WO2016013520A1

WO2016013520A1 - Color filter and solid-state imaging element

Info

Publication number: WO2016013520A1
Application number: PCT/JP2015/070581
Authority: WO
Inventors: 大貴瀧下; 啓之山本; 啓佑有村; 高桑　英希; 嶋田　和人
Original assignee: 富士フイルム株式会社
Priority date: 2014-07-25
Filing date: 2015-07-17
Publication date: 2016-01-28
Also published as: JPWO2016013520A1; KR101876281B1; JP6297155B2; TW201604592A; KR20160145168A; TWI666472B

Abstract

The present invention provides: a color filter which has color pixels of four or more colors, and which is able to be produced easily; and a solid-state imaging element. A color filter according to the present invention has color pixels of four or more colors, and at least one of the color pixels is a multilayer color pixel that is obtained by laminating a multilayer film layer wherein a plurality of films having different refractive indexes are laminated and a coloring agent-containing composition layer which contains a coloring agent.

Description

Color filter, solid-state image sensor

The present invention relates to a color filter and a solid-state imaging device.

A solid-state imaging device usually includes a color filter having red, green, and blue color pixels that are two-dimensionally arranged on a substrate such as a semiconductor substrate or a glass substrate.
In recent years, color filters having various color pixels (color filters) in addition to the three colors of red, green, and blue have been applied to solid-state imaging devices (for example, Patent Document 1). Patent Document 1 discloses a mode in which magenta, cyan, and yellow (yellow) color pixels are used together with green, red, and blue color pixels.

Furthermore, from the viewpoint of application to night vision cameras and the like, an attempt has been made to give each pixel of red, green, and blue colors the ability to detect the infrared region (preferably the near infrared region). Yes. For example, in Patent Literature 2, the infrared region detection capability is imparted by using an optical filter that transmits specific infrared light together with red light, green light, and blue light.

JP 2006-270364 A JP 2011-50049 A

On the other hand, when using magenta, cyan, and yellow color pixels as described in Patent Document 1, it is necessary to develop a color material / composition for each color to be added. Not necessarily preferred.
Further, since the types of colorants to be used are increased, the number of steps for producing each color pixel is increased, and the work time for replacing the colorants is increased, which is not preferable in terms of productivity.

In addition, Patent Document 2 describes that an optical filter is used to transmit visible light in a specific wavelength region and infrared light in a specific wavelength region. There is no description. In consideration of industrial points, such a color filter that transmits specific light is also required to have excellent manufacturing suitability.
That is, it has been desired to provide a color filter that can be manufactured more easily and can transmit visible light in a specific wavelength region and infrared light in a specific wavelength region.

In view of the above circumstances, the first embodiment of the present invention is to provide a color filter having four or more color pixels that can be easily manufactured.
Another object of the first embodiment of the present invention is to provide a solid-state imaging device including the color filter.

In view of the above situation, the second embodiment of the present invention has an object to provide a color filter having color pixels that transmit specific visible light and specific infrared light, which can be easily manufactured. To do.
Another object of the second embodiment of the present invention is to provide a solid-state imaging device including the color filter.

As a result of diligent investigations on the problems of the prior art, the present inventors have found that the above-described problems can be solved by using a multilayer film layer in which a plurality of films having different refractive indexes are stacked.
That is, the present inventors have found that the problem of the first embodiment can be solved by the following configuration.

(1) It has four or more color pixels,
A color filter, wherein at least one of the color pixels is a multilayer color pixel formed by laminating a multilayer film layer in which a plurality of films having different refractive indexes are laminated and a colorant-containing composition layer containing a colorant.
(2) The color pixel contains at least a red pixel composed of a colorant-containing composition layer containing a red colorant, a green pixel composed of a colorant-containing composition layer containing a green colorant, and a blue colorant The color filter according to (1), comprising a blue pixel comprising the colorant-containing composition layer.
(3) The red pixel has a maximum value in the transmission spectrum at a wavelength of 575 nm or more, the green pixel has a maximum value in the transmission spectrum at a wavelength of 480 nm or more and less than 575 nm, and the blue pixel has a maximum value in the transmission spectrum at a wavelength of less than 480 nm. The color filter according to (2).
(4) A color pixel is formed by laminating at least a red pixel, a green pixel, a blue pixel, a multilayer film layer in which a plurality of films having different refractive indexes are laminated, and a colorant-containing composition layer containing a green colorant. Including a first laminated color pixel and a second laminated color pixel formed by laminating a multilayer film layer in which a plurality of films having different refractive indexes are laminated and a colorant-containing composition layer containing a blue colorant. The color filter according to (2) or (3).
(5) The multilayer film layer has a transmittance of 30% or less within a wavelength range of 480 to 500 nm, or a transmittance of 30% or less within a wavelength range of 580 to 600 nm. The color filter according to any one of (4).
(6) The color filter according to any one of (1) to (5), wherein the multilayer film layer is a layer formed using a coating solution.
(7) A solid-state imaging device comprising the color filter according to any one of (1) to (6).

Further, the present inventors have found that the problem of the second embodiment can be solved by the following configuration.

(8) a first color pixel that transmits first visible light and first infrared light, a second color pixel that transmits second visible light and second infrared light, and third visible light and third infrared light. A third color pixel that transmits light;
The first visible light, the second visible light, and the third visible light have different wavelength distributions;
A color filter in which the first infrared light, the second infrared light, and the third infrared light have different wavelength distributions.
(9) The color filter according to (8), wherein at least one of the first color pixel, the second color pixel, and the third color pixel includes a multilayer film layer in which a plurality of films having different refractive indexes are stacked.
(10) The color filter according to (9), wherein the multilayer film layer is a layer formed using a coating solution.
(11) The color filter according to any one of (8) to (10), wherein the first visible light is red light, the second visible light is blue light, and the third visible light is green light.
(12) The first color pixel is formed by laminating a red pixel composed of a colorant-containing composition layer containing a red colorant, and a first multilayer film layer in which a plurality of films having different refractive indexes are laminated,
The second color pixel is formed by laminating a blue pixel composed of a colorant-containing composition layer containing a blue colorant, and a second multilayer film layer in which a plurality of films having different refractive indexes are laminated,
The third color pixel is formed by laminating a green pixel composed of a colorant-containing composition layer containing a green colorant, and a third multilayer film layer in which a plurality of films having different refractive indexes are laminated. The color filter according to any one of (11).
(13) The first multilayer film layer has a light transmittance in the first infrared wavelength region (light transmittance in the first infrared wavelength region) of 50% or more, and is in the second infrared wavelength region. The light transmittance (light transmittance in the second infrared wavelength region) and the light transmittance in the third infrared wavelength region (light transmittance in the third infrared wavelength region) each show 20% or less,
The second multilayer film has a light transmittance of 50% or more in the second infrared wavelength region, and has a light transmittance in the first infrared wavelength region and a light transmittance in the third infrared wavelength region. Indicates 20% or less,
The third multilayer film has a light transmittance of 50% or more in the third infrared wavelength region, and has a light transmittance in the first infrared wavelength region and a light transmittance in the second infrared wavelength region. The color filter according to any one of (8) to (12), wherein each represents 20% or less.
(14) The color filter according to (13), wherein the width of the first infrared wavelength region, the width of the second infrared wavelength region, and the width of the third infrared wavelength region are each 30 nm or more.
(15) The center wavelength of the first infrared light is located on the shorter wavelength side than the center wavelength of the second infrared light and the center wavelength of the third infrared light.
Alternatively, the wavelength region of the first infrared light is located on a shorter wavelength side than the wavelength region of the second infrared light and the wavelength region of the third infrared light, and the wavelength region of the first infrared light is any one of (8) to (14) The color filter described.
(16) The center wavelength of the second infrared light is located on the shorter wavelength side than the center wavelength of the third infrared light, or
The color filter according to any one of (8) to (15), wherein the wavelength region of the second infrared light is located on a shorter wavelength side than the wavelength region of the third infrared light.
(17) The first infrared wavelength region is located between wavelengths 700-800 nm, the second infrared wavelength region is located between wavelengths 900-1000 nm, and the third infrared wavelength region is between wavelengths 1050-1200 nm The color filter according to (13) or (14), which is located in
(18) The first infrared wavelength region is located between wavelengths 700-800 nm, the second infrared wavelength region is located between wavelengths 800-900 nm, and the third infrared wavelength region is between wavelengths 900-1000 nm The color filter according to (13) or (14), which is located in

According to the first embodiment of the present invention, it is possible to provide a color filter having four or more color pixels that can be easily manufactured.
In addition, according to the first embodiment of the present invention, it is possible to provide a solid-state imaging device including the color filter.

According to the second embodiment of the present invention, it is possible to provide a color filter having color pixels that transmit specific visible light and infrared light, which can be easily manufactured.
Moreover, according to the 2nd embodiment of this invention, a solid-state image sensor provided with the said color filter can also be provided.

It is an image figure which shows an example of the relationship between a wavelength and the transmittance | permeability when a multilayer film layer and a colorant containing composition layer are combined. It is a partially expanded plan view of the 1st suitable example of the color filter of the 1st embodiment of the present invention. FIG. 3 is a cross-sectional view taken along line AA in FIG. 2. FIG. 3 is a cross-sectional view taken along line BB in FIG. 2. It is a partially expanded plan view of a second preferred example of the color filter of the first embodiment of the present invention. FIG. 6 is a cross-sectional view taken along the line CC in FIG. 5. FIG. 6 is a cross-sectional view taken along the line DD in FIG. 5. It is a partially expanded plan view of a third preferred example of the color filter of the first embodiment of the present invention. FIG. 9 is a cross-sectional view taken along line EE in FIG. 8. FIG. 9 is a cross-sectional view taken along line FF in FIG. 8. It is a functional block diagram of the imaging device to which the solid-state imaging device using the color filter of the first embodiment of the present invention is applied. (A) is a transmission spectrum diagram of the multilayer film layer 1, and (B) is a transmission spectrum diagram of the multilayer film layer 2. (A) is a transmission spectrum diagram of each of a red pixel, a blue pixel, and a green pixel, and (B) is a red color pixel, a multilayer color pixel composed of a multilayer film layer 1 and a green pixel, and a multilayer film layer 1 It is a transmission spectrum figure of each lamination type color pixel with a blue pixel. (A) is a transmission spectrum diagram of each of a red pixel, a blue pixel, and a green pixel, and (B) is a blue pixel, a multilayer color pixel of the multilayer film layer 2 and the green pixel, and the multilayer film layer 2. It is a transmission spectrum figure of each lamination type color pixel with a red pixel. It is a partially expanded sectional view of one embodiment of the color filter of the second embodiment of the present invention. (A) represents a transmission spectrum diagram of red light and first infrared light transmitted through the first color pixel, and (B) represents a transmission spectrum diagram of blue light and second infrared light transmitted through the second color pixel. (C) represents a transmission spectrum diagram of green light and third infrared light transmitted through the third color pixel. It is the spectrum figure of the light which permeate | transmitted the 1st color pixel produced in the Example, the 2nd color pixel, and the 3rd color pixel.

Below, the color filter and solid-state image sensor of this invention are explained in full detail.
The description of the components in the present invention described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

In the description of the group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes those having no substituent and those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In this specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition.
The solid content concentration in this specification refers to the solid content concentration at 25 ° C.

In this specification, “monomer” and “monomer” are synonymous. The monomer in this specification is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.

In the present specification, the weight average molecular weight is defined as a polystyrene equivalent value by GPC (gel permeation chromatography) measurement. In this specification, the weight average molecular weight (Mw) is, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgelｇSuper AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15.0 cm) as a column. Can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

<First Embodiment>
Hereinafter, the color filter of the first embodiment of the present invention will be described in detail.
A feature of the color filter of the first embodiment of the present invention is that a multilayer film layer in which a plurality of films having different refractive indexes are stacked is used. As will be described later, the multilayer film layer increases the transmittance in a specific wavelength range by appropriately adjusting the refractive index of the included film and the number of films, respectively, or transmits in a specific wavelength range. Only the rate can be lowered. By laminating such a multilayer film layer and a colorant-containing composition layer, it is possible to adjust the range of wavelengths that pass through the laminate in which the two layers are laminated. More specifically, a description will be given with reference to FIG. 1A is a multilayer film layer that transmits light in a high wavelength region, and FIG. 1B is a colorant-containing composition layer that transmits light in a low wavelength region. The two layers have different wavelength ranges of light that can be transmitted. Then, when the two layers are stacked, only light that can be transmitted through both layers is transmitted, as shown in FIG. That is, by laminating the multilayer film layer and the colorant-containing composition layer, the color of the formed laminate is different from that of the colorant-containing composition layer. In such an embodiment, by using a multilayer film layer, different color pixels can be formed from one colorant-containing composition layer. That is, it is not necessary to use a colorant-containing composition containing another colorant, and a plurality of color pixels can be formed, which is excellent in terms of cost and productivity.

The color filter of the present invention has at least four color pixels. In other words, the color filter includes at least four types of pixels having different colors. Typical color pixels include R (red) pixels, G (green) pixels, and B (blue) pixels. In addition, C (cyan) pixels, M (magenta) pixels, and Y (yellow). ) Pixels.
In the present invention, color pixels having the same type of hue but having different shades are also color pixels having different colors. In other words, color pixels having the same color and having different shades in chromaticity are different color pixels. More specifically, it is assumed that the color of the dark green pixel G1 is different from that of the pixel G2 that exhibits the same type of hue (green) as the pixel G1 and is lighter than the pixel G1.
As will be described later, in the stacked color pixel, the color of the colorant-containing composition layer used can be adjusted by the multilayer film layer. Thus, for example, when a color pixel is produced using a composition containing a specific green colorant, a multilayer disposed in advance on the substrate while producing a dark green pixel by directly applying the composition onto the substrate. A thin green pixel can be produced by applying the composition on the film layer.
Note that a red pixel (for example, a pixel composed of a colorant-containing composition layer containing a red colorant) preferably has a maximum value in a transmission spectrum at a wavelength of 575 nm or more (preferably 575 nm or more and 670 nm or less), and a green pixel. (For example, a pixel comprising a colorant-containing composition layer containing a green colorant) preferably has a maximum value in the transmission spectrum at a wavelength of 480 nm or more and less than 575 nm, and a blue pixel (for example, a colorant containing a blue colorant) It is preferable that the maximum pixel in the transmission spectrum has a maximum value of less than 480 nm (preferably, 400 nm or more and less than 480 nm) in the transmission spectrum.

In addition, the manufacturing method in particular of each color pixel is not restrict | limited, A well-known method is employ | adopted. For example, it is preferably formed from a composition containing a colorant described later. That is, each color pixel preferably includes a colorant-containing composition layer containing a predetermined colorant (for example, a red colorant, a green colorant, and a blue colorant).
As will be described later, when the color pixel is a stacked color pixel, it is manufactured by a method described later.

The shape of each color pixel is not particularly limited, and an optimal size is appropriately selected according to the application to be used, but is preferably a substantially square shape. In that case, the upper limit of the size of one side is preferably 10 μm or less, more preferably 5 μm or less, and the lower limit is preferably 0.1 μm or more, more preferably 0.5 μm or more.
Although the thickness of each color pixel is not particularly limited, the upper limit value is preferably 10 μm or less, more preferably 5 μm or less, and the lower limit value is 0.1 μm or more in terms of the balance between performance as a color pixel and thinning. preferable.

In the color filter of the present invention, at least one of the color pixels is a laminated color formed by laminating a multilayer film layer in which a plurality of films having different refractive indexes are laminated and a colorant-containing composition layer containing a colorant. Pixel.
In the following, first, the layers constituting the stacked color pixel will be described in detail, and then the configuration of the color filter will be described in detail.

<Multilayer film layer>
The multilayer film layer is a laminated body in which a plurality of films having different refractive indexes are laminated. By adjusting the refractive index and film thickness of the film used, the optical path difference of light is adjusted, and transmission at a desired wavelength is performed. The rate can be controlled.
As one preferred embodiment of the multilayer film layer, the transmittance in the wavelength range of 480 to 500 nm is 30% or less (note that 20% or less is preferable and 10% or less is more preferable. The lower limit is not particularly limited. , 0% may be mentioned). By arranging blue pixels, green pixels, and the like on such a multilayer film layer, the color of each pixel can be adjusted.
As another preferred embodiment of the multilayer film layer, the transmittance within the wavelength range of 580 to 600 nm is 30% or less (note that 20% or less is preferable and 10% or less is more preferable. The lower limit is particularly limited. A multilayer film layer is 0%). By arranging a green pixel, a red pixel, or the like on such a multilayer film layer, the color of each pixel can be adjusted.
The thickness of the multilayer film layer is not particularly limited, and an optimal thickness is appropriately selected according to the application to be used. However, the upper limit value is 5 μm or less in terms of the balance between the performance as a color pixel and thinning. Preferably, it is 3 μm or less, and the lower limit is preferably 0.1 μm or more, more preferably 0.3 μm or more.

As one embodiment of the multilayer film layer, an embodiment in which high refractive layers and low refractive layers are alternately laminated on each other can be mentioned. The high refractive layer and the low refractive layer are layers having different refractive indexes, and the high refractive layer has a higher refractive index than the low refractive layer.
The thickness of the high refractive layer and the low refractive layer may be the same or different from each other. Each of the high refractive layer and the low refractive layer may be independently composed of only one high refractive layer or low refractive layer, or may be composed of two or more high refractive layers or low refractive layers.
The alternating lamination in the present invention refers to a laminated structure in which the low refractive layer and the high refractive layer are replaced on the film surface, but it is not always necessary to be a laminated body of only the low refractive layer and the high refractive layer. . For example, a third layer having a refractive index different from that of the low refractive layer and the high refractive layer such as a middle refractive layer may be provided between the low refractive layer and the high refractive layer. The middle refractive layer is intended to mean a layer having a refractive index higher than that of the low refractive layer and lower than that of the high refractive layer.
The multilayer film layer is preferably formed by coating. That is, the layer is preferably formed using a coating liquid containing a predetermined component. The components contained in the coating solution will be described in detail later.
The total of the low refractive layer and the high refractive layer in one multilayer film layer is preferably 5 layers or more, more preferably 8 layers or more, and may be 10 layers or more. As an upper limit, it is 60 layers or less, for example, it can also be 30 layers or less, can also be 25 layers or less, and also can be 20 layers or less. Furthermore, when it has a 3rd layer (for example, medium refractive layer), it is preferable that the total number which combined them is the said range.

In the present invention, the difference in refractive index between the low refractive layer and the high refractive layer is preferably 0.5 or more, preferably 0.55 or more, and can be 0.6 or more. It can also be 65 or more. The upper limit value of the difference in refractive index between the low refractive layer and the high refractive layer can be, for example, 0.8 or less, and can be 0.75 or less.
Hereinafter, the high refractive layer and the low refractive layer will be described in detail.

[High refractive layer]
The high refractive layer is a layer having a higher refractive index than the low refractive layer described later (preferably a layer having a refractive index of 0.5 or more). The refractive index of the high refractive layer is preferably 1.5 to 3.0, and more preferably 1.7 to 2.3.
The highly refractive layer is preferably a layer containing a resin. The layer containing a resin may be a so-called layer containing a high refractive resin, or a composition containing a resin, particles and a solvent (hereinafter sometimes referred to as “high refractive composition”) is applied. May be formed. The resin used for forming the high refractive layer is a polymer chain composed of repeating units derived from a polymerizable monomer or a compound having a polymer chain composed of repeating units derived from a polymerizable monomer as a partial structure. Preferably there is. Preferably, it is a layer formed by applying a highly refractive composition.
Details of the highly refractive composition will be described below.

(High refractive composition)
(resin)
Examples of the resin contained in the highly refractive composition include resins capable of dispersing particles described later.
Specifically, the following embodiments are exemplified.
The first embodiment of the resin is an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, an alkyl group, an aryl group, a phenol group, a group having an alkyleneoxy chain A resin containing a group selected from the group consisting of an imide group, a heterocyclic group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group .
Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, and the like, and preferably at least one selected from a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. Carboxylic acid groups are particularly preferred.
The acid value is preferably 20 to 300 mgKOH / g, more preferably 50 to 250 mgKOH / g, and still more preferably 50 to 210 mgKOH / g.

More preferably, it is resin represented by General formula (1).
General formula (1)

In general formula (1), R ¹ represents an (m + n) -valent linking group, and R ² represents a single bond or a divalent linking group. A ¹ is an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, an alkyl group, an aryl group, a group having an alkyleneoxy chain, an imide group, a heterocyclic ring 1 having at least one group selected from the group consisting of a group (heterocyclic structure), an alkyloxycarbonyl group, an alkylaminocarbonyl group, a sulfonamide group, a carboxylate group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group Represents a valent substituent. The n A ¹ and R ² may be the same or different. m represents a positive number of 8 or less, n represents 1 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer chain. The m P ¹ may be the same or different.

Hereinafter, each group in General formula (1) is demonstrated in detail.
A ¹ is an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group, an alkoxysilyl group 1 having at least one kind of structure capable of adsorbing to metal oxide particles such as a heterocyclic group, a functional group having adsorption ability to metal oxide particles described later such as a group, an epoxy group, an isocyanate group and a hydroxyl group Represents a valent substituent.
Hereinafter, the site having the ability to adsorb to the metal oxide particles (the functional group and the structure) will be collectively referred to as “adsorption site” as appropriate.

As long as at least one kind of adsorption site is contained in one A ¹ , two or more kinds may be contained.
In the present invention, the “monovalent substituent having at least one kind of adsorption site” includes the aforementioned adsorption site, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to It is a monovalent substituent formed by bonding up to 100 oxygen atoms, 1 to 400 hydrogen atoms, and a linking group consisting of 0 to 40 sulfur atoms. When the adsorption site itself can constitute a monovalent substituent, the adsorption site itself may be a monovalent substituent represented by A ¹ .
First, the adsorption site constituting A ¹ will be described below.

Preferred examples of the “acid group” include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, and a boric acid group, and a carboxylic acid group, a sulfonic acid group, and a monosulfuric acid group. An ester group, a phosphoric acid group, and a monophosphate ester group are more preferable, a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group are still more preferable, and a carboxylic acid group is particularly preferable.

As the “urea group”, for example, —NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, 6 or more carbon atoms) And an aryl group having a carbon number of 7 or more.) —NR ¹⁵ CONHR ¹⁷ (wherein R ¹⁵ and R ¹⁷ are each independently a hydrogen atom or a group having 1 carbon atom). An alkyl group having up to 10 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms are more preferred, and —NHCONHR ¹⁷ (wherein R ¹⁷ is a hydrogen atom or having 1 to 10 carbon atoms) An alkyl group, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms are particularly preferred.

As the “urethane group”, for example, —NHCOOR ¹⁸ , —NR ¹⁹ COOR ²⁰ , —OCONHR ²¹ , —OCONR ²² R ²³ (where R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are And each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like. -NHCOOR ¹⁸ , -OCONHR ²¹ (Here, R ¹⁸ and R ²¹ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms). , —NHCOOR ¹⁸ , —OCONHR ²¹ (wherein R ¹⁸ and R ²¹ each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms). table Are particularly preferred.

Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a crown ether.

Examples of the “group having a basic nitrogen atom” include an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), a guanidyl group represented by the following formula (a1), Preferred examples include an amidinyl group represented by (a2).

In formula (a1), R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
In formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

Among these, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are each independently a group having 1 to 10 carbon atoms. An alkyl group, a phenyl group, and a benzyl group.), A guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 10 carbon atoms; Represents a phenyl group and a benzyl group. ], Amidinyl in group [wherein (a2) represented by the formula (a2), each independently R ¹³ and R ¹⁴ represents an alkyl group, a phenyl group, a benzyl group having 1 to 10 carbon atoms. ] Is more preferable.
In particular, an amino group (—NH ₂ ), the above substituted imino group, a guanidyl group represented by the above formula (a1), an amidinyl group represented by the above formula (a2), and the like are preferably used.
The alkyl group moiety in the “alkyloxycarbonyl group” is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group and an ethyl group.
The alkyl group moiety in the “alkylaminocarbonyl group” is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
Examples of the “carboxylic acid group” include groups composed of ammonium salts of carboxylic acids.
In the “sulfonamide group”, a hydrogen atom bonded to a nitrogen atom may be substituted with an alkyl group (such as a methyl group), an acyl group (such as an acetyl group or a trifluoroacetyl group), and the like.

Examples of the “heterocyclic structure” include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, Dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, imide groups, hydantoin, indole, quinoline, carbazole, acridine, acridone Anthraquinone is a preferred example, pyrroline, pyrrolidine, pyrazole, pyrazoline, pyrazolidine, imidazole , Triazole, pyridine, piperidine, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, benzimidazolone, imide groups such as benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, carbazole, acridine, acridone, Anthraquinone is more preferred.

The “heterocyclic structure” may further have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Such as an aryloxy group having 6 to 16 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a sulfonamido group, an N-sulfonylamido group, an acetoxy group and the like, an acyloxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group, etc. Alkoxy groups having 1 to 20 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate And carbonic acid ester groups. Here, these substituents may be bonded to the heterocyclic ring through a linking group constituted by combining the following structural units or the above structural units.

The “alkoxysilyl group” may be any of monoalkoxysilyl group, dialkoxysilyl group, trialkoxysilyl group, but is preferably trialkoxysilyl group, such as trimethoxysilyl group, triethoxysilyl group, etc. Is mentioned.
Examples of the “epoxy group” include a substituted or unsubstituted oxirane group (ethylene oxide group). As an epoxy group, it can represent with the following general formula (a3), for example.

In the general formula (a3),
R ^EP1 to R ^EP3 each independently represent a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group. R ^EP1 and R ^EP2 , R ^EP2 and R ^EP3 may be bonded to each other to form a ring structure. * Represents a connecting hand.

The linking group bonded to the adsorption site may be a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200. And a linking group consisting of 0 to 20 sulfur atoms is preferred, and this organic linking group may be unsubstituted or may further have a substituent.
Specific examples of this linking group include the following structural units or groups constituted by combining the above structural units.

When the linking group has a further substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. C1-C6 alkoxy such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamide group, N-sulfonylamide group, acetoxy group, etc., C1-C6 acyloxy group, methoxy group, ethoxy group, etc. Groups, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, etc. It is done.

In the above, A ¹ is a monovalent substitution having at least one group selected from the group consisting of an acid group, a urea group, a urethane group, a sulfonamide group, an imide group and a group having a coordinating oxygen atom. It is preferably a group.
In particular, from the viewpoint of improving the interaction with the metal oxide particles, improving the refractive index, and reducing the viscosity of the composition, A ¹ is a monovalent substitution having at least one functional group of pKa5-14. More preferably, it is a group.
Here, “pKa” has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
Examples of the functional group of pKa5 to 14 include a urea group, a urethane group, a sulfonamide group, an imide group, and a group having a coordinating oxygen atom.
Specifically, for example, a urea group (about pKa 12 to 14), a urethane group (about pKa 11 to 13), —COCH ₂ CO— (about pKa 8 to 10) as a coordinating oxygen atom, a sulfonamide group (About pKa 9 to 11).

A ¹ is preferably represented as a monovalent substituent represented by the following general formula (4).

In General Formula (4), B ¹ represents an adsorption site, and R ²⁴ represents a single bond or a (a + 1) -valent linking group. a represents an integer of 1 to 10, and B ¹ existing in the general formula (4) may be the same or different.

Examples of the adsorption site represented by B ¹ include the same adsorption sites as those constituting A ¹ in the general formula (1), and preferred examples are also the same.
Among them, an acid group, a urea group, a urethane group, a sulfonamide group, an imide group or a group having a coordinating oxygen atom is preferable, and a urea group, a functional group having a pKa of 5 to 14 is more preferable. It is more preferably a urethane group, a sulfonamide group, an imide group or a group having a coordinating oxygen atom.

R ²⁴ represents a single bond or a (a + 1) -valent linking group, and a represents 1 to 10. Preferably, a is 1 to 7, more preferably a is 1 to 5, and particularly preferably a is 1 to 3.
(A + 1) valent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and Groups consisting of 0 to 20 sulfur atoms are included and may be unsubstituted or further substituted.

Specific examples of the (a + 1) -valent linking group include the following structural units or groups formed by combining these structural units (which may form a ring structure).

R ²⁴ may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and (A + 1) valent linking groups consisting of 0 to 10 sulfur atoms are preferred, single bonds or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 More preferred are (a + 1) valent linking groups consisting of up to oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond, or 1 to 10 carbons (A + 1) valent linkage consisting of atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms The group is particularly preferred.

Among the above, when the (a + 1) -valent linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. C1-C6 acyloxy groups such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc., carbon atoms such as methoxy groups, ethoxy groups, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate, etc. And the like.

In general formula (1), R ² represents a single bond or a divalent linking group. The n R ^{2 s} may be the same or different.
Divalent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 To 20 sulfur atoms are included, which may be unsubstituted or further substituted.

Specific examples of the divalent linking group include the following structural units or groups formed by combining these structural units.

R ² may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and Divalent linking groups consisting of 0 to 10 sulfur atoms are preferred, single bonds, or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 More preferred are divalent linking groups consisting of oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond or 1 to 10 carbon atoms, 0 Particularly preferred are divalent linking groups consisting of from 1 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms.

Among the above, when the divalent linking group has a substituent, examples of the substituent include carbon numbers such as an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group, etc. having 6 to 16 carbon atoms, methoxy group, ethoxy group, etc. To 6 to 6 alkoxy groups, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, cyano group, carbonic acid such as t-butyl carbonate, etc. An ester group etc. are mentioned.

In general formula (1), R ¹ represents a (m + n) -valent linking group. m + n satisfies 3 to 10.
Examples of the (m + n) -valent linking group represented by R ¹ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200. Groups consisting of up to 20 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or may further have a substituent.

Specific examples of the (m + n) -valent linking group include the following structural units or groups formed by combining these structural units (which may form a ring structure).

(M + n) -valent linking groups include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, and Groups consisting of 0 to 10 sulfur atoms are preferred, 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 And more preferably a group consisting of 0 to 7 sulfur atoms, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, Particular preference is given to groups consisting of 1 to 80 hydrogen atoms and 0 to 5 sulfur atoms.

Among the above, when the (m + n) -valent linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. C1-C6 acyloxy groups such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc., carbon atoms such as methoxy groups, ethoxy groups, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate, etc. And the like.

Specific examples of the (m + n) -valent linking group represented by R ¹ [specific examples (1) to (17)] are shown below. However, the present invention is not limited to these.

Among the above specific examples, from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents, preferred (m + n) -valent linking groups are (1), (2), (10), ( 11), (16), and (17).

In general formula (1), m represents a positive number of 8 or less. m is preferably 0.5 to 5, more preferably 1 to 4, and particularly preferably 1 to 3.
In the general formula (1), n represents 1 to 9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.

In the general formula (1), P ¹ represents a polymer chain and can be selected from known polymers according to the purpose. The m P ¹ may be the same or different.
Among the polymers, a vinyl monomer polymer or copolymer, an ester polymer, an ether polymer, a urethane polymer, an amide polymer, an epoxy polymer, a silicone polymer, and modifications thereof are used to form a polymer chain. Or copolymer [for example, polyether / polyurethane copolymer, copolymer of polyether / vinyl monomer polymer, etc. (any of random copolymer, block copolymer, graft copolymer, etc. May also be included). At least one selected from the group consisting of vinyl monomers, selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof. At least one kind is more preferred, and a polymer or copolymer of vinyl monomers is particularly preferred.

It is preferred that the polymer chain P ¹ contains at least one repeating unit.
The number k of repeating units of at least one repeating unit in the polymer chain P ¹ is preferably 3 or more from the viewpoint of achieving steric repulsion and improving dispersibility, achieving a high refractive index and a low viscosity. More preferably, it is 5 or more.
In addition, from the viewpoint of allowing the metal oxide particles to be densely present in the cured film and achieving a high refractive index, the number k of repeating units of at least one repeating unit is preferably 50 or less, and 40 or less. Is more preferable, and it is still more preferable that it is 30 or less.

The polymer is preferably soluble in an organic solvent. If the affinity with the organic solvent is low, the affinity with the dispersion medium is weakened, and it may be impossible to secure an adsorption layer sufficient for stabilizing the dispersion.
Although it does not restrict | limit especially as a vinyl monomer, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, styrene , Vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, vinyl monomers having an acid group, and the like are preferable.
Preferred examples of these vinyl monomers include paragraphs 0089 to 0094, 0096 and 0097 of JP-A-2007-277514 (paragraphs 0105 to 0117 and 0119 to 0119 in the corresponding US Patent Application Publication No. 2010/233595). The vinyl monomers described in 0120) are mentioned, the contents of which are incorporated herein.

In addition to the above compounds, for example, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group containing It can be appropriately synthesized by an addition reaction between a monomer and monoisocyanate.

Among the resins represented by the general formula (1), a resin represented by the following general formula (2) is preferable.

In the general formula (2), A ² represents an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, an alkyl group, an aryl group, or an alkyleneoxy chain. A group selected from the group consisting of a group having an imide group, a heterocyclic group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. The monovalent substituent which has a seed is represented. The n A ² may be the same or different.
Incidentally, A ² has the same meaning as A ¹ in the general formula (1), a preferable embodiment thereof is also the same.

In the general formula (2), R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group. The n R ^{4 s} may be the same or different. The m R ^{5 s} may be the same or different.
As the divalent linking group represented by R ⁴ or R ⁵ , the same divalent linking groups as those represented by R ² in the general formula (1) can be used, and a preferred embodiment is also used. It is the same.

In the general formula (2), R ³ represents an (m + n) -valent linking group. m + n satisfies 3 to 10.
Examples of the (m + n) -valent linking group represented by R ³ include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 100 atoms. Groups consisting of up to 20 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or may further have a substituent.
Specifically, the (m + n) -valent linking group represented by R ³ is the same as the (m + n) -valent linking group represented by R ¹ in the general formula (1). The preferred embodiments are also the same.

In general formula (2), m represents a positive number of 8 or less. m is preferably 0.5 to 5, more preferably 1 to 4, and particularly preferably 1 to 3.
In the general formula (2), n represents 1 to 9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.

Further, P ² of the general formula (2) represents a polymer chain, can be selected according to the purpose or the like from such known polymers. The m P ² may be the same or different. The preferred embodiment of the polymer is the same as P ¹ in the general formula (1).

Of the resins represented by the general formula (2), those satisfying all of R ³ , R ⁴ , R ⁵ , P ² , m, and n shown below are most preferable.
R ³ : Specific examples (1), (2), (10), (11), (16), or (17)
R ⁴ : A single bond or the following structural unit or a combination of these structural units: “1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10” A divalent linking group comprising an oxygen atom, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms (which may have a substituent, for example, Alkyl group having 1 to 20 carbon atoms such as methyl group and ethyl group, aryl group having 6 to 16 carbon atoms such as phenyl group and naphthyl group, hydroxyl group, amino group, carboxyl group, sulfonamide group, N-sulfonyl group C1-C6 acyloxy groups such as amide groups and acetoxy groups, C1-C6 alkoxy groups such as methoxy groups and ethoxy groups, halogen atoms such as chlorine and bromine, methoxycarbonyl groups An ethoxycarbonyl group, an alkoxycarbonyl group having from 2 to 7 carbon atoms such as cyclohexyl oxycarbonyl group, a cyano group, such as carbonic acid ester group such as t- butyl carbonate.)

R ⁵ : single bond, ethylene group, propylene group, the following group (a), or the following group (b)
In the following groups, R ¹² represents a hydrogen atom or a methyl group, and l represents 1 or 2.

P ² : Polymer or copolymer of vinyl monomer, ester polymer, ether polymer, urethane polymer and modified products thereof m: 1 to 3
n: 3-6

The second embodiment of the resin is a resin containing a graft copolymer.
In the graft copolymer, the number of atoms excluding hydrogen atoms per graft chain is preferably 40 to 10,000, more preferably 100 to 500, and still more preferably 150 to 260.
As the polymer structure of the graft chain, a poly (meth) acrylic structure, a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, a polyether structure, or the like can be used.
For the resin containing the graft copolymer, for example, the description in paragraphs 0080 to 0126 of JP-A-2014-063125 can be referred to, and the contents thereof are incorporated in the present specification.

A third embodiment of the resin is an oligoimine resin containing a nitrogen atom in at least one of the main chain and the side chain. The oligoimine resin includes a repeating unit having a partial structure X having a functional group of pKa14 or less, a side chain containing a side chain Y having 40 to 10,000 atoms, and at least a main chain and a side chain. A resin having a basic nitrogen atom on one side is preferred.
For the oligoimine-based resin, for example, the description in paragraphs 0225 to 0267 of JP-A-2014-063125 can be referred to, and the contents thereof are incorporated in the present specification.

A fourth embodiment of the resin is a siloxane resin obtained by hydrolyzing a silane compound containing the silane compound represented by any one of the general formulas (2) to (4) and subjecting the hydrolyzate to a condensation reaction. It is.
R ⁰ _2-n R ¹ _n Si (OR ⁹ ) ₂ General formula (2)
In general formula (2), R ⁰ represents hydrogen, an alkyl group, an alkenyl group, or a phenyl group. R ¹ represents a monovalent condensed polycyclic aromatic group. R ⁹ represents hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group, and may be the same or different. n is 1 or 2. When n is 2, the plurality of R ¹ may be the same or different.
R ² Si (OR ¹⁰ ) ₃ General formula (3)
In general formula (3), R ² represents a monovalent fused polycyclic aromatic group. R ¹⁰ represents hydrogen, methyl group, ethyl group, propyl group or butyl group, and may be the same or different.
(R ¹¹ O) _m R ⁴ _3-m Si—R ³ —Si (OR ¹² ) _l R ⁵ _3-l General formula (4)
In the general formula (4), R ³ represents a divalent condensed polycyclic aromatic group. R ⁴ and R ⁵ represent hydrogen, an alkyl group, an alkenyl group, or an aryl group, and may be the same or different. R ¹¹ and R ¹² represent hydrogen, a methyl group, an ethyl group, a propyl group, or a butyl group, and may be the same or different. m and l are each independently an integer of 1 to 3.
For example, the description of paragraphs 0017 to 0044 of JP-A-2010-007057 can be referred to for the siloxane resin, the contents of which are incorporated herein.

It is also preferable that the highly refractive composition contains an epoxy resin.
As commercially available products of epoxy resins, for example, as bisphenol A type epoxy resins, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON860 , EPICLON 1050, EPICLON 1051, EPICLON 1055 (above, manufactured by DIC Corporation), etc., and as bisphenol F type epoxy resin, JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above, manufactured by DIC Corporation), LCE-21, RE-602S As described above, JER152, JER154, JER157S70, JER157S65 (above Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740. EPICLON N-770, EPICLON N-775 (manufactured by DIC Corporation), and the like. EPICLON N-680, EPICLON N-690, EPICLON N-695 (above DIC Corporation), EOCN-1020 (above, Nippon Kayaku Co., Ltd.), etc. AD EKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 Chemical Industry Co., Ltd.), Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (manufactured by Nagase ChemteX Corporation). In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), JER1031S (manufactured by Japan Epoxy Resin Co., Ltd.) and the like.

The molecular weight of the resin is preferably 2,000 to 200,000, more preferably 2,000 to 15,000, and even more preferably 2,500 to 10,000 in terms of weight average molecular weight.

The amount of the resin in the highly refractive composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more with respect to the total mass of the composition. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.
The solid content concentration of the resin in the highly refractive composition is preferably 5% by mass or more, more preferably 8% by mass or more, and further preferably 10% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less.
Only one type of resin may be included, or two or more types of resins may be included. When two or more types are included, the total amount is preferably within the above range.

(particle)
The particles contained in the highly refractive composition preferably include metal oxide particles.
The metal oxide particles are preferably inorganic particles that have a high refractive index and are colorless, white, or transparent. Titanium (Ti), zirconium (Zr), aluminum (Al), silicon (Si), zinc (Zn) or oxide particles of magnesium (Mg) and the like, titanium dioxide (TiO ₂₎ particles is preferably from zirconium dioxide (ZrO ₂₎ particles, titanium dioxide particles are more preferable.
In the metal oxide particles, the lower limit of the primary particle diameter is preferably 1 nm or more, and the upper limit is preferably 100 nm or less, more preferably 80 nm or less, and further preferably 50 nm or less. The average particle size can also be used as an index of the primary particle size. The average particle diameter of the metal oxide particles is measured by using a dynamic light scattering method for a diluted solution obtained by diluting a mixed solution or dispersion containing the metal oxide particles 80 times with propylene glycol monomethyl ether acetate. The value obtained by doing. This measurement is the number average particle diameter obtained by using Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd.
For the metal oxide particles, for example, the description in paragraphs 0023 to 0027 of JP-A-2014-062221, can be referred to, and the contents thereof are incorporated in the present specification.

The amount of particles in the highly refractive composition is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more with respect to the total mass of the composition. Although there is no restriction | limiting in particular in an upper limit, 40 mass% or less is preferable and 30 mass% or less is more preferable.
Further, the solid content concentration of the particles in the highly refractive composition is preferably 60% by mass or more, and more preferably 70% by mass or more. The upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less.
One type of particle may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.

(solvent)
As the solvent contained in the highly refractive composition, an organic solvent is preferable. Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. , Alkyl oxyacetates (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )), 2- Xylpropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy) Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2- Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. And as ethers For example, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene Glycol mono n-butyl ether, propylene glycol mono tert-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones For example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and aromatic hydrocarbons include, for example, toluene and xylene.
Particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol methyl ether, dipropylene glycol dimethyl ether, propylene glycol mono n-butyl ether, propylene glycol mono tert-butyl ether, and propylene glycol methyl ether acetate.
As other solvents contained in the highly refractive composition, for example, the description in paragraphs 0065 to 0067 of JP-A-2014-063125 can be referred to, and the contents thereof are incorporated in the present specification.
50 mass% or more is preferable in the whole quantity of a composition, and, as for the quantity of the solvent in a highly refractive composition, 60 mass% or more is more preferable. In the total amount of the composition, the upper limit is preferably 99.9% by mass or less, more preferably 95% by mass or less, and further preferably 90% by mass or less.
The solvent may contain only 1 type and may contain 2 or more types. When two or more types are included, the total amount falls within the above range.

(Surfactant)
The high refractive composition may contain various surfactants from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. A fluorochemical surfactant is preferred. In the case of forming a film using a coating liquid to which a composition containing a fluorosurfactant is applied, the interfacial tension between the coated surface and the coating liquid decreases, and the wettability to the coated surface is improved. The applicability to the coated surface is improved. For this reason, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

The fluorine-containing surfactant preferably has a fluorine content of 3 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.

Examples of the fluorosurfactant include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, and F-143. F-144, R-30, F-437, F-475, F-479, F-482, F-554, F-780, F-781, F-781F (Above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) and the like.

Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sparse 20000 (manufactured by Nippon Lubrizol Corporation), and the like.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

Specific examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

Examples of silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.

Only one type of surfactant may be used, or two or more types may be combined.
The content of the surfactant is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass with respect to the total mass of the composition.

(Polymerization inhibitor)
The high refractive composition may contain a polymerization inhibitor.
Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like. Of these, p-methoxyphenol is preferred.
The addition amount of the polymerization inhibitor is preferably 0.001 to 5% by mass with respect to the total mass of the composition.

(Other additives)
The highly refractive composition may contain other additives. Specific examples include a curing agent, a polymerizable compound, a polymerization initiator, a resin other than the above resin (for example, an alkali-soluble resin and a binder), a plasticizer, a sensitizer, and an ultraviolet absorber.
Examples of the alkali-soluble resin include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) A multi-component copolymer comprising acrylate / (meth) acrylic acid / other monomers can be preferably used. Further, a copolymer of 2-hydroxyethyl (meth) acrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2 -Hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene A macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used.
For these additives, for example, the description in paragraphs 0133 to 0224 of JP-A-2014-063125 can be referred to, and the contents thereof are incorporated in the present specification.

In addition, as a polymerization initiator, a photoinitiator and a thermal polymerization initiator are mentioned.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to light rays from the ultraviolet light region to the visible light region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones. Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And compounds described in the specification.

From the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums Compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

More preferred are trihalomethyltriazine compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, acetophenone compound, trihalomethyltriazine compound, α-aminoketone Particularly preferred is at least one compound selected from the group consisting of compounds, oxime compounds, triallylimidazole dimer, and benzophenone compounds.

In particular, when the highly refractive composition of the present invention is used for the production of a solid-state imaging device, a fine pattern may be formed in a sharp shape, and the development is performed with no residue in the unexposed area along with curability. is important. From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, when a fine pattern is formed, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and it is necessary to keep the addition amount of the photopolymerization initiator low. Considering the point, it is particularly preferable to use an oxime compound as a photopolymerization initiator for forming a fine pattern. Further, the use of an oxime compound can improve the color transfer.
As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm can also be used.
As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

More preferred examples of the photopolymerization initiator include oxime compounds.
Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane Examples include -2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Examples thereof include compounds described in 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797, JP-A 2006-342166, and the like.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. Further, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (made by ADEKA) can also be used.

Further, as oxime compounds other than those described above, compounds described in JP-A-2009-519904 in which an oxime is linked to the carbazole N-position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039, in which a nitro group is introduced into the dye moiety, ketoxime compounds described in International Patent Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule A compound described in US Pat. No. 7,556,910 contained therein, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used.
Preferably, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

In general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In General Formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
In the general formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.

In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and compounds described in JP-A 2013-164471 ( C-3). This content is incorporated herein.

In the present invention, a compound represented by the following general formula (1) or (2) can also be used as a photopolymerization initiator.

In the formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or When an arylalkyl group having 7 to 30 carbon atoms is represented and R ¹ and R ² are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R ³ and R ⁴ are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, wherein X is a direct bond or carbonyl Indicates a group.

In the formula ^(2), R ^1, R 2, ^{R 3} and ^{R 4} have the same meanings as ^R ^1, R 2, ^{R 3} and ^{R 4} in Formula (1), ^{R 5} ^is -R 6, -OR ⁶ , —SR ⁶ , —COR ⁶ , —CONR ⁶ R ⁶ , —NR ⁶ COR ⁶ , —OCOR ⁶ , —COOR ⁶ , —SCOR ⁶ , —OCSR ⁶ , —COSR ⁶ , —CSOR ⁶ , —CN, halogen R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms; X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.

In the above formulas (1) and (2), R ¹ and R ² are preferably each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
Specific examples of the compounds represented by formula (1) and formula (2) include, for example, compounds described in paragraph numbers 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.

Specific examples of oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited thereto.

The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 455 nm.
The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, more preferably from 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
For the molar extinction coefficient of the compound, a known method can be used. For example, in a UV-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian), an ethyl acetate solvent is used at a concentration of 0.01 g / L. It is preferable to measure.
You may use the photoinitiator used for this invention in combination of 2 or more type as needed.

The content of the photopolymerization initiator is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, and even more preferably from 1 to 20%, based on the total solid content of the highly refractive composition. % By mass. Within this range, better sensitivity and pattern formability can be obtained. The highly refractive composition may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

Examples of thermal polymerization initiators include various azo compounds and peroxide compounds. Examples of azo compounds include azobis compounds. Examples of peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

Specific examples of the high refractive composition include the dispersion composition described in claim 1 of JP-A-2014-062221, and the siloxane-based resin composition described in claim 1 of JP-A-2010-007057. The contents of which are incorporated herein by reference. Moreover, the preferable range of these compositions is mentioned as an example of the preferable range of the high refractive composition of this invention.

The film thickness of the highly refractive layer is appropriately determined so as to achieve a desired optical path difference, but is, for example, 50 nm or more, and may be 60 nm or more. The upper limit is, for example, 600 nm or less, 500 nm or less, or 300 nm or less.

[Low refractive layer]
The low refractive layer is a layer having a lower refractive index than that of the high refractive layer (preferably a layer having a refractive index lower by 0.5 or more). The refractive index of the low refractive layer is preferably 1.0 to 1.5, more preferably 1.1 to 1.5.
The low refractive layer is preferably a layer containing a resin. The layer containing the resin may be a so-called low-refractive resin, that is, a layer made of a resin having a refractive index lower than that of the above-described high-refractive resin, or a composition containing resin, particles, and a solvent (hereinafter, , Sometimes referred to as “low refractive composition”). The resin used for forming the low refractive layer is a polymer chain composed of repeating units derived from a polymerizable monomer or a compound having a polymer chain composed of repeating units derived from a polymerizable monomer as a partial structure. Preferably there is. Preferably, it is a layer formed by applying a low refractive composition.
Details of the low refractive composition will be described below. Note that the low refractive composition may include at least particles and a solvent. That is, the low-refractive index composition may be an embodiment that does not contain a resin.

(Low refractive composition)
(resin)
Examples of the resin used in the low refractive layer include a resin containing at least one of a siloxane resin and a fluorine-based resin.
A siloxane resin can be obtained through hydrolysis and condensation using an alkoxysilane raw material. Specifically, the siloxane resin is, for example, a part or all of alkoxy groups of alkyltrialkoxysilane is hydrolyzed to be converted into silanol groups, and at least part of the generated silanol groups is condensed to form Si—O—. A Si bond is formed. The siloxane resin preferably has a silsesquioxane structure represented by the following general formula (5).
(R ¹ SiO _3/2 ) _n General formula (5)
In general formula (5), R ¹ represents an alkyl group having 1 to 3 carbon atoms. n represents an integer of 20 to 1000.
The fluorine-based resin is a resin containing fluorine in a substance molecule, specifically, polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroalkyl. Examples include vinyl ether copolymers, tetrafluoroethylene / ethylene copolymers, hexafluoropropylene / propylene copolymers, polyvinylidene fluoride, vinylidene fluoride / ethylene copolymers, and the like.

For details of the siloxane resin and the fluorine-based resin, for example, description in paragraphs 0014 to 0060 of JP-A-2014-063125 can be referred to, and the contents thereof are incorporated in the present specification.
In addition, in the present invention, as a resin contained in the low refractive composition, a hydrolyzate of a predetermined silicon compound described in paragraphs 0016 to 0024 of JP2013-253145A, paragraph 0030 of JP2012-0214772A. The compounds described in -0043 can be referred to, the contents of which are incorporated herein.
The amount of the resin in the low refractive composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.
Further, the solid content concentration of the resin in the low refractive composition is preferably 5% by mass or more, more preferably 8% by mass or more, and further preferably 10% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less.
Only one type of resin may be included, or two or more types of resins may be included. When two or more types are included, the total amount is preferably within the above range.

(particle)
Examples of the particles used in the low refractive layer include hollow particles and non-hollow particles. As the hollow particles, hollow structure or porous fine particles may be used. The hollow particle has a structure having a cavity inside and refers to a particle having a cavity surrounded by an outer shell, and the porous particle refers to a porous particle having a large number of cavities. Hereinafter, the hollow particles or the porous particles are appropriately referred to as “specific particles”. The specific particles may be organic particles or inorganic particles. Metal oxide particles are preferable, and silica particles are more preferable.
For the particles used in the low refractive layer, for example, the description in paragraphs 0047 to 0055 of JP 2014-063125 A can be referred to, and the contents thereof are incorporated in the present specification.

One preferred embodiment of the particles used in the low refractive layer is beaded beads, and beaded silica (beaded colloidal silica) (particle aggregate in which a plurality of silica particles are linked in a chain) is more preferable. .
A bead-like particle has a shape in which particles are connected and / or branched like a bead. Specific examples include those having a chain structure in which spherical particles (for example, colloidal silica) are connected in a bead shape, and those in which the connected colloidal silica is branched.
Because of the steric hindrance, the beaded particles cannot occupy the space densely, and as a result, a region with a higher porosity can be easily formed, and the region can easily have a low refractive index.

The amount of particles in the low refractive composition is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more with respect to the total mass of the composition. Although there is no restriction | limiting in particular in an upper limit, 40 mass% or less is preferable and 30 mass% or less is more preferable.
The solid content concentration of the particles in the low refractive composition is preferably 60% by mass or more, and more preferably 70% by mass or more. The upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less.
One type of particle may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.

(solvent)
The solvent contained in the low refractive composition is the same as the solvent contained in the high refractive composition, and the preferred range and blending amount are also the same.
(Other additives)
The low refractive composition used in the present invention may contain other additives. Other additives are the same as those described in the above-mentioned highly refractive composition, and the blending amounts and the like are also the same.
Specific examples of the low-refractive composition include a curable composition for forming a low-refractive film according to claim 11 of JP2014-063125, and a siloxane-based composition according to claim 1 of JP2013-253145A. Resin compositions are exemplified and their contents are incorporated herein. Moreover, the preferable range of these compositions is mentioned as an example of the preferable range of the high refractive composition of this invention.
The film thickness of the low refractive layer is appropriately determined so as to achieve a desired optical path difference. The upper limit is, for example, 600 nm or less, 500 nm or less, or 300 nm or less.

(Manufacturing method of multilayer film layer)
The method for producing a multilayer film layer includes, for example, a step of applying a high refractive composition containing particles, a resin, and a solvent to form a high refractive layer, and a surface of the high refractive layer, particles, a resin, A step of forming a low refractive layer by applying a low refractive composition containing a solvent; By adopting such a method, the multilayer film layer can be preferably manufactured. Since the multilayer film layer can be manufactured by coating, productivity can be improved as compared with a known multilayer film layer.
In the above description, the low refractive layer is provided on the high refractive layer. However, the order may be reversed. That is, a step of forming a low refraction layer by applying a low refraction composition and a step of forming a high refraction layer by applying a high refraction composition on the surface of the low refraction layer may be performed.
In the following, a procedure for forming the high refractive layer and then forming the low refractive layer will be described in detail.

In the step of forming the high refractive layer by applying the high refractive composition, when the high refractive layer is composed of one high refractive layer, the number of times of coating is usually one, but the high refractive layer is applied simultaneously or sequentially. Then, two or more highly refractive layers may be formed. Although the coating method in this invention is not specifically limited, The appropriate well-known coating method is applicable. For example, a spray method, a roll coating method, a spin coating method (spin coating method), a bar coating method, or the like can be applied. For example, in the case of spin coating, the coating time can be 30 seconds to 3 minutes per high refractive layer, and further, the coating time can be 30 seconds to 2 minutes.
As an application amount, it is preferable to apply so that the film thickness after curing becomes a desired condition.
As needed, it is preferable to heat-treat etc. to the apply | coated coating film and to remove the solvent contained in a coating film. Specifically, after coating, it is preferable to perform post-baking to volatilize part or all of the solvent. The post-baking is preferably performed at 100 to 300 ° C. for 30 seconds to 8 minutes, more preferably at 150 to 250 ° C. for 1 to 5 minutes for the high refractive layer.

The low refractive composition and the high refractive composition are preferably filtered with a filter before coating for the purpose of removing foreign substances and reducing defects. If it is conventionally used for the filtration use etc., it can use without being specifically limited.

After the high refractive layer is formed, a low refractive layer is formed on the surface by applying a low refractive composition. The method for forming the low refraction layer is the same as in the formation of the high refraction layer except that the high refraction composition is changed to the low refraction composition, and the preferred range is also the same. However, the post-baking of the low refractive layer is preferably performed at 80 to 240 ° C. for 30 seconds to 8 minutes, more preferably at 80 to 120 ° C. for 1 to 5 minutes.
Furthermore, a multilayer film layer can be obtained by alternately laminating high refractive layers and low refractive layers.
As the high refractive layer and the low refractive layer, in addition to the above-described materials, a curable resin such as a siloxane resin disclosed in paragraphs 0011 and after of JP2014-74874 (WO2013 / 099945) is contained in a solvent. A resin composition for forming a light-transmitting cured film and a composition for forming a high refractive index layer disclosed in paragraphs 0097 and after can also be used.
In addition, you may arrange | position a multilayer film layer in a pattern form as needed. Note that the patterning method is not particularly limited, and a known method can be employed.

(Colorant-containing composition layer)
The colorant-containing composition layer is a layer formed from a composition containing a predetermined colorant.
As the composition, a colored photocurable composition containing a colorant and a photocurable component is preferably used. This photocurable component is a photocurable composition usually used in the photolithographic method, and includes at least a binder resin (such as an alkali-soluble resin), a photosensitive polymerization component (such as a photopolymerization monomer), and a photopolymerization initiator. Compositions can be used. For such a colored photocurable composition, for example, the matters described in paragraphs 0017 to 0064 of JP-A-2005-326453 can be suitably applied.

Also, instead of using a colored photocurable composition, a colorant-containing composition layer can be formed using a non-photosensitive colored thermosetting composition. The colored thermosetting composition contains a colorant and a thermosetting compound, and the colorant concentration in the total solid content is preferably 50% by mass or more and less than 100% by mass. The thermosetting compound is not particularly limited as long as the film can be cured by heating. For example, a compound having a thermosetting functional group can be used. As this thermosetting compound, for example, those having at least one group selected from an epoxy group, a methylol group, an alkoxymethyl group and an acyloxymethyl group are preferable.

The type of the colorant contained in the colorant-containing composition layer is not particularly limited, and conventionally known colorants such as various dyes and pigments are used according to the type of each color pixel. Usually, a red colorant, a green colorant, a blue colorant and the like are used.
More specifically, examples of the pigment include various conventionally known inorganic pigments or organic pigments. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having an average particle size as small as possible. 0.01 μm to 0.1 μm is preferable, and 0.01 μm to 0.05 μm is more preferable. In addition, it is preferable to select an inorganic pigment having high light resistance as the pigment, and the following can be exemplified (the pigments other than Y color, G color, and B color are also exemplified below). In the following, C.I. I. 15: 3 is a representative example.
C. I. Pigment yellow 11,24,108,109,110,138,139,150,151,154,167,180,185;
C. I. Pigment Green 7, 36, 37, 58, 59
C. I. Pigment orange 36, 71;
C. I. Pigment red 122,150,171,175,177,209,224,242,254,255,264;
C. I. Pigment Violet 19, 23, 32
C. I. Pigment blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment Black 1

When the colorant is a dye, it can be uniformly dissolved in the composition to obtain a non-photosensitive thermosetting colored resin composition. There is no restriction | limiting in particular in the dye which can be used in this invention, A well-known dye can be used for color filters. The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Dyes such as xanthene, phthalocyanine, benzopyran and indigo can be used. These dyes may be multimers. Furthermore, you may combine dye and a pigment.
The colorant content of the colorant-containing composition layer is not particularly limited, but is preferably 50% by mass or more and less than 100% by mass, and 55% by mass with respect to the total mass of the colorant-containing composition layer. More preferred is 90% by mass or less.

In the composition used for forming the colorant-containing composition layer, various additives such as a binder, a curing agent, a curing catalyst, a solvent, a filler, and the like other than those described above are provided as long as the effects of the present invention are not impaired. A polymer compound, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a dispersant and the like can be blended. As these various additives, descriptions in paragraphs 0032 to 0040 of JP 2010-078680 A can be referred to, and the contents thereof are incorporated in the present specification.

For the colorant-containing composition layer, a colored photocurable composition or a colored thermosetting composition is applied to the multilayer film layer directly or via another layer and dried, and then subjected to light irradiation treatment or heat treatment. It is formed by. The colorant-containing composition is preferably filtered with a filter before coating for the purpose of removing foreign substances and reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration.
Hereinafter, one aspect using the colored photocurable composition containing the green colorant will be described in detail.
First, a laminate in which a multilayer film layer is arranged at a predetermined position on a substrate is prepared, and then a colored photocurable composition containing a green colorant dispersed in a solvent is spin coated to form a multilayer film on the substrate. After applying the layer on the surface on which the layer is present, a pre-bake treatment is performed. After the pre-bake treatment of the colored photocurable composition, the colored photocurable composition on the multilayer film layer is exposed using, for example, a well-known exposure device such as a stepper. The exposure light beam from the stepper is irradiated to the green pixel formation region of the colored photocurable composition from the opening of the mask, and the green pixel formation region is cured. After completion of the exposure process, the colored photocurable composition is developed using a known developer. Thereby, except the green pixel formation area (uncured area) of the colored photocurable composition is removed, and a colorant-containing composition layer is formed on the multilayer film layer.

The layer thickness of the colorant-containing composition layer is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm, from the viewpoint of color pixel performance and thinning balance.

<Preferred embodiment>
As one of the preferred embodiments of the color filter of the first embodiment of the present invention, a red pixel comprising a colorant-containing composition layer (red color layer) containing a red colorant, and a colorant containing a green colorant A multilayer film in which a green pixel composed of a containing composition layer (green colored layer), a blue pixel composed of a colorant-containing composition layer (blue colored layer) containing a blue colorant, and a plurality of films having different refractive indexes are laminated The aspect which has a laminated color pixel formed by laminating | stacking a layer and the said red colored layer, the said green colored layer, or the said blue colored layer is mentioned. If it is this aspect, the color filter can have a color pixel of four or more colors, although the kind of colorant used is 3 types (a red colorant, a green colorant, and a blue colorant).
Hereinafter, specific examples of preferred embodiments of the color filter of the first embodiment of the present invention will be described in detail.
FIG. 2 shows a partially enlarged plan view of a first preferred example of the color filter of the first embodiment of the present invention. 3 is a cross-sectional view taken along the line AA, and FIG. 4 is a cross-sectional view taken along the line BB.
As shown in FIG. 2, the color filter 10 includes a plurality of color pixels and is disposed on the substrate 12. As color pixels, a red pixel (R) 14, a green pixel (G1) 16, a blue pixel (B1) 18, a first stacked color pixel (G2) 20, and a second stacked color pixel (B2). 22 color pixels, and these color pixels are arranged two-dimensionally (planarly) on the substrate 12.
As shown in FIG. 3, the red pixel (R) 14, the green pixel (G1) 16, and the blue pixel (B1) 18 are arranged side by side on the substrate.
As shown in FIG. 4, the first stacked color pixel (G2) 20 is a stacked body of the first multilayer film layer 24 and the green pixel (G1) 16. The first stacked color pixel (G2) 20 includes the green pixel (G1) 16, but the first multilayer color layer (G2) 20 has a green color (G1) due to the first multilayer film layer 24. ) Different from 16. That is, the green pixel (G1) 16 and the first stacked color pixel (G2) 20 have different colors.
Further, as shown in FIG. 4, the second stacked color pixel (B2) 22 is a stacked body of the second multilayer film layer 26 and the blue pixel (G1) 18. The second stacked color pixel (B2) 22 includes the blue pixel (G1) 18, but the second multilayer color layer (B2) 22 has an overall color of the blue pixel (B1) due to the second multilayer film layer 26. ) 18 is different. That is, the blue pixel (B1) 18 and the second stacked color pixel (B2) 22 have different colors.
In the said aspect, as a coloring agent used, the red coloring agent used in order to form red pixel (R) 14, and the green coloring agent used in order to form green pixel (G1) 16, Three kinds of blue colorants used to form the blue pixel (B1) 18 are used, but the first multilayer film layer 24 and the second multilayer film layer 26 are used to generate 5 Color pixels of color are arranged on the substrate.

In the above embodiment, two (two types) of stacked color pixels, ie, the first stacked color pixel (G2) 20 and the second stacked color pixel (B2) 22 are used. In, it is sufficient that at least one (one type) stacked color pixel is used. Three (three types) or more of stacked color pixels may be used.
In the first stacked color pixel (G2) 20, the green pixel (G1) 16 is included, but a green color different from the green colorant included in the green pixel (G1) 16 is shown. Other green pixels containing a colorant may be included. The second stacked color pixel (B2) 22 may also include other blue pixels including a blue colorant of a different type from the blue colorant included in the blue pixel (B1) 18.
Further, the first multilayer film layer 24 and the second multilayer film layer 26 may be the same layer or different layers.
In consideration of the productivity and cost of the color filter, the colorant-containing composition layer included in the stacked color pixel contains a colorant that is not a stacked color pixel included in the color filter. The same layer as the composition layer is preferably used.

The type of substrate used is not particularly limited. For example, a glass substrate, a resin substrate, or the like is used as appropriate, and when applying a color filter to a solid-state imaging device, photoelectric conversion that photoelectrically converts light from a subject. A semiconductor substrate on which a photodiode as an element is arranged may be used as the substrate.

FIG. 5 shows a partially enlarged plan view of a second preferred example of the color filter of the first embodiment of the present invention. FIG. 6 is a cross-sectional view taken along the line CC, and FIG. 7 is a cross-sectional view taken along the line DD.
As shown in FIG. 5, the color filter 100 includes a plurality of color pixels and is disposed on the substrate 12. As color pixels, a red pixel (R) 114, a green pixel (G1) 116, a blue pixel (B1) 118, a first stacked color pixel (G2) 20, and a second stacked color pixel (B2). 22 color pixels, and these color pixels are arranged two-dimensionally (planarly) on the substrate 12.
In the second preferred example and the first preferred example described above, the heights of the red pixel (R) 114, the green pixel (G1) 116, and the blue pixel (B1) 118 are the same as the first stacked color pixel ( G2) 20 and the second stacked color pixel (B2) 22 are the same as in the first preferred example except that the height is adjusted to be the same as that of the second stacked color pixel (B2) 22.
By adopting such a form, there is no step on the surface of the color filter 100, and the flatness of the layer disposed thereon is further improved.

In FIG. 5, the heights of the red pixel (R) 114 itself, the green pixel (G1) 116 itself, and the blue pixel (B1) 118 themselves are increased. However, as shown in the color filter 200 of FIGS. By providing the transparent resin layer 28, the heights of the red pixel (R) 14, the green pixel (G 1) 16, and the blue pixel (B 1) 18 are set to the first stacked color pixel (G 2) 20, It is also possible to adjust the height to the second stacked color pixel (B2) 22.
FIG. 8 shows a partially enlarged plan view of a third preferred example of the color filter of the first embodiment of the present invention. 9 is a cross-sectional view taken along the line EE, and FIG. 10 is a cross-sectional view taken along the line FF.

The color filter of the first embodiment of the present invention can be applied to various applications, and examples thereof include a solid-state image sensor. That is, the solid-state image sensor containing the color filter of 1st embodiment of this invention is mentioned. The configuration of the solid-state imaging device is not particularly limited and may include known modes. For example, a photodiode, an insulating layer, the color filter of the first embodiment of the present invention, a flat layer, a microlens, and the like may be used as a semiconductor substrate (substrate). The structure provided above is mentioned.
Next, an imaging apparatus will be described as an example to which the solid-state imaging device of the present invention is applied. An example of the imaging device is a camera module.
FIG. 11 is a functional block diagram of the imaging apparatus. The imaging apparatus emits infrared light, the lens optical system 1, the solid-state imaging device 110, the signal processing unit 120, the signal switching unit 130, the control unit 140, the signal storage unit 150, the light emission control unit 160, and the like. Infrared LED 170 as a light emitting element and

image output units

180 and 181 are provided. In addition, as the solid-state image sensor 110, the solid-state image sensor provided with the color filter of this invention mentioned above can be used. In addition, the configuration other than the solid-state imaging device 110 and the lens optical system 1 can be formed entirely or partially on the same semiconductor substrate. Regarding each configuration of the imaging apparatus, paragraphs 0032 to 0036 of JP 2011-233983 A can be referred to, and the contents thereof are incorporated in the present specification.

<Second Embodiment>
Hereinafter, specific examples of preferred embodiments of the color filter of the second embodiment of the present invention will be described in detail.
Note that in this specification, visible light refers to light in a wavelength region of 400 nm to less than 700 nm, and infrared light refers to light in a wavelength region of 700 nm to 1000 μm. Near-infrared light is intended for light in the wavelength region of 700 nm to 2500 nm. The red light is intended for light having a central wavelength of about 640 nm (preferably, light having a wavelength of 575 nm to 670 nm), and the green light is light having a central wavelength of about 530 nm (preferably having a wavelength of 480 nm to less than 575 nm). The blue light means light having a center wavelength of about 435 nm (preferably light having a wavelength of 400 nm or more and less than 480 nm). The first infrared light is intended for light in the first infrared wavelength region, the second infrared light is intended for light in the second infrared wavelength region, and the third infrared light is the third red light. Intended for light in the outside wavelength region.
The color filter of the second embodiment of the present invention is suitable for photographing a color image (color still image or color moving image) of a subject in the dark, and is preferably applied to a night vision camera (particularly a color night vision camera). can do. As will be described in detail later, the color filter according to the second embodiment of the present invention can transmit visible light having three different wavelength distributions and infrared light having three different wavelength distributions. Therefore, for example, when irradiating a subject with predetermined infrared light and transmitting the infrared light reflected from the subject through this color filter, together with visible light having three different wavelength distributions (wavelength intensity distributions) Three types of infrared light having different wavelength distributions (wavelength intensity distributions) can be obtained. Each transmitted infrared light is imaged on an imaging surface that captures an optical image such as a CCD image sensor, and an in-plane intensity distribution of each infrared light is obtained, thereby obtaining an image of the subject by each infrared light. be able to. An infrared color image of a subject can be captured by, for example, displaying red, green, and blue single colors on each of the three types of images obtained. Note that a visible light color image of a subject can also be captured using three types of visible light that are simultaneously transmitted.
As a suitable aspect of the color filter of this embodiment, the aspect in which the multilayer film layer mentioned above is contained in the color pixel which comprises a color filter is mentioned. In particular, the multilayer film layer is preferably a layer formed with a coating solution. If a multilayer film layer formed of such a coating solution is used, the production of the color filter becomes industrially easier and the light transmittance of the obtained color filter is excellent.

FIG. 15 is a partially enlarged cross-sectional view of the color filter according to the second embodiment of the present invention.
As shown in FIG. 15, the color filter 300 includes a plurality of color pixels and is disposed on the substrate 12. The color pixels include a first color pixel 30 that transmits red light and first infrared light, a second color pixel 32 that transmits blue light and second infrared light, and green light and third infrared light. There is a third color pixel 34 to be transmitted.
First, the first color pixel 30 is a first multilayer in which a red pixel (R) 214 composed of a colorant-containing composition layer (red color layer) containing a red colorant and a plurality of films having different refractive indexes are laminated. A film layer 36 is laminated. As shown in FIG. 16A, the first color pixel 30 transmits red light (R) and first infrared light (IR1). More specifically, only the red light (R) among the light in the visible light region incident on the first color pixel 30 can pass through the red pixel (R) 214, and the infrared light incident on the first color pixel 30. Of the light in the light region, only the first infrared light (IR1) can pass through the first multilayer film layer 36.
As shown in FIG. 16A, the red light (R) and the first infrared light (IR1) have a continuous wavelength band, but the present invention is not limited to this mode, and the wavelength of the red light is not limited. The range and the wavelength range of the first infrared light may not be continuous.

The second color pixel 32 is a second multilayer film layer in which a blue pixel (B) 218 made of a colorant-containing composition layer (blue color layer) containing a blue colorant and a plurality of films having different refractive indexes are laminated. 38 is laminated. As shown in FIG. 16B, the second color pixel 32 transmits blue light (B) and second infrared light (IR2). More specifically, only the blue light (B) among the light in the visible light region incident on the second color pixel 32 can pass through the blue pixel (B) 218, and the infrared light incident on the second color pixel 32. Of the light in the light region, only the second infrared light (IR2) can pass through the second multilayer film layer 38.

The third color pixel 34 includes a green pixel (B) 216 composed of a colorant-containing composition layer (green color layer) containing a green colorant, and a third multilayer film layer in which a plurality of films having different refractive indexes are laminated. 40 is laminated. As shown in FIG. 16C, the third color pixel 34 transmits green light (G) and third infrared light (IR3). More specifically, only the green light (G) among the light in the visible light region incident on the third color pixel 34 can pass through the green pixel (G), and the infrared light incident on the third color pixel 34. Of the light in the region, only the third infrared light (IR3) can pass through the third multilayer film layer 40.

As shown in FIG. 16, the light passing through the color filter 300 includes three types of visible light (first visible light that is light in the first visible wavelength region and second visible light that is light in the second visible wavelength region). Light and third visible light that is light in the third visible wavelength region) and three types of infrared light (first infrared light, second infrared light, and third infrared light). It is done. Further, the red light (R) that is the first visible light, the blue light (B) that is the second visible light, and the green light (G) that is the third visible light have different wavelength distributions, and The first infrared light (IR1), the second infrared light (IR2), and the third infrared light (IR3) also have different wavelength distributions.
Note that the three wavelength distributions of visible light described above are different, in other words, the wavelength regions of the visible lights are different from each other. That is, the ranges of the first visible wavelength region, the second visible wavelength region, and the third visible wavelength region are intended to be different from each other.
In addition, the fact that the wavelength distributions of the three infrared lights are different means that the ranges of the first infrared wavelength region, the second infrared wavelength region, and the third infrared wavelength region are different from each other.
As described above, since the position of the center wavelength of the infrared light transmitted through each color pixel is different, the image (imaging signal) obtained from each infrared light is colored based on this difference, and color imaging is performed. A signal can be obtained. More specifically, an image captured with red light and first infrared light is displayed in red, an image captured with blue light and second infrared light is displayed in blue, and green light and first infrared light are displayed. By displaying an image captured with 3 infrared light in green, the image obtained with visible light and infrared light can be colored.

The definition (for example, shape, size, material, etc.) of the red pixel (R) 214, the green pixel (G) 216, and the blue pixel (B) 218 is the definition described in the first embodiment. The definition of the colorant-containing composition layer (red colored layer, green colored layer, blue colored layer) is also synonymous with the definition described in the first embodiment.
The definitions of the first multilayer film layer 36, the second multilayer film layer 38, and the third multilayer film layer 40 are the same as the definitions of the multilayer film layers described in the first embodiment. More specifically, the preferred ranges of the configuration (material, thickness, number of layers, etc.) of the first multilayer film layer 36, the second multilayer film layer 38, and the third multilayer film layer 40 are the same as those in the first embodiment described above. It is the same as the description of the multilayer film layer described in the embodiment, and an embodiment in which the high refractive layer and the low refractive layer are alternately laminated is preferably mentioned.
It is to be noted that the transmitted infrared is controlled by controlling the refractive index and the film thickness of each multilayer film layer (the first multilayer film layer 36, the second multilayer film layer 38, and the third multilayer film layer 40). The area of light can be adjusted.
As described above, since each multilayer film layer can be manufactured using a coating solution, it is excellent in industrial production suitability.

In the embodiment of FIG. 15, the center wavelength of the first infrared light (IR1), the center wavelength of the second infrared light (IR2), and the center wavelength of the third infrared light (IR2) are respectively near infrared light. It is preferable to correspond.
In the embodiment of FIG. 15, as shown in FIG. 16, the center wavelength of the first infrared light (IR1) is the same as that of the second infrared light (IR2) and the third infrared light (IR2). The center wavelength of the second infrared light is located on the shorter wavelength side than the center wavelength, and the center wavelength of the second infrared light is located on the shorter wavelength side than the center wavelength of the third infrared light. In other words, the center wavelength of the first infrared wavelength region is located on the shorter wavelength side than the center wavelength of the second infrared wavelength region and the center wavelength of the third infrared wavelength region, and the center of the second infrared wavelength region. The wavelength is located on the shorter wavelength side than the center wavelength in the third infrared wavelength region. The center wavelength of each infrared wavelength region is intended to be a wavelength intermediate between the infrared wavelength regions (the median value of the shortest wavelength and the longest wavelength), for example, a specific infrared wavelength region over 800 to 900 nm. If there is, the center wavelength is 850 nm.
The above relationship is preferably satisfied in the wavelength range of 700 to 2000 nm, more preferably in the wavelength range of 700 to 1200 nm. That is, the center wavelength of each light (first infrared light, second infrared light, and third infrared light) in the wavelength range of 700 to 2000 nm (preferably 700 to 1200 nm) satisfies the above relationship. Is preferred.
The center wavelength of each light is the center value of the wavelength region of each light.

As shown in FIG. 16A, the first multilayer film layer 36 has a light transmittance in the first infrared wavelength region (WR1) (light transmittance in the first infrared wavelength region (WR1)) of 50. % Or more (preferably 60% or more, more preferably 70% or more. The upper limit is not particularly limited, but 100% can be mentioned), and the light transmittance in the second infrared wavelength region (WR2) ( The light transmittance in the second infrared wavelength region (WR2)) and the light transmittance in the third infrared wavelength region (WR3) (light transmittance in the third infrared wavelength region (WR3)) are each 20%. It is preferable to show the following (preferably 10% or less, more preferably 5% or less. Although the lower limit is not particularly limited, 0% may be mentioned). That is, the first multilayer film layer 36 has a light transmittance in the first infrared wavelength region (WR1), a light transmittance in the second infrared wavelength region (WR2), and a third infrared wavelength region (WR3). It is preferable that the light transmittance is higher.
As shown in FIG. 16B, the second multilayer film layer 38 has a light transmittance of 50% or more (preferably 60% or more, more preferably 70% or more) in the second infrared wavelength region (WR2). The upper limit is not particularly limited, but 100% may be mentioned.) And the light transmittance in the first infrared wavelength region (WR1) and the light transmittance in the third infrared wavelength region (WR3) are respectively It is preferably 20% or less (preferably 10% or less, more preferably 5% or less. The lower limit is not particularly limited, but 0% may be mentioned). That is, the second multilayer film 38 has a light transmittance in the second infrared wavelength region (WR2), a light transmittance in the first infrared wavelength region (WR1), and a third infrared wavelength region (WR3). It is preferable that the light transmittance is higher.
As shown in FIG. 16C, the third multilayer film layer 40 has a light transmittance of 50% or more (preferably 60% or more, more preferably 70% or more) in the third infrared wavelength region (WR3). The upper limit is not particularly limited, but 100% may be mentioned.) And the light transmittance in the first infrared wavelength region (WR1) and the light transmittance in the second infrared wavelength region (WR2) are respectively It is preferably 20% or less (preferably 10% or less, more preferably 5% or less. The lower limit is not particularly limited, but 0% may be mentioned). That is, the third multilayer film layer 40 has light transmittance in the third infrared wavelength region (WR3), light transmittance in the first infrared wavelength region (WR1), and second infrared wavelength region (WR2). It is preferable that the light transmittance is higher.
As described above, when each multilayer film layer shows a high transmittance in a specific infrared wavelength region, a clearer color can be obtained by selecting the infrared light irradiated to the subject in accordance with each infrared wavelength region. An image can be obtained. Specifically, three types of infrared light sources that can irradiate light having a center wavelength in each of the first infrared wavelength region to the third infrared wavelength region are selected, and the subject is irradiated. By passing the light reflected from the subject through the color filter, it is possible to selectively transmit only specific infrared light in a specific color pixel. As a result, the light is mainly derived from specific infrared light. Image can be obtained, and a clearer color image can be formed.
The width of the first infrared wavelength region (WR1), the width of the second infrared wavelength region (WR2), and the width of the third infrared wavelength region (WR3) are from the viewpoint of application to a night vision camera or the like. These are each preferably 30 nm or more, and more preferably 40 nm or more. The upper limit is not particularly limited, but is often 100 nm or less, and is often 60 nm or less.
The center wavelength of the first infrared wavelength region and the center wavelength of the second infrared wavelength region are at least 30 nm or more (preferably 50 nm or more, more preferably 70 nm or more. The upper limit is not particularly limited, but is preferably 100 nm or less. .) It is preferable that they are separated.
Further, the center wavelength of the second infrared wavelength region and the center wavelength of the third infrared wavelength region are at least 30 nm or more (preferably 50 nm or more, more preferably 70 nm or more. The upper limit is not particularly limited, but is preferably 100 nm or less. .) It is preferable that they are separated.

From the viewpoint of application to a night vision camera or the like, the first infrared wavelength region (WR1) is located between wavelengths 700 to 800 nm, and the second infrared wavelength region (WR2) is between wavelengths 900 to 1000 nm. And the third infrared wavelength region (WR3) is preferably located between wavelengths 1050 and 1200 nm.
The first infrared wavelength region (WR1) is located between wavelengths 700 to 800 nm, the second infrared wavelength region (WR2) is located between wavelengths 800 to 900 nm, and the third infrared wavelength region (WR3) ) Is preferably located between wavelengths of 900 to 1000 nm.

In FIG. 15, the first color pixel is formed by stacking the red pixel (R) 214 and the first multilayer film layer 36, and the second color pixel is formed by stacking the blue pixel (B) 218 and the second multilayer film layer 38. Thus, although the aspect in which the third color pixel is composed of the green pixel (G) 216 and the third multilayer film layer 40 has been described, the present invention is not limited to this combination.
For example, a color pixel composed of a red pixel (R) 214 and a first multilayer film layer 36, a color pixel composed of a blue pixel (R) 218 and a third multilayer film layer 40, and a green pixel (G) 216 And the aspect provided with the color pixel comprised from the 2nd multilayer film layer 38 may be sufficient.
Also, a color pixel composed of a red pixel (R) 214 and a second multilayer film layer 38, a color pixel composed of a blue pixel (R) 218 and a first multilayer film layer 36, and a green pixel (G) 216. And the aspect provided with the color pixel comprised from the 3rd multilayer film layer 40 may be sufficient.
In addition, a color pixel composed of a red pixel (R) 214 and a second multilayer film layer 38, a color pixel composed of a blue pixel (R) 218 and a third multilayer film layer 40, and a green pixel (G) 216. And the aspect provided with the color pixel comprised from the 1st multilayer film layer 36 may be sufficient.
Also, a color pixel composed of the red pixel (R) 214 and the third multilayer film layer 40, a color pixel composed of the blue pixel (R) 218 and the first multilayer film layer 36, and a green pixel (G) 216. And the aspect provided with the color pixel comprised from the 2nd multilayer film layer 38 may be sufficient.
Further, the color pixel composed of the red pixel (R) 214 and the third multilayer film layer 40, the color pixel composed of the blue pixel (R) 218 and the second multilayer film layer 38, and the green pixel (G) 216. And the aspect provided with the color pixel comprised from the 1st multilayer film layer 36 may be sufficient.

Further, in FIG. 16, the three wavelengths of the infrared light (first infrared light (IR1), second infrared light (IR2), and third infrared light (IR3)) are different from each other. Although it explained in full detail, it is not limited to this aspect, The wavelength range of 1st infrared light (IR3) is from the wavelength range of 2nd infrared light (IR2), and the wavelength range of 3rd infrared light (IR2). May be positioned on the short wavelength side, and the wavelength range of the second infrared light may be positioned on the short wavelength side of the wavelength range of the third infrared light.

Further, the color filter of the second embodiment described above further includes an infrared ray containing an infrared ray absorbent (for example, an infrared ray absorbing dye) in order to control the wavelength range of light transmitted through each color pixel. A light absorbing layer may be included. The arrangement position of the infrared light absorption layer is not particularly limited. For example, when the infrared light absorption layer is included in the first color pixel, the infrared light absorption is performed on the surface of the first multilayer film layer opposite to the red pixel. A layer may be disposed.

The color filter of the second embodiment of the present invention can be applied to various applications, and examples thereof include a solid-state image sensor. The configuration of the solid-state imaging device is not particularly limited and may include known modes. For example, a photodiode, an insulating layer, a color filter according to the second embodiment of the present invention, a flat layer, a microlens, and the like may be used as a semiconductor substrate (substrate). The structure provided above is mentioned.
As an example to which the solid-state imaging device of the present invention is applied, the aspect described with reference to FIG.
As a suitable example of the imaging apparatus, there is an imaging apparatus described in Japanese Patent Application Laid-Open No. 2011-50049. More specifically, the imaging apparatus includes an irradiation unit (specifically, an infrared LED), an imaging unit (specifically, the above-described solid-state imaging device), and a color specification setting unit, and the irradiation unit has different wavelength intensities. Irradiates the subject with infrared rays having a distribution, and the imaging unit picks up images of the subjects with different infrared intensity having different wavelength intensity distributions reflected by the subject, forms image information representing each image, and sets the color specification The unit sets color information for displaying each image represented by the formed image information with a different single color in the image information. According to such an imaging apparatus, it is possible to form a color image having a natural color arrangement as much as possible even in the dark.
Here, the color specification means that the brightness of an image under visible light or the in-plane intensity distribution of a specific physical quantity is expressed by the brightness of the color.
The imaging unit is a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor, a CMOS (Complementary Metal Organic Semiconductor) image sensor, an APD (Avalanche Photodiode or Iconoscope), or an image dissector or iconoscope. Sachicon, Plumbicon, New Bicon, New Cosbicon, Carnicon, Trinicon, HARP (High-gain Avalanche Rushing Amorphous Photoconductor), Magnetic Focus Image Intensifier, or Electric Field Focus Image An imaging tube or imaging plate such as an intensifier or a microchannel plate, or a bolometer imaging element such as a MEMS (Micro Electro Mechanical System) bolometer, or a pyroelectric imaging element.
The color specification setting is to set in advance what color the brightness of the image is displayed when displaying the image. The color setting can be set, for example, by setting the transmission timing of the image information or image signal, or by sequentially corresponding the image information or image signal to the reference trigger. Also, setting by separately generating color information or color setting signal, setting by superimposing color information or color setting signal on image information or image signal, setting by address in memory It can also be performed by setting or labeling or flagging in signal processing.
As such an image pickup apparatus, an image pickup apparatus (image pickup apparatus) described in JP 2011-50049 A (corresponding US Patent Application Publication No. 2012/0212619) can be referred to, and the contents thereof are described in this specification. Embedded in the book. The imaging apparatus further includes a control processing unit, a display unit, an image storage unit, a separation unit, and the like described in JP 2011-50049 A (corresponding US Patent Application Publication No. 2012/0212619). May be.

Examples of the present invention will be described below, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

<Example A>
[Preparation of highly bent dispersion B-1]
A mixed solution having the following composition was mixed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)). A highly bent dispersion B-1 was prepared.
Titanium oxide 28.9 parts Dispersant: Dispersant (C-5) described in Examples of JP-A-2014-62221 (see below) 6.4 parts Organic solvent: Propylene glycol methyl ether acetate (PGMEA )
64.7 parts

[High refractive chemical solution 1]
The following components were mixed to prepare a highly refractive chemical solution 1.
・ High bending dispersion B-1 84.7 parts ・ 45 parts by mass of PGMEA 45% by weight of the following alkali-soluble resin 1 ・ Epoxy resin (EX211L Nagase ChemteX) 2.9 parts ・ Epoxy resin (JER157S65 Mitsubishi Chemical) 0 .7 parts Surfactant 1: Megafac manufactured by DIC Corporation
F-781F in 10 wt% PGMEA solution 3.4 parts Polymerization inhibitor: p-methoxyphenol 0.002 parts Organic solvent 1: PGMEA 7.4 parts

Alkali-soluble resin 1 (hereinafter structural formula)

[Preparation of low refractive chemical 1]
The following components were mixed to prepare a low refractive chemical solution 1. In addition, the obtained low refractive chemical liquid 1 contained beaded colloidal silica particles.
Low refractive composition B-1 (JP 2013-253145 Example 1-1) 75.3 parts Surfactant 1: Megafac manufactured by DIC Corporation
0.1 parts of 10 mass% PGMEA solution of F-781F, organic solvent 1: 24.6 parts of ethyl lactate

(Manufacture of multilayer layers (part 1))
Fabrication of a multilayer film layer using the three types of chemical solutions, the high refractive chemical solution 1 (n = 1.91), the low refractive chemical solution 1 (n = 1.23), and the low refractive chemical solution 2 (n = 1.4). went. Note that n in the parentheses means the refractive index of a layer formed from each liquid.
As the low-refractive-index chemical solution 2, the siloxane curable composition A-1 described in Examples after paragraph 0376 of JP 2014-74874 (WO2013 / 099945) was used.
The low refractive chemical solutions 1 and 2 were applied using a spin coater and dried on a hot plate at 100 ° C. for 120 seconds to form a film. The high refractive chemical solution 1 was applied using a spin coater and dried at 200 ° C. for 1 minute on a hot plate to form a film.
On the substrate (8-inch glass wafer), the above-described coating and heating steps were repeated to produce a multilayer film layer described in Table 1. In addition, the optical film thickness in Table 1 intends (physical film thickness × refractive index). In Table 1, “1” to “21” represent the numbers of layers arranged from the substrate side. For example, “2” represents the characteristics of the second layer from the substrate side.

Transmission spectrum diagrams of the multilayer film layer 1 and the multilayer film layer 2 in Table 1 are shown in FIGS. It was confirmed that the multilayer film layer 1 and the multilayer film layer 2 have low transmittance in a predetermined wavelength region.
Specifically, in the multilayer film layer 1, the transmittance in the wavelength range of 480 to 500 nm is 30% or less, and in the multilayer film layer 2, the transmittance in the wavelength range of 580 to 600 nm. Was 30% or less.

<Example 1>
As shown in FIGS. 2 to 4, the above-described method (manufacture of multilayer layers (parts thereof) is performed at predetermined positions on the substrate (positions of the first multilayer layer 24 and the second multilayer layer 26 described in FIGS. 2 to 4)). 1)), the multilayer film layer 1 is prepared, and a red pixel (corresponding to the red pixel 14 in FIG. 2), a green pixel (corresponding to the green pixel 16 in FIG. 2), and a blue color at predetermined positions on the substrate. Each pixel (corresponding to the blue pixel 18 in FIG. 2) is arranged, and further, a green pixel (corresponding to the green pixel 16 on the first multilayer film layer 24 in FIG. 4) is arranged on the multilayer film layer 1. A blue pixel (corresponding to the blue pixel 18 on the second multilayer film layer 26 in FIG. 4) was arranged on each of them to produce a color filter.
The patterning procedure for producing the multilayer film layer 1 was carried out with reference to the procedures in paragraphs 0418 to 0421 of JP2013-54081A.

Moreover, a red pixel, a green pixel, and a blue pixel are pixels produced using the composition containing each colorant (a red colorant, a green colorant, or a blue colorant), respectively.
As a composition containing a red colorant, “red colored radiation-sensitive composition RS” described in paragraphs 0273 and 0274 of JP2012-198408A was used.
As a composition containing a green colorant, “colored radiation-sensitive composition GS-1” described in paragraph 0272 of JP2012-198408A was used.
As a composition containing a blue colorant, “blue colored radiation-sensitive composition BS” described in paragraph 0276 of JP2012-198408A was used.
The patterning method for each color pixel was carried out with reference to the procedures in paragraphs 0278 to 0280 of JP2012-198408A.

FIG. 13A shows a transmission spectrum diagram of a red pixel, a green pixel, and a blue pixel, and FIG. 13B shows a red pixel, a stacked color pixel of the multilayer film layer 1 and the green pixel, and a multilayer pixel. The transmission spectrum of the laminated color pixel of the film layer 1 and a blue pixel is shown.
In FIG. 13A, the transmission spectrum of the red pixel is represented by “R”, the transmission spectrum of the green pixel is represented by “G1”, and the transmission spectrum of the blue pixel is represented by “B1”. In FIG. The transmission spectrum of the pixel is “R”, the transmission spectrum of the multilayer color pixel of the multilayer film layer 1 and the green pixel is “G2”, and the transmission spectrum of the multilayer color pixel of the multilayer film layer 1 and the blue pixel is “B2”. It is represented by
As can be seen from the spectrum, by using the multilayer film layer 1, it is possible to produce a color pixel having a color different from that of the green pixel and the blue pixel. That is, a multicolor color filter could be produced.

<Example 2>
The multilayer film layer 2 is used in place of the multilayer film layer 1 and a red pixel is used in place of the blue pixel arranged on the multilayer film layer 1. A color filter was manufactured.
FIG. 14A shows a transmission spectrum diagram of a red pixel, a green pixel, and a blue pixel, and FIG. 14B shows a blue pixel, a stacked color pixel composed of a multilayer film layer 2 and a green pixel, and a multilayer pixel. The transmission spectrum of the laminated color pixel of the film layer 2 and the red pixel is shown.
In FIG. 14A, the transmission spectrum of the red pixel is represented by “R”, the transmission spectrum of the green pixel is represented by “G1”, and the transmission spectrum of the blue pixel is represented by “B1”. The transmission spectrum of the pixel is “B”, the transmission spectrum of the multilayer color pixel of the multilayer film layer 2 and the green pixel is “G3”, and the transmission spectrum of the multilayer color pixel of the multilayer film layer 2 and the red pixel is “R3”. It is represented by
As can be seen from the spectrum, by using the multilayer film layer 2, it is possible to produce a color pixel having a color different from that of the green pixel and the red pixel. That is, a multicolor color filter could be produced.

In addition, although the aspect using the red pixel, the green pixel, and the blue pixel has been described above, magenta, cyan, and yellow (yellow) color pixels are used instead of the red pixel, the green pixel, and the blue pixel. Also in the case of using the multilayer film layer 1 or the multilayer film layer 2 as in Examples 1 and 2, a multicolor color filter could be produced.
In addition, as a composition used for producing magenta, cyan, and yellow (yellow) color pixels, “colored radiation-sensitive composition M-1” described in Examples in JP-A-2014-41301 is used. “Colored radiation-sensitive composition Cy-1” and “colored radiation-sensitive composition Y-1” were used, respectively.

<Example B>
As shown in FIG. 15, the first multilayer film layer 36, the second multilayer film layer 38, and the first multilayer film layer are formed at predetermined positions on the substrate by a method described later (manufacture of multilayer film layer (2)). 3 multilayer films 40 are formed, and further, a red pixel (corresponding to the red pixel 214 in FIG. 15) is formed on the first multilayer film 36, and a blue pixel (on the blue pixel 218 in FIG. Corresponding) and a green pixel (corresponding to the green pixel 216 in FIG. 15) are respectively arranged on the third multilayer film layer 40 to produce a color filter.
The patterning procedure for producing the first multilayer film layer 36 to the third multilayer film layer 40 was carried out with reference to the procedures in paragraphs 0418 to 0421 of JP2013-54081A.

(Manufacture of multilayer film layer (2))
A multilayer film was prepared using the two types of chemical solutions, the high refractive chemical solution 1 (n = 1.91) and the low refractive chemical solution 1 (n = 1.23). Note that n in the parentheses means the refractive index of a layer formed from each liquid.
The low refractive chemical solution 1 was applied using a spin coater and dried on a hot plate at 100 ° C. for 120 seconds to form a film. The high refractive chemical solution 1 was applied using a spin coater and dried at 200 ° C. for 1 minute on a hot plate to form a film.
On the substrate (8-inch glass wafer), the above coating and heating steps were repeated to produce a multilayer film layer described in Table 2. In addition, the optical film thickness in Table 2 intends (physical film thickness × refractive index). Further, the number of layers in Table 2 represents the number of the layers arranged from the substrate side, and for example, “2” represents the characteristics of the second layer from the substrate side.

FIG. 17 also shows a transmission spectrum diagram of light transmitted through the first color pixel, the second color pixel, and the third color pixel.
As shown in FIG. 17, visible light and infrared light are transmitted from each color pixel, have different wavelength distributions, and the positions of the central wavelengths of the respective lights are different.
As shown in FIG. 17, the first color pixel has a light transmittance of 80% or more at a wavelength of 700 to 750 nm (corresponding to the first infrared wavelength region), and a wavelength of 920 to 980 nm (second infrared wavelength). The light transmittance in the region (corresponding to the region) is 10% or less, and the light transmittance in the wavelength 1090 to 1150 nm (corresponding to the third infrared wavelength region) is 10% or less.
Further, the second color pixel has a light transmittance of 10% or less at a wavelength of 700 to 750 nm (corresponding to the first infrared wavelength region), and a light transmittance at a wavelength of 920 to 980 nm (corresponding to the second infrared wavelength region). The transmittance is 90% or more, and the light transmittance at a wavelength of 1090 to 1150 nm (corresponding to the third infrared wavelength region) is 10% or less.
The third color pixel has a light transmittance of 10% or less at a wavelength of 700 to 750 nm (corresponding to the first infrared wavelength region), and a light transmittance at a wavelength of 920 to 980 nm (corresponding to the second infrared wavelength region). The transmittance is 10% or less, and the light transmittance at a wavelength of 1090 to 1150 nm (corresponding to the third infrared wavelength region) is 90% or more.

1: Lens optical system, 10, 100, 200, 300: Color filter, 12: Substrate, 14, 114, 214: Red pixel, 16, 116, 216: Green pixel, 18, 118, 218: Blue pixel, 20: First laminated color pixel, 22: second laminated color pixel, 24: first multilayer film layer, 26: second multilayer film layer, 28: transparent resin layer, 30: first color pixel, 32: second color Pixel, 34: third color pixel, 36: first multilayer film layer, 38: second multilayer film layer, 40: third multilayer film layer, 110: solid-state imaging device, 120: signal processing unit, 130: signal switching unit 140: control unit, 150: signal storage unit, 160: light emission control unit, 170: infrared LED, 180, 181: image output unit

Claims

Having four or more color pixels,
A color filter, wherein at least one of the color pixels is a multilayer color pixel formed by laminating a multilayer film layer in which a plurality of films having different refractive indexes are laminated and a colorant-containing composition layer containing a colorant.
The color pixel is at least a red pixel comprising a colorant-containing composition layer containing a red colorant, a green pixel comprising a colorant-containing composition layer containing a green colorant, and a color containing a blue colorant The color filter of Claim 1 containing the blue pixel which consists of an agent containing composition layer.
The red pixel has a maximum value in a transmission spectrum at a wavelength of 575 nm or more, the green pixel has a maximum value in a transmission spectrum at a wavelength of 480 nm or more and less than 575 nm, and the blue pixel has a maximum value in a transmission spectrum at a wavelength of less than 480 nm. The color filter according to claim 2.
The color pixel is formed by laminating at least the red pixel, the green pixel, the blue pixel, a multilayer film layer in which a plurality of films having different refractive indexes are laminated, and a colorant-containing composition layer containing a green colorant. And a second stacked color pixel formed by stacking a multilayer film layer formed by stacking a plurality of films having different refractive indexes and a colorant-containing composition layer containing a blue colorant. The color filter according to claim 2 or 3.
The multilayer film layer has a transmittance of 30% or less within a wavelength range of 480 to 500 nm, or a transmittance of 30% or less within a wavelength range of 580 to 600 nm. The color filter according to any one of the above.
The color filter according to any one of claims 1 to 5, wherein the multilayer film layer is a layer formed using a coating liquid.
A solid-state imaging device comprising the color filter according to any one of claims 1 to 6.