JP2019049759A - Composition for infrared transmission filter, infrared transmission composition layer, infrared transmission filter, method for manufacturing infrared transmission filter, and infrared sensor - Google Patents

Abstract

To provide a composition for an infrared transmission filter which can prepare an infrared transmission filter that is extremely thin (0.5 μm, for example) and also can transmit infrared rays (specifically, near-infrared rays) in a state in which there is less noises derived from visible light, an infrared transmission composition layer using the composition, an infrared transmission filter using the composition, and a method for manufacturing the infrared transmission filter, using the composition, and an infrared sensor using the composition.SOLUTION: There are provided a composition for an infrared transmission filter containing a near-infrared transmission black color material, an infrared transmission composition layer using the composition, an infrared transmission filter using the composition, a method for manufacturing the infrared transmission filter, using the composition, and an infrared sensor using the composition.SELECTED DRAWING: None

Description

  The present invention relates to a composition for an infrared transmission filter, an infrared transmission composition layer, an infrared transmission filter, a method for producing an infrared transmission filter, and an infrared sensor.

  The color filter is an integral component of a solid-state imaging device or a liquid crystal display. In particular, color filters for solid-state imaging devices are required to be improved in color separation and color reproducibility.

  Such a color filter is formed to include colored regions (colored cured films) of a plurality of hues, and usually at least red, green and blue colored regions (hereinafter referred to as “colored pattern” or “colored (Also referred to as a “pixel”). As a method of forming a colored pattern, first, a colored radiation-sensitive composition having any one of red, green, and blue colorants in a first hue is applied, exposed, developed, and heat-treated as necessary. After forming the colored pattern of the said hue, the process of the same application, exposure, development in the 2nd hue and the 3rd hue, and heat processing as needed will be repeated.

As a coloring agent in color filters, pigments are widely used because they have sharp color tone and high coloring power, and in particular, pigments which are finely divided and exhibit suitable color separation properties may be used. preferable.
In recent years, in solid-state imaging devices, it has been required to make the colored pixels fine (for example, a colored pattern of one side of 1.0 μm or less) for the purpose of resolution improvement. However, with the miniaturization of colored pixels, It is known that noise increases.

Solid-state imaging devices are used as light sensors in various applications.
For example, near infrared rays have a longer wavelength than visible light, so they are less likely to be scattered, and can be used for distance measurement, three-dimensional measurement, etc. In addition, because the near infrared rays are invisible to humans, animals, etc., even if the subject is illuminated with a near infrared light source at night, the subject is taken notice of nocturnal wildlife, and the other party is stimulated as a crime prevention use It can also be used for shooting without shooting. Such an optical sensor that senses near-infrared light can be developed for various applications, and development of a color filter that can be used for a solid-state imaging device that senses near-infrared light has been awaited.

For example, there is known a resin black matrix in which absorption of light is small in the near infrared to infrared wavelength region and light transmittance in this wavelength region is high (for example, Patent Document 1). The transmission in the infrared region is insufficient, and in particular, it is difficult to use as an infrared transmission filter in an infrared sensor for detecting a near infrared region.
Also, in recent years, a very thin infrared transmission filter (for example, having a thickness of 0.5 μm) is required, but as the thickness becomes thinner, the light shielding property to visible light of the infrared transmission filter tends to be reduced (that is, And noise from the visible light component is likely to occur), and as a result, there is a problem that the performance as an infrared sensor is lowered.

JP, 2009-69822, A

The present invention has been made in view of the above-mentioned circumstances, and an object thereof is to achieve the following object.
That is, according to the present invention, an infrared ray transmission filter capable of transmitting infrared rays (particularly, near infrared rays) can be formed even in a very thin state (for example, 0.5 μm in thickness) with little noise derived from visible light components. An object of the present invention is to provide a composition for an infrared transmission filter, and an infrared transmission composition layer, an infrared transmission filter, a method of manufacturing an infrared transmission filter, and an infrared sensor using the same.

The inventors of the present invention conducted intensive studies in view of the above-mentioned facts and found that an infrared transmission filter formed using a composition for an infrared transmission filter containing a near infrared transmission black color material can achieve the above-mentioned problem. The present invention has been completed. That is, the present invention is as follows.
(1)
A composition for an infrared transmission filter comprising a near infrared transmission black color material, wherein the near infrared transmission black color material is a bisbenzofuranone-based pigment, and the content of the bisbenzofuranone-based pigment is the infrared transmission. The content is 20% by mass or more based on the total solid content of the composition for a filter, and the composition for an infrared transmission filter further contains a colorant different from the bisbenzofuranone-based pigment, and the colorant is an organic pigment And at least one selected from a yellow pigment, an orange pigment, a red pigment, a green pigment, a violet pigment and a blue pigment, and the content of the colorant is The composition for an infrared transmission filter, which is 1 to 300 parts by mass with respect to 100 parts by mass of the bisbenzofuranone-based pigment.
(2)
The composition for an infrared transmission filter according to (1), wherein a content of the bisbenzofuranone-based pigment is 40 to 80% by mass with respect to a total solid content of the composition for an infrared transmission filter.
(3)
The composition for an infrared transmission filter according to (1) or (2), wherein an average particle size of the bisbenzofuranone-based pigment is 50 nm or less.
(4)
The composition for an infrared transmission filter according to (3), wherein the average particle diameter of the bisbenzofuranone-based pigment is 1 to 50 nm.
(5)
The composition for an infrared transmitting filter according to any one of (1) to (4), wherein the bisbenzofuranone-based pigment is a compound having the following structure.

(6)
The composition for an infrared transmission filter according to any one of (1) to (5), wherein the colorant is at least one selected from a yellow pigment and a blue pigment.
(7)
The composition for an infrared transmission filter according to (6), wherein the colorant is a yellow pigment.
(8)
The composition for an infrared transmission filter according to (6), wherein the colorant is a yellow pigment and a blue pigment.
(9)
The yellow pigment is C.I. I. Pigment Yellow 139, and the blue pigment is C.I. I. Pigment Blue 15: 6, the composition for an infrared transmission filter according to (8).
(10)
The composition for an infrared transmission filter according to any one of (1) to (9), wherein the content of the coloring agent is 1 to 200 parts by mass with respect to 100 parts by mass of the bisbenzofuranone-based pigment.
(11)
The composition for an infrared transmission filter according to any one of (1) to (9), wherein the content of the coloring agent is 1 to 60% by mass with respect to the total solid content of the composition for an infrared transmission filter .
(12)
The composition for infrared transmission filters as described in (11) whose content of the said coloring agent is 1-30 mass% with respect to the total solid of the composition for said infrared transmission filters.
(13)
Furthermore, the composition for an infrared transmission filter according to any one of (1) to (12), further comprising a polymer dispersant, wherein the polymer dispersant has an acid value of 60 mg KOH / g or more. A composition for an infrared transmission filter, which is at least one selected from the group consisting of a resin, a resin having an amine group, and an oligoimine resin.
(14)
Furthermore, the composition for infrared rays permeable filters of any one of (1)-(13) which contains a polymeric compound.
(15)
For the infrared transmission filter according to (14), wherein the polymerizable compound is one or more selected from the group consisting of radical polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) Composition.

In the above general formula, n is 0 to 14 and m is 1 to 8. A plurality of R and T in one molecule may be identical to or different from each other. When T is an oxyalkylene group, the terminal at the carbon atom side is bonded to R.
In each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5), at least one of a plurality of R is -OC (= O) CH = CH ₂ or -OC (= O) represents a group represented by C (CH ₃ ) = CH ₂ .
(16)
The composition for infrared transmission filters as described in (14) or (15) whose content of the said polymeric compound is 2-25 mass% with respect to the total solid of the composition for said infrared transmission filters.
(17)
Furthermore, the composition for infrared rays permeable filters of any one of (1)-(16) which contains a photoinitiator.
(18)
Furthermore, the composition for infrared rays permeable filters of any one of (1)-(17) which contains alkali-soluble resin.
(19)
The composition for infrared transmission filters as described in (18) whose content of the said alkali-soluble resin is 1-15 mass% with respect to the total solid of the composition for said infrared transmission filters.
(20)
The composition for infrared transmission filters as described in (19) whose content of the said alkali-soluble resin is 3-10 mass% with respect to the total solid of the composition for said infrared transmission filters.
(21)
Furthermore, the composition for infrared rays permeable filters of any one of Claims 1-20 containing surfactant.
(22)
The composition for an infrared transmitting filter according to (21), wherein the surfactant is a fluorine-based surfactant.
(23)
In the formation of a film having a film thickness of 0.5 μm, any one of (1) to (22) in which the standard deviation in the wavelength range of 400 to 630 nm of the light transmittance in the thickness direction of the film is 6.0 or less The composition for an infrared ray transmission filter according to claim 1.
(24)
When a film having a film thickness of 0.5 μm is formed, the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 650 nm is 20% or less, and the light transmittance of the film in the thickness direction The composition for an infrared transmission filter according to any one of (1) to (23), wherein the minimum value in the wavelength range of 800 nm to 1300 nm is 80% or more.
(25)
The infrared rays permeable composition layer formed from the composition for infrared rays permeable filters of any one of (1)-(24).
(26)
The infrared rays permeable composition layer as described in (25) whose film thickness is 1.8 micrometers or less.
(27)
The infrared rays transmission filter formed from the composition for infrared rays transmission filters of any one of (1)-(24).
(28)
Applying the composition for an infrared transmission filter according to any one of (1) to (24) on a substrate to form an infrared transmission composition layer, and forming the infrared transmission composition layer into a pattern A method for producing an infrared ray transmitting filter, comprising the steps of: exposing; and developing the infrared ray transmitting composition layer after exposure to form a pattern.
(29)
The infrared sensor containing the infrared rays permeable filter as described in (27).
The present invention relates to the composition for an infrared transmission filter described in the above (1) to (29), an infrared transmission composition layer, an infrared transmission filter, a method for producing an infrared transmission filter, and an infrared sensor, The matters will be described for reference.

[1]
A composition for a color filter, comprising a near infrared transmitting black color material.
[2]
Furthermore, the composition for color filters as described in said [1] which contains a photoinitiator and a polymeric compound.
[3]
The above-mentioned [1] or [2], wherein the near-infrared transmitting black color material is at least one selected from the group consisting of bisbenzofuranone-based pigments, azomethine-based pigments, perylene-based pigments, and azo-based dyes. The composition for color filters as described in 4.
[4]
When a film having a film thickness of 0.5 μm is formed, the standard deviation of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 630 nm is 6.0 or less The composition for color filters according to any one of the above.
[5]
In any one of the above [1] to [4], which contains a near infrared transmitting black pigment as the near infrared transmitting black color material, and the average particle diameter of the near infrared transmitting black pigment is 50 nm or less The composition for color filters as described.
[6]
When a film having a film thickness of 0.5 μm is formed, the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 650 nm is 20% or less, and the light transmittance of the film in the thickness direction The composition for a color filter according to any one of the above [1] to [5], wherein the minimum value in the wavelength range of 800 nm to 1300 nm is 80% or more.
[7]
Furthermore, the composition for a color filter according to any one of the above [1] to [6], which contains a polymer dispersant, wherein the polymer dispersant is a resin having an acid value of 60 mg KOH / g or more. The composition for color filters which is 1 or more types selected from resin which has an amine group, and an oligoimine resin.
[8]
Furthermore, the composition for color filters according to any one of the above [1] to [7], which further comprises a colorant different from the near infrared transmissive black coloring material.
[9]
The infrared rays permeable filter formed from the composition for color filters of any one of said [1]-[8].
[10]
Applying the color filter composition according to any one of the above [1] to [8] onto a substrate to form an infrared ray transmitting composition layer, and exposing the infrared ray transmitting composition layer in a pattern And a step of developing the infrared ray transmitting composition layer after exposure to form a pattern.
[11]
An infrared sensor comprising the infrared ray transmission filter according to the above [9] or the infrared ray transmission filter obtained by the method for producing an infrared ray transmission filter according to the above [10].

  According to the present invention, it is possible to create an infrared ray transmission filter that can transmit infrared rays (especially, near infrared rays) even in a very thin layer (for example, 0.5 μm in thickness) with little noise originating from visible light components and the like It is possible to provide an infrared ray transmission filter composition, an infrared ray transmission filter, a method of producing an infrared ray transmission filter, and an infrared ray sensor using the same.

  Hereinafter, the present invention will be described in detail.

  Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments. In addition, the numerical range represented using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

The composition for an infrared transmission filter of the present invention contains a near infrared transmission black color material.
The composition for infrared ray transmission filters of the present invention is typically a black composition, and since it transmits near infrared rays, it can also be said to be a near infrared rays transmitting composition.

  Below, each component which can comprise the composition of this invention is demonstrated.

<(A) Near Infrared Transparent Black Color Material>
As described above, the composition for the infrared transmission filter of the present invention contains a near infrared transmission black color material.
According to such a composition for an infrared transmission filter of the present invention, even if it is very thin (for example, the thickness is 0.5 μm), the infrared light (particularly, near infrared light) with less noise originating from visible light components and the like It is possible to create an infrared transmission filter that can transmit light.

  The near infrared transmitting black color material in the composition for infrared light transmitting filter of the present invention is a color material which selectively transmits near infrared light, and the film thickness is 0.5 μm by the composition for infrared light transmitting filter And, when a film having a concentration of 60% by mass with respect to the total solid content of the film of the film itself (near-infrared light transmitting black material) is formed, the light transmittance of the film in the thickness direction is in the range of 400 to 650 nm. It is preferable that it is the coloring material which can make the maximum value in 30% or less, and can make the minimum value in the range of wavelength 800nm-1300nm 80% or more, and the light transmittance of the film thickness direction of 400-650nm. It is particularly preferable that the coloring material can have a maximum value in the range of 20% or less and a minimum value in the range of wavelengths of 800 nm to 1300 nm can be 80% or more.

The measuring method of the spectral characteristics of the film | membrane formed from the composition in this invention, film thickness, etc. is shown below.
The composition of the present invention is coated on a glass substrate by a method such as spin coating so that the film thickness after drying is 0.5 μm, a film is provided, and drying is performed at 100 ° C. for 120 seconds on a hot plate. did.
The film thickness of the film was measured using a stylus surface profiler (DEKTAK150 manufactured by ULVAC, Inc.) after drying the film having the film.
The dried substrate having this film is transmitted in a wavelength range of 300 to 1300 nm using a spectrophotometer (ref. Glass substrate) of an ultraviolet visible near infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) The rate was measured.

  The near infrared transmitting black color material may be a near infrared transmitting black pigment or a near infrared transmitting black dye, but is preferably a near infrared transmitting black pigment.

As the near infrared transmitting black pigment, bisbenzofuranone type pigments, azomethine type pigments, perylene type pigments and the like can be suitably mentioned.
As a near-infrared transmission black dye, an azo-type dye etc. can be mentioned suitably.

  That is, the near infrared transmitting black color material is preferably at least one selected from the group consisting of bisbenzofuranone pigments, azomethine pigments, perylene pigments, and azo dyes, and is preferably bisbenzofuranone pigments. It is more preferable that it is 1 or more types selected from the group which consists of a pigment, an azomethine type pigment, and an azo type dye, and it is still more preferable that it is a bisbenzo furanone type pigment.

Examples of the bisbenzofuranone-based pigment include those described in JP-A-2012-528448, JP-A-2010-534726, JP-A-2012-515234, etc. For example, "IRGAPHOR BK" manufactured by BASF Corp. It is available as
Examples of the azomethine pigment include those described in JP-A-1-170601, JP-A-2-34664 and the like, and can be obtained, for example, as "Chromo fine black A1103" manufactured by Dainichiseika.
Although an azo dye is not specifically limited, The compound etc. which are represented by a following formula (A-1) can be mentioned suitably.

The composition for an infrared transmitting filter of the present invention preferably contains a near infrared transmitting black pigment as a near infrared transmitting black color material, and in this case, the average particle diameter of the near infrared transmitting black pigment is 50 nm or less Is preferably 30 nm or less. The average particle size of the near infrared transmitting black pigment is usually 1 nm or more.
Here, the average particle size of the pigment in the present specification is based on measurement using MICROTRACUPA 150 manufactured by Nikkiso Co., Ltd.
It is preferable that it is 20-80 mass% with respect to the total solid of the composition for infrared transmission filters of this invention, and, as for content of a near-infrared permeation | transmission black coloring material, it is more preferable that it is 40-80 mass%. preferable.

<(B) Colorant>
The composition for infrared transmission filter of the present invention may contain a colorant (B) different from the above-mentioned near infrared transmission black color material.
As a coloring agent (B), a pigment, a dye, etc. can be mentioned.

The pigment is preferably an organic pigment, and the following can be mentioned. However, the present invention is not limited to these.
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 35, 53, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , Etc. 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 (or more, and yellow pigment),
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 13, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Above, orange pigment),
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 25: 2, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 208, 209, 210, 216, 220, 224, 242, 246, 254, 255, 264, 270, 272, 279, etc. (above, red Pigment)

C. I. Pigment Green 7, 10, 36, 37, 58 (above, green pigment),
C. I. Pigment Violet 1,19,23,27,32,37,42 etc. (above, purple pigment),
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 22, 60, 64, 66, 79, 80 (the above, blue pigment),
C. I. Pigment Black 1, 7, 31, 32, Lumogen Black FK 4280 (manufactured by BASF), Lumogen Black FK 4281 (manufactured by BASF), etc. (above, black pigment)
These organic pigments can be used alone or in various combinations.

  The dye is not particularly limited, and dyes conventionally known for color filters can be used.

  The chemical structure includes pyrazole azo type, anilino azo type, triphenylmethane type, anthraquinone type, anthrapyridone type, benzylidene type, oxonol type, pyrazolotriazole azo type, pyridone azo type, cyanine type, phenothiazine type, pyrrolopyrazole azomethine type, Dyes such as xysatins, phthalocyanines, benzopyrans, indigos, and pyromethenes can be used. In addition, multimers of these dyes may be used.

Moreover, as a dye, an acid dye and / or its derivative may be able to be used conveniently.
In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be usefully used.

Although the specific example of an acid dye is given to the following, it is not limited to these. For example,
acid black 1,2,24,48; acid blue 1,7,9,15,18,23,25,29,40 to 45,62,70,74,80,83,86 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; acid chrome violet K; acid Fuchsin; acid green 1,3,5 Acid orange 6,7,8,10,12,50,51,52,56,63,74,95;
red 1,4,8,14,17,18,26,29,31,34,35,37,42,44,45,51,52,57,66,73,80,87,88,91 , 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 25, 34, 36, 42, 54, 72, 73 , 76, 79, 99, 89, 111, 112, 114, 116, 184, 243; Food Yellow 3; and derivatives of these dyes.

  Further, azo, xanthene and phthalocyanine acid dyes other than the above are also preferable, and C.I. I. Solvent Blue 44, 38; C.I. I. Acid dyes such as Solvent orange 45; Rhodamine B, Rhodamine 110 and derivatives of these dyes are also preferably used.

Among them, dyes such as triarylmethanes, anthraquinones, azomethines, benzylidenes, oxonols, cyanines, phenothiazines, pyrrolopyrazole azomethines, xanthenes, phthalocyanines, benzopyrans, indigos and pyrazoles It is preferable that it is a coloring agent selected from anilino azo type, pyrazolo triazole azo type, pyridone azo type, and anthrapyridone type pyrromethene type.
Furthermore, the pigment and the dye may be used in combination.

  The content of the colorant (B) is preferably 1 to 60% by mass, and more preferably 1 to 30% by mass, relative to the total solid content of the composition for an infrared transmission filter of the present invention.

The composition for infrared transmission filter of the present invention is one or two or more kinds of colorants different from the near infrared transmission black coloring material (A) (for example, yellow pigment, orange pigment, red pigment, green pigment, purple pigment) And at least one colorant selected from the group consisting of a blue pigment, a black pigment, etc.) to form a film having a thickness of 0.5 .mu.m, which will be described in detail later. The standard deviation of the light transmittance in the wavelength range of 400 to 630 nm can be further reduced.
In this case, the coloring agent (B) is in the range of 1 part by mass to 300 parts by mass, preferably in the range of 1 part by mass to 200 parts by mass with respect to 100 parts by mass of the near infrared transmissive black color material (A). is there.
When the composition for infrared transmission filters of the present invention contains a pigment as the colorant (B), the average particle diameter of the pigment is preferably 300 nm or less, and more preferably 200 nm or less. The average particle size of the pigment as the colorant (B) is usually 10 nm or more.

  The near-infrared transmitting black pigment having the above-mentioned average particle diameter (or a mixed pigment of the near-infrared transmitting black pigment having the above-mentioned average particle diameter and the pigment as the colorant (B)) A black pigment (or the above-mentioned mixed pigment) can be prepared by mixing and dispersing as a pigment mixed liquid, preferably mixed with a dispersant and a solvent, using, for example, a grinder such as a bead mill or roll mill. . The pigments thus obtained are usually in the form of pigment dispersions.

-Refinement of pigment-
In the present invention, it is preferable to use fine and sized pigments. Fineness of the pigment is prepared by preparing a highly viscous liquid composition together with the pigment, the water-soluble organic solvent and the water-soluble inorganic salt, and applying a stress and grinding using a wet grinding apparatus etc. To be achieved.

The water-soluble organic solvent used in the step of refining the pigment is methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether And propylene glycol, propylene glycol monomethyl ether acetate and the like.
In addition, other solvents which have low water solubility or do not have water solubility as long as they are adsorbed to the pigment by using a small amount and are not washed away in waste water, such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, Nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, butyl acetate, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl An isobutyl ketone, cyclohexanone, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and the like may be used.
The solvent used in the pigment refining step may be one type alone, or two or more types may be mixed and used as needed.

Examples of the water-soluble inorganic salt used in the step of refining the pigment in the present invention include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like.
The amount of the water-soluble inorganic salt used in the refining step is 1 to 50 times by mass that of the pigment, and the larger the amount is, the more effective there is attrition effect, but the more preferable amount is 1 to 10 times by mass in terms of productivity. In addition, it is preferable to use an inorganic salt having a water content of 1% or less.
The amount of the water-soluble organic solvent used in the micronization step is in the range of 50 parts by mass to 300 parts by mass, preferably 100 parts by mass to 200 parts by mass with respect to 100 parts by mass of the pigment.

  There are no particular restrictions on the operating conditions of the wet pulverizing apparatus in the pigment refining process, but the operating conditions when the apparatus is a kneader are the number of rotations of the blades in the apparatus in order to effectively advance the grinding by the pulverizing media. 10 to 200 rpm is preferable, and the one having a relatively large rotation ratio of two axes is preferable because the grinding effect is large. The operation time is preferably 1 hour to 8 hours in combination with the dry grinding time, and the internal temperature of the apparatus is preferably 50 to 150 ° C. The water-soluble inorganic salt, which is a grinding media, preferably has a grinding particle size of 5 to 50 μm, a sharp particle size distribution, and a spherical shape.

(Preparation of pigment dispersion)
The composition for infrared transmission filter of the present invention comprises the near infrared transmitting black pigment as the near infrared transmitting black color material (A) (or the near red as the near infrared transmitting black color material (A) In the case of containing an extrapermeable black pigment, and a pigment as a coloring agent (B)), this (or these) pigment is necessary, and other components such as a pigment dispersant, an organic solvent, a pigment derivative, and a polymer compound The pigment dispersion is prepared by dispersing it together with a pigment dispersion, etc., and mixing the pigment dispersion obtained with (C) a photopolymerization initiator, (D) a polymerizable compound, and other components added as necessary. Is preferred.
The composition of the pigment dispersion and the method of preparing the pigment dispersion will be described in detail below.

  The preparation method of the pigment dispersion is not particularly limited, but as a method of dispersion, for example, a pigment and a pigment dispersant are preliminarily mixed and dispersed in advance by a homogenizer or the like, and zirconia beads are used. The dispersion can be carried out by finely dispersing using a bead disperser (for example, Dispermat manufactured by GETZMANN Co., Ltd.) or the like.

<Pigment dispersant>
Examples of pigment dispersants that can be used to prepare pigment dispersions include polymer dispersants (also referred to as dispersion resins) [for example, resins having an amine group (polyamide amines and their salts, etc.), oligoimine resins, polycarboxylic acids and their substances Salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic copolymers, naphthalene sulfonic acid formalin condensates], and polyoxyethylene alkyl phosphates, poly Surfactants, such as oxyethylene alkylamine and alkanolamine, and pigment derivatives can be mentioned.
Polymer dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers according to their structures.
Further, as the polymer dispersant, a resin having an acid value of 60 mg KOH / g or more (more preferably, an acid value of 60 mg KOH / g or more and 300 mg KOH / g or less) can be preferably mentioned.
The polymer dispersant is preferably at least one selected from the group consisting of a resin having an acid value of 60 mg KOH / g or more, a resin having an amine group, and an oligoimine resin. Thereby, the dispersibility of the near infrared transmissive black pigment can be further improved, and more near infrared transmissive black pigments can be contained in the composition, so that the visible light component can be shielded more. As a result, it is possible to create an infrared transmission filter capable of transmitting infrared (particularly, near infrared) light with less noise originating from visible light components.

  Examples of terminal-modified polymers having anchor sites on the pigment surface include polymers having a phosphoric acid group at the ends described in JP-A-3-112992 and JP-A-2003-533455, etc., JP-A-2002 Examples thereof include polymers having a sulfonic acid group at the terminal as described in JP-273191 and the like, and polymers having a partial skeleton and a heterocyclic ring of an organic dye described in JP-A-9-77994 and the like. In addition, polymers described in JP-A-2007-277514 in which two or more anchor sites (acid group, basic group, partial skeleton of organic dye, heterocyclic ring, etc.) are introduced at the polymer end are also used. It is excellent in dispersion stability and preferable.

  As a graft type polymer having an anchor site to the pigment surface, for example, poly (lower alkyleneimine) described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, etc. A reaction product of polyester), a reaction product of polyallylamine and polyester described in JP-A-9-169821 and the like, and a macromonomer described in JP-A-10-339949, JP-A-2004-37986 etc. Copolymers with nitrogen atom monomers, graft polymers having a partial skeleton or a heterocyclic ring of the organic dye described in Japanese Patent Application Laid-Open Nos. 2003-238837, 2008-9426, 2008-81732, etc. And copolymers of a macromonomer and an acid group-containing monomer described in JP-A-2010-106268, etc. It is. In particular, the amphoteric dispersion resin having a basic group and an acidic group described in JP2009-203462A is from the viewpoint of the dispersibility of the pigment dispersion, the dispersion stability, and the developability of the colored radiation-sensitive composition. Particularly preferred.

  A known macromonomer can be used as a macromonomer to be used when producing a graft type polymer having an anchor site to a pigment surface by radical polymerization, and a macromonomer AA-6 (terminally manufactured by Toagosei Co., Ltd.) Poly (methyl methacrylate) in which the group is methacryloyl, AS-6 (polystyrene in which the terminal group is methacryloyl), AN-6S (copolymer of styrene and acrylonitrile in which the terminal is methacryloyl), AB-6 Butyl acrylate having a methacryloyl group as the terminal group, Plaxel FM 5 (ε-caprolactone 5 molar equivalent adduct of 2-hydroxyethyl methacrylate) manufactured by Daicel Chemical Industries, Ltd., FA 10 L (2-hydroxyethyl acrylate) ε-caprolactone (10 molar equivalent adduct), and JP-A-2-2720 The polyester macromonomer etc. which are described in 09 are mentioned. Among these, polyester macromonomers that are particularly flexible and have excellent solvent-solvent properties are the dispersibility of the pigment dispersion, the dispersion stability, and the developability of the colored radiation-sensitive composition using the pigment dispersion. Particularly preferred is a polyester macromonomer represented by a polyester macromonomer described in JP-A 2-272009.

  As a block type polymer which has an anchor site | part to the pigment surface, the block type polymer of Unexamined-Japanese-Patent No. 2003-49110, 2009-52010 grade | etc., Is preferable.

  The pigment dispersant is also available as a commercial product, and as such specific examples, “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (containing an acid group) manufactured by BYK Chemie Polymers), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) "," BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), manufactured by EFKA Co., Ltd. " "EFKA 4047, 4050 to 4010 to 4165 (polyurethane-based), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (polycarbonate) Fatty acid polyester), 6745 (phthalocyanine) Conductor), 6750 (azo pigment derivative) "," Adispar PB 821, PB 822, PB 880, PB 881 "manufactured by Ajinomoto Fan Techno Co.," Flower TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co., Ltd.," Polyflow No. 50E, No. 300 (acrylic copolymer), manufactured by Kushimoto Chemical Co., Ltd. “Disparone KS-860, 873 SN, 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyether ester), DA-703-50, DA -705, DA-725 ", Kao Corporation" Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "," homogenol L-18 " (Polymer polycarboxylic acid), “Emulgen 920, 930, 935, 985 "Ethylene nonyl phenyl ether" "," Acetamine 86 (stearylamine acetate) ", manufactured by Nippon Lubrizol Co., Ltd." Sorsparse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 (Polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer), “Nikkole T106 (polyoxyethylene sorbitan monooleate), manufactured by Nikko Chemical Co., Ltd., MYS-IEX (polyoxyethylene Monostearate), manufactured by Kawaken Fine Chemical Co., Ltd. Hinoacto T-8000 E, etc., Shin-Etsu Chemical Co., Ltd. manufactured, organosiloxane polymer KP 341, manufactured by Yusho Co., Ltd. “W001: cationic surfactant”, Nonionic surfactants such as oxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, etc. Agent, anionic surfactant such as “W004, W005, W017”, etc., Morishita Sangyo Co., Ltd. “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 ", San Nopco's" Dispers Aid 6, Dispers Aid 8, Dispers Aid 15, Dispers Aid 9100 ", etc. Child dispersant, Adeka Co., Ltd. product "ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, P72, P77, P84, F87, P94, L101, P101, P103, F108, L121, P-123" And "Ionette S-20" manufactured by Sanyo Chemical Industries, Ltd. and the like.

  These pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant. The pigment dispersant may be used in combination with an alkali-soluble resin described later as a pigment dispersant together with a terminal modified polymer having an anchor site on the pigment surface, a graft polymer, and a block polymer. . In addition, you may use the compound represented by alkali-soluble resin and a general formula (ED) mentioned later as a pigment dispersant.

The content of the pigment dispersant in the pigment dispersion is preferably 1 to 80 parts by mass, more preferably 5 to 70 parts by mass, and 10 to 60 parts by mass with respect to 100 parts by mass of the pigment. More preferable.
Specifically, in the case of using a polymer dispersant, the use amount thereof is preferably in the range of 5 to 100 parts by mass conversion, and in the range of 10 to 80 parts based on 100 parts by mass of the pigment. Is more preferred.
Here, the amount of pigment means the total amount of the near infrared transmitting black pigment and the pigment different therefrom (that is, the pigment as the colorant (B)).

<Pigment derivative>
The pigment dispersion preferably further contains a pigment derivative.
The pigment derivative is a compound having a structure in which a part of the organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group. From the viewpoint of dispersibility and dispersion stability, the pigment derivative preferably contains a pigment derivative having an acidic group or a basic group.

Examples of organic pigments for constituting pigment derivatives include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments And isoindoline based pigments, isoindolinone based pigments, quinophthalone based pigments, srene based pigments, metal complex based pigments and the like.
Moreover, as an acidic group which a pigment derivative has, a sulfonic acid, carboxylic acid, and its quaternary ammonium salt are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is especially preferable. As a basic group which a pigment derivative has, an amino group is preferable and especially a tertiary amino group is preferable.

  As the pigment derivative, particularly, quinoline type, benzimidazolone type and isoindoline type pigment derivatives are preferable, and quinoline type and benzimidazolone type pigment derivatives are more preferable.

1-50 mass% is preferable with respect to the total mass of a pigment, and, as for content of the pigment derivative in a pigment dispersion liquid, 3-30 mass% is more preferable. The pigment derivative may use only 1 type and may use 2 or more types together.
When a pigment derivative is used in combination, the amount of the pigment derivative used is preferably in the range of 1 to 30 parts by mass conversion with respect to 100 parts by mass of the pigment, and more preferably in the range of 3 to 20 parts. Preferably, it is particularly preferably in the range of 5 to 15 parts.
Here, the amount of pigment means the total amount of the near infrared transmitting black pigment and the pigment different therefrom (that is, the pigment as the colorant (B)).

<Organic solvent>
The pigment dispersion preferably contains an organic solvent.
The organic solvent is selected depending on the solubility of each component contained in the pigment dispersion, and the coating property when the pigment dispersion is applied to a colored radiation-sensitive composition. As the organic solvent, esters, ethers, ketones and aromatic hydrocarbons are used. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, diethylene glycol monoethyl ether acetate, diethylene glycol mono Butyl ether acetate, propylene glycol methyl ether and propylene glycol monomethyl ether acetate are preferable, and it is also preferable to use (F) an organic solvent which can be contained in the colored radiation-sensitive composition described later.

  As content of the organic solvent in a pigment dispersion liquid, 50-95 mass% is preferable, and 70-90 mass% is more preferable.

<Polymer compound>
The pigment dispersion further contains a polymer compound from the viewpoints of improvement of dispersion stability and control of developability when the pigment dispersion is applied to a colored radiation-sensitive composition, in addition to the above-described components. It is also good.

As the polymer compound, for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer ( In particular, (meth) acrylic acid type copolymers having a carboxylic acid group and a polymerizable group in the side chain are preferable), naphthalene sulfonic acid formalin condensates and the like. Such a polymeric material adsorbs to the surface of the pigment and acts to prevent reaggregation, so a terminally modified polymer, a graft polymer, and a block polymer having an anchor site on the pigment surface Preferable examples include graft copolymers containing, as copolymer units, a monomer containing a heterocycle and a polymerizable oligomer having an ethylenically unsaturated bond.
Other polymer materials further include polyamidoamine phosphate, high molecular weight unsaturated polycarboxylic acid, polyether ester, aromatic sulfonic acid formalin polycondensate, polyoxyethylene nonylphenyl ether, polyester amine, polyoxyethylene sorbitan Monoolate polyoxyethylene monostearate etc. are mentioned.

These polymeric materials may be used alone or in combination of two or more.
As content of the polymeric material in a pigment dispersion liquid, 20-80 mass% is preferable with respect to a pigment, 30-70 mass% is more preferable, and 40-60 mass% is still more preferable.

[Preparation of Colored Radiation-Sensitive Composition]
The composition described above (typically, a composition for an infrared transmission filter comprising (A) a near infrared transmitting black colorant (for example, a pigment dispersion) and, if necessary, a colorant (B), A composition for an infrared transmission filter, comprising each component such as a polymerization initiator, (D) polymerizable compound and, if necessary, (E) ultraviolet absorber, (F) alkali soluble resin, (G) organic solvent, surfactant and the like It is a thing.
Here, the composition for an infrared transmission filter containing (A) near infrared transmitting black color material, (C) photopolymerization initiator, and (D) a polymerizable compound is a colored radiation sensitive composition (more preferably Can be said to be a black radiation sensitive composition).
This colored radiation-sensitive composition is used to form the infrared transmission filter of the present invention, and for example, a colored cured film obtained by polymerizing and curing the colored radiation-sensitive composition is used as the infrared transmission filter.
Hereinafter, each component which may be further contained in the composition (especially colored radiation-sensitive composition) in the present invention will be described in detail.
In the composition of the present invention, the total solid content refers to the total mass of components excluding the organic solvent from the total composition of the composition.

As used herein, the term "alkyl group" refers to a "linear, branched and cyclic" alkyl group, and may be substituted or unsubstituted.
Further, in the present specification, “(meth) acrylate” represents both or either of acrylate and methacrylate, “(meth) acrylic” represents both or either of acrylic and methacryl, ) Acryloyl "represents both or either of acryloyl and methacryloyl.

  In the present specification, "monomer" and "monomer" are synonymous. A monomer as used herein 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 refers to a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group involved in the polymerization reaction.

  Moreover, in the notation of the group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes those having no substituent as well as 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, the term "process" is included in the term if the intended function of the process is achieved, even if it can not be clearly distinguished from other processes, not only the independent process .
In the present invention, "radiation" means visible radiation, ultraviolet radiation, far ultraviolet radiation, electron beam, X-ray and the like.

<(C) Photopolymerization initiator>
The composition for infrared transmission filter (typically, colored radiation-sensitive composition) of the present invention preferably contains (C) a photopolymerization initiator.
As a photoinitiator (Hereinafter, it may only be mentioned a "polymerization initiator".) In this invention, what is known as a photoinitiator mentioned below can be used.

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

  As the photopolymerization initiator, for example, a halogenated hydrocarbon derivative (for example, one having a triazine skeleton, one having an oxadiazole skeleton, etc.), an acylphosphine compound such as an acyl phosphine oxide, a hexaarylbiimidazole, an oxime derivative And oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone and the like. Among these, oxime compounds are preferable.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include, for example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, an F. compound. C. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-58241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Patent No. 4212976 The compounds described in the specification, and the like can be mentioned.

  Examples of the compounds described in the above-mentioned US Pat. No. 4,129,976 include compounds having an oxadiazole skeleton (eg, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tribromomethyl-5-styryl-1,3,4- And the like.

  In addition, as polymerization initiators other than the above, acridine derivatives (eg, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, etc., polyhalogen compounds (eg, four) Carbon bromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone etc., coumarins (eg, 3- (2-benzofuranoyl) -7-diethylamino coumarin, 3- (2-benzofuroyl) -7- (1-) Pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis ( 5,7-Di-n-propoxycoumarin), 3,3'-carbo -Bis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-Pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, and also JP-A-5-19475 and JP-A-7-2721028. 2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, etc., coumarin compounds, etc., acyl phosphine oxides (eg, bis (2,4,4) , 6-Trimethylbenzoyl) -phenylphosphi Oxides, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenyl phosphine oxide, LucirinTPO, etc., metallocenes (eg, bis (η5-2,4-cyclopentadien-1-yl)- Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 5−5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.), Compounds described in JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and U.S. Pat. No. 3,615,455 can be mentioned.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-Ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or its tetramethyl ester, 4,4'-bis (dialkylamino) benzophenones (eg, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bisdicyclohexyl Amino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4'-dimethylamino bene Zophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butyl anthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (eg, benzoin methyl ether, benzoin ethyl ether, benzo Down propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

As a polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acyl phosphine compound can also be used suitably. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.
As a hydroxyacetophenone type initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (brand name: all are BASF Corporation make) can be used. As aminoacetophenone initiators, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Corp.) can be used. As the aminoacetophenone initiator, a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long wave light source such as 365 nm or 405 nm can also be used. Moreover, IRGACURE-819 and DAROCUR-TPO (brand name: all are BASF Corporation make) which are commercial items can be used as an acyl phosphine type initiator.

More preferably, an oxime compound is mentioned as a polymerization initiator.
Since the composition contains an oxime compound as a polymerization initiator, the property dependence of the pattern on the time from application of the composition to exposure (PCD: Post Coating Delay) (hereinafter, also simply referred to as "PCD dependence") ) Will be good.
As a specific example of an oxime compound, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-80068, and the compound of Unexamined-Japanese-Patent No. 2006-342166 can be used.

  Examples of oxime compounds such as oxime derivatives which can be suitably used as a polymerization initiator in the present invention include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one and 3-propionyloxyiminobutane -2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4- (4- Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like can be mentioned.

As oxime compounds, J.I. C. S. Perkin II (1979) pp. 1653-1660), J.F. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. The compounds described in JP-A-2000-80068, JP-A-2000-80068, JP-A-2004-534797, JP-A-2006-342166, and the like can be given.
Among commercially available products, IRGACURE OXE-01 (manufactured by BASF), IRGACURE OXE-02 (manufactured by BASF), and TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) are also suitably used.

  Further, as an oxime compound other than the above, a compound described in JP-A-2009-519904, in which an oxime is linked to the N-position of carbazole, a compound described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into a benzophenone moiety, Compounds described in JP-A-2010-15025 and U.S. Patent Publication 2009-292039, in which a nitro group is introduced to a dye site, ketooxime compounds described in WO2009-131189, the same triazine skeleton and oxime skeleton The compound described in US Pat. No. 7,556,910, which is contained in the molecule, or the compound described in JP-A 2009-221114, which has an absorption maximum at 405 nm and good sensitivity to a g-line light source may be used.

Preferably, the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A can also be suitably used. Among cyclic oxime compounds, cyclic oxime compounds fused to a carbazole dye described in JP-A-2010-32985 and JP-A-2010-185072 have high light absorption and high sensitivity. preferable.
In addition, the compound described in JP-A-2009-242469, which has an unsaturated bond at a specific site of the oxime compound, can also be suitably used, since high sensitivity can be achieved by regenerating the active radical from the polymerization inactive radical. it can.

Most preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-269779, and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.
Specifically, as the oxime compound, a compound represented by the following general formula (OX-1) is preferable. In addition, the N—O bond of the oxime may be an oxime compound of (E) form, an oxime compound of (Z) form, or a mixture of (E) form and (Z) form. .

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 nonmetal atomic group.
Examples of the monovalent nonmetal 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. Also, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by the other 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, an aryl group and the like.

  As an alkyl group which may have a substituent, a C1-C30 alkyl group is preferable. Specifically, the description in JP-A-2012-032556, paragraph 0026 and the like can be referred to, and the contents thereof are incorporated in the present specification.

  As an aryl group which may have a substituent, a C6-C30 aryl group is preferable. A C6-C30 aryl group is preferable. Specifically, the description in JP-A-2012-032556, paragraph 0027 and the like can be referred to, and the contents thereof are incorporated in the present specification.

  As an acyl group which may have a substituent, a C2-C20 acyl group is preferable. Specifically, the description in paragraph 0028 etc. of JP 2012-032556 A can be referred to, and the contents thereof are incorporated in the present specification.

  As an alkoxycarbonyl group which may have a substituent, a C2-C20 alkoxycarbonyl group is preferable. Specifically, the description in paragraph 0030 of JP 2012-032556 A can be referred to, and the contents thereof are incorporated in the present specification.

  As an aryloxy carbonyl group which may have a substituent, the description of Unexamined-Japanese-Patent No. 2012-032556 stage 0030 etc. can specifically be considered, and these content is integrated in this specification.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocycle containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
Specifically, the description in JP-A-2012-032556, paragraph 0031 and the like can be referred to, and the contents thereof are incorporated in the present specification.

  As an alkylthio carbonyl group which may have a substituent, the description of Unexamined-Japanese-Patent No. 2012-032556 stage 0032 etc. can be referred to, and these content is integrated in this-application specification.

  As the arylthiocarbonyl group which may have a substituent, specifically, the description in paragraph 0033 and the like of JP 2012-032556 A can be referred to, and the contents thereof are incorporated in the present specification.

  In the general formula (OX-1), the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. Also, these groups may have one or more substituents. As the substituent, the above-mentioned substituents can be exemplified. Moreover, the substituent mentioned above may be further substituted by the other substituent.

Among them, particularly preferred is the structure shown below.
In the following structures, Y, X and n have the same meanings as Y, X and n in General Formula (OX-2) described later, and preferred examples are also the same.

As a bivalent organic group represented by A in general formula (OX-1), a C1-C12 alkylene group, a cycloalkylene group, an alkynylene group is mentioned. Also, these groups may have one or more substituents. As the substituent, the above-mentioned substituents can be exemplified. Moreover, the substituent mentioned above may be further substituted by the other substituent.
Among them, as A in the formula (OX-1), from the viewpoint of enhancing sensitivity and suppressing coloring due to heating and aging, unsubstituted alkylene group, alkyl group (for example, methyl group, ethyl group, tert-butyl group, dodecyl) Group) substituted alkylene group, alkenyl group (eg, vinyl group, allyl group) substituted alkylene group, aryl group (eg, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group) Groups, phenanthryl groups, styryl groups) -substituted alkylene groups are preferred.

The aryl group represented by Ar in General Formula (OX-1) is preferably an aryl group having a carbon number of 6 to 30, and may have a substituent. As the substituent, those similar to the substituents introduced into the substituted aryl group mentioned as the specific example of the aryl group which may have a substituent can be exemplified.
Among them, a substituted or unsubstituted phenyl group is preferable from the viewpoint of enhancing sensitivity and suppressing coloring due to heating and aging.

  In Formula (OX-1), a structure in which the structure of “SAr” formed of Ar and S adjacent to each other is described in paragraph 0040 of JP 2012-032556 A, and the like is preferable. The contents of these are incorporated herein.

  The oxime compound is preferably a compound represented by the following general formula (OX-2).

(In the general formula (OX-2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n is 0) It is an integer of ~ 5.)
R, A and Ar in the general formula (OX-2) have the same meanings as R, A and Ar in the general formula (OX-1), and preferred examples are also the same.

  As the monovalent substituent represented by X in General Formula (OX-2), an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic ring And halogen atoms. Also, these groups may have one or more substituents. As the substituent, the above-mentioned substituents can be exemplified. Moreover, the substituent mentioned above may be further substituted by the other substituent.

Among these, as X in the general formula (OX-2), an alkyl group is preferable from the viewpoint of solvent solubility and improvement of absorption efficiency in a long wavelength region.
Moreover, n in general formula (OX-2) represents the integer of 0-5, and the integer of 0-2 is preferable.

  Examples of the divalent organic group represented by Y in General Formula (OX-2) include the structures shown below. In the groups shown below, "*" represents a bonding position between Y and the adjacent carbon atom in General Formula (OX-2).

  Among them, as the photopolymerization initiator, those having a structure shown below are preferable from the viewpoint of high sensitivity.

  Furthermore, it is preferable that an oxime compound is a compound represented by the following general formula (OX-3).

In general formula (OX-3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5 .
R, X, A, Ar and n in the general formula (OX-3) have the same meanings as R, X, A, Ar and n in the general formula (OX-2), and preferred examples are also the same. It is.

  Hereinafter, although the specific example of the oxime compound suitably used is shown below, this invention is not limited to these.

  The oxime compound has a maximum absorption wavelength in a wavelength range of 350 nm to 500 nm, preferably an absorption wavelength in a wavelength range of 360 nm to 480 nm, and particularly preferably one having a high absorbance at 365 nm and 455 nm.

The oxime compound preferably has a molar absorption coefficient at 365 nm or 405 nm of 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 200, from the viewpoint of sensitivity. And particularly preferably 1,000.
The molar absorption coefficient of the compound may be a known method, and specifically, for example, 0.01 g of ethyl acetate solvent is used in an ultraviolet-visible spectrophotometer (Varry Carry-5 spctrophotometer) It is preferable to measure at a concentration of / L.

The photopolymerization initiators used in the present invention may be used in combination of two or more as needed.
The content (total content in the case of two or more types) of the photopolymerization initiator in the composition for the infrared transmission filter is preferably in the range of 0.1 to 20% by mass with respect to the total solid content of the composition More preferably, it is in the range of 0.5 to 10% by mass, particularly preferably in the range of 1 to 8% by mass. Within this range, good sensitivity and patternability can be obtained.

  The composition for an infrared transmission filter may contain a sensitizer for the purpose of improving the radical generation efficiency of the photopolymerization initiator and increasing the photosensitive wavelength. As a sensitizer which can be used for this invention, what sensitizes with respect to above-mentioned (C) photoinitiator with an electron transfer mechanism or an energy transfer mechanism is preferable.

As a sensitizer used for the composition for infrared rays permeable filters, the compound described in stage number-of Unexamined-Japanese-Patent No. 2008-32803 is mentioned, for example.
The content of the sensitizer in the composition is preferably 0.1% by mass to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency to the deep part and initiation decomposition efficiency, and is preferably 0.5% % To 15% by mass is more preferable.
The sensitizers may be used alone or in combination of two or more.

<(D) polymerizable compound>
The composition for infrared ray transmission filter (typically, colored radiation-sensitive composition) of the present invention preferably contains (D) a polymerizable compound.
Specifically, the polymerizable compound is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Among them, a polyfunctional polymerizable compound having four or more functions is preferable, and five or more functions are more preferable.
Such compounds are widely known in the relevant industrial field, and they can be used in the present invention without particular limitation. These may be, for example, any of chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof and multimers thereof. The polymerizable compounds in the present invention may be used singly or in combination of two or more.

More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid etc.) and esters thereof, amides, etc. And multimers thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. is there. Also, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group etc. with monofunctional or polyfunctional isocyanates or epoxies, monofunctional or multifunctional Dehydration condensation products with functional carboxylic acids and the like are also suitably used. Also, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as isocyanate group and epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and halogen groups Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as tosyloxy group with monofunctional or polyfunctional alcohols, amines and thiols. As another example, instead of the above unsaturated carboxylic acid, it is also possible to use unsaturated phosphonic acid, a vinyl benzene derivative such as styrene, a vinyl ether, an allyl ether or the like, and a group of compounds replaced.
As these specific compounds, compounds described in Paragraph Nos. [0095] to [0108] of JP-A-2009-288705 can be suitably used in the present invention.

Further, as the polymerizable compound, a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or more under normal pressure is also preferable. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tritriol (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso Those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as anurate, glycerin or trimethylol ethane and then forming (meth) acrylate, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane (meth) acrylates as described in JP-A-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates which is a reaction product of an epoxy resin and (meth) acrylic acid, and mixtures thereof.
Polyfunctional (meth) acrylate obtained by reacting a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group with a polyfunctional carboxylic acid can also be mentioned.
Moreover, as a preferable polymerizable compound, it has a fluorene ring described in JP-A-2010-160418, JP-A-2010-129825, each patent, JP-A-4364216 and the like, and an ethylenically unsaturated group is bifunctional or more. It is also possible to use a compound having a cardo resin.

  Moreover, as a compound which has a boiling point of 100 degreeC or more under a normal pressure, and has at least 1 addition polymerizable ethylenic unsaturated group, Paragraph No. [0254]-[0257] of Unexamined-Japanese-Patent No. 2008-292970. The compounds described in are also suitable.

  In addition to the above, radically polymerizable monomers represented by the following formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the above general formula, n is 0 to 14 and m is 1 to 8. A plurality of R and T in one molecule may be identical to or different from each other.
In each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5), at least one of a plurality of R is -OC (= O) CH = CH ₂ or -OC (= O) represents a group represented by C (CH ₃ ) = CH ₂ .
As specific examples of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5), the compounds described in paragraph Nos. 0248 to 0251 of JP-A-2007-269779 are referred to. It can also be suitably used in the invention.

  Further, compounds obtained by adding ethylene oxide or propylene oxide to the above-mentioned polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof are also converted into (meth) acrylates, It can be used as a polymerizable compound.

Among them, as a polymerizable compound, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku Co., Ltd. Dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues.
In addition, as a polymerizable compound, 2- (meth) acryloyloxyethyl caproate acid phosphate (commercially available as PM-20 manufactured by Nippon Kayaku Co., Ltd.), urethane acrylate (commercially available as Shin-Nakamura Chemical Co., Ltd.) U-6 LPA) etc. are also mentioned suitably.
These oligomer types can also be used. The aspect of a preferable polymeric compound is shown below.

  The polymerizable compound is a polyfunctional monomer, and may have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. If the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is, but, if necessary, to the hydroxyl group of the above ethylenic compound Non-aromatic carboxylic acid anhydride may be reacted to introduce an acid group. In this case, specific examples of non-aromatic carboxylic acid anhydrides used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydride Maleic acid is mentioned.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. Polyfunctional monomers having an acid group are preferred,
Particularly preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. As a commercial item, M-510, M-520 etc. are mentioned, for example as a polybasic acid modified | denatured acryl oligomer by Toagosei Co., Ltd. make.

Although one of these polymerizable compounds may be used alone in the composition for an infrared transmission filter in the present invention, two of them may be used because it is difficult to obtain a single compound in the production of the polymerizable compound. You may mix and use the above.
Moreover, you may use together the polyfunctional monomer which does not have an acidic radical, and the polyfunctional monomer which has an acidic radical as a polymeric compound as needed.
As a preferable acid value of the polyfunctional monomer which has an acidic radical, it is 0.1-40 mg-KOH / g, Especially preferably, it is 5-30 mg-KOH / g. When the acid value of the polyfunctional monomer is too low, the development dissolution property is deteriorated, and when too high, the production and handling become difficult, the photopolymerization performance is deteriorated, and the curability such as the surface smoothness of the pixel is deteriorated. Therefore, in the case of using two or more kinds of polyfunctional monomers having different acid groups in combination, or in the case of using a polyfunctional monomer having no acid group, the acid group as the entire polyfunctional monomer is adjusted to fall within the above range. Is preferred.

Moreover, it is also a preferable aspect to contain the polyfunctional monomer which has a caprolactone structure as a polymeric compound.
The polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule, and examples thereof include trimethylol ethane, ditrimethylol ethane, trimethylol propane, ditrimethylol propane, pentaerythritol, and di Ε-caprolactone modified polyfunctional (meth) acrylate obtained by esterifying (meth) acrylic acid and ε-caprolactone with a polyhydric alcohol such as pentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine Can be mentioned. Among them, polyfunctional monomers having a caprolactone structure represented by the following general formula (Z-1) are preferable.

  In the general formula (Z-1), all six Rs are groups represented by the following general formula (Z-2), or 1 to 5 of the six Rs have the following general formula (Z And the remainder is a group represented by the following general formula (Z-3).

In general formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents 1 or 2, and "*" represents a bond.

In general formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond. )

Such polyfunctional monomers having a caprolactone structure are commercially available, for example, from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (1) to (3) , The number of groups represented by the formula (2) = 2, the compound wherein all R ¹ are hydrogen atoms, DPCA-30 (the same formula, m = 1, the number of the groups represented by the formula (2) = 3 , Compounds wherein R ¹ is all hydrogen atoms, DPCA-60 (same formula, m = 1, number of groups represented by formula (2) = 6, compounds wherein all R ¹ are hydrogen atoms), DPCA- And 120 (in the formula, m = 2, the number of groups represented by formula (2) = 6, a compound in which all R ^{1 s} are hydrogen atoms), and the like.
In the present invention, polyfunctional monomers having a caprolactone structure can be used alone or in combination of two or more.

The polymerizable compound in the present invention is preferably a polymerizable compound containing an alkyleneoxy group having 2 or more carbon atoms (e.g., an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, etc.).
Among the polymerizable compounds containing an alkyleneoxy group having 2 or more carbon atoms, at least one selected from the group of compounds represented by the following general formula (i) or (ii) is particularly preferable.

In the general formulas (i) and (ii), E each independently represents-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)- Each y independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom or a carboxyl group.
In General Formula (i), the total of acryloyl group and methacryloyl group represented by X is three or four, m each independently represents an integer of 0 to 10, and the sum of each m is 0 to 40 It is an integer. However, when the sum of each m is 0, any one of X is a carboxyl group.
In the general formula (ii), the total of acryloyl group and methacryloyl group represented by X is 5 or 6, n is each independently an integer of 0 to 10, and the sum of each n is 0 to 60. It is an integer. However, when the sum of each n is 0, any one of X is a carboxyl group.

In general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and, as for the sum of each m, the integer of 4-8 is especially preferable.
In general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Moreover, the integer of 3-60 is preferable, the integer of 3-24 is more preferable, and, as for the sum of each n, the integer of 6-12 is especially preferable.
In general formula (i) or formula (ii) in the _{- ((CH 2) y CH} 2 O) - or _{- ((CH 2) y CH} (CH 3) O) - , the oxygen atom side ends Preferred is a form in which X binds to X.

  The compounds represented by general formula (i) or (ii) may be used alone or in combination of two or more. In particular, in the general formula (ii), a form in which all six Xs are acryloyl groups is preferable.

  The compound represented by the general formula (i) or (ii) has a ring-opening skeleton by ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol which is a conventionally known step. The compound can be synthesized from the step of bonding and the step of introducing a (meth) acryloyl group by, for example, reacting (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opened skeleton. Each step is a well-known step, and those skilled in the art can easily synthesize a compound represented by general formula (i) or (ii).

Among the compounds represented by the general formulas (i) and (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples thereof include compounds represented by the following formulas (a) to (f) (hereinafter, also referred to as “exemplified compounds (a) to (f)”), and among them, exemplified compounds (a) and (f) b), (e) and (f) are preferred.

  In particular, as the polymerizable compound, the exemplified compound (b) is effective, and the effects of the present invention can be significantly improved.

  Commercially available products of the polymerizable compounds represented by the general formulas (i) and (ii) are, for example, SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmar, manufactured by Nippon Kayaku Co., Ltd. Examples include DPCA-60, which is a hexafunctional acrylate having six pentylene oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutylene oxy chains.

  Furthermore, as a polymerizable compound, Journal of Japan Adhesive Association Vol. 20, no. Those introduced as photocurable monomers and oligomers in 7 (pages 300 to 308) can also be used.

  The content of the polymerizable compound in the composition for an infrared transmission filter is preferably 2 to 50% by mass, more preferably 2 to 30% by mass, still more preferably 2 to 25% by mass with respect to the total solid content of the composition. % By mass is more preferred.

<(E) UV absorber>
Furthermore, it is preferable that the composition for infrared transmission filters of the present invention (typically, a colored radiation-sensitive composition) contains (E) a UV absorber.
The ultraviolet absorber is a compound having an absorption coefficient of more than 100 per 1 g at a wavelength of 365 nm and 10 or less per 1 g of a wavelength of 400 nm or more. In addition, an absorption coefficient is a value measured by the ultraviolet visible spectrophotometer (Varian make, Carry-5 spectrophotometer) at the density | concentration of 0.01 g / L using an ethyl acetate solvent.

  When the absorption coefficient per 1 g at a wavelength of 365 nm is 100 or less, the addition amount for obtaining the ultraviolet absorption effect increases and the prescription likelihood decreases. When the absorption coefficient per 1 g at a wavelength of 400 nm or more exceeds 10, visible It is not preferable because it affects the device spectrum of the area.

  As a ultraviolet absorber in this invention, the compound represented by the following general formula (I) which is a conjugated diene type compound is preferable. When this conjugated diene-based compound is used, the fluctuation of development performance is suppressed especially when low illuminance exposure is performed, and the exposure illuminance dependency related to the pattern lineability of the pattern line width, film thickness, spectral spectrum, etc. It can be more effectively suppressed.

In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² May be the same as or different from each other, but do not simultaneously represent a hydrogen atom.

The alkyl group represented by R ¹ and R ² may have a substituent, and as the substituent of the alkyl group having a substituent, for example, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, Acyloxy group, halogen atom, acylamino group, acyl group, alkylthio group, arylthio group, hydroxy group, cyano group, alkyloxycarbonyl group, aryloxycarbonyl group, substituted carbamoyl group, substituted sulfamoyl group, nitro group, substituted amino group, alkyl A sulfonyl group, an arylsulfonyl group, etc. are mentioned.

The aryl group having 6 to 20 carbon atoms represented by R ¹ and R ² may be a single ring or a condensed ring, and may be a substituted aryl group having a substituent or an unsubstituted aryl group. It may be.

Also, R ¹ and R ² may form a cyclic amino group together with the nitrogen atom. Examples of the cyclic amino group include piperidino group, morpholino group, pyrrolidino group, hexahydroazepino group, piperazino group and the like.

Among the above, as R ¹ and R ² , a lower alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, octyl 2-ethylhexyl, tert-octyl, etc., or substituted or unsubstituted phenyl groups (eg, tolyl, phenyl, anisyl, mesityl, chlorophenyl, 2,4-di-t-amylphenyl etc.) preferable. It is also preferable that R ¹ and R ² be combined to form a ring (eg, a piperidine ring, a pyrrolidine ring, a morpholine ring, etc.) containing a nitrogen atom represented by N in the formula.

In the general formula (I), R ³ and R ⁴ represent an electron withdrawing group. Here, the electron withdrawing group is an electron withdrawing group having a Hammett's substituent constant σ _p value (hereinafter simply referred to as “σ _p value”) of 0.20 or more and 1.0 or less. Preferably, it is an electron withdrawing group having a σ _p value of 0.30 or more and 0.8 or less.
Hammett's law, in 1935, used L. L. et al. To quantitatively discuss the effects of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by the Hammett's rule include σ _p values and σ _m values, and these values are described in many general textbooks. A. Dean, "Lange's Handbook of Chemistry", 12th Edition, 1979 (Mc Graw-Hill) and "Regional Development of Chemistry", No. 122, pp. 96-103, 1979 (Nanegado), Chemical Reviews, Vol. Pp. 165-195 (1991). In the present invention, it does not mean that the values known in the literature are limited to only certain substituents described in these documents, but even if the value is unknown based on Hammett's law, it is within the range Of course, it is included as long as it is included in.

Specific examples of the electron withdrawing group having a σ _p value of 0.20 or more and 1.0 or less include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, Dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, at least An alkyl group substituted by two or more halogen atoms, an alkoxy group substituted by at least two or more halogen atoms, an aryloxy group substituted by at least two or more halogen atoms, and at least two or more halogen atoms Substituted alkyl groups Amino group, at least two an alkylthio group substituted with a halogen atom, sigma _p value of 0.20 or more other electron-withdrawing aryl group substituted with group, a heterocyclic group, a chlorine atom, a bromine atom, an azo group And selenocyanate groups. Among these substituents, a group capable of further having a substituent may further have a substituent as mentioned above.

Among the above, in the present invention, R ³ is preferably a group selected from a cyano group, -COOR ⁵ , -CONHR ⁵ , -COR ⁵ , -SO ₂ R ⁵ , and R ⁴ is cyano ^{group, -COOR 6, -CONHR 6, -COR} 6, a group selected from _-SO 2 ^{R 6} is preferred. R ⁵ and ^{R 6} each independently represents an alkyl group, or an aryl group having 6 to 20 carbon atoms having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms represented by R ⁵ and R ^{6 have the same} meanings as in the case of R ¹ and R ² , and preferred embodiments are also the same.
Among them, R ³ and R ⁴ are preferably an acyl group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, sulfamoyl group Particularly, an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group and a sulfamoyl group are preferable.
Also, R ³ and R ⁴ may be bonded to each other to form a ring.

In addition, at least one of the above R ¹ , R ² , R ³ and R ⁴ may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. Also, it may be a copolymer with another monomer.
When it is the above-mentioned copolymer, examples of other monomers include acrylic acid, α-chloroacrylic acid, α-alacrylic acid (eg, esters derived from acrylic acids such as methacrylic acid, preferably lower alkyl esters) And amides (eg, acrylamide, methacrylamide, t-butyl acrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-hexyl) Acrylate, octyl methacrylate, and lauryl methacrylate, methylene bis acrylamide etc.), vinyl esters such as vinyl acetate, vinyl propionate, vinyl laurate etc., acrylonitrile Lyl, methacrylonitrile, aromatic vinyl compounds (eg, styrene and derivatives thereof such as vinyltoluene, divinylbenzene, vinylacetophenone, sulfostyrene, and styrenesulfinic acid), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, There are vinyl alkyl ether (for example, vinyl ethyl ether etc.), maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, 2- and 4-vinylpyridine and the like.
Among these, acrylic esters, methacrylic esters and aromatic vinyl compounds are particularly preferred.
Two or more comonomer compounds can also be used together. For example, n-butyl acrylate and divinylbenzene, styrene and methyl methacrylate, methyl acrylate and methacrylate acid can be used.

  Hereinafter, preferable specific examples [exemplified compounds (1) to (14)] of the compound represented by the general formula (I) will be shown. However, the present invention is not limited to these.

  The compounds represented by the above general formula (I) are disclosed in JP-B-44-29620, JP-A-53-128333, JP-A-61-169831, JP-A-63-53543, JP-A-63-53543. The compound can be synthesized by the method described in JP-A-63-53544 and JP-A-63-56651.

In the present invention, the various ultraviolet absorbers may be used alone or in combination of two or more.
The composition for an infrared transmission filter may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is in terms of mass relative to the total solid mass of the composition of the present invention, The content is preferably 0.01% or more and 10% or less, and more preferably 0.01% or more and 5% or less.
When the content of the ultraviolet absorber is less than this range, the roughness of the side wall in the colored pattern is deteriorated, and a fine pattern shape (particularly, a rectangle) can not be formed finely. Decreases.

  Moreover, as a ratio (E / C) of the (E) ultraviolet absorber with respect to the said (C) photoinitiator, it is 0.25-1.25 on a mass basis. If the ratio E / C is less than 0.25, the roughness of the side walls in the colored pattern is deteriorated, and a fine pattern shape (particularly, a rectangle) can not be formed finely, and if it exceeds 1.25, The sensitivity is reduced. Among them, the ratio E / C is preferably in the range of 0.3 to 1.1, and more preferably in the range of 0.4 to 1.0, for the same reason as described above.

  Furthermore, the composition of the present invention can contain components such as (F) an alkali soluble resin, an organic solvent, a surfactant and the like.

<(F) Alkali-soluble resin>
It is also preferable that the composition for infrared transmission filter (typically, colored radiation-sensitive composition) of the present invention further contains (F) an alkali-soluble resin. By containing the alkali-soluble resin, developability and pattern formation are improved.
The alkali-soluble resin may be a linear organic polymer, and at least one alkali-soluble resin in a molecule (preferably, a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a promoting group.

The alkali soluble resin will be described.
As the alkali-soluble resin, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable from the viewpoint of heat resistance, and from the viewpoint of control of developability, Acrylic resins, acrylamide resins and acrylic / acrylamide copolymer resins are preferred.
Examples of groups promoting alkali solubility (hereinafter, also referred to as acid groups) include, for example, carboxyl groups, phosphoric acid groups, sulfonic acid groups, and phenolic hydroxyl groups, but they are soluble in organic solvents and developed with weak alkaline aqueous solutions. Possible are preferred, and (meth) acrylic acid is mentioned as being particularly preferred. These acid groups may be of only one type, or of two or more types.
As a monomer capable of providing an acid group after the polymerization, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, 2-isocyanatoethyl (meth) And monomers having an isocyanate group such as acrylate. The monomers for introducing these acid groups may be only one type or two or more types. In order to introduce an acid group into an alkali-soluble binder, for example, a monomer having an acid group and / or a monomer capable of providing an acid group after polymerization (hereinafter, may be referred to as “monomer for introducing an acid group”). ) May be polymerized as a monomer component. In addition, when introduce | transducing an acidic radical by using as a monomer component the monomer which can provide an acidic radical after superposition | polymerization, the process for providing an acidic radical which is mentioned later after superposition | polymerization is needed.

  For example, a known radical polymerization method can be applied to the production of the alkali-soluble resin. The polymerization conditions such as temperature, pressure, kind of radical initiator and amount thereof, kind of solvent, etc. when producing an alkali-soluble resin by radical polymerization method can be easily set by those skilled in the art, and the conditions are determined experimentally. You can also do so.

  As the alkali-soluble resin, a polymer having a carboxylic acid in a side chain is preferable. As such a polymer, the description in paragraph 0253 of JP 2012-162684 A can be referred to, and the contents thereof are incorporated in the present specification. .

As the alkali-soluble resin, it is preferable to contain a resin (a) having a repeating unit derived from a compound represented by the following general formula (ED) (hereinafter, also appropriately referred to as “ether dimer”).
By using the resin (a), the composition in the present invention can be made to have good PCD dependency.

In general formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group.

In the general formula (ED), the hydrocarbon group represented by R ¹ and R ² is preferably a hydrocarbon group having 1 to 25 carbon atoms.
Moreover, the said hydrocarbon group may have a substituent.
The above-mentioned hydrocarbon group is not particularly limited, but, for example, a straight chain such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl etc. Or branched alkyl groups; aryl groups such as phenyl; alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; Examples thereof include an alkoxy-substituted alkyl group such as 1-methoxyethyl and 1-ethoxyethyl; an alkyl group substituted by an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like, and a primary or secondary carbon substituent which is not easily released by heat is preferable in view of heat resistance.

  As a specific example of the said ether dimer, description of Unexamined-Japanese-Patent No. 2012-162684 Paragraph 0257 grade | etc. Can be considered, and these content is integrated in this-application specification.

  The proportion of the ether dimer in the monomer for obtaining the resin (a) is not particularly limited, but is preferably 2 to 60% by mass, more preferably 5 to 55% by mass, and still more preferably in the total monomer components. Is 5 to 50% by mass.

  The resin (a) may be a copolymer obtained by copolymerizing other monomers with an ether dimer.

  Other monomers copolymerizable with the ether dimer include, for example, a monomer for introducing an acid group, a monomer for introducing a radically polymerizable double bond, and an epoxy group. Monomers, and other copolymerizable monomers other than these may be mentioned. Such monomers may be used alone or in combination of two or more.

As a monomer for introducing an acid group, for example, a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid, a monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, maleic anhydride, anhydride The monomer etc. which have carboxylic acid anhydride groups, such as itaconic acid, etc. are mentioned. Among these, (meth) acrylic acid is particularly preferable.
Further, the monomer for introducing an acid group may be a monomer capable of giving an acid group after polymerization, and for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, The monomer which has epoxy groups, such as glycidyl (meth) acrylate, the monomer which has isocyanate groups, such as 2-isocyanato ethyl (meth) acrylate, etc. are mentioned. When using a monomer for introducing a radically polymerizable double bond, when using a monomer capable of giving an acid group after polymerization, it is necessary to carry out a treatment for giving an acid group after polymerization. The treatment for providing an acid group after polymerization varies depending on the type of monomer, and examples thereof include the following treatments. In the case of using a monomer having a hydroxyl group, for example, a treatment of adding an acid anhydride such as succinic acid anhydride, tetrahydrophthalic acid anhydride, maleic acid anhydride and the like can be mentioned. In the case of using a monomer having an epoxy group, for example, a compound having an amino group and an acid group such as N-methylaminobenzoic acid, N-methylaminophenol or the like is added, or, for example, (meth) acrylic Examples of the treatment include adding an acid anhydride such as succinic acid anhydride, tetrahydrophthalic acid anhydride and maleic acid anhydride to a hydroxyl group formed after the addition of an acid such as an acid. In the case of using a monomer having an isocyanate group, for example, treatment to which a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid is added can be mentioned.

  When the monomer for obtaining the resin (a) contains a monomer for introducing an acid group, the content is not particularly limited, but 5 to 70% by mass in all the monomer components Preferably, it is 10 to 60% by mass.

  Examples of monomers for introducing a radically polymerizable double bond include, for example, monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride Monomers having an epoxy group; monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m- or p-) vinylbenzyl glycidyl ether; . When using a monomer for introducing a radically polymerizable double bond, it is necessary to carry out a treatment for giving a radically polymerizable double bond after polymerization. The treatment for providing a radically polymerizable double bond after polymerization differs depending on the type of the monomer capable of providing a radically polymerizable double bond, and examples thereof include the following treatments. In the case of using a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m- or p-) A treatment in which a compound having an epoxy group such as vinylbenzyl glycidyl ether and a radically polymerizable double bond is added. In the case of using a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride, a treatment of adding a compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a radically polymerizable double bond Can be mentioned. When using a monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m- or p-) vinylbenzyl glycidyl ether, (meth) The process to which the compound which has acidic radicals, such as acrylic acid, and a radically polymerizable double bond is added is mentioned.

  When the monomer for obtaining the resin (a) contains a monomer for introducing a radically polymerizable double bond, the content ratio thereof is not particularly limited, but it is preferably 5 to 5% of all monomer components. 70 mass% is preferable, and more preferably 10 to 60 mass%.

As a monomer for introducing an epoxy group, for example, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m- or p-) vinylbenzyl glycidyl ether, etc. It can be mentioned.
When the monomer for obtaining the resin (a) contains a monomer for introducing an epoxy group, the content is not particularly limited, but 5 to 70% by mass in all the monomer components Preferably, it is 10 to 60% by mass.

  As another copolymerizable monomer, the description of Unexamined-Japanese-Patent No.2012-0466929 Paragraph 0328 grade can be considered, for example, and these content is integrated in this-application specification.

  When the monomer for obtaining the resin (a) contains other copolymerizable monomers, the content is not particularly limited, but 95% by mass or less is preferable, and 85% by mass or less More preferable.

The weight average molecular weight of the resin (a) is not particularly limited, but from the viewpoint of the viscosity of the colored radiation sensitive composition and the heat resistance of the coating film formed by the composition, it is preferably 2000 to 200000, more preferably It is 5000-100000, More preferably, it is 5000-20000.
When the resin (a) has an acid group, the acid value is preferably 30 to 500 mg KOH / g, more preferably 50 to 400 mg KOH / g.

The resin (a) can be easily obtained by polymerizing at least the above-mentioned monomers essentially containing an ether dimer. At this time, a cyclization reaction of the ether dimer proceeds simultaneously with the polymerization to form a tetrahydropyran ring structure.
There is no restriction | limiting in particular as a polymerization method applied to the synthesis | combination of resin (a), Although the conventionally well-known various polymerization methods can be employ | adopted, it is especially preferable to be based on the solution polymerization method. Specifically, for example, the resin (a) can be synthesized according to the method for synthesizing the resin (a) described in JP-A-2004-300204.

  Hereinafter, although the exemplary compound of resin (a) is shown, this invention is not limited to these. The composition ratio of the exemplified compounds shown below is mol%.

  Among these alkali-soluble resins, particularly preferred are benzyl (meth) acrylate / (meth) acrylic acid copolymer and benzyl (meth) acrylate / (meth) acrylic acid / other monomer carnal multicomponent Polymer is included. In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate, 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 macromonomer / Benzyl methacrylate / methacrylic acid copolymer and the like.

Moreover, in order to improve the crosslinking efficiency of the composition in the present invention, an alkali-soluble resin having a polymerizable group may be used.
As an alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acrylic group, an allyloxyalkyl group or the like in a side chain is useful. As an alkali-soluble resin containing these polymerizable groups, an isocyanate group and an OH group are reacted in advance to leave one unreacted isocyanate group, and a compound containing a (meth) acryloyl group and an acrylic resin containing a carboxyl group And an unsaturated group-containing acrylic resin obtained by the reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule. Resin, acid pendant epoxy acrylate resin, polymerizable double bond-containing acrylic resin obtained by reacting acrylic resin containing OH group with dibasic acid anhydride having polymerizable double bond, acrylic resin containing OH group and isocyanate JP-A-2002-229207 discloses a resin in which a compound having a polymerizable group is reacted. Resin obtained by basic treatment of a resin having an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2003-335814. And the like.

The acid value of the alkali-soluble resin is preferably 30 mg KOH / g to 200 mg KOH / g, more preferably 50 mg KOH / g to 150 mg KOH / g, and most preferably 70 to 120 mg KOH / g.
Moreover, as a weight average molecular weight (Mw) of alkali-soluble resin, 2,000-50,000 are preferable, 5,000-30,000 are more preferable, 7,000-20,000 are the most preferable.

  The content of the alkali-soluble resin in the composition for an infrared transmission filter is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, based on the total solid content of the composition, particularly preferably Is 3 to 10% by mass.

<(G) Organic solvent>
The composition of the present invention (typically, a colored radiation-sensitive composition) preferably contains (G) an organic solvent.
Examples of the organic solvent (G) include the following.
As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate ( For example, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc.), 3-oxypropionic acid alkyl esters (eg, Methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate etc.), 2- Oxypro Alkyl acid esters (eg, methyl 2-hydroxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropion) Propyl, 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-methyl propionate etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate etc. And as ethers, for example, Ethylene 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 monomethyl ether acetate, propylene Glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone etc., and aromatic hydrocarbons such as toluene, xylene etc. Is preferably mentioned.

The organic solvents may be used alone or in combination of two or more.
When two or more organic solvents are used in combination, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid is particularly preferable. A mixed solution composed of two or more selected from methyl, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate

  The amount of the organic solvent contained in the composition for an infrared transmission filter is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, with respect to the total amount of the composition. More preferably, it is 25% by mass to 75% by mass.

<Sensitizer>
The composition for infrared transmission filter (typically, colored radiation-sensitive composition) of the present invention has a sensitizer for the purpose of improving the generation efficiency of the initiation species of the polymerization initiator and increasing the photosensitive wavelength. You may contain. As a sensitizer, the sensitizer which has an absorption wavelength in the wavelength range of 300 nm-450 nm is mentioned.

  Examples of sensitizers include phenanthrene, anthracene, pyrene, perylene, triphenylene, polynuclear aromatics such as 9, 10-dialkoxyanthracene, fluorescein, eosin, erythrosine, rhodamine B, xanthene such as rose bengal. , Thioxanthones, Cyanines, Merocyanines, Phthalocyanines, Thionines, Thiazines such as Methylene Blue, Toluidine Blue, Acridines, Anthraquinones, Squariums, Coumarins, Phenothiazines, Phenazines, Styrylbenzenes, Azo Compounds , Diphenylmethane, triphenylmethane, distyrylbenzenes, carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyrromethene compounds, pyrazo Triazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, aromatic ketone compounds such as Michler's ketone, and heterocyclic compounds such as N- aryl oxazolidinone and the like.

<Chain transfer agent>
Depending on the photopolymerization initiator to be used, it is preferable to add a chain transfer agent to the composition for infrared transmission filter of the present invention (typically, a colored radiation-sensitive composition). Examples of chain transfer agents include N, N-dialkylaminobenzoic acid alkyl esters and thiol compounds, and examples of thiol compounds include 2-mercaptobenzothiazole, 2-mercapto-1-phenylbenzimidazole and 3-mercaptopropion An acid etc. can be used individually or in mixture of 2 or more types.

<Polymerization inhibitor>
In the composition for infrared transmission filter (typically, colored radiation-sensitive composition) in the present invention, unnecessary thermal polymerization of the polymerizable compound is prevented during the production or storage of the colored radiation-sensitive composition. It is desirable to add a small amount of a polymerization inhibitor in order to
As a polymerization inhibitor which can be used in the present invention, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-) t-Butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine cerous salt and the like. Among them, p-methoxyphenol is preferred.
The addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the composition.

<Substrate adhesive agent>
Furthermore, in the present invention, a substrate adhesion agent capable of improving substrate adhesion may be added to the composition for infrared transmission filter (typically, colored radiation-sensitive composition).
As the substrate adhesion agent, it is preferable to use a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent. As a silane coupling agent, for example, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyl Trimethoxysilane, γ-aminopropyltriethoxysilane, phenyltrimethoxysilane, and the like can be mentioned. Among them, γ-methacryloxypropyltrimethoxysilane is preferable as the substrate adhesion agent.

  The content of the substrate adhesion agent is the total solid content of the composition for infrared transmission filter of the present invention from the viewpoint of leaving no residue in the unexposed area when the composition for infrared transmission filter is exposed and developed. In contrast, the content is preferably 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 20% by mass, and particularly preferably 1% by mass to 10% by mass .

<Surfactant>
Various surfactants may be added to the composition for infrared transmission filter (typically, colored radiation-sensitive composition) of the present invention from the viewpoint of further improving the coating property. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, a silicone surfactant and the like can be used.

In particular, the composition for an infrared transmission filter contains a fluorine-based surfactant to further improve the liquid properties (in particular, the flowability) when prepared as a coating liquid, and therefore uniformity of the coating thickness and saving of the coating thickness. Liquidity can be further improved.
That is, in the case of film formation using a coating liquid to which a composition containing a fluorine-based surfactant is applied, the wettability to the surface to be coated is reduced by reducing the interfacial tension between the surface to be coated and the coating liquid. Is improved, and the coatability on the surface to be coated is improved. For this reason, even in the case where a thin film of about several μm is formed with a small amount of liquid, it is effective in that film formation with a uniform thickness with small thickness unevenness can be more suitably performed.

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

  Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F44, R30, F437, F475, F479, and the like. The F482, the F554, the F780, the F781 (above, made by DIC Corporation), the Florard FC430, the same FC431, the same FC171 (above, Sumitomo 3M Co., Ltd.), Surfron S-382, the same SC-101 The SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (all manufactured by Asahi Glass Co., Ltd.) and the like can be mentioned.

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerine ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl 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, Sol Perth 20000 (manufactured by Nippon Lubrizol Corporation), and the like.

  Specific examples of cationic surfactants 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 poly flow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

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

  As silicone type surfactant, for example, Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, Toray silicone SH8400 (more than Toray Dow Corning ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, made by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (above, Shin-Etsu Silicone Co., Ltd.) , BYK 307, BYK 323, BYK 330 (above, manufactured by Big Chemie Co., Ltd.), and the like.

Only one surfactant may be used, or two or more surfactants may be combined.
The amount of surfactant added is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass, based on the total solid content of the composition for a color filter. is there.

<Other ingredients>
In the composition for infrared ray transmission filter (typically, colored radiation-sensitive composition) in the present invention, chain transfer such as N, N-dialkylaminobenzoic acid alkyl ester or 2-mercaptobenzothiazole, if necessary Agents, thermal polymerization initiators such as azo compounds and peroxide compounds, thermal polymerization components, ultraviolet light absorbers such as multifunctional thiols and epoxy compounds, alkoxybenzophenones for the purpose of enhancing film strength and sensitivity, and dioctyl phthalate It may contain various additives such as plasticizers, developability improvers such as low molecular weight organic carboxylic acids, other fillers, polymer compounds other than the above-mentioned specific binders and alkali-soluble resins, antioxidants, anticoagulants, etc. it can.
Also, a thermosetting agent can be added to increase the degree of curing of the film by post-heating after development. Examples of the thermosetting agent include azo compounds, thermal polymerization initiators such as peroxides, novolak resins, resol resins, epoxy compounds, styrene compounds and the like.

The composition for an infrared transmission filter of the present invention has a light transmittance in the thickness direction of the film of at most 20% at a wavelength of 400 to 650 nm when the film having a film thickness of 0.5 μm is formed. The minimum value of the light transmittance in the thickness direction of the film in the range of wavelength 800 nm to 1300 nm is preferably 80% or more.
The requirements for the light transmittance may be achieved by any means, but, for example, by adjusting the type and content of the near infrared transmitting black colorant (more specifically, the near infrared transmitting) By making the kind and content of the black coloring material the above-mentioned preferable ones, the condition of the light transmittance can be suitably achieved.

In the composition for an infrared transmission filter of the present invention, when a film having a thickness of 0.5 μm is formed, the standard deviation of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 630 nm is 6.0. The following is preferable, 4.0 or less is more preferable, and 3.0 or less is particularly preferable.
The requirements for the light transmittance may be achieved by any means, but, for example, a bisbenzofuranone-based pigment is used as a near-infrared transmissive black colorant, and the pigment concentration in the film is 20 to 80. It can be suitably achieved by setting the content to be in mass%, more preferably 40 to 80 mass%, particularly preferably 50 to 80 mass%.
Further, as described above, the standard deviation can be further reduced by using the near-infrared transmissive black coloring material in combination with a chromatic coloring agent as the coloring agent (B).

[Preparation of Colored Radiation-Sensitive Composition]
The composition for the infrared transmission filter in the present invention may be prepared by using the above-described near-infrared transmission black color material (when the near-infrared transmission black color material is a near-infrared transmission black pigment, preparing a pigment dispersion in advance Stirring and mixing together with each component such as a photopolymerization initiator, a polymerizable compound, and, if necessary, a UV absorber, an alkali-soluble resin, a surfactant, and the like, the following filtration is performed if necessary, and a coloring feeling Radioactive compositions can be prepared.

The colored radiation-sensitive composition in the present invention is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects. It can be used without particular limitation as long as it is conventionally used for filtration applications and the like. For example, a filter made of a fluorine resin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon-6 or nylon-6, 6, a polyolefin resin such as polyethylene or polypropylene (including high density and ultrahigh molecular weight) It can be mentioned. Among these materials, polypropylene (including high density polypropylene) is preferable.
The pore diameter of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 2.5 μm, and more preferably about 0.01 to 2.0 μm. By setting this range, it is possible to reliably remove fine foreign substances that inhibit the preparation of uniform and smooth colored radiation-sensitive compositions in the subsequent steps.

When using filters, different filters may be combined. At this time, the filtering with the first filter may be performed only once or may be performed twice or more.
Moreover, you may combine the 1st filter of the hole diameter which is different within the range mentioned above. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it is possible to select from various filters provided by Nippon Pall Ltd., Advantech Toyo Ltd., Nippon Entegris Ltd. (old Japan Microlith Ltd.) or Kitz Micro Filter Inc. .
The second filter can be formed of the same material as the first filter described above.
For example, the filtering with the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

[Production of infrared ray transmission filter by colored radiation-sensitive composition]
Next, the infrared ray transmission filter of the present invention and the method of manufacturing the same will be described.
The infrared ray transmission filter of the present invention is formed from the composition for infrared ray transmission filter of the present invention described above, but on the substrate, the composition for infrared ray transmission filter of the present invention (preferably colored radiation sensitive composition It is preferable to have a colored region (colored pattern) (preferably, a black region (black pattern)) obtained by using the
Hereinafter, the infrared ray transmission filter of the present invention will be described in detail through a method for producing the same (a method for producing an infrared ray transmission filter of the present invention).

The method of forming colored pixels constituting the infrared transmission filter of the present invention is a method of preparing the above-mentioned colored radiation-sensitive composition and providing it by the photolithographic method, or preparing the above-mentioned colored radiation-sensitive composition A method such as a method of providing can be adopted.
Among these, a method of preparing a colored radiation-sensitive composition and providing it by a photolithography method is a preferred embodiment because it is easy to provide a fine pattern in an arbitrary shape.
Hereinafter, a method of preparing an infrared transmission filter for solid-state imaging device application by preparing a colored radiation-sensitive composition and providing each colored pixel by a photolithographic method will be described. It is not limited.

  The method for producing an infrared ray transmitting filter of the present invention comprises the steps of applying the above-mentioned colored radiation-sensitive composition on a substrate to form an infrared ray transmitting composition layer (colored layer) (colored layer forming step); The method is characterized by including a step of exposing the composition layer in a pattern (exposure step), and a step of developing the infrared ray transmitting composition layer after exposure to form a pattern (developing step).

<Colored layer formation process>
In the colored layer forming step, the colored radiation-sensitive composition is applied onto the substrate body to form a colored layer (infrared ray transmitting composition layer) composed of the colored radiation-sensitive composition.

As a substrate that can be used in this process, for example, CCD used in solid-state imaging device, photoelectric conversion element substrate in CMOS organic CMOS, silicon substrate etc., alkali-free glass used in liquid crystal display etc., soda glass, Pyrex (registration Trademarks) glass, quartz glass, and those having a transparent conductive film attached thereto, and the like. These substrates may have a black matrix formed to isolate each pixel.
Moreover, on these substrates, if necessary, a subbing layer may be provided to improve the adhesion with the upper layer, to prevent the diffusion of substances, or to planarize the substrate surface.

  As a coating method of the colored radiation-sensitive composition of the present invention on a substrate, various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, screen printing can be applied. .

  Drying (pre-baking) of the colored layer (infrared ray transmitting composition layer) applied on the substrate can be carried out at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds with a hot plate, an oven or the like.

  The film thickness after drying (pre-baking) of the colored layer is in the range of 0.55 μm to 1.8 μm, preferably 0.60 μm to less than 1.8 μm, and more preferably 0.70 μm to 1.6 μm, 0.80 micrometers or more and 1.4 micrometers or less are especially preferable.

<Exposure process>
In the exposure step, the colored layer (infrared ray transmitting composition layer) formed in the colored layer forming step is exposed in a pattern.
In the exposure in this step, it is preferable to perform the exposure of the colored layer by exposing it through a predetermined mask pattern and curing only the colored layer irradiated with light. As the radiation that can be used for exposure, particularly radiations such as g-rays, h-rays and i-rays are preferably used, and i-rays are particularly preferable. Irradiation dose is preferably ^{30mJ / cm 2 ~1500mJ / cm 2} , more preferably ^{50mJ / cm 2 ~1000mJ / cm 2} , 80mJ / cm 2 ~500mJ / cm 2 being most preferred.

<Development process>
Subsequent to the exposure step, an alkali development treatment (developing step) is carried out to elute the uncured part after exposure to the developer and leave the photocured part. This development step can form a patterned film composed of colored pixels.
The development method may be any of a dip method, a shower method, a spray method, a paddle method, etc. These may be combined with a swing method, a spin method, an ultrasonic method or the like.
Before the developer is touched, the surface to be developed may be moistened with water or the like in advance to prevent uneven development.

As a developing solution, an organic alkali developing solution which does not cause damage to a circuit of a base or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.
Examples of the alkaline agent contained in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4, 0] organic alkaline compounds such as -undecene, and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate and the like.
As a developing solution, an alkaline aqueous solution diluted with pure water is preferably used so that the concentration of these alkaline agents is 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass. . When a developer composed of such an alkaline aqueous solution is used, generally, after development, the developer is washed (rinsed) with pure water to wash away excess developer and then dried.

In the production method of the present invention, after performing the colored layer forming step, the exposing step, and the developing step described above, the formed colored pattern is cured by post-heating (post-baking) or post-exposure if necessary. A curing step may be included. Post-baking is a heat treatment after development for complete curing, and is usually heat-cured at 100 ° C. to 270 ° C.
When light is used, it can be performed by g-line, h-line, i-line, excimer laser such as KrF or ArF, electron beam, X-ray, etc. The irradiation time is preferably 10 seconds to 180 seconds, and more preferably 30 seconds to 60 seconds. In the case of combined use of post-exposure and post-heating, it is preferable to carry out post-exposure first.

The infrared ray transmission filter is manufactured by performing the colored layer formation step, the exposure step, and the development step (further, if necessary, a curing step) described above.
The infrared transmission filter may be configured of only colored pixels exhibiting specific spectral characteristics of the present invention, or red, green, blue, magenta, yellow, cyan, black, colored pixels exhibiting the above-described spectral characteristics. A color filter having colored pixels such as colorless may be configured. When a color filter is configured together with pixels of other colors, colored pixels exhibiting specific spectral characteristics of the present invention may be provided first or later.

  The colored radiation-sensitive composition in the present invention can be easily cleaned and removed using a known cleaning liquid even when it adheres to, for example, the nozzle of the coating device discharge unit, the piping portion of the coating device, the inside of the coating device, etc. . In this case, in order to carry out more efficient cleaning and removal, it is preferable to use the organic solvent described above as the organic solvent contained in the colored radiation-sensitive composition as the cleaning solution.

Also, JP-A-7-128867, JP-A-7-146562, JP-A-8-278637, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, and the like. The cleaning solution described in JP2007-2101A, JP2007-2102A, JP2007-281523A, etc. is also suitably used as a cleaning fluid for cleaning and removing the colored radiation-sensitive composition of the present invention. Can.
As the washing solution, it is preferable to use an alkylene glycol monoalkyl ether carboxylate or an alkylene glycol monoalkyl ether.
These organic solvents usable as the cleaning solution may be used alone or in combination of two or more.
When mixing 2 or more types of organic solvents, the mixed solvent formed by mixing the organic solvent which has a hydroxyl group, and the organic solvent which does not have a hydroxyl group is preferable. The mass ratio of the organic solvent having a hydroxyl group to the organic solvent having no hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 80/20. The mixed solvent is a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), and the ratio thereof is particularly preferably 60/40.
In addition, in order to improve the permeability of the washing solution to the colored radiation-sensitive composition, the above-described surfactant may be added to the washing solution as a surfactant which may be contained in the colored radiation-sensitive composition.

  In addition, the infrared transmission filter of the present invention manufactured by the method of manufacturing the infrared transmission filter of the present invention can be suitably mounted on a solid-state imaging device such as a CCD sensor, a CMOS sensor, an organic CMOS sensor, or a CIGS image sensor. . In particular, it is preferable to be mounted on a solid-state imaging device of a high resolution CCD sensor, a CMOS sensor, or an organic CMOS sensor having a size of more than one million pixels. The infrared transmission filter of the present invention can be disposed, for example, between the light receiving portion of each pixel constituting the CCD element and the microlens for collecting light.

[Infrared sensor]
The infrared sensor of the present invention comprises the infrared transmission filter of the present invention. The configuration of the infrared sensor according to the present invention is a configuration provided with an infrared transmission filter, and is not particularly limited as long as it functions as a solid-state imaging device, and examples thereof include the following configurations.

A transfer electrode comprising a plurality of photodiodes and polysilicon and the like that constitute a light receiving area of a solid-state imaging device (CCD sensor, CMOS sensor, organic CMOS sensor, etc.) is provided on a substrate, and the photodiode and transfer electrode are formed on the substrate. It has a light shielding film made of tungsten or the like in which only the light receiving portion of the photodiode is opened, and has a device protective film made of silicon nitride or the like formed on the light shielding film to cover the entire light shielding film and the photodiode light receiving portion It is a structure which has the infrared rays permeable filter of this invention on a device protective film.
Further, the device has a light condensing means (for example, a micro lens etc., hereinafter the same) on the device protection layer and under the infrared light transmission filter (closer to the substrate) or has the light collection means on the infrared light transmission filter It may be a configuration or the like.

  The organic CMOS sensor includes a thin film panchromatic photosensitive organic photoelectric conversion film and a CMOS signal readout substrate as a photoelectric conversion layer, and an organic material plays a role of capturing light and converting it into an electric signal. This is a two-layer hybrid structure in which the inorganic material plays a role in extracting a signal to the outside, and in principle, the aperture ratio can be 100% with respect to incident light. The organic photoelectric conversion film is a structure-free continuous film and can be laid on a CMOS signal reading substrate, so it does not require an expensive microfabrication process and is suitable for pixel miniaturization.

  Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Examples 6 to 7 shall be read as reference examples. In addition, unless there is particular notice, "part" and "%" are mass references.

Preparation of Pigment Dispersion B-1
A mixture of the following compositions was used with zirconia beads of 0.3 mm in diameter, and a near-infrared transmitting black pigment was used in a bead mill (high pressure disperser NANO-3000-10 (manufactured by Nippon B E Co., Ltd.) with decompression mechanism) The pigment dispersion liquid B-1 was prepared by mixing and dispersing until the average particle diameter shown in Table 1 was obtained.
Color material: IRGAPHOR BK 13.0 parts manufactured by BASF Co. Dispersant: Dispersion resin 1 5.2 parts below Organic solvent: Propylene glycol methyl ether acetate (PGMEA)
81.8 copies

Preparation of Pigment Dispersion B-2 to B-16
Pigment dispersions B-2 to B-16 were prepared in the same manner as in the above [Preparation of pigment dispersion B-1] except that each component described in Table 1 was used in the amount described in Table 1. did.
In Table 1, the numerical values in parentheses after each component indicate the amount (unit: part) of the component used.
In addition, in preparation of the pigment dispersion liquid which does not contain a near-infrared permeation | transmission black pigment, mixing time using high pressure dispersing machine NANO-3000-10 was made into 3 hours.

[Measurement of Average Particle Size of Pigment]
The average particle diameter (volume basis) of the near-infrared transmissive black pigment was measured using MICROTRACUPA 150 manufactured by Nikkiso Co., Ltd. for the pigment dispersions B-1 to B-3. The measurement results are shown in Table 1.

  The abbreviations of the components in the table and the contents of the abbreviations are as follows. In the following dispersion resin 1 and dispersion resin 2, numerical values (numerical values indicated simultaneously with the main chain repeating unit) shown simultaneously with the respective structural units represent molar ratios of the structural units. The numerical value shown at the side chain repeat site indicates the number of repeats of the repeat site.

[Near Infrared Transmissive Black Color Material (A)]
The one listed above was used.

[Colorant (B)]
Lumogen Black FK4280: black pigment manufactured by BASF Lumogen Black FK4281: black pigment manufactured by BASF Y139: C.I. I. Pigment Yellow 139
Y150: C.I. I. Pigment Yellow 150
R254: C. I. Pigment Red 254
G36: C. I. Pigment Green 36
PV23: C.I. I. Pigment Violet 23
B15: 6: C.I. I. Pigment Blue 15: 6
Carbon black MS-10E: Black pigment manufactured by Mitsubishi Chemical Corporation

[Dispersant related]

Dispersion resin 3: EFKA4401 (resin having an amine group) manufactured by BASF.
Dispersion resin 4: Alkali-soluble resin-3 described in paragraphs [0172] and [0173] of JP-A-2009-69822
Dispersion resin 5: DISPERBYK-161 manufactured by Big Chemie
Dispersion resin 6: DISPERBYK-110 manufactured by Big Chemie

Dispersant 1: Dispersant 1 described in paragraph [0175] of JP-A-2009-69822
S12000: Lopurisol Solpers 12000
Acrylic resin 1: Acrylic resin derivative described in paragraph [0083] of JP 2012-18384: Pigment derivative 1 described in paragraph [0090] JP 2012-18384 A

(Examples 1 to 10, Comparative Examples 1 to 6)
[Preparation of Colored Radiation-Sensitive Composition]
The components described in Table 2 below were mixed in the amounts described in Table 2 below to prepare colored radiation-sensitive compositions of Examples 1 to 10 and Comparative Examples 1 to 6, respectively. The numerical values in Table 2 indicate the used amount (unit: parts by mass) of the corresponding component.

  The contents of each component in Table 2 are shown below.

· Alkali-soluble resin 2: Alkali-soluble resin-1 (epoxy acrylate resin) described in paragraph [0170] of JP-A-2009-69822
· Alkali-soluble resin 3: Acrylic resin described in paragraph [0083] of JP-A-2012-18384

Polymerizable compound 4: U-6 LPA (urethane acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.
Polymerizable compound 5: PM-21 (2- (meth) acryloyloxyethyl caproate acid phosphate) manufactured by Nippon Kayaku Co., Ltd.
・ Polymerizable compound 6: Aronix M-402 manufactured by Toagosei Co., Ltd.

A-1 (Near Infrared Transmissive Black Color Material (A)): Azo Dye Represented by the Following Formula (A-1)

Photopolymerization initiator 2: Photopolymerization initiator 1 (oxime-based initiator) described in paragraph [0177] of JP-A-2009-69822
Photopolymerization initiator 3: IRGACURE OXE-02 manufactured by BASF.

Surfactant 1: 1.00 wt% PGMEA solution of Megafac F-781F manufactured by DIC Co., Ltd. Surfactant 2: 1.00 wt% PGMEA solution of BYK-330 manufactured by BIC-Chemie Japan Co., Ltd. Polymerization inhibitor: p-methoxyphenol

Organic solvent 1: Propylene glycol methyl ether acetate (PGMEA)
Organic solvent 2: 3-methoxybutyl acetate Organic solvent 3: cyclohexanone

  Spectral characteristics were evaluated using each of the obtained colored radiation-sensitive compositions. The results are summarized in Table 3.

[Spectral characteristics]
Each colored radiation-sensitive composition is spin-coated on a glass substrate, applied to a post-baked film thickness of 0.5 μm, dried on a hot plate at 100 ° C. for 120 seconds, and dried. Further, heat treatment (post-baking) was performed for 300 seconds using a hot plate at 200.degree.
The light transmittance of a substrate having a colored layer in the wavelength range of 300 to 1300 nm was measured using a spectrophotometer (ref. Glass substrate) of an ultraviolet visible near infrared spectrophotometer U-4100 (manufactured by Hitachi High-Technologies) .

(Infrared transmittance)
Based on the measurement method described in the above [Spectral characteristics], the minimum value X _min of light transmittance in the wavelength range of 800 nm to 1300 nm was evaluated based on the following evaluation criteria.
<Evaluation criteria>
A: 80% ≦ X _min
B: X _min <80%

(Visible light transmittance)
Based on the measurement method described in the above [Spectral characteristics], the maximum value Y _max of light transmittance in the wavelength range of 400 nm to 650 nm was evaluated based on the following evaluation criteria.
<Evaluation criteria>
A: Y _max ≦ 20%
B: 20% <Y _max

Here, in the colored radiation-sensitive compositions of Examples 1 to 3 and 6, the concentration of the near-infrared transmitting black material with respect to the total solid content of the composition for the infrared transmission filter (and, consequently, the film to be formed) is It is 60% by mass.
In addition, IRGAPHOR BK used in Example 1 was compared with Lumogen Black FK 4280, Lumogen Black FK4281, carbon black MS-10E, C.I. I. Pigment Black 31 and C.I. I. The maximum value Y _max of the light transmittance in the above wavelength range of 400 nm to 650 nm in the case of replacing with each of Pigment Black 32 (the amount used is the same amount as IRGAPHOR BK in Example 1) exceeds 30% in all It was a thing.

(Visible light absorbance)
Based on the measurement method described in the above [Spectral characteristics], the average value Z _ave of the absorbance in the wavelength range of 400 nm to 630 nm was evaluated based on the following evaluation criteria. The higher the rating, the higher the visible light absorbance and the better the performance.
<Evaluation criteria>
5: 0.90 ≦ Z _ave
4: 0.80 Z Z _ave <0.90
3: 0.75 ≦ Z _ave <0.80
2: 0.70 ≦ Z _ave <0.75
1: Z _ave <0.70

(Visible light flatness)
The standard deviation σ of the light transmittance in the wavelength range of 400 nm to 630 nm was evaluated based on the following evaluation criteria based on the measurement method described in the above [Spectral characteristics]. The higher the rating, the smaller the standard deviation and the better the performance. The standard deviation σ can be easily calculated from data of light transmittance in the wavelength range of 400 nm to 630 nm by well-known calculation software or the like.
<Evaluation criteria>
5: 1.0 <σ ≦ 2.0
4: 2.0 <σ ≦ 3.0
3: 3.0 <σ ≦ 6.0
2: 6.0 <σ ≦ 10.0
1: 10.0 <σ

  The above results are shown in Table 3.

As compared with the infrared ray transmission filter of the comparative example formed of the colored radiation-sensitive composition of the comparative example, all of the infrared ray transmission filters of the example formed of the colored radiation-sensitive composition of the example The rate was high, the visible light transmittance was low, and the visible light absorbance was high.
Therefore, according to the colored radiation-sensitive composition of the example, it was found that infrared rays (particularly, near infrared rays) can be transmitted in a state in which noise derived from visible light components is small.
In addition, in the examples in which the near infrared transmitting black color material is used in combination with an appropriate coloring agent so as to compensate for the range where the absorbance is small, the visible light flatness is further improved.

[Production of Infrared Transmission Filter]
Each of the colored radiation-sensitive compositions of Examples 1 to 10 is coated on a silicon wafer using a spin coater so that the film thickness after drying is 0.5 μm, and 120 using a hot plate at 100 ° C. Heat treatment (pre-baking) was performed for a second.
Then, i-ray stepper exposure apparatus FPA-3000i5 + (Canon (Ltd.)) was used, 50 mJ / cm ² to 50~750mJ / cm ² using a photomask having a square pixel pattern of 1.4μm angle is formed By performing exposure in steps, the optimum exposure amount for resolving the square pixel pattern was determined, and exposure was performed with this optimum exposure amount.
After that, the silicon wafer on which the exposed coating film is formed is placed on the horizontal rotation table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2060 (Fuji Film Electronics Co., Ltd.) Paddling development was performed at 23 ° C. for 60 seconds using Materials Inc. to form a colored pattern on a silicon wafer.
The silicon wafer on which the colored pattern was formed was rinsed with pure water and then spray dried.
Further, heat treatment (post-baking) was performed for 300 seconds using a hot plate at 200 ° C. to obtain a silicon wafer having a colored pattern as an infrared ray transmission filter of each of Examples 1 to 10.
The infrared transmission filters of Examples 1 to 10 formed as described above all had high infrared light transmittance, low visible light transmittance, and high visible light absorbance.
Therefore, according to the composition for an infrared ray transmission filter of the present invention, even if it is very thin (for example, 0.5 μm in thickness), infrared rays (particularly near infrared rays) can be It has been found that a transparent infrared transmission filter is obtained.

Claims (29)

  A composition for an infrared transmission filter comprising a near infrared transmission black color material, wherein the near infrared transmission black color material is a bisbenzofuranone-based pigment, and the content of the bisbenzofuranone-based pigment is the infrared transmission. The content is 20% by mass or more based on the total solid content of the composition for a filter, and the composition for an infrared transmission filter further contains a colorant different from the bisbenzofuranone-based pigment, and the colorant is an organic pigment And at least one selected from a yellow pigment, an orange pigment, a red pigment, a green pigment, a violet pigment and a blue pigment, and the content of the colorant is The composition for an infrared transmission filter, which is 1 to 300 parts by mass with respect to 100 parts by mass of the bisbenzofuranone-based pigment.   The composition for infrared transmission filters according to claim 1, wherein the content of the bisbenzofuranone-based pigment is 40 to 80% by mass with respect to the total solid content of the composition for infrared transmission filters.   The composition for infrared transmission filters according to claim 1 or 2, wherein an average particle diameter of the bisbenzofuranone-based pigment is 50 nm or less.   The composition for an infrared transmission filter according to claim 3, wherein an average particle diameter of the bisbenzofuranone-based pigment is 1 to 50 nm. The composition for infrared transmission filters according to any one of claims 1 to 4, wherein the bisbenzofuranone-based pigment is a compound having the following structure.
  The composition for an infrared transmission filter according to any one of claims 1 to 5, wherein the colorant is at least one selected from a yellow pigment and a blue pigment.   The composition for infrared transmission filters according to claim 6, wherein the coloring agent is a yellow pigment.   The composition for an infrared transmission filter according to claim 6, wherein the colorant is a yellow pigment and a blue pigment.   The yellow pigment is C.I. I. Pigment Yellow 139, and the blue pigment is C.I. I. The composition for infrared ray transmission filter according to claim 8, which is Pigment Blue 15: 6.   The composition for an infrared transmission filter according to any one of claims 1 to 9, wherein the content of the coloring agent is 1 to 200 parts by mass with respect to 100 parts by mass of the bisbenzofuranone-based pigment.   The composition for infrared transmission filters according to any one of claims 1 to 9, wherein the content of the coloring agent is 1 to 60% by mass with respect to the total solid content of the composition for infrared transmission filters.   The composition for infrared transmission filters according to claim 11, wherein the content of the coloring agent is 1 to 30% by mass with respect to the total solid content of the composition for infrared transmission filters.   Furthermore, the composition for an infrared transmission filter according to any one of claims 1 to 12, further comprising a polymer dispersant, wherein the polymer dispersant is a resin having an acid value of 60 mg KOH / g or more. A composition for an infrared transmission filter, which is at least one selected from the group consisting of a resin having an amine group and an oligoimine resin.   Furthermore, the composition for infrared rays permeable filters of any one of Claims 1-13 containing a polymeric compound. The infrared transmissive filter according to claim 14, wherein the polymerizable compound is at least one selected from the group consisting of radical polymerizable monomers represented by the following general formulas (MO-1) to (MO-5). Composition.



In the above general formula, n is 0 to 14 and m is 1 to 8. A plurality of R and T in one molecule may be identical to or different from each other. When T is an oxyalkylene group, the terminal at the carbon atom side is bonded to R.
In each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5), at least one of a plurality of R is -OC (= O) CH = CH ₂ or -OC (= O) represents a group represented by C (CH ₃ ) = CH ₂ .   The composition for infrared transmission filters according to claim 14 or 15, wherein the content of the polymerizable compound is 2 to 25% by mass with respect to the total solid content of the composition for infrared transmission filters.   Furthermore, the composition for infrared rays permeable filters of any one of Claims 1-16 containing a photoinitiator.   Furthermore, the composition for infrared rays permeable filters of any one of Claims 1-17 containing alkali-soluble resin.   The composition for infrared transmission filters according to claim 18, wherein the content of the alkali-soluble resin is 1 to 15% by mass with respect to the total solid content of the composition for infrared transmission filters.   The composition for infrared transmission filters according to claim 19, wherein the content of the alkali-soluble resin is 3 to 10% by mass with respect to the total solid content of the composition for infrared transmission filters.   Furthermore, the composition for infrared rays permeable filters of any one of Claims 1-20 containing surfactant.   22. The composition for an infrared transmission filter according to claim 21, wherein the surfactant is a fluorine-based surfactant.   The standard deviation in the wavelength range of 400 to 630 nm of the light transmittance in the thickness direction of the film when the film having a film thickness of 0.5 μm is formed is 6.0 or less. The composition for infrared ray transmission filters according to Item.   When a film having a film thickness of 0.5 μm is formed, the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 650 nm is 20% or less, and the light transmittance of the film in the thickness direction The composition for an infrared transmission filter according to any one of claims 1 to 23, wherein the minimum value in the wavelength range of 800 nm to 1300 nm is 80% or more.   The infrared rays permeable composition layer formed from the composition for infrared rays permeable filters of any one of Claims 1-24.   The infrared ray transmitting composition layer according to claim 25, having a film thickness of 1.8 μm or less.   The infrared rays permeable filter formed from the composition for infrared rays permeable filters of any one of Claims 1-24.   A process for forming an infrared ray transmitting composition layer by applying the composition for infrared ray transmitting filter according to any one of claims 1 to 24 on a substrate, and exposing the infrared ray transmitting composition layer in a pattern. A process for producing an infrared ray transmission filter, comprising the steps of: developing the infrared ray transmitting composition layer after exposure to form a pattern. An infrared sensor comprising the infrared transmission filter according to claim 27.