WO2019021733A1

WO2019021733A1 - Rinsing liquid-resistant hydrophilic member and method for manufacturing same

Info

Publication number: WO2019021733A1
Application number: PCT/JP2018/024496
Authority: WO
Inventors: 拓史野村; 敏裕平野; 勇貴中村
Original assignee: セントラル硝子株式会社
Priority date: 2017-07-28
Filing date: 2018-06-28
Publication date: 2019-01-31

Abstract

[Problem] To provide a hydrophilic member which is highly resistant to cationic surfactants. [Solution] A hydrophilic member to be used in water sections such as bathroom or washstand, said hydrophilic member comprising a base material, an inorganic oxide coating film which is formed on the base material and provided with a surface layer having an uneven structure, and a starch compound fixed to the uneven structure, wherein: the inorganic oxide coating film comprises a composite oxide of silicon oxide with at least one member selected from the group consisting of zirconium oxide, aluminum oxide and zinc oxide; and the starch compound is a cationic or anionic starch compound.

Description

Rinse resistant hydrophilic member and method of manufacturing the same

The present invention relates to a hydrophilic member that can be suitably used in a bathroom.

In recent years, an article provided with a base material and an inorganic oxide film formed on the base material is provided with a fine uneven structure on the surface of the film, and exhibits hydrophilicity by the surface tension of water entering the uneven structure. An article (see, for example, Patent Documents 1, 2 and 3) is used as a hydrophilic member or an antifogging mirror used around water such as a bathroom or a wash basin.

In Patent Documents 2 and 3, a composite of a surfactant or a hydrophilic polymer such as polyacrylic acid, polysaccharide-based polymer, soluble starch and the like and a chemical species having the property of being able to gradually release the substance such as polyethylene glycol There is disclosed a hydrophilic member in which a material is fixed on a film having the above-mentioned concavo-convex structure.

In the hydrophilic member disclosed in Patent Document 4, the starch compound is supported on the concavo-convex structure of the surface layer of the inorganic oxide film, and the hydrophilicity is improved by the starch compound.

Patent Document 5 is a hydrophilic film-formed article having a substrate and a film in which oxide fine particles are dispersed on the surface of the substrate and held by a metal oxide layer, and the metal oxide layer No. 10, a hydrophilic film-formed article comprising silicon oxide and aluminum oxide is described.

Japanese Patent Application Laid-Open No. 7-164971 Unexamined-Japanese-Patent No. 2000-265162 Unexamined-Japanese-Patent No. 2000-265163 JP, 2005-047259, A JP, 2015-110313, A

The hydrophilic member is used in the environment around the water such as a bathroom or a wash basin where the hair rinse solution containing the cationic surfactant is used, so the surface of the hydrophilic member is the cationic surfactant. It is an environment that is easily exposed to chemicals.

The hydrophilic member surface tends to be easily negatively charged due to the hydrophilic nature of the surface. Therefore, when the cationic surfactant adheres to the surface of the hydrophilic member, a unit having a positive charge of the cationic surfactant adheres to the surface. As a result, in the hydrophilic member in which the cationic surfactant is attached to the surface, the hydrophobic group of the cationic surfactant is oriented outward from the surface of the hydrophilic member. If this phenomenon continues, the hydrophilicity of the surface of the hydrophilic member decreases. This phenomenon is likely to occur around water, such as a bathroom or a wash basin, where the rinse solution is frequently used.

From the above, the present invention easily maintains hydrophilicity even when in contact with a cationic surfactant, that is, it has good resistance to the cationic surfactant (hereinafter referred to as "rinse resistance"), An object is to provide a hydrophilic member.

In order to solve the above-mentioned subject, the present inventors are a hydrophilic member which consists of a film which has an uneven structure in a surface layer, a starch compound supported by the uneven structure, and a substrate which were indicated by patent documents 2 I focused on This is because the article is expected to have good antifouling properties as disclosed in Patent Document 2. In the present invention, we considered the factors that are effective in improving the resistance to rinse liquid, and came up with the idea of how to make the starch compound be closely supported on the film.

That is, a bathroom or a washstand comprising: a base material; an inorganic oxide film having a surface layer having a concavo-convex structure formed on the base material; and a starch compound fixed to the concavo-convex structure. In hydrophilic members used around water,
The inorganic oxide film is
Silicon oxide,
A composite oxide comprising or consisting of at least one selected from the group consisting of zirconium oxide, aluminum oxide and zinc oxide,
The starch compound is a cationic or anionic starch compound, or a mixture of a cationic starch compound and an anionic starch compound.
It is a hydrophilic member resistant to rinse liquid.

The cationic starch compound is a derivative of a naturally occurring polymer starch compound and is a compound modified so that the starch compound has a positive charge, and is a compound widely used in, for example, the pulp industry. The cationic starch compound can be obtained by reacting a hydroxyl group in a starch compound of a natural polymer, and a salt having a reactive group of a cationic group and the hydroxyl group in the unit on the plus side.

The anionic starch compound is a derivative of a naturally occurring high molecular weight starch compound, which has been modified so that the starch compound has a negative charge. The anionic starch compound can be obtained by reacting a hydroxyl group in a starch compound of a natural polymer with a salt having a reactive group of an anion group and the hydroxyl group in the unit on the plus side.

The complex oxide of the inorganic oxide film is preferably a complex oxide such as a silicon oxide-zirconium oxide system, a silicon oxide-zirconium oxide-aluminum oxide system, or a silicon oxide-zinc oxide system. Oxides such as zirconium, aluminum and zinc have high isoelectric point. Since the hydrophilic member of the present invention is used in an environment where neutral water (such as tap water, for example, water of pH 5 to 9) is used, the location of the compound in the complex oxide is as follows: It tends to be positively charged. Therefore, a site which tends to be positively charged is generated in the complex oxide due to these oxides, and adhesion to the inorganic oxide film of the anionic starch compound which is likely to be negatively charged is improved. Conceivable.

On the other hand, silicon compounds have lower isoelectric point than oxides such as zirconium, aluminum and zinc. The hydrophilic member of the present invention is used in an environment where neutral water (such as tap water, for example, water having a pH of 5 to 9) is used, so the location where the silicon compound in the complex oxide is negative Tend to be charged. Therefore, a site which tends to be negatively charged is generated in the complex oxide due to these oxides, and the adhesion of the cationic starch compound which is likely to be positively charged to the inorganic oxide film is improved. Conceivable.

In the hydrophilic member, the cationic starch compound can also contact the positively charged site of the inorganic oxide film, and the anionic starch compound can also contact the negatively charged site of the inorganic oxide film. In this case, there is also concern that the repulsion of both charges may potentially adversely affect the adhesion of the starch compound to the uneven structure of the inorganic oxide. The same may be of concern in the case of mixtures of cationic starch compounds and anionic starch compounds. However, in the inorganic oxide film based on the composite oxide of the present invention, surprisingly, only the effect of improving the adhesion of the starch compound to the uneven structure was observed. This was successful in improving the rinse liquid resistance of the hydrophilic member of the present invention.

The hydrophilic member is preferably
Preparing the substrate;
A coating solution containing a hydrolyzate and / or a condensate of a precursor compound of a composite oxide is applied to the substrate to form the inorganic oxide film in which the surface layer forms a concavo-convex structure on the substrate. Process,
Forming a starch compound layer composed of a cationic or anionic starch compound that is thicker than the film thickness of the inorganic oxide film on the inorganic oxide film, and filling the surface roughness structure with the starch compound;
Wiping the starch compound layer to expose the surface layer of the hydrophilic member;
Obtained by the method.

The hydrophilic member of the present invention is excellent in rinse liquid resistance because the adhesion of the starch compound on the surface layer where the concavo-convex structure is formed is good. Therefore, the hydrophilic member of the present invention is suitable for use in an environment where a rinse solution containing a cationic surfactant is used, in particular, around water such as a bathroom or a wash basin.

The hydrophilic member of the present invention is a hydrophilic member having a surface layer on which a concavo-convex structure is formed, and is an inorganic oxide having the above-mentioned base material and a surface layer on which the concavo-convex structure is formed. A coating, and a starch compound fixed to the uneven structure,
The inorganic oxide film is silicon oxide,
A composite oxide comprising or consisting of at least one selected from the group consisting of zirconium oxide, aluminum oxide and zinc oxide,
The starch compound is a cationic or anionic starch compound, and is in contact with the complex oxide.

Each configuration will be described in detail below.
[Base material]
The base material used in the present invention is not particularly limited as long as it is expected to be hydrophilic, but, for example, a glass plate, a mirror, a reflector, a protective plate, a tile, a dish, metal, metal plating Articles, ceramics and the like are preferable, and a glass plate and a mirror are preferable.

In order to improve the adhesion to the inorganic oxide film, it is preferable that the substrate such as a glass plate be sufficiently polished in advance with an abrasive such as cerium oxide to carefully remove surface dirt and the like. .

The substrate is usually used in the form of a rectangle, but may be in other forms, for example, various shapes such as a circle, an ellipse, and a triangle. The size is determined appropriately depending on the application. Also, depending on the application, the thickness is usually set to, for example, the strength required in the mode to be used. As the substrate, not only a substrate having a flat surface, but also a substrate having unevenness on the surface, a substrate on which a pattern is formed, or a substrate having a curvature may be used.

[Inorganic oxide film]
The inorganic oxide film is formed on the base material and has a surface layer on which a concavo-convex structure is formed.

The inorganic oxide film is
Silicon oxide,
At least one selected from the group consisting of zirconium oxide, aluminum oxide and zinc oxide,
It consists of complex oxide which contains or consists of.

The shape of the concavo-convex structure of the inorganic oxide film is expressed as a parameter according to JIS (JIS B 0601: 2001) as the surface roughness of the surface of the inorganic oxide film, and Ra (arithmetic mean roughness) is 5 nm It is preferable that the range of about 20 nm and Rx (maximum height roughness) be 50 nm to 150 nm.

The film thickness of the inorganic oxide film is not particularly limited, and may be 20 nm to 200 nm, preferably 40 nm to 140 nm. The film thickness here is the distance from the top of the convex portion (the highest point among the observed points) to the substrate in the uneven structure.

The uneven structure formed on the surface of the inorganic oxide film is, for example,
A composite oxide obtained by dispersing fine particles of an organic compound such as a fluorocarbon resin is formed on a substrate and then heated at a temperature above the thermal decomposition temperature of the fine particle of the organic compound to decompose the fine particles of the organic compound Alternatively, the inorganic oxide film may include inorganic oxide fine particles, and the uneven structure may be formed by the inorganic oxide fine particles. The latter is described in more detail elsewhere herein.

The complex oxide may be a silicon oxide as an essential component, and may contain any of zirconium oxide, aluminum oxide, and zinc oxide, or may contain two or more of these oxides. By using a silicon oxide as an essential component, the adhesion between the cationic starch compound and the inorganic oxide film is improved, and the inorganic oxide tends to have a stable structure. Further, zirconium oxide, aluminum oxide, zinc oxide or the like improves the adhesion of the anionic starch compound and improves the alkali resistance of the inorganic oxide film. In consideration of these, the complex oxide may contain 5 mol% to 65 mol%, and further 15 mol% to 45 mol% of silicon oxide. The balance may be at least one selected from the group consisting of zirconium oxide, aluminum oxide and zinc oxide.

In addition, the inorganic oxide film may include inorganic oxide fine particles, and the uneven structure formed on the surface of the inorganic oxide film may be formed of the inorganic oxide fine particles. In this case, the compounding ratio of the inorganic oxide fine particles in the composite oxide is adjusted so that the surface layer of the inorganic oxide film has an uneven structure due to the shape of the inorganic oxide fine particles. For example, when the amount of the composite oxide and the inorganic oxide fine particles is 100 mol%, the content of the inorganic oxide fine particles is 30 mol% to 80 mol%, further 35 mol% to 70 mol%, Furthermore, it may be 40 mol% to 60 mol%.

Examples of the inorganic oxide fine particles include fine particles of silicon oxide, aluminum oxide, zirconium oxide, iron oxide and the like. Among them, fine particles (silicon oxide fine particles) made of silicon oxide are preferable. The silicon oxide fine particles may be amorphous silicon oxide or crystalline silicon oxide, and in particular, colloidal silica is suitably used.

The average particle diameter of the inorganic oxide fine particles may be preferably 20 to 100 nm, more preferably 30 to 80 nm, and still more preferably 30 to 60 nm. The concavo-convex structure of the surface layer of the film is influenced by the size of the inorganic oxide fine particles, so a fine concavo-convex structure is obtained.

The average particle size can be determined as follows. The film is observed on a scale that allows the shape of the fine particle to be clearly observed by optical microscope observation such as a scanning electron microscope. Next, the diameters of all the particles in the observation range are measured, and the value of the simple average is determined. This value is taken as the average particle size.

The projections of the concavo-convex structure are usually formed by the inorganic oxide fine particles present in the vicinity of the surface layer of the inorganic oxide film.
The surface of the inorganic compound fine particle may or may not be covered with the complex oxide other than the inorganic compound fine particle.

The complex oxide is
A precursor compound of silicon oxide,
The inorganic oxide film can be easily obtained if it comprises or consists of a polycondensate with at least one precursor compound selected from the group consisting of zirconium oxide, aluminum oxide and zinc oxide .

The inorganic oxide film can be formed by applying a coating liquid containing the inorganic oxide fine particles and a hydrolyzate and / or a condensate of a precursor compound of a composite oxide to the substrate. The precursor compound of the complex oxide undergoes a hydrolysis and polycondensation reaction between in the coating solution and the formation of the inorganic oxide film on the substrate to form a complex oxide.

Examples of the precursor compounds include tetramethoxysilane, tetraethoxysilane, tetrachlorosilane, monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltrichlorosilane, (3-mercapto) trimethoxysilane, and (3-aminopropyl) trile. Methoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane, zirconium oxychloride, zirconium oxynitrate, zirconium oxyacetate, telora isopropoxyzirconium, tetranormal butoxy zirconium, tetraethoxy zirconium, zirconium acetylacetonate, aluminum ethylaceto Acetate diisopropylate, aluminum di normal butoxy monoethyl acetoacetate, aluminum Tris acetylacetonate, aluminum tris ethylacetoacetate, aluminum bis ethylacetoacetate monoacetylacetonate, aluminum ethylacetoacetate diisopropylate and the like.

In the coating solution, the concentration (referred to as “solid content concentration”) of the inorganic oxide fine particles and the precursor compound of the inorganic oxide when converted to the complex oxide is 1 mass% to 10 mass%. May contain a solvent for concentration control. In order to accelerate the hydrolysis of the precursor compound, 0.1% by mass to 30% by mass of water may be included, or 0.1% by mass to 10% by mass of an acid catalyst such as nitric acid, acetic acid, sulfuric acid, etc. May be.

The solvent for controlling the concentration is preferably an alcohol solvent, and specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, butylene glycol, and the like. Pentylene glycol, hexylene glycol, 1-methoxy-2-propanol, further esters such as ethyl acetate, butyl acetate, amyl acetate, and further, cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and mixtures thereof A suitable amount of methyl silicones such as dimethyl silicone or a fluorine-based leveling agent may be added as a leveling agent. An alcohol-based or cellosolv-based one or a mixture thereof originally contained in the solution may be selected in consideration of the evaporation rate of the solution and the film viscosity. It is also possible to use two or more of the solvents in combination.

The method for applying the coating solution for forming the inorganic oxide film to the substrate is not particularly limited, but in terms of productivity and the like, for example, spin coating, bar coating, A known means such as reverse roll coating method, other roll coating method, curtain coating method, spray coating method can be adopted, and by appropriately masking, a film is formed on an arbitrary shape and pattern as well as partial film formation. be able to. After application of the coating liquid to the substrate, the substrate may be heated, for example, at 100 ° C. to 200 ° C. for 10 minutes to 60 minutes.

The mechanism by which the inorganic oxide fine particles form the concavo-convex structure can be described as follows. When a coating solution containing a hydrolyzate and / or a condensate of a precursor compound of a complex oxide containing inorganic oxide fine particles as a part of the composition and a solvent is applied to a substrate, the liquid film of the coating solution becomes a base It is formed on the material. The inorganic oxide fine particles are dispersed in the liquid film, and the inorganic oxide fine particles are disposed on the liquid surface of the liquid film. From the liquid film, the solvent evaporates, and the polycondensation reaction of the hydrolyzate and / or the condensate of the precursor compound of the complex oxide proceeds, and from the liquid state, it becomes a solid with volume contraction. It is converted to an inorganic oxide film. Through this process, the inorganic oxide fine particles arranged on the liquid surface are fixed to the surface layer of the film, and a concavo-convex structure consisting of the particle layer is formed on the surface layer. At this time, the space between the particles is a recess, and the particles are a protrusion. In the concavo-convex structure, at least the recess comes to include the complex oxide. The complex oxide is included in the surface layer of the inorganic oxide film.

[Cationic Starch Compound]
The cationic starch compound is a derivative of a starch compound of a natural polymer, which is modified so that the starch compound has a positive charge, and includes a hydroxyl group in the starch compound of the natural polymer, a cationic group and the hydroxyl group. It can be obtained by reacting with a salt having a reactive group such as a hydroxyl group, a carboxyl group, an epoxy group, an isocyanate group, an amino group or the like in the unit on the plus side. Examples of the salt include 3-chloro-2-hydroxypropyltrimethylammonium chloride or 2,3-glycidylpropyltrimethylammonium chloride, trimethylacetohydrazide ammonium chloride, 2-hydroxyethyltrimethylammonium hydroxide, (2-hydroxyethyl And trimethylammonium bromide and the like.

The cationic starch is commercially available from the market, for example, POSIT-200 manufactured by Sanki Co., Ltd., POSIT-300, POSIT-400, paper strength agent DD series manufactured by Seiko PMC Co., Ltd., Matsutani Kagaku An Excel cat 2220 manufactured by Co., Ltd., an Excel cat 330, and the like can be used.

[Anionic starch compound]
The anionic starch compound is a derivative of a starch compound of a natural polymer, which is modified so that the starch compound has a negative charge, and includes a hydroxyl group in the starch compound of a natural polymer, an anion group and the hydroxyl group. It can be obtained by reacting with a salt having a reactive group of, for example, a hydroxyl group, a carboxyl group, an epoxy group, an isocyanate group, an amino group, a phosphoric acid ester or the like in the unit on the minus side.

Examples of the salt include sodium hydroxyacetate or sodium sarcosine, sodium (2-carbamoylphenoxy) acetate, sodium 3-cyclohexylamino-2-hydroxypropanesulfonate, sodium 4-hydroxy-3-methoxybenzoate, chloroacetic acid Sodium, sodium monohydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium trimetaphosphate, sodium lauryl phosphate, sodium creatine phosphate and the like can be mentioned.

The anionic starch compound is available from the market, and for example, manufactured by Nippon Shokuhin Kaseki's Huaka L, Kasumi W, MS # 4600 made by Nippon Shokuhin Kako Co., Ltd., made by Matsutani Chemical Industry Co., Ltd. Sorbitose C-5F, Neil gum T85, etc. can be used.

The starch compound may be a mixture of a cationic starch compound and an anionic starch compound. When a mixture is used, the mixing ratio of the cationic starch compound to the anionic starch compound is, for example, 10% by mass to 99% by mass of the latter, and the ratio of the remaining part to the former, preferably 40 The ratio may be from mass% to 99 mass%, with the balance being the former.

In addition, according to a preferred method of producing a hydrophilic member of the present invention,
Preparing a substrate (1);
A coating solution containing a hydrolyzate and / or a condensate of a precursor compound of a composite oxide is applied to the substrate to form the inorganic oxide film in which the surface layer forms a concavo-convex structure on the substrate. Step (2),
A starch compound layer comprising a cationic or anionic starch compound or a mixture of a cationic starch compound and an anionic starch compound, which is thicker than the inorganic oxide film thickness, on an inorganic oxide film Forming a surface layer and filling the surface relief structure with a starch compound (3);
And D. wiping the starch compound layer to expose the surface layer of the hydrophilic member (4).

Since the steps (1) and (2) have been described above, the steps (3) and (4) will be described in detail below.

In the step (3), a starch compound layer comprising a cationic or anionic starch compound or a cationic starch compound on the inorganic oxide film so as to be thicker than the film thickness of the inorganic oxide film A starch compound layer is formed, which is a mixture with an anionic starch compound. By the formation of the starch compound layer, the concavo-convex structure of the inorganic oxide film surface layer is filled with the starch compound.

The starch compound layer can also play a role of protecting the inorganic oxide film, and thus is preferably included as a packing form of the hydrophilic member of the present invention. The thickness of the starch compound layer may be 1 μm to 100 μm, and more preferably 5 μm to 50 μm, from the production of the hydrophilic member to the packaging form. Moreover, in the packing form of the hydrophilic member of this invention, protective papers, such as a kraft paper, may be stuck on the said starch compound layer.

The starch compound layer can be obtained by applying a coating solution containing a cationic or / and anionic starch compound on the inorganic oxide film. For example, it is diluted with water such that the content of the starch compound is preferably 1% by mass to 60% by mass, more preferably 5% by mass to 40% by mass, and still more preferably 10% by mass to 30% by mass. Thus, a coating solution for forming the starch compound layer is obtained. The application of the coating solution onto the inorganic oxide film can be carried out by coating with a roller, brush coating, or the like.

After the coating solution is applied, the applied starch compound is preferably heated at 50 ° C. to 100 ° C. For this heat treatment means, it is possible to use a hot air blower type dryer that is generally distributed.

By this heating, the gelatinization of the starch compound is promoted, and the starch compound can be easily permeated into the uneven structure. And, when the starch compound reaches a room temperature state, the cationic or / and anionic starch compound incorporated into the concavo-convex structure ages and solidifies, and thus the starch to the concavo-convex structure of the surface layer of the inorganic oxide film Fixation of the compound becomes strong.

The step (4) can be performed by wiping the starch compound layer. The operation of wiping the starch compound layer can be performed with a water-containing foamable elastic body such as urethane foam sponge or melamine foam sponge. Through this operation, the surface layer having the concavo-convex structure formed on the hydrophilic member is exposed.

Since the hydrophilic compound elutes the starch compound with time and the hydrophilicity due to the starch compound decreases, the coating liquid containing the anionic starch compound is periodically applied to form a foamable elastic material containing water. By rubbing the surface of the member with the body, it is possible to restore the hydrophilicity. At that time, after applying a coating agent having a starch compound, the member is subjected to heat treatment at 50 ° C. to 100 ° C. which can promote gelatinization of the starch compound and allow the starch compound to penetrate with a member having a fine surface uneven structure. Is preferred. For this heat treatment means, it is possible to use a hot air blower type dryer that is generally distributed.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to such examples.

The members obtained in the present example and the comparative example were evaluated by the methods described below.
<Initial water contact angle>
As an evaluation of the initial water contact angle of the hydrophilic member, place a 2 μl droplet of ion-exchanged water on the surface of the hydrophilic member, place the droplet, and make an angle between the droplet after 5 seconds and the surface of the hydrophilic member The contact angle was measured at room temperature (25.degree. C.) using a contact angle meter (model DM-501 manufactured by Kyowa Interface Science). The smaller the initial water contact angle, the better the hydrophilicity.

<Rinse liquid resistance>
A rinse solution was prepared by diluting ASIENCE Conditioner (manufactured by Kao) with water to 5% by weight. The rinse solution was spread on the surface of a 10 cm square hydrophilic member at room temperature (25 ° C.) and dried at 60 ° C. for 20 minutes. After drying, the surface of the hydrophilic member was cleaned with a sponge using Bath Magicline (manufactured by Kao). Thereafter, pure water was applied to the surface of the hydrophilic member vertically erected, uniformly wetted and allowed to stand, and the state of the water film on the surface of the hydrophilic member after 20 seconds was visually observed. Even after 20 seconds, if a water film is formed on 70% or more of the surface area (100 cm ² ) of the surface of the hydrophilic member, the rinse solution is again sprayed and dried to form a water film. The area repeated was repeated until the area of the surface of the hydrophilic member was less than 70%. Evaluate the limit number of cycles where water film is formed on the area of 70% or more after 20 seconds, pass those with more than 30 cycles (o), and reject less than 30 (x) And

Example A1
(Preparation of base material)
The glass side surface of a glass mirror (300 mm.times.1000 mm.times.5 mm) produced by the silvering method was sufficiently polished with cerium oxide, then washed with water and then dried to obtain a substrate.

(Preparation of Coating Solution for Forming Inorganic Oxide Film)
112 g of tetraethoxysilane (hereinafter also referred to as "TEOS", manufactured by Tama Chemical Co., Ltd.),
1472 g of a solution in which zirconium oxychloride octahydrate (manufactured by Kishida Chemical Co., Ltd.) is diluted to 10% by mass with Alkosol K (a mixed solvent of ethanol, isopropanol, and methyl ethyl ketone manufactured by Sugar Chemical Industry Co., Ltd.)
208 g (85 g of silica) of colloidal silica (MA-ST-L, manufactured by Nissan Chemical Industries, average particle diameter 40 to 50 nm) having a solid content concentration of 40.7 mass%,
120 g of aluminum ethyl acetoacetate diisopropylate (S-75P, manufactured by Kawaken Fine Chemicals Co., Ltd.),
168 g of deionized water, 4112 g of Alkosol K, and 1808 g of 1-methoxy-2-propanol
The mixture was stirred at 25 ° C. for 3 hours to obtain a coating solution for forming an inorganic oxide film having a solid content concentration of 3.5% by mass in terms of total oxides.

(Formation of inorganic oxide film)
A coating solution for forming an inorganic oxide film is applied to the glass side surface of the substrate by roll coating, and then the substrate is heat treated at 160 ° C. for 20 minutes, and the surface layer has an uneven structure. An oxide film was formed. In the inorganic oxide film, the silicon oxide fine particles and the inorganic oxide binder were 43 mol% and 57 mol%, respectively. Moreover, the thickness of the film was 50 nm.

Fixation of cationic starch compound to the uneven structure of inorganic oxide film
Glue made of cationic starch compound (trade name: Excelcat 220, Matsutani Chemical Co., Ltd.)
Product was diluted 5 times by weight ratio with water at about 25 ° C. to obtain a coating solution for fixing starch. Apply the starch compound on the inorganic oxide film by rubbing the surface of the inorganic oxide film with Woroller B (manufactured by Otsuka Brush Manufacturing Co., Ltd.) containing the coating solution on the surface of the inorganic oxide film. did. Thereafter, the starch compound was dried at 80 ° C. for 3 hours to form a layer composed of the starch compound, which was formed as a result of excessive application of the starch compound on the inorganic oxide film. On the layer, flat-gloss kraft paper (manufactured by Nippon Paper Industries, product name "Capital Wrap") was adhered as a protective paper to obtain a packed hydrophilic member.

The protective paper is peeled off from the article, the surface of the inorganic oxide surface membrane is rubbed with a moistened sponge, the excessively applied starch compound is removed from the inorganic oxide film, and the hydrophilic member of the present invention is obtained. Obtained.

Example A2
A hydrophilic member was obtained by performing the same operation as in Example A1 except that the cationic starch compound was changed to another product number (trade name: Excelcat 330, manufactured by Matsutani Chemical Co., Ltd.).

Example A3
The same operation as in Example A1 was carried out except that the preparation of the coating solution for forming the inorganic oxide film was as follows, to obtain a hydrophilic member.
“224 g of TEOS (manufactured by Tama Chemical Co., Ltd.),
905 g of a solution in which zirconium oxychloride octahydrate (manufactured by Kishida Chemical Co., Ltd.) is diluted to 10 mass% with Alkosol K (a mixed solvent of ethanol, isopropanol, and methyl ethyl ketone manufactured by Sugar Chemical Industry Co., Ltd.)
Colloidal silica (MA-ST-L, manufactured by Nissan Chemical Industries, Ltd., average particle size 40 to 50 nm) having a solid content concentration of 40.7 mass% as silicon oxide particles: 254 g (103 g of silica) and 579 g of ion exchange water and,
In order to form an inorganic oxide film having a solid content concentration of 3% by mass in terms of total oxides, by stirring 4631 g of Alkosol K and 2026 g of 1-methoxy-2-propanol at 25 ° C. for 3 hours A coating solution was obtained. "
In the inorganic oxide film of this example, the silicon oxide fine particles and the inorganic oxide binder were 49 mol% and 51 mol%, respectively.

Comparative Example A1
A hydrophilic member was obtained in the same manner as in Example 1 except that the starch compound of Example A1 was changed to a natural polymer starch compound (trade name: Yamato glue, manufactured by Yamato Co., Ltd.).

Comparative Example A2
The same operation as in Example 1 was carried out except that the starch compound of Example A1 was not applied, to obtain a hydrophilic member.

Comparative Example A3
The same operation as in Example 1 was carried out except that the inorganic oxide fine particles of Example A1 were not added, to obtain a hydrophilic member.

Comparative Example A4
The coating solution for obtaining the inorganic oxide film was prepared by stirring 166 g of TEOS, 58 g of 0.5 N nitric acid, 3400 g of Alkosol K and 376 g of 1-methoxy-2-propanol at 25 ° C. for 3 hours. The same operation as in Example A1 was performed except that the solid content concentration was 3% by mass in terms of total oxides, to obtain a hydrophilic member.

As Table 1 shows, Examples A1 to A3, which are hydrophilic members belonging to the scope of the technical scope of the present invention, are member surfaces as compared with Comparative Examples A1 to A4 which do not belong to the scope of the technical scope of the present invention. It was found that the hydrophilicity and the rinse resistance of the above were good. Moreover, when comparative example A3 and A4 were compared, the number of cycles of rinse resistance was better in the case of comparative example 4. In consideration of the respective components of the inorganic oxide film of Comparative Example 3 and the inorganic oxide film of Comparative Example 4, it is understood that the surface of the inorganic oxide film of Comparative Example A4 tends to be negatively charged. . Therefore, it is considered that the adhesion of the cationic starch compound is improved and the number of cycles is increased. Comparative Examples A3 and A4 can also be considered as the results supporting the improvement in the adhesion of the cationic starch compound to the inorganic oxide film in the hydrophilic member of the present invention.

Example B1
(Preparation of base material)
The glass side surface of a glass mirror (300 mm.times.1000 mm.times.5 mm) produced by the silvering method was sufficiently polished with cerium oxide, then washed with water and dried to obtain a substrate.

(Preparation of Coating Solution for Forming Inorganic Oxide Film)
Colloidal silica was used as the inorganic oxide fine particles, and zirconium oxychloride octahydrate and aluminum ethyl acetoacetate diisopropylate were used as the composite oxide raw material. 112 g of tetraethoxysilane (hereinafter referred to as "TEOS", manufactured by Tama Chemical Co., Ltd.) and zirconium oxychloride octahydrate (manufactured by Kishida Chemical Co., Ltd.), Alkosol K (manufactured by Sugar Chemical Industry, ethanol, isopropanol, methyl ethyl ketone) 1472 g of a solution diluted to 10% by mass with a mixed solvent) and 208 g of colloidal silica (MA-ST-L, manufactured by Nissan Chemical Industries, average particle size 40 nm to 50 nm) having a solids concentration of 40.7% by mass 85 g), 120 g of aluminum ethylacetoacetate diisopropylate (S-75P, manufactured by Kawaken Fine Chemicals Co., Ltd.), 168 g of ion exchanged water, 4112 g of Alkosol K, and 1808 g of 1-methoxy-2-propanol Stirring at 3 ° C for 3 hours, solid content concentration is 3.5 qualities in terms of total oxides An amount of a coating solution for forming an inorganic oxide film was obtained.

(Formation of inorganic oxide film)
A coating solution for forming an inorganic oxide film is applied by roll coating on the glass side surface of the substrate, and then the substrate is heat treated at 160 ° C. for 20 minutes to form a surface layer having an uneven structure. To form an inorganic oxide film having In the inorganic oxide film, the silicon oxide fine particles and the composite oxide were 40 mol% and 60 mol%, respectively. The silicon oxide in the composite oxide was 26 mol%. Moreover, the thickness of the film was 50 nm.

(Fixation of anionic starch compound to inorganic oxide film)
Coating to form a starch compound layer by diluting a paste consisting of an anionic starch compound (trade name: Neil Gum T85, manufactured by Matsutani Chemical Industry Co., Ltd.) with water at about 25 ° C. in a weight ratio of 5 times by weight I got a liquid. The above-mentioned starch compound was applied onto the inorganic oxide film by rubbing the surface layer of the inorganic oxide film with Woroller B (manufactured by Otsuka Brush Manufacturing Co., Ltd.) containing the coating solution on the inorganic oxide film. .

Thereafter, the starch compound was dried at 80 ° C. for 3 hours to form a starch compound layer having a thickness of 20 μm on the inorganic oxide film. On the layer, flat sheet Kraft paper (manufactured by Nippon Paper Industries, product name "Capital Wrap") was adhered as a protective paper and packed.

The protective paper is peeled off from the article and rubbed with the sponge containing the inorganic oxide film, and the starch compound layer is wiped to expose the surface layer of the hydrophilic member to form a relief structure, thereby making the hydrophilic member I got

Example B2
A hydrophilic member was obtained by the same work as Example B1, except that the anionic starch compound was changed to those of other product numbers (trade name: Sorbitose C-5F, manufactured by Matsutani Chemical Industry Co., Ltd.).

Example B3
The same operation as in Example B1 was performed except that preparation of a coating solution for forming an inorganic oxide film was performed as follows, to obtain a hydrophilic member.

A solution of 224 g of TEOS (manufactured by Tama Chemical Co., Ltd.) and zirconium oxychloride octahydrate (manufactured by Kishida Chemical Co., Ltd.) diluted to 10% by mass with Alkosol K (a mixed solvent of ethanol, isopropanol and methyl ethyl ketone, manufactured by Sugar Chemical Industry) 905 g and 254 g (103 g of silica content) of colloidal silica (MA-ST-L, manufactured by Nissan Chemical Industries, average particle diameter 40 nm to 50 nm) with a solid content concentration of 40.7 mass% as silicon oxide fine particles and 579 g Of deionized water, 4631 g of Alkosol K, and 2026 g of 1-methoxy-2-propanol at 25 ° C. for 3 hours to give an inorganic oxide having a solid content concentration of 3% by mass in terms of total oxides The coating liquid for forming an object film was obtained.

In the inorganic oxide film of this example, the silicon oxide fine particles and the composite oxide were 48 mol% and 52 mol%, respectively. The silicon oxide content in the composite oxide was 59 mol%. Moreover, the thickness of the film was 50 nm.

Comparative Example B1
A hydrophilic member was obtained by performing the same operation as in Example B1 except that the starch compound of Example 1 was changed to a natural polymer starch compound (trade name: Yamato glue, manufactured by Yamato Co., Ltd.).

Comparative Example B2
The same operation as in Example 1 was carried out except that the starch compound of Example B1 was not applied, to obtain a hydrophilic member.

Comparative Example B3
The same operation as in Example 1 was carried out except that the colloidal silica of the inorganic oxide fine particles of Example B1 was not added to the coating solution, to obtain a hydrophilic member. In this comparative example, since the inorganic oxide fine particles (colloidal silica) were not added to the coating liquid for obtaining the inorganic oxide film, unevenness due to the inorganic oxide fine particles was observed on the surface of the inorganic oxide film. It was smooth. Moreover, the thickness of the film was 50 nm.

Comparative Example B4
The coating solution for obtaining the inorganic oxide film was prepared by stirring 166 g of TEOS, 58 g of 0.5 N nitric acid, 3400 g of Alkosol K and 376 g of 1-methoxy-2-propanol at 25 ° C. for 3 hours. The same operation as in Example B1 was performed except that the solid content concentration was 3% by mass in terms of total oxides, to obtain a hydrophilic member. In this comparative example, since the inorganic oxide fine particles (colloidal silica) were not added to the coating liquid for obtaining the inorganic oxide film, unevenness due to the inorganic oxide fine particles was observed on the surface of the inorganic oxide film. It was smooth. The film was a film of silicon oxide alone, and the film thickness was 50 nm.

Table 2 shows the evaluation results of each example and each comparative example. As Table 2 shows, Examples B1 to B3, which are hydrophilic members belonging to the scope of the technical scope of the present invention, have member surfaces compared to Comparative Examples B1 to B4 which do not belong to the scope of the technical scope of the present invention. It was found that the hydrophilicity and the rinse solution resistance of the above were good.

Moreover, when comparative example B3 and B4 were compared, the number of cycles of rinse solution resistance was better in the case of comparative example B3. Considering the respective components of the inorganic oxide film of Comparative Example B3 and the inorganic oxide film of Comparative Example B4, it is understood that the surface of the inorganic oxide film of Comparative Example B3 has a stronger tendency to be positively charged. . Therefore, it is considered that the adhesion of the anionic starch compound is improved and the number of cycles is increased. Comparative Examples B3 and B4 can also be considered as the results supporting the improvement in the adhesion of the anionic starch compound to the inorganic oxide film in the hydrophilic member of the present invention.

Example C1
The starch compound is a mixture of a cationic starch compound (trade name: Excelcat 220, manufactured by Matsutani Chemical Co., Ltd.) and an anionic starch compound (trade name: Neil Gum T85, manufactured by Matsuya Chemical Industry Co., Ltd.) The same operation as in Example A1 was performed except that the former was 20% by mass and the latter was 80% by mass, to obtain a hydrophilic member. The initial water contact angle of the hydrophilic member of this example was 8 °, and the rinse resistance was 88 cycles, and the hydrophilicity and the rinse resistance of the surface of the member were good.

Example C2
The same procedure as in Example C1 was performed except that the mixing ratio of the cationic starch compound to the anionic starch compound was 50 mass% for the former and 50 mass% for the latter, to obtain a hydrophilic member. . The initial water contact angle of the hydrophilic member of this example was 8 °, and the rinse resistance was 60 cycles, and the hydrophilicity and the rinse resistance of the surface of the member were good.

Example C3
The same procedure as in Example C1 was performed except that the mixing ratio of the cationic starch compound to the anionic starch compound was 80 mass% for the former and 20 mass% for the latter, to obtain a hydrophilic member. .
The initial water contact angle of the hydrophilic member of this example was 8 °, and the rinse resistance was 48 cycles, and the hydrophilicity and the rinse resistance of the surface of the member were good.

Claims

A water circumference of a bathroom or a wash basin comprising: a base material; an inorganic oxide film having a surface layer having a concavo-convex structure formed on the base material; and a starch compound fixed to the concavo-convex structure In the hydrophilic member used in
The inorganic oxide film is
Silicon oxide,
A composite oxide comprising or consisting of at least one selected from the group consisting of zirconium oxide, aluminum oxide and zinc oxide,
The starch compound is a cationic starch compound
Rinse resistant hydrophilic member.
A water circumference of a bathroom or a wash basin comprising: a base material; an inorganic oxide film having a surface layer having a concavo-convex structure formed on the base material; and a starch compound fixed to the concavo-convex structure In the hydrophilic member used in
The inorganic oxide film is
Silicon oxide,
A composite oxide comprising or consisting of at least one selected from the group consisting of zirconium oxide, aluminum oxide and zinc oxide,
The starch compound is an anionic starch compound
Rinse resistant hydrophilic member.
A water circumference of a bathroom or a wash basin comprising: a base material; an inorganic oxide film having a surface layer having a concavo-convex structure formed on the base material; and a starch compound fixed to the concavo-convex structure In the hydrophilic member used in
The inorganic oxide film is
Silicon oxide,
A composite oxide comprising or consisting of at least one selected from the group consisting of zirconium oxide, aluminum oxide and zinc oxide,
The starch compound is a mixture of a cationic starch compound and an anionic starch compound.
Rinse resistant hydrophilic member.
The said inorganic oxide film contains an inorganic oxide fine particle, The uneven structure formed in the surface layer of the said inorganic oxide film is formed by this inorganic oxide fine particle, The characteristics of Claim 1 thru | or 3 The hydrophilic member as described in any one.
The hydrophilic member according to any one of claims 1 to 4, wherein the convex portion surface of the concavo-convex structure is exposed from the starch compound.
The protective structure of a hydrophilic member according to any one of claims 1 to 5,
The protective structure comprises a starch compound layer composed of the starch compound, which is formed on the inorganic oxide film and is thicker than the film thickness of the inorganic oxide film,
The starch compound layer fills the uneven structure.
Protective structure of hydrophilic member.
A method of manufacturing a hydrophilic member according to any one of claims 1 to 6, wherein
Preparing a substrate (1);
A coating solution containing a hydrolyzate and / or a condensate of a precursor compound of a composite oxide is applied to the substrate to the substrate to form an inorganic oxide film in which the surface layer forms an uneven structure. Step (2)
Form a starch compound layer composed of a cationic or anionic starch compound, or a mixture of a cationic starch compound and an anionic starch compound, on the inorganic oxide film, which is thicker than the film thickness of the inorganic oxide film And filling the surface relief structure with a starch compound (3),
Wiping the starch compound layer to expose the surface layer of the hydrophilic member (4).
Method of producing a hydrophilic member
8. The method for producing a hydrophilic member according to claim 7, wherein in the step (3), a protective paper such as kraft paper is stuck on the starch compound layer.