WO2019239808A1

WO2019239808A1 - Photocatalyst composite material, display protection member for signage, protective member for touch panel, protective member for solar cell, protective member for sensor cover, display for signage, touch panel, solar cell, and sensor cover

Info

Publication number: WO2019239808A1
Application number: PCT/JP2019/019960
Authority: WO
Inventors: 安永　正; 英宏望月; 彰洋朝倉; 裕之八重樫
Original assignee: 富士フイルム株式会社
Priority date: 2018-06-11
Filing date: 2019-05-20
Publication date: 2019-12-19

Abstract

Provided is a photocatalyst composite material comprising: a photocatalyst layer containing titanium oxide particles and an amorphous titanium peroxide-type inorganic binder; and an inorganic particle-containing layer containing inorganic particles and a siloxane resin including an organic structure. The number average particle size of the inorganic particles is 5-100 nm and the film thickness of the inorganic particle-containing layer is 50-250 nm. Also provided are a display protection member for signage, a protective member for a touch panel, a protective member for a solar cell, a protective member for a sensor cover, a display for signage, a touch panel, a solar cell, and a sensor cover that contain the photocatalyst composite material.

Description

Photocatalyst composite material, signage display protective member, touch panel protective member, solar cell protective member, sensor cover protective member, signage display, touch panel, solar cell, and sensor cover

The present disclosure relates to a photocatalyst composite material, a signage display protective member, a touch panel protective member, a solar cell protective member, a sensor cover protective member, a signage display, a touch panel, a solar cell, and a sensor cover.

In recent years, for the purpose of imparting functions such as antifouling, antibacterial, antiviral, deodorant, and antifungal, forming a layer containing a photocatalytic material on the surface of glass, resin, etc. has been studied and partially put into practical use. .

Japanese Patent Application Laid-Open No. 9-262481 discloses a method for producing a photocatalyst comprising a catalyst supported on a substrate and using the photocatalyst and an amorphous titanium peroxide sol. Has been.
Japanese Patent Laid-Open No. 2002-88276 discloses that anatase-type titanium oxide fine particles are contained in an aqueous solution containing a peroxide group-containing amorphous titanium oxide in a range of 0.5 wt% to 2.0 wt% (in terms of titanium oxide) in an amount of 0.025 wt%. There is described an antifouling coating agent characterized in that it is contained in a range of 1.2 wt% or less and a silicone surfactant is contained in a range of 0.01 wt% or more and less than 0.8 wt%. .
Japanese Patent Application Laid-Open No. 2003-55580 describes a water-based paint characterized by containing fine particles of a titania-based peroxo compound, peroxotitanic acid, and silica fine particles.
Japanese Unexamined Patent Application Publication No. 2013-104035 describes a titanium oxide coating solution containing at least the following components.
(A) Titanium oxide particles (B) Peroxotitanic acid (C) chelating agent as binder component (D) Water (E) Alcohol

In addition, formation of a functional layer on the layer containing the photocatalytic material has also been studied.
JP 2010-99651 A discloses a composite material manufacturing method in which a photocatalyst layer and a functional layer are formed on the surface of a base material, and after forming a photocatalyst layer containing a photocatalyst on the surface of the base material, Forming a functional layer containing an organic substance decomposable with a photocatalyst on the surface; activating the photocatalyst in the photocatalyst layer by irradiating the functional layer with light; and decomposing the organic substance in the functional layer; And a method for producing a composite material, wherein the functional layer has an organic content of 10 to 40% by mass.
In International Publication No. 2002/100494, a photocatalyst film is formed on the surface of a substrate, and a hydrophilic substance film is formed on the surface of the antifogging element. An anti-fogging element using a coating agent obtained by allowing hydrogen peroxide to act on titanium oxide gel (ortho titanic acid) or dispersing photocatalyst particles in a titanium oxide solution is described.

In recent years, it has been studied to form a functional layer on the surface of a substrate such as glass or resin in order to impart functions such as an antireflection function, a hard coat function such as scratch resistance, and a hydrophilic function.

Japanese Patent Application Laid-Open No. 2014-111717 discloses an aqueous composition in which an epoxy group-containing alkoxysilane, an epoxy group-free alkoxysilane, and a metal complex are mixed, and the epoxy group-containing alkoxysilane and the epoxy group-free The proportion of the epoxy group-containing alkoxysilane is 20 to 85% by mass with respect to the total alkoxysilane composed of alkoxysilane, and the proportion of the metal complex to the epoxy group-containing alkoxysilane is 17 to 70 mol%. An aqueous composition is described.

The inventors added the function of the functional layer by forming the functional layer described above on the layer containing the photocatalytic material as described in JP 2010-99651 A or WO 2002/100654. In this case, it has been found that the photocatalytic activity may decrease.

A problem to be solved by an embodiment according to the present disclosure is a photocatalyst composite material that is excellent in photocatalytic activity on the surface on the inorganic particle-containing layer side and that is provided with a function of the inorganic particle-containing layer, and a signage including the photocatalyst composite material Display protective member, Touch panel protective member including the photocatalyst composite material, Solar cell protective member including the photocatalyst composite material, Sensor cover protective member including the photocatalyst composite material, Signage including the signage display protective member It is to provide a display, a touch panel including the touch panel protection member, a solar cell including the solar cell protection member, or a sensor cover including the sensor cover protection member.

Means for solving the above problems include the following aspects.
<1> a photocatalyst layer containing titanium oxide particles and an amorphous titanium peroxide type inorganic binder;
A siloxane resin containing an organic structure, and an inorganic particle-containing layer containing inorganic particles,
The number average particle diameter of the inorganic particles is 5 nm to 100 nm,
A photocatalyst composite material, wherein the inorganic particle-containing layer has a thickness of 50 nm to 250 nm.
<2> The photocatalyst composite material according to <1>, wherein the titanium oxide particles are anatase-type titanium oxide particles.
<3> The photocatalytic composite material according to <1> or <2>, wherein the organic structure in the siloxane resin containing the organic structure is a crosslinked structure.
<4> The photocatalyst composite material according to any one of <1> to <3>, wherein the inorganic particle-containing layer is a layer formed by curing a composition containing an alkoxysilane compound and inorganic particles.
<5> The photocatalyst composite material according to <4>, wherein the alkoxysilane compound includes an epoxy group-containing alkoxysilane compound and an epoxy group-free alkoxysilane compound.
<6> The photocatalyst composite material according to any one of <1> to <5>, wherein the inorganic particles contain at least one kind of particles selected from the group consisting of silica, alumina, and zirconia.
<7> The photocatalyst composite material according to any one of <1> to <6>, further including a base material layer on the opposite side of the photocatalyst layer from the inorganic particle-containing layer.
<8> A signage display protection member comprising the photocatalyst composite material according to any one of the above items <1> to <7>.
<9> A touch panel protective member comprising the photocatalyst composite material according to any one of the above items <1> to <7>.
<10> A solar cell protective member comprising the photocatalyst composite material according to any one of the above items <1> to <7>.
<11> A sensor cover protective member comprising the photocatalyst composite material according to any one of the above items <1> to <7>.
<12> A signage display comprising the signage display protection member according to <8>.
<13> A touch panel comprising the touch panel protective member according to <9>.
<14> A solar cell comprising the solar cell protective member according to <10>.
<15> A sensor cover including the sensor cover protective member according to <11>.

According to the embodiment according to the present disclosure, a photocatalyst composite material having excellent photocatalytic activity on the surface on the inorganic particle-containing layer side and having the function of the inorganic particle-containing layer added, and a signage display protection member including the photocatalyst composite material , A touch panel protective member including the photocatalyst composite material, a solar cell protective member including the photocatalyst composite material, a sensor cover protective member including the photocatalyst composite material, a signage display including the signage display protective member, and the touch panel A touch panel including the protective member for a solar cell, a solar cell including the solar cell protective member, or a sensor cover including the sensor cover protective member can be provided.

Hereinafter, the contents of the present disclosure will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.
In the present disclosure, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical description. . Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
In the present disclosure, “(meth) acryl” is a term used in a concept including both acryl and methacryl, and “(meth) acryloyl” is a term used as a concept including both acryloyl and methacryloyl. is there.
In the present disclosure, the term “process” is included in the term as long as the intended purpose of the process is achieved, even when the process is not clearly distinguished from other processes.
In the present disclosure, the amount of each component of the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when a plurality of substances corresponding to each component are present in the layer.
In the present disclosure, unless otherwise specified, the molecular weight in the polymer component is a polystyrene-reduced weight average molecular weight (Mw) or number average molecular weight measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. (Mn).
In the present disclosure, a combination of preferable embodiments is a more preferable embodiment.

(Photocatalyst composite)
The photocatalyst composite material according to the present disclosure includes a photocatalyst layer including titanium oxide particles and an amorphous titanium peroxide type inorganic binder, and a siloxane resin including an organic structure and an inorganic particle containing layer including inorganic particles, and The number average particle diameter of the inorganic particles is 5 nm to 100 nm, and the film thickness of the inorganic particle-containing layer is 50 nm to 250 nm.

The photocatalyst composite material according to the present disclosure has excellent photocatalytic activity on the surface on the inorganic particle-containing layer side, and has a function added by the inorganic particle-containing layer.
The details of the estimation mechanism that can obtain the above effect are estimated as follows.
The photocatalyst layer according to the present disclosure includes titanium oxide particles and an amorphous titanium peroxide type inorganic binder.
The present inventors show that the photocatalytic layer containing an amorphous titanium peroxide type inorganic binder exhibits higher photocatalytic activity than the photocatalytic layer comprising titanium oxide particles and an organic binder type binder. It confirmed by the experiment which compares. For this reason, the photocatalyst layer concerning this indication takes the above-mentioned composition.
When the photocatalyst layer according to the present disclosure is irradiated with, for example, ultraviolet rays, radicals (hydroxy radicals, superoxide anion radicals, etc.) are generated by the photocatalytic action of the titanium oxide particles. It is known that effects such as odor and mold prevention can be obtained. In the present disclosure, the excellent effects of antifouling, antibacterial, antiviral, deodorant, antifungal and the like are also referred to as “excellent photocatalytic activity”.
The inorganic particle-containing layer according to the present disclosure is used as a functional layer. The functional layer is used as an antireflection layer, a hard coat layer, etc. depending on the film thickness and composition, and has a function of improving antireflection properties, scratch resistance, thermal conductivity, chemical resistance, etc. .
Here, if the functional layer using the material used for the conventional antireflection layer, hard coat layer, etc. is simply laminated on the conventional photocatalyst layer, the functional layer surface of radicals probably generated in the photocatalyst layer In some cases, the photocatalytic activity on the surface on the functional layer side may be reduced due to a problem related to migration to the surface.
The degree of decrease in photocatalytic activity varies depending on the material, film structure, film thickness, etc. of the functional layer.
The mechanism by which the decline occurs is probably not simple and involves multiple physical processes. Therefore, the inventors have experimentally confirmed suitable parameters and configurations for each material, the photocatalyst layer is an inorganic binder-type photocatalyst layer, the functional layer is an inorganic particle-containing layer, and the inorganic particle-containing layer It was found that the decrease in the photocatalytic activity can be solved by appropriately selecting the particle diameter of the inorganic particles contained in the film and the film thickness of the inorganic particle-containing layer.
That is, the present inventors include a specific photocatalyst layer of an inorganic binder type, a siloxane resin containing an organic structure, and inorganic particles, the number average particle diameter of the inorganic particles being 5 nm to It has been found that it is effective to provide a photocatalyst composite material including an inorganic particle-containing layer having a thickness of 100 nm and a thickness of 50 nm to 250 nm.
This is probably because the inorganic particle-containing layer has a porous structure so that radicals generated in the above-mentioned photocatalyst layer pass through the pores of the inorganic particle-containing layer and the inorganic particle-containing layer side of the photocatalyst composite material. It is assumed that this is because high photocatalytic activity can be maintained by reaching the surface.

<Photocatalyst layer>
The photocatalyst composite material according to the present disclosure includes titanium oxide particles and an amorphous titanium peroxide type inorganic binder.

[Titanium oxide particles]
The titanium oxide particles used in the present disclosure are particles having photocatalytic activity.
The titanium oxide particles in the present disclosure may be any crystal form of rutile, anatase, and brookite, but are preferably anatase from the viewpoint of photocatalytic activity.

The shape of the titanium oxide particles in the present disclosure is not particularly limited, but is preferably substantially spherical.
The number average particle diameter of the titanium oxide particles in the present disclosure is preferably 2 nm to 200 nm, and more preferably 5 nm to 50 nm.
In the present disclosure, unless otherwise specified, the number average particle size is SU-8030 FE-SEM manufactured by Hitachi High-Technologies Corporation (field emission scanning electron microscope, acceleration voltage 2 kV, acquisition of secondary electron image) ) To calculate.
Specifically, the dispersed particles are observed by FE-SEM, the projected area of the particles is obtained from the obtained photograph, the equivalent circle diameter is obtained therefrom, and this is used as the primary particle size. The number average particle diameter in the present disclosure can be calculated as an arithmetic average value of the equivalent circle diameter (primary particle diameter) obtained by measuring the projected area of 300 or more particles.
As the titanium oxide particles in the present disclosure, a number average particle diameter may be calculated from the commercially available products by the FE-SEM, and a material having a desired particle diameter may be selected and used.

The content of titanium oxide (TiO ₂ ) in the titanium oxide particles in the present disclosure is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total mass of the titanium oxide particles, and 80 More preferably, it is more than 90 mass%, and it is especially preferable that it is 90 mass% or more.
Examples of the components other than TiO ₂ contained in the titanium oxide particles include SO ₄ and Na ₂ O, but are not limited thereto, and may contain other components.

The content of the titanium oxide particles in the present disclosure is preferably 5% by mass to 95% by mass and more preferably 10% by mass to 90% by mass with respect to the total mass of the photocatalyst layer.
In addition, the photocatalyst layer in the present disclosure may contain one kind of titanium oxide particles or two or more kinds of titanium oxide particles.

[Amorphous titanium peroxide type inorganic binder]
The photocatalytic layer in the present disclosure includes an amorphous titanium peroxide type inorganic binder.
The amorphous titanium peroxide type inorganic binder is an amorphous binder containing a Ti—O bond.
For example, the amorphous titanium peroxide type inorganic binder is preferably obtained by heating peroxotitanic acid.
Specifically, it is considered that by heating peroxotitanic acid at 100 ° C. to 150 ° C. for several hours, oxygen atoms or hydroxyl groups are desorbed from peroxotitanic acid to obtain titanium oxide. However, since the heating temperature is low, the titanium oxide does not crystallize and is considered to exist as amorphous titanium oxide (amorphous titanium peroxide).
In the present disclosure, such amorphous titanium oxide is referred to as an amorphous titanium peroxide type inorganic binder.
In the present disclosure, an anatase phase may be formed on at least part of amorphous titanium oxide by increasing the heating temperature of peroxotitanic acid, increasing the heating time, or the like.
The peroxotitanic acid is not particularly limited, but can be obtained by allowing hydrogen peroxide to act on titanium hydroxide (orthotitanic acid).
Titanium hydroxide is obtained, for example, by reaction of titanium tetrachloride with a base.
As a method for obtaining peroxotitanic acid and titanium hydroxide, the disclosure of JP-A-9-262481 can also be referred to.

The content of the amorphous titanium peroxide type inorganic binder is preferably 5% by mass to 95% by mass and more preferably 10% by mass to 90% by mass with respect to the total mass of the photocatalyst layer.
Moreover, the photocatalyst layer in this indication may contain an amorphous titanium peroxide type inorganic binder individually by 1 type, and may use 2 or more types together.

[Other ingredients]
The photocatalyst layer in the present disclosure may further include other components.
As other components, known additives such as surfactants are used without particular limitation.

[Film thickness]
Although the film thickness of a photocatalyst layer is not specifically limited, From a viewpoint of photocatalytic activity, it is preferable that it is 50 nm or more, It is more preferable that it is 100 nm or more, It is further more preferable that it is 200 nm or more.
The film thickness is preferably 2000 nm or less, and more preferably 1000 nm or less, from the viewpoint of suppressing the occurrence of cracks or poor adhesion due to an increase in shrinkage stress during coating film formation.

[Method for producing photocatalyst layer]
The photocatalyst layer in the present disclosure can be obtained by applying the composition for forming a photocatalyst layer to, for example, a substrate described later and heating.
The composition for forming a photocatalyst layer preferably contains the above-described titanium oxide particles and peroxotitanic acid.
As an example, the composition for forming a photocatalyst layer is prepared by adding and dispersing titanium oxide particles in a composition containing peroxotitanic acid and a solvent.
As the composition containing peroxotitanic acid and a solvent, a commercially available product can be used. For example, Tio Sky Coat A liquid (Tio Systems Co., Ltd.) can be used.
Moreover, in order to make the film thickness of a photocatalyst layer into the above-mentioned range, you may employ | adopt methods, such as performing the application | coating and heating of the composition for photocatalyst layer formation several times, etc. to thicken the composition for photocatalyst layer formation. .
The coating method of the composition for forming a photocatalyst layer is not particularly limited, and a known method may be used. Examples thereof include slit coating, spin coating, curtain coating, and inkjet coating.
A method for heating the composition for forming a photocatalyst layer is not particularly limited, and a known method may be used. Examples thereof include a method using a heating means such as a heater, an oven, a hot plate, an infrared lamp, and an infrared laser.
What is necessary is just to adjust a heating time and heating temperature suitably as a heating time and heating temperature in manufacture of the above-mentioned amorphous titanium peroxide type | mold inorganic binder.

In order to increase the adhesion between the photocatalyst layer and the base material layer, an easy adhesion layer described later may be provided between the inorganic particle-containing layer and the base material layer.

<Inorganic particle content layer>
The inorganic particle-containing layer includes a siloxane resin having an organic structure and inorganic particles.
When the inorganic particle-containing layer is a hard coat layer described later, the inorganic particle-containing layer is preferably the outermost layer in the photocatalyst composite material according to the present disclosure.
Moreover, when an inorganic particle content layer is an antireflection layer mentioned later, you may have protective layers, such as a well-known hard-coat layer, on an inorganic particle content layer.

[Inorganic particles]
The inorganic particle-containing layer in the present disclosure includes inorganic particles.
The inorganic particles may be crosslinked with a siloxane resin having an organic structure in the inorganic particle-containing layer.
Examples of the inorganic particles include metal oxide particles that are transparent to light having a wavelength of 350 nm from the viewpoint of photocatalytic activity.
Further, when the photocatalyst composite material according to the present disclosure is used for applications such as a show window, a touch panel, a solar cell, or a sensor cover, which will be described later, a metal oxide that is transparent to light having a wavelength of 400 nm to 700 nm. Particles are preferred.
In the present disclosure, being transparent to light of wavelength A means that the transmittance of light of wavelength A is 50% or more. The transmittance is preferably 70% or more, and more preferably 80% or more.
Further, being transparent with respect to wavelengths A to B means that the arithmetic average value of all the transmittances is 50 when the transmittance of light having a wavelength between wavelengths A and B is measured in increments of 10 nm. It means that it is more than%. The transmittance is preferably 70% or more, and more preferably 80% or more.
The transmittance is measured using a spectrophotometer “V670” (manufactured by JASCO Corporation).

As a specific example of the metal oxide particles, it is preferable to include at least one kind of particles selected from the group consisting of silica, alumina, and zirconia. In particular, from the viewpoint of crosslinkability with an alkoxysilane compound described later, it is preferable to include silica particles.
In order to improve antireflection, it is preferable to contain silica particles, to improve chemical resistance or thermal conductivity, it is preferable to include alumina particles, and to improve chemical resistance. It is preferable that zirconia particles are included.

As the silica particles, dry powdery silica produced by combustion of silicon tetrachloride can be used, but colloidal silica in which silicon dioxide or a hydrate thereof is dispersed in water is more preferably used. Although it does not specifically limit as a commercial item of a silica particle, Specifically, Nissan Chemical Industries Ltd. Snowtex series (for example, Snowtex 033) etc. are mentioned.
The number average particle size of the colloidal silica is preferably 3 nm to 50 nm, more preferably in the range of 4 nm to 50 nm, further preferably in the range of 4 nm to 40 nm, and in the range of 5 nm to 35 nm. Is particularly preferred.

The colloidal silica is more preferably adjusted to have a pH of 2 to 7 when added to the inorganic particle-containing layer forming composition described later. When the pH is 2 to 7, the stability of silanol, which is a hydrolyzate of the alkoxysilane compound, is better than when the pH is less than 2 or greater than 7, and the silanol dehydration condensation reaction is faster. An increase in the viscosity of the coating liquid due to the progress can be suppressed.

The number average particle diameter of the inorganic particles in the present disclosure is 5 nm to 100 nm, preferably 10 nm to 80 nm, and more preferably 20 nm to 40 nm.
As the inorganic particles in the present disclosure, a number average particle diameter may be calculated by using the above-mentioned FE-SEM from commercially available products, and a material having a desired particle diameter may be selected and used.
The shape of the inorganic particles in the present disclosure is not particularly limited, but is preferably substantially spherical from the viewpoint of dispersibility.

The content of the inorganic particles is preferably more than 0% by mass and 80% by mass or less, more preferably 1% by mass to 70% by mass with respect to the total mass of the inorganic particle-containing layer in the present disclosure. More preferably, the content is from mass% to 65 mass%.
The inorganic particle-containing layer in the present disclosure may contain one kind of inorganic particles or two or more kinds in combination.

[Siloxane resin containing organic structure]
The organic structure in the siloxane resin containing an organic structure is preferably a crosslinked structure.
When the organic structure is a crosslinked structure, the siloxane resins may be crosslinked with each other, or the siloxane resin and the inorganic particles may be crosslinked.
The organic structure included as the crosslinked structure is preferably a structure represented by any of the following formulas 1-1 to 1-3.

In Formula 1-1 to Formula 1-3, R ¹¹ represents a single bond, an oxygen atom, an aryleneoxy group, an aryleneoxyalkylene group, or an alkylene group, and R ¹² to R ¹⁴ each independently represent a hydrogen atom or Represents an alkyl group, and at least two of R ¹² to R ¹⁴ may be bonded to each other to form a ring structure; R ²¹ represents a single bond or an alkylene group; R ³¹ represents a single bond, alkyleneoxy; Represents a carbonyl group, an alkyleneaminocarbonyl group, an alkyleneoxy group, an oxygen atom or an arylene group, R ³² represents a hydrogen atom or an alkyl group, and ** and * each independently represent a bonding site with another structure. .

The structure represented by Formula 1-1 is formed, for example, by using an alkoxysilane compound having an epoxy group as an alkoxysilane compound described later.
In Formula 1-1, R ¹¹ is preferably an oxygen atom or an alkyleneoxyalkylene group.
In formula 1-1, it is preferable that all of R ¹² to R ¹⁴ are hydrogen atoms. Further, when at least two of R ¹² to R ¹⁴ are bonded to form a ring structure, it is preferable that R ¹² or R ¹³ and R ¹⁴ are bonded. Moreover, as said ring structure, a hydrocarbon ring is preferable and a cyclohexane ring is more preferable.
In Formula 1-1, the target to which * which is a bonding site is bonded is not particularly limited, but is preferably an Si atom or an organic group contained in the siloxane resin, and more preferably an Si atom contained in the siloxane resin. preferable.
In Formula 1-1, the target to which ** which is a bonding site is bonded is not particularly limited, but is preferably an atom contained in the siloxane resin or resin particle. As said atom, it is preferable that they are an oxygen atom or a nitrogen atom.
For example, when 3-glycidoxypropyltrimethoxysilane is used as the alkoxysilane compound, * is bonded to a Si atom, R ¹¹ is a propyleneoxy group, and R ¹² to R ¹⁴ are hydrogen atoms. In that case, for example, ** is bonded to an oxygen atom in the siloxane resin, an oxygen atom in the resin particle, a nitrogen atom in the resin particle, or the like.

The structure represented by Formula 1-2 is formed, for example, by using an alkoxysilane compound having an isocyanate group as an alkoxysilane compound described later.
In Formula 1-2, R ²¹ represents a single bond or an alkylene group, and is preferably an alkylene group having 2 to 10 carbon atoms.
In Formula 1-2, the target to which * which is a bonding site is bonded is not particularly limited, but is preferably an Si atom or an organic group contained in the siloxane resin, and more preferably an Si atom contained in the siloxane resin. preferable.
In Formula 1-2, the target to which ** which is a binding site is bonded is not particularly limited, but is preferably an atom contained in a siloxane resin or resin particles. As said atom, it is preferable that they are an oxygen atom or a nitrogen atom.
For example, when 3-isocyanatopropyltriethoxysilane is used as the alkoxysilane compound, * is bonded to an Si atom and R ²¹ is a propylene group. In that case, for example, ** is bonded to an oxygen atom in the siloxane resin, an oxygen atom in the resin particle, a nitrogen atom in the resin particle, or the like.

The structure represented by Formula 1-3 is formed, for example, by using an alkoxysilane compound having an ethylenically unsaturated group as an alkoxysilane compound described later.
In Formula 1-3, R ³¹ preferably represents an alkyleneoxycarbonyl group, an alkyleneaminocarbonyl group, or an arylene group, an alkyleneoxycarbonyl group having 2 to 10 carbon atoms, an alkyleneaminocarbonyl group having 2 to 10 carbon atoms, or phenylene More preferred is an alkyleneoxycarbonyl group having 2 to 10 carbon atoms.
In Formula 1-3, the target to which * which is a bonding site is bonded is not particularly limited, but is preferably an Si atom or an organic group contained in the siloxane resin, and more preferably an Si atom contained in the siloxane resin. preferable.
In Formula 1-3, the target to which the binding site ** binds is not particularly limited, but is preferably a structure represented by Formula 1-3.
For example, when 3-methacryloxypropylmethyldiethoxysilane is used as the alkoxysilane compound, * is bonded to the Si atom and R ³¹ is a propyleneoxycarbonyl group. In that case, for example, ** polymerizes with methacryloxy groups in other 3-methacryloxypropylmethyldiethoxysilanes.

Moreover, the siloxane resin containing an organic structure used in the present disclosure may further have a group such as an alkyl group, an amide group, a urethane group, a urea group, an ester group, a hydroxy group, or a carboxy group as the organic structure. .

From the viewpoint of long-term stability of the photocatalyst composite material, the total content of the organic structure is preferably 90% by mass or less, and more preferably 75% by mass or less.

[Inorganic particle-containing layer forming composition]
In the present disclosure, the inorganic particle-containing layer is preferably a layer formed by curing a composition containing an alkoxysilane compound and inorganic particles (hereinafter also referred to as “inorganic particle-containing layer forming composition”). .
That is, the siloxane resin containing the organic structure is preferably a condensate of an alkoxysilane compound.
The alkoxysilane compound is preferably a water-soluble or water-dispersible material from the viewpoint of reducing environmental pollution caused by VOC (volatile organic compounds).
The inorganic particle-containing layer forming composition is preferably an aqueous composition containing water as a solvent. Since both the titanium oxide particles and the amorphous titanium peroxide type inorganic binder in the photocatalyst layer have low solubility in water, the composition for forming an inorganic particle-containing layer contains water, so that the photocatalyst is formed after the formation of the photocatalyst layer. Even when the inorganic particle-containing layer forming composition is applied on the layer, mixing between layers is prevented.
Moreover, it is preferable that the composition for inorganic particle content layer formation does not contain an organic solvent substantially. In the present disclosure, “substantially free” means that the content is less than 1% by mass, and preferably less than 0.1% by mass. By substantially not containing an organic solvent, what is evaporated when the composition for forming an inorganic particle-containing layer is applied and dried is mainly a water component. For this reason, compared with the case where an organic solvent is included, the load to an environment can be reduced significantly.

Further, the alkoxysilane compound preferably includes a crosslinkable group-containing alkoxysilane compound and a crosslinkable group-free alkoxysilane compound, an epoxy group-containing alkoxysilane compound, an epoxy group-free alkoxysilane compound, It is preferable to contain.

Both the crosslinkable group-containing alkoxysilane compound and the crosslinkable group-free alkoxysilane compound have a hydrolyzable group. This hydrolyzable group is hydrolyzed in, for example, an acidic aqueous solution to produce silanol, and the silanols are condensed to produce a siloxane resin.
In the composition for forming an inorganic particle-containing layer in the present disclosure, a part of the crosslinkable group-containing alkoxysilane compound and the crosslinkable group-free alkoxysilane compound may be hydrolyzed.

-Crosslinkable group-containing alkoxysilane compound-
Examples of the crosslinkable group in the crosslinkable group-containing alkoxysilane compound include an epoxy group, an isocyanate group, and a radical polymerizable group.
Examples of the crosslinkable group-containing alkoxysilane compound include an epoxy group-containing alkoxysilane compound, an isocyanate group-containing alkoxysilane compound, a radical polymerizable group-containing alkoxysilane compound, and the like, and preferably includes an epoxy group-containing alkoxysilane compound.

<< epoxy group-containing alkoxysilane compound >>
The epoxy group-containing alkoxysilane compound is an alkoxysilane compound having an epoxy group. The epoxy group-containing alkoxysilane compound only needs to have one or more epoxy groups in one molecule, and the number of epoxy groups is not particularly limited. In addition to the epoxy group, the epoxy group-containing alkoxysilane compound may further have a group such as an alkyl group, an amide group, a urethane group, a urea group, an ester group, a hydroxy group, or a carboxy group.

Examples of the epoxy group-containing alkoxysilane compound used in the present disclosure include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, And 3-glycidoxypropyltriethoxysilane. Examples of commercially available epoxy group-containing alkoxysilane compounds include KBE-403 (manufactured by Shin-Etsu Chemical Co., Ltd.).

<< Isocyanate group-containing alkoxysilane compound >>
The isocyanate group-containing alkoxysilane compound is an alkoxysilane compound having an isocyanate group. The isocyanate group-containing alkoxysilane compound only needs to have one or more isocyanate groups in one molecule, and the number of isocyanate groups is not particularly limited. The isocyanate group-containing alkoxysilane compound may further have groups such as an alkyl group, an amide group, a urethane group, a urea group, an ester group, a hydroxy group, and a carboxy group in addition to the isocyanate group.

Examples of the isocyanate group-containing alkoxysilane compound used in the present disclosure include 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, and the like. Examples of commercially available isocyanate group-containing alkoxysilane compounds include KBE-9007 (manufactured by Shin-Etsu Chemical Co., Ltd.).

<< Radically polymerizable group-containing alkoxysilane compound >>
The radical polymerizable group-containing alkoxysilane compound is an alkoxysilane compound having a radical polymerizable group. The radical polymerizable group-containing alkoxysilane compound may be any compound having one or more radical polymerizable groups in one molecule, and the number of radical polymerizable groups is not particularly limited.
Although it does not specifically limit as a radically polymerizable group, (meth) acryloxy group, (meth) acrylamide group, vinylphenyl group, vinyl group, an allyl group, etc. are mentioned.
The radical polymerizable group-containing alkoxysilane compound may further have groups such as an alkyl group, an amide group, a urethane group, a urea group, an ester group, a hydroxy group, and a carboxy group in addition to the radical polymerizable group.

Examples of the radically polymerizable group-containing alkoxysilane compound used in the present disclosure include vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropyltrimethoxysilane. , 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane and the like. Commercially available products of radical polymerizable group-containing alkoxysilane compounds include KBM-1003, KBE-1003, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103 (Shin-Etsu Chemical ( Etc.).
Moreover, when the composition for inorganic particle content layer formation contains a radically polymerizable group containing alkoxysilane compound, the composition for inorganic particle content layer formation may further contain a well-known radical polymerization initiator.

<< Content >>
From the viewpoint of improving the stability of the inorganic particle-containing layer forming composition and the alkali resistance of the resulting inorganic particle-containing layer, relative to the total mass of the alkoxysilane compound contained in the inorganic particle-containing layer forming composition, The content of the crosslinkable group-containing alkoxysilane compound is preferably 20% by mass to 85% by mass. The content of the crosslinkable group-containing alkoxysilane compound is preferably 20% by mass or more, more preferably 25% by mass or more, and further preferably 30% by mass or more. Moreover, it is preferable that content of a crosslinkable group containing alkoxysilane compound is 85 mass% or less, It is more preferable that it is 80 mass% or less, It is still more preferable that it is 75 mass% or less.

-Crosslinkable group-free alkoxysilane compound-
The crosslinkable group-free alkoxysilane compound is an alkoxysilane compound having no crosslinkable group. The non-crosslinkable group-containing alkoxysilane compound may be an alkoxysilane compound having no crosslinkable group, and has a group such as an alkyl group, an amide group, a urethane group, a urea group, an ester group, a hydroxy group, or a carboxy group. You may do it.

The crosslinkable group-free alkoxysilane compound is preferably a tetraalkoxysilane compound, a trialkoxysilane compound, or a mixture thereof. More preferably, it is a mixture of a tetraalkoxysilane compound and a trialkoxysilane compound. When the tetraalkoxysilane compound and trialkoxysilane compound are mixed and contained, when the inorganic particle-containing layer is formed, sufficient hardness can be obtained while having appropriate flexibility.

When the crosslinkable group-free alkoxysilane compound is a mixture of a tetraalkoxysilane compound and a trialkoxysilane compound, the molar ratio of the tetraalkoxysilane compound to the trialkoxysilane compound is 25:75 to 85:15. It is preferably 30:70 to 80:20, more preferably 30:70 to 65:35. By controlling the molar ratio within the above range, the degree of polymerization of the alkoxysilane compound can be controlled within a desired range, or the hydrolysis rate and the solubility of the aluminum chelate can be easily controlled.

The tetraalkoxysilane compound is a tetrafunctional alkoxysilane compound, and preferably has 1 to 4 carbon atoms in each alkoxy group. Among these, a tetramethoxysilane compound or a tetraethoxysilane compound is particularly preferably used. By setting the number of carbon atoms to 4 or less, the hydrolysis rate of the tetraalkoxysilane compound when mixed with acidic water does not become too slow, and the time required for dissolution until a uniform aqueous solution is reduced. Thereby, the manufacturing efficiency at the time of manufacturing an inorganic particle content layer can be improved. Examples of commercially available tetraalkoxysilane compounds include KBE-04 (manufactured by Shin-Etsu Chemical Co., Ltd.).

The trialkoxysilane compound is a trifunctional alkoxysilane compound represented by the following formula A.
R-Si (OR ¹ ) ₃ formula A
In Formula A, R represents an organic group having 1 to 15 carbon atoms that does not contain an amino group, and R ¹ represents an alkyl group having 4 or less carbon atoms.

The trifunctional alkoxysilane compound represented by Formula A preferably does not contain an amino group as a functional group. That is, the trifunctional alkoxysilane compound has an organic group R having no amino group. When R does not have an amino group, when it is mixed with a tetrafunctional alkoxysilane compound and hydrolyzed, dehydration condensation is hardly promoted between the produced silanols, and the stability of the composition for forming an inorganic particle-containing layer is improved. improves.

In the formula A, R may be an organic group having a molecular chain length such that the carbon number is in the range of 1 to 15. By setting the number of carbon atoms to 15 or less, the flexibility of the inorganic particle-containing layer does not become too large, and sufficient hardness can be obtained. Moreover, the inorganic particle content layer excellent in brittleness can be obtained by making the carbon number of R into the said range. Furthermore, the adhesiveness of a photocatalyst layer and an inorganic particle content layer can be improved.
The organic group represented by R may have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Adhesion with a photocatalyst layer can be improved because an organic group has a hetero atom.

Trialkoxysilane compounds include 3-chloropropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, propyltrimethoxysilane, phenyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-ureidopropyltriethoxysilane, methyl Examples thereof include triethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, phenyltriethoxysilane, and phenyltrimethoxysilane. Of these, methyltriethoxysilane and methyltrimethoxysilane are particularly preferably used. Examples of commercially available trialkoxysilane compounds include KBE-13 (manufactured by Shin-Etsu Chemical Co., Ltd.).

-Inorganic particles-
The composition for forming an inorganic particle-containing layer includes inorganic particles. The inorganic particles in the composition for forming an inorganic particle-containing layer are the same as the inorganic particles in the above-described inorganic particle-containing layer, and the preferred embodiments are also the same.
The content of the inorganic particles in the composition for forming an inorganic particle-containing layer is the content of the inorganic particles relative to the total solid content of the composition for forming an inorganic particle-containing layer from the viewpoint of photocatalytic activity and alkali resistance of the inorganic particle-containing layer. When x mass%, it is preferable that 0 mass% <x mass% ≦ 80 mass%. As for x mass%, it is more preferable that it is 1 mass% or more, and it is still more preferable that it is 3 mass% or more. Further, x mass% is preferably 80 mass% or less, more preferably 70 mass% or less, and further preferably 65 mass% or less.

Moreover, when content of the inorganic particle with respect to the total solid of the composition for forming an inorganic particle-containing layer is x mass%, the content of the crosslinkable group-containing alkoxysilane compound with respect to the total mass of the alkoxysilane compound is y mass%. Then, y mass% ≧ x mass% −5 mass% is preferable, and y mass% ≧ x mass% is more preferable. By setting the mass% relationship between y mass% and x in the above range, higher alkali resistance of the inorganic particle-containing layer can be obtained, and the change in haze value when immersed in an alkaline solution can be suppressed. . Furthermore, the stability of the inorganic particle-containing layer forming composition can be enhanced.

-Metal complex (curing agent)-
The composition for forming an inorganic particle-containing layer preferably contains a metal complex (curing agent).
Moreover, it is preferable that the inorganic particle content layer in this indication contains a metal complex.
As the metal complex, a metal complex composed of Al, Mg, Mn, Ti, Cu, Co, Zn, Hf and Zr is preferable, and these can be used in combination.

The metal complex in the present disclosure can be easily obtained by reacting a metal alkoxide with a chelating agent. Examples of chelating agents include β-diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane, and β-keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate.

Preferable specific examples of the metal complex include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris (acetyl) Acetate) and other aluminum chelate compounds, ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethylacetoacetate), alkyl acetoacetate magnesium monoisopropylate, magnesium bis (acetylacetonate) and other magnesium chelate compounds, zirconium tetraacetylacetate Narate, zirconium tributoxyacetylacetonate, zirconium Chill acetonate bis (ethyl acetoacetate), manganese acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, titanium acetylacetonate and titanium oxy acetylacetonate. Of these, aluminum tris (acetylacetonate), aluminum tris (ethyl acetoacetate), magnesium bis (acetylacetonate), magnesium bis (ethylacetoacetate), zirconium tetraacetylacetonate, and storage stability Considering availability, aluminum tris (acetylacetonate) and aluminum tris (ethylacetoacetate), which are aluminum chelate complexes, are particularly preferable. Examples of commercially available products include aluminum chelate A (W), aluminum chelate D, aluminum chelate M (manufactured by Kawaken Fine Chemical Co., Ltd.), and the like.

It is preferable that the content of the metal complex is 17 mol% to 70 mol% with respect to the total molar amount of the crosslinkable group-containing alkoxysilane compound. The content is more preferably 20 mol% or more. The content is preferably 70 mol% or less, more preferably 65 mol% or less, and still more preferably 60 mol% or less.
By including the metal complex in the above lower limit or higher, excellent alkali resistance can be obtained when the metal particle-containing layer is formed. Moreover, by setting it as the said upper limit or less, the dispersibility of the metal complex in the composition for inorganic particle content layer formation can be made favorable, and manufacturing cost can be held down.

-Other additives-
A surfactant may be added to the inorganic particle-containing layer forming composition and the inorganic particle-containing layer used in the present disclosure for the purpose of improving the smoothness of the layer and reducing the friction of the coating film surface. . Examples of the surfactant include surfactants described in paragraphs 0039 to 0044 of JP-A No. 2014-117717.
Further, the inorganic particle-containing layer may be colored by dispersing pigments, dyes, and other particles. Furthermore, an antioxidant or the like may be added to the inorganic particle-containing layer forming composition and the inorganic particle-containing layer used in the present disclosure for the purpose of improving the weather resistance.

[Film thickness]
The film thickness of the inorganic particle-containing layer can be controlled by adjusting the coating amount of the inorganic particle-containing layer forming composition.
The thickness of the inorganic particle-containing layer may be designed according to the use, but is 50 nm to 250 nm, preferably 100 nm to 200 nm.

[Method for producing inorganic particle-containing layer]
An inorganic particle content layer is formed by apply | coating the composition for inorganic particle content layer formation on a photocatalyst layer, and drying.
The application method of the composition for forming an inorganic particle-containing layer is not particularly limited, and a known method may be used. Examples of the application method include slit coating, spin coating, curtain coating, and inkjet coating.
A method for heating the composition for forming an inorganic particle-containing layer is not particularly limited, and a known method may be used. For example, a method using a heating means such as a heater, an oven, a hot plate, an infrared lamp, or an infrared laser may be mentioned. It is done.
An easy-adhesion layer described later may be included between the inorganic particle-containing layer and the photocatalyst layer.

[Characteristics of inorganic particle-containing layer]
It is preferable that the aspect with an inorganic particle content layer is a hard-coat layer.
When using an inorganic particle content layer as a hard-coat layer, it is preferable that the pencil hardness of the surface of an inorganic particle content layer is B or more, and it is more preferable that it is HB or more.
The pencil hardness means a value measured based on JIS K5600-5-4: 1999. A high uni from Mitsubishi Pencil Co., Ltd. is used as the pencil.
The hard coat layer can be provided with a plurality of functions such as a hard coat layer excellent in reflectance reduction, a hard coat layer excellent in thermal conductivity, and a hard coat layer excellent in chemical resistance.

Moreover, it is preferable that the aspect with an inorganic particle content layer is an antireflection layer.
When the inorganic particle-containing layer is used as an antireflection layer, the refractive index of the inorganic particle-containing layer is preferably in the range of 1.3 to 1.7, more preferably 1.4 to 1.6. .
Unless otherwise specified, the refractive index is a value measured at 25 ° C. by ellipsometry at a wavelength of 600 nm.

<Base material layer>
The photocatalyst composite material according to the present disclosure preferably includes a base material layer on the opposite side of the photocatalyst layer from the inorganic particle-containing layer.
A base material layer is a layer formed with a base material, and a resin base material, a glass base material, a metal base material etc. are mentioned as a base material in a base material layer.
The resin substrate is not particularly limited, but polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polybutylene naphthalate (PBN), polyarylates, polyethersulfone, polycarbonate, poly Ether ketone, polysulfone, polyphenylene sulfide, polyester liquid crystal polymer, triacetyl cellulose, cellulose derivatives, polypropylene, polyamides, polyimides, polycycloolefins, and the like are preferable. Among these, PET, PEN, or triacetyl cellulose is more preferable, and PET or PEN is still more preferable.
The resin base material may be stretched and is preferably biaxially stretched. Biaxial stretching refers to stretching in both directions by regarding the width direction and longitudinal direction of the resin film as uniaxial. Thus, the biaxially stretched polyester film has very good mechanical strength because the molecular orientation in the biaxial direction is sufficiently controlled. The draw ratio is not particularly limited, but the draw ratio in one direction is preferably 1.5 to 7 times, more preferably 2 to 5 times. In particular, a polyester film that has been biaxially stretched at a stretching ratio of 2 to 5 times per uniaxial direction has a very excellent mechanical strength because the molecular orientation is controlled more efficiently and effectively, Suitable as a polyester film.
Although it does not restrict | limit especially as a glass base material, A transparent glass plate, a type | mold glass plate, a netted glass plate, a wire-containing glass plate, a tempered glass plate, a heat ray reflective glass plate, a heat ray absorption glass plate, Low-E (Low Emissivity, A glass substrate such as a low reflection glass plate can be used.
Although it does not restrict | limit especially as a metal base material, An aluminum plate, a steel plate, a copper plate, other alloy plates, etc. are mentioned.

The base material used as the base material layer may be surface-treated, and is preferably subjected to corona treatment or glow treatment for the simplicity of the process. By these treatments, the surface of the substrate is hydrophilized and the paintability can be improved, so that the adhesion with the photocatalyst layer or the adhesion with the easy adhesion layer can be increased. The corona treatment at normal pressure has a simpler process than the glow treatment at reduced pressure, but the glow treatment has a higher effect of improving the adhesion.

<Easily adhesive layer>
The photocatalyst composite material according to the present disclosure may have an easy adhesion layer for the purpose of improving the adhesion between the base material layer and the photocatalyst layer, or the photocatalyst layer and the inorganic particle-containing layer.
For example, the photocatalyst composite material according to the present disclosure may include an easy-adhesion layer between the base material layer and the photocatalyst layer and / or between the photocatalyst layer and the inorganic particle-containing layer.
The easy-adhesion layer is obtained by, for example, applying a coating liquid composed of a binder, a curing agent, and a surfactant to the surface on which the photocatalyst layer of the substrate is provided or the surface on which the inorganic particle-containing layer of the photocatalyst layer is formed. It is formed. Organic or inorganic particles may be appropriately added to the easy adhesion layer. Although it does not specifically limit as a particle, For example, metal oxide particle is mentioned, Specifically, particles, such as a tin oxide, a zirconium oxide, a zinc oxide, a titanium oxide, a cerium oxide, niobium oxide, are preferable. These particles may be used alone or in combination of two or more. Examples of commercially available particles include ET series such as ET-500W, FT-2000 and other FT series, SN series such as SN-100P, and FS series such as FS-10D (manufactured by Ishihara Sangyo Co., Ltd.). It is done.

Although the binder contained in an easily bonding layer is not specifically limited, From an adhesive viewpoint, it is preferable that at least 1 of polyester, a polyurethane, an acrylic resin, a styrene butadiene copolymer, and polyolefin is included. In addition, when not performing surface treatment on the surface of a base material, it is preferable that a binder contains at least 1 among polyester, a polyurethane, and polyolefin, and it is more preferable that it is polyolefin.
In addition, a binder having water solubility or water dispersibility is particularly preferable from the viewpoint that the load on the environment is small. Commercially available binders include, for example, Carbodilite series such as Carbodilite V-02-L2 (manufactured by Nisshinbo Co., Ltd.), Takelac WS series such as Takerak WS-5100 (manufactured by Mitsui Chemicals), Arrow Base SE1013N An arrow base series (made by Unitika Co., Ltd.) such as HARDREN series (made by Toyobo Co., Ltd.) such as HARDREN NZ1004.

The thickness of the easy-adhesion layer can be adjusted as appropriate by adjusting the coating amount. The thickness of the easy adhesion layer is more preferably in the range of 0.01 μm to 5 μm. If the thickness is 0.01 μm or more, the adhesion is likely to be sufficient, and if it is 5 μm or less, the thickness of the easy-adhesion layer tends to be uniform. A more preferable thickness range is 0.02 μm to 3 μm. Only one layer may be sufficient as an easily bonding layer, and the aspect which piled up this may be sufficient. When a plurality of easy-adhesion layers are stacked, the total thickness of all the easy-adhesion layers is regarded as the thickness of the easy-adhesion layer.

<Other layers>
The photocatalyst composite material according to the present disclosure may have a shielding layer between the base material layer and the photocatalyst layer.
In the case of having a shielding layer, for example, radicals generated in the photocatalytic layer are considered to be trapped by the shielding layer, so that deterioration due to radicals such as a resin substrate in the substrate layer is suppressed.
As the shielding layer, for example, a layer similar to the inorganic particle-containing layer or a layer similar to the inorganic particle-containing layer can be used as the shielding layer except that the inorganic particle-containing layer is not included.

<Application>
The photocatalyst composite material in the present disclosure is preferably a protective member, and is preferably a signage display protective member, a touch panel protective member, a solar cell protective member, or a sensor cover protective member.
By including the photocatalyst layer, the photocatalyst composite material in the present disclosure has one or a plurality of effects such as antifouling, antibacterial, antiviral, deodorant, and antifungal. Moreover, the photocatalyst composite material in the present disclosure has one or more of effects such as antireflection properties, scratch resistance, thermal conductivity, and chemical resistance, depending on the composition of the inorganic particle-containing layer.
Therefore, the photocatalyst composite material according to the present disclosure can be used, for example, as a protective member having excellent antifouling properties and excellent scratch resistance and antireflection properties.

(Signage display protection member, signage display)
The signage display protection member according to the present disclosure includes the photocatalyst composite material according to the present disclosure.
The signage display according to the present disclosure includes the signage display protection member according to the present disclosure.
The signage display protective member according to the present disclosure is excellent in photocatalytic activity on the surface on the inorganic particle-containing layer side. For example, by using the inorganic particle-containing layer as the surface of the outermost layer in the signage display, the adhesion of dirt is prevented. can do.
As a signage display protection member, for example, a photocatalyst composite material formed by laminating a photocatalyst layer and an inorganic particle-containing layer in this order on a signage display may be used as a signage display protection member. Alternatively, for example, a photocatalyst composite material in which a resin film is used as a base material layer and a photocatalyst layer and an inorganic particle-containing layer are laminated in this order on the base material layer is produced as a signage display protection member. You may paste and use it for the signage display.
The signage display is not particularly limited, and a known image display device such as a liquid crystal display, a plasma display, an organic EL (electroluminescence) display, a CRT (Cathode Ray Tube) display, electronic paper, or a PDP (plasma display panel) is used. It is done.

(Protective material for touch panel, touch panel)
The protective member for a touch panel according to the present disclosure includes the photocatalyst composite material according to the present disclosure.
The touch panel according to the present disclosure includes the touch panel protective member according to the present disclosure.
Since the protective member for a touch panel according to the present disclosure is excellent in photocatalytic activity on the surface on the inorganic particle-containing layer side, for example, by using the inorganic particle-containing layer as a touch part (touch part) on the touch panel, dirt such as fingerprints Can be prevented, or the removal of dirt can be facilitated.
As a protective member for a touch panel, for example, a photocatalyst composite material formed by laminating a photocatalyst layer and an inorganic particle-containing layer in this order on a member that becomes an outermost layer in a conventional touch panel is used as a protective member for a touch panel. Also good. Alternatively, for example, a photocatalyst composite material in which a resin film is used as a base material layer and a photocatalyst layer and an inorganic particle-containing layer are laminated in this order on the base material layer is produced as a touch panel protection member. You may affix and use on the member used as the outermost layer in a touch panel.
As the touch panel, a known touch panel is used without particular limitation, and for example, the description in JP-A-2002-48913 can be referred to.

(Protective member for solar cell, solar cell)
The solar cell protective member according to the present disclosure includes the photocatalyst composite material according to the present disclosure.
The solar cell concerning this indication is provided with the protection member for solar cells concerning this indication.
Since the protective member for solar cell according to the present disclosure is excellent in photocatalytic activity on the surface on the inorganic particle-containing layer side, for example, the inorganic particle-containing layer is used as the outermost layer in the solar cell front sheet to prevent adhesion of dirt. can do.
As a solar cell protective member, for example, a photocatalyst composite formed by laminating a photocatalyst layer and an inorganic particle-containing layer in this order on a member (for example, a solar cell front sheet) that is the outermost layer in a conventional solar cell. You may form and use a material as a protection member for solar cells. Alternatively, for example, a photocatalyst composite material in which a resin film is used as a base material layer, and a photocatalyst layer and an inorganic particle-containing layer are laminated in this order on the base material layer is produced as a solar cell protection member. Alternatively, it may be used by being attached to a member that is the outermost layer in a conventional solar cell.
Regarding the solar cell front sheet, the description in JP-A-2011-62877 can be referred to.

(Protective member for sensor cover, sensor cover)
The protective member for a sensor cover according to the present disclosure includes the photocatalyst composite material according to the present disclosure.
The sensor cover according to the present disclosure includes the sensor cover protection member according to the present disclosure.
Since the protective member for a sensor cover according to the present disclosure is excellent in photocatalytic activity on the surface on the inorganic particle-containing layer side, for example, by making the inorganic particle-containing layer the outermost layer in the sensor cover, it is possible to prevent adhesion of dirt. it can.
As the sensor cover protection member, for example, a photocatalyst composite material formed by laminating a photocatalyst layer and an inorganic particle-containing layer in this order on a member that is an outermost layer in a conventional sensor cover is formed as a sensor cover protection member. May be used. Alternatively, for example, a photocatalyst composite material in which a resin film is used as a base material layer, and a photocatalyst layer and an inorganic particle-containing layer are laminated on the base material layer in this order is produced as a sensor cover protection member. You may affix and use on the member used as the outermost layer in the conventional sensor cover.
Examples of the sensor cover include a sensor cover in a camera module, and the description in JP-A-2016-130746 can be referred to.

(Other uses)
Other protective members including the photocatalytic composite material according to the present disclosure include a liquid crystal display, a plasma display, an organic EL (electroluminescence) display, a CRT (Cathode Ray Tube) display, electronic paper, a PDP (plasma display panel) electromagnetic wave shielding film, and the like. It is also suitably used as a protective member.

Hereinafter, the present disclosure will be described in detail by way of examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the embodiment of the present disclosure. Therefore, the scope of the embodiment of the present disclosure is not limited to the specific examples shown below. In this example, “parts” and “%” mean “parts by mass” and “mass%” unless otherwise specified.

(Examples 1 to 7 and Comparative Examples 1 to 4)
<Production of photocatalytic composite material>
[Production of photocatalyst layer]
A composition was prepared by thickening Tiosky Coat A solution, which is an aqueous solution, by the following thickening method. After dropping the obtained composition onto a glass substrate, the composition was spread using a spin coater (MS-A100, manufactured by Mikasa Co., Ltd.) with the number of revolutions adjusted to the film thickness shown in Table 1.
Next, the water was dried at a predetermined temperature with a hot plate (digital hot plate HP-2SA manufactured by ASONE) to form a photocatalyst layer (TiO ₂ layer).
For example, in the case of forming a 500 nm photocatalyst layer, the composition was dropped on glass, spin-coated at a rotation speed of 800 rpm × 30 s, and dried on a hot plate at 120 ° C. for 10 minutes.
Tio Sky Coat A Solution (Tio Systems Co., Ltd.) is an aqueous composition mainly composed of anatase type (crystalline) titanium oxide particles having a number average particle diameter of 5 nm to 20 nm and peroxotitanic acid.

<Thickening method of Tio Sky Coat A solution>
The thickening of the Tio Sky Coat A solution was performed by adding a thickener to the Tio Sky Coat A solution and mixing.
As the thickener, a 10% aqueous solution of hydroxyalkyl (1 to 3 carbon atoms) cellulose was used.
For example, when 13.1% of the above thickener is added to the Tiosky Coat A liquid and 13.1% of the total mass of the Tiosky Coat A liquid and the above thickener, the spin rotation speed is 800 rpm × 30 s. The film thickness of the photocatalyst layer formed per time is 100 nm. Further, when 30.7% of the thickener is added to the total mass of the Tiosky Coat A solution and the thickener, a photocatalyst layer having a film thickness of 500 nm is formed under the same formation conditions as described above. be able to.

[Preparation of inorganic particle-containing layer]
-Preparation of inorganic particle-containing layer forming composition-
The compound as described in the following composition was mixed and the inorganic particle content layer forming composition was prepared.
In Comparative Example 2, no inorganic particles were added.

-composition-
Epoxy group-containing alkoxysilane compound (3-glycidoxypropyltriethoxysilane) (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-403): 80 parts by mass Tetraalkoxysilane (tetraethoxysilane, Shin-Etsu Chemical Co., Ltd.) Manufactured, KBE-04): 20 parts by mass / acetic acid aqueous solution (manufactured by Daicel Chemical Industries, Ltd., 1% aqueous solution of industrial acetic acid): 100 parts by mass / aluminum chelate complex (produced by Kawaken Fine Chemicals, aluminum chelate D): 22 .1 part by mass Inorganic particles listed in Table 1: 200 parts by mass Surfactant A (manufactured by Sanyo Chemical Industries, Ltd., 10% diluted solution of sanded BL, anionic): 0.2 parts by mass Agent B (Sanyo Chemical Industries, Ltd., 10% diluted solution of NAROACTY CL-95, nonionic): 0.2 parts by mass

The inorganic particle-containing layer forming composition was prepared according to the following procedure.
An epoxy group-containing alkoxysilane compound (KBE403) was added to 100 parts by mass of a 1% aqueous acetic acid solution and sufficiently hydrolyzed, and then tetraalkoxysilane (KBE04) was added. Subsequently, an aluminum chelate complex was added in a necessary mass part with respect to the epoxy group-containing alkoxysilane compound, and inorganic particles described in Table 1 were added thereto. Thereafter, 0.2% by mass of a 10% diluted solution of surfactant A (Sandet BL) and a 10% diluted solution of surfactant B (Narrow Acty CL-95) are added to a solid content concentration of 15%. Thus, water was added to obtain a composition for forming an inorganic particle-containing layer.

-Preparation of inorganic particle-containing layer-
On the photocatalyst layer produced by the above-described method, the inorganic particle-containing layer forming composition prepared in each Example or Comparative Example was dropped, and a spin coater (MS-A100 manufactured by Mikasa Corporation) was used. The coating was spread by adjusting the number of revolutions so that the film thickness described was obtained. Next, moisture was dried at a predetermined temperature using a hot plate (Digital Hot Plate HP-2SA manufactured by ASONE Co., Ltd.) to form an inorganic particle-containing layer to obtain a photocatalyst composite material.
The spin coating conditions and drying conditions were adjusted according to the film thickness of the inorganic particle-containing layer prepared in each example or comparative example.
For example, in the case of forming a 100 nm thin film, after dropping the composition for forming an inorganic particle-containing layer, spin coating at a rotational speed of 4,000 rpm × 30 s is performed, and drying is performed at 170 ° C. for 2 minutes on a hot plate. A photocatalytic composite material was obtained.
In Comparative Example 1, the inorganic particle-containing layer was not prepared.

<Evaluation of photocatalytic activity>
For the obtained photocatalyst composite material, the photocatalytic activity on the surface on the inorganic particle-containing layer side (the surface on the photocatalyst layer side when no inorganic particle-containing layer is provided) is determined by a method substantially in accordance with JIS R 1703-2: 2014. Evaluation was performed.
Specifically, 35 mL of a 10 μmol / L methylene blue (MB) aqueous solution was brought into contact with a 50 mm square region of the photocatalyst composite, irradiated with ultraviolet light under the conditions described later, and the methylene blue concentration was measured by absorbance. did.
For the exposure, a halogen lamp MAX-302 manufactured by Asahi Spectroscopic Co., Ltd. was used, and a bandpass filter (transmission center wavelength 350 nm, FWHM (full width at half maximum) 10 nm) was used, and the exposure intensity was 1 mW / cm ² .
For the measurement of the decomposition activity of the photocatalytic reaction, a spectrometer HP 8453 manufactured by Agilent was used.
The absorption spectrum of the aqueous MB solution was measured before and after UV exposure, and the number of MB-decomposed molecules was calculated from the absorbance at 664 nm.
Since the MB decomposition reaction on the surface of the photocatalyst proceeds as a zero-order reaction, the decomposition activity index (nmol / (L × min)) is a minimum of the decomposition MB concentration (nmol / L) with respect to the exposure time (min). The slope was obtained by linear regression by multiplication. The linear regression was performed using the result of irradiation for 60 minutes under the exposure conditions described above. Linear regression was performed at intercept 0. The decomposed MB density was calculated as a difference from the density at exposure time 0.
According to preliminary studies, the degradation activity index measured in this system is about 60% of the literature value according to the JIS standard (JIS R 1703-2: 2014), and the relative relationship between the literature value and the measured value is maintained. know. In the above JIS standard, 3 nmol / (L × min) or more is a sufficiently high decomposition activity. In this measurement, when it is 5 nmol / (L × min) or more, “A +”, less than 5 nmol / (L × min), 3 nmol / When “A” is greater than (L × min), less than “A”, less than 3 nmol / (L × min), and when “B” is less than 1 nmol / (L × min), less than 1 nmol / (L × min) Evaluated as “C”.
The evaluation results are shown in Table 1.

<Evaluation of scratch resistance>
Friction and wear test made by Shinto Kagaku Co., Ltd. against the surface of the photocatalyst composite material obtained in each example or comparative example on the inorganic particle-containing layer side (the surface on the photocatalyst layer side when there is no inorganic particle-containing layer) Using a machine HYDON Type 18, a scratch test was performed 10 times with a continuous load of 0-100 g with a sapphire needle of r = 0.03 mm at a moving speed of 600 mm / min.
After the scratch test, the case where no scratches were visually observed on the surface of the photocatalyst composite material on the inorganic particle-containing layer side was evaluated as “A”, and the case where scratches were observed was evaluated as “B”. If the evaluation result is A, it can be said that the scratch resistance is excellent.

<Evaluation of antireflection properties>
With respect to the photocatalyst composite material in each Example or Comparative Example, the reflectance of the surface on the side opposite to the glass substrate was measured.
The surface opposite to the glass substrate is the surface on the inorganic particle-containing layer side in the example where the inorganic particle-containing layer is formed, and in the example where the inorganic particle-containing layer is not formed, the photocatalyst layer The side surface.
The reflectance is measured using an ultraviolet-visible infrared spectrophotometer (model number: UV3100PC, manufactured by Shimadzu Corporation), and the reflectance (%) in light having a wavelength of 400 to 800 nm is measured using an integrating sphere. The average value at a wavelength of 400 to 800 nm was taken as the reflectance.
Evaluation as “A” when the reflectance is low by 1% or more with respect to Comparative Example 1 having no inorganic particle-containing layer, and evaluation as “B” when the reflectance does not decrease or the decrease in reflectance is less than 1%. did.

<Evaluation of chemical resistance>
The photocatalyst composite material in each example or comparative example was immersed in a 5% aqueous sodium hydroxide solution at 30 ° C. for 24 hours.
After the immersion, the surface of the photocatalyst composite on the inorganic particle-containing layer side was visually confirmed. The case where change such as discoloration was not recognized was evaluated as “A”, and the case where change was recognized was evaluated as “B”. If the evaluation result is A, it can be said that the chemical resistance is excellent.

In Table 1, “-” means that the corresponding item has not been evaluated.
The details of the inorganic particles described in Table 1 are as follows.
S1: Silica particles, Snowtex OXS, manufactured by Nissan Chemical Industries, Ltd. S2: Silica particles, Snowtex OZL, manufactured by Nissan Chemical Industries, Ltd. A1: Alumina particles, AS-520-A, Nissan Chemical Industries (・ Z1: Zirconia particles, ZR40-BL, manufactured by Nissan Chemical Industries, Ltd. ・ S3: Silica particles, Snowtex O, Nissan Chemical Industries, Ltd. ・ S4: Silica particles, Snowtex MP-4540M, Nissan Made by Chemical Industry Co., Ltd.

From the results described in Table 1, it can be seen that the photocatalyst composite material according to the present disclosure is excellent in photocatalytic activity on the surface on the inorganic particle-containing layer side and has a function added by the inorganic particle-containing layer.
In the evaluation of scratch resistance, antireflection property and / or chemical resistance, an evaluation result of “A” means that a function by the inorganic particle-containing layer is added.

The disclosure of Japanese Patent Application No. 2018-111457 filed on June 11, 2018 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference, Incorporated herein by reference.

Claims

A photocatalyst layer containing titanium oxide particles and an amorphous titanium peroxide type inorganic binder;
A siloxane resin containing an organic structure, and an inorganic particle-containing layer containing inorganic particles,
The number average particle diameter of the inorganic particles is 5 nm to 100 nm,
A photocatalyst composite material, wherein the inorganic particle-containing layer has a thickness of 50 nm to 250 nm.
The photocatalyst composite material according to claim 1, wherein the titanium oxide particles are anatase type titanium oxide particles.
The photocatalyst composite material according to claim 1 or 2, wherein an organic structure in the siloxane resin containing the organic structure is a crosslinked structure.
The photocatalyst composite material according to any one of claims 1 to 3, wherein the inorganic particle-containing layer is a layer formed by curing a composition containing an alkoxysilane compound and inorganic particles.
The photocatalyst composite material according to claim 4, wherein the alkoxysilane compound includes an epoxy group-containing alkoxysilane compound and an epoxy group-free alkoxysilane compound.
The photocatalyst composite material according to any one of claims 1 to 5, wherein the inorganic particles contain at least one kind of particles selected from the group consisting of silica, alumina, and zirconia.
The photocatalyst composite material according to any one of claims 1 to 6, further comprising a base material layer on a side of the photocatalyst layer opposite to the inorganic particle-containing layer.
A signage display protective member comprising the photocatalyst composite material according to any one of claims 1 to 7.
A touch panel protective member comprising the photocatalyst composite material according to any one of claims 1 to 7.
A solar cell protective member comprising the photocatalyst composite material according to any one of claims 1 to 7.
A sensor cover protective member comprising the photocatalyst composite material according to any one of claims 1 to 7.
A signage display comprising the signage display protection member according to claim 8.
A touch panel comprising the touch panel protective member according to claim 9.
A solar cell comprising the solar cell protective member according to claim 10.
A sensor cover comprising the sensor cover protective member according to claim 11.