WO2020129456A1

WO2020129456A1 - Photocatalyst composite material, signage display protection member, touch panel protection member, solar cell protection member, sensor cover protection member, signage display, touch panel, solar cell, and sensor cover

Info

Publication number: WO2020129456A1
Application number: PCT/JP2019/043868
Authority: WO
Inventors: 安永　正; 裕之八重樫; 英宏望月; 充倉沢
Original assignee: 富士フイルム株式会社
Priority date: 2018-12-19
Filing date: 2019-11-08
Publication date: 2020-06-25

Abstract

The present invention provides: a photocatalyst composite material including, in order, an inorganic-particle-containing layer that includes inorganic particles and a siloxane resin including an organic structure, a photocatalyst layer that includes titanium oxide, and a reflection-preventing layer that includes an amorphous titanium peroxide binder and a siloxane resin including an organic structure, the inorganic-particle-containing layer having a thickness of 80-115 nm and a reflectivity of less than 1.5, and the reflection-preventing layer having a thickness of 20-140 nm and a reflectivity of 1.50-1.90; and a practical application for the photocatalyst composite material.

Description

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

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

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

Japanese Unexamined Patent Publication (Kokai) No. 9-262481 discloses a method for producing a photocatalyst body in which a catalyst is carried and fixed on a substrate, and which uses a photocatalyst and an amorphous titanium peroxide sol.
In JP-A-2002-88276, an aqueous solution containing a peroxide group-containing amorphous titanium oxide in a range of 0.5 wt% or more and 2.0 wt% or less (as titanium oxide) contains 0.025 wt of anatase-type titanium oxide fine particles. The antifouling coating agent is contained in the range of 0.1% to 1.2% by weight, and the silicone-based surfactant is contained in the range of 0.01% to less than 0.8% by weight.
Japanese Unexamined Patent Publication No. 2003-55580 describes an aqueous coating material containing fine particles of a titania-based peroxo compound, peroxotitanic acid, and fine particles of silica.
Japanese Patent Laid-Open 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 (D) Water (E) Alcohol as binder component

Further, formation of a functional layer on the layer containing the photocatalytic material is also under study.
Japanese Patent Laid-Open No. 2010-99651 discloses a method for producing a composite material in which a photocatalyst layer and a functional layer are formed on the surface of a base material, after forming a photocatalyst layer containing a photocatalyst on the surface of the base material, It has a step of forming a functional layer containing an organic substance that can be decomposed by a photocatalyst, and a step of irradiating the functional layer with light to activate the photocatalyst in the photocatalyst layer to decompose the organic substance in the functional layer. , A method for producing a composite material in which the content of organic substances in the functional layer is 10 to 40% by mass.
In WO 2002/100634, a photocatalyst film is formed on a surface of a base material, and a hydrophilic substance film is formed on the photocatalyst film so as to be porous. As an example, an antifogging element using a coating agent in which photocatalyst particles are dispersed in a titanium peroxide solution obtained by allowing hydrogen peroxide to act on titanium hydroxide gel (orthotitanic acid) is described.

Also, in recent years, it has been considered 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 hydrophilicizing function.

JP-A-2014-111717 discloses an aqueous composition obtained by mixing an epoxy group-containing alkoxysilane, an epoxy group-free alkoxysilane, and a metal complex, wherein the epoxy group-containing alkoxysilane and the epoxy group-free The ratio of the epoxy group-containing alkoxysilane to the total alkoxysilane composed of alkoxysilane is 20 to 85% by mass, and the ratio of the metal complex to the epoxy group-containing alkoxysilane is 17 to 70 mol %. An aqueous composition is described.

When the above-mentioned functional layer is formed on the layer containing the photocatalytic material as described in JP-A-2010-99651 and WO 2002/100634, the functional layer may improve antireflection property, for example. It is speculated that it can be added. However, the antireflection property obtained from the two-layer structure of the layer containing the photocatalyst material and the functional layer may be insufficient, and a better antireflection property is required.

The embodiment of the present disclosure relates to providing a photocatalyst composite material having excellent photocatalytic activity on the surface of the inorganic particle-containing layer side and excellent antireflection property when light enters from the inorganic particle-containing layer side.
Another embodiment of the present disclosure is excellent in photocatalytic activity on the surface of the inorganic particle-containing layer side, and a signage display protection provided with a photocatalyst composite material having excellent antireflection properties when light enters from the inorganic particle-containing layer side. Member, touch panel protection member including the photocatalyst composite material, solar cell protection member including the photocatalyst composite material, sensor cover protection member including the photocatalyst composite material, signage display including the signage display protection member, the above The present invention relates to providing a touch panel including a touch panel protection member, a solar cell including the solar cell protection member, or a sensor cover including the sensor cover protection member.

The present disclosure includes the following aspects.
<1> A siloxane resin containing an organic structure, an inorganic particle-containing layer containing inorganic particles, a photocatalyst layer containing titanium oxide, an amorphous titanium peroxide type inorganic binder, and an antireflection containing a siloxane resin containing an organic structure A layer in this order, the inorganic particle-containing layer has a thickness of 80 nm to 115 nm and a refractive index of less than 1.50, and the antireflection layer has a thickness of 20 nm to 140 nm, and , A photocatalytic composite material having a refractive index of 1.50 to 1.90.
<2>
The photocatalyst composite material according to <1>, wherein the titanium oxide contained in the photocatalyst layer is anatase type titanium oxide.
<3>
The photocatalyst composite material according to <1> or <2>, wherein the photocatalyst layer has a refractive index of 1.5 or more and 2.5 or less.
<4>
The photocatalyst composite material according to any one of <1> to <3>, wherein the antireflection layer has a thickness of 60 nm to 90 nm.
<5>
The photocatalyst composite material according to any one of <1> to <4>, wherein the antireflection layer has a refractive index of 1.55 to 1.86.
<6> The inorganic particle-containing layer has a thickness of 80 nm to 100 nm, and the antireflection layer has a thickness of 70 nm to 80 nm and a refractive index of 1.70 to 1.85. <5> The photocatalyst composite material according to any one of <5>.
<7> The photocatalyst composite material according to any one of <1> to <6>, further including a base material layer on a side of the antireflection layer opposite to the photocatalyst layer side.
<8> A display protection member for signage, comprising the photocatalyst composite material according to any one of <1> to <7>.
<9> A touch panel protection member including the photocatalytic composite material according to any one of <1> to <7>.
<10> A protective member for a solar cell, comprising the photocatalytic composite material according to any one of <1> to <7>.
<11> A sensor cover protective member including the photocatalyst composite material according to any one of <1> to <7>.
<12> A signage display including the signage display protection member according to <8>.
<13> A touch panel comprising the touch panel protection member according to <9>.
<14> A solar cell including the solar cell protection member according to <10>.
<15> A sensor cover including the sensor cover protective member according to <11>.

According to the embodiment of the present disclosure, it is possible to provide a photocatalyst composite material having excellent photocatalytic activity on the surface of the inorganic particle-containing layer side and excellent antireflection properties when light is incident from the inorganic particle-containing layer side. ..
Further, according to another embodiment of the present disclosure, a photocatalyst composite material having excellent photocatalytic activity on the surface of the inorganic particle-containing layer side and having excellent antireflection property when light is incident from the inorganic particle-containing layer side is provided. Signage display protection member, touch panel protection member including the photocatalyst composite material, solar cell protection member including the photocatalyst composite material, sensor cover protection member including the photocatalyst composite material, signage including the signage display protection member. 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.

The description of the constituent elements described below may be made based on a representative embodiment of the present disclosure, but the present disclosure is not limited to such an embodiment.
In the present disclosure, the numerical range represented by “to” means a range including the numerical values before and after “to” as the lower limit value and the upper limit value.
In the numerical ranges described stepwise in the present disclosure, the upper limit or the lower limit described in one numerical range may be replaced with the upper limit or the lower limit of the numerical range described in other stages. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, “(meth)acryl” is a term used as a concept including both acryl and methacryl, and “(meth)acryloxy” is a term used as a concept including both acryloxy and methacryloxy. is there.
In the present disclosure, the term “process” is included in this term as long as the intended purpose of the process is achieved, not only when it is an independent process but also when it cannot be 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 a plurality of substances corresponding to each component are present in the composition. ..
Unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure are gels using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both manufactured by Tosoh Corporation). It is a molecular weight detected by a solvent THF (tetrahydrofuran) and a differential refractometer by a permeation chromatography (GPC) analyzer and converted by using polystyrene as a standard substance. In addition, in the present disclosure, a combination of preferable modes is a more preferable mode.

<<Photocatalyst composite>>
A photocatalyst composite material according to the present disclosure includes (i) a siloxane resin containing an organic structure, and an inorganic particle-containing layer containing inorganic particles, (ii) a photocatalyst layer containing titanium oxide, and (iii) an amorphous titanium peroxide type. An inorganic binder and an antireflection layer containing a siloxane resin having an organic structure are included in this order, and the inorganic particle-containing layer has a thickness of 80 nm to 115 nm and a refractive index of less than 1.50. The antireflection layer has a thickness of 20 nm to 140 nm and a refractive index of 1.50 to 1.90.

The inorganic particle-containing layer according to the present disclosure has a function of improving antireflection property when light is incident on the photocatalyst composite material from the inorganic particle-containing layer side.
Here, when a functional layer made of a material used for a layer having a conventional antireflection function is simply laminated on a conventional photocatalyst layer, the functional layer of radicals generated in the photocatalyst layer is probably used. Due to the problem of migration to the surface, the photocatalytic activity on the surface of the photocatalyst composite material on the inorganic particle-containing layer side may decrease.

The reason why the above drop occurs is probably not simple and involves multiple physical processes. The inventors of the present application have used a photocatalyst layer, have a functional layer as (a) a siloxane resin containing an organic structure and (b) an inorganic particle-containing layer containing inorganic particles, and have a thickness of the inorganic particle-containing layer. It has been found that a proper selection can suppress a decrease in photocatalytic activity when a functional layer is laminated on the photocatalytic layer.
In the photocatalyst composite material of the present disclosure, the inorganic particle-containing layer and the photocatalyst layer are configured as described above, whereby the inorganic particle-containing layer can form a porous structure. Thereby, the radicals generated in the photocatalyst layer can reach the surface of the inorganic particle-containing layer through the pores of the inorganic particle-containing layer, and as a result, the photocatalyst composite material of the present disclosure is presumed to be able to maintain high photocatalytic activity. ..
Further, the photocatalyst composite material according to the present disclosure has excellent antireflection properties when light enters from the inorganic particle-containing layer side.
The above effect is to provide an antireflection layer containing an amorphous titanium peroxide type inorganic binder and a siloxane resin, a photocatalyst layer, and an inorganic particle-containing layer arranged on the side opposite to the antireflection layer side of the photocatalyst layer, It is presumed that a combination of making the refractive index of the antireflection layer larger than that of the inorganic particle-containing layer and setting the thickness of the antireflection layer within a specific range are manifested together.
As described above, the photocatalyst composite material of the present disclosure is excellent in photocatalytic activity on the surface of the inorganic particle-containing layer side and is also excellent in antireflection property when light is incident from the inorganic particle-containing layer side.

<Photocatalyst layer>
The photocatalyst layer in the present disclosure contains titanium oxide, and may contain other components as necessary.

(Titanium oxide)
The titanium oxide used in the present disclosure has photocatalytic activity.
When the photocatalyst layer in the present disclosure is irradiated with, for example, ultraviolet rays, radicals (for example, hydroxy radicals, superoxide anion radicals, etc.) are generated by the photocatalytic action of titanium oxide, and thus, antifouling, antibacterial, antiviral, deodorant The effects such as mold prevention can be obtained. In the present disclosure, the excellent effects of the above-mentioned antifouling, antibacterial, antiviral, deodorant, antifungal, etc. are also referred to as “excellent photocatalytic activity”.

The titanium oxide that can be used in the present disclosure is not particularly limited, and examples thereof include anatase type, rutile type, and brookite type. Among them, the anatase type is preferable from the viewpoint of photocatalytic activity.
The photocatalyst layer in the present disclosure may contain titanium oxide alone, or may contain two or more kinds of titanium oxide particles. The photocatalyst layer according to the present disclosure preferably contains anatase type titanium oxide.
Confirmation that the titanium oxide contained in the photocatalyst layer is anatase type titanium oxide can be performed by X-ray diffraction measurement or Raman spectroscopy measurement.

The existing form of titanium oxide is not particularly limited, but may be a mode in which titanium oxide particles are contained in the photocatalyst layer (hereinafter, also referred to as the first mode), or a titanium oxide film formed by vapor deposition or the like. May be used as the photocatalyst layer (hereinafter, also referred to as a second mode).

[First embodiment]
Hereinafter, first, as a first aspect, an aspect in which the photocatalyst layer contains titanium oxide particles will be described.

The shape of the titanium oxide particles in the present disclosure is not particularly limited, but it 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, more preferably 5 nm to 50 nm.
In the present disclosure, unless otherwise specified, the number average particle size is calculated using a SU-8030 type FE-SEM (field emission scanning electron microscope, accelerating voltage 2 kV, secondary electron image acquisition) manufactured by Hitachi High-Technologies Corporation. To do.
Specifically, it can be determined from the photograph obtained by observing the dispersed particles by FE-SEM. The projected area of each particle is determined, and the equivalent circle diameter of each particle is determined from the projected area, which is used as the particle diameter (that is, the primary particle diameter) of each particle. The number average particle diameter in the present disclosure can be calculated as the arithmetic mean value of the calculated equivalent circle diameters by measuring the projected area of 300 or more particles to determine the equivalent circle diameter of each particle.
As the titanium oxide particles in the present disclosure, the number average particle diameter of commercially available titanium oxide particles may be calculated by the FE-SEM, and products 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, and more preferably 80% by mass with respect to the total mass of the titanium oxide particles. It is more preferably at least mass%, particularly preferably at least 90 mass%.
Components other than TiO ₂ contained in the titanium oxide particles include, for example, SO ₄ ²⁻ , Na ₂ O, etc., but are not limited thereto and may contain other components.
As a specific example of titanium oxide particles, Tio Sky Coat A liquid (manufactured by Tio Systems Co., Ltd.) containing anatase type titanium oxide particles can be used.

The content of the titanium oxide particles in the present disclosure is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, based on the total mass of the antireflection layer.
Further, the photocatalyst layer in the present disclosure may contain titanium oxide particles alone, or may contain two or more kinds of titanium oxide particles.

(Amorphous titanium peroxide type inorganic binder)
The photocatalyst layer in the present disclosure is preferably a layer containing anatase type titanium oxide particles as the above titanium oxide and 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, an oxygen atom or a hydroxy group is eliminated from peroxotitanic acid to obtain a titanium oxide. However, since the heating temperature is low, it is considered that the titanium oxide does not crystallize and exists as amorphous titanium oxide (that is, amorphous titanium peroxide).
In the present disclosure, such amorphous titanium oxide is referred to as an amorphous titanium peroxide type inorganic binder.
Further, in the present disclosure, an anatase phase may be formed in at least a part of amorphous titanium oxide by increasing the heating temperature of peroxotitanic acid, lengthening the heating time, or the like.
The method for producing peroxotitanic acid is not particularly limited, but it can be obtained by allowing hydrogen peroxide to act on titanium hydroxide (eg orthotitanic acid).
Titanium hydroxide is obtained, for example, by reacting titanium tetrachloride with a base.
As a method for obtaining peroxotitanic acid and titanium hydroxide, JP-A-9-262481 can be referred to.

The content of the amorphous titanium peroxide type inorganic binder is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, based on the total mass of the photocatalyst layer.
Further, the photocatalyst layer in the present disclosure may contain one kind of amorphous titanium peroxide type inorganic binder alone, or may use two or more kinds in combination.

The fact that the amorphous titanium peroxide type inorganic binder is contained in the photocatalyst layer can be judged by carrying out the structure identification by the analysis peak and the confirmation that the crystal peak does not appear by X-ray diffraction measurement or Raman spectroscopy measurement. it can.

(Other ingredients)
The photocatalyst layer in the present disclosure may further contain other components.
As other components, known additives such as surfactants can be used without particular limitation.

[Method of forming photocatalyst layer]
The photocatalyst layer in the present disclosure can be obtained, for example, by applying the composition for forming a photocatalyst layer on the antireflection layer described below and heating.
The composition for forming a photocatalyst layer preferably contains the above-mentioned 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 to a composition containing peroxotitanic acid and a solvent.
As the composition containing peroxotitanic acid and a solvent, a commercially available product may be used, and for example, TIO SKYCOAT A liquid (manufactured by Tio Systems Co., Ltd.) may be used.
Further, in order to make the thickness of the photocatalyst layer within the above range, it is preferable to thicken the composition for forming the photocatalyst layer. A thickener can be used for thickening. Examples of the thickener include hydroxyalkyl (C1 to C3) cellulose and the like.

In forming the photocatalyst layer, a method of applying the photocatalyst layer forming composition and heating (that is, drying) a plurality of times may be adopted.
The method of applying the composition for forming a photocatalyst layer is not particularly limited, and a known method may be used, and examples thereof include slit coating, spin coating, curtain coating, inkjet coating and the like.
The heating method for drying the photocatalyst layer-forming composition after coating (that is, the coating film) is not particularly limited and may be a known method, for example, a heater, an oven, a hot plate, an infrared lamp, an infrared ray. Examples include a method using a laser.
The heating time and the heating temperature at the time of heating may be appropriately adjusted in consideration of the heating time and the heating temperature in the production of the above-mentioned amorphous titanium peroxide type inorganic binder.

[Second mode]
As a second aspect of the photocatalyst layer, an aspect in which an anatase type titanium oxide film formed by a vapor deposition method or the like is used as the photocatalyst layer will be described. The details other than the method of forming a film by the vapor deposition method and the like are the same as those in the first aspect, and the preferable aspects are also the same.

The method for forming the anatase-type titanium oxide film is not particularly limited and may be formed by a known method. For example, a titanium oxide film is formed on the antireflection layer by a known vapor deposition method or the like. After that, for example, a method of heating at 400° C. or higher and 700° C. or lower to change the crystal structure of titanium oxide to anatase type can be mentioned.
Here, in order to adjust the refractive index of the photocatalyst layer within the above range, it is also preferable that the photocatalyst layer is made porous (that is, made porous).
The method for making the porous is not particularly limited, and a known method can be used.

-Thickness-
The thickness of the photocatalyst layer is not particularly limited, but from the viewpoint of photocatalytic activity, it is preferably 50 nm or more, more preferably 100 nm or more, and further preferably 200 nm or more.
Further, the thickness is preferably 2,000 nm or less, and preferably 1,000 nm or less from the viewpoint of suppressing the occurrence of cracks and poor adhesion due to an increase in shrinkage stress during coating film formation. More preferable.
The thickness of the photocatalyst layer is a value measured with a contact-type film thickness meter (for example, contact-type film thickness meter manufactured by Anritsu Corporation).

-Refractive index-
In the present disclosure, the refractive index of the photocatalyst layer is preferably 1.5 or more and 2.5 or less, more preferably 1.6 to 2.4, and further preferably 1.7 to 2.3. More preferable.
In the present disclosure, the refractive index is a value measured at 25° C. by ellipsometry (for example, high speed spectroscopic ellipsometer M-2000U, JA Woollam Japan Co., Ltd.) at a wavelength of 600 nm, unless otherwise specified. is there.

<Inorganic particle-containing layer>
The inorganic particle-containing layer contains a siloxane resin having an organic structure and inorganic particles, and has a thickness of 80 nm to 115 nm and a refractive index of less than 1.5.
When the inorganic particle-containing layer contains a siloxane resin having an organic structure and inorganic particles and has a thickness of 80 nm to 115 nm, the photocatalytic activity on the surface of the photocatalyst composite on the inorganic particle-containing layer side can be improved. it can. Further, by setting the refractive index of the inorganic particle-containing layer to less than 1.5 and setting the refractive index of the antireflection layer described later to 1.50 to 1.90, excellent antireflection property can be realized.
When the inorganic particle-containing layer is a hard coat layer having a protective function, the inorganic particle-containing layer is preferably the outermost layer in the photocatalyst composite material according to the present disclosure.
In addition, when the inorganic particle-containing layer is a layer having an antireflection function, a protective layer such as a known hard coat layer may be further provided on the inorganic particle-containing layer.

-Thickness-
The thickness of the inorganic particle-containing layer in the present disclosure is 80 nm to 115 nm.
When the thickness of the inorganic particle-containing layer is 80 nm or more, the reflectance can be suppressed and the antireflection property is improved.
When the thickness of the inorganic particle-containing layer is 115 nm or less, reflection can be suppressed low, and the photocatalytic composite material has excellent photocatalytic activity.
The thickness of the inorganic particle-containing layer can be controlled by adjusting the coating amount of the composition for forming an inorganic particle-containing layer described below.
The thickness of the inorganic particle-containing layer may be designed according to the application, but from the above viewpoint, it is preferably 80 nm to 100 nm.
The thickness of the inorganic particle-containing layer is a value measured by using Dektak150 manufactured by Bruker.

-Refractive index-
In the present disclosure, the refractive index of the inorganic particle-containing layer is less than 1.5. This can improve the antireflection property. From the above viewpoint, the refractive index of the inorganic particle-containing layer is preferably 1.3 or more and less than 1.5, and more preferably 1.4 or more and less than 1.5.
The refractive index of the inorganic particle-containing layer includes the type of siloxane resin having an organic structure, the material of the inorganic particles contained, the content of the inorganic particles, the structure of the inorganic particle-containing layer (for example, a porous structure, etc.), the inorganic particle-containing layer. Can be adjusted according to the thickness of the.
The refractive index of the inorganic particle-containing layer can be measured by the same method as the method for measuring the refractive index of the photocatalyst layer described above.

(Inorganic particles)
The inorganic particle-containing layer in the present disclosure contains inorganic particles.
The inorganic particles may be crosslinked with a siloxane resin having an organic structure in the inorganic particle-containing layer.
From the viewpoint of photocatalytic activity of the photocatalyst layer, examples of the inorganic particles include metal oxide particles that are transparent to light having a wavelength of 350 nm.
In addition, metal oxide particles that are transparent to light having a wavelength of 400 nm to 700 nm are preferable in applications such as signage, touch panels, solar cells, and sensor covers described below.
In the present disclosure, being transparent to the light of the wavelength A means that the transmittance of the light of the wavelength A is 50% or more. The transmittance is preferably 70% or more, more preferably 80% or more. In other words, the reflectance is preferably less than 50%, more preferably less than 20%, and even more preferably less than 10% with respect to the light of wavelength A.
Further, “transparent to wavelengths A to B” means that when the transmittance of light having a wavelength between wavelength A and wavelength B is measured in steps of 10 nm, the arithmetic average value of all transmittances is 50. % Or more. The transmittance is preferably 70% or more, more preferably 80% or more.
Further, the transmittance is measured using a spectrophotometer V670 (manufactured by JASCO Corporation).

Specific examples of the metal oxide particles include silicon dioxide (silica), aluminum oxide (alumina), zirconium oxide (zirconia), and the like, and include silica particles from the viewpoint of crosslinkability with an alkoxysilane compound described later. It is preferable.
Also, from the viewpoint of further improving the antireflection property, the inorganic particles in the present disclosure preferably include silica particles, and the silica particles are preferably colloidal silica.
Commercially available products may be used as the silica particles, and examples of the commercially available products include Snowtex series (colloidal silica; manufactured by Nissan Chemical Industries, Ltd.; eg: Snowtex OXS, Snowtex OZL, Snow). Tex AK-A) and the like.

As the silica particles, dry powdery silica produced by combustion of silicon tetrachloride can be used, and colloidal silica in which silicon dioxide or a hydrate thereof is dispersed in water is more preferable. Specific examples thereof include, but are not limited to, Snowtex series manufactured by Nissan Chemical Industries, Ltd. such as Snowtex 033.
The number average particle diameter of the colloidal silica is preferably 3 nm to 100 nm, more preferably 3 nm to 50 nm, further preferably 4 nm to 50 nm, further preferably 4 nm to 40 nm, further preferably 5 nm to 35 nm is particularly preferable.

The colloidal silica is more preferably adjusted to have a pH in the range of 2 to 7 when added to the composition for forming an inorganic particle-containing layer described below. When the pH is 2 to 7, the stability of silanol, which is a hydrolyzate of an alkoxysilane compound, is better, and the increase in viscosity of the coating solution due to the rapid progress of the dehydration condensation reaction of this silanol can be suppressed. it can.

The number average particle diameter of the inorganic particles in the present disclosure is preferably 3 nm to 100 nm, more preferably 4 nm to 50 nm, further preferably 4 nm to 40 nm, and particularly preferably 5 nm to 35 nm. ..
As the inorganic particles in the present disclosure, the number average particle diameter of commercially available inorganic particles may be calculated by the FE-SEM, and a product containing a desired particle diameter may be selected and used.
The shape of the inorganic particles in the present disclosure is not particularly limited, but from the viewpoint of dispersibility, it is preferably substantially spherical.

With respect to the total mass of the inorganic particle-containing layer in the present disclosure, the content of the inorganic particles is preferably more than 0 mass% and 80 mass% or less, more preferably 1 mass% to 70 mass%, 3 It is more preferable that the amount is from 65% by mass to 65% by mass.
The inorganic particle-containing layer in the present disclosure may contain one type of inorganic particles alone, or may use two or more types in combination.

(Siloxane resin containing organic structure)
The inorganic particle-containing layer contains a siloxane resin having an organic structure.
Here, the “organic structure” refers to a partial structure containing a carbon atom and bonded to —SiO— constituting the siloxane resin.
The organic structure in the siloxane resin containing the organic structure in the inorganic particle-containing layer is preferably a crosslinked structure. The “crosslinked structure” refers to a partial structure in which —SiO— skeletons are connected to each other to form a two-dimensional or three-dimensional network structure.
Further, at least one of the organic structure in the siloxane resin contained in the inorganic particle-containing layer and the organic structure in the siloxane resin contained in the antireflection layer is preferably a crosslinked structure, and contained in the inorganic particle-containing layer. It is more preferable that both the organic structure in the siloxane resin and the organic structure in the siloxane resin contained in the antireflection layer are crosslinked structures.
When the organic structure is a crosslinked structure, the siloxane resins may be crosslinked, or the siloxane resin and the inorganic particles may be crosslinked.
The above organic structure can be confirmed by an intensity ratio of peak intensities calculated by a conventional method from nuclear magnetic resonance spectrum (NMR) measurement. Further, the crosslinked structure can be confirmed by not dissolving when the siloxane resin is dissolved in an organic solvent (for example, toluene).

The organic structure contained as the above-mentioned 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 are each independently a hydrogen atom or an alkyl group. 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, and R ³¹ represents a single bond, an alkyleneoxycarbonyl group, an alkylene group. It represents an aminocarbonyl 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 the alkoxysilane compound described below.
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. When at least two members out of R ¹² to R ¹⁴ combine to form a ring structure, it is preferable that R ¹² or R ¹³ and R ¹⁴ bond together. Further, the above-mentioned ring structure is preferably a hydrocarbon ring, more preferably a cyclohexane ring.
In Formula 1-1, the target to which *, which is the binding site, is bound is not particularly limited, but is preferably a Si atom or an organic group contained in the siloxane resin, and more preferably a Si atom contained in the siloxane resin. preferable.
In formula 1-1, the target to which the binding site, ●, is bound is not particularly limited, but is preferably an atom contained in the siloxane resin. The atom is preferably an oxygen atom.
For example, when 3-glycidoxypropyltrimethoxysilane is used as the alkoxysilane compound, * is bonded to the Si atom, R ¹¹ is a propyleneoxy group, and R ¹² to R ¹⁴ are hydrogen atoms. In that case, for example, ● bonds to an oxygen atom or the like in the siloxane resin.

The structure represented by Formula 1-2 is formed, for example, by using an alkoxysilane compound having an isocyanate group as the 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 the binding site, is bound is not particularly limited, but is preferably a Si atom or an organic group contained in the siloxane resin, and more preferably a Si atom contained in the siloxane resin. preferable.
In Formula 1-2, the target to which the binding site, ●, is bound is not particularly limited, but is preferably an atom contained in the siloxane resin. The atom is preferably an oxygen atom.
For example, when 3-isocyanatopropyltriethoxysilane is used as the alkoxysilane compound, * is bonded to the Si atom and R ²¹ is a propylene group. In that case, for example, ● bonds to an oxygen atom or the like in the siloxane resin.

The structure represented by Formula 1-3 is formed, for example, by using an alkoxysilane compound having an ethylenically unsaturated group as the alkoxysilane compound described later.
In Formula 1-3, R ³¹ preferably represents an alkyleneoxycarbonyl group, an alkyleneaminocarbonyl group or an arylene group, and has an alkyleneoxycarbonyl group having 2 to 10 carbon atoms, an alkyleneaminocarbonyl group having 2 to 10 carbon atoms or phenylene. A group is more preferable, and an alkyleneoxycarbonyl group having 2 to 10 carbon atoms is further preferable.
In formula 1-3, the target to which *, which is the binding site, is bound is not particularly limited, but is preferably a Si atom or an organic group contained in the siloxane resin, and more preferably a 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 it is preferably a structure represented by another 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, ● will polymerize with the methacryloxy group in the other 3-methacryloxypropylmethyldiethoxysilane.

Further, 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, a carboxy group or the like as an 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, based on the total mass of the siloxane resin.
The lower limit of the total content of the organic structure can be 5% by mass or more with respect to the total mass of the siloxane resin in terms of improving the film strength.

The inorganic particle-containing layer may contain one kind of siloxane resin containing an organic structure, or may contain two or more kinds thereof.
The content of the siloxane resin containing an organic structure in the inorganic particle-containing layer is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 35% by mass or more, based on the total mass of the inorganic particle-containing layer. .. The content of the siloxane resin containing an organic structure in the inorganic particle-containing layer is preferably 99% by mass or less, more preferably 97% by mass or less, and further preferably 90% 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 above-mentioned alkoxysilane compound is preferably a water-soluble or water-dispersible material from the viewpoint of reducing environmental pollution due to VOCs (volatile organic compounds).
The composition for forming an inorganic particle-containing layer is preferably an aqueous composition containing water as a solvent. Titanium oxide particles in the above-mentioned photocatalyst layer, and, since the amorphous titanium peroxide type inorganic binder has low solubility in water, the composition for forming an inorganic particle-containing layer contains water as a solvent, after the formation of the photocatalyst layer, Even when the composition for forming an inorganic particle-containing layer is applied onto the photocatalyst layer, mixing between layers can be suppressed.
Further, the composition for forming a layer containing inorganic particles preferably contains substantially no organic solvent. In the present disclosure, “not substantially containing” means that the content is less than 1% by mass, and preferably less than 0.1% by mass. When the composition for forming an inorganic particle-containing layer is applied and dried by substantially not containing an organic solvent, a component that evaporates mainly becomes a water component. Therefore, the load on the environment can be significantly reduced as compared with the case where the organic solvent is included.

The alkoxysilane compound preferably contains a crosslinkable group-containing alkoxysilane compound and a crosslinkable group-free alkoxysilane compound, and contains an epoxy group-containing alkoxysilane compound and an epoxy group-free alkoxysilane compound. Is more preferable.

Both the crosslinkable group-containing alkoxysilane compound and the non-crosslinkable group-containing alkoxysilane compound can have a hydrolyzable group. The hydrolyzable group is hydrolyzed in, for example, an acidic aqueous solution to produce silanol, and the silanols are condensed with each other to produce a siloxane resin.
In the composition for forming an inorganic particle-containing layer according to the present disclosure, a part of the crosslinkable group-containing alkoxysilane compound and the non-crosslinkable group-containing 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, and a radically polymerizable group-containing alkoxysilane compound, and preferably include 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 may be one having at least one epoxy group in one molecule, and the number of epoxy groups is not particularly limited. The epoxy 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 epoxy 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, and 2-(3,4 -Epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, Examples thereof include 3-glycidoxypropyltriethoxysilane. Examples of commercially available products include KBE-403 (manufactured by Shin-Etsu Chemical Co., Ltd.).

~ Isocyanate group-containing alkoxysilane compounds ~
The isocyanate group-containing alkoxysilane compound is an alkoxysilane compound having an isocyanate group. The isocyanate group-containing alkoxysilane compound may be any alkoxysilane compound having 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 and 3-isocyanatepropyltrimethoxysilane. Examples of commercially available products include KBE-9007 (manufactured by Shin-Etsu Chemical Co., Ltd.).

~ Alkoxysilane compounds containing radically polymerizable groups ~
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 alkoxysilane compound having one or more radical polymerizable groups in one molecule, and the number of radical polymerizable groups is not particularly limited.
The radically polymerizable group is not particularly limited, and examples thereof include (meth)acryloxy group, (meth)acrylamide group, vinylphenyl group, vinyl group, and allyl group.
The radical polymerizable 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 and a carboxy group in addition to the radical polymerizable group.

Examples of the radical 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. Examples of commercially available products include KBM-1003, KBE-1003, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.).
When the composition for forming an inorganic particle-containing layer contains a radically polymerizable group-containing alkoxysilane compound, the composition for forming an inorganic particle-containing layer may further contain a known radical polymerization initiator.

The content of the crosslinkable group-containing alkoxysilane compound, the stability of the inorganic particle-containing layer forming composition, and from the viewpoint of improving the alkali resistance of the resulting inorganic particle-containing layer, to the inorganic particle-containing layer forming composition. It is preferably 20% by mass to 85% by mass with respect to the total mass of the alkoxysilane compound contained. The content of the crosslinkable group-containing alkoxysilane compound is more preferably 25% by mass or more and 30% by mass or more based on the total mass of the alkoxysilane compound contained in the composition for forming an inorganic particle-containing layer. Is more preferable. Further, the content of the crosslinkable group-containing alkoxysilane compound is more preferably 80% by mass or less, and further preferably 75% by mass or less.

(Crosslinkable group-free alkoxysilane compound)
The crosslinkable group-free alkoxysilane compound is an alkoxysilane compound having no crosslinkable group. The crosslinkable group-free alkoxysilane compound may be any 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 have.

The crosslinkable group-free alkoxysilane compound is preferably a tetraalkoxysilane compound or a trialkoxysilane compound, or a mixture of a tetraalkoxysilane compound and a trialkoxysilane compound. The crosslinkable group-free alkoxysilane compound is preferably a mixture of a tetraalkoxysilane compound and a trialkoxysilane compound, and by mixing and containing a tetraalkoxysilane compound and a trialkoxysilane compound, the inorganic particle-containing layer is formed. When 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 and the trialkoxysilane compound is 25:75 to 85:15. The ratio is preferably 30:70 to 80:20, more preferably 30:70 to 65:35. By setting the molar ratio within the above range, it becomes easy to control the degree of polymerization of the alkoxysilane compound within a desired range and control the hydrolysis rate and the solubility of the aluminum chelate.

The tetraalkoxysilane compound is a tetrafunctional alkoxysilane compound, and it is more preferable that each alkoxy group has 1 to 4 carbon atoms. Among them, a tetramethoxysilane compound or a tetraethoxysilane compound is particularly preferably used. By setting the number of carbon atoms of each alkoxy group to 4 or less, the hydrolysis rate of the tetraalkoxysilane compound when mixed with acidic water does not become too low, and the time required for dissolution to form a uniform aqueous solution is further improved. It gets shorter. Thereby, the formation efficiency at the time of forming an inorganic particle content layer can be raised. Examples of commercially available products 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 the formula A, R is an organic group containing no amino group and having 1 to 15 carbon atoms, and R ¹ is an alkyl group having 4 or less carbon atoms.

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

In the formula A, R may be any organic group having a molecular chain length of 1 to 15 carbon atoms. By setting the carbon number to 15 or less, the flexibility of the inorganic particle-containing layer does not become too large, and sufficient hardness can be obtained. Further, by setting the carbon number of R within the above range, an inorganic particle-containing layer having excellent brittleness can be obtained. Furthermore, the adhesion between the photocatalyst layer and the inorganic particle-containing layer can be improved.
Further, R is preferably a group in which the Si atom in formula A and the carbon atom in R are directly bonded.
Further, the organic group represented by R may have a hetero atom such as oxygen, nitrogen or sulfur. When the organic group has a hetero atom, the adhesion with the photocatalyst layer can be improved.

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

The content of the crosslinkable group-free alkoxysilane compound is an inorganic particle-containing layer from the viewpoint of improving the stability of the composition for forming an inorganic particle-containing layer, and from the viewpoint of improving the alkali resistance of the obtained inorganic particle-containing layer. It is preferably 15% by mass to 80% by mass based on the total mass of the alkoxysilane compound contained in the composition for forming. The content of the crosslinkable group-free alkoxysilane compound is more preferably 20% by mass or more and 30% by mass or more based on the total mass of the alkoxysilane compound contained in the composition for forming an inorganic particle-containing layer. More preferably,
The content of the crosslinkable group-free alkoxysilane compound is more preferably 75% by mass or less, further preferably 70% by mass or less.

(Inorganic particles)
The inorganic particle-containing layer forming composition contains 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-mentioned 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, from the viewpoint of photocatalytic activity and alkali resistance of the inorganic particle-containing layer, the content of the inorganic particles based on the total solid content of the composition for forming an inorganic particle-containing layer is x. When it is defined as mass %, it is preferable that 0 mass %<x mass %≦80 mass %. The x mass% is more preferably 1 mass% or more, further preferably 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.

Further, when the content of the inorganic particles with respect to the total solid content 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 relationship between y mass% and mass% of x to be in the above range, it is possible to obtain higher alkali resistance of the inorganic particle-containing layer, and to change the 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 (hardener))
The inorganic particle-containing layer forming composition preferably contains a metal complex (curing agent). That is, the inorganic particle-containing layer in the present disclosure preferably contains a metal complex.
As the metal complex, a metal complex having at least one metal selected from the group consisting 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, 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(ethylacetoacetate), alkylacetoacetate aluminum diisopropylate, aluminum monoacetylacetate bis(ethylacetoacetate), aluminum tris(acetyl). Acetonate) and other aluminum chelate compounds, ethyl acetoacetate magnesium monoisopropylate, magnesium bis(ethylacetoacetate), alkylacetoacetate magnesium monoisopropylate, magnesium bis(acetylacetonate) and other magnesium chelate compounds, zirconium tetraacetylacetate Examples include nato, zirconium tributoxyacetylacetonate, zirconium acetylacetonate bis(ethylacetoacetate), manganese acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, titanium acetylacetonate, and titanium oxyacetylacetonate. Of these, preferred are aluminum tris(acetylacetonate), aluminum tris(ethylacetoacetate), magnesium bis(acetylacetonate), magnesium bis(ethylacetoacetate), and zirconium tetraacetylacetonate, which are storage stable. Considering the properties and 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, and aluminum chelate M (manufactured by Kawaken Fine Chemicals Co., Ltd.).

The content of the metal complex is preferably 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 more preferably 65 mol% or less, further preferably 60 mol% or less.
When the content of the metal complex is 17 mol% or more, excellent alkali resistance can be obtained when the inorganic particle-containing layer is formed. Further, when the content of the metal complex is 70 mol% or less, the dispersibility of the metal complex in the composition for forming an inorganic particle-containing layer can be improved, and the manufacturing cost can be suppressed.

(Other additives)
The inorganic particle-containing layer forming composition used in the present disclosure, and the inorganic particle-containing layer may contain a surfactant for the purpose of improving the smoothness of the layer and reducing the friction on the surface of the coating film. .. Examples of the surfactant include the surfactants described in paragraphs 0039 to 0044 of JP-A-2014-111717.
The inorganic particle-containing layer may be colored by dispersing a pigment, a dye, or other particles. Furthermore, an antioxidant and the like may be added to the composition for forming an inorganic particle-containing layer and the inorganic particle-containing layer used in the present disclosure for the purpose of improving weather resistance.

[Method of forming inorganic particle-containing layer]
The inorganic particle-containing layer is formed by applying the composition on the photocatalyst layer and heating (that is, drying).
The method of applying the composition for forming an inorganic particle-containing layer is not particularly limited, and a known method may be used, and examples thereof include slit coating, spin coating, curtain coating, inkjet coating and the like.
The heating method for drying the composition for forming an inorganic particle-containing layer (that is, the coating film) is not particularly limited, and a known method may be used, for example, a heater, an oven, a hot plate, an infrared lamp, an infrared laser. And the like.
An easily-adhesive layer described below may be provided between the inorganic particle-containing layer and the photocatalyst layer.

[Characteristics of layer containing inorganic particles]
The inorganic particle-containing layer is a layer having an antireflection function. In addition, the inorganic particle-containing layer can be provided with a plurality of functions such as excellent scratch resistance.
The refractive index is a value measured at 25° C. by ellipsometry at a wavelength of 600 nm unless otherwise specified.

<Antireflection layer>
The antireflection layer in the present disclosure contains an amorphous titanium peroxide type inorganic binder and a siloxane resin having an organic structure, has a thickness of 20 nm to 140 nm and a refractive index of 1.50 to 1.90.
In the photocatalyst composite material of the present disclosure, from the viewpoint of antireflection property, an antireflection layer may be provided between the substrate and the photocatalyst layer, and the thickness and refractive index of the antireflection layer may be specified as described above. is important. Furthermore, in the antireflection layer in the present disclosure, for example, an amorphous titanium peroxide type inorganic binder that is a component that can be included in the photocatalyst layer, and a siloxane resin that is a component included in the inorganic particle-containing layer can be used. Work efficiency can be improved.

-Thickness-
The thickness of the antireflection layer is 20 nm to 140 nm. As a result, the reflectance can be suppressed low and the antireflection property can be improved.
From the same viewpoint as above, the thickness of the antireflection layer is preferably 40 nm to 110 nm, more preferably 50 nm to 100 nm, further preferably 60 nm to 90 nm, and particularly preferably 70 nm to 80 nm.
The thickness of the antireflection layer can be measured by the same method as the method for measuring the thickness of the inorganic particle-containing layer described above.

-Refractive index-
In the photocatalyst composite material of the present disclosure, the refractive index of the antireflection layer is 1.50 to 1.90. Thereby, the antireflection property can be further improved.
From the same viewpoint as above, the refractive index of the antireflection layer is preferably 1.55 to 1.86, more preferably 1.70 to 1.85.
The refractive index of the antireflection layer can be measured by the same method as described above.
The refractive index of the antireflection layer is adjusted by the type and content of the siloxane resin having an organic structure and the amorphous titanium peroxide type inorganic binder, the structure of the antireflection layer (for example, a porous structure), the thickness of the antireflection layer, and the like. It is possible.
For example, the refractive index of the antireflection layer can be adjusted by changing the ratio of the content of the amorphous titanium peroxide type inorganic binder to the content of the siloxane resin having an organic structure.

(Amorphous titanium peroxide type inorganic binder)
The antireflection layer in the present disclosure includes an amorphous titanium peroxide type inorganic binder.
As the amorphous titanium peroxide type inorganic binder in the antireflection layer, the same specific examples as the specific examples given in the description of the amorphous titanium peroxide type inorganic binder in the photocatalyst layer can be used, and the preferred embodiments are also the same.

The content of the amorphous titanium peroxide type inorganic binder is 5% by mass to 95% by mass based on the total mass of the siloxane resin containing an organic structure described below and the amorphous titanium peroxide type inorganic binder in the antireflection layer. It is more preferably from 18% by mass to 93% by mass.
Further, the antireflection layer in the present disclosure may contain one type of amorphous titanium peroxide type inorganic binder alone, or may use two or more types in combination.
The fact that the amorphous titanium peroxide type inorganic binder is contained in the antireflection layer can be confirmed by the same method as the method for confirming that the photocatalyst layer contains the amorphous titanium peroxide type inorganic binder.

(Siloxane resin containing organic structure)
The antireflection layer in the present disclosure includes a siloxane resin having an organic structure.
As the siloxane resin containing an organic structure in the antireflection layer, the same siloxane resin containing an organic structure in the above-mentioned inorganic particle-containing layer can be used, and the preferred embodiments are also the same.

The content of the siloxane resin containing an organic structure is preferably 20% by mass to 80% by mass, and 30% by mass with respect to the total mass of the siloxane resin containing an organic structure and the amorphous titanium peroxide type inorganic binder in the antireflection layer. % To 70% by mass is more preferable.

In the antireflection layer, the ratio of the content of the siloxane resin containing an organic structure to the content of the amorphous titanium peroxide type inorganic binder is preferably 20/80 to 80/20, and 30/70 to 70/30 is more preferable.

(Titanium oxide)
The antireflection layer in the present disclosure may include titanium oxide.
Specific examples of the titanium oxide that may be contained in the antireflection layer in the present disclosure are the same as the specific examples given in the description of the titanium oxide, and the preferred embodiments are also the same.

(Other ingredients)
The antireflection layer in the present disclosure may further contain other components.
As other components, known additives such as surfactants can be used without particular limitation.

[Method of forming antireflection layer]
The antireflection layer in the present disclosure can be obtained by applying the composition for forming an antireflection layer to, for example, a base material described later and heating (that is, drying).
The antireflection layer-forming composition preferably contains the alkoxysilane compound in the inorganic particle-containing layer described above and peroxotitanic acid.
As an example, the antireflection layer-forming composition is prepared by mixing and dispersing an alkoxysilane compound 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, and for example, TIO SKYCOAT C liquid (manufactured by Tio Systems Co., Ltd.) can be used.
Further, in order to set the thickness of the antireflection layer in the above range, the composition for thickening the antireflection layer is thickened, and the coating and heating (that is, drying) of the composition for antireflection layer formation are performed a plurality of times. May be adopted.

The method of applying the composition for forming an antireflection layer is not particularly limited, and a known method may be used, and examples thereof include slit coating, spin coating, curtain coating, inkjet coating and the like.
The heating method for drying the antireflection layer-forming composition (that is, the coating film) is not particularly limited and may be a known method, for example, a heater, an oven, a hot plate, an infrared lamp, an infrared laser, or the like. Are listed.
The heating time and the heating temperature at the time of heating may be appropriately adjusted with reference to the description of the heating time and the heating temperature in the production of the above-mentioned amorphous titanium peroxide type inorganic binder.

As described above, in the photocatalyst composite material of the present disclosure, the inorganic particle-containing layer has a thickness of 80 nm to 100 nm, the antireflection layer has a thickness of 60 nm to 90 nm, and the refractive index of 1.55 to 1 Preferably, the inorganic particle-containing layer has a thickness of 80 nm to 100 nm, the antireflection layer has a thickness of 70 nm to 80 nm, and a refractive index of 1.70 to 1.85. More preferably.

<Base material layer>
The photocatalyst composite material according to the present disclosure preferably further includes a base material layer on the side of the antireflection layer opposite to the side having the photocatalyst layer (that is, the photocatalyst layer side).
The base material layer is a layer formed of a base material, and examples of the base material in the base material layer include a resin base material, a glass base material, and a metal base material.
The resin substrate is not particularly limited, but polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polybutylene naphthalate (PBN), polyarylates, polyether sulfone, polycarbonate, poly Ether ketone, polysulfone, polyphenylene sulfide, polyester type liquid crystal polymer, triacetyl cellulose, cellulose derivative, polypropylene, polyamides, polyimide, polycycloolefins and the like are preferable. Among the above, PET, PEN, or triacetyl cellulose is more preferable, and PET or PEN is further preferable.
The resin substrate may be stretched and is preferably biaxially stretched. Biaxial stretching means stretching in both directions by regarding the width direction and the longitudinal direction of the resin film as uniaxial. The biaxially stretched polyester film has extremely excellent mechanical strength because the biaxial molecular orientation is sufficiently controlled. The draw ratio is not particularly limited, but the draw ratio per one axial direction is preferably 1.5 times to 7 times, and more preferably 2 times to 5 times. In particular, a polyester film biaxially stretched with a draw ratio of 2 to 5 times per uniaxial direction has very excellent mechanical strength because its molecular orientation is controlled more efficiently and effectively. It is suitable as a polyester film.
The glass substrate is not particularly limited, but it is a transparent glass plate, a shaped glass plate, a netted glass plate, a wire glass plate, a tempered glass plate, a heat ray reflective glass plate, a heat ray absorbing glass plate, Low-E (Low Emissivity, A glass substrate such as a (low reflection) glass plate may be used.
The metal base material is not particularly limited, and examples thereof include an aluminum plate, a steel plate, a copper plate, and other alloy plates.

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

<Easy adhesion layer>
The photocatalyst composite material according to the present disclosure has a base material and an antireflection layer, an antireflection layer and a photocatalyst layer, or an easy adhesion layer for the purpose of improving the adhesiveness between the photocatalyst layer and the inorganic particle-containing layer. Good.
The easy-adhesion layer is formed, for example, by applying a coating liquid containing a binder, a curing agent, and a surfactant to the surface of the substrate on which the antireflection layer is provided, the surface on which the photocatalytic layer of the antireflection layer is provided, or the inorganic material of the photocatalytic layer. It is formed by coating on the surface on which the particle-containing layer is formed. Organic or inorganic particles may be appropriately added to the easy-adhesion layer. The particles are not particularly limited, but examples thereof include metal oxides, and specifically, tin oxide, zirconium oxide, zinc oxide, titanium oxide, cerium oxide, niobium oxide and the like are preferable, and these are used alone or in two kinds. You may use together the above. Examples of commercially available products include ET-500W and other ET series, FT-2000 and other FT series, SN-100P and other SN series, FS-10D and other FS series (manufactured by Ishihara Sangyo Co., Ltd.) and the like.

The binder contained in the easy-adhesion layer is not particularly limited, but preferably contains at least one of polyester, polyurethane, acrylic resin, styrene-butadiene copolymer and polyolefin from the viewpoint of adhesiveness. When the surface of the substrate is not surface-treated, the binder preferably contains at least one of polyester, polyurethane and polyolefin, more preferably polyolefin.
Further, as the binder, a water-soluble or water-dispersible binder is particularly preferable in that the load on the environment is small. Examples of commercially available products include Carbodilite series such as Carbodilite V-02-L2 (manufactured by Nisshinbo Co., Ltd.), Takerak WS series such as Takerak WS-5100 (manufactured by Mitsui Chemicals Inc.), Arrowbase SE1013N, Examples include Arrow Base series (manufactured by Unitika Ltd.) and Hardren series (manufactured by Toyobo Co., Ltd.) such as Hardlen NZ1004.
However, the binder used for the easy-adhesion layer does not include the above-mentioned amorphous titanium peroxide type inorganic binder.

The thickness of the easy-adhesion layer can be appropriately adjusted by adjusting the coating amount. The thickness of the easily adhesive layer is more preferably in the range of 0.01 μm to 5 μm. If the thickness is 0.01 μm or more, the adhesiveness tends 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. The easy-adhesion layer may be a single layer or a plurality of layers. When a plurality of easy-adhesion layers are stacked, the above thickness indicates the total thickness of all the easy-adhesion layers.

<Other layers>
The photocatalyst composite material according to the present disclosure may have a shielding layer between the base material layer and the antireflection layer.
For example, it is considered that radicals generated in the photocatalyst layer or the antireflection layer are trapped by the shielding layer, so that deterioration of the base material layer due to radicals such as the resin base material 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 except that it does not contain inorganic particles can be used as the shielding layer.

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

(Display protection member for signage, display for signage)
The display protection member for signage according to the present disclosure includes the photocatalytic composite material according to the present disclosure.
The signage display according to the present disclosure includes a signage display protection member according to the present disclosure.The signage display protection member according to the present disclosure has excellent photocatalytic activity on the surface of the inorganic particle-containing layer side, and thus, for example, contains inorganic particles. By making the layer the surface of the outermost layer in the display for signage, it is possible to prevent the attachment of dirt.
Further, the photocatalyst composite material according to the present disclosure is excellent in antireflection property, and thus by being used as a signage display protection member, it is possible to suppress reflection of light on the signage display and improve the visibility of the display image. It will be possible.
As the signage display protection member, for example, on a signage display, a photocatalyst composite material formed by laminating an antireflection layer, a photocatalyst layer and an inorganic particle-containing layer in this order is used as a signage display protection member. Alternatively, for example, a resin film as a base material layer, a photocatalyst composite material in which an antireflection layer, a photocatalyst layer and an inorganic particle-containing layer are laminated in this order on the base material layer is attached to a signage display as a signage display protection member. You may use it.
Further, the signage in the present disclosure is preferably a digital signage.
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. To be

(Protective member for touch panel, touch panel)
A touch panel protection member according to the present disclosure includes the photocatalytic composite material according to the present disclosure.
A touch panel according to the present disclosure includes the touch panel protection member according to the present disclosure.
The protective member for a touch panel according to the present disclosure has excellent photocatalytic activity on the surface of the inorganic particle-containing layer side, and therefore, for example, by using the inorganic particle-containing layer as a touch portion (that is, a portion that the hand touches) in the touch panel, fingerprints and the like It is possible to prevent the adhesion of dirt or facilitate the removal of dirt.
Further, since the photocatalyst composite material according to the present disclosure has excellent antireflection properties, it is used as a touch panel protection member in a touch panel display device, for example, to suppress reflection of light on the touch panel display device and to improve visibility of a display image or the like. It becomes possible to improve.
As the touch panel protection member, for example, a photocatalyst composite material formed by laminating an antireflection layer, a photocatalyst layer and an inorganic particle-containing layer in this order on the outermost member of a conventional touch panel is formed as the touch panel protection member. Or a resin film as a base material layer, and a photocatalyst composite material in which an antireflection layer, a photocatalyst layer, and an inorganic particle-containing layer are laminated in this order on the base material layer as a protective member for a touch panel in the conventional touch panel. You may stick and use it for the member used as the outermost layer.
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 members for solar cells, solar cells)
The solar cell protection member according to the present disclosure includes the photocatalyst composite material according to the present disclosure.
A solar cell according to the present disclosure includes the solar cell protection member according to the present disclosure.
Since the protective member for a solar cell according to the present disclosure has excellent photocatalytic activity on the surface of the inorganic particle-containing layer side, for example, by forming the inorganic particle-containing layer as the outermost layer in the solar cell front sheet, the adhesion of dirt is prevented. can do.
Moreover, since the photocatalyst composite material according to the present disclosure has excellent antireflection properties, it is possible to suppress reflection of light on the solar cell panel and improve the power generation efficiency of the solar cell by using it as a solar cell protection member. Becomes
As the solar cell protective member, for example, an antireflection layer, a photocatalyst layer, and an inorganic particle-containing layer are laminated in this order on a member (for example, a solar cell front sheet) that is an outermost layer in a conventional solar cell protective member. The photocatalyst composite material formed as described above may be formed and used as a protective member for a solar cell, for example, a resin film as a base material layer, and an antireflection layer, a photocatalyst layer and an inorganic particle-containing layer on the base material layer The photocatalyst composite material laminated in order may be used as a protective member for a solar cell by being attached to a member which is the outermost layer in a conventional solar cell.
Regarding the front sheet for solar cells, the description in JP 2011-62877 A or the like can be referred to.

(Protective member for sensor cover, sensor cover)
The sensor cover protection member 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.
The protective member for a sensor cover according to the present disclosure has excellent photocatalytic activity on the surface of the inorganic particle-containing layer side, and therefore, for example, by forming the inorganic particle-containing layer as the outermost layer in the sensor cover, it is possible to prevent adhesion of dirt. it can.
Further, since the photocatalyst composite material according to the present disclosure has excellent antireflection properties, it can be used as a protective member for a sensor cover, for example, to suppress reflection of light on the sensor cover and improve sensor sensitivity.
Examples of the sensor include LiDAR (Light Detection and Ranging) using infrared rays.
In the case of LiDAR, it is possible to improve the measurement accuracy when, for example, measuring a scattering hole for laser irradiation emitted in a pulse shape.
As the sensor cover protection member, for example, a photocatalyst composite material formed by laminating an antireflection layer, a photocatalyst layer, and an inorganic particle-containing layer in this order on the outermost member of a conventional sensor cover is used as a sensor cover protection member. It may be formed as a member and used, for example, a photocatalyst composite material in which a resin film is used as a base material layer, an antireflection layer, a photocatalyst layer and an inorganic particle-containing layer are laminated in this order on the base material layer, and a protective member for a sensor cover. Alternatively, it may be attached to the outermost member of the conventional sensor cover and used.
Examples of the sensor cover include a sensor cover in a camera module, and the description in JP-A-2016-130746 and the like can be referred to.

(Other uses)
In addition, the protective member including the photocatalyst composite material according to the present disclosure includes 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 shield film, and the like. It is also suitably used as a protective member of.

Hereinafter, the present disclosure will be described in detail with reference to Examples. The materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the embodiments of the present disclosure. Therefore, the scope of the embodiments of the present disclosure is not limited to the specific examples shown below. In the examples, “parts” and “%” mean “parts by mass” and “mass %” unless otherwise specified.
In this example, the thickness and the refractive index were measured by the method described above.

<<Example 1 to Example 5, Example 7 to Example 10, and Comparative Example 1 to Comparative Example 17>>
<Preparation of photocatalytic composite material>
(Preparation of composition for forming photocatalyst layer)
A composition for forming a photocatalyst layer was prepared by thickening Tyo Sky Coat A solution which is an aqueous solution by the following method.
Tio Sky Coat A liquid (manufactured by Tio Systems) is an aqueous composition containing anatase type (crystalline) titanium oxide particles having a number average particle diameter of 5 nm to 20 nm and peroxotitanic acid as main components.

<Thickening method of Tio Sky Coat A liquid>
As the thickener, a 10% aqueous solution of hydroxyalkyl (1 to 3 carbon atoms) cellulose was used.
The above-mentioned thickener was added to the above-mentioned Tiosky coat A liquid in an amount of 30.7% based on the total mass of the above-mentioned Tiosky coat A liquid and the above-mentioned thickener to increase the viscosity.

(Preparation of Inorganic Particle-Containing Layer Forming Composition)
The compounds described in the composition below were mixed in the following procedure to prepare a composition for an inorganic particle-containing layer.
The epoxy group-containing alkoxysilane compound (KBE403) was added to 100 parts by mass of a 1% acetic acid aqueous solution and sufficiently hydrolyzed, and then tetraalkoxysilane (KBE04) was added. An aluminum chelate complex was added to an epoxy group-containing alkoxysilane compound, and inorganic particles S1 (silica particles, Snowtex OXS, manufactured by Nissan Chemical Industries, Ltd., number average particle diameter 4 nm) were added thereto. After that, 0.2 part by mass of each of surfactant A (10% diluted solution of Sandet BL) and surfactant B (10% diluted solution of Narrow Acty CL-95) is added to give a solid content concentration of 15%. Thus, water was added to obtain a composition for forming an inorganic particle-containing layer.
-composition-
-Epoxy group-containing alkoxysilane compound (3-glycidoxypropyltriethoxysilane (crosslinkable group-containing alkoxysilane compound), Shin-Etsu Chemical Co., Ltd., KBE-403): 80 parts by mass-Tetraalkoxysilane (tetraethoxy) Silane (alkoxysilane compound containing no crosslinkable group), Shin-Etsu Chemical Co., Ltd., KBE-04): 20 parts by mass acetic acid aqueous solution (manufactured by Daicel Chemical Industries, Ltd., 1% aqueous acetic acid solution): 100 Parts by mass, aluminum chelate complex (Kawaken Fine Chemicals Co., Ltd., aluminum chelate D): 22.1 parts by mass, inorganic particles S1: 200 parts by mass, surfactant A (manufactured by Sanyo Kasei Co., Ltd., Sanded BL) 10% diluted solution, anionic): 0.2 parts by mass Surfactant B (manufactured by Sanyo Kasei Co., Ltd., 10% diluted solution of Naloacty CL-95, nonionic): 0.2 parts by mass

(Preparation of composition for forming antireflection layer)
The compounds described in the following composition were mixed according to the following procedure to prepare a composition for forming an antireflection layer.
Epoxy group-containing alkoxysilane compound (3-glycidoxypropyltriethoxysilane) in 100 parts by mass of 1% acetic acid aqueous solution (manufactured by Daicel Chemical Industries, Ltd., 1% aqueous acetic acid solution) (Shin-Etsu Chemical Co., Ltd.) (KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd., manufactured by Shin-Etsu Chemical Co., Ltd., KBE-04) was added to the mixture, and 80 parts by mass of KBE-403) was added to sufficiently hydrolyze. A composition was obtained.
Then, Tiosky Coat C liquid was added to the above siloxane resin-containing composition, and water was added so that the solid content concentration became 15%, and the composition for forming an antireflection layer used in each Example or Comparative Example. I made it a thing.
-composition-
・Epoxy group-containing alkoxysilane compound (3-glycidoxypropyltriethoxysilane (crosslinkable group-containing alkoxysilane compound), Shin-Etsu Chemical Co., Ltd., KBE-403): 80 parts by mass ・Tetraalkoxysilane (tetraethoxy) Silane (alkoxysilane compound containing no crosslinkable group), Shin-Etsu Chemical Co., Ltd., KBE-04): 20 parts by mass acetic acid aqueous solution (manufactured by Daicel Chemical Industries, Ltd., 1% aqueous acetic acid solution): 100 Parts by mass Tiosky Coat C liquid (aqueous composition containing peroxotitanic acid (titanium oxide particles are not included), manufactured by Tio Systems): Peroxotitanic acid (titanium peroxide) in the composition for forming antireflection layer Is the amount described in Table 1-Siloxane resin-containing composition: Amount that the siloxane resin is the amount described in Table 1.

[Formation of antireflection layer]
After the composition for forming an antireflection layer obtained above was dropped on a glass substrate (refractive index 1.50), a spin coater (MS-A100 manufactured by Mikasa Co., Ltd.) was used. The number of rotations was adjusted so that the thickness was as described, and the coating was spread.
Then, using a hot plate (Digital Hot Plate HP-2SA manufactured by As One Co., Ltd.), water was dried under the conditions of 170° C. for 2 minutes to form an antireflection layer.
Further, that the formed antireflection layer contains an amorphous titanium peroxide type inorganic binder, it is necessary to confirm the structure identification by the analysis peak and the confirmation that the crystal peak does not appear by X-ray diffraction measurement or Raman spectroscopy measurement. Confirmed by. The fact that the antireflection layer has a crosslinked structure (organic structure) was confirmed by immersing the antireflection layer formed above in toluene and the siloxane resin was not dissolved.
The thickness of the antireflection layer was measured using Dektak150 manufactured by Bruker.
Further, in Table 2, the antireflection layer was not formed for the examples or comparative examples described as "-" in the column of the antireflection layer of each example or comparative example.

[Formation of photocatalyst layer]
After dropping the composition for forming a photocatalyst layer on the antireflection layer produced by the above method, a spin coater (MS-A100 manufactured by Mikasa Co., Ltd.) was used to rotate at a rotation speed of 800 rpm (revolutions per minute)×30 seconds. Spin coated and spread.
Then, the water in the applied composition for forming a photocatalyst layer was dried on a hot plate (Digital Hot Plate HP-2SA manufactured by As One Co., Ltd.) at 120° C. for 10 minutes, and the photocatalyst layer (TiO 2) having a thickness of 500 nm after drying was dried. _Two layers with a refractive index of 1.94) were formed.
The thickness of the photocatalyst layer was measured using a contact type film thickness meter manufactured by Anritsu Corporation.

[Formation of layer containing inorganic particles]
The composition for forming an inorganic particle-containing layer was dropped on the photocatalyst layer produced by the above method, and the thickness after drying was set to the thickness shown in Table 2 using a spin coater (MS-A100 manufactured by Mikasa Co., Ltd.). The number of rotations was adjusted so that it was spread. Then, the water in the applied composition for forming an inorganic particle-containing layer is dried on a hot plate (Digital Hot Plate HP-2SA manufactured by As One Co., Ltd.) at a predetermined temperature for a drying time to form an inorganic particle-containing layer. , A photocatalyst composite material.
The thickness of the inorganic particle-containing layer was measured using Dektak150 manufactured by Bruker.
The fact that the inorganic particle-containing layer has a crosslinked structure (organic structure) was confirmed by immersing the inorganic particle-containing layer formed above in toluene and dissolving the siloxane resin.
Further, in Table 2, in the column of the inorganic particle-containing layer of each Example or Comparative Example, the inorganic particle-containing layer was not formed for the Examples or Comparative Examples described as "-".

<<Example 6>>
In the formation of the photocatalyst layer of Example 1, a 1:1 (mass ratio) mixed solution of the Tiosky coat A liquid and the Tiosky coat A liquid (in Table 2, simply “A liquid+C liquid”) was used. A photocatalyst composite material was obtained by the same method as in Example 1 except that the photocatalyst composite material was changed to.

<Measurement of water contact angle>
[Removal of organic substances on the surface of photocatalyst composite material]
An ultraviolet irradiator equipped with a low-pressure mercury lamp was used to irradiate the surface of the photocatalyst composite material on the inorganic particle-containing layer side with ultraviolet light for 5 minutes at an irradiation intensity of 20 mW/cm ² . The wavelength of the ultraviolet rays to be irradiated was 365 nm.
UVGL-25 manufactured by UVP Co., Ltd. was used as the ultraviolet irradiator.

[Application of oleic acid]
200 μl of oleic acid was dropped on the surface of the photocatalyst composite material on the side of the inorganic particle-containing layer, and then spread evenly with a non-woven fabric, and wiped off so that the applied amount of oleic acid was 2.0±0.2 mg per 100 cm ^2. I adjusted it with.
As the oleic acid, one manufactured by Tokyo Chemical Industry Co., Ltd. was used.

[UV irradiation and evaluation of water contact angle]
After applying the oleic acid, an ultraviolet irradiator equipped with a low-pressure mercury lamp was used to irradiate the surface of the photocatalyst composite material on the inorganic particle-containing layer side with ultraviolet light at an irradiation intensity of ² mW/cm ² . The wavelength of the ultraviolet rays to be irradiated was 365 nm.
As the UV irradiator, the above UVGL-25 manufactured by UVP was used.
The water contact angle is measured every 1 hour from the start of ultraviolet irradiation, and the time from the time when the water contact angle reaches the peak to the time when the water contact angle becomes less than 10° is measured and evaluated according to the following evaluation criteria. , And in the column of “<10° arrival time (h)” in Table 2.
It can be said that the shorter the “time when the water contact angle is less than 10°”, the more excellent the photocatalytic activity on the surface of the inorganic particle-containing layer side.
The contact angle of water was measured using DM-501 manufactured by Kyowa Interface Science Co., Ltd., and the contact angle of water droplets (pure water, 2.0 μL) on the surface of the inorganic particle-containing layer side at 25° C. (after 0.2 seconds). ) Was measured.
As the pure water, one manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was used.
-Evaluation criteria-
A: The time until the water contact angle becomes less than 10° is within 10 hours.
B: The time until the water contact angle becomes less than 10° is more than 10 hours and 100 hours or less.
C: The time until the water contact angle becomes less than 10° exceeds 100 hours.

<Evaluation of antireflection property>
The reflectance of the surface on the inorganic particle-containing layer side was measured with respect to the photocatalyst composite material in each Example or Comparative Example.
The reflectance was measured using an ultraviolet-visible infrared spectrophotometer (model number: UV3100PC, manufactured by Shimadzu Corporation), and the reflectance (%) in light having a wavelength of 400 nm to 800 nm was measured using an integrating sphere. The average value in the wavelength range of 400 nm to 800 nm was defined as the reflectance.
The numerical values of the measured reflectance are shown in Table 2. It can be said that the lower the value of the reflectance is, the more excellent the antireflection property is.

<Evaluation of scratch resistance>
On the surface of the photocatalyst composite material obtained in each Example or Comparative Example on the side of the inorganic particle-containing layer, a friction wear tester HYDON Type 18 manufactured by Shinto Kagaku Co., Ltd. was used, and 0 g was obtained with a sapphire needle of r=0.03 mm. A scratch test was performed 10 times at a moving speed of 600 mm/min under a continuous load of up to 100 g.
After the scratch test, the case where no scratch was visually observed on the surface of the photocatalyst composite material on the side of the inorganic particle-containing layer was evaluated as "A", and the case where a scratch was observed was evaluated as "B". If the evaluation result is A, it can be said that the scratch resistance is excellent.

In Table 1, "-" means that the component corresponding to each item is not included.
In Table 1, the content of titanium peroxide and siloxane resin is the content with respect to the total mass of titanium peroxide and siloxane resin.

In Table 2, "-" means that the component corresponding to each item is not included.
In Table 2, the content of the amorphous titanium peroxide type inorganic binder and the siloxane resin is the content with respect to the total mass of the amorphous titanium peroxide type inorganic binder and the siloxane resin.

From the results shown in Table 2, Examples 1 to 10 were excellent in photocatalytic activity and antireflection property. Among them, Example 1 in which the thickness of the antireflection layer was 50 nm to 100 nm was more excellent in antireflection property than Example 7 in which the thickness was 20 nm and Example 8 in which the thickness was 140 nm. In addition, Example 1 in which the refractive index of the antireflection layer is 1.55 to 1.86 is Example 5 in which the refractive index is 1.51 and Example 6 in which the refractive index is 1.90. And the antireflection property was excellent as compared with Example 10.
On the other hand, Comparative Examples 3 and 5 in which the thickness of the antireflection layer is less than 20, Comparative Example 1 in which the thickness is more than 140, Comparative Examples 5 and 6 in which the refractive index of the antireflection layer is less than 1.5, and Comparative Example 2 having a refractive index of more than 1.90, Comparative Examples 7 to 10 in which no antireflection layer was provided, and Comparative Examples 15 and 17 were inferior in antireflection property.

The disclosure of Japanese Patent Application No. 2018-237716 filed on Dec. 19, 2018 is incorporated herein by reference in its entirety.
All publications, patent applications, and technical standards mentioned herein are to the same extent as if each individual publication, patent application, and technical standard were specifically and individually noted to be incorporated by reference, Incorporated herein by reference.

Claims

A siloxane resin containing an organic structure, and an inorganic particle-containing layer containing inorganic particles,
A photocatalyst layer containing titanium oxide,
An amorphous titanium peroxide type inorganic binder, and an antireflection layer containing a siloxane resin containing an organic structure, in this order,
The inorganic particle-containing layer has a thickness of 80 nm to 115 nm and a refractive index of less than 1.50,
The photocatalytic composite material, wherein the antireflection layer has a thickness of 20 nm to 140 nm and a refractive index of 1.50 to 1.90.
The photocatalyst composite material according to claim 1, wherein the titanium oxide contained in the photocatalyst layer is anatase-type titanium oxide.
The photocatalyst composite material according to claim 1 or 2, wherein the refractive index of the photocatalyst layer is 1.5 or more and 2.5 or less.
The photocatalyst composite material according to any one of claims 1 to 3, wherein the antireflection layer has a thickness of 60 nm to 90 nm.
The photocatalytic composite material according to any one of claims 1 to 4, wherein the antireflection layer has a refractive index of 1.55 to 1.86.
The inorganic particle-containing layer has a thickness of 80 nm to 100 nm,
The photocatalyst composite material according to claim 1, wherein the antireflection layer has a thickness of 70 nm to 80 nm and a refractive index of 1.70 to 1.85.
The photocatalyst composite material according to any one of claims 1 to 6, further comprising a base material layer on a side of the antireflection layer opposite to the photocatalyst layer side.
A display protection member for signage, comprising the photocatalytic composite material according to any one of claims 1 to 7.
A protective member for a touch panel, which comprises the photocatalytic composite material according to any one of claims 1 to 7.
A solar cell protective member comprising the photocatalytic composite material according to any one of claims 1 to 7.
A sensor cover protective member comprising the photocatalytic 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 protection 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 protection member according to claim 11.