JP2008050402A - Scale fixing prevention product and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a product having a coating film with a high scale fixing preventing effect and a high continuity of it capable of easily removing the deposited scale, and its manufacturing method. <P>SOLUTION: A surface of the product substrate is coated with a coating liquid containing a Si-containing component and a Zr-containing component and is heat-treated to form a first layer comprising a coating film-formation substance having a Si oxide component and a Zr oxide component. A coating liquid containing the Si-containing component and an organic substance component selected from polymers and/or monomers dissolved or dispersed into water is coated on it and is heat-treated to form a second layer containing a Si oxide component and the organic substance component. Thereby, the product having the scale fixing prevention coating layer is manufactured. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a scale adhesion preventing product in which scale adhesion is prevented, and a method for producing the same, and in particular, it has excellent durability of the scale prevention effect and can be easily removed even when scale adheres to the surface of a product substrate. The present invention relates to a scale fixing product and a manufacturing method thereof.
In the present invention, “scale adhesion” means a state where “scale scale adheres to the surface of various product substrates and cannot be easily removed from the product substrate even if the adhered scale solidifies.” Further, in the present invention, “scale prevention” means that “fixed scale can be easily removed from the product substrate”.

  Contamination due to scale sticking can be found in any place where water adheres and dries, such as kitchens, bathrooms, toilets, and washrooms. Scale is a deposit of an inorganic component dissolved in water as the water evaporates, and solidifies so strongly that it cannot be removed, especially when left for a long period of time. If it is attempted to forcibly remove the adhered scale using a chemical or an abrasive, the product substrate may be damaged.

  Conventionally, it has been proposed to form a water-repellent coating film or a hydrophilic coating film on the surface of a product substrate for the purpose of preventing adhesion of scale.

  For example, Patent Documents 1, 2, and 3 disclose, as a scale adhesion prevention product in which the hydrophilic coating film is formed on the surface of a product substrate, a co-polymer containing polyacrylic acid or a polyacrylic acid monomer in a Li-containing siliceous film. A scale adhesion prevention product is disclosed which includes a coalescence and forms a hydrophilic film with excellent adhesion to the product substrate surface.

  Patent Document 4 discloses a hydrophilic coating film containing polyethylene glycol in a Zr-containing siliceous film, which is excellent in durability against various detergents and chemicals of acid, neutral and alkaline, This is said to prevent adhesion of dirt such as water scale and to be easily removed even if dirt is attached.

Further, Patent Documents 5 and 6 are obtained by forming a coating containing silicon dioxide and zirconia on the surface of a product substrate, diffusing lithium ions in the coating, and dispersing the lithium ions. An excellent hydrophilic coating film is disclosed.
JP 2003-301273 A JP 2003-299606 A JP2002-302637 JP 2005-281443 A JP2002-019007 JP 2006-015754 A

  However, the scale adhesion preventing coating film according to the background art has the following problems.

  That is, water becomes a polka dot on the water repellent coating film, and the polka dot falls on the inclined surface, so that the water scale is prevented from sticking. However, the polka dots remain on the horizontal surface, and if the water evaporates as it is, the traces of the polka dots become scaled and the scale remains markedly conspicuous. Furthermore, if polka dots are repeatedly generated and dried after being left for a long time, the scale adheres firmly and cannot be removed.

On the other hand, in the hydrophilic coating film, since water spreads slightly on the coating, it becomes very inconspicuous even if it dries and scales precipitate. However, if wetting and drying are repeated for a long period of time, the scale will increase in thickness, and will remain firmly fixed and cannot be removed.
Each of the above background arts has a certain effect against scale dirt, but when used for a long time, there is a problem that it cannot be firmly fixed on the surface of the product substrate and removed. It was.

  The present invention has been made in view of the problems of the above-described background art, and the effect of preventing the adhesion of scales lasts for a long period of time. The effect of preventing the adhesion of scales is excellent, and the attached scales can be easily removed. An object of the present invention is to provide a scale fixing product having a scale fixing coating film and a method for manufacturing the same.

  The present inventor diligently studied to solve the above problems, and found that a polymer dissolved and / or dispersed in water on the first layer made of a film-forming material having a silicon oxide component and a zirconium oxide component and / or By forming a second layer made of a film-forming substance containing an organic component containing a monomer and a silicon oxide component, the anti-sticking coating is excellent in preventing the sticking of scale and can easily remove the attached scale. The inventors have found that a film can be obtained and have completed the present invention.

That is, the scale fixing product of the present invention includes a product base and a scale fixing coating film formed on the surface of the base,
The scale fixing coating film includes a first layer made of a film forming material having a silicon oxide component and a zirconium oxide component, and is formed on the first layer, and is dissolved in the silicon oxide component and water. Or a second layer made of a film-forming material containing an organic component containing at least one selected from a polymer and / or a monomer to be dispersed.
In the scale fixing product of the present invention, the organic component for the second layer is selected from polyacrylic acid, polyacrylate, acrylic polymer or monomer, polyethylene glycol, polyvinyl pyrrolidone, polyvinyl alcohol, and carboxymethyl cellulose. Preferably it contains more than one species.

Moreover, the method for producing the scale fixing product of the present invention comprises a silicon-containing component containing at least one selected from silica sol, silicon alkoxide and a partial hydrolysis product thereof, and silicate on the surface of the product substrate, A coating solution containing a zirconia sol, zirconium alkoxide and a partially hydrolyzed product thereof, and a zirconium-containing component containing at least one selected from zirconium salts is applied and heat-treated to form a heat-treated product produced by the heat treatment. Forming a first layer;
Further, on the first layer, a silica-containing component containing at least one selected from silica sol, silicon alkoxide and a partial hydrolysis product thereof, and silicate, and a polymer and / or monomer dissolved or dispersed in water. A coating liquid containing at least one selected organic substance component is applied and heat-treated to form a second layer made of the heat-treated product, thereby forming a scale adhesion preventing coating layer. Is.

The scale adhesion preventing product of the present invention has an excellent scale adhesion preventing effect for a long period of time, and scale can be easily removed by a simple operation. For this reason, no strong chemicals or abrasives are required to remove the adhered scale, which has the effect of reducing labor and reducing the burden on the environment.
In addition, the method for producing a scale sticking prevention product of the present invention can easily and efficiently produce a scale sticking prevention product exhibiting the above-described effects.

"Drinkage prevention product"
First, an embodiment of a scale fixing product will be described. A feature of the scale fixing product according to the present invention is that a scale fixing coating layer having a two-layer structure comprising a first layer formed on the surface of the product substrate and a second layer formed on the first layer is provided. It is in having.
The first layer is made of a film forming material having a silicon oxide component and a zirconium oxide component, and the second layer is at least one of a silicon oxide component and a polymer and / or monomer dissolved or dispersed in water. It consists of a film-forming substance having an organic component containing seeds.
The product substrate is not particularly limited, and includes, for example, inorganic products such as glass, ceramics and ceramics, organic products such as plastic, and metal products such as stainless steel.

The first layer is for imparting high water resistance to the second layer formed on the first layer, and is made of a film forming material containing a silicon oxide component and a zirconium oxide component, for example, In addition, the following film forming substances (1) to (4) or a mixed substance thereof are included.
(1) A silicon (Si) atom and a zirconium (Zr) atom are bonded via an oxygen (O) atom and include a structure represented by the following (formula 1), for example, a chemical bond represented by (formula 2) Consists of a silicon-zirconium oxide in the molecular skeleton, and these silicon-zirconium oxides are made of a film-forming substance formed by forming a three-dimensional network structure.
｜ ｜
-Si-O-Zr-O- (Formula 1)
｜ ｜
｜ ｜ ｜
—Si—O—Si—O—Zr—O— (Formula 2)
｜ ｜ ｜

(2) Silicon (Si) atoms are bonded to each other through oxygen (O) atoms, and are composed of a silicon oxide having a chemical bond represented by the following (formula 3) in the molecular skeleton. A three-dimensional network structure formed from a film-forming substance in which fine particles of free zirconium oxide are dispersed and confined in this three-dimensional network structure.
｜ ｜
-Si-O-Si-O- (Formula 3)
｜ ｜
(3) Zirconium (Zr) atoms are bonded through oxygen (O) atoms, and are composed of a zirconium oxide having a chemical bond represented by the following (formula 4) in the molecular skeleton. A three-dimensional network structure is formed, and silicon oxide fine particles are dispersed in the network structure, and are made of a confined film-forming substance.
｜ ｜
-Zr-O-Zr-O- (Formula 4)
｜ ｜
(4) A coating film in which fine particles of silicon oxide and zirconium oxide are dispersed and mixed with each other.
In the first layer of the scale fixing product of the present invention, the compound having the silicon-zirconium oxide structure (1), the compounds (2) and (4) having a silicon oxide structure, and the compound having a zirconium oxide structure (3) and (4) form a strong integral coating. In the present specification, such a first layer film of the present invention is referred to as “a first layer made of a film forming material containing a silicon oxide component and a zirconium oxide component”.

The mass ratio of silicon (Si) and zirconium (Zr) contained in the first layer is such that silicon (Si) is converted to silicon dioxide (SiO ₂ ), and zirconium (Zr) is converted to zirconium oxide (ZrO ₂ ). When converted, it is preferably in the range of 1: 9 to 9: 1. If the mass ratio of silicon (Si) and zirconium (Zr) contained in the first layer is out of this range, the film hardness and water resistance of the anti-scale coating film composed of the first layer and the second layer will be described. May be insufficient.

In addition to silicon (Si), zirconium (Zr), and oxygen (O), the first layer contains one or more of Mg, Ca, Zn, Al, P, and Ti components as subcomponents. Also good. When these subcomponents are contained in the first layer, the film hardness and water resistance of the scale adhesion preventing coating film composed of the first layer and the second layer are further improved.
The content of the secondary component, in terms of silicon to (Si) to silicon dioxide (SiO _2), in the case of zirconium (Zr) in terms of zirconium oxide (ZrO _2), zirconium oxide, silicon dioxide (SiO ₂₎ ( The total amount of ZrO ₂ ) is preferably in the range of 0.01% by mass to 10% by mass. When the added amount of the subcomponent is less than 0.01% by mass, it is meaningless to add the subcomponent. On the other hand, when the added amount exceeds 10% by mass, the scale adhesion preventing coating film composed of the first and second layers is used. The film strength and water resistance may be reduced.

Further, the first layer is formed by heat treatment in which the silicon-zirconium oxide component and / or the silicon oxide component and / or the zirconium oxide component is supplied from a coating solution containing sol particles. It is preferable.
When the first layer is formed from a coating solution containing sol particles, the film quality becomes dense and the film strength is large, and further, the first layer is thinned and becomes transparent, thereby improving the design properties such as the hue of the product substrate. The first layer is preferable because it does not decrease or decreases.

  Further, the film thickness of the first layer is not particularly limited, but is usually preferably 0.01 μm or more and 2 μm or less. When the film thickness of the first layer is less than 0.01 μm, the water resistance of the second layer formed on the first layer is not sufficiently improved. On the other hand, when the film thickness of the first layer exceeds 2 μm, the first layer This is not preferable because the layer coating may be peeled off or whitened.

  The second layer is a film formed on the first layer and containing a silicon oxide component, and the film is selected from a polymer and / or a monomer that dissolves or disperses in water. It contains one or more organic components and forms a surface that directly contacts scale.

The adhesion mechanism of scale is thought to be due to the precipitation of inorganic components (silicic acid component, calcium component, magnesium component, etc.) dissolved in water, and accumulation and solidification after standing for a long time. When the content of is relatively large, the precipitate becomes siliceous, and this is not easily dissolved in acid or alkali, so it is very difficult to remove.
The main component of the second layer is the same as the silicic acid component, which is one of the main components of scale, and since it binds easily and directly with the silicic acid component in the scale, the scale is easily fixed. When the layer contains at least one organic component selected from a polymer and / or a monomer that dissolves or disperses in water, the adhesion of scale is eased and can be easily removed.

  The organic component containing at least one polymer and / or monomer that dissolves or disperses in water is not particularly limited as long as it is a polymer and / or monomer that dissolves or disperses in water. Examples include acids, polyacrylates, acrylic polymers or monomers, polyethylene glycol, polyvinyl pyrrolidone, polyvinyl alcohol, carboxymethyl cellulose, and the like, and these compounds are particularly suitable for use in preventing scale adhesion. it can.

As the polyacrylic acid or polyacrylic acid salt, those having a weight average molecular weight of 1,000 to 1,000,000 are particularly suitable for the present invention since they are particularly excellent in preventing scale adhesion. Examples of the polyacrylic acid salt include sodium salt and potassium salt of polyacrylic acid.
As the above-mentioned acrylic polymer or monomer, a polymer obtained by polymerizing 2-hydroxyethyl methacrylate is suitable because it is particularly excellent in preventing scale adhesion. The 2-hydroxyethyl methacrylate easily undergoes a crosslinking reaction during the heat treatment in the production process of the present invention, and the whole amount or a part amount thereof is polymerized.
As the polyethylene glycol, those having a weight average molecular weight of 200 to 20000 are particularly suitable because they are particularly excellent in preventing scale adhesion.

In the second layer, the ratio of silicon oxide to an organic component containing at least one selected from a polymer and / or monomer dissolved or dispersed in water is such that the silicon oxide is changed to silicon dioxide (SiO ₂ ). In terms of conversion, it is preferably 0.1% by mass to 100% by mass, more preferably 1% by mass to 50% by mass with respect to this silicon dioxide (SiO ₂ ). When the added amount of the organic component is less than 0.1% by mass, a sufficient anti-caking effect cannot be obtained. On the other hand, when the added amount of the organic component exceeds 100% by mass, the first layer and the second layer are added. This is not preferable because the scale film for preventing adhesion of scales may be whitened.

The second layer includes a silicon oxide component and an additive component made of one or more compounds of Li, Na, K, Mg, Ca, Zn, Al, P, and Zr in addition to the organic component. It may be. When these additive components are contained in the second layer, the effect of preventing adhesion of scale may be further improved.
In the present invention, the reason why the effect of preventing the adhesion of scale is improved is not necessarily clear, but these additional components are once combined with the silicon oxide component in the second layer, and the silicate ions in the scale directly become the second layer. This is considered to prevent bonding with the silicon oxide component therein.

Moreover, it is preferable that the silicon oxide component of the second layer is formed by heat treatment of an application layer containing an aqueous silica silicate solution or a silica sol solution containing silica sol particles.
When the silicon oxide component of the second layer is formed from a coating liquid containing sol particles of silicon oxide, the film quality of the second layer obtained becomes dense, the film strength is high, and the second layer is thinned. If it becomes transparent, the design properties such as the hue of the product substrate are not lowered or reduced by the second layer.

  Further, the film thickness of the second layer is not particularly limited, but is usually preferably 0.01 μm or more and 2 μm or less. If the film thickness of the second layer is less than 0.01 μm, the effect of preventing the adhesion of scale may be insufficient, and if the film thickness of the second layer exceeds 2 μm, the formed second layer film is Since it may peel from one layer or whiten, it is not preferable.

  In the above embodiment of the scale fixing product of the present invention, it is the second layer that exhibits the scale fixing effect as described above, but this layer alone can be a scale fixing coating film having excellent practicality. Absent. The reason for this is that the scale adhesion preventing coating film composed of only the second layer has insufficient water resistance. In general, a place where scale dirt adheres is a place where it frequently comes into contact with water, and thus high water resistance is required. The main component of the second layer is a silicon oxide component, which is poor in water resistance, and does not have sufficient water resistance especially against hot water and alkaline detergents. Further, the water resistance of the water-soluble resin is not sufficient. Further, Mg, Ca, Zn, Al, P, and Zr in the subcomponents have the effect of improving the water resistance of the second layer, but even when these are used, the water resistance is still not sufficient.

  Therefore, the first layer is indispensable to make up for the lack of water resistance of the second layer. The first layer contains a silicon oxide component and a zirconium oxide component as the composition, but the addition of the zirconium oxide component to the silicon oxide component dramatically improves the water resistance of the second layer. The first layer contributes not only to its own high water resistance but also to the improvement of the water resistance of the second layer. This is presumably because there is a chemical interaction between the first layer and the second layer.

Further, in the above embodiment of the scale fixing product of the present invention, as described above, the scale fixing coating film formed on the surface of the product base is composed of the first layer and the second layer. However, various primer layers for improving the adhesion may be interposed between the surface of the product substrate and the first layer, and the adhesion between the first layer and the second layer may be further interposed. The primer layer for improving may be interposed.
Examples of the primer layer between the product substrate surface and the first layer include a film made of a silane coupling agent.
Examples of the primer layer between the first layer and the second layer include a film made of an alkali silicate such as sodium silicate or potassium silicate.

"Production method of scale prevention products"
The method for producing a scale-fixing prevention product of the present invention comprises a silicon-containing component selected from silica sol, silicon alkoxide and a partial hydrolysis product thereof, and silicate, zirconia sol, zirconium alkoxide and Applying a coating solution containing a partial hydrolysis product and a zirconium-containing component selected from zirconium salts, heat-treating, and forming a first layer of the heat-treated product;
Next, on the first layer, at least one selected from a silica-containing component selected from silica sol, silicon alkoxide and its partial hydrolysis product, and silicate, and a polymer and / or monomer dissolved or dispersed in water. Applying a coating liquid containing a seed-containing organic substance component, heat-treating, and forming a second layer containing a silicon oxide component and the organic substance component as a product of the heat treatment;
It is composed of

Hereinafter, the manufacturing method of the scale adhesion preventing product of the present invention will be specifically described.
First, in order to improve the adhesion, the product substrate is preferably subjected to a coating or pre-coating treatment by a known technique such as a primer, a frame, or a corona discharge treatment.
After performing pre-coating treatment as required, a first layer is formed on the surface of the product substrate. The coating liquid for forming the first layer includes a silicon-containing component containing at least one selected from silica (SiO ₂ ) sol, silicon alkoxide and its partial hydrolysis product, and silicate, and zirconia (ZrO ₂ ). A coating solution containing a zirconium-containing component containing at least one selected from sol, zirconium alkoxide and its partial hydrolysis product, and a zirconium salt, and a dispersion medium as required.

In the coating solution for forming the first layer, it is preferable that at least one of the silicon and / or zirconium oxide components contained therein is a sol. For example, when a silica (SiO ₂ ) sol and / or a zirconia (ZrO ₂ ) sol is used, a film having a high hardness can be obtained. Therefore, a silica and / or zirconia colloidal particle dispersion, or a silicon alkoxide and / or zirconium It is preferable to use a partially hydrolyzed solution obtained by adding water to alkoxide with an acid as a catalyst. Moreover, when it is a coating liquid containing sol particles, not only is it easy to paint, but also the curability of the coating film is improved.
Examples of the acid for the hydrolysis catalyst include inorganic acids such as nitric acid and hydrochloric acid.

Examples of the silicate include sodium silicate, lithium silicate, potassium silicate, and ammonium silicate.
Examples of the zirconium salt include zirconium oxynitrate and zirconium oxychloride.

  The dispersion medium for the first layer-forming coating solution dissolves or disperses the silicon-containing component and the zirconium-containing component. For example, water and an organic solvent or a mixture thereof can be used. Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol.

The mass ratio of silicon (Si) and zirconium (Zr) contained in the coating solution forming the first layer is calculated by converting silicon (Si) to silicon dioxide (SiO ₂ ) and zirconium (Zr) to zirconium oxide ( In terms of ZrO ₂ ), it is preferably in the range of 1: 9 to 9: 1, and if it is outside this range, the resulting first layer will have insufficient hardness or insufficient water resistance. There is.
Further, the solid content in the coating solution for forming the first layer, that is, the amount of the film-forming component is preferably in the range of 1% by mass to 10% by mass. Film defects due to excess are likely to occur.
Further, the Mg, Ca, Zn, Al, P, and Ti components added as subcomponents to the coating solution for forming the first layer must be dissolved or dispersed in water or an organic solvent as a dispersion medium. . Specifically, a salt of each element metal is suitable. The amount added is preferably a solid content in the coating solution, that is, a range of 1% by mass or more and 100% by mass or less with respect to the total amount of film forming components, and if it is outside this range, a sufficient effect cannot be obtained, Or there is a possibility that water resistance and hardness may be lowered.

The first layer forming coating solution is applied to the surface of the product substrate. As a coating method, a known spray method, dipping method, roll method or the like can be applied, and there is no particular limitation.
And a coating film is dried and heat-processed. Heat treatment temperature and heat treatment time are as high as possible within a range that does not adversely affect the substrate, and it is preferable to perform heat treatment for a long time because the film strength of the film and the water resistance of the film increase, but the degree of drying A short heat treatment at the heat treatment temperature is sufficient.
The specific heat treatment temperature is usually room temperature to 500 ° C when the product substrate is an inorganic product such as glass, more preferably 80 to 500 ° C, and room temperature when the product substrate is plastic. A temperature of ˜150 ° C. is preferred, more preferably 80 ° C. to 130 ° C., and when the product substrate is a metal, a temperature of room temperature to 300 ° C. is preferred, and 80 ° C. to 300 ° C. is more preferred.
The atmosphere during the heat treatment is not particularly limited, but is usually an air atmosphere.

Next, a second layer is formed on the first layer. As the coating solution for forming the second layer, a silicon-containing component containing at least one selected from silica (SiO ₂ ) sol, silicon alkoxide and its partial hydrolysis product, and silicate, and dissolved or dispersed in water An organic component containing at least one selected from polymers and / or monomers to be used and a coating liquid containing a dispersion medium as required are used. Examples of the organic component dissolved or dispersed in the water include polyacrylic acid, polyacrylic acid salt, acrylic polymer or monomer, polyethylene glycol, polyvinyl pyrrolidone, polyvinyl alcohol, carboxymethyl cellulose and the like. it can.

The dispersion medium dissolves or disperses the silicon-containing component and the organic component, and water, an organic solvent, or a mixture of water and an organic solvent can be used.
Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol.
When silicon alkoxide is used as the silicic acid-containing component, an acid may be contained as a catalyst for hydrolysis. Examples of such acids include inorganic acids such as nitric acid and hydrochloric acid.

In the coating solution for forming the second layer, it is preferable to use an alkali silicate compound and / or silica (SiO ₂ ) sol as a silicon-containing component. Examples of alkali silicate compounds include lithium silicate, sodium silicate, potassium silicate, and ammonium silicate. Products with various molar ratios are commercially available, and these commercially available products can be used.
In the alkali silicate compound, the type of alkali is not particularly limited, but the molar ratio of silicic acid (SiO ₂ ) / alkali (R ₂ O) is preferably in the range of 7.5 to 1. If it is out of this range, the water resistance of the second layer may be insufficient and the film formability may deteriorate.

The solid content concentration of the silicon-containing component in the coating solution for forming the second layer, that is, the film forming component concentration is preferably 1 to 20% by mass. If it is out of this range, the coating film thickness cannot be obtained sufficiently, and conversely, the viscosity becomes too large and application may be difficult. As the sol particles, colloidal silica or a hydrolyzate of alkoxysilane is suitable.
The organic component is added to the coating solution for forming the second layer. The amount of the organic component added is preferably in the range of 0.1 to 100% by mass with respect to the silicon dioxide (SiO ₂ ) when the silicon (Si) -containing component is converted to silicic acid (SiO ₂ ). If it is out of this range, there is a possibility that a sufficient effect of preventing adhesion of scales cannot be obtained, or that the coating film is whitened due to an excessive amount.

Li, Na, K, Mg, Ca, Zn, Al, P, and Zr may be added as additive components to the coating solution for forming the second layer. In the case of adding Li, Na, K, it is automatically covered by using those alkali silicates. For Mg, Ca, Zn, Al, P, and Zr, it is preferable to use a salt of each element or an alkoxide.
The addition amount of these additive components needs to be in a range in which precipitation or gelation does not occur due to reaction with the silicon-containing component. Specifically, it is the range of 0.1-20 mass% with respect to a silicon containing component. If it is out of this range, there is a possibility that a sufficient effect of preventing scale adhesion cannot be obtained, or precipitation or gelation may occur due to excessive amount.

In the method of the present invention, the second layer forming coating solution is applied onto the first layer. As a coating method, a known spray method, dipping method, roll method or the like can be applied, and there is no particular limitation. Then, the formed coating film is dried and heat-treated. Heat treatment temperature and heat treatment time are as high as possible within a range that does not adversely affect the substrate, and it is preferable to perform heat treatment for a long time because the film strength of the film and the water resistance of the film are increased. A short heat treatment at the heat treatment temperature is sufficient.
The specific heat treatment temperature is usually room temperature to 500 ° C when the product substrate is an inorganic product such as glass, more preferably 80 to 500 ° C, and room temperature when the product substrate is plastic. A temperature of ˜150 ° C. is suitable, more preferably 80 to 130 ° C., and when the product substrate is a metal, a temperature of room temperature to 300 ° C. is preferred, and 80 to 300 ° C. is more preferred.
The atmosphere during the heat treatment is not particularly limited, but is usually an air atmosphere.
Before forming the second layer, the primer layer forming coating solution may be applied on the first layer and heat-treated to form the primer layer, and then the second layer may be formed. This makes it possible to improve the adhesion between the first layer and the second layer.

  The present invention will be described in detail with reference to the following examples and comparative examples.

Example 1
A coating solution for forming a first layer was prepared by mixing 10 parts by mass of zirconium alkoxide, 79 parts by mass of isopropyl alcohol, 10 parts by mass of a silica sol solution containing 30% by mass of silica sol, and 1 part by mass of a 60% by mass nitric acid aqueous solution. This first layer-forming coating solution is applied onto the surface of a stainless steel substrate by a roller so that the film thickness after heat treatment is 0.5 μm, and heat-treated in an air atmosphere at 250 ° C. for 30 minutes. A first layer made of a coating having a zirconium oxide component was formed. This first layer was a film firmly bound to the stainless steel substrate.
Next, 50 parts by mass of No. 3 sodium silicate solution, 49 parts by mass of water, and 1 part by mass of sodium polyacrylate having a weight average molecular weight of 6000 were mixed to prepare a coating solution for forming a second layer. This first layer forming coating solution is applied onto the first layer by a roller so that the film thickness after heat treatment is 0.5 μm, and heat-treated in an air atmosphere at 250 ° C. for 30 minutes, so that silicon oxide and poly A second layer containing sodium acrylate was formed to produce a scale sticking prevention product of Example 1. The second layer was firmly bound to the first layer.

Comparative Example 1
On the surface of the same stainless steel substrate as used in Example 1, only the second layer forming coating solution of Example 1 was applied by roller so that the film thickness after heat treatment was 0.5 μm. The product was processed in the same manner as in No. 1 to prepare a comparative scale-sticking prevention product.

Example 2
A coating solution for forming a first layer was prepared by mixing 10 parts by mass of methyl silicate, 80 parts by mass of isopropyl alcohol, and 10 parts by mass of an aqueous solution containing 30% by mass of zirconium nitrate. This first layer-forming coating solution is dip-coated on an acrylic resin substrate so that the film thickness after heat treatment is 0.5 μm, and heat-treated in an air atmosphere at 80 ° C. for 30 minutes. The 1st layer which consists of a film which has a component was formed. The first layer coating was firmly bound to the acrylic resin plate.
Next, a primer layer-forming coating solution was applied on the first layer and dried naturally to form a primer layer. As the primer layer-forming coating solution, a 1% by mass aqueous solution of No. 45 lithium silicate solution (Nippon Chemical Industry, product name) was used.
Next, 50 parts by mass of No. 45 lithium silicate aqueous solution, 49 parts by mass of an aqueous solution containing 1% by mass of zinc nitrate, and 1 part by mass of polyethylene glycol (weight average molecular weight 1000) were mixed to prepare a coating solution for forming a second layer. . This second layer-forming coating solution is dip-coated on the primer layer so that the film thickness after heat treatment is 0.5 μm, and heat-treated in an air atmosphere at 80 ° C. for 30 minutes to obtain silicon oxide and polyethylene glycol. A second-layer coating containing the above was formed to produce a scale-fixing prevention product of Example 2. The second layer was strongly bonded to the first layer.

Comparative Example 2
On the surface of the acrylic resin substrate used in Example 2, only the second layer-forming coating solution of Example 2 was applied by roller so that the film thickness after heat treatment was 0.5 μm. Thereafter, the same as in Example 2 To obtain a comparative water scale anti-sticking product.

Example 3
10 parts by mass of ethyl silicate, 79 parts by mass of isopropyl alcohol, 1 part by mass of an aqueous solution containing 10% by mass of nitric acid, 9 parts by mass of zirconia sol (isopropyl alcohol solvent dispersion) containing 30% by mass of zirconia sol, 1 part by mass of calcium nitrate Were mixed to prepare a coating solution for forming a first layer. This first layer-forming coating solution is spray-coated on a glass substrate so that the film thickness after heat treatment is 0.5 μm, and heat-treated in an air atmosphere at 450 ° C. for 30 minutes to form a first layer made of a heat-treated product. Formed. This first layer had a silicon oxide component and a zirconium oxide component, and was a film firmly bonded to the glass substrate.
Next, a primer layer forming coating solution was applied onto the first layer, and heat treatment was performed in an air atmosphere at 450 ° C. for 30 minutes to form a primer layer. As the primer layer forming coating solution, the one used in Example 2 was used.
Next, 2 parts by mass of ethyl silicate, 89 parts by mass of isopropyl alcohol, 1 part by mass of a 10% by mass nitric acid aqueous solution, 6 parts by mass of zirconia sol liquid (isopropyl alcohol solvent dispersion) containing 3% by mass of zirconia sol, 2-hydroxy methacrylate A coating solution for forming a second layer was prepared by mixing 0.1 part by mass of ethyl. This coating solution for forming the second layer is spray-coated on the primer layer so as to have a film thickness of 0.5 μm after heat treatment, and heat-treated in an air atmosphere at 450 ° C. for 30 minutes to obtain silicon oxide and methacrylic acid 2 -A second layer composed of a film containing a polymer produced by crosslinking hydroxyethyl was formed to obtain an anti-scale product.

Comparative Example 3
On the surface of the same glass plate used in Example 3, only the second layer forming coating solution described in Example 3 was applied by roller so that the film thickness after heat treatment was 0.5 μm, and thereafter The product was processed in the same manner as in Example 3 to prepare a comparative scale-sticking prevention product.

Example 4
A coating solution for forming a first layer was prepared by mixing 10 parts by mass of zirconium alkoxide, 79 parts by mass of isopropyl alcohol, 10 parts by mass of a silica sol solution containing 30% by mass of silica sol, and 1 part by mass of a 60% by mass nitric acid aqueous solution. This first layer forming coating solution is spray-coated on the surface of the stainless steel substrate so that the film thickness after the heat treatment is 0.5 μm, and is heat-treated in an air atmosphere at 250 ° C. for 10 minutes. A first layer made of a coating having a zirconium oxide component was formed.
Next, a primer layer-forming coating solution was applied onto the first layer, and heat-treated in an air atmosphere at 250 ° C. for 10 minutes to form a primer layer. As a primer layer forming coating solution, a JIS No. 3 sodium silicate diluted solution was used.
Next, 50 parts by weight of No. 45 lithium silicate aqueous solution, 10 parts by weight of an acrylic resin emulsion (manufactured by Nippon Shokubai Co., Ltd., Epostor MX050W) and 40 parts by weight of water were mixed to prepare a coating solution for forming a second layer. This coating solution for forming the second layer is spray-coated on the primer layer so that the film thickness after the heat treatment is 0.5 μm, and heat-treated in an air atmosphere at 250 ° C. for 10 minutes. A second layer made of a coating containing was formed to produce a scale-fixing prevention product.

Comparative Example 4
On the surface of the same stainless steel plate as used in Example 4, only the second layer forming coating solution described in Example 4 was applied by roller so that the film thickness after heat treatment was 0.5 μm. The product was treated in the same manner as in Example 3 to produce a comparative water scale sticking prevention product.

Comparative Example 5
On the surface of the same stainless steel substrate as used in Example 1, the first layer forming coating solution described in Example 1 was applied by roller so that the film thickness after heat treatment was 0.5 μm. The product was treated in the same manner as in Example 1 to prepare a comparative water scale anti-sticking product.

"Evaluation"
The water resistance and scale sticking prevention performance of the scale sticking prevention coating films of the scale sticking prevention products of Examples 1 to 4 and Comparative Examples 1 to 5 were measured and evaluated by the following methods. The evaluation results are shown in Table 1.
(water resistant)
The test sample was immersed in boiling water for 24 hours, and the property of the coating film for preventing adhesion of scale to the sample was visually observed and recorded.
(Scale prevention performance)
In Examples 1-4 and Comparative Example 5, on the scale adhesion prevention coating film after completion of the water resistance test, and in Comparative Examples 1-4, on the surface of the product substrate after completion of the water resistance test. 10 ml of tap water was dropped and left in an air atmosphere at 20 ° C. for 30 days to deposit scale. The deposited scale was rubbed with a sponge, and the ease of removing scale was visually observed and recorded.

From the results of the performance evaluation shown in Table 1, the scale adhesion prevention products of Examples 1 to 4 are superior in scale adhesion prevention effect and easy to scale compared with the scale adhesion prevention products of Comparative Examples 1 to 5. It was confirmed that it can be easily removed by a simple method.
In addition, the scale adhesion preventing coating films of the scale adhesion preventing products of Examples 1 to 4 were also excellent in water resistance, and therefore, it was also confirmed that the scale adhesion preventing effect lasted for a long period of time.

  The scale anti-sticking product of the present invention can maintain an excellent scale anti-sticking effect over a long period of time, and can be easily removed even if scale adheres. In addition, the production method is also industrially useful because it can easily and efficiently produce a product for preventing scale adhesion having the above-mentioned performance.

Claims (3)

A product substrate, and a scale fixing coating film formed on the surface of the substrate,
The scale fixing coating film includes a first layer made of a film-forming material having a silicon oxide component and a zirconium oxide component, and is formed on the first layer, and is formed on the silicon oxide component and water. A scale adhesion prevention product comprising: a second layer made of a film-forming substance containing an organic component containing at least one selected from a polymer and / or a monomer that dissolves or disperses.   The organic material component for the second layer includes at least one selected from polyacrylic acid, polyacrylate, acrylic polymer or monomer, polyethylene glycol, polyvinyl pyrrolidone, polyvinyl alcohol, and carboxymethyl cellulose. Product with prevention of scale adhesion as described. On the surface of the product substrate, a silicon-containing component containing at least one selected from silica sol, silicon alkoxide and its partial hydrolysis product, and silicate, zirconia sol, zirconium alkoxide and its partial hydrolysis product, and Applying a coating solution containing a zirconium-containing component containing at least one selected from zirconium salts, and heat-treating to form a first layer comprising the heat-treated product;
Further, on the first layer, a silicon-containing component containing at least one selected from silica sol, silicon alkoxide and a partial hydrolysis product thereof, and silicate, and a polymer and / or monomer dissolved or dispersed in water are selected. And applying a heat treatment to form a second layer made of the heat treatment product, thereby forming a scale adhesion preventing coating layer. Manufacturing method of scale prevention products.