JPWO2016121855A1 - Color wheel for projection display device, method for manufacturing the same, and projection display device including the same - Google Patents

Abstract

It is an object of the present invention to provide a color wheel for a projection display device in which phosphors are not peeled off over a long period of time and the discoloration of emitted light is further reduced. In order to solve the above problems, a substrate (1), a ceramic binder formed on the substrate (1) and made of a reaction product of a ceramic precursor, and a light adjustment layer including at least one of a phosphor and a diffusion material A color wheel for a projection display device having (2).

Description

  The present invention relates to a color wheel for a projection display device, a manufacturing method thereof, and a projection display device including the same.

  2. Description of the Related Art In recent years, a projection display device (projector) that enlarges and projects a screen of a personal computer, a playback moving image from various image playback devices, or the like onto a screen or the like has been developed. Conventionally, in such a projection type display device, a projector using a high-intensity discharge lamp as a light source has been mainly used.

  On the other hand, in recent years, a projection type display device using a light emitting diode or a laser has been proposed. For example, a projection display device that arranges three types of light sources of red, green, and blue and performs color display by combining these light sources has been proposed (for example, Patent Document 1).

  In addition, a projection display device having a light source that emits ultraviolet light and a color wheel that includes three kinds of phosphor-containing layers that emit red, green, and blue excitation light when irradiated with ultraviolet light has also been proposed. (For example, Patent Documents 2 and 3). In the display device, color display is performed by combining light of each color emitted from the color wheel. The color wheel is usually composed of a disk-shaped substrate and a phosphor layer formed on the substrate, and the phosphor layer contains a phosphor and a binder resin.

Japanese Patent Laid-Open No. 11-084271 JP 2012-247624 A JP 2012-68465 A

  In recent years, there is a demand for miniaturization and power saving in a projection display device. However, as in Patent Document 1, when there are three types of light sources, a mechanism for cooling the heat generated by the light sources is necessary. Thus, there is a problem that miniaturization and power saving are difficult.

  On the other hand, as in Patent Documents 2 and 3, a projection display device having a color wheel can perform color display even if there is only one light source. Therefore, there is an advantage that the apparatus can be downsized. However, the resin binder in the phosphor layer of the color wheel deteriorates due to light and heat from the light source, and there is a problem that the phosphor is peeled off or the resin itself is colored and the phosphor layer is discolored. It was. In addition, when the substrate is made of an inorganic material, there is a problem that peeling between the substrate and the phosphor layer is likely to occur due to thermal shock.

  The present invention has been made in view of the above problems, and the phosphor and the diffusing material do not peel off over a long period of time, and further, there is little discoloration of emitted light, etc. A manufacturing method and a projection display device including the same are provided.

The first of the present invention relates to a color wheel for a projection display device shown below.
[1] For a projection display device having a substrate, a ceramic binder formed on the substrate and made of a reaction product of a ceramic precursor, and a light adjustment layer containing at least one of a phosphor and a diffusion material Color wheel.
[2] The color wheel for a projection display device according to [1], wherein the ceramic precursor is one or more polysiloxane precursors selected from the group consisting of polysilazane, an alkoxysilane monomer, and an alkoxysilane oligomer.
[3] The ceramic binder according to [1] or [2], wherein the ceramic binder includes polysiloxane, and 5 to 50 mol% of a structural unit derived from bifunctional alkoxysilane is included in all the structural units of the polysiloxane. Color wheel for projection display devices.

[4] The diffusion material is made of one or more inorganic compounds selected from the group consisting of titanium oxide, silicon oxide, barium sulfate, barium titanate, boron nitride, zinc oxide, and aluminum oxide, and has an average primary particle size. The color wheel for a projection display device according to any one of [1] to [3], which is a particle of 100 nm to 10 μm.
[5] The light adjustment layer includes the diffusion material and the phosphor, and includes the diffusion material in a range of 34% by mass to less than 70% by mass with respect to the total amount of the phosphor and the diffusion material. A color wheel for a projection display device according to any one of to [4].
[6] The substrate has at least a reflective surface made of metal on a surface adjacent to the light adjustment layer, and the light adjustment layer includes a structure derived from a mercapto group-containing coupling agent. 5] The color wheel for a projection display device according to any one of [5].
[7] Any of [1] to [6], wherein the light adjusting layer has an end portion thinner than a center portion, and the end portion has a thickness of 50 to 70% with respect to the thickness of the center portion. A color wheel for a projection display device according to claim 1.

2nd of this invention is related with the manufacturing method of the color wheel for projection type display apparatuses shown below.
[8] A method for manufacturing a color wheel for a projection display device according to any one of [1] to [7], wherein the particle includes at least one of the phosphor and the diffusing material, and a solvent. A step of applying a containing solution onto the substrate and drying to obtain a particle-containing film; and a ceramic precursor-containing composition containing the ceramic precursor is applied onto the particle-containing film, and heat-cured to adjust the light. Forming a layer, and a method of manufacturing a color wheel for a projection display device.
[9] A method for manufacturing a color wheel for a projection display device according to any one of [1] to [7], wherein at least one of the phosphor and the diffusion material, the ceramic precursor, A method for producing a color wheel for a projection type display device, comprising: applying a composition for forming a light adjustment layer comprising: to the substrate and curing by heating to form the light adjustment layer.
[10] The method for producing a color wheel for a projection display device according to [8] or [9], wherein the ceramic precursor-containing composition or the light adjusting layer forming composition is applied by a spray or a dispenser.
[11] The color wheel for a projection display device according to [8] or [9], wherein the ceramic precursor-containing composition or the light adjustment layer forming composition is applied by spraying while rotating the substrate. Manufacturing method.

A third aspect of the present invention relates to a projection display device described below.
[12] A projection display device including the color wheel for a projection display device according to any one of [1] to [7].

  According to the color wheel for a projection type display device of the present invention, a projection type display device can be obtained in which phosphors and diffusing materials do not peel over a long period of time, and further, there is little discoloration of light emitted from the color wheel. .

It is a top view which shows an example of the color wheel for projection display apparatuses of this invention. It is a top view which shows the other example of the color wheel for projection display apparatuses of this invention. It is A-A 'sectional drawing of the color wheel for projection display apparatuses of FIG. It is a figure for demonstrating the spray apparatus for apply | coating the composition for light adjustment layer forming. It is a schematic diagram of the projection type display apparatus of this invention.

  Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made without departing from the scope of the invention.

1. Color wheel for projection display device The color wheel for projection display device of the present invention (hereinafter also referred to as “color wheel”) has a structure in which a substrate and a light adjustment layer containing a diffusing material or a phosphor are laminated. . The color wheel is installed between the light source and the projection optical system in the projection display device, and functions to diffuse light from the light source or convert light from the light source into light of another specific wavelength.

  As shown in FIG. 1, in the color wheel of the present invention, only one type of light adjustment layer 2 may be formed on one substrate 1. On the other hand, as shown in FIG. 2, different types of light adjustment layers 2 a to 2 c may be formed in different regions of one substrate 1. For example, when the light from the light source of the projection display device is blue light, the light adjustment layer 2a including a phosphor that receives blue light and emits green, and the fluorescence that emits red by receiving blue light It can be set as the color wheel 100 containing the light adjustment layer 2b containing a body, and the light adjustment layer 2c containing the diffusion material for diffusing blue light. When the light from the light source of the projection display device is ultraviolet light, etc., the light adjustment layer 2a including a phosphor that emits green light by receiving ultraviolet light, and the fluorescence that emits red light by receiving ultraviolet light. The color wheel 100 can include the light adjustment layer 2b including a body and the light adjustment layer 2c including a phosphor that emits blue light when receiving ultraviolet light. In this way, by combining a plurality of light adjustment layers 2, the three primary colors of light can be reproduced even if only one type of light source is used. The type of light adjustment layer included in the color wheel 100, the region where the light adjustment layer is formed, and the like are appropriately selected according to the type of the projection display device, the wavelength of light from the light source, the structure of the optical system, and the like. Selected.

  Further, as shown in FIG. 5, the color wheel of the present invention is a transmissive color wheel that transmits light incident from one surface of the color wheel 100 to the other surface side (hereinafter referred to as “transmissive color wheel”). May also be referred to). Further, it may be a reflective color wheel that reflects light incident on the color wheel 100 in a predetermined direction (hereinafter also referred to as “reflective color wheel”). In any color wheel, light incident on the light adjustment layer is diffused and / or wavelength-converted by a diffusing material or a phosphor.

  Here, in the color wheel for a projection display device, not only strong light is emitted from a light source, but also heat from the light source is received. For this reason, the conventional color wheel including the binder resin has problems such as the phosphor and diffusing particles falling off due to the deterioration of the binder resin, and the light emitted from the light adjusting layer being discolored due to the coloring of the binder resin. In addition, if the substrate is an inorganic material such as a metal material or a glass substrate, the linear expansion coefficients of the substrate and the light adjustment layer are greatly different, and the light adjustment layer is easily peeled off due to thermal shock.

  On the other hand, in the color wheel for a projection display device of the present invention, the binder is made of a reaction product of a ceramic precursor. For this reason, even when heat or light is received from the light source, the phosphor and the diffusing particles are less likely to fall off, and the discoloration is less. As a result, the light adjustment layer can stably perform light diffusion and wavelength conversion over a long period of time. Further, even when subjected to a thermal shock, peeling at the interface between the light adjustment layer and the substrate hardly occurs.

1-1. Substrate The substrate of the color wheel for a projection display device of the present invention is a member for holding the light adjustment layer. The shape of the substrate is not particularly limited and is appropriately selected according to the use of the color wheel and the like, and can be the same as a substrate for a general projection display device.

  Here, when the color wheel is a transmissive color wheel, light from the light source enters the light adjustment layer of the color wheel, and the light is diffused and / or wavelength-converted. Thereafter, the light passes through the substrate and is guided to the projection optical system through a predetermined path. That is, the substrate is required to have optical transparency. Examples of such a light-transmitting substrate include a substrate made of a heat-resistant transparent resin and a substrate made of a light-transmitting ceramic. From the viewpoint of the heat resistance and discoloration resistance of the substrate, the light-transmitting property is used. It is preferable that the substrate is made of ceramic. Particularly preferred is a glass substrate.

  On the other hand, when the color wheel is a reflective color wheel, light from the light source enters the light adjustment layer, and the light is diffused and / or wavelength-converted. Thereafter, the light is reflected at the interface between the substrate and the light adjustment layer or the like and guided to the projection optical system through a predetermined path. That is, the substrate is required to have light reflectivity. An example of such a light-reflective substrate is a substrate having a reflective surface made of metal. Specifically, it can be a substrate made of metal, or a substrate in which a layer made of a metal having high reflectivity such as silver is laminated on the surface of a base member made of resin, ceramic, metal or the like. In the board | substrate with which the metal layer is laminated | stacked, a metal reflective surface is normally arrange | positioned at the light adjustment layer side from a viewpoint of improving the adhesiveness of a board | substrate and a light adjustment layer.

1-2. Light Adjustment Layer The light adjustment layer has a function of diffusing and / or wavelength-converting light in the color wheel. The light adjustment layer includes at least one of a diffusing material and a phosphor and a ceramic binder, and the diffusing material and the phosphor are bound by the ceramic binder.

  The thickness of the light adjustment layer is preferably 1 to 1000 μm, more preferably 30 to 500 μm. When the thickness of the light adjustment layer is 1 μm or more, the light diffusibility and the wavelength conversion property by the light adjustment layer are likely to increase. On the other hand, if the thickness of the light adjustment layer is 1000 μm or less, the projection display device can be miniaturized. Here, as shown in FIG. 3, the thickness of the light adjustment layer is a region of 10% with respect to the width (W) including the center in the width direction when the width of the light adjustment layer is W. It is set as the average value of the thickness of the light adjustment layer of W1). The thickness is measured with a stylus type surface shape measuring instrument or the like.

  Here, the thickness of the light adjustment layer may be uniform in the entire region, but as shown in the schematic cross-sectional view of FIG. 3 (AA ′ cross-sectional view of FIG. 1), the center of the light adjustment layer 2 The end portion is preferably thinner than the portion. If the thickness of the end portion of the light adjustment layer 2 is thin to some extent, cracks are unlikely to occur during the formation of the light adjustment layer, and the thermal shock resistance of the light adjustment layer is likely to increase. As shown in FIG. 3, the thickness of the end is the thickness of the region (W2 and W2 ′) from the end of the light adjustment layer 2 to 10% of the width (W) of the light adjustment layer 2. Average value. And it is preferable that the thickness of the edge part of the light adjustment layer 2 is 50 to 70% with respect to the thickness of the center part of a light adjustment layer, More preferably, it is 50 to 65%, More preferably, it is 50 to 60 %. When the thickness of the end portion of the light adjustment layer is within the above range, the strength of the light adjustment layer is likely to increase. The shape of the end portion of the light adjustment layer can be adjusted by a method of applying a composition for forming the light adjustment layer, as will be described later.

  Here, when only the light diffusibility is required for the light adjustment layer, the light adjustment layer includes a ceramic binder and a diffusion material. In this case, the light adjustment layer preferably contains 5 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 5 to 30% by mass of the ceramic binder with respect to the mass of the light adjustment layer. % By mass. When the amount of the ceramic binder is 5% by mass or more, the diffusion material is sufficiently bound, and the diffusion material does not easily fall off. On the other hand, when the amount of the binder is 50% by mass or less, the amount of the diffusion material is relatively sufficient.

  Moreover, when only the light diffusibility is calculated | required by the adjustment layer, it is preferable that 50-95 mass% of diffusion materials are contained with respect to the mass of a light adjustment layer, More preferably, it is 60-95 mass%, More preferably, it is 70. It is -95 mass%. When the amount of the diffusing material is 50% by mass or more, the light that has passed through the light adjustment layer is easily diffused. However, if the amount of the diffusing material is excessive, light cannot sufficiently enter the light adjusting layer, and it is difficult to obtain sufficient light diffusibility. On the other hand, when the amount of the diffusing material is 95% by mass or less, the light from the light source is sufficiently diffused by the light adjustment layer.

  When the light adjustment layer is also required to have wavelength conversion of light, it is preferable that the light adjustment layer includes at least a ceramic binder and a phosphor, and further includes a diffusion material. When the diffusing material is included together with the phosphor, the light wavelength-converted by the phosphor is more easily diffused. Furthermore, the light from the light source incident on the light adjustment layer is diffused, so that the light is easily absorbed by the phosphor. That is, the wavelength conversion property of light by the light adjustment layer is likely to increase. Furthermore, if the diffusion is insufficient, the incident light is extracted as it is from the light adjustment layer, and from the viewpoint that it is difficult to extract only light of a desired wavelength, the diffusion particles are formed in the light adjustment layer. It is preferably included.

  When the wavelength adjustment property of light is calculated | required by the light adjustment layer, it is preferable that the quantity of the ceramic binder contained in a light adjustment layer is 5-50 mass% with respect to the mass of a light adjustment layer, More preferably, it is 5-5. It is 40 mass%, More preferably, it is 5-30 mass%. When the amount of the ceramic binder is 5% by mass or more, the diffusing material and the phosphor are sufficiently bound, and the diffusing material and the like are not easily dropped. On the other hand, when the amount of the binder is 50% by mass or less, the amount of the diffusing material or the phosphor is relatively sufficient, and the light diffusibility and the wavelength conversion property of the light adjustment layer are easily increased.

  On the other hand, the amount of the phosphor contained in the light adjustment layer is preferably 50 to 95% by mass, more preferably 60 to 95% by mass, and still more preferably based on the mass of the light adjustment layer. It is 70-95 mass%. When the amount of the phosphor is in the above range, the wavelength conversion property of the light adjustment layer is likely to be improved.

  The amount of the diffusing particles contained in the light adjusting layer is preferably 34% by mass or more and less than 70% by mass, more preferably 34-60% by mass, based on the total amount of the phosphor and the diffusing particles. More preferably, it is 34 to 50% by mass. When the amount of the diffusing particles contained in the light adjustment layer is within the above range, the wavelength conversion property of the light adjustment layer is likely to be improved. In addition, if the light diffusibility by the diffusing particles is insufficient, that is, if the amount of the diffusing particles is too small, as described above, the light having the wavelength incident on the light adjusting layer is emitted from the light adjusting layer as it is, It becomes difficult to extract light having a desired wavelength. On the other hand, if the amount of diffusing particles contained in the light adjustment layer is excessive, the required light extraction efficiency may be reduced. On the other hand, when the amount of the light diffusing particles is within the above range, the balance between the light diffusibility and the light extraction property becomes good.

-Diffusion particle The diffusion particle contained in a light adjustment layer will not be restrict | limited especially if it is a particle with high light diffusibility, It may be an inorganic particle whose average primary particle diameter is 100 nm-10 micrometers. The average primary particle size of the diffusing particles is more preferably 100 nm to 5 μm, and even more preferably 200 nm to 2.5 μm. When the average primary particle size of the diffusing particles is within the above range, light is easily diffused sufficiently in the light adjusting layer. The average primary particle size in the present invention refers to the value of D50 measured with a laser diffraction particle size distribution meter. Examples of the laser diffraction particle size distribution measuring device include a laser diffraction particle size distribution measuring device manufactured by Shimadzu Corporation.

  The total reflectance of the diffusing particles is preferably 80% or more, and more preferably 90% or more. The total reflectance of the diffusing particles can be measured with a Hitachi spectrophotometer U4100 manufactured by Hitachi High-Tech.

Specific examples of the diffusion particles include zinc oxide (ZnO), silicon oxide (SiO ₂ ), barium titanate (BaTiO ₃ ), barium sulfate (BaSO ₄ ), titanium oxide (TiO ₂ ), and boron nitride (BrN). , Magnesium oxide (MgO), calcium carbonate (CaCO ₃ ), aluminum oxide (Al ₂ O ₃ ), barium sulfate (BaO), zirconium oxide (ZrO ₂ ), and the like. From the viewpoints of light diffusibility and handleability, the diffusing particles are more preferably titanium oxide, silicon oxide, barium sulfate, barium titanate, boron nitride, zinc oxide, and aluminum oxide. The light adjusting layer may contain only one kind of diffusing particles or two or more kinds.

-Phosphor The average primary particle diameter of the phosphor contained in the light adjusting layer is preferably 1 to 30 µm, more preferably 5 to 30 µm, and even more preferably 10 to 30 µm. The larger the average primary particle size of the phosphor particles, the higher the luminous efficiency (wavelength conversion efficiency). On the other hand, if the particle size of the phosphor is too large, a gap generated between the phosphors becomes large, and light from the light source easily passes through the light adjustment layer as it is, and a desired wavelength conversion property may not be obtained. is there. The average primary particle diameter of the phosphor is measured by the same method as that for the aforementioned diffusion material.

  The phosphor is not particularly limited as long as it is excited by a specific wavelength (excitation wavelength) and emits fluorescence having a wavelength different from the wavelength of the excitation light. For example, a phosphor that converts excitation light of ultraviolet to near ultraviolet light or blue wavelength into green, red, or the like can be used.

Examples of phosphors for green light emission include sulfide-based ZnS: Cu, Al, oxynitride-based (Si, Al) ₆ (O, N) ₈ : Eu, silicate-based Zn ₂ SiO ₄ : Mn, Zn ₂ SiO ₄ : Mn, (Ba, Sr) ₂ SiO ₄ : Eu, aluminate-based BaAl ₁₂ O ₁₉ : Mn, BaMgAl ₁₄ O ₂₃ : Mn, SrAl ₁₂ O ₁₉ : Mn, ZnAl ₁₂ O ₁₉ : Mn, CaAl ₁₂ O ₁₉ : Mn and the like are included.

On the other hand, examples of red phosphors include sulfite (Ca, Sr) S: Eu, nitride (Ca, Sr) ₂ Si ₅ N ₈ : Eu, (Ca, Sr) AlSiN ₃ : Eu, Ca, SiN ₂ : Eu, silicate system Y ₂ SiO ₅ : Eu, aluminate system, Y ₃ Al ₅ O ₁₂ : Eu, apatite system Zn ₃ (P 0 ₄ ) ₂ : Mn, other Y ₂ O ₃ : Eu, YBO ₃ : Eu, (Y, Gd) BO ₃ : Eu, GdBO ₃ : Eu, ScBO ₃ : Eu, LuBO ₃ : Eu, and the like.

-Ceramic binder A ceramic binder is obtained by reacting a ceramic precursor, and may be a polymer obtained by chemically reacting a ceramic precursor.

  The ceramic precursor is not particularly limited as long as the ceramic can be obtained by reaction, and examples thereof include alkoxides of various metals from which the ceramic can be obtained by hydrolysis and polycondensation, and polysilazane from which the ceramic can be obtained by deammonia method. Etc. are included. The ceramic precursor is preferably a polysiloxane precursor from the viewpoint of ease of preparation of the ceramic binder, and is one or more compounds selected from the group consisting of polysilazane, alkoxysilane monomer, and alkoxysilane oligomer. Is more preferable. The ceramic precursor is particularly preferably an alkoxysilane oligomer. When the ceramic precursor is a polysiloxane precursor, the hydroxyl group present on the substrate surface and the silicon in the polysiloxane are likely to form a siloxane bond, and the adhesion between the substrate and the light adjustment layer is likely to increase.

Here, polysilazane is a compound represented by the general formula (I): (R ¹ R ² SiNR ³ ) _n . In the general formula (I), R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group, an aryl group, a vinyl group or a cycloalkyl group, but R ¹ , R ² and R ³ At least one of them is a hydrogen atom, preferably all are hydrogen atoms. n represents an integer of 1 to 60. The molecular shape of polysilazane may be any shape, for example, linear or cyclic.

  Polysilazane becomes polysiloxane by hydrolysis and deammonification. Specifically, polysiloxane is obtained by subjecting the polysilazane represented by the above formula (I) to heating, excimer light treatment, UV light treatment, etc. in the presence of a reaction accelerator and a solvent as necessary.

The monomer or oligomer of alkoxysilane may be a monomer or oligomer of a bifunctional alkoxysilane compound, a trifunctional alkoxysilane compound, or a tetrafunctional alkoxysilane compound. When the binder contains polysiloxane, the polysiloxane preferably contains a structure derived from bifunctional alkoxysilane. If the polysiloxane contains a structure derived from a bifunctional alkoxysilane, the resulting polysiloxane has increased flexibility, and the thermal resistance to cold shock of the polysiloxane is likely to increase. In addition, cracks and the like hardly occur during the formation of the light adjustment layer. On the other hand, when the structure derived from the bifunctional alkoxysilane is excessive, the light adjustment layer tends to have low resistance to light and heat. Therefore, the amount of the structure derived from the bifunctional alkoxysilane contained in the polysiloxane is preferably 5 to 50 mol%, more preferably 10 to 30 mol%, based on all the structural units of the polysiloxane. The amount of the structural unit derived from the bifunctional alkoxysilane compound and the amount of the structural unit derived from other alkoxysilane (trifunctional or tetrafunctional alkoxysilane compound) contained in the polysiloxane is ²⁹ Si-NMR (for example, JEOL Ltd.) It is possible to measure by company LA400).

Here, examples of the tetrafunctional alkoxysilane compound include a compound represented by the following general formula (II).
Si (OR ⁴ ) ₄ (II)
In said general formula (II), R < ⁴ > represents an alkyl group or a phenyl group each independently, Preferably it represents a C1-C5 alkyl group or a phenyl group.

  Specific examples of tetrafunctional silane compounds include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrapentyloxysilane, tetraphenyloxysilane, trimethoxymonoethoxysilane, dimethoxydiethoxysilane, and triethoxymonomethoxy. Silane, trimethoxymonopropoxysilane, monomethoxytributoxysilane, monomethoxytripentyloxysilane, monomethoxytriphenyloxysilane, dimethoxydipropoxysilane, tripropoxymonomethoxysilane, trimethoxymonobutoxysilane, dimethoxydibutoxysilane, Triethoxymonopropoxysilane, diethoxydipropoxysilane, tributoxymonopropoxysilane, dimethoxymonoethoxymonobutoxy Orchid, diethoxymonomethoxymonobutoxysilane, diethoxymonopropoxymonobutoxysilane, dipropoxymonomethoxymonoethoxysilane, dipropoxymonomethoxymonobutoxysilane, dipropoxymonoethoxymonobutoxysilane, dibutoxymonomethoxymonoethoxysilane, Alkoxy silanes such as dibutoxy monoethoxy monopropoxy silane, monomethoxy monoethoxy monopropoxy monobutoxy silane, or aryloxy silane are included. Among these, tetramethoxysilane and tetraethoxysilane are preferable.

Examples of the trifunctional silane compound include a compound represented by the following general formula (III).
R ⁵ Si (OR ⁶ ) ₃ (III)
In the general formula (III), R ⁶ each independently represents an alkyl group or a phenyl group, preferably an alkyl group having 1 to 5 carbon atoms, or a phenyl group. R ⁵ represents a hydrogen atom or an alkyl group.

  Specific examples of trifunctional silane compounds include trimethoxysilane, triethoxysilane, tripropoxysilane, tripentyloxysilane, triphenyloxysilane, dimethoxymonoethoxysilane, diethoxymonomethoxysilane, dipropoxymonomethoxysilane, di Propoxymonoethoxysilane, dipentyloxylmonomethoxysilane, dipentyloxymonoethoxysilane, dipentyloxymonopropoxysilane, diphenyloxylmonomethoxysilane, diphenyloxymonoethoxysilane, diphenyloxymonopropoxysilane, methoxyethoxypropoxysilane, monopropoxydimethoxysilane Monopropoxydiethoxysilane, monobutoxydimethoxysilane, monopentyloxydiethoxysilane, monophenyl Monohydrosilane compounds such as ruoxydiethoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltripentyloxysilane, methylmonomethoxydiethoxysilane, methylmonomethoxydipropoxysilane, methylmonomethoxydipentyl Monomethylsilane compounds such as oxysilane, methylmonomethoxydiphenyloxysilane, methylmethoxyethoxypropoxysilane, methylmonomethoxymonoethoxymonobutoxysilane; ethyltrimethoxysilane, ethyltripropoxysilane, ethyltripentyloxysilane, ethyltriphenyloxy Silane, ethyl monomethoxydiethoxysilane, ethyl monomethoxydipropoxysilane, ethyl monomethoxydipentyloxy Monoethylsilane compounds such as lan, ethylmonomethoxydiphenyloxysilane, ethylmonomethoxymonoethoxymonobutoxysilane; propyltrimethoxysilane, propyltriethoxysilane, propyltripentyloxysilane, propyltriphenyloxysilane, propylmonomethoxydi Monopropylsilane compounds such as ethoxysilane, propylmonomethoxydipropoxysilane, propylmonomethoxydipentyloxysilane, propylmonomethoxydiphenyloxysilane, propylmethoxyethoxypropoxysilane, propylmonomethoxymonoethoxymonobutoxysilane; butyltrimethoxysilane, Butyltriethoxysilane, Butyltripropoxysilane, Butyltripentyloxysilane, Butyltriphenyl Monobutylsilane compounds such as oxysilane, butylmonomethoxydiethoxysilane, butylmonomethoxydipropoxysilane, butylmonomethoxydipentyloxysilane, butylmonomethoxydiphenyloxysilane, butylmethoxyethoxypropoxysilane, butylmonomethoxymonoethoxymonobutoxysilane Is included.

Among these trifunctional silane compounds, a compound in which R ⁵ represented by the general formula (III) is a methyl group is preferable from the viewpoint of reactivity and the like. Examples of the trifunctional silane compound in which R ⁵ represented by the general formula (III) is a methyl group include methyltrimethoxysilane and methyltriethoxysilane, and methyltrimethoxysilane is particularly preferable.

Examples of the bifunctional silane compound include a compound represented by the following general formula (IV).
R ⁷ R ⁸ Si (OR ⁹ ) ₂ (IV)
In said general formula (IV), R < ⁹ > represents an alkyl group or a phenyl group each independently, Preferably it represents a C1-C5 alkyl group or a phenyl group. R ⁷ and R ⁸ represent a hydrogen atom or an alkyl group.

  Examples of bifunctional alkoxysilane compounds include dimethoxysilane, diethoxysilane, dipropoxysilane, dipentyloxysilane, diphenyloxysilane, methoxyethoxysilane, methoxypropoxysilane, methoxypentyloxysilane, methoxyphenyloxysilane, ethoxypropoxy. Silane, ethoxypentyloxysilane, ethoxyphenyloxysilane, methyldimethoxysilane, methylmethoxyethoxysilane, methyldiethoxysilane, methylmethoxypropoxysilane, methylmethoxypentyloxysilane, methylmethoxyphenyloxysilane, ethyldipropoxysilane, ethylmethoxy Propoxysilane, ethyldipentyloxysilane, ethyldiphenyloxysilane, propyldimethoxysilane, Propylmethoxyethoxysilane, propylethoxypropoxysilane, propyldiethoxysilane, propyldipentyloxysilane, propyldiphenyloxysilane, butyldimethoxysilane, butylmethoxyethoxysilane, butyldiethoxysilane, butylethoxypropoxysilane, butyldipropoxysilane , Butylmethyldipentyloxysilane, butylmethyldiphenyloxysilane, dimethyldimethoxysilane, dimethylmethoxyethoxysilane, dimethyldiethoxysilane, dimethyldipentyloxysilane, dimethyldiphenyloxysilane, dimethylethoxypropoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane , Diethylmethoxypropoxysilane, diethyldiethoxysilane, die Luethoxypropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dipropyldipentyloxysilane, dipropyldiphenyloxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dibutyldipropoxysilane, dibutylmethoxypentyloxysilane, dibutylmethoxy Phenyloxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldipropoxysilane, methylethyldipentyloxysilane, methylethyldiphenyloxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, methylbutyldimethoxysilane, methyl Butyldiethoxysilane, methylbutyldipropoxysilane, methylethylethoxypropoxysilane, Includes ethylpropyldimethoxysilane, ethylpropylmethoxyethoxysilane, dipropyldimethoxysilane, dipropylmethoxyethoxysilane, propylbutyldimethoxysilane, propylbutyldiethoxysilane, dibutylmethoxyethoxysilane, dibutylmethoxypropoxysilane, dibutylethoxypropoxysilane, etc. It is. Of these, dimethoxysilane, diethoxysilane, methyldimethoxysilane, and methyldiethoxysilane are preferable.

  The polysiloxane can be obtained by heat-treating the monomer of the silane compound or the oligomer thereof in the presence of an acid catalyst, water, and a solvent, if necessary.

-Mercapto group containing coupling agent Moreover, the structure derived from a mercapto group containing silane coupling agent may be contained in the light adjustment layer. That is, a mercapto group-containing coupling agent may be included in the composition for forming the light adjusting layer. Usually, in a mercapto group-containing coupling agent, a mercapto group reacts with an organic group contained in polysiloxane, and a metal atom or the like in the coupling agent reacts with an OH group or the like present on a ceramic precursor or a substrate surface. Therefore, when a mercapto group-containing coupling agent is included in the composition, the adhesion between the substrate and the light adjustment layer is likely to increase. In particular, when a layer made of metal, that is, a metal reflecting surface is present on the surface of the substrate, the adhesion between the substrate and the light adjustment layer tends to increase.

  The type of the coupling agent is not particularly limited, but is preferably a silane coupling agent. Specifically, it may be 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, or the like. Among these, the light adjusting layer may contain a structure derived from one kind of compound, or may contain a structure derived from two or more kinds of compounds.

  The amount of the structure derived from the mercapto group-containing coupling agent added during the preparation of the light adjusting layer is preferably 0.1 to 5 parts by mass, more preferably 100 parts by mass of the ceramic precursor described above. 1 to 5 parts by mass.

Inorganic oxide fine particles The light adjustment layer may contain inorganic oxide fine particles having a particle system of less than 100 nm. The average primary particle size of the inorganic oxide fine particles is preferably 5 nm or more and less than 100 nm, more preferably 5 to 80 nm, still more preferably 5 to 50 nm. When the average primary particle size of the inorganic oxide fine particles is within such a range, the strength of the light adjustment layer is easily increased, and cracks and the like during the formation of the light adjustment layer are further suppressed.

  Examples of the inorganic oxide fine particles include silicon oxide, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide and the like. The surface of the inorganic oxide fine particles may be treated with a silane coupling agent or a titanium coupling agent.

The inorganic oxide fine particles may be porous particles. When the inorganic oxide fine particles are porous particles, the specific surface area is preferably 200 m ² / g or more. When the inorganic oxide fine particles are porous, the solvent contained in the composition for forming the light adjustment layer enters the porous voids of the inorganic oxide fine particles when the light adjustment layer is formed, and the composition The viscosity of the product increases, making it easier to apply.

  The amount of the inorganic oxide fine particles is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, and further preferably 0.1 to 5% by mass with respect to the mass of the light adjustment layer. % By mass. When the amount of the inorganic oxide fine particles is 1% by mass or more, the strength of the light adjustment layer tends to increase. On the other hand, when the amount of the inorganic oxide fine particles is excessive, the amount of the diffusing material, the phosphor, the binder, etc. is relatively reduced, and the light diffusibility and the wavelength conversion property by the light adjustment layer are insufficient. The strength of the layer may be reduced.

  Moreover, the light adjusting layer may contain a clay compound. When the clay compound is included, the viscosity of the composition for forming the light adjusting layer is likely to increase, and the phosphor and the diffusing material are easily dispersed uniformly. That is, the phosphor and the diffusing material are difficult to settle in the composition, and the diffusing material and the phosphor are easily uniformly dispersed in the obtained light adjustment layer. Moreover, when the clay compound is contained in the light adjustment layer, the strength of the light adjustment layer is likely to increase.

  Examples of clay compounds include layered silicate minerals, imogolite, allophane and the like. The layered silicate mineral is preferably a clay mineral having a mica structure, a kaolinite structure, or a smectite structure.

  Examples of layered silicate minerals include natural or synthetic hectorite, saponite, stevensite, hydelite, montmorillonite, nontrite, bentonite, laponite, and other smectite clay minerals, Na-type tetralithic fluoromica, Li-type Non-swelling mica genus clay minerals such as swellable mica genus clay minerals such as tetrasilic fluorinated mica, Na type fluorine teniolite, Li type fluorine teniolite, muscovite, phlogopite, fluorine phlogopite, sericite, potassium tetrasilicon mica , And vermiculite and kaolinite, or mixtures thereof.

  Examples of commercially available clay compounds include Laponite XLG (synthetic hectorite analogues manufactured by LaPorte, UK), Laponite RD (Synthetic hectorite analogues manufactured by LaPorte, UK), Thermabis (Synthetic hectors manufactured by Henkel, Germany) Light-like substance), smecton SA-1 (saponite-like substance manufactured by Kunimine Industry Co., Ltd.), Bengel (natural bentonite sold by Hojun Co., Ltd.), Kunivia F (natural montmorillonite sold by Kunimine Industry Co., Ltd.), bee gum (USA) , Natural hectorite manufactured by Vanderbilt), Daimonite (synthetic swellable mica manufactured by Topy Industries, Ltd.), Micromica (synthetic non-swellable mica manufactured by Coop Chemical Co., Ltd.), Somasifu (Coop Chemical Co., Ltd.) Synthetic swelling mica), SWN (synthetic smectite manufactured by Coop Chemical Co.), SWF (co Synthetic smectite manufactured by Pchemical Co., Ltd.), M-XF (white mica manufactured by Repco Co., Ltd.), S-XF (metal mica manufactured by Repco Co., Ltd.), PDM-800 (fluorine manufactured by Topy Industries, Ltd.) Phlogopite), sericite OC-100R (sericite manufactured by Oakem Tsusho Co., Ltd.), PDM-K (G) 325 (potassium tetrasilicon mica manufactured by Topy Industries, Ltd.), and the like.

  It is preferable that content of a clay compound is 0.1-5 mass% with respect to the mass of a light adjustment layer, and it is more preferable that it is 0.2-2 mass%. When the content of the clay compound is 0.1% by mass or more, the viscosity of the composition for forming the light adjusting layer is sufficiently increased. On the other hand, the applicability | paintability for forming a light adjustment layer is excellent in the quantity of a clay compound being 2 mass% or less.

  The surface of the clay compound may be modified (surface treatment) with an ammonium salt or the like in consideration of compatibility with other components.

-Metal alkoxide or metal chelate The light adjusting layer may contain a structure derived from metal alkoxide or metal chelate. That is, the composition for forming the light adjusting layer may contain a metal alkoxide or a metal chelate. These metal alkoxides or metal chelates form metalloxane bonds with the above-mentioned ceramic precursors and the like to form strong bonds. Therefore, the adhesion between the substrate and the light adjustment layer tends to increase.

The type of metal element contained in the metal alkoxide or metal chelate is not particularly limited as long as it is a bivalent or higher-valent metal element (excluding Si), but is preferably a group 4 or group 13 element. That is, specifically, the metal alkoxide or metal chelate is preferably a compound represented by the following general formula (V).
M ^{m +} X _n Y _m−n (V)
In general formula (V), M represents a Group 4 or Group 13 metal element, and m represents the valence (3 or 4) of M. X represents a hydrolyzable group, and n represents the number of X groups (an integer of 2 or more and 4 or less). However, m ≧ n. Y represents a monovalent organic group.

  In the general formula (V), the group 4 or group 13 metal element represented by M is preferably aluminum, zirconium, or titanium, and particularly preferably zirconium. A cured product of an alkoxide or chelate containing a zirconium element does not have an absorption wavelength in a light emission wavelength region of a light source of a general projection display device. Therefore, it is difficult for the cured product of zirconium alkoxide or chelate to absorb light from the light source of the projection display device.

  In the general formula (V), the hydrolyzable group represented by X may be a group that is hydrolyzed with water to form a hydroxyl group. Preferable examples of the hydrolyzable group include a lower alkoxy group having 1 to 5 carbon atoms, an acetoxy group, a butanoxime group, a chloro group and the like. In general formula (V), all the groups represented by X may be the same group or different groups.

  As described above, the hydrolyzable group represented by X is hydrolyzed when the metal element forms a metalloxane bond with a hydroxyl group or the like on the surface of the substrate. Therefore, the compound produced after hydrolysis is preferably neutral and light boiling. Therefore, the group represented by X is preferably a lower alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group or an ethoxy group.

  In the general formula (V), the monovalent organic group represented by Y may be a monovalent organic group contained in a general silane coupling agent. Specifically, an aliphatic group, an alicyclic group, an aromatic group, an oil having 1 to 1000 carbon atoms, preferably 500 or less, more preferably 100 or less, further preferably 40 or less, and particularly preferably 6 or less. It may be a ring aromatic group. The organic group represented by Y may be an aliphatic group, an alicyclic group, an aromatic group, or a group in which an alicyclic aromatic group is bonded via a linking group. The linking group may be an atom such as O, N, or S, or an atomic group containing these.

  The organic group represented by Y may have a substituent. Examples of the substituent include halogen atoms such as F, Cl, Br, and I; vinyl group, methacryloxy group, acryloxy group, styryl group, mercapto group, epoxy group, epoxycyclohexyl group, glycidoxy group, amino group, cyano group, Organic groups such as nitro group, sulfonic acid group, carboxy group, hydroxy group, acyl group, alkoxy group, imino group and phenyl group are included.

  Specific examples of the metal alkoxide or metal chelate containing the aluminum element represented by the general formula (V) include aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum tri-t-butoxide, aluminum triethoxide and the like. It is.

  Specific examples of the metal alkoxide or metal chelate containing a zirconium element represented by the general formula (V) include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra n-propoxide, zirconium tetra i-propoxide, zirconium. Examples include tetra n-butoxide, zirconium tetra i-butoxide, zirconium tetra t-butoxide, zirconium dimethacrylate dibutoxide, dibutoxyzirconium bis (ethylacetoacetate), and the like.

  Specific examples of the metal alkoxide or metal chelate containing the titanium element represented by the general formula (V) include titanium tetraisopropoxide, titanium tetra n-butoxide, titanium tetra i-butoxide, titanium methacrylate triisopropoxide, titanium. Examples include tetramethoxypropoxide, titanium tetra n-propoxide, titanium tetraethoxide, titanium lactate, titanium bis (ethylhexoxy) bis (2-ethyl-3-hydroxyhexoxide), titanium acetylacetonate, and the like.

  However, the metal alkoxide or metal chelate exemplified above is a part of a commercially available organometallic alkoxide or metal chelate that is easily available. Metal alkoxides or metal chelates shown in the list of coupling agents and related products in Chapter 9 “Optimum Utilization Technology for Coupling Agents” published by the National Science and Technology Research Institute are also applied to the composition for forming the light control layer. .

  The amount of metal element derived from metal alkoxide or metal chelate (excluding Si element) contained in the light adjustment layer is 0.5 to 20 mol% with respect to the total number of moles of Si element contained in the light adjustment layer. It is preferable that it is 1-10 mol%. When the amount of the metal element is 0.5 mol% or more, the adhesion between the light adjustment layer and the substrate is likely to increase. On the other hand, when the amount of the metal alkoxide or metal chelate is 10 mol% or less, the amount of the diffusing particles and the phosphor is relatively increased, and the light diffusibility and the wavelength conversion property by the light adjustment layer are likely to be increased. The amount of the metal element and the amount of the Si element can be calculated by energy dispersive X-ray spectroscopy (EDX).

-Film formation method of light adjustment layer The above-mentioned light adjustment layer can be formed by applying the above-mentioned ceramic precursor, diffusion material, phosphor and the like on a substrate and curing them. Specifically, there are the following two methods.
(I) A method (first method) of applying a composition for forming a light adjustment layer containing the above-described phosphor, diffusing particles, ceramic precursor, etc. on a substrate and curing it by heating to obtain a light adjustment layer
(Ii) A step of forming a particle-containing film by applying and solidifying a particle-containing solution containing particulate components such as phosphors and diffusing particles and a solvent, and a ceramic precursor on the particle-containing film Applying the ceramic precursor-containing composition and heating and curing to obtain a light adjustment layer (second method)

(First method)
In the first method, the above-described phosphor, diffusing particles, and ceramic precursor are mixed with a mercapto group-containing coupling agent, inorganic fine particles, and the like as necessary to prepare a light adjustment layer forming composition. The composition for forming a light adjusting layer may contain a solvent. The solvent is not particularly limited as long as the compatibility with the ceramic precursor and the like is good. For example, water; monoalcohol such as methanol, ethanol, propanol, butanol; ethylene glycol, propylene glycol, diethylene glycol, glycerin, 1,3- It may be butanediol, 1,4-butanediol, or the like. The composition for forming a light adjusting layer may contain only one type of solvent or two or more types of solvents. Here, the boiling point of the solvent is preferably 250 ° C. or less from the viewpoint of the formation efficiency of the light adjusting layer.

  The application method of the composition for forming a light adjusting layer is not particularly limited, and may be a conventionally known method such as a bar coating method, a spin coating method, a spray coating method, a dispensing method, a jet dispensing method, an ink jet method, and a screen printing method. . In particular, according to the spray coating method, the composition for forming a light adjustment layer can be applied only to a desired region by applying a region other than the region to be coated while masking. Moreover, according to the dispensing method, the composition for light adjustment layer formation can be apply | coated only to a desired area | region. Therefore, according to these methods, a plurality of types of light adjustment layers can be formed on the substrate.

  Moreover, when a board | substrate is a disk, the composition for light adjustment layer formation can be apply | coated by uniform thickness by spraying the composition for light adjustment layer formation, rotating a board | substrate.

  Further, according to the spray method, it is possible to form light adjustment layers having different thicknesses at the center and the end. Specifically, the shape of the light adjustment layer can be controlled by adjusting the positions of the substrate and the nozzle of the spray device. For example, when the position of the substrate and the nozzle is sufficiently far from each other, the composition for forming a light adjustment layer is uniformly applied, so that the thickness of the obtained light adjustment layer is uniform. On the other hand, when the distance between the substrate and the nozzle is short, the thickness of the region (center portion) close to the nozzle increases, and the thickness of the region far from the nozzle (that is, the end portion) decreases.

  Here, after apply | coating the composition for light adjustment layer formation by the said method, the composition for light adjustment layer formation is dried and hardened. At this time, the ceramic precursor contained in the composition for forming a light adjusting layer reacts to become ceramic, and the diffusion material and the phosphor are bound by the binder. The temperature at which the composition for forming a light adjusting layer is dried and cured is preferably 100 ° C or higher, more preferably 150 to 300 ° C. When the heating temperature is less than 100 ° C., water generated during the dehydration condensation of the ceramic precursor and the solvent contained in the composition for forming the light adjustment layer cannot be sufficiently removed, and the light resistance of the light adjustment layer may be reduced. There is sex.

  When the ceramic precursor is polysilazane, the coating film is irradiated with UVU radiation (e.g., excimer light) having a wavelength in the range of 170 to 230 nm and cured, and further heat-cured to obtain a finer material. A film is formed.

(Spray coating device)
As described above, the spray coating apparatus for coating the composition for forming a light adjusting layer can be configured as shown in FIG. 4, for example. In the coating apparatus 200, the light adjustment layer forming composition 220 is supplied to the coating liquid tank 210. The light adjusting layer forming composition 220 in the coating liquid tank 210 is supplied with pressure to the head 240 through the connecting pipe 230. The light adjustment layer forming composition 220 supplied to the head 240 is discharged from the nozzle 250 and applied onto the substrate 1. The light adjustment layer forming composition 220 is discharged from the nozzle 250 by wind pressure. An opening that can be freely opened and closed is provided at the tip of the nozzle 250, and the opening may be opened and closed to control on / off of the discharge operation.

When applying the light adjusting layer forming composition 220 with the spray device, it is preferable to perform the following operations (1) to (6) and condition settings.
(1) The tip portion of the nozzle 250 is disposed immediately above the substrate 1 and the light adjustment layer forming composition 220 is sprayed from directly above the substrate 1. The composition may be ejected while relatively moving the substrate 1 and the nozzle 250. When the substrate 1 is circular, the application may be performed while rotating the substrate 1.

  (2) The injection amount of the light adjustment layer forming composition 220 is controlled according to the viscosity of the composition and the thickness of the light adjustment layer. As long as coating is performed under the same conditions, the spray amount is constant and the coating amount per unit area is constant. The variation with time of the injection amount of the composition 220 for forming a light adjusting layer is within 10%, preferably within 1%. The injection amount of the light adjustment layer forming composition 220 is adjusted by the relative movement speed of the nozzle 250 with respect to the substrate 1, the injection pressure from the nozzle 250, and the like. In general, when the viscosity of the light adjustment layer forming composition 220 is high, the relative movement speed of the nozzle 250 is slowed and the injection pressure is set high. The relative movement speed of the nozzle is usually about 30 mm / s to 200 mm / s; the injection pressure is usually about 0.01 MPa to 0.2 MPa.

(3) If necessary, the temperature of the nozzle 250 is adjusted, and the viscosity at the time of jetting of the light adjustment layer forming composition 220 is adjusted.
(4) Moreover, the temperature of the board | substrate 1 is adjusted as needed. The temperature adjustment mechanism of the substrate 1 can be installed on a moving table (not shown) on which the substrate 1 is placed. When the temperature of the substrate 1 is 30 to 100 ° C., the solvent in the light adjusting layer forming composition 220 can be quickly volatilized, and the light adjusting layer forming composition 220 can be prevented from dripping from the substrate 1. .

  (5) The environmental atmosphere (temperature / humidity) of the coating apparatus 200 is constant, and the injection of the light adjustment layer forming composition 220 is stabilized. In particular, when the light adjustment layer forming composition 220 contains polysilazane, the polysilazane may absorb moisture and the light adjustment layer forming composition 220 itself may solidify. Therefore, it is preferable to reduce the humidity when jetting the composition 220 for forming a light adjusting layer.

  The nozzle 250 may be cleaned during the spraying / coating operation of the light adjustment layer forming composition 220. In this case, a cleaning tank storing a cleaning liquid is installed in the vicinity of the coating apparatus 200. The tip of the nozzle 250 is immersed in the cleaning tank, for example, while the injection of the composition for forming a light adjustment layer 220 is stopped, thereby preventing the tip of the nozzle 250 from drying. Further, during the suspension of the spraying / coating operation, the light adjusting layer forming composition 220 may be cured and the spray holes of the nozzle 250 may be clogged. Therefore, it is preferable to immerse the nozzle 250 in a cleaning tank or to clean the nozzle 250 at the start of the spraying / coating operation.

(Second method)
In the second method, a particle-containing solution containing particulate components such as diffusing particles, phosphor particles, inorganic oxide fine particles, and viscosity compounds and a solvent is prepared and applied. The solvent contained in the particle-containing solution may be the same as the solvent contained in the above-described light adjustment layer forming composition.

  The method for applying the particle-containing solution is not particularly limited, and may be a conventionally known method such as a bar coating method, a spin coating method, a spray coating method, a dispensing method, a jet dispensing method, an ink jet method, or a screen printing method. In particular, the spray coating method and the dispensing method are preferable because the application of the particle-containing solution is easy as described above. The spray coating apparatus used for coating the particle-containing solution can be the same as the coating apparatus for the light adjusting layer forming composition described above.

  After the application of the particle-containing solution, the solvent contained in the coating film is dried to solidify the coating film. The temperature at which the solvent is dried is usually 20 to 200 ° C, preferably 25 to 150 ° C. There exists a possibility that a coating film may not fully dry that the temperature at the time of solvent drying is less than 20 degreeC. On the other hand, if the drying temperature exceeds 200 ° C., the substrate or the like may be affected.

  Then, the ceramic precursor containing composition containing a ceramic precursor is apply | coated on a particle | grain containing film | membrane, and is heat-hardened. When the ceramic precursor-containing composition is applied onto the particle-containing film, the ceramic precursor enters between the phosphor, the diffusion material, the inorganic oxide fine particles, the clay compound, and the like. As a result, in the obtained light adjustment layer, phosphors, diffusion materials, and the like are bound by a ceramic binder.

  The ceramic precursor-containing composition may contain a solvent, if necessary. The solvent that can be contained in the ceramic precursor-containing composition is the same as the solvent contained in the light adjusting layer forming composition described above.

  The method for applying the ceramic precursor-containing composition is not particularly limited, and may be a conventionally known method such as a bar coating method, a spin coating method, a spray coating method, a dispensing method, a jet dispensing method, and an ink jet method. As described above, when adjusting the thickness of the end portion of the light adjusting layer, it is preferable to apply the ceramic precursor-containing composition by a spray coating method. The spray coating apparatus used for coating the ceramic precursor-containing composition can be the same as the coating apparatus for the light adjusting layer forming composition described above.

  Then, after coating the ceramic precursor-containing composition, the coating film is heated to 100 ° C. or higher, preferably 150 to 300 ° C., and the coating film is dried and cured. If the heating temperature is less than 100 ° C., water generated during the dehydration condensation of the ceramic precursor cannot be sufficiently removed, and the light resistance and the like of the obtained light adjusting layer may be lowered.

2. About the Projection Display Device The projection display device of the present invention includes the color wheel for the projection display device described above. A schematic diagram of a projection display device 300 of the present invention is shown in FIG. FIG. 5 is a schematic diagram when the color wheel is a transmissive color wheel. The projection display device 300 of the present invention includes at least a light source 110, a color wheel 100, and a projection optical system 114. Light emitted from the light source 100 is collected by the lens 111 and the like, and is applied to the color wheel 100 described above. At this time, light from the light source is diffused and / or wavelength-converted by a light adjustment layer (not shown) of the color wheel 100. Then, the light transmitted through the color wheel 100 is condensed on the projection optical system 114 via the lens 112, the mirror 113, and the like, and an image is displayed on the screen.

  The wavelength of the light emitted from the light source 110 is not particularly limited, and the light has a wavelength that can excite the phosphor included in the light adjustment layer of the color wheel 100. The light source can be, for example, an LED element that can irradiate ultraviolet to near ultraviolet light or light having a blue wavelength. The projection optical system 114, the lenses 111 and 112, the mirror 113, and the like can be the same as those included in a general projection display device.

  In the projection display device of the present invention, the light adjustment layer included in the color wheel 100 is less likely to be colored, and the diffusion material and the phosphor are less likely to fall off. Therefore, high-quality image display is possible over a long period of time.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by this. In addition, the thickness of each layer was measured using the stylus type surface shape measuring device Dektak150.

[Comparative Example 1]
50 g of green phosphor (GAL545 manufactured by Intematix) was mixed with 100 g of silicone resin (OE6336 manufactured by Toray Dow Corning) to obtain a composition for forming a light control layer. The composition was bar-coated on a circular glass substrate (outer diameter 50 mm, inner diameter 10 mm, thickness 1 mm). Then, it heated at 150 degreeC for 3 hours, the said silicone resin was hardened, and the light adjusting layer was obtained. The thickness of the light adjustment layer was 100 μm.

[Comparative Example 2]
50 g of titanium oxide (TA-100, manufactured by Fuji Titanium Industry Co., Ltd., particle size 600 nm) was mixed with 100 g of a silicone resin (OE 6336 manufactured by Toray Dow Corning) to obtain a composition for forming a light adjusting layer. The composition was bar-coated on a circular glass substrate (outer diameter 50 mm, inner diameter 10 mm, thickness 1 mm). Then, it heated at 150 degreeC for 3 hours, the said silicone resin was hardened, and the light adjusting layer was obtained. The thickness of the light adjustment layer was 100 μm.

[Example 1]
(Preparation of particle-containing solution)
4 g of silicon oxide (RX300, manufactured by Nippon Aerosil Co., Ltd., particle size 7 nm), 4 g of smectite (Lucentite SWN, manufactured by Corp Chemical Co.), and 77 g of green phosphor (GAL545, manufactured by Intematix) were mixed in 100 g of propylene glycol. A particle-containing solution was prepared.

(Adjustment of ceramic precursor-containing composition)
100 g of methyltrimethoxysilane, 300 g of tetramethoxysilane, 400 g of methanol, and 400 g of acetone were mixed and stirred. Further, 546 g of water and 470 μL of 60% nitric acid were added to the mixed solution and stirred for 3 hours to obtain a ceramic precursor-containing composition.

(Preparation of light adjustment layer solution)
A mask was placed on the same glass substrate as in Comparative Example 1, and the aforementioned particle-containing solution was applied by spraying. The particle-containing solution was dried at 150 ° C. for 1 hour to form a particle-containing film. At this time, the distance between the spray nozzle and the substrate was 100 mm, and the coating speed (relative speed between the substrate and the spray device) was 50 mm / s. Further, at the time of spray coating, a part of the substrate was covered with a mask, and the light adjusting layer forming coating solution was coated in a ring shape with a width of 18 mm.
Thereafter, the ceramic precursor-containing composition described above was applied onto the particle-containing film under the same conditions as the particle-containing solution, and fired at 150 ° C. for 1 hour. As a result, a light adjustment layer in which phosphor particles and the like were bound with a ceramic binder was obtained. The thickness of the light adjustment layer was 100 μm, and the thickness of the end was also 100 μm. The thickness of the central portion is the average thickness of a region of 1.8 mm (10% with respect to the width) including the center of the ring-shaped light adjusting layer having a width of 18 mm. On the other hand, the thickness of the end portion is the average thickness (average value of both end portions) of a region 1.8 mm (10% relative to the width) from the end portion of the light adjusting layer.

[Example 2]
Light adjustment in the same manner as in Example 1 except that the ceramic precursor-containing composition of Example 1 was changed to a polysilazane-containing solution (NN120, manufactured by AZ Electronic Materials, 20% by mass of polysilazane, 80% by mass of dibutyl ether). A layer was obtained. The thickness of the light adjustment layer was 100 μm at both the center and the end.

[Example 3]
A light adjusting layer was obtained in the same manner as in Example 1 except that the phosphor in the particle-containing solution of Example 1 was changed to titanium oxide (TA-100, manufactured by Fuji Titanium Industry Co., Ltd., particle size 600 nm). The thickness of the light adjustment layer was 100 μm at both the center and the end.

[Example 4]
A light adjustment layer was produced in the same manner as in Example 1 except that the following ceramic precursor-containing liquid was used. The thickness of the light adjustment layer was 100 μm at both the center and the end. Moreover, it was 5 mol% when the quantity of the structural unit derived from the bifunctional alkoxysilane in the structural unit of the polysiloxane contained in a light adjustment layer was measured by ²⁹ Si-NMR.

(Adjustment of ceramic precursor-containing composition)
15 g of dimethyldimethoxysilane, 100 g of methyltrimethoxysilane, 300 g of tetramethoxysilane, 400 g of methanol, and 400 g of acetone were mixed and stirred. Further, 546 g of water and 470 μL of 60% nitric acid were added and stirred for 3 hours to obtain a ceramic precursor-containing composition.

[Example 5]
A light adjustment layer was produced in the same manner as in Example 1 except that the following ceramic precursor-containing liquid was used. The thickness of the light adjustment layer was 100 μm at both the center and the end. Moreover, it was 50 mol% when the quantity of the structural unit derived from the bifunctional alkoxysilane in the structural unit of the polysiloxane contained in a light adjustment layer was measured by ²⁹ Si-NMR.

(Adjustment of ceramic precursor-containing composition)
200 g of dimethyldimethoxysilane, 50 g of methyltrimethoxysilane, 250 g of tetramethoxysilane, 400 g of methanol, and 400 g of acetone were mixed and stirred. Further, 546 g of water and 470 μL of 60% nitric acid were added and stirred for 3 hours to obtain a ceramic precursor-containing composition.

[Example 6]
A light adjustment layer was produced in the same manner as in Example 1 except that the following ceramic precursor-containing liquid was used. The thickness of the light adjustment layer was 100 μm at both the center and the end. Moreover, it was 60 mol% when the quantity of the structural unit derived from the bifunctional alkoxysilane in the structural unit of the polysiloxane contained in a light adjustment layer was measured by ²⁹ Si-NMR.

(Adjustment of ceramic precursor-containing composition)
300 g of dimethyldimethoxysilane, 50 g of methyltrimethoxysilane, 250 g of tetramethoxysilane, 400 g of methanol, and 400 g of acetone were mixed and stirred. Further, 546 g of water and 470 μL of 60% nitric acid were added and stirred for 3 hours to obtain a ceramic precursor-containing composition.

[Example 7]
A light adjustment layer was produced in the same manner as in Example 1 except that the following ceramic precursor-containing liquid was used. The thickness of the light adjustment layer was 100 μm at both the center and the end. Moreover, when the quantity of the structural unit derived from the bifunctional alkoxysilane in the structural unit of the polysiloxane contained in a light adjustment layer was measured by ²⁹ Si-NMR, it was 3 mol%.

(Adjustment of ceramic precursor-containing composition)
10 g of dimethyldimethoxysilane, 150 g of methyltrimethoxysilane, 350 g of tetramethoxysilane, 400 g of methanol, and 400 g of acetone were mixed and stirred. Further, 546 g of water and 470 μL of 60% nitric acid were added and stirred for 3 hours to obtain a ceramic precursor-containing composition.

[Example 8]
A light adjustment layer was produced in the same manner as in Example 1 except that the following ceramic precursor-containing liquid was used. The thickness of the light adjustment layer was 100 μm at both the center and the end. Moreover, it was 30 mol% when the quantity of the structural unit derived from the bifunctional alkoxysilane in the structural unit of the polysiloxane contained in a light adjustment layer was measured by ²⁹ Si-NMR.

(Adjustment of ceramic precursor-containing composition)
115 g of dimethyldimethoxysilane, 95 g of methyltrimethoxysilane, 300 g of tetramethoxysilane, 400 g of methanol, and 400 g of acetone were mixed and stirred. Further, 546 g of water and 470 μL of 60% nitric acid were added and stirred for 3 hours to obtain a ceramic precursor-containing composition.

[Example 9]
A light adjustment layer was prepared in the same manner as in Example 1 except that the following particle-containing solution was used. The thickness of the light adjustment layer was 100 μm at both the center and the end. Moreover, when the quantity of the structural unit derived from bifunctional alkoxysilane in the structural unit of the polysiloxane contained in a light adjustment layer was measured by ²⁹ Si-NMR, the said structural unit was not contained.

(Preparation of particle-containing solution)
77 g of green phosphor (GAL545, manufactured by Intematix) was mixed in 100 g of propylene glycol to prepare a particle-containing solution.

[Example 10]
The particle-containing solution of Example 1 and the ceramic precursor-containing solution of Example 8 were mixed to obtain a light adjustment layer forming composition. The said composition for light adjustment layer formation was apply | coated, and the light adjustment layer was formed. The coating conditions were the same as the coating method for the particle-containing solution in Example 1. After application of the composition for forming a light adjusting layer, it was dried at 100 ° C. for 1 hour. Then, it dried at 150 degreeC for 1 hour, and obtained the light adjustment layer.
The thickness of the light adjustment layer was 100 μm at both the center and the end. Moreover, it was 30 mol% when the quantity of the structural unit derived from the bifunctional alkoxysilane in the structural unit of the polysiloxane contained in a light adjustment layer was measured by ²⁹ Si-NMR.

[Example 11]
A light adjustment layer was prepared in the same manner as in Example 9 except that the following particle-containing solution was used. The thickness of the light adjustment layer was 100 μm at both the center and the end. Moreover, when the quantity of the structural unit derived from bifunctional alkoxysilane in the structural unit of the polysiloxane contained in a light adjustment layer was measured by ²⁹ Si-NMR, the said structural unit was not contained.

(Preparation of particle-containing solution)
77 g of titanium oxide (TA-100, manufactured by Fuji Titanium Industry Co., Ltd., particle size 600 nm) was mixed in 100 g of propylene glycol, and this was used as a particle-containing solution.

[Evaluation]
About the color wheel for projection type display apparatuses produced by the comparative examples 1 and 2 and Examples 1-11, durability and crack tolerance were evaluated with the following method. The results are shown in Table 1.

(Durability evaluation)
A 1w blue laser (wavelength 405 nm) was irradiated for 1000 hours from the front of the color wheel on the light adjustment layer side, and the luminance of light emitted from the glass substrate side was measured. The luminance at the start of laser irradiation and the rate of change after irradiation for 1000 hours (luminance after irradiation / luminance before irradiation × 100) are shown. The luminance was measured using a spectral radiance meter CS-1000A manufactured by Konica Minolta Sensing. Durability was evaluated according to the following criteria.
A: Change rate is 90% or more O: Change rate is 80% or more and less than 90% Δ: Change rate is 70% or more and less than 80% X: Change rate is less than 70%

(Crack resistance evaluation A)
Using a heat shock tester, the crack resistance of the light adjustment layer was measured. Specifically, 1000 cycles were performed, with one cycle of −40 ° C. for 30 minutes and 100 ° C. for 30 minutes. The occurrence of cracks when the cycle was performed was visually observed with a microscope. And it evaluated on the following references | standards.
◎: No crack 〇: Slight cracks that cannot be visually confirmed △: Cracks that can be visually confirmed have occurred, but there are no practical problems ×: Cracks that can be visually confirmed have occurred And there are practical problems

  As shown in Table 1 above, the light control layer containing a phosphor or a diffusing material and containing a ceramic binder obtained by reacting a ceramic precursor has high durability and cracks are generated even by a thermal cycle. It was difficult (Examples 1 to 11). In particular, when the ceramic binder is polysiloxane and the structure derived from bifunctional alkoxysilane is contained in an amount of 5 mol% or more, the crack resistance of the light adjusting layer is likely to increase (Examples 5, 6, 8, and 10). ). Since the flexibility of the light adjustment layer has increased, it is assumed that cracks are less likely to occur. However, when the structure derived from bifunctional alkoxysilane was contained in an amount of more than 50 mol%, the durability slightly decreased (Example 6). It is presumed that the film easily deteriorates and the durability is lowered by increasing the amount of organic groups contained in the structure derived from the bifunctional alkoxysilane.

  In addition, the comparison between Examples 1 and 3 showed that the same result was obtained in both cases where the particles contained in the light adjustment layer were a phosphor and a diffusion material. Moreover, it was shown from the comparison of Example 8 and 10 that the same result is obtained both when the phosphor and the alkoxysilane oligomer are applied separately and when they are applied as a single solution. In addition, when inorganic oxide microparticles | fine-particles were not contained with fluorescent substance and the diffusion material, crack tolerance fell a little (Example 9).

  On the other hand, when the binder of the light adjusting layer was a silicone resin, the durability was low and the crack resistance was also low (Comparative Example 1 and Comparative Example 2). It is presumed that cracks are likely to occur in the binder due to the thermal shock, and that the binder is also deteriorated by laser light.

[Example 12]
A light adjustment layer was prepared in the same manner as in Example 8 except that the following particle-containing solution was used. The thickness of the light adjustment layer was 100 μm at both the center and the end. Moreover, it was 30 mol% when the quantity of the structural unit derived from the bifunctional alkoxysilane in the structural unit of the polysiloxane contained in a light adjustment layer was measured by ²⁹ Si-NMR.

(Preparation of particle-containing solution)
4 g of silicon oxide (RX300, manufactured by Nippon Aerosil Co., Ltd., particle size: 7 nm), 4 g of smectite (Lucentite SWN, manufactured by Corp Chemical), and 77 g of green phosphor (GAL545, manufactured by Intematix) were mixed in 100 g of propylene glycol. did. 33 g of titanium oxide (TA-100, manufactured by Fuji Titanium Industry Co., Ltd., particle size 600 nm) was further mixed with the mixed solution.

[Example 13]
A light adjusting layer was obtained in the same manner as in Example 12 except that the amount of titanium oxide in the particle-containing solution was changed to 40 g.

[Example 14]
A light adjustment layer was obtained in the same manner as in Example 12 except that the amount of titanium oxide in the particle-containing solution was changed to 63 g.

[Example 15]
A light adjusting layer was obtained in the same manner as in Example 12 except that the amount of titanium oxide in the particle-containing solution was changed to 180 g.

[Example 16]
A light adjustment layer was obtained in the same manner as in Example 12 except that the amount of titanium oxide in the particle-containing solution was changed to 230 g.

[Example 17]
A light adjustment layer was obtained in the same manner as in Example 14 except that the following particle-containing solution was used.

(Preparation of particle-containing solution)
77 g of green phosphor (GAL545, manufactured by Intematix) and 63 g of titanium oxide (TA-100, manufactured by Fuji Titanium Industry Co., Ltd., particle size 600 nm) were mixed with 100 g of propylene glycol.

[Evaluation]
About the color wheel for projection type display apparatuses produced by the comparative example 1 and Examples 8, 12-17, the transmittance | permeability suppression of excitation light was evaluated with the following method. The results are shown in Table 2.

(Evaluation of transmission suppression of excitation light)
Light was irradiated by a blue LED from the front of the light adjustment layer of each color wheel. And the intensity | strength of the blue light (light with a wavelength of 460 nm) radiate | emitted from the board | substrate (glass substrate) side was measured. The measuring device was a spectral radiance meter CS-1000A manufactured by Konica Minolta Sensing. Moreover, as a reference, light was emitted from the front of one surface of the glass substrate with a blue LED, and the intensity of blue light (light having a wavelength of 460 nm) emitted from the other surface was measured.

The light adjustment layer of each color wheel includes a phosphor that receives blue light and emits green light. That is, the color wheel is required to emit green light. In contrast, when blue light, which is light from the light source, passes through the light adjustment layer, that is, when blue light is observed on the substrate side in the above measurement, not only green light but also blue light is emitted as light emitted from the light adjustment layer. Will also be included. As a result, desired green light is not emitted.
Therefore, the degree of transmission of blue light as excitation light was evaluated based on the intensity ratio calculated by the following equation. Evaluation was based on the following criteria.
Intensity ratio: Intensity of blue light measured on substrate side of each color wheel / intensity of reference blue light × 100
A: The intensity ratio is less than 3%. O: The intensity ratio is 3% or more and less than 5%. Δ: The intensity ratio is 5% or more and less than 10%. X: The intensity ratio is 10% or more.

  As shown in Table 2 above, when the light adjustment layer contains a diffusion material (titanium oxide), blue light that is excitation light was difficult to pass through the light adjustment layer (Examples 12 to 17). However, when the amount of the diffusing material was excessive, the amount of light emitted from the light adjustment layer became very small (Example 16). It is presumed that the diffusing material shields the excitation light of the phosphor and the amount of light is reduced.

[Comparative Example 1b]
A color wheel for a projection display device was produced in the same manner as in Comparative Example 1, except that silver was deposited to a thickness of 200 nm on a glass substrate and a light adjustment layer was produced on the substrate.

[Example 14b]
Except that silicon oxide, smectite, and titanium oxide (diffusion material) were not added to the particle-containing solution, silver was deposited to a thickness of 200 nm on a glass substrate, and a light adjustment layer was produced on the substrate, as in Example 14. A color wheel for a projection display device was prepared.

[Example 18]
A color wheel for a projection display device was produced in the same manner as in Example 14b except that 12.7 g of 3-mercaptopropylmethyldimethoxysilane was mixed with the ceramic precursor-containing composition.

[Evaluation]
The adhesion of the color wheel for a projection display device produced in Comparative Example 1b, Example 14b, and Example 18 was evaluated by the following method. The results are shown in Table 3.

(Adhesion evaluation)
Each wheel was allowed to stand for 1000 hours in an environment of a temperature of 60 ° C. and a humidity of 90% Rh. Thereafter, a 50 w blue laser was irradiated for 1000 h from the front of the color wheel on the light adjustment layer side, and the luminance of the light emitted from the glass substrate side was measured. Thereafter, the surface of the light adjustment layer was visually observed with a microscope, and it was confirmed whether there was peeling between the substrate and the light adjustment layer.
◎: No peeling at all 〇: No peeling at all ×: There is peeling

  As shown in Table 3, when the binder of the light adjustment layer was polysiloxane (Examples 14b and 18), the adhesion between the substrate and the light adjustment layer was increased. It is presumed that the adhesion between the substrate and the light adjustment layer has increased since Si in the polysiloxane and OH groups on the substrate surface form Si—O bonds. Furthermore, when a mercapto group-containing silane coupling agent is added during the formation of the light adjustment layer, the adhesion between the substrate and the light adjustment layer is increased, and the light adjustment layer is very difficult to peel off.

[Example 19]
A light adjustment layer was formed in the same manner as in Example 14 except that the distance between the nozzle of the spray device and the substrate was 30 mm and the coating speed (relative speed between the substrate and the spray device) was 100 mm / s. The thickness of the edge part of the obtained light adjusting layer was 50% (50 μm) with respect to the thickness (100 μm) of the center part.

[Example 20]
A light adjustment layer was formed in the same manner as in Example 14 except that the distance between the nozzle of the spray device and the substrate was 70 mm, and the coating speed (relative speed between the substrate and the spray device) was 70 mm / s. The thickness of the edge part of the obtained light adjusting layer was 70% (70 μm) with respect to the thickness (100 μm) of the center part.

[Example 21]
A light adjustment layer was formed in the same manner as in Example 14 except that the distance between the nozzle of the spray device and the substrate was 50 mm and the coating speed (relative speed between the substrate and the spray device) was 85 mm / s. The thickness of the edge part of the obtained light adjusting layer was 60% (60 μm) with respect to the thickness (100 μm) of the center part.

[Evaluation]
About the color wheel for projection type display apparatuses produced in Example 14 and 19-21, crack resistance was evaluated with the following method. The results are shown in Table 4.

(Crack resistance evaluation B)
The crack resistance of the light adjusting layer was adjusted using a heat shock tester. More specifically, 1000 cycles were performed with one cycle of −40 ° C. for 30 minutes and 125 ° C. for 30 minutes. The occurrence of cracks when the cycle was performed was visually observed with a microscope. And it evaluated on the following references | standards.
◎: No crack 〇: Slight cracks that cannot be visually confirmed △: Cracks that can be visually confirmed have occurred, but there are no practical problems ×: Cracks that can be visually confirmed have occurred And there are practical problems

  As shown in Table 4, in Examples 19 to 21 having the light adjustment layer whose end portion is thinner than the thickness of the central portion, compared to Example 14 having the flat light adjustment layer, the crack resistance is higher. It was easy to increase. When the thickness of the light adjustment layer is reduced at the end, it is presumed that the distortion generated during the film formation of the light adjustment layer is easily relieved and the stress applied during the cooling cycle is also easily relieved.

  This application claims the priority based on Japanese Patent Application No. 2015-017343 of an application on January 30, 2015. The contents described in the application specification and the drawings are all incorporated herein.

  In the color wheel for a projection display device of the present invention, even if it is used for a long period of time, the light adjustment layer is not easily colored, and the phosphor and the diffusing material are not easily dropped. Therefore, it can be applied to various projection display devices.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Light adjustment layer 100 Color wheel for projection display device

Claims (12)

A substrate,
A ceramic binder formed on the substrate and made of a reaction product of a ceramic precursor, and a light adjusting layer containing at least one of a phosphor and a diffusion material;
A color wheel for a projection display device.   The color wheel for a projection display device according to claim 1, wherein the ceramic precursor is one or more polysiloxane precursors selected from the group consisting of polysilazane, an alkoxysilane monomer, and an alkoxysilane oligomer. 3. The projection display device according to claim 1, wherein the ceramic binder includes polysiloxane, and 5 to 50 mol% of a structural unit derived from bifunctional alkoxysilane is included in all the structural units of the polysiloxane. Color wheel.   The diffusion material is made of one or more inorganic compounds selected from the group consisting of titanium oxide, silicon oxide, barium sulfate, barium titanate, boron nitride, zinc oxide, and aluminum oxide, and has an average primary particle size of 100 nm to 10 μm. The color wheel for a projection display device according to any one of claims 1 to 3, wherein the color wheel is a particle. 5. The light adjustment layer according to claim 1, wherein the light adjustment layer includes the diffusion material and the phosphor, and includes the diffusion material in a range of 34% by mass to less than 70% by mass with respect to a total amount of the phosphor and the diffusion material. A color wheel for a projection display device according to any one of the above. The substrate has at least a metal reflecting surface made of metal on a surface adjacent to the light adjustment layer;
The color wheel for projection display devices according to any one of claims 1 to 5, wherein the light adjustment layer includes a structure derived from a mercapto group-containing coupling agent. The light adjusting layer has an end portion with a thickness smaller than that of the center portion,
The color wheel for a projection display device according to any one of claims 1 to 6, wherein a thickness of the end portion is 50 to 70% with respect to a thickness of the center portion. It is a manufacturing method of the color wheel for projection type display devices according to any one of claims 1 to 7,
Applying a particle-containing solution containing at least one of the phosphor and the diffusing material and a solvent on the substrate and drying to obtain a particle-containing film;
Applying a ceramic precursor-containing composition containing the ceramic precursor on the particle-containing film, heating and curing to form the light adjustment layer;
A method for manufacturing a color wheel for a projection display device. It is a manufacturing method of the color wheel for projection type display devices according to any one of claims 1 to 7,
Projection including a step of applying a composition for forming a light adjustment layer including at least one of the phosphor and the diffusing material and the ceramic precursor on the substrate, and heating and curing to form the light adjustment layer. Manufacturing method of color wheel for type display device.   The method for producing a color wheel for a projection display device according to claim 8 or 9, wherein the ceramic precursor-containing composition or the light adjusting layer forming composition is applied by spraying or a dispenser.   The method for producing a color wheel for a projection display device according to claim 8 or 9, wherein the ceramic precursor-containing composition or the light adjustment layer forming composition is applied by spraying while rotating the substrate.   The projection type display apparatus containing the color wheel for projection type display apparatuses as described in any one of Claims 1-7.

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