JP2023174763A - Coating agent and coating film - Google Patents

Abstract

To provide a coating agent that can form a coating film having excellent hydrophilicity.SOLUTION: The present invention relates to a coating agent, in which, by applying to a glass substrate and drying at a temperature condition of 20 degrees to 150 degrees, when a coating film having a thickness of 70 to 2,000 nm is obtained, the static contact angle when a static contact angle between a water droplet and the surface of the coating film is measured using θ/2 method by a contact angle measuring device is 10° or less.SELECTED DRAWING: None

Description

The present invention relates to a coating agent capable of forming a coating film exhibiting superhydrophilicity, and a coating film formed using the coating agent.

BACKGROUND ART The development of superhydrophilic coating materials has been progressing for the purpose of improving antifogging and antifouling properties. Examples of materials exhibiting hydrophilicity include organic materials using organic polymers containing hydroxyl groups (e.g., Patent Document 1), inorganic materials using photocatalysts (e.g., Patent Document 2), and silica. Inorganic silica materials (for example, Patent Documents 3 and 4) are known. However, with organic materials, it is necessary to form a coating by UV curing or heat curing, which may be difficult to apply on-site. Furthermore, in order for a hydrophilic film made of titanium oxide to exhibit hydrophilicity, it is necessary to irradiate it with ultraviolet rays. Therefore, when used in an environment where ultraviolet rays are not sufficiently irradiated, such as indoors, a problem arises in that hydrophilicity cannot be exhibited.

For example, a superhydrophilic film made of amorphous silica produced by a sol-gel method has been proposed as a film that can exhibit hydrophilic properties regardless of whether the environment is sufficiently irradiated with ultraviolet rays. (For example, see Patent Document 5). Further, superhydrophilic membranes using amorphous silica into which hydrophilic functional groups have been introduced have also been proposed (see, for example, Patent Documents 6 and 7).

Japanese Patent Application Publication No. 2001-356201 Patent No. 3844182 specification Japanese Patent Application Publication No. 9-156959 Japanese Patent Application Publication No. 2015-096459 Japanese Patent Application Publication No. 2008-174617 Re-publication No. 2013-001975 Japanese Patent Application Publication No. 2000-239607

However, coating films made of inorganic polymers produced using the sol-gel method do not have sufficient adhesion to the substrate, and in particular, when a thick film is formed, the adhesion to the substrate sometimes decreases. The obtained film has a problem in that it has low resistance to constant temperature and humidity (an environment where temperature and humidity are constantly applied), and interference fringes are likely to occur due to the difference in refractive index between the base material and the coating film. In such a case, it may be possible to add an organic polymer to impart flexibility to the coating film, but this may cause problems in that the transparency, hardness, and durability of the resulting coating film are reduced. In addition, in the inorganic hydrophilic coating liquid containing an amorphous silicate compound obtained by hydrolyzing and condensing a tetrafunctional silicon compound proposed in Patent Document 6, the present inventors have found that It was found that there is room for improvement in abrasion resistance. The siliceous coating proposed in Patent Document 7 imparts hydrophilicity by converting sulfide groups to sulfonic acid groups, and requires heating to about 200° C. to form the coating.

Furthermore, coating agents made of inorganic polymers may complicate the coating process. Furthermore, depending on the base material, such as a base material with low hydrophilicity, even if the coating agent is applied, the leveling property may be poor and the workability may not be sufficient.

The present invention has been made to solve these problems. One of the objects of the present invention is to provide a coating agent that can form a coating film with excellent hydrophilicity.

The objects of the present invention are achieved by the following [1] to [9].
[1] When a coating film with a thickness of 70 to 2,000 nm is obtained by coating on a glass substrate and drying at a temperature of 20 to 150 degrees, the θ/2 method is obtained using a contact angle measuring device. A coating agent that has a static contact angle of 10° or less when the static contact angle between the surface of the coating film and a water droplet is measured using
[2] After obtaining a coating film with a thickness of 70 to 2,000 nm by applying it to a glass substrate and drying it at a temperature of 20 to 150 degrees, it was dried at 65 degrees Celsius and 95% RH for 100 hours. When left to stand, the static contact angle when the static contact angle between the surface of the coating film and the water droplet after being left is measured using a contact angle measuring device using the θ/2 method is 10° or less, The coating agent of [1] above;
[3] After obtaining a coating film with a thickness of 70 to 2,000 nm by coating it on a glass substrate and drying it at a temperature of 20 to 150 degrees, heat water at 50 degrees Celsius at a rate of 100 ml/hour. When the contact angle measuring device is used to measure the static contact angle between the surface of the coating film and the water droplet after treatment with hot water using the θ/2 method, the static contact angle is 10°. The coating agent according to [1] or [2], which is as follows;
[4] After obtaining a coating film with a thickness of 70 to 2,000 nm by coating it on a glass substrate and drying it at a temperature of 20 to 150 degrees, if it is left for 100 hours at 150 degrees C. [1] above, wherein the static contact angle between the surface of the coating film and the water droplet after being left is measured to be 10° or less using a contact angle measuring device using the θ/2 method. ~ Any coating agent of [3];
[5] After obtaining a coating film with a thickness of 70 to 2,000 nm by coating on a glass substrate and drying at a temperature of 20 to 150 degrees, a xenon lamp with a continuous spectrum of 300 to 400 nm is applied. The surface of the coating film was irradiated for 1000 hours by repeating a cycle of 102 minutes of irradiation, followed by ¹⁸ minutes of irradiation, and water spray under the conditions of a black panel temperature of 63 °C and a lamp intensity of 60 W/m2. When the test is conducted, the static contact angle between the surface of the coating film and the water droplet after the test is measured using a contact angle measuring device using the θ/2 method, and the static contact angle is 10° or less. The coating agent according to any one of [1] to [4] above;
[6] A coating film formed using the coating agent according to any one of [1] to [5] above;
[7] Electrostatic charge removal film, antifouling film, antibacterial film, anti-mold film, deodorant film, anti-fingerprint film, anti-fog film, foam suppression film, or lubricant film The coating film of the above [6] used as;
[8] The coating film of [6] above, which is used as a coating film for printing plates in offset printing, a coating film for heat exchangers, or a coating film for heat pipes.

According to the embodiments of the present invention, it is possible to provide a coating agent that can form a coating film with excellent hydrophilicity.

It is a figure which shows the example of use of the coating agent corresponding to at least one embodiment of this invention.

Hereinafter, each component of the coating agent of the present invention, the manufacturing method, the method of forming a coating film, etc. will be explained. The coating agent of the present invention is applied to a glass substrate and dried at a temperature of 20 to 150 degrees to obtain a coating film with a thickness of 70 to 2,000 nm. When the static contact angle between the surface of the coating film and the water droplet is measured using the θ/2 method, the static contact angle is 10° or less. For example, a coating agent in which fine particles of a water-insoluble metal compound, an inorganic polymer, and transparent nanofibers are dispersed in a solvent, a fine particle of a water-insoluble metal compound having a superhydrophilic functional group on its surface, and an inorganic polymer in a solvent. A coating film with a static contact angle of 10° or less can be obtained by using a coating agent in which fine particles of a water-insoluble metal compound, an inorganic polymer, and a refractive index modifier are dispersed in a solvent. can. The contact angle of the coating film is preferably 5° or less, more preferably 3° or less.

(fine particles of water-insoluble metal compound)
In the present invention, water-insoluble metal compound fine particles (hereinafter sometimes referred to as metal fine particles) are used. As the metal fine particles, fine particles of metal oxides or metal hydroxides that are insoluble in water can be used. The metal is not particularly limited as long as it is a water-insoluble fine particle, but metals represented by the elemental symbols Mg, Al, Si, Ca, Ti, Zn, Nb, Zr, Sn, Ta, Ce, and Hf are I can give an example. In addition to these metal oxides or metal hydroxides, fine particles containing silicate compounds can also be used. Among these, fine particles containing Si atoms, such as silicon dioxide and silicate compounds, are preferable because the resulting coating film has excellent hydrophilicity.

Colloidal metal particles are used. The average particle diameter of the metal fine particles is preferably 1 nm or more, more preferably 3 nm or more, and even more preferably 5 nm or more. Further, the average particle diameter of the metal fine particles is preferably 500 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less. By using fine metal particles having such a particle size, the transparency and hardness of the resulting coating film can be improved. An example of the colloidal metal fine particles is colloidal silica. The average particle diameter of colloidal silica can be measured by the BET method or the like.

The content (solid content) of metal fine particles in the coating agent is preferably 20% by mass or more, and preferably 40% by mass or more, based on the total content (solid content) of metal fine particles and inorganic polymer. More preferably, it is 50% by mass. When the content of metal fine particles is less than 20% by mass, the hardness of the resulting coating film may decrease. Further, the content of metal fine particles in the coating agent is preferably 90% by mass or less, more preferably 85% by mass or less, and 80% by mass with respect to the total content of metal fine particles and inorganic polymer. It is more preferable that it is the following. If the content of metal fine particles exceeds 90% by mass, the resulting coating film tends to have poor adhesion to the substrate and hydrophilicity.

In addition, in the second embodiment described below, at least a part of the metal compound among the metal compound and the inorganic polymer has a superhydrophilic functional group.

(Inorganic polymer)
The coating agent of the present invention contains an inorganic polymer. The inorganic polymer preferably has, for example, a Si--O bond, an Al--O bond, a Ti--O bond, a Zr--O bond, or a Sn--O bond, and also has a hydroxyl group in the molecule.

Note that the inorganic polymer in this specification includes not only so-called polymers but also oligomers, and inorganic polymers also include low polymers with a molecular weight of 10,000 or less. The inorganic polymer may be combined with other inorganic polymers when forming the coating film.

As the inorganic polymer, an inorganic polymer obtained from a metal alkoxide, that is, one obtained by hydrolysis of an alkoxy group in the metal alkoxide and further dehydration condensation can be used. Examples of metal alkoxides include M(OR) ₄ (M is a metal atom, R is a hydrogen atom or a monovalent hydrocarbon group), M(OR ¹ ) ₃ R ² (M is a metal atom, R ¹ represents a hydrogen atom or a monovalent hydrocarbon group, R ² represents a monovalent hydrocarbon group), M(OR ¹ ) ₂ R ² ₂ (M represents a metal atom, R ¹ represents a hydrogen atom or a monovalent hydrocarbon group) hydrogen group, R ² represents a monovalent hydrocarbon group), and the like. Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, and the like.

When the metal atom is Si, specific examples of silicon alkoxide include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, and tetra- t-Butoxysilane or its derivatives, etc., methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltriisobutoxysilane, methyltri-t-butoxy Silane or its derivatives, etc., dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldiisobutoxysilane, dimethyldi-t-butoxysilane or its derivatives, etc. etc. Among these silicon alkoxides, tetramethoxysilane and tetraethoxysilane are preferred.

When the metal atom is Al, specific examples of aluminum alkoxide include tetraethoxyaluminum, tetraisopropoxyaluminum, and derivatives thereof.

When the metal atom is Ti, specific examples of titanium alkoxide include tetraisopropoxytitanium, tetra-n-butoxytitanium, and derivatives thereof.

When the metal atom is Zr, specific examples of zirconium alkoxide include tetra-n-butoxyzirconium, tetra-t-butoxyzirconium or derivatives thereof, zirconium oxynitrate, zirconium oxychloride, and the like.

When the metal atom is Sn, specific examples of tin alkoxide include tetra-n-butoxytin, tetra-t-butoxytin, and derivatives thereof.

Note that these metal alkoxides are just examples, and other metal alkoxides or derivatives thereof can be used. These metal alkoxides or derivatives thereof may be used alone or in combination of two or more.

The content (solid content) of the inorganic polymer in the coating agent is preferably 10% by mass or more, and preferably 30% by mass or more, based on the total content (solid content) of the metal fine particles and the inorganic polymer. The content is more preferably 40% by mass. When the content of the inorganic polymer is less than 10% by mass, the adhesion of the obtained coating film to the substrate tends to decrease, and the hydrophilicity tends to decrease. Further, the content of the inorganic polymer in the coating agent is preferably 80% by mass or less, more preferably 70% by mass or less, and 60% by mass based on the total content of the metal fine particles and the inorganic polymer. It is more preferable that it is the following. If the content of the inorganic polymer exceeds 80% by mass, the hardness of the resulting coating film may decrease.

(solvent)
The coating agent of the present invention contains a solvent. As the solvent, water, an alcoholic solvent containing water, and glycol ether can be used. Examples of alcoholic solvents include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, and 2-methylbutanol. , sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethyl Hexanol, sec-octanol, n-nonyl alcohol, 2,4,6-dimethylheptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclo Examples include lower aliphatic alcohol solvents such as hexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, and diacetone alcohol. Examples of the glycol ether include ethylene glycol monobutyl ether and its derivatives, propylene glycol monoalkyl ether, petylene glycol monoalkyl ether, diethylene glycol monobutyl ether and derivatives thereof. These alcoholic solvents and glycol ethers can be used alone or in combination. By using water, an alcoholic solvent containing water, or glycol ether, metal particles and inorganic polymers can be stably dispersed.

In the coating agent of the present invention, it is preferable to adjust the amount of solvent so that the solid content concentration is 0.1% by mass or more. When the solid content concentration is less than 0.1% by mass, a large amount of coating agent is required to form a coating film of a desired thickness, which tends to reduce work efficiency. The amount of solvent is preferably adjusted so that the solid content concentration is 30% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. When the solid content concentration exceeds 30% by mass, the storage stability of the coating agent tends to decrease.

(catalyst)
By adding a catalyst to the coating agent of the present invention, the hydrolysis reaction and/or polycondensation reaction of the inorganic polymer can be promoted. Although the type of catalyst is not particularly limited, it is preferable to use, for example, a nonionic catalyst. When a nonionic catalyst is used, a superhydrophilic film can be formed even on a substrate that is highly corrosive to acids and bases, compared to when an acid catalyst or a base catalyst is used. Examples of nonionic catalysts include droxyaldehyde derivatives (or hydroxyketone derivatives), hydroxycarboxylic acid derivatives, allyl alcohol derivatives, and hydroxynitrile derivatives.

(Other additives)
The coating agent of the present invention may contain a surfactant such as a leveling agent for the purpose of smoothing the coating film, a thickener for the purpose of preventing repellency, and a coloring pigment depending on the purpose. Other additives can be added as long as they do not affect the hydrophilicity of the coating film formed using the coating agent of the present invention.

<First embodiment>
A first embodiment of the present invention relates to a coating agent in which fine particles of a water-insoluble metal compound, an inorganic polymer, and transparent nanofibers are dispersed in a solvent. According to the embodiments of the present invention, it is possible to provide a coating agent that is excellent in hydrophilicity, hot water resistance, and coatability, and can form a coating film that is less prone to cracking.

(transparent nanofiber)
The coating agent of the present invention contains transparent nanofibers. Transparent nanofibers refer to, for example, fibers that are transparent and have a fiber diameter of 100 nm or less. Even when transparent nanofibers are used, the resulting coating film has excellent transparency, hardness, and durability. In addition, by using transparent nanofibers, the adhesion to the substrate does not deteriorate even when the resulting coating film is made thick, and the hydrophilicity and durability of the coating film (for example, hot water resistance, (heat resistance, temperature and humidity resistance, weather resistance, etc.) are also improved. Furthermore, the coating properties when applying the coating agent are improved, and a homogeneous coating film without color unevenness can be obtained.

In the coating film formed using the coating agent of the present invention, the transparent nanofibers are unevenly distributed on the substrate side of the coating film, while the inorganic polymer is unevenly distributed on the surface of the coating film. It is thought that by increasing the height difference), it is possible to exhibit more superhydrophilicity and crack resistance.

It is preferable to use nanofibers made of a polysaccharide having a six-membered ring structure as the transparent nanofibers. Examples of transparent nanofibers made of polysaccharides include cellulose nanofibers and nanofibers having chitin or chitosan structural units. The cellulose nanofibers are preferably cellulose nanofibers containing structural units called microfibrils obtained by TEMPO treatment, or cellulose nanofibers obtained by physical crushing using biomass as a raw material.

The fiber diameter of the transparent nanofibers is preferably 2 nm or more. The fiber diameter of the transparent nanofiber is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 20 nm or less. When the fiber diameter of transparent nanofibers exceeds 100 nm, transparency tends to decrease.

The content of transparent nanofibers in the coating agent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1% by mass or more based on the total solid content. is even more preferable. When the content of transparent nanofibers is less than 0.1% by mass, the effect of adding transparent nanofibers may not be sufficient. The content of transparent nanofibers is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less based on the total solid content. When the content of transparent nanofibers is 10% by mass or more, the transparency, hardness, durability, and fluidity of the resulting coating film tend to decrease.

(Second embodiment)
A second embodiment of the present invention is a coating agent in which fine particles of a water-insoluble metal compound and an inorganic polymer are dispersed in a solvent, wherein the fine particles of the metal compound have a superhydrophilic functional group on at least a part of the surface of the fine particles. It has the following. According to the coating agent of the second embodiment, the coating film produced using the coating agent not only has excellent superhydrophilicity, but also has excellent constant temperature and humidity resistance, heat resistance, and excellent long-term resistance. Can exhibit hydrophilic properties.

In the second embodiment, the water-insoluble metal compound fine particles have a superhydrophilic functional group on at least a portion of the surface of the water-insoluble metal compound fine particles described above. It is only necessary that some of the fine particles of the metal compound used have superhydrophilic functional groups on their surfaces, and it is not necessary that all the fine particles used have functional groups on their surfaces. Further, the inorganic polymer may have a superhydrophilic functional group.

（ただし、式（１）中、Ｒ^１は炭素数１～１０のアルキル基由来の構造単位、Ａ^１は一価の陽イオンである。）で表される構造を有するスルホン酸基又はスルホン酸塩基、式（２）：

（ただし、式（２）中、Ｒ^２は炭素数１～１０のアルキル基由来の構造単位、Ａ^２は一価の陽イオンである。）で表される構造を有するカルボン酸塩基、ポリエーテル基、若しくは、ウレイド基を含有する官能基であることが好ましい。 The superhydrophilic functional group can be employed without particular limitation as long as it imparts superhydrophilicity to the surface of the metal compound and inorganic polymer used in the present invention, but it is important to note that the superhydrophilicity and constant temperature resistance of the film to be formed Since it is excellent in both humidity stability and weather resistance, the superhydrophilic functional group has the formula (1):

(However, in formula (1), R ¹ is a structural unit derived from an alkyl group having 1 to 10 carbon atoms, and A ¹ is a monovalent cation.) Base, formula (2):

(However, in formula (2), R ² is a structural unit derived from an alkyl group having 1 to 10 carbon atoms, and A ² is a monovalent cation.) or a functional group containing a ureido group.

In formulas (1) and (2), the number of carbon atoms in R ¹ and R ² is more preferably 1 or more, and even more preferably 2 or more, each independently. The number of carbon atoms is more preferably 5 or less, and even more preferably 3 or less. When the carbon number is within this range, the film formed using the coating agent of the present invention will have excellent oxidation resistance, and as a result, a film with excellent weather resistance can be formed.

（ただし、式（４）中、Ｒ^１は炭素数１～１０のアルキル基由来の構造単位、Ａ^１は一価の陽イオンである。）で表される化合物の水酸基と、金属化合物の微粒子に存在する水酸基とを加水分解反応させることにより得ることができる。加水分解反応は、酸性又はアルカリ性の条件下で行うことができる。また、水不溶性の金属化合物の微粒子に、スルホン酸基又はスルホン酸塩基を導入する際には、たとえば、水不溶性の金属化合物の微粒子、溶媒の存在下、触媒により無機ポリマーを合成する反応を４～６時間の反応を行った後、スルホン酸基又はスルホン酸塩基を有する化合物を添加して、さらに２～３時間の反応を行うことが考えられる。あるいは、コーティング剤に屈折率調整剤をさらに含める場合であれば、たとえば、屈折率調整剤、溶媒の存在下、触媒により無機ポリマーを合成する反応を２～３時間の反応を行った後、水不溶性の金属化合物の微粒子を添加して２～３時間の反応を行い、さらにスルホン酸基又はスルホン酸塩基を有する化合物を添加して、２～３時間の反応を行うことが考えられる。 Examples of methods for introducing sulfonic acid groups or sulfonic acid groups into fine particles of water-insoluble metal compounds include:
Formula (4):

(However, in formula (4), R ¹ is a structural unit derived from an alkyl group having 1 to 10 carbon atoms, and A ¹ is a monovalent cation.) and fine particles of a metal compound. It can be obtained by a hydrolysis reaction with a hydroxyl group present in . The hydrolysis reaction can be carried out under acidic or alkaline conditions. In addition, when introducing a sulfonic acid group or a sulfonic acid group into fine particles of a water-insoluble metal compound, for example, a reaction of synthesizing an inorganic polymer using a catalyst in the presence of a solvent and a fine particle of a water-insoluble metal compound is performed. After carrying out the reaction for ~6 hours, it is conceivable to add a sulfonic acid group or a compound having a sulfonic acid group and carry out the reaction for an additional 2 to 3 hours. Alternatively, if the coating agent further includes a refractive index adjusting agent, for example, after carrying out a reaction to synthesize an inorganic polymer using a catalyst in the presence of a refractive index adjusting agent and a solvent for 2 to 3 hours, water It is conceivable to add fine particles of an insoluble metal compound and conduct a reaction for 2 to 3 hours, and then add a sulfonic acid group or a compound having a sulfonic acid group and conduct a reaction for 2 to 3 hours.

Examples of the compound represented by formula (4) include ethanol-2-sulfonic acid, sodium ethanol-2-sulfonate, propanol-3-sulfonic acid, sodium propanol-3-sulfonate, and butanol-4-sulfonic acid. and sodium butanol-4-sulfonate. Among them, it is preferable to use ethanol-2-sulfonic acid and sodium ethanol-2-sulfonate because they can impart high hydrophilicity.

Examples of the polyether group to be introduced into the water-insoluble metal compound fine particles include polyalkylene oxide groups such as polyethylene oxide (PEO) groups and polypropylene oxide (PPO) groups. The molecular weight of the polyether group is not particularly limited as long as it exhibits superhydrophilicity, but it is preferably about 3000 or less.

A method for introducing polyether groups into water-insoluble metal compound fine particles is to perform a hydrolysis reaction between the hydroxyl groups of polyalkylene oxide having hydroxyl groups at both ends and the hydroxyl groups present on the surface of the metal compound fine particles. be able to. The hydrolysis reaction can be carried out under acidic or alkaline conditions.

(Third embodiment)
A third embodiment of the present invention is a coating agent in which fine particles of a water-insoluble metal compound, an inorganic polymer, and a refractive index modifier are dispersed in a solvent. According to the coating agent of the third embodiment, interference fringes caused by the difference in refractive index between the resulting coating film and the base material are suppressed.

The refractive index adjusting agent is preferably oxide fine particles of at least one metal selected from the group consisting of Mg, Al, Ca, Ti, Zn, Nb, Zr, Sn, Ta, Ce, and Hf. Among these, when using titanium oxide as a refractive index adjusting agent, since the refractive index of this compound is extremely high, it is necessary to add a small amount to fine particles of a metal compound with a low refractive index such as silicon dioxide. This is preferable because it can improve the refractive index. In addition, when using zirconia oxide as a refractive index adjusting agent, unlike titanium oxide, it does not cause a reaction that photodecomposes organic substances, so even if the coating agent is applied directly to a resin substrate for outdoor use, it will not deteriorate the substrate. It has the advantage that superhydrophilicity can be imparted without the need for hydrophilicity.

As the refractive index adjusting agent, it is preferable to use one in which the difference between the refractive index of fine particles of a water-insoluble metal compound and the refractive index of the refractive index adjusting agent is 0.1 or more, and one in which the difference is 0.3 or more. It is more preferable to use 0.5 or more, and even more preferable to use 0.5 or more. If the difference between the refractive index of the water-insoluble metal compound fine particles and the refractive index of the refractive index adjusting agent is less than 0.1, the effect of adjusting the refractive index of the coating film tends to be insufficient. Furthermore, the larger the difference between the refractive index of the fine particles of the water-insoluble metal compound and the refractive index of the refractive index regulator, the greater the effect of adding the refractive index regulator.

The average particle diameter of the metal oxide fine particles is preferably 1 nm or more, more preferably 3 nm or more, and even more preferably 5 nm or more. Further, the average particle diameter of the metal fine particles is preferably 500 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less. By using metal oxide fine particles having such a particle size as a refractive index adjusting agent, the transparency of the resulting coating film can be improved by suppressing interference fringes.

The content (solid content) of the refractive index adjusting agent in the coating agent is preferably 5% by mass or more, and 10% by mass or more based on the total content (solid content) of the metal fine particles and inorganic polymer. The content is more preferably 15% by mass or more, even more preferably 20% by mass or more. When the content of the refractive index adjusting agent is less than 5% by mass, the resulting coating film may not have a sufficient effect of suppressing interference fringes. Further, the content of the refractive index adjusting agent in the coating agent is preferably 80% by mass or less, more preferably 70% by mass or less, based on the total content of the metal fine particles and the inorganic polymer. It is more preferably at most 60% by mass, particularly preferably at most 60% by mass. When the content of the refractive index adjusting agent exceeds 80% by mass, the transparency of the resulting coating film tends to decrease, and the adhesion to the substrate tends to decrease.

(Method for manufacturing coating agent)
The coating agent of the first embodiment of the present invention can be obtained, for example, by adding transparent nanofibers to a mixed dispersion in which fine metal particles and an inorganic polymer are dispersed in a solvent, and dispersing the mixture by stirring. Specifically, a dispersion of transparent nanofibers in water, alcohol, or glycol ether is added to a mixed dispersion of metal fine particles and an inorganic polymer. The coating agent of the second embodiment of the present invention is obtained, for example, by adding metal fine particles into which a superhydrophilic group has been introduced and a solvent to an inorganic polymer, and dispersing the mixture by stirring. The coating agent of the third embodiment of the present invention can be obtained, for example, by adding transparent nanofibers to a mixed dispersion of metal fine particles and an inorganic polymer, and dispersing the mixture by stirring. Specifically, a dispersion of transparent nanofibers in water, alcohol, or glycol ether is added to a mixed dispersion of metal fine particles and an inorganic polymer.

(Method for forming coating film)
Methods for forming a coating film on a substrate using the coating agent of the first to third embodiments of the present invention include a method of applying the coating agent to the surface of the substrate, and a method of dipping the substrate in the coating agent. can be mentioned. A method of applying a coating agent to the surface of a substrate is particularly preferred because it is simple, inexpensive, and allows easy control of the required thickness of the film.

The coating method is not particularly limited, and any known technique may be used. For example, coating methods such as a spin coating method, a dipping method, a spray method, a flow coating method, a bar coating method, a roller coating method, a reverse method, a flexographic method, and a printing method such as gravure printing can be appropriately employed.

Further, in order to improve the adhesion between the base material and the coating film, the surface of the base material may be pretreated. Examples of the pretreatment method include corona discharge treatment, glow discharge treatment, treatment with ionizing active rays such as ultraviolet rays, electron beams, and radiation, surface roughening treatment, chemical treatment, and primer treatment.

By subjecting the coating agent of the present invention to the above-mentioned primer treatment, it is possible to form a coating film according to the present invention even on so-called difficult-to-adhesive substrates such as olefin-based materials, and as a result, the coating film according to the present invention can be formed on the surface of the difficult-to-adhere substrate. Can impart superhydrophilicity. In addition, when a hard coat is formed in addition to the primer treatment, the coating film according to the present invention can be formed even on a substrate that has irregularities and a large amount of liquid absorption. In this case, the coating film made of the coating agent of the present invention can impart both superhydrophilicity and abrasion resistance to the substrate.

As the base material, glass, plastic, metal, ceramics, etc. can be coated.

A coating film is formed by drying the coating agent applied to the surface of the base material. Even when the coating agent of the present invention is dried at room temperature, it is possible to form a coating film without any problem. During drying, heating is preferably performed at 60°C or higher, more preferably at 120°C or higher. In addition, the heating temperature is set to 150° C. or lower from the viewpoint of the obtained film properties. Heating conditions are not particularly limited, but may be continuous or batchwise, and may be heated under normal pressure or reduced pressure. If the film is allowed to stand at room temperature for a certain period of time before heat treatment, it is possible to form a more uniform coating film.

(Coating film)
The thickness of the coating film in the first to third embodiments of the present invention is 70 nm or more, preferably 100 nm or more, and 2,000 nm or less. When the thickness of the coating film is less than 70 nm, superhydrophilicity tends to decrease. The thickness of the coating film is preferably 500 nm or less, more preferably 250 nm or less. Furthermore, when the thickness of the coating film is greater than 2,000 nm, the adhesiveness with the base material decreases, and the film tends to peel off easily.

The coating films formed using the coating agents of the first to third embodiments of the present invention have excellent hydrophilicity and exhibit superhydrophilicity. For example, a coating film with a thickness of 70 to 2,000 nm is obtained by applying it to a glass substrate and drying it at a temperature of 20 to 150 degrees, and then leaving it at 65 degrees Celsius and 95% RH for 100 hours. (when performing a high temperature and high humidity resistance test), the static contact angle between the surface of the coating film and the water droplet after being left standing was measured using a contact angle measuring device using the θ/2 method. It is preferable that the coating agent has a static contact angle of 10 degrees or less, and more preferably a coating agent that has a static contact angle of 5 degrees or less.

For example, after obtaining a coating film with a thickness of 70 to 2,000 nm by coating it on a glass substrate and drying it at a temperature of 20 to 150 degrees, add 50 degrees Celsius hot water at 100 ml/hour for 10 hours. When contacted (when performing a hot water resistance test), the static contact angle between the surface of the coating film and the water droplet after treatment with hot water is measured using a contact angle measurement device using the θ/2 method. It is preferable that the coating agent has a static contact angle of 10 degrees or less when the coating is applied, and more preferably a coating agent that has a static contact angle of 6 degrees or less.

For example, if a coating film with a thickness of 70 to 2,000 nm is obtained by applying it to a glass substrate and drying it at a temperature of 20 to 150 degrees, and then leaving it for 100 hours at 150 degrees Celsius (heat resistant When the static contact angle between the surface of the coating film and the water droplet after being left standing was measured using a contact angle measuring device using the θ/2 method, the static contact angle was 10°. It is preferable that the coating agent has the following properties, and it is more preferable that the coating agent has a static contact angle of 6° or less.

For example, after obtaining a coating film with a thickness of 70 to 2,000 nm by coating it on a glass substrate and drying it at a temperature of 20 to 150 degrees, use a xenon lamp with a continuous spectrum of 300 to 400 nm to A 1000-hour irradiation test was performed on the surface of ^the coating film by repeating a cycle of irradiation for 102 minutes, followed by irradiation for 18 minutes, and water spraying under the conditions of a black panel temperature of 63°C and a lamp intensity of 60 W/m2. (when conducting a weather resistance test), when the static contact angle between the surface of the coating film and the water droplet after the test was measured using a contact angle measuring device using the θ/2 method. It is preferable that the coating agent has a static contact angle of 10 degrees or less, and more preferably a coating agent that has a static contact angle of 5 degrees or less.

In the above-mentioned high temperature and high humidity resistance test, hot water resistance test, heat resistance test, and weather resistance test, the method for obtaining a coating film in which the static contact angle of the coating film after the test is equal to or less than the desired value is as follows: For example, a coating agent in which fine particles of a water-insoluble metal compound, an inorganic polymer, and transparent nanofibers are dispersed in a solvent, a metal compound in which at least one of the metal compound and the inorganic polymer has a superhydrophilic functional group, and an inorganic polymer. Examples include a method of forming a film using a coating agent dispersed in a solvent, or a coating agent in which fine particles of a water-insoluble metal compound, an inorganic polymer, and a refractive index adjuster are dispersed in a solvent.

(Application)
Applications of the coating agents of the first to third embodiments of the present invention are not particularly limited, but they can also be used for surface coating of buildings, heat exchangers, heat pipes, etc. In addition, it can be used for surface coatings such as eyeglass lenses, camera lenses, underwater glasses, car window glasses, helmet shields, and mirrors and lenses used in humid places.

The present invention will be described in detail below along with effects specific to the application, but the present invention is not limited to these applications. The coating agents of the first to third embodiments all have effects for the following uses. In any of the applications, the conventional techniques have a problem of low durability, and although the effect is confirmed immediately after application, the effect is not exhibited after a long period of time. The coating agent of the present invention has good on-site applicability and can be applied in multiple layers using a primer, so it can impart superhydrophilicity to various substrates and has high durability. Therefore, it can be used at a practical level.

<Static electricity removal film>
A coating film formed on the surface of a substrate using the coating agent of the present invention is used for the purpose of eliminating static electricity. The coating film according to the present invention imparts superhydrophilicity to the surface of the substrate, and as a result, water can be retained on the surface of the substrate. The conductivity of the water provides an effect of eliminating static electricity. Furthermore, when a coating film is formed by incorporating metal particles or wires such as silver into the coating agent of the present invention, conductivity due to water can be developed independent of the amount of moisture (humidity) in the atmosphere. Therefore, high antistatic properties can be obtained while maintaining the transparency of the coating film, and it is possible to prevent dust and the like from adhering due to static electricity.

<Antifouling membrane>
A coating film formed on the surface of a substrate using the coating agent of the present invention is used for the purpose of antifouling. The coating film according to the present invention can impart superhydrophilicity to the surface of a base material and retain water on the surface of the base material. As a result, the dirt components do not come into direct contact with the base material, and it is possible to prevent dirt from adhering to the base material. Further, even if dirt is attached, by spraying water on the surface of the coating film, a water film spreads between the dirt and the coating film, and the dirt can be removed together with running water. Detailed applications of such antifouling films include window glass, car bodies, tire wheels, and the underside of car bodies, interior materials for building materials, sinks, bathrooms, window films, boots, and belt conveyors. This produces the effect.

As a further specific example of an antifouling film, the coating agent of the present invention can be used to form a coating film on power equipment, such as electric pole insulators, overhead wires, etc., to prevent salt from seawater from adhering to these equipment. Salt damage that can significantly reduce insulation performance can be prevented.

Further, as a further specific example of the antifouling film, there is a case where a coating film is formed on the surface of a toilet bowl using the coating agent of the present invention. Formation of a coating film makes it difficult for dirt to adhere, and dirt can be removed by running water. When a coating film is formed by combining materials with antibacterial properties, it is possible to prevent the growth of various bacteria. Since it has a good antifouling effect and dirt removal efficiency with running water, it can lead to water conservation.

Further examples of the antifouling film include cases in which a coating film is formed on the inner wall surface of a toilet tank or a water tank made of porcelain tiles. In such a case, as in the application to the toilet bowl surface, the formation of a coating film makes it difficult for dirt to adhere, and the dirt can be removed by running water. When a coating film is formed by combining materials with antibacterial properties, it is possible to prevent the growth of various bacteria.

Note that durability can be further improved by forming a coating film on materials such as toilet bowls, toilet tanks, ceramics such as porcelain tiles, glass, and mirrors by following steps 1 to 6.
Step 1: Clean the surface to which you want to make it hydrophilic using a neutral detergent or alcohol.
Step 2: Polish the surface with a sponge or the like that has a surface polishing effect (this surface polishing makes it possible to apply the coating agent more uniformly).
Step 3: Leave to dry at room temperature until there are no water drops.
Step 4: From a distance of about 20 to 25 cm from the surface to be coated, spray the coating agent filled in a commercially available spray container vigorously (squeeze the spray lever all at once) 2 to 3 times (the sprayed coating agent will form islands on the surface). (To the extent that the entire surface to be coated is wetted without forming a lump or dripping).
Step 5: Rinse with water before the coating solution dries completely (this will enable more even application).
Step 6: Leave to dry at room temperature so that there are no water droplets (several minutes to several hours above room temperature).
Note that each of Steps 2, 3, and 5 can be omitted.

<For antibacterial or antifungal use>
By forming a coating film by combining the coating agent of the present invention with Ag particles and Cu particles that have antibacterial properties, the resulting film not only has superhydrophilic properties with high drainage properties, but also has antibacterial and antifungal properties. Becomes excellent.

<For deodorant>
The coating agent of the present invention can impart highly durable superhydrophilicity to a substrate, or in other words, can impart superoleophilicity. Based on this superoleophilicity, it is possible to adsorb so-called malodorous substances and can be suitably used as a deodorant. Conventional deodorants are ionic deodorants, and the deodorizing mechanism by the coating agent of the present invention is different. It utilizes the surface energy of the coating agent of the present invention, and can be expected to be effective against non-ionic malodorous substances such as alcohol-based, aromatic-based, solvent-based, and gasoline-based substances. Furthermore, as a deodorant, it can also be used as a spray-type space deodorizer, and is expected to exhibit a deodorizing effect by forming a film on the object to be sprayed.

<Fingerprint prevention film>
Since the film formed by the coating agent of the present invention can impart high lipophilicity to the base material, the wettability with oleic acid, which is an oil component of sebum, is improved. Therefore, even if a fingerprint is attached to a glass surface or the like, the fingerprint trace can be made less noticeable compared to a case where a film of the coating agent of the present invention is not applied.

<Anti-fog film>
A coating film formed on the surface of a substrate using the coating agent of the present invention is used for the purpose of antifogging. Since the coating film according to the present invention imparts superhydrophilicity to the surface of the substrate, the surface of glossy substrates such as mirrors, automobile rearview mirrors, and camera lenses becomes less likely to fog. Furthermore, when using the window glass of a house as a base material, it has the effect of making it difficult for dew condensation, ice formation, and frost to form.

As an application example of an anti-fog film, when the coating agent of the present invention is applied to a substrate in the form of a strip, when the substrate is exposed to freezing conditions, an amorphous state is formed at the interface between the coating agent-applied area and the non-applied area. can be formed. As a result, new expressions of designs and patterns are possible.

Furthermore, a further example of the application of the antifogging film is a design using dew condensation. In other words, when the coating agent of the present invention is applied to glass 1 in a design as shown in Figure 1 (snowflake design 2 in the figure), no dew condensation occurs on the design 2, and no condensation occurs on the other parts. This will result in condensation. As a result, it can be used for new design expression methods, such as designs that are normally unrecognizable, but appear in weather conditions that cause condensation.

<Offset printing version>
A coating film formed on the surface of a water-repellent film base material using the coating agent of the present invention is used as a hydrophilic film for offset printing. The coating agent of the present invention is applied to a desired portion of a water-repellent film to make use of the fact that superhydrophilicity can be imparted only to the desired portion.

<Improvement of heat exchanger performance>
The coating film formed on the substrate surface using the coating agent of the present invention utilizes the superhydrophilicity imparted to the substrate surface to improve the wettability of the surface and exchange heat through the thermal conductivity of water. The performance of the device can be improved. Examples of heat exchangers include evaporators, condensers, and heat sinks of air conditioners.

<Improving the hydrophilic performance of heat pipes>
The coating film formed on the inner surface of the heat pipe using the coating agent of the present invention utilizes the superhydrophilicity imparted to the surface of the base material to disturb the surface tension of water, allowing heat exchange in the heat pipe. Efficiency can be improved.

<For suppressing bubble generation>
A coating film formed on the surface of a substrate using the coating agent of the present invention is used to suppress the generation of bubbles. If the wettability between the solid surface of the base material and the liquid that comes into contact with it is not good, the generation of bubbles will be promoted during solid-liquid contact. Foam generation in such cases can occur, for example, when pouring a carbonated drink into a glass, excessive foam may be generated, making the drink taste unpleasant, or when a sample is placed in a glass container, etc. for observation using an optical or ultrasonic microscope. It may generate bubbles and obstruct observation. The film formed using the coating agent of the present invention can improve the wettability of the substrate surface by utilizing the superhydrophilicity imparted to the substrate surface, and can suppress the generation of bubbles.

<For lubrication>
A coating film formed on the surface of a substrate using the coating agent of the present invention is used for lubricating purposes. For example, by forming a coating film on the surface of a base material such as the surface of a skating rink, the superhydrophilicity imparted to the surface of the base material also imparts lubricity.

Hereinafter, the coating agent of the present invention will be explained using Examples. However, the present invention is not limited to the following examples.

(Example 1; coating agent of the first embodiment)
Under a nitrogen atmosphere, 20.9 g of tetraethoxysilane (manufactured by Tama Chemical Industries, Ltd.) and colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-XS, Sears particle size 4 to 6 nm) , solid content 20 wt%, solvent: 30.1 g of water, 8.4 g of ethanol as a solvent, and 40.7 g of ion-exchanged water were added, and nitric acid (manufactured by Kanto Kagaku Co., Ltd., trade name: nitric acid 1. 38) was placed in a reaction vessel so that the pH of the entire solution was 2, and stirred at 40°C for 9 hours to obtain an inorganic polymer solution (A).

Next, 2% by mass of chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) as transparent nanofibers and as a solvent were added to the total amount of the obtained inorganic polymer solution (A). Ethanol was added at a volume ratio of 0.7%, and the mixture was stirred at 25° C. for 1 hour to obtain a coating agent. The solid content concentration of the obtained coating agent was 2% by mass.

The obtained coating agent was applied to the surface of a 76 mm x 52 mm glass substrate (manufactured by Matsunami Glass Industries Co., Ltd., thickness 1.5 mm) by the bar coating method using a bar coater (bar No. 7), and heated at 150°C. The coating was dried by heating for 15 minutes to obtain a coating film.

<Evaluation>
The coating films obtained on glass substrates and polycarbonate substrates were tested for initial physical properties and durability evaluation. Specifically, the appearance, hydrophilicity, adhesion test using a grid test according to JIS K 5600-5-6:99, scratch hardness test using the pencil method according to JIS K 5600-5-4:99, and resistance. Steel wool properties and alcohol resistance were evaluated as initial physical properties. In addition, to evaluate the durability of the obtained coating film, hot water resistance, heat resistance, moist heat resistance, abrasion resistance, and weather resistance were evaluated by measuring the water contact angle after the test. Each evaluation method is as described below.

(Appearance; transparency)
The transmittance of the glass substrate on which the coating film was formed was measured using a haze meter (HM-150, manufactured by Murakami Color Institute Co., Ltd.). The coating film obtained in Example 1 was transparent.

(hydrophilicity; water contact angle)
The static contact angle between the surface of the coating film and the water droplet was measured using a θ/2 method using a contact angle measuring device (FAMAS, manufactured by Kyowa Interface Science Co., Ltd.). The static contact angle of the surface of the coating film obtained in Example 1 was less than 10°.

(Adhesion)
In accordance with JIS K 5600-5-6:99, apply the cutter blade perpendicular to the coating film and make six parallel cuts at 1 mm intervals, then change the direction by 90 degrees and make perpendicular cuts. Six cuts were made. A piece of tape with a length of 75 mm was taken out, the tape was applied to the grid-cut portion of the coating film, and the tape was rubbed firmly with a finger so that the coating film could be seen through. The tape was applied and pulled off in approximately 1 second at an angle close to 60°. The amount of adhesion was evaluated according to the JIS classification of 0 to 5. The amount of adhesion when using the coating film obtained in Example 1 was classified as 0.

(scratching hardness)
In accordance with JIS K 5600-5-4:99, a 7 mm straight line was drawn and the type of marks on the surface of the coating film was visually evaluated. The scratch hardness of the surface of the coating film obtained in Example 1 could be evaluated as 6H.

(Steel wool resistance)
Using #0000 steel wool, the center portion of the coating film surface was rubbed back and forth 10 times under a load of 500 g/ ^cm2 , and changes in the surface were visually observed. There were no scratches on the surface of the coating film obtained in Example 1.

(Alcohol resistance)
The surface of the coating film was wiped back and forth 100 times using absorbent cotton (15 mm x 15 mm, impregnated amount: 1 ml) impregnated with pure ethanol, and surface changes were visually observed. The surface of the coating film obtained in Example 1 did not change before and after the test.

(hot water resistance)
The coating film surface of the glass substrate on which the coating film was formed was kept in contact with 50°C hot water at 100 ml/hour for 100 hours, and changes in the appearance of the coating film were visually confirmed. The contact angle was measured. There was no visual change, and the static contact angle remained less than 10° after the test.

(Heat-resistant)
The glass substrate on which the coating film was formed was left at 150° C. for 100 hours, and changes in the appearance of the coating film were visually confirmed, and the static contact angle of the surface of the coating film with water was measured.

(Moisture heat resistance)
The glass substrate on which the coating film was formed was left for 100 hours at 65° C. and 95% RH, and changes in the appearance of the coating film were visually confirmed, and the static contact angle of the surface of the coating film with water was measured.

(wear resistance)
The glass substrate on which the coating film was formed was mounted on a flat reciprocating test stand and rubbed with a 500g load using a 20 x 20 mm flat friction element (Crecia EF, manufactured by Nippon Paper Crecia Co., Ltd.). The static contact angle of the surface with water was measured. The static contact angle was less than 10°.

(Weatherability)
A xenon arc lamp weather resistance test was conducted in accordance with JIS B 7754:91. Using a xenon lamp with a continuous spectrum from 300 to 400 nm, with a black panel temperature of 63 °C and a lamp intensity of 60 W/ ^m2 , irradiation for 102 minutes was repeated, followed by a cycle of 120 minutes of 18 minutes of irradiation and water spray. The surface of the coating film was irradiated for 1000 hours, changes in the appearance of the coating film were visually confirmed, and the static contact angle of the surface of the coating film with water was measured. The static contact angle was less than 10°.

(Example 2; coating agent of the first embodiment)
Using the inorganic polymer solution (A) of Example 1, cellulose nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s AMa-10002) were used as transparent nanofibers in the production of the coating agent of Example 1. A coating agent was produced in the same manner as in Example 1 except for this, and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 3; coating agent of the first embodiment)
In the production of the inorganic polymer solution (A) of Example 1, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-S, BET particle size 8 to 11 nm, solid content 30 wt%, solvent A coating agent was produced in the same manner as in Example 1 except that 20.0 g of water) and 51.2 g of ion-exchanged water were used, and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 4; coating agent of the first embodiment)
In the production of the inorganic polymer solution (A) of Example 1, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-30, BET particle size 10 to 15 nm, solid content 30 wt%, solvent A coating agent was produced in the same manner as in Example 1 except that 20.0 g of water) and 51.2 g of ion-exchanged water were used, and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 5; coating agent of the first embodiment)
In the production of the inorganic polymer solution (A) of Example 1, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-UP, average particle diameter of 40 to 100 nm by dynamic light scattering method, A coating agent was produced in the same manner as in Example 1 except that the solid content was 20 wt %, the solvent was 30.1 g (water), and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 6; coating agent of the first embodiment)
In the production of the inorganic polymer solution (A) of Example 1, 16.7 g of tetraethoxysilane was added to spherical colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-OS, BET particles). A coating agent was produced in the same manner as in Example 1, except that the diameter was 8 to 11 nm, the solid content was 20 wt%, the solvent was 36.1 g (water), the ethanol was changed to 6.7 g, and the ion exchange water was changed to 41.0 g. , the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 7; coating agent of the first embodiment)
Using the inorganic polymer solution (A) of Example 6, cellulose nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s AMa-10002) were used as transparent nanofibers in the production of the coating agent of Example 6. A coating agent was produced in the same manner as in Example 6 except for this, and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 8; coating agent of the first embodiment)
In the production of the inorganic polymer solution (A) of Example 1, 20.8 g of tetraethoxysilane was added to chain colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-OUP, dynamic Same as Example 1 except that the average particle diameter by optical scattering method was 40 to 100 nm, solid content 15 wt%, solvent; water) was changed to 40.0 g, ethanol was changed to 8.3 g, and ion exchange water was changed to 30.8 g. A coating agent was manufactured and its initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 9; coating agent of second embodiment)
In a nitrogen atmosphere, 18.8 g of tetraethoxysilane (manufactured by Tama Chemical Industries, Ltd.) and colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-XS, Sears particle size 4 to 6 nm) , solid content 20 wt%, solvent: 30.1 g of water, 7.5 g of ethanol as a solvent, 37.6 g of ion-exchanged water, and nitric acid (manufactured by Kanto Kagaku Co., Ltd., trade name: nitric acid 1.38) as a catalyst. The solution was placed in a reaction container so that the pH of the entire solution was 2, and stirred at 40° C. for 6 hours. Thereafter, 6.0 g of a sulfonate compound (manufactured by Kiyosumi Institute, trade name: KS-S10X) was added as a compound imparting a superhydrophilic functional group, and the mixture was further stirred at 40°C for 3 hours to dissolve the inorganic polymer. (A) was obtained.
Next, 0.7% by volume of ethanol was added as a solvent to the total amount of the obtained inorganic polymer solution (A), and the mixture was stirred at 25°C for 1 hour to obtain a coating agent. Gender was evaluated. The results are shown in Table 1.

(Example 10; coating agent of second embodiment)
Using the inorganic polymer solution (A) of Example 9, chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) were added as transparent nanofibers to the inorganic polymer in the production of the coating agent of Example 9. A coating agent was produced in the same manner as in Example 9 except that 2% by mass was added based on the total amount of solution (A), and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 11; coating agent of second embodiment)
In the production of the inorganic polymer solution (A) of Example 9, 7.5 g of methanol was used instead of ethanol as a solvent, and after stirring at 40°C for 4 hours, the sulfonate compound was added, and the mixture was stirred at 40°C for 2 hours. An inorganic polymer solution (A) was produced in the same manner as in Example 9 except for stirring. To the total amount of this inorganic polymer solution (A), 0.7% by volume of methanol was added as a solvent and stirred at 25°C for 1 hour to produce a coating agent, and the initial physical properties and durability were evaluated. Ta. The results are shown in Table 1.

(Example 12; coating agent of second embodiment)
Using the inorganic polymer solution (A) of Example 11, chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) were added as transparent nanofibers to the inorganic polymer in the production of the coating agent of Example 11. A coating agent was produced in the same manner as in Example 11 except that 2% by mass was added based on the total amount of solution (A), and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 13; coating agent of second embodiment)
In the production of the inorganic polymer solution (A) of Example 11, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-UP, average particle diameter of 40 by dynamic light scattering method) ~100 nm, solid content 20 wt%, solvent; water) A coating agent was produced in the same manner as in Example 9 except that the amount was changed to 30.1 g, and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 14; coating agent of second embodiment)
Using the inorganic polymer solution (A) of Example 13, chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) were added as transparent nanofibers to the inorganic polymer in the production of the coating agent of Example 13. A coating agent was produced in the same manner as in Example 13 except that 2% by mass was added based on the total amount of solution (A), and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 15; coating agent of second embodiment)
In the production of the inorganic polymer solution (A) of Example 9, 20.7 g of tetraethoxysilane, 18.7 g of colloidal silica, and 15.5 g of methanol and 28.0 g of ion-exchanged water were used as solvents at 40°C. After stirring for 4 hours at Solution (A) was produced. To the total amount of this inorganic polymer solution (A), 0.7% by volume of methanol was added as a solvent and stirred at 25°C for 1 hour to produce a coating agent, and the initial physical properties and durability were evaluated. Ta. The results are shown in Table 1.

(Example 16; coating agent of second embodiment)
In the production of the inorganic polymer solution (A) of Example 15, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-UP, average particle diameter of 40 to 100 nm by dynamic light scattering method, An inorganic polymer solution (A) was obtained in the same manner as in Example 15, except that the solid content was 20 wt% and the solvent was 8.4 g (water). To this inorganic polymer solution (A), chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) were added as transparent nanofibers in an amount of 2% by mass based on the total amount of the inorganic polymer solution (A). A coating agent was produced in the same manner as in Example 15 except for this, and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 17; coating agent of second embodiment)
In the production of the inorganic polymer solution (A) of Example 9, 15.0 g of tetraethoxysilane and colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-OS, BET) were added. Particle size: 8 to 11 nm, solid content: 20 wt%, solvent; water) 36.0 g, ethanol to 19.5 g, ion exchange water to 24.8 g, and sulfonic acid compound to 4.8 g. A coating agent was produced in the same manner as in Example 9, and its initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 18; coating agent of second embodiment)
Using the inorganic polymer solution (A) of Example 17, chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) were added as transparent nanofibers to the inorganic polymer in the production of the coating agent of Example 17. A coating agent was produced in the same manner as in Example 17 except that 2% by mass was added based on the total amount of solution (A), and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 19; coating agent of second embodiment)
In the production of the inorganic polymer solution (A) of Example 9, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-OUP, average particle diameter of 40 by dynamic light scattering method) ~100nm, solid content 15wt%, solvent; water), 40.1g of water, ethanol to 9.9g, and ion-exchanged water to 25.5g, a coating agent was produced in the same manner as in Example 9, and the initial Physical properties and durability were evaluated. The results are shown in Table 1.

(Example 20; coating agent of second embodiment)
Using the inorganic polymer solution (A) of Example 19, chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) were added as transparent nanofibers to the inorganic polymer in the production of the coating agent of Example 19. A coating agent was produced in the same manner as in Example 19 except that 2% by mass was added based on the total amount of solution (A), and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 21; coating agent of third embodiment)
In a nitrogen atmosphere, 20.6 g of tetraethoxysilane (manufactured by Tama Chemical Co., Ltd.), 15.0 g of ethanol as a solvent, 17.5 g of ion-exchanged water, and titania sol (manufactured by Taki Chemical Co., Ltd.) as a refractive index adjuster were added. , trade name; Tynoc AM-15, secondary particle size 20 nm, solid content 15 wt%) was placed in a reaction vessel, and after stirring at 40°C for 6 hours, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name) was added to a reaction vessel. ; Added 24.5 g of Snowtex (registered trademark) ST-XS, Sears particle size 4 to 6 nm, solid content 20 wt%, solvent; water) and stirred at 40 ° C. for 3 hours, then imparted with superhydrophilic functional groups. 3.8 g of a sulfonate compound (manufactured by Kiyosumi Institute, trade name: KS-S10X) was added as a compound, and nitric acid (manufactured by Kanto Kagaku Co., Ltd., trade name: nitric acid 1.38 g) was added as a catalyst. The mixture was placed in a reaction container so that the pH was 2, and stirred at 40° C. for 3 hours to obtain an inorganic polymer solution (A).
Next, 0.7% by volume of ethanol was added as a solvent to the total amount of the obtained inorganic polymer solution (A), and the mixture was stirred at 25°C for 1 hour to produce a coating agent. The initial physical properties and durability were evaluated in the same manner as in Example 1, except that the film was formed using No. 12). The results are shown in Table 1.

(Example 22; coating agent of third embodiment)
Using the inorganic polymer solution (A) of Example 21, chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) were added as transparent nanofibers to the inorganic polymer in the production of the coating agent of Example 21. A coating agent was produced in the same manner as in Example 21 except that 2% by mass was added based on the total amount of solution (A), and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 23; coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 21, 14.6 g of tetraethoxysilane, 19.8 g of ethanol, 12.4 g of ion-exchanged water, and titania sol (manufactured by Taki Chemical Co., Ltd., Same as Example 21 except that the product name was changed to 33.2 g (trade name: Tynoc M-6, secondary particle size 10 nm, solid content 6 wt%), the colloidal silica was changed to 17.4 g, and the sulfonate compound was changed to 2.7 g. A coating agent was produced in the same manner, and its initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 24; coating agent of third embodiment)
Using the inorganic polymer solution (A) of Example 23, chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) were added as transparent nanofibers to the inorganic polymer in the production of the coating agent of Example 23. A coating agent was produced in the same manner as in Example 23, except that 2% by mass was added based on the total amount of solution (A), and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 25; coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 21, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-UP, average particle diameter of 40 by dynamic light scattering method) ~100 nm, solid content 20 wt%, solvent: water) A coating agent was produced in the same manner as in Example 21, and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 26; coating agent of third embodiment)
Using the inorganic polymer solution (A) of Example 25, chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) were added as transparent nanofibers to the inorganic polymer in the production of the coating agent of Example 25. A coating agent was produced in the same manner as in Example 25 except that 2% by mass was added based on the total amount of solution (A), and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 27; coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 21, 14.6 g of tetraethoxysilane, 19.8 g of ethanol, 12.4 g of ion-exchanged water, and titania sol (manufactured by Taki Chemical Co., Ltd., Change the colloidal silica to colloidal silica (manufactured by Nissan Chemical Industries, Ltd., product name: Snowtex (registered trademark) ST-). Coating was carried out in the same manner as in Example 21, except that UP, dynamic light scattering average particle diameter 40 to 100 nm, solid content 20 wt%, solvent; water) was changed to 17.4 g, and the sulfonate compound was changed to 2.7 g. The initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 28; coating agent of third embodiment)
Using the inorganic polymer solution (A) of Example 27, chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) were added as transparent nanofibers to the inorganic polymer in the production of the coating agent of Example 27. A coating agent was produced in the same manner as in Example 27 except that 2% by mass was added based on the total amount of solution (A), and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 29; coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 21, colloidal silica was used as colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-OS, BET particle size 8 to 11 nm, solid content 20 wt). A coating agent was produced in the same manner as in Example 21, except that the solvent was changed to (%, solvent; water), and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 30; coating agent of third embodiment)
Using the inorganic polymer solution (A) of Example 29, chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) were added as transparent nanofibers to the inorganic polymer in the production of the coating agent of Example 29. A coating agent was produced in the same manner as in Example 29 except that 2% by mass was added based on the total amount of solution (A), and the initial physical properties and durability were evaluated. The results are shown in Table 1.

(Example 31; coating agent of third embodiment)
In the production of the inorganic polymer solution (A) in Example 21, the amount of ion-exchanged water was changed to 9.3 g, and the colloidal silica was changed to colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-OUP). A coating agent was produced in the same manner as in Example 21, except that the average particle diameter according to dynamic light scattering was 40 to 100 nm, solid content was 15 wt%, solvent was 32.7 g (water), and the initial physical properties and durability were determined. We conducted an evaluation. The results are shown in Table 2.

(Example 32; Coating agent of third embodiment)
Using the inorganic polymer solution (A) of Example 31, chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) were added as transparent nanofibers to the inorganic polymer in the production of the coating agent of Example 31. A coating agent was produced in the same manner as in Example 31 except that 2% by mass was added based on the total amount of solution (A), and the initial physical properties and durability were evaluated. The results are shown in Table 2.

(Example 33; coating agent of third embodiment)
In a nitrogen atmosphere, 19.2 g of tetraethoxysilane (manufactured by Tama Chemical Industries, Ltd.) and colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-XS, Sears particle size 4 to 6 nm) , solid content 20 wt%, solvent: 13.2 g of water, 17.7 g of ethanol as a solvent, 9.2 g of ion exchange water, and titania sol (manufactured by Taki Chemical Co., Ltd., trade name: TYNOC AM) as a refractive index adjuster. -15, secondary particle size 20 nm, solid content 15 wt%) was placed in a reaction vessel and stirred at 40°C for 6 hours. KS-S10X) was added as a catalyst, and nitric acid (manufactured by Kanto Kagaku Co., Ltd., product name: nitric acid 1.38) was added to the reaction vessel so that the pH of the entire solution was 2. The mixture was stirred at 40° C. for 3 hours to obtain an inorganic polymer solution (A).
Next, 0.7% by volume of ethanol was added as a solvent to the total amount of the obtained inorganic polymer solution (A), and the mixture was stirred at 25°C for 1 hour to produce a coating agent. Initial physical properties and durability were evaluated under similar conditions. The results are shown in Table 2.

(Example 34; coating agent of third embodiment)
Using the inorganic polymer solution (A) of Example 33, chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) were added as transparent nanofibers to the inorganic polymer in the production of the coating agent of Example 33. A coating agent was produced in the same manner as in Example 33 except that 2% by mass was added based on the total amount of solution (A), and the initial physical properties and durability were evaluated. The results are shown in Table 2.

(Example 35; coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 33, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-UP, average particle diameter of 40 by dynamic light scattering method) ~100 nm, solid content 20 wt%, solvent: water) A coating agent was produced in the same manner as in Example 33, and the initial physical properties and durability were evaluated. The results are shown in Table 2.

(Example 36; Coating agent of third embodiment)
Using the inorganic polymer solution (A) of Example 35, chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) were added as transparent nanofibers to the inorganic polymer in the production of the coating agent of Example 35. A coating agent was produced in the same manner as in Example 35 except that 2% by mass was added based on the total amount of solution (A), and the initial physical properties and durability were evaluated. The results are shown in Table 2.

(Example 37; Coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 33, colloidal silica was used as colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-OS, BET particle size 8 to 11 nm, solid content 20 wt). A coating agent was produced in the same manner as in Example 33, except that the solvent was changed to (%, solvent; water), and the initial physical properties and durability were evaluated. The results are shown in Table 2.

(Example 38; coating agent of third embodiment)
Using the inorganic polymer solution (A) of Example 37, chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) were added as transparent nanofibers to the inorganic polymer in the production of the coating agent of Example 37. A coating agent was produced in the same manner as in Example 37 except that 2% by mass was added based on the total amount of solution (A), and the initial physical properties and durability were evaluated. The results are shown in Table 2.

(Example 39; Coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 33, 18.4 g of tetraethoxysilane and colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-OUP, Optical light scattering method Average particle size 40-100 nm, solid content 15 wt%, solvent; 16.8 g of water, 37.4 g of titania sol, 4.7 g of sulfonate compound, and 17.1 g of ethanol as a solvent. A coating agent was produced in the same manner as in Example 33, except that 4.7 g of ion-exchanged water was used, and the initial physical properties and durability were evaluated. The results are shown in Table 2.

(Example 40; coating agent of third embodiment)
Using the inorganic polymer solution (A) of Example 39, chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) were added as transparent nanofibers to the inorganic polymer in the production of the coating agent of Example 39. A coating agent was produced in the same manner as in Example 39 except that 2% by mass was added based on the total amount of solution (A), and the initial physical properties and durability were evaluated. The results are shown in Table 2.

(Example 41; coating agent of third embodiment)
In a nitrogen atmosphere, 22.7 g of tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd.), 14.3 g of methanol as a solvent, 20.2 g of ion-exchanged water, and zirconia sol (Sakai Chemical Industry Co., Ltd.) as a refractive index modifier were added. (manufactured by Kanto Kagaku Co., Ltd., product name: SZR-W, product name: D ₅₀ 3 nm, solid content: 30 wt%, solvent: water) and 16.1 g of nitric acid (manufactured by Kanto Kagaku Co., Ltd., product name: nitric acid 1.38) as a catalyst. After stirring at 40°C for 2 hours, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-XS, Sears particle size 4 After adding 20.2 g of ~6 nm, solid content 20 wt%, solvent: water and stirring for 2 hours, a sulfonate compound (manufactured by Kiyosumi Institute Co., Ltd., trade name: KS) was added as a compound that imparts a superhydrophilic functional group. -S10X) was added and stirred at 40°C for 2 hours to obtain an inorganic polymer solution (A).
Next, 0.7% by volume of methanol was added as a solvent to the total amount of the obtained inorganic polymer solution (A), and the mixture was stirred at 25°C for 1 hour to produce a coating agent. The initial physical properties and durability were evaluated in the same manner as in Example 1, except that the film was formed using No. 12). The results are shown in Table 2.

(Example 42; Coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 41, ethanol was used instead of methanol as a solvent, and after stirring at 40°C for 3 hours, colloidal silica was added, and after stirring at 40°C for 3 hours, sulfonic acid A salt compound was added and stirred at 40°C for 3 hours to produce an inorganic polymer solution (A). Chitin nanofibers (manufactured by Sugino Machine Co., Ltd. , trade name; BiNFi-s SFo-20002) 2% by mass, and a coating agent was produced in the same manner as in Example 41, except that 0.7% by volume of ethanol was added as a solvent, and the initial physical properties and durability were evaluated. I did it. The results are shown in Table 2.

(Example 43; Coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 41, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-UP, average particle diameter of 40 by dynamic light scattering method) ~100 nm, solid content 20 wt%, solvent: water) A coating agent was produced in the same manner as in Example 41, and the initial physical properties and durability were evaluated. The results are shown in Table 2.

(Example 44; coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 42, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-UP, average particle diameter of 40 by dynamic light scattering method) ~100 nm, solid content 20 wt%, solvent: water) A coating agent was produced in the same manner as in Example 42, and the initial physical properties and durability were evaluated. The results are shown in Table 2.

(Example 45; coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 41, colloidal silica was used as colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-OS, BET particle size 8 to 11 nm, solid content 20 wt). A coating agent was produced in the same manner as in Example 41, except that the solvent was changed to (%, solvent; water), and the initial physical properties and durability were evaluated. The results are shown in Table 2.

(Example 46; Coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 42, colloidal silica was used as colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-OS, BET particle size 8 to 11 nm, solid content 20 wt). A coating agent was produced in the same manner as in Example 42, except that the solvent was changed to (%, solvent; water), and the initial physical properties and durability were evaluated. The results are shown in Table 2.

(Example 47; coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 41, the amount of tetraethoxysilane was changed to 22.6 g, the solvent was changed to 14.0 g of methanol, and 13.6 g of ion-exchanged water, and the colloidal silica was changed to colloidal silica (Nissan Chemical Industries, Ltd.). Example 41, except that the product name was changed to Snowtex (registered trademark) ST-OUP, average particle size measured by dynamic light scattering method: 40 to 100 nm, solid content: 15 wt%, solvent: water) (26.8 g) A coating agent was produced in the same manner as above, and its initial physical properties and durability were evaluated. The results are shown in Table 2.

(Example 48; coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 47, ethanol was used instead of methanol as the solvent, and after stirring at 40°C for 3 hours, colloidal silica was added and stirring at 40°C for 3 hours, and then sulfonic acid was added. A salt compound was added and stirred at 40°C for 3 hours to produce an inorganic polymer solution (A). Chitin nanofibers (manufactured by Sugino Machine Co., Ltd. , trade name: BiNFi-s SFo-20002) 2% by mass, and a coating agent was produced in the same manner as in Example 47 except that 0.7% by volume of ethanol was added as a solvent, and the initial physical properties and durability were evaluated. I did it. The results are shown in Table 2.

(Example 49; coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 41, tetraethoxysilane was changed to 19.0 g, zirconia sol was changed to 26.7 g, the solvent was changed to 16.5 g of ethanol and 22 g of ion-exchanged water, and the solution was heated at 40°C for 30 minutes. After stirring for an hour, the amount of colloidal silica was changed to 9.6 g, and after adding colloidal silica and stirring at 40°C for 3 hours, the sulfonate compound was added and stirred at 40°C for 3 hours, and the inorganic polymer solution was (A), and based on the total amount of this inorganic polymer solution (A), 2% by mass of chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) as transparent nanofibers and 2% by mass as a solvent. A coating agent was produced in the same manner as in Example 41, except that 0.7% by volume of ethanol was added, and the initial physical properties and durability were evaluated under the same conditions as in Example 1. The results are shown in Table 2.

(Example 50; coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 49, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-UP, average particle diameter of 40 by dynamic light scattering method) ~100 nm, solid content 20 wt%, solvent: water), and the coating agent was manufactured in the same manner as in Example 49, except that transparent nanofibers were not used in the manufacturing of the coating agent, and evaluation of initial physical properties and durability. I did it. The results are shown in Table 2.

(Example 51; coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 49, colloidal silica was used as colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-OS, BET particle size 8 to 11 nm, solid content 20 wt). A coating agent was produced in the same manner as in Example 49, except that the solvent was changed to water), and the initial physical properties and durability were evaluated. The results are shown in Table 2.

(Example 52; coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 49, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (registered trademark) ST-OUP, average particle size of 40 by dynamic light scattering method) ~100nm, solid content 15wt%, solvent; water) 12.8g, ion-exchanged water was changed to 18.8g, and coating was carried out in the same manner as in Example 49, except that transparent nanofibers were not used in the production of the coating agent. The initial physical properties and durability were evaluated. The results are shown in Table 2.

(Example 53; coating agent of third embodiment)
In a nitrogen atmosphere, 14.6 g of tetramethoxysilane (manufactured by Tama Chemical Industry Co., Ltd.), 21.9 g of methanol as a solvent, 12.1 g of ion-exchanged water, and zirconia sol (Sakai Chemical Industry Co., Ltd.) as a refractive index modifier were added. product name: SZR-W, D ₅₀ 3 nm, solid content 30 wt%, solvent: water) 45.3 g, and a sulfonate compound (manufactured by Kiyosumi Institute Co., Ltd., Add 6.4 g of KS-S10X (trade name; KS-S10X), add nitric acid (manufactured by Kanto Kagaku Co., Ltd., trade name: nitric acid 1.38) as a catalyst to a reaction vessel so that the pH of the entire solution is 2, and heat at 40°C. The mixture was stirred for 6 hours to obtain an inorganic polymer solution (A).
Next, based on the total amount of the obtained inorganic polymer solution (A), 2% by mass of chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) were added as transparent nanofibers, and methanol was added as a solvent. was added in an amount of 0.7% by volume and stirred at 25° C. for 1 hour to produce a coating agent, and its initial physical properties and durability were evaluated. The results are shown in Table 2.

(Example 54; coating agent of third embodiment)
In the production of the inorganic polymer solution (A) of Example 31, 15.8 g of tetraethoxysilane, 20.7 g of ethanol, 17.7 g of ion-exchanged water, and ceria sol (Daiichi Ki Elements Chemical Co., Ltd.) instead of titania sol were used. Colloidal silica _was changed to colloidal silica (manufactured by Nissan Chemical Industries, Ltd., product name: Snowtex (registered trademark) ST). - OUP, dynamic light scattering average particle size 40 to 100 nm, solid content 15 wt%, solvent: water) 25.1 g, and the sulfonate compound was changed to 6.8 g, but in the same manner as Example 31. A coating agent was manufactured and its initial physical properties and durability were evaluated. The results are shown in Table 2.

(Comparative example 1)
In manufacturing the coating agent of Example 1, a coating agent was manufactured in the same manner as in Example 1 except that transparent nanofibers were not used, and the initial physical properties and durability were evaluated. The results are shown in Table 3.

(Comparative example 2)
A coating agent was produced in the same manner as in Example 21, except that the amount of ethanol was changed to 18.8 g in the production of the inorganic polymer solution (A) of Example 21, and the sulfonate compound was not used. Gender was evaluated. The results are shown in Table 3.

(Comparative example 3)
In the production of the inorganic polymer solution (A) in Example 41, methanol was changed to 21.5 g, and chitin nanofibers (manufactured by Sugino Machine Co., Ltd., trade name: BiNFi-s SFo-20002) were added to the inorganic nanofibers as transparent nanofibers. A coating agent was produced in the same manner as in Example 41 except that 2% by mass was added based on the total amount of the polymer solution (A) and no sulfonate compound was used, and the initial physical properties and durability were evaluated. The results are shown in Table 3.

(Comparative example 4)
A coating agent was produced in the same manner as in Example 53 except that methanol was changed to 28.3 g and the sulfonate compound was not used in producing the inorganic polymer solution (A) of Example 53, and the initial physical properties and durability were evaluated. Gender was evaluated. The results are shown in Table 3.

(Evaluation; board change)
A polycarbonate substrate (manufactured by Takiron C.I. Co., Ltd., thickness: 1.5 mm) was coated with the coating agent obtained in Example 1 and subjected to corona treatment on the surface of 70 mm x 50 mm by bar coating method using a bar coater (bar No. 7). 5 mm) and was dried by heating at 120° C. for 15 minutes to obtain a coating film. The above corona treatment was performed using Corona Fit CFG-500 manufactured by Shinko Denki Co., Ltd. until the surface became hydrophilic. In addition, the coating agents obtained in Examples 33 to 40, 49 to 52, and Comparative Examples 1 to 3 were used with bar No. 1 as a polycarbonate substrate and a bar coater. The coating film was evaluated under the same conditions as above except that No. 12 was used. The results are shown in Table 3.

The coating agents obtained in Example 53 and Comparative Example 4 were evaluated using an aluminum substrate (A6061P plate, 70 mm x 30 mm, thickness 0.3 mm) and a bar coater using Bar No. The coating film obtained by applying a coating agent onto the substrate surface using No. 12 and drying it by heating at 150° C. for 15 minutes was tested. The results are shown in Table 3.

Claims (8)

Fine particles of a water-insoluble metal compound,
A coating agent in which an inorganic polymer having a Si-O bond, an Al-O bond, a Ti-O bond, a Zr-O bond, or a Sn-O bond and a hydroxyl group in the molecule is dispersed in a solvent,
The metal compound fine particles have the formula (1) on at least a part of the fine particle surface:

(However, in formula (1), R ¹ is a structural unit derived from an alkyl group having 1 to 10 carbon atoms, and A ¹ is a monovalent cation.) Base or formula (2):

(However, in formula (2), R ² is a structural unit derived from an alkyl group having 1 to 10 carbon atoms, and A ² is a monovalent cation.) having a functional group containing a group or a ureido group,
When a coating film with a thickness of 70 to 2,000 nm is obtained by applying it to a glass substrate and drying at a temperature of 20 to 150 degrees, it is measured using a contact angle measuring device using the θ/2 method. A coating agent that has a static contact angle of 10° or less when the static contact angle between the surface of the coating film and a water droplet is measured. When a coating film with a thickness of 70 to 2,000 nm was obtained by applying it to a glass substrate and drying at a temperature of 20 to 150 degrees, and then leaving it for 100 hours at 65 degrees Celsius and 95% RH. Claim 1, wherein the static contact angle between the surface of the coating film and the water droplet after being left is measured to be 10° or less using a contact angle measuring device using the θ/2 method. Coating agent described in. After coating on a glass substrate and drying at a temperature of 120 to 150 degrees to obtain a coating film with a thickness of 70 to 2,000 nm, contact with 50 degrees Celsius hot water at 100 ml/hour for 100 hours. When the static contact angle between the surface of the coating film and the water droplet after treatment with hot water is measured using a contact angle measuring device using the θ/2 method, the static contact angle is 10° or less. , The coating agent according to claim 1 or 2. After coating on a glass substrate and drying at a temperature of 20 to 150 degrees to obtain a coating film with a thickness of 70 to 2,000 nm, when left at 150 degrees for 100 hours, the contact angle Any one of claims 1 to 3, wherein the static contact angle between the surface of the coating film and the water droplet after being left is measured to be 10° or less using a measuring device using the θ/2 method. Coating agent described in Crab. After obtaining a coating film with a thickness of 70 to 2,000 nm by coating on a glass substrate and drying at a temperature of 20 to 150 degrees, black A 1000-hour irradiation test was conducted on the surface of the coating film at a panel temperature of 63°C and a lamp intensity of 60 W/ ^m2 , by repeating a cycle of irradiation for 102 minutes, followed by 18 minutes of irradiation, and water spraying. When the static contact angle between the surface of the coating film and the water droplet after the test is measured using a contact angle measuring device using the θ/2 method, the static contact angle is 10° or less. The coating agent according to any one of claims 1 to 4. A coating film formed using the coating agent according to any one of claims 1 to 5. Used as a static electricity removal film, an antifouling film, an antibacterial film, an anti-mold film, a deodorant film, an anti-fingerprint film, an anti-fog film, a foam suppression film, or a lubricating film. The coating film according to claim 6. The coating film according to claim 6, which is used as a coating film for printing plates in offset printing, a coating film for heat exchangers, or a coating film for heat pipes.

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