JP5673286B2 - Articles and cooking utensils with excellent corrosion resistance and fingerprint resistance, and methods for producing articles with excellent corrosion resistance and fingerprint resistance - Google Patents

Description

  The present invention relates to an article and a cooking utensil excellent in corrosion resistance and fingerprint resistance, and a method for producing an article excellent in corrosion resistance and fingerprint resistance, and in particular, excellent in corrosion resistance to ingredients containing an alkaline substance during cooking, and fingerprint contamination. It relates to articles related to cooking utensils that are difficult to see.

  Conventionally used cooking utensils are often corroded by foodstuffs containing alkalinity, and the appearance of the surface is impaired. In particular, umami components such as tomatoes and kelp contain organic acids and sodium or potassium compounds, so that when such umami components are exposed to high temperatures of 300 ° C. or higher, organic matter is scattered. As a result, only the alkali component remains as ash, and as a result, severe corrosion occurs in the cooking utensil. This phenomenon is particularly noticeable in cooking utensils such as a radiant heater.

Such corrosion by alkali at high temperature is equivalent to an alkali melting reaction, and most materials corrode. For example, a silicate compound that is an inorganic material typically used for cooking utensils or the like cannot withstand an alkali melting reaction.
As a material resistant to alkali, a noble metal such as platinum is known, but such a noble metal is very expensive and is not realistic as a material used for cooking utensils.
In addition to the corrosion resistance, the cooking utensils have many opportunities to be touched by people, so that many fingerprints adhere to the surface. Since fingerprints adhering to the surface of such cooking utensils impair the beauty of the kitchen or kitchen, a method for making the fingerprints difficult to see has been desired.

On the other hand, in cooking utensils, in order to prevent scorching dirt generated in a relatively low temperature range of 200 ° C. to 300 ° C., the surface is coated with a fluororesin or a silicone resin. The temperature is about 300 ° C., and when it is higher than this, the antifouling effect is not exhibited and it is not suitable for use.
Further, the fluororesin and the silicone resin have a drawback that the adhesion with the base material is poor and the film coated on the base material is easy to peel off.

Therefore, a method of coating ceramics on the surface of the base material instead of fluororesin or silicone resin has been studied.
For example, a method of applying an oxyzirconium salt to the surface of a base material and heat-treating it to form a water-repellent zirconium oxide layer on the surface to easily remove dirt adhered to the surface of the base material (Patent Document 1), Or the method (patent document 2) etc. which form the membrane | film | coat containing a zirconium oxide on the surface of a base material are proposed.
Such a zirconium oxide-based coating film can withstand a high temperature of 300 ° C. or more and has excellent adhesion to the substrate.

Japanese Patent Laid-Open No. 10-203882 Japanese Patent No. 4004529

However, in the conventional zirconium oxide-based coating film, the thickness of the coating film needs to be 50 nm or more in order to ensure the corrosion resistance against the alkali melting reaction, but when the thickness exceeds 50 nm, it is a new interference color. There is a problem that a rainbow color is generated, and the surface of the cooking utensil appears to be contaminated with oil due to the rainbow color, and the aesthetic appearance is remarkably impaired.
In addition, when fingerprints adhere to the surface of a cooking utensil, there is a problem that the beauty of the kitchen or kitchen is impaired, and a method for making the fingerprints difficult to see has been desired.

  The present invention has been made in order to solve the above-described problems, and has excellent corrosion resistance to foods containing an alkaline substance during cooking, and is excellent in corrosion resistance and fingerprint resistance in which fingerprint stains are difficult to see. It is an object of the present invention to provide a device and a method for producing an article excellent in corrosion resistance and fingerprint resistance.

  As a result of intensive studies to solve the above problems, the present inventors have formed a coating containing zirconium oxide having a thickness of 50 nm or more on the surface of the base material. However, there is a problem that the generation of rainbow colors as interference colors is remarkable and the appearance is impaired. Therefore, the surface roughness of the base material is set to 0.3 μm or more in advance and the glossiness value is glossy. It is found that if the color is adjusted to 100% or less, the generation of rainbow colors as interference colors can be suppressed, and fingerprint adhesion becomes difficult to see. Further, a film containing magnesium further on the film containing zirconium oxide It has been found that the formation of rainbow colors as interference colors and the adhesion of fingerprints can be effectively suppressed without impairing the corrosion resistance, and the present invention has been completed.

That is, the article excellent in corrosion resistance and fingerprint resistance according to the present invention forms a film containing zirconium oxide on the surface of a substrate having a surface roughness Ra of 0.3 μm or more and a glossiness gloss value of 100% or less. Do Te Ri, on a film containing the zirconium oxide, characterized in that it is formed film further containing magnesium.

Before Kimotozai is ceramics, metal complexes, it is preferably made of any one or two or more metals.

  The cooking utensil of the present invention is a cooking utensil provided with an article excellent in corrosion resistance and fingerprint resistance of the present invention, and is characterized by being usable at 300 ° C. or higher.

In the method for producing an article excellent in corrosion resistance and fingerprint resistance according to the present invention, the surface of the substrate is adjusted so that the surface roughness Ra is 0.3 μm or more and the glossiness gloss value is 100% or less, A film containing zirconium oxide is formed on the surface, and a film containing magnesium is further formed on the film containing zirconium oxide .

In another method of manufacturing an article excellent in corrosion resistance and fingerprint resistance according to the present invention, the surface of a substrate is heated, and then a coating solution containing a zirconium compound is applied to the heated surface, and the surface is coated on the surface. A film containing zirconium oxide having a surface roughness Ra of 0.3 μm or more and a glossiness gloss value of 100% or less is formed , and a film containing magnesium is further formed on the film containing zirconium oxide. To do.

According to the article excellent in corrosion resistance and fingerprint resistance according to the present invention, a film containing zirconium oxide is formed on the surface of a substrate having a surface roughness Ra of 0.3 μm or more and a glossiness gloss value of 100% or less. Therefore, it is possible to improve the corrosion resistance to ingredients containing alkaline substances during cooking, to prevent the generation of rainbow colors as interference colors, and to make it difficult to see dirt caused by fingerprints. .
If a film containing magnesium is further formed on the film containing zirconium oxide, this rainbow color generation can be further prevented without impairing the corrosion resistance to the food containing alkaline substance, resulting from the adhesion of fingerprints. Dirt can also be made more difficult to see.

  According to the method for producing an article excellent in corrosion resistance and fingerprint resistance according to the present invention, the surface of the substrate is adjusted so that the surface roughness Ra is 0.3 μm or more and the glossiness gloss value is 100% or less, Next, since a film containing zirconium oxide is formed on the surface, an article that is excellent in corrosion resistance to ingredients containing an alkaline substance during cooking, does not generate iridescence, and is difficult to see dirt caused by fingerprint adhesion, It can be obtained inexpensively.

  According to another method of manufacturing an article excellent in corrosion resistance and fingerprint resistance according to the present invention, the surface of the substrate is heated, and then a coating solution containing a zirconium compound is applied to the heated surface, Since a film containing zirconium oxide having a surface roughness Ra of 0.3 μm or more and a glossiness gloss value of 100% or less is formed on the top, it has excellent corrosion resistance against ingredients containing alkaline substances during cooking, and no rainbow color is generated. In addition, it is possible to easily and inexpensively obtain an article that is difficult to see dirt caused by fingerprint attachment.

The form for implementing the manufacturing method of the articles | goods excellent in corrosion resistance and fingerprint resistance, and the articles | goods excellent in corrosion resistance and fingerprint resistance of this invention are demonstrated.
This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.

[Goods with excellent corrosion resistance and fingerprint resistance]
The article excellent in corrosion resistance and fingerprint resistance according to the present embodiment is a film containing zirconium oxide (ZrO ₂ ) on the surface of a substrate having a surface roughness Ra of 0.3 μm or more and a glossiness gloss value of 100% or less. (Hereinafter, also simply referred to as a zirconia film).

The base material constitutes the main body of the article having excellent corrosion resistance and fingerprint resistance according to the present embodiment, and various shapes are selected and used depending on the shape and specifications of the target article. Examples of this base material include frying pans, pans, cooking plates, fish dishes for grilled fish, cooking tools such as grills, various dishes, stove tops, stove parts, ovens, and the like used in kitchens and kitchens. Appliances and parts used for cooking food, such as internal parts.
The substrate is not particularly limited as long as it can withstand the heat treatment in forming the above-described article having excellent corrosion resistance and fingerprint resistance. For example, glass that is heat resistant to heat treatment at about 300 ° C. 1 type or 2 types or more of ceramics, such as crystallized glass and ceramics, metal composites, such as a basket, and metals, such as stainless steel.

The surface roughness Ra on the surface of the substrate is preferably 0.3 μm or more, more preferably 0.4 μm or more, and further preferably 0.5 μm or more.
Here, the reason why the surface roughness Ra is set to 0.3 μm or more is that when the surface roughness Ra is less than 0.3 μm, the generation of iridescent interference colors becomes remarkable, and the stains due to the adhesion of fingerprints are also conspicuous. Because it detracts from aesthetics.

The gloss gloss value on the surface of the substrate is preferably 100% or less, more preferably 90% or less, and still more preferably 80% or less.
Here, the reason why the glossiness gloss value is set to 100% or less is that, when the glossiness gloss value exceeds 100%, the occurrence of rainbow interference colors becomes remarkable, as with the surface roughness Ra, and is caused by the adhesion of fingerprints. This is because the stains that are made become conspicuous and detract from the beauty.

The zirconia film may be any film containing zirconium oxide in an amount of 80% by mass to 100% by mass, preferably 90% by mass to 100% by mass, and is not particularly limited. Examples of components other than zirconium oxide in the coating include silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), yttrium oxide (Y ₂ O ₃ ), and calcium oxide (CaO).
Here, when the content of zirconium oxide (ZrO ₂ ) is less than 80% by mass, the corrosion resistance against the alkali melting reaction becomes insufficient, which is not preferable. On the other hand, when the content exceeds 100% by mass, Corrosion resistance to the melting reaction is saturated, and further effects cannot be obtained.

The thickness of the zirconia film is preferably 50 nm or more and 1000 nm or less, more preferably 100 nm or more and 200 nm or less.
If the thickness is less than 50 nm, the corrosion resistance against the alkali melting reaction becomes insufficient. On the other hand, if the thickness exceeds 1000 nm, cracks may occur and the aesthetic appearance of the surface of the cooking utensil or the like may be impaired.

  Here, in order to further prevent the generation of the rainbow color that is an interference color and to make the stain due to the adhesion of fingerprints more inconspicuous, a film further containing magnesium (hereinafter referred to as a magnesium-containing film) is formed on the zirconia film. (Also referred to as).

The magnesium-containing film may be a film containing 20% by mass or more and 100% by mass or less, and preferably 30% by mass or more and 80% by mass or less of a magnesium compound such as magnesium oxide. In the case of only the film, the alkali resistance is good, but the water resistance and acid resistance are insufficient.
Therefore, it is preferable to improve water resistance and acid resistance by adding zirconium oxide or aluminum oxide to the magnesium compound.
Since the magnesium compound has a refractive index with respect to visible light smaller than that of zirconium oxide, it has the effects of suppressing the generation of iridescence and making the stains caused by the adhesion of fingerprints inconspicuous.

[kitchenware]
The cooking utensil of the present embodiment is a cooking utensil provided with the article having excellent corrosion resistance and fingerprint resistance, and can be used at 300 ° C. or higher.
Examples of such cooking utensils include cooking utensils such as frying pans, pans, hot plates for cooking, and grills used in kitchens and kitchens, various dishes, stove tops, stove parts, oven parts, etc. Examples include utensils and parts used for cooking.

[Method for producing article having excellent corrosion resistance and fingerprint resistance]
There are two methods for producing an article excellent in corrosion resistance and fingerprint resistance according to this embodiment. These two methods will be described sequentially.
A. Article manufacturing method-Part 1
A method of adjusting the surface of the substrate so that the surface roughness Ra is 0.3 μm or more and the glossiness gloss value is 100% or less, and then forming a zirconia film on the surface.

First, the surface of the substrate is adjusted so that the surface roughness Ra is 0.3 μm or more and the glossiness gloss value is 100% or less. Examples of the adjustment method include polishing with an abrasive such as alumina and corundum, and treatment with a chemical such as an ammonium fluoride solution.
The surface roughness Ra can be measured using a surface roughness measuring device such as Tencor p-10. The glossiness gloss value can be measured using a 60 ° gloss meter.
The substrate having the surface roughness Ra and the gloss gloss value thus prepared is washed with a detergent and then cleaned with water.

Next, a coating solution containing a zirconium compound is applied to this surface.
As a zirconium compound, a zirconia sol or each alkoxide is suitable.
The zirconia sol is not particularly limited. For example, those having an average particle size of 5 nm or less, preferably 1 nm or less, have excellent mechanical properties by heat treatment at a relatively low temperature of about 300 ° C. It is preferable because a film can be easily formed.

Although it does not restrict | limit especially as said zirconium alkoxide, For example, a zirconium tetra normal butoxide and a zirconium tetrapropoxide can be mentioned. These zirconium tetranormal butoxide and zirconium tetrapropoxide can be dissolved in an organic solvent such as alcohol, have an appropriate hydrolysis rate, and are easy to handle, so that a film with uniform film quality can be formed.
Since this zirconium alkoxide has high hygroscopicity and is very unstable, it is preferable to use a chelate compound of zirconium alkoxide obtained by chelating zirconium alkoxide.

Examples of the chelate compound of zirconium alkoxide include a compound of zirconium alkoxide and a chelating agent.
Examples of chelating agents include ethanolamines such as monoethanolamine, diethanolamine and triethanolamine, β-diketones such as acetylacetone, methyl acetoacetate, ethyl acetoacetate, diethyl malonate, β-keto acid esters such as ethyl phenoxyacetate, acetic acid And carboxylic acids such as lactic acid, citric acid, benzoic acid and malic acid. In particular, when an acid is used, a weak acid is preferable.

The proportion of the zirconium compound in this coating solution is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 3% by mass or less in terms of zirconia.
When the proportion of the zirconium compound is less than 0.1% by mass, the film thickness of the obtained film is thin and sufficient corrosion resistance cannot be obtained, while when it exceeds 10% by mass, the film peels off.

  When adding a chelating agent to this coating liquid, it is preferable to add a chelating agent to a solvent simultaneously with an alkoxide. Thereby, it is possible to prevent the alkoxide from absorbing moisture. The addition amount of the chelating agent is preferably 10 mol% or more and 100 mol% or less with respect to the number of moles of alkoxide. If the addition amount is less than 10 mol%, a sufficient moisture absorption preventing effect of the alkoxide cannot be obtained. On the other hand, if the addition amount exceeds 100 mol%, the chelation proceeds excessively and solidifies, which is not preferable.

Yttrium (Y) or calcium (Ca) can be added to the zirconium compound as a zirconia stabilizer. Moreover, a silicon compound etc. can also be added as an increase effect.
The silicon compound is not particularly limited as long as it is a silicon compound that can be converted into a silicon oxide by heat treatment, and examples thereof include colloidal silica and silicon alkoxide.

  As the solvent used in this coating solution, any zirconium compound and silicon compound can be used without particular limitation as long as they can dissolve or disperse the zirconium compound and the silicon compound when they contain the above-described zirconium compound. In addition to lower alcohols such as water, methanol, ethanol, 2-propanol and 1-butanol, ethers such as ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), and ethylene glycol monobutyl ether (butyl cellosolve) (Cellosolves), ketones such as acetone, dimethyl ketone, diethyl ketone and methyl ethyl ketone, glycols such as ethylene glycol, higher alcohols and esters. In particular, when water is used as a solvent, the stability of the coating solution is reduced if water is contained in an amount that is greater than or equal to the amount of hydrolysis of the alkoxide.

  There is no restriction | limiting in particular as an application | coating method, A spray method, a dip method, a brush coating method etc. are applicable. In coating, the thickness of the coating film is preferably adjusted so that the film thickness after heat treatment is in the range of 0.05 μm to 1 μm.

The coating film thus obtained is subjected to a heat treatment time of not less than 1 minute and not more than 24 hours at a heat treatment temperature of not less than 250 ° C. and not more than the heat resistant temperature of the substrate, preferably not less than 400 ° C. and not more than the heat resistant temperature of the substrate. And heat treatment to form a zirconia film. The atmosphere during the heat treatment is not particularly limited, and is usually performed in an air atmosphere.
Here, when the heat treatment temperature is lower than 250 ° C., the mechanical strength of the obtained zirconia film becomes insufficient. In addition, since there exists a possibility that a base material may deform | transform if heat processing temperature is too high, it is necessary to adjust according to the base material which uses heat processing temperature.
As described above, a zirconia film can be formed on the surface of the substrate.

Here, it is preferable to form a magnesium-containing film on the zirconia film in order to eliminate the generation of rainbow colors from the zirconia film and to make the stain caused by the adhesion of fingerprints less noticeable.
The magnesium-containing film can be obtained by applying a coating solution containing a magnesium compound to the surface of the zirconia film and heat-treating it.

  As the magnesium compound, magnesium alkoxide such as magnesium methoxide, magnesium ethoxide, magnesium propoxide and magnesium butoxide, magnesium salt soluble in a solvent such as magnesium nitrate, and the like can be used.

In order to improve the water resistance and acid resistance of the magnesium-containing film, it is preferable to add a zirconium compound or an aluminum compound to the magnesium compound.
As this aluminum compound, alumina sol or an alkoxide thereof is suitable. Examples of the alkoxide include aluminum butoxide and aluminum propoxide. In particular, aluminum alkoxide is preferable because it can be dissolved in an organic solvent.

  As a solvent used in this coating solution, any solvent that can dissolve or disperse a magnesium compound or an aluminum compound can be used without particular limitation. For example, water, methanol, ethanol, 2-propanol, 1- In addition to lower alcohols such as butanol, ethers (cellosolves) such as ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), acetone, dimethyl ketone, diethyl ketone And ketones such as methyl ethyl ketone, glycols such as ethylene glycol, higher alcohols, esters and the like. In particular, when water is used as a solvent, the stability of the coating solution is lowered when water in an amount greater than the hydrolysis amount of magnesium or aluminum alkoxide is contained, so the amount must be less than the hydrolysis amount of alkoxide. .

The ratio of the magnesium compound in this coating solution is preferably 10% by mass or more and 90% by mass or less with respect to the total solid content (magnesia + zirconia + alumina) in terms of magnesia.
When the proportion of the magnesium compound is less than 10% by mass in terms of magnesia, the corrosion resistance against the alkali melting reaction becomes insufficient. On the other hand, when it exceeds 90% by mass, the water resistance, acid resistance, or wear resistance is decreased. Absent.
As a method for adding the magnesium compound, a method of directly mixing in a solution containing a zirconium compound or an aluminum compound is preferable.

By the way, since aluminum alkoxide has high hygroscopicity and is very unstable, it is preferable to use a chelate compound of aluminum alkoxide obtained by chelating aluminum alkoxide.
Examples of the aluminum alkoxide chelate compound include a compound of an aluminum alkoxide and a chelating agent.
Examples of chelating agents include ethanolamines such as monoethanolamine, diethanolamine and triethanolamine, β-diketones such as acetylacetone, methyl acetoacetate, ethyl acetoacetate, diethyl malonate, β-keto acid esters such as ethyl phenoxyacetate, acetic acid And carboxylic acids such as lactic acid, citric acid, benzoic acid and malic acid. In particular, when an acid is used, a weak acid is preferable.

  There is no restriction | limiting in particular as an application | coating method, A spray method, a dip method, a brush coating method etc. are applicable. In coating, the thickness of the coating film is preferably adjusted so that the film thickness after heat treatment is in the range of 50 nm to 1000 nm.

The coating film thus obtained is subjected to a heat treatment time of not less than 1 minute and not more than 24 hours at a heat treatment temperature of not less than 250 ° C. and not more than the heat resistant temperature of the substrate, preferably not less than 400 ° C. and not more than the heat resistant temperature of the substrate. And heat treatment to form a magnesium-containing film. The atmosphere during the heat treatment is not particularly limited, and is usually performed in an air atmosphere.
Here, when the heat treatment temperature is less than 250 ° C., the mechanical strength of the obtained magnesium-containing coating becomes insufficient.
As described above, the magnesium-containing film can be laminated on the surface of the zirconia film.

B. Manufacturing method of articles-2
The surface of the substrate is heated, and then a coating solution containing a zirconium compound is applied to the heated surface, and the surface roughness Ra is 0.3 μm or more and the glossiness gloss value is 100% or less on the surface. A method of forming a film containing zirconium oxide.

In this method, the surface of the substrate is heated to have a surface temperature of 250 to 500 ° C., preferably 300 to 450 ° C., and the heated surface contains the above-described zirconium compound. The coating solution is applied using a spray or the like.
In the coating solution containing the zirconium compound, the solvent evaporates and the zirconium compound reacts to produce zirconium oxide at the stage where the surface temperature adheres to the surface of the substrate having a surface temperature of 250 ° C. or higher.
As a result, a zirconia film having a surface roughness Ra of 0.3 μm or more and a glossiness gloss value of 100% or less is formed on the surface of the substrate.
As described above, a zirconia film can be formed on the surface of the substrate.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited by these Examples.

A. Crystallized glass stove top “Example 1”
A stove top made of crystallized glass is prepared, and the surface of the stove top is dipped and corroded with a 3% ammonium fluoride solution to obtain a surface roughness Ra of 0.4 μm and a gloss gloss value of 80%. Prepared and cleaned this surface.

Next, a zirconium oxide sol aqueous dispersion (ZrO ₂ content: 2% by mass; manufactured by Sumitomo Osaka Cement) was applied to this surface by brushing so that the average film thickness after baking was 50 nm. The base material with a film | membrane of Example 1 in which the zirconia film | membrane was formed in the surface was heat-processed at 750 degreeC inside for 1 hour.

"Example 2"
Magnesium nitrate and aluminum isopropoxide were dissolved in 2-propanol so that the solid content was 2% by mass and the oxide solid content ratio was MgO / (Al ₂ O ₃ + MgO) = 30%. Was made.
Next, this coating solution was applied to the substrate with a coating obtained according to Example 1 by brushing, and heat-treated at 600 ° C. for 1 hour in the air, so that the magnesia coating was formed on the zirconia coating. The formed base material with a film of Example 2 was produced.

"Example 3"
A substrate with a film of Example 3 was produced according to Example 1 except that the average film thickness after baking in Example 1 was changed from 50 nm to 200 nm.

"Comparative Example 1"
A substrate with a film of Comparative Example 1 was produced in the same manner as in Example 1 except that the surface of the stove top was not subjected to immersion corrosion.

"Comparative Example 2"
A substrate with a film of Comparative Example 2 was produced in the same manner as in Example 2 except that the surface of the stove top was not subjected to immersion corrosion.

B. Smoked oven cavity "Example 4"
A smoke oven cavity (oven casing) was prepared.
On the other hand, 10 parts by mass of zirconium tetrabutoxide, 0.5 parts by mass of tetramethoxysilane, 5 parts by mass of acetylacetone, and 84.5 parts by mass of 2-propanol were mixed to obtain a coating solution.

Next, the oven cavity is preheated to 250 ° C., the surface of the hot oven cavity is spray-coated with 50 g of the coating liquid, and then the oven cavity is heated and baked at 400 ° C. for 10 minutes. A substrate with a coating of Example 4 having a zirconia coating formed on the surface was prepared.
This zirconia film had an average film thickness of 80 nm, a surface roughness Ra of 0.3 μm, and a glossiness gloss value of 50%.

"Example 5"
The surface of the smoked oven cavity obtained according to Example 4 was spray-coated with 50 g of a 1% by mass magnesium nitrate aqueous solution, and then the oven cavity was heated and baked at 400 ° C. for 10 minutes. The base material with a film of Example 5 in which a magnesia film was formed on the film was produced.

"Example 6"
A substrate with a film of Example 6 was produced in the same manner as in Example 4 except that the average film thickness after baking in Example 4 was changed from 80 nm to 200 nm.

“Comparative Example 3”
Without preheating the oven cavity, 50 g of the coating solution of Example 4 was spray-coated on the surface of the oven cavity, and then baked at 400 ° C. for 10 minutes to form a zirconia film on the surface. A substrate with a film was prepared. The surface roughness Ra of this zirconia film was 0.06 μm, and the glossiness gloss value was 90%.

“Comparative Example 4”
A substrate with a coating of Comparative Example 4 was produced according to Example 4 except that the oven cavity was not preheated.

C. Stainless steel frying pan "Example 7"
A stainless steel frying pan was prepared, the surface of the frying pan was subjected to a hairline treatment, the surface was polished, the surface roughness Ra was adjusted to 0.5 μm, and the gloss gloss value was adjusted to 90%, followed by washing.

Next, 10 parts by mass of zirconium tetrabutoxide, 10 parts by mass of ethyl acetoacetate, and 80.0 parts by mass of 2-propanol were mixed to obtain a coating solution.
Next, dip coating is performed in which the above-mentioned frying pan is dipped and pulled up in this coating liquid, and then baked at 250 ° C. for 30 minutes to produce a substrate with a film of Example 7 in which a zirconia film is formed on the surface. did.
The average film thickness of this zirconia film was 0.1 μm.

"Example 8"
Magnesium nitrate and zirconium butoxide were dissolved in 2-propanol so that the solid content was 2% by mass and the oxide solid content ratio was MgO / (ZrO ₂ + MgO) = 30% to prepare a coating solution of Example 8.
Next, dip coating is performed by immersing and lifting the substrate with a coating obtained according to Example 1 in this coating solution, and heat treatment is performed at 250 ° C. for 1 hour in the air, whereby magnesia and A substrate with a film of Example 8 on which a zirconia composite oxide film was formed was produced.

"Example 9"
A substrate with a film of Example 9 was produced according to Example 7 except that the average film thickness after baking in Example 7 was changed from 0.1 μm to 200 nm.

"Comparative Example 5"
A substrate with a film of Comparative Example 5 was produced according to Example 6 except that the hairline treatment was not performed.

“Comparative Example 6”
A substrate with a film of Comparative Example 6 was produced according to Example 7 except that the hairline treatment was not performed.

"Evaluation of film"
The film | membrane characteristic of the base material with a film of Examples 1-9 and the base material with a film of Comparative Examples 1-6 was evaluated. The evaluation results are shown in Tables 1 to 3.
Here, the first example is a stove top made of crystallized glass that is not formed with a film, the second example is a smoked oven cavity that is not formed with a film, and a stainless steel frying pan that is not formed with a film. It was set as Conventional Example 3.
The evaluation method is as follows.

(1) Surface roughness Ra
It measured using Tencor p-10 (surface roughness measuring apparatus).
(2) Glossiness gloss value Measured using a 60 ° gloss meter.
(3) Alkali resistance 1 g of potassium carbonate was placed on a substrate with a film, and the degree of corrosion in the film when heated at 500 ° C. for 1 hour was visually observed.
(4) Interference color Evaluated visually.
(5) Visibility of fingerprints Evaluated visually.

  In Table 2, in Examples 4 to 6, the surface roughness and the gloss gloss value of the substrate with a film (= Example 4) after the spray film was formed in Conventional Example 6 were measured. Moreover, Comparative Examples 3-4 measured the surface roughness and glossiness gloss value of the base material with a film (= Comparative Example 3) after forming the spray film in Conventional Example 6.

According to Tables 1 to 3, when the surface roughness Ra of the surface of the substrate is 0.3 μm or more and the glossiness gloss value is 100% or less, and a film containing zirconia is formed on this surface, iridescent It was possible to suppress the occurrence and make it difficult to see the fingerprint.
Furthermore, when a layer containing magnesium was laminated on a film containing zirconia, the generation of rainbow colors was further suppressed, and the fingerprint could be made more difficult to see.

  The article excellent in corrosion resistance and fingerprint resistance according to the present invention is formed by forming a film containing zirconium oxide on the surface of a substrate having a surface roughness Ra of 0.3 μm or more and a glossiness gloss value of 100% or less. Can improve the corrosion resistance of ingredients containing alkaline substances during cooking, can prevent the generation of rainbow colors that are interference colors, and can make it difficult to see dirt caused by fingerprints. Therefore, not only cooking utensils used for cooking food such as frying pans, pans, cooking hot plates, cooking tools such as grills, various dishes, stove tops, stove parts, oven parts, etc. Even in the field of articles requiring high corrosion resistance and fingerprint resistance, the industrial significance is extremely large.

Claims (5)

The surface roughness Ra is the surface of the substrate and gloss gloss value than 0.3μm is not more than 100%, Ri Na to form a film containing zirconium oxide,
An article excellent in corrosion resistance and fingerprint resistance, wherein a film containing magnesium is further formed on the film containing zirconium oxide . The article having excellent corrosion resistance and fingerprint resistance according to claim 1 , wherein the substrate is made of one or more of ceramics, metal composites, and metals. A cooking utensil provided with an article excellent in corrosion resistance and fingerprint resistance according to claim 1 or 2 ,
A cooking utensil that can be used at 300 ° C. or higher. The surface of the substrate is adjusted so that the surface roughness Ra is 0.3 μm or more and the glossiness gloss value is 100% or less, and then a film containing zirconium oxide is formed on the surface ,
A method for producing an article excellent in corrosion resistance and fingerprint resistance, wherein a film containing magnesium is further formed on the film containing zirconium oxide . The surface of the substrate is heated, and then a coating solution containing a zirconium compound is applied to the heated surface, and the surface roughness Ra is 0.3 μm or more and the glossiness gloss value is 100% or less on the surface. Forming a film containing zirconium oxide ,
A method for producing an article excellent in corrosion resistance and fingerprint resistance, wherein a film containing magnesium is further formed on the film containing zirconium oxide .