JP2023177561A - Pigment composition for use in optical lens for infrared sensor or infrared communication device or optical waveguide for infrared sensor or infrared communication device, film, optical lens, and optical waveguide - Google Patents

Abstract

To provide a pigment composition that is applied as a high-refractive-index material for use in optical lenses or optical waveguides for infrared sensors or infrared communication devices, using 900-1600 nm light beams, the pigment composition exhibiting a high refractive index and offering superior transparency, heat resistance, and light resistance.SOLUTION: The present invention provides a pigment composition for use in optical lenses for infrared sensors or infrared communication devices or optical waveguides for infrared sensors or infrared communication devices, the pigment composition containing a pigment and a resin, the pigment containing at least one selected from a specific compound group, including the compound of the following structure.SELECTED DRAWING: None

Description

The present invention relates to a pigment composition used for an optical lens for an infrared sensor or an infrared communication device, or an optical waveguide for an infrared sensor or an infrared communication device, and a film, an optical lens, and an optical waveguide containing the pigment composition.

BACKGROUND ART Conventionally, a surface protective layer made of an inorganic or organic material has been provided on the surface of glass, film, and sheet used for sensor elements such as CCDs and CMOS, and display elements such as displays. In recent years, a coating layer in which high refractive index layers and low refractive index layers are alternately laminated has been used for the purpose of imparting functions such as antireflection and optical waveguide to the above-mentioned surface protective layer. Among these, high refractive index layers include high refractive index inorganic films formed by vapor deposition of ceramics such as titania, zirconia, and alumina, and high refractive index organic films made of aromatic-containing resins, depending on the purpose. There is. However, when a high refractive index inorganic film is used, there are problems such as insufficient adhesion to the substrate and brittleness of the film. Therefore, in recent years, high refractive index organic films have been widely used.

In addition, organic electroluminescent (hereinafter referred to as organic EL) panels, which are attracting attention as next-generation displays, use silicon oxide, silicon nitride, It has a laminated structure of an inorganic layer made of alumina or the like and an organic layer made of an organic encapsulant whose main component is acrylic resin or epoxy resin. These inorganic layers and organic layers are laminated alternately. Here, the smaller the difference in refractive index between the inorganic layer and the organic layer, the higher the light extraction efficiency, so the higher the refractive index of the organic layer is, the better. Therefore, an organic encapsulant with a high refractive index is required.

Furthermore, in recent years, molded bodies using three-dimensional printing apparatuses have been widely used in the medical field, optical field, and the like. As a modeling resin used for three-dimensional modeling, a photocurable resin is used (Patent Documents 1 and 2). In particular, in lens moldings used for medical equipment, microscopes, various cameras, etc., resins for stereolithography with a high refractive index are required in order to make lenses thinner.

High refractive index organic materials for surface protective layers, organic encapsulants for organic EL panels, and stereolithography resins include resins containing sulfur and fluorene, which has a structure in which aromatic rings are conjugated. There are known resins (Patent Documents 2, 3, and 4).

Recently, sensing and communication using near-infrared rays have become widespread, including solid-state image sensors for photographing objects at night, infrared sensors such as Lidar used for distance measurement, and infrared communication devices that propagate light through optical waveguides. It is becoming popular. It is important to use an optical material with a high refractive index in the near-infrared region for lenses and the like for condensing these light rays.

Patent Document 5 discloses a composition used for manufacturing an infrared transmission filter and the like that blocks visible light and transmits near infrared rays, and a film obtained using the composition, and the film has a wavelength of 800 nm or more. It is stated that the refractive index is high in the range of . However, the material described in Patent Document 5 has a maximum refractive index in a wavelength region shorter than 900 nm. Therefore, there is room for improvement in the refractive index in the wavelength range of 900 to 1600 nm, which has been particularly widely used in recent years in sensing and communication using near-infrared rays. Furthermore, since the dispersibility of the dye used is not sufficient, problems remain in terms of transparency of the film obtained from the composition.

Patent Document 6 discloses a film-like material for optical members containing an organic dye that exhibits a high refractive index and high transmittance in the near-infrared region, but the amount of the dye added is very small and is sufficiently high. Refractive index is not available.

Patent Document 7 discloses a resin composition containing a thermoplastic resin and a coloring material that exhibits a high refractive index and high transmittance in the near-infrared region, but it does not have sufficient light resistance or heat resistance, There was a problem in terms of practicality.

Japanese Patent Application Publication No. 2011-157543 JP2019-019245A Japanese Patent Application Publication No. 2000-281787 JP2011-168721A International Publication No. 2019/065475 International Publication No. 2020/085499 International Publication No. 2020/138050

Among sensing and communications using near-infrared rays, sensing and communications using 900-1600 nm light rays, which have become particularly widespread in recent years, require optical lenses to condense these rays and propagate these rays. It is important to use an optical material with a high refractive index, high transparency, and high durability for the optical waveguide.
However, at present, no progress has been made in developing high refractive index materials with sufficient durability.

In view of the above-mentioned problems, the present invention provides a high refractive index material for use in optical lenses or optical waveguides for infrared sensors or infrared communication devices that use light rays of 900 to 1600 nm, which has a high refractive index, transparency, The purpose of the present invention is to provide a pigment composition with excellent heat resistance and light resistance.

That is, the present invention provides a pigment composition for use in an optical lens for an infrared sensor or an infrared communication device, or an optical waveguide for an infrared sensor or an infrared communication device,
The present invention relates to a pigment composition containing a pigment and a resin, the pigment containing at least one selected from the group consisting of compounds represented by the following general formula (1), (2), or (3).

General formula (1)

General formula (4)

(** represents the bond with the 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 are never hydrogen at the same time.
X ₁₀₁ to X ₁₁₂ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, a substituted Aryloxy group which may have a substituent, arylalkyl group which may have a substituent, cycloalkyl group which may have a substituent, alkylthio group which may have a substituent, Arylthio group that may have a substituent, amino group, alkylamino group that may have a substituent, arylamino group that may have a substituent, cyano group, halogen atom, nitro group, Represents a hydroxyl group, -SO ₃ H, -COOH, or a monovalent to trivalent metal salt or alkylammonium salt of these acidic groups. Two adjacent groups among the groups represented by X ₁₀₁ to X ₁₁₂ may be connected to form a 5-membered ring or a 6-membered ring together with the carbon atoms to which they are bonded. ]

[In general formulas (2) and (3), X ₁ to X ₄₀ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, a substituted an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an arylalkyl group which may have a substituent, a cycloalkyl group which may have a substituent, Alkylthio group that may have a substituent, arylthio group that may have a substituent, amino group, alkylamino group that may have a substituent, aryl that may have a substituent It represents an amino group, a cyano group, a halogen atom, a nitro group, a hydroxyl group, or -SO ₃ H, -COOH, or a monovalent to trivalent metal salt or alkylammonium salt of these acidic groups. Two adjacent groups among the groups represented by X ₁ to X ₄₀ may be connected to form a 5-membered ring or a 6-membered ring together with the carbon atoms to which they are bonded.
M represents a metal atom. ]

The present invention relates to the above pigment composition, wherein M is a divalent metal atom.
The present invention relates to the above pigment composition, wherein the content of the pigment is 30% by mass or more based on the total mass of solid content in the pigment composition.

The present invention further relates to the above pigment composition comprising a curing agent and a solvent.

The present invention relates to a membrane containing the above pigment composition.

The present invention relates to an optical lens containing the above pigment composition.

The present invention relates to an optical waveguide containing the above pigment composition.

According to the present invention, in the application of a high refractive index material used for an optical lens or optical waveguide for an infrared sensor or an infrared communication device, it has a particularly high refractive index in the wavelength range of 900 to 1600 nm, and has good transparency and heat resistance. , and a pigment composition for a high refractive index material having excellent light resistance.

FIG. 1 shows an infrared absorption spectrum of one embodiment of the present invention. FIG. 2 shows an infrared absorption spectrum of one embodiment of the present invention. FIG. 3 shows an infrared absorption spectrum of one embodiment of the present invention. FIG. 4 shows an infrared absorption spectrum of one embodiment of the present invention. FIG. 5 shows an infrared absorption spectrum of one embodiment of the present invention. FIG. 6 shows an infrared absorption spectrum of one embodiment of the present invention. FIG. 7 shows an infrared absorption spectrum of one embodiment of the present invention.

<About the pigment composition of the present invention>
The pigment composition used for the optical lens or optical waveguide for infrared sensors or infrared communication devices of the present invention has at least one compound selected from the following general formula (1), (2) or (3) as a pigment. A pigment composition containing one type of pigment.

<Compound represented by general formula (1)>
The compound represented by general formula (1) will be explained.

General formula (1)

General formula (4)

(** represents the bond with the 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 are never hydrogen at the same time.
X ₁₀₁ to X ₁₁₂ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, a substituted Aryloxy group which may have a substituent, arylalkyl group which may have a substituent, cycloalkyl group which may have a substituent, alkylthio group which may have a substituent, Arylthio group that may have a substituent, amino group, alkylamino group that may have a substituent, arylamino group that may have a substituent, cyano group, halogen atom, nitro group, Represents a hydroxyl group, -SO ₃ H, -COOH, or a monovalent to trivalent metal salt or alkylammonium salt of these acidic groups. Two adjacent groups among the groups represented by X ₁₀₁ to X ₁₁₂ may be connected to form a 5-membered ring or a 6-membered ring together with the carbon atoms to which they are bonded.

The "alkyl group" of the alkyl group that may have a substituent is, for example, a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group. , n-octyl group, stearyl group, and 2-ethylhexyl group.
"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-tetrafluoromethyl group, 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, Examples include 2,4-dichlorobenzyl group.

Examples of the "aryl group" of an aryl group that may have a substituent include a phenyl group, a naphthyl group, an anthryl group (anthracenyl 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 Examples include anthraquinonyl group.

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, Examples include straight chain or branched alkoxyl groups such as 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy, and 2-ethylhexyloxy.
"Substituted alkoxyl group" includes, for example, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2-ditrifluoropropoxy group, Examples include fluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, and benzyloxy group.

Examples of the "aryloxy group" of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, an anthryloxy group, and the "aryloxy group having a substituent" include, for example, p -methylphenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group, and the like.
Examples of the "arylalkyl group which may have a substituent" include a benzyl group, a 2-phenylpropan-yl group, a styryl group, a diphenylmethyl group, and a triphenylmethyl group.

Examples of the "cycloalkyl group" of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, and an adamantyl group.
Examples of the "cycloalkyl group having a substituent" include a 2,5-dimethylcyclopentyl group and a 4-tert-butylcyclohexyl group.

The "alkylthio group" of the alkylthio group which may have 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, etc. can be mentioned.
Examples of the "alkylthio group having a substituent" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, and a phenylcarbonylaminoethylthio group.

Examples of the "arylthio group" of the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and the like.
Examples of "arylthio group having a substituent" include chlorophenylthio group, trifluoromethylphenylthio group, cyanophenylthio group, nitrophenylthio group, 2-aminophenylthio group, 2-hydroxyphenylthio group, etc. .

The "alkylamino group" of the alkylamino group which may have a substituent is, for example, a 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, etc.

The "arylamino group" of the arylamino group which may have a substituent is, for example, anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group. group, 2-biphenylamino group, 3-biphenylamino group, 4-biphenylamino group, 1-fluorenamino group, 2-fluorenamino group, 2-thiazoleamino group, p-terphenylamino group, etc.

Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

Examples of acidic groups include -SO ₃ H and -COOH, and monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, aluminum salts, etc. Can be 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. Examples include quaternary alkyl ammonium salts of

Among the above substituents, preferred substituents for X ₁₀₁ to X ₁₁₂ include hydrogen atom, methoxy group, fluorine atom, chlorine atom, and bromine atom.
Two adjacent groups among the groups represented by X ₁₀₁ to X ₁₁₂ may be connected to form a 5- or 6-membered ring with the carbon atoms to which they are bonded. The 5-membered ring or 6-membered ring may have a substituent. Examples of such 5-membered rings include a cyclopentene ring, cyclopentadiene ring, imidazole ring, thiazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiophene ring, furan ring, and pyrrole ring. , 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.

<Compound represented by general formula (2) or general formula (3)>
The compound represented by general formula (2) or general formula (3) of the present invention will be explained.

[In the formula, X ₁ to X ₄₀ are each independently a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aryl group that may have a substituent. Alkoxyl group, aryloxy group that may have a substituent, arylalkyl group that may have a substituent, cycloalkyl group that may have a substituent, Good alkylthio group, arylthio group that may have a substituent, amino group, alkylamino group that may have a substituent, arylamino group that may have a substituent, cyano group, halogen atom , a nitro group, a hydroxyl group, -SO ₃ H, -COOH, or a monovalent to trivalent metal salt or alkylammonium salt of these acidic groups. Two adjacent groups among the groups represented by X ₁ to X ₄₀ may be connected to form a 5-membered ring or a 6-membered ring together with the carbon atoms to which they are bonded.
M represents a metal atom. ]

The "alkyl group" of the alkyl group that may have a substituent is, for example, a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group. , n-octyl group, stearyl group, and 2-ethylhexyl group. "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-tetrafluoromethyl group, 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, Examples include 2,4-dichlorobenzyl group.

Examples of the "aryl group" of an aryl group that may have a substituent include 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 Examples include anthraquinonyl group.

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, Examples include straight chain or branched alkoxyl groups such as 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy, and 2-ethylhexyloxy.
"Substituted alkoxyl group" includes, for example, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2-ditrifluoropropoxy group, Examples include fluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, and benzyloxy group.

Examples of the "aryloxy group" of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, an anthryloxy group, and the "aryloxy group having a substituent" include, for example, p -methylphenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group, and the like.
Examples of the "arylalkyl group which may have a substituent" include a benzyl group, a 2-phenylpropan-yl group, a styryl group, a diphenylmethyl group, and a triphenylmethyl group.

Examples of the "cycloalkyl group" of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, and an adamantyl group. Examples of the "cycloalkyl group having a substituent" include a 2,5-dimethylcyclopentyl group and a 4-tert-butylcyclohexyl group.

The "alkylthio group" of the alkylthio group which may have 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, etc. can be mentioned.
Examples of the "alkylthio group having a substituent" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, and a phenylcarbonylaminoethylthio group.

Examples of the "arylthio group" of the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and the like.
Examples of "arylthio group having a substituent" include chlorophenylthio group, trifluoromethylphenylthio group, cyanophenylthio group, nitrophenylthio group, 2-aminophenylthio group, 2-hydroxyphenylthio group, etc. .

The "alkylamino group" of the alkylamino group which may have a substituent is, for example, a 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, etc.

The "arylamino group" of the arylamino group which may have a substituent is, for example, anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group. group, 2-biphenylamino group, 3-biphenylamino group, 4-biphenylamino group, 1-fluorenamino group, 2-fluorenamino group, 2-thiazoleamino group, p-terphenylamino group, etc.

Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

Examples of acidic groups include -SO ₃ H and -COOH, and monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, aluminum salts, etc. Can be 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. Examples include quaternary alkyl ammonium salts of

Two adjacent groups among the groups represented by X ₁ to X ₄₀ may be connected to form a 5-membered ring or a 6-membered ring with the carbon atoms to which they are bonded. The 5-membered ring or 6-membered ring may have a substituent. Examples of such 5-membered rings include a cyclopentene ring, cyclopentadiene ring, imidazole ring, thiazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiophene ring, furan ring, and pyrrole ring. , 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.

Among the above substituents, preferred substituents for X ₁ to X ₄₀ include hydrogen atom, methyl group, methoxy group, fluorine atom, chlorine atom, bromine atom, and -SO ₃ H.

M represents a metal atom. Examples of metal atoms include Zn, Co, Ni, Ru, Pt, Mn, Sn, Ti, and Ba. Among these, divalent metal atoms are preferred, and Zn, Co, and Ni are more preferred. The dimer represented by the general formula (2) or the trimer represented by the general formula (3) provides a compound with good heat resistance.

(Synthesis method of compound represented by general formula (1), (2) or (3))
A method for synthesizing the compound represented by general formula (1), (2) or (3) will be described below.
For the compound represented by general formula (1), (2) or (3), a compound represented by general formula (5) is used as a raw material. The compound represented by general formula (5) can be obtained according to the synthesis method described in JP-A No. 2012-224593.
General formula (5)

[Wherein, X ₂₀₁ to X ₂₀₈ have the same meanings as X ₁ to X ₄₀ and X ₁₀₁ to X ₁₁₂ . ]
The compound represented by the general formula (1) can be obtained by reacting the compound represented by the general formula (5) with a boron compound or a metal complex. A Lewis acid such as titanium tetrachloride or aluminum chloride is added if necessary.

The reaction temperature is not particularly limited, but 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 can be dissolved is preferred. Specific examples include tetrahydrofuran, toluene, xylene, bromobenzene and the like.
If boron compounds are used, boric acid esters are preferred, with 2-aminoethyl diphenylborinate being particularly preferred.
The reaction time is not particularly limited, but the progress of the reaction may be confirmed using a MALDI TOF-MS spectrum or a spectrophotometer to confirm the disappearance of the raw materials.
The compound represented by general formula (2) or general formula (3) can be obtained by reacting the compound represented by general formula (5) with a metal salt in a solvent.
Examples of raw metal salts include acetates, acetylacetone complexes, metal halides, and the like.

The reaction temperature is not particularly limited, but is preferably in the range of 20 to 120°C, more preferably 20 to 50°C.

The reaction solvent is not particularly limited, but one in which the intermediate and metal salt can be dissolved is preferred. Specific examples include tetrahydrofuran, toluene, and N-methylpyrrolidone.
The amount of the metal salt used is 0.5 mol or more, preferably 1.0 to 3.0 mol, per 1 mol of the compound represented by general formula (5).
The reaction time is not particularly limited, but the progress of the reaction may be confirmed using a MALDI TOF-MS spectrum or a spectrophotometer to confirm the disappearance of the raw materials.
In the production of compounds represented by general formula (2) or general formula (3), general formula (2) (hereinafter referred to as dimer) and general formula (3) (hereinafter referred to as trimer) are used. It can be confirmed by the TOF-MS spectrum that the compound represented by formula (6) is produced as a mixture, and the compound represented by general formula (6) (hereinafter referred to as a tetramer) is produced as a subcomponent. The production ratio of dimers, trimers, and tetramers is calculated by calculating the intensity (relative intensity) of each molecular ion peak relative to the sum of all molecular ion peak intensities in the TOF-MS spectrum, and then calculating the relative intensity ratio. It was considered as a molar ratio.

General formula (6)

[In the formula, X ₄₉ to X ₈₀ have the same meanings as X ₁ to X ₄₀ . ]
During synthesis, if the molar ratio of the metal salt to the compound represented by general formula (6) is high, the production ratio of trimers will be high. The molar ratio of the tetramer is preferably 30.0% by mass or less based on all molecules of the generated compound.
The compound represented by the general formula (2) or the general formula (3) has absorption in a specific near-infrared region (700 nm to 800 nm), and has little absorption in the visible light region (480 nm to 650 nm). When used as an infrared absorbing dye, it has excellent functionality as a near infrared absorbing agent.
Examples of the compound represented by general formula (1) in the present invention include the following compounds, but the present invention is not limited thereto.

Examples of the compound represented by the general formula (2) in the present invention include the following compounds, but the present invention is not limited thereto.

Examples of the compound represented by general formula (3) in the present invention include the following compounds, but the present invention is not limited thereto.

<About the optical properties of the pigment composition>
The optical properties of the pigment composition of the present invention will be explained below.
The pigment composition of the present invention contains a pigment represented by general formula (1), (2) or (3).
The pigments represented by general formulas (1), (2), or (3) are all near-infrared absorbing pigments that have high absorption in the near-infrared region.
The present inventors have discovered that when a film formed by a pigment composition has high absorption in a certain wavelength region, it has a particularly high refractive index at a wavelength near the bottom on the longer wavelength side.
When the pigment represented by general formula (2) is formed into a coating film as a pigment composition, it has high absorption in the range of 700 to 870 nm and bottoms out in the range of 900 to 1000 nm. Therefore, the coating film has a particularly high refractive index in the range of 900 to 1000 nm. Furthermore, it has a high refractive index even in the range of 1000 to 1600 nm.
When the pigments represented by the general formulas (1) and (3) are formed into a coating film as a pigment composition, they have high absorption in the range of 800 to 1000 nm and bottom out in the range of 1000 to 1200 nm. Therefore, the coating film has a particularly high refractive index in the range of 1000 to 1200 nm. Furthermore, it has a high refractive index even in the range of 1200 to 1600 nm.

In the pigment composition of the present invention, the pigment content is preferably 30% by mass or more based on the total mass of solids in the pigment composition. The content is more preferably 40% by mass or more, further preferably 50% by mass or more, particularly preferably 60% or more.
Since the content of the pigment is 30% by mass or more based on the total mass of solids in the pigment composition, the pigment represented by general formula (2) has high absorption in the range of 700 to 870 nm, and has a high absorption in the range of 900 to 870 nm. It is possible to obtain a film with a high refractive index in the wavelength region of 1600 nm, and pigments represented by general formulas (1) and (3) have high absorption in the wavelength region of 800 to 1000 nm and high absorption in the wavelength region of 1000 to 1600 nm. A film with a refractive index can be obtained.
The upper limit of the content of the pigment is not particularly limited, but it is preferable that it is less than 95% by mass because it provides excellent dispersibility of the pigment, provides a highly transparent film, and provides excellent stability as a pigment composition. .

In addition, in this specification, the solid content means all components excluding volatile components such as organic solvents from the pigment composition.

In the pigment composition of the present invention, when a film having a thickness of 1 μm is formed, in its absorption spectrum, the maximum value of absorbance at 700 to 1200 nm is preferably 1.0 or more, more preferably 2.0 or more. , more preferably 3.0 or more. In particular, when containing a pigment represented by general formula (2), the maximum value of absorbance at 700 to 870 nm is preferably 1.0 or more, more preferably 2.0 or more, and still more preferably 3.0 or more. preferable. In addition, when pigments represented by general formulas (1) and (3) are included, the maximum value of absorbance at 800 to 1000 nm is preferably 1.0 or more, more preferably 2.0 or more, and 3. More preferably 0 or more.
Furthermore, when the pigment composition of the present invention forms a film with a thickness of 1 μm, it is preferable that its absorption spectrum has low absorbance in the wavelength band of the light beam used as the high refractive index material. This is because when condensing or propagating light rays, in order to reduce light loss, it is preferable that a high proportion of light rays be transmitted, that is, that absorption is small. In one embodiment of the pigment composition of the present invention, when a film having a thickness of 1 μm is formed, it is preferable that the absorbance at 940 nm is less than 0.3 in the absorption spectrum.

<Other organic pigments>
The pigment composition of the present invention may contain an organic pigment other than the pigment represented by general formula (1), (2) or (3).

Examples of other near-infrared absorbing dyes include cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, anthraquinone compounds, aminium compounds, diimmonium compounds, and indigo compounds (general formulas (1), (2), or (3)). ), croconium compounds, azo compounds, quinoid complex compounds, dithiol metal complex compounds, and the like.
Examples of the yellow pigment include Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1 , 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97 , 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150 , 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182 , 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221, 231, 233, 234.

Examples of red pigments include C.I. I. Pigment Red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 97, 122, 123, 146, 149, 150, 168, 169, 170, 176, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 209, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, 268, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, and 296.
Examples of orange pigments include C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, 73.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1:2, 1:3, 2, 2:1, 2:2, 3, 8, 9, 10, 10:1, 11, 12, 15, 15:1, 15:2, 15: 3, 15:4, 15:6, 16, 18, 19, 22, 24, 24:1, 53, 56, 56:1, 57, 58, 59, 60, 61, 62, 64.

Examples of green pigments include C.I. I. Pigment Green 7, 10, 36, 37, 58, 62, and 63.
It is also preferable to use aluminum phthalocyanine pigments, and aluminum phthalocyanine pigments described in JP-A No. 2004-333817, Japanese Patent No. 4893859, etc. can also be used.
Examples of the purple pigment include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50.

(Inorganic pigment)
The pigment composition of the present invention may contain an inorganic pigment. Inorganic pigments include, for example, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine blue, deep blue, chromium oxide green, cobalt green, and amber. , synthetic iron black. Inorganic pigments are used in combination with organic pigments in order to balance saturation and brightness while ensuring good coating properties, sensitivity, developability, etc.

(dye)
In addition, dyes can also be used in combination. As dyes, for example, oil-soluble dyes, acid dyes, basic dyes, etc. can all be used in combination, and anthraquinone dyes, monoazo dyes, disazo dyes, oxazine dyes, aminoketone dyes, xanthene dyes, quinoline dyes, etc. Examples include dyes based on dyes based on dyes based on dyes such as dyes based on dyes based on dyes based on triphenylmethane, dyes based on cyanine, and dyes based on squarylium. All of these dyes can be used in combination.

Hereinafter, the above pigments and dyes may be collectively referred to as colorants.
Furthermore, a UV absorber can also be used in combination. Examples of the UV absorber include benzotriazole UV absorbers, triazine UV absorbers, benzophenone UV absorbers, benzoate UV absorbers, and cyanoacrylate UV absorbers, all of which can be used in combination. .

When it is desired to control not only the performance as a high refractive index material but also the transmission and absorption in a specific wavelength region, the above dyes and ultraviolet absorbers are preferably used.

For example, when sensing near-infrared rays, if you want to cut out a region with a shorter wavelength than that light, you can add a yellow pigment or an ultraviolet absorber to a blue pigment, red pigment, or violet pigment, and use it to function as an IR pass material. can have.

<Resin>
The pigment composition of the present invention contains a resin. Examples of the resin include those that function as a binder resin and those that function as a dispersant. The binder resin is one in which a pigment is dispersed, and includes thermoplastic resins, thermosetting resins, and the like. The resin-type dispersant that functions as a dispersant will be described later.

Examples of thermoplastic resins include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. , polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin.

The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light region. Further, since the colored composition for color filters of the present invention is in the form of an alkali-developable colored resist material, it is preferable to use an alkali-soluble vinyl resin copolymerized with an ethylenically unsaturated monomer containing an acidic group.

Examples of alkali-soluble resins copolymerized with acidic group-containing ethylenically unsaturated monomers include resins having acidic groups such as carboxy groups and sulfone groups. Specifically, the alkali-soluble resin includes an acrylic resin having an acidic group, an α-olefin/(anhydrous) maleic acid copolymer, a styrene/styrene sulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or Examples include isobutylene/(anhydrous) maleic acid copolymer. Among them, at least one resin selected from the group consisting of acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers, particularly acrylic resins having acidic groups, is preferably used because of its high heat resistance and transparency. used.

In order to improve the photosensitivity of an alkali-soluble resin copolymerized with an acidic group-containing ethylenic unmonomer, an energy ray-curable resin having an ethylenically unsaturated active double bond can also be used. Further, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond in its side chain from the viewpoint of various resistances.

Examples of active energy ray-curable resins having ethylenically unsaturated double bonds include resins into which unsaturated ethylenically double bonds are introduced by methods (a) and (b) shown below.

[Method (a)]
As method (a), unsaturated epoxy groups are added to the side chain epoxy groups of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers. The carboxy group of an unsaturated monobasic acid having an ethylenic double bond is subjected to an addition reaction, and the generated hydroxy group is further reacted with a polybasic acid anhydride to introduce an unsaturated ethylenic double bond and a carboxy group. There is a way.

Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4 epoxybutyl (meth)acrylate, and 3,4 epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)acrylate is preferred.

Examples of unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl, alkoxyl, halogen, nitro, and cyano substituted products of (meth)acrylic acid, etc. Examples include monocarboxylic acids, and these may be used alone or in combination of two or more.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and these may be used alone or in combination of two or more. good. To increase the number of carboxyl groups, if necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to remove the remaining anhydride. It is also possible to hydrolyze the group. Moreover, when etrahydrophthalic anhydride or maleic anhydride, which has unsaturated ethylenic double bonds, is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be further increased.

As a method similar to method (a), for example, the side chain of a copolymer obtained by copolymerizing an unsaturated ethylenically monomer having a carboxy group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is subjected to an addition reaction on a part of the carboxyl group to introduce an unsaturated ethylenic double bond and a carboxy group.

[Method (b)]
As method (b), by using an unsaturated ethylenic monomer having a hydroxy group and copolymerizing it with another unsaturated monobasic acid monomer having a carboxy group or other monomers. There is a method in which the side chain hydroxy groups of the obtained copolymer are reacted with an isocyanate group of an unsaturated ethylenically monomer having an isocyanate group.

Examples of the unsaturated ethylenically monomer having a hydroxy group include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, Examples include hydroxyalkyl (meth)acrylates such as glycerol (meth)acrylate and cyclohexanedimethanol mono(meth)acrylate, and these may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and/or butylene oxide, etc. to the above hydroxyalkyl (meth)acrylate, (poly)γ-valerolactone, (poly)ε-caprolactone, etc. , and/or (poly)ester mono(meth)acrylate to which (poly)12-hydroxystearic acid or the like is added can also be used. From the viewpoint of suppressing coating film foreign matter, 2-hydroxyethyl (meth)acrylate or glycerol (meth)acrylate is preferred.

Examples of the unsaturated ethylenic monomer having an isocyanate group include, but are not limited to, 2-(meth)acryloyloxyethyl isocyanate or 1,1-bis[(meth)acryloyloxy]ethyl isocyanate. It is also possible to use two or more types together.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000, in order to preferably disperse the colorant. Further, the number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw/Mn is preferably 10 or less.
From the viewpoint of pigment dispersibility, permeability, and heat resistance, the binder resin contains a carboxy group that acts as a colorant adsorption group and an alkali-soluble group during development, and a group that has affinity for colorant carriers and solvents other than the binder resin. The balance between functional aliphatic groups and aromatic groups is important for the dispersibility, permeability, and durability of pigments and salt-forming compounds, and it is preferable to use a resin with an acid value of 20 to 300 mgKOH/g. If the acid value is less than 20 mgKOH/g, the solubility in a developer is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH/g, no fine pattern will remain.

Here, the colorant carrier refers to a resin or other low-molecular component that supports the colorant through affinity, adsorption, or the like.

From the viewpoint of film-forming properties and various resistances, it is preferable to use the binder resin in an amount of 30% by mass or more based on the total mass of the colorant (100% by mass). From the viewpoint of developing properties, it is preferable to use it in an amount of 500% by mass or less.

<Organic solvent>
The colored composition of the present invention may contain an organic solvent in order to sufficiently disperse and permeate the coloring agent into the colorant carrier and to facilitate molding of the high refractive index material.

Examples of organic solvents include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, and 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 monoisopropyl 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, 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 Examples include monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

Among them, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and benzyl are used because they have good pigment dispersibility and solubility. It is preferable to use aromatic alcohols such as alcohols and ketones such as cyclohexanone. In particular, propylene glycol monomethyl ether acetate is more preferred from the viewpoints of safety and hygiene and low viscosity.

These organic solvents can be used alone or in combination of two or more. When a mixed solvent of two or more types is used, it is preferable that the above-mentioned preferred organic solvent is contained in an amount of 65 to 95% by mass.

In addition, the organic solvent is used in an amount of 800 to 4000% by mass, based on the total mass of the colorant (100% by mass), from the viewpoint of adjusting the pigment composition to an appropriate viscosity and improving the formability of the high refractive index material. It is preferable to use it in

<Dispersion>
The pigment composition of the present invention can be produced in a coloring agent carrier consisting of a pigment and, if necessary, a resin and a solvent, preferably together with a dispersion aid such as a pigment derivative, using a three-roll mill, a two-roll mill, or a sand mill. It can be manufactured by finely dispersing it using various dispersion means such as , kneader, attritor, etc. Further, the colored composition of the present invention can also be produced by mixing pigments, dyes, other colorants, etc. separately dispersed in a colorant carrier.

(Dispersion aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a dye derivative, a resin-type dispersant, or a surfactant can be used as appropriate. Dispersion aids have excellent dispersion of colorants and are highly effective in preventing re-agglomeration of colorants after dispersion. When used, a film with high spectral transmittance can be obtained.

《Pigment derivative》
Examples of pigment derivatives include compounds in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced into an organic pigment, anthraquinone, acridone, or triazine. Those described in Japanese Patent Publication No. 63-305173, Japanese Patent Publication No. 57-15620, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63-17102, Japanese Patent Publication No. 5-9469, etc. can be used. They can be used alone or in combination of two or more.

From the viewpoint of improving the dispersibility of the pigment, the amount of the pigment derivative is preferably 0.5% by mass or more, more preferably 1% by mass or more, and most preferably 3% by mass, based on the total amount of pigment (100% by mass). % or more. Further, from the viewpoint of heat resistance and light resistance, the content is preferably 40% by mass or less, more preferably 35% by mass or less, based on the total amount of added pigment (100% by mass).

《Resin type dispersant》
Resin-type dispersants have a pigment-affinity site that has the property of adsorbing to pigments and a site that is compatible with the colorant carrier, and have the function of adsorbing the added pigment and stabilizing its dispersion in the colorant carrier. It is something that does. Specifically, resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkylene imine) with polyesters having free carboxyl groups, and their salts. Water-soluble oil-based dispersants such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resins, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, phosphoric esters, etc. are used, and these can be used alone or in combination of two or more, but It is not necessarily limited to these.

Commercially available resin type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by BYK Chemie Japan. , 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, manufactured by Japan Lubrizol, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFK manufactured by BASF Japan A-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4
401,4402,4403,4406,4408,4300,4310,4320,4330,4340,450,451,453,4540,4550,4560,4800,5010,5065,5066,5070,7500,7554,1101,120, 150, 1501, 1502, 1503, etc., and Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine Techno.

《Block acrylic basic dispersant》
In the pigment composition of the present invention, it is preferable to use a block acrylic type basic dispersant as the resin type dispersant. The block acrylic basic dispersant is a block type acrylic polymer having a basic group. Among these, it is more preferable that one block is a polymer of an ethylenically unsaturated monomer having a basic group, and the other block is a polymer of an ethylenically unsaturated monomer having no basic group. .

When the block acrylic type basic dispersant is an AB type block, a more preferable embodiment is as described above, but in the case of a BAB type block, the A block is a polymer of ethylenically unsaturated monomers having a basic group. It is more preferable that the B block is a polymer of ethylenically unsaturated monomers having no basic group.

By using a block acrylic basic dispersant as a resin type dispersant, the block with a basic group adsorbs to the surface of the pigment, while the other block without a basic group maintains its affinity with the solvent. It is thought that good dispersibility is achieved by acting as a steric hindrance.

In general, resin-type dispersants tend to achieve good dispersibility when used in combination with dye derivatives, but when block acrylic-type basic dispersants are used, they can be used without dye derivatives due to the above mechanism. Good dispersibility is often obtained. Since the dye derivative often has a different spectrum from the pigment used in the present invention, the pigment composition can exhibit a higher refractive index by not using the dye derivative.

As the ethylenically unsaturated monomer having a basic group, an ethylenically unsaturated monomer having a tertiary amino group and an ethylenically unsaturated monomer having a quaternary ammonium salt are preferable, and these may be used in combination. is particularly preferred.

Examples of ethylenically unsaturated monomers having a tertiary amino group include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and dipropylaminoethyl methacrylate, and examples of ethylenically unsaturated monomers having a quaternary ammonium group include: Methacrylic acid dimethylaminoethyl methyl chloride salt, methacrylic acid dimethylaminoethylbenzyl chloride salt, methacrylic acid dimethylaminoethylpropyl chloride salt, methacrylic acid dimethylaminoethylbutyl chloride salt, methacrylic acid diethylaminoethylmethyl chloride salt, methacrylic acid diethylaminoethylbenzyl chloride salt salt, methacrylic acid diethylaminoethylpropyl chloride salt, methacrylic acid diethylaminoethylbutyl chloride salt, acrylic acid dimethylaminoethylmethyl chloride salt, acrylic acid dimethylaminoethylbenzyl chloride salt, acrylic acid dimethylaminoethylpropyl chloride salt, dimethyl acrylate Examples include aminoethyl butyl chloride salt.

When an ethylenically unsaturated monomer having a tertiary amino group and an ethylenically unsaturated monomer having a quaternary ammonium salt are used together as the ethylenically unsaturated monomer having a basic group, a block acrylic base is used. There are two typical methods for synthesizing dispersants.
The first method is to synthesize these ethylenically unsaturated monomers separately and use them as a mixture when polymerizing a block having a basic group.
The second method is to polymerize a block that has a basic group using an ethylenically unsaturated monomer that has a tertiary amino group, and then polymerize the other block that does not have a basic group, resulting in block polymerization. After completing this step, a part of the tertiary amino group is converted into a quaternary ammonium salt by reacting with a quaternizing agent such as benzyl chloride. Examples of the quaternizing agent include alkyl halides such as benzyl chloride, iodobutane, iodopropane, iodoethane, bromobutane, bromopropane, bromoethane, and chlorobutane.
When an ethylenically unsaturated monomer having a tertiary amino group or an ethylenically unsaturated monomer having a quaternary ammonium salt has an amide bond in its molecule, it is easily adsorbed on the surface of an organic pigment. This is preferable because higher dispersibility can be obtained.

When synthesizing a block polymer, for example, an A block is synthesized first, and then a B block is synthesized, thereby producing an AB block polymer. Furthermore, a BAB block polymer can be produced by first synthesizing a B block, then synthesizing an A block, and further synthesizing a B block. Note that the order of combining the A block and B block is arbitrary.
The radical polymerization initiator used in living radical polymerization is preferably an azo compound or a peroxide.

Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(methyl isobutyrate), 1,1 '-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2, 2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), or 2,2'- Azobis[2-(2-imidazolin-2-yl)propane] is mentioned.
Examples of peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and di(2-ethoxyethyl)peroxydicarbonate. carbonate, t-butyl peroxyneodecanoate, t-butyl peroxy bivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, or diacetyl peroxide. The polymerization initiators may be used alone or in combination of two or more types.
The reaction temperature for polymerization is preferably 40 to 150°C, more preferably 50 to 110°C. The reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

Living radical polymerization can be performed by any known polymerization method, but RAFT polymerization (reversible addition-fragmentation chain transfer polymerization) is preferred. RAFT polymerization is a method in which monomers are radically polymerized in the presence of a RAFT agent, and the molecular weight and molecular weight distribution of the polymer can be easily controlled.
The RAFT agent is a compound having a chain transfer effect and a polymerization initiation effect, and includes, for example, a dithiobenzoate type, a trithiocarbonate type, a dithiocarbamate type, a xanthet type, and a disulfide type which is a precursor thereof.

Examples of the dithiobenzoate type include 2-cyano-2-propyl dithiobenzoate, 4-cyano-4-(thiobenzoylthio)pentanoic acid, and 2-phenyl-2-propyl benzodithioate.
Examples of the trithiocarbonate type include 4-[(2-carboxyethylsulfanylthiocarbonyl)sulfanyl]-4-cyanopentanoic acid, 2-{[(2-carboxyethyl)sulfanylthiocarbonyl]sulfanyl}propanoic acid, -Cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, 2-cyano-2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propane, 2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid, 4- Methyl cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoate, 2-methyl-2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid, S,S-dibenzyltrithiocarbonate, trithiocarbonic acid bis[ 4-(allyloxycarbonyl)benzyl], trithiocarbonate = bis[4-(2,3-dihydroxypropoxycarbonyl)benzyl], trithiocarbonate = bis{4-[ethyl-(2-acetyloxyethyl)carbamoyl]benzyl} , trithiocarbonate bis{4-[ethyl-(2-hydroxyethyl)carbamoyl]benzyl}, and trithiocarbonate=bis[4-(2-hydroxyethoxycarbonyl)benzyl].
Examples of the dithiocarbamate type include 2'-cyanobutan-2'-yl 4-chloro-3,5-dimethylpyrazole-1-carbodithioate, 2'-cyanobutan-2'-yl 3,5-dimethylpyrazole-1-carbodithioate, -2'-yl, cyanomethyl 3,5-dimethylpyrazole-1-carbodithioate, and cyanomethyl N-methyl-N-phenyldithiocarbamate.
Examples of the disulfide type include bis(dodecylsulfanylthiocarbonyl) disulfide and bis(thiobenzoyl) disulfide. These are preferred for the production of AB block polymers.
Among these, trithiocarbonate type compounds are preferred because they are easy to control the reaction during synthesis; ) sulfanyl]propane, methyl 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoate, bis{4-[ethyl-(2-hydroxyethyl)carbamoyl]benzyl} trithiocarbonate}, bis(dodecylsulfanylthiocarbonyl) ) Disulfide is more preferred.
The amount of the RAFT agent used is preferably 0.1 to 10 parts by weight per 100 parts by weight of the monomer.

In the synthesis of the block acrylic basic dispersant, it is preferable to use an organic solvent. Examples of organic solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Examples include ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, or diethylene glycol monobutyl ether acetate. The organic solvents may be used alone or in combination of two or more.

(Resin-type dispersant having a carboxyl group)
Further, the resin-type dispersant used in the present invention preferably contains the following (S1) or (S2), for example, as a resin-type dispersant having a carboxyl group.
(S1) A resin-type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and/or a tetracarboxylic dianhydride.
(S2) A polymer obtained by polymerizing ethylenically unsaturated monomers in the presence of a reaction product of the hydroxyl group of a compound having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and/or tetracarboxylic dianhydride. A resin-type dispersant that is a combination.

[Resin type dispersant (S1)]
The resin type dispersant (S1) can be produced by a known method such as WO2008/007776, JP2008-029901, JP2009-155406, and the like. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal. For example, an ethylenically unsaturated monomer (r) is polymerized in the presence of a compound (q) having a hydroxyl group. It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since it is preferable that there be a plurality of terminal hydroxyl groups, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.
That is, a more preferable example of a polymer having two hydroxyl groups at one end is a polymer having monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. It can be obtained as a polymer (p1) obtained by polymerizing an ethylenically unsaturated monomer (r) containing The hydroxyl group of the polymer (p) having a hydroxyl group reacts with the acid anhydride group of tricarboxylic anhydride and/or tetracarboxylic dianhydride to form an ester bond, while the anhydride ring opens and the carboxylic acid occurs.

[Resin type dispersant (S2)]
The resin-type dispersant (S2) can be produced by a known method such as JP-A No. 2009-155406, JP-A No. 2010-185934, and JP-A No. 2011-157416. By polymerizing the ethylenically unsaturated monomer (r) in the presence of a reaction product of the hydroxyl group of (q) and the acid anhydride group of tricarboxylic anhydride and/or tetracarboxylic dianhydride. can get. Among them, in the presence of a reaction product between the hydroxyl group of a compound (q1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of tricarboxylic acid anhydride and/or tetracarboxylic dianhydride. In addition, it is preferably a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing monomer (r1).
The difference between (S1) and (S2) is whether the polymer site in which the ethylenically unsaturated monomer (r) is polymerized is introduced first or later. The molecular weight etc. may differ slightly depending on various conditions, but if the raw materials and reaction conditions are the same, theoretically the same product can be produced.
The resin type dispersant may be used alone or in combination of two or more types.

《Surfactant》
As surfactants, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalene sulfonate, sodium alkyl diphenyl ether disulfonate. , anionic surfactants such as monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Cationic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; amphoteric surfactants such as alkyl betaines such as alkyldimethylaminoacetic acid betaines, and alkylimidazolines; these may be used alone or in combination of two or more. They can be used in combination.

When adding a resin-type dispersant or surfactant, the blending amount is preferably 0.1 to 200% by mass, more preferably 0.1 to 150% by mass, based on the total amount of colorant (100% by mass). It is. When the blending amounts of the resin-type dispersant and surfactant are within the above ranges, preferred dispersibility can be achieved.

<Photopolymerizable monomer>
The colored composition of the present invention can further be used as a photosensitive colored composition by adding a photopolymerizable monomer and/or a photopolymerization initiator. The photopolymerizable monomers of the present invention include monomers or oligomers that can be cured by ultraviolet rays, heat, etc. to produce transparent resins, and these can be used alone or in combination of two or more. The blending amount of the monomer is preferably 5 to 50% by mass, based on the total mass of the colorant (100% by mass), and more preferably 10 to 30% by mass from the viewpoint of photocurability and developability. preferable.

Examples of monomers and oligomers that can be cured by ultraviolet rays or heat to produce transparent resins include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. , cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di( meth)acrylate, trimethylolpropane tri(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, ester acrylate, methylolated melamine Various acrylic esters and methacrylic esters such as (meth)acrylic ester, epoxy (meth)acrylate, urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol tri Examples include vinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, and acrylonitrile.

<Photopolymerization initiator>
The pigment composition of the present invention can be cured by irradiation with ultraviolet rays. The amount of the photopolymerization initiator used is preferably 5 to 200% by mass, based on the total amount of the colorant, and preferably 10 to 150% by mass from the viewpoint of photocurability and developability. More preferred.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-Hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl] Acetophenone compounds such as -1-[4-(4-morpholinyl)phenyl]-1-butanone or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin , benzoin-based compounds such as 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- Benzophenone compounds such as 4'-methyldiphenyl sulfide or 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 2, Triazine compounds such as 4-trichloromethyl-(4'-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], or Oxime ester compounds such as O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene) hydroxylamine; bis(2,4,6-trimethylbenzoyl)phenyl Phosphine compounds such as phosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethyl anthraquinone; Borate compounds; Carbazole compounds; Imidazole or a titanocene-based compound.

These photopolymerization initiators can be used alone or in combination of two or more in any ratio as necessary. The content of these photopolymerization initiators is preferably 5 to 200% by mass, based on the total amount of colorants in the coloring composition (100% by mass), and 10 to 150% by mass from the viewpoint of photocurability and developability. % is more preferable.

<Sensitizer>
Furthermore, the pigment composition of the present invention can contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, Polymethine dyes such as anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, 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, tetraquinoxalyloporphyrin derivatives Radin 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-alpha Siloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4 Examples include '-tetra(t-butylperoxycarbonyl)benzophenone and 4,4'-diethylaminobenzophenone.

More specifically, there are "Pigment Handbook" (edited by Makoto Okawara et al., 1986, Kodansha), "Chemistry of Functional Pigments" (edited by Makoto Okawara et al., 1981, CMC), "Dye Handbook" (edited by Shin Okawara et al., 1981, CMC), and " Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (CMC, 1986). In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region may also be included.

Two or more sensitizers may be used in any ratio as necessary. The amount of the sensitizer used is preferably 3 to 60% by mass based on the total mass of the photopolymerization initiator contained in the pigment composition (100% by mass). From the viewpoint of developability, the content is more preferably 5 to 50% by mass.

<Amine compounds>
Further, the pigment composition of the present invention can contain an amine compound that has the function of reducing dissolved oxygen. Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethylparatoluidine.

<Leveling agent>
It is preferable to add a leveling agent to the pigment composition of the present invention in order to improve the leveling properties of the composition. As the leveling agent, dimethylsiloxane having a polyether structure or polyester structure in its main chain is preferred. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Industries and BYK-333 manufactured by BYK Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in its main chain and dimethylsiloxane having a polyester structure in its main chain can also be used together. The content of the leveling agent is usually preferably 0.003 to 0.5% by mass based on the total mass of the pigment composition (100% by mass).

Particularly preferred as a leveling agent is a type of surfactant that has a hydrophobic group and a hydrophilic group in its molecule.Although it has a hydrophilic group, it has low solubility in water, and when added to a pigment composition, it It is useful to have a low ability to reduce surface tension, and to have good wettability to glass plates despite the low ability to reduce surface tension, and the amount added is sufficient so that defects in the film due to bubbling do not appear. It is preferable to use a material that can suppress electrification. As a leveling agent having such preferable properties, dimethylpolysiloxane having polyalkylene oxide units can be preferably used. Polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

In addition, the bonding forms of polyalkylene oxide units with dimethylpolysiloxane are pendant type, in which polyalkylene oxide units are bonded to repeating units of dimethylpolysiloxane, terminal modified type, in which polyalkylene oxide units are bonded to the terminals of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any linear block copolymer type in which the polymers are alternately and repeatedly bonded. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Dow Corning Toray Co., Ltd., such as FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ -2207, but is not limited to these.

An anionic, cationic, nonionic, or amphoteric surfactant can also be added to the leveling agent. Two or more surfactants may be used in combination.

Examples of the anionic surfactant to be added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, and alkyldiphenyl ether. Sodium disulfonate, 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 Examples include phosphoric acid esters.

Examples of the cationic surfactant added auxiliary to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Examples of nonionic surfactants to be added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monomer. Examples include stearate, polyethylene glycol monolaurate, alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Further, the pigment composition of the present invention may contain a curing agent, a curing accelerator, etc., as necessary, in order to assist the curing of the thermosetting resin. Effective curing agents include phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc., but are not particularly limited to these.Thermosetting resins Any curing agent may be used as long as it can react with the curing agent. Among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred. Examples of the curing accelerator include amine compounds (for example, 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 derivative bicyclic amidine compounds and their salts (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.), guanamine compounds (e.g., melamine, guanamine, acetoguanamine, benzoguanamine, 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.) can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15% by mass based on the total amount of the thermosetting resin.

<Other additive components>
The pigment composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Furthermore, an adhesion improver such as a silane coupling agent may be included in order to improve adhesion to the base material.

Examples of storage stabilizers include quaternary ammonium chloride such as benzyl trimethyl chloride and diethyl hydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples include organic phosphines and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the total amount of colorant (100% by weight).

Examples of adhesion improvers include vinyl silanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth)acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and β-( 3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxy Epoxysilanes such as cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ - Silane coupling agents such as aminosilanes such as aminopropyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane are listed. It will be done. The adhesion improver can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount of colorant in the pigment composition (100% by weight).

<Removal of coarse particles>
The pigment composition of the present invention can be prepared by mixing coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, by means of centrifugation, sintered filters, membrane filters, etc. Preferably, dust is removed. As described above, it is preferable that the pigment composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Membrane>
A film obtained by curing the pigment composition of the present invention by solvent volatilization, exposure (photocuring), or heating (thermal curing) is also an object of the present invention.

Examples of the light beam used for exposure include ultraviolet rays, electron beams, and X-rays. As the light source used for ultraviolet irradiation, sunlight, chemical lamps, low pressure mercury lamps, high pressure mercury lamps, metal halide lamps, xenon lamps, UV-LEDs, etc. can be used. Further, after exposure, post-baking may be performed to stabilize the physical properties of the cured product. The post-baking method is not particularly limited, but is usually carried out using a hot plate, oven, etc. at 50 to 260° C. for 1 to 120 minutes.

The heating conditions for thermosetting are not particularly limited, but are usually appropriately selected from the range of 50 to 300° C. and 1 to 120 minutes. Further, the heating means is not particularly limited, but examples thereof include a hot plate, an oven, and the like.

The film formed from the pigment composition of the present invention has a high refractive index in the wavelength range of 900 to 1600 nm, and forms an optical lens for an infrared sensor or an infrared communication device, or an optical waveguide for an infrared sensor or an infrared communication device. Suitable as a material.

The pigment composition of the present invention can be formed into any shape such as a dome shape or a sheet shape.
For example, it can be molded as follows. The pigment composition of the present invention containing a photopolymerization initiator and a photopolymerizable monomer is potted onto a transparent substrate such as glass, and a desired mold is pressed onto the pigment composition, thereby forming the mold. It can be cured by filling the inside with a pigment composition and irradiating it with light. Then, by removing the mold, a cured product of the pigment composition integrated on the transparent substrate can be obtained. Alternatively, it is also possible to fill the pigment composition into a transparent mold that transmits light and photocure it. By such a manufacturing method, for example, a hybrid lens can be manufactured. Further, the pigment composition of the present invention can be cured by itself in a mold to form an optical component such as an optical lens.

Moreover, it can also be molded as a microlens. An etchback method is known as one of the methods for manufacturing microlenses. A resist pattern is formed on the coating film of the pigment composition of the present invention, and this resist pattern is reflowed by heat treatment to form a lens pattern. By using the lens pattern formed by reflowing this resist pattern as an etching mask, the underlying coating film of the pigment composition of the present invention is etched back, and the lens pattern shape is transferred to the coating film of the pigment composition of the present invention. Fabricate a microlens. In addition, as another method for manufacturing microlenses, a resist pattern is formed by exposing and developing the pigment composition of the present invention containing a photopolymerization initiator and an alkali-soluble resin, and the microlens is reflowed by heat treatment. There is also a method of manufacturing.

In addition, when molding as an optical waveguide, a resist pattern is formed by exposing and developing the pigment composition of the present invention containing a photopolymerization initiator and an alkali-soluble resin, and a resist pattern is formed by exposing and developing the pigment composition of the present invention containing a photopolymerization initiator and an alkali-soluble resin. By exposing and developing another resin composition or pigment composition having a different refractive index to form adjacent resist patterns, a core and a cladding are formed, and an optical waveguide can be produced.

In this specification, an optical lens for an infrared sensor or an infrared communication device refers to a lens for condensing infrared rays, such as a spectacle lens, an optical equipment lens, an optoelectronic lens, a laser lens, and a pickup lens. Lenses, automotive camera lenses, mobile camera lenses, digital camera lenses, OHP lenses, and microlenses are included.

In this specification, an optical waveguide for an infrared sensor or an infrared communication device refers to a waveguide for propagating infrared rays, and its shape is not limited, such as a sheet shape or a plate shape. Applications include, for example, cables used for optical communications in computers and sensor devices, optical interconnections used for optical communications inside devices, and cables used in optical paths for sensing infrared rays, such as infrared sensors. Also included are the materials used.

The present invention will be explained in more detail below, but the present invention is not limited to these examples unless it deviates from the technical idea of the present invention. In addition, hereinafter, "parts by mass" will be simply written as "parts", and "% by mass" will be simply written as "%".

(Manufacture of pigment (a))
In a reaction vessel, 10.7 parts of aniline, 120 parts of bromobenzene, and 25.7 parts of diazabicyclooctane were added and stirred. Then, 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 the mixture was refluxed for 10 hours. After the reaction was completed, methanol was added and filtered to obtain a green powder. This was separated between dichloromethane and water, and the organic layer was concentrated to obtain 14.6 parts of compound (1).

[Compound (1)]

In a reaction vessel, 13.5 parts of compound (1), 9.0 parts of bis(2,4-pentanedionato)zinc(II), and 120 parts of tetrahydrofuran were mixed and stirred, and the mixture was heated to 40°C for 5 hours. Stirred. The reaction solution, which had been cooled to 30° C. while being stirred, was poured into 500 parts of methanol with stirring to obtain a blue slurry. This slurry was filtered, washed with 500 parts of methanol, washed with 500 parts of water, and dried to obtain 12.2 parts of pigment (a). As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of pigment (a) is compound (a-1), and compound (a-2) (hereinafter referred to as trimer) and compound (a-3) (hereinafter referred to as tetramer) are also Formation was confirmed by TOF-MS. The infrared absorption spectrum of pigment (a) is shown in FIG.
Compound (a-1)

Compound (a-2) Compound (a-3)

(Manufacture of pigment (b))
The same procedure as in the synthesis of pigment (a) was performed except that 9.0 parts of bis(2,4-pentanedionato)zinc(II) used in the synthesis of pigment (a) was changed to 25.0 parts. 11.7 parts of pigment (b) were obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of pigment (b) was compound (a-2). The infrared absorption spectrum of pigment (b) is shown in FIG.

(Manufacture of pigment (c))
Pigment (a) except that 9.0 parts of bis(2,4-pentanedionato)zinc(II) used in the synthesis of pigment (a) was changed to 15.0 parts of zinc acetate dihydrate. The same operation as in the synthesis was performed to obtain 12.3 parts of pigment (c). As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of pigment (c) was compound (a-1). FIG. 3 shows the infrared absorption spectrum of pigment (c).

(Manufacture of pigment (d))
Compound (2) was prepared in the same manner as in the synthesis of compound (1), except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 18.5 parts of 2,3-dichloroaniline. I got 17.8 copies.

[Compound (2)]

The same procedure as in the synthesis of pigment (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of pigment (b) was changed to 15.8 parts of compound (2), and pigment (d) was synthesized. 14.6 parts of was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of pigment (d) was compound (d-1). The infrared absorption spectrum of pigment (d) is shown in FIG.
Compound (d-1)

(Manufacture of pigment (e))
Compound (3) was prepared in the same manner as in the synthesis of compound (1), except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 14.6 parts of 3,4-difluoroaniline. I got 16.2 copies.

[Compound (3)]

The same procedure as in the synthesis of pigment (b) was carried out to prepare pigment (e), except that 13.5 parts of compound (1) used in the synthesis of pigment (b) was changed to 14.7 parts of compound (3). I received 13.4 copies of this. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of pigment (e) was compound (e-1). The infrared absorption spectrum of pigment (e) is shown in FIG.

Compound (e-1)

(Manufacture of pigment (f))
The same procedure as for the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 19.8 parts of 4-bromoaniline, and compound (4) was synthesized by 20.8 parts of 4-bromoaniline. I got 0 copies.

[Compound (4)]

The same procedure as in the synthesis of pigment (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of pigment (b) was changed to 19.7 parts of compound (4), and pigment (f) was synthesized. 15.0 parts of was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of pigment (f) was compound (f-1).

Compound (f-1)

(Manufacture of pigment (g))
The same procedure as in the synthesis of compound (1) was carried out, 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 synthesized in 14.9 parts of p-toluidine. I got it.

[Compound (5)]

Pigment (g) was prepared in the same manner as in the synthesis of compound (b), except that 13.5 parts of compound (1) used in the synthesis of pigment (b) was changed to 14.0 parts of compound (5). 13.2 copies were obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of pigment (g) was compound (g-1).

Compound (g-1)

(Manufacture of pigment (h))
Compound (6) was prepared in the same manner as in the synthesis of compound (1), except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 16.0 parts of 4-(methylthio)aniline. I got 16.4 copies.

[Compound (6)]

The same procedure as in the synthesis of compound (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of pigment (b) was changed to 15.0 parts of compound (6), and pigment (h) was synthesized. 14.2 copies of this were obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of pigment (h) was compound (h-1).

Compound (h-1)

(Manufacture of pigment (i))
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 20.0 parts of sulfanilic acid, and 17.5 parts of compound (7) was obtained. Ta.

[Compound (7)]

The same procedure as in the synthesis of compound (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of pigment (b) was changed to 16.0 parts of compound (6), and compound (i) 15.2 copies of this were obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of compound (i) was compound (i-1).

Compound (i-1)

(Manufacture of pigment (j))
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 14.2 parts of 4-amino-2-methylphenol. ) was obtained.

[Compound (8)]

The same procedure as in the synthesis of compound (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of pigment (b) was changed to 14.5 parts of compound (8), and pigment (j) was obtained. 13.1 parts were obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of pigment (j) was compound (j-1).

Compound (j-1)

(Manufacture of pigment (k))
The same procedure as in the synthesis of compound (1) was carried out, 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 (9) was synthesized in 17.2 parts of 3-methoxyaniline. I got 3 copies.

[Compound (9)]

The same procedure as in the synthesis of pigment (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of pigment (b) was changed to 14.5 parts of compound (9), and pigment (k) was synthesized. 12.8 parts of was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of pigment (k) was compound (k-1).

Compound (k-1)

(Manufacture of pigment (l))
The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 21.3 parts of 4-phenoxyaniline, and compound (10) was synthesized in 18. I got 8 copies.

[Compound (10)]

The same procedure as in the synthesis of compound (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of pigment (b) was changed to 16.5 parts of compound (10), and pigment (l) 15.3 copies were obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of pigment (l) was compound (l-1).

Compound (l-1)

(Manufacture of pigment (m))
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 18.8 parts of N,N-diethyl-1,4-phenylenediamine. , 18.8 parts of compound (11) were obtained.

[Compound (11)]

The same procedure as in the synthesis of pigment (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of pigment (b) was changed to 15.7 parts of compound (11), and pigment (m) was synthesized. 14.2 copies of this were obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of pigment (m) was compound (m-1).

Compound (m-1)

(Production of compound (n))
The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 13.7 parts of 4-cyanoaniline, and compound (12) was synthesized in 16. I got 0 copies.

[Compound (12)]

The same procedure as in the synthesis of pigment (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of pigment (b) was changed to 15.2 parts of compound (12), and pigment (n) was synthesized. 14.6 parts of was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of pigment (n) was compound (n-1).

Compound (n-1)

(Production of compound (o))
The same procedure as in the synthesis of compound (1) was carried out, except that 10.0 parts of indigo used in the synthesis of compound (1) was changed to 16.0 parts of Bat Blue 35, and compound (13) was synthesized in 19.5 parts. I got it.

[Compound (13)]

The same procedure as in the synthesis of pigment (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of pigment (b) was changed to 18.7 parts of compound (13), and pigment (o) was synthesized. 17.5 copies were obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of pigment (o) was compound (o-1).

Compound (o-1)

(Manufacture of pigment (p))
The same procedure as in the synthesis of compound (1) was carried out, 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 compound (14) was synthesized with 24.4 parts of indigo. I got it.

[Compound (14)]

The same procedure as in the synthesis of pigment (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of pigment (b) was changed to 23.9 parts of compound (14), and pigment (p) 21.5 parts of was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of pigment (p) was compound (p-1).

Compound (p-1)

(Manufacture of pigment (q))
9.0 parts of bis(2,4-pentanedionato)zinc(II) used in the synthesis of pigment (a) was mixed with 8.8 parts of bis(2,4-pentanedionato)nickel(II) hydrate. The same procedure as in the synthesis of pigment (a) was performed except that 11.5 parts of pigment (q) was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of pigment (q) was compound (q-1). The infrared absorption spectrum of pigment (q) is shown in FIG.

Compound (q-1)

(Manufacture of pigment (r))
The same procedure as in the synthesis of pigment (c) except that 15.0 parts of zinc acetate dihydrate used in the synthesis of pigment (c) was changed to 17.0 parts of nickel (II) acetate tetrahydrate. 10.1 parts of pigment (r) was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of pigment (r) was compound (q-2).

Compound (q-2)

(Manufacture of pigment(s))
9.0 parts of bis(2,4-pentanedionato)zinc(II) used in the synthesis of pigment (a) was changed to 12.6 parts of bis(2,4-pentanedionato)cobalt(II). Except for this, the same operation as in the synthesis of pigment (a) was performed to obtain 12.7 parts of pigment (s). As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The main component of pigment (s) was compound (s-1). The infrared absorption spectrum of pigment (s) is shown in FIG.

Compound (s-1)

(Synthesis of pigment (t))
A pigment (t) having the following structure was obtained according to JP-A-2012-224593.
Pigment (t)

The composition of the obtained compound is shown in Table 1.

<Production of finely divided pigment>
(Production of yellow finely divided pigment (PY-1))
Isoindoline yellow pigment C. I. 200 parts of Pigment Yellow 139 ("Paliotol Yellow L 2146HD" manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. Next, this kneaded material was poured into 8 liters of warm water, and stirred for 2 hours while heating to 80° C. to form a slurry. This slurry was filtered and repeatedly washed with water to remove sodium chloride and diethylene glycol, and then dried at 85° C. for a day and night to obtain a yellow finely divided pigment (PY-1).

(Manufacture of blue finely divided pigment (PB-1))
Phthalocyanine blue pigment C. I. 100 parts of Pigment Blue 15:6 ("Lionor Blue ES" manufactured by Toyo Color Co., Ltd.), 800 parts of crushed common salt, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 12 hours. did. This mixture was poured into 3,000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry. After repeated filtration and water washing to remove salt and solvent, the mixture was heated to about 70°C for 24 hours. It was dried to obtain 98 parts of blue finely divided pigment (PB-1). The average primary particle diameter of the obtained pigment was 28 nm.

(Production of purple finely divided pigment (PV-1))
Dioxazine-based purple pigment C. I. 120 parts of Pigment Violet 23 ("Fast Violet RL" manufactured by Clariant), 1600 parts of ground common salt, and 100 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90° C. for 18 hours. This mixture was poured into 5000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry. After repeated filtration and water washing to remove the salt and solvent, the mixture was heated to about 70°C for 24 hours. It was dried to obtain 118 parts of a purple finely divided pigment (PV-1). The average primary particle diameter of the obtained pigment was 26 nm.

<Preparation method of binder resin solution>
(Binder resin solution 1)
70.0 parts of cyclohexanone was placed in a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, and the temperature was raised to 80°C. After purging the inside of the reaction vessel with nitrogen, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), A mixture of 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours to obtain a solution of an acrylic resin having a mass average molecular weight 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. Methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Binder resin solution 1 was prepared by adding the following. Here, the mass average molecular weight (Mw) of the binder resin was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

(Binder resin solution 2)
370 parts of cyclohexanone was charged into a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile. part of the mixture was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, and then a solution of 1.0 part of azobisisobutyronitrile dissolved 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 replaced with air, and 9.3 parts of acrylic acid (100% of glycidyl groups) was mixed with 0.0 parts of trisdimethylaminophenol. 5 parts and 0.1 part of hydroquinone were put into the above container, and the reaction was continued at 120°C for 6 hours, and the reaction was terminated when the solid content acid value reached 0.5 to obtain a copolymer solution. 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 a carboxy group and a copolymer solution. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Binder resin solution 2 was prepared. The mass average molecular weight (Mw) was 19,000.

<Preparation method of resin type dispersant solution>
(Resin type dispersant solution 1): Block acrylic type basic dispersant [Synthesis of monomer (bb-1)]
A reaction vessel equipped with a stirrer and a thermometer was charged with 60 parts of 2-isocyanatoethyl methacrylate, 29 parts of 3-(dimethylamino)propylamine, and 120 parts of THF, and stirred at room temperature for 5 hours. After confirming the completion of the reaction by FT-IR, the solvent was distilled off using a rotary evaporator to obtain 73 parts of the following monomer (bb-1) as a pale yellow transparent liquid (yield: 82%). ). The obtained compound was identified by ¹ H-NMR.

Monomer (bb-1)

[Synthesis of monomer (bb-2)]
A reaction vessel equipped with a stirrer and a thermometer was charged with 6.6 parts of monomer (bb-1) obtained in the synthesis of monomer (bb-1) and 5 parts of ion-exchanged water, and stirred at room temperature. % aqueous hydrochloric acid solution was added dropwise. Completion of the reaction was confirmed by amine value measurement, and 20 parts of a monomer (bb-2) aqueous solution was obtained as a pale yellow transparent liquid. The obtained compound was identified by ¹ H-NMR.

Monomer (bb-2)

17.7 parts of methyl methacrylate, 53.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reaction tank equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and the mixture was heated for 50 minutes while flowing nitrogen. The mixture was stirred at ℃ for 1 hour, and the inside of the system was purged with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 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 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content.
Next, 20 parts of PGMAc, 21.2 parts of monomer (bb-1) as a second block monomer, and 27 parts of monomer (bb-2) aqueous solution (nonvolatile content 38%) were put into this reaction tank, and heated to 110°C with nitrogen. The reaction was continued by stirring while maintaining the atmosphere. After 2 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of nonvolatile content, and the reaction solution was cooled to room temperature to stop the polymerization. did.
PGMAc was added to the previously synthesized block copolymer solution so that the nonvolatile content was 40% by mass. In this way, a resin-type dispersant solution 1 having an amine value per nonvolatile content of 50 mgKOH/g, a quaternary ammonium salt value of 20 mgKOH/g, and a mass average molecular weight (Mw) of 9,800 was obtained.

(Resin-type dispersant solution 2): Block acrylic-type basic dispersant In a reaction apparatus equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer, 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and tetramethylethylene diamine were added. 13.2 parts were charged, and the mixture was stirred at 50° C. for 1 hour while flowing nitrogen, and the inside of the system was purged 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 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content.
Next, 61 parts of PGMAc and 20 parts of dimethylaminoethyl methacrylate (hereinafter referred to as DM) as a second block monomer were charged into this reactor, and the reaction was continued by stirring while maintaining the temperature at 110° C. and a nitrogen atmosphere. Two hours after adding dimethylaminoethyl methacrylate, the polymerization solution was sampled to measure the nonvolatile content, and it was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of nonvolatile content, and the reaction solution was cooled to room temperature. Polymerization was stopped by cooling.

PGMAc was added to the previously synthesized block copolymer solution so that the nonvolatile content was 40% by mass. In this way, a resin-type dispersant solution 2 having a poly(meth)acrylate skeleton and a tertiary amino group and having an amine value per nonvolatile content of 71.4 mgKOH/g and a mass average molecular weight of 9900 (Mw) was obtained.

(Resin-type dispersant solution 3): Block acrylic-type basic dispersant In a reaction apparatus equipped with a gas inlet pipe, a condenser, a stirring blade, and a thermometer, 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and tetramethylethylene diamine were added. 13.2 parts were charged, and the mixture was stirred at 50° C. for 1 hour while flowing nitrogen, and the inside of the system was purged 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 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content.

Next, 61 parts of PGMAc and 25.6 parts of an aqueous solution of methacryloyloxyethyltrimethylammonium chloride ("Acryester DMC78" manufactured by Mitsubishi Rayon Co., Ltd.) as a second block monomer were introduced into the reactor, and the temperature was maintained at 110°C under a nitrogen atmosphere. The mixture was stirred while the reaction was continued. Two hours after adding methacryloyloxyethyltrimethylammonium chloride, the polymerization solution was sampled to measure the nonvolatile content, and it was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of nonvolatile content. Polymerization was stopped by cooling to room temperature.

PGMAc was added to the previously synthesized block copolymer solution so that the nonvolatile content was 40% by mass. In this way, a resin-type dispersant solution 3 having a poly(meth)acrylate skeleton and a quaternary ammonium base and having an amine value per nonvolatile content of 29.4 mgKOH/g and a mass average molecular weight of 9800 (Mw) was obtained.

(Resin type dispersant solution 4): Block acrylic type basic dispersant
In a reaction vessel equipped with a stirrer and a thermometer, 55 parts of 4-dimethylamino-1,2-epoxybutane and 120 parts of tetrahydrofuran (THF) were charged, heated and stirred at 70°C, and 35 parts of methacrylic acid was added over 60 minutes. dripped. After completion of the dropwise addition, the mixture was heated and stirred at 70° C. for another 2 hours, and after confirming completion of the reaction by ¹ H-NMR, it was allowed to cool to room temperature. The reaction solution was sequentially washed with 300 parts of ion-exchanged water, 200 parts of saturated sodium bicarbonate, and 200 parts of saturated brine, and then 20 g of magnesium sulfate was added to the organic layer, followed by stirring and filtration. The solvent of the obtained solution was distilled off using a rotary evaporator to obtain 31 parts of the following monomer (bb-3) as a pale yellow transparent liquid (yield: 42%). The obtained compound was identified by ¹ H-NMR.
Monomer (bb-3)

17.6 parts of methyl methacrylate, 52.8 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reaction tank equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and the mixture was heated for 50 minutes while flowing nitrogen. The mixture was stirred at ℃ for 1 hour, and the inside of the system was purged with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 parts of propylene glycol monomethyl ether acetate were charged, and the temperature was raised to 110°C under a nitrogen stream to start polymerization of the first block. . After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content.

Next, 25 parts of PGMAc and 25.1 parts of ethylenically unsaturated monomer (bb-3) as a second block monomer were added to this reaction tank, and the mixture was stirred while maintaining the temperature at 110°C and a nitrogen atmosphere. The reaction continued. Two hours after adding the ethylenically unsaturated monomer (bb-3), the polymerization solution was sampled to measure the nonvolatile content, and it was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of nonvolatile content. confirmed.

Furthermore, 4.5 parts of benzyl chloride was added to this reactor, and the mixture was stirred for 3 hours while maintaining the temperature at 110° C. and nitrogen atmosphere, and then cooled.
PGMAc was added to the previously synthesized block copolymer solution so that the nonvolatile content was 40% by mass. In this way, a resin-type dispersant solution 4 having an amine value per nonvolatile content of 50 mgKOH/g, a quaternary ammonium salt value of 20 mgKOH/g, a mass average molecular weight (Mw) of 9,800, and a nonvolatile content of 40% by mass was prepared. Obtained.

(Resin type dispersant solution 5)
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 50 parts of methyl methacrylate, 50 parts of n-butyl methacrylate, and 45.4 parts of PGMAc, and the mixture was replaced with nitrogen gas. The inside of the reaction vessel was heated to 70° C., 6 parts of 3-mercapto-1,2-propanediol were added, and further 0.12 part of AIBN (azobisisobutyronitrile) was added, and the mixture was reacted for 12 hours. It was confirmed by non-volatile content measurement that 95% had reacted. Next, 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added, and the mixture was heated to 120°C. The mixture was allowed to react for 7 hours. After measuring the acid value, it was confirmed that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. PGMAc was added to adjust the nonvolatile content to 40%. In this way, a resin type dispersant solution 5 having an acid value of 43, a mass average molecular weight of 9000, a poly(meth)acrylate skeleton, and an aromatic carboxy group was obtained.

<Manufacture of pigment composition>
[Example 1]
(Manufacture of pigment composition (X-1))
After uniformly stirring and mixing a mixture having the composition shown below, it was dispersed in an Eiger mill for 3 hours using zirconia beads with a diameter of 0.5 mm, and then filtered with a 0.5 μm filter to obtain pigment composition (X-1). Created.
Pigment (a): 10.0 parts Resin type dispersant solution 1: 10.0 parts Binder resin solution 1: 30.0 parts PGMAc (methoxypropyl acetate): 50.0 parts

[Examples 2 to 25, Production Examples 1 to 3, Comparative Examples 1 to 4]
(Production of pigment compositions (X-2) to (X-28), (XX-1) to (XX-4))
Pigment compositions (X-2) to (X-28), (XX-1) to (XX-4) were prepared in the same manner as in (X-1) except that the compositions were changed as shown in Tables 4 to 7. was created.
In the production of (XX-1), metal-free naphthalocyanine was used in place of pigment (a). The average primary particle size of the metal-free naphthalocyanine was 50 nm.
The following dye (H-1) was used to prepare (XX-2), the following dye (H-2) was used to prepare (XX-3), and the following dye (H-3) was used to prepare (XX-4). were used in place of pigment (a), respectively.

[Example 26]
(Manufacture of pigment composition (Y-1))
Pigment composition (Y-1) was prepared by mixing 30 parts of pigment composition (X-26), 20 parts of (X-27), 20 parts of (X-28), and 30 parts of (X-1).

(Comparative example 5)
(Manufacture of resin composition (Z-1))
85 parts of fluorene bifunctional acrylate (Oxol EA-0200 manufactured by Osaka Gas Chemical Co., Ltd.), 10 parts of trimethylolpropane triacrylate (NK Ester A-TMPT manufactured by Shin-Nakamura Chemical Co., Ltd.), Irgacure 184 (manufactured by BASF) ) were mixed to prepare a resin composition (Z-1).
Irgacure 184 is a photopolymerization initiator, and this resin composition does not contain a solvent.
Note that the fluorene-based bifunctional acrylate (Ogsol EA-0200 manufactured by Osaka Gas Chemical Co., Ltd.) is a high refractive index acrylate monomer with a refractive index of 1.6 or more in the visible region.

<Evaluation of pigment composition>
The pigment composition (X-1) of Example 1 was applied onto a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater with the rotation speed adjusted, and after drying at 100°C for 10 minutes, a film was formed. A substrate on which a 1.0 μm thick film was formed was obtained.
The absorption spectrum of the film was measured for this substrate using an absorption photometer, and the following items were evaluated.

(Maximum value of absorbance between 700 and 1200 nm)
〇++: 3.0 or more 〇+: 2.0 or more and less than 3.0 〇: 1.0 or more and less than 2.0 ×: less than 1.0

(Absorbance at 940nm)
A: Less than 0.3 B: 0.3 or more

(Refractive index)
Next, spectroscopic ellipsometry was performed on this substrate using a spectroscopic ellipsometer ("M-220" manufactured by JASCO Corporation) to determine the refractive index at 940 nm, 1310 nm, and 1550 nm.
Note that if the absorbance at 940 nm is 0.3 or more, the accuracy of the measured value of the refractive index may be lowered, and this is not appropriate as a practical sensing wavelength, so the refractive index is not measured. In that case, it is written as "-".

(light resistance)
A light resistance test was performed on the substrate on which the above-described film with a thickness of 1.0 μm was formed by exposing it to an illumination intensity of 60 W/m ² at 300 to 400 nm for 20 hours using a xenon weather meter.

The change in absorbance at the maximum absorption wavelength between 700 and 1200 nm before and after the test was evaluated.
〇: The rate of decrease in absorbance at the maximum absorption wavelength is less than 5% △: The rate of decrease in absorbance at the maximum absorption wavelength is 5% or more, but less than 30% ×: The rate of decrease in absorbance at the maximum absorption wavelength is 30% or more

(Heat-resistant)
The substrate on which the above-mentioned film with a thickness of 1.0 μm was formed was subjected to heat treatment at 230° C. for 20 minutes, and a heat resistance test was conducted.
Judgment was made regarding the change in absorbance at the maximum absorption wavelength between 700 and 1200 nm.
〇: The rate of decrease in absorbance at the maximum absorption wavelength is less than 5% △: The rate of decrease in absorbance at the maximum absorption wavelength is 5% or more, but less than 30% ×: The rate of decrease in absorbance at the maximum absorption wavelength is 30% or more

(transparency)
The haze of the substrate on which the above-described film with a thickness of 1.0 μm was formed was measured using a haze meter, and the transparency was determined.
〇: Haze is less than 0.5 △: Haze is 0.5 or more and less than 1.0 ×: Haze is 1.0 or more

For Examples 2 to 26 and Comparative Examples 1 to 5, the above evaluation was performed in the same manner as in Example 1.

The resin composition (Z-1) of Comparative Example 5 was coated and dried for 10 minutes at 100°C in the same manner as in Example 1, and then exposed to UV light (exposure amount: 800 mJ/cm2) to form a film with a thickness of 1.0 μm. A formed substrate was obtained.

Furthermore, since the resin composition (Z-1) has no absorption in the wavelength range of 700 to 1200 nm, the above light resistance and heat resistance tests were not conducted.

These results are shown in Table 5.

[Example 27]
(Manufacture of curable composition (XC-1))
A curable composition (XC-1) was prepared by stirring and mixing a mixture having the following composition to make it uniform.
Pigment composition (X-1): 100 parts EHPE3150 (epoxy curing agent, manufactured by Daicel Chemical Industries, Ltd.): 5.0 parts PGMAc: 20.0 parts

The resin composition (XC-1) obtained in Example 27 was applied onto a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater with the rotation speed adjusted, and dried at 100°C for 10 minutes. Thereafter, a substrate on which a film with a thickness of 1.0 μm was formed was obtained.
The absorption spectrum of the film was measured for this substrate using an absorption photometer, and the following items were evaluated.

(Maximum value of absorbance from 700 to 1200 nm)
〇++: 3.0 or more 〇+: 2.0 or more and less than 3.0 〇: 1.0 or more and less than 2.0 ×: less than 1.0

(Absorbance at 940nm)
A: Less than 0.3 B: 0.3 or more

(Refractive index)
Next, spectroscopic ellipsometry was performed on this substrate using a spectroscopic ellipsometer ("M-220" manufactured by JASCO Corporation) to determine the refractive index at 940 nm, 1310 nm, and 1550 nm.

(curability)
The substrate on which the 1.0 μm thick film was formed was heat-treated at 200° C. for 5 minutes, then rubbed 50 times with a hammer wrapped in gauze swollen with methyl ethyl ketone, and the film was observed. The criteria for judgment are shown below.
○: Membrane is intact.
Δ: Peeling occurs in part of the film.
×: The film is completely dissolved.

The composition and evaluation results of Example 27 are shown in Tables 6 and 7.

[Example 28]
(Manufacture of photosensitive composition (XR-1))
A photosensitive composition (XR-1) was prepared by stirring and mixing a mixture having the composition shown below to make it uniform.

Pigment composition (X-1): 100.0 parts Photopolymerizable monomer ("Aronix M-402" manufactured by Toagosei Co., Ltd.): 4.0 parts Photopolymerization initiator ("Irgacure 907" manufactured by BASF Corporation) : 1.0 parts PGMAc: 20.0 parts

The photosensitive composition (XR-1) obtained in Example 28 was applied to a glass substrate by spin coating, and then dried at 70° C. for 20 minutes. Next, after cooling this substrate to room temperature, it was exposed to ultraviolet light at 300 mJ/cm ² using an ultra-high pressure mercury lamp.

Thereafter, this substrate was spray developed with a 0.2% by mass aqueous sodium carbonate solution at 23° C. for 30 seconds, washed with ion-exchanged water, and dried. Furthermore, heat treatment was performed at 230° C. for 30 minutes in a clean oven.

By adjusting the rotation speed during spin coating in the above method, a glass substrate on which a film with a thickness of 1.0 μm was formed was obtained.
The absorption spectrum of the film was measured for this substrate using an absorption photometer, and the following items were evaluated.

(Maximum value of absorbance from 700 to 1200 nm)
〇++: 3.0 or more 〇+: 2.0 or more and less than 3.0 〇: 1.0 or more and less than 2.0 ×: less than 1.0

(Absorbance at 940nm)
A: Less than 0.3 B: 0.3 or more

(Refractive index)
Next, spectroscopic ellipsometry was performed on this substrate using a spectroscopic ellipsometer ("M-220" manufactured by JASCO Corporation) to determine the refractive index at 940 nm, 1310 nm, and 1550 nm.

(curability)
The substrate on which the 1.0 μm thick film was formed was heat-treated at 200° C. for 5 minutes, then rubbed 50 times with a hammer wrapped in gauze swollen with methyl ethyl ketone, and the film was observed. The criteria for judgment are shown below.
○: Membrane is intact.
Δ: Peeling occurs in part of the film.
×: The film is completely dissolved.
The composition and evaluation results of Example 28 are shown in Tables 8 and 9.

From the above, the pigment composition of the present invention has a particularly high refractive index in the wavelength range of 900 to 1600 nm, and can be made into a cured product with excellent transparency, heat resistance, and light resistance, so it is suitable for use in optical lenses and optical waveguides. Useful.

Claims (7)

A pigment composition for use in an optical lens for an infrared sensor or an infrared communication device, or an optical waveguide for an infrared sensor or an infrared communication device, the pigment composition comprising:
A pigment composition containing a pigment and a resin, the pigment containing at least one selected from the group consisting of compounds represented by the following general formula (1), (2), or (3).

General formula (1)

General formula (4)

(** represents the bond with the 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 are never hydrogen at the same time.
X ₁₀₁ to X ₁₁₂ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, a substituted Aryloxy group which may have a substituent, arylalkyl group which may have a substituent, cycloalkyl group which may have a substituent, alkylthio group which may have a substituent, Arylthio group that may have a substituent, amino group, alkylamino group that may have a substituent, arylamino group that may have a substituent, cyano group, halogen atom, nitro group, Represents a hydroxyl group, -SO ₃ H, -COOH, or a monovalent to trivalent metal salt or alkylammonium salt of these acidic groups. Two adjacent groups among the groups represented by X ₁₀₁ to X ₁₁₂ may be connected to form a 5-membered ring or a 6-membered ring together with the carbon atoms to which they are bonded. ]


[In general formulas (2) and (3), X ₁ to X ₄₀ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, a substituted an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an arylalkyl group which may have a substituent, a cycloalkyl group which may have a substituent, Alkylthio group that may have a substituent, arylthio group that may have a substituent, amino group, alkylamino group that may have a substituent, aryl that may have a substituent It represents an amino group, a cyano group, a halogen atom, a nitro group, a hydroxyl group, or -SO ₃ H, -COOH, or a monovalent to trivalent metal salt or alkylammonium salt of these acidic groups. Two adjacent groups among the groups represented by X ₁ to X ₄₀ may be connected to form a 5-membered ring or a 6-membered ring together with the carbon atoms to which they are bonded.
M represents a metal atom. ] The pigment composition according to claim 1, wherein M is a divalent metal atom. The pigment composition according to claim 1 or 2, wherein the content of the pigment is 30% by mass or more based on the total mass of solid content in the pigment composition. The pigment composition according to claim 1 or 2, further comprising a curing agent and a solvent. A film comprising the pigment composition according to claim 1 or 2. An optical lens comprising the pigment composition according to claim 1 or 2. An optical waveguide comprising the pigment composition according to claim 1 or 2.

Images