WO2021039669A1

WO2021039669A1 - Functional film, functional film laminate, composition for forming functional film, method for producing composition for forming functional film, and method for producing functional film laminate

Info

Publication number: WO2021039669A1
Application number: PCT/JP2020/031716
Authority: WO
Inventors: 佐藤　光史; 裕己永井
Original assignee: 学校法人工学院大学
Priority date: 2019-08-28
Filing date: 2020-08-21
Publication date: 2021-03-04
Also published as: JP7477889B2; JPWO2021039669A1

Abstract

A functional film containing amorphous titanium oxide, wherein the content of oxygen atoms is in the 0.5-1.9 mol range per mol of titanium atoms contained in the functional film, a functional film containing amorphous silicon oxide, and the use thereof.

Description

A method for producing a functional film, a functional film laminate, a composition for forming a functional film, a method for producing a composition for forming a functional film, and a method for producing a functional film laminate.

The present disclosure relates to a functional film, a functional film laminate, a composition for forming a functional film, a method for producing a composition for forming a functional film, and a method for producing a functional film laminate.

There are various functional films that impart functions such as imparting hydrophilicity to the surface of the substrate, protecting the surface of a hard substrate such as glass, shielding ultraviolet rays of a desired wavelength, and imparting electrical conductivity. It is being considered.
For example, by imparting hydrophilicity to the windows of vehicles, windows of buildings, mirrors, outer walls of buildings, etc., it is possible to obtain a functional film having effects such as self-cleaning property and anti-fog on the surface of the base material. ..
Further, various transparent conductive films have been developed as one of the functional films. Heat treatment is often required to form a conductive film, and a resin substrate that is not suitable for heating, a conductive material such as carbon nanotubes that is not suitable for heating, and lithium such as lithium _{hexafluorophosphate (LiPF 6).} It is difficult to use a solid electrolyte raw material or the like, and there is a demand for a method for producing a functional membrane that does not require heat treatment.

The methods for forming a metal film and a metal oxide film useful for a conductive film are roughly classified into a vapor phase method and a wet method, and any of them can form a thin film containing a metal atom. Since the vapor phase method requires large-scale equipment, it is not suitable for producing a general-purpose metal film and a metal oxide film that require a film having a desired area at low cost. Therefore, the wet method is attracting attention. To.
Among them, the molecular precursor method, which is one of the wet methods, is attracting attention.

According to the molecular precursor method, a metal-containing film can be formed on a substrate by the coating method using a precursor solution containing a solvent suitable for coating and a metal complex soluble in the solvent. Therefore, the degree of freedom in selecting the composition of the metal film, the base material, and the like is high as compared with the method of depositing the metal film on the base material by another wet method such as the plating method.
As a method for forming a metal film using the precursor method, a method of applying a metal film forming composition containing a specific cationic metal complex and heating to form a metal film is disclosed, and energy is applied instead of heating. It is described that ultraviolet rays are used in (see International Publication No. 2017/135330).
As a hydrophilic film, it contains a metal oxide and a hydrophilic compound such as polyoxyalkylene glycol, which are useful for forming a hydrophilic antifogging coating film, and in elemental analysis of the surface, element C and a metal derived from the metal oxide. A coating film having an element concentration ratio of 10 or more to an element has been proposed. As the metal oxide that imparts hydrophilicity due to the photocatalytic reaction, anatase-type, rutile-type, and brookite-type titanium oxides are cited as preferable examples (see JP-A-2018-172566).

The technique described in International Publication No. 2017/135330 is useful for forming dense metal films and metal oxide films. However, even by the method described in International Publication No. 2017/135330, some heating is required to form a metal film from the composition for forming a metal film containing a metal complex. In addition, although there is a reference to the formation of a cured film by ultraviolet rays, the details and the physical characteristics of the obtained cured film have not been examined at present.

The coating film and coating composition described in JP-A-2018-172566 are useful for forming an anti-fog film on a hard substrate. However, since the film formation depends on the hydrophilic compound and preferably the isocyanate compound used in combination with the hydrophilic compound, there is still room for improvement in the strength and durability of the coating film.

An object of an embodiment of the present invention is a functional film having functions such as hydrophilicity, surface protection, and ultraviolet absorption, a functional film laminate having a functional film on a substrate, and a functional film laminate. It is to provide a manufacturing method.
An object of another embodiment of the present invention is to provide a composition for forming a functional film containing a complex compound useful for forming a functional film, and a method for producing the same.

The disclosure includes the following embodiments:
<1> A functional film containing amorphous titanium oxide, wherein the content of oxygen atoms per 1 mol of titanium atoms contained in the functional film is in the range of 0.5 mol to 1.9 mol. Sexual membrane.
<2> After irradiating with ultraviolet light under the conditions of ultraviolet light with a wavelength of 254 nm, intensity: 4 mW / cm ² , and irradiation time: 10 minutes, the pure water contact angle of the surface measured at 25 ° C is 10 ° or less <1>. The functional membrane described.
<3> The ultraviolet transmittance of a wavelength of 350 nm or less is 10% or less, the near-ultraviolet transmittance of a wavelength of more than 350 nm and 400 nm or less is less than 80%, and the visible light transmittance of a wavelength of more than 400 nm and 750 nm or less is 80. The functional membrane according to <1> or <2>, which is% or more.

<4> A functional film containing amorphous silicon oxide, wherein the content of oxygen atoms per 1 mol of silicon atoms contained in the functional film is in the range of 1.0 mol or more and less than 2.0 mol. Functional membrane.
<5> The functional film according to <4>, which is a protective film for a base material.

<6> Further, 0.1 parts by mass to 10 parts by mass of a conductive material selected from the group consisting of carbon nanotubes, carbon black, and conductive metal particles with respect to 1 part by mass of titanium or silicon contained in the functional film. wherein parts by weight, the four-probe electrical conductivity as measured by the needle method is 10 ⁶ [Omega] cm or less <1> to <5> functional film according to any one of.
<7> The functional membrane according to <4>, which further contains a lithium compound and is a lithium solid electrolyte membrane.

<8> A functional film laminate having a base material and the functional film according to any one of <1> to <7> on the base material.
<9> The base material is a base material selected from the group consisting of a fluorine-doped tin oxide base material, an indium-doped tin oxide base material, a resin base material, a blue plate glass base material, a metal base material, and a ceramic base material. 8> The functional film laminate according to 8.

<10> A composition for forming a functional film, which comprises a solvent containing an alcohol and an anionic titanium complex or an anionic silicon complex.
<11> The composition for forming a functional film according to <10>, wherein the anionic titanium complex or the anionic silicon complex is a complex having oxalic acid or ethylenediaminetetraacetic acid as a ligand.

<12> A step of mixing a solvent containing an alcohol, at least one selected from the group consisting of an oxalic acid compound, an amine compound and an aminocarboxylic acid, and a titanium compound or a silicon oxide compound to obtain a mixture. A method for producing a composition for forming a functional film, which comprises a step of adding water or hydrogen peroxide to the mixture and refluxing the mixture.
<13> The step of applying the functional film-forming composition according to <10> or <11> to a base material to form a functional film-forming composition layer, and forming on the base material. A method for producing a functional film laminate, which comprises a step of irradiating the functional film-forming composition layer with ultraviolet rays to remove organic substances from the functional film-forming composition to obtain a functional film.

According to an embodiment of the present invention, a functional film having functions such as hydrophilicity, surface protection, and ultraviolet absorption, a functional film laminate having a functional film on a substrate, and a functional film laminate. A manufacturing method can be provided.
According to another embodiment of the present invention, it is possible to provide a composition for forming a functional film containing a complex compound useful for forming a functional film, and a method for producing the same.

It is a graph which shows the absorption spectrum of the composition for forming a functional film (I) obtained in Example 1. FIG. ^{A functional film I 2} , a functional film I ⁴ , a functional film I ⁸ or a functional film I ¹⁶ was formed on the quartz glass substrate (control example) and the quartz glass substrate obtained in Example 1, respectively. It is a graph which shows the absorption spectrum of a laminated body. For the composition layer for forming the functional film (I), the functional film I ² , the functional film I ⁴ , the functional film I ⁸ , and the functional film I ¹⁶ by X-ray diffraction (XRD). It is a graph which shows the XRD pattern obtained by this. The surface image and the cross-sectional image of the functional film (I) obtained in Example 1 observed by FE-SEM, (a) is the surface image and the cross-sectional image of the ^{functional film I 2, and (b) is the function.} It is a surface image and a cross-sectional image of the sex film I ⁴ , (c) is a surface image and a cross-sectional image of the ^{functional film I 8} , and (d) is a surface image and a cross-sectional image of the ^{functional film I 16.}

Hereinafter, specific embodiments of the functional film, the functional film laminate, the functional film-forming composition, the method for producing the functional film-forming composition, and the method for producing the functional film laminate of the present disclosure will be described. It will be described in detail. The present disclosure is not limited to the following embodiments, and can be carried out by various modified examples as long as it does not contradict the gist thereof.

The numerical range described by using "-" in the present disclosure represents a numerical range including the numerical values before and after "-" as the lower limit value and the upper limit value.
In the present disclosure, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
In the present disclosure, the amount of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. ..
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
Further, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.

<Functional membrane>
[1. Functional membrane: first aspect]
The first aspect of the functional film of the present disclosure is a functional film containing amorphous titanium oxide, wherein the content of oxygen atoms per 1 mol of titanium atoms contained in the functional film is 0.5 mol. It is in the range of ~ 1.9 mol.
Hereinafter, the first aspect of the functional film of the present disclosure containing amorphous titanium oxide may be referred to as the functional film (I) of the present disclosure.
The content of oxygen atoms per 1 mol of titanium atoms contained in the functional film (I) of the present disclosure is in the range of 0.5 mol to 1.9 mol, and is in the range of 1.0 mol to 1.7 mol. It is preferably in the range of 1.2 mol to 1.7 mol, more preferably.
The molar ratio of titanium atoms to oxygen atoms contained in the functional film (I) was analyzed by X-ray Photoelectron Spectroscopy as described in detail in the following examples. It can be calculated from the XPS spectrum.

When the content of oxygen atoms per 1 mol of titanium atoms is less than 0.5 mol, it is difficult to produce a uniform film.
The content of oxygen atoms per mole of titanium atoms in a known titanium dioxide film is 2.0. The functional film (I) of the present disclosure exhibits good hydrophilicity and ultraviolet absorption by setting the content of oxygen atoms per 1 mol of titanium atoms to 1.9 mol or less. On the other hand, when the content of oxygen atoms per 1 mol of titanium atoms exceeds 1.9 mol, even a metal film containing amorphous titanium oxide has high hydrophilicity as in the functional film (I) of the present disclosure. Is difficult to express.
As will be described later, the functional membrane (I) of the present disclosure is formed by irradiating a functional membrane precursor layer composed of a composition for forming a functional membrane (I) containing an anionic titanium complex with ultraviolet rays. Is preferable. When the functional membrane is changed from the functional membrane precursor layer to the functional membrane by irradiation with ultraviolet rays, oxygen is easily removed by the reaction, and the content of oxygen atoms per 1 mol of titanium atoms in the functional membrane (I) is generally high. It is smaller than a typical titanium dioxide film. As a result, the titanium atom in the functional film (I) has a bond (dangling bond) formed by removing oxygen and occupied by electrons (unpaired electrons) that are not involved in the bond. It is considered that the functional film (I) is easily bonded to water due to the dangling bond contained in the titanium atom, and exhibits higher hydrophilicity than a general titanium dioxide film.
The functional film (I) is exposed to ultraviolet light having a wavelength of 254 nm, an intensity of 4 mW / cm ² , and an irradiation time of 10 minutes, and then measured at 25 ° C. with a pure water contact angle of 10 ° or less. It is preferably a functional membrane.
The method for measuring the pure water contact angle on the surface of the functional membrane will be described later.

[2. Composition for forming a functional film: first aspect]
In the present disclosure, the composition for forming the functional film (I) is hereinafter referred to as the composition for forming the functional film (I). The composition for forming the functional film (I) contains a solvent containing an alcohol and an anionic titanium complex, and may contain other components if desired.
The anionic titanium complex is preferably a complex having oxalic acid or ethylenediaminetetraacetic acid as a ligand from the viewpoint of better photodegradability when irradiated with ultraviolet rays.

[3. Method for Producing Composition for Forming Functional Film (I)]
The composition for forming the functional film (I) is obtained by mixing a solvent containing alcohol, at least one selected from the group consisting of an oxalic acid compound, an amine compound and an aminocarboxylic acid, and a titanium compound to obtain a mixture. It is obtained by a method for producing a composition for forming a functional film, which comprises a step and a step of adding water or hydrogen peroxide to the obtained mixture and refluxing the mixture.
The mixture used in the method for producing the composition for forming the functional film (I) is, for example, a solvent containing alcohol, an oxalic acid compound such as oxalic acid or oxalic acid dihydrate, and titanium tetraisopropoxide or the like. Titanium compounds can be obtained by mixing.
Examples of the solvent include alcohols having 1 to 5 carbon atoms such as methanol, ethanol and propanol, water, ether and the like, and the obtained functional film (I) forming composition has better coatability on the substrate. Ethanol is preferable from the viewpoint of the presence.

To give an example of a composition for forming a functional film (I), specifically, a oxalic acid compound such as oxalic acid dihydrate is added to a solvent containing an alcohol such as ethanol, and butylamine is optionally added. An amine compound such as the above is further added, and the mixture is refluxed for about 0.5 to 2 hours and cooled to room temperature (25 ° C .: the same applies hereinafter).
Then, a titanium compound such as titanium tetraisopropoxide is added, and the mixture is further refluxed for 2 to 4 hours and cooled to room temperature to obtain a mixture.
To the obtained mixture, 31 mass% hydrogen peroxide solution is added, the mixture is further refluxed for 0.3 hours to 1 hour, and cooled to room temperature to obtain titanium having oxalic acid as a ligand, which is an anionic titanium complex. A composition for forming a functional film (I) containing a complex can be obtained.

The obtained functional film (I) forming composition contains a solvent and a titanium complex having oxalic acid or ethylenediaminetetraacetic acid as a ligand.
It is presumed that the titanium complex having oxalic acid as a ligand exhibits the following structure.

In order to obtain a complex having ethylenediaminetetraacetic acid as a ligand, ethylenediaminetetraacetic acid is used in place of the oxalic acid compound contained in the composition for forming the functional membrane (I) in the step of obtaining the mixture. It may be used.

[4. Method for manufacturing functional film (I) laminate]
In the method for producing the functional film (I) laminate, the functional film (I) forming composition containing the above-mentioned alcohol-containing solvent and anionic titanium complex is applied to a base material to provide the functional film (I). The step of forming the composition layer for formation and the functional film-forming composition layer formed on the substrate are irradiated with ultraviolet rays to remove organic substances from the functional film-forming composition and have functionality. Includes the step of obtaining a film.
The composition layer for forming the functional film (I) formed on the surface of the base material by applying the composition for forming the functional film (I) to an arbitrary base material is hereinafter referred to as the composition layer (I). Sometimes. By irradiating the composition layer (I) formed on the base material with ultraviolet rays, organic substances and the like in the composition layer (I) are removed, and a functional film (I) is formed on the surface of the base material. , A functional film (I) laminate can be obtained.

The composition for forming the functional film (I) can be applied to the base material by a known method, for example, a coating method or a dipping method. From the viewpoint that a uniform composition layer (I) can be easily formed, it is preferable to apply the coating method. As the coating method, a known coating method such as spray coating or spin coating can be applied.
In the obtained composition layer (I), the composition layer (I) may be dried for the purpose of reducing the amount of the solvent contained in the composition layer (I) prior to the irradiation with ultraviolet rays. Drying can be performed by a known method.
Examples of the drying method include a method of drying in a drying zone of 50 ° C. to 80 ° C. for 5 to 10 minutes, a method of blowing warm air, a method of naturally drying at room temperature, and the like, and the composition layer (I). From the viewpoint of uniformity, the method of drying in the drying zone is preferable.

By irradiating the composition layer (I) with ultraviolet rays, the organic substances contained in the composition layer (I) are removed, and as a result, a functional film containing titanium derived from the titanium complex and oxygen is formed.
The irradiation intensity of ultraviolet rays can be appropriately selected according to the purpose. ^{The ultraviolet irradiation conditions effective for removing organic substances can be 1 mW / cm 2} (1 mJ / cm ² ) or more with ultraviolet rays having a wavelength of 380 nm or less. As the ultraviolet rays, ultraviolet rays having a wavelength of 150 nm to 380 nm are preferable. The irradiation intensity may be a 1 mW / cm ² or more, preferably 3 mW / cm ² or more, 4 mW / cm ² or more is more preferable. There is no particular limitation on the upper limit of the irradiation intensity. Considering the irradiation intensity and the effect of removing organic substances, it can be set to 10 mW / cm ² or less.
As for the ultraviolet irradiation, for example, in the examples shown below, ultraviolet rays having a wavelength of 254 nm (intensity 4 mW / cm ² : 4 mJ / cm ² ) are irradiated for 2 hours to 16 hours, and good results are obtained.
As described above, it is one of the advantages of the method for producing a functional film of the present disclosure that a functional film can be formed by irradiation with low-energy ultraviolet rays.

During irradiation with ultraviolet rays, it is preferable to set the temperature of the base material to 30 ° C. to 40 ° C. from the viewpoint of improving the film forming efficiency of the functional film.
For example, when a resin composition containing a cross-linking agent is cured by ultraviolet irradiation, there is a concern that curing may be inhibited by oxygen in the air. However, in the film formation of the functional film (I) of the present disclosure, ultraviolet irradiation is used. In order to form a film containing metal as a main component by decomposing and removing organic substances such as a ligand component contained in the composition layer (I) and a component derived from a residual solvent, an atmosphere in which oxygen is present, for example, an atmosphere. UV irradiation inside is possible.

In order to prevent dust and the like from being mixed into the functional membrane (I), it is also preferable that the ultraviolet irradiation is performed in a clean space such as a clean bench. When the functional film (I) is experimentally formed, a laminate having the composition layer (I) is placed on a base material in a clean bench equipped with a germicidal lamp, and the germicidal lamp is used. It may be irradiated with ultraviolet rays. The humidity in the clean bench is preferably in the range of 40% RH to 60% RH in consideration of antistatic properties and the like.

[5. Composition for forming functional film (I) and physical properties of functional film (I)]
The composition for forming the functional film (I) has an ultraviolet absorbing ability due to the titanium of the anionic titanium complex having oxalic acid as a ligand, which exists dissolved in a solvent.
Functionality obtained in Example 1 described later, which contains an anionic titanium (IV) complex having oxalic acid as a ligand and has a ^{concentration of Ti 4+ contained in the composition of 0.4 mmol (mmol) / g.} When the absorption spectrum of a solution obtained by diluting the film (I) forming composition 40-fold with ethanol was measured, it had an absorption band characteristic of 377 nm in the wavelength range of 350 nm to 550 nm, and in the ultraviolet region of 300 nm or less. It was found to have strong absorption.
From this, it can be expected that the functional film (I) obtained by using the composition for forming the functional film (I) has an excellent ultraviolet shielding ability.

The functional film (I) of the present disclosure has an ultraviolet transmittance of 10% or less at a wavelength of 350 nm or less, a near-ultraviolet transmittance of more than 350 nm and 400 nm or less of less than 80%, and a wavelength of more than 400 nm and 750 nm. The following visible light transmittance is preferably 80% or more.
The light transmittance of each wavelength of the functional film (I) is 200 nm-in the double beam mode of the device using a spectrophotometer (Hitachi U-2800: trade name) manufactured by Hitachi, Ltd. with reference to quartz glass. It is measured by measuring the wavelength range of 1100 nm.
In the present disclosure, the value measured by the above method is used as the light transmittance.
The functional film (I) has high visible light transmittance, is visually transparent, and has good ultraviolet blocking property. Therefore, for example, a resin material and a resin molded body that are easily deteriorated by ultraviolet rays are exposed to ultraviolet rays. It is useful as an ultraviolet protective film for resins such as resin molded bodies because it can be protected from UV rays and does not easily affect the appearance and hue.

It is considered that the functional film (I) exhibits good hydrophilicity when the composition layer (I) containing titanium oxide, which is a raw material, becomes an amorphous titania film by irradiation with ultraviolet rays.
The composition for forming a functional film (I) containing an anionic titanium complex having oxalic acid as a ligand contains an oxalate ligand, a peroxo ligand, and a butylammonium salt of a Ti (IV) complex and functions. By irradiating the composition layer (I) composed of the composition for forming the sex film (I) with ultraviolet rays, an amorphous titania film is formed, and the hydrophilicity equal to or higher than the hydrophilicity shown _{by the crystalline TiO 2 is obtained.} Shown.
By ultraviolet irradiation, the anionic titanium complex containing oxalic acid as a ligand contained in the composition layer (I) is efficiently decomposed, and the organic component which is the ligand of the complex is removed. In addition, the oxygen atoms remaining in the titanium complex from which the organic components have been removed deprive the water contained in the air of oxygen atoms to become oxygen (O ₂ ), which is removed from the composition layer (I). To. Therefore, the composition layer (I) has a lower oxygen content per titanium atom than general titania, that is, titanium dioxide. For example, titanium dioxide has 2 oxygen atoms per mol of titanium atoms. The content of oxygen atoms per 1 mol of titanium atoms is in the range of 0.5 mol to 1.9 mol, whereas it is mol.
Therefore, the titanium atom in the composition layer (I) has a bond (dangling bond) formed by removing oxygen and occupied by electrons (unpaired electrons) that are not involved in the bond. The present inventors believe that the ring bond makes it easier to bond with water and exhibits higher hydrophilicity than a general titania film.

According to the study by the present inventors, the functional film (I) obtained by irradiating the composition layer (I) with ultraviolet rays has an ultraviolet light having a wavelength of 254 nm, an intensity of 4 mW / cm ² , and an irradiation time of 10 minutes. The pure water contact angle of the surface measured at 25 ° C. after irradiation with ultraviolet rays under the conditions is preferably 10 ° or less, and more preferably 5 ° or less.
In the present disclosure, the pure water contact angle is measured at 25 ° C. using a contact angle meter in accordance with the method described in JIS R3257 (1999). In the present disclosure, the arithmetic mean value of the values obtained by measuring 5 times is adopted as the pure water contact angle.

[6. Functional membrane: second aspect]
The second aspect of the functional film of the present disclosure is a functional film containing amorphous silicon oxide, in which the content of oxygen atoms per 1 mol of silicon atoms contained in the functional film is 1.0 mol or more. It is in the range of less than 2.0 mol. The content of oxygen atoms per 1 mol of silicon atoms is preferably in the range of 1.0 mol to 1.95 mol, more preferably in the range of 1.2 mol to 1.9 mol.

Hereinafter, the second aspect of the functional film of the present disclosure containing amorphous silicon oxide may be referred to as the functional film (II) of the present disclosure.
The functional film (II) is useful as a protective film for the base material.
The substrate to which the functional film (II) can be applied as the protective film is not particularly limited as long as it is a solid substrate. For example, the functional film (II) of the present disclosure is applied to any of a glass base material, a ceramic base material, a metal base material, a resin base material, a fiber reinforced resin base material, and a composite material base material of each of the above materials. it can.
Further, since the functional film (II) can be formed by a coating method, it can also be applied as a protective film for a base material that is not on a flat plate, such as a resin molded product.
Among them, the functional film (II) has good adhesion to a silicon-containing base material such as glass due to the amorphous silicon contained in the functional film (II).

When the amorphous silicon oxide film further contains a lithium compound, the functional film (II) can be a lithium solid electrolyte membrane.
Examples of the lithium compound include lithium hexafluorophosphate (LiPF ₆ ), lithium tetrachloride (LiCl ₄ ), lithium iodide (LiI) and the like.
_{For example, LiPF 6} used as a lithium compound has poor heat resistance, and it is difficult to include it in a film that requires heating at 100 ° C. or higher for film formation. However, as will be described later, since the functional film (II) of the present disclosure can be formed by irradiating with ultraviolet rays at room temperature, LiPF ₆ can be stably contained and a high-purity lithium solid can be contained. It becomes an electrolyte membrane.
Here, the room temperature refers to an environmental temperature in which temperature control such as heating or cooling is not performed. According to the study by the present inventors, the functional film (II) can be formed by, for example, irradiating with ultraviolet rays under a temperature condition in the range of 10 ° C. to 40 ° C.
Functional film (II) is, the content of LiPF ₆ in a functional film (II) in the case of containing LiPF ₆ can be appropriately selected depending on the purpose. Among them, from the viewpoint of easiness of expressing the function as a solid electrolyte, it is preferable to contain 1 mol to 2 mol of _{LiPF 6 with respect to 1 mol of silicon atoms contained in the functional membrane (II).}

[7. Composition for forming a functional film: second aspect]
The composition for forming the functional film (II) is hereinafter referred to as the composition for forming the functional film (II). The composition for forming the functional film (II) contains a solvent containing an alcohol and an anionic silicon complex, and may contain other components if desired.
The anionic silicon complex is preferably a complex having oxalic acid as a ligand from the viewpoint of better photodegradability of the organic component when irradiated with ultraviolet rays.

[8. Method for Producing Composition for Forming Functional Film (II)]
The composition for forming a functional membrane (II) is prepared by mixing a solvent containing an alcohol, a oxalic acid compound, and a silicon compound to obtain a mixture, and adding water or hydrogen peroxide to the obtained mixture. The step of refluxing is included.
In the composition for forming the functional film (II), for example, a oxalic acid compound such as oxalic acid or oxalic acid dihydrate and a silicon compound such as tetraethyl orthosilicate (TEOS) are added to a solvent containing alcohol. , Mix to obtain a mixture, and water or hydrogen peroxide solution is added to the obtained mixture to reflux the mixture.
Specifically, as a method for producing a composition for forming a functional film (II), for example, a silicon compound such as tetraethyl orthosilicate (TEOS) and oxalic acid are added to a solvent containing an alcohol such as ethanol, and 0. Reflux for about 5 to 2 hours and cool to room temperature (25 ° C .: the same applies hereinafter) to obtain a mixture, and then add 1 mass of pure water to 1 part by mass of silicon oxide contained in the obtained mixture. A method including addition of a portion and further stirring for 0.5 to 2 hours can be mentioned. In this way, a composition for forming a functional membrane (II) containing an anionic silicon complex can be obtained.

The obtained functional film (II) forming composition contains a solvent containing an alcohol and a silicon complex having oxalic acid as a ligand.
When a thyrium compound such as LiPF ₆ described above or an additive such as a conductive material described later is added to the composition for forming a functional membrane (II), for example, TEOS and oxalic acid are added. After refluxing the containing liquid, it may be added and stirring may be continued.

[9. Method for manufacturing functional film (II) laminate]
In the method for producing a functional film (II) laminate, a composition for forming a functional film (II) containing the above-mentioned solvent containing alcohol and an anionic silicon complex is applied to a substrate to provide functionality. The step of forming the film-forming composition layer and the functional film-forming composition layer formed on the substrate are irradiated with ultraviolet rays to remove organic substances from the functional film-forming composition and function. Includes the step of obtaining a sex film.
The composition for forming the functional film (II) may be applied to an arbitrary base material, and the surface of the base material may be referred to as a composition layer for forming the functional film (II) (hereinafter referred to as a composition layer (II)). By irradiating the formed composition layer for forming the functional film (II) with ultraviolet rays, organic substances and the like in the composition layer (II) are removed, and the functional film is formed on the surface of the substrate. (II) is formed, and a functional film (II) laminate having a base material and a functional film (II) formed on the base material can be obtained.
In addition, in the method for producing the functional film (II), instead of the composition for forming the functional film (I) used in the above-mentioned functional film (I), the composition for forming the functional film (II) is used. It can be carried out in the same manner except that it is used, and the preferred embodiment is also the same.

[10. Other components that may be contained in the composition for forming a functional film)
The functional film (I) forming composition and the functional film (II) forming composition of the present disclosure have an effect in addition to a solvent containing an alcohol and an anionic titanium complex or an anionic silicon complex, respectively. Various other components may be further included depending on the purpose, as long as they are not impaired. Hereinafter, both or at least one of the composition for forming a functional film (I) and the composition for forming a functional film (II) may be collectively referred to as a "composition for forming a functional film".
Examples of other components include conductive materials, non-conductive inorganic or organic particles, surfactants, ionic conductors, and the like, in addition to the above-mentioned lithium compounds.

(Conductive material)
When the composition for forming a functional film contains a conductive material, it is possible to impart electrical conductivity to the obtained functional film (I) or functionality (II).
As the conductive material, known materials can be used without limitation. Examples of the conductive material include one or more conductive materials selected from the group consisting of carbon nanotubes, carbon black, and conductive metal particles.
When the composition for forming a functional film contains a conductive material, the obtained functional film (I) or functional film (II) has conductivity. The measure of conductivity, the electric resistance value measured by the four probe method is preferably at 10 ⁶ [Omega] cm or less.
The electric resistance value of the functional membrane (I) or the functional membrane (II) can be measured by the following method. The smaller the electric resistance value, the better the electric conductivity.
The measurement is performed using a digital multimeter: Iwatsu Electric Co., Ltd .: formerly manufactured by Iwatsu Electric Co., Ltd., VOAC7512, KEITHLEY, and Model2010 Multimeter (all trade names). The electricity of the functional membrane (I) or the functional membrane (II) is obtained by measuring 5 points by the four-probe method and calculating the average value at 3 points excluding the maximum and minimum values of the measured values. Let it be the resistance value.
According to the four-probe method, the volume resistivity of the conductive material can be measured. There is a two-terminal method as a simpler method for measuring electrical resistance, and in the two-terminal method, the resistance value between the two terminals is measured. In the four-probe method, since each of the four needles functions as a pair of current terminals and a voltage terminal, the influence of contact resistance can be reduced as in the two-terminal method.
In general, the electric resistance value by the two-terminal method is affected by the contact resistance, and the value is larger than the electric resistance value by the four-probe method. Thus, the two long electrical resistance by terminal method is less 10 ⁶ Omega, since the electrical resistance lower value by the four probe method, if it is an electric resistance value 10 ⁶ [Omega] cm or less according to four-probe method Can be estimated. The two-probe resistance method applied to the measurement of the electric resistance value in the examples described later is substantially synonymous with the two-terminal method except that the measurement terminals are different, and the measurement results are almost the same.

As described above, the functional film (I) and the functional film (II) of the present disclosure can be produced only by irradiating ultraviolet rays at room temperature without heating, and therefore, they are heated in addition to conductive metal particles and the like. Therefore, carbon nanotubes, carbon black, and the like, which are conductive materials that are easily deteriorated, can also be preferably used.
When the composition for forming a functional film contains a conductive material, the content of the conductive material is 0.1 part by mass to 10 parts by mass with respect to 1 part by mass of titanium atom or silicon atom contained in the composition for forming a functional film. It is preferably parts by mass, and more preferably 1 part to 5 parts by mass.

(Surfactant)
The composition for forming a functional film can contain a surfactant. When the composition for forming a functional film contains a surfactant, the coating surface property can be improved at the time of forming the composition layer (I) or the composition layer (II). Further, when the composition for forming a functional film contains a solid component such as the conductive material described above, the dispersibility of the solid component is further improved by containing the surfactant.

[11. Functional membrane laminate]
The functional film laminate of the present disclosure (hereinafter, may be simply referred to as a laminate) is a functional film laminate having a base material and at least one of the above-mentioned functional films on the base material. Is.
That is, the laminate of the present disclosure has a base material and at least one of the functional film (I) and the functional film (II) on the base material.
Since the functional film (I) or the functional film (II) of the present disclosure does not require heating and can be produced only by irradiation with ultraviolet rays at room temperature, the laminate in the functional film laminate may be a metal substrate or the like. In addition, a laminated body can be formed by using a base material having low heat resistance.

(Base material)
The base material of the laminate is not particularly limited, and either an inorganic base material or an organic base material can be used.
The base material is a base material selected from the group consisting of a fluorine-doped tin oxide (FTO) substrate, an indium-doped tin oxide (ITO) base material, a resin base material, a blue plate glass base material, a metal base material, and a ceramic base material. be able to.
Among them, a fluorine-doped tin oxide (FTO) substrate, an indium-doped tin oxide (ITO) substrate, a resin substrate, etc., which are known as a substrate having low heat resistance and are difficult to form a metal film, were used. In some cases, the effect of this disclosure can be said to be significant.

The functional film (I) of the present disclosure is useful as a protective film (ultraviolet protective film) from ultraviolet rays such as a resin material because it has good visible light transmittance, excellent transparency, and high ultraviolet shielding property.
Further, since the surface has good hydrophilicity, it can be applied to various applications requiring an antifogging function. Among them, since it has good light transmission, resin protection, and anti-fog property, it is useful as a protective layer for vehicle lights, lighting fixtures used outdoors, and its versatility.

The film thickness of the functional film (I) can be appropriately selected depending on the intended purpose. When the functional film (I) is applied to an ultraviolet protective film of a molded product made of a resin material, it can be, for example, in the range of 10 nm to 1 μm, preferably in the range of 100 nm to 1 μm. When the functional film (I) is applied to an ultraviolet protective film that requires transparency, it can be in the range of, for example, 10 nm to 1 μm, preferably in the range of 50 nm to 300 nm.
When the functional film (I) is applied to an application for imparting an antifogging function to a vehicle light, a lighting fixture, or the like, it can be in the range of, for example, 10 nm to 1 μm, preferably in the range of 50 nm to 300 nm. ..
The film thickness of the functional film can be measured by a known method. Measurement methods include non-contact optical measurement methods such as ellipsometers and reflection spectroscopic film thickness meters, stylus step meters, three-dimensional shape measuring instruments, interatomic force microscopes (AMFs), and field emission scanning electron microscopes (Field Emissions). -A contact-type measurement method such as cross-sectional observation by electron microscopy such as Scanning Electron Microscope (FE-SEM) can be mentioned.
In the present disclosure, a method of observing and measuring a cross section by FE-SEM and a method of measuring using a stylus type step meter DEKTAK-3 (Veeco) are adopted according to the characteristics of the film.

The functional film (II) of the present disclosure is useful as a protective film for various substrates because it has good visible light transmittance, excellent transparency, and good adhesion to various substrates such as glass substrates. Is. Further, it can be applied to a transparent conductive film containing a conductive material such as carbon nanotube, a lithium solid electrolyte membrane containing a lithium compound such as _{LiPF 6, and the like.}
The film thickness of the functional film (II) can be appropriately selected depending on the intended purpose. When the functional film (II) is applied to a protective film of various substrates such as those described in glass, it can be in the range of 10 nm to 1 μm, preferably in the range of 50 nm to 300 nm. When the functional film (II) is applied to a transparent isoelectric film, it can be in the range of 10 nm to 1 μm, preferably in the range of 50 nm to 300 nm.
When the functional membrane (II) is applied to a lithium solid electrolyte membrane application, it can be in the range of, for example, 10 nm to 1 μm, preferably in the range of 50 nm to 800 nm.

Hereinafter, the functional membrane of the present disclosure will be specifically described with reference to examples thereof together with a method for producing the same, but the present disclosure is not limited to the following examples, and various modified examples are used as long as the gist is not exceeded. Can be carried out.

[Example 1]
(Production of composition for forming functional film (I))
1. 1. Synthesis of butylammonium hydrogen oxalate hemihydrate 19.6 g (156 mmol (mmol)) of oxalic acid and 11.4 g (156 mmol) of butylamine were added to 100 mL of ethanol and refluxed for 1 hour. The solution was cooled to room temperature, and the resulting white powder was filtered under reduced pressure to isolate it, and then air-dried overnight (12 hours) to obtain butylammonium hydrogen oxalate hemihydrate.

2. 2. Functionality (I) Preparation of Membrane-Forming Composition In 5.00 g of ethanol, 1.13 g (3.96 mmol) of Ti (IV) isopropoxide and half butylammonium hydrogen oxalate obtained above were added. 1.37 g (7.92 mmol) of hydrate was added, and the mixture was refluxed for 3 hours. The solution was then cooled to room temperature to give a mixture. Further, 0.44 g (3.96 mmol) of 31 mass% hydrogen peroxide solution was added to the obtained mixture, and the mixture was refluxed for 0.5 hours to obtain a composition for forming a functional membrane (I). ^{The concentration of Ti 4+ in} the obtained functional film (I) forming composition was 0.4 mmol / g.

(Formation of composition layer for forming functional film (I) and formation of functional film (I) by irradiation with ultraviolet rays)
100 μL (microliter) of the composition for forming the functional film (I) obtained above was dropped onto ^{a quartz glass substrate (20 × 20 mm 2) as a base material with a micropipette.}
Then, by a two-step spin coating method (first step: 500 rpm (rotation / minute, the same applies hereinafter) for 5 seconds, second step: 2000 rpm for 30 seconds), the composition layer for forming the functional film (I) is made of quartz glass. Formed on a substrate. The formed functional film (I) forming composition layer was dried at 70 ° C. for 10 minutes to form a film.
In the examples, a dried film made of a composition for forming a functional film (I) and uncured before irradiation with ultraviolet rays is referred to as a functional film precursor layer.
Then, the functional film precursor layer composed of the obtained functional film (I) forming composition was subjected to ultraviolet light (intensity: 4 mW / cm) at 254 nm in a clean bench having a humidity of 40% RH to 60% RH. ² ) was irradiated to obtain a functional membrane (I). The irradiation time was 2 hours, 4 hours, 8 hours and 16 hours. The functional membranes (I) were designated as functional membranes I ² , functional membranes I ⁴ , functional membranes I ⁸ and functional membranes I ¹⁶ , respectively, according to the ultraviolet irradiation time.

(Composition for forming functional film (I) and evaluation of each functional film (I))
1. 1. Ultraviolet Absorption of Functional Film (I) Forming Composition The absorption spectrum of the obtained functional film (I) forming composition diluted 40-fold with ethanol was measured.
The measurement was carried out using the spectrophotometer described above, using a quartz glass cell as a cell, and having an optical path length of 1 mm.
The results are shown in FIG. FIG. 1 is a graph showing an absorption spectrum of the functional film (I) forming composition obtained in Example 1.
As shown in FIG. 1, an absorption band characteristic of a central wavelength of 377 nm was observed in the wavelength range of 350 nm to 550 nm. Further, strong absorption was observed in the ultraviolet region (for example, 250 nm to 350 nm). On the other hand, absorption decreased at a wavelength of 450 nm or more, and almost no absorption was observed at a wavelength of 550 nm or more.
From this, it can be seen that the composition for forming the functional film (I) has an ultraviolet absorbing ability and has a good visible light transmittance of a wavelength of 450 nm or more.

2. 2. Functional film I ² , functional film I ⁴ , functional film I ⁸ and functional film I ^{16 on} an ultraviolet-absorbing quartz glass substrate, respectively, functional film I ² , functional film I ⁴ , and functional film I 2. The ultraviolet absorption of the laminate on which the functional film I ⁸ or the functional film I ¹⁶ was formed and the ultraviolet absorption of the quartz glass substrate were measured by the same apparatus as above.
The results are shown in FIG. ^{FIG. 2 shows a functional film in which a functional film I 2} , a functional film I ⁴ , a functional film I ⁸ or a functional film I ¹⁶ is formed on a quartz glass substrate (control example) and the quartz glass substrate, respectively. It is a graph which shows the absorption spectrum of a laminated body. As a reference example, the absorption spectrum of the untapped cured functional film precursor layer formed on the quartz glass substrate is also shown.
In FIG. 2, the absorption spectrum of the quartz glass substrate as a control example is shown by a thick solid line. In addition, as a reference example, the absorption spectrum of the uncured functional membrane precursor layer is shown by a fine solid line.

^{The absorption spectrum of the laminate having the functional film I 2} on the quartz glass substrate which is the functional film (I) laminate of the present disclosure is shown by a broken line, and the absorption spectrum of the laminate having the functional film I ⁴ is thickened. ^{The absorption spectrum of the laminated body having the functional film I 8} is shown by a broken line, and the absorption spectrum of the laminated body having the functional film I ¹⁶ is shown by a dashed line. In the graph of FIG. 2, the graphs of the absorption spectra of the laminated body having ^{the functional film I 2} and the laminated body having the functional film I ^{4 are substantially overlapped.} Therefore, the absorption spectrum of the laminated body having the functional film I ² is confirmed by ^{the graph of the absorption spectrum of the laminated body having the functional film I 4} shown by the thick broken line.

As shown in FIG. 2, it can be seen that the quartz glass substrate itself is visually transparent and has good light transmission in the ultraviolet to visible region.
It was confirmed that each laminate having the functional film (I) of the present disclosure absorbs light in the ultraviolet region having a wavelength shorter than about 275 nm, and the light transmittance in the wavelength in the visible light region exceeds 80%. Was done.
From the comparison between the reference example and the absorption spectrum of each functional membrane (I) laminate, the functional membrane (I) having short wavelength ultraviolet absorption can be obtained by irradiating the functional membrane precursor layer with ultraviolet rays. It turns out that it can be done.

Further, when the refractive index of each functional film (I) laminate was measured using a laser ellipsometer (MARY-102: trade name, Fibrabo Co., Ltd.), the functional membrane I ² laminate, functionality It was confirmed that the refractive index of all of the Membrane I ⁴ laminate, the Functional Membrane I ⁸ laminate, and the Functional Membrane I ^{16 laminate was in the range of 1.78 to 1.79.}

3. 3. The composition layer for forming the functional film (I) ^{and the XRD pattern of the functional film I 2} , the functional film I ⁴ , the functional film I ⁸ and the functional film I ¹⁶ The composition for forming the functional film (I). The layer (the above-mentioned functional film precursor layer which is an uncured film after drying and before irradiation with ultraviolet rays), the functional film I ² , the functional film I ⁴ , the functional film I ⁸ and the like. The functional membrane I ¹⁶ was analyzed by X-ray division (XRD). The device is as shown below.
The obtained XRD pattern is shown in FIG. Data of a quartz glass substrate as a control example (described as "Quarts glass" in FIG. 3) is also shown. In FIG. 3, F ₀ represents the XRD pattern of the functional film precursor layer composed of the composition layer for forming the functional film (I), F ₂ represents the XRD pattern of the functional film I ² , and F ₄ represents the function. The XRD pattern of the sex membrane I ⁴ _{is represented, F 8} represents the XRD pattern of the functional membrane I ⁸ _{, and F 16} represents the XRD pattern of the functional membrane I ¹⁶ .
As shown in FIG. 3, no obvious peak was observed other than the halo peak of the quartz glass substrate. Therefore, the composition layer for forming the functional film (I), the functional film I ² , the functional film I ⁴ , It can be seen that both the functional film I ⁸ and the functional film I ^{16 are amorphous.}

4, a functional film I ratio functional film I ⁴ of each element was calculated from the XPS spectrum of ^4, was analyzed by X-ray photoelectron spectroscopy (X-ray Photoelectron Spectroscopy), were measured by the following methods XPS spectra.
The XPS spectrum was measured using a photoelectron spectrometer JPS-9030 (trade name: manufactured by JEOL Ltd.) and Mg Kα (1253.6 eV) rays as an X-ray source.
From analysis results, the XPS spectrum of functional film I ^4, 5 one element: at Ti, O, C, N, and the ratio of the relative element calculated from each peak area and the sensitivity factor of Si, molar basis , Ti: 12.0%, O: 53.8%, C: 32.5%, N: 0.9% and Si: 0.9%. The O / Ti ratio of the Ti—O bond having a binding energy of 528.4 eV was calculated to be about 1.53, and the content of oxygen atoms per 1 mol of titanium atoms was 1.53 mol.

5. Evaluation of the film thickness and film hardness of the functional film I ² , the functional film I ⁴ , the functional film I ⁸ and the functional film I ¹⁶ ^{The obtained functional film I 2} , the functional film I ⁴ , and the functional film The surfaces and sides of I ⁸ and the functional membrane I ¹⁶ were observed with a field emission scanning electron microscope (FE-SEM). FIG. 4 is a surface image and a cross-sectional image of the functional film (I) obtained in Example 1 observed by FE-SEM, and FIG. 4A is a surface image and a cross-sectional image of the functional film I ^2. b) is a surface image and a cross-sectional image of the ^{functional film I 4} , (c) is a surface image and a cross-sectional image of the ^{functional film I 8} , and (d) is a surface image and a cross-sectional image of the ^{functional film I 16.} Is.
From the surface image of each functional film (I), it was observed that fine particles containing titanium of 10 nm to 20 nm were densely packed, and no cracks were confirmed from the surface image.
The film thicknesses measured from the cross-sectional images were functional film I ² : 170 nm, functional film I ⁴ : 170 nm, functional film I ⁸ : 160 nm, and functional film I ¹⁶ : 160 nm, respectively.
The pencil hardness of the surface of the functional film ^{is 6H for all of the functional film I 2} , the functional film I ⁴ , the functional film I ⁸ and the functional film I ¹⁶ :, which means that the surface is hard. all right.

6. Pure water contact angle of functional membrane I ² , functional membrane I ⁴ , functional membrane I ⁸ and functional membrane I ¹⁶ Pure water contact angle of each functional membrane (I) at 25 ° C. by the method described above. Was measured.
The measurement was performed before irradiation with ultraviolet rays (functional membrane precursor layer), immediately after irradiation with ultraviolet rays (UV light of 254 nm, intensity: 4 mW / cm ² , irradiation time: 10 minutes) (0 hr), and dark for 1 hour after irradiation with ultraviolet rays. After leaving it in the place (1 hr), it went.
Further, as the comparative functional membrane, the contact angle of the functional membrane precursor layer and the pure water immediately after irradiation with ultraviolet rays was similarly measured for the titanium dioxide film (Ti: O molar ratio of 1: 2).
After leaving it in a dark place for 1 hour, it was irradiated with ultraviolet rays again under the same conditions, and then the pure water contact angle was measured again (in the table, "immediately after re-irradiation with ultraviolet rays" is described). The results are shown in Table 1 below.

It can be seen that all of the functional membranes (I) obtained in Example 1 have better hydrophilicity than the titanium dioxide membrane (Ti: O molar ratio of 1: 2) which is a comparative functional membrane. ..
Further, it can be seen that the hydrophilicity is remarkably improved by irradiating the functional membrane with ultraviolet rays again. That is, it can be seen that when each functional film is left in a dark place, the hydrophilicity is slightly lowered with time, but the hydrophilicity is further improved by irradiating with ultraviolet rays again. Therefore, when the functional membrane of the present disclosure is placed in an environment exposed to ultraviolet rays, it can be expected that the highly hydrophilic state will continue.

[Example 2]
(Production of composition for forming functional membrane (II-CTN))
In Example 2, a functional film (II) containing carbon nanotubes was prepared and evaluated. The functional membrane (II) containing carbon nanotubes is referred to as a functional membrane (II-CTN), and the composition for producing the functional membrane (II-CTN) is a composition for forming a functional membrane (II-CTN). It is called.

1. 1. Preparation of Composition for Forming Functional Membrane (II-CTN) To 10.0 g of ethanol, 1.3 g of tetraethyl orthosilicate (TEOS) and 1.1 g of oxalic acid were added, and the mixture was refluxed for 1 hour and Si ^4+. A silicic acid complex solution containing 0.5 mmol / g was obtained.
Then, the mass ratio of carbon (C) and silicon (Si) of the aqueous dispersion of carbon nanotubes (MWCNT aqueous solution, MWNT-INK) diluted 20-fold with pure water to the obtained silicic acid complex solution was 8. A composition for forming a functional film (II-CTN) was obtained by adding an amount of 1: 1. That is, carbon and Si ^{4+ contained in the obtained composition for forming a functional film (II-CTN)} The content ratio of C: Si 4+ = 8: 1 in ^{terms of mass ratio.}

(Formation of a composition layer for forming a functional film (II-CTN) and formation of a functional film (II-CTN) by irradiation with ultraviolet rays)
100 μL (microliter) of the functional film (II-CTN) forming composition obtained above was dropped onto ^{a quartz glass substrate (20 × 20 mm 2) as a base material with a micropipette.}
Then, a composition layer for forming a functional film (II-CTN) was formed on a quartz glass substrate by a two-step spin coating method (first step: 500 rpm for 5 seconds, second step: 2000 rpm for 30 seconds). It was dried at 70 ° C. for 10 minutes to form this functional membrane (II-CTN) precursor layer.
The obtained functional membrane (II-CTN) precursor layer was irradiated with ultraviolet rays at the same wavelength and intensity as in Example 1 for 6 hours to obtain a functional membrane (II-CTN).

(Evaluation of functional membrane (II-CTN))
1. 1. Film Thickness Measurement The film thickness of the obtained functional film (II-CTN) was measured using DEKTAK-3 (Sloan). The measurement was performed by a stylus method in which a diamond probe having a tip radius of 2.5 μm was used to scan 3000 μm. The step difference from the surface of the base material produced by masking was measured at 5 points, and the average value of 3 points excluding the maximum and minimum was taken as the film thickness. The resolution is 10 nm. As a result, the thickness of the film was 100 nm.

2. 2. Electrical resistance The electrical resistance of the membrane measured by the two-probe resistance method of the functional membrane (II-CTN) was 3.73 MΩcm.
The electric resistance value by the two-probe resistance method was measured using a digital multimeter (Iwatsu Electric Co., Ltd .: former Iwatsu Electric Co., Ltd., VOAC7523H: trade name). Five points were measured at a distance of 1 cm between the two probes, and the average value of the three points excluding the minimum and maximum values was taken as the electrical resistance value.
As a result of the measurement, it can be seen that the functional membrane (II-CTN) has good electrical conductivity.
The electric resistance of the film measured by a two-probe resistance method is that it is 3.73Emuomegacm, it is clear that at 10 ⁶ [Omega] cm or less in electric resistance was measured by four-point probe method.

3. 3. Evaluation of Light Transparency Using the above-mentioned device, the wavelength range of 200 nm to 1100 nm was measured using quartz glass as a control example.
As a result, the transmittance in the ultraviolet light region of less than 450 nm is 80% or more, the transmittance in the visible light region of 450 nm or more is 90% or more, and the functional film (II-CTN) is ultraviolet light and visible light. It can be seen that the transmittance of the light is excellent.
From the above evaluation, it can be seen that the functional film (II-CTN) is a transparent electrically conductive film having excellent transparency of ultraviolet light and visible light.

[Example 3]
(Production of composition for forming functional film (II-Li))
In Example 3, a functional film (II) _{containing LiPF 6} was prepared and evaluated. The _{functional film (II) containing LiPF 6} is referred to as a functional film (II-Li), and the composition for producing the functional film (II-Li) is a composition for forming the functional film (II-Li). Called a thing.
1. 1. Preparation of Composition for Forming Functional Membrane (II-Li) To 10.0 g of ethanol, 1.3 g of tetraethyl orthosilicate (TEOS) and 1.1 g of oxalic acid were added, refluxed for 1 hour, and Si. A mixed solution containing 0.5 mmol / g of ^{4+ was obtained.}
_{Then, 0.05 g of LiPF 6} powder was mixed with 2.2 g of the obtained mixed solution to obtain a composition for forming a functional film (II-Li) having ^{a Li + ion concentration of 0.15 mmol / g.} ..

(Formation of a composition layer for forming a functional film (II-Li) and formation of a functional film (II-Li) by irradiation with ultraviolet rays)
First, an FTO glass substrate (manufactured by AGC) is etched with zinc and hydrochloric acid to mask areas other than the etched region, and 25 μL of the functional film (II-Li) forming composition obtained above is applied to FTO glass. Dropped onto the substrate.
Then, a composition layer for forming a functional film (II-Li) was formed on the FTO substrate by a two-step spin coating method (first step: 500 rpm for 5 seconds, second step: 2000 rpm for 30 seconds).
The film made of the composition for forming the functional film (II-Li) is irradiated with ultraviolet rays at the same intensity as in Example 1 for 2 hours and 16 hours to obtain the functional film (II-Li) ² and the functionality. Membrane (II-Li) ¹⁶ was obtained.

(Evaluation of functional membrane (II-Li))
The ionic conductivity of the functional membrane (II-Li) ² and the functional membrane (II-Li) ¹⁶ measured by an impedance analyzer was 10 ^-4 Scm ^-1 and 10 ^-3 Scm ^-1 , respectively. ..
According to the method for producing a functional membrane of the present disclosure, it can be seen that wiring of a lithium solid electrolyte membrane can be formed on an FTO glass substrate without heating.

The disclosure of Japanese Patent Application 2019-156070 filed on August 28, 2019 is incorporated herein by reference.
All documents, patent applications, and technical standards described in this disclosure are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated by reference during disclosure.

Claims

A functional film containing amorphous titanium oxide,
A functional film in which the content of oxygen atoms per 1 mol of titanium atoms contained in the functional film is in the range of 0.5 mol to 1.9 mol.
The function according to claim 1, wherein the pure water contact angle of the surface measured at 25 ° C. after irradiation with ultraviolet rays under the conditions of ultraviolet light having a wavelength of 254 nm, intensity: 4 mW / cm 2, and irradiation time: 10 minutes is 10 ° or less. Sex membrane.
The ultraviolet transmittance of a wavelength of 350 nm or less is 10% or less, the near-ultraviolet transmittance of a wavelength of more than 350 nm and 400 nm or less is less than 80%, and the visible light transmittance of a wavelength of more than 400 nm and 750 nm or less is 80% or more. The functional membrane according to claim 1 or 2.
A functional film containing amorphous silicon oxide,
A functional film in which the content of oxygen atoms per 1 mol of silicon atoms contained in the functional film is in the range of 1.0 mol or more and less than 2.0 mol.
The functional film according to claim 4, which is a protective film for the base material.
Further, a conductive material selected from the group consisting of carbon nanotubes, carbon black, and conductive metal particles is contained in an amount of 0.1 part by mass to 10 parts by mass with respect to 1 part by mass of titanium or silicon contained in the functional film. ,
Four probe electrical resistance value measured by the probe method is functional film according to any one of claims 1 to 5 is 10 6 [Omega] cm or less.
The functional membrane according to claim 4, further containing a lithium compound and being a lithium solid electrolyte membrane.
With the base material
A functional film laminate having the functional film according to any one of claims 1 to 7 on the substrate.
8. The base material is a base material selected from the group consisting of a fluorine-doped tin oxide base material, an indium-doped tin oxide base material, a resin base material, a blue plate glass base material, a metal base material, and a ceramic base material. The functional film laminate according to.
A composition for forming a functional film containing a solvent containing alcohol and an anionic titanium complex or an anionic silicon complex.
The functional film-forming composition according to claim 10, wherein the anionic titanium complex or anionic silicon complex is a complex having oxalic acid or ethylenediaminetetraacetic acid as a ligand.
A step of mixing a solvent containing an alcohol, at least one selected from the group consisting of an oxalic acid compound, an amine compound and an aminocarboxylic acid, and a titanium compound or a silicon oxide compound to obtain a mixture, and
A method for producing a composition for forming a functional film, which comprises a step of adding water or hydrogen peroxide to the obtained mixture and refluxing the mixture.
A step of applying the functional film-forming composition according to claim 10 or 11 to a substrate to form a functional film-forming composition layer, and
A functional film laminate including a step of irradiating the functional film-forming composition layer formed on a substrate with ultraviolet rays to remove organic substances from the functional film-forming composition to obtain a functional film. Production method.