JP6724354B2 - Near infrared absorbing dye and its use - Google Patents

Description

The present invention relates to a specific near infrared absorbing dye. The present invention also relates to a near-infrared absorbing material characterized by containing a specific near-infrared absorbing dye, and a near-infrared cut filter comprising the near-infrared absorbing material.

The main applications of near-infrared absorbing materials are near-infrared absorbing films and near-infrared absorbing plates that block heat rays for energy saving, agricultural near-infrared absorbing films for selective use of sunlight, and near-infrared absorbing heat. Recording media using, near-infrared cut filter for electronic equipment, near-infrared filter for photography, protective glasses, sunglasses, heat ray blocking film, dye for optical recording, optical character reading recording, copy protection for confidential documents, electrophotographic photoreceptor, Laser fusion etc. are mentioned.

Phthalocyanine-based materials, cyanine-based materials, and diimonium-based materials are known as typical near-infrared absorbing dyes. As the phthalocyanine-based material, a phthalocyanine compound having a substituent or a naphthalocyanine compound (see, for example, Patent Document 1), a phthalocyanine compound having an amino group (see, for example, Patent Documents 2 to 6), a phthalocyanine compound having an aryloxy group (for example, see Patent Documents 2 to 6). , Patent Document 7), fluorine-containing phthalocyanine compounds (see, for example, Patent Documents 8 and 9), and the like. However, since the absorption band peculiar to phthalocyanine exists in the visible light region (400 nm to 700 nm), the transparency of visible light is insufficient. In addition, heat resistance and light resistance are not always satisfactory.

On the other hand, cyanine-based materials and diimonium-based materials are materials that are excellent in near-infrared absorbing ability and have extremely good visible light transparency, and various materials are known (for example, see Patent Documents 10 to 14). .. Furthermore, these dyes also have high solubility and resin compatibility. However, the stability as a dye is extremely low, and heat resistance and light resistance are not satisfied.

JP, 10-78509, A JP, 2004-18561, A JP 2001-106689 A JP, 2000-63691, A Japanese Patent Laid-Open No. 06-025548 Japanese Patent Laid-Open No. 2000-026748 JP, 2013-241563, A Japanese Patent Laid-Open No. 05-078364 JP, 06-107663, A JP, 2007-219114, A JP, 2010-072575, A JP 05-247437 A JP, 2005-325292, A JP, 2003-096040, A

The problem to be solved by the present invention is that there is little absorption in the visible region (400 nm to 700 nm), excellent near-infrared absorption ability, and a highly durable near-infrared absorbing dye, and a near-infrared absorbing material containing the same. Another object of the present invention is to provide a near infrared ray cut filter including the near infrared ray absorbing material.

The present inventors have accomplished the present invention as a result of earnest researches for solving the above problems.
That is, the present invention relates to a near infrared absorbing dye [A] represented by the following general formula (1).

The present invention also relates to a near infrared absorbing material containing the near infrared absorbing dye [A].

The present invention also relates to the near-infrared absorbing material, which further comprises a resin type dispersant.

The present invention also relates to the near-infrared absorbing material, which further comprises a photopolymerizable monomer.

The present invention also relates to a near-infrared cut filter comprising the near-infrared absorbing material.

Furthermore, the present invention is a method for producing a near-infrared absorbing material containing a near-infrared absorbing dye [A] represented by the following general formula (1) and a resin-type dispersant. Disclosed is a method for producing a near-infrared absorbing material, which comprises dispersing with a mold dispersant.

General formula (1)

X represents a heterocycle which may have a substituent. R _{1 to} R ₅ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. aryloxy group which may be, sulfo ^{_{group, SO 3 - M +, -SO}} 2 NR 6 R 7, -COOR 8, -CONR 9 R 10, a nitro group, a cyano group, a halogen atom. M ⁺ represents an inorganic or organic cation, and R _{6 to} R ₁₀ each independently represent a hydrogen atom or an alkyl group which may have a substituent.

INDUSTRIAL APPLICABILITY According to the present invention, a near-infrared absorbing dye which is excellent in durability such as heat resistance and light resistance, as well as being excellent in near-infrared absorbing ability with little absorption in the visible region (400 nm to 700 nm), and a near-infrared absorbing material containing the same Can be obtained. Further, according to the present invention, it is possible to provide a near-infrared cut filter containing the near-infrared absorbing material having the excellent characteristics.

Hereinafter, the present invention will be described in detail.
<Near infrared absorbing dye [A]>
The near-infrared absorbing dye [A] represented by the general formula (1) of the present invention will be described in detail.

General formula (1)

X represents a heterocycle which may have a substituent. R _{1 to} R ₅ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. aryloxy group which may be, sulfo ^{_{group, SO 3 - M +, -SO}} 2 NR 6 R 7, -COOR 8, -CONR 9 R 10, a nitro group, a cyano group, a halogen atom. M ⁺ represents an inorganic or organic cation, and R _{6 to} R ₁₀ each independently represent a hydrogen atom or an alkyl group which may have a substituent.

The heterocycle in X refers to one in which one or more atoms (heteroatoms) other than carbon atoms are contained in the atoms constituting the ring system. A typical hetero atom includes a nitrogen atom, an oxygen atom, and a sulfur atom, and one hetero ring may contain plural kinds of hetero atoms. Those containing an oxygen atom and/or a sulfur atom as a hetero atom of the heterocycle are preferable from the viewpoint of spectral properties, imparting durability and difficulty of synthesis. Examples of the heterocycle include a 3-membered to 10-membered saturated or unsaturated heterocyclic ring, and among them, a 4-membered to 7-membered saturated or unsaturated heterocyclic ring provides durability and synthesis. It is preferable from the viewpoint of difficulty.

The “substituent” in X includes “an alkyl group which may have a substituent”, “an aryl group which may have a substituent”, and “a substituent which has a substituent” in R _{1 to} R ₅ described later. Alkoxy group", "aryloxy group optionally having substituents", "halogen atom", alkenyl group, aralkyl group, hydroxyl group, amino group, substituted amino group, oxo group, and the like. The substituents may combine with each other to form a ring. Further, one heterocycle may have a plurality of substituents.

The following structures are mentioned as specific examples of the "heterocycle optionally having substituent(s)" in X, but the present invention is not limited thereto.

Examples of the “alkyl group which may have a substituent” in R _{1 to} R ₅ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a tert-amyl group, a 2-ethylhexyl group, Stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, cyclohexyl group, dimethylcyclohexyl group and the like can be mentioned. Of these, a methyl group, an ethyl group, and an n-propyl group are preferable from the viewpoint of durability and synthesis difficulty.

Examples of the “aryl group which may have a substituent” in R _{1 to} R ₅ include a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group and a 4-bromophenyl group. Group, 2-methoxyphenyl group, 4-diethylaminophenyl group, 3-nitrophenyl group, 4-cyanophenyl group and the like. Among these, phenyl group and 4-methylphenyl group are endurance-imparting and synthetic. It is preferable from the viewpoint of difficulty.

Examples of the “alkoxy group having a substituent” in R _{1 to} R ₅ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-octyloxy group, and a 2-ethylhexyloxy group. Group, a trifluoromethoxy group, a cyclohexyloxy group, a stearyloxy group, and the like. Among these, a methoxy group, an ethoxy group, and a trifluoromethoxy group are preferable from the viewpoint of durability and synthesis difficulty.

Examples of the “aryloxy group which may have a substituent” in R _{1 to} R ₅ include a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group and a 4-chloro-2- group. Examples thereof include a methylphenyloxy group, a 4-tert-butylphenyloxy group, a 4-methoxyphenyloxy group, a 4-diethylaminophenyloxy group, a 4-nitrophenyloxy group and the like, and among them, a phenoxy group and 4-methyl group. A phenyloxy group and a naphthyloxy group are preferable from the viewpoint of durability and synthesis difficulty.

As the “inorganic or organic cation” of M ⁺ in R _{1 to} R ₅ , known ones can be adopted without limitation, and specifically, metal atom, ammonium compound, pyridinium compound, imidazolium compound, phosphonium compound, sulfonium. A compound etc. can be mentioned. Of these, trivalent metal atoms and ammonium compounds are preferable from the viewpoint of durability and synthesis difficulty.

Examples of the “halogen atom” in R _{1 to} R ₅ include fluorine, bromine, chlorine and iodine.

R ₁ to R ₅ is at least one of a sulfo group, _SO ³ - is preferably ^{M +} or a halogen atom, a sulfo group among them, _SO ³ - and more preferably ^{M +.}

The “alkyl group which may have a substituent” in R _{6 to} R ₁₀ has the same meaning as R _{1 to} R ₅ .

<Near infrared absorbing material>
The near-infrared absorbing material of the present invention comprises a near-infrared absorbing dye [A] represented by the general formula (1) as an essential component, a resin type dispersant, a photopolymerizable monomer, a photopolymerization initiator, a binder resin, It is composed of an organic solvent, a sensitizer, and other auxiliary components.

The near-infrared absorbing dye [A] in the near-infrared absorbing material of the present invention may be used alone or as a mixture of two or more kinds at an arbitrary ratio as necessary.

The content of the near-infrared absorbing dye [A] of the present invention can be adjusted as necessary, but it is preferably contained in the near-infrared absorbing material in an amount of 0.01 to 50% by mass, and 0.1 to 30% by mass. It is more preferable to make it contain by mass %. Within this range, the near infrared absorptivity can be more suitably imparted, and at the same time, the invisibility can be imparted.

In the near-infrared absorbing material of the present invention, it is desirable that the near-infrared absorbing dye [A] is dispersed in a resin type dispersant and used in a fine particle dispersed state. Use in a fine particle dispersed state has the advantage of improving the durability of the compound. The near-infrared absorbing dye [A] used in the present invention preferably has an average primary particle size at dispersion of 1 to 500 nm, more preferably 10 to 200 nm, and particularly preferably 10 to 100 nm. When the average primary particle diameter of the fine particles is 1 nm or more, the surface energy of the particles is small, aggregation is less likely to occur, the fine particles are easily dispersed, and the dispersed state is easily maintained, which is preferable. If the average primary particle size of the fine particles is 200 nm or less, the influence of particle scattering is reduced and the absorption spectrum becomes sharp, which is preferable.

The average primary particle diameter of the near-infrared absorbing dye [A] was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and major axis diameter of the individual primary particles of the dye were measured, and the average was taken as the particle diameter of the primary particles of the dye. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating it to a cube having the obtained particle diameter, and the volume average particle diameter was taken as the average primary particle diameter.

(Method for producing near-infrared absorbing dye [A])
As a method for producing the near-infrared absorbing dye [A], 1,8-diaminonaphthalene represented by the following general formula (3) and a heterocyclic ketone represented by the following general formula (4) are used as a solvent together with a catalyst. After heating and refluxing in the solution to cause condensation, 3,4-dihydroxy-3-cyclobutene-1,2-dione represented by the following formula (5) is added, and the mixture is further heated to reflux and condensed to give the compound represented by the general formula (1): A method for producing the near-infrared absorbing dye [A] represented by Further, when at least one of R _{1 to} R ₅ is SO ₃ ⁻ M ⁺ , by counter exchange between the hydrogen ion of the sulfo group of the dye substituted with the sulfo group and the compound having the target cation, SO _A production method for obtaining a dye substituted with ₃ ^- M ⁺ is conceivable, and counter exchange can be carried out by a known method, but the near infrared absorbing dye [A] used in the present invention is limited by these production methods. It is not something that will be done.

<Resin type dispersant>
The resin-type dispersant that can be used in the present invention has a pigment affinity site having a property of adsorbing to a dye and a site compatible with the dye carrier, and is adsorbed to the dye to disperse it in the dye carrier. It acts to stabilize. In particular, a resin having a controlled structure such as a graft type (comb type) or a block type is preferably used.
As the main chain and/or side chain skeleton of the resin type dispersant, specifically, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid Ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, poly(lower alkyleneimine) and polyester having a free carboxyl group Oily dispersants such as amides and salts thereof formed by the reaction, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, Water-soluble resins such as polyvinyl alcohol and polyvinylpyrrolidone, water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide/propylene oxide addition compounds, and phosphoric acid ester-based compounds are used, and these may be used alone or in combination of two or more. It can be mixed and used. Above all, those having a (meth)acrylic copolymer as a main chain and/or a side chain are preferable.
Specific examples of the dye adsorbing group of the resin type dispersant include acidic adsorbing groups such as aromatic carboxylic acid groups and phosphoric acid groups, and primary amino groups, secondary amino groups, tertiary amino groups, and 4 amino groups. Examples include basic type adsorption groups such as primary ammonium salts. Among them, a resin type dispersant having an aromatic carboxylic acid group, a tertiary amino group or a quaternary ammonium salt as a dye adsorbing group is preferable from the viewpoint of near-infrared absorbing ability and durability. A resin-type dispersant having an ammonium salt as a dye adsorption group is particularly preferable.

Examples of commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167 manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti. -Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, 21324 or Lactimon, Lactimon-WS or Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650 manufactured by Lubrizol Japan. , 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000. , 76500 and the like, EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, manufactured by BASF. 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. Azisper PA111, PB711, PB821, PB822, PB824 etc. are mentioned.

These resin-type dispersants may be used alone or as a mixture of two or more kinds at an arbitrary ratio according to need. These resin type dispersants are preferably 5 to 200% by weight, based on the total amount of dyes in the near infrared absorbing material (100% by weight), and 10 to 150% by weight from the viewpoint of optical characteristics and durability. Is more preferable.

<Photopolymerizable monomer>
The photopolymerizable monomer that can be used in the present invention includes a monomer or an oligomer that is cured by ultraviolet rays or heat to form a transparent resin, and these are used alone or in combination of two or more. You can The amount of the monomer blended is preferably 5 to 400 parts by weight, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability, with respect to 100 parts by weight of the dye.

Examples of the monomer or oligomer that is cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. , Cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di( (Meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di (Meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, ester acrylate, methylolated melamine (Meth)acrylic acid esters, epoxy (meth)acrylates, urethane acrylates and other various acrylic acid and methacrylic acid esters, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol triester Examples thereof include, but are not limited to, vinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, and acrylonitrile.

<Photopolymerization initiator>
In the near-infrared absorbing material of the present invention, when the composition is cured by UV irradiation to form a filter segment by a photolithographic method, a photopolymerization initiator or the like is added to the solvent-developing or alkali-developing colored resist material. Can be prepared in the form of The amount of the photopolymerization initiator used is preferably 5 to 200 parts by weight, and 10 to 150 parts by weight from the viewpoint of photocurability and developability, based on 100 parts by weight of the total amount of the dye. Is more preferable.

As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1 Acetophenone compounds such as -[4-(4-morpholinyl)phenyl]-1-butanone or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin, benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′. -Methyldiphenyl sulfide, or a benzophenone compound such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 A thioxanthone compound such as diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-( p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6- Bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s- Triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4- Triazine compounds such as trichloromethyl-(4'-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoi Oxime)], 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 a phosphine compound such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; a quinone compound such as 9,10-phenanthrenequinone, camphorquinone or ethylanthraquinone; a borate compound; A carbazole-based compound; an imidazole-based compound; or a titanocene-based compound or the like is used.

These photopolymerization initiators may be used either individually or in combination of two or more at an optional ratio, if desired. These photopolymerization initiators are preferably 5 to 200% by weight, based on the total amount of dyes in the near infrared absorbing material (100% by weight), and 10 to 150% by weight from the viewpoint of photocurability and developability. % Is more preferable.

<Binder resin>
The binder resin is preferably a resin having a spectral transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. When used in the form of an alkali-developable resist material, it is preferable to use an alkali-soluble vinyl resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic group. Further, an active energy ray-curable resin having an ethylenically unsaturated double bond can be used for the purpose of further improving photosensitivity and solvent resistance.

In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain for an alkali development type resist, a coating foreign matter does not occur after applying the near infrared absorbing material of the present invention, and the resist The stability of the dye in the material is improved, which is preferable. When a linear resin that does not have an ethylenically unsaturated double bond in the side chain is used, the dye is difficult to be trapped in the resin in the liquid in which the resin and the dye coexist The components tend to aggregate/precipitate, but by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain, the dye tends to be trapped in the resin in the liquid in which the resin and the dye are mixed, In the solvent resistance test, the dye is less likely to elute, the dye component is less likely to aggregate/precipitate, and the resin is three-dimensionally cross-linked when the film is formed by exposure to active energy rays to fix the dye molecule. It is presumed that the colorant component is less likely to aggregate/precipitate even if the solvent is removed in the subsequent developing step.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably 10,000 to 80,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw/Mn is preferably 10 or less.

When a binder resin is used as a near infrared ray absorbing material, an aliphatic carboxyl group that acts as an alkali-soluble group at the time of development is taken into consideration from the viewpoint of permeability, developability and heat resistance of the near infrared ray absorbing dye (A) of the present invention. The balance between the aliphatic group and the aromatic group that act as the group, the dye carrier and the affinity group for the solvent is important, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH/g. When the acid value is less than 20 mgKOH/g, the solubility in a developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH/g, no fine pattern will remain.

The binder resin is preferably used in an amount of 30 parts by weight or more based on 100 parts by weight of the total weight of the dye, since it has good film-forming properties and various resistances, and has a high dye concentration and capable of exhibiting good optical characteristics. Therefore, it is preferably used in an amount of 500 parts by weight or less.

(Thermoplastic resin)
Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate. , Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. .. Above all, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as an aliphatic carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin/(anhydrous) maleic acid copolymer, a styrene/styrene sulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or Examples thereof include isobutylene/(anhydrous) maleic acid copolymer. Among them, an acrylic resin having an acidic group and at least one resin selected from styrene/styrene sulfonic acid copolymers, and particularly an acrylic resin having an acidic group are preferably used because they have high heat resistance and transparency.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the methods (a) and (b) shown below.

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

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

Examples of the unsaturated monobasic acid include (meth)acrylic acid, crotonic acid, α-position haloalkyl of (meth)acrylic acid, alkoxyl, halogen, nitro, monocarboxylic acids such as cyano-substituted compounds, and the like. Or two or more kinds may be used in combination.

Examples of polybasic acid anhydrides include succinic anhydride and maleic anhydride, and these may be used alone or in combination of two or more kinds.

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

[Method (b)]
As the method (b), an unsaturated ethylenic monomer having a hydroxyl group is used, and a monomer of an unsaturated monobasic acid having another aliphatic carboxyl group and another monomer are copolymerized. There is a method of reacting the side chain hydroxyl group of the copolymer thus obtained with the isocyanate group of the unsaturated ethylenic monomer having an isocyanate group.

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

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2-(meth)acryloyloxyethylisocyanate, 1,1-bis[(meth)acryloyloxy]ethylisocyanate, and the like, but are not limited thereto. Alternatively, two or more types can be used together.

(Thermosetting resin)
Examples of the thermosetting resin used as the binder resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, cardo resin, and phenol resin.

Examples of the thermosetting resin include epoxy compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, cardo compounds, and phenol compounds. It is not limited to this. By including such a thermosetting resin, the resin reacts when the filter segment is fired, the crosslinking density of the coating film is increased, the heat resistance is improved, and the effect of suppressing pigment aggregation during firing of the filter segment is obtained. To be
Among these, epoxy resin, cardo resin, or melamine resin is preferable.

<Organic solvent>
In the near-infrared ray absorbing material of the present invention, a dye is sufficiently dissolved in a monomer, a resin, etc. and coated on a substrate such as a glass substrate so that a dry film thickness is 0.2 to 5 μm to form a filter segment. A solvent may be included to facilitate this.

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, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl -1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m. -Diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propylacetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene Glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether Ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether , Dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether , Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol Monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclo Hexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like can be mentioned.

Among them, alkyl lactates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, glycol acetates such as ethylene glycol monoethyl ether acetate, aromatic alcohols such as benzyl alcohol, and the like. It is preferable to use ketones such as cyclohexanone.

These organic solvents can be used alone or in combination of two or more. When two or more kinds of mixed solvents are used, it is preferable that the above preferable organic solvent is contained in an amount of 65 to 95% by weight based on 100 parts by weight of the whole organic solvent. Particularly, it is preferable that propylene glycol monomethyl ether acetate is the main component, and it is preferable that the content of propylene glycol monomethyl ether acetate is 65 to 100% by weight in the total organic solvent.
Further, the organic solvent can adjust the near-infrared absorbing material to have an appropriate viscosity and form a filter segment having a desired uniform film thickness, so that the amount of the dye is 500 to 4000 parts by weight based on 100 parts by weight of the total weight of the dye. It is preferable to use.

<Sensitizer>
Further, the near infrared ray absorbing material of the present invention can contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones represented by dibenzalacetone, etc., 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives. , Polymethine dyes such as xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonole derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, spiropyran derivative, spirooxazine derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, biimidazole derivative, α -Acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4 , 4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-diethylaminobenzophenone and the like.

More specifically, Nobu Okawara et al., "Dye Handbook" (1986, Kodansha), Nobu Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Tadaburo Ikemori et al. Examples of the sensitizer include those described in "Special Function Material" (1986, CMC), but are not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region may be contained.

Two or more kinds of sensitizers may be used in an arbitrary ratio, if necessary. The compounding amount of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the total weight of the photopolymerization initiator contained in the near-infrared absorbing material. From the viewpoint of 5 to 50 parts by weight is more preferable.

<Multifunctional thiol>
The near-infrared absorbing material of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups, and examples thereof include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, and ethylene. Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N- Dibutylamino)-4,6-dimercapto-s-triazine and the like can be mentioned.
These polyfunctional thiols can be used singly or as a mixture of two or more kinds at an arbitrary ratio according to need.

The content of the functional thiol is preferably 0.1 to 30% by weight, and more preferably 1 to 20% by weight, based on the weight (100% by weight) of the total solid content of the near infrared absorbing material. When the content of the polyfunctional thiol is less than 0.1% by weight, the effect of adding the polyfunctional thiol is insufficient, and when it exceeds 30% by weight, the sensitivity is too high and the resolution is lowered.

<Antioxidant>
The near infrared ray absorbing material of the present invention may contain an antioxidant. The antioxidant has a high transmittance of the coating film in order to prevent the photopolymerization initiator and the thermosetting compound contained in the near-infrared absorbing material from being oxidized and yellowing due to the thermal process during thermosetting or ITO annealing. can do. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented and a high transmittance of the coating film can be obtained.
The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function, and specifically, as a antioxidant, a hindered phenol type, a hindered amine type. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers and antioxidants can be used.
Among these antioxidants, from the viewpoint of compatibility of the transmittance and the sensitivity of the coating film, preferred are hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants or sulfur antioxidants. Agents. Further, more preferably, it is a hindered phenol antioxidant, a hindered amine antioxidant, or a phosphorus antioxidant.
These antioxidants can be used singly or as a mixture of two or more kinds at an arbitrary ratio according to need. The content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the near-infrared absorbing material (100% by weight) because the sensitivity is good.

<Amine compound>
Further, the near infrared ray absorbing material of the present invention may contain an amine compound having a function of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylparatoluidine and the like can be mentioned.

<Leveling agent>
A leveling agent is preferably added to the near-infrared absorbing material of the present invention in order to improve the leveling property of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by BYK Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used together. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight based on 100% by weight of the total amount of the near infrared absorbing material.

Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a small hydrophilicity even though having a hydrophilic group, when added to the coloring composition, It has the characteristic of low surface tension lowering ability, and it is useful that it has good wettability to the glass plate in spite of the low surface tension lowering ability. Those that can sufficiently suppress the charging property can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

In addition, the bonding 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 end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. It may be of a linear block copolymer type in which alternately and repeatedly bonded. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -207, but not limited thereto.

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.

Examples of anionic surfactants that are supplementarily added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, and alkyldiphenyletherdisulfonic acid. Sodium, 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 phosphate Examples thereof include esters.

Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants that are supplementarily added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate. Examples thereof include polyethylene glycol monolaurate and the like; alkylbetaine such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazoline, and fluorine-based or silicone-based surfactants.

<Curing agent, curing accelerator>
Further, the near-infrared absorbing material of the present invention may contain a curing agent, a curing accelerator, etc., if necessary, in order to assist the curing of the thermosetting resin. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. are effective, but are not particularly limited to these, and thermosetting resins Any curing agent may be used as long as it can react with. Among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferable. Examples of the curing accelerator include amine compounds (eg, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl). -N,N-dimethylbenzylamine etc.), quaternary ammonium salt compound (eg triethylbenzylammonium chloride etc.), blocked isocyanate compound (eg dimethylamine etc.), imidazole derivative bicyclic amidine compound and salts thereof (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.), guanamine compounds (eg melamine, guanamine, acetoguanamine, benzoguanamine 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) and the like can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the thermosetting resin.

<Other near infrared absorbing dyes>
The near-infrared absorbing material of the present invention may contain other near-infrared absorbing dyes in addition to the near-infrared absorbing dye [A] of the present invention. Examples of near infrared absorbing dyes other than the near infrared absorbing dye [A] that can be used in the near infrared absorbing material of the present invention include cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, aminium compounds, diimmonium compounds, croconium compounds, Examples thereof include, but are not limited to, azo compounds, quinoid type complex compounds, and dithiol metal complex compounds.

<Other additive components>
The near infrared ray absorbing material of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Further, an adhesion improver such as a silane coupling agent may be contained in order to improve the adhesion to the transparent substrate.

Examples of the storage stabilizer include benzyl trimethyl chloride, quaternary ammonium chlorides such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples thereof include organic phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the colorant.

Examples of the adhesion improver include vinyl silanes such as vinyl tris(β-methoxyethoxy)silane, vinyl ethoxy silane and vinyl trimethoxy silane, (meth)acryl silanes such as γ-methacryloxypropyl trimethoxy silane, 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(amino Ethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples of the silane coupling agent include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total amount of the coloring agent in the coloring composition.

<Method of manufacturing near-infrared absorbing material>
The near-infrared absorbing material of the present invention is preferably obtained by dispersing the near-infrared absorbing dye [A] in a resin using a resin type dispersant. As the resin, a resin type dispersant itself may be used, or a binder resin may be used. As a specific method for producing the near-infrared absorbing material of the present invention, the near-infrared absorbing dye [A] is mixed with a resin-type dispersant and, if necessary, a binder resin, an organic solvent, and other dispersion aids. It is preferable to finely disperse and produce it using various dispersing means such as a kneader, a kneader, a two roll mill, a three roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor.

<Removal of coarse particles>
The near-infrared absorbing material of the present invention has a coarse particle of 5 μm or more, preferably a coarse particle of 1 μm or more, and more preferably a coarse particle of 0.5 μm or more, and mixed by means of centrifugal separation, a sintering filter, a membrane filter or the like. It is preferable to remove the dust. As described above, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. It is more preferably 0.3 μm or less.

<Method of manufacturing near infrared cut filter>
The near infrared ray cut filter of the present invention can be manufactured by a printing method or a photolithography method. Since the filter segment can be formed by the printing method only by repeating the printing and drying of the near-infrared absorbing material prepared as a printing ink, the filter manufacturing method is low in cost and excellent in mass productivity. There is. Furthermore, the development of printing technology enables printing of fine patterns having high dimensional accuracy and smoothness. For printing, it is preferable that the composition is such that the ink does not dry and solidify on the printing plate or on the blanket. Further, it is important to control the fluidity of the ink on the printing machine, and the ink viscosity can be adjusted by the dispersant and the extender pigment.

When the filter segment is formed by the photolithography method, the near-infrared absorbing material prepared as the solvent developing type or alkali developing type resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. Depending on the method, it is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern, which is provided in contact or non-contact with the film. After that, after dipping in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, repeat the same operation for other colors to manufacture a filter. You can Furthermore, in order to accelerate the polymerization of the resist material, heating can be carried out as necessary. According to the photolithography method, it is possible to manufacture a filter with higher accuracy than the above printing method.

The transparent substrate is not particularly limited, but a sheet-shaped, film-shaped, or plate-shaped transparent substrate can be used as the shape. The color is also colorless and colored, and is not particularly limited. Examples of the material of the transparent base material include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and triacetyl cellulose (TAC). Examples thereof include acrylic resins such as methyl methacrylate copolymers, styrene resins, polysulfone resins, polyether sulfone resins, polycarbonate resins, vinyl chloride resins, polymethacrylimide resins, and glass plates.

Upon development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developing solution, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. In order to increase the UV exposure sensitivity, after coating and drying the above colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. After that, ultraviolet exposure can be performed.

The near-infrared cut filter of the present invention can be manufactured by an electrodeposition method, a transfer method, an inkjet method, etc. in addition to the above method, and the near-infrared absorbing material of the present invention can be used in any method.

<Use of near infrared cut filter>
The near-infrared cut filter of the present invention has little absorption in the visible region (400 nm to 700 nm), is excellent in near-infrared absorbing ability, and is also excellent in durability such as heat resistance and light resistance. Therefore, as a wavelength selection filter, such as near-infrared absorption film and near-infrared absorption plate that blocks heat rays for energy saving, near-infrared absorption film for agriculture for the purpose of selective use of sunlight, near-infrared cut filter for electronic devices, etc. Can be used for a wide range of purposes.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In Examples and Comparative Examples, “parts” and “%” mean “parts by mass” and “mass %”, respectively.
Further, "PGMAc" is propylene glycol monomethyl ether acetate, "Aronix M-402" is dipentaerythritol hexaacrylate, "OXE-02" is ethanone, 1-[9-ethyl-6-(2-methylbenzoyl). -9H-carbazol-3-yl]-,1-(0-acetyloxime) is meant.

(Method for identifying near-infrared absorbing dye [A])
Elemental analysis and MALDI TOF-MS spectrum were used for the identification of the squarylium dye used in the present invention. For the elemental analysis, 2400 CHN Elemant Analyzer manufactured by Perkin Elmer was used. The MALDI TOF-MS spectrum was identified by using the MALDI mass spectrometer autoflexIII manufactured by Bruker Daltonix Co., Ltd., with the coincidence between the molecular ion peak of the obtained mass spectrum and the calculated mass number. It was

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

(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 TPC gel column (manufactured by Tosoh Corporation), GPC equipped with an RI detector (Tosoh Corporation, HLC-8120GPC), and THF is used as a developing solvent. It is the polystyrene-equivalent weight average molecular weight (Mw).

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

<Production of near-infrared absorbing dye>
[Example 1]
(Production of near infrared absorbing dye [A-1])
To 400 parts of toluene, 40.0 parts of 1,8-diaminonaphthalene, 25.6 parts of tetrahydro-4H-pyran-4-one, and 0.087 part of p-toluenesulfonic acid monohydrate were mixed and mixed with nitrogen gas. The mixture was heated and stirred in the atmosphere and refluxed for 3 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, a dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and an atmosphere of nitrogen gas was added. The mixture was heated and stirred in the medium, and the mixture was refluxed for 8 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the solvent was distilled off, and 200 parts of hexane was added while stirring the obtained reaction mixture. The obtained black-brown precipitate was filtered off, washed successively with hexane, ethanol and acetone and dried under reduced pressure to give 65.8 parts of near-infrared absorbing dye [A-1] (yield: 97%). Got As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-1].

Near infrared absorbing dye [A-1]

[Example 2]
(Production of near infrared absorbing dye [A-2])
22.6 parts of 2,6-dimethyl-dihydro-4H-pyran-4-one were used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the preparation of the near infrared absorbing dye [A-1]. The same operation as in the production of the near-infrared absorbing dye [A-1] was performed except that the above was used to obtain 70.9 parts (yield: 95%) of the near-infrared absorbing dye [A-2]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-2].

Near infrared absorbing dye [A-2]

[Example 3]
(Production of near infrared absorbing dye [A-3])
Near-infrared rays except that 32.5 parts of 1-ethyl-4-piperidone were used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production of absorption dye [A-1] was carried out to obtain 70.6 parts (yield: 95%) of near infrared absorption dye [A-3]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-3].

Near infrared absorbing dye [A-3]

[Example 4]
(Production of near infrared absorbing dye [A-4])
Instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-1], 2,9.6 parts of 2,2,6,6-tetramethyl-4-piperidone was added in an amount of 39.6 parts. The same operation as in the production of the near-infrared absorbing dye [A-1] was performed except that the above was used to obtain 76.3 parts (yield: 94%) of the near-infrared absorbing dye [A-4]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-4].

Near infrared absorbing dye [A-4]

[Example 5]
(Production of near-infrared absorbing dye [A-5])
Near-infrared absorbing dye [A-1] except that 29.7 parts of 4-oxothiane was used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of near-infrared absorbing dye [A-1]. The same operation as in the production of [-1] was performed to obtain 68.8 parts (yield: 96%) of near-infrared absorbing dye [A-5]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-5].

Near infrared absorbing dye [A-5]

[Example 6]
(Production of near infrared absorbing dye [A-6])
53.7 parts of 2-phenyl-1,3-dithian-5-one was used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near infrared absorbing dye [A-1]. Other than the above, the same operation as in the production of the near-infrared absorbing dye [A-1] was carried out to obtain 88.9 parts (yield: 94%) of the near-infrared absorbing dye [A-6]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-6].

Near infrared absorbing dye [A-6]

[Example 7]
(Production of near infrared absorbing dye [A-7])
Near infrared absorbing dye [A-1] except that 36.3 parts of alloxane was used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of near infrared absorbing dye [A-1]. ] The same operation as in the production of] was performed to obtain 74.9 parts (yield: 96%) of near-infrared absorbing dye [A-7]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-7].

Near infrared absorbing dye [A-7]

[Example 8]
(Production of near infrared absorbing dye [A-8])
Near-infrared absorbing dye [A-1] except that 18.4 parts of 3-oxetanone were used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of near-infrared absorbing dye [A-1]. The same operation as in the production of [-1] was carried out to obtain 56.1 parts (yield: 92%) of near-infrared absorbing dye [A-8]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-8].

Near infrared absorbing dye [A-8]

[Example 9]
(Production of near infrared absorbing dye [A-9])
Near-infrared absorbing dye, except that 22.0 parts of tetrahydrofuran-3-one was used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of near-infrared absorbing dye [A-1]. The same operation as in the production of [A-1] was carried out to obtain 59.9 parts (yield: 93%) of near-infrared absorbing dye [A-9]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-9].

Near infrared absorbing dye [A-9]

[Example 10]
(Production of near infrared absorbing dye [A-10])
32.0 parts of 1-azabicyclo[3,2,1]octane-3-one instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near infrared absorbing dye [A-1]. The same operation as in the production of the near-infrared absorbing dye [A-1] was performed except that the above was used to obtain 69.4 parts (yield: 94%) of the near-infrared absorbing dye [A-10]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-10].

Near infrared absorbing dye [A-10]

[Example 11]
(Production of near infrared absorbing dye [A-11])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near infrared absorbing dye [A-1], 1,8-diamino-3- The same operation as in the production of the near-infrared absorbing dye [A-1] was performed except that 43.5 parts of methylnaphthalene and 68.0 parts of 2-benzyl-6-phenyl-dihydro-4H-pyran-4-one were used. This was carried out to obtain 101.5 parts (yield: 91%) of the near infrared absorbing dye [A-11]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-11].

Near infrared absorbing dye [A-11]

[Example 12]
(Production of near infrared absorbing dye [A-12])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near infrared absorbing dye [A-1], 1,8-diamino-4- Production of near-infrared absorbing dye [A-1] except that 57.2 parts of trifluoromethylnaphthalene and 35.5 parts of 2-methyl-2-azabicyclo[2,2,2]octane-5-one were used. The same operation was performed to obtain 87.2 parts (yield: 93%) of the near infrared absorbing dye [A-12]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-12].

Near infrared absorbing dye [A-12]

[Example 13]
(Production of near infrared absorbing dye [A-13])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near infrared absorbing dye [A-1], 1,8-diamino-3- Near-infrared rays were obtained by the same procedure as in the production of the near-infrared absorbing dye [A-1] except that 59.2 parts of phenylnaphthalene and 49.9 parts of 1-isopropyloctahydroquinolin-4(1H)-one were used. 103.9 parts (yield: 95%) of absorbing dye [A-13] was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-13].

Near infrared absorbing dye [A-13]

[Example 14]
(Production of near infrared absorbing dye [A-14])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near infrared absorbing dye [A-1], 1,8-diamino-3- Near-infrared rays were produced in the same manner as in the production of the near-infrared absorbing dye [A-1] except that 62.8 parts of p-tolylnaphthalene and 35.5 parts of hexahydroindolizine-7(1H)-one were used. 91.2 parts (yield: 92%) of absorbing dye [A-14] was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-14].

Near infrared absorbing dye [A-14]

[Example 15]
(Production of near infrared absorbing dye [A-15])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near infrared absorbing dye [A-1], 1,8-diamino-3- Same as the production of near-infrared absorbing dye [A-1] except that 47.6 parts of methoxynaphthalene and 70.9 parts of 2-(4-chlorophenyl)-6-(trifluoromethyl)piperidin-4-one were used. Was performed to obtain 102.4 parts (yield: 94%) of near infrared absorbing dye [A-15]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-15].

Near infrared absorbing dye [A-15]

[Example 16]
(Production of near infrared absorbing dye [A-16])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the preparation of the near infrared absorbing dye [A-1], 1,8-diamino-2- The same operation as in the production of the near-infrared absorbing dye [A-1] was performed except that 61.2 parts of trifluoromethoxynaphthalene and 41.9 parts of thiochroman-4-one were used, and the near-infrared absorbing dye [A-16 ] 94.9 parts (yield: 90%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-16].

Near infrared absorbing dye [A-16]

[Example 17]
(Production of near infrared absorbing dye [A-17])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the preparation of the near infrared absorbing dye [A-1], 1,8-diamino-2- Near-infrared rays were produced in the same manner as in the production of the near-infrared absorbing dye [A-1] except that 63.3 parts of phenoxynaphthalene and 35.8 parts of 2,6-dimethyl-4H-thiopyran-4-one were used. 85.6 parts (yield: 92%) of absorbing dye [A-17] was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-17].

Near infrared absorbing dye [A-17]

[Example 18]
(Production of near infrared absorbing dye [A-18])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near infrared absorbing dye [A-1], 1,8-diamino-3- Similar to the preparation of near-infrared absorbing dye [A-1] except that 66.8 parts of p-tolyloxynaphthalene and 33.2 parts of 6-(hydroxymethyl)dihydro-2H-pyran-3(4H)-one were used. Was performed to obtain 92.8 parts (yield: 92%) of near infrared absorbing dye [A-18]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-18].

Near infrared absorbing dye [A-18]

[Example 19]
(Production of near infrared absorbing dye [A-19])
Aside from using 60.2 parts of 4,5-diaminonaphthalene-1-sulfonic acid instead of 40.0 parts of 1,8-diaminonaphthalene used in the production of the near-infrared absorbing dye [A-1], The same operation as in the production of the infrared absorbing dye [A-1] was carried out to obtain 81.1 parts (yield: 93%) of the near infrared absorbing dye [A-19]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-19].

Near infrared absorbing dye [A-19]

[Example 20]
(Production of near infrared absorbing dye [A-20])
22.6 parts of 2,6-dimethyl-dihydro-4H-pyran-4-one were used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the preparation of the near infrared absorbing dye [A-19]. The same operation as in the production of the near-infrared absorbing dye [A-19] was carried out except that the above was used to obtain 86.5 parts (yield: 92%) of the near-infrared absorbing dye [A-20]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-20].

Near infrared absorbing dye [A-20]

[Example 21]
(Production of near infrared absorbing dye [A-21])
Near-infrared rays except that 32.5 parts of 1-ethyl-4-piperidone were used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-19]. The same operation as in the production of absorption dye [A-19] was carried out to obtain 87.2 parts (yield: 93%) of near-infrared absorption dye [A-21]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-21].

Near infrared absorbing dye [A-21]

[Example 22]
(Production of near infrared absorbing dye [A-22])
Instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near infrared absorbing dye [A-19], 39.6 parts of 2,2,6,6-tetramethyl-4-piperidone were added. The same operation as in the production of the near-infrared absorbing dye [A-19] was carried out except that it was used to obtain 94.6 parts (yield: 94%) of the near-infrared absorbing dye [A-22]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-22].

Near infrared absorbing dye [A-22]

[Example 23]
(Production of near infrared absorbing dye [A-23])
Near infrared absorbing dye [A-19] except that 29.7 parts of 4-oxothiane was used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of near infrared absorbing dye [A-19]. By performing the same operation as in the production of [-19], 82.9 parts (yield: 91%) of near infrared absorbing dye [A-23] was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-23].

Near infrared absorbing dye [A-23]

[Example 24]
(Production of near infrared absorbing dye [A-24])
53.7 parts of 2-phenyl-1,3-dithian-5-one was used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near infrared absorbing dye [A-19]. Other than the above, the same operation as in the production of the near-infrared absorbing dye [A-19] was performed to obtain 103.7 parts (yield: 91%) of the near-infrared absorbing dye [A-24]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-24].

Near infrared absorbing dye [A-24]

[Example 25]
(Production of near infrared absorbing dye [A-25])
Near infrared absorbing dye [A-19] except that 36.3 parts of alloxane was used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of near infrared absorbing dye [A-19]. ] The same operation as in the production of] was performed to obtain 90.6 parts (yield: 93%) of a near infrared absorbing dye [A-25]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-25].

Near infrared absorbing dye [A-25]

[Example 26]
(Production of near infrared absorbing dye [A-26])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near infrared absorbing dye [A-1], 4,5-diamino-N- Except for using 67.1 parts of ethylnaphthalene-1-sulfoamide and 39.9 parts of hexahydropyrano[3,2-b]pyran-3(2H)-one, a near infrared absorbing dye [A-1] The same operation as in production was carried out to obtain 101.1 parts (yield: 94%) of a near infrared absorbing dye [A-26]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-26].

Near infrared absorbing dye [A-26]

[Example 27]
(Production of near infrared absorbing dye [A-27])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-1], 4,5-diamino-1- The same operation as in the production of the near-infrared absorbing dye [A-1] was performed except that 51.1 parts of naphthoic acid and 29.1 parts of 1-azabicyclo[2.2.1]heptan-3-one were used, 73.9 parts (yield: 91%) of near-infrared absorbing dye [A-27] was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-27].

Near infrared absorbing dye [A-27]

[Example 28]
(Production of near infrared absorbing dye [A-28])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-1], 4,5-diamino-1- Near-infrared rays were obtained by performing the same operation as in the production of the near-infrared absorbing dye [A-1] except that 54.7 parts of methyl naphthoate and 48.3 parts of 1-methyl-4-phenylpiperidin-3-one were used. 95.2 parts (yield: 92%) of absorption dye [A-28] was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-28].

Near infrared absorbing dye [A-28]

Example 29
(Production of near infrared absorbing dye [A-29])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near infrared absorbing dye [A-1], 4,5-diamino-N- The same operation as in the production of the near-infrared absorbing dye [A-1] except that 58.0 parts of ethylnaphthamide and 36.8 parts of 5,5-dimethyldihydro-2H-thiopyran-3(4H)-one were used. Was performed to obtain 87.1 parts (yield: 91%) of a near infrared absorbing dye [A-29]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-29].

Near infrared absorbing dye [A-29]

[Example 30]
(Production of near infrared absorbing dye [A-30])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near infrared absorbing dye [A-1], 1,8-diamino-3- The same operation as in the production of the near-infrared absorbing dye [A-1] was performed except that 51.4 parts of nitrophthalene and 41.9 parts of isothiochroman-4-one were used, and the near-infrared absorbing dye [A-29] was obtained. 87.7 parts (yield: 93%) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-30].

Near infrared absorbing dye [A-30]

[Example 31]
(Production of near infrared absorbing dye [A-31])
Near-infrared rays except that 48.7 parts of 1,8-diaminonaphthalene used in the production of the near-infrared absorbing dye [A-1] was replaced with 48.7 parts of 1,8-diamino-4-chloronaphthalene. The same operation as in the production of absorption dye [A-1] was carried out to obtain 70.1 parts (yield: 92%) of near infrared absorption dye [A-31]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-31].

Near infrared absorbing dye [A-31]

[Example 32]
(Production of near infrared absorbing dye [A-32])
Instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the preparation of the near infrared absorbing dye [A-31], 22.7 parts of 2,6-dimethyl-dihydro-4H-pyran-4-one are used. The same operation as in the production of the near-infrared absorbing dye [A-31] was performed except that the above was used to obtain 79.6 parts (yield: 96%) of the near-infrared absorbing dye [A-32]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-32].

Near infrared absorbing dye [A-32]

[Example 33]
(Production of near infrared absorbing dye [A-33])
Near-infrared rays except that 32.5 parts of 1-ethyl-4-piperidone were used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-31]. The same operation as in the production of absorption dye [A-31] was carried out to obtain 78.6 parts (yield: 95%) of near infrared absorption dye [A-33]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-33].

Near infrared absorbing dye [A-33]

Example 34
(Production of near-infrared absorbing dye [A-34])
Instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near infrared absorbing dye [A-31], 39.6 parts of 2,2,6,6-tetramethyl-4-piperidone were used. The same operation as in the production of the near-infrared absorbing dye [A-31] was performed except that the above was used to obtain 81.5 parts (yield: 91%) of the near-infrared absorbing dye [A-34]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-34].

Near infrared absorbing dye [A-34]

Example 35
(Production of near infrared absorbing dye [A-35])
Near infrared absorbing dye [A-31] except that 29.7 parts of 4-oxothiane was used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of near infrared absorbing dye [A-31]. The same operation as in the production of -31] was carried out to obtain 74.5 parts (yield: 93%) of a near infrared absorbing dye [A-35]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-35].

Near infrared absorbing dye [A-35]

Example 36
(Production of near-infrared absorbing dye [A-36])
53.7 parts of 2-phenyl-1,3-dithian-5-one was used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near infrared absorbing dye [A-31]. Other than the above, the same operation as in the production of the near-infrared absorbing dye [A-31] was carried out to obtain 96.7 parts (yield: 94%) of the near-infrared absorbing dye [A-36]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-36].

Near infrared absorbing dye [A-36]

[Example 37]
(Production of near infrared absorbing dye [A-37])
Near infrared absorbing dye [A-31] except that 36.3 parts of alloxane was used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of near infrared absorbing dye [A-31]. The same operation as in the production of] was performed to obtain 80.3 parts (yield: 93%) of a near infrared absorbing dye [A-37]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-37].

Near infrared absorbing dye [A-37]

[Example 38]
(Production of near infrared absorbing dye [A-38])
Instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near infrared absorbing dye [A-31], 33.2 parts of 2,2-dimethyl-1,3-dioxan-5-one The same operation as in the production of the near-infrared absorbing dye [A-31] was performed except that the above was used to obtain 79.3 parts (yield: 95%) of the near-infrared absorbing dye [A-38]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-38].

Near infrared absorbing dye [A-38]

Example 39
(Production of near infrared absorbing dye [A-39])
Instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the preparation of the near infrared absorbing dye [A-31], 51.7 parts of 1,5-dithiaspiro[5.5]undecan-3-one were used. The same operation as in the production of the near-infrared absorbing dye [A-31] was carried out except that the above was used to obtain 91.9 parts (yield: 91%) of the near-infrared absorbing dye [A-39]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-39].

Near infrared absorbing dye [A-39]

[Example 40]
(Production of near infrared absorbing dye [A-40])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the preparation of the near infrared absorbing dye [A-1], 1,8-diamino-4, The same operation as in the production of the near-infrared absorbing dye [A-1] was performed except that 57.4 parts of 5-dichloronaphthalene and 33.8 parts of 2-methyl-1,3-oxathian-5-one were used, 87.7 parts (yield: 95%) of near infrared absorbing dye [A-40] was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near-infrared absorbing dye [A-40].

Near infrared absorbing dye [A-40]

Example 41
(Production of near-infrared absorbing dye [A-41])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the preparation of the near infrared absorbing dye [A-1], 1,8-diamino-4, Near-infrared absorbing dye [A-1] except that 79.9 parts of 5-dibromonaphthalene and 35.3 parts of 5H-pyrazolo[5,1-b][1,3]oxazin-6(7H)-one were used. ], and 103.8 parts (yield: 90%) of near-infrared absorbing dye [A-41] was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-41].

Near infrared absorbing dye [A-41]

Example 42
(Production of near infrared absorbing dye [A-42])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the preparation of the near infrared absorbing dye [A-1], 1,8-diamino-2- Except that 46.3 parts of naphthonitrile and 37.9 parts of 1,4-dithiepan-6-one were used, the same operation as in the production of the near-infrared absorbing dye [A-1] was performed, and the near-infrared absorbing dye [A -42] 78.7 parts (yield: 92%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a near infrared absorbing dye [A-42].

Near infrared absorbing dye [A-42]

The results of mass spectrometry and elemental analysis performed on the near-infrared absorbing dyes synthesized in Examples 1 to 42 are shown in Tables 1 and 2.

[Example 43]
(Production of near-infrared absorbing dye [A-43])
20.0 parts of near-infrared absorbing dye [A-19] was added to 300 parts of water, stirred and redispersed, and then adjusted to pH 9.0 with 26% aqueous ammonia and dissolved. 235.5 parts of an 8% tetrabutylammonium bromide aqueous solution was gradually added to this solution. Precipitates appeared one after another from the dropped portion, and the pH gradually decreased with addition. No bleed was observed after the addition was completed. The precipitate was filtered off from the slurry, washed with water, and dried at 80° C. to obtain 33.1 parts (yield: 99%) of near-infrared absorbing dye [A-43].

[Example 44]
(Production of near infrared absorbing dye [A-44])
Instead of 235.5 parts of the 8% tetrabutylammonium bromide aqueous solution used in the production of the near infrared absorbing dye [A-43], 194.4 parts of an 8% 1,2-dimethyl-3-propylimidazolium iodide aqueous solution was added. The same operation as in the production of the near-infrared absorbing dye [A-43] was performed except that it was used to obtain 27.1 parts (yield: 98%) of the near-infrared absorbing dye [A-44].

[Example 45]
(Production of near infrared absorbing dye [A-45])
Near infrared absorption except that 125.4 parts of an 8% 1-butylpyridinium chloride aqueous solution was used instead of 235.5 parts of the 8% tetrabutylammonium bromide aqueous solution used in the production of the near infrared absorbing dye [A-43]. The same operation as in the production of the dye [A-43] was carried out to obtain 27.2 parts (yield: 99%) of a near infrared absorbing dye [A-45].

[Example 46]
(Production of near-infrared absorbing dye [A-46])
Near infrared absorption except that 271.2 parts of an 8% ethyltriphenylphosphonium bromide aqueous solution was used instead of 235.5 parts of the 8% tetrabutylammonium bromide aqueous solution used in the production of the near infrared absorption dye [A-43]. The same operation as in the production of Dye [A-43] was carried out to obtain 35.8 parts (yield: 99%) of near-infrared absorbing dye [A-46].

[Example 47]
(Production of near infrared absorbing dye [A-47])
The near infrared absorbing dye [A-43] was replaced with 23% 8% aqueous solution of tetrabutylammonium bromide used in the production of the near infrared absorbing dye [A-43], except that 114.7 parts of 8% aqueous trimethylsulfonium bromide solution was used. The same operation as in the production of A-43] was carried out to obtain 23.8 parts (yield: 98%) of near-infrared absorbing dye [A-47].

[Example 48]
(Production of near infrared absorbing dye [A-48])
Near-infrared absorbing dye [A-43] except that 76.7 parts of 8% aluminum sulfate aqueous solution was used instead of 235.5 parts of 8% tetrabutylammonium bromide aqueous solution used in the production of near-infrared absorbing dye [A-43]. The same operation as in the production of -43] was carried out to obtain 20.2 parts (yield: 99%) of near-infrared absorbing dye [A-48].

[Comparative Example 1]
(Production of near-infrared absorbing dye [B-1])
The following near-infrared absorbing dye [B-1] was synthesized with reference to Japanese Patent No. 3590694.

Near infrared absorbing dye [B-1]

Et represents an ethyl group.

<Method for producing binder resin solution>
(Preparation of binder resin solution): Random copolymer 70.0 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirrer in a separable 4-necked flask, and heated to 80°C. After purging the inside of the reaction vessel with nitrogen, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (Toagosei Co., Ltd. A mixture of 7.4 parts of company-made "Aronix M110") and 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropping was completed, 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 was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content, and the non-volatile content was adjusted to 20% by weight in the resin solution synthesized above. A binder resin solution was prepared by adding ether acetate.

<Method for producing resin type dispersant>
(Resin-type dispersant 1 solution): Block copolymer 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and tetramethylethylenediamine 13.2 in a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer. Part of the system was charged and stirred at 50° C. for 1 hour while flowing nitrogen, and the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to start the polymerization of the first block. After the polymerization for 4 hours, the polymerization solution was sampled to measure the solid content, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the nonvolatile content.
Next, 61 parts of PGMAc and 20 parts of dimethylaminoethyl methacrylate (hereinafter referred to as DM) as a second block monomer were charged into this reaction apparatus, and the reaction was continued while stirring at 110° C. under a nitrogen atmosphere. Two hours after the addition of dimethylaminoethyl methacrylate, the polymerization solution was sampled to measure the solid content, and it was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of non-volatile content, and the reaction solution was allowed to reach room temperature. The polymerization was stopped by cooling.
Propylene glycol monomethyl ether acetate was added to the previously synthesized block copolymer solution so that the nonvolatile content was 40% by weight. In this way, a resin type having a poly(meth)acrylate skeleton having an amine value per solid content of 71.4 mgKOH/g, a weight average molecular weight of 9900 (Mw), and a nonvolatile content of 40% by weight and having a tertiary amino group A dispersant 1 solution was obtained.

<Manufacture of near infrared absorbing material>
[Example 49]
(Near infrared absorbing material (D-1))
A mixture having the following composition was uniformly stirred and mixed, and then dispersed with an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered with a 0.5 μm filter to prepare a near infrared absorbing material.
Near infrared absorbing dye [A-1]: 10.0 parts Resin type dispersant 1 solution: 7.5 parts Binder resin solution: 35.0 parts Propylene glycol monomethyl ether acetate: 47.5 parts

[Examples 50 to 96 and Comparative Example 2]
(Near infrared absorbing material (D-2 to 49))
Hereinafter, the near-infrared absorbing material (D-1) was used in the same manner as the near-infrared absorbing material (D-1) except that the composition and amount of the near-infrared absorbing dye, the resin type dispersant solution, the binder resin solution and the solvent were changed to those shown in Table 3. D-2 to 49) were prepared.

<Evaluation of near infrared absorbing material>
The near-infrared absorbing materials (D-1 to 49) obtained in Examples and Comparative Examples were tested for average primary particle diameter, spectral characteristics, and resistance (light resistance, heat resistance) by the following method. ⊚ is a very good level, ∘ is a good level, and x is a level not suitable for practical use. The results are shown in Table 4.

(Average primary particle size when the near infrared absorbing dye is dispersed)
The average primary particle size of the near-infrared absorbing dye was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and major axis diameter of the individual primary particles of the dye were measured, and the average was taken as the particle diameter of the primary particles of the dye. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating it to a cube having the obtained particle diameter, and the volume average particle diameter was taken as the average primary particle diameter.

(Evaluation of spectral characteristics)
The obtained near-infrared absorbing material was spin-coated on a glass substrate having a thickness of 1.1 mm using a spin coater to a film thickness of 1.0 μm, dried at 60° C. for 5 minutes, and then at 230° C. for 5 minutes. It heated and produced the board|substrate. The absorption spectrum of the obtained substrate was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) in the wavelength range of 300 to 900 nm. When the absorbance at the maximum absorption wavelength was 1, "average absorbance at 400 to 700 nm" was evaluated according to the following criteria. The maximum absorption wavelength of the near-infrared absorbing dye coating film of the present invention exists in the near-infrared region (700 to 900 nm). When this absorbance is set to 1, the smaller the absorbance at 400 to 700 nm, the steeper the spectral shape is, and the higher transparency in the visible light region and the higher coloring in the near infrared region are compatible. It can be said that it has excellent spectral characteristics.
◎: Less than 0.05 ○: 0.05 or more, less than 0.1 ×: 0.1 or more

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

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

The near-infrared absorbing material prepared by dispersing the near-infrared absorbing dye of the present invention with a resin-type dispersant has little absorption in the visible region (400 nm to 700 nm), and also has excellent near-infrared absorbing ability and spectral characteristics. Is excellent, and further excellent in light resistance and heat resistance. In particular, the near-infrared absorbing material in which the hetero atom in the heterocyclic ring which may have a substituent in X of the general formula (1) is an oxygen atom or a sulfur atom was a good result.
The near-infrared absorbing material prepared by dispersing the near-infrared absorbing dye [B-1], which is not the near-infrared absorbing dye of the present invention, with a resin-type dispersant had poor light resistance and heat resistance. (Comparative example 2)

<Production of photosensitive near-infrared absorbing material>
Example 97
(Photosensitive near-infrared absorbing material (R-1))
After stirring and mixing the following mixture to be uniform, 1. The mixture was filtered through a 0 μm filter to obtain a photosensitive near infrared ray absorbing material (R-1).
Near infrared absorbing material (D-1): 50.0 parts Binder resin solution: 7.5 parts Photopolymerizable monomer ("Aronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization initiator ( BAOX "OXE-02"): 1.5 parts Propylene glycol monomethyl ether acetate: 39.0 parts

[Examples 97 to 107 and Comparative Example 3]
(Photosensitive near-infrared absorbing material (R-2 to 12))
Hereinafter, the photosensitive near-infrared absorbing materials (R-2 to 12) are the same as the photosensitive near-infrared absorbing material (R-1) except that the near-infrared absorbing material is changed to the kind of the near-infrared absorbing material shown in Table 5. Got

<Evaluation of photosensitive near-infrared absorbing material>
The photosensitive near-infrared absorbing materials (R-1 to 12) obtained in Examples and Comparative Examples were tested for spectral characteristics and resistance (light resistance, heat resistance) by the following methods. ⊚ is a very good level, ∘ is a good level, and x is a level not suitable for practical use. The results are shown in Table 6.

(Evaluation of spectral characteristics)
The obtained photosensitive near-infrared absorbing material was applied onto a glass substrate having a thickness of 100 mm×100 mm and a thickness of 1.1 mm by a spin coater so as to have a film thickness of 1.0 μm, and then dried at 70° C. for 20 minutes. Ultraviolet light was used for exposure with an integrated light amount of 150 mJ/cm ² using an ultra-high pressure mercury lamp, and development was performed 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 obtained spectrum of the substrate was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation) to measure an absorption spectrum in a wavelength range of 300 to 900 nm. When the absorbance at the maximum absorption wavelength was 1, "average absorbance at 400 to 700 nm" was evaluated according to the following criteria. The maximum absorption wavelength of the near-infrared absorbing dye coating film of the present invention exists in the near-infrared region (700 to 900 nm). When this absorbance is set to 1, the smaller the absorbance at 400 to 700 nm, the steeper the spectral shape is, and the higher transparency in the visible light region and the higher coloring in the near infrared region are compatible. It can be said that it has excellent spectral characteristics.
◎: Less than 0.05 ○: 0.05 or more, less than 0.1 ×: 0.1 or more

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

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

In the case of a photosensitive near-infrared absorbing material, the result is similar to that of the near-infrared absorbing material, and a photosensitive near-infrared containing a near-infrared absorbing material prepared by dispersing the near-infrared absorbing dye of the present invention with a resin type dispersant. The absorber has little absorption in the visible region (400 nm to 700 nm), is excellent in near-infrared absorbing ability, has good spectral characteristics, and is also excellent in light resistance and heat resistance. Particularly, in the near-infrared absorbing dye used in (R-1, R-2, R4 to 11), the hetero atom in the heterocyclic ring which may have a substituent in X of the general formula (1) is an oxygen atom. Or, since it was a sulfur atom, the result was very good.
The photosensitive near-infrared absorbing material containing the near-infrared absorbing material produced by dispersing the near-infrared absorbing dye [B-1] which is not the near-infrared absorbing dye of the present invention with a resin type dispersant has light resistance and The heat resistance was deteriorated. (Comparative Example 3)

<Manufacture of near infrared cut filter>
[Examples 108 to 113]
The photosensitive near-infrared absorbing material (R-1) of the present invention was applied on a glass substrate having a thickness of 1.1 mm by a spin coater, and heat-treated for 1 minute on a hot plate at 100°C.
Then, using an ultra-high pressure mercury lamp USH-200DP (manufactured by USHIO INC.), pattern exposure was performed through a photomask at an exposure dose of 1000 mJ/cm ² to form a near infrared absorption cut filter of 100 μm square. ..
The coating film after exposure was formed into a 400 μm×400 μm pattern by using a 0.2 wt% sodium carbonate aqueous solution as a developing solution and removing the uncured portion of the coating film by a shower developing method at a developing solution pressure of 0.1 mPa. It was Then, it heated at 100 degreeC 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 material (R-4, 5, 7, 10, 11) of the present invention, similar to the near-infrared absorption cut filter (F-1), the near-infrared cut filters (F-2 to 6) are used. ) Got.

<Evaluation of near infrared cut filter>
The near-infrared cut filters (F-2 to 6) were tested for spectral characteristics and durability (light resistance, heat resistance) in the same manner as in the evaluation of the photosensitive near-infrared absorbing material. The results are shown in Table 7.

The near-infrared cut filter manufactured in this way was very excellent in spectral characteristics. In particular, the absorption was small in the visible region (400 nm to 700 nm), the near-infrared absorption ability was excellent, and the spectral characteristics were good. Further, it has excellent light resistance and heat resistance, and therefore, it can be said that it has excellent performance as a near infrared cut filter.

Claims (6)

A near infrared absorbing dye [A] represented by the following general formula (1).
General formula (1)

(X represents a heterocycle selected from the group consisting of the following substituent groups.
R _{1 to} R ₅ are each independently a hydrogen atom, a methyl group which may have a substituent, an ethyl group, or an n-propyl group , a phenyl group which may have a substituent, or 4-methylphenyl. Group , optionally substituted methoxy group, ethoxy group, or trifluoromethoxy group, optionally substituted phenoxy group, 4-methylphenyloxy group , or naphthyloxy group, sulfo group, SO ₃ ^- M ^+, represents _{-SO 2 NR 6 R 7, -COOR} 8, -CONR 9 R 10, a nitro group, a cyano group, and fluorine, bromine, chlorine, and a halogen atom selected from the group consisting of iodine.
M ⁺ represents an aluminum atom, an ammonium compound, a pyridinium compound, an imidazolium compound, a phosphonium compound, or a sulfonium compound, and R _{6 to} R ₁₀ are each independently a hydrogen atom and a methyl group which may have a substituent. , Ethyl group, or n-propyl group . These substituents represent a fluorine atom. )

Substituent group
A near infrared ray absorbing material comprising the near infrared ray absorbing dye [A] according to claim 1. The near-infrared absorbing material according to claim 2, further comprising a resin type dispersant. The near-infrared absorbing material according to claim 2 or 3, further comprising a photopolymerizable monomer. A near infrared ray cut filter comprising the near infrared ray absorbing material according to claim 2. A method for producing a near-infrared absorbing material comprising a near-infrared absorbing dye [A] represented by the following general formula (1) and a resin-type dispersant, wherein the near-infrared absorbing dye [A] is dispersed with a resin-type dispersant. A method for producing a near infrared ray absorbing material, comprising:
General formula (1)

(X represents a heterocycle selected from the group consisting of the following substituent groups.
R _{1 to} R ₅ are each independently a hydrogen atom, a methyl group which may have a substituent, an ethyl group, or an n-propyl group , a phenyl group which may have a substituent, or 4-methylphenyl. Group , optionally substituted methoxy group, ethoxy group, or trifluoromethoxy group, optionally substituted phenoxy group, 4-methylphenyloxy group , or naphthyloxy group, sulfo group, SO ₃ ^- M ^+, represents _{-SO 2 NR 6 R 7, -COOR} 8, -CONR 9 R 10, a nitro group, a cyano group, and fluorine, bromine, chlorine, and a halogen atom selected from the group consisting of iodine.
M ⁺ represents an aluminum atom, an ammonium compound, a pyridinium compound, an imidazolium compound, a phosphonium compound, or a sulfonium compound, and R _{6 to} R ₁₀ are each independently a hydrogen atom and a methyl group which may have a substituent. , Ethyl group, or n-propyl group . These substituents represent a fluorine atom. )

Substituent group