JP2023071494A - Near-infrared absorbing composition, optical filter, infrared camera, and infrared sensor - Google Patents

Abstract

To provide a near-infrared absorbing composition that has excellent concealability on the near-infrared region, is low in initial viscosity, has excellent storage stability, and causes little foreign matter, and an optical filter including the same, an infrared camera having the optical filter, and an infrared sensor.SOLUTION: A near-infrared absorbing composition includes a compound (A) having an indigo skeleton with a maximum absorption wavelength of 700-1300 nm, a binder resin, and a metal component including metal atoms selected from Li, Na, K, Cs, Mg, Ca, Fe, and Zr. The total amount of the metal atoms included in the metal component (excluding the compound (A) having an indigo skeleton) is 1-1000 mass ppm relative to 100 mass% of the near-infrared absorbing composition.SELECTED DRAWING: None

Description

The present invention relates to near-infrared absorbing compositions, optical filters, infrared cameras, and infrared sensors.

2. Description of the Related Art CCDs (charge-coupled devices) and CMOSs (complementary metal-oxide semiconductors), which are solid-state imaging devices for color images, are used in video cameras, digital still cameras, mobile phones with camera functions, and the like. These solid-state imaging devices use silicon photodiodes that are sensitive to near-infrared rays in their light-receiving portions. Therefore, in the solid-state imaging device, a near-infrared cut filter (optical filter) may be used to correct visibility. A near-infrared cut filter is manufactured using, for example, a near-infrared absorbing composition containing a near-infrared absorbing agent.

Indigo dyes, phthalocyanine dyes, naphthalocyanine dyes, pyrrolopyrrole dyes, phthalocyanine dyes, cyanine dyes, diimonium dyes, dithiolene dyes, porphyrin dyes, squarylium dyes, croconium dyes, and the like are known as near-infrared absorbers.

As an indigo dye-based compound, Patent Document 1 discloses a boron compound. Further, Patent Document 2 discloses a palladium complex. However, there is no description regarding the stability and the reduction of foreign matter in near-infrared absorptive compositions containing these compounds.

JP 2012-224593 A JP 2013-87233 A

The present invention provides a near-infrared absorptive composition that has excellent hiding properties in the near-infrared region, has a low initial viscosity, has excellent storage stability, and generates little foreign matter, an optical filter using the same, and the optical filter. An object of the present invention is to provide an infrared camera and an infrared sensor that

The present inventors have made intensive studies to solve the above problems, and found that a compound (A) having an indigo skeleton having a maximum absorption wavelength of 700 to 1300 nm, a resin, Li, Na, K, Cs , Mg, Ca, Fe, and a near-infrared absorbing composition containing a metal component containing a metal atom selected from Zr, in which the metal atom contained in the metal component (excluding the compound (A) having an indigo skeleton) The total amount is 1 to 1000 ppm by mass with respect to 100% by mass of the near-infrared absorbing composition, and the near-infrared absorbing composition has excellent hiding properties in the near infrared region, low initial viscosity, and storage stability. The present inventors have found that they are excellent in the properties of the resin, and that the generation of foreign matter is small, leading to the present invention.

That is, the present invention provides a compound (A) having an indigo skeleton having a maximum absorption wavelength of 700 to 1300 nm, a binder resin, and metal atoms selected from Li, Na, K, Cs, Mg, Ca, Fe, and Zr. and a near-infrared absorbing composition containing a metal component (excluding the compound (A) having an indigo skeleton), wherein the total amount of the metal atoms contained in the metal component (excluding the compound (A) having an indigo skeleton) is 100% by mass of the near-infrared absorbing composition Relative to, 1 to 1000 ppm by mass, it relates to a near-infrared absorbing composition.

The present invention also relates to the near-infrared absorbing composition, wherein the compound (A) having an indigo skeleton contains a compound represented by the following general formula (1).

General formula (1)

（＊＊は窒素原子との結合手を表す）

[一般式（１）中、Ｒ_１とＲ_２は、それぞれ独立して、水素原子、一般式（４）で表される基、配位子を持つ金属原子を表す。Ｒ_１とＲ_２が同時に水素であることはない。
Ｘ_１～Ｘ_１２はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルコキシル基、置換基を有していてもよいアリールオキシ基、置換基を有していてもよいアリールアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよいアルキルチオ基、置換基を有していてもよいアリールチオ基、アミノ基、置換基を有していてもよいアルキルアミノ基、置換基を有していてもよいアリールアミノ基、シアノ基、ハロゲン原子、ニトロ基、水酸基、または、－ＳＯ₃Ｈ、－ＣＯＯＨ、これら酸性基の１価～３価の金属塩、もしくは、アルキルアンモニウム塩を表す。Ｘ_１～Ｘ_１２で示される基のうち隣り合う２個の基は、連結してそれぞれが結合する炭素原子と共に５員環又は６員環を形成してもよい。］ general formula (4)

(** represents a bond with a nitrogen atom)

[In general formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, a group represented by general formula (4), or a metal atom having a ligand. R ₁ and R ₂ cannot be hydrogen at the same time.
X ₁ to X ₁₂ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, a substituted an aryloxy group optionally having a group, an arylalkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, an alkylthio group optionally having a substituent, optionally substituted arylthio group, amino group, optionally substituted alkylamino group, optionally substituted arylamino group, cyano group, halogen atom, nitro group, It represents a hydroxyl group, —SO ₃ H, —COOH, monovalent to trivalent metal salts of these acidic groups, or alkylammonium salts. Two adjacent groups among the groups represented by X ₁ to X ₁₂ may be linked to form a 5- or 6-membered ring together with the carbon atoms to which they are attached. ]

The present invention also relates to the near-infrared absorbing composition further comprising a photopolymerizable monomer and/or a photopolymerization initiator.

The present invention also relates to the near-infrared absorbing composition, which contains an organic dye having absorption in the range of 400 nm to 700 nm.

The present invention also relates to an optical filter having a coating formed from the near-infrared absorbing composition on a substrate.

The present invention also relates to an infrared camera comprising the optical filter.

The present invention also relates to an infrared sensor comprising the optical filter.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a near-infrared absorptive composition which has excellent hiding properties in the near-infrared region, has a low initial viscosity, has excellent storage stability, and generates little foreign matter. Further, it is possible to provide an optical filter using the near-infrared absorbing composition, an infrared camera equipped with the optical filter, and an infrared sensor.

Terms used herein are defined. "(Meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" unless otherwise specified , “acryloyl and/or methacryloyl”, “acrylic and/or methacrylic”, “acrylic acid and/or methacrylic acid”, “acrylate and/or methacrylate”, or “acrylamide and/or methacrylamide”. References herein to "C.I." mean Color Index (C.I.). Colorants include pigments and dyes.

<Near-infrared absorbing composition>
The near-infrared absorbing composition of the present invention comprises a compound (A) having an indigo skeleton having a maximum absorption wavelength of 700 to 1300 nm, a binder resin, Li, Na, K, Cs, Mg, Ca, Fe, and Zr. A near-infrared absorbing composition containing a metal component containing a metal atom selected from the total amount of the metal atoms contained in the metal component (excluding the compound (A) having an indigo skeleton) is near-infrared absorbing It is characterized by being 1 to 1000 ppm by mass with respect to 100% by mass of the composition.

By using the near-infrared absorptive composition of the present invention, it is possible to produce a film or the like that generates less foreign matter. It is speculated that the mechanism by which such an effect is obtained is as follows. That is, the indigo skeleton of the compound (A) having an indigo skeleton contained in the near-infrared absorbing composition of the present invention has a structure capable of coordinating to a metal atom as described later. easy to incorporate into Therefore, if too many metal atoms are mixed in from impurities contained in the manufacturing process or various raw materials to be added, it is thought that changes in crystal form and inhibition of resin adsorption will occur, resulting in deterioration of storage stability and generation of foreign substances. . However, by setting the total amount of the specific metal atoms contained in the metal component to 1 to 1000 ppm by mass with respect to 100% by mass of the near-infrared absorptive composition, while preventing changes in crystal form and inhibition of resin adsorption, indigo It is considered that the dispersibility was further improved by appropriately incorporating metal atoms into the compound (A) having a skeleton. As a result, it is considered that the near-infrared absorbing composition exhibited effects of low initial viscosity, maintenance of high storage stability, good light-shielding properties, and reduction of foreign matters in the film formed from the near-infrared absorbing composition.

The near-infrared absorbing composition of the present invention contains a metal component containing metal atoms (hereinafter also referred to as specific metal atoms) selected from Li, Na, K, Cs, Mg, Ca, Fe, and Zr. The total amount of specific metal atoms is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less, relative to the entire near-infrared absorbing composition. The lower limit of the total amount of specific metal atoms is not particularly limited, but is preferably 1 ppm by mass or more, more preferably 5 ppm by mass or more, relative to the entire near-infrared absorbing composition. Within the above range, it is possible to obtain a near-infrared absorptive composition capable of suppressing costs, excellent in storage stability, and capable of forming an optical filter with little generation of foreign substances.

The content of each specific metal atom contained in the near-infrared absorbing composition of the present invention is preferably 100 ppm by mass or less, and 50 ppm by mass or less, relative to the entire near-infrared absorbing composition. is more preferred.

Further, when the compound (A) having an indigo skeleton is a metal complex, or when a part of the organic dye structure contains metal atoms such as Ni, Zn, Pt, Mn, Pd and Co, the compound or These metal atoms may be present that are not part of the organic dye structure. The smaller the number of such metal atoms, the better, and they can be removed in the same manner as the specific metal atoms by the following method. Furthermore, it is preferable that the concentration of Cs, Ti, Si, and the like mixed in with materials (for example, catalysts) used in the manufacturing process of various raw materials of the near-infrared absorbing composition is low.

Various raw materials contained in the near-infrared absorbing composition or methods for removing metal atoms mixed in from the apparatus during the manufacturing process include JP-A-2010-83997, JP-A-2018-36521, and JP-A-7-198928. Japanese Patent Laid-Open Nos. 8-333521, 2009-7432, etc., a method of washing with water, and a method of removing magnetic foreign matter with a magnet described in Japanese Patent Laid-Open No. 2011-48736. Use method accordingly.

The content of specific metal atoms can be measured by inductively coupled plasma emission spectroscopy (ICP).

<Compound (A) having an indigo skeleton>
Compound (A) having an indigo skeleton has a maximum absorption wavelength of 700 to 1300 nm and functions as a near-infrared absorbing dye. Compound (A) having an indigo skeleton is represented by the following general formulas (1) to (3).

General formula (1)

general formula (2)

General formula (3)

（＊＊は窒素原子との結合手を表す） general formula (4)

(** represents a bond with a nitrogen atom)

In general formulas (1) to (4), R ₁ to R ₆ each independently represent a hydrogen atom, a group represented by general formula (4), or a metal atom having a ligand.
X ₁ to X ₂₂ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, a substituted an aryloxy group optionally having a group, an arylalkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, an alkylthio group optionally having a substituent, optionally substituted arylthio group, amino group, optionally substituted alkylamino group, optionally substituted arylamino group, cyano group, halogen atom, nitro group, It represents a hydroxyl group, —SO ₃ H, —COOH, monovalent to trivalent metal salts of these acidic groups, or alkylammonium salts. Two adjacent groups among the groups represented by X ₁ to X ₂₂ may be linked to form a 5- or 6-membered ring together with the carbon atoms to which they are attached.

The "alkyl group" of the alkyl group optionally having a substituent is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, and an n-hexyl group. , n-octyl group, stearyl group, 2-ethylhexyl group, and other linear or branched alkyl groups. "Alkyl group having a substituent" includes, for example, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoro propyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group and the like.

The "aryl group" of the aryl group optionally having a substituent includes, for example, a phenyl group, a naphthyl group, an anthryl group and the like.
"Aryl group having a substituent" includes, for example, p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2- aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-amino Anthraquinonyl group and the like can be mentioned.

The "alkoxyl group" of the alkoxyl group which may have a substituent is, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, Linear or branched alkoxyl groups such as 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy and 2-ethylhexyloxy groups can be mentioned.
The "substituted alkoxyl group" includes, for example, a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditri fluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

The "aryloxy group" of the aryloxy group which may have a substituent includes, for example, a phenoxy group, a naphthoxy group, an anthryloxy group, and the like. -methylphenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group and the like.

"Optionally substituted arylalkyl group" includes, for example, benzyl group, 2-phenylpropan-yl group, styryl group, diphenylmethyl group, triphenylmethyl group and the like.

The "cycloalkyl group" of the cycloalkyl group which may have a substituent includes, for example, a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like. Examples of "substituted cycloalkyl group" include 2,5-dimethylcyclopentyl group, 4-tert-butylcyclohexyl group and the like.

The "alkylthio group" of the alkylthio group optionally having a substituent is, for example, a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, an octadecylthio group, and the like. is mentioned.
Examples of the "substituted alkylthio group" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group and the like.

The "arylthio group" of the arylthio group which may have a substituent includes, for example, a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group and the like.
"Arylthio group having a substituent" includes, for example, a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, a 2-hydroxyphenylthio group, and the like. .

The "alkylamino group" of the optionally substituted alkylamino group includes, for example, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, Octylamino group, nonylamino group, decylamino group, dodecylamino group, octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert -pentylamino group, tert-octylamino group, neopentylamino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1 -adamantamino group, 2-adamantamino group and the like.

The "arylamino group" of the arylamino group optionally having a substituent is, for example, anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4-biphenylamino group, 1-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group and the like.

Halogen atoms include fluorine, chlorine, bromine and iodine.

Examples of acidic groups include --SO ₃ H and --COOH, and examples of monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, and aluminum salts. mentioned. Examples of alkylammonium salts of acidic groups include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, palmityltrimethylammonium, lauryltrimethylammonium, dilauryldimethylammonium and distearyldimethylammonium salts. and quaternary alkylammonium salts of.

Among the above substituents, preferable substituents for X ₁ to X ₂₂ include a hydrogen atom, a methoxy group, a fluorine atom, a chlorine atom and a bromine atom.

Two adjacent groups among the groups represented by X ₁ to X ₂₂ may be linked to form a 5- or 6-membered ring together with the carbon atoms to which they are attached. The 5- or 6-membered ring may have a substituent. Such five-membered rings include cyclopentene ring, cyclopentadiene ring, imidazole ring, thiazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiophene ring, furan ring, pyrrole ring and the like. , cyclohexane ring, cyclohexene ring, cyclohexadiene ring, benzene ring, pyridine ring, piperazine ring, piperidine ring, morpholine ring, pyrazine ring, pyrone ring, pyrrolidine ring and the like.

R ₁ to R ₆ represent a hydrogen atom, a substituent represented by general formula (4), or a metal atom having a ligand.

Metal atoms include Cu, Zn, Co, Ni, Ru, Pd, Pt, Mn, Sn, Ti, Ba, and the like. A divalent metal atom is preferred, and Zn and Pd are more preferred. When Zn or Pd is used as the metal atom, a compound (A) having an indigo skeleton with low absorption in the visible light region can be obtained.

Ligands of metal atoms having ligands are not particularly limited, but are β-diketonato ligands, olefins, conjugated ketones, nitriles, amines, carboxylate ligands, carbon monoxide, phosphines, phosphinites, phosphonites. , and phosphite. The ligand may be a chelating ligand. Among them, the ligand represented by the general formula (5) is preferable because a stable compound can be obtained.

general formula (5)

X ₂₃ and X ₂₄ each independently represent an optionally substituted alkyl group or an optionally substituted aryl group. M represents a metal atom, metal oxide, metal halide or metal hydroxide.

The “alkyl group” of the alkyl group optionally having substituent(s) and the “aryl group” of the aryl group optionally having substituent(s) of X ₂₃ and X ₂₄ are synonymous with X ₁ to X ₂₂ . .

When the compound (A) having an indigo skeleton contains the compound represented by the general formula (1), a near-infrared absorptive composition having excellent hiding properties in the near-infrared region can be obtained, which is preferable.

(Method for synthesizing compound (A) having indigo skeleton)
The compound (A) having an indigo skeleton can be synthesized using compounds represented by general formulas (6) to (8) as raw materials.

general formula (6)

general formula (7)

general formula (8)

In general formulas (6) to (8), X ₂₅ to X ₄₂ have the same meanings as X ₁ to X ₂₂ .

The compound represented by general formula (6) can be obtained according to the synthesis method described in JP-A-2012-224593.

The compound represented by the general formula (7) is obtained by adding the compound represented by the general formula (8) and a compound having an aniline skeleton in a solvent to aluminum chloride and 1,4-diazabicyclo[2.2.2]octane. can be obtained by reacting in the presence of The amount of aluminum chloride to be used is preferably 1.5 to 2.5 mol per 1 mol of the compound represented by general formula (8).
The amount of the compound having an aniline skeleton to be used is preferably 1.0 to 2.0 mol per 1 mol of the compound represented by general formula (8). The amount of 1,4-diazabicyclo[2.2.2]octane to be used is preferably 2.5 to 5.0 mol per 1 mol of the compound represented by general formula (8). Although the reaction solvent is not particularly limited, examples thereof include toluene, xylene, chlorobenzene, bromobenzene and the like.

Examples of the compound represented by the general formula (8) include Bat Blue 1, 5, 35 and the like.

A compound (A) having an indigo skeleton can be obtained by reacting a compound represented by general formulas (6) to (8) with a boron compound or a metal complex. If necessary, a Lewis acid such as titanium tetrachloride or aluminum chloride is added.

Although the reaction temperature is not particularly limited, it is preferably in the range of 40 to 170°C, more preferably 50 to 130°C.

The reaction solvent is not particularly limited, but one in which the intermediate and the boron compound or metal complex are dissolved is preferred. Specific examples include tetrahydrofuran, toluene, xylene, bromobenzene and the like.

When boron compounds are used, borinic acid esters are preferred, and 2-aminoethyl diphenylborate is particularly preferred.

The reaction time is not particularly limited, but the progress of the reaction may be confirmed by MALDI TOF-MS spectrum or spectrophotometer to confirm the disappearance of the raw materials.

Examples of the compound (A) having an indigo skeleton having a maximum absorption wavelength of 700 to 1300 nm include the following compounds, but the present invention is not limited thereto.

<Other near-infrared absorbing dyes>
The near-infrared absorbing composition of the present invention can contain other near-infrared absorbing dyes in addition to the compound (A) having an indigo skeleton. Thereby, the spectrum can be appropriately adjusted. Other near-infrared absorbing dyes include, for example, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, anthraquinone compounds, aminium compounds, diimmonium compounds, and indigo dye-based compounds (excluding the compound (A) having an indigo skeleton). , croconium compounds, azo compounds, quinoid type complex compounds, dithiol metal complex compounds, and the like.
The content of the compound (A) having an indigo skeleton in the present invention is preferably in the range of 2 to 70% by mass based on the total weight (100% by mass) of the near-infrared absorbing composition. Further, when other near-infrared absorbing dye is used in combination as the near-infrared absorbing dye, the weight ratio of the other near-infrared absorbing dye/compound (A) having an indigo skeleton is 5/95 to 50/50. is preferred.

<Organic dye having a maximum absorption wavelength in the range of 400 nm or more and less than 700 nm>
The near-infrared absorbing composition of the present invention can contain an organic dye having a maximum absorption wavelength in the range of 400 nm or more and less than 700 nm, other than the compound (A) having an indigo skeleton and other near-infrared absorbing dyes. By containing an organic dye having maximum absorption in a specific region of 400 nm or more and less than 700 nm in accordance with the wavelength of the light source for sensing, it is a near-infrared absorbing composition that blocks external improper light and increases sensing accuracy. can be used.

Examples of organic dyes having a maximum absorption wavelength in the range of 400 nm or more and less than 700 nm include blue dyes, green dyes, yellow dyes, purple dyes, red dyes, and the like.
Organic pigments may be organic pigments, for example, diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, or polyazo, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthantrone, indane Anthraquinone pigments such as thorone, pyranthrone, or violanthrone, quinacridone pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, phthalocyanine pigments, threne pigments, or Metal complex pigments and the like are included.
Dyes may also be used as organic dyes, and examples thereof include anthraquinone dyes, monoazo dyes, disazo dyes, oxazine dyes, aminoketone dyes, xanthene dyes, quinoline dyes, and triphenylmethane dyes. mentioned. when using dyes. A method of incorporating a polar group of an anionic dye or cationic dye into a resin to impart solubility in an organic solvent is effective.

(blue pigment)
Examples of blue pigments include C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like.

As a blue dye, C.I. I. acid blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34, 35, 37, 40, 41, 41:1, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 62, 62:1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 8485, 86, 88, 89, 90, 90:1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127: 1, 128, 129, 135, 137, 138, 143, 145, 147, 150, 155, 159, 169, 174, 175, 176, 183, 198, 203, 204, 205, 206, 208, 213, 227, 230, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280 and the like.

Also, C.I. I. Direct Blue 1, 2, 3, 4, 6, 7, 8, 8:1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21:1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98: 1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129130, 130:1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158: 1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 213, 215, 225, 226, 229, 230, 231, 242, 243, 244, 253, 254, 260, 263 and the like.

(green pigment)
Examples of green pigments include C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59, C.I. I. Pigment Green 62, C.I. I. Pigment Green 63 and the like.

As a green dye, C.I. I. Solvent Green 3, 20, 28, C.I. I. Acid Green 25, 27, 36, 37, 38, 41, 42, 44, C.I. I. bat greens 3, 6, 8 and the like.

(yellow pigment)
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 231, 233, 234, etc.

As a yellow dye, C.I. I. Acid yellow 2,3,4,5,6,7,8,9,9:1,10,11,11:1,12,13,14,15,16,17,17:1,18,20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40:1, 41, 42, 42:1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199 and the like.

Also, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44:1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134 and the like.

(purple pigment)
Examples of purple pigments include C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like.

As a purple dye, C.I. I. acid violet 1, 2, 3, 4, 5, 5:1, 6, 7, 7:1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, 109, etc. is mentioned.

Also, C.I. I. Direct Violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97 and the like.

(red pigment)
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 , 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208 , 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254 , 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 291, 295, 296, etc. mentioned.

Orange pigments that work similarly to red pigments include, for example, C.I. I. Orange pigments such as Pigment Orange 36, 38, 43, 51, 55, 59, 61, 73 can be used.

As a red dye, C.I. I. acid red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25:1, 26, 26:1, 26:2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76: 1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131, 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 249, 252, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388 and the like.

Also, C.I. I. Direct Red 1, 2, 2: 1, 4, 5, 6, 7, 8, 10, 10: 1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26: 1, 28, 29, 31, 33, 33: 1, 34, 35, 36, 37, 39, 42, 43, 43: 1, 44, 46, 49, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67, 67:1, 68, 72, 72:1, 73, 74, 75, 77, 78, 79, 81, 81:1, 85, 86, 88, 89, 90, 97, 100, 101, 101:1, 107, 108, 110, 114, 116, 117, 120, 121, 122, 122:1, 124, 125, 127, 127:1, 127:2, 128, 129, 130, 132, 134, 135, 136, 137, 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238 and the like.

Also, C.I. I. Solvent Red 52, 135, 146, 149, 168, 179, 207 and the like are also included.

Although the dyes described above have good spectral characteristics and excellent color development properties, they have problems with light resistance and heat resistance, and their characteristics may not be sufficient for use in optical filters.
Therefore, in order to improve these drawbacks, in the case of the form of a basic dye, it is preferable to chlorinate it with an organic acid or perchloric acid before use. As the organic acid, it is preferable to use an organic sulfonic acid or an organic carboxylic acid. Among them, it is preferable to use naphthalenesulfonic acid such as Tobias acid and perchloric acid in terms of resistance.
Moreover, it is preferable to use it after forming a salt with a resin having an anionic group, and it is also preferable to use it after forming a salt with a resin having a betaine structure and an organic acid.
In addition, in the case of anionic dyes including acid dyes and direct dyes, it is preferable to use a compound having a cationic group or a resin having a cationic group as a salt-forming compound using a counterion to improve heat resistance, light resistance, and solvent resistance. It is preferable in terms of sex.
In addition, it is preferable to form a salt with a resin having a cationic group for use, and more preferably to form a salt with a resin having a cationic group in its side chain and an organic acid.
It is also preferable to sulfonamidate the anionic dye and use it as a sulfonic acid amide compound from the viewpoint of durability.

For coating applications, the blue dye is C.I. I. Pigment Blue 15:3 or Pigment Blue 15:6, yellow pigment is C.I. I. Pigment Yellow 139, purple pigment is C.I. I. Pigment Violet 23 is preferably used. In molding applications, the blue pigment is C.I. I. Pigment Blue 15:3 or Pigment Blue 15:6, yellow pigment is C.I. I. Pigment Yellow 147, red pigment is C.I. I. Solvent Red 52 is preferred.

<Dye derivative>
The near-infrared absorptive composition of the present invention can contain a dye derivative, if necessary. A dye derivative is a compound having an acidic group, a basic group, a neutral group, or the like in an organic dye residue. Dye derivatives include, for example, compounds having acidic substituents such as sulfo, carboxy, or phosphate groups, and amine salts thereof, sulfonamide groups, or terminally basic substituents such as tertiary amino groups. compounds, and compounds having neutral substituents such as phenyl groups and phthalimidoalkyl groups.
Organic dyes include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, benzoiso Indole pigments such as indole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo and polyazo.

Specifically, diketopyrrolopyrrole-based dye derivatives, JP 2001-220520, WO2009/081930, WO2011/052617, WO2012/102399, JP 2017-156397, phthalocyanine Dye derivatives, JP-A-2007-226161, WO2016/163351 pamphlet, JP-A-2017-165820, Japanese Patent No. 5753266, anthraquinone-based dye derivatives, JP-A-63-264674, JP-A-09 -272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325, quinacridone dye derivatives, JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383, dioxazine-based dye derivatives, JP-A-2011-162662, thiazineindigo-based dye derivatives, JP-A-2007-314785, triazine-based dye derivatives , JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681 , JP-A-2009-57478 for benzoisoindole-based dye derivatives, JP-A-2003-167112 for quinophthalone-based dye derivatives, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012 -226110, naphthol dye derivatives, JP 2012-208329, JP 2014-5439, azo dye derivatives, JP 2001-172520, JP 2012-172092, acidic Substituents, JP-A-2004-307854, basic substituents, JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404 The dye derivatives described are mentioned. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply as a compound. A compound having a substituent such as a neutral group is synonymous with a dye derivative.

These dye derivatives can be used singly or in combination of two or more.

The dye derivative is preferably added in an amount of 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, even more preferably 5 to 50 parts by mass, based on 100 parts by mass of the dye.

When the dye is a pigment, a dye derivative is added and subjected to a pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, solvent salt milling, etc., so that the dye derivative is adsorbed on the surface of the pigment. , the primary particles of the pigment can be made finer than when the dye derivative is not added.

By adding a dye derivative to the pigment and performing a dispersion treatment such as wet dispersion using two rolls, three rolls, or beads, the dye derivative is adsorbed on the pigment surface, and the pigment surface becomes polar and the resin-type dispersant is adsorbed. is promoted, compatibility with pigments, dye derivatives, resin-type dispersants, solvents, and other additives is improved, and dispersion stability and viscosity stability over time of the near-infrared absorbing composition are improved. Further, by improving the compatibility, the coating film has excellent stability over time when the near-infrared absorbing composition is applied to a glass substrate or the like, and the waiting time from application of the near-infrared absorbing composition to exposure (PCD: Post Coating Delay) and the waiting time from exposure to heat treatment (PED: Post Exposure Delay), stability and characteristic dependency of pattern shape, and line width sensitivity stability are improved. In addition, since the surface of the pigment is adsorbed and coated with the pigment derivative and the resin-type dispersant, it is possible to suppress the precipitation of crystals due to aggregation and sublimation of the pigment when the coating film is heated and baked. Further, variation in development time and development residue are suppressed.

<Resin Dispersant>
The near-infrared absorbing composition of the present invention can contain a resin-type dispersant, if necessary. The resin-type dispersant has a pigment-affinity site that has a property of adsorbing to the pigment, and a relaxation site that has a high affinity with components other than the pigment and causes steric repulsion between the dispersed particles. As the resin-type dispersant, a resin having a controlled structure such as a graft-type (comb-type) or block-type is preferably used.

Resin-type dispersants, in terms of resin systems, include, for example, urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof; poly(lower alkyleneimine) and polyesters having free carboxyl groups Amide and its salts formed by the reaction of; (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl Pyrrolidone, etc.; polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, phosphate esters, and the like.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 142, 154, 161, 162, 163, 164, 165, 166 manufactured by BYK-Chemie Japan. or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, 21324 or Lactimon, Lactimon-WS or Bykumen, SOLSPERSE-3000, 9000, 13000, 13240 manufactured by Nippon Lubrizol, 13650,13940,16000,17000,18000,20000,21000,24000,26000,27000,28000,31845,32000,32500,32550,33500,32600,34750,35100,36600,3 8500, 41000, 41090, 53095, 55000, EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408 manufactured by BASF, such as 56000, 76500 ,4300,4310,4320,4330,4340,450,451,453,4540,4550,4560,4800,5010,5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503,etc , Ajinomoto Fine-Techno Co., Inc. Ajisper PA111, PB711, PB821, PB822, PB824, and the like.

Resin-type dispersants can be used alone or in combination of two or more.

The content of the resin-type dispersant is preferably 0.1 to 200 parts by mass, more preferably 0.1 to 150 parts by mass, per 100 parts by mass of the dye. Good dispersibility can be obtained when used in an appropriate amount.

<Binder resin>
The near-infrared absorbing composition of the present invention contains a binder resin. The binder resin is a resin having a transmittance of 80% or more in the entire wavelength range of 400-700 nm. Note that the transmittance is preferably 95% or more. In terms of curing properties, binder resins include, for example, thermoplastic resins, thermosetting resins, active energy ray-curable resins, and the like. In addition, the active energy ray-curable resin may have an active energy ray-reactive functional group in a thermoplastic resin or a thermosetting resin. In terms of physical properties, the binder resin is preferably an alkali-soluble resin from the viewpoint of developability. Alkali solubility is for imparting development solubility in the alkali development process during optical filter production, and an acidic group is required.

Binder resin can be used individually or in combination of 2 or more types.

The content of the binder resin is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, per 100 parts by mass of the dye. When contained in an appropriate amount, a film can be easily formed, and good color characteristics can be easily obtained.

(Thermoplastic resin)
Thermoplastic resins include, for example, acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, Examples include polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.
Alkali-soluble thermoplastic resins include, for example, resins having acidic groups such as carboxyl groups and sulfone groups. Alkali-soluble thermoplastic resins include, for example, acrylic resins having acidic groups, α-olefin/(anhydride) maleic acid copolymers, styrene/styrenesulfonic acid copolymers, and ethylene/(meth)acrylic acid copolymers. , or isobutylene/(anhydride) maleic acid copolymer. Among these, an acrylic resin having an acidic group and a styrene/styrenesulfonic acid copolymer are preferred from the standpoint of improving developability, heat resistance and transparency.

(Active energy ray-curable alkali-soluble resin)
The active energy ray-curable alkali-soluble resin preferably has an ethylenically unsaturated double bond. Ethylenically unsaturated double bonds can be introduced, for example, by methods (i) and (ii) shown below. The resin is three-dimensionally crosslinked by the effect of the active energy ray, thereby increasing the crosslink density and improving the chemical resistance.

[Method (i)]
Method (i) is, for example, a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with another monomer, and adding an ethylenically unsaturated divalent A carboxyl group of unsaturated monobasic acid having a double bond is subjected to an addition reaction. Then, the produced hydroxyl group is reacted with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond and a carboxyl group.

Ethylenically unsaturated monomers having an epoxy group include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with unsaturated monobasic acid.

Unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and α-position haloalkyl, alkoxyl, halogen, nitro, and cyano substituted products of (meth)acrylic acid. Carboxylic acid etc. are mentioned.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. If necessary, such as increasing the number of carboxyl groups, using a tricarboxylic anhydride such as trimellitic anhydride or using a tetracarboxylic dianhydride such as pyromellitic dianhydride, the remaining It is also possible to hydrolyze the anhydride group.

Other monomers include the following. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate (meth)acrylates such as acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate;
Alternatively, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone (meth)acrylamide, or (meth)acrylamide such as acryloylmorpholine Styrenes such as acrylamides styrene or α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, fatty acid vinyls such as vinyl acetate or vinyl propionate etc.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4- Phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimide Hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, N-substituted maleimides such as 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, phenyl ethoxylate Acrylates, ethylene oxide (EO)-modified (meth)acrylates of phenol, EO- or propylene oxide (PO)-modified (meth)acrylates of paracumylphenol, EO-modified (meth)acrylates of nonylphenol, PO-modified (meth)acrylates of nonylphenol, etc. is mentioned.

As a method similar to method (i), for example, an ethylenically unsaturated monomer having a carboxyl group and a part of the side chain carboxyl group of a copolymer obtained by copolymerizing another monomer 2) is a method of subjecting an ethylenically unsaturated monomer having an epoxy group to an addition reaction to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
Method (ii) is obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another monomer, and adding an ethylenically unsaturated monomer having an isocyanate group to the side chain hydroxyl group of the copolymer. This is a method of reacting the isocyanate group of the monomer.

Ethylenically unsaturated monomers having a hydroxyl group are, for example, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, Hydroxyalkyl methacrylates such as glycerol mono(meth)acrylate or cyclohexanedimethanol mono(meth)acrylate can be mentioned. In addition, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to hydroxyalkyl (meth)acrylate, poly γ-valerolactone, poly ε-caprolactone, and/or poly Polyester mono(meth)acrylates to which 12-hydroxystearic acid or the like is added are also included. 2-Hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred from the viewpoint of suppressing foreign matter on the coating film, and from the viewpoint of sensitivity, it is preferable to use one having 2 to 6 hydroxyl groups. is preferred, and glycerol mono(meth)acrylate is more preferred.

Examples of ethylenically unsaturated monomers having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[methacryloyloxy]ethyl isocyanate, and the like. be done.

Other monomers that can constitute the alkali-soluble resin include, in addition to the other ethylenically unsaturated monomers already described, N-substituted maleimides, alkyleneoxy group-containing monomers, and phosphate ester group-containing ethylenically unsaturated monomers. monomers, carboxyl group-containing ethylenically unsaturated monomers, and the like.
N-substituted maleimides include, for example, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy- 4-methyl-3-maleimidocoumarin, 4,4′-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N′-1,3-phenylenedimaleimide, N, N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitro phenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine and the like. Examples of alkyleneoxy group-containing monomers include EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, and paracumylphenol. Examples include EO- or propylene oxide (PO)-modified (meth)acrylates, nonylphenol EO-modified (meth)acrylates, nonylphenol PO-modified (meth)acrylates, and the like.

As the carboxyl group-containing ethylenically unsaturated monomer, the monomers already described can be used.

The phosphate ester group-containing ethylenically unsaturated monomer is, for example, a compound obtained by reacting the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer with a phosphorylating agent such as phosphorus pentoxide or polyphosphoric acid. be.

(Alkali-soluble resin having no ethylenically unsaturated double bond)
The near-infrared absorbing composition of the present invention can contain an alkali-soluble resin having no ethylenically unsaturated double bonds in order to adjust the degree of curing of the film.

The weight-average molecular weight (Mw) of the alkali-soluble resin in the invention is preferably 4,000 or more and 100,000 or less, more preferably 5,000 or more and 50,000 or less, in order to impart solubility in alkali development. Also, the value of Mw/Mn is preferably 10 or less. If the weight-average molecular weight (Mw) is less than 4,000, the adhesiveness to the substrate is lowered and the exposed pattern is less likely to remain. If it exceeds 100,000, the solubility in alkali development will be lowered, and a residue will be generated to deteriorate the linearity of the pattern.

The acid value of the alkali-soluble resin in the present invention is from 50 to 200 (KOHmg/g), preferably from 20 to 300, more preferably from 90 to 170, in order to impart solubility in alkali development. is. If the acid value is less than 50, the solubility in alkali development is lowered, and residues are generated, resulting in poor pattern linearity. If the acid value is excessively high, the adhesion to the substrate is lowered, and the exposure pattern is less likely to remain.

Each raw material used for synthesizing the binder resin can be used alone or in combination of two or more.

(Thermosetting compound)
In the present invention, it is preferable that the binder resin is used in combination with the thermoplastic resin and further contains a thermosetting compound. For example, when an optical filter is produced using the near-infrared absorbing composition of the present invention, the inclusion of a thermosetting compound reacts when the filter segment is baked to increase the crosslink density of the coating film, thereby increasing the heat resistance of the filter segment. It is possible to obtain the effect of suppressing a decrease in transmittance in the range of 480 nm to 650 nm, which is a region with high relative luminosity, by suppressing dye aggregation during baking of the filter segment.

The thermosetting compound may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin.
Examples of thermosetting compounds include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds, but the present invention is limited thereto. not to be Epoxy compounds and oxetane compounds are preferably used in the near-infrared absorbing composition of the present invention.

Epoxy compounds include, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted polycondensates of various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), phenol polymers with various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols and ketones Polycondensates with (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol , α,α,α',α'-biphenyldimethanol, etc.), polycondensation products of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.) , polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, and the like.

The content of the thermosetting compound is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass, per 100 parts by mass of the dye. Appropriate heat resistance can be obtained by using an appropriate amount.

The near-infrared absorbing composition can contain a curing agent and a curing accelerator to assist curing of the thermosetting compound. Curing agents include, for example, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like. Curing accelerators include, for example, amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl -N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives bicyclic amidine compounds and salts thereof (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2- ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4 -diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc.) mentioned.

The contents of the curing agent and the curing accelerator are preferably 0.01 to 15 parts by mass, respectively, for 100 parts by mass of the thermosetting compound.

<Polymerizable compound>
The near-infrared absorbing composition of the present invention can be made into a photosensitive near-infrared absorbing composition by containing a polymerizable compound and a photopolymerization initiator. Polymerizable compounds include monomers or oligomers that are cured by ultraviolet rays, heat, or the like to form transparent resins.

Polymerizable compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) Acrylates, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetra Ethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A Diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, methylolated Various acrylic and methacrylic esters such as melamine (meth)acrylate, epoxy (meth)acrylate, urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile and the like.

(Polymerizable compound having acid group)
The polymerizable compound can contain a photopolymerizable monomer having an acid group. Examples of acid groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups.

Photopolymerizable monomers having an acid group include, for example, polyhydric alcohols and (meth)acrylic acid esters of free hydroxyl group-containing poly(meth)acrylates and dicarboxylic acids; Examples thereof include esterified products with hydroxyalkyl (meth)acrylates. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. , malonic acid, succinic acid, glutaric acid, free carboxyl group-containing monoesters with dicarboxylic acids such as phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4- Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxy Monohydroxy monoacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, or free carboxyl group-containing oligoesters with monohydroxy monomethacrylates, and the like can be mentioned.

(Polymerizable compound having urethane bond)
The polymerizable compound can contain a monomer having an ethylenically unsaturated bond and a urethane bond. The monomer is, for example, a polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, or reacting a polyfunctional isocyanate with an alcohol and further reacting a (meth)acrylate having a hydroxyl group. and polyfunctional urethane acrylates obtained by

(Meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ) acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate , glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and carboxy(meth)acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

Polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate and the like.

A polymerizable compound can be used individually or in combination of 2 or more types.

The blending amount of the polymerizable compound is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, based on 100% by mass of the non-volatile matter of the near-infrared absorbing composition. Curability and developability are further improved when blended in an appropriate amount.

<Photoinitiator>
Photoinitiators include, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1 -hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl] -2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, etc. Acetophenone compounds; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone , 4-benzoyl-4'-methyldiphenyl sulfide, or benzophenone compounds such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone , isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)- s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2 -piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis (Trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6- Triazine, or triazine compounds such as 2,4-trichloromethyl-(4′-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O- benzoyloxime)], or oxime ester compounds such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); Phosphine compounds such as (2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Quinones such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds. Among these, oxime ester compounds are preferred.

A photoinitiator can be used individually or in combination of 2 or more types.

(Oxime ester compound)
In oxime ester-based compounds, the absorption of ultraviolet light causes cleavage of the NO bond of the oxime to produce iminyl radicals and alkyloxy radicals. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. When the dye concentration of the near-infrared absorbing composition is high, the ultraviolet transmittance of the coating film may be low and the degree of curing of the coating film may be low. be.

Oxime ester compounds are oximes described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc. Ester-based photopolymerization initiators can be mentioned.

The content of the photopolymerization initiator is preferably 2 to 200 parts by mass, more preferably 2 to 150 parts by mass, per 100 parts by mass of the dye. When blended in an appropriate amount, the photocurability and developability are further improved.

<Sensitizer>
Furthermore, the near-infrared absorbing composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives , naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxyesters , acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3′ or 4,4′- tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone and the like.

Among the above sensitizers, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives can be mentioned as sensitizers capable of particularly suitable sensitization. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.

More specifically, edited by Shin Okawara et al., "Dye Handbook" (1986, Kodansha), edited by Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al. Special Functional Materials" (1986, CMC), but are not limited to these. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be included.

A sensitizer can be used alone or in combination of two or more.

The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator. When contained in an appropriate amount, curability and developability are further improved.

<Thiol chain transfer agent>
The near-infrared absorbing composition of the present invention preferably contains a thiol chain transfer agent as a chain transfer agent. By using a thiol together with a photopolymerization initiator, in the radical polymerization process after light irradiation, it acts as a chain transfer agent and generates thiyl radicals that are less susceptible to polymerization inhibition by oxygen. becomes sensitivity.

Moreover, polyfunctional aliphatic thiols bonded to aliphatic groups such as methylene and ethylene groups having two or more thiol groups are preferred. More preferred are polyfunctional aliphatic thiols having 4 or more thiol groups. By increasing the number of functional groups, the polymerization initiation function is improved, and it is possible to cure from the surface of the pattern to the vicinity of the substrate.

Polyfunctional thiols include, for example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropio trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s- Examples include triazines, preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

A thiol-based chain transfer agent can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, based on 100% by mass of the non-volatile matter of the near-infrared absorbing composition. When contained in an appropriate amount, the photosensitivity and tapered shape are improved, and wrinkles are less likely to occur on the coating surface.

<Polymerization inhibitor>
The near-infrared absorbing composition of the present invention can contain a polymerization inhibitor. This makes it possible to suppress exposure due to diffracted light from the mask during photolithographic exposure, making it easier to obtain a pattern of a desired shape.

Examples of polymerization inhibitors include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2- Propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4- Alkylcatechol compounds such as tert-butylcatechol and 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propyl Alkylresorcinol compounds such as resorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, Alkylhydroquinone compounds such as 2,5-di-tert-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine and tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine oxide, etc. phosphine oxide compounds, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol, phloroglucine and the like.

The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass based on 100 parts by mass of the non-volatile matter of the near-infrared absorbing composition. Within this range, the effect of the polymerization inhibitor is increased, and the straightness of the taper, the wrinkles of the coating film, the pattern resolution, etc. are improved.

<Ultraviolet absorber>
The near-infrared absorbing composition of the invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorption function, and includes benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds. .

The content of the ultraviolet absorber is preferably 5 to 70% by weight based on the total 100% by weight of the photopolymerization initiator and the ultraviolet absorber. When contained in an appropriate amount, the resolution after development is further improved.

Further, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the non-volatile matter of the near-infrared absorbing composition. When contained in an appropriate amount, the adhesion between the substrate and the film is further improved, and good resolution can be obtained.

Benzotriazole compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5 -bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy- 5′-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethyl ethyl)-4-hydroxy, a mixture of C7-9 side chain and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-( 2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 2-(2H-benzotriazol-2-yl)-4-(1,1 ,3,3-tetramethylbutyl)phenol, 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2 -(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3,5 -di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert- Butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro- 2H-benzotriazol-2-yl)phenyl]propionate and the like. In addition, oligomer type and polymer type compounds having a benzotriazole structure can also be used.

Triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6 -bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxyphenyl )-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidate ester reaction product, 2,4-bis "2-hydroxy-4- butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyl oxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine and the like. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.

Benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2 , 2′,4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

Salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tertbutylphenyl salicylate. In addition, oligomer type and polymer type compounds having a salicylic acid ester structure can also be used.

<Antioxidant>
The near-infrared absorbing composition of the present invention can contain an antioxidant. Antioxidants prevent the photopolymerization initiators and thermosetting compounds contained in the near-infrared absorbing composition from oxidizing and yellowing due to the heat process during thermosetting and ITO annealing. can be improved. Especially when the colorant concentration of the near-infrared absorbing composition is high, the amount of the coating film cross-linking component is reduced. You can see it getting stronger. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process and to obtain a high transmittance of the coating film.

Antioxidants include, for example, hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present invention, the antioxidant is preferably a compound containing no halogen atoms.

Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred from the viewpoint of achieving both transmittance and sensitivity of the coating film.

An antioxidant can be used individually or in combination of 2 or more types.

Further, the content of the antioxidant is more preferably 0.5 to 5.0% by mass based on 100% by mass of the solid content of the near-infrared absorbing composition, since the transmittance, spectral characteristics, and sensitivity are good. .

<Amine compound>
The near-infrared absorbing composition can contain an amine-based compound to reduce dissolved oxygen.
Amine compounds include, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl p-toluidine and the like.

<Leveling agent>
The near-infrared absorbing composition can contain a leveling agent to improve the leveling properties of the composition during coating. The leveling agent is preferably, for example, dimethylsiloxane having a polyether structure or polyester structure in its main chain. Examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Co., Ltd. and BYK-333 manufactured by BYK Chemie. Examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie. A dimethylsiloxane having a polyether structure in its main chain and a dimethylsiloxane having a polyester structure in its main chain can be used in combination. The content of the leveling agent is preferably 0.003 to 0.5% by mass based on 100% by mass of non-volatile matter in the near-infrared absorbing composition.

A leveling agent is, for example, a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, and is a compound that has a hydrophilic group but has low solubility in water and can lower the surface tension. A dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used as the leveling agent. Polyalkylene oxide units include, for example, polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane is a pendant type in which the polyalkylene oxide unit is bonded to the repeating unit of dimethylpolysiloxane, a terminal modified type in which the terminal is bonded to the terminal of dimethylpolysiloxane, and a dimethylpolysiloxane. It may be of any linear block copolymer type with alternating repeating bonds. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Dow Corning Toray, for example FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ- 2207 can be mentioned.

Anionic, cationic, nonionic, or amphoteric surfactants can be added to the leveling agent as auxiliaries. Two or more kinds of surfactants may be mixed and used.

Examples of anionic surfactants that are added to the leveling agent are polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, and alkyldiphenyl ether disulfones. monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphorus and acid esters.

Cationic surfactants added to the leveling agent include, for example, alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added auxiliary to the leveling agent include, for example, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monosterate. Alkylbetaines such as betaine alkyldimethylaminoacetate; amphoteric surfactants such as alkylimidazoline; and fluorine-based and silicone-based surfactants.

<Storage stabilizer>
The near-infrared absorbing composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Storage stabilizers include, for example, benzyltrimethyl chloride, quaternary ammonium chloride such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. organic phosphines, phosphites, and the like. The storage stabilizer can be used in an amount of 0.1 to 10% by mass based on the total amount of the coloring agent (100% by mass).

<Adhesion improver>
The near-infrared absorptive composition of the present invention may contain an adhesion improver such as a silane coupling agent in order to improve adhesion to the substrate. By improving the adhesion with the adhesion improving agent, the reproducibility of fine lines is improved and the resolution is improved.

Examples of adhesion improvers include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- (Meth)acrylsilanes such as methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane Silane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl- butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, aminosilanes such as hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxy mercaptos such as silane, 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureides such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide and silane coupling agents such as isocyanates such as , 3-isocyanatopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of the colorant in the near-infrared absorbing composition. Within this range, the effect is enhanced and the balance between adhesion, resolution, and sensitivity is good, which is more preferable.

<Organic solvent>
A near-infrared absorptive composition contains an organic solvent. This facilitates adjustment of the viscosity of the composition.

Organic solvents include, for example, ethyl lactate, butyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1, 4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate , 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m -xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-Diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol mono Isopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether , ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, Cyclopentanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene Glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene Glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate , isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, and the like.

Among the above organic solvents, in the case of coating applications, it is preferable to include an organic solvent having a boiling point of 120° C. or higher and 180° C. or lower at 1 atm from the viewpoint of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy- 4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc. are preferred, and propylene glycol monomethyl ether acetate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. is more preferred.

<Method for producing near-infrared absorbing composition>
The near-infrared absorbing composition of the present invention is prepared by dispersing a dye in a dye carrier such as a dispersant or a binder resin and/or an organic solvent, preferably together with a dispersing aid (a dye derivative or a surfactant), using a kneader, It can be produced by finely dispersing using various dispersing means such as a two-roll mill, three-roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, or attritor (dye dispersion). At this time, two or more kinds of dyes and the like may be dispersed in the dye carrier at the same time, or those dispersed in the dye carrier separately may be mixed. If the pigment such as a dye has high solubility, specifically, if it has high solubility in the organic solvent used, and if it is dissolved by stirring and no foreign matter is confirmed, it is manufactured by finely dispersing as described above. No need.

When used as a photosensitive near-infrared absorptive composition (resist material), it can be prepared as a solvent-developable or alkali-developable near-infrared absorptive composition. The solvent-developable or alkali-developable near-infrared absorbing composition comprises the dye dispersion, a photopolymerizable monomer and/or a photopolymerization initiator, and optionally a solvent, other dispersing aids, and It can be adjusted by mixing additives and the like. The photopolymerization initiator may be added at the stage of preparing the near-infrared absorbing composition, or may be added later to the prepared near-infrared absorbing composition.

<Removal of coarse particles>
The near-infrared absorptive composition of the present invention is produced by means of centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or a membrane filter, etc., to obtain coarse particles of 5 μm or more, preferably 1 μm or more, more preferably coarse particles of 1 μm or more. It is preferable to remove coarse particles of 0.5 μm or more and mixed dust. As such, the near-infrared absorbing composition preferably does not substantially contain particles of 0.5 µm or more. More preferably, it is 0.3 μm or less.

<Amount of water in the near-infrared absorbing composition>
The near-infrared absorbing composition of the present invention preferably has a water content of 0.1 to 2.0% by mass based on the entire near-infrared absorbing composition.

When the water content is within the above range, the near-infrared absorbing composition is excellent in dispersion stability and sensitivity even after being stored for a long time.

The content of water is preferably 1.8% by mass or less, more preferably 1.6% by mass or less, relative to the total amount of the near-infrared absorbing composition. If the water content is sufficiently small within this range, problems with the dispersion stability and sensitivity of the near-infrared absorbing composition are less likely to occur even after long-term storage.

A method for controlling the water content is not particularly limited, and a known method can be used. Examples thereof include a method of producing a near-infrared absorbing composition while blowing in a dry inert gas, and a method of adding molecular sieves and dehydrating after production. Among them, the method of manufacturing while blowing dry inert gas is preferable.

The water content can be measured by a known method such as the Karl Fischer method.

<Amount of toluene in near-infrared absorbing composition>
The near-infrared absorbing composition of the present invention may contain toluene, and when it contains toluene, the toluene content is preferably 0.1 to 10 mass ppm. The upper limit of the toluene content is preferably 9 mass ppm or less, more preferably 8 mass ppm or less, and even more preferably 7 mass ppm or less. The lower limit is preferably 0.2 ppm by mass or more, more preferably 0.3 ppm by mass or more, and even more preferably 0.4 ppm by mass or more.

<Optical filter>
Next, the optical filter of the present invention will be explained.
[Method for producing an optical filter]
The optical filter can be produced by a method of coating the near-infrared absorbing composition of the present invention on various plastic substrates or glass substrates, a method of kneading the composition into a plastic material and molding it, and the like. As long as a film that transmits near-infrared rays is formed, it can be produced by various methods regardless of the method. By combining a film produced by these methods with a photodiode, it can be used as various sensors such as an illuminance sensor, a distance sensor, a medical sensor, a touch sensor such as a display, and a biometric authentication sensor. Furthermore, the near-infrared absorbing composition of the present invention can be used as an optical filter for solid-state imaging devices by patterning it on a photodiode using a photolithography method. The details of the optical filter produced by the photolithography method will be described below.

The optical filter segments according to the present invention can be formed using known methods without particular limitation, but optical lithography is preferably used.
When the optical filter segment is formed on a predetermined corresponding photoelectric conversion element, it is formed from a negative-type photosensitive near-infrared absorbing composition, and the thickness of the negative-type resist layer in this case is 0.1 to 3. It shall be set in the range of .0 μm.

A plurality of portions corresponding to a plurality of photoelectric conversion elements to be formed on the surface of the negative resist layer formed of the negative near-infrared absorptive film are pattern-exposed using a photomask. Generally, a photomask has a size four to five times the size of a pattern to be actually formed, and is reduced to 1/4 to 1/5 during pattern exposure.

A typical photomask is a 4- to 5-fold reticle and has a pattern whose size is 4- to 5-fold larger than the size of the pattern to be exposed on the surface of the negative resist layer. Then, a stepper exposure apparatus (not shown) is used to reduce the photomask pattern to 1/4 to 1/5 and expose the surface of the negative resist layer.

After the exposure step, an alkali development treatment (development step) is performed to dissolve the uncured portion after exposure into the developer and leave the photocured portion. This developing step can form a patterned film composed of optical filter segments.

The developing method may be a dip method, a shower method, a spray method, a paddle method, or the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like.
It is also possible to prevent uneven development by moistening the surface to be developed with water or the like before contacting the developer. As the developer, an organic alkaline developer is desirable, which does not damage the underlying circuits. The development temperature is usually 20 to 30° C., and the development time is 20 to 90 seconds.

Examples of alkaline agents contained in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, organic alkaline compounds such as choline, pyrrole and piperidine, sodium hydroxide, hydroxide Inorganic compounds such as potassium, sodium hydrogencarbonate, potassium hydrogencarbonate, and the like are included.

As a developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, is preferably used. In the case of using a developer comprising such an alkaline aqueous solution, generally, after development, the film is washed with pure water to wash away excess developer and dried.

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

An optical filter is produced by the near-infrared absorbing layer forming step, exposure step, and developing step (and, if necessary, a curing step) as described above.

<Infrared camera, infrared sensor>
The infrared camera and infrared sensor of the present invention have the optical filter of the present invention. Types of infrared cameras include near-infrared cameras, surveillance cameras, in-vehicle cameras, medical cameras, inspection and analysis cameras, etc. Types of infrared sensors include temperature sensors, distance sensors, medical sensors, and displays. touch sensors, biometric authentication sensors, and the like. The configuration of the infrared camera and infrared sensor is not particularly limited as long as it has the optical filter of the present invention and functions as an infrared camera and infrared sensor.

EXAMPLES The present invention will be described below based on examples, but the present invention is not limited by these. In the examples and comparative examples, "parts" means "mass parts". "PGMAC" means propylene glycol monomethyl ether acetate.

(Maximum absorption wavelength of indigo compound (A))
The maximum absorption wavelength of the indigo compound (A) is obtained by making the indigo compound (A) into a 40 ppm solution with N-methyl-2-pyrrolidone, and then determining the wavelength at which the maximum absorbance is shown in the absorption spectrum in the range of 400 to 1300 nm. The wavelength was measured with an ultraviolet-visible-near-infrared spectrophotometer U-4150 (manufactured by Hitachi High-Technologies Corporation).

(Method for measuring specific metal atom in near-infrared absorbing composition)
The amount of specific metal atoms in the near-infrared absorbing composition is measured by an ICP emission spectrometer Varian 720-ES manufactured by Agilent Technologies after decomposing the powder obtained by drying the near-infrared absorbing composition at 180° C. with microwaves. bottom.

(Acid value of resin type dispersant and binder resin)
The acid value of the resin-type dispersant and the binder resin was obtained by potentiometric titration using a 0.1N potassium hydroxide/ethanol solution. The acid value of the resin-type dispersant and binder resin indicates the acid value of the non-volatile matter.

(Weight-average molecular weight (Mw) of acidic resin-type dispersant and binder resin)
The weight-average molecular weight (Mw) of the acidic resin-type dispersant and the binder resin was determined by GPC (HLC-8120GPC, manufactured by Tosoh Corporation) equipped with an RI detector using a TSKgel column (manufactured by Tosoh Corporation), using THF as a developing solvent. It is a polystyrene-equivalent weight average molecular weight (Mw) measured using

(Weight average molecular weight (Mw) of basic resin type dispersant)
The weight-average molecular weight (Mw) of the basic resin-type dispersant was determined by GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using a TSKgel column (manufactured by Tosoh Corporation), and 3 mM triethylamine and 10 mM LiBr as developing solvents. is a polystyrene-equivalent weight average molecular weight (Mw) measured using an N,N-dimethylformamide solution of

(Amine value of resin type dispersant)
The amine value of the resin-type dispersant was obtained by potentiometric titration using a 0.1N hydrochloric acid aqueous solution, and then converted to the equivalent of potassium hydroxide. The amine value of the resin-type dispersant indicates the amine value of the non-volatile matter.

(Quaternary ammonium salt value of resin type dispersant)
The quaternary ammonium salt value of the resin-type dispersant was determined by titration with a 0.1N aqueous solution of silver nitrate using a 5% aqueous solution of potassium chromate as an indicator, and then converted to the equivalent of potassium hydroxide. The quaternary ammonium salt value of the resin-type dispersant below indicates the quaternary ammonium salt value of the non-volatile matter.

(Production of indigo compound (A-1a))
In a reactor, 10.7 parts of aniline, 120 parts of bromobenzene, and 25.7 parts of diazabicyclooctane were added and stirred. After that, 95.2 parts of a 1 mol/l toluene solution of titanium tetrachloride was added dropwise. After dropping, 10.0 parts of indigo was added and refluxed for 10 hours. After completion of the reaction, methanol was added and filtered to obtain a green powder. 14.6 parts of compounds (1) were obtained by liquid-separating this with a dichloromethane and water and concentrating an organic layer.

[Compound (1)]

14.0 parts of compound (1), 24.7 parts of palladium acetylacetonate, and 150 parts of tetrahydrofuran were heated to reflux in a three-necked flask under a nitrogen atmosphere for 4 hours. After cooling to room temperature, methanol was added to give a blue slurry. This slurry was filtered, washed with 300 parts of methanol, washed twice with 300 parts of deionized water, and dried to obtain 13.5 parts of indigo compound (A-1a). The maximum absorption wavelength of the indigo compound (A-1a) was 905 nm.

Indigo compound (A-1a)

(Production of indigo compound (A-1b))
15.0 parts of the indigo compound (A-1a) and 300 parts of N,N-dimethylformamide are placed in a beaker, heated and stirred at room temperature for 1 hour, filtered, washed with 500 parts of methanol and 2000 parts of ion-exchanged water, Dried.

(Production of indigo compound (A-1c))
In the production of the indigo compound (A-1a), the indigo compound (A-1a) was washed with 300 parts of methanol instead of washing with 300 parts of methanol and then washing twice with 300 parts of deionized water. The same operation as in production was performed.

(Production of indigo compound (A-2))
The indigo compound (A 14.1 parts of indigo compound (A-2) was obtained by the same operation as in the production of -1a). The maximum absorption wavelength of the indigo compound (A-2) was 835 nm.

Indigo compound (A-2)

(Production of indigo compound (A-3))
Same as the production of indigo compound (A-1a), except that 24.7 parts of palladium acetylacetonate used in the production of indigo compound (A-1a) was changed to 26.4 parts of cobalt (II) acetylacetonate. to obtain 12.8 parts of indigo compound (A-3). The maximum absorption wavelength of the indigo compound (A-3) was 890 nm.

Indigo compound (A-3)

(Production of indigo compound (A-4))
Same as the production of indigo compound (A-1a), except that 24.7 parts of palladium acetylacetonate used in the production of indigo compound (A-1a) was changed to 30.0 parts of nickel (II) acetylacetonate. to obtain 12.8 parts of indigo compound (A-4). The maximum absorption wavelength of the indigo compound (A-4) was 756 nm.

Indigo compound (A-4)

(Production of indigo compound (A-5))
The same procedure as in the production of the indigo compound (A-1a) was performed, except that 24.7 parts of palladium acetylacetonate used in the production of the indigo compound (A-1a) was changed to 42.3 parts of palladium hexafluoroacetylacetonate. By the operation, 15.6 parts of indigo compound (A-5) was obtained. The maximum absorption wavelength of the indigo compound (A-5) was 915 nm.

Indigo compound (A-5)

(Production of indigo compound (A-6))
The same operation as in the synthesis of compound (1) was performed except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 18.5 parts of 2,3-dichloroaniline to obtain compound (2). 17.8 parts were obtained.

[Compound (2)]

The same operation as for the indigo compound (A-1c) was performed, except that 14.0 parts of the compound (1) used in the production of the indigo compound (A-1c) was changed to 16.4 parts of the compound (2), 14.4 parts of indigo compound (A-6) were obtained. The maximum absorption wavelength of the indigo compound (A-6) was 925 nm.

Indigo compound (A-6)

(Production of indigo compound (A-7))
10.7 parts of aniline used in the synthesis of compound (1) was changed to 12.0 parts of 4-fluoroaniline, the same operation as in the synthesis of compound (1) was performed, and compound (3) was obtained in 15.0 parts. 0 copies were obtained.

[Compound (3)]

The same operation as in the production of indigo compound (A-2) was performed, except that 14.0 parts of compound (1) used in the production of indigo compound (A-2) was changed to 15.2 parts of compound (3). 16.8 parts of indigo compound (A-7) was obtained. The maximum absorption wavelength of the indigo compound (A-7) was 835 nm.

Indigo compound (A-7)

(Production of indigo compound (A-8))
The same operation as in the synthesis of compound (1) was performed except that 10.0 parts of indigo used in the synthesis of compound (1) was changed to 22.0 parts of Bat Blue 5, and 25.4 parts of compound (4) was obtained. I got it.

[Compound (4)]

The same operation as in the production of the indigo compound (A-2) was performed, except that 14.0 parts of the compound (1) used in the production of the indigo compound (A-2) was changed to 24.7 parts of the compound (4). 16.8 parts of indigo compound (A-8) was obtained. The maximum absorption wavelength of the indigo compound (A-8) was 845 nm.

Indigo compound (A-8)

(Production of indigo compound (A-9a))
14.0 parts of compound (1), 17.6 parts of 2-aminoethyl diphenylborinate, 25.8 parts of titanium tetrachloride, and 150 parts of toluene are placed in a three-necked flask and heated under reflux for 2 hours under a nitrogen atmosphere. bottom. After cooling to room temperature, methanol was added to give a blue slurry. This slurry was filtered, washed with 300 parts of methanol, washed twice with 300 parts of water, and dried to obtain 13.2 parts of an indigo compound (A-9a). The maximum absorption wavelength of the indigo compound (A-9a) was 1000 nm.

Indigo compound (A-9a)

(Production of indigo compound (A-9b))
15.0 parts of the indigo compound (A-9a) and 300 parts of N,N-dimethylformamide are placed in a beaker, heated and stirred at room temperature for 1 hour, filtered, washed with 500 parts of methanol and 2000 parts of deionized water, and dried. bottom. The maximum absorption wavelength of the indigo compound (A-9b) was 1000 nm.

(Production of indigo compound (A-9c))
In the production of the indigo compound (A-9a), the indigo compound (A-9a) was washed with 300 parts of methanol instead of washing with 300 parts of methanol and then washing twice with 300 parts of deionized water. The same operation as in production was performed. The maximum absorption wavelength of the indigo compound (A-9c) was 1000 nm.

(Production of indigo compound (A-10))
The same operation as in the synthesis of compound (1) was performed except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 12.3 parts of p-toluidine, and compound (5) was obtained at 15.0 parts. I got it.

[Compound (5)]

The same operation as in the production of indigo compound (A-9b) was performed, except that 14.0 parts of compound (1) used in the production of indigo compound (A-9b) was changed to 15.0 parts of compound (5). to obtain 14.2 parts of indigo compound (A-10). The maximum absorption wavelength of the indigo compound (A-10) was 1050 nm.

Indigo compound (A-10)

(Production of indigo compound (A-11))
The same procedure as in the synthesis of compound (1) was performed except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 16.5 parts of 1-naphthylamine, and 18.8 parts of compound (6) was obtained. I got it.

[Compound (6)]

The same operation as in the production of indigo compound (A-9b) was performed, except that 14.0 parts of compound (1) used in the production of indigo compound (A-9b) was changed to 17.6 parts of compound (6). 14.9 parts of indigo compound (A-11) was obtained. The maximum absorption wavelength of the indigo compound (A-11) was 1070 nm.

Indigo compound (A-11)

(Production of indigo compound (A-12))
The same operation as in the synthesis of compound (1) was performed except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 14.2 parts of 3-methoxyaniline, and compound (7) was obtained in 17. Got 3 copies.

[Compound (7)]

The same operation as in the production of indigo compound (A-9c) was performed, except that 14.0 parts of compound (1) used in the production of indigo compound (A-9c) was changed to 15.9 parts of compound (7). 14.1 parts of indigo compound (A-12) was obtained. The maximum absorption wavelength of the indigo compound (A-12) was 1055 nm.

Indigo compound (A-12)

(Production of indigo compound (A-13))
In a reactor, 7.1 parts of aniline, 120 parts of bromobenzene, and 25.7 parts of diazabicyclooctane were added and stirred. After that, 8.7 parts of aluminum chloride and 10.0 parts of indigo were added and refluxed for 10 hours. After completion of the reaction, methanol was added and filtered to obtain a green powder. This was separated with dichloromethane and water, and the organic layer was concentrated to obtain 11.8 parts of compound (8).

[Compound (8)]

12.0 parts of compound (8), 19.6 parts of palladium acetylacetonate, and 150 parts of tetrahydrofuran were heated under reflux in a three-necked flask under a nitrogen atmosphere for 4 hours. After cooling to room temperature, methanol was added to give a blue slurry. This slurry was filtered, washed with 300 parts of methanol, washed twice with 300 parts of deionized water, and dried to obtain 14.3 parts of an indigo compound (A-13). The maximum absorption wavelength of the indigo compound (A-13) was 795 nm.

Indigo compound (A-13)

(Production of indigo compound (A-14))
14.0 parts of compound (1), 9.2 parts of 2-aminoethyl diphenylborinate, 9.8 parts of titanium tetrachloride, and 150 parts of toluene are heated under reflux for 2 hours in a three-necked flask under a nitrogen atmosphere. bottom. After cooling to 50° C., 12.5 parts of palladium acetylacetonate was added and stirred for 2 hours. After cooling to room temperature, methanol was added to give a blue slurry. This slurry was filtered, washed with 300 parts of methanol, washed with 200 parts of ionized water, and dried to obtain 13.2 parts of an indigo compound (A-14). The maximum absorption wavelength of the indigo compound (A-14) was 950 nm.

Indigo compound (A-14)

(Production of indigo compound (A-15))
10.0 parts of indigo, 58.7 parts of dichlorobis(triphenylphosphine)palladium, and 150 parts of tetrahydrofuran were heated to reflux in a three-necked flask under a nitrogen atmosphere for 4 hours. Methanol was added to give a blue slurry. This slurry was filtered, washed with 300 parts of methanol, washed twice with 300 parts of deionized water, and dried to obtain 7.2 parts of an indigo compound (A-15). The maximum absorption wavelength of the indigo compound (A-15) was 760 nm.

Indigo compound (A-15)

(Production of indigo compound (A-1d))
In the production of the indigo compound (A-1a), the indigo compound (A-1a ) was performed in the same manner as in the production of

(Production of indigo compound (A-9d))
In the production of the indigo compound (A-9a), the indigo compound (A-9a) was changed from washing with 300 parts of methanol and then washing twice with 300 parts of ion-exchanged water to washing with 300 parts of ion-exchanged water. ) was performed in the same manner as in the production of

(Production of indigo compound (A-9e))
14.0 parts of compound (1), 17.6 parts of 2-aminoethyl diphenylborinate, 25.8 parts of titanium tetrachloride, and 150 parts of toluene are placed in a three-necked flask and heated under reflux for 2 hours under a nitrogen atmosphere. bottom. After cooling to room temperature, it was concentrated and recrystallized with methanol/hexane to obtain 5.2 parts of indigo compound (A-9e). The maximum absorption wavelength of the indigo compound (A-9e) was 1000 nm.

<Method for producing binder resin solution>
(Production of binder resin 1 solution)
70.0 parts of cyclohexanone was charged into a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirring device, and the temperature was raised to 80°C. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumylphenol ethylene oxide-modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.) 7.4 parts, A mixture of 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for an additional 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. A binder resin 1 solution was prepared by adding ether acetate.

(Production of binder resin 2 solution)
A separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and after replacing the inside of the flask with nitrogen, the distillate was added from the dropping tube. A mixture of 18 parts of cyclopentanyl methacrylate, 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. . After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, then a solution obtained by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100°C for 1 hour. Next, the inside of the container was changed to air exchange, and 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl groups), and the mixture was heated at 120°C. The reaction was continued for 6 hours, and when the solid content acid value reached 0.5, the reaction was terminated to obtain a solution of an acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. A binder resin 2 solution was prepared by adding acetate. The weight average molecular weight (Mw) was 19,000.

(Production of binder resin 3 solution)
207 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80°C, and the inside of the reaction vessel was replaced with nitrogen. After that, from a dropping tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix (registered trademark) M110” manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile were added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and the total amount of the copolymer solution obtained was stirred while injecting dry air for 1 hour. After cooling to room temperature, 2-methacryloyloxyethyl isocyanate (Showa Denko Co., Ltd. A mixture of 6.5 parts of Karenz (registered trademark) MOI"), 0.08 part of dibutyl tin laurate and 26 parts of propylene glycol monomethyl ether acetate was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for an additional hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. A binder resin 3 solution was prepared by adding ether acetate. The weight average molecular weight (Mw) was 18,000.

<Method for producing resin-type dispersant solution>

(Production of basic resin-type dispersant 1 solution)
A reaction vessel equipped with a stirrer and a thermometer was charged with 41 parts of N,N-dimethylpropanediamine and 120 parts of chloroform, stirred at room temperature, and 50 parts of methacrylic acid chloride was added dropwise over 1 hour. After stirring at room temperature for 3 hours and confirming the completion of the reaction by ¹ H-NMR, the reaction solution was washed successively with 300 parts of ion-exchanged water and 200 parts of saturated brine, and 20 g of magnesium sulfate was added to the organic layer. was added, and after stirring, filtration was performed. The solvent in the obtained solution was distilled off with a rotary evaporator to obtain 58 parts of compound [B] represented by the following formula (9) as a pale yellow transparent liquid (yield 85%). Identification of the obtained compound was carried out by ¹ H-NMR.

formula (9)

15.7 parts of methyl methacrylate, 47.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer, and the mixture was stirred for 50 minutes while flowing nitrogen. The mixture was stirred at ℃ for 1 hour, and the inside of the system was replaced with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) are charged, and the temperature is raised to 110° C. under a nitrogen stream to form the first block. started to polymerize. After polymerization for 4 hours, the polymerization solution was sampled and solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of non-volatile matter.
Next, 25 parts of PGMAc and 30.3 parts of the above compound [B] as a second block monomer were added to the reactor, and the mixture was stirred while maintaining the temperature at 110° C. under a nitrogen atmosphere to continue the reaction. Two hours after the addition of the compound [B] represented by the above formula (9), the polymerization solution was sampled and the solid content was measured. It was confirmed.
Further, 6.8 parts of benzyl chloride was added to the reactor, stirred for 3 hours while maintaining the temperature at 110° C. under a nitrogen atmosphere, and then cooled.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by mass. Thus, a basic resin-type dispersant 1 having an amine value per solid content of 70 mgKOH/g, a quaternary ammonium salt value of 30 mgKOH/g, a weight average molecular weight (Mw) of 9,800, and a nonvolatile content of 40% by mass A solution was obtained.

(Production of basic resin type dispersant 2 solution)
60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, and the mixture was heated at 50°C for 1 hour while flowing nitrogen. After stirring, the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 20 parts of dimethylaminoethyl methacrylate (hereinafter referred to as DM) as a second block monomer were added to the reactor, and the mixture was stirred while maintaining the temperature at 110° C. under a nitrogen atmosphere to continue the reaction. Two hours after the addition of dimethylaminoethyl methacrylate, the polymerization solution was sampled and the nonvolatile content was measured to confirm that the polymerization conversion rate of the second block was 98% or more in terms of the nonvolatile content. Polymerization was stopped by cooling.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by mass. Thus, a basic resin-type dispersant 2 solution having an amine value per non-volatile content of 71.4 mgKOH/g, a weight average molecular weight of 9,900 (Mw), and a non-volatile content of 40% by mass was obtained.

(Production of basic resin-type dispersant 3 solution)
60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, and the mixture was heated at 50°C for 1 hour while flowing nitrogen. After stirring, the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 25.6 parts of an aqueous solution of methacryloyloxyethyltrimethylammonium chloride as a second block monomer ("Acryester DMC78" manufactured by Mitsubishi Rayon Co., Ltd.) were added to the reactor, and the temperature was maintained at 110°C under a nitrogen atmosphere. The reaction was continued while stirring. Two hours after the addition of methacryloyloxyethyltrimethylammonium chloride, the polymerization solution was sampled and the nonvolatile content was measured. Polymerization was terminated by cooling to room temperature.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by mass. Thus, a basic resin-type dispersant 3 solution having an amine value per non-volatile content of 29.4 mgKOH/g, a weight average molecular weight of 9,800 (Mw), and a non-volatile content of 40% by mass was obtained.

(Production of acidic resin-type dispersant 4 solution)
10 parts of methacrylic acid, 90 parts of methyl methacrylate, 50 parts of ethyl acrylate, 50 parts of tert-butyl acrylate, and 50 parts of propylene glycol monomethyl ether acetate were charged into a reaction vessel equipped with a gas inlet tube, temperature, condenser, and stirrer, and nitrogen gas was added. replaced with The inside of the reaction vessel was heated to 50° C. with stirring, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90° C., and the mixture was reacted for 7 hours while adding a solution obtained by adding 0.1 part of 2,2′-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate. Solid content measurement confirmed that 95% had reacted.
19 parts of pyromellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst are added and reacted at 100° C. for 7 hours. rice field. After confirming that 98% or more of the acid anhydride is half-esterified by measuring the acid value, the reaction is terminated. An acidic resin type dispersant 4 solution having a molecular weight of 70 mgKOH/g and a weight average molecular weight of 8500 (Mw) was obtained.

(Production of resin-type dispersant 5 solution)
DISPER-BYK111 (manufactured by BYK-Chemie Japan; acid value: 129 mgKOH/g, solid content: 95%) was diluted in the same manner as the resin type dispersant 1 solution to prepare a resin type dispersant 5 solution.

<Production of near-infrared absorbing composition>
[Example 1]
(Near-infrared absorbing composition (D-1))
After uniformly stirring and mixing a mixture having the following composition, zirconia beads having a diameter of 0.5 mm were dispersed in an Eiger mill for 3 hours, and then filtered through a 0.5 μm filter to prepare a near-infrared absorbing composition. .
Indigo compound (A-1a): 10.0 parts Resin type dispersant 1 solution: 15.0 parts Binder resin 1 solution: 20.0 parts PGMAc: 55.0 parts Near infrared absorbing composition (D-1) whole , the total amount of specific metal atoms was 180 ppm.

[Examples 2 to 19, 41 to 56, Comparative Examples 1 to 3]
(Near-infrared absorbing compositions (D-2) to (D-19), (D-41) to (D-59))
Below, in the same manner as the near-infrared absorbing composition (D-1), except that the indigo compound, resin-type dispersant solution, binder resin solution, PGMAc, and other solvents were changed to the compositions and amounts shown in Table 1, Infrared absorbing compositions (D-2) to (D-19) and (D-41) to (D-59) were prepared.

[Example 20]
(Near-infrared absorbing composition (D-20))
After uniformly stirring and mixing a mixture having the following composition, zirconia beads having a diameter of 0.5 mm were dispersed in an Eiger mill for 3 hours, and then filtered through a 0.5 μm filter to prepare a near-infrared absorbing composition. .
Indigo compound (A-1a): 7.0 parts Other near-infrared absorbing dye (X-1): 3.0 parts Resin type dispersant 1 solution: 15.0 parts Binder resin 1 solution: 20.0 parts PGMAc : 55.5 parts The total amount of specific metal atoms was 200 ppm with respect to the entire near-infrared absorbing composition (D-20).

[Examples 21 to 38]
(Near-infrared absorbing compositions (D-21) to (D-38))
Below, the near-infrared absorbing composition (D-20) was prepared in the same manner as the near-infrared absorbing composition (D-20) except that the near-infrared absorbing dye, resin-type dispersant solution, binder resin solution, and PGMAc were changed to the compositions and amounts shown in Table 1. Absorbent compositions (D-21) to (D-38) were prepared. (X-1) to (X-14) are other near-infrared absorbing dyes shown below.

[Example 39]
(Near-infrared absorbing composition (D-39))
After uniformly stirring and mixing a mixture having the following composition, zirconia beads having a diameter of 0.5 mm were dispersed in an Eiger mill for 3 hours, and then filtered through a 0.5 μm filter to prepare a near-infrared absorbing composition. .
Indigo compound (A-7): 9.0 parts Dye derivative (G-1): 1.0 parts Resin type dispersant 1 solution: 15.0 parts Binder resin 1 solution: 20.0 parts PGMAc: 55.0 parts The total amount of specific metal atoms was 370 ppm with respect to the entire near-infrared absorbing composition (D-39).

[Example 40]
(Near-infrared absorbing composition (D-40))
Below, the near-infrared absorbing composition (D-39) was prepared in the same manner as the near-infrared absorbing composition (D-39), except that the dye derivative, the resin-type dispersant solution, the binder resin solution, and PGMAc were changed to the compositions and amounts shown in Table 1. Product (D-40) was prepared. The total amount of specific metal atoms was 390 ppm with respect to the entire near-infrared absorbing composition (D-40).
Compounds represented by the following structural formulas (G-1) and (G-2) were used as dye derivatives.

(G-1)

(G-2)

Table 1 shows the compositions and specific metal atom contents of the near-infrared absorbing compositions (D-1 to D-59).

<Evaluation of near-infrared absorbing composition>
The near-infrared absorbing compositions (D-1 to 59) obtained in Examples and Comparative Examples were tested for light-shielding properties in the near-infrared region, initial viscosity, storage stability, and aggregated foreign matter by the following methods. . Table 2 shows the results.

(Evaluation of light shielding properties in the near-infrared region)
The resulting near-infrared absorbing composition is coated on a glass substrate of 100 mm × 100 mm and 1.1 mm thick using a spin coater, baked in an oven at 230 ° C. for 20 minutes, and the thickness of the coating film after heat treatment. A coated substrate was prepared so that the thickness was 1.0 μm. The film thickness was measured using DEKTAK. The light shielding properties in the near-infrared region were evaluated by measuring the transmittance of the produced substrate at the maximum absorption wavelength (700 to 1300 nm). In addition, ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level not suitable for practical use.
◎: maximum transmittance less than 3.0% ○: maximum transmittance 3.0% or more, less than 5.0% △: maximum transmittance 5.0% or more, less than 7.0% ×: maximum transmittance is 7.0% or more

(Initial viscosity evaluation)
The viscosity (initial viscosity) of the near-infrared absorbing composition was measured at 25° C. on the day of preparation using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 20 rpm. In the following evaluation results, ⊚ is very good, ◯ is good, Δ is a level that does not pose a problem in use despite high viscosity, and × is a level that poses a problem in use.
◎: less than 10.0 [mPa s]
○: 10.0 or more to less than 15.0 [mPa s]
△: 15.0 or more to less than 20.0 [mPa s]
×: 20.0 or more [mPa s]

(Evaluation of storage stability)
The viscosity of the obtained near-infrared absorbing composition immediately after preparation and after storage at 10° C. for one month was measured using an E-type viscometer. The ratio of (viscosity after storage for one month)/(viscosity immediately after preparation) was calculated and evaluated according to the following criteria. In addition, ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level not suitable for practical use.
◎: Viscosity ratio is 1.00 or more and less than 1.02 ○: Viscosity ratio is 1.02 or more and less than 1.05 △: Viscosity ratio is 1.05 or more and less than 1.10 ×: Viscosity ratio is 1.10 that's all

(Evaluation of aggregated foreign matter)
The resulting near-infrared absorbing composition is coated on a glass substrate of 100 mm × 100 mm and 1.1 mm thick using a spin coater, baked in an oven at 230 ° C. for 20 minutes, and the thickness of the coating film after heat treatment. A coated substrate was prepared so that the thickness was 1.0 μm. The film thickness was measured using DEKTAK. After that, the obtained substrate was heated at 250° C. for 1 hour, and the surface was observed. A metallographic microscope "BX60" manufactured by Olympus Systems was used for the evaluation. Magnification was set to 500 times, and the number of particles observable in arbitrary 5 fields of transmission was counted and evaluated. In addition, ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level not suitable for practical use.
◎: The number of foreign substances is 5 or more and less than 10 ○: The number of foreign substances is 10 or more and less than 20 △: The number of foreign substances is 20 or more and less than 60 ×: The number of foreign substances is 60 or more

From the results in Table 2, the near-infrared absorbing composition of the present invention was excellent in light-shielding properties in the near-infrared region, had good initial viscosity and good storage stability, and generated little foreign matter.

<Production of photosensitive near-infrared absorbing composition>
[Example 101]
(Photosensitive near-infrared absorbing composition (R-1))
The following mixture was uniformly stirred and mixed, and filtered through a 1.0 μm filter to obtain a photosensitive near-infrared absorbing composition (R-1).
Near-infrared absorbing composition (D-1): 50.0 parts Binder resin 2 solution: 7.5 parts Photopolymerization initiator (manufactured by Toagosei Co., Ltd. "Aronix M-402"): 2.0 parts Photopolymerization initiation Agent ("OXE-02" manufactured by BASF Japan): 1.5 parts PGMAc: 39.0 parts

[Examples 102 to 111 and Comparative Examples 101 and 102]
(Photosensitive near-infrared absorbing composition (R-2) to (R-13))
Hereinafter, a photosensitive near-infrared absorbing composition in the same manner as the photosensitive near-infrared absorbing composition (R-1) except that the near-infrared absorbing composition was changed to the type of near-infrared absorbing composition shown in Table 3. Products (R-2) to (R-13) were obtained.

<Evaluation of photosensitive near-infrared absorbing composition>
The photosensitive near-infrared absorbing compositions (R-1) to (R-13) obtained in Examples and Comparative Examples were tested for light-shielding properties in the near-infrared region, initial viscosity, storage stability, and aggregated foreign matter. The following method was used. Table 3 shows the results.

(Evaluation of light shielding properties in the near-infrared region)
The resulting photosensitive coloring composition was spin-coated onto a glass substrate having a thickness of 1.1 mm using a spin coater, dried at 60° C. for 5 minutes, and then exposed to ultraviolet rays of 100 mJ/cm ² using an ultra-high pressure mercury lamp. , spray-developed with an alkaline developer consisting of a 0.2% by mass sodium carbonate aqueous solution, and then baked at 230 ° C. for 20 minutes so that the thickness of the coating film after heat treatment was 1.0 μm. was made. The film thickness was measured using DEKTAK. The light shielding properties in the near-infrared region were evaluated by measuring the transmittance of the produced substrate at the maximum absorption wavelength (700 to 1300 nm). In addition, ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level not suitable for practical use.
◎: maximum transmittance less than 3.0% ○: maximum transmittance 3.0% or more, less than 5.0% △: maximum transmittance 5.0% or more, less than 7.0% ×: maximum transmittance is 7.0% or more

(Initial viscosity evaluation)
The viscosity (initial viscosity) of the photosensitive near-infrared absorbing composition was measured at 25° C. on the day of preparation using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 20 rpm. . In the following evaluation results, ⊚ is very good, ◯ is good, Δ is a level that does not pose a problem in use despite high viscosity, and × is a level that poses a problem in use.
◎: less than 10.0 [mPa s]
○: 10.0 or more to less than 15.0 [mPa s]
△: 15.0 or more to less than 20.0 [mPa s]
×: 20.0 or more [mPa s]

(Evaluation of storage stability)
The viscosity of the resulting photosensitive near-infrared absorbing composition immediately after preparation and after storage at 10° C. for one month was measured using an E-type viscometer. The ratio of (viscosity after storage for one month)/(viscosity immediately after preparation) was calculated and evaluated according to the following criteria. In addition, ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level not suitable for practical use.
◎: Viscosity ratio is 1.00 or more and less than 1.02 ○: Viscosity ratio is 1.02 or more and less than 1.05 △: Viscosity ratio is 1.05 or more and less than 1.10 ×: Viscosity ratio is 1.10 that's all

(Evaluation of aggregated foreign matter)
The resulting photosensitive near-infrared absorptive composition was spin-coated on a glass substrate having a thickness of 1.1 mm using a spin coater, dried at 60° C. for 5 minutes, and exposed to 100 mJ/cm using an ultra-high pressure mercury lamp. ² , spray-developed with an alkaline developer consisting of a 0.2% by mass sodium carbonate aqueous solution, and then baked at 230° C. for 20 minutes so that the thickness of the coating film after heat treatment was 1.0 μm. A coated substrate was produced. The film thickness was measured using DEKTAK. After that, the obtained substrate was heated at 250° C. for 1 hour, and the surface was observed. A metallographic microscope "BX60" manufactured by Olympus Systems was used for the evaluation. Magnification was set to 500 times, and the number of particles observable in arbitrary 5 fields of transmission was counted and evaluated. In addition, ⊚ is a very good level, ⊙ is a very good level, ◯ is a good level, Δ is a practical level, and x is a level not suitable for practical use.
◎: The number of foreign substances is 5 or more and less than 10 ○: The number of foreign substances is 10 or more and less than 20 △: The number of foreign substances is 20 or more and less than 60 ×: The number of foreign substances is 60 or more

From the results of Table 3, the results of the photosensitive near-infrared absorbing composition (R) were the same as those of the near-infrared absorbing composition (D), and Examples 101 to 111 exhibited light-shielding properties in the near-infrared region. Good initial viscosity, good storage stability, and less foreign matter generation.

<Production of near-infrared cut filter>
[Examples 112 to 114]
(Near infrared absorption cut filter (F-1) to (F-3))
A glass substrate having a thickness of 1.1 mm was coated with the photosensitive near-infrared absorbing composition (R-1) of the present invention by a spin coater, and pre-baked by heat treatment on a hot plate at 100° C. for 1 minute.
Then, using an ultra-high pressure mercury lamp USH-200DP (manufactured by Ushio Inc.), pattern exposure was performed through a photomask at an exposure amount of 1000 mJ/cm ² in order to form a 100 μm square near-infrared absorption cut filter. .
The uncured portion of the exposed film was removed by a shower development method using a 0.2% by weight sodium carbonate aqueous solution as a developer at a developer pressure of 0.1 mPa to form a pattern of 400 μm×400 μm. After that, it was post-baked at 100° C. for 120 minutes. The film thickness of the near-infrared absorption cut filter (F-1) after heat treatment was 1.0 μm.
Near-infrared cut filters (F-2) to (F- 3) was obtained.

<Evaluation of near-infrared cut filter>
Near-infrared cut filters (F-1) to (F-3) were tested for light-shielding properties in the near-infrared region and aggregated foreign matter in the same manner as in the evaluation of the photosensitive near-infrared absorbing composition. Table 4 shows the results.

From the results in Table 4, Examples 112 to 114 were excellent in the light shielding property in the near-infrared region, and generated less foreign matter.

<Production of near-infrared absorptive composition (visible region absorptive composition) containing organic dye having maximum absorption wavelength in the range of 400 nm or more and less than 700 nm>

(Blue colored composition)
After uniformly stirring and mixing a mixture having the following composition, zirconia beads with a diameter of 0.5 mm were used to disperse the mixture with an Eiger mill for 3 hours, followed by filtration through a 0.5 μm filter to prepare a blue colored composition.
C. I. Pigment Blue PB15: 6: 10.0 parts Resin type dispersant 1 solution: 15.0 parts Binder resin 1 solution: 20.0 parts PGMAc: 55.0 parts

(Purple colored composition)
After uniformly stirring and mixing a mixture having the following composition, zirconia beads with a diameter of 0.5 mm were used to disperse the mixture with an Eiger mill for 3 hours, followed by filtration through a 0.5 μm filter to prepare a purple colored composition.
C. I. Pigment violet PV23: 10.0 parts Resin type dispersant 1 solution: 15.0 parts Binder resin 1 solution: 20.0 parts PGMAc: 55.0 parts

(Yellow colored composition)
After uniformly stirring and mixing a mixture having the following composition, zirconia beads with a diameter of 0.5 mm were used to disperse the mixture with an Eiger mill for 3 hours, followed by filtration through a 0.5 μm filter to prepare a yellow colored composition.
C. I. Pigment yellow PY139: 10.0 parts Resin type dispersant 1 solution: 15.0 parts Binder resin 1 solution: 20.0 parts PGMAc: 55.0 parts

[Example 115]
(Visible light region absorbing composition (P-1))
The following mixture was uniformly stirred and mixed, and then filtered through a 1.0 μm filter to obtain a visible light absorbing composition (P-1).
Near-infrared absorbing composition (D-1): 10.0 parts Blue pigment composition: 20.0 parts Purple pigment composition: 10.0 parts Yellow pigment composition: 10.0 parts Binder resin 1 solution: 7. 5 parts photopolymerizable compound (manufactured by Toagosei Co., Ltd. "Aronix M-402"): 2.0 parts photopolymerization initiator (manufactured by BASF Japan "OXE-02"): 1.5 parts PGMAc: 39.0 parts

[Examples 116 to 118, Comparative Example 103]
(Visible light region absorbing compositions (P-2) to (P-5))
Hereinafter, a visible light region absorbing composition ( P-2) to (P-5) were obtained.

<Evaluation of Visible Light Region Absorbing Composition>
The resulting visible light region-absorbing composition was evaluated for light-shielding properties at 400 to 800 nm, initial viscosity, storage stability, and aggregated foreign matter as described below.

(Evaluation of light blocking property at 400 to 800 nm)
The obtained visible light region absorbing composition is coated on a glass substrate of 100 mm × 100 mm and 1.1 mm thick using a spin coater, and baked in an oven at 230 ° C. for 20 minutes to form a coating film after heat treatment. A coated substrate was produced so as to have a thickness of 1.0 μm. The film thickness was measured using DEKTAK. The light-shielding property in the visible region was evaluated by measuring the maximum transmittance of the produced substrate at 400 to 800 nm. In addition, ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level not suitable for practical use.
◎: maximum transmittance less than 3.0% ○: maximum transmittance 3.0% or more, less than 5.0% △: maximum transmittance 5.0% or more, less than 7.0% ×: maximum transmittance is 7.0% or more

(Initial viscosity evaluation)
Viscosity of the resulting visible light region-absorbing composition was measured at 25° C. on the day of preparation using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 20 rpm (initial viscosity). It was measured. In the following evaluation results, ⊚ is very good, ◯ is good, Δ is a level that does not pose a problem in use despite high viscosity, and × is a level that poses a problem in use.
◎: less than 10.0 [mPa s]
○: 10.0 or more to less than 15.0 [mPa s]
△: 15.0 or more to less than 20.0 [mPa s]
×: 20.0 or more [mPa s]

(Evaluation of storage stability)
The viscosity of the resulting visible light region-absorbing composition immediately after preparation and after storage at 10° C. for one month was measured using an E-type viscometer. The ratio of (viscosity after storage for one month)/(viscosity immediately after preparation) was calculated and evaluated according to the following criteria. In addition, ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level not suitable for practical use.
◎: Viscosity ratio is 1.00 or more and less than 1.02 ○: Viscosity ratio is 1.02 or more and less than 1.05 △: Viscosity ratio is 1.05 or more and less than 1.10 ×: Viscosity ratio is 1.10 that's all

(Evaluation of aggregated foreign matter)
The obtained visible light region absorbing composition is coated on a glass substrate of 100 mm × 100 mm and 1.1 mm thick using a spin coater, and baked in an oven at 230 ° C. for 20 minutes to form a coating film after heat treatment. A coated substrate was produced so as to have a thickness of 1.0 μm. The film thickness was measured using DEKTAK. After that, the obtained substrate was heated at 250° C. for 1 hour, and the surface was observed. A metallographic microscope "BX60" manufactured by Olympus Systems was used for the evaluation. Magnification was set to 500 times, and the number of particles observable in arbitrary 5 fields of transmission was counted and evaluated. In addition, ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level not suitable for practical use.
◎: The number of foreign substances is 5 or more and less than 10 ○: The number of foreign substances is 10 or more and less than 20 △: The number of foreign substances is 20 or more and less than 60 ×: The number of foreign substances is 60 or more

From the results of Table 5, Examples 115 to 118 absorb light in the entire range of 400 to 800 nm by including both the compound (A) having an indigo skeleton and an organic dye having a maximum absorption wavelength in the range of 400 nm or more and less than 700 nm. are doing. Furthermore, the initial viscosity and storage stability are excellent.

<Film production for various applications>
From the above results, it can be seen that optical films using the colored compositions prepared in the examples are excellent in near-infrared cameras, surveillance cameras, in-vehicle cameras, medical cameras, inspection/analysis cameras, temperature sensors, and distance sensors. It is expected to be suitable for use in sensors, medical sensors, touch sensors such as displays, biometric authentication sensors, and the like.

Claims (7)

A compound (A) having an indigo skeleton having a maximum absorption wavelength of 700 to 1300 nm, a binder resin, and a metal component containing metal atoms selected from Li, Na, K, Cs, Mg, Ca, Fe, and Zr. The total amount of the metal atoms contained in the metal component (excluding the compound (A) having an indigo skeleton) is 1 to 1000 with respect to 100% by mass of the near-infrared absorbing composition. A near-infrared absorptive composition that is mass ppm. The near-infrared absorbing composition according to claim 1, wherein the compound (A) having an indigo skeleton contains a compound represented by the following general formula (1).

General formula (1)

general formula (4)

(** represents a bond with a nitrogen atom)

[In general formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, a group represented by general formula (4), or a metal atom having a ligand. R ₁ and R ₂ cannot be hydrogen at the same time.
X ₁ to X ₁₂ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, a substituted an aryloxy group optionally having a group, an arylalkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, an alkylthio group optionally having a substituent, optionally substituted arylthio group, amino group, optionally substituted alkylamino group, optionally substituted arylamino group, cyano group, halogen atom, nitro group, It represents a hydroxyl group, —SO ₃ H, —COOH, monovalent to trivalent metal salts of these acidic groups, or alkylammonium salts. Two adjacent groups among the groups represented by X ₁ to X ₁₂ may be linked to form a 5- or 6-membered ring together with the carbon atoms to which they are attached. ] 3. The near-infrared absorbing composition according to claim 1, further comprising a photopolymerization monomer and/or a photopolymerization initiator. The near-infrared absorbing composition according to any one of claims 1 to 3, further comprising an organic dye having a maximum absorption wavelength in the range of 400 nm or more and less than 700 nm. An optical filter having a coating formed from the near-infrared absorbing composition according to any one of claims 1 to 4. An infrared camera comprising the optical filter according to claim 5 . An infrared sensor comprising the optical filter according to claim 5 .