JP2022091099A - Near-infrared absorptive dye, near-infrared absorptive composition and optical filter - Google Patents

Abstract

To provide a near-infrared absorptive dye having transparency from 480 nm to 650 nm, which is a region with high luminous efficiency, heat resistance and light resistance, and excellent in 700 nm to 900 nm near-infrared absorption.SOLUTION: The above problem is solved by a near-infrared absorptive dye having a specific structure. Also, the above problem is solved by a near-infrared absorptive composition including the near-infrared absorptive dye having the specific structure and a binder resin, and further a near-infrared absorptive composition containing an organic dye having absorption at 400 nm to 700 nm.SELECTED DRAWING: None

Description

The present invention relates to a near-infrared absorbing dye, a near-infrared absorbing composition, and an optical filter.

The near-infrared absorbing material includes, for example, a near-infrared absorbing film that blocks heat rays, a near-infrared absorbing plate, an agricultural near-infrared absorbing film that selectively uses sunlight, a recording medium that uses the absorbed heat of near-infrared rays, and electronic devices. Used in a wide range of applications such as near-infrared cut filter for photography, near-infrared filter for photography, protective glasses, sunglasses, heat ray blocking film, dye for optical recording, optical character reading and recording, for preventing copying of confidential documents, electrophotographic photosensitive member, laser fusion, etc. Has been done.

Among these, the near-infrared cut filter for camera sensors is required to have high transparency in the region of high luminous efficiency of 480 nm to 650 nm and high shielding of 700 nm to 1000 nm in the region of no luminous efficiency. Will be done. In addition, near-infrared cut filters for cameras are required to have extremely high heat resistance and light resistance, such as for in-vehicle applications used in harsh environments and for mounting on devices that require processing at high temperatures.
Luminous efficiency is an index of brightness perceived by the human eye at each wavelength.

Cyanine-based pigments, diimonium-based pigments, phthalocyanine-based pigments, and squarylium-based pigments are known as typical near-infrared absorbing pigments. However, the uses of cyanine-based dyes and diimonium-based dyes are limited because they have low heat resistance and light resistance and are poor in durability in various environments.

As the phthalocyanine dye, a phthalocyanine compound or a naphthalocyanine compound having a substituent (for example, see Patent Document 1), a phthalocyanine compound having an amino group (for example, see Patent Documents 2 to 6), and a phthalocyanine compound having an aryloxy group (for example, see Patent Document 1). , Patent Document 7), fluorine-containing phthalocyanine compounds (see, for example, Patent Documents 8 and 9) and the like are disclosed.

Japanese Unexamined Patent Publication No. 10-78509 Japanese Unexamined Patent Publication No. 2004-18561 Japanese Unexamined Patent Publication No. 2001-106689 Japanese Unexamined Patent Publication No. 2000-63691 Japanese Patent Application Laid-Open No. 06-025548 Japanese Patent Application Laid-Open No. 2000-026748 Japanese Unexamined Patent Publication No. 2013-241563 Japanese Patent Application Laid-Open No. 05-078364 Japanese Patent Application Laid-Open No. 06-107663

Among these, the naphthalocyanine compound has extremely high heat resistance and light resistance when used as a pigment, and has a feature of widely absorbing light of 700 nm to 900 nm. However, since the aggregation due to the association of aromatic rings is very strong, there is a problem that the dispersion stability is poor and the transparency is low, that is, the transmittance in the region of high luminous efficiency of 480 nm to 650 nm is low.

An object of the present invention is to provide a near-infrared absorbing dye having both heat resistance and light resistance and excellent near-infrared absorbing property of 700 nm to 900 nm, as well as transparency of 480 nm to 650 nm, which is a region having high relative luminous efficiency. ..

That is, the present invention relates to a near-infrared absorbing dye represented by the following general formula (1) or the following general formula (4).

[一般式（４）中、Ｒ_３１～Ｒ_５４は、それぞれ独立に、水素原子、ハロゲン原子、ニト
ロ基、ニトリル基、カルボキシル基、スルホン基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいシクロアルキル基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアリールチオ基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいアリールアミノ基、または置換基を有してもよいスルファモイル基を表す。
Ｍ₂は、Ｓｉ、Ｇｅ、Ｓｎを表す。
Ｚ₂およびＺ₃は、それぞれ独立に、前記一般式（２）で表される単量体単位を含む重合体部位、または前記一般式（３）で表されるリン化合物部位であり、＊は、Ｍ₂との結合手
である。] [In the general formula (1), R ₁ to R ₂₄ are independently hydrogen atom, halogen atom, nitro group, nitrile group, carboxyl group, sulfone group, alkyl group and substituent which may have a substituent. It has an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, and a substituent. May have an alkylthio group, an arylthio group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, or a sulfamoyl which may have a substituent. Represents a group.
M ₁ represents Ga and In.
Z ₁ is a polymer moiety containing a monomer unit represented by the general formula (2) or a phosphorus compound moiety represented by the general formula (3), and * is a bond with M ₁ . ..
In the general formula (2), X is -CONH-R _25- , -COO-R _26- , -CONH-R ₂₇ -O-, or -COO-R ₂₈ -O-, and is R ₂₅ to R ₂₈ . Is an alkylene group, an arylene group, or an alkylene group or arylene linked by -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO- between carbon atoms. Represents a group. Y represents a hydrogen or methyl group.
In the general formula (3), R ₂₉ and R ₃₀ may independently have a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent, respectively. Representing an aryloxy group which may have an alkoxyl group or a substituent, R ₂₉ and R ₃₀ may be bonded to each other to form a ring. ]

General formula (4)

[In the general formula (4), R ₃₁ to R ₅₄ independently have a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, and an alkyl group and a substituent which may have a substituent. It has an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, and a substituent. May have an alkylthio group, an arylthio group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, or a sulfamoyl which may have a substituent. Represents a group.
M ₂ represents Si, Ge, Sn.
Z ₂ and Z ₃ are each independently a polymer moiety containing a monomer unit represented by the general formula (2) or a phosphorus compound moiety represented by the general formula (3), and * indicates. , M ₂ is a bond. ]

The present invention also relates to a near-infrared absorbing composition containing the near-infrared absorbing dye and a binder resin.

The present invention also relates to the near-infrared absorbing composition containing a photopolymerizable compound and a photopolymerization initiator.

The present invention also relates to the near-infrared absorbing composition containing an organic dye having absorption at 400 nm to 700 nm.

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

According to the present invention described above, a near-infrared absorbing dye and a near-infrared absorbing dye having both heat resistance and light resistance and excellent near-infrared absorbing ability of 700 nm to 900 nm, as well as transparency of 480 nm to 650 nm, which is a region having high luminous efficiency, and near-infrared absorption. Sexual compositions and optical filters can be provided.

<Near infrared absorbent dye>
The near-infrared absorbing dye of the present invention (hereinafter referred to as the dye of the present invention) is represented by the general formula (1) or the general formula (4). The dye of the present invention widely absorbs light of 700 nm to 900 nm by binding a moiety represented by the general formula (2) or the general formula (3) to a naphthalocyanine moiety having high heat resistance and light resistance. At the same time, it is possible to improve the transparency in the region of high relative visibility of 480 nm to 650 nm. Thereby, the transparency, heat resistance and light resistance can be compatible with each other.

In general, naphthalocyanine dyes have a strong cohesive force due to the association of aromatic rings, and often have a crystal structure and exist as a pigment. In that case, it becomes difficult to dissolve in a normal solvent, and a dispersion can be obtained by dispersing using a dispersant or the like. However, the film formed from the dispersion liquid exhibits strong absorption due to the association of aromatic rings, and has low transparency due to deterioration of dispersion stability, that is, a transmission of 480 nm to 650 nm, which is a region having high luminous efficiency. The sex gets worse.

On the other hand, the dye-containing coating film of the present invention is a region having high relative sensitivity by controlling the association of aromatic rings by binding a specific polymer or phosphorus compound to naphthalocyanine as an axial ligand. The permeability from 480 nm to 650 nm is increased. This is because a specific polymer or phosphorus compound causes appropriate steric hindrance, and the naphthalocyanine sites have a structure in which it is difficult for them to associate with each other.

[一般式（４）中、Ｒ_３１～Ｒ_５４は、それぞれ独立に、水素原子、ハロゲン原子、ニト
ロ基、ニトリル基、カルボキシル基、スルホン基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいシクロアルキル基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアリールチオ基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいアリールアミノ基、または置換基を有してもよいスルファモイル基を表す。
Ｍ₂は、Ｓｉ、Ｇｅ、Ｓｎを表す。
Ｚ₂およびＺ₃は、それぞれ独立に、前記一般式（２）で表される単量体単位を含む重合体部位、または前記一般式（３）で表されるリン化合物部位であり、＊は、Ｍ₂との結合手
である。] [In the general formula (1), R ₁ to R ₂₄ independently have a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, and an alkyl group and a substituent which may have a substituent. It has an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, and a substituent. May have an alkylthio group, an arylthio group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, or a sulfamoyl which may have a substituent. Represents a group.
M ₁ represents Ga and In.
Z ₁ is a polymer moiety containing a monomer unit represented by the general formula (2) or a phosphorus compound moiety represented by the general formula (3), and * is a bond with M ₁ . ..
In the general formula (2), X is -CONH-R _25- , -COO-R _26- , -CONH-R ₂₇ -O-, or -COO-R ₂₈ -O-, and is R ₂₅ to R ₂₈ . Is an alkylene group, an arylene group, or an alkylene group or arylene linked by -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO- between carbon atoms. Represents a group. Y represents a hydrogen atom or a methyl group.
In the general formula (3), R ₂₉ and R ₃₀ may independently have a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent, respectively. Representing an aryloxy group which may have an alkoxyl group or a substituent, R ₂₉ and R ₃₀ may be bonded to each other to form a ring. ]

General formula (4)

[In the general formula (4), R ₃₁ to R ₅₄ independently have a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, and an alkyl group and a substituent which may have a substituent. It has an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, and a substituent. May have an alkylthio group, an arylthio group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, or a sulfamoyl which may have a substituent. Represents a group.
M ₂ represents Si, Ge, Sn.
Z ₂ and Z ₃ are each independently a polymer moiety containing a monomer unit represented by the general formula (2) or a phosphorus compound moiety represented by the general formula (3), and * indicates. , M ₂ is a bond. ]

The dye of the present invention is composed of a naphthalocyanine moiety, a polymer moiety containing a monomer unit represented by the general formula (2), or a phosphorus compound moiety represented by the general formula (3). The naphthalocyanine moiety is preferably made from naphthalocyanine represented by the following general formula (5) or the following general formula (6).

(Naphthalocyanine)

In the general formula (5) and the general formula (6), R ₁ to R ₂₄ and R ₃₁ to R ₅₄ are independently hydrogen atom, halogen atom, nitro group, nitrile group, carboxyl group, sulfone group and substituent, respectively. An alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxyl group which may have a substituent, and a substituent which may have a substituent. A good aryloxy group, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, an alkylamino group which may have a substituent, and an arylamino group which may have a substituent. , Or a sulfamoyl group which may have a substituent.
M ₁ represents Ga and In, and M ₂ represents Si, Ge and Sn.

The "alkyl group" of the alkyl group which may have a substituent is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group. , N-octyl group, stearyl group, 2-ethylhexyl group and other linear or branched alkyl groups. The "alkyl group having a substituent" is, for example, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, 2,2,3,3-tetrafluoro. Propyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-ptylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, Examples thereof include a 2,4-dichlorobenzyl group.

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

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

The "alkoxyl group" of the alkoxyl group which may have a substituent includes, 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, and the like. Examples thereof include a linear or branched alkoxyl group such as 2,3-dimethyl-3-pentyloxy, n-hexyloxy group, n-octyloxy group, stearyloxy group and 2-ethylhexyloxy group.
The "alkoxyl group having a substituent" includes, for example, a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, and a 2,2-ditri. Examples thereof include a fluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, a benzyloxy group and the like.

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 like.
The "aryloxy group having a substituent" is, for example, p-methylphenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-. Examples thereof include a chlorophenoxy group.

The "alkylthio group" of the alkylthio group which may have a substituent includes, for example, a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, an octadecylthio group and the like. Can be mentioned.
Examples of the "alkylthio group having a substituent" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group and the like.

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 the "arylthio group having a substituent" include a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, a 2-hydroxyphenylthio group and the like. ..

The "alkylamine group" of the alkylamine group which may have a substituent is, for example, a methylamine group, an ethylamine group, a propylamine group, a butylamine group, a pentylamine group, a hexylamine group, an octylamine group, a decylamine group, and the like. Dodecylamine group, octadecylamine group and the like can be mentioned.
Examples of the "alkylamine group having a substituent" include a methoxyethylamine group, an aminoethylamine group, a benzylaminoethylamine group, a methylcarbonylaminoethylamine group, a phenylcarbonylaminoethylamine group and the like.

Examples of the "arylamine group" of the arylamine group which may have a substituent include a phenylamine group, a 1-naphthylamine group, a 2-naphthylamine group, a 9-anthrylamine group and the like.
Examples of the "arylamine group having a substituent" include a chlorophenylamine group, a trifluoromethylphenylamine group, a cyanophenylamine group, a nitrophenylamine group, a 2-aminophenylamine group, a 2-hydroxyphenylamine group and the like. Will be.

<Method of synthesizing naphthalocyanine>
The general industrial manufacturing method of naphthalocyanine represented by the general formula (5) or the following general formula (6) is described below.
-Wyler method Using substituted or unsubstituted anhydrous naphthalenedicarboxylic acid or substituted or unsubstituted anhydrous naphthalenedicarboxylic acid imide, urea and gallium trichloride, indium trichloride, silicon tetrachloride, germanium tetrachloride, or tetrachloride A method of reacting at high temperature in the presence of tin.
Phtalodinitrile method Substituted or unsubstituted 2,3-dicyanonaphthalene is added to DBU (1,8) in an alcohol solvent such as n-amyl alcohol, n-hexyl alcohol, 1-methoxyethanol and 1-ethoxyethanol. -Gallium trichloride in the presence of strong bases such as diazabicyclo [5.4.0] undecene-7), DBN (1,5-diazabicyclo [4.3.0] nonen-5), or (metal) alkoxide. , Indium trichloride, silicon tetrachloride, germanium tetrachloride, or tin tetrachloride.
-Diiminoisoindrin method Substitutable or unsubstituted 1,3-diiminobenzo [f] isoindrin of 2-dimethylaminoethanol, quinoline, DBU (1,8-diazabicyclo [5.4.0] undecene-7) A method of reacting with gallium trichloride, indium trichloride, silicon tetrachloride, germanium tetrachloride, or tin tetrachloride in the presence of such a strong base.

Examples of naphthalocyanine include the following compounds.

In addition to the above compounds, naphthalocyanine can use isomers having different introduction positions of substituents.

(Polymer site)
One form of the near-infrared absorbing dye represented by the general formula (1) or the general formula (4) includes a phosphoric acid group in a polymer moiety containing a monomer unit represented by the general formula (2) and a na. Metal cations in the phthalocyanine moiety form a salt.
The polymer moiety is formed by vinyl-polymerizing a monomer represented by the general formula (7), which is a raw material thereof. As the polymer moiety, a monomer represented by the general formula (7) and other monomers other than the monomer represented by the general formula (7) can be used.

General formula (7)

In the general formula (7), X represents -CONH-R _25- , -COO-R _26- , -CONH-R ₂₇ -O-, -COO-R ₂₈ -O-, and R ₂₅ to R ₂₈ are. The carbon atom and the carbon atom represent an alkylene group or an arylene group which may be linked by -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO-.
Examples of the alkylene group include a methylene group, an ethylene group, a propylene group and a butylene group. Examples of the arylene group include phenylene, naphthylene, biphenylene group, terphenylene group and anthrylene group. Examples of R ₂₅ to R ₂₈ include a methylene group, an ethylene group, a propylene group, and a butylene group.
Y represents a hydrogen atom or a methyl group.

The monomer represented by the general formula (7) is, for example, (2- (meth) acryloyloxyethyl) acid phosphate, (2- (meth) acryloyloxypropyl) acid phosphate, (2- (meth) acryloyloxyisopropyl). Acid phosphate can be mentioned.

Other monomers include, for example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, and vinyl alcohols. Examples thereof include esters, styrenes, (meth) acrylonitrile, acid group-containing monomers, and thermally crosslinkable group-containing monomers.

Examples of the (meth) acrylic acid esters include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n-butyl (meth) acrylic acid. Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , (Meta) t-octyl acrylate, (meth) dodecyl acrylate, (meth) octadecyl acrylate, (meth) acetoxyethyl acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ( 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, (meth) ) Benzyl acrylate, (meth) diethylene glycol monomethyl ether acrylate, (meth) diethylene glycol monoethyl ether acrylate, (meth) triethylene glycol monomethyl ether acrylate, (meth) triethylene glycol monoethyl ether acrylate, (meth) Polyethylene Glycol Acrylic Acid Monomethyl Ether, (Meta) Polyethylene Glycol Monoethyl Ether Acrylate, (Meta) β-Phenoxyethoxyethyl Acrylic Acid, Nonyl Phenoxy Polyethylene Glycol (Meta) Acrylic Acid, Dicyclopentenyl (Meta) Acrylic Acid, (Meta) ) Dicyclopentenyloxyethyl acrylate, (meth) trifluoroethyl acrylate, (meth) octafluoropentyl acrylate, (meth) perfluorooctylethyl acrylate, (meth) dicyclopentanyl acrylate, (meth) Examples thereof include tribromophenyl acrylate and tribromophenyloxyethyl (meth) acrylate.

Examples of crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like.

Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

Examples of the itaconic acid diesters include dimethyl itaconic acid, diethyl itaconic acid, and dibutyl itaconate.

Examples of (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-. Butylacryl (meth) amide, N-t-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, Examples thereof include N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholin, and diacetoneacrylamide.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and the like.

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene and chloromethylstyrene. , Hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc, etc.), methyl vinyl benzoate, α-methylstyrene and the like.

The acid group-containing monomer is, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloracrylic acid and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid and itaconic anhydride. , Unsaturated dicarboxylic acids such as citraconic acid, anhydrous citraconic acid, mesaconic acid or their anhydrides; unsaturated polyvalent carboxylic acids having a valence of 3 or more or their anhydrides; Mono-hypervalent polyvalent carboxylic acid mono (meta ) Acryloyloxyalkyl] esters; mono (meth) acrylates of both-terminal carboxypolymers such as ω-carboxy-polycaprolactone monoacrylate and ω-carboxy-polycaprolactone monomethacrylate can be mentioned.

The heat-crosslinkable group in the heat-crosslinkable group-containing monomer becomes, for example, a cross-linking point of the near-infrared absorbing dye, and contributes to the improvement of the heat resistance of the near-infrared absorbing dye. Examples of the thermally crosslinkable group include a hydroxyl group, a carboxylic acid anhydride, a primary or secondary amino group, an imino group, an oxetanyl group, a tert-butyl group, an epoxy group, a mercapto group, an isocyanate group and the like. Among these, a hydroxyl group, a carboxyl group, an oxetanyl group, a tert-butyl group, an isocyanate group and a (meth) acryloyl group are preferable, and a hydroxyl group is more preferable in terms of storage stability and reactivity.

The hydroxyl group-containing monomer is not particularly limited, and is, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-. Examples thereof include hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate, or a caprolactone adduct of these monomers (number of moles is 1 to 5). Among these, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable from the viewpoint of heat resistance.

Examples of the oxetanyl group-containing monomer include 3- (acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, and 3- (methacryloyloxymethyl). ) 3-Ethyloxetane, 3- (Acryloyloxymethyl) 3-butyloxetane, 3- (methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane and 3- (methacryloyloxymethyl) 3 -Hexil oxetane and the like can be mentioned.

Examples of the tert-butyl group-containing monomer include tert-butyl acrylate and tert-butyl methacrylate.

Examples of the isocyanate group-containing monomer include 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate, 4-isocyanate butyl acrylate and the like. The isocyanate group includes, for example, a blocked isocyanate group. A blocked isocyanate group is a functional group that can suppress the reactivity of an isocyanate group by protecting the isocyanate group with another functional group under normal conditions, while deprotecting the isocyanate group by heating to regenerate an active isocyanate group. It is a group.

Commercially available products of the blocked isocyanate group-containing monomer include, for example, 2-[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate (Carens MOI-BP, manufactured by Showa Denko KK); 2- (O- [1') methacrylic acid. -Methylprovideneamino] Carboxamino) Ethyl (Carens MOI-BM, manufactured by Showa Denko KK) and the like can be mentioned.

These monomers can be used alone or in combination of two or more.

The amount of the monomer represented by the general formula (7) used for the synthesis of the polymer moiety is preferably 1 to 30% by mass, more preferably 5 to 15% by mass, based on 100% by mass of all the monomers. Optical characteristics are improved when used in an appropriate amount.

The amount of the thermally crosslinkable group-containing monomer used is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, based on 100% by mass of all the monomers. Heat resistance improves when used in an appropriate amount.

Examples of the method for synthesizing the polymer moiety include anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, living radical polymerization and the like. Among these, free radical polymerization or living radical polymerization is preferable.

The free radical polymerization method uses a polymerization initiator. Examples of the polymerization initiator include azo compounds and organic peroxides.
Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane1-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)
-Imidazoline-2-yl) propane] and the like. Organic peroxides include, for example, benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydi. Examples thereof include carbonate, tert-butylperoxyneodecanoate, tert-butylperoxyvivarate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.

The polymerization initiator can be used alone or in combination of two or more.

The polymerization temperature is preferably 40 to 150 ° C, more preferably 50 to 110 ° C. The polymerization time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

In the living radical polymerization method, side reactions that occur in general radical polymerization are suppressed and the growth of the polymerization occurs uniformly, so that a block polymer or a polymer having a narrow molecular weight distribution can be synthesized.

Among various polymerization methods, the living radical polymerization method is preferably an atomic transfer radical polymerization method using an organic halide or a sulfonyl halide compound as a polymerization initiator and using a transition metal complex as a catalyst. This method is preferable in that monomers having various structures can be polymerized and that a polymerization temperature applicable to existing equipment can be adopted. The atom transfer radical polymerization method can be carried out by the methods described in References 1 to 8 below.

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Mattyjaszewski et al., Chem. Rev. 2001,101,2921
(Reference 3) Mattyjaszewski et al., J. Mol. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Sien
ce, 1996, 272,866
(Reference 5) WO96 / 030421 (Reference 6) WO97 / 018247 (Reference 7) Japanese Patent Application Laid-Open No. 9-208616 (Reference 8) Japanese Patent Application Laid-Open No. 8-411117

It is preferable to use an organic solvent for the synthesis of the polymer moiety. Examples of the organic solvent 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, and ethylene glycol monoethyl ether acetate. , Ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like.

The weight average molecular weight of the polymer moiety is preferably 5000 to 20000, preferably 8000 to 15000. Having an appropriate molecular weight improves optical properties and heat resistance.

The glass transition temperature (Tg) of the polymer moiety is preferably −50 to 150 ° C., more preferably 20 to 80 ° C. The optical characteristics are improved by an appropriate Tg.

The organic solvent can be used alone or in combination of two or more.

(Phosphorus compound)
One form of the near-infrared absorbing dye represented by the general formula (1) or the general formula (4) is a phosphoric acid group in the phosphorus compound moiety represented by the general formula (3) and a metal cation in the naphthalocyanine moiety. Formed the salt.
The raw material of the phosphorus compound moiety is a phosphorus compound represented by the general formula (8).

General formula (8)

In the general formula (8), R ₂₉ and R ₃₀ may independently have a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent, respectively. Representing an aryloxy group which may have an alkoxyl group or a substituent, R ₂₉ and R ₃₀ may be bonded to each other to form a ring.
W represents a hydroxy group or a chlorine atom.

An "alkyl group" of an alkyl group which may have a substituent, an "aryl group" of an aryl group which may have a substituent, an "alkoxyl group" of an alkoxyl group which may have a substituent, and a substituent. Examples of the "aryloxy group" of the aryloxy group which may have the above are the same as those exemplified in R ₁ to R ₂₄ in the general formula (5) or the general formula (6).

As the phosphorus compound represented by the general formula (8), at least one of R ₂₉ and R ₃₀ has an aryl group or a substituent which may have a substituent from the viewpoint of dispersibility and color characteristics. May be aryloxy groups, more preferably R ₂₉ and R ₃₀ are both aryl groups or aryloxy groups, and both R ₂₉ and R ₃₀ are phenyl or phenoxy groups. Is even more preferable.

Typical examples of phosphorus compounds include, but are not limited to, the structures shown below.

(Synthesis method of near-infrared absorbing dye)
The dye of the present invention is a polymer obtained by vinyl-polymerizing a monomer containing naphthalocyanine represented by the general formula (5) or the general formula (6) and a monomer represented by the general formula (7) (hereinafter referred to as a polymer). It is also synthesized by reacting a phosphorus compound represented by the general formula (8) or a polymer (also referred to as a polymer).
In addition, both the polymer and the phosphorus compound may be reacted simultaneously or sequentially with the naphthalocyanine represented by the general formula (5) or the general formula (6).

(Preparation of near-infrared absorbing dye)
In the synthesis of the dye of the present invention, for example, naphthalocyanine, a polymer or a phosphorus compound represented by the general formula (5) or the general formula (6) is added to an organic solvent, and the mixture is heated and stirred for several hours. Then, the reaction solution is put into water, the precipitated product is filtered, washed with water, and dried.

Regarding the ratio of the naphthalocyanine moiety and the polymer moiety, the molar ratio of the phosphate group derived from the monomer represented by the general formula (7) among the naphthalocyanine moiety and the polymer moiety is the naphthalocyanine moiety / general formula ( The phosphate group derived from the monomer shown in 7) is preferably 0.5 to 1.5, and preferably 0.8 to 1.2. When used at an appropriate ratio, the absorption due to the association of aromatic rings in the vicinity of 650 nm to 700 nm becomes very weak, and the permeability in the region of high luminous efficiency of 480 nm to 650 nm becomes high.

Regarding the ratio of the naphthalocyanine moiety and the phosphorus compound moiety, the addition amount of the phosphorus compound represented by the general formula (8) is from 0.8 molar equivalent with respect to the naphthalocyanine pigment from the viewpoint of dispersibility and color characteristics. 2.0 molar equivalents are preferred, and 1.0 to 1.5 molar equivalents are more preferred.

(Form of near-infrared absorbing dye)
The dye of the present invention has high transparency in the region of high luminous efficiency of 480 nm to 650 nm, and is excellent in absorption of near infrared rays. This is noticeable when the substrate is coated to form a coating. When coating on a substrate, it may be used by dissolving it in a solvent or the like, or it may be used by obtaining a dispersion liquid by using a dispersant or the like. It can also be used as a near-infrared absorbing composition by adding a binder resin.

The near-infrared absorbing composition may contain other near-infrared absorbing dyes in addition to the near-infrared absorbing dye of the present invention. This allows the spectroscopy to be adjusted as appropriate. Other near-infrared absorbing dyes include, for example, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, anthraquinone compounds, aminium compounds, diimmonium compounds, croconium compounds, azo compounds, quinoid-type complex compounds, dithiol metal complex compounds and the like. Can be mentioned.

<Organic dye with absorption between 400 nm and 700 nm>
The near-infrared absorbing composition of the present invention may contain an organic dye other than the near-infrared absorbing dye of the present invention. Since the near-infrared absorbing dye of the present invention has strong absorption in 700 nm to 900 nm, it blocks light of 400 nm to 900 nm and emits light of 900 nm or more by combining with an organic dye having absorption in 400 nm to 700 nm. It can also be used as a transmitting near-infrared absorbing composition (hereinafter, also referred to as a visible light region absorbing composition). However, in this case, in order to secure the transmittance of 900 nm or more, it is necessary to use a near-infrared absorbing dye having less absorption of 900 nm or more.

Examples of the organic dye having absorption at 400 nm to 700 nm include a blue dye, a yellow dye, a purple dye, and a red dye.
As the organic pigment, an organic pigment may be used, for example, an azo pigment such as a diketopyrrolopyrrole pigment, azo, disazo, or polyazo, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, antoanthron, and indan. Anthraquinone pigments such as thoron, pyranthron, or biolantron, quinacridone pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, slen pigments or metal complex pigments. Pigments and the like can be mentioned.
Further, a dye may be used as the organic dye, for example, anthraquinone dye, monoazo dye, disazo dye, oxazine dye, aminoketone dye, xanthene dye, quinoline dye, triphenylmethane dye and the like. Can be mentioned. When using dyes. A method of incorporating into a resin by using polar groups of anionic dyes and cationic dyes and imparting solubility in an organic solvent is effective.

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

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

In addition, C.I. I. Direct Blue 1, 2, 3, 4, 6, 7, 8, 8: 1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21: 1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98: 1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129130, 130: 1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158: 1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 213, 215, 225, 226, 229, 230, 231, 242, 243, 244, 253, 254, 260, 263 and the like (yellow pigment).
Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,41,42,43,48,53,55,61,62,62: 1,63,65,73,74,75,81,83,87,93,94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 231, 233, 234 and the like can be mentioned.

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

In addition, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 8
4, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134 and the like can also be mentioned (purple dye).
Examples of the purple pigment include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like can be mentioned.

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

In addition, C.I. I. Direct Violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97 and the like can also be mentioned (red pigment).
Examples of the red pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 10
1, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 291, 295, 296 and the like.
Examples of the orange pigment that works in the same manner as the red pigment include C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61 and other orange pigments can be used.
As the red dye, C.I. I. Acid Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25: 1, 26, 26: 1, 26: 2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76: 1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131, 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167,170,171,172,173,175,176,177,181,229,231, 237,239,240,241,2
42, 249, 252, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388 and the like can be mentioned.

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

In addition, C.I. I. Solvent red 52, 135, 146, 149, 168, 179, 207 and the like can also be mentioned.

Although the above dyes have good spectral characteristics and excellent color development properties, they have problems in light resistance and heat resistance, and the characteristics may not be sufficient for use in a near-infrared cut filter.
Therefore, in order to improve these drawbacks, in the case of the basic dye form, it is preferable to use an organic acid or perchloric acid to form chloride. As the organic acid, it is preferable to use an organic sulfonic acid or an organic carboxylic acid. Above all, it is preferable to use naphthalene sulfonic acid such as tobias acid and perchloric acid in terms of resistance.
Further, it is preferable to use it by forming a chloride with a resin having an anionic group, and it is also preferable to use it by forming a salt together with a resin having a betaine structure and an organic acid.
In the case of acid dyes and anionic dyes including direct dyes, it is recommended to use a compound having a cationic group or a resin having a cationic group as a salt-forming compound as a counter ion for heat resistance, light resistance and solvent resistance. It is preferable in terms of sex.
Further, it is preferable to use it by forming a chloride with a resin having a cationic group, and it is more preferable to use it by forming a salt together with a resin having a cationic group in the side chain and an organic acid.
Further, it is also preferable that the anionic dye is sulfonamided and used as a sulfonic acid amide compound in terms of resistance.
For coating applications, the blue pigment is Pigment. Blue. 15: 3 or Pigment. Blue. 15: 6, the yellow pigment is Pigment. Yellow. 139, the purple pigment is Pigment. Violet. It is preferable to use 23. For molding purposes, the blue pigment is Pigment. Blue. 15: 3 or Pigment. Blue. 15: 6, the yellow pigment is Pigment. Yellow. 147, the red dye is Solvent. Red. 52 is preferable.

<UV absorber>
The near-infrared absorbing composition of the present invention may contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, cyanoacrylate-based organic compounds, salicylate-based organic compounds, and the like.

The content of the UV absorber is 5 to 5 in 100% by mass of the total of the photopolymerization initiator and the UV absorber.
70% by mass is preferable. Highly compatible with light sensitivity and resolution. When the near-infrared absorbing composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the non-volatile content of the near-infrared absorbing composition. If the total content of the photopolymerization initiator and the ultraviolet absorber is less than the above, the adhesion is weakened and pixel peeling occurs, and if it is more than the above, the sensitivity may be excessively high and the resolution may be deteriorated.

Examples of the benzotriazole-based organic compound include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, and octyl-3 [3-tert. -Butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro) -2H-benzotriazole-2-yl) phenyl] propionate mixture, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2
-(3-t butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'- Hydroxy-5'-t-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3- (2H-benzotriazole-2-yl)-(1,1) -Dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester compound, 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) Examples thereof include phenol and 2- (2H-benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol.

Commercially available products are BASF's "TINUVIN P", "TINUVIN PS", "TINUVIN 109", "TINUVIN 234", "TINUVIN 326", and "TI".
NUVIN 328 "," TINUVIN 329 "," TINUVIN 360 "," T
INUVIN 384-2 "," TINUVIN 900 "," TINUVIN 928 "
, "TINUVIN 99-2", "TINUVIN 1130", "ADEKA STAB LA-29" manufactured by ADEKA, "RUNA-93" manufactured by Otsuka Chemical Co., Ltd. and the like.

The triazine-based organic compound is, for example, 2- [4,6-di (2,4-kisilyl) -1,3,5-triazine-2-yl] -5-octyloxyphenol 2- [4,6-]. Bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl) Reaction product of -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl-glycidate ester, 2,4-bis "2-hydroxy-4-butoxyphenyl" -6- (2,4-dibutoxyphenyl) -1,3-5-triazine and the like can be mentioned.

Commercially available products are "KEMISORB 102" manufactured by Chemipro Kasei Co., Ltd. and "TINU" manufactured by BASF.
VIN 400 "," TINUVIN 405 "," TINUVIN 460 "," TIN
UVIN 477-DW "," TINUVIN 479 "," TINUVIN 1577 "
, ADEKA's "ADEKA STAB LA-46", "ADEKA STAB LA-F70", Sun Chemical's "CYASORB UV-1164" and the like.

Benzophenone-based organic compounds include, for example, 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid-3 water temperature, 2-hydroxy-4-n. -Octoxybenzophenone, 2,2-di-hydroxy-4-methoxybenzophenone and the like can be mentioned.

Commercially available products are "KEMIPROB 10", "KEMISORB 11", "KEMISORB 11S", "KEMISORB 12", and "KEMISORB1" manufactured by Chemipro Kasei Co., Ltd.
11 ”,“ SEESORB 101 ”,“ SEESORB 107 ”manufactured by Sipro Kasei Co., Ltd.,“ ADEKA STAB 1413 ”manufactured by ADEKA, and the like.

<Binder resin>
The near-infrared absorbing composition of the present invention contains the dye of the present invention, a binder resin and the like.
The binder resin is, for example, a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region when a film having a thickness of 2 μm is formed. Examples of the binder resin include thermoplastic resins and photosensitive resins. Further, it is preferable that the film formed from the near-infrared absorbing composition is patterned by a photolithography method. In this case, the binder resin is preferably an alkali-soluble resin. The alkali-soluble resin can be used as a photosensitive alkali-soluble resin by imparting a polymerizable unsaturated group.

The thermoplastic resin is, for example, an acrylic resin, a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, a polyvinyl acetate, or a polyurethane-based resin. Examples thereof include resins, 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 alkali-soluble resin include resins having an acidic group such as a carboxyl group and a sulfone group. The alkali-soluble resin is, for example, "acrylic resin having an acidic group, α-olefin / (anhydrous) maleic acid copolymer, styrene / styrene sulfonic acid copolymer, ethylene / (meth) acrylic acid copolymer, or isobutylene. / (Anhydrous) maleic acid copolymer and the like. Among these, an acrylic resin having an acidic group in terms of good transparency and a styrene / styrene sulfonic acid copolymer are preferable, and an acrylic resin having an acidic group. Is more preferable.

The photosensitive resin is, for example, a (meth) acrylic compound or silicic acid having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group on a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group. Examples thereof include a resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting with the above. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Esterified resin can also be mentioned.

As the photosensitive alkali-soluble resin, for example, a resin synthesized by the following methods (i) and (ii) is preferable. As a result, the crosslink density of the film formed from the near-infrared absorbing composition by light irradiation is further improved.

[Method (i)]
In method (i), for example, first, an epoxy group-containing monomer and a polymer of other monomers are synthesized. Next, a method of adding a monocarboxyl group-containing monomer to the epoxy group of the polymer and reacting the generated hydroxyl group with a polybasic acid anhydride to obtain an alkali-soluble resin can be mentioned.

Epoxy group-containing monomers include, for example, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 3,4-epoxycyclohexyl. Examples include (meth) acrylate. Among these, glycidyl (meth) acrylate is preferable from the viewpoint of reactivity.

Examples of the monocarboxyl group-containing monomer include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano substituents. Monocarboxylic acid and the like can be mentioned.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like.

The monomer and polybasic acid anhydride can be used alone or in combination of two or more.

Further, as a method similar to the method (i), for example, a carboxyl group-containing monomer and other monomers are synthesized to prepare a polymer. Next, a method of adding an epoxy group-containing monomer to a part of the carboxyl groups of the polymer to obtain a photosensitive alkali-soluble resin can be mentioned.

[Method (ii)]
In the method (ii), for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers are synthesized to prepare a polymer. Next, a method of reacting the hydroxyl group of the polymer with the isocyanate group of the isocyanate group-containing monomer can be mentioned.

The hydroxyl group-containing monomer is, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, or Examples thereof include hydroxyalkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate. Further, a polyether mono (meth) acrylate obtained by superpolymerizing the above hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, and (poly) ε-caprolactone. And / or (poly) ester mono (meth) acrylate to which (poly) 12-hydroxystearic acid or the like is added. Among these, 2-hydroxyethyl methacrylate and glycerol mono (meth) acrylate are preferable. Further, glycerol mono (meth) acrylate is preferable in terms of light sensitivity.

Examples of the monomer having an isocyanate group include 2- (meth) acryloylethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, and 1,1-bis [methacryloyloxy] ethyl isocyanate.

The weight average molecular weight (Mw) of the binder resin is preferably 5,000 to 100,000, more preferably 7,000 to 50,000. When used as an alkali-soluble resin, when the weight average molecular weight is 5,000 to 100,000, the film is less likely to be thinned during development, and the non-pixel portion is less easily removed during development. The number average molecular weight (Mn) is preferably 2,500 to 40,000. The value of Mw / Mn is preferably 10 or less. In addition, Mw and Mn are. Polystyrene-equivalent molecular weight measured using HLC-8220GPC (manufactured by Tosoh Corporation) as a gel permeation chromatography (GPC) device, TSK-GEL SUPER HZM-N connected in duplicate as a column, and tetrahydrofuran as a solvent. Is.

The acid value of the alkali-soluble resin is preferably 20 to 300 mgKOH / g. Having an appropriate acid value improves developability.

The amount of the binder resin used is preferably 20 to 500 parts by mass with respect to 100 parts by mass of the dye of the present invention. When used in an appropriate amount, film formation becomes easy.

<Thermosetting compound>
The near-infrared absorbing composition can contain a thermosetting compound. Since the crosslink density is improved in the heating process, the heat resistance is improved. The thermosetting compound is a small molecule compound or a polymer (thermosetting resin) and is not limited by the molecular weight.
Examples of the thermosetting compound include an epoxy compound, an oxetane compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, and a phenol compound. Among these, epoxy compounds and oxetane compounds are preferable.

<Organic solvent>
The near-infrared absorbing composition can contain an organic solvent. This facilitates the viscosity adjustment of the composition.

Examples of the organic solvent 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-Cyclohexene-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 monotersial 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 Dipropylene ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethylate , Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol Monoethyl Ether, Propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monobutyl Ether, Propylene Glycol Monopropyl Ether, Propylene Glycol Monomethyl Ether, Propylene Glycol Monomethyl Ether Acetate, Propylene Glycol Monomethyl Ether Propionate, benzyl Alcohol, Methyl Isobutyl Ketone, Methyl Examples thereof include cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like.

These organic solvents may be used alone or in admixture of two or more. When two or more kinds of mixed solvents are used, it is preferable that the above organic solvent is contained in an amount of 65 to 95% by mass.

<Preparation of near-infrared absorbing composition>
The near-infrared absorbing composition of the present invention can be prepared by dissolving a mixture containing a near-infrared absorbing dye, a binder resin and the like in a solvent or the like, or may be dispersed using a dispersant or the like. .. Further, using a dispersant and a dispersion aid (for example, a dye derivative), finely dispersed and produced by using various dispersion means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. Can be done.

When dispersing the near-infrared absorbing dye, a dispersant (for example, a resin-type dispersant), a dispersion aid (for example, a surfactant) and the like can be appropriately used. The dispersion aid is excellent in dispersing the near-infrared absorbing dye and has a great effect of preventing reaggregation after dispersion. Therefore, when the near-infrared absorbing dye is dispersed by using the dispersion aid, the transmission in the visible region is transmitted. An optical filter with high properties can be obtained.

(Dispersant)
In the near-infrared absorbing composition of the present invention, a dispersant may be used in order to disperse the near-infrared absorbing dye. Examples of the dispersant include a resin type dispersant.
The resin-type dispersant has a dye-affinity site having a property of adsorbing to a dye and a relaxation site having an affinity with a material other than the dye. Resin-type dispersants include, for example, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, and poly. Siloxanes, long-chain polyaminoamidophosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly (lower alkyleneimine) with polyesters having free carboxyl groups, salts thereof, etc. Oil-based dispersants, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, water-soluble resins such as polyvinylpyrrolidone, etc. Examples thereof include water-soluble polymer compounds, polyester-based compounds, modified polyacrylate-based compounds, ethylene oxide / propylene oxide-added compounds, and phosphoric acid ester-based compounds.

The resin type dispersant can be used alone or in combination of two or more.

Commercially available resin-type dispersants include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, manufactured by Big Chemie Japan. 170, 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, 20000, 21000, manufactured by Japan Lubrizol, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen.
, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47 manufactured by BASF Japan. , 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 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. Examples thereof include PB822 and PB824.

(Dispersion aid)
In the near-infrared absorbing composition of the present invention, a dispersion aid may be used in order to disperse the near-infrared absorbing dye. Examples of the dispersion aid include surfactants, resin-type dispersants, dye derivatives and the like.

Surfactants include, for example, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalrine sulfonate, alkyldiphenyl ether disulfonic acid. Anionic surfactants such as sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc. Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; Chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazolin. These can be used alone or in combination of two or more.

When the resin type dispersant and the surfactant are added, the blending amount is preferably 0.1 to 200 parts by weight, more preferably 0.1 to 150 parts by weight, based on 100 parts by weight of the dye. Good dispersibility can be obtained by using an appropriate amount.

Examples of the dye derivative include a compound in which an organic pigment, anthraquinone, acrydone or triazine is introduced with a basic substituent, an acidic substituent or a phthalimide methyl group which may have a substituent, and examples thereof include JP-A-63. -The ones described in Japanese Patent Publication No. 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, and these are independent. Alternatively, two or more types can be mixed and used.

The blending amount of the dye derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the dye from the viewpoint of improving the dispersibility of the added dye. .. Further, from the viewpoint of heat resistance and light resistance, the amount is preferably 40 parts by weight or less, more preferably 35 parts by weight or less, based on 100 parts by weight of the dye.

<Photopolymerizable compound>
The near-infrared absorbing composition can contain a photopolymerizable compound and a photopolymerization initiator. As a result, photosensitive is obtained, and it can also be used as a photosensitive composition for a near-infrared cut filter.

The photopolymerizable compound is a compound containing a polymerizable unsaturated group, and is, for example, a monomer or an oligomer. Examples of the photopolymerizable compound include an acid group-containing monomer, a urethane bond-containing monomer, and other monomers.

The monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin are, for example, 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 (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (meth) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, 1,6-Hexanediol Diglycidyl Ether Di (Meta) 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, methylolation Various acrylic acid esters such as (meth) acrylic acid ester, epoxy (meth) acrylate, urethane acrylate and methacrylic acid ester of melamine, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol Examples thereof include, but are not limited to, trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.

The photopolymerizable compound can be used alone or in combination of two or more.

The blending amount of the photopolymerizable compound is preferably 5 to 400 parts by mass, more preferably 10 to 300 parts by mass with respect to 100 parts by mass of the dye of the present invention.

<Photopolymerization initiator>
The photopolymerization initiator is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1 -Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- Acetphenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one;
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal;
Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, or 3,3', 4,4'-tetra (t-butyl) Peroxycarbonyl) Benzophenone compounds such as benzophenone;
Thioxanthone compounds such as thioxanthone, 2-chlorthioxanthone, 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) Methyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine. System compounds;
1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or O- (acetyl) -N- (1-phenyl-2-oxo-2- (4') -Methoxy-naphthyl) ethylidene) Oxime ester compounds such as hydroxylamine;
Phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, or 2,4,6-trimethylbenzoyldiphenylphosphine oxide;
Quinone compounds such as 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone;
Borate compounds;
Carbazole compounds;
Imidazole compounds;
Alternatively, a titanocene-based compound or the like can be mentioned.

The photopolymerizable initiator can be used alone or in combination of two or more.

The blending amount of the photopolymerization initiator is preferably 2 to 200 parts by mass, more preferably 3 to 150 parts by mass with respect to 100 parts by mass of the dye of the present invention.

<Sensitizer>
The near-infrared absorbing composition can contain a sensitizer.

Examples of the sensitizer include unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives and anthraquinone. Polymethine dyes such as derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives, aclysine derivatives, azine derivatives, thiadine derivatives, oxadin derivatives, indolin derivatives. , Azulene derivative, Azurenium derivative, Squalylium derivative, Porphyrin derivative, Tetraphenylporphyrin derivative, Triarylmethane derivative, Tetrabenzoporphyrin derivative, Tetrapyrazinoporphyrazine derivative, Phthalocyanin derivative, Tetraazaporphyrazine derivative, Tetraquinoxalyloporphyrazine Derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrilium derivatives, tetraphyllin derivatives, anurene derivatives, spiropyrane derivatives, spiroxazine derivatives, thiospiropyrane derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxy Esters, acylphosphine oxides, methylphenylgrioxylates, benzyls, 9,10-phenanslenquinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalofenone, 3,3'or 4,4' -Tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone and the like can be mentioned.

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

The blending amount of the sensitizer is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the photopolymerization initiator.
~ 50 parts by mass is more preferable.

<Multifunctional thiol>
The near-infrared absorbing composition can contain a polyfunctional thiol as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups, for example, hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene. Glycolbisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropanetristhioglycolate, trimethylolpropanetristhiopropionate, trimethylolpropanetris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, tristrimercaptopropionate (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene,
Examples thereof include 2,4,6-trimercapto-s-triazine and 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine.

Polyfunctional thiols can be used alone or in combination of two or more.

The content of the polyfunctional thiol is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, based on 100% by mass of the non-volatile content of the near-infrared absorbing composition. When an appropriate amount is contained, an appropriately crosslinked film can be easily obtained.

<Antioxidant>
The near-infrared absorbing composition may contain an antioxidant. The antioxidant can prevent the photopolymerization initiator and the thermosetting compound from being oxidized and yellowed by the heating step. As a result, the transmittance of the coating film can be increased.

The "antioxidant" in the present invention is a compound having an ultraviolet absorbing function, a radical catching function, or a peroxide decomposition function. Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, sulcylic acid ester-based, and triazine-based compounds.

Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants or sulfur-based antioxidants are preferable, and hindered phenol-based antioxidants are preferable from the viewpoint of achieving both film permeability and sensitivity. Agents, hindered amine-based antioxidants, or phosphorus-based antioxidants are more preferred.

The antioxidant can be used alone or in combination of two or more.

The content of the antioxidant is preferably 0.5 to 5.0% by mass based on 100% by mass of the non-volatile content of the near-infrared absorbing composition.

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

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

The leveling agent is, for example, a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, and is a compound having a hydrophilic group but having low solubility in water and capable of lowering the surface tension. As the leveling agent, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes, for example, a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

The binding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are repeatedly bonded alternately. Didimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning, for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-. 2207 can be mentioned.

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

Anionic surfactants to be added as an auxiliary to the leveling agent include, for example, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalline sulfonate, alkyldiphenyl ether disulfone. Sodium acid, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphorus Acid esters and the like can be mentioned.

Examples of the chaotic surfactant added as an auxiliary to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as an auxiliary to the leveling agent include, for example, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphoric acid ester, and polyoxyethylene sorbitan monosteer. Rate, polyethylene glycol monolaurate and the like; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazolin, and fluorine-based and silicone-based surfactants can be mentioned.

<Other additives>
The near-infrared absorbent composition may contain a storage stabilizer to stabilize the viscosity of the composition over time. Further, an adhesion improving agent such as a silane coupling agent can be contained in order to enhance the adhesion with the substrate.

Storage stabilizers include, for example, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphoric acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Organic phosphine, phosphite, etc. The content of the storage stabilizer is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the dye of the present invention.

Adhesion improvers include, for example, vinylsilanes 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-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ- Examples thereof include aminosilanes such as aminopropyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. .. The content of the adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the dye of the present invention.

<Removal of coarse particles>
The near-infrared absorbing composition was mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably 0.5 μm or more of coarse particles by means of centrifugation, sintering filter, membrane filter, or the like. It is preferable to remove dust. As described above, the near-infrared absorbing composition preferably contains substantially no particles of 0.5 μm or more, and preferably 0.3 μm or less.

<Molding application>
The near-infrared absorbing dye of the present invention can also be used in molding applications. The molding application is an application for producing a film or a three-dimensional body by a method other than coating.
When the near-infrared absorbing composition is used for molding, it is preferably a melt-kneaded product of a near-infrared absorbing dye and a thermoplastic resin which is a binder resin.

(Thermoplastic resin)
Examples of the thermoplastic resin include polyolefin resin, acrylic resin, polystyrene resin, polyester resin, polyamide resin, polycarbonate resin, cycloolefin resin, polyetherimide resin and the like.

(Polyamide resin)
The polyamide resin is a crystalline resin, and can be synthesized, for example, by subjecting a carboxylic acid component and a compound (Am) having two or more amino groups to a dehydration condensation reaction.

Examples of the carboxylic acid component include adipic acid, sebacic acid, isophthalic acid, terephthalic acid and the like. As the carboxylic acid component, a compound having 3 or more carboxyl groups can be used.
As the compound (Am) having two or more amino groups, for example, known ones can be used, for example, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylene. Aliphatic polyamines such as tetramine; aliphatic polyamines containing alicyclic polyamines such as isophoronediamine and dicyclohexylmethane-4,4'-diamine; aromatic polyamines such as phenylenediamine and xylylenediamine; 1,3-diamino-2 -Propanol, 1,4-diamino-2-butanol, 1-amino-3- (aminomethyl) -3,5,5-trimethylcyclohexane-1-ol, 4- (2-aminoethyl) -4,7, Examples thereof include diaminoalcohols such as 10-triazadecane-2-ol, 3- (2-hydroxypropyl) -o-xylene-α, and α'-diamine.
Examples of commercially available products of the polyamide resin include 6 nylon (manufactured by Toray Industries, Inc.), 66 nylon (manufactured by Toray Industries, Inc.), 610 nylon and the like.

(Polycarbonate resin)
The polycarbonate resin is an amorphous resin and is synthesized by reacting an aromatic dihydroxy compound with a carbonic acid precursor such as phosgene or a carbonic acid diester. In the case of a synthetic reaction using phosgene, for example, an interfacial method is preferable. Further, in the case of a synthetic reaction using a carbonic acid diester, a transesterification method in which the reaction is carried out in a molten state is preferable.

The aromatic dihydroxy compound is, for example, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2 , 2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) Propane, 1,1-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3, Bis (hydroxyaryl) alkanes such as 5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1, Bis (hydroxyaryl) cycloalkans such as 1-bis (4-hydroxyphenyl) cyclohexane Dihydroxydiaryl ethers such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4 , 4'-Dihydroxydiphenylsulfide, 4,4'-dihydroxy-3,3'-dihydroxydiarylsulfides such as dimethyldiphenylsulfide, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-3,3 Examples thereof include dihydroxydiaryl sulfoxides such as'-dimethyldiphenyl sulfoxide, dihydroxydiaryl sulfone such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone. Further, piperazine, dipiperidyl hydroquinone, resorcin, and 4,4'-dihydroxydiphenyls may be mixed and used.

Examples of the carbonate precursor include diaryl carbonates such as phosgene, diphenyl carbonate and ditril carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

The viscosity average molecular weight of the polycarbonate resin is preferably 15,000 to 30,000, more preferably 16,000 to 27,000. The viscosity average molecular weight in the present specification is a value converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent.

Commercially available polycarbonate resin products include, for example, Iupiron H-4000 (manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 16,000), Iupiron S-3000 (manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 23,000), and Iupiron E-2000. (Manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 27,000) and the like.

(Cycloolefin resin)
The cycloolefin resin is an amorphous resin having an alicyclic structure in the main chain and / or the side chain. Examples of the type of alicyclic structure include norbornene polymers, monocyclic cyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof. Among these, the norbornene polymer is preferable because it is excellent in moldability and transparency. The norbornene monomer is, for example, bicyclo [2.2.1] hept-2-ene (trivial name: norbornene), tricyclo [4.3.0.12.5] deca-3,7-diene (common name: norbornene). Trivial name: dicyclopentadiene), 7,8-benzotricyclo [4.3.0.12.5] deca-3-ene (trivial name: metanotetrahydrofluorene), tetracyclo [4.4.0.12 5.17, 10] Dodeca-3-ene (trivial name: tetracyclododecene) and the like can be mentioned.
Examples of commercially available cycloolefin resins include Topas (manufactured by Polyplastics) and Appel (manufactured by Mitsui Chemicals).

(Polyetherimide resin)
The polyetherimide resin is an amorphous resin having a glass transition temperature of more than 180 ° C., has good transparency, high strength, high heat resistance, high elastic modulus, and a wide range of chemical resistance. Therefore, it is widely used in various applications such as automobiles, telecommunications, aerospace, electrical / electronic, transportation and healthcare.
One of the processes for producing a polyetherimide resin is the polymerization of an alkali metal salt of a dihydroxyaromatic compound such as bisphenol A disodium salt (BPA · Na2) and bis (halophthalimide). The molecular weight of the obtained polyetherimide resin can be controlled by two methods. The first method is to use a molar excess of bis (halophthalimide) with respect to the alkali metal salt of the dihydroxyaromatic compound. The second method is to prepare bis (phthalic anhydride) in the presence of a monofunctional compound such as phthalic anhydride that forms a terminal capping agent. Phthalic anhydride reacts with some of the organic diamines to form monohalo-bis (phthalimide). Monohalo-bis (phthalimide) acts as a terminal capping agent in the polymerization step by reaction with phenoxide terminal groups in the growing polymer chain.
Examples of commercially available polyetherimide resins include ULTEM (manufactured by Saudi Basic Industry Corporation).

The thermoplastic resin is preferably a crystalline resin having a melting point of 100 to 500 ° C. or an amorphous resin having a glass transition temperature of 60 to 300 ° C. Both the melting point and the glass transition temperature can be measured by a differential scanning calorimeter, a thermogravimetric differential thermal analyzer, or the like.

The near-infrared absorbing composition may contain additives in addition to the near-infrared absorbing dye and the thermoplastic resin. Examples of the additive include an ultraviolet absorber, a light stabilizer, an antioxidant, a colorant, a dispersant and the like. These additives are compounds known for molded article applications.

(Additives used for molding)
UV absorbers are used to impart UV resistance to articles. Examples of the ultraviolet absorber include benzophenone type, benzotriazole type, triazine type, salicylic acid ester type and the like. The content of the ultraviolet absorber is preferably 0.01 to 5% by mass in 100% by mass of the composition.

The light stabilizer is used to impart UV resistance to the molded product, and is preferably used in combination with the UV absorber. As the light stabilizer, for example, a hindered amine light stabilizer is preferable. The content of the light stabilizer is preferably 0.01 to 5% by mass in 100% by mass of the composition.

Antioxidants are used to reduce the deterioration of an article when the article is exposed to natural light or an artificial light source and becomes hot. As the antioxidant, for example, monophenol-based, bisphenol-based, polymer-type phenol-based, sulfur-based, phosphoric acid-based and the like are preferable. The content of the antioxidant is preferably 0.01 to 5% by mass in 100% by mass of the composition.

Dispersants are used to more evenly disperse the near-infrared absorbing pigment in the article. As the dispersant, for example, polyolefin wax, fatty acid wax, fatty acid ester wax, partially saponified fatty acid ester wax, saponified fatty acid wax and the like are preferable. The content of the dispersant is preferably 50 to 250 parts by mass with respect to 100 parts by mass of the near-infrared absorbing pigment.

(Preparation of near-infrared absorbing composition for molding)
The near-infrared absorbing composition for molding can be produced by melt-kneading a near-infrared absorbing dye and a thermoplastic resin. The melt-kneading temperature varies depending on the resin, but is preferably 230 ° C. or higher, more preferably 270 ° C. or higher. It is preferable to cool after melt-kneading. The upper limit of the melt kneading temperature is not limited because it differs depending on the type of the thermoplastic resin. The upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower. Further, the upper limit needs to be lower than the sublimation temperature or the decomposition temperature of the near-infrared absorbing dye of the present invention.

Examples of the melt kneading apparatus include a single-screw kneading extruder, a twin-screw kneading extruder, and a tandem twin-screw kneading extruder.

The near-infrared absorbing composition for molding is preferably produced as a so-called masterbatch. When a masterbatch is prepared and then melt-kneaded together with a diluted resin (thermoplastic resin) to prepare a molded product, the near-infrared absorbing dye of the present invention can be obtained as compared with the molded product produced without passing through the masterbatch. It is easy to disperse uniformly in the molded product, and the aggregation of the near-infrared absorbing dye can be suppressed. This improves the transparency of the molded product. The masterbatch is preferably formed into pellets using a pelletizer after the melt kneading.
When produced as a masterbatch, the content of the near-infrared absorbing dye is preferably 0.01 to 20% by mass, more preferably 0.05 to 2% by mass in 100% by mass of the composition.

The molded product of the present specification is produced by molding a near-infrared absorbing composition. The near-infrared absorbing composition can be molded as it is to produce a molded product. When the near-infrared absorbing composition is a masterbatch, a molded product can be produced by melt-kneading with a diluted resin (thermoplastic resin) and then molding. The mass ratio of the masterbatch (X) to the diluted resin (Y) is preferably X / Y = 1/5 to 1/500. Within this range, the molded product can easily obtain good optical characteristics.

The near-infrared absorbing composition prepared for coating or molding can be used, for example, for the following applications.

<Use>
(Heat absorber)
The near-infrared absorbing composition can be used as a heat ray absorbing material. Sunlight contains near-infrared rays having a wavelength of 700 to 2000 nm, and among them, the intensity of near-infrared rays having a wavelength of 700 to 1000 nm is particularly strong. Near infrared rays have the property of raising the temperature of a substance and are called heat rays. Among them, by absorbing and blocking near infrared rays having a particularly strong intensity of 700 to 1000 nm, it is possible to suppress an increase in the temperature of the substance.
Placing a film or film formed from a near-infrared absorbing composition on the windows of a building or car has the effect of suppressing the temperature rise inside the room or car due to sunlight. In addition, the above film can be used in agricultural greenhouses and the like, and has the effect of suppressing the temperature rise inside the greenhouse. The same applies to protective goggles, eyeglasses, and sunglasses, which can be used to block heat rays.

(Optical recording medium)
The near-infrared absorbing composition can be used as an optical recording medium. Irradiation of a film or molded body formed from a near-infrared absorbing composition with near-infrared rays changes the crystalline state of the dye and changes the refractive index of the film or molded body. This principle is used for recording media such as optical discs.

(Laser welding material / laser marking material)
The near-infrared absorbing composition can be used as a laser welding material or a laser marking material.
When the coating film or molded body formed from the near-infrared absorbing composition is irradiated with a laser having a wavelength absorbed by the near-infrared absorbing dye, the dye absorbs the laser light and generates heat, so that the thermoplastic resin is melted and carbonized. When it melts, it can be welded to other resins, and laser welding uses this principle. Laser marking uses carbonization to turn black.
In the case of laser welding, welding is usually performed by containing carbon or the like, but in the case of a near-infrared absorbing dye, by irradiating a near-infrared laser, the near-infrared absorbing dye generates heat and the thermoplastic resins are separated from each other. Weld. Similarly, laser marking can be performed by generating heat from the near-infrared absorbing dye and melting / carbonizing the thermoplastic resin.

(Optical filter)
The near-infrared absorbing composition can be used as an optical filter. For example, a digital camera recognizes colors by decomposing the light received during imaging with red, green, and blue filters and sending it to a photodiode that converts the light into an electrical signal. However, the photodiode also reacts to near-infrared rays and converts it into an electric signal, so a filter that blocks this is required. The coating film or molded product formed from the near-infrared absorbing composition can be used as a filter for blocking the near-infrared rays. It is important that the filter that blocks near infrared rays has little absorption in the visible region. If there is a lot of absorption in the visible region, the received light will be colored, which will adversely affect the color recognition of the photodiode. Since the near-infrared absorbing dye of the present invention has little absorption in the visible region and high invisibility, it has little adverse effect on the color recognition of the photodiode.

(Biometric sensor)
The near-infrared absorbing composition can be used for a sensor for biometric authentication (fingerprint authentication or vein authentication), or a touch sensor or touch panel incorporating the sensor.
For example, smartphones, tablet PCs, etc., bank ATMs, multimedia terminals, etc. are equipped with biometric authentication functions such as fingerprint authentication and finger vein authentication for security protection. In particular, the development of fingerprint authentication technology used for smartphones and tablet PCs is rapid, and as the photodiodes change from inorganic to organic, the authentication range has increased to the screen size (full screen), and organic EL displays, liquid crystal displays, etc. A fingerprint authentication sensor with a built-in display has been developed.
However, since many fingerprint sensors with a built-in display irradiate the fingerprint with various light sources installed in the display and sense the reflected light, illegal external light (such as sunlight or LED lighting) is used. When a sensor has a wide range of wavelengths and is subject to strong light), there is a problem of noise during imaging, and there is some concern about accuracy when using it outdoors. The same applies to finger vein authentication for bank ATMs and multimedia terminals, and measures such as covering the store with strong lighting and sunny stores to block outside light are taken.
The coating film or molded body using the near-infrared absorbing composition of the present invention is effective in solving these problems by absorbing and preventing the incidental light from the outside on the sensor.
For example, when used for smartphones and tablet PCs, when set on the front surface of the panel, it is necessary to have designability, but the material using the near-infrared absorbing composition for coating of the present invention, the coating film obtained by coating, Alternatively, the molded product obtained by using the near-infrared absorbing composition for molding has an advantage that it can be suitably used because it has no absorption in the visible region and is invisible, that is, has high transparency. Further, since the near-infrared absorbing composition of the present invention has excellent heat resistance, it can be preferably used in terms of a process for manufacturing a sensor, a touch sensor incorporating the sensor, and a touch panel.
In addition, the external light that becomes noise in biometric authentication applications is light of 650 nm to 1000 nm that passes through the living body, and in particular, light of 650 nm to 800 nm overflows in the living space, so it is possible to cut light in this wavelength region. Increase the accuracy of biometric authentication. Blue dyes and green dyes often absorb in the visible light region of 650 nm to 700 nm, and by combining blue dyes and green dyes with near-infrared absorbing pigments, invisibility is reduced, but the accuracy of biometric authentication is improved. Can be enhanced.

The blue dye is, for example, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment blue 15: 1 and the like. The green pigment is, for example, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59, C.I. I. Pigment Green 62, C.I. I. Pigment Green 63 can be mentioned. In addition, C.I. I. Means a color index (CI).

(display)
A coating or molding formed from the near-infrared absorbing composition can also be incorporated into the display. Specific examples thereof include a liquid crystal display with a touch panel function such as an electronic blackboard. This liquid crystal display with a touch panel function has three functions of display, writing, and saving, and the built-in touch panel also adopts optical methods such as infrared scanning method and infrared projection method. The above-mentioned noise caused by external light was a problem. Since liquid crystal displays with a touch panel function are often used in schools, accuracy and responsiveness to touch are important. By incorporating a coating film obtained by applying the near-infrared absorbing composition for coating of the present invention or a molded product obtained by using the near-infrared absorbing composition for molding into a display, external light that becomes noise can be cut. Therefore, it is preferable.
Further, the coating film or the molded product can be preferably used as an antireflection film for various displays using a liquid crystal display, an organic EL, a Mini-LED, or a Micro-LED. By suppressing the reflection of not only visible light but also light in the near infrared region, there is an advantage that the black display on the display can be made blacker. Since the near-infrared absorbing composition of the present invention has excellent heat resistance, it can be preferably used for the resistance of the process required for manufacturing a display.

(Near infrared transmission filter)
LEDs with wavelengths such as 940 nm have become widespread, and are used for distance measurement in automatic driving, biometric authentication (fingerprint authentication, iris authentication, face authentication, vein authentication, etc., or a combination thereof), and light detection in various sensors. There is. However, since light rays of all wavelengths such as ultraviolet rays, visible light, and near infrared rays exist in the atmosphere, a filter that blocks light other than the light of the wavelength to be detected is required. Therefore, by combining a near-infrared absorbing dye that absorbs light of 700 to 900 nm with a dye that absorbs visible light, an ultraviolet absorber, etc., only light having a wavelength longer than the absorption wavelength of the near-infrared absorbing dye is transmitted and is short. Light of wavelength can be used as a near-infrared transmission filter to block. Since the near-infrared absorbing composition of the present invention absorbs light of 700 to 900 nm well, it transmits light of 940 nm by combining with an organic dye that absorbs 400 to 700 nm, and a light having a shorter wavelength than that. It is excellent as a near-infrared transmission filter that shields light.

As described above, the optical filter using the near-infrared absorbing composition includes a near-infrared cut filter and a near-infrared transmissive filter. The near-infrared cut filter is mainly composed of a near-infrared absorbing dye and has a role of blocking near-infrared rays and transmitting visible light. On the other hand, the near-infrared ray transmitting filter is composed of dyes such as blue, red, and yellow that absorb visible light in addition to the near-infrared absorbing dye, and the visible light and the near-infrared ray in the wavelength range absorbed by the near-infrared absorbing dye. It has the role of blocking near infrared rays and transmitting near infrared rays with longer wavelengths.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples. In addition, "part" means "part by mass", and "%" means "mass%".

Hereinafter, "PGMAc" is propylene glycol monomethyl ether acetate, "PGME" is propylene glycol monomethyl ether, "Aronix M-402") is dipentaerythritol hexaacrylate, and "OXE-02") is etanone, 1. -[9-Ethr-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime).

(Method for identifying gallium phthalocyanine dye, indium naphthalocyanine dye, silicon naphthalocyanine dye, germanium naphthalocyanine dye, tin naphthalocyanine dye and near-infrared absorbing dye)
The MALDI TOF-MS spectrum was used to identify the gallium phthalocyanine dye, indium naphthalocyanine dye, silicon naphthalocyanine dye, germanium naphthalocyanine dye, tin naphthalocyanine dye and near-infrared absorbing dye used in the present invention. For the MALDI TOF-MS spectrum, the obtained compound was identified by the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation using the MALDI mass spectrometer autoflex III manufactured by Bruker Daltonics.

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

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

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

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

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

<Manufacturing of near-infrared absorbing dye>
(Synthesis of naphthalocyanine pigment (A-1))
In the reaction vessel, 178 parts of 2,3-dicyanonaphthalene, 890 parts of n-amyl alcohol, 137 parts of DBU (1,8-Diazabicyclo [5.4.0] underc-7-ene) and 40 parts of gallium trichloride were added. The mixture was stirred and stirred, and after the temperature was raised, the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry is filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 159 parts of a chlorogallium naphthalocyanine pigment (1-1) represented by the following chemical formula (1-1). Obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

Chlorogallium naphthalocyanine pigment (1-1)

Then, in the reaction vessel, 159 parts of the chlorogallium naphthalocyanine pigment was added to 1500 parts of concentrated sulfuric acid under an ice bath, and the mixture was stirred for 1 hour. Subsequently, this sulfuric acid solution was poured into 1000 parts of cold water at 3 ° C., and the generated precipitate was treated in the order of filtration, washing with water, washing with a 2.5% sodium hydroxide aqueous solution, and washing with water, and dried to 120 parts. Naphthalocyanine pigment (A-1) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 799.49.

Naphthalocyanine pigment (A-1)

(Synthesis of naphthalocyanine pigment (A-2))
178 parts of 2,3-dicyanonaphthalene used in the synthesis of naphthalocyanine pigment (A-1), 890 parts of n-amyl alcohol, DBU (1,8-Diazabiciclo [5.4.0] undec-7-ene) 137. Naphthalocyanine pigments (A) except that 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts and quinoline 1135 parts were used instead of the parts, respectively. The same operation as in the synthesis of -1) was carried out to obtain 125 parts of the naphthalocyanine pigment (A-2). As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 927.48.

Naphthalocyanine pigment (A-2)

(Synthesis of naphthalocyanine pigment (A-3))
To 1500 parts of concentrated sulfuric acid, 100 parts of the naphthalocyanine pigment (A-1) was added under an ice bath. Then, 151 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 25 ° C. for 6 hours. Subsequently, this sulfuric acid solution is poured into 9000 parts of cold water at 3 ° C., and the generated precipitate is treated in the order of filtration, washing with water, washing with 1% sodium hydroxide aqueous solution, and washing with water, and dried to 170 parts. A phthalocyanine pigment (A-3) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. When the number of bromine substitutions was calculated for the obtained naphthalocyanine pigment (A-3), the average number was 8.4, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the target compound was identified. The molecular weight was 1462.25.

Naphthalocyanine pigment (A-3)

(Synthesis of naphthalocyanine pigment (A-4))
4,9-Dibutoxy instead of 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts used in the synthesis of naphthalocyanine pigment (A-2) Except for the use of -1H-benzo [f] isoindole-1,3 (2H) -diimine 339 parts, the same operation as the synthesis of the naphthalocyanine pigment (A-2) was performed, and 237 parts of the naphthalocyanine pigment (237 parts). A-4) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1376.33.

Naphthalocyanine pigment (A-4)

(Synthesis of naphthalocyanine pigment (A-5))
4,9-dichloro instead of 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts used in the synthesis of naphthalocyanine pigment (A-2) Except for the use of -1H-benzo [f] isoindole-1,3 (2H) -diimine 264 parts, the same operation as the synthesis of naphthalocyanine pigment (A-2) was carried out, and 185 parts of naphthalocyanine pigment (185 parts). A-5) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1075.05.

Naphthalocyanine pigment (A-5)

(Synthesis of naphthalocyanine pigment (A-6))
5-Nitro-1H instead of 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts used in the synthesis of naphthalocyanine pigment (A-2) -Benzo [f] isoindole-1,3 (2H) -Except for the use of 232 parts of diimine, the same operation as for the synthesis of the naphthalocyanine pigment (A-2) was carried out, and 162 parts of the naphthalocyanine pigment (A-) were performed. 6) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 937.27.

Naphthalocyanine pigment (A-6)

(Synthesis of naphthalocyanine pigment (A-7))
Instead of 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts used in the synthesis of the naphthalocyanine pigment (A-2), 1,3-diimino The same procedure as for the synthesis of the naphthalocyanine pigment (A-2) was carried out except that 245 parts of -2,3-dihydro-1H-benzo [f] isoindole-6,7-dicarbonitrile was used, and 171 parts were used. Naphthalocyanine pigment (A-7) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 999.56.

Naphthalocyanine pigment (A-7)

(Synthesis of naphthalocyanine pigment (A-8))
Instead of 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts used in the synthesis of the naphthalocyanine pigment (A-2), 1,3-diimino Except for the use of 239 parts of -2,3-dihydro-1H-benzo [f] isoindole-5-carboxylic acid, the same operation as the synthesis of the naphthalocyanine pigment (A-2) was carried out, and 167 parts of naphthalocyanine was used. Pigment (A-8) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 975.53.

Naphthalocyanine pigment (A-8)

(Synthesis of naphthalocyanine pigment (A-9))
Instead of 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts used in the synthesis of the naphthalocyanine pigment (A-2), 1,3-diimino Except for the use of 275 parts of -2,3-dihydro-1H-benzo [f] isoindole-5-sulfonic acid, the same operation as for the synthesis of the naphthalocyanine pigment (A-2) was carried out, and 192 parts of naphthalocyanine were performed. Pigment (A-9) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1119.74.

Naphthalocyanine pigment (A-9)

(Synthesis of naphthalocyanine pigment (A-10))
4-Phenyl-1H instead of 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts used in the synthesis of naphthalocyanine pigment (A-2) -The operation was the same as for the synthesis of the naphthalocyanine pigment (A-2) except that 271 parts of benzo [f] isoindole-1,3 (2H) -diimine was used, and 190 parts of the naphthalocyanine pigment (A-) was performed. 10) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1103.87.

Naphthalocyanine pigment (A-10)

(Synthesis of naphthalocyanine pigment (A-11))
6,7-dimethyl instead of 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts used in the synthesis of naphthalocyanine pigment (A-2) Except for the use of -1H-benzo [f] isoindole-1,3 (2H) -diimine 223 parts, the same operation as the synthesis of the naphthalocyanine pigment (A-2) was carried out, and 156 parts of the naphthalocyanine pigment (15 parts) were performed. A-11) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 911.70.

Naphthalocyanine pigment (A-11)

(Synthesis of naphthalocyanine pigment (A-12))
Instead of the 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts used in the synthesis of the naphthalocyanine pigment (A-2), 5- (neopentyl) Oxy) -1H-benzo [f] isoindole-1,3 (2H) -Diimine 281 parts were used, but the same operation as the synthesis of naphthalocyanine pigment (A-2) was performed, and 197 parts of naphthalocyanine were used. Pigment (A-12) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1144.02.

Naphthalocyanine pigment (A-12)

(Synthesis of naphthalocyanine pigment (A-13))
6-Phenoxy-1H instead of 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts used in the synthesis of naphthalocyanine pigment (A-2) -Benzo [f] isoindole-1,3 (2H) -Except for the use of 287 parts of diimine, the same operation as the synthesis of the naphthalocyanine pigment (A-2) was carried out, and 201 parts of the naphthalocyanine pigment (A-) was performed. 13) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1167.87.

Naphthalocyanine pigment (A-13)

(Synthesis of naphthalocyanine pigment (A-14))
6- (Isopropylthio) instead of 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts used in the synthesis of naphthalocyanine pigment (A-2) ) -1H-benzo [f] isoindole-1,3 (2H) -Diimine 269 parts were used, but the same operation as the synthesis of naphthalocyanine pigment (A-2) was performed, and 188 parts of naphthalocyanine pigment were used. (A-14) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1096.07.

Naphthalocyanine pigment (A-14)

(Synthesis of naphthalocyanine pigment (A-15))
6- (Phenylthio) instead of 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts used in the synthesis of naphthalocyanine pigment (A-2) Except for the use of -1H-benzo [f] isoindole-1,3 (2H) -diimine 303 parts, the same operation as the synthesis of the naphthalocyanine pigment (A-2) was carried out, and 212 parts of the naphthalocyanine pigment ( A-15) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1232.13.

Naphthalocyanine pigment (A-15)

(Synthesis of naphthalocyanine pigment (A-16))
N-tert-butyl instead of 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts used in the synthesis of naphthalocyanine pigment (A-2) The same procedure as for the synthesis of the naphthalocyanine pigment (A-2) was carried out except that 266 parts of -1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-6-amine was used. 186 parts of naphthalocyanine pigment (A-16) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1083.97.

Naphthalocyanine pigment (A-16)

(Synthesis of naphthalocyanine pigment (A-17))
Instead of 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts used in the synthesis of the naphthalocyanine pigment (A-2), 1,3-diimino The same procedure as for the synthesis of the naphthalocyanine pigment (A-2) was carried out except that 300 parts of -Np-tolyl-2,3-dihydro-1H-benzo [f] isoindole-6-amine was used. 210 parts of naphthalocyanine pigment (A-17) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight is 122
It was 0.04.

Naphthalocyanine pigment (A-17)

(Synthesis of naphthalocyanine pigment (A-18))
6-Cyclohexyl-1H instead of 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts used in the synthesis of naphthalocyanine pigment (A-2) -Benzo [f] isoindole-1,3 (2H) -Except for the use of 277 parts of diimine, the same operation as the synthesis of the naphthalocyanine pigment (A-2) was carried out, and 194 parts of the naphthalocyanine pigment (A-) was performed. 18) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1128.06.

Naphthalocyanine pigment (A-18)

(Synthesis of naphthalocyanine pigment (A-19))
Instead of 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts used in the synthesis of the naphthalocyanine pigment (A-2), 1,3-diimino The same procedure as for the synthesis of the naphthalocyanine pigment (A-2) was carried out except that 302 parts of -N, N-dimethyl-2,3-dihydro-1H-benzo [f] isoindole-6-sulfonamide was used. , 211 parts of naphthalocyanine pigment (A-19) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1228.01.

Naphthalocyanine pigment (A-19)

(Synthesis of naphthalocyanine pigment (A-20))
6,7-Dichloro instead of 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts used in the synthesis of naphthalocyanine pigment (A-2) 227 Except for the use of -4,9-dimethoxy-1H-benzo [f] isoindole-1,3 (2H) -diimine 324 parts, the same operation as the synthesis of naphthalocyanine pigment (A-2) was performed. A part of the naphthalocyanine pigment (A-20) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1315.26.

Naphthalocyanine pigment (A-20)

(Synthesis of naphthalocyanine pigment (A-21))
4,9-dibromo instead of 1,3-diimino-2,3-dihydro-1H-benzo [f] isoindole-4,9-diol 227 parts used in the synthesis of naphthalocyanine pigment (A-2) Except for the use of -6-ethoxy-1H-benzo [f] isoindole-1,3 (2H) -diimine 397 parts, the same operation as the synthesis of the naphthalocyanine pigment (A-2) was performed, and 278 parts were used. A naphthalocyanine pigment (A-21) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1606.87.

Naphthalocyanine pigment (A-21)

(Synthesis of naphthalocyanine pigment (A-22))
The same operation as the synthesis of the naphthalocyanine pigment (A-1) was performed except that 50 parts of indium trichloride was used instead of 40 parts of gallium trichloride used in the synthesis of the naphthalocyanine pigment (A-1). 140 parts of naphthalocyanine pigment (A-22) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 844.58.

Naphthalocyanine pigment (A-22)

(Synthesis of naphthalocyanine pigment (A-23))
To 1500 parts of concentrated sulfuric acid, 100 parts of the above naphthalocyanine pigment (A-22) was added under an ice bath. Then, 151 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 25 ° C. for 6 hours. Subsequently, this sulfuric acid solution is poured into 9000 parts of cold water at 3 ° C., and the generated precipitate is treated in the order of filtration, washing with water, washing with 1% sodium hydroxide aqueous solution, and washing with water, and dried to produce 180 parts. A phthalocyanine pigment (A-23) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. When the number of bromine substitutions was calculated for the obtained naphthalocyanine pigment (A-23), the average number was 8.4, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the target compound was identified. The molecular weight was 1507.35.

Naphthalocyanine pigment (A-23)

(Synthesis of naphthalocyanine pigment (A-24))
The same operation as the synthesis of the naphthalocyanine pigment (A-5) was performed except that 50 parts of indium trichloride was used instead of 40 parts of gallium trichloride used in the synthesis of the naphthalocyanine pigment (A-5). 197 parts of naphthalocyanine pigment (A-24) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1120.14.

Naphthalocyanine pigment (A-24)

(Synthesis of naphthalocyanine pigment (A-25))
The same operation as the synthesis of the naphthalocyanine pigment (A-1) was performed except that 43 parts of silicon tetrachloride was used instead of 40 parts of gallium trichloride used in the synthesis of the naphthalocyanine pigment (A-1). 121 parts of naphthalocyanine pigment (A-25) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 774.86.

Naphthalocyanine pigment (A-25)

(Synthesis of naphthalocyanine pigment (A-26))
The same operation as the synthesis of the naphthalocyanine pigment (A-2) was performed except that 43 parts of silicon tetrachloride was used instead of 40 parts of gallium trichloride used in the synthesis of the naphthalocyanine pigment (A-2). Seven parts of naphthalocyanine pigment (A-26) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 902.85.

Naphthalocyanine pigment (A-26)

(Synthesis of naphthalocyanine pigment (A-27))
To 1500 parts of concentrated sulfuric acid, 100 parts of the above naphthalocyanine pigment (A-25) was added under an ice bath. Then, 151 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 25 ° C. for 6 hours. Subsequently, this sulfuric acid solution is poured into 9000 parts of cold water at 3 ° C., and the generated precipitate is treated in the order of filtration, washing with water, washing with 1% sodium hydroxide aqueous solution, and washing with water, and dried to 170 parts. A phthalocyanine pigment (A-27) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. When the number of bromine substitutions was calculated for the obtained naphthalocyanine pigment (A-27), the average number was 8.4, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the target compound was identified. The molecular weight was 1420.62.

Naphthalocyanine pigment (A-27)

(Synthesis of naphthalocyanine pigment (A-28))
The same operation as the synthesis of the naphthalocyanine pigment (A-4) was performed except that 43 parts of silicon tetrachloride was used instead of 40 parts of gallium trichloride used in the synthesis of the naphthalocyanine pigment (A-4). 223 parts of naphthalocyanine pigment (A-28) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1050.42.

Naphthalocyanine pigment (A-28)

(Synthesis of naphthalocyanine pigment (A-29))
The same operation as the synthesis of the naphthalocyanine pigment (A-5) was performed except that 43 parts of silicon tetrachloride was used instead of 40 parts of gallium trichloride used in the synthesis of the naphthalocyanine pigment (A-5). 166 parts of naphthalocyanine pigment (A-29) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1334.70.

Naphthalocyanine pigment (A-29)

(Synthesis of naphthalocyanine pigment (A-30))
The same operation as the synthesis of the naphthalocyanine pigment (A-6) was performed except that 43 parts of silicon tetrachloride was used instead of 40 parts of gallium trichloride used in the synthesis of the naphthalocyanine pigment (A-6). 151 parts of naphthalocyanine pigment (A-30) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 912.64.

Naphthalocyanine pigment (A-30)

(Synthesis of naphthalocyanine pigment (A-31))
The same operation as the synthesis of the naphthalocyanine pigment (A-1) was performed except that 53 parts of germanium tetrachloride was used instead of 40 parts of gallium trichloride used in the synthesis of the naphthalocyanine pigment (A-1). 125 parts of naphthalocyanine pigment (A-31) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 819.41.

Naphthalocyanine pigment (A-31)

(Synthesis of naphthalocyanine pigment (A-32))
To 1500 parts of concentrated sulfuric acid, 100 parts of the above naphthalocyanine pigment (A-31) was added under an ice bath. Then, 151 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 25 ° C. for 6 hours. Subsequently, this sulfuric acid solution is poured into 9000 parts of cold water at 3 ° C., and the generated precipitate is treated in the order of filtration, washing with water, washing with 1% sodium hydroxide aqueous solution, and washing with water, and dried to 170 parts. A phthalocyanine pigment (A-32) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. When the number of bromine substitutions was calculated for the obtained naphthalocyanine pigment (A-32), the average number was 8.4, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the target compound was identified. The molecular weight was 1465.16.

Naphthalocyanine pigment (A-32)

(Synthesis of naphthalocyanine pigment (A-33))
The same operation as the synthesis of the naphthalocyanine pigment (A-5) was performed except that 53 parts of germanium tetrachloride was used instead of 40 parts of gallium trichloride used in the synthesis of the naphthalocyanine pigment (A-5). 185 parts of naphthalocyanine pigment (A-33) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1094.97.

Naphthalocyanine pigment (A-33)

(Synthesis of naphthalocyanine pigment (A-34))
The same operation as the synthesis of the naphthalocyanine pigment (A-1) was performed except that 65 parts of tin tetrachloride was used instead of 40 parts of gallium trichloride used in the synthesis of the naphthalocyanine pigment (A-1). 140 parts of naphthalocyanine pigment (A-34) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 865.48.

Naphthalocyanine pigment (A-34)

(Synthesis of naphthalocyanine pigment (A-35))
To 1500 parts of concentrated sulfuric acid, 100 parts of the above naphthalocyanine pigment (A-34) was added under an ice bath. Then, 151 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 25 ° C. for 6 hours. Subsequently, this sulfuric acid solution is poured into 9000 parts of cold water at 3 ° C., and the generated precipitate is treated in the order of filtration, washing with water, washing with 1% sodium hydroxide aqueous solution, and washing with water, and dried to produce 180 parts. A phthalocyanine pigment (A-35) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. When the number of bromine substitutions was calculated for the obtained naphthalocyanine pigment (A-35), the average number was 8.4, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the target compound was identified. The molecular weight was 1511.24.

Naphthalocyanine pigment (A-35)

(Synthesis of naphthalocyanine pigment (A-36))
The same operation as the synthesis of the naphthalocyanine pigment (A-5) was performed except that 65 parts of tin tetrachloride was used instead of 40 parts of gallium trichloride used in the synthesis of the naphthalocyanine pigment (A-5). 200 parts of naphthalocyanine pigment (A-36) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1141.04.

Naphthalocyanine pigment (A-36)

(Synthesis of comparative naphthalocyanine pigment (K-1))
The same operation as in the synthesis of the chlorogallium naphthalocyanine pigment (1-1) was carried out to obtain 127 parts of the naphthalocyanine pigment (K-1). As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 817.93.

Comparative naphthalocyanine pigment (K-1)

(Synthesis of comparative naphthalocyanine pigment (K-2))
Similar to the synthesis of chlorogallium naphthalocyanine pigment (1-1) except that 40 parts of silicon tetrachloride was used instead of 40 parts of gallium trichloride used in the synthesis of chlorogallium naphthalocyanine pigment (1-1). The operation was carried out to obtain 127 parts of naphthalocyanine pigment (P-2). As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 881.75.

Comparative naphthalocyanine pigment (K-2)

<Manufacturing method of resin (B)>
(Synthesis of resin (B-1))
A reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, 100 parts of PGMAc, methyl 4-cyano-4-cyano-4- (dodecylthiocarbonothio oilthio) pentanoate (hereinafter abbreviated as "BM1448"). After charging 3 parts and heating to 80 ° C. in a nitrogen atmosphere, 48 parts of methyl methacrylate, 29 parts of ethyl methacrylate, 19 parts of tertiary butyl acrylate, 2,2'-azobis (2,4-dimethylvaleronitrile) ( Hereinafter, "V6
5 "is abbreviated. ) The mixture consisting of 1 part was added dropwise over 4 hours. After completion of the dropping, the mixture was kept at 90 ° C. for 2 hours, and then a mixture consisting of 5 parts of 2-methacryloyloxyethyl acid phosphate (hereinafter abbreviated as "P-1M"; molecular weight 228) and 100 parts of PGME was added dropwise in 1 hour. did. Then, after holding at 90 ° C. for 12 hours, PGME was added to obtain a 30% by mass solution of the resin (B-1). The Tg of this resin (B-1) was 37 ° C.

<Manufacturing method of near-infrared absorbing dye>
[Example 1]
(Synthesis of near-infrared absorbing dye (C-1))
A near-infrared absorbing dye composed of a naphthalocyanine pigment (A-1) and a phosphorus compound was produced by the following procedure. Four parts of diphenylphosphoric acid was added to 200 parts of N-methylpyrrolidone, and the mixture was sufficiently stirred and mixed, and then heated to 50 ° C. After adding 10 parts of the naphthalocyanine pigment (A-1) little by little to this solution, the mixture was stirred at 90 ° C. for 120 minutes. The end point of the reaction was confirmed, for example, by dropping the reaction solution onto the filter paper and setting the end point at the point where the bleeding disappeared. Subsequently, this reaction solution was injected into 2000 parts of water, and the generated precipitate was treated in the order of filtration and washing with water, and dried to obtain 11 parts of a near-infrared absorbing dye (C-1).

Near-infrared absorbent dye (C-1)

[Examples 2 to 62, Comparative Examples 1 to 4]
Hereinafter, the near-infrared absorbing dye (C-2) is the same as the near-infrared absorbing dye (C-1) except that the amount of the naphthalocyanine pigment and the phosphorus compound is changed to the amounts shown in Table 1-1 and Table 1-2. -(C-62), (C-65)-(C-68) were synthesized.
The structural formulas of the near-infrared absorbing dyes (C-2) to (C-62) and (C-65) to (C-68) obtained in Examples 2 to 64 and Comparative Examples 1 to 4 are described below. Is shown.

[Example 63]
(Synthesis of near-infrared absorbing dye (C-63))
A near-infrared absorbing dye (C-63) composed of a naphthalocyanine pigment (A-1) and a resin (B-1) was synthesized by the following procedure. 65 parts of the resin (B-1) was added to 200 parts of N-methylpyrrolidone, and the mixture was sufficiently stirred and mixed, and then heated to 50 ° C. After adding 10 parts of the naphthalocyanine pigment (A-1) little by little to this solution, the mixture was stirred at 90 ° C. for 120 minutes. The end point of the reaction was confirmed, for example, by dropping the reaction solution onto the filter paper and setting the end point at the point where the bleeding disappeared. Subsequently, this reaction solution was injected into 2000 parts of water, and the generated precipitate was treated in the order of filtration and washing with water, and dried to obtain 63 parts of a near-infrared absorbing dye (C-63).
At this time, the molar ratio of the naphthalocyanine pigment (A-1) and P-1M contained in the resin (B-1) is the P- contained in the naphthalocyanine pigment (A-1) / resin (B-1). It was 1M = 0.9 / 1.

[Example 64]
(Synthesis of near-infrared absorbing dye (C-64))
Near-infrared absorption except that 10 parts of naphthalocyanine pigment (A-25) was used instead of 10 parts of naphthalocyanine pigment (A-1) used in the synthesis of near-infrared absorbent dye (C-63). The same operation as the synthesis of the sex dye (C-63) was carried out to obtain 63 parts of a near-infrared absorbing dye.
At this time, the molar ratio of the naphthalocyanine pigment (A-25) and the P-1M contained in the resin (B-1) is the P- contained in the naphthalocyanine pigment (A-25) / resin (B-1). It was 1M = 0.9 / 1.

<Manufacturing method of binder resin solution>
(Preparation of binder resin solution): 70.0 parts of cyclohexanone was charged in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a random copolymer separable 4-neck flask, and the temperature was raised to 80 ° C. After replacing 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, and paracumylphenol ethylene oxide-modified acrylate (Toa Synthetic Co., Ltd.) A mixture of 7.4 parts of "Aronix M110" manufactured by the same company and 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monoethyl is prepared so that the non-volatile content is 20% by mass in the previously synthesized resin solution. A binder resin solution was prepared by adding ether acetate.

<Manufacturing method of resin type dispersant>
(Resin-type dispersant 1 solution): Block copolymer [Synthesis of monomer (b-1)]
60 parts of 2-isosianatoethyl methacrylate, 29 parts of 3- (dimethylamino) propylamine, and 120 parts of THF were charged in a reaction vessel equipped with a stirrer and a thermometer, and the mixture was stirred at room temperature for 5 hours. After confirming that the reaction was completed by FT-IR, the solvent was distilled off by a rotary evaporator to obtain 73 parts of the following monomer (b-1) as a pale yellow transparent liquid (yield 82%). ). Identification of the obtained compound was carried out by 1H-NMR.

Monomer (b-1)

[Synthesis of monomer (b-2)]
In a reaction vessel equipped with a stirrer and a thermometer, 6.6 parts of the monomer (b-1) and 5 parts of ion-exchanged water obtained by synthesizing the monomer (b-1) were charged, stirred at room temperature, and then 35. 8 parts of a% hydrochloric acid aqueous solution was added dropwise. It was confirmed by measuring the amine value that the reaction was completed, and 20 parts of a monomer (b-2) aqueous solution was obtained as a pale yellow transparent liquid. Identification of the obtained compound was carried out by 1H-NMR.

Monomer (b-2)

In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 17.7 parts of methyl methacrylate, 53.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and 50 parts were flowed with nitrogen. The mixture was stirred at ° C. for 1 hour, and the inside of the system was replaced with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to start the polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 20 parts of PGMAc, 21.2 parts of the monomer (b-1) as the second block monomer, and 27 parts of the aqueous solution of the monomer (b-2) (nonvolatile content 38%) were put into this reaction tank, and the temperature was 110 ° C. and nitrogen. The reaction was continued by stirring while maintaining the atmosphere. After 2 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of the non-volatile 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 non-volatile content was 40% by mass. In this way, a basic resin type having an amine value of 50 mgKOH / g per non-volatile component, a quaternary ammonium salt value of 20 mgKOH / g, a weight average molecular weight (Mw) of 9,800, and a non-volatile content of 40% by mass. One dispersant solution was obtained.

(2 solutions of resin-type dispersant): 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, 13.2 parts of tetramethylethylenediamine in a reaction device equipped with a block copolymer gas introduction tube, a condenser, a stirring blade, and a thermometer. The part was charged, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen to replace the inside of the system 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 start the polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 20 parts of dimethylaminoethyl methacrylate (hereinafter referred to as DM) as a second block monomer were added to this reaction device, and the mixture was stirred while maintaining a nitrogen atmosphere at 110 ° C. to continue the reaction. Two hours after the addition of dimethylaminoethyl methacrylate, the polymerization solution was sampled and the non-volatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of the non-volatile content, and the reaction solution was brought to room temperature. It was cooled to stop the polymerization.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by mass. In this way, the base is a poly (meth) acrylate skeleton having an amine value per non-volatile content of 71.4 mgKOH / g, a weight average molecular weight of 9900 (Mw), and a non-volatile content of 40% by mass, and has a tertiary amino group. Two solutions of the sex resin type dispersant were obtained.

(Resin-type dispersant 3 solution): 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, 13.2 parts of tetramethylethylenediamine in a reaction device equipped with a block copolymer gas introduction tube, a condenser, a stirring blade, and a thermometer. The part was charged, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen to replace the inside of the system 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 start the polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 25.6 parts of a methacryloyloxyethyltrimethylammonium chloride aqueous solution (“Acryester DMC78” manufactured by Mitsubishi Rayon Co., Ltd.) as a second block monomer were added to this reaction device, and the temperature was maintained at 110 ° C. under a nitrogen atmosphere. The reaction was continued with stirring. Two hours after the addition of methacryloyloxyethyltrimethylammonium chloride, the polymerization solution was sampled and the non-volatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of the non-volatile content, and the reaction solution was prepared. The polymerization was stopped by cooling to room temperature.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by mass. In this way, it is a poly (meth) acrylate skeleton having an amine value of 29.4 mgKOH / g per non-volatile content, a weight average molecular weight of 9800 (Mw), and a non-volatile content of 40% by mass, and has a quaternary ammonium base. Three solutions of the sex resin type dispersant were obtained.

(Resin type dispersant 4 solution): Block copolymer
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. Dropped. After the dropping was completed, the mixture was further heated and stirred at 70 ° C. for 2 hours, and after confirming that the reaction was completed by ^{1 1} H-NMR, the mixture was allowed to cool to room temperature. The reaction solution was washed successively with 300 parts of ion-exchanged water, 200 parts of saturated sodium hydrogen carbonate, and 200 parts of saturated saline, 20 g of magnesium sulfate was added to the organic layer, and the mixture was stirred and then filtered. The solvent of the obtained solution was distilled off by a rotary evaporator to obtain 31 parts of the following structure-containing monomer (b-3) as a pale yellow transparent liquid (yield 42%. Identification of the obtained compound was performed. ¹ Performed by 1 H-NMR.

Ethylene unsaturated monomer (b-3)

In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 17.6 parts of methyl methacrylate, 52.8 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and 50 parts were flowed with nitrogen. The mixture was stirred at ° C. for 1 hour, and the inside of the system was replaced with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 parts of propylene glycol monomethyl ether acetate were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to start the polymerization of the first block. .. After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 25 parts of PGMAc and 25.1 parts of an ethylenically unsaturated monomer (b-3) as a second block monomer were added to this reaction vessel, and the mixture was stirred while maintaining a nitrogen atmosphere at 110 ° C. The reaction was continued. Two hours after the addition of the ethylenically unsaturated monomer (b-3), the polymerization solution was sampled and the non-volatile content was measured. confirmed.
Further, 4.5 parts of benzyl chloride was added to this reaction device, and the mixture was stirred for 3 hours while maintaining the atmosphere of 110 ° C. and nitrogen, and then cooled.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by mass. In this way, a basic resin type having an amine value of 50 mgKOH / g per non-volatile component, a quaternary ammonium salt value of 20 mgKOH / g, a weight average molecular weight (Mw) of 9,800, and a non-volatile content of 40% by mass. A dispersant 4 solution was obtained.

(5 solutions of resin type dispersant)
A reaction vessel equipped with a gas introduction 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 replaced with nitrogen gas. The inside of the reaction vessel was heated to 70 ° C., 6 parts of 3-mercapto-1,2-propanediol was added, and 0.12 parts of AIBN (azobisisobutyronitrile) was further added, and the reaction was carried out for 12 hours. It was confirmed that 95% of the reaction occurred by measuring the non-volatile content. 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 temperature was 120 ° C. Was reacted for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMAc was added to adjust the non-volatile content to 40%. In this way, 5 solutions of an acidic resin-type dispersant having an acid value of 43, a weight average molecular weight of 9000, a poly (meth) acrylate skeleton, and an aromatic carboxyl group were obtained.

(6 solutions of resin type dispersant)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 6 parts of 3-mercapto-1,2-propanediol, 9.7 parts of pyromellitic acid anhydride, 0.01 parts of monobutyltin oxide, PGMAc88. Nine parts were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., 50 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, and hydroxymethyl. 20 parts of methacrylate was charged, 0.12 part of AIBN and 26.8 parts of PGMAc were added, and the reaction was carried out for 10 hours. The reaction was terminated after confirming that the polymerization proceeded by 95% by measuring the non-volatile content. PGMAc was added to adjust the non-volatile content to 40% to obtain 6 solutions of an acidic resin-type dispersant having an acid value of 43, a weight average molecular weight of 9000, a poly (meth) acrylate skeleton, and an aromatic carboxyl group.

(7 solutions of resin type dispersant)
PGMAc was added to BYK-P104 (manufactured by BIC Chemie Japan: 50% non-volatile content) to adjust the non-volatile content to 40% to obtain a resin-type dispersant 7 solution.

(8 solutions of resin type dispersant)
Disperbyk-171 (manufactured by Big Chemie Japan: non-volatile content 39.5%),
PGMAc was added to adjust the non-volatile content to 40%, and a resin-type dispersant 8 solution was obtained.

(9 solutions of resin type dispersant)
Disperbyk-142 (manufactured by Big Chemie Japan: 60% non-volatile content), PG
MAc was added to adjust the non-volatile content to 40%, and a resin-type dispersant 9 solution was obtained.

(10 solutions of resin type dispersant)
Non-volatile 40% PGMAc solution of the following copolymer

<Manufacturing of near-infrared absorbent composition>
[Example 65]
Near-infrared absorbing composition (D-1)
After uniformly stirring and mixing the mixture having the following composition, the mixture was dispersed in an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter having a diameter of 0.5 μm to prepare a near-infrared absorbing composition. ..
Near-infrared absorbing dye (C-1): 10.0 parts Resin-type dispersant 1 solution: 7.5 parts Binder resin solution: 35.0 parts PGMAc: 47.5 parts

[Examples 66 to 146, Comparative Examples 5 to 8]
Hereinafter, the near-infrared absorbing composition (D-1) except that the near-infrared absorbing dye, the resin-type dispersant solution, the binder resin solution, and the solvent are changed to the compositions and amounts shown in Tables 2-1 and 2-2. In the same manner as above, the near-infrared absorbing compositions (D-2) to (D-82) and (D-111) to (D-114) were prepared.

[Example 147]
Near-infrared absorbing composition (D-83)
After uniformly stirring and mixing the mixture having the following composition, the mixture was dispersed in an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter having a diameter of 0.5 μm to prepare a near-infrared absorbing composition. ..
Near-infrared absorbing dye (C-1): 7.0 parts Other near-infrared absorbing dye (X-1): 3.0 parts Resin-type dispersant 1 solution: 7.5 parts Binder resin solution: 35.0 Part PGMAc: 47.5 parts

[Examples 148 to 174]
Hereinafter, the same applies to the near-infrared absorbing composition (D-83) except that the composition and amount of the near-infrared absorbing dye, the resin-type dispersant solution, the binder resin solution, and the solvent are changed to the compositions and amounts shown in Table 2-1. Near-infrared absorbing compositions (D-84) to (D-110) were prepared. In addition, (X-1) to (X-)
14) is another near-infrared absorbing dye shown below.

<Evaluation of near-infrared absorbing composition>
The near-infrared absorbing compositions (D-1 to 114) obtained in Examples and Comparative Examples were tested for spectral characteristics and resistance (light resistance, heat resistance) by the following methods. In addition, ⊚ is a very good level, ○ is a good level, Δ is a practical level, and × is a level unsuitable for practical use. The results are shown in Table 3.

(Evaluation of dispersion stability)
The viscosity of the obtained near-infrared absorbing composition was measured and used as the initial viscosity. Further, an accelerated test was conducted at 40 ° C. for 7 days, and the accelerated viscosity with time was measured. As the rate of change due to acceleration, "accelerated aging viscosity / initial viscosity" was calculated, and the dispersion stability was evaluated according to the following criteria.
⊚: less than 1.05 ○: 1.05 or more, less than 1.10 Δ: 1.10 or more, less than 1.3 ×: 1.3 or more

(Evaluation of spectral characteristic 1)
The obtained near-infrared absorbing composition was spin-coated on a glass substrate having a thickness of 1.1 mm using a spin coater so that the film thickness after drying was 1.0 μm, and dried at 60 ° C. for 5 minutes. , 230 ° C. for 5 minutes to prepare a substrate. The spectroscopy of the obtained substrate is measured by a spectrophotometer (U-4100).
The absorption spectrum in the wavelength range of 300 to 1000 nm was measured using Hitachi High-Technologies Corporation). For the obtained substrate, the ratio (W / X) of the maximum value (W) of the absorbance at 700 to 900 nm and the minimum value (X) of the absorbance at 480 to 650 nm was determined and evaluated according to the following criteria. The larger this ratio (W / X) is, the smaller the absorption at the wavelength with the lowest absorption in the region with high luminous efficiency (480 nm to 650 nm) and the wavelength with the maximum transparency, as opposed to the absorption at 700 to 900 nm. It can be said that the transparency is high.
◎: 30 or more ○: 15 or more and less than 30 Δ: 5 or more and less than 15 ×: less than 5

(Evaluation of spectral characteristics 2)
With respect to the substrate obtained above, the ratio (W / Y) of the maximum value (W) of the absorbance at 700 to 900 nm and the maximum value (Y) of the absorbance at 480 to 650 nm was determined and evaluated according to the following criteria. The larger the ratio (W / Y), the smaller the absorption in the region with high luminous efficiency (480 nm to 650 nm) with respect to the absorption in 700 to 900 nm, and the higher the transparency in the region that is perceived brightly by the human eye. It can be said that.
◎: 2.0 or more ○: 1.5 or more and less than 2.0 Δ: 1.0 or more and less than 1.5 ×: less than 1.0

(Light resistance test)
A test substrate was prepared by the same procedure as the spectral characterization, placed in a light resistance tester (“SUNTEST CPS +” manufactured by TOYOSEIKI), and left for 24 hours. The absorbance of the near-infrared absorbing film at the spectroscopic maximum absorption wavelength was measured, the residual ratio to that before light irradiation was determined, and the light resistance was evaluated according to the following criteria. The survival rate was calculated using the following formula.
Residual rate = (absorbance after irradiation) ÷ (absorbance before irradiation) × 100
◎: Residual rate is 95% or more ○: Residual rate is 90% or more and less than 95% ×: Residual rate is less than 90%

(Heat resistance test)
A test substrate was prepared by the same procedure as the spectral characterization, and was additionally heated at 210 ° C. for 20 minutes as a heat resistance test. The absorbance of the near-infrared absorbing film at the spectroscopic maximum absorption wavelength was measured, the residual ratio to that before the heat resistance test was determined, and the heat resistance was evaluated according to the following criteria. The survival rate was calculated using the following formula.
Residual rate = (absorbance after heat resistance test) ÷ (absorbance before heat resistance test) x 100
◎: Residual rate is 95% or more ○: Residual rate is 90% or more and less than 95% ×: Residual rate is less than 90%

From the results in Table 3, Examples 65 to 174 have low absorption at 480 nm to 650 nm, which has high luminous efficiency, and have excellent near-infrared absorption ability, excellent near-infrared absorption ability at 700 nm to 900 nm, and further light resistance. Has excellent properties and heat resistance.

<Manufacturing of photosensitive near-infrared absorbing composition>
[Example 175]
After stirring and mixing the following mixture so as to be uniform, 1. Filtration with a 0 μm filter gave a photosensitive near-infrared absorbing composition (R-1).
Near-infrared absorbing composition (D-1): 50.0 parts Binder resin solution: 7.5 parts Photopolymerization initiator ("Aronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization initiator (BASF Japan "OXE-02"): 1.5 copies PGMAc: 39.0 copies

[Examples 176 to 194 and Comparative Examples 9 to 12]
Hereinafter, the photosensitive near-infrared absorbing composition is the same as that of the photosensitive near-infrared absorbing composition (R-1) except that the near-infrared absorbing composition is changed to the type of the near-infrared absorbing composition shown in Table 4. Objects (R-2) to (R-24) were obtained.

<Evaluation of photosensitive near-infrared absorbing composition>
The photosensitive near-infrared absorbing compositions (R-1) to (R-24) obtained in Examples and Comparative Examples were tested for spectral characteristics and resistance (heat resistance, light resistance) by the following methods. rice field. In addition, ⊚ is a very good level, ○ is a good level, Δ is a practical level, and × is a level unsuitable for practical use. The results are shown in Table 4.

(Evaluation of dispersion stability)
The viscosity of the obtained photosensitive near-infrared absorbing composition was measured and used as the initial viscosity. Further, an accelerated test was conducted at 40 ° C. for 7 days, and the accelerated viscosity with time was measured.
As the rate of change due to acceleration, the viscosity with time for acceleration / initial viscosity was calculated and evaluated according to the following criteria.
⊚: less than 1.05 ○: 1.05 or more, less than 1.10 Δ: 1.10 or more, less than 1.3 ×: 1.3 or more

(Evaluation of spectral characteristic 1)
The obtained photosensitive near-infrared absorbing composition was spin-coated on a glass substrate having a thickness of 1.1 mm using a spin coater so that the film thickness after drying was 1.0 μm, and dried at 60 ° C. for 5 minutes. Then, it was heated at 230 ° C. for 5 minutes to prepare a substrate. The spectrum of the obtained substrate was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation) to measure the absorption spectrum in the wavelength range of 300 to 1000 nm. For the obtained substrate, the ratio (W / X) of the maximum value (W) of the absorbance at 700 to 900 nm and the minimum value (X) of the absorbance at 480 to 650 nm was determined and evaluated according to the following criteria.
◎: 30 or more ○: 15 or more and less than 30 Δ: 5 or more and less than 15 ×: less than 5

(Evaluation of spectral characteristics 2)
With respect to the substrate obtained above, the ratio (W / Y) of the maximum value (W) of the absorbance at 700 to 900 nm and the maximum value (Y) of the absorbance at 480 to 650 nm was determined and evaluated according to the following criteria.
◎: 2.0 or more ○: 1.5 or more and less than 2.0 Δ: 1.0 or more and less than 1.5 ×: less than 1.0

(Light resistance test)
A test substrate was prepared by the same procedure as the spectral characterization, placed in a light resistance tester (“SUNTEST CPS +” manufactured by TOYOSEIKI), and left for 24 hours. The absorbance of the near-infrared absorbing film at the spectroscopic maximum absorption wavelength was measured, the residual ratio to that before light irradiation was determined, and the light resistance was evaluated according to the following criteria. The survival rate was calculated using the following formula.
Residual rate = (absorbance after irradiation) ÷ (absorbance before irradiation) × 100
◎: Residual rate is 95% or more ○: Residual rate is 90% or more and less than 95% ×: Residual rate is less than 90%

(Heat resistance test)
A test substrate was prepared by the same procedure as the spectral characterization, and was additionally heated at 210 ° C. for 20 minutes as a heat resistance test. The absorbance of the near-infrared absorbing film at the spectroscopic maximum absorption wavelength was measured, the residual ratio to that before the heat resistance test was determined, and the heat resistance was evaluated according to the following criteria. The survival rate was calculated using the following formula.
Residual rate = (absorbance after heat resistance test) ÷ (absorbance before heat resistance test) x 100
◎: Residual rate is 95% or more ○: Residual rate is 90% or more and less than 95% ×: Residual rate is less than 90%

From the results in Table 4, Examples 175 to 194 have low absorption at 480 nm to 650 nm, which has high luminous efficiency, and have excellent near-infrared absorption ability, excellent near-infrared absorption ability at 700 nm to 900 nm, and light resistance. Excellent in properties and heat resistance

<Manufacturing of near-infrared cut filter>
[Examples 195 to 200]
The photosensitive near-infrared absorbing composition (R-1) of the present invention was applied onto a glass substrate having a thickness of 1.1 mm with a spin coater, and heat-treated on a hot plate at 100 ° C. for 1 minute as a prebake.
Then, using an ultra-high pressure mercury lamp USH-200DP (manufactured by Ushio, Inc.), 100
In order to form a μm square near-infrared absorption cut filter, pattern exposure was performed with an exposure amount of 1000 mJ / cm ² through a photomask.
A 0.2 mass% sodium carbonate aqueous solution was used as a developing solution for the exposed film, and an uncured portion of the film was removed by a shower developing method at a developing solution pressure of 0.1 mPa to form a pattern of 400 μm × 400 μm. Then, it was post-baked at 100 ° C. for 120 minutes. The film thickness of the near-infrared absorption cut filter (F-1) after the heat treatment was 1.0 μm.
The photosensitive near-infrared absorbing compositions (R-2) to (R-6) also have the same near-infrared absorbing cut filter (F-1) as the near-infrared cut filters (F-2) to (F-). 6) was obtained.

<Evaluation of near infrared cut filter>
The near-infrared cut filters (F-1) to (F-6) were tested for spectral characteristics and durability (heat resistance, light resistance) in the same manner as in the evaluation of the photosensitive near-infrared absorbent composition. The results are shown in Table 5.

From the results in Table 5, Examples 195 to 200 were excellent in spectral characteristics. It absorbs little at 480 nm to 650 nm, which has high luminous efficiency, and has excellent near-infrared absorption ability, and also has excellent near-infrared absorption ability at 700 nm to 900 nm, and also has excellent light resistance and heat resistance. Therefore, it is suitable for a near-infrared cut filter.

<Manufacturing of a near-infrared absorbing composition (visible light region absorbing composition) containing an organic dye having absorption in the range of 400 nm to 700 nm>
(Blue coloring composition)
After uniformly stirring and mixing the mixture having the following composition, the mixture was dispersed in an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter having a diameter of 0.5 μm to prepare a blue colored composition.
C. I. Pigment Blue PB15: 6: 10.0 parts Resin-type dispersant 2 solution: 7.5 parts Binder resin solution: 35.0 parts PGMAc: 47.5 parts

(Purple coloring composition)
After uniformly stirring and mixing the mixture having the following composition, the mixture was dispersed in an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter having a diameter of 0.5 μm to prepare a purple colored composition.
C. I. Pigment Violet PV23: 10.0 parts Resin type dispersant 2 solution: 7.5 parts Binder resin solution: 35.0 parts PGMAc: 47.5 parts

(Yellow coloring composition)
After uniformly stirring and mixing the mixture having the following composition, the mixture was dispersed in an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter having a diameter of 0.5 μm to prepare a yellow colored composition.
C. I. Pigment Yellow PY139: 10.0 parts Resin type dispersant 2 solution: 7.5 parts Binder resin solution: 35.0 parts PGMAc: 47.5 parts

[Example 201]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain a visible light region absorbent composition (P-1).
Near-infrared absorbing composition (D-1): 10.0 parts blue pigment composition: 20.0 parts purple pigment composition: 10.0 parts yellow pigment composition: 10.0 parts binder resin solution: 7.5 parts Part Photopolymerizable compound (“Aronix M-402” manufactured by Toa Synthetic Co., Ltd.): 2.0 parts Photopolymerization initiator (“OXE-02” manufactured by BASF Japan): 1.5 parts PGMAc: 39.0 parts

[Examples 202 to 210]
Hereinafter, the visible light region absorbent composition (P-1) is the same as that of the visible light region absorbent composition (P-1) except that the near infrared ray absorbent composition is changed to the type of the near infrared ray absorbent composition shown in Table 6. P-2) to (P-10) were obtained.

The obtained visible light region absorbing composition was spin-coated on a glass substrate having a thickness of 1.1 mm using a spin coater so as to have a film thickness of 2.0 μm, dried at 60 ° C. for 5 minutes, and then 230 ° C. The substrate was prepared by heating in 5 minutes.
The function of the filter is, for example, whether or not near-infrared rays can be transmitted and whether or not light rays in other wavelength regions can be cut.
Hereinafter, the transmittance at 940 nm and the absorbency in the wavelength range of 400 to 800 nm were evaluated.

(Absorbability of 400 to 800 nm)
A transmission spectrum in the wavelength range of 400 to 800 nm was measured on the obtained substrate using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: Transmittance is less than 2% in all regions of 400 to 800 nm Δ: Transmittance is 2% or more in some regions of 400 to 800 nm ×: Transmittance is 2% or more in all regions of 400 to 800 nm

(940 nm transparency)
The transmittance of the obtained substrate was measured at 940 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: 80% or more Δ: 40% or more and less than 80% ×: less than 40%

(Light resistance test)
The obtained substrate was used as a light resistance tester ("SUNTEST CPS +" manufactured by TOYOSEIKI.
") And left for 24 hours. At this time, the test was carried out with a wide band light having an irradiance of 47 mW / cm2 and a radiation illuminance of 300 to 800 nm. Then, a transmission spectrum in the wavelength range of 400 to 800 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: Transmittance is less than 2% in all regions of 400 to 800 nm Δ: Transmittance is 2% or more in some regions of 400 to 800 nm ×: Transmittance is 2% or more in all regions of 400 to 800 nm

(Heat resistance test)
The obtained substrate was additionally heated at 210 ° C. for 20 minutes as a heat resistance test. Then, a transmission spectrum in the wavelength range of 400 to 800 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: Transmittance is less than 2% in all regions of 400 to 800 nm Δ: Transmittance is 2% or more in some regions of 400 to 800 nm ×: Transmittance is 2% or more in all regions of 400 to 800 nm

From the results in Table 6, Examples 201 to 210 absorb light in the entire region of 400 to 800 nm by containing both a near-infrared absorbing dye and a dye that absorbs visible light of 400 to 700 nm, and near infrared rays of 940 nm. Can be transmitted through.

<Manufacturing of near-infrared absorbing composition for molding>
(Thermoplastic resin (E))
(E-1) Polyester MA-2101M (polyester resin, manufactured by Unitika Ltd., crystalline resin, melting point 264 ° C.)
(E-2) Amylan CM3001-N (polyamide resin, manufactured by Toray Industries, Inc., crystalline resin, melting point 265 ° C.)
(E-3) Iupiron S-3000 (polycarbonate resin, manufactured by Mitsubishi Engineering Plastics, amorphous resin, glass transition temperature 145 ° C)
(E-4) Topas (cycloolefin resin, manufactured by Polyplastics, amorphous resin, glass transition temperature 78 ° C.)
(E-5) Apel (Cycloolefin resin, manufactured by Mitsui Chemicals, amorphous resin, glass transition temperature 135 ° C)
(E-6) ULTEM (polyetherimide resin, manufactured by Saudi Basic Industry Corporation, amorphous resin, glass transition temperature 217 ° C)

[Example 112]
(Manufacturing of masterbatch)
One part of the near-infrared absorbing dye 1 (C-1) and 99 parts of the thermoplastic resin (E-1) were put into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) with a screw diameter of 30 mm from the same supply port. After melt-kneading at 300 ° C., a master batch (M-1) was prepared by cutting into pellets using a pelletizer.

(Film molding)
[Example 211]
5 parts of the obtained masterbatch (M-1) was mixed with 95 parts of the thermoplastic resin (E-1) of the diluted resin, and the temperature was 300 ° C. using a T-die molding machine (manufactured by Toyo Seiki). A film (Q-1) having a thickness of 250 μm was formed by melting and mixing with.

[Examples 212 to 256, Comparative Examples 13 to 16]
Similar to Example 211, films (Q-2) to (Q-50) having a thickness of 250 μm were formed using the materials shown in Table 7-1.

<Near infrared absorption>

(Evaluation of spectral characteristic 1)
For the obtained film, the absorption spectrum in the wavelength range of 300 to 1000 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation). For the obtained substrate, the ratio (W / X) of the maximum value (W) of the absorbance at 700 to 900 nm and the minimum value (X) of the absorbance at 480 to 650 nm was determined and evaluated according to the following criteria.
◎: 30 or more ○: 15 or more and less than 30 Δ: 5 or more and less than 15 ×: less than 5

(Evaluation of spectral characteristics 2)
With respect to the obtained film, the ratio (W / Y) of the maximum value (W) of the absorbance at 700 to 900 nm and the maximum value (Y) of the absorbance at 480 to 650 nm was determined and evaluated according to the following criteria.
◎: 2.0 or more ○: 1.5 or more and less than 2.0 Δ: 1.0 or more and less than 1.5 ×: less than 1.0

(transparency)
The transparency of the obtained film was visually evaluated.
〇: No turbidity is observed.
Δ: Some turbidity is observed.
×: Clearly turbidity is observed.

(Light resistance)
A test film was prepared by the same procedure as the near-infrared absorption evaluation, placed in a light resistance tester (“SUNTEST CPS +” manufactured by TOYOSEIKI), and the irradiance was 47 mW / cm ² , 30.
It was irradiated with a wide band of light of 0 to 800 nm and left for 24 hours. Next, the test film was taken out, the absorbance of the test film at the maximum absorption wavelength was measured, the residual ratio to the absorbance before light irradiation was determined, and the light resistance was evaluated according to the following criteria. The survival rate was calculated using the following formula.
Residual rate = (absorbance after irradiation) ÷ (absorbance before irradiation) × 100
○: Residual rate is 90% or more Δ: Residual rate is 85% or more and less than 90% ×: Residual rate is less than 85%,

From the results in Table 7-2, Examples 211 to 256 have low absorption at 480 nm to 650 nm, which has high luminous efficiency, and are excellent in near-infrared absorption ability, and are also excellent in near-infrared absorption ability at 700 nm to 900 nm. Has excellent light resistance

<Manufacturing of Visible Light Region Absorbable Composition for Molding>
[Example 257]
(Manufacturing of masterbatch)
1 part of near-infrared absorbing dye (C-1), 1 part of Pigment Blue 15: 3, 1 part of Pigment Yellow 147, 1 part of Solvent Red 52, 96 parts of thermoplastic resin (E-1) It is put into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) with a screw diameter of 30 mm from the supply port, melt-kneaded at 300 ° C, and then cut into pellets using a pelletizer to make a master batch (MP-1). Made.

(Film molding)
5 parts of the obtained masterbatch (MP-1) was mixed with 95 parts of the thermoplastic resin (E-1) of the diluted resin, and the temperature was 300 ° C. using a T-die molding machine (manufactured by Toyo Seiki). A film (QP-1) having a thickness of 250 μm was formed by melting and mixing with.

[Examples 258 to 268]
Similar to Example 257, films (QP-2) to (QP-12) having a thickness of 250 μm were formed using the materials shown in Table 8-1.

The suitability of the near-infrared filter was evaluated for the obtained film. The function of the filter is, for example, whether or not near-infrared rays can be transmitted and whether or not light rays in other wavelength regions can be cut.
Hereinafter, the transmittance at 940 nm and the absorbency in the wavelength range of 400 to 800 nm were evaluated.

(Absorbability of 400 to 800 nm)
The transmission spectrum of the obtained film in the wavelength range of 400 to 800 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: Transmittance is less than 2% in all regions of 400 to 800 nm Δ: Transmittance is 2% or more in some regions of 400 to 800 nm ×: Transmittance is 2% or more in all regions of 400 to 800 nm

(940 nm transparency)
The transmittance of the obtained film was measured at 940 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: 80% or more Δ: 40% or more and less than 80% ×: less than 40%

(transparency)
The transparency of the obtained film was visually evaluated.
〇: No turbidity is observed.
Δ: Some turbidity is observed.
×: Clearly turbidity is observed.

(Light resistance)
The obtained film was used as a light resistance tester (“SUNTEST CP” manufactured by TOYOSEIKI).
It was placed in S + ”) and left for 24 hours. At this time, the test was carried out with a wide band light having an irradiance of 47 mW / cm2 and a radiation illuminance of 300 to 800 nm. Then, a transmission spectrum in the wavelength range of 400 to 800 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: Transmittance is less than 2% in all regions of 400 to 800 nm Δ: Transmittance is 2% or more in some regions of 400 to 800 nm ×: Transmittance is 2% or more in all regions of 400 to 800 nm

From the results in Table 8-2, Examples 257 to 268 absorb light in the entire region of 400 to 800 nm by containing both a near-infrared absorbing dye and a dye that absorbs visible light of 400 to 700 nm, and have a thickness of 940 nm. Can transmit near infrared rays.

Claims (5)

A near-infrared absorbing dye represented by the following general formula (1) or the following general formula (4).

[In the general formula (1), R ₁ to R ₂₄ are independently hydrogen atom, halogen atom, nitro group, nitrile group, carboxyl group, sulfone group, alkyl group and substituent which may have a substituent. It has an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, and a substituent. May have an alkylthio group, an arylthio group that may have a substituent, an alkylamino group that may have a substituent, an arylamino group that may have a substituent, or a substituent. Represents a sulfamoyl group.
M ₁ represents Ga and In.
Z ₁ is a polymer moiety containing a monomer unit represented by the general formula (2) or a phosphorus compound moiety represented by the general formula (3), and * is a bond with M ₁ . ..
In the general formula (2), X is -CONH-R _25- , -COO-R _26- , -CONH-R ₂₇ -O-, or -COO-R ₂₈ -O-, and is R ₂₅ to R ₂₈ . Is an alkylene group, an arylene group, or an alkylene group or arylene linked by -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO- between carbon atoms. Represents a group. Y represents a hydrogen atom or a methyl group.
In the general formula (3), R ₂₉ and R ₃₀ may independently have a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent, respectively. Representing an aryloxy group which may have an alkoxyl group or a substituent, R ₂₉ and R ₃₀ may be bonded to each other to form a ring. ]

General formula (4)

[In the general formula (4), R ₃₁ to R ₅₄ independently have a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, and an alkyl group and a substituent which may have a substituent. It has an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, and a substituent. May have an alkylthio group, an arylthio group that may have a substituent, an alkylamino group that may have a substituent, an arylamino group that may have a substituent, or a substituent. Represents a sulfamoyl group.
M ₂ represents Si, Ge, Sn.
Z ₂ and Z ₃ are each independently a polymer moiety containing a monomer unit represented by the general formula (2) or a phosphorus compound moiety represented by the general formula (3), and * indicates. , _M2 . ] A near-infrared absorbing composition comprising the near-infrared absorbing dye according to claim 1 and a binder resin. The near-infrared absorbing composition according to claim 2, further comprising a photopolymerizable compound and a photopolymerization initiator. The near-infrared absorbing composition according to claim 2 or 3, further containing an organic dye having absorption at 400 nm to 700 nm. An optical filter having a coating film formed on a substrate by the near-infrared absorbing composition according to any one of claims 2 to 4.