JP7476760B2 - Near infrared absorbing dye, near infrared absorbing composition, and near infrared cut filter - Google Patents

Description

The present invention relates to a near-infrared absorbing dye.

Near-infrared absorbing materials are used in a wide range of applications, including near-infrared absorbing films that block heat rays, near-infrared absorbing plates, agricultural near-infrared absorbing films that selectively utilize sunlight, recording media that utilize the heat absorbed by near-infrared rays, near-infrared cut filters for electronic devices, near-infrared filters for photography, protective glasses, sunglasses, heat-blocking films, dyes for optical recording, optical character reading and recording, confidential document duplication prevention, electrophotographic photoreceptors, and laser fusion.

Among these, near-infrared cut filters for camera sensors are required to have high transmittance in the region of 480 nm to 650 nm, which is a region with high luminous efficiency, and high shielding ability in the region of 700 nm to 1000 nm, which is a region with no luminous efficiency. Furthermore, near-infrared cut filters for cameras are required to have extremely high heat resistance and light resistance, for example, when used in vehicles in harsh environments or when mounted on devices that require processing at high temperatures.
The relative luminous efficiency is an index of the brightness perceived by the human eye at each wavelength.

Representative near-infrared absorbing dyes include cyanine dyes, diimonium dyes, phthalocyanine dyes, and squarylium dyes. However, cyanine dyes and diimonium dyes have low heat and light resistance and poor durability in various environments, so their applications are limited.

Disclosed phthalocyanine dyes include phthalocyanine or naphthalocyanine compounds having a substituent (see, for example, Patent Document 1), phthalocyanine compounds having an amino group (see, for example, Patent Documents 2 to 6), phthalocyanine compounds having an aryloxy group (see, for example, Patent Document 7), and fluorine-containing phthalocyanine compounds (see, for example, Patent Documents 8 and 9).

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

Among these, naphthalocyanine compounds have the characteristics of being extremely heat-resistant and light-resistant when used as pigments, and absorbing a wide range of light from 700 nm to 900 nm. However, because the aggregation caused by the association of aromatic rings is very strong, there is an issue that the dispersion stability is poor and transparency is low, in other words, the transmittance is low in the range of 480 nm to 650 nm, which is the region with high relative luminous efficiency.

The present invention aims to provide a near-infrared absorbing dye that combines transmittance in the 480-650 nm range, which is a region with high relative luminosity, with heat resistance and light resistance, and has excellent near-infrared absorption in the 700-900 nm range.

The present invention relates to a near-infrared absorbing dye represented by the following general formula (1):

[In general formula (1), R ₁ to R ₂₄ each independently represent a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, 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, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, 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 group which may have a substituent.
M represents Al.
Z is a polymer moiety containing a monomer unit represented by formula (2) or a phosphorus compound moiety represented by formula (3), and * is a bond to M.
In general formula (2), X is -CONH- _R25- , -COO- _R26- , -CONH- _R27 -O-, -COO- _R28 -O-, _R25 to _R28 each represent an alkylene group or an arylene group in which carbon atoms may be linked by -O-, -CO-, -COO-, -OCO-, -CONH- or -NHCO-, and _R31 represents a hydrogen atom or a methyl group.
In the general formula (3), R ₂₉ and R ₃₀ each independently represent a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent, and R ₂₉ and R ₃₀ may be bonded to each other to form a ring.

The present invention described above makes it possible to provide a near-infrared absorbing dye, a near-infrared absorbing composition, and a near-infrared cut filter that have excellent near-infrared absorption in the 700-900 nm range and that combine transmittance in the 480-650 nm range, which is a region with high relative luminous efficiency, with heat resistance and light resistance.

<Near infrared absorbing dye>
The near-infrared absorbing dye of the present invention (hereinafter referred to as the dye of the present invention) is represented by the following general formula (1). The dye of the present invention can absorb a wide range of light from 700 nm to 900 nm while improving the transmittance in the region of 480 nm to 650 nm, which is a region with high relative luminous efficiency, by bonding a moiety of general formula (2) or general formula (3) to a naphthalocyanine moiety that has high heat resistance and light fastness. This makes it possible to achieve both the transmittance, heat resistance, and light fastness.

In general, naphthalocyanine dyes have strong cohesive forces due to the association of aromatic rings, and often exist as pigments in a crystalline structure. In such cases, they are difficult to dissolve in normal solvents, and a dispersion can be obtained by dispersing them using a dispersant, but the coating made from this dispersion exhibits strong absorption due to the association of aromatic rings in the vicinity of 350 nm to 450 nm and in the vicinity of 650 nm to 700 nm, resulting in poor transmittance in the region of high relative luminosity, 480 nm to 650 nm.

In contrast, the coating containing the dye of the present invention controls the association of aromatic rings by bonding a specific axial phosphorus compound to aluminum naphthalocyanine, and increases the transmittance in the region of high luminosity, 480 nm to 650 nm. This is because the dye of the present invention has a structure in which the phosphorus compound provides moderate steric hindrance, making it difficult for the naphthalocyanine moieties to associate with each other.

[In general formula (1), R ₁ to R ₂₄ each independently represent a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, 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, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, 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 group which may have a substituent.
M represents Al.
Z is a polymeric phosphorus compound moiety containing a monomer unit represented by formula (2) or a phosphorus compound moiety represented by formula (3), and * is a bond to M.
In general formula (2), X is -CONH- _R25- , -COO- _R26- , -CONH- _R27 -O-, -COO- _R28 -O-, _R25 to _R28 each represent an alkylene group or an arylene group in which carbon atoms may be linked by -O-, -CO-, -COO-, -OCO-, -CONH- or -NHCO-, and _R31 represents a hydrogen atom or a methyl group.
In the general formula (3), R ₂₉ and R ₃₀ each independently represent a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent, and R ₂₉ and R ₃₀ may be bonded to each other to form a ring.

The dye of the present invention is composed of an aluminaphthalocyanine portion and a polymer portion containing a monomer unit represented by general formula (2) or a phosphorus compound portion represented by general formula (3). The aluminaphthalocyanine portion is preferably made from an aluminaphthalocyanine represented by the following general formula (4).

<Alumina phthalocyanine>

General formula (4)

In general formula (4), R ₁ to R ₂₄ each independently represent a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, 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, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, 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 group which may have a substituent.
M represents Al.

The "alkyl group" of the alkyl group which may have a substituent includes, for example, a straight-chain or branched alkyl group such as 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, a n-hexyl group, a n-octyl group, a stearyl group, and a 2-ethylhexyl group. The "alkyl group having a substituent" includes, for example, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2,2,3,3-tetrafluoropropyl group, a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2-nitropropyl group, a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group, and 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, and anthryl group.
Examples of the "substituted aryl group" include a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-aminophenyl group, a 2-methyl-4-chlorophenyl group, a 4-hydroxy-1-naphthyl group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinonyl group, and a 2-aminoanthraquinonyl group.

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 "substituted cycloalkyl group" include a 2,5-dimethylcyclopentyl group, a 4-tert-butylcyclohexyl group, and the like.

Examples of the "alkoxyl group" of the alkoxyl group which may have a substituent include straight-chain or branched alkoxyl groups such as 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, a 2,3-dimethyl-3-pentyloxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group, and a 2-ethylhexyloxy group.
Examples of the "substituted alkoxyl group" include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, and a benzyloxy group.

Examples of the "aryloxy group" of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, and an anthryloxy group.
Examples of the "substituted aryloxy group" include a p-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, and a 2-methyl-4-chlorophenoxy group.

Examples of the "alkylthio group" of the alkylthio group which may have a substituent include 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, and an octadecylthio group.
Examples of the "substituted alkylthio group" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, and a phenylcarbonylaminoethylthio group.

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

Examples of the "alkylamine group" of the alkylamine group which may have a substituent include a methylamine group, an ethylamine group, a propylamine group, a butylamine group, a pentylamine group, a hexylamine group, an octylamine group, a decylamine group, a dodecylamine group, and an octadecylamine group.
Examples of the "substituted alkylamine group" include a methoxyethylamine group, an aminoethylamine group, a benzylaminoethylamine group, a methylcarbonylaminoethylamine group, and a phenylcarbonylaminoethylamine group.

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, and a 9-anthrylamine group.
Examples of the "substituted arylamine group" include a chlorophenylamine group, a trifluoromethylphenylamine group, a cyanophenylamine group, a nitrophenylamine group, a 2-aminophenylamine group, and a 2-hydroxyphenylamine group.

<Method of synthesizing aluminaphthalocyanine>
A typical industrial process for producing aluminaphthalocyanine is described below.
(1) Wyler Method: This method involves reacting a substituted or unsubstituted naphthalenedicarboxylic anhydride or a substituted or unsubstituted naphthalenedicarboxylic anhydride imide with urea in the presence of aluminum chloride at high temperature.
(2) Phthalodinitrile Method This method involves reacting a substituted or unsubstituted 2,3-dicyanonaphthalene with aluminum chloride in an alcoholic solvent such as n-amyl alcohol, n-hexyl alcohol, 1-methoxyethanol, or 1-ethoxyethanol in the presence of a strong base such as DBU (1,8-diazabicyclo[5.4.0]undecene-7), DBN (1,5-diazabicyclo[4.3.0]nonene-5), or a (metal) alkoxide.
(3) Diiminoisoindoline Method: A method in which substituted or unsubstituted 1,3-diiminobenzo[f]isoindoline is reacted with aluminum chloride in the presence of a strong base such as 2-dimethylaminoethanol, quinoline, or DBU (1,8-diazabicyclo[5.4.0]undecene-7).

Examples of alumina phthalocyanine include the following compounds:

<Polymer Part>
One embodiment of the near infrared absorbing dye represented by general formula (1) is a salt formed between a phosphate group in a polymer moiety containing a monomer unit represented by general formula (2) and an aluminum cation in a naphthalocyanine moiety.
The polymer segment is formed by vinyl polymerization of the raw material monomer represented by general formula (5). The polymer segment may contain the monomer represented by general formula (5) and other monomers in addition to the monomer represented by general formula (5).

General formula (5)

In general formula (5), X is -CONH- _R25- , -COO- _R26- , -CONH- _R27 -O-, -COO- _R28 -O-, and _R25 to _R28 each represent an alkylene group or an arylene group in which carbon atoms 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 a phenylene group, a naphthylene group, a biphenylene group, a terphenylene group, and an anthrylene group. Examples of R ₂₅ to R ₂₈ include a methylene group, an ethylene group, a propylene group, and a butylene group.
_R31 represents a hydrogen atom or a methyl group.

Examples of the monomer represented by general formula (5) include (2-(meth)acryloyloxyethyl) acid phosphate, (2-(meth)acryloyloxypropyl) acid phosphate, and (2-(meth)acryloyloxyisopropyl) acid phosphate.

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, vinyl alcohol esters, styrenes, (meth)acrylonitrile, acid group-containing monomers, and thermally crosslinkable group-containing monomers.

Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, t-octyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, acetoxyethyl (meth)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, benzyl (meth)acrylate, Examples of the acrylate include diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monoethyl ether (meth)acrylate, β-phenoxyethoxyethyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tribromophenyl (meth)acrylate, and tribromophenyloxyethyl (meth)acrylate.

Examples of crotonate esters include butyl crotonate and hexyl crotonate.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, and vinyl benzoate. Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

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

Examples of itaconate diesters include dimethyl itaconate, diethyl itaconate, 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, N-n-butylacryl(meth)amide, N-t-butyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide, N-(2-methoxyethyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-benzyl(meth)acrylamide, (meth)acryloylmorpholine, and diacetone acrylamide.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (e.g., t-Boc, etc.), methyl vinylbenzoate, and α-methylstyrene.

Examples of the acid group-containing monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; trivalent or higher unsaturated polyvalent carboxylic acids or their anhydrides; mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as mono(2-acryloyloxyethyl) succinate, mono(2-methacryloyloxyethyl) succinate, mono(2-acryloyloxyethyl) phthalate, and mono(2-methacryloyloxyethyl) phthalate; and mono(meth)acrylates of polymers with carboxy terminals at both ends such as ω-carboxy-polycaprolactone monoacrylate and ω-carboxy-polycaprolactone monomethacrylate.

The thermally crosslinkable group in the thermally crosslinkable group-containing monomer becomes, for example, a crosslinking point of the near-infrared absorbing dye, and contributes to improving 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, and an isocyanate group. Among these, in terms of storage stability and reactivity, a hydroxyl group, a carboxyl group, an oxetanyl group, a tert-butyl group, an isocyanate group, and a (meth)acryloyl group are preferred, and a hydroxyl group is more preferred.
Examples of the hydroxyl group-containing monomer include, but are not limited to, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate, and caprolactone adducts of these monomers (molar number: 1 to 5), etc. Among these, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferred from the viewpoint of heat resistance.

Examples of oxetanyl group-containing monomers include 3-(acryloyloxymethyl) 3-methyloxetane, 3-(methacryloyloxymethyl) 3-methyloxetane, 3-(acryloyloxymethyl) 3-ethyloxetane, 3-(methacryloyloxymethyl) 3-ethyloxetane, 3-(acryloyloxymethyl) 3-butyloxetane, 3-(methacryloyloxymethyl) 3-butyloxetane, 3-(acryloyloxymethyl) 3-hexyloxetane, and 3-(methacryloyloxymethyl) 3-hexyloxetane.

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

Examples of isocyanate group-containing monomers include 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate, and 4-isocyanate butyl acrylate. The isocyanate group includes, for example, a blocked isocyanate group. A blocked isocyanate group is a functional group that, under normal conditions, protects an isocyanate group with another functional group to suppress the reactivity of the isocyanate group, but can be deprotected by heating to regenerate an active isocyanate group.

Commercially available blocked isocyanate group-containing monomers include, for example, 2-[(3,5-dimethylpyrazolyl)carboxyamino]ethyl methacrylate (KarenzMOI-BP, manufactured by Showa Denko K.K.); 2-(O-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate (KarenzMOI-BM, manufactured by Showa Denko K.K.); etc.

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

The amount of the monomer represented by general formula (5) used in the synthesis of the polymer portion is preferably 1 to 30 mass % and more preferably 5 to 15 mass % of the total monomers (100 mass %). When an appropriate amount is used, the optical properties are improved.

The amount of the thermocrosslinkable group-containing monomer used is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass, based on 100% by mass of the total monomers. Using an appropriate amount improves heat resistance.

Methods for synthesizing the polymer moiety include, for example, anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization. Among these, free radical polymerization and living radical polymerization are preferred.

The free radical polymerization method uses a polymerization initiator, such as an azo compound or an organic peroxide.
Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. Examples of organic peroxides include benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, and diacetyl peroxide.

Polymerization initiators can be used alone or in combination of two or more types.

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.

Living radical polymerization suppresses side reactions that occur in general radical polymerization and allows the polymerization to grow uniformly, making it possible to synthesize block polymers and polymers with narrow molecular weight distributions.

Among the various living radical polymerization methods, the atom transfer radical polymerization method, which uses an organic halide or a sulfonyl halide compound as a polymerization initiator and a transition metal complex as a catalyst, is preferred. This method is preferred in that it can polymerize monomers with a variety of structures and can adopt a polymerization temperature that is compatible with existing equipment. 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) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al., J. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) WO96/030421 (Reference 6) WO97/018247 (Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-41117

It is preferable to use an organic solvent for synthesizing the polymer portion. Examples of organic solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

The weight average molecular weight of the polymer portion is preferably 5,000 to 20,000, and more preferably 8,000 to 15,000. Having an appropriate molecular weight improves optical properties and heat resistance.

The glass transition temperature (Tg) of the polymer portion is preferably -50 to 150°C, and more preferably 20 to 80°C. A moderate Tg improves the optical properties.

Organic solvents can be used alone or in combination of two or more types.

<Phosphorus Compounds>
One form of the near infrared absorbing dye represented by general formula (1) is a salt formed by a phosphate group in the phosphorus compound moiety represented by general formula (3) and an aluminum cation in the naphthalocyanine moiety.
The raw material for the phosphorus compound portion is a phosphorus compound represented by the general formula (6).
In general formula (6), R ₂₉ and R ₃₀ each independently represent a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent, and R ₂₉ and R ₃₀ may be bonded to each other to form a ring.
Y represents a hydroxy group or chlorine.

General formula (6)

Examples of the "alkyl group" of an optionally substituted alkyl group, the "aryl group" of an optionally substituted aryl group, the "alkoxy group" of an optionally substituted alkoxy group, and the "aryloxy group" of an optionally substituted aryloxy group are the same as those exemplified for R ₁ to _R in general formula (4).

In the phosphorus compound represented by general formula (6), from the viewpoints of dispersibility and color characteristics, it is preferable that at least one of R ₂₉ and R ₃₀ is an aryl group which may have a substituent or an aryloxy group which may have a substituent, it is more preferable that both of R ₂₉ and R ₃₀ are an aryl group or an aryloxy group, and it is even more preferable that both of R ₂₉ and R ₃₀ are a phenyl group or a phenoxy group.

Representative examples of phosphorus compounds include the structures shown below, but the present invention is not limited to these.

<Method of synthesizing near-infrared absorbing dye>
The dye of the present invention is synthesized by reacting an aluminaphthalocyanine represented by general formula (4) with a polymer obtained by vinyl polymerization of a monomer containing a monomer represented by general formula (5) (hereinafter, also referred to as a polymer) or a phosphorus compound represented by general formula (6).
The aluminaphthalocyanine represented by the general formula (4) may be reacted with both the polymer and the phosphorus compound simultaneously or successively.

(Preparation of near-infrared absorbing dye)
The dye of the present invention can be synthesized, for example, by adding the aluminaphthalocyanine represented by the general formula (4), a polymer, or a phosphorus compound to an organic solvent and heating and stirring for several hours, then pouring the reaction solution into water, filtering the precipitated product, washing with water, and drying it.

Regarding the ratio of the aluminaphthalocyanine moiety and the polymer moiety, the molar ratio of the aluminaphthalocyanine moiety and the phosphate group derived from the monomer represented by general formula (5) in the polymer moiety is preferably aluminaphthalocyanine moiety/phosphate group derived from the monomer represented by general formula (5) = 0.5 to 1.5, and more preferably 0.8 to 1.2. When used at an appropriate ratio, the absorption due to the association of aromatic rings in the region of 650 nm to 700 nm becomes very weak, and the transmittance in the region of 480 nm to 650 nm, which is the region of high relative luminous efficiency, becomes high.

Regarding the ratio of the aluminaphthalocyanine moiety and the phosphorus compound moiety, the amount of the phosphorus compound represented by general formula (6) added is preferably 0.8 to 2.0 molar equivalents relative to the naphthalocyanine pigment, and more preferably 1.0 to 1.5 molar equivalents, from the viewpoints of dispersibility and color characteristics.

<Form of near infrared absorbing dye>
The dye of the present invention has high transmittance in the region of 480 nm to 650 nm, which is a region with high relative luminous efficiency, and is excellent in near-infrared absorption. This is particularly evident when the dye is applied to a substrate to form a coating. When the dye is applied to a substrate, it may be dissolved in a solvent or the like, or a dispersion may be prepared using a dispersant or the like. It may 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 spectrum to be adjusted appropriately. Examples of other near-infrared absorbing dyes include cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, aminium compounds, diimmonium compounds, croconium compounds, azo compounds, quinoid complex compounds, dithiol metal complex compounds, etc.

<Organic dyes with absorption in the range of 400 nm to 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. The near infrared absorbing dye of the present invention has strong absorption in the range of 700 nm to 900 nm, and therefore, by combining it with an organic dye having absorption in the range of 400 nm to 700 nm, it can be used as a near infrared absorbing composition (hereinafter also referred to as a visible light absorbing composition) that blocks light rays of 400 nm to 900 nm and transmits light of 900 nm or more. However, in this case, in order to ensure the transmittance at 900 nm, it is necessary to use a near infrared absorbing dye that has little absorption at 900 nm.

Examples of the organic dye having absorption in the range of 400 nm to 700 nm include at least a blue dye, a yellow dye, and further a purple dye or a red dye.
The organic colorant may be an organic pigment, and examples thereof include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, or polyazo, anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthranthrone, indanthrone, pyranthrone, or violanthrone, quinacridone pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, threne pigments, and metal complex pigments.
In addition, dyes may be used as the organic coloring matter, and examples of such dyes include anthraquinone dyes, monoazo dyes, disazo dyes, oxazine dyes, aminoketone dyes, xanthene dyes, quinoline dyes, and triphenylmethane dyes. When using dyes, it is effective to incorporate the dyes into the resin using the polar group of anionic dyes or cationic dyes to impart solubility in organic solvents.

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

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

Also, C.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, 129, 130, 13 0:1, 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, etc. can also be used.
(yellow pigment)
Examples of yellow pigments include C.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, and the like.

Yellow dyes include C.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, etc.

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

Purple dyes include C.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.

Also usable are C.I. Direct Violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97, and the like.
(Red pigment)
Examples of red pigments include C.I. 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, 1 01, 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, 21 Examples of the fluorine-containing compounds include fluorine-containing ...
As an orange pigment that functions similarly to a red pigment, for example, orange pigments such as C.I. Pigment Orange 36, 38, 43, 51, 55, 59, and 61 can be used.
Red dyes include C.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, 5 6, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76:1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131 , 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 249, 2 52, 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, etc.

Also, C.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, 11 6, 117, 120, 121, 122, 122:1, 124, 125, 127, 127:1, 127:2, 128, 129, 130, 132, 134, 135, 136, 137, 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238, etc. can also be used.

Although the above dyes have good spectral characteristics and excellent color development, they have problems with light resistance and heat resistance, and their characteristics may not be sufficient for use in near-infrared cut filters.
Therefore, in order to overcome these drawbacks, in the case of a basic dye, it is preferable to use an organic acid or perchloric acid to form a salt. As the organic acid, it is preferable to use an organic sulfonic acid or an organic carboxylic acid. Among them, it is preferable to use a naphthalenesulfonic acid such as Tobias acid or perchloric acid in terms of resistance.
It is also preferable to use a resin having an anionic group and form a salt therewith, and it is also preferable to use a resin having a betaine structure and form a salt therewith with an organic acid.
In the case of anionic dyes including acid dyes and direct dyes, it is preferable to use a compound having a cationic group or a resin having a cationic group as a counter ion to form a salt, from the viewpoints of heat resistance, light fastness, and solvent resistance.
It is also preferable to use the compound by forming a salt with a resin having a cationic group, and more preferably to use the compound by forming a salt with a resin having a cationic group on the side chain and an organic acid.
In addition, the anionic dye may be preferably used in the form of a sulfonamide compound by sulfonamidation in terms of durability.
For coating applications, it is preferable to use Pigment. Blue. 15:3 or Pigment. Blue. 15:6 as the blue pigment, Pigment. Yellow. 139 as the yellow pigment, and Pigment. Violet. 23 as the purple pigment. For molding applications, it is preferable to use Pigment. Blue. 15:3 or Pigment. Blue. 15:6 as the blue pigment, Pigment. Yellow. 147 as the yellow pigment, and Solvent. Red. 52 as the red pigment.

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

The content of the ultraviolet absorber is preferably 5 to 70% by mass, with the total of the photopolymerization initiator and the ultraviolet absorber being 100% by mass. This allows a high degree of compatibility between photosensitivity and resolution. Note that when the coloring composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

In addition, 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 photosensitive coloring composition. If the total content of the photopolymerization initiator and the ultraviolet absorber is less than the above, adhesion may weaken and pixel peeling may occur, and if it is more than the above, the sensitivity may be too high, resulting in poor resolution.

Benzotriazole organic compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, a mixture of octyl-3[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 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-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and straight chain alkyl ester compound, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol.

Commercially available products include BASF's "TINUVIN P", "TINUVIN PS", "TINUVIN 109", "TINUVIN 234", "TINUVIN 326", "TINUVIN 328", "TINUVIN 329", "TINUVIN 360", "TINUVIN 384-2", "TINUVIN 900", "TINUVIN 928", "TINUVIN 99-2", and "TINUVIN 1130", ADEKA's "ADEKA STAB LA-29", and Otsuka Chemical's "RUNA-93".

Examples of triazine-based organic compounds include 2-[4,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl-glycidic acid ester, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3-5-triazine, etc.

Commercially available products include "KEMISORB 102" manufactured by Chemipro Chemicals, "TINUVIN 400", "TINUVIN 405", "TINUVIN 460", "TINUVIN 477-DW", "TINUVIN 479", and "TINUVIN 1577" manufactured by BASF, "ADEKA STAB LA-46" and "ADEKA STAB LA-F70" manufactured by ADEKA, and "CYASORB UV-1164" manufactured by Sun Chemical.

Examples of benzophenone-based organic compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3H2O, 2-hydroxy-4-n-octoxybenzophenone, and 2,2-dihydroxy-4-methoxybenzophenone.

Commercially available products include "KEMISORB 10," "KEMISORB 11," "KEMISORB 11S," "KEMISORB 12," and "KEMISORB 111" manufactured by Chemipro Chemicals, "SEESORB 101" and "SEESORB 107" manufactured by Shipro Chemicals, and "ADEKA STAB 1413" manufactured by ADEKA Corporation.

<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 preferably 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 coating having a thickness of 2 μm is formed. Examples of the binder resin include thermoplastic resins and photosensitive resins. In addition, the coating formed from the near-infrared absorbing composition is preferably 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 providing a polymerizable unsaturated group.

Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane 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 alkali-soluble resins include resins having acidic groups such as carboxyl groups and sulfonic groups. Examples of alkali-soluble resins include acrylic resins having acidic groups, α-olefin/maleic acid (anhydride) copolymers, styrene/styrene sulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, and isobutylene/maleic acid (anhydride) copolymers. Among these, acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers are preferred in terms of good transparency, and acrylic resins having acidic groups are more preferred.

Examples of photosensitive resins include resins in which a polymer having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups is reacted with a (meth)acrylic compound having reactive substituents such as an isocyanate group, an aldehyde group, and an epoxy group, or with cinnamic acid, to introduce photocrosslinkable groups such as (meth)acryloyl groups and styryl groups into the polymer. Other examples include resins in which 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 a hydroxyalkyl (meth)acrylate.

The photosensitive alkali-soluble resin is preferably a resin synthesized by, for example, the method (i) or (ii) below. This further improves the crosslink density of the coating formed from the photosensitive coloring composition by light irradiation.

[Method (i)]
In the method (i), for example, a polymer of an epoxy group-containing monomer and other monomers is first synthesized, and then a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to obtain an alkali-soluble resin (C2).

Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

Examples of monocarboxyl group-containing monomers include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc.

The monomers and polybasic acid anhydrides can be used alone or in combination of two or more types.

In addition, a method similar to method (i) can be used in which, for example, a carboxyl group-containing monomer and other monomers are synthesized to produce a polymer. Then, an epoxy group-containing monomer is added to some of the carboxyl groups of the polymer to obtain a photosensitive alkali-soluble resin.

[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, and then the hydroxyl group of the polymer is reacted with an isocyanate group of an isocyanate group-containing monomer.

Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to the above-mentioned hydroxyalkyl (meth)acrylates, and (poly)ester mono(meth)acrylates obtained by addition of (poly)γ-valerolactone, (poly)ε-caprolactone, and/or (poly)12-hydroxystearic acid. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred. In terms of photosensitivity, glycerol mono(meth)acrylate is also preferred.

Examples of monomers 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, and more preferably 7,000 to 50,000. When used as an alkali-soluble resin, a weight average molecular weight of 5,000 to 100,000 makes it difficult for the film to be reduced during development, and improves the ability to remove non-pixel areas during development. The number average molecular weight (Mn) is preferably 2,500 to 40,000. The Mw/Mn value is preferably 10 or less. Mw and Mn are polystyrene-equivalent molecular weights measured using a gel permeation chromatography (GPC) device HLC-8220GPC (manufactured by Tosoh Corporation) with two TSK-GEL SUPER HZM-N columns connected in series and tetrahydrofuran as the solvent.

The acid value of the alkali-soluble resin is preferably 20 to 300 mg KOH/g. A moderate acid value improves developability.

The amount of binder resin used is preferably 20 to 500 parts by weight per 100 parts by weight of the dye of the present invention. Using an appropriate amount makes it easier to form a coating.

<Thermosetting Compound>
The near infrared absorbing composition preferably uses a binder resin and a thermosetting compound in combination, which improves the crosslink density during the heating process and thereby improves heat resistance.

The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin.
Examples of the thermosetting compound include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

Epoxy compounds include, for example, polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, Examples of such epoxy resins include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, α,α,α',α'-benzene dimethanol, biphenyl dimethanol, α,α,α',α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethyl biphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, glycidyl amine epoxy resins, and glycidyl ester epoxy resins.

The amount of the thermosetting compound is preferably 0.5 to 300 parts by weight, and more preferably 1.0 to 50 parts by weight, per 100 parts by weight of the dye of the present invention. Using an appropriate amount will provide appropriate heat resistance.

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

The amount of the curing agent and curing accelerator used is preferably, for example, 0.01 to 15 parts by mass each per 100 parts by mass of the thermosetting compound.

<Organic Solvent>
The near infrared absorbing composition may contain an organic solvent, which makes it easier to adjust the viscosity of the composition.

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

These organic solvents can be used alone or in combination of two or more. When using a mixed solvent of two or more, it is preferable that the above preferred organic solvents are 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 and a binder resin, etc., in a solvent, etc., or may be dispersed using a dispersant, etc. Also, the near infrared absorbing composition can be produced by finely dispersing the composition using a dispersant and a dispersion assistant (e.g., a dye derivative) using various dispersing means, such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor.

When dispersing the near-infrared absorbing dye, a dispersant (e.g., a resin-type dispersant), a dispersion aid (e.g., a surfactant), etc. can be used as appropriate. Dispersion aids are excellent at dispersing near-infrared absorbing dyes and have a large effect of preventing re-aggregation after dispersion, so when the near-infrared absorbing dye is dispersed using a dispersion aid, a near-infrared cut filter with high transmittance in the visible range can be obtained.

<Dispersant>
The near infrared absorbing composition of the present invention may contain a dispersant to disperse the near infrared absorbing composition. Examples of the dispersant include a resin-type dispersant.
The resin type dispersant has a dye affinity site that has the property of adsorbing to the dye, and a relaxation site that has affinity with materials other than the dye. Examples of the resin type dispersant include polyurethane, polyacrylate and other polycarboxylate esters, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylate esters, and modified products thereof, oil-based dispersants such as amides formed by the reaction of poly(lower alkylene imine) with polyesters having free carboxyl groups and salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, and phosphate esters.

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

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, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, and Anti-Terra-U, 203, 204, BYK-P104, P104S, 220S, 6919, Lactimon, Lactimon-WS, Bykumen, etc. manufactured by Lubrizol Japan Co., Ltd. SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 440 manufactured by BASF Japan Ltd. 2, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd.

<Dispersion aid>
The near infrared absorbing composition of the present invention may contain a dispersing aid to disperse the near infrared absorbing composition. Examples of the dispersing aid include a surfactant, a resin-type dispersing agent, and a dye derivative.

Examples of surfactants include anionic surfactants such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; and amphoteric surfactants such as alkyl betaines such as alkyl dimethylaminoacetate betaines and alkyl imidazolines. These can be used alone or in combination of two or more.

When a resin-type dispersant or surfactant is added, the amount is preferably 0.1 to 55 parts by weight, and more preferably 0.1 to 45 parts by weight, per 100 parts by weight of colorant. If the amount of resin-type dispersant or surfactant is less than 0.1 parts by weight, it is difficult to obtain the desired effect, and if the amount is more than 55 parts by weight, the excess dispersant may adversely affect the dispersion.

The dye derivatives include compounds in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent has been introduced into an organic pigment, an anthraquinone, an acridone, or a triazine. For example, those described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, and JP-B-5-9469 can be used, and these can be used alone or in a mixture of two or more kinds.

The 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, per 100 parts by weight of the colorant, from the viewpoint of improving the dispersibility of the added colorant. Also, 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, per 100 parts by weight of the colorant.

<Photopolymerizable Compound>
The near-infrared absorbing composition may contain a photopolymerizable compound and a photopolymerization initiator, which provides photosensitivity and allows the composition to be used as a photosensitive composition for a near-infrared cut filter.

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

Examples of monomers and oligomers that harden when exposed to ultraviolet light or heat to produce a transparent resin include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, and bisphenol A diglycidyl. Examples of the acrylates include, but are not limited to, ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, ester acrylate, (meth)acrylic acid ester of methylol melamine, epoxy (meth)acrylate, urethane acrylate, and various other acrylates and methacrylates, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

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

The amount of the photopolymerizable compound is preferably 5 to 400 parts by weight, and more preferably 10 to 300 parts by weight, per 100 parts by weight of the dye of the present invention.

<Photopolymerization initiator>
Examples of the photopolymerization initiator include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one;
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzil dimethyl ketal;
Benzophenone-based compounds such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone;
Thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2,4-diethylthioxanthone;
Triazine-based compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;
Oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], or O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine;
Phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide;
Quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone;
Borate-based compounds;
Carbazole compounds;
Imidazole compounds;
Alternatively, titanocene compounds and the like may be used.

Photopolymerization initiators can be used alone or in combination of two or more types.

The amount of the photopolymerization initiator is preferably 2 to 200 parts by weight, and more preferably 3 to 150 parts by weight, per 100 parts by weight of the dye of the present invention.

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

Sensitizers include, for example, chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. Examples of such compounds include phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalylporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 4,4'-diethylaminobenzophenone.

Sensitizers can be used alone or in combination of two or more types.

The amount of sensitizer to be added is preferably 3 to 60 parts by weight, and more preferably 5 to 50 parts by weight, per 100 parts by weight of photopolymerization initiator.

<Multifunctional thiol>
The near infrared absorbing composition can contain a polyfunctional thiol as a chain transfer agent.
The polyfunctional thiol may be any compound having two or more thiol groups, and examples thereof include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris(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.

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

The content of the polyfunctional thiol is preferably 0.1 to 30 mass% and more preferably 1 to 20 mass% based on 100 mass% of the nonvolatile content of the near-infrared absorbing composition. If an appropriate amount is contained, it is easy to obtain a moderately crosslinked coating.

<Antioxidants>
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 during the heating process, thereby increasing the transmittance of the coating film.

In the present invention, an "antioxidant" is a compound that has an ultraviolet absorbing function, a radical scavenging 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, salicylic acid ester-based, and triazine-based compounds.

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

Antioxidants can be used alone or in combination of two or more types.

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

<Amine compounds>
The near infrared absorbing composition may contain an amine compound for reducing dissolved oxygen.
Examples of the amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine.

<Leveling Agent>
The near infrared absorbing composition may contain a leveling agent to improve the leveling properties of the composition during coating. The leveling agent is preferably, for example, dimethylsiloxane having a polyether structure or polyester structure in the main chain. Examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Co., Ltd. and BYK-333 manufactured by BYK-Chemie. Examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie. Dimethylsiloxane 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 in 100% by mass of the nonvolatile content of the near infrared absorbing composition.

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

The bonding form of the polyalkylene oxide units with the dimethylpolysiloxane may be any of a pendant type in which the polyalkylene oxide units are bonded to the repeating units of the dimethylpolysiloxane, a terminal modified type in which the polyalkylene oxide units are bonded to the terminals of the dimethylpolysiloxane, and a linear block copolymer type in which the polyalkylene oxide units are bonded alternately and repeatedly to the dimethylpolysiloxane. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Dow Corning Toray Co., Ltd., and examples of such products include FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, and FZ-2207.

The leveling agent may be supplemented with an anionic, cationic, nonionic, or amphoteric surfactant. Two or more types of surfactants may be mixed together.

Examples of anionic surfactants that are added to the leveling agent as an auxiliary include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, etc.

Examples of cationic surfactants that are added supplementarily to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples of nonionic surfactants that are added supplementarily to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; alkyl betaines such as alkyl dimethylamino acetate betaine, amphoteric surfactants such as alkyl imidazolines, and fluorine-based and silicone-based surfactants.

<Other additives>
The near infrared absorbing composition may contain a storage stabilizer to stabilize the viscosity of the composition over time, and may also contain an adhesion improver such as a silane coupling agent to improve adhesion to a substrate.

Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites. The content of the storage stabilizer is preferably 0.1 to 10 parts by mass per 100 parts by mass of the dye of the present invention.

Examples of adhesion improvers include vinyl silanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth)acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane. Examples of the silane coupling agent include epoxy silanes such as N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltriethoxysilane, and 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, relative to 100 parts by mass of the dye of the present invention.

<Removal of coarse particles>
It is preferable to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust from the near infrared absorbing composition by means of centrifugation, a sintered filter, a membrane filter, etc. In this way, it is preferable that the near infrared absorbing composition does not substantially contain particles of 0.5 μm or more, and 0.3 μm or less is preferable.

<Molding applications>
The near infrared absorbing dye of the present invention can also be used in molding applications. The molding applications are applications in which films or three-dimensional objects are produced by methods other than coating.
When the near-infrared absorbing composition is used for molding purposes, it is preferably a melt-kneaded product of a near-infrared absorbing dye and a thermoplastic resin that 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, and polyetherimide resin.

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

Examples of the carboxylic acid component include adipic acid, sebacic acid, isophthalic acid, terephthalic acid, etc. The carboxylic acid component may be a compound having three or more carboxyl groups.
The compound (Am) having two or more amino groups may be, for example, a known compound, and examples thereof include aliphatic polyamines such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and triethylenetetramine; aliphatic polyamines including alicyclic polyamines such as isophoronediamine and dicyclohexylmethane-4,4'-diamine; aromatic polyamines such as phenylenediamine and xylylenediamine; and diamino alcohols such as 1,3-diamino-2-propanol, 1,4-diamino-2-butanol, 1-amino-3-(aminomethyl)-3,5,5-trimethylcyclohexane-1-ol, 4-(2-aminoethyl)-4,7,10-triazadecan-2-ol, and 3-(2-hydroxypropyl)-O-xylene-α,α'-diamine.
Commercially available polyamide resins include, for example, nylon 6 (manufactured by Toray Industries, Inc.), nylon 66 (manufactured by Toray Industries, Inc.), nylon 610, and the like.

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

Examples of aromatic dihydroxy compounds include bis(hydroxyaryl)alkanes such as 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-3,5-dibromophenyl)propane, and 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane; bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, etc. Also, piperazine, dipiperidyl hydroquinone, resorcin, and 4,4'-dihydroxydiphenyls may be used in combination.

Examples of the carbonate precursor include phosgene, diaryl carbonates such as diphenyl carbonate and ditolyl 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, and more preferably 16,000 to 27,000. Note that the viscosity average molecular weight in this 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 resins include, for example, Iupilon H-4000 (manufactured by Mitsubishi Engineering Plastics Corporation, viscosity average molecular weight 16,000), Iupilon S-3000 (manufactured by Mitsubishi Engineering Plastics Corporation, viscosity average molecular weight 23,000), and Iupilon E-2000 (manufactured by Mitsubishi Engineering Plastics Corporation, viscosity average molecular weight 27,000).

(Cycloolefin resin)
Cycloolefin resins are amorphous resins having an alicyclic structure in the main chain and/or side chain. Examples of the alicyclic structure include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrogenated versions of these. Among these, norbornene polymers are preferred because of their excellent moldability and transparency. Examples of norbornene monomers include bicyclo[2.2.1]hept-2-ene (common name: norbornene), tricyclo[4.3.0.1 ^2,5 ]deca-3,7-diene (common name: dicyclopentadiene), 7,8-benzotricyclo[4.3.0.1 ^2,5 ]deca-3-ene (common name: methanotetrahydrofluorene), and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene (common name: tetracyclododecene).
Commercially available cycloolefin resins include, for example, Topas (manufactured by Polyplastics Co., Ltd.) and APEL (manufactured by Mitsui Chemicals, Inc.).

(Polyetherimide resin)
Polyetherimide resins are amorphous resins with a glass transition temperature of over 180° C., and have good transparency, high strength, high heat resistance, high elastic modulus, and wide range of chemical resistance, which has led to their widespread use in a variety of applications such as automobiles, telecommunications, aerospace, electrical/electronics, transportation, and healthcare.
One process for the production of polyetherimide resins is by polymerization of an alkali metal salt of a dihydroxy aromatic compound, such as bisphenol A disodium salt (BPA.Na2), with a bis(halophthalimide). The molecular weight of the resulting polyetherimide resin can be controlled in two ways. The first method is to use a molar excess of the bis(halophthalimide) relative to the alkali metal salt of the dihydroxy aromatic compound. The second method is to prepare the bis(halophthalic anhydride) in the presence of a monofunctional compound, such as phthalic anhydride, which forms an end-capping agent. The phthalic anhydride reacts with a portion of the organic diamine to form the monohalo-bis(phthalimide). The monohalo-bis(phthalimide) serves as an end-capping agent in the polymerization step by reaction with the phenoxide end groups in the growing polymer chain.
An example of a commercially available polyetherimide resin is ULTEM (manufactured by Saudi Basic Industries Corporation).

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

The near-infrared absorbing composition may contain additives other than the near-infrared absorbing pigment and the thermoplastic resin. Examples of additives include ultraviolet absorbers, light stabilizers, antioxidants, colorants, and dispersants. These additives are compounds known for use in molded articles.

<Additives used in molding applications>
The ultraviolet absorbing agent is used to impart ultraviolet resistance to the molded article. Examples of the ultraviolet absorbing agent include benzophenone-based, benzotriazole-based, triazine-based, and salicylic acid ester-based agents. The content of the ultraviolet absorbing agent is preferably 0.01 to 5% by mass in 100% by mass of the composition.

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

Antioxidants are used to reduce deterioration of molded articles when they are exposed to natural or artificial light sources and become hot. Preferred antioxidants include monophenol-based, bisphenol-based, polymeric phenol-based, sulfur-based, and phosphoric acid-based antioxidants. The content of the antioxidant is preferably 0.01 to 5% by mass in 100% by mass of the composition.

The dispersant is used to disperse the near-infrared absorbing pigment more uniformly in the molded product. For example, polyolefin wax, fatty acid wax, fatty acid ester wax, partially saponified fatty acid ester wax, saponified fatty acid wax, etc. are preferred dispersants. The content of the dispersant is preferably 50 to 250 parts by mass per 100 parts by mass of the near-infrared absorbing pigment.

<Preparation of near-infrared absorbing composition for molding>
The near infrared absorbing composition can be produced by melt-kneading the near infrared absorbing pigment and the 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 varies depending on the type of thermoplastic resin. If forced to give, the upper limit is preferably 500°C or lower, more preferably 450°C or lower. In addition, the upper limit must be lower than the sublimation temperature or decomposition temperature of the near infrared absorbing pigment of the present invention.

Examples of melt kneading devices include single-screw kneading extruders, twin-screw kneading extruders, and tandem twin-screw kneading extruders.

The near infrared absorbing composition for molding is preferably prepared as a so-called master batch. When a master batch is prepared and then melt-kneaded with a diluent resin (thermoplastic resin) to prepare a molded body, the near infrared absorbing pigment of the present invention can be easily dispersed uniformly in the molded body and the aggregation of the near infrared absorbing pigment can be suppressed, compared with a molded body prepared without using a master batch. This improves the transparency of the molded body. The master batch is preferably prepared by molding into pellets using a pelletizer after the melt-kneading.
When prepared as a master batch, the content of the near infrared absorbing pigment is preferably from 0.01 to 20% by mass, and more preferably from 0.05 to 2% by mass, based on 100% by mass of the composition.

The near-infrared cut filter of the present invention preferably has a coating formed from a near-infrared absorbing composition, and preferably further has a substrate. The coating includes a film formed by coating, and a molded body produced by molding. The uses are described below.

<Applications other than molding>
(Optical recording medium)
Near-infrared cut filters can be used as optical recording media. When a near-infrared cut filter is irradiated with near-infrared light, the crystalline state of the dye changes, and the refractive index of the coating or molded body changes. This principle is used in recording media such as optical disks.

(Laser welding materials/Laser marking materials)
Near infrared cut filters can be used in laser welding or laser marking materials.
When a near-infrared cut filter is irradiated with a laser with a wavelength that is absorbed by the near-infrared absorbing dye, the dye absorbs the laser light and generates heat, causing the resin to melt and carbonize. When melted, it can be fused to other resins, making marking possible.

(Optical Filter)
The near-infrared cut filter can be used as an optical filter. For example, a digital camera recognizes color by separating the light it receives when capturing an image using red, green, and blue filters and sending the separated light to a photodiode that converts the light into an electrical signal. However, the photodiode also reacts to near-infrared light and converts it into an electrical signal, so a filter that blocks this is necessary. The near-infrared cut filter of the present invention can be used as a near-infrared cut filter.

(Biometric sensor)
Near-infrared cut filters can be used in sensors for biometric authentication (fingerprint authentication or vein authentication), or in touch sensors and touch panels that incorporate such sensors.
For example, biometric authentication functions such as fingerprint authentication and finger vein authentication are installed for security purposes in smartphones, tablet PCs, bank ATMs, multimedia terminals, etc. Fingerprint authentication technology used in smartphones and tablet PCs in particular has been developing rapidly, and as the authentication range expands to the screen size (full screen), fingerprint authentication sensors built into displays such as organic electroluminescence displays and liquid crystal displays have been developed.
However, most fingerprint sensors built into displays use an optical system that shines various light sources inside the display onto the fingerprint and senses the reflected light, so if unauthorized external light (strong light with a wide range of wavelengths, such as sunlight or LED lighting) enters the sensor, it causes noise when capturing an image, which makes the accuracy somewhat unreliable for outdoor use. The same is true for finger vein authentication in bank ATMs and multimedia terminals, and in stores with strong lighting or good sunlight, measures are taken to block external light, such as putting a cover over the device.
The near-infrared cut filter of the present invention is effective in solving these problems by absorbing and preventing unauthorized external light from being incident on the sensor.
For example, when used in smartphones or tablet computers, when they are set on the front of the panel, they must also have a good design, and near-infrared cut filters have the advantage of being suitable for use due to their high transmittance in the visible range.In addition, near-infrared cut filters have excellent heat resistance, so they can also be used favorably in the manufacturing process of sensors, or touch sensors and touch panels that incorporate such sensors.

(display)
The near-infrared cut filter can be incorporated into a display. Specifically, a liquid crystal display with a touch panel function such as an electronic whiteboard can be mentioned. This liquid crystal display with a touch panel function has three functions: display, writing, and storage. The touch panel built into this liquid crystal display also uses optical methods such as an infrared scanning method and an infrared projection method, and the noise caused by the above-mentioned external light is an issue. Since liquid crystal displays with a touch panel function are often used in schools and the like, accuracy and good response to touch are important. By incorporating the near-infrared cut filter of the present invention into a display, it is preferable because it can cut out external light that becomes noise.
The near-infrared cut filter of the present invention can also be preferably used as an anti-reflection film for various displays using liquid crystal, organic EL, Mini-LED, and Micro-LED. By suppressing the reflection of not only visible light but also light in the near-infrared region, it has the advantage of being able to make the black display on the display darker. Since the near-infrared cut filter of the present invention has excellent heat resistance, it can also be preferably used in terms of the resistance required for the process of display manufacturing.

<Near-infrared cut filter that transmits 900 nm (visible light absorbing filter)>
LEDs with wavelengths of 850 nm, 870 nm, 900 nm, 940 nm, etc. are becoming widespread and are being used for distance measurement in autonomous driving, biometric authentication (fingerprint authentication, iris authentication, face authentication, vein authentication, etc., or a combination of these), and light detection in various sensors. However, since light rays of all wavelengths, including ultraviolet light, visible light, and near-infrared light, exist in the atmosphere, a filter is required to block light of wavelengths other than those to be detected. Therefore, by combining a near-infrared absorbing dye that absorbs light in the 700 to 900 nm range with a dye that absorbs visible light, an ultraviolet absorber, etc., it is possible to transmit only light with wavelengths longer than the absorption wavelength of the near-infrared absorbing dye, and block light with wavelengths shorter than that. The near-infrared cut filter (hereinafter also referred to as a visible light absorbing filter) using the visible light absorbing composition of the present invention absorbs light of 700 nm to 900 nm, and particularly absorbs light of 700 to 800 nm well, and therefore, in order to block visible light of shorter wavelengths than this, by combining it with an organic dye having absorption at 400 nm to 700 nm, it is possible to block light from the visible light region to around 800 nm.Therefore, it can be used as a visible light absorbing filter that transmits light of 900 nm and blocks light of shorter wavelengths than that as noise, for example.
<Method of manufacturing visible light absorbing filter>
The visible light region absorbing composition can be prepared by coating various plastic substrates or glass substrates, kneading into plastic materials and molding, etc. As long as a film that transmits infrared rays is formed, it can be prepared by various methods. Furthermore, the near-infrared cut filter of the present invention can be used as a near-infrared cut filter for solid-state imaging devices by patterning on a photodiode using a photolithography method using the photosensitive composition for near-infrared cut filters of the present invention. The solid-state imaging device in which a near-infrared cut filter is prepared by a photolithography method will be described in detail below.

<Solid-state imaging device having a visible light absorbing filter layer>
A solid-state imaging element having a near-infrared filter layer will be described. A typical infrared sensor has a photodiode and a visible light absorbing filter layer on the photodiode. There are no particular limitations on the structure as long as the structure functions as a solid-state imaging element. For example, the following structure can be mentioned.

The substrate has a plurality of photodiodes constituting the light receiving area of a solid-state imaging device (CCD sensor, CMOS sensor, etc.) and transfer electrodes made of polysilicon or the like, a light shielding film made of tungsten or the like with only the light receiving parts of the photodiodes open on the photodiodes and transfer electrodes, a device protection film made of silicon nitride or the like formed on the light shielding film so as to cover the entire light shielding film and the light receiving parts of the photodiodes, and the near-infrared cut filter of the present invention on the device protection film.

Furthermore, the device may have a focusing means (e.g., a microlens, etc.; the same applies below) on the device protection layer and below the near-infrared cut filter (the side closer to the substrate), or may have a focusing means on a visible light absorbing filter.

The organic CMOS sensor is composed of a thin panchromatic organic photoelectric conversion film as a photoelectric conversion layer and a CMOS signal readout substrate, and has a two-layer hybrid structure in which the organic material captures light and converts it into an electrical signal, while the inorganic material takes on the role of extracting the electrical signal to the outside. In principle, the aperture ratio for incident light can be 100%. The organic photoelectric conversion film is a structure-free continuous film that can be laid on the CMOS signal readout substrate, so it does not require expensive microfabrication processes and is suitable for pixel miniaturization.

The near-infrared cut filter segment for a solid-state imaging element according to the present invention can be formed using any known method without any particular limitation. However, since the filter segments of the imaging element are very fine, ranging from submicrons to several tens of microns, it is preferable to use optical lithography.
When the near-infrared cut filter segment is formed on a corresponding photoelectric conversion element, a negative resist layer is formed from a negative photosensitive green composition, and the thickness of the negative resist layer in this case is set in the range of 0.1 to 3.0 μm.

The surface of the negative resist layer is exposed to a pattern using a photomask, with multiple portions corresponding to the multiple photoelectric conversion elements to be formed. Typically, the photomask has dimensions 4 to 5 times larger than the dimensions of the pattern to be actually formed, and is reduced to 1/4 to 1/5 during pattern exposure.

A typical photomask is a 4-5x reticle, which has a pattern that is 4-5 times larger than the dimensions of the pattern to be exposed on the surface of the negative resist layer. Then, using a stepper exposure device (not shown), the photomask pattern is reduced to 1/4-1/5 and exposed onto the surface of the negative resist layer.

Following the exposure step, an alkaline development process (development step) is performed, which dissolves the uncured parts after exposure into the developer, leaving only the photocured parts. This development step allows the formation of a patterned coating made of near-infrared cut filter segments.

The development method may be any of a dip method, a shower method, a spray method, a paddle method, etc., and these may be combined with a swing method, a spin method, an ultrasonic method, etc.
It is also possible to prevent uneven development by pre-wetting the surface to be developed with water or the like before contacting the developing solution. As the developing solution, an organic alkaline developing solution that does not cause damage to the underlying circuitry is preferable. The developing temperature is usually 20 to 30°C, and the developing time is 20 to 90 seconds.

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

As the developer, an alkaline aqueous solution in which the alkaline agent is diluted with pure water to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, is preferably used. When using a developer made of such an alkaline aqueous solution, after development, the substrate is generally washed with pure water to remove excess developer, and then dried.

Finally, the filter segment thus formed is subjected to a hardening treatment.
In the method for producing a solid-state imaging device, after the above-mentioned colored layer forming step, exposure step, and development step are performed, a curing step of curing the formed colored pattern by post-heating (post-baking) or post-exposure may be included as necessary. Post-baking is a heating treatment after development to complete the curing, and is usually a thermal curing treatment at 100 to 270° C. When light is used, it can be performed by g-rays, h-rays, i-rays, excimer lasers such as KrF and ArF, electron beams, X-rays, etc., but it is preferable to perform it at a low temperature of about 20 to 50° C. using an existing high-pressure mercury lamp, and the irradiation time is 10 to 180 seconds, preferably 30 to 60 seconds.
In the case where post-exposure and post-heating are used in combination, it is preferable to carry out post-exposure first.

The near-infrared cut filter is produced by the near-infrared cut layer forming process, the exposure process, and the development process (and, if necessary, the curing process) described above.

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

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Note that "parts" means "parts by mass" and "%" means "% by mass."

In the following, "PGMAc" means propylene glycol monomethyl ether acetate, "PGME" means propylene glycol monomethyl ether, "Aronix M-402" means dipentaerythritol hexaacrylate, and "OXE-02" means ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime).

(Method of Identifying Aluminaphthalocyanine Pigments and Near-Infrared Absorbing Dyes)
The aluminaphthalocyanine dye and near infrared absorbing dye used in the present invention were identified by MALDI TOF-MS spectroscopy. The MALDI TOF-MS spectroscopy was performed using a Bruker Daltonics MALDI mass spectrometer AutoflexIII, and the compounds were identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

(Acid value of resin type dispersant and binder resin)
The acid values of the resin-type dispersant and the binder resin were determined by potentiometric titration using a 0.1 N potassium hydroxide-ethanol solution. The acid values of the resin and the resin-type dispersant indicate the acid values of the non-volatile components.

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

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

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

<Production of near infrared absorbing dye>
(Synthesis of naphthalocyanine pigment (A-1))
In a reaction vessel, 1135 parts of quinoline, 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol, and 40 parts of anhydrous aluminum chloride were mixed and stirred, and the mixture was heated and refluxed at 136°C for 5 hours. The reaction solution was cooled to 30°C while stirring, and poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water while stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 159 parts of chloroaluminum naphthalocyanine represented by the following chemical formula (1-1). As a result of mass spectrometry and elemental analysis by TOF-MS, 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.

Chloroaluminum Naphthalocyanine Pigment (1-1)

Next, 10 parts of the above chloroaluminum naphthalocyanine was added to 100 parts of concentrated sulfuric acid in a reaction vessel in an ice bath, and the mixture was stirred for 1 hour. Subsequently, this sulfuric acid solution was poured into 1,000 parts of cold water at 3°C, and the resulting precipitate was filtered, washed with water, washed with a 2.5% aqueous sodium hydroxide solution, and washed with water, and then dried to obtain 8 parts of naphthalocyanine pigment (A-1). As a result of mass analysis and elemental analysis using TOF-MS, the compound obtained was identified by the agreement between the molecular ion peak in the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 884.74.

Naphthalocyanine pigment (A-1)

Synthesis of naphthalocyanine pigment (A-2) Instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol and 1135 parts of quinoline used in the synthesis of naphthalocyanine pigment (A-1), 178 parts of 2,3-dicyanonaphthalene, 890 parts of n-amyl alcohol, and 137 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) were used, respectively, and the same operation as in the synthesis of naphthalocyanine pigment (A-1) was performed to obtain 125 parts of naphthalocyanine pigment (A-2). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation were consistent, and the obtained compound was identified. The molecular weight was 756.75.

Naphthalocyanine pigment (A-2)

(Synthesis of naphthalocyanine pigment (A-3))
100 parts of the above naphthalocyanine pigment (A-2) was added to 1500 parts of concentrated sulfuric acid under 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 was poured into 9000 parts of cold water at 3°C, and the resulting precipitate was filtered, washed with water, washed with a 1% aqueous sodium hydroxide solution, and washed with water, and then dried to obtain 170 parts of naphthalocyanine pigment (A-3). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. When the number of bromine substitutions was calculated for the obtained naphthalocyanine pigment (A-3), it was found to be 8.4 on average, and a peak corresponding to the same molecular weight was also confirmed from the mass spectrum, and the target compound was identified. The molecular weight was 1419.51.

Naphthalocyanine pigment (A-3)

(Synthesis of naphthalocyanine pigment (A-4))
The same procedure as in the synthesis of naphthalocyanine pigment (A-1) was carried out, except that 339 parts of 4,9-dibutoxy-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (A-1), to obtain 237 parts of naphthalocyanine pigment (A-4). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1333.59.

Naphthalocyanine pigment (A-4)

(Synthesis of naphthalocyanine pigment (A-5))
The same procedure as in the synthesis of naphthalocyanine pigment (A-1) was carried out, except that 264 parts of 4,9-dichloro-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (A-1), to obtain 185 parts of naphthalocyanine pigment (A-5). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1032.31.

Naphthalocyanine pigment (A-5)

(Synthesis of naphthalocyanine pigment (A-6))
The same procedure as in the synthesis of naphthalocyanine pigment (A-1) was carried out, except that 232 parts of 5-nitro-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (A-1), to obtain 162 parts of naphthalocyanine pigment (A-6). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 905.08.

Naphthalocyanine pigment (A-6)

(Synthesis of naphthalocyanine pigment (A-7))
The same procedure as in the synthesis of naphthalocyanine pigment (A-1) was carried out, except that 245 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-6,7-dicarbonitrile was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (A-1), to obtain 171 parts of naphthalocyanine pigment (A-7). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 956.82.

Naphthalocyanine pigment (A-7)

(Synthesis of naphthalocyanine pigment (A-8))
The same procedure as in the synthesis of naphthalocyanine pigment (A-1) was carried out, except that 239 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-5-carboxylic acid was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (A-1), to obtain 167 parts of naphthalocyanine pigment (A-8). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 932.79.

Naphthalocyanine pigment (A-8)

(Synthesis of naphthalocyanine pigment (A-9))
The same procedure as in the synthesis of naphthalocyanine pigment (A-1) was carried out, except that 275 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-5-sulfonic acid was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (A-1), to obtain 192 parts of naphthalocyanine pigment (A-9). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1077.0.

Naphthalocyanine pigment (A-9)

(Synthesis of naphthalocyanine pigment (A-10))
The same procedure as in the synthesis of naphthalocyanine pigment (A-1) was carried out, except that 271 parts of 4-phenyl-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (A-1), to obtain 190 parts of naphthalocyanine pigment (A-10). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1061.13.

Naphthalocyanine pigment (A-10)

(Synthesis of naphthalocyanine pigment (A-11))
The same procedure as in the synthesis of naphthalocyanine pigment (A-1) was carried out, except that 223 parts of 6,7-dimethyl-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (A-1), to obtain 156 parts of naphthalocyanine pigment (A-11). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 868.96.

Naphthalocyanine pigment (A-11)

(Synthesis of naphthalocyanine pigment (A-12))
The same procedure as in the synthesis of naphthalocyanine pigment (A-1) was carried out, except that 281 parts of 5-(neopentyloxy)-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (A-1), to obtain 197 parts of naphthalocyanine pigment (A-12). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1101.28.

Naphthalocyanine pigment (A-12)

(Synthesis of naphthalocyanine pigment (A-13))
The same procedure as in the synthesis of naphthalocyanine pigment (A-1) was carried out, except that 287 parts of 6-phenoxy-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (A-1), to obtain 201 parts of naphthalocyanine pigment (A-13). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1125.13.

Naphthalocyanine pigment (A-13)

(Synthesis of naphthalocyanine pigment (A-14))
The same procedure as in the synthesis of naphthalocyanine pigment (A-1) was carried out, except that 269 parts of 6-(isopropylthio)-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (A-1), to obtain 188 parts of naphthalocyanine pigment (A-14). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1053.33.

Naphthalocyanine pigment (A-14)

(Synthesis of naphthalocyanine pigment (A-15))
The same procedure as in the synthesis of naphthalocyanine pigment (A-1) was carried out, except that 303 parts of 6-(phenylthio)-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (A-1), to obtain 212 parts of naphthalocyanine pigment (A-15). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1189.39.

Naphthalocyanine pigment (A-15)

(Synthesis of naphthalocyanine pigment (A-16))
The same operation as in the synthesis of naphthalocyanine pigment (A-1) was carried out, except that 266 parts of N-tert-butyl-1,3-diimino-2,3-dihydro-1H-benzo[f]isoindol-6-amine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindol-4,9-diol used in the synthesis of naphthalocyanine pigment (A-1), to obtain 186 parts of naphthalocyanine pigment (A-16). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1041.23.

Naphthalocyanine pigment (A-16)

(Synthesis of naphthalocyanine pigment (A-17))
The same operation as in the synthesis of naphthalocyanine pigment (A-1) was carried out, except that 300 parts of 1,3-diimino-N-p-tolyl-2,3-dihydro-1H-benzo[f]isoindole-6-amine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (A-1), to obtain 210 parts of naphthalocyanine pigment (A-17). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1177.3.

Naphthalocyanine pigment (A-17)

(Synthesis of naphthalocyanine pigment (A-18))
The same procedure as in the synthesis of naphthalocyanine pigment (A-1) was carried out, except that 277 parts of 6-cyclohexyl-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (A-1), to obtain 194 parts of naphthalocyanine pigment (A-18). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1085.32.

Naphthalocyanine pigment (A-18)

(Synthesis of naphthalocyanine pigment (A-19))
The same operation as in the synthesis of naphthalocyanine pigment (A-1) was carried out, except that 302 parts of 1,3-diimino-N,N-dimethyl-2,3-dihydro-1H-benzo[f]isoindole-6-sulfonamide was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (A-1), to obtain 211 parts of naphthalocyanine pigment (A-19). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1185.27.

Naphthalocyanine pigment (A-19)

(Synthesis of naphthalocyanine pigment (A-20))
The same procedure as in the synthesis of naphthalocyanine pigment (A-1) was carried out, except that 324 parts of 6,7-dichloro-4,9-dimethoxy-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (A-1), to obtain 227 parts of naphthalocyanine pigment (A-20). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1272.52.

Naphthalocyanine pigment (A-20)

(Synthesis of naphthalocyanine pigment (A-21))
The same procedure as in the synthesis of naphthalocyanine pigment (A-1) was carried out, except that 397 parts of 4,9-dibromo-6-ethoxy-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (A-1), to obtain 278 parts of naphthalocyanine pigment (A-21). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1564.13.

Naphthalocyanine pigment (A-21)

[Synthesis of Comparative Naphthalocyanine Pigment (P-1)]
Instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol and 1135 parts of quinoline used in the synthesis of chloroaluminum naphthalocyanine pigment (1-1), 178 parts of 2,3-dicyanonaphthalene, 890 parts of n-amyl alcohol, and 137 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) were used, respectively, and the same operation as in the synthesis of chloroaluminum naphthalocyanine pigment (1-1) was performed to obtain 127 parts of naphthalocyanine pigment (P-1). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation were matched, and the obtained compound was identified. The molecular weight was 774.25.

Comparative naphthalocyanine pigment (P-1)

<Method for producing resin (B)>
(Synthesis of Resin (B-1))
A reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was charged with 100 parts of PGMAc and 3 parts of methyl 4-cyano-4-(dodecylthiocarbonothioylthio)pentanoate (hereinafter abbreviated as "BM1448"), and the temperature was raised to 80°C in a nitrogen atmosphere, and then a mixture consisting of 48 parts of methyl methacrylate, 29 parts of ethyl methacrylate, 19 parts of tertiary butyl acrylate, and 1 part of 2,2'-azobis(2,4-dimethylvaleronitrile) (hereinafter abbreviated as "V65") was added dropwise over 4 hours. After the dropwise addition was completed, 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 over 1 hour. After the mixture was kept at 90° C. for 12 hours, PGME was added to obtain a 30% by mass solution of resin (B-1). The Tg of this resin (B-1) was 37° C.

<Method for producing near infrared absorbing dye>
(Synthesis of near infrared absorbing dye 1 (C-1))
Near infrared absorbing dye 1 consisting of naphthalocyanine pigment (A-2) and a phosphorus compound was produced by the following procedure. 5 parts of diphenyl phosphoric acid was added to 200 parts of N-methylpyrrolidone, and the mixture was thoroughly stirred and mixed, and then heated to 50°C. 10 parts of naphthalocyanine pigment (A-2) was gradually added to this solution, and 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 a filter paper and determining that no bleeding had occurred. Subsequently, the reaction solution was poured into 2000 parts of water, and the resulting precipitate was filtered, washed with water, and dried to obtain 12 parts of near infrared absorbing dye 1 (C-1).

Near infrared absorbing dye 1 (C-1)

(Examples 2 to 34, Comparative Examples 1 and 2)
Hereinafter, near-infrared absorbing dyes 2 to 34 and comparative near-infrared absorbing dyes 1 and 2 were synthesized in the same manner as for near-infrared absorbing dye 1, except that the near-infrared absorbing dye and the phosphorus compound were changed to the types and amounts shown in Table 1. Note that, for comparative near-infrared absorbing dye 1, naphthalocyanine pigment (A-2) was used, and for comparative near-infrared absorbing dye 2, naphthalocyanine pigment (P-1) was used.
The structural formulas of the near infrared absorbing dyes (C-2 to C-34, 36, and 37) obtained in Examples 2 to 34 and Comparative Examples 1 and 2 are shown below.

(Synthesis of near infrared absorbing dye (C-35))
Near infrared absorbing dye 2 consisting of naphthalocyanine pigment (A-2) and resin (B-1) was produced by the following procedure. 65 parts of resin (B-1) were added to 200 parts of N-methylpyrrolidone, and the mixture was thoroughly stirred and mixed, and then heated to 50°C. 10 parts of naphthalocyanine pigment (A-2) were gradually added to this solution, and 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 filter paper and determining that no bleeding had occurred. Subsequently, the reaction solution was poured into 2000 parts of water, and the resulting precipitate was filtered, washed with water, and dried to obtain 63 parts of near infrared absorbing dye (C-35).
At this time, the molar ratio of the naphthalocyanine pigment (A-2) and the P-1M contained in the resin (B-1) was naphthalocyanine pigment (A-2)/P-1M contained in the resin (B-1)=0.9/1.

<Method for producing binder resin solution>
(Preparation of binder resin solution): Random copolymer A separable 4-neck flask was equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer. 70.0 parts of cyclohexanone was charged in a reaction vessel, which was then heated to 80 ° C. and substituted with nitrogen in the reaction vessel. From the dropping tube, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 0.4 parts of 2,2'-azobisisobutyronitrile were 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 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content. Propylene glycol monoethyl ether acetate was added to the previously synthesized resin solution so that the non-volatile content was 20 mass% to prepare a binder resin solution.

<Method of producing resin-type dispersant>
(Resin-type dispersant 1 solution): Block copolymer [Synthesis of monomer (b-1)]
In a reaction vessel equipped with a stirrer and a thermometer, 60 parts of 2-isocyanatoethyl methacrylate, 29 parts of 3-(dimethylamino)propylamine, and 120 parts of THF were charged and stirred at room temperature for 5 hours. After confirming the completion of the reaction by FT-IR, the solvent was distilled off with a rotary evaporator to obtain 73 parts of the following monomer (b-1) as a pale yellow transparent liquid (yield 82%). The obtained compound was identified 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) obtained by the synthesis of the monomer (b-1) and 5 parts of ion-exchanged water were charged and stirred at room temperature, and then 8 parts of a 35% aqueous hydrochloric acid solution was added dropwise. The completion of the reaction was confirmed by measuring the amine value, and 20 parts of an aqueous solution of the monomer (b-2) was obtained as a pale yellow transparent liquid. The obtained compound was identified by 1H-NMR.

Monomer (b-2)

A reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 17.7 parts of methyl methacrylate, 53.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen, 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 initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content.
Next, 20 parts of PGMAc, 21.2 parts of monomer (b-1) as a second block monomer, and 27 parts of an aqueous solution of monomer (b-2) (non-volatile content 38%) were added to this reaction tank, and the reaction was continued by stirring while maintaining a nitrogen atmosphere at 110° C. After 2 hours, a sample of the polymerization solution was taken to measure the non-volatile content, and it was confirmed that the polymerization conversion rate of the second block was 98% or more calculated from the non-volatile content, and the reaction solution was cooled to room temperature to terminate the polymerization.
PGMAc was added to the block copolymer solution synthesized above so that the nonvolatile content was 40% by mass. In this way, a resin-type dispersant 1 solution was obtained, which had an amine value per nonvolatile content of 50 mgKOH/g, a quaternary ammonium salt value of 20 mgKOH/g, a weight average molecular weight (Mw) of 9,800, and a nonvolatile content of 40% by mass.

(Resin-type dispersant 2 solution): Block copolymer 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reaction apparatus equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, and the mixture was stirred at 50° C. for 1 hour while flowing nitrogen, and the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content.
Next, 61 parts of PGMAc and 20 parts of dimethylaminoethyl methacrylate (hereinafter referred to as DM) as a second block monomer were added to this reaction apparatus, and the reaction was continued by stirring while maintaining a nitrogen atmosphere at 110° C. Two hours after the addition of dimethylaminoethyl methacrylate, a sample was taken from the polymerization solution and the nonvolatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more calculated from the nonvolatile content, and the reaction solution was cooled to room temperature to terminate the polymerization.
PGMAc was added to the block copolymer solution synthesized above so that the non-volatile content was 40% by mass. In this way, a resin-type dispersant 2 solution having a poly(meth)acrylate skeleton and a tertiary amino group with 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 was obtained.

(Resin-type dispersant 3 solution): Block copolymer 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reaction apparatus equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, and the mixture was stirred at 50° C. for 1 hour while flowing nitrogen, and the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content.
Next, 61 parts of PGMAc and 25.6 parts of an aqueous solution of methacryloyloxyethyl trimethyl ammonium chloride ("Acryester DMC78" manufactured by Mitsubishi Rayon Co., Ltd.) as a second block monomer were added to the reactor, and the reaction was continued by stirring while maintaining 110° C. and a nitrogen atmosphere. Two hours after the addition of methacryloyloxyethyl trimethyl ammonium chloride, the polymerization solution was sampled and the nonvolatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more calculated from the nonvolatile content, and the reaction solution was cooled to room temperature to stop the polymerization.
PGMAc was added to the block copolymer solution synthesized above so that the non-volatile content was 40% by mass. In this way, a resin-type dispersant 3 solution was obtained, which has an amine value per non-volatile content of 29.4 mgKOH/g, a weight average molecular weight of 9800 (Mw), a non-volatile content of 40% by mass, a poly(meth)acrylate skeleton, and a quaternary ammonium salt group.

(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, and the mixture was heated and stirred at 70° C., and 35 parts of methacrylic acid was added dropwise over 60 minutes. After completion of the dropwise addition, the mixture was heated and stirred at 70° C. for another 2 hours, and the reaction was confirmed to be complete by ¹ H-NMR, and then 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 bicarbonate, and 200 parts of saturated saline, and then 20 g of magnesium sulfate was added to the organic layer, and the mixture was stirred and filtered. The solvent of the obtained solution was distilled off with a rotary evaporator, and 31 parts of the following structure-containing monomer (b-3) was obtained as a pale yellow transparent liquid (yield 42%). The obtained compound was identified by ¹ H-NMR.

Ethylenically unsaturated monomer (b-3)

In a reaction vessel equipped with a gas inlet 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 the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen, 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 initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content.
Next, 25 parts of PGMAc and 25.1 parts of ethylenically unsaturated monomer (b-3) as a second block monomer were added to this reaction tank, and the reaction was continued by stirring while maintaining a nitrogen atmosphere at 110° C. Two hours after the addition of the ethylenically unsaturated monomer (b-3), a sample was taken from the polymerization solution and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate of the second block was 98% or more based on the nonvolatile content.
Further, 4.5 parts of benzyl chloride was added to the reaction vessel, and the mixture was stirred for 3 hours while maintaining the temperature at 110° C. under a nitrogen atmosphere, and then cooled.
PGMAc was added to the block copolymer solution synthesized above so that the non-volatile content was 40% by mass. In this way, a resin-type dispersant 4 solution was obtained, which had an amine value per non-volatile content of 50 mgKOH/g, 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.

(Resin-type dispersant 5 solution)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 50 parts of methyl methacrylate, 50 parts of n-butyl methacrylate, and 45.4 parts of PGMAc were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 70 ° C., 6 parts of 3-mercapto-1,2-propanediol were added, and 0.12 parts of AIBN (azobisisobutyronitrile) were further added, and the reaction was carried out for 12 hours. It was confirmed that 95% had reacted 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 reaction was carried out at 120 ° C. for 7 hours. It was confirmed by measuring the acid value that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. PGMAc was added to adjust the non-volatile content to 50%. In this way, a solution of resin-type dispersant 5 having an acid value of 43, a weight average molecular weight of 9000, a poly(meth)acrylate skeleton and an aromatic carboxyl group was obtained.

(Resin-type dispersant 6 solution)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 6 parts of 3-mercapto-1,2-propanediol, 9.7 parts of pyromellitic anhydride, 0.01 parts of monobutyltin oxide, and 88.9 parts of PGMAc were charged and replaced with nitrogen gas. 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 20 parts of hydroxymethyl methacrylate were charged, and 0.12 parts of AIBN and 26.8 parts of PGMAc were added and reacted for 10 hours. The reaction was terminated after confirming that the polymerization had progressed to 95% by measuring the non-volatile content. PGMAc was added to adjust the nonvolatile content to 50%, to obtain a solution of Resin Type Dispersant 6 having an acid value of 43, a weight average molecular weight of 9000, a poly(meth)acrylate skeleton and an aromatic carboxyl group.

(Resin-type dispersant 7 solution)
BYK-P104 (BYK Japan: 50% non-volatile content)
(Resin-type dispersant 8 solution)
Disperbyk-171 (manufactured by BYK Japan: non-volatile content 39.5%)
(Resin-type dispersant 9 solution)
Disperbyk-142 (manufactured by BYK Japan: non-volatile content 60%)
(Resin-type dispersant 10 solution)
A 20% non-volatile solution of the following copolymer in PGMAc

<Production of near-infrared absorbing composition>
(Example 36)
Near infrared absorbing composition (D-1)
A mixture having the following composition was stirred and mixed uniformly, dispersed in an Eiger mill using zirconia beads having a diameter of 0.5 mm for 3 hours, and then filtered through a 0.5 μm filter to prepare a near-infrared absorbing composition.
Near infrared absorbing dye 1 (C-1): 10.0 parts Resin type dispersant 1 solution: 7.5 parts Binder resin solution: 35.0 parts PGMAc: 47.5 parts

(Examples 37 to 79, Comparative Examples 3 and 4)
Hereinafter, near infrared absorbing compositions (D-2) to (D-44), (D-59) and (D-60) were prepared in the same manner as for 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 were changed to the compositions and amounts shown in Table 2-1.

(Example 80)
Near infrared absorbing composition (D-45)
A mixture having the following composition was stirred and mixed uniformly, dispersed in an Eiger mill using zirconia beads having a diameter of 0.5 mm for 3 hours, and then filtered through a 0.5 μm filter to prepare a near-infrared absorbing composition.
Near infrared absorbing dye 1 (C-1): 7.0 parts Near infrared absorbing dye (X-1): 3.0 parts Resin type dispersant 1 solution: 7.5 parts Binder resin solution: 35.0 parts PGMAc: 47.5 parts

(Examples 81 to 93)
Hereinafter, near infrared absorbing compositions (D-46) to (D-58) were prepared in the same manner as for near infrared absorbing composition (D-45), except that the near infrared absorbing dye, resin-type dispersant solution, binder resin solution, and solvent were changed to the compositions and amounts shown in Table 2-1. Note that (X-1) to (X-14) are the near infrared absorbing dyes shown below.

<Evaluation of near infrared absorbing composition>
For the near infrared absorbing compositions (D-1 to 60) obtained in the Examples and Comparative Examples, tests for average primary particle size, spectral characteristics, and resistance (light resistance, heat resistance) were performed by the following methods. Note that ◎ is an extremely good level, ○ is a good level, △ is a practical level, and × is a level not suitable for practical use. The results are shown in Table 2-2.

(Evaluation of Dispersion Stability)
The viscosity of the obtained near infrared absorbing composition was measured and defined as the initial viscosity. Further, an accelerated test was performed at 40° C. for 7 days to measure the accelerated viscosity over time. The rate of change due to acceleration was calculated as "accelerated viscosity over time/initial viscosity", and the dispersion stability was evaluated according to the following criteria.
◎: Less than 1.05 ○: 1.05 or more, less than 1.10 △: 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 1.1 mm thick glass substrate using a spin coater so that the film thickness after drying was 1.0 μm, and the substrate was dried at 60° C. for 5 minutes, and then heated at 230° C. for 5 minutes to prepare a substrate. The absorption spectrum of the obtained substrate was measured in the wavelength range of 300 to 1000 nm using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation). For the obtained substrate, the ratio (W/X) of the maximum absorbance (W) at 700 to 900 nm and the minimum absorbance (X) at 480 to 650 nm was obtained and evaluated according to the following criteria. It can be said that the larger this ratio (W/X), the lower the absorption at the wavelength with the lowest absorption in the region with high relative luminosity (480 nm to 650 nm) for absorption in the near infrared rays, and the higher the transmittance at the wavelength with the maximum transmittance.
◎: 30 or more ○: 15 or more, less than 30 △: 5 or more, less than 15 ×: Less than 5

(Evaluation of Spectral Characteristics 2)
For the substrates obtained above, the ratio (Y/Z) of the maximum absorbance (Y) in the range of 800 to 900 nm to the minimum absorbance (Z) in the range of 480 to 650 nm was determined and evaluated according to the following criteria.
◎: 15 or more ○: 10 or more, less than 15 △: 10 or more, less than 3 ×: less than 3

(Lightfastness test)
A test substrate was prepared in the same manner as in the spectral characteristic evaluation, and placed in a light resistance tester (TOYOSEIKI's "SUNTEST CPS+") and left for 24 hours. The absorbance at the spectral maximum absorption wavelength of the near-infrared absorbing film was measured, and the remaining ratio to that before light irradiation was calculated, and the light resistance was evaluated according to the following criteria. The remaining ratio 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, but less than 95%. ×: Residual rate is less than 90%.

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

From the results in Table 2-2, Examples 36 to 93 have low absorption in the range of 480 nm to 650 nm, where the relative luminous efficiency is high, and have excellent near-infrared absorption ability, especially in the range of 800 nm to 900 nm, and also have excellent light resistance and heat resistance.

<Production of Photosensitive Near-Infrared Absorbing Composition>
(Example 94)
The following mixture was stirred and mixed to a uniform consistency, and then filtered through a 1.0 μm filter to obtain a photosensitive near-infrared absorbing composition (R-1).
Near infrared absorbing composition (D-1): 50.0 parts Binder resin solution: 7.5 parts Photopolymerization initiator ("Aronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization initiator ("OXE-02" manufactured by BASF Japan Ltd.): 1.5 parts PGMAc: 39.0 parts

(Examples 95 to 103 and Comparative Examples 5 and 6)
Hereinafter, photosensitive near infrared absorbing compositions (R-2) to (R-12) were obtained in the same manner as in the photosensitive near infrared absorbing composition (R-1), except that the near infrared absorbing composition was changed to the type of near infrared absorbing composition shown in Table 3.

<Evaluation of Photosensitive Near-Infrared Absorbing Composition>
The photosensitive near infrared absorbing compositions (R-1 to 12) obtained in the Examples and Comparative Examples were tested for spectral characteristics and resistance (heat resistance, light resistance) by the following methods. ⊚ indicates a very good level, ◯ indicates a good level, △ indicates a practically usable level, and × indicates a level not suitable for practical use. The results are shown in Table 3.

(Evaluation of Dispersion Stability)
The viscosity of the photosensitive near infrared absorbing composition thus obtained was measured and recorded as the initial viscosity. Further, an accelerated test was carried out at 40° C. for 7 days to measure the accelerated viscosity over time.
The rate of change due to acceleration was calculated as accelerated viscosity/initial viscosity, and evaluated according to the following criteria.
◎: Less than 1.05 ○: 1.05 or more, less than 1.10 △: 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 1.1 mm thick glass substrate using a spin coater so that the film thickness after drying was 1.0 μm, and the substrate was dried at 60° C. for 5 minutes, and then heated at 230° C. for 5 minutes to prepare a substrate. The absorption spectrum of the obtained substrate was measured in the wavelength range of 300 to 1000 nm using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation). For the obtained substrate, the ratio (W/X) of the maximum absorbance (W) at 700 to 900 nm and the minimum absorbance (X) at 480 to 650 nm was obtained and evaluated according to the following criteria. It should be noted that the larger this ratio (W/X), the lower the absorption at the wavelength with the lowest absorption in the region with high relative luminosity (480 nm to 650 nm) for absorption in the near infrared rays, and the higher the transmittance at the wavelength with the maximum transmittance.
◎: 30 or more ○: 15 or more, less than 30 △: 5 or more, less than 15 ×: Less than 5

(Evaluation of Spectral Characteristics 2)
For the substrates obtained above, the ratio (Y/Z) of the maximum absorbance (Y) in the range of 800 to 900 nm to the minimum absorbance (Z) in the range of 480 to 650 nm was determined and evaluated according to the following criteria.
◎: 15 or more ○: 10 or more, less than 15 △: 10 or more, less than 3 ×: less than 3

(Lightfastness test)
A test substrate was prepared in the same manner as in the spectral characteristic evaluation, and placed in a light resistance tester (TOYOSEIKI's "SUNTEST CPS+") and left for 24 hours. The absorbance at the spectral maximum absorption wavelength of the near-infrared absorbing film was measured, and the remaining ratio to that before light irradiation was calculated, and the light resistance was evaluated according to the following criteria. The remaining ratio 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, but less than 95%. ×: Residual rate is less than 90%.

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

From the results in Table 3, Examples 94 to 103 have low absorption in the 480-650 nm range, which has high luminosity, and have excellent near-infrared absorption, especially in the 800-900 nm range, and also have excellent light resistance and heat resistance.

<Production of Near-Infrared Cut Filter>
(Examples 104 to 106)
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 using a spin coater, and then heat-treated on a hot plate at 100° C. for 1 minute as a pre-bake.
Next, using an ultra-high pressure mercury lamp USH-200DP (manufactured by Ushio Inc.), pattern exposure was performed through a photomask at an exposure dose of 1000 mJ/cm ² to form a near-infrared absorption cut filter of 100 μm square.
The exposed coating was subjected to shower development using a 0.2 mass% aqueous sodium carbonate solution as a developer at a developer pressure of 0.1 mPa to remove uncured portions of the coating, forming a pattern of 400 μm×400 μm. This was followed by post-baking for 120 minutes at 100° C. The film thickness of the near-infrared absorption cut filter (F-1) after heat treatment was 1.0 μm.
For the photosensitive near infrared absorbing compositions (R-2, 3), near infrared absorbing cut filters (F-2, 3) were obtained in the same manner as for the near infrared absorbing cut filter (F-1).

<Evaluation of near-infrared cut filters>
The near infrared cut filters (F-1 to 3) were subjected to tests for spectral characteristics and durability (heat resistance and light resistance) in the same manner as in the evaluation of the photosensitive near infrared absorbing composition. The results are shown in Table 4.

From the results in Table 4, Examples 104 to 106 had excellent spectral characteristics. They had little absorption in the range of 480 nm to 650 nm, where the relative luminosity is high, and had excellent near-infrared absorption, especially in the range of 800 nm to 900 nm, and also had excellent light resistance and heat resistance. Therefore, they are suitable for near-infrared cut filters.

<Production of near-infrared absorbing composition (visible light absorbing composition) containing an organic dye having absorption in the range of 400 nm to 700 nm>
(Blue colored composition)
The mixture having the following composition was stirred and mixed uniformly, dispersed in an Eiger mill using zirconia beads having a diameter of 0.5 mm for 3 hours, and then filtered through a 0.5 μm filter 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)
A mixture having the following composition was stirred and mixed uniformly, and then dispersed in an Eiger mill using zirconia beads having a diameter of 0.5 mm for 3 hours, and then filtered through a 0.5 μm filter 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)
A mixture having the following composition was stirred and mixed uniformly, dispersed in an Eiger mill using zirconia beads having a diameter of 0.5 mm for 3 hours, and then filtered through a 0.5 μm filter 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 107)
The following mixture was stirred and mixed to be homogeneous, and then filtered through a 1.0 μm filter to obtain a visible light absorbing composition (P-1).
Near infrared absorbing composition (D-1): 10.0 parts Blue pigment composition: 20.0 parts Purple pigment composition: 10.0 parts Yellow pigment composition: 10.0 parts Binder resin solution: 7.5 parts Photopolymerizable compound ("Aronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization initiator ("OXE-02" manufactured by BASF Japan Ltd.): 1.5 parts PGMAc: 39.0 parts

(Examples 108 to 111)
Hereinafter, except that the near infrared absorbing composition was changed to the type of near infrared absorbing composition shown in Table 5, the same procedure as for the visible light absorbing composition (P-1) was performed to obtain visible light absorbing compositions (P-2) to (P-5).

The obtained visible light absorbing composition was spin-coated onto a 1.1 mm thick glass substrate using a spin coater to a film thickness of 2.0 μm, dried at 60° C. for 5 minutes, and then heated at 230° C. for 5 minutes to prepare a substrate.
The function of the filter is, for example, whether or not it is capable of transmitting near-infrared light and whether or not it is capable of cutting off light in other wavelength regions.
The transmittance at 900 nm and the absorbance in the wavelength range of 400 to 800 nm were evaluated below.

(400-800 nm absorbance)
The transmission spectrum of the obtained substrate was measured in the wavelength range of 400 to 800 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
○: The transmittance is less than 2% in the entire region from 400 to 800 nm. △: The transmittance is 2% or more in a part of the region from 400 to 800 nm. ×: The transmittance is 2% or more in the entire region from 400 to 800 nm.

(900 nm Transmittance)
The transmittance of the obtained substrate at 900 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
○: 80% or more △: 40% or more but less than 80% ×: Less than 40%

(Lightfastness test)
The obtained substrate was placed in a light resistance tester (TOYOSEIKI "SUNTEST CPS+") and left for 24 hours. At this time, the test was performed with a broadband light of 300 to 800 nm at an irradiance of 47 mW/cm2. Thereafter, the transmission spectrum in the wavelength range of 400 to 800 nm was measured using a spectrophotometer (U-4100, Hitachi High-Technologies Corporation).
○: The transmittance is less than 2% in the entire region from 400 to 800 nm. △: The transmittance is 2% or more in a part of the region from 400 to 800 nm. ×: The transmittance is 2% or more in the entire region from 400 to 800 nm.

(Heat resistance test)
The obtained substrate was additionally heated for 20 minutes at 210° C. as a heat resistance test, after which the transmission spectrum in the wavelength range of 400 to 800 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
○: The transmittance is less than 2% in the entire region from 400 to 800 nm. △: The transmittance is 2% or more in a part of the region from 400 to 800 nm. ×: The transmittance is 2% or more in the entire region from 400 to 800 nm.

From the results in Table 5, Examples 107 to 111 contain both a near-infrared absorbing dye and a dye that absorbs visible light in the range of 400 to 700 nm, and thus absorb light in the entire range of 400 to 800 nm and transmit near-infrared light of 900 nm.

<Production 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) Amilan CM3001-N (polyamide resin, manufactured by Toray Industries, crystalline resin, melting point 265°C)
(E-3) Iupilon S-3000 (polycarbonate resin, manufactured by Mitsubishi Engineering Plastics Corporation, amorphous resin, glass transition temperature 145° C.)
(E-4) Topas (cycloolefin resin, manufactured by Polyplastics Co., Ltd., amorphous resin, glass transition temperature 78° C.)
(E-5) APEL (cycloolefin resin, manufactured by Mitsui Chemicals, Inc., amorphous resin, glass transition temperature 135° C.)
(E-6) ULTEM (polyetherimide resin, manufactured by Saudi Basic Industries Corporation, amorphous resin, glass transition temperature 217°C)

(Example 112)
<Masterbatch manufacturing>
One part of the near-infrared absorbing dye 1 (C-1) and 99 parts of the thermoplastic resin (E-1) were fed into a twin-screw extruder (manufactured by The Japan Steel Works, Ltd.) having a screw diameter of 30 mm through the same supply port, melt-kneaded at 300°C, and then cut into pellets using a pelletizer to prepare a master batch (M-1).

<Film Forming>
95 parts of the thermoplastic resin (E-1) as the dilution resin was mixed with 5 parts of the obtained master batch (M-1), and the mixture was melt-mixed at a temperature of 300° C. using a T-die molding machine (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to form a film (X-1) having a thickness of 250 μm.

(Examples 113 to 134, Comparative Examples 7 and 8)
Similarly to Example 112, films (X-2) to (X-25) having a thickness of 250 μm were formed using the materials shown in Table 6-1.

＜Near infrared absorption＞

(Evaluation of Spectral Characteristic 1)
The absorption spectrum of the obtained film was measured in the wavelength range of 300 to 1000 nm using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation). The ratio (W/X) of the maximum absorbance (W) at 700 to 900 nm to the minimum absorbance (X) at 480 to 650 nm was determined for the obtained substrate, and the evaluation was performed according to the following criteria. It can be said that the larger this ratio (W/X), the lower the absorption at the wavelength with the lowest absorption in the region with high relative luminosity (480 nm to 650 nm) for near-infrared absorption, and the higher the transmittance at the wavelength with the maximum transmittance.
◎: 30 or more ○: 15 or more, less than 30 △: 5 or more, less than 15 ×: Less than 5

(Evaluation of Spectral Characteristics 2)
For the obtained film, the ratio (Y/Z) of the maximum absorbance value (Y) in the range of 800 to 900 nm to the minimum absorbance value (Z) in the range of 480 to 650 nm was determined and evaluated according to the following criteria.
◎: 15 or more ○: 10 or more, less than 15 △: 10 or more, less than 3 ×: less than 3

<Transparency>
The transparency of the obtained film was evaluated visually.
◯: No turbidity observed at all.
△: Slight turbidity observed.
×: Turbidity is clearly observed.

<Light resistance>
A test film was prepared in the same manner as in the evaluation of near-infrared absorption, placed in a light resistance tester (TOYOSEIKI "SUNTEST CPS+"), irradiated with broadband light of 300 to 800 nm at an irradiance of 47 mW/cm ² , and left for 24 hours. The test film was then removed, and the absorbance at the maximum absorption wavelength of the test film was measured, and the remaining ratio to the absorbance before light irradiation was calculated, and the light resistance was evaluated according to the following criteria. The remaining ratio was calculated using the following formula.
Residual rate = (absorbance after irradiation) ÷ (absorbance before irradiation) × 100
○: Residual rate is 90% or more △: Residual rate is 85% or more but less than 90% ×: Residual rate is less than 85%

From the results in Table 6-2, Examples 112 to 134 have low absorption in the 480 nm to 650 nm range, which has high relative visibility, and have excellent near-infrared absorption, especially in the 800 nm to 900 nm range, and also have excellent light resistance.

<Production of visible light absorbing composition for molding>
(Example 135)
<Masterbatch manufacturing>
One part of near-infrared absorbing dye 1 (C-1), one part of Pigment Blue 15:3, one part of Pigment Yellow 147, one part of Solvent Red 52, and 96 parts of thermoplastic resin (E-1) were fed into a twin-screw extruder (manufactured by The Japan Steel Works, Ltd.) having a screw diameter of 30 mm through the same supply port, melt-kneaded at 300°C, and then cut into pellets using a pelletizer to prepare a master batch (MP-1).

<Film Forming>
95 parts of the thermoplastic resin (E-1) as the dilution resin was mixed with 5 parts of the obtained master batch (MP-1), and the mixture was melt-mixed at a temperature of 300° C. using a T-die molding machine (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to form a film (XP-1) having a thickness of 250 μm.

(Examples 136 to 140)
Similarly to Example 135, films (XP-2) to (XP-6) having a thickness of 250 μm were formed using the materials shown in Table 7-1.

The obtained film was evaluated for suitability as a near-infrared filter. The filter function is, for example, whether it can transmit near-infrared rays and whether it can block light in other wavelength ranges.
The transmittance at 900 nm and the absorbance in the wavelength range of 400 to 800 nm were evaluated below.

(400-800 nm absorbance)
The transmission spectrum of the obtained film was measured in the wavelength range of 400 to 800 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
○: The transmittance is less than 2% in the entire region from 400 to 800 nm. △: The transmittance is 2% or more in a part of the region from 400 to 800 nm. ×: The transmittance is 2% or more in the entire region from 400 to 800 nm.

(900 nm Transmittance)
The transmittance of the obtained film at 900 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
○: 80% or more △: 40% or more but less than 80% ×: Less than 40%

(transparency)
The transparency of the obtained film was evaluated visually.
◯: No turbidity observed at all.
△: Slight turbidity observed.
×: Turbidity is clearly observed.

(Light resistance)
The obtained film was placed in a light resistance tester (TOYOSEIKI "SUNTEST CPS+") and left for 24 hours. At this time, the test was performed with a broadband light of 300 to 800 nm at an irradiance of 47 mW/cm2. Thereafter, the transmission spectrum in the wavelength range of 400 to 800 nm was measured using a spectrophotometer (U-4100, Hitachi High-Technologies Corporation).
○: The transmittance is less than 2% in the entire region from 400 to 800 nm. △: The transmittance is 2% or more in a part of the region from 400 to 800 nm. ×: The transmittance is 2% or more in the entire region from 400 to 800 nm.

From the results in Table 7-2, Examples 135 to 140 contain both a near-infrared absorbing dye and a dye that absorbs visible light in the range of 400 to 700 nm, and thus absorb light in the entire range of 400 to 800 nm and transmit near-infrared light of 900 nm.

Claims (6)

A near infrared absorbing dye represented by the following general formula (1):
[In general formula (1), R ₁ to R ₂₄ each independently represent a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, 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, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, 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 group which may have a substituent.
M represents Al.
Z is a polymer moiety containing a monomer unit represented by formula (2) or a phosphorus compound moiety represented by formula (3), and * is a bond to M.
In general formula (2), X is -CONH- _R25- , -COO- _R26- , -CONH- _R27 -O-, -COO- _R28 -O-, _R25 to _R28 each represent an alkylene group or an arylene group in which the carbon atoms may be linked by -O-, -CO-, -COO-, -OCO-, -CONH- or -NHCO-, and _R31 represents a hydrogen atom or a methyl group.
In the general formula (3), R ₂₉ and R ₃₀ each independently represent a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent, and R ₂₉ and R ₃₀ may be bonded to each other to form a ring. A near-infrared absorbing composition comprising the near-infrared absorbing dye of claim 1 and a binder resin. The near infrared absorbing composition according to claim 2, further comprising a thermosetting compound. The near-infrared absorbing composition according to claim 2 or 3, further comprising a photopolymerizable compound and a photopolymerization initiator. The near infrared absorbing composition according to any one of claims 2 to 4, further comprising an organic dye having absorption in the range of 400 nm to 700 nm. A near-infrared cut filter having a coating formed from the near-infrared absorbing composition according to any one of claims 2 to 5.