens such as commercial ovens, electric ovens (including commercial ones), electric ovens with commercial storage, 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 non-adhesiveness (against oil and scorch), antifouling property and heat resistance of the composite material for cooking appliances of the present invention can be utilized particularly effectively, and furthermore, with a spatula or scourer. Wear and damage can be improved.

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

In these, the non-adhesiveness, heat resistance and transparency of the composite material for a cooking appliance of the present invention, and the energy ray resistance in the case of a microwave oven 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 non-adhesiveness of the composite material for cooking appliances of the present invention (burn, sticky soil, 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 scratches 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) possessed by the composite material for cooking appliances of the present invention, transparency can be particularly effectively utilized.

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

In these, the non-adhesiveness and antifouling properties of the composite material for cooking appliances of the present invention can be particularly effectively utilized.

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

In these, the non-adhesiveness (with respect to burning and sticking dirt), heat resistance and transparency of the lid of the composite material for a cooking appliance of the present invention can be utilized particularly effectively, and Abrasion with a spatula, performance deterioration due to scratching, and appearance deterioration can be improved.

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

In these, the non-adhesiveness, heat resistance and transparency possessed by the composite material for a cooking appliance of the present invention can be particularly effectively utilized, and abrasion and damage due to scouring can be improved.

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

In these, the non-adhesiveness, antifouling property, heat resistance, and steam resistance of the composite material for cooking appliances of the present invention can be particularly effectively utilized, and the abrasion and damage due to scouring etc. can be reduced. it can.

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

In these, the non-adhesiveness, antifouling property, heat resistance and hot water resistance of the composite material for a cooking appliance of the present invention can be particularly effectively utilized, and wear and scratches caused by 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.

In these, the non-adhesiveness (with respect to scorching and sticking dirt) and heat resistance of the composite material for cooking appliances 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 non-adhesiveness, antifouling property and hot water resistance of the composite material for a cooking appliance 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 non-adhesiveness, antifouling property, transparency and heat resistance of the composite material for cooking appliances of the present invention can be particularly effectively utilized.

Further, other cooking appliances to which the composite material for cooking appliances of the present invention can be preferably applied include the following.

[0204] Examples of the above range (b) include porridge cookers and rice warmers.

Examples of the range of the above (a) include various cooking utensils (such as for slicing), cooking utensils, cooking machinery and utensils, cooking utensils (for food etc.), cooking iron plates, cooking utensils and equipment, and 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 of (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.

As the above range, 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-made heater.

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.

[0210] Examples of the above range include gyoza, electromagnetic low range, gas evaporator, and steam evaporator.

[0211]

[Table 1]

[0212]

[Table 2]

[0213]

[Table 3]

[0214]

[Table 4]

[0215]

[Table 5]

[0216]

[Table 6]

[0219]

[Table 7]

[0218]

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

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

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

[0221]

Embedded image

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

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

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

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

While the supply of tetrafluoroethylene was continued, the amount of tetrafluoroethylene gas was about 40 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 under the 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, and the pressure is reduced and the pressure is increased. Repeated.

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

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

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

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

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 injected so that the internal pressure became 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 concentration of the polymer in the aqueous dispersion was 21.6%, and the particle size was 156 nm.

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

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

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

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

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

(4) Firing The wet coating film obtained in (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 carried out on the coating liquid and the film obtained in Example 1.

Dispersion stability of coating liquid The coating liquid 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 transparency of the coating film after firing obtained in the above (4) was measured for haze value with a haze meter.

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

Adhesion According to JIS K5400, 100 crosscuts were formed on the coating, and a cellophane adhesive tape was stuck on the crosscut surface, and this was strongly pulled in the direction perpendicular to the coating, and the peeling state of the coating was observed. 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-repellent contact angle of the coating film was measured by a contact angle meter.

Abrasion Resistance Using a flannel cloth (cotton No. 300) under a load of 1.5 kg / 4 cm ² , the contact angle with water after rubbing the coating 3000 times was measured in the same manner as described above.

Table 8 shows the results of the test.

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

Coating, baking and testing were performed in the same manner as in Example 1 except that this coating liquid was applied using a 6 mil applicator. Table 8 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 8 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 8 shows the results.

Comparative Example 2 Coating, sintering and evaluation were performed in the same manner as in Example 1 using only the silica sol solution to which the aqueous dispersion of the fluorinated copolymer was not added. Table 8 shows the results.

[0269]

[Table 8]

As is clear from the results shown in Table 8, 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, tests for the thickness, adhesion, non-adhesion and water repellency of the coating film were carried out in the same manner as in Example 1.

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 coating (neoflon powder coating ACX-3, manufactured by Daikin Industries, Ltd.)
After 1) was electrostatically coated, it was baked at 350 ° C. for 30 minutes to form a film.

A gray-brown coating of the primer was obtained.

Using the PFA powder coated plate, self-command 4
The same test was performed. The results are shown in Table 2.

[0277]

[Table 9]

[0278]

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

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

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

In the process of further 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 fluorinated ethylenic polymer (A) in the film is bonded to the film. Dispersibility with metal oxide (B) (gel), interfacial adhesion, and adhesion to a substrate were improved.

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

As a result, the composite material for a cooking appliance of the present invention
It has a coating with excellent adhesion on its surface, and has not only water repellency and transparency, but also performance such as heat resistance, non-adhesion, chemical resistance, low friction, low refraction, and antireflection. And can add a great deal of added value to various types of cooking appliances.

[Brief description of the drawings]

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

[Explanation of symbols]

 1 Test plate 2 Adhesive tape 3 Adhesive part

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI A47J 37/12 A47J 37/12 41/00 41/00 B02C 18/08 B02C 18/08 B C08F 216/04 C08F 216/04 216 / 18 216/18 220/04 220/04 220/22 220/22 224/00 224/00 C09D 129/02 C09D 129/02 129/10 129/10 133/02 133/02 133/04 133/04 137 / 00 137/00 F24C 1/00 F24C 1/00 (72) Inventor Masahiro Kumegawa 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd.Yodogawa Works (72) Inventor Noritoshi Oka, Nishi, Settsu-shi, Osaka Ichitsuya 1-1, Daikin Industries, Ltd. Yodogawa Works (72) Inventor Tetsuo Shimizu 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works

Claims (42)

[Claims] 1. A method for producing a functional group-containing fluorine-containing ethylenic monomer having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylate, a carboxyester group and an epoxy group. 0.05 to 50 mol% of at least one monomer and 50 to 99.95 mol% of at least one monomer of the fluorine-containing ethylenic monomer having no functional group (b) A composite material for a cooking appliance having a coating on the surface of a base material in which fine particles of a functional group-containing fluorine-containing ethylenic polymer (A) obtained by copolymerization are dispersed in a metal oxide (B) layer. 2. The functional group-containing fluorine-containing ethylenic monomer (a) is represented by the formula (1): CX ₂ ＣCX ¹ -R _f -Y (1) (where Y is -CH ₂ OH,- COOH, carboxylate, carboxyester group or epoxy group, X and X ¹ are the same or different, and are a hydrogen atom or a fluorine atom,
R _f is a divalent fluorinated alkylene group having 1 to 40 carbon atoms,
A fluorine-containing oxyalkylene group having 1 to 40 carbon atoms, a fluorine-containing alkylene group containing an ether group having 1 to 40 carbon atoms or a fluorine-containing oxyalkylene group containing an ether bond having 1 to 40 carbon atoms) The composite material for a cooking appliance according to claim 1, which is a kind of fluorine-containing ethylenic monomer containing a functional group. 3. The composite material for a cooking appliance 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 composite material for a cooking appliance according to claim 1 or 2, which is a mixed monomer of up to 15 mol%. 5. The fluorinated ethylenic monomer having no functional group (b) is a tetrafluoroethylene 40-80.
The composite material for a cooking appliance 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 composite material for a cooking appliance according to claim 1, wherein said metal oxide (B) is an oxide of silicon. 7. The cooking appliance composite according to claim 1, wherein the metal oxide (B) is an aluminum oxide. 8. The cooking appliance composite according to claim 1, wherein the metal oxide (B) is a titanium oxide. 9. The method according to claim 1, wherein the base material is a metal base material.
9. The composite material for a cooking appliance according to any one of 8. 10. The substrate according to claim 1, wherein said substrate is a glass substrate.
9. The composite material for a cooking appliance according to any one of items 1 to 8. 11. The composite material for a cooking appliance according to claim 1, wherein the base material is a synthetic resin base material. 12. The composite material for a cooking appliance according to claim 1, wherein the base material is a ceramic. 13. A cooking appliance using the composite material for a cooking appliance according to any one of claims 1 to 12. 14. A cooking device using the composite material for a cooking appliance according to claim 1. Description: 15. A hot plate using the composite material for a cooking appliance according to any one of claims 1 to 12. 16. A hot plate using the composite material for cooking appliances according to claim 3 or 4 for a metal heating surface. 17. A hot plate using the cooking appliance composite according to claim 4 for a glass lid. 18. A microwave oven using the composite material for a cooking appliance according to claim 1. Description: 19. A microwave oven using the composite material for cooking equipment according to claim 3 on a metal inner surface. 20. A microwave oven using the cooking material composite according to claim 3 or 4 for a cooking plate. 21. A microwave oven using the composite material for cooking appliances according to claim 4 for a glass door. 22. A heating pot using the composite material for a cooking appliance according to claim 1. Description: 23. A heating pan using the composite material for a cooking appliance according to claim 3 on a metal heating surface. 24. A heating pan using the composite material for cooking equipment according to claim 4 for a glass lid. 25. A frying pan using the composite material for a cooking appliance according to any one of claims 1 to 12. 26. A frying pan obtained by using the composite material for a cooking appliance according to claim 3 on a metal heating surface. 27. A fryer comprising the composite material for a cooking appliance according to claim 1. Description: 28. A fryer using the composite material for cooking appliances according to claim 3 or 4 on a metal inner surface. 29. A fryer using the composite material for a cooking appliance according to claim 4 on a glass inner surface. 30. A rice cooker using the composite material for a cooking appliance according to claim 1. Description: 31. A rice cooker using the composite material for cooking appliances according to claim 3 or 4 on a metal inner surface. 32. A rice cooker using the composite material for a cooking appliance according to claim 3 for a metal inner lid. 33. A jar using the composite material for a cooking appliance according to any one of claims 1 to 12. 34. A jar using the composite material for cooking appliances according to claim 3 or 4 on a metal inner surface. 35. A jar using the composite material for a cooking appliance according to claim 3 or 4 for a metal inner lid. 36. A tableware or container using the composite material for a cooking appliance according to any one of claims 1 to 12. 37. A metal tableware or container made from the composite material for a cooking appliance according to claim 3 or 4. 38. A tableware or container made of glass using the composite material for a cooking appliance according to claim 4 or 5. 39. A cooking appliance for food processing using the composite material for a cooking appliance according to any one of claims 1 to 12. 40. A food mixing cooking appliance using the cooking appliance composite according to any one of claims 1 to 12. 41. A cooking appliance for cutting food using the composite material for a cooking appliance according to any one of claims 1 to 12. 42. A bakery appliance using the composite material for a cooking appliance according to any one of claims 1 to 12.