JP2022022070A - Near-infrared absorbing dye and near-infrared absorbing composition - Google Patents

Abstract

To provide a near-infrared absorbing dye which strikes a balance between transmissivity and both heat resistance and light resistance.SOLUTION: A vinyl polymer being a polymer of a vinyl monomer represented by the following formula is bonded to a phthalocyanine moiety having high heat resistance and light resistance, thereby improving transmissivity in 480-630 nm being a region having high spectral luminous efficiency. (In the formula, X represents -CONH-R1-, -COO-R2- or the like; and Y represents H or a methyl group.)SELECTED DRAWING: None

Description

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

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

Among these, the near-infrared cut filter for camera sensors is required to have high transparency in the region of high luminous efficiency of 480 nm to 630 nm and high shielding of 700 to 1000 nm in the region of no luminous efficiency. Will be done. As a method for cutting near infrared rays, there are methods other than dyes such as a dielectric multilayer film, but it is important that the dyes have high absorbability at least for 700 nm, which is the boundary region between visible light and near infrared rays.
In addition, near-infrared cut filters for cameras are required to have extremely high heat resistance and light resistance, such as for in-vehicle applications used in harsh environments and for mounting on devices that require processing at high temperatures.
Luminous efficiency is an index of brightness perceived by the human eye at each wavelength.

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

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

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

However, although the conventional near-infrared absorbing composition using a phthalocyanine dye has high heat resistance and light resistance, an absorption band peculiar to phthalocyanine exists in the vicinity of 650 nm to 700 nm, so that it is a region having high relative sensitivity of 480 nm. There was a problem that the permeability of about 630 nm was insufficient.

The present invention has both transparency of 480 nm to 630 nm, which is a region with high luminous efficiency, and heat resistance and light resistance, and has excellent near-infrared absorption at 700 nm, which is a boundary region between visible light and near-infrared light. The purpose is to provide an absorbent dye.

The present invention is a near-infrared absorbing dye having a site represented by the following general formula (1).

[In the general formula (1), X ₁ to X ₄ are each independently an alkyl group which may have a substituent.
It has an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, and a substituent. It represents an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent.
Y _l to Y ₄ independently represent a halogen atom, a nitro group, a phthalimide methyl group which may have a substituent, or a sulfamoyl group which may have a substituent.
M represents Al.
m ₁ , m ₂ , m ₃ , m ₄ , n ₁ , n ₂ , n ₃ , and n ₄ independently represent integers from 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ respectively. + N ₃ , m ₄ + n ₄ are 0 to 4, respectively, and may be the same or different.
Z is a vinyl polymer having a unit represented by the general formula (2). * Indicates the binding site with M.
In the general formula (2), X is -CONH-R _1- , -COO-R _2- , -CONH-R ₃ -O-, -COO-R ₄ -O-, and R ₁ to R ₄ are alkylene groups. , An arylene group, or an alkylene group or an arylene group having an -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO- linking group between carbon atoms. show. Y represents a hydrogen atom or a methyl group. ]

According to the above invention, the transmissivity of 480 nm to 630 nm, which is a region with high luminous efficiency, is compatible with heat resistance and light resistance, and the near infrared absorption of 700 nm, which is the boundary region between visible light and near infrared rays, is excellent. Near-infrared absorbing dyes, near-infrared absorbing compositions, and near-infrared cut filters can be provided.

<Near infrared absorbent dye>
The present invention is a near-infrared absorbing dye (hereinafter referred to as the dye of the present invention) having a site represented by the following general formula (1). The dye of the present invention can improve the permeability of 480 nm to 630 nm, which is a region having high luminous efficiency, by binding the vinyl polymer represented by the general formula (2) to the phthalocyanine moiety having high heat resistance and light resistance. Thereby, the transparency, heat resistance and light resistance can be compatible with each other.

In general, phthalocyanine dyes have a strong cohesive force due to the association of aromatic rings, and often have a crystal structure and exist as a pigment. In that case, it becomes difficult to dissolve in a normal solvent, and a dispersion can be obtained by dispersing using a dispersant or the like, but the film to be produced has strong absorption due to the association of aromatic rings around 650 nm to 700 nm. Since it is expressed, the permeability in the region of high luminosity sensitivity of 480 nm to 630 nm is deteriorated.

On the other hand, there are dyes in which a substituent such as a long-chain alkyl group is introduced into the aromatic ring of the phthalocyanine dye to increase the solubility in a solvent or the like and weaken the aggregation due to the association of the aromatic rings. In that case, the film obtained by dissolving it in a solvent or the like and applying it has weak absorption due to the association of aromatic rings in the vicinity of 650 nm to 700 nm, and has high permeability in the region of high luminous efficiency of 480 nm to 630 nm. However, since absorption due to the association of aromatic rings in the vicinity of 650 nm to 700 nm also exists to some extent, it cannot be said that the permeability in the visible region with high visual sensitivity of 480 nm to 630 nm is sufficiently high. It is speculated that the aromatic rings are partially associated in the coating.

On the other hand, the coating film containing the dye of the present invention has very weak absorption due to the association of aromatic rings in the vicinity of 650 nm to 700 nm, and has high permeability in the region of high luminous efficiency of 480 nm to 630 nm. This is because the dye of the present invention has a structure in which the phthalocyanine sites do not easily associate with each other because the vinyl polymer causes steric hindrance.

In the general formula (1), X ₁ to X ₄ independently have an alkyl group which may have a substituent, an aryl group which may have a substituent, and a cycloalkyl which may have a substituent. A group, a heterocyclic 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, or Represents an arylthio group which may have a substituent.
Y _l to Y ₄ independently represent a halogen atom, a nitro group, a phthalimide methyl group which may have a substituent, or a sulfamoyl group which may have a substituent.
M represents Al.
m ₁ , m ₂ , m ₃ , m ₄ , n ₁ , n ₂ , n ₃ , and n ₄ independently represent integers from 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ respectively. + N ₃ , m ₄ + n ₄ are 0 to 4, respectively, and may be the same or different.
Z is a vinyl polymer having a unit represented by the general formula (2). * Indicates the binding site with M.
In the general formula (2), X is -CONH-R _1- , -COO-R _2- , -CONH-R ₃ -O-, -COO-R ₄ -O-, and R ₁ to R ₄ are alkylene groups. , An arylene group, or an alkylene group or an arylene group having an -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO- linking group between carbon atoms. show. Y represents a hydrogen atom or a methyl group. ]

The dye of the present invention is composed of an aluminum phthalocyanine moiety and a vinyl polymer. The aluminum phthalocyanine moiety is preferably made from aluminum phthalocyanine represented by the following general formula (3).

<Aluminum phthalocyanine>
General formula (3)

In the general formula (3), X ₁ to X ₄ independently have an alkyl group which may have a substituent, an aryl group which may have a substituent, and a cycloalkyl which may have a substituent. A group, a heterocyclic 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, or Represents an arylthio group which may have a substituent.

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

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

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

Examples of the "heterocyclic group" of the heterocyclic group which may have a substituent include a pyridyl group, a pyrazil group, a piperidino group, a pyranyl group, a morpholino group, an acridinyl group and the like. Examples of the "heterocyclic group having a substituent" include a 3-methylpyridyl group, an N-methylpiperidyl group, an N-methylpyrrolill group and the like.

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

Examples of the "aryloxy group" of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, an anthryloxy group and the like, and the "aryloxy group having a substituent" is, for example, p. -Methylphenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group and the like can be mentioned.

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

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

Y _l to Y ₄ independently represent a halogen atom, a nitro group, a phthalimide methyl group which may have a substituent, or a sulfamoyl group which may have a substituent.
M represents Al.
m ₁ , m ₂ , m ₃ , m ₄ , n ₁ , n ₂ , n ₃ , and n ₄ independently represent integers from 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ respectively. + N ₃ , m ₄ + n ₄ are 0 to 4 independently of each other. These may be the same or different.

<Aluminum phthalocyanine synthesis method>
The general industrial manufacturing method of aluminum phthalocyanine is described below.
(1) Wyler method A method of reacting urea with aluminum chloride at a high temperature using substituted or unsubstituted phthalic anhydride or substituted or unsubstituted phthalic anhydride imide.
(2) Phtalodinitrile method Substituted or unsubstituted phthalodinitrile is added to DBU (1,8-) in an alcohol solvent such as n-amyl alcohol, n-hexyl alcohol, 1-methoxyethanol and 1-ethoxyethanol. Reacts with aluminum chloride in the presence of strong bases such as diazabicyclo [5,4,0] undecene-7), DBN (1,5-diazabicyclo [4,3,0] nonen-5), or (metal) alkoxide. How to make it.
(3) Diiminoisoindoline method Substituted or unsubstituted 1,3-diiminoisoindoline can be obtained from 2-dimethylaminoethanol, quinoline, DBU (1,8-diazabicyclo [5,4,0] undecene-7). A method of reacting with aluminum chloride in the presence of such a strong base.

Examples of the aluminum phthalocyanine include the following compounds.

<Vinyl polymer>
The vinyl polymer is a polymer of the vinyl monomer represented by the general formula (4). The vinyl monomer represented by the general formula (4) has a phosphoric acid group. The phosphate group in the vinyl polymer and the aluminum cation in the phthalocyanine moiety form a salt. In addition to the vinyl monomer represented by the general formula (4), other monomers can be used for the synthesis of the vinyl polymer.

General formula (4)

In the general formula (4), X is -CONH-R _1- , -COO-R _2- , -CONH-R ₃ -O-, -COO-R ₄ -O-, and R ₁ to R ₄ are alkylene groups. , An arylene group, or an alkylene group or an arylene group having an -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO- linking group between carbon atoms. show. Y represents a hydrogen or methyl group.
Examples of the alkylene group include a methylene group, an ethylene group, a propylene group and a butylene group. Examples of the arylene group include phenylene, naphthylene, biphenylene group, terphenylene group and anthrylene group.
Examples of R ₁ , R ₂ , R ₃ and R ₄ include a methylene group, an ethylene group, a propylene group and a butylene group.

The vinyl monomer represented by the general formula (4) is, for example, (2- (meth) acryloyloxyethyl) acid phosphate, (2- (meth) acryloyloxypropyl) acid phosphate, (2- (meth) acryloyloxyisopropyl) acid. Phosphate can be mentioned.

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

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

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

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

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

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

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

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

The acid group-containing monomer is, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloracrylic acid, and dermal acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic anhydride. , Unsaturated dicarboxylic acids such as citraconic acid, anhydrous citraconic acid, mesaconic acid or their anhydrides; unsaturated polyvalent carboxylic acids having a valence of 3 or more or their anhydrides; Mono- (2-methacryloyloxyethyl) mono- (2-acryloyloxyethyl) mono (2-acryloyloxyethyl) phthalate, mono- (2-methacryloyloxyethyl) monovalent or higher valent carboxylic acid mono [(meth) ) Acryloyloxyalkyl] esters; mono (meth) acrylates of both-terminal carboxypolymers such as ω-carboxy-polycaprolactone monoacrylate and ω-carboxy-polycaprolactone monomethacrylate can be mentioned.

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

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

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

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

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

Commercially available products of the blocked isocyanate group-containing monomer include, for example, 2-[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate (Carens MOI-BP, manufactured by Showa Denko KK); 2- (0- [1') methacrylic acid. Methylprovideneamino] Carboxamino) Ethyl (Carens MOI-BM, manufactured by Showa Denko KK) and the like can be mentioned.

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

The amount of the vinyl monomer represented by the general formula (4) used for synthesizing the vinyl polymer moiety is preferably 1 to 30% by mass, more preferably 5 to 15% by mass, based on 100% by mass of all the monomers. Optical characteristics are improved when used in an appropriate amount.

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

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

The free radical polymerization method uses a polymerization initiator. Examples of the polymerization initiator include azo compounds and organic peroxides.
Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane1-carbonitrile), 2, 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), or 2,2'-azobis [2- (2-imidazolin-2-yl) Propane] and the like. Organic peroxides include, for example, benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydi. Examples thereof include carbonate, tert-butylperoxyneodecanoate, tert-butylperoxyvivarate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.

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

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

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

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

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

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

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

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

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

<Synthesis method of near-infrared absorbing dye>
The dye of the present invention is synthesized by reacting aluminum phthalocyanine represented by the general formula (3) with a vinyl polymer.

(Preparation of near-infrared absorption dye)
For the synthesis of the dye of the present invention, for example, aluminum phthalocyanine represented by the general formula (3), a vinyl polymer, and an organic solvent are added, and the mixture is heated and stirred for several hours. Then, the reaction solution is put into water, the precipitated product is filtered, washed with water, and dried.
Alternatively, the composition containing the dye of the present invention can be prepared by dispersing the composition containing both the aluminum phthalocyanine represented by the general formula (3) and the vinyl polymer.

Regarding the ratio of the aluminum phthalocyanine moiety (A) and the vinyl polymer (B), the aluminum phthalocyanine moiety (A) and the phosphoric acid group derived from the vinyl monomer represented by the general formula (4) among the vinyl polymers (B) are used. The molar ratio of
The phosphoric acid group derived from the vinyl monomer represented by the aluminum phthalocyanine moiety (A) / general formula (4) = 0.5 to 1.5 is preferable, and 0.8 to 1.2 is more preferable. When used at an appropriate ratio, the absorption due to the association of aromatic rings in the vicinity of 650 nm to 700 nm becomes very weak, and the permeability in the region of high luminous efficiency of 450 nm to 650 nm becomes high.

<Form of near-infrared absorbing dye>
The dye of the present invention has high transparency in the region of high luminous efficiency of 480 nm to 630 nm, and is excellent in absorption of near infrared rays. This is noticeable when the substrate is coated to form a coating. When coating on a substrate, it may be used by dissolving it in a solvent or the like, or it may be used by obtaining a dispersion liquid by using a dispersant or the like. It can also be used as a near-infrared absorbing composition by adding a binder resin.

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

The near-infrared absorbing composition of the present invention contains the dye of the present invention, a binder resin and the like.

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

The thermoplastic resin is, for example, an acrylic resin, a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, a polyvinyl acetate, or a polyurethane-based resin. Examples thereof include resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

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

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

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

[Method (i)]
In method (i), for example, first, an epoxy group-containing monomer and a polymer of other monomers are synthesized. Next, a method of adding a monocarboxyl group-containing monomer to the epoxy group of the polymer and reacting the generated hydroxyl group with a polybasic acid anhydride to obtain an alkali-soluble resin (C2) can be mentioned.

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

The monocarboxyl group-containing monomer is, for example, (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted. Examples thereof include monocarboxylic acids such as the body.

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

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

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

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

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

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

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

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

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

<Thermosetting compound>
In the near-infrared absorbing composition, it is preferable to use a binder resin and a thermosetting compound in combination, which improves the crosslink density in the heating step and thus improves the 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 preferable.

Examples of the epoxy compound include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) and phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted). Dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthoaldehyde, glutaaldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Polymers of various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols and ketones. Polycondensate with (acemonate, methylethylketone, methylisobutylketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'-benzenedimethanol, biphenyldimethanol , Α, α, α', α'-biphenyldimethanol, etc.), and phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.) , Polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylizing alcohols and the like, alicyclic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins and the like.

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

The near-infrared absorbing composition may contain a curing agent and a curing accelerator in order to assist the curing of the thermosetting compound. Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like. The curing accelerator may be, for example, an amine compound (eg, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, eg). Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Ethyl-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4) -Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) Can be mentioned.

The amount of the curing agent and the curing accelerator used is preferably 0.01 to 15 parts by mass, respectively, with respect to 100 parts by mass of the thermosetting compound.

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

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, and 1,4-dioxane. , 2-Heptanone, 2-Methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene , O-Dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, Ethylene Glycol Monoethyl Ether, Ethylene Glycol Monoethyl Ether Acetate, Ethylene Glycol Monotershary Butyl Ether, Ethylene Glycol Monobutyl Ether, Ethylene Glycol Monobutyl Ether Acetate, Ethylene Glycol Monopropyl Ether, Ethylene Glycol Monohexyl Ether, Ethylene Glycol Monomethyl Ether, Ethylene Glycol Monomethyl Ether Acetate, Diisobutyl Ketone, Diethylene Glycol Diethyl Ether, Diethylene Glycol Diethyl 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 Diethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethylate , Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol Monoethyl Ether, Propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monobutyl Ether, Propylene Glycol Monopropyl Ether, Propylene Glycol Monomethyl Ether, Propylene Glycol Monomethyl Ether Acetate, Propylene Glycol Monomethyl Ether Propionate, benzyl Alcohol, Methyl Isobutyl Ketone, Methyl Examples thereof include cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like.

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

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

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

In another production method, for example, the aluminum phthalocyanine represented by the general formula (3) and the vinyl polymer are mixed without being reacted in advance, and then a dispersant and a dispersion aid (for example, a dye derivative) are added and dispersed. , The dispersion of the near-infrared absorbing dye of the present invention can be obtained.

It is presumed that the aluminum phthalocyanine represented by the general formula (3) is finely dispersed and reacts with the vinyl polymer during the dispersion step, and as a result, the near-infrared absorbing dye of the present invention is obtained.

However, when a vinyl polymer is added and mixed with a near-infrared absorbing composition obtained by finely dispersing aluminum phthalocyanine represented by the general formula (3) using various dispersion means, the spectral characteristics of the dye of the present invention are obtained. Cannot be obtained.
It is presumed that this is because the aluminum phthalocyanine represented by the general formula (3) is already finely dispersed, and even if it is mixed with a vinyl polymer, no reaction occurs and the dye of the present invention is not synthesized. ..

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

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

Commercially available resin-type dispersants are, for example, Disperbyk manufactured by Big Chemie Japan.
-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 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykuman. Etc., SOLSERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, manufactured by Japan Lubrizol. 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, manufactured by BASF Japan. 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajinomoto Fine Techno Co., Ltd. Ajispar PA111, PB711, PB821, PB822, PB824 and the like can be mentioned.

≪Dispersion aid≫
Surfactants include, for example, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalrine sulfonate, alkyldiphenyl ether disulfonic acid. Anionic surfactants such as sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, etc. Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; Chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazolin can be mentioned.

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

The blending amount of the dispersion aid is preferably 0.1 to 55% by mass, more preferably 0.1 to 45% by mass, based on 100% by mass of the dye of the present invention. Good dispersibility can be obtained by using an appropriate amount.

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

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

The monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth). Acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (meth) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, 1,6-Hexanediol Diglycidyl Ether Di (Meta) Acrylate, Bisphenol A Diglycidyl Ether Di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolation Various acrylic acid esters such as (meth) acrylic acid ester, epoxy (meth) acrylate, urethane acrylate and methacrylic acid ester of melamine, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol Examples thereof include, but are not limited to, trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.

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

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

<Photopolymerization initiator>
The photopolymerization initiator is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1 -Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- Acetphenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one; benzoin, Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4 Benzophenone compounds such as'-methyldiphenylsulfide or 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, Thioxanthone compounds such as 4-diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (P-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6 -Bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4 Triazine compounds such as -trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzo) Iloxime)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6) -Trimethylbenzoyl) phenylphosphine oxide, or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone; borate compounds; Examples thereof include carbazole-based compounds; imidazole-based compounds; and titanosen-based compounds.

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

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

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

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

The blending amount of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the photopolymerization initiator.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Adhesion improvers include, for example, vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and β- (3). , 4-Epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ- Examples thereof include aminosilanes such as aminopropyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. .. The content of the adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the dye of the present invention.

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

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

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

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

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

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

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

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

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

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

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

(Polyetherimide resin)
The polyetherimide resin is an amorphous resin having a glass transition temperature of more than 180 ° C., has good transparency, high strength, high heat resistance, high elastic modulus, and a wide range of chemical resistance. Therefore, it is widely used in various applications such as automobiles, telecommunications, aerospace, electrical / electronic, transportation and healthcare.
One of the processes for producing a polyetherimide resin is the polymerization of an alkali metal salt of a dihydroxyaromatic compound such as bisphenol A disodium salt (BPA · Na ₂ ) with bis (halophthalimide). The molecular weight of the obtained polyetherimide resin can be controlled by two methods. The first method is to use a molar excess of bis (halophthalimide) with respect to the alkali metal salt of the dihydroxyaromatic compound. The second method is to prepare bis (phthalic anhydride) in the presence of a monofunctional compound such as phthalic anhydride that forms a terminal capping agent. Phthalic anhydride reacts with some of the organic diamines to form monohalo-bis (phthalimide). Monohalo-bis (phthalimide) acts as a terminal-capping agent in the polymerization step by reaction with phenoxide terminal groups in the growing polymer chain.
Examples of commercially available polyetherimide resins include ULTEM (manufactured by Saudi Basic Industry Corporation).

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

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

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

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

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

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

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

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

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

The near-infrared cut filter of the present invention preferably has a film formed of the near-infrared absorbing composition, and more preferably has a base material. The coating film includes a film formed by coating and a molded body produced by molding. The usage will be described below.

<Use>
The near-infrared absorbing dye of the present invention has both heat resistance and light resistance as well as transparency of 480 nm to 630 nm, which is a region having high relative visibility, and absorbs near infrared rays of 700 nm, which is a boundary region between visible light and near infrared light. Excellent in sex. The absorption wavelength region of near infrared rays is mainly about 700 to 750 nm.
(Optical recording medium)
The near-infrared cut filter can be used as an optical recording medium. Irradiation of the near-infrared cut filter with near-infrared rays changes the crystalline state of the dye and changes the refractive index of the coating or molded product. This principle is used for recording media such as optical discs.

(Laser welding material / laser marking material)
The near-infrared cut filter can be used for laser welding materials or laser marking materials. When the near-infrared cut filter is irradiated with a laser having a wavelength absorbed by the near-infrared absorbing dye, the dye absorbs the laser light and generates heat, so that the resin melts and carbonizes. When it melts, it can be welded to another resin, so marking is possible.

(Optical filter)
The near-infrared cut filter can be used as an optical filter. For example, a digital camera recognizes colors by decomposing the light received during imaging with red, green, and blue filters and sending it to a photodiode that converts the light into an electrical signal. However, the photodiode also reacts to near-infrared rays and converts it into an electric signal, so a filter that blocks this is required. The near-infrared cut filter of the present invention can be used as a near-infrared cut filter.

(Biometric sensor)
The near-infrared cut filter can be used for a sensor for biometric authentication (fingerprint authentication or vein authentication), or a touch sensor or touch panel incorporating the sensor.
For example, smartphones, tablet PCs, etc., bank ATMs, multimedia terminals, etc. are equipped with biometric authentication functions such as fingerprint authentication and finger vein authentication for security protection. In particular, the development of fingerprint authentication technology used for smartphones and tablet PCs is rapid, and as the authentication range increases to the screen size (full screen), fingerprint authentication sensors with built-in displays have been developed for organic EL displays, liquid crystal displays, etc. There is. However, since many fingerprint sensors with a built-in display irradiate the fingerprint with various light sources installed in the display and sense the reflected light, illegal external light (such as sunlight or LED lighting) is used. When a sensor has a wide range of wavelengths and is subject to strong light), there is a problem of noise during imaging, and there is some concern about accuracy when using it outdoors. The same applies to finger vein authentication for bank ATMs and multimedia terminals, and measures such as covering the store with strong lighting and sunny stores to block outside light are taken.
The near-infrared cut filter of the present invention is effective in solving these problems by absorbing and preventing the incident of illegal external light on the sensor.
For example, when it is used for a smartphone or a tablet personal computer, when it is set on the front surface of the panel, it is necessary to have a design, but the near-infrared cut filter has an advantage that it can be preferably used because it has high transparency in the visible region. Further, since the near-infrared cut filter has excellent heat resistance, it can be preferably used in terms of a process for manufacturing a sensor, a touch sensor incorporating the sensor, and a touch panel.

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

The near-infrared absorbing dye of the present invention has both heat resistance and light resistance as well as transparency of 480 nm to 630 nm, which is a region having high relative visibility, and absorbs near infrared rays of 700 nm, which is a boundary region between visible light and near infrared light. Excellent in sex. In other words, the transmittance of light in the wavelength region that is perceived brightly by the human eye is high, and the light in the region that is difficult for the human eye to see is shielded as noise. It can be reproduced. However, since the near-infrared absorption wavelength region of the near-infrared absorbing dye is mainly about 700 to 750 nm, in order to shield light having a wavelength longer than this region, another near-infrared absorbing dye may be combined or combined. It is preferable to combine a dielectric multilayer film.

(Near infrared transmission filter)
In addition, LEDs with wavelengths of 850 nm, 870 nm, 900 nm, 940 nm, etc. have become widespread, and distance measurement and biometric authentication (fingerprint authentication, iris authentication, face authentication, vein authentication, etc., or a combination thereof) in automatic driving have become widespread. Used for light detection in sensors. However, since light rays of all wavelengths such as ultraviolet rays, visible light, and near infrared rays exist in the atmosphere, a filter that blocks light other than the light of the wavelength to be detected is required. Therefore, by combining a near-infrared absorbing dye that absorbs light of 700 to 1000 nm with a dye that absorbs visible light, an ultraviolet absorber, etc., only light with a wavelength longer than the absorption wavelength of the near-infrared absorbing dye is transmitted, and more than that. Light of short wavelength can be blocked. Specifically, it is preferable to combine the near-infrared absorbing dye with a blue dye, a yellow dye, and a red or purple dye. For coating applications, the blue pigment is Pigmen
t. Blue. 15: 3 or Pigment. Blue. 15: 6, the yellow pigment is Pigment. Yellow. 139, purple pigment is Pigment. Violet. It is preferable to use 23. For molding purposes, the blue pigment is Pigment. Blue. 15: 3 or Pigment. Blue. 15: 6, the yellow pigment is Pigment. Yellow. 147, the red dye is Solvent. Red. 52 is preferable.

Since the near-infrared absorption wavelength region of the near-infrared absorbing dye of the present invention is mainly about 700 to 750 nm, it is visible when the above-mentioned dyes are combined in order to block visible light having a shorter wavelength than this. It is possible to block light rays from the light region to around 750 nm. Thereby, for example, it can be used as a near-infrared transmission filter that transmits light rays of 850 nm and shields light rays having a shorter wavelength as noise.

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

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

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

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

(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 GPC (manufactured by Tosoh Co., Ltd., HLC-8120GPC) equipped with an RI detector using a TSKgel column (manufactured by Tosoh Co., Ltd.) and THF is used as a developing solvent. It is a polystyrene-equivalent weight average molecular weight (Mw) measured in the above.

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

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

<Manufacturing of near-infrared absorbing dye>
(Manufacturing of phthalocyanine pigment (A-1))
In the reaction vessel, 225 parts of phthalodinitrile and 78 parts of aluminum chloride anhydride were mixed and stirred with 1250 parts of n-amyl alcohol. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine 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 with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.
Chlorophthalocyanine pigment (1-1)

Then, in the reaction vessel, 10 parts of the above chloroaluminum phthalocyanine was added to 100 parts of concentrated sulfuric acid under an ice bath, and the mixture was stirred for 1 hour. Subsequently, this sulfuric acid solution was poured into 1000 parts of cold water at 3 ° C., and the generated precipitate was treated in the order of filtration, washing with water, washing with a 2.5% sodium hydroxide aqueous solution, and washing with water, and dried to 8 parts. Phthalocyanine pigment (A-1) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 574.96.
Phthalocyanine pigment (A-1)

Synthesis of phthalocyanine pigment (A-2) 50 parts of 3-tetrafluoropropyloxy-1,3-diiminoisoindoline was used instead of 225 parts of phthalocyanine nitrile used in the synthesis of phthalocyanine pigment (A-1). Except for the above, the same operation as for the synthesis of the phthalocyanine pigment (A-1) was carried out to obtain a 40-part phthalocyanine pigment (A-2). As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 556.51.
Phthalocyanine pigment (A-2)

(Synthesis of phthalocyanine pigment (A-3))
To 1500 parts of concentrated sulfuric acid, 100 parts of the above chloroaluminum phthalocyanine was added under an ice bath. Then, 199 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 generated precipitate was treated in the order of filtration, washing with water, washing with 1% sodium hydroxide aqueous solution, and washing with water, dried, and 165 parts of phthalocyanine. Pigment (A-3) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (A-3), the average number was 8.4, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the target compound was identified. The molecular weight was 1187.68.
Phthalocyanine pigment (A-3)

(Synthesis of phthalocyanine pigment (A-4))
Similar to the synthesis of phthalocyanine pigment (A-1) except that 40 parts of 4- (4-pyridinyl) phthalocyanine nitrile was used instead of 225 parts of phthalocyanine nitrile used in the synthesis of phthalocyanine pigment (A-1). To obtain 34 parts of a phthalocyanine pigment (A-4). As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 864.85.
Phthalocyanine pigment (A-4)

(Synthesis of phthalocyanine pigment (A-5))
Instead of 225 parts of phthalocyanine nitrile and 1250 parts of n-amyl alcohol used in the synthesis of phthalocyanine pigment (A-1), 3- (3,5-dimethyl) cyclohexyloxy-1,3-diiminoisoindoline, respectively. The same operation as for the synthesis of the phthalocyanine pigment (A-1) was carried out except that 50 parts and 300 parts of quinoline were used to obtain 35 parts of the phthalocyanine pigment (A-5). As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1061.3.
Phthalocyanine pigment (A-5)

(Synthesis of phthalocyanine pigment (A-6))
The same operation as the synthesis of the phthalocyanine pigment (A-1) was performed except that 50 parts of 4-propylthiophthalocyanine nitrile was used instead of the 225 parts of the phthalocyanine nitrile used in the synthesis of the phthalocyanine pigment (A-1). This was carried out to obtain 45 parts of a phthalocyanine pigment (A-6). As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 853.09.
Phthalocyanine pigment (A-6)

(Synthesis of phthalocyanine pigment (A-7))
The same operation as the synthesis of the phthalocyanine pigment (A-1) was performed except that 25 parts of 4-methylphthalocyanine nitrile was used instead of the 225 parts of the phthalocyanine nitrile used in the synthesis of the phthalocyanine pigment (A-1). , 20 parts of phthalocyanine pigment (A-7) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 612.62.
Phthalocyanine pigment (A-7)

(Synthesis of hydroxyaluminum phthalocyanine (8-1))
Instead of 50 parts of 3- (3,5-dimethyl) cyclohexyloxy-1,3-diiminoisoindoline used in the synthesis of the phthalocyanine pigment (A-5), 3- (2,2-bis (trifluoromethyl) ) Propyl) Except for using 60 parts of oxy-1,3-diiminoisoindoline, the same operation as the synthesis of the phthalocyanine pigment (A-5) was carried out to obtain 50 parts of hydroxyaluminum phthalocyanine (8-1). rice field. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1332.81.
Hydroxyaluminum phthalocyanine (8-1)

(Synthesis of phthalocyanine pigment (A-8))
Instead of 100 parts of chloroaluminum phthalocyanine and 199 parts of 1,3-dibromo-5,5-dimethylhydantoin used in the synthesis of the phthalocyanine pigment (A-3), the hydroxyaluminum phthalocyanine (8-) obtained above, respectively. 1) Except for the use of 10 parts and 5.4 parts of N-bromosuccinimide, the same operation as the synthesis of the phthalocyanine pigment (A-3) was carried out, and 10.5 parts (y85%) of the phthalocyanine pigment (A-) was performed. 8) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1648.4.
Phthalocyanine pigment (A-8)

(Synthesis of phthalocyanine pigment (A-9))
The same operation as the synthesis of the phthalocyanine pigment (A-1) was performed except that 50 parts of 4-butoxyphthalocyanine nitrile was used instead of the 225 parts of the phthalocyanine nitrile used in the synthesis of the phthalocyanine pigment (A-1). , 43 parts of phthalocyanine pigment (A-9) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 844.93.
Phthalocyanine pigment (A-9)

(Synthesis of phthalocyanine pigment (A-10))
Instead of 50 parts of 3- (3,5-dimethyl) cyclohexyloxy-1,3-diiminoisoindoline used in the synthesis of the phthalocyanine pigment (A-5), 3- (2,6-dimethyl) phenyloxy- Except for the use of 20 parts of 1,3-diiminoisoindoline, the same operation as the synthesis of the phthalocyanine pigment (A-5) was carried out to obtain 18 parts of the phthalocyanine pigment (A-10). As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 1037.11.
Phthalocyanine pigment (A-10)

(Synthesis of phthalocyanine pigment (A-11))
The same operation as the synthesis of the phthalocyanine pigment (A-1) was performed except that 50 parts of 4-phenylthiophthalocyanine nitrile was used instead of the 225 parts of the phthalocyanine nitrile used in the synthesis of the phthalocyanine pigment (A-1). This was carried out to obtain 40 parts of a phthalocyanine pigment (A-11). As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 989.16.
Phthalocyanine pigment (A-11)

(Synthesis of phthalocyanine pigment (A-12))
To 1000 parts of concentrated sulfuric acid, 100 parts of the above chloroaluminum phthalocyanine was added under an ice bath. Then, 80 parts of N-oxymethylphthalimide was gradually added, heated to 80 ° C., and stirred for 8 hours. Subsequently, this sulfuric acid solution was poured into 8000 parts of cold water at 3 ° C., and the generated precipitate was treated in the order of filtration and washing with water, and dried to obtain 155 parts of a phthalocyanine pigment (A-4). As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 874.79.

Phthalocyanine pigment (A-12)

[Synthesis of comparative phthalocyanine pigment (Pc-1)]
The same operation as the synthesis of the phthalocyanine pigment (A-1) was performed except that 77 parts of copper chloride was used instead of 78 parts of the aluminum chloride anhydride used in the synthesis of the phthalocyanine pigment (A-1), and 30 parts were performed. Comparative phthalocyanine pigment (Pc-1) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.
Comparative phthalocyanine pigment (Pc-1)

[Synthesis of comparative phthalocyanine pigment (Pc-2)]
The same operation as the synthesis of the phthalocyanine pigment (A-1) was performed except that 75 parts of zinc chloride was used instead of 78 parts of the aluminum chloride anhydride used in the synthesis of the phthalocyanine pigment (A-1), and 32 parts. Comparative phthalocyanine pigment (Pc-2) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.
Comparative phthalocyanine pigment [Pc-2]

[Synthesis of comparative phthalocyanine pigment (Pc-3)]
Except for using 50 parts of 3,6-dihexylphthalonitrile and 7 parts of copper chloride, respectively, instead of 225 parts of phthalocyanine nitrile and 78 parts of aluminum chloride anhydride used in the synthesis of phthalocyanine pigment (A-1). The same operation as the synthesis of the phthalocyanine pigment (A-1) was carried out to obtain 10 parts of a comparative phthalocyanine pigment (Pc-3). As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified with the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.
Comparative phthalocyanine pigment [Pc-3]

<Manufacturing method of resin (B)>
(Synthesis of resin B-1)
In a reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, 100 parts of PGMAc, methyl 4-cyano-4- (dodecylthiocarbonothio oilthio) pentanoate (hereinafter,
Abbreviated as "BM1448". ) 3 parts are charged and the temperature is raised to 80 ° C. in a nitrogen atmosphere, then 48 parts of methyl methacrylate, 29 parts of ethyl methacrylate, 19 parts of tertiary butyl acrylate, 2,2'-azobis (2,4-dimethylvaleronitrile). (Hereinafter, abbreviated as "V65".) A mixture consisting of one part was added dropwise over 4 hours. After completion of the dropping, the mixture was kept at 90 ° C. for 2 hours, and then a mixture consisting of 5 parts of 2-methacryloyloxyethyl acid phosphate (hereinafter abbreviated as "P-1M"; molecular weight 228) and 100 parts of PGME was added dropwise in 1 hour. did. Then, after holding at 90 ° C. for 12 hours, PGME was added to obtain a 30% by mass solution of the resin (B-1). The Tg of this resin (B-1) was 37 ° C.

(Synthesis of resin B-2)
The same operation as in the synthesis of resin B-1 was performed except that 45 parts of dicyclopentanyl methacrylate was used instead of 29 parts of ethyl methacrylate and 19 parts of tertiary butyl acrylate used in the synthesis of resin B-1. , A 30% by mass solution of the polymer (B-2) was obtained. The Tg of this resin (B-1) was 122 ° C.

(Synthesis of resin B-3)
Except for the fact that 10 parts of P-1M were used instead of 5 parts of P-1M used in the synthesis of resin B-1, the same operation as in the synthesis of resin B-1 was carried out, and 30 of the polymer (B-3) was carried out. A mass% solution was obtained. The Tg of this resin (B-3) was 38 ° C.

(Synthesis of resin B-4)
A reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 100.0 parts of PGMAC and 100 parts of PGME in a separable 4-necked flask, and the temperature was raised to 80 ° C., and 48 parts of methyl methacrylate and 29 parts of ethyl methacrylate were charged. , 19 parts of tertiary butyl acrylate, 5 parts of P-1M, 1 part of 2,2'-azobis (2,4-dimethylvaleronitrile) (hereinafter abbreviated as "V65") was added dropwise over 2 hours. .. After completion of the dropping, the reaction was continued for another 3 hours, and PGME was added to obtain a 30% by mass solution of the resin (B-4).

<Manufacturing method of near-infrared absorbing dye>
(Synthesis of near-infrared absorbing dye 1)
A near-infrared absorbing dye 1 composed of a phthalocyanine pigment (A-1) and a resin (B-1) was produced by the following procedure. 88 parts of the resin (B-1) was added to 200 parts of NMP, and the mixture was sufficiently stirred and mixed, and then heated to 50 ° C. After adding 10 parts of the phthalocyanine pigment (A-1) little by little to this solution, the mixture was stirred at 90 ° C. for 120 minutes. The end point of the reaction was confirmed, for example, by dropping the reaction solution onto the filter paper and setting the end point at the point where the bleeding disappeared. Subsequently, this reaction solution was injected into 2000 parts of water, and the generated precipitate was treated in the order of filtration and washing with water, and dried to obtain 88 parts of the near-infrared absorbing dye 1. The molar ratio of the phthalocyanine pigment (A-1) and the P-1M contained in the resin (B-1) is P-1M = 0 contained in the phthalocyanine pigment (A-1) / resin (B-1). It was 0.9 / 1.

(Examples 2 to 20, Comparative Examples 1 to 5)
Hereinafter, the near-infrared absorbent dyes 2 to 20 and the comparative near-infrared absorbent dyes are the same as those of the near-infrared absorbent dye 1 except that the composition and amount of the near-infrared absorbent dye, resin, and solvent are changed to those shown in Table 1. 1 to 5 were synthesized. The comparative near-infrared absorbing dye 1 is a phthalocyanine pigment (A-1), the comparative near-infrared absorbing dye 2 is a phthalocyanine pigment (A-2), and the comparative near-infrared absorbing dye 3 is a comparative phthalocyanine pigment (Pc-1). , The comparative phthalocyanine pigment (Pc-2) was used for the comparative near-infrared absorbing dye 4, and the comparative phthalocyanine pigment (Pc-3) was used for the comparative near-infrared absorbing dye 5.

<Manufacturing method of binder resin solution>
(Preparation of binder resin solution): 70.0 parts of cyclohexanone was charged in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a random copolymer separable 4-neck flask, and the temperature was raised to 80 ° C. After replacing the inside of the reaction vessel with nitrogen, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, and paracumylphenol ethylene oxide-modified acrylate (Toa Synthetic Co., Ltd.) A mixture of 7.4 parts of "Aronix M110" manufactured by Aronix M110 and 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monoethyl is prepared so that the non-volatile content is 20% by mass in the previously synthesized resin solution. A binder resin solution was prepared by adding ether acetate.

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

[Synthesis of monomer (b-9)]
In a reaction vessel equipped with a stirrer and a thermometer, 6.6 parts of the monomer (b-5) and 5 parts of ion-exchanged water obtained by synthesizing the monomer (b-5) were charged, stirred at room temperature, and then 35. 8 parts of a% hydrochloric acid aqueous solution was added dropwise. It was confirmed by measuring the amine value that the reaction was completed, and 20 parts of a monomer (b-9) aqueous solution was obtained as a pale yellow transparent liquid. Identification of the obtained compound was carried out by 1H-NMR.
Monomer (b-9)

In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 17.7 parts of methyl methacrylate, 53.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and 50 parts were flowed with nitrogen. The mixture was stirred at ° C. for 1 hour, and the inside of the system was replaced with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to start the polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 20 parts of PGMAc, 21.2 parts of the monomer (b-5) as the second block monomer, and 27 parts of the aqueous solution of the monomer (b-9) (nonvolatile content 38%) were put into this reaction tank, and the temperature was 110 ° C. and nitrogen. The reaction was continued by stirring while maintaining the atmosphere. After 2 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of the non-volatile content, and the reaction solution was cooled to room temperature to stop the polymerization. did.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by mass. In this way, one solution of a resin-type dispersant having an amine value of 50 mgKOH / g per non-volatile component, a quaternary ammonium salt value of 20 mgKOH / g, a weight average molecular weight (Mw) of 9,800, and a non-volatile content of 40% by mass is prepared. Obtained.

(2 solutions of resin-type dispersant): 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, 13.2 parts of tetramethylethylenediamine in a reaction device equipped with a block copolymer gas introduction tube, a condenser, a stirring blade, and a thermometer. The part was charged, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen to replace the inside of the system with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to start the polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 20 parts of dimethylaminoethyl methacrylate (hereinafter referred to as DM) as a second block monomer were added to this reaction apparatus, and the mixture was stirred while maintaining a nitrogen atmosphere at 110 ° C. to continue the reaction. Two hours after the addition of dimethylaminoethyl methacrylate, the polymerization solution was sampled and the non-volatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of the non-volatile content, and the reaction solution was brought to room temperature. It was cooled to stop the polymerization.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by mass. In this way, it is a poly (meth) acrylate skeleton having an amine value of 71.4 mgKOH / g per non-volatile component, a weight average molecular weight of 9900 (Mw), and a non-volatile content of 40% by mass, and is a resin type having a tertiary amino group. A dispersant 2 solution was obtained.

(3 solutions of resin-type dispersant): 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, 13.2 parts of tetramethylethylenediamine in a reaction device equipped with a block copolymer gas introduction tube, a condenser, a stirring blade, and a thermometer. The part was charged, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen to replace the inside of the system with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to start the polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 25.6 parts of an aqueous solution of methacryloyloxyethyltrimethylammonium chloride (“Acryester DMC78” manufactured by Mitsubishi Rayon Co., Ltd.) as a second block monomer were added to this reactor, and the temperature was maintained at 110 ° C. under a nitrogen atmosphere. The reaction was continued with stirring. Two hours after the addition of methacryloyloxyethyltrimethylammonium chloride, the polymerization solution was sampled and the non-volatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of the non-volatile content, and the reaction solution was prepared. The polymerization was stopped by cooling to room temperature.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by mass. In this way, it is a poly (meth) acrylate skeleton having an amine value per non-volatile content of 29.4 mgKOH / g, a weight average molecular weight of 9800 (Mw), and a non-volatile content of 40% by mass, and is a resin type having a quaternary ammonium base. A dispersant 3 solution was obtained.

(Resin type dispersant 4 solution): Block copolymer
In a reaction vessel equipped with a stirrer and a thermometer, 55 parts of 4-dimethylamino-1,2-epoxybutane and 120 parts of tetrahydrofuran (THF) were charged, heated and stirred at 70 ° C., and 35 parts of methacrylic acid was added over 60 minutes. Dropped. After the dropping was completed, the mixture was further heated and stirred at 70 ° C. for 2 hours, and after confirming that the reaction was completed by ^{1 1} H-NMR, the mixture was allowed to cool to room temperature. The reaction solution was washed successively with 300 parts of ion-exchanged water, 200 parts of saturated sodium hydrogen carbonate, and 200 parts of saturated saline, 20 g of magnesium sulfate was added to the organic layer, and the mixture was stirred and then filtered. The solvent of the obtained solution was distilled off by a rotary evaporator to obtain 31 parts of the following structure-containing monomer (b-1) as a pale yellow transparent liquid (yield 42%. Identification of the obtained compound was performed. ¹ Performed by H-NMR.
Ethylene unsaturated monomer (b-1)

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

(5 solutions of resin type dispersant)
In a reaction vessel equipped with a gas introduction 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 was added, and 0.12 parts of AIBN (azobisisobutyronitrile) was further added, and the reaction was carried out for 12 hours. It was confirmed that 95% of the reaction occurred by measuring the non-volatile content. Next, 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo- [5.4.0] -7-undecene) as a catalyst were added, and the temperature was 120 ° C. Was reacted for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMAc was added to adjust the non-volatile content to 50%. In this way, a resin-type dispersant 5 solution 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.

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

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

<Manufacturing of near-infrared absorbent composition>
(Example 21)
Near-infrared absorbing composition (D-1)
After uniformly stirring and mixing the mixture having the following composition, the mixture was dispersed in an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter having a diameter of 0.5 μm to obtain a near-infrared absorbing composition (D-. 1) was produced.
Near-infrared absorbing dye 1: 10.0 parts Resin-type dispersant 1 solution: 7.5 parts Binder resin solution: 35.0 parts PGMAc: 47.5 parts

(Examples 22 to 51, Comparative Examples 6 to 10)
Hereinafter, the near-infrared absorbing composition (D) except that the near-infrared absorbing dye, the resin type dispersant solution, the binder resin solution, the vinyl polymer solution having a phosphoric acid group, and the solvent are changed to the compositions and amounts shown in Table 2 In the same manner as in -1), the near-infrared absorbing compositions (D-2) to (D-31) and (D-47) to (D-51) were prepared.

(Example 52)
Near-infrared absorbing composition (D-32)
After uniformly stirring and mixing the mixture having the following composition, the mixture was dispersed in an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter having a diameter of 0.5 μm to obtain a near-infrared absorbing composition (D-. 32) was produced.
Near-infrared absorbing dye 2: 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 53 to 66)
Hereinafter, the near-infrared absorbing composition except that the near-infrared absorbing dye, the resin type dispersant solution, the binder resin solution, the vinyl polymer solution having a phosphoric acid group, and the solvent are changed to the compositions and amounts shown in Table 2-1. Near-infrared absorbing compositions (D-33) to (D-46) were prepared in the same manner as in (D-32). In addition, (X-1) to (X-14) are near-infrared absorbing dyes shown below.

<Evaluation of near-infrared absorbing composition>
The near-infrared absorbing compositions (D-1 to 49) obtained in Examples and Comparative Examples were tested for spectral characteristics and resistance (light resistance, heat resistance) by the following methods. In addition, ⊚ is a very good level, ○ is a good level, Δ is a practical level, and × is a level unsuitable for practical use. The results are shown in Table 2.

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

(Evaluation of spectral characteristics 1-1)
The obtained near-infrared absorbing composition was spin-coated on a glass substrate having a thickness of 1.1 mm using a spin coater so that the film thickness after drying was 1.0 μm, and dried at 60 ° C. for 5 minutes. , 230 ° C. for 5 minutes to prepare a substrate. The spectrum of the obtained substrate was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation) to measure the absorption spectrum in the wavelength range of 300 to 1000 nm. The ratio (X / Y) of the maximum value (X) of the absorbance at 670 to 700 nm and the maximum value (Y) of the absorbance at 480 to 650 nm was determined and evaluated according to the following criteria.
◎: 3.0 or more ○: 2 or more, less than 3.0 Δ: 1 or more and less than 2 ×: less than 1.

(Evaluation of spectral characteristics 1-2)
With respect to the substrate obtained above, the ratio (X / Y) of the maximum value (X) of the absorbance at 670 to 700 nm and the maximum value (Y) of the absorbance at 480 to 630 nm was determined and evaluated according to the following criteria. It should be noted that the larger this ratio (X / Y) is, the less the absorption is in the region with high luminous efficiency (480 nm to 630 nm) with respect to the absorption in the near infrared rays, and the higher the transparency in the region that is perceived brightly by the human eye. I can say.
◎: 4 or more ○: 3 or more and less than 4 Δ: 2 or more and less than 3 ×: less than 2

(Evaluation of spectral characteristics 2-1)
With respect to the substrate obtained above, the ratio (X / Z) of the maximum value (X) of the absorbance at 670 to 700 nm and the minimum value (Z) of the absorbance at 480 to 650 nm was determined and evaluated according to the following criteria.
◎: 300 or more ○: 100 or more, less than 300 Δ: 50 or more, less than 100 ×: less than 50

(Evaluation of spectral characteristics 2-2)
With respect to the substrate obtained above, the ratio (X / Z) of the maximum value (X) of the absorbance at 670 to 700 nm and the minimum value (Z) of the absorbance at 480 to 630 nm was determined and evaluated according to the following criteria. It should be noted that the larger this ratio (X / Z) is, the less the absorption is at the wavelength where the absorption is the lowest in the region where the luminous efficiency is high (480 nm to 630 nm), and the more the absorption is at the wavelength where the transparency is maximum. It can be said that the transparency is high.
◎: 300 or more ○: 100 or more, less than 300 Δ: 50 or more, less than 100 ×: less than 50

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

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

From the results shown in Table 2-3, Examples 21 to 66 have low absorption at 400 nm to 630 nm, which has high luminous efficiency, are excellent in near-infrared absorption ability, and are also excellent in light resistance and heat resistance.

<Manufacturing of photosensitive near-infrared absorbing composition>
(Example 67)
After stirring and mixing the following mixture so as to be uniform, 1. Filtration with a 0 μm filter gave a photosensitive near-infrared absorbing composition (R-1).
Near-infrared absorbent composition (D-3): 50.0 parts Binder resin solution: 7.5 parts Photopolymerizable monomer ("Aronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization started Agent (BASF Japan "OXE-02"): 1.5 parts PGMAc: 39.0 parts

(Examples 68 to 75 and Comparative Examples 11 to 13)
Hereinafter, the photosensitive near-infrared absorbing composition is the same as that of the photosensitive near-infrared absorbing composition (R-1) except that the near-infrared absorbing composition is changed to the type of the near-infrared absorbing composition shown in Table 3. Objects (R-2) to (R-12) were obtained.

<Evaluation of photosensitive near-infrared absorbing composition>
The photosensitive near-infrared absorbing compositions (R-1 to 12) obtained in Examples and Comparative Examples were tested for spectral characteristics and resistance (heat resistance, light resistance) by the following methods. In addition, ⊚ is a very good level, ○ is a good level, Δ is a practical level, and × is a level unsuitable for practical use. The results are shown in Table 2-3.

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

(Spectroscopic characterization 1-1)
The obtained photosensitive near-infrared absorbing composition was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater to a thickness of 1.0 μm, and then at 70 ° C. for 20 minutes. After drying, the film was exposed to ultraviolet rays with an integrated light amount of 150 mJ / cm ² using an ultra-high pressure mercury lamp, and developed with an alkaline developer at 23 ° C. to obtain a coated substrate. Then, after heating at 210 ° C. for 5 minutes and allowing to cool, the absorbance of the obtained substrate was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies) to measure the absorption spectrum in the wavelength range of 300-1000 nm, and the absorption spectrum was measured from 670 to 670. The ratio (X / Y) of the maximum value (X) of the absorbance at 700 nm and the maximum value (Y) of the absorbance at 480 to 650 nm was determined. The evaluation criteria are as follows.
◎: 3.0 or more ○: 2 or more, less than 3.0 Δ: 1 or more and less than 2 ×: less than 1.

(Spectroscopic characterization 1-2)
For the substrate obtained above, the ratio (X / Y) of the maximum value (X) of the absorbance at 670 to 700 nm and the maximum value (Y) of the absorbance at 480 to 630 nm was determined. The evaluation criteria are as follows. The larger the ratio (X / Y), the less the absorption in the region with high luminous efficiency (480 nm to 630 nm) with respect to the absorption in the near infrared rays, and the brighter the human eye. It can be said that the perceived area is highly transparent.
◎: 4 or more ○: 3 or more and less than 4 Δ: 2 or more and less than 3 ×: less than 2

(Evaluation of spectral characteristics 2-1)
With respect to the substrate obtained above, the ratio (X / Z) of the maximum value (X) of the absorbance at 670 to 700 nm and the minimum value (Z) of the absorbance at 480 to 650 nm was determined and evaluated according to the following criteria.
◎: 300 or more ○: 100 or more, less than 300 Δ: 50 or more, less than 100 ×: less than 50

(Evaluation of spectral characteristics 2-2)
With respect to the substrate obtained above, the ratio (X / Z) of the maximum value (X) of the absorbance at 670 to 700 nm and the minimum value (Z) of the absorbance at 480 to 630 nm was determined and evaluated according to the following criteria. It should be noted that the larger this ratio (X / Z) is, the less the absorption is at the wavelength where the absorption is the lowest in the region where the luminous efficiency is high (480 nm to 630 nm), and the more the absorption is at the wavelength where the transparency is maximum. It can be said that the transparency is high.
◎: 300 or more ○: 100 or more, less than 300 Δ: 50 or more, less than 100 ×: less than 50

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

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

From the results shown in Table 3, Examples 67 to 75 have low absorption at 400 nm to 630 nm, which has high luminous efficiency, are excellent in near-infrared absorption ability, and are also excellent in light resistance and heat resistance.

<Manufacturing of near-infrared cut filter>
[Examples 76 to 78]
The photosensitive near-infrared absorbing composition (R-1) of the present invention was applied onto a glass substrate having a thickness of 1.1 mm with a spin coater, and heat-treated on a hot plate at 100 ° C. for 1 minute as a prebake.
Then, using an ultra-high pressure mercury lamp USH-200DP (manufactured by Ushio, Inc.), 100μ
In order to form an m-square near-infrared absorption cut filter, pattern exposure was performed with an exposure amount of 1000 mJ / cm ² through a photomask.
The exposed film was used as a developer using a 0.2 mass% sodium carbonate aqueous solution, and the uncured portion of the film was removed by a shower development method at a developer pressure of 0.1 mPa to form a pattern of 400 μm × 400 μm. Then, it was post-baked at 100 ° C. for 120 minutes. The film thickness of the near-infrared absorption cut filter (F-1) after the heat treatment was 1.0 μm.
As for the photosensitive near-infrared absorbing composition (R-2, 3), a near-infrared cut filter (F-2, 3) was obtained in the same manner as the near-infrared absorption cut filter (F-1).

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

From the results in Table 4, Examples 76 to 78 were excellent in spectral characteristics. In particular, it has excellent near-infrared absorption ability with little absorption at 400 nm to 630 nm, which has high luminous efficiency, has good spectral characteristics, and is excellent in light resistance and heat resistance. Therefore, it is suitable for a near-infrared cut filter.

<Manufacturing of near-infrared transmissive composition>
(Blue coloring composition)
The mixture having the following composition was uniformly stirred and mixed, dispersed with an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter of 0.5 μm to prepare a blue colored composition.
C. I. Pigment Blue PB15: 6: 10.0 parts Resin-type dispersant 2 solution: 7.5 parts Binder resin solution: 35.0 parts PGMAc: 47.5 parts

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

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

(Example 79)
After stirring and mixing the following mixture so as to be uniform, 1. Filtration with a 0 μm filter gave a near-infrared transmissive composition (P-1).
Near-infrared absorbing composition (D-4): 10.0 parts blue pigment composition: 20.0 parts purple pigment composition: 10.0 parts yellow pigment composition: 10.0 parts binder resin solution: 7.5 parts Part Photopolymerizable monomer (“Aronix M-402” manufactured by Toa Synthetic Co., Ltd.): 2.0 parts Photopolymerization initiator (“OXE-02” manufactured by BASF Japan): 1.5 parts PGMAc: 39.0 parts

(Examples 80 to 84)
Hereinafter, the photosensitive near-infrared ray transmitting composition is the same as that of the photosensitive near infrared ray transmitting composition (P-1) except that the near infrared ray absorbing composition is changed to the type of the near infrared ray absorbing composition shown in Table 5. Objects (P-2) to (P-6) were obtained.

The obtained near-infrared absorbing composition was spin-coated on a glass substrate having a thickness of 1.1 mm using a spin coater to a film thickness of 2.0 μm, dried at 60 ° C. for 5 minutes, and then dried at 230 ° C. The substrate was prepared by heating for 5 minutes.
The function of the filter is, for example, to be able to transmit near infrared rays and to cut light rays in other wavelength regions.
Hereinafter, the transmittance at 850 nm and the absorbency in the wavelength range of 400 to 700 nm were evaluated.

(Absorbability of 400-700 nm)
A transmission spectrum in a wavelength range of 400 to 700 nm was measured on the obtained substrate using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: Transmittance is less than 2% in the entire region of 400 to 700 nm Δ: Transmittance is 2% or more in some regions of 400 to 700 nm ×: Transmittance is 2% or more in the entire region of 400 to 700 nm

(850 nm transparency)
The transmittance of the obtained substrate was measured at 850 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: 80% or more Δ: 40% or more and less than 80% ×: less than 40%

(Light resistance test)
The obtained substrate was used as a light resistance tester ("SUNTEST CPS +" manufactured by TOYOSEIKI.
") And left for 24 hours. At this time, the test was carried out with a wide band light having an irradiance of 47 mW / cm2 and a radiation illuminance of 300 to 800 nm. Then, a transmission spectrum in the wavelength range of 400 to 700 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: Transmittance is less than 2% in the entire region of 400 to 700 nm Δ: Transmittance is 2% or more in some regions of 400 to 700 nm ×: Transmittance is 2% or more in the entire region of 400 to 700 nm

(Heat resistance test)
The obtained substrate was additionally heated at 210 ° C. for 20 minutes as a heat resistance test. Then, a transmission spectrum in the wavelength range of 400 to 700 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: Transmittance is less than 2% in the entire region of 400 to 700 nm Δ: Transmittance is 2% or more in some regions of 400 to 700 nm ×: Transmittance is 2% or more in the entire region of 400 to 700 nm

From the results in Table 5, Examples 79 to 84 absorb light in the entire region of 400 to 700 nm by containing both a near-infrared absorbing dye and a dye that absorbs visible light of 400 to 700 nm, and near infrared rays of 850 nm. Can be transmitted through.

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

(Example 85)
<Manufacturing of masterbatch>
One part of the near-infrared absorbing dye 1 and 99 parts of the thermoplastic resin (B-1) are put into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) with a screw diameter of 30 mm from the same supply port, and melt-mixed at 300 ° C. After smelting, it was cut into pellets using a pelletizer to prepare a master batch (M-1).

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

(Examples 86 to 107, Comparative Examples 14 to 16)
Similar to Example 1, films (X-2) to (X-23) and (XY-1) to (XY-3) having a thickness of 250 μm were molded using the materials shown in Table 6-1.

<Near infrared absorption>
(Evaluation of spectral characteristics 1-1)
For the obtained film, the absorption spectrum in the wavelength range of 400 to 1000 nm was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies), and the maximum value (X) of the absorbance at 670 to 700 nm and 480. The ratio (X / Y) of the maximum value (Y) of the absorbance at ~ 650 nm was determined and evaluated according to the following criteria.
◎: 3.0 or more ○: 2 or more, less than 3.0 Δ: 1 or more and less than 2 ×: less than 1.

(Evaluation of spectral characteristics 1-2)
The ratio (X / Y) of the maximum value (X) of the absorbance at 670 to 700 nm and the maximum value (Y) of the absorbance at 480 to 630 nm was determined for the obtained film and evaluated according to the following criteria. It should be noted that the larger this ratio (X / Y) is, the less the absorption is in the region with high luminous efficiency (480 nm to 630 nm) with respect to the absorption in the near infrared rays, and the higher the transparency is in the region that is perceived brightly by the human eye.
◎: 4 or more ○: 3 or more and less than 4 Δ: 2 or more and less than 3 ×: less than 2

(Evaluation of spectral characteristics 2-1)
The ratio (X / Z) of the maximum value (X) of the absorbance at 670 to 700 nm and the minimum value (Z) of the absorbance at 480 to 650 nm was determined for the obtained film and evaluated according to the following criteria.
⊚: 300 or more ○: 100 or more and less than 300 Δ: 50 or more and less than 100 ×: less than 50 (evaluation of spectral characteristics 2)
The ratio (X / Z) of the maximum value (X) of the absorbance at 670 to 700 nm and the minimum value (Z) of the absorbance at 480 to 630 nm was determined for the obtained film and evaluated according to the following criteria. It should be noted that the larger this ratio (X / Z) is, the less the absorption is at the wavelength where the absorption is the lowest in the region where the luminous efficiency is high (480 nm to 630 nm), and the more the absorption is at the wavelength where the transparency is maximum, with respect to the absorption in the near infrared rays. Highly transparent.
◎: 300 or more ○: 100 or more, less than 300 Δ: 50 or more, less than 100 ×: less than 50

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

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

<Manufacturing of near-infrared ray transmissive composition for molding>
(Example 108)
<Manufacturing of masterbatch>
1 part of near-infrared absorbing dye 2, 1 part of pigment blue 15: 3, 1 part of pigment yellow 147, 1 part of solvent red 52, 96 parts of thermoplastic resin (B-1) screwed from the same supply port It was put into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) having a diameter of 30 mm, melt-kneaded at 300 ° C., and then cut into pellets using a pelletizer to prepare a master batch (DD-1).

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

(Examples 109 to 119, Comparative Examples 17 to 22)
Similar to Example 100, films (XX-2) to (X-12) and (XXY-1) to (XXY-6) having a thickness of 250 μm were molded using the materials shown in Table 7-1.

The suitability of the near-infrared filter was evaluated for the obtained film. The function of the filter is, for example, to be able to transmit near infrared rays and to cut light rays in other wavelength regions.
Hereinafter, the transmittance at 850 nm and the absorbency in the wavelength range of 400 to 700 nm and 700 to 750 nm were evaluated.

(Absorbability of 400-700 nm)
The transmission spectrum of the obtained film in the wavelength range of 400 to 700 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: Transmittance is less than 2% in the entire region of 400 to 700 nm Δ: Transmittance is 2% or more in some regions of 400 to 700 nm ×: Transmittance is 2% or more in the entire region of 400 to 700 nm

(Absorbability of 700 to 750 nm)
The transmission spectrum of the obtained film in the wavelength range of 700 to 750 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: Transmittance is less than 2% in all regions of 700 to 750 nm Δ: Transmittance is 2% or more in some regions of 700 to 750 nm ×: Transmittance is 2% or more in all regions of 700 to 750 nm

(850 nm transparency)
The transmittance of the obtained film was measured at 850 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: 80% or more Δ: 40% or more and less than 80% ×: less than 40%

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

(Light resistance)
The obtained film was used as a light resistance tester ("SUNTEST CP" manufactured by TOYOSEIKI Co., Ltd.
It was placed in S + ”) and left for 24 hours. At this time, the test was carried out with a wide band light having an irradiance of 47 mW / cm2 and a radiation illuminance of 300 to 800 nm. Then, a transmission spectrum in the wavelength range of 400 to 700 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
◯: Transmittance is less than 2% in all regions of 400 to 700 nm Δ: Transmittance is 2% or more in some regions of 400 to 700 nm ×: Transmittance is 2% or more in all regions of 400 to 700 nm

From the results in Table 7-2, Examples 108 to 119 absorb light in the entire region of 400 to 750 nm by containing both a near-infrared absorbing dye and a dye that absorbs visible light of 400 to 700 nm, and have a thickness of 850 nm. Can transmit near infrared rays.

Claims (6)

A near-infrared absorbing dye having a site represented by the following general formula (1).

[In the general formula (1), X ₁ to X ₄ independently have an alkyl group which may have a substituent, an aryl group which may have a substituent, and a cyclo which may have a substituent. An alkyl group, a heterocyclic 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, or , Represents an arylthio group which may have a substituent.
Y _l to Y ₄ independently represent a halogen atom, a nitro group, a phthalimide methyl group which may have a substituent, or a sulfamoyl group which may have a substituent.
M represents Al.
m ₁ , m ₂ , m ₃ , m ₄ , n ₁ , n ₂ , n ₃ , and n ₄ independently represent integers from 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ respectively. + N ₃ , m ₄ + n ₄ are 0 to 4, respectively, and may be the same or different.
Z is a vinyl polymer having a unit represented by the general formula (2). * Indicates the binding site with M. In the general formula (2), X is -CONH-R _1- , -COO-R _2- , -CONH-R ₃ -O-, -COO-R ₄ -O-, and R ₁ to R ₄ are alkylene groups. , An arylene group, or an alkylene group or an arylene group having an -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO- linking group between carbon atoms. show. Y represents a hydrogen atom or a methyl group. ] A near-infrared absorbing composition comprising the near-infrared absorbing dye according to claim 1 and a binder resin. The near-infrared absorbing composition according to claim 2, wherein the maximum value of the absorbance of the coating film having a thickness of 2 μm at 670 to 700 nm is three times or more the maximum value of the absorbance at 480 to 630 nm. The near-infrared absorbing composition according to claim 2 or 3, further comprising a thermosetting compound. The near-infrared absorbing composition according to any one of claims 2 to 4, further comprising a photopolymerizable monomer and a photopolymerization initiator. A near-infrared cut filter formed by the near-infrared absorbing composition according to any one of claims 2 to 5.