阅读说明：本技术 防污皮膜、玻璃陶瓷产品、防污皮膜形成用涂料以及玻璃陶瓷产品的制造方法 (Antifouling coating film, glass ceramic product, coating material for forming antifouling coating film, and method for producing glass ceramic product ) 是由 前田大作 茂启二郎 于 2019-09-05 设计创作，主要内容包括：本发明的防污皮膜包含：成分(A)：锆；成分(B)：镧；以及成分(C)：选自由硅、磷和硼组成的组中的至少一种,其中,当将成分(A)、成分(B)和成分(C)的质量换算成作为氧化物的质量时,成分(A)和成分(B)的总计质量相对于防污皮膜的质量为90％以上且95％以下,当将成分(B)的质量/(成分(A)和成分(B)的总计质量)×100设为X时,X为20％以上且50％以下,成分(C)的质量相对于防污皮膜的质量为5％以上且[6+(X-20)/6]％以下。(The antifouling coating film of the present invention comprises: component (A): zirconium; component (B): lanthanum; and component (C): at least one selected from the group consisting of silicon, phosphorus, and boron, wherein when the mass of the component (a), the component (B), and the component (C) is converted to the mass as an oxide, the total mass of the component (a) and the component (B) is 90% or more and 95% or less with respect to the mass of the antifouling film, and when the mass of the component (B/(the total mass of the component (a) and the component (B) × 100 is X, X is 20% or more and 50% or less, and the mass of the component (C) is 5% or more and [6+ (X-20)/6% or less with respect to the mass of the antifouling film.)

1. An antifouling coating film, comprising:

component (A): zirconium;

component (B): lanthanum; and

component (C): at least one selected from the group consisting of silicon, phosphorus and boron, wherein,

when the mass of the component (A), the component (B) and the component (C) is converted into the mass of the oxides thereof,

the ratio of the total mass of the component (A) and the component (B) to the mass of the antifouling coating film is 90% to 95%,

x is 20% or more and 50% or less, where X is a ratio obtained from the formula of mass of the component (B)/total mass of the component (A) and the component (B) × 100,

the proportion of the mass of the component (C) to the mass of the antifouling coating film is 5% or more and [6+ (X-20)/6] or less.

2. A glass-ceramic product, comprising:

a substrate made of glass-ceramic; and the antifouling coating film according to claim 1 formed on the surface of the substrate.

3. The glass ceramic product according to claim 2,

the apparent reflectance R of the surface of the antifouling coating₁% of the apparent reflectance R of the substrate surface₂% difference (R)₁-R₂) Is more than 1 percent.

4. An antifouling coating film-forming coating material, comprising:

component (a): at least one selected from the group consisting of zirconium oxide, zirconium ion, and zirconium oxide precursor;

component (b): at least one selected from the group consisting of lanthanum oxide, lanthanum ion, and lanthanum oxide precursor;

component (c): at least one selected from the group consisting of an oxide, an oxide ion, and an oxide precursor of an element which is at least one selected from the group consisting of silicon, phosphorus, and boron; and

a dispersion medium in which, among others,

when the mass of the component (a), the component (b) and the component (c) is converted into the mass of oxides thereof,

the ratio of the total mass of the component (a) and the component (b) to the mass of the total solid content of the coating material is 90% to 95%,

x is 20% or more and 50% or less, where X is a ratio obtained from the formula of mass of the component (b)/(total mass of the component (a) and the component (b) × 100,

the mass ratio of the component (c) to the total solid content is 5% or more and [6+ (X-20)/6 ]% or less.

5. A method for producing a glass ceramic product, comprising the steps of:

a step of applying the antifouling coating film-forming coating material according to claim 4 to the surface of a substrate made of a glass ceramic to form a coating film; and

and a step of forming an antifouling coating film on the surface of the base by heat-treating the coating film at a temperature of 650 ℃ or higher and 950 ℃ or lower.

Technical Field

The present invention relates to an antifouling coating film, a glass ceramic product, a coating material for forming an antifouling coating film, and a method for producing a glass ceramic product.

The present application claims priority based on japanese patent application No. 2018-171189, which was filed in japan on 13/9/2018, and the contents thereof are incorporated herein.

Background

Glass ceramic products are widely used as top plates for gas furnaces, induction heaters, and radiant heater products because of their excellent properties such as heat resistance, appearance, and high surface hardness. However, glass ceramic products have a disadvantage that cleaning is difficult when substances such as foods are burnt at high temperatures. In order to compensate for such a disadvantage of cleanability, it has been studied to form an antifouling coating film made of a fluororesin or an inorganic material on the surface of a glass substrate constituting a glass ceramic product.

However, the antifouling coating film formed on the surface of the glass substrate has the following drawbacks.

A glass ceramic product in which an antifouling film made of a fluororesin is formed on the surface of a glass substrate has a disadvantage of being easily deteriorated under temperature conditions such as exceeding 300 ℃ or abrasion conditions.

As an antifouling coating film made of an inorganic material, for example, an antifouling coating film made of silicon oxide and zirconium oxide is known (for example, refer to patent document 1).

However, the antifouling coating film of patent document 1 has the following technical problems: the scorched food containing sugar has poor cleaning performance; and if a contaminant containing an acid or an alkali is burned on the surface of the antifouling coating film at a high temperature, the antifouling coating film is corroded and the appearance is changed. On the other hand, regarding the appearance, particularly, for example, with a thick antifouling film in which the difference between the apparent reflectance of the surface of the antifouling film and the apparent reflectance of the surface of the glass substrate on which the antifouling film is not formed is 1% or more, the change in the interference color of the antifouling film due to corrosion is likely to be conspicuous. Therefore, the film thickness of the antifouling coating film must be reduced. However, reducing the film thickness of the antifouling coating film not only limits the appearance of the product, but also is disadvantageous in that the function of the antifouling coating film deteriorates.

Examples of the deterioration of the function of the antifouling coating film when the film thickness of the antifouling coating film is reduced include (1) a reduction in the abrasion resistance and the cleanability of the coating film; and (2) if the antifouling coating film-forming coating material is applied thinly to the surface of the glass substrate to form a coating film and the drying temperature of the coating film is increased to, for example, 850 ℃.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 5403094

Disclosure of Invention

Technical problem to be solved by the invention

The present invention has been made in view of the above circumstances, and an object thereof is to provide an antifouling film, a glass ceramic product, an antifouling film forming coating material, and a method for producing a glass ceramic product, which can easily clean a burned sugar-containing pollutant, can improve the durability against the corrosive action of an acid or an alkali contained in the pollutant, and can improve the mechanical strength such as abrasion resistance without impairing the cleanability and chemical durability (durability against an acid or an alkali).

Means for solving the technical problem

The present inventors have conducted extensive studies to solve the above-described technical problems, and as a result, have found that an antifouling film capable of improving the above-described problems can be obtained by forming an antifouling film having the following characteristics, and have completed the present invention.

That is, an antifouling coating film according to a first aspect of the present invention includes: component (A): zirconium; component (B): lanthanum; and component (C): at least one selected from the group consisting of silicon, phosphorus, and boron, wherein when the mass of the component (a), the component (B), and the component (C) is converted into the mass of an oxide and used, the ratio of the total mass of the component (a) and the component (B) to the mass of the antifouling film is 90% or more and 95% or less, and when the ratio obtained from the formula of mass of the component (B/(the total mass of the component (a) and the component (B) × 100 is X, X is 20% or more and 50% or less, and the ratio of the mass of the component (C) to the mass of the antifouling film is 5% or more and [6+ (X-20)/6 ]% or less.

The glass ceramic product according to the second aspect of the present invention is characterized by comprising: a substrate; and an antifouling coating film according to the first aspect of the present invention formed on the surface of the base.

In the glass ceramic product, the apparent reflectance R of the surface of the antifouling coating film is preferably₁% of the apparent reflectance R of the substrate surface₂% difference (R)₁-R₂) Is more than 1 percent.

A third aspect of the present invention provides an antifouling coating film-forming paint comprising: component (a): at least one selected from the group consisting of zirconium oxide, zirconium ion, and zirconium oxide precursor; component (b): at least one selected from the group consisting of lanthanum oxide, lanthanum ion, and lanthanum oxide precursor; component (c): at least one selected from the group consisting of an oxide, an oxide ion, and an oxide precursor of an element which is at least one selected from the group consisting of silicon, phosphorus, and boron; and a dispersion medium, wherein when the mass of the component (a), the component (b), and the component (c) is converted into the mass of an oxide and used, the ratio of the total mass of the component (a) and the component (b) to the mass of the total solid content of the coating material is 90% or more and 95% or less, when the ratio obtained by the formula of mass of the component (b/(the total mass of the component (a) and the component (b) × 100 is defined as X, X is 20% or more and 50% or less, and the ratio of the mass of the component (c) to the mass of the total solid content is 5% or more and [6+ (X-20)/6 ]% or less.

A method for producing a glass ceramic product according to a fourth aspect of the present invention is characterized by comprising: a step of applying the antifouling coating film-forming coating material of the present invention to the surface of a substrate to form a coating film; and a step of forming an antifouling coating film on the surface of the base by heat-treating the coating film at a temperature of 650 ℃ to 950 ℃.

Effects of the invention

According to the present invention, there can be provided an antifouling film, a glass ceramic product, an antifouling film-forming coating material, and a method for producing a glass ceramic product, which can easily clean a burned sugar-containing pollutant, can improve the durability against the corrosive action of an acid or an alkali contained in the pollutant, and can improve the mechanical strength such as abrasion resistance without impairing the cleanability and chemical durability (durability against an acid or an alkali).

Detailed Description

Embodiments of the antifouling coating film, glass ceramic product, antifouling coating film-forming paint, and method for producing glass ceramic product of the present invention will be described.

The present embodiment is specifically described for better understanding of the gist of the invention, and does not limit the invention unless otherwise specified.

The type, number, ratio, time, etc. can be changed, omitted, added, replaced, and other changes without departing from the spirit of the present invention. In the respective embodiments, preferred examples may be shared with each other.

[ antifouling coating films ]

The antifouling coating film of the present embodiment has the following characteristics. Namely, the method comprises the following steps: component (A): zirconium; component (B): lanthanum; and component (C): at least one selected from the group consisting of silicon, phosphorus, and boron. When the mass of the component (a), the component (B), and the component (C) is converted to the mass as an oxide, the ratio of the total mass of the component (a) and the component (B) to the mass of the antifouling coating film is 90% to 95%. The ratio X represented by the formula of mass of the component (B)/(total mass of the component (a) and the component (B) × 100 is 20% or more and 50% or less. The proportion of the mass of the component (C) to the mass of the antifouling film is 5% or more and [6+ (X-20)/6 ]% or less.

In the following description, components (a) to (C) may be respectively described as (a) zirconium, (B) lanthanum, and (C) silicon.

The antifouling coating film of the present embodiment is preferably provided on an arbitrarily selected region of an arbitrarily selected substrate, for example, at least a part of the surface of the substrate, that is, a region where scorching stains or oil stains of foods or the like may adhere.

Examples of the substrate to which the antifouling coating film of the present embodiment is applied include cooking articles such as a top plate of a gas furnace, an Induction Heating (IH) furnace, a radiation furnace, and the like, an oven tray of an oven, an oven case, and an oven floor, which are products.

Examples of the other substrate include a glaze-treated product having a glaze-treated surface, a transparent or black glass ceramic, and the like.

Examples of the glaze-treated product include a top plate of various ranges, an enamel-made oven tray, an oven case, a pottery-made or magnetic-made oven tray, and an oven floor plate.

Examples of the transparent or black crystallized glass include crystallized glass for a ceiling of a gas furnace, a ceiling of an IH furnace, and a ceiling of a radiant furnace. The transparent glass also includes glass colored on the back surface of the transparent crystallized glass.

However, the antifouling coating film of the present embodiment can be applied to various fields other than the above.

The antifouling coating film of the present embodiment includes: (A) zirconium; (B) lanthanum; and (C) at least one selected from the group consisting of silicon, phosphorus, and boron.

Component (A): the zirconium of the component (A) may be a simple substance of zirconium element in the antifouling coating film, and may be zirconium oxide (zirconium oxide: ZrO)₂) The zirconium element may be a mixture of a simple substance of zirconium and zirconium oxide. That is, the component (A) preferably contains a zirconium atomElemental substance and/or zirconium oxide.

Component (B): the lanthanum as the component (B) in the antifouling coating film may be a simple lanthanum element or may be lanthanum oxide (lanthanum oxide: La)₂O₃) Or a mixture of the simple lanthanum element and lanthanum oxide. That is, the component (B) preferably contains at least one of a simple substance of lanthanum element and an oxide of lanthanum.

Component (C): the silicon of the component (C) may be a simple substance of silicon in the antifouling coating film, and may be silicon oxide (silicon oxide: SiO)₂) The silicon oxide may be a mixture of a simple substance of silicon and silicon oxide.

Component (C): the phosphorus as the component (C) may be a phosphorus element in the antifouling coating film, and may be phosphorus oxide (phosphorus pentoxide: P)₂O₅) The phosphorus element can also be a mixture of a phosphorus element and a phosphorus oxide.

Component (C): the boron as the component (C) in the antifouling coating film may be a simple boron element or may be a boron oxide (boron oxide: B)₂O₃) The boron element may be a mixture of a boron element and a boron oxide.

That is, the component (C) preferably contains at least one of a simple substance of silicon element, silicon oxide, a simple substance of phosphorus element, a phosphorus oxide, a simple substance of boron element, and a boron oxide.

In the antifouling film of the present embodiment, when the mass of the component (a), the component (B), and the component (C) is converted into the mass as an oxide, the total mass of the component (a) and the component (B) is 90% or more and 95% or less, preferably 92.5% or more and 95% or less, with respect to the mass (total mass) of the antifouling film. Further preferably 93.0% or more and 95.0% or less.

If the total mass of the component (a) and the component (B) is 90% or more based on the mass (total mass) of the antifouling film, the antifouling film is not deteriorated in the cleanability and the chemical durability against acids and alkalis. On the other hand, if the total mass of the component (a) and the component (B) is not more than 95% with respect to the mass (total mass) of the antifouling film, the abrasion resistance of the antifouling film is not reduced.

The conversion into the mass as an oxide may mean that the mass values are obtained by arbitrarily selected measurement on the basis that silicon, at least one of phosphorus and boron, zirconium and lanthanum contained in the material used for forming the antifouling coating are all oxides.

The mass (total mass) of the antifouling coating film may be a value obtained by summing up a mass in terms of an oxide of the component (a), a mass in terms of an oxide of the component (B), and a mass in terms of an oxide of the component (C).

In the antifouling coating film of the present embodiment, when the mass of the component (a), the component (B), and the component (C) is converted to the mass as an oxide, the ratio X obtained from the formula of mass of the component (B)/(total mass of the component (a) and the component (B) × 100 is 20% or more and 50% or less, preferably 25% or more and 45% or less, and more preferably 30% or more and 40% or less.

When X is 20% or more, the chemical durability (durability against acid and alkali) of the antifouling film is not lowered, and when the antifouling film is applied to a glass ceramic product, the apparent reflectance R on the surface of the antifouling film, which will be described later, is₁% of the apparent reflectance R of the surface of the glass ceramic substrate₂% difference (R)₁-R₂) In the case of the antifouling coating of 1% or more, the change in appearance of the antifouling coating does not increase even after removing scorching of an acid/alkali-containing substance such as ketchup or jam. On the other hand, if X is not more than 50%, the adhesion of the antifouling coating to the glass ceramic substrate will not be reduced when the antifouling coating is applied to the glass ceramic product.

In the antifouling film of the present embodiment, when the mass of the component (a), the component (B), and the component (C) is converted to the mass as an oxide, the ratio of the mass of the component (C) to the mass (total mass) of the antifouling film is 5% or more and [6+ (X-20)/6 ]% or less.

If the above-mentioned ratio is 5% or more, the abrasion resistance of the antifouling coating film is not lowered. On the other hand, if the ratio is not more than [6+ (X-20)/6]% of the total amount of the components does not decrease the detergency of the antifouling coating film. Further, since the chemical durability (durability against acids and alkalis) of the antifouling coating film does not decrease, the antifouling coating film is applied to glassIn the case of ceramic products, the apparent reflectance R on the surface of an antifouling coating film described later₁% of the apparent reflectance R of the surface of the glass ceramic substrate₂% difference (R)₁-R₂) In the case of the antifouling coating of 1% or more, the change in appearance of the antifouling coating does not increase even after removing scorching of an acid/alkali-containing substance such as ketchup or jam.

In the antifouling film of the present embodiment, when the mass of the component (a), the component (B), and the component (C) is converted into the mass as an oxide, the ratio of the mass of the component (C) to the mass (total mass) of the antifouling film can be arbitrarily selected within the above range. For example, the concentration may be 5.0 to 11.0%, preferably 5.5 to 10.0%, more preferably 6.0 to 9.5%, and still more preferably 6.5 to 8.6%. But is not limited to only these examples.

The mass of the component (a), the component (B), and the component (C) contained in the antifouling coating film is measured as, for example, the oxide, and examples thereof include a fluorescent X-ray method and a method using an electron probe microanalyzer.

For example, the converted mass of the component (A) may be ZrO₂The mass of (b) is a value measured by quantitatively analyzing the antifouling coating film by a fluorescent X-ray method. The component (B) may be present in a mass of La₂O₃The mass of (b) is a value measured by the same method as described above, and the mass of the component (C) may be SiO₂、P₂O₅、B₂O₃The mass of at least one of the above-mentioned compounds is measured by the same method as described above.

The antifouling coating film of the present embodiment is formed by heating, and therefore preferably does not contain a dispersion medium such as a solvent. The antifouling coating film of the present embodiment may be formed only from the component (a), the component (B), and the component (C).

The antifouling coating film of the present embodiment may contain a predetermined amount, for example, a small amount of the component (D) other than the components (a), (B), and (C), for example, a binder or a surfactant. The proportion of the component (D) may be, for example, 0 to 10% by mass, or 0.01 to 8.0% by mass, or 0.1 to 6.0% by mass, relative to the total amount of the components (a) to (C) (the elements, oxides, and mixtures are also calculated as the above-mentioned respective components) and the component (D) of the antifouling film. The proportion may be 0.5 to 4.0 mass% or 1.0 to 2.0 mass%.

The proportions of the components (A) to (C) can be arbitrarily selected with respect to the total amount containing the component (D). For example, the content may be 90.0 to 100% by mass, or 93.0 to 99.9% by mass. The proportion may be 95.0 to 99.7 mass%, or 97.0 to 99.5 mass%, or 98.0 to 99.0 mass%. But is not limited to only these examples.

The thickness of the antifouling coating film of the present embodiment can be arbitrarily selected, and for example, may be 1nm to 1mm, preferably 10nm or more and 200nm or less, more preferably 15nm or more and 150nm or less, and further preferably 20nm or more and 120nm or less.

If the thickness of the antifouling coating film is 10nm or more, sufficient antifouling property can be imparted to the substrate provided with the antifouling coating film. On the other hand, if the thickness of the antifouling coating film is 200nm or less, the antifouling coating film has sufficient impact resistance, and therefore cracks are less likely to be generated by external force. Further, since the gloss of the antifouling coating film can be suppressed, the appearance such as the color tone of the substrate itself provided with the antifouling coating film is not impaired.

The method for measuring the thickness of the antifouling film of the present embodiment can be arbitrarily selected, but a method of observing the cross section of the antifouling film by a Transmission Electron Microscope (TEM), an optical film thickness measurement method, and the like can be cited.

Preferred examples of the method for producing the antifouling film according to the present embodiment will be described.

The antifouling film of the present embodiment is formed by applying a coating material for forming an antifouling film, which will be described later, to at least a part of an arbitrarily selected substrate, for example, a surface of the substrate, in a region where scorching or oil stains of a substance such as food may occur, and drying the coating material as necessary. The coating film can be obtained by heat-treating the coating film.

Examples of the coating method of the antifouling coating film-forming coating material include a spray coating method, a bar coating method, a spin coating method, a dip coating method, a roll coating method, and a screen printing method.

The conditions of the heat treatment can be arbitrarily selected, and for example, the heating temperature is preferably 650 ℃ or higher and 950 ℃ or lower, more preferably 700 ℃ or higher and 900 ℃ or lower, and further preferably 800 ℃ or higher and 900 ℃ or lower. But is not limited to these conditions. The thickness of the obtained coating film can be arbitrarily selected, but is, for example, preferably 10nm or more and 200nm or less, more preferably 15nm or more and 150nm or less, and further preferably 20nm or more and 120nm or less. The heating environment can be arbitrarily selected, and for example, heating may be performed in an atmospheric environment.

According to the antifouling coating film of the present embodiment, the cleaning property against scorching of the antifouling coating film, particularly scorching of sugar-containing pollutants that are difficult to remove in conventional inorganic antifouling coating films, can be improved.

Further, the antifouling coating film of the present embodiment can improve the durability against acids and alkalis, as compared with conventional inorganic antifouling coatings. This makes the antifouling coating film less likely to be corroded by the pollutant. Therefore, the apparent reflectance R is also at the surface of the antifouling coating film described later₁% of the apparent reflectance R of the surface of the glass ceramic substrate₂% difference (R)₁-R₂) In the antifouling coating film having a thickness of 1% or more, for example, even in an antifouling coating film having a relatively large film thickness, appearance change due to change in interference color of the antifouling coating film after removal of scorch hardly occurs. As a result, the range of choices of the appearance of the product is expanded. Further, by increasing the thickness of the antifouling coating film, the cleaning property and the wear resistance can be improved as compared with an antifouling coating film having a small thickness, and the function of the antifouling coating film can be suppressed from being lowered by high-temperature firing at 850 ℃.

Further, according to the antifouling coating film of the present embodiment, the abrasion resistance can be improved while maintaining the cleaning property and the durability against acid and alkali.

[ glass ceramic product ]

The glass ceramic product of the present embodiment has: a substrate made of glass-ceramic; and an antifouling coating film of the present embodiment formed on the surface of the base.

Examples of the glass ceramic product according to the present embodiment include cooking articles such as a top plate of a gas furnace, an Induction Heating (IH) furnace, a radiant furnace, and the like, an oven tray of an oven, an oven case, and an oven floor. However, it is not limited to these examples. Any glass-ceramic product can be used as long as it is a product in which stains may occur.

In the glass ceramic product of the present embodiment, the apparent reflectance R of the surface of the antifouling coating film provided on the base is₁% of the apparent reflectance R of the substrate surface₂% difference (R)₁-R₂) Preferably 1% or more, preferably 3% or more and 20% or less.

If difference (R)₁-R₂) When the content is 1% or more, not only the cleaning property and the abrasion resistance can be improved, but also the function of the antifouling coating film can be suppressed from being lowered by high-temperature firing at 850 ℃.

In the glass ceramic product of the present embodiment, the apparent reflectance (R) of the surface of the antifouling coating film is measured₁) % and apparent reflectance (R) of the substrate surface₂) % of the total amount of the components, which is determined by the following method, may be mentioned Japanese Industrial Standard JIS Z8722: 2009 "color measurement method — method described in reflection object color and transmission object color".

As the substrate, a substrate made of glass ceramics similar to the substrate exemplified as the substrate used in the antifouling coating film of the present embodiment can be cited.

The thickness of the substrate is not particularly limited, and may be appropriately adjusted depending on the kind of the glass ceramic product, the place (position) to which the glass ceramic product is applied, and the like.

The glass ceramic product of the present embodiment has the antifouling coating film of the present embodiment. Therefore, the cleaning property of the inorganic anti-fouling film against scorching, particularly, the scorching of sugar-containing contaminants that are difficult to remove in the conventional inorganic anti-fouling film, can be improved. Further, according to the glass ceramic product of the present embodiment, the durability of the antifouling film against acid and alkali can be improved as compared with the conventional inorganic antifouling film. Further, according to the glass ceramic product of the present embodiment, the abrasion resistance of the antifouling coating film can be improved while maintaining the cleanability and the durability against acids and alkalis of the antifouling coating film.

[ antifouling coating Forming coating Material ]

The antifouling coating film-forming coating material of the present embodiment includes: component (a): at least one selected from the group consisting of zirconium oxide, zirconium ion, and zirconium oxide precursor; component (b): at least one selected from the group consisting of lanthanum oxide, lanthanum ion, and lanthanum oxide precursor; component (c): at least one selected from the group consisting of an oxide, an oxide ion, and an oxide precursor of an element which is at least one selected from the group consisting of silicon, phosphorus, and boron; and a dispersion medium. When the mass of the component (a), the component (b), and the component (c) is converted to the mass as an oxide, the ratio of the total mass of the component (a) and the component (b) to the mass of the total solid component is 90% or more and 95% or less, the ratio X represented by the formula of mass of the component (b/(total mass of the component (a) and the component (b) × 100 is 20% or more and 50% or less, and the ratio of the mass of the component (c) to the mass of the total solid component is 5% or more and [6+ (X-20)/6 ]% or less.

The antifouling coating film forming paint of the present embodiment is used for forming the antifouling coating film of the present embodiment.

In the antifouling coating film-forming coating material of the present embodiment, the zirconium oxide is zirconium oxide (ZrO)₂). The ion of zirconium oxide being selected from Zr²⁺、Zr³⁺、Zr⁴⁺、ZrO⁺、ZrO²⁺、Zr₂O⁴⁺And Zr₂O₂ ²⁺At least one of (1). The zirconium oxide precursor is at least one selected from the group consisting of zirconium nitrate, zirconyl nitrate, zirconium acetate, zirconium oxychloride, zirconium sulfate, zirconium oxychloride, zirconium hydroxide, zirconium methoxide, zirconium ethoxide, zirconium propoxide, and zirconium butoxide.

In the antifouling coating film-forming coating material of the present embodiment, the lanthanum oxide is lanthanum oxide (La)₂O₃). The lanthanum oxide ion is selected from La³⁺、LaO⁺、LaO₂ ^-、La₂O⁴⁺And La₂O₂ ²⁺At least one of (1). The lanthanum oxide precursor is at least one selected from the group consisting of lanthanum nitrate, lanthanum oxynitrate, lanthanum acetate, lanthanum oxychloride, lanthanum sulfate, lanthanum hydroxide, lanthanum methoxide, lanthanum ethoxide, lanthanum propoxide, and lanthanum butoxide.

In the antifouling coating film-forming coating material of the present embodiment, the silicon oxide is silicon oxide (SiO)₂). The ions of the silicon oxide are selected from Si⁴⁺And SiO²⁺At least one of (1). The silicon oxide precursor is at least one selected from the group consisting of sodium silicate, lithium silicate, potassium silicate, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

In the antifouling coating film-forming coating material of the present embodiment, the phosphorus oxide is phosphorus pentoxide (P)₂O₅). The ion of phosphorus oxide is selected from P⁵⁺、PO³⁺、PO₂ ⁺、PO₃ ^-、PO₄ ^3-、P₂O⁸⁺、P₂O₂ ⁶⁺、P₂O₃ ⁴⁺And P₂O₄ ²⁺At least one of (1). The phosphorus oxide precursor is at least one selected from phosphoric acid and triphenyl phosphate.

In the antifouling coating film-forming coating material of the present embodiment, the boron oxide is boron oxide (B)₂O₃). The ions of boron oxide being selected from B³⁺、BO⁺、BO^2-、B₂O⁴⁺And B₂O₂ ²⁺At least one of (1). The boron oxide precursor is at least one selected from boric acid, boron trichloride and boron hydroxide.

In the antifouling coating film-forming paint of the present embodiment, when the mass of the component (a), the component (b), and the component (c) is converted to the mass as an oxide, the ratio of the total mass of the component (a) and the component (b) to the mass of the total solid content of the antifouling coating film-forming paint (the total mass of the component (a), the component (b), and the component (c)) is 90% to 95%, and preferably 92.5% to 95%. Further preferably 93.0% or more and 95.0% or less.

If the total mass of the component (a) and the component (b) is 90% or more based on the total mass of the solid components of the antifouling coating film-forming coating material, the antifouling coating film cleaning property and the chemical durability against acids and bases are not reduced. On the other hand, if the total mass of the component (a) and the component (b) is not more than 95% with respect to the total mass of the solid components of the antifouling coating film-forming coating material, the abrasion resistance of the antifouling coating film is not reduced.

In the antifouling coating film-forming coating material of the present embodiment, when the ratio obtained by the formula of mass/(total mass of component (a) and component (b) × 100 is represented by X when the mass of component (a), component (b), and component (c) is converted to the mass as an oxide, X is 20% or more and 50% or less, preferably 25% or more and 45% or less, and more preferably 30% or more and 40% or less.

When X is 20% or more, the chemical durability (durability against acids and alkalis) of the antifouling film formed using the antifouling film forming paint is not lowered. When the antifouling coating is applied to a glass ceramic product, the apparent reflectance R on the surface of the antifouling coating is also₁% of the apparent reflectance R of the surface of the glass ceramic substrate₂% difference (R)₁-R₂) In the case of the antifouling coating of 1% or more, the change in appearance of the antifouling coating after removing scorching of an acid/alkali-containing substance such as ketchup or jam does not increase. On the other hand, if X is not more than 50%, when an antifouling film formed using the antifouling film forming coating material is applied to a glass ceramic product, adhesion of the antifouling film to the glass ceramic substrate is not reduced.

In the antifouling coating film-forming paint of the present embodiment, when the mass of the component (a), the component (b), and the component (c) is converted to the mass of the oxide, the ratio of the mass of the component (c) to the mass of the total solid content of the antifouling coating film-forming paint is 5% or more and [6+ (X-20)/6 ]% or less.

When the mass of the component (c) is 5% or more based on the total solid content of the antifouling film-forming coating material, the antifouling film is formedThe abrasion resistance of the antifouling coating film formed by the coating material is not reduced. On the other hand, when the ratio of the mass of the component (c) to the mass of the total solid content of the antifouling coating film-forming paint is not more than [6+ (X-20)/6%](ii) the detergency of the antifouling film formed using the antifouling film forming coating material is not reduced. Further, the chemical durability (durability against acids and alkalis) of the antifouling coating film is not reduced. Therefore, when the antifouling coating is applied to a glass ceramic product, the apparent reflectance R on the surface of the antifouling coating₁% of the apparent reflectance R of the surface of the glass ceramic substrate₂% difference (R)₁-R₂) In the case of the antifouling coating of 1% or more, the change in appearance of the antifouling coating after removing scorching of an acid/alkali-containing substance such as ketchup or jam does not increase.

Examples of the method for measuring the mass of the component (a), the component (b), and the component (c) contained in the antifouling coating film-forming paint include a fluorescent X-ray method and an ICP emission spectrometry method.

The content of the total solid content (component (a), component (b), and component (c)) in the paint can be arbitrarily selected, but is preferably 0.2 mass% or more and 5.0 mass% or less, more preferably 0.25 mass% or more and 4.5 mass% or less, and further preferably 0.3 mass% or more and 3.0 mass% or less.

When the total solid content (component (a), component (b), and component (c)) is 0.2 mass% or more, the viscosity stability of the coating material is not lowered, the thickness of the antifouling coating film is not excessively small, and the cleanability, chemical durability against acid and alkali, and abrasion resistance are not lowered. On the other hand, if the total solid content (component (a), component (b), and component (c)) is not more than 5 mass%, the thickness of the antifouling film is not excessively large, and unevenness in appearance or peeling due to insufficient adhesion is less likely to occur.

The dispersion medium is not particularly limited as long as it is a solvent capable of dissolving or dispersing the above-mentioned component (a), component (b) and component (c). Examples of such solvents include lower alcohols such as water, methanol, ethanol, 2-propanol and 1-butanol, and ethers (cellosolves) such as ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve) and propylene glycol monobutyl ether; ketones such as acetone, dimethyl ketone, diethyl ketone, and methyl ethyl ketone; glycols such as ethylene glycol; dimethyl sulfoxide, and the like. These solvents may be used alone or in combination of two or more. The amount of the dispersion medium can be arbitrarily selected, and for example, can be 95.0 to 99.8% by mass, preferably 97 to 99.7% by mass, and more preferably 96.0 to 99.0% by mass, based on the coating material. But is not limited to only these examples.

The antifouling coating film-forming coating material of the present embodiment may contain a surfactant, a binder, and the like to such an extent that antifouling properties are not impaired.

The surfactant is not particularly limited, and may be arbitrarily selected so long as it can disperse the component (a), the component (b), and the component (c) in the dispersion medium. The amount of the surfactant can be arbitrarily selected.

Examples of the binder that can be arbitrarily selected include ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, guar gum, carrageenan, sodium alginate, corn starch, xanthan gum, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, a carboxyvinyl polymer, sodium hyaluronate, and sodium chondroitin sulfate. The amount of binder can be arbitrarily selected.

According to the coating material for forming an antifouling film of the present embodiment, an antifouling film having improved cleanability against scorching of an antifouling film, particularly scorching of sugar-containing pollutants that are difficult to remove in conventional inorganic antifouling films, can be formed. Further, according to the antifouling coating film forming coating material of the present embodiment, an antifouling coating film having improved durability against acids and alkalis can be formed as compared with a conventional inorganic antifouling coating film. Further, according to the antifouling coating film forming paint of the present embodiment, an antifouling coating film having improved abrasion resistance while maintaining cleanliness and durability against acids and alkalis can be formed.

[ method for producing glass ceramic product ]

In the method for producing a glass ceramic product according to the present embodiment, the antifouling film-forming coating material according to the present embodiment is applied to the surface of a base made of a glass ceramic to form a coating film, and the coating film is heat-treated at a temperature of 650 ℃ to 950 ℃ inclusive to form an antifouling film on the surface of the base.

In the method for producing a glass ceramic product according to the present embodiment, the coating material for forming an antifouling coating film is applied to at least a part of the surface of the substrate, for example, in a region where scorching stains or oil stains of a substance such as food may occur, to form a coating film.

Examples of the coating method of the antifouling coating film-forming coating material include a spray coating method, a bar coating method, a spin coating method, a dip coating method, a roll coating method, and a screen printing method.

When the antifouling coating film-forming coating material is applied, the thickness of the coating film can be arbitrarily selected, and for example, the film thickness after the heat treatment is preferably adjusted so as to be in the range of 10nm to 200 nm.

The coating film thus formed is dried using a hot air dryer or the like. Then, in order to dissipate the dispersion medium, binder, and the like contained in the coating film, the coating film is subjected to heat treatment at a temperature of 650 ℃ or higher and 950 ℃ or lower in an atmospheric environment using, for example, a high-temperature baking furnace, to obtain the antifouling film of the present embodiment.

If the heat treatment temperature is not lower than 650 ℃, the strength of the obtained antifouling coating film is not lowered, and therefore, it is preferable. On the other hand, if the heat treatment temperature is not more than 950 ℃, the matrix is not deformed, and therefore, it is preferable.

According to the method for producing a glass ceramic product of the present embodiment, a glass ceramic product having an antifouling film with improved cleanability against scorching of an antifouling film, particularly scorching of sugar-containing pollutants that are difficult to remove in conventional inorganic antifouling films, can be produced. Further, according to the method for producing a glass ceramic product of the present embodiment, a glass ceramic product having an antifouling coating film with improved durability against acids and alkalis can be produced as compared with a conventional inorganic antifouling coating film. Further, according to the method for producing a glass ceramic product of the present embodiment, a glass ceramic product having an antifouling coating film with improved abrasion resistance while maintaining cleanliness and durability against acids and alkalis can be produced.

Examples

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[ Components of antifouling coating Forming paint for spray coating ]

The following components (1) to (5) were used as components of the antifouling coating forming paint for spray coating of examples 1 to 56 and comparative examples 2 to 65. The compounding ratios of these components are shown in Table 1.

(1) Aqueous dispersion of zirconium oxide fine particles (aqueous dispersion containing 4 mass% of zirconium oxide fine particles having an average particle diameter of 3 nm)

(2) 5% aqueous solution of lanthanum nitrate hexahydrate

(3) Silica sol (aqueous dispersion containing 10 mass% of silica particles having an average particle diameter of 3 nm)

(4) 1% aqueous solution of phosphoric acid

(5) 1% aqueous solution of boric acid

[ Components of antifouling coating Forming coating composition for Screen printing ]

The above components (1) to (5) and the following component (6) were used as components of the antifouling coating film forming paint for screen printing of the antifouling coating films of examples 57 to 100. The compounding ratios of these components are shown in Table 1.

(6) Hydroxyethyl cellulose

[ Table 1]

Table 2 shows the mass ratios of the zirconium, lanthanum, silicon, phosphorus and boron calculated from the compounding of the components shown in table 1 as oxides, and the contents (% by mass) of the mass in terms of the oxides with respect to the total mass of the antifouling coating film-forming paint.

[ Table 2]

[ preparation of antifouling coating Forming paint for spray coating ]

The coating was adjusted according to the formulation in tables 1 and 2. First, the above components (1) to (5) were added in the order of (I) an aqueous dispersion of zirconium oxide fine particles, (II) a 5% aqueous solution of lanthanum nitrate hexahydrate, and (III) a silica sol, (1% aqueous solution of phosphoric acid), or (1% aqueous solution of boric acid) so that the total mass of the antifouling coating forming paint became 100g, while stirring the components in a 200mL PYREX (registered trademark) beaker with a magnetic stirrer. Thereafter, as a solvent, propylene glycol monobutyl ether and a surfactant were mixed in this order. As a result, the antifouling film forming coating materials for spray coating of examples 1 to 56 and comparative examples 2 to 65 were obtained.

[ preparation of antifouling coating Forming paint for Screen printing ]

The components (1) to (5) were charged into a 900mL glass bottle which can be sealed with a lid having a stirring seal, and (I) an aqueous dispersion of zirconium oxide fine particles, (II) a 5% aqueous solution of lanthanum nitrate hexahydrate, and (III) a silica sol, a 1% aqueous solution of phosphoric acid, or a 1% aqueous solution of boric acid were added in this order according to the compounding ratio of tables 1 and 2 so that the total mass of the antifouling coating forming paint became 300 g. Thereafter, propylene glycol monobutyl ether as a solvent, hydroxyethyl cellulose as a binder, and a surfactant were sequentially added to prepare a raw material solution.

Next, the raw material solution in the glass bottle was stirred at 600rpm for 2 hours by a stirring blade made of teflon (registered trademark) inserted into the glass bottle through the stirring seal of the glass bottle cap. As a result, the antifouling film forming coating materials for screen printing of examples 57 to 100 were obtained. During stirring, the glass bottle was heated in a 40.5 ℃ warm bath.

[ measurement of the content of non-volatile component in the antifouling coating film-forming coating Material ]

The antifouling coating film-forming coatings of examples 1 to 100 and comparative examples 2 to 65 were measured for the content of nonvolatile components by the following method.

30g of the antifouling coating film-forming paint was extracted from a magnetic flat plate and fired at 800 ℃ for 1 hour in an electric furnace. After that, the mass of the sample remaining in the magnetic crucible was measured. The ratio (mass%) of the mass of the sample remaining in the magnetic crucible to the mass of the extracted antifouling coating forming paint was calculated. The results are shown in Table 3.

[ Table 3]

From the results in table 3, it was confirmed that the content of the obtained nonvolatile component was substantially the same as the content (mass%) shown in table 2, which is the ratio of the mass of zirconium, lanthanum, silicon, phosphorus, and boron in terms of oxides to the total mass of the antifouling coating film forming paint.

[ formation of antifouling coating film ]

(glass ceramic substrate)

Black crystallized glass Ceran (Ceran) manufactured by SCHOTT company is used as the glass ceramic substrate.

The glass ceramic substrate was cut into a 50mm × 100mm rectangle to prepare a spray test piece.

Then, the glass ceramic substrate was cut into a square having a side of 170mm to prepare a test piece for screen printing.

(spray coating)

The test piece for spray coating was placed in a region of 20cm × 25cm in a partially air-exhausted pattern. The coating film was formed by spraying the antifouling coating film-forming paint for spraying onto the surface of the test piece for spraying by the spraying method.

As shown in Table 4 below, the amount of the antifouling coating forming paint to be sprayed was changed to 10.0mL, 4.2mL, 1.5mL, and 1.0mL in the case of spraying.

[ Table 4]

(Screen printing)

The paint for forming an antifouling coating film used for screen printing was kept in a constant-temperature water bath at 25 ℃ for 30 minutes. Then, 3 types of screen mesh made of TETRON (registered trademark) manufactured by Mitani Micronics co., ltd. having a square printing area with one side of 170mm were used for printing.

As shown in Table 5 below, the 3 kinds of screens were (1) 420/inch in mesh number, 27 μm in wire diameter, and 40 μm in mesh thickness (yarn thickness), (2) 355/inch in mesh number, 35 μm in wire diameter, and 61 μm in mesh thickness, (3) 255/inch in mesh number, 40 μm in wire diameter, and 60 μm in mesh thickness, respectively.

Using these screens made of TETRON (registered trademark), a paint for forming an antifouling coating film for screen printing was applied to the surface of the above-mentioned test piece for screen printing, and a coating film was formed.

[ Table 5]

(Heat treatment of spray coating film)

The test piece on which the coating film was formed by spraying was dried at room temperature. Thereafter, heat treatment was performed in an electric furnace.

The temperature of the heat treatment by the electric furnace was set to 800 ℃ or 900 ℃, and the test piece was placed in the electric furnace after the temperature in the electric furnace was sufficiently stabilized. Thereafter, the resultant was heat-treated for 30 minutes to form an antifouling film.

(Heat treatment of Screen-printed coating film)

The test piece on which the coating film was formed by screen printing was dried in a dryer maintained at 100 ℃ for 10 minutes. Thereafter, heat treatment was performed in an electric furnace.

The temperature of the heat treatment in the electric furnace was set to 800 ℃ or 900 ℃ and the temperature in the electric furnace was sufficiently stabilized. Thereafter, the test piece was placed in an electric furnace and heat-treated for 30 minutes to form an antifouling coating film.

[ measurement of the amount of each component of the antifouling coating film adhered ]

The ZrO of the surface of the test piece per square meter was determined by quantitative analysis by fluorescent X-ray method₂、La₂O₃、SiO₂、P₂O₅、B₂O₃The amount of adhesion of (a).

However, in the glass ceramic substrate, a part or all of the above components may be contained in the substrate itself. Therefore, it is not possible to directly measure only the amount of the antifouling coating film formed on the surface of the test piece as the glass ceramic substrate by the fluorescent X-ray method. That is, it is possible to measure the value of the substrate as well. Therefore, the content of the antifouling coating component formed on the surface of the test piece was indirectly analyzed by the following method.

In the case of spray coating, a stainless steel plate is placed in the coating region together with the glass ceramic substrate, and the same coating film is also formed on the steel plate.

In the case of screen printing, a coating film was formed on a stainless steel plate under the same conditions as those used for forming a coating film on a glass ceramic substrate.

Thereafter, the stainless steel plate on which the coating film was formed by spray coating and the stainless steel plate on which the coating film was formed by screen printing were dried in a dryer at 250 ℃ for 10 minutes. Then, the amount of each component adhering to the antifouling coating film formed on the surface of each stainless steel sheet was measured by quantitative analysis by a fluorescent X-ray method.

The measurement results are shown in tables 6 to 9 as the component amounts of the antifouling films of examples 1 to 100, and in tables 10 to 12 as the component amounts of the antifouling films of comparative examples 2 to 65.

[ measurement of the perceived reflectance on the surface of the antifouling coating ]

Using a spectrophotometer V-770 manufactured by JASCO Corporation, the wavelength was measured in the range of 380nm to 800nm5 DEG reflection spectra of the surface of the fouling film and the surface of the glass ceramic substrate. The apparent reflectance R of the antifouling coating surface was measured by the following calculation formula (. alpha.)₁% and apparent reflectance R of the surface of the glass-ceramic substrate₂％。

Apparent reflectance (%) ═ Σ R (λ) V (λ)/Σ V (λ) … … (α)

(however, in the calculation formula (α), R represents reflectance (%), and V represents relative visibility.)

The apparent reflectance R of the surface of the antifouling coating₁% of the apparent reflectance R of the surface of the glass ceramic substrate₂% difference (R)₁-R₂) Is set to Δ R.

Tables 6 to 9 show Δ R of examples 1 to 100, and tables 10 to 12 show Δ R of comparative examples 2 to 65.

[ Table 6]

[ Table 7]

[ Table 8]

[ Table 9]

[ Table 10]

[ Table 11]

[ Table 12]

[ evaluation of adhesion of antifouling coating film ]

The surface of the uncoated glass ceramic substrate of comparative example 1 and the surfaces of the antifouling coatings of examples 1 to 100 and comparative examples 2 to 65 were rubbed 20 times by applying a load of 1kg to the copper brush. The evaluation was x (no good) for the case where the scratch occurred, and o (good) for the case where the scratch did not occur. The results are shown in tables 13 to 17.

[ evaluation of abrasion resistance of antifouling coating film ]

A nonwoven sponge containing resin abrasive grains was cut into a square with a side of 2 cm. A reciprocating abrasion test was performed on the surface of the uncoated glass ceramic substrate of comparative example 1 and the surfaces of the antifouling films of examples 1 to 100 and comparative examples 2 to 65 by applying a load of 600g using the cut sponge. The evaluation criteria were as follows. The results are shown in tables 13 to 17.

After 500 reciprocations, a case where 5 or more scratches were observed by visual observation under a 3-wavelength light source was defined as "x" (failure)

After 1000 reciprocations, a case where 5 or more scratches were observed by visual observation under a 3-wavelength light source was defined as "Δ" (acceptable)

After 1500 reciprocations, a case where 5 or more scratches were observed by visual observation under a 3-wavelength light source was evaluated as "o" (good)

At the end of 1500 reciprocations, the case where 5 or more scratches could not be visually confirmed was "excellent" (excellent)

[ evaluation of detergency ]

Granulated sugar and tomato ketchup were burnt on the surfaces of the uncoated glass ceramic substrate of comparative example 1 and the antifouling films of examples 1 to 100 and comparative examples 2 to 65. Thereafter, evaluation of cleanability was performed. The procedure for evaluating the cleanability was as follows.

0.5g of granulated sugar and 1g of tomato paste were attached to the surface of the test piece, respectively.

Next, the test piece with the granulated sugar and the tomato paste adhered thereto was placed on a radiation cooking heater. The output of the heater was maintained for 15 minutes so that the surface temperature of the test piece became 350 ℃. + -. 20 ℃, and the surface of the antifouling coating film was scorched with sugar and tomato paste.

Next, the test piece was immersed in a water bath for 5 minutes after cooling at room temperature.

Next, the test piece was taken out from the water tank and dried at room temperature.

Next, the nonwoven sponge containing the resin abrasive grains was cut into a square with a side of 2 cm. A600 g load was applied using the cut sponge, and a reciprocating friction test was performed on the scorched portion of the test piece surface. The nonwoven sponge was rubbed against each other 25 times, and it was visually evaluated whether or not the remaining area of char was more than 10% of the area to which char was originally attached. If the friction coefficient exceeds the predetermined value, 100 further reciprocating rubs are applied (after 125 total reciprocating rubs are performed). After that, the residual area of scorch was visually evaluated. The evaluation criteria were set as follows. The results are shown in tables 13 to 17.

When the surface was rubbed 25 times, the surface was "excellent" in a case where 90% or more of the burned area was removed from the area of the first burned portion

After 25 times of the reciprocating rubbing, more than 10% of the scorched area remained relative to the initially adhered scorched area, and a total of 125 times of the reciprocating rubbing allowed removal of 90% or more of the scorched area was defined as "o" (good)

A case where 50% or more and less than 90% of the burnt area adhered at first was removed after 125 times of back-and-forth rubbing was regarded as "Delta" (acceptable)

After 125 times of back-and-forth rubbing, a case where more than 50% of the area of the scorched particles originally adhered was left was defined as "X" (defective)

[ evaluation of appearance Change due to scorching ]

After scorch of the tomato ketchup was removed by the evaluation of the above cleanability, the changes in the appearance of the uncoated glass ceramic substrate, and the uncoated glass ceramic substrates and the antifouling films of examples 1 to 100 and comparative examples 2 to 65 were evaluated by the following evaluation criteria. The results are shown in tables 13 to 17.

When the appearance of the antifouling coating film was not changed at all, the film was rated as "O" (good)

The appearance of the antifouling coating film slightly changed was "Δ" (acceptable)

The appearance of the antifouling coating film was significantly changed and was defined as "x" (failure)

[ Table 13]

[ Table 14]

[ Table 15]

[ Table 16]

[ Table 17]

From the results in tables 13 to 17, it was confirmed that in all examples, the cleaning property (burnout) was improved regardless of the amount of adhesion of the antifouling film and the firing temperature of the antifouling film, as compared with the uncoated glass ceramic substrate in comparative example 1 in which the antifouling film was not formed.

As is clear from the results in tables 13 to 17, the following results can be obtained if examples 1 to 8 are compared with comparative examples 34 to 41. That is, it was confirmed that, when the ratio of the mass of the oxide converted into lanthanum to the total mass of the oxide converted into zirconium and the mass of the oxide converted into lanthanum is X%, if X is less than 20%, the cleaning property is lowered. Further, if X is less than 20%, the chemical durability (durability against acids and alkalis) of the antifouling coating film is also reduced. Further, it was confirmed that in the antifouling coating film having Δ R of 1% or more, the change in appearance of the antifouling coating film after removing the scorch of the tomato paste was large.

From the results in tables 13 to 17, it is understood that the following results can be obtained if examples 25 to 32 are compared with comparative examples 18 to 25. That is, it was confirmed that if the mass of the oxide in terms of lanthanum exceeds 50% of the total mass of the oxide in terms of zirconium and the oxide in terms of lanthanum, the adhesion of the antifouling coating to the glass ceramic substrate is reduced.

As is clear from the results in tables 13 to 17, the following results can be obtained if examples 33 to 40 are compared with comparative examples 2 to 9. That is, it was confirmed that if the mass of the oxide in terms of silicon, phosphorus, or boron is less than 5% relative to the mass of the antifouling coating film, the abrasion resistance of the antifouling coating film is reduced.

As is clear from the results in tables 13 to 17, the following results can be obtained if examples 1 to 24 are compared with comparative examples 42 to 65. That is, it was confirmed that if the ratio of the total mass of oxides of silicon, phosphorus and boron in terms of oxide to the total mass of oxides of zirconium and lanthanum in terms of oxide exceeds [6+ (X-20)/6 ]%, the cleaning property of the antifouling coating film is lowered. Further, when the ratio of the mass of the oxide converted into lanthanum to the total mass of the oxide converted into zirconium and the mass of the oxide converted into lanthanum is X%, if the total mass of the oxides converted into silicon, phosphorus and boron exceeds [6+ (X-20)/6 ]%, the chemical durability (durability against acid and alkali) of the antifouling coating film is also reduced. Therefore, it was confirmed that in the antifouling coating film having Δ R of 1% or more, the change in appearance of the antifouling coating film after removing the scorch of the tomato paste was large.

From the results in tables 13 to 17, it is understood that the following results can be obtained if examples 25 to 32 are compared with comparative examples 10 to 17. That is, it was confirmed that if the total mass of the mass in terms of zirconium oxide and the mass in terms of lanthanum oxide is less than 90% of the mass of the antifouling coating film (the mass obtained by adding the mass in terms of oxide of the component (c)) the detergency is lowered. Further, if the total mass of the zirconium oxide and the lanthanum oxide in terms of the mass of the antifouling coating is less than 90% with respect to the mass of the antifouling coating, the chemical durability of the antifouling coating is also reduced. Therefore, it was confirmed that in the antifouling coating film having Δ R of 1% or more, the change in appearance of the antifouling coating film after removing the scorch of the tomato paste was large.

Industrial applicability

Provided are an antifouling coating film, a glass ceramic product, an antifouling coating film-forming coating material, and a method for producing a glass ceramic product, which can easily clean burnt sugar-containing pollutants, can improve the durability against the corrosive action of acids or bases contained in the pollutants, and can improve the mechanical strength such as abrasion resistance without impairing the cleanability and chemical durability.