JPH11109126A - Near-infrared radiation absorption filter, and display element using the filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a filter which is excellent in color and taste, solubility, and stability, and high in pigment concentration after polymerization when the monomer is polymerized to form a film by providing a near-infrared radiation absorption filter consisting of a resin composition containing a specified pigment. SOLUTION: A resin composition contains the pigments expressed in formulae I, II or III. In the formula I, Z<1> and Z<2> are the non-metallic atom group to form 5-membered or 6-membered heterocycle containing nitrogen which can be respectively condensed, R<1> and R<2> are alkyl group, alkenyl group or aralkyl group, L denotes a coupling group in which five, seven or nine methine groups are bonded in a conjugate manner through double bond, and a, b and c denote respectively 0 or 1, and x denotes anion. In the formula II, R<10> -R<24> are respectively hydrogen atom, alkyl group, etc., X<1> is an oxygen atom or NR<18> , X<2> is an oxygen atom or NR<19> , X<3> as an oxygen atom or NR<20> , X<4> is an oxygen atom or NR<21> , R<22> -R<24> denote a hydrogen atom or monovalent group, n denotes an integer from 1 to 3, and m denotes the integer 0 or 1 to 6.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a near-infrared absorption filter comprising a resin composition containing a coloring matter.

[0002]

2. Description of the Related Art In recent years, the transmission of light in the near-infrared region has been adjusted by various types of filters in various industrial fields. For example, it is used as a film in agriculture to promote the growth of crops, in heat-shielding plates in buildings and vehicles, in the electronics industry for sharp cut filters for infrared sensors, or for sunglasses and protective glasses. Further, recently, in a plasma display device (PDP), a problem of malfunction of a remote control device (remote control) due to generated infrared light has occurred.
Therefore, an attempt is made to solve this problem by adding an infrared absorber to a plastic plate used as a protective plate for a glass plate. Dyes used for these purposes include phthalocyanine dyes in JP-A-63-270765, anthraquinone dyes in JP-A-4-87770, aminium dyes in JP-A-3-161644,
Japanese Patent Publication No. 1-114801 discloses a metal complex compound and the like, but all have a problem that the color is poor, the solubility is poor, and the color disappears during the polymerization process due to absorption in the visible region. there were.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to provide color,
An object of the present invention is to provide a filter having excellent solubility and stability. Also, in order to increase the strength of the film of the dye-containing layer,
When a film is formed by polymerizing a monomer, it is an object of the present invention to provide a filter having a high dye concentration after polymerization.

[0004]

[MEANS FOR SOLVING THE PROBLEMS] The above objects are achieved by the following (1),
This has been achieved by the resin composition containing the dye of (2) or (3).

[0005]

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In the formula, Z ¹ and Z ² are non-metallic atomic groups forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may be respectively condensed, and R ¹ and R ² are each an alkyl group , An alkenyl group, or an aralkyl group, L is a linking group in which 5, 7, or 9 methine groups are conjugated with a double bond, and a, b, and c are each 0 or 1 And x is an anion.

[0007]

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Where R^Ten, R¹¹, R¹², R¹³, R¹⁴, R
^Fifteen, R¹⁶And R¹⁷Represents a hydrogen atom, an alkyl group,
Cycloalkyl group, aryl group, aralkyl group or hete
Represents a ring group;^TenAnd R¹¹And or R¹²And R¹³as well as,
Or R¹³And R¹⁴And or R ¹⁴And R^FifteenAnd or R¹⁶And R
¹⁷May combine with each other to form a 5- or 6-membered ring. X
¹Is an oxygen atom, or NR¹⁸To X^TwoIs an oxygen atom or NR
¹⁹To X^ThreeIs an oxygen atom or NR²⁰To X^FourIs an oxygen atom
Or NR^{twenty one}And R¹⁸, R¹⁹, R²⁰And R^{twenty one}Is it
Hydrogen atom, alkyl group, cycloalkyl group, aryl
A aralkyl group or a heterocyclic group;¹⁸And R^Ten
And / or R¹⁹And R¹¹And or R²⁰And R¹⁶And or
R^{twenty one}And R¹⁷Are linked to each other to form a 5- or 6-membered ring
Is also good. R^{twenty two}, R^{twenty three}And R^{twenty four}Is a hydrogen atom or a monovalent group
Wherein n is an integer of 1 to 3, m is 0 or 1 to 6
Represents an integer.

[0009]

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Wherein R ³⁰ is CONHR ³⁵ , SO ₂ NHR ³⁵ , NHSO
₂ R ³⁵ , NHCOR ³⁵ , NHCONHR ³⁵ (R ³⁵ represents alkyl, aryl, heterocycle), hydrogen atom, halogen atom, carboxyl group, sulfo group, R ³¹ represents hydrogen atom, alkyl group, NHSO ₂ R ³⁵ represents a group represented by NHCOR ³⁵ (R ³⁵ has the same meaning as described above), and R ³² represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, an amino group, or a halogen atom. n represents an integer of 0 to 3. R ³³ and R ³⁴ each represent an alkyl group, an aryl group or an aralkyl group, and R ³³ and R ³⁴ and / or R ³²
And R ³³ and / or R ³² and R ³⁴ may combine with each other to form a 5- or 6-membered ring.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The general formulas (1) to (3) will be described in detail. In the formula, Z ¹ and Z ² are each a non-metallic atomic group forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may be condensed. Examples of the nitrogen-containing heterocyclic ring and its condensed ring include an oxazole ring,
Isoxazole ring, benzoxazole ring, naphthoxazole ring, thiazole ring, benzothiazole ring, naphthothiazole ring, indolenine ring, benzoindolenine ring, imidazole ring, benzimidazole ring, naphthimidazole ring, quinoline ring, pyridine ring, pyrrolo Examples include a pyridine ring, a floppyrrole ring, an indolizine ring, an imidazoquinoxaline ring, and a quinoxaline ring. The nitrogen-containing heterocycle is preferably a 5-membered ring rather than a 6-membered ring. More preferably, a 5-membered nitrogen-containing heterocycle is condensed with a benzene ring or a naphthalene ring. Indolenine and benzoindolenine rings are most preferred.

The nitrogen-containing heterocycle and the ring condensed therewith may have a substituent. Examples of the substituent include an alkyl group (eg, methyl, ethyl, propyl), an alkoxy group (eg, methoxy, ethoxy), an aryloxy group (eg, phenoxy, p-chlorophenoxy), a halogen atom (Cl, Br, F), an alkoxycarbonyl group (eg, ethoxycarbonyl), a cyano group, a nitro group, a sulfo group (may be a salt) and a carboxyl group (may be a salt).

R ¹ and R ² are an alkyl group, an alkenyl group or an aralkyl group, respectively. Particularly, an alkyl group is preferable. The alkyl group preferably has 1 to 10 carbon atoms, and is a halogen atom (Cl, Br, F), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), a hydroxyl group, a carboxyl group (may be a salt).
And a sulfo group (or a salt). The alkenyl group preferably has 2 to 10 carbon atoms, and includes 2-pentenyl, vinyl, allyl, 2-butenyl and 1-propenyl. The alkenyl group may be substituted with the substituent described for the alkyl group. The aralkyl group preferably has 7 to 12 carbon atoms and includes benzyl and phenethyl. Aralkyl groups are represented by Z ¹ and Z
^It may be substituted with the substituent described in ² .

L is a linking group in which 5, 7, or 9 methine groups are conjugated with a double bond. The number of methine groups is preferably 7 or 9, and more preferably 7. The methine group may combine with each other to form a 5- or 6-membered ring. Further, the methine group may have a substituent. The substituted methine group is preferably a central (meso-position) methine group. Examples of the substituent include a methyl group,
Ethyl group, methoxy group, phenoxy group, halogen atom (Cl, Br, F), aryl group (including phenyl and naphthyl, and may have a substituent. Examples of the substituent include methyl, ethyl, methoxy, ethoxy , Phenoxy, Cl, B
r, F, ethoxycarbonyl, cyano, nitro, etc.), —NR ³ R ⁴ ｛R ³ and R ⁴ are each a hydrogen atom, alkyl (as defined above), aryl (as defined above), —OR _{^{3, -SR 3, SO 2 R}} 3 (R 3 is above synonymous), can be mentioned a hydroxyl group or a ketone.

A, b and c are each 0 or 1; c is generally zero. However, when the anionic substituent forms an inner salt with N ⁺ like carboxyl, c becomes 0. x is an anion. Examples of anions include halide ions (Cl ⁻ , Br ⁻ , I ⁻ ), p-toluenesulfonic acid ion, ethyl sulfate ion, PF ₆ ⁻ , B
F ₄ ^-, ClO ₄ ^- can be mentioned.

In the general formula (2), the alkyl group represented by R ¹⁰ to R ²¹ is an alkyl group having 1 to 20, more preferably 1 to 12 carbon atoms (eg, methyl, ethyl,
Propyl, butyl, hexyl, undecyl).
Further, a halogen atom (F, Cl, Br), an alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl), a hydroxy group, an alkoxy group (for example, methoxy, ethoxy, phenoxy, isobutoxy) or an acyloxy group (for example, acetyloxy, Butyryloxy, hexylyloxy, benzoyloxy), a sulfo group (or a salt), a carboxyl group (or a salt), or the like. Examples of the cycloalkyl group represented by R ¹⁰ to R ²¹ include cyclopentyl and cyclohexyl. The aryl group represented by R ¹⁰ to R ²¹ is
Those having 6 to 12 carbon atoms are preferable, and examples thereof include a phenyl group and a naphthyl group. The aryl group may be substituted. Examples of the substituent include an alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, butyl), an alkoxy group having 1 to 6 carbon atoms (eg, methoxy, ethoxy),
Aryloxy group (for example, phenoxy, p-chlorophenoxy), halogen atom (F, Cl, Br), alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl), amino group (for example, methylamino,
Acetylamino, methanesulfonamide), cyano group,
Includes nitro groups, carboxyl groups (which may be salts) and sulfo groups (which may be salts). The aralkyl group represented by R ¹⁰ to R ²¹ is preferably an aralkyl group having 7 to 12 carbon atoms (eg, benzyl, phenylethyl) and has a substituent (eg, methyl, methoxy, chloro atom). You may. The heterocyclic group of R ¹⁰ represented by R ^21, thienyl, furyl, pyrrolyl, pyrazolyl, pyridyl, be mentioned indolyl, and the like can.
Examples of the monovalent group represented by R ²² to R ²⁴ include the substituents described above for the aryl group. R ¹⁰ and R ^11, R ¹² and R ^13, R ¹³ and R ^14, R ¹⁴ and R ^15, R ¹⁶ and R
^17, R ¹³ and R ^10, R ¹⁹ and R ^11, R ²⁰ and R ^16, R ²¹ and R ¹⁷
May combine with each other to form a cyclopentane or cyclohexane ring. m represents 0 or an integer of 1 to 6,
It may be a mixture.

In the general formula (3), the alkyl group represented by R ³⁰ to R ³⁵ is an alkyl group having 1 to 20, more preferably 1 to 12 carbon atoms (eg, methyl, ethyl,
Propyl, butyl, hexyl, undecyl).
Also, a halogen atom (F, Cl, Br), an alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl), a hydroxy group, an alkoxy group (for example, methoxy, ethoxy, phenoxy, isobutoxy), an acyloxy group (for example, acetyloxy, Butyryloxy,
Hexyloxy, benzoyloxy), a carboxyl group (may be a salt) or a sulfo group (may be a salt).

The aryl group represented by R ³³ to R ³⁵ is 6
To 12 carbon atoms are preferable, and examples thereof include a phenyl group and a naphthyl group. The aryl group may be substituted. Examples of the substituent include an alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, butyl), an alkoxy group having 1 to 6 carbon atoms (eg, methoxy, ethoxy),
Aryloxy group (for example, phenoxy, p-chlorophenoxy), halogen atom (F, Cl, Br), alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl), amino group (for example, methylamino,
Acetylamino, methanesulfonamide), cyano group,
Includes nitro, carboxyl or sulfo groups. R
^The aralkyl group represented by ³³ and R ³⁴ is preferably an aralkyl group having 7 to 12 carbon atoms (eg, benzyl, phenylethyl), and a substituent (eg, methyl, methoxy, chloro atom, carboxyl, sulfo) You may have.

The heterocyclic ring represented by R ³⁵ includes pyridine, 1,3-thiazole, 1,3,4-triazole,
Benzothiazole, benzimidazole, benzoxazole, 1,2,4-thiadiazole and the like can be mentioned. The halogen atoms represented by R ³⁰ and R ³² are F, B
r and Cl. The alkoxy group represented by R ^32, methoxy, ethoxy, phenoxy, may be mentioned isobutoxy and the like. The amino group represented by R ^32, there may be mentioned methylamino, acetylamino, methane sulfonamide. R ³³ and R ³⁴ may combine with each other to form a piperazine, piperidine, morpholine or pyrrolidine ring. R ³² and R ³³ and / or R ³² and R ³⁴ may combine with each other to form a 5- or 6-membered ring, for example, a julolidine or tetrahydroquinoline ring.

Examples of the alkoxy group represented by R ³² include methoxy, ethoxy and the like.
The amino group represented by R ^32, -NHCOR
_{^{35, -NHSO 2 R 35, -NHCONHR}} 35, -NHCOOR 35, NHR
³⁵ (R ³⁵ is as defined above) and NH ₂ . Examples of the halogen atom represented by R ³⁰ and R ³² include F, Cl, and Br. Examples of the dye preferably used in the present invention are shown below.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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The dye used in the present invention is described in US Pat.
Nos. 095,854 and 3,671,648;
2-123252, JP-A-6-43583, US
No. 5,380,635, JP-A-5-323500, JP-A-5-323501, Japanese Patent Application No. 9-9002 and the like can be synthesized. The dye used in the present invention can be used by dissolving it in a usual organic solvent or water. Further, it may be used by directly dissolving it in the monomer used for the polymerization. The dye can be used in the form of solid fine particles. In order to obtain solid fine particles, a known disperser can be used. Examples of the disperser include a ball mill, a vibrating ball mill, a planetary ball mill, a sand mill, a colloid mill, a jet mill and a roller mill. The disperser is disclosed in Japanese Patent Laid-Open No. 52-92716 and International Patent No. 88/07.
No. 4794. Vertical or horizontal media dispersers are preferred. Dispersion is performed in a suitable medium (eg, water, alcohol)
May be carried out in the presence of It is preferable to use a surfactant for dispersion. As the surfactant for dispersion, an anionic surfactant (Japanese Patent Application Laid-Open No. 52-92716 and International Patent 8).
8/074794) is preferably used. If necessary, an anionic polymer, a nonionic surfactant or a cationic surfactant may be used.

After dissolving the dye in an appropriate solvent, the poor solvent may be added to obtain fine powder. Also in this case, the above-mentioned surfactant for dispersion may be used. Alternatively, the dye may be dissolved by adjusting the pH, and then the pH may be changed to obtain fine crystals of the dye.

The resin of the resin composition used in the present invention is not particularly limited as long as it is a resin which is transparent and does not greatly absorb or scatter. Specifically, polycarbonate resins, acrylic resins such as methyl methacrylate, polyvinyl resins such as polystyrene / polyvinyl chloride / polyvinylidene chloride, polyolefin resins such as polyethylene / polypropylene, and vinyl acetate resins such as polybutyral / polyvinyl acetate. Examples thereof include resins, polyester resins such as PET, and polyamide resins. These resins may be used by blending two or more resins. Further, the above resin can be used by sandwiching the resin between transparent glass.

The resin composition used in the present invention may contain various additives used in producing a resin material. Examples of the additives include a colorant, a polymerization regulator, an antioxidant, an ultraviolet absorber, a flame retardant, a plasticizer, and a release agent. In addition, various antioxidants and ultraviolet inhibitors may be used to increase the stability of the dye.

Examples of a method for molding a resin composition containing an infrared dye include extrusion molding, injection molding, cast polymerization, press molding, calender molding, and cast film formation.

Further, a filter can also be prepared by preparing a film containing a dye and subjecting the film to hot pressing or heat laminating on a transparent resin sheet. Further, a filter can be obtained by printing or coating a transparent resin with an acrylic resin ink or paint containing a pigment.

The monomers used in the present invention include vinyl compounds (ethylene, propylene, styrene, vinyl chloride, vinyl acetate, acrylonitrile, acrylic acid, methyl acrylate, vinyl butyl ether) and vinylidene compounds (isobutylene, vinylidene chloride, vinylidene cyanide) , Methacrylonitrile, methyl methacrylate), diene compounds (butadiene, chloroprene, isoprene,
Cyanobutadiene), cyclic compound (ethylene oxide,
Caprolactam) and the like.

As the polymerization initiator used in the present invention, any polymerization initiator used for polymer synthesis can be used. Preferred initiators include thermal polymerization initiators for azo compounds (such as 2,2-azobisisobutyronitrile) and organic peroxides (such as benzoyl peroxide).

[0042]

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited by the following examples. Example 1 In a stainless beaker, 40 ppm of the dye of the compound (4) was dissolved in 100 g of methyl methacrylate. To this mixture, 0.01 g of dioctyl sulfosuccinate sodium salt as a release agent, 0.15 g of 2,2'-azobisisobutyronitrile as a polymerization initiator, and 0.2 g of benzotriazole as an ultraviolet absorber were added and mixed. did. This was poured into a 3 mm mold and heated at 60 ° C. for 5 hours and then at 120 ° C. for 2 hours to complete the polymerization to obtain a filter.

Example 2 Instead of the compound (4) used in Example 1, the compounds (5), (10), (21), (32) and (73) of the present invention and a comparative dye (a) were used. A filter was obtained in the same manner as in Example 1.

[0044]

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Example 3 (Preparation of solid fine particle dispersion of dye) Compound (16) was treated as a wet cake without drying as much as possible, and 15 g of a 5% carboxymethylcellulose aqueous solution was added to 2.5 g of dry solids. The total amount was 63.3 g, and the mixture was mixed well to form a slurry. 100 cc of glass beads having a diameter of 0.8 to 1.2 mm and a slurry are placed in a dispersing machine (1 / 16G, sand grinder mill, manufactured by Imex Co., Ltd.) and dispersed for 12 hours so that the pigment concentration becomes 2%. Water was added and the dispersion was added in place of the dye shown in Example 1 to obtain a filter. Table 1 shows the results.

Example 4 The dispersion obtained in Example 3 was applied to a polyethylene terephthalate film with the following coating solution to prepare a coated sample.

───────────────────────────────────Coating liquid──────────ゼ ラ チ ン Gelatin 3 g / m ² Solid fine particle dispersion of dye (16) 25 mg / m ² 1,2-bis (vinyl Sulfonylacetamide) ethane (hardener) 56 mg / m ² Compound A 20 mg / m ² ────

[0048]

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The filter coated with the compound (16) was λmax9
Long wavelength absorption of 30 nm was obtained, and there was no problem with the color. When the filter of the present invention was set in front of the plasma display device (PDP), the hue of the image of the PDP did not deteriorate. Further, the problem of malfunction of the remote controller due to the infrared light generated from the PDP could be prevented.

(Evaluation of Filter) The spectral absorption of the obtained filter was measured using a spectrophotometer (U-2000, manufactured by Hitachi, Ltd.), and the value of the maximum absorption wavelength (λmax) was obtained. Further, the spectral absorption in the monomer before polymerization was measured to obtain the value of the maximum absorption wavelength (λmax). Also, the value of the absorbance ratio of λmax before and after polymerization (filter / monomer) was determined. Table 1 shows the above results.

[0051]

[Table 1]

It was found that the compound of the present invention retained the absorption of the monomer even after the polymerization, whereas the comparative dye had lost its color after the polymerization. Furthermore, the compound of the present invention was found to have good color and good solubility.

Claims (4)

[Claims] 1. A compound represented by the following general formula (1), (2) or (3)
Near-Infrared Absorption Filter Made of Resin Composition Containing Dye
- Embedded imageWhere Z¹And Z^TwoIs a 5-membered or a 5-membered ring
Is a group of non-metallic atoms forming a 6-membered nitrogen-containing heterocyclic ring,
R¹And R^TwoIs an alkyl group, an alkenyl group,
Or L is an aralkyl group, and L is 5, 7 or 9 methine
A linking group in which the groups are conjugated with a double bond
A, b and c are each 0 or 1, and x is
Nion. Embedded imageWhere R^Ten, R¹¹, R¹², R¹³, R¹⁴, R^Fifteen, R¹⁶as well as
R¹⁷Represents a hydrogen atom, an alkyl group,
Group, aryl group, aralkyl group or heterocyclic group
Then R^TenAnd R¹¹And or R¹²And R¹³And or R¹³When
R¹⁴And or R ¹⁴And R^FifteenAnd or R¹⁶And R¹⁷Are each other
To form a 5- or 6-membered ring. X¹Is oxygen source
Child or NR¹⁸To X^TwoIs an oxygen atom or NR¹⁹To X^Three
Is an oxygen atom or NR²⁰To X^FourIs an oxygen atom or NR^{twenty one}
And R¹⁸, R¹⁹, R²⁰And R^{twenty one}Is the hydrogen source
, Alkyl group, cycloalkyl group, aryl group, ara
A alkyl group or a heterocyclic group;¹⁸And R^TenAnd / or
R¹⁹And R¹¹And or R²⁰And R¹⁶And or R^{twenty one}And R¹⁷
May be connected to each other to form a 5- or 6-membered ring. R
^{twenty two}, R^{twenty three}And R^{twenty four}Represents a hydrogen atom or a monovalent group, and n
Represents an integer of 1 to 3, and m represents 0 or an integer of 1 to 6.
You. Embedded imageWhere R³⁰Is CONHR³⁵, SO_TwoNHR³⁵, NHSO_TwoR³⁵, NHCOR
³⁵, NHCONHR³⁵A group represented by the formula (R³⁵Is alkyl,
Aryl, heterocycle), hydrogen atom, halogen atom, cal
A boxyl group or a sulfo group;³¹Is a hydrogen atom,
Group, NHSO_TwoR³⁵, NHCOR³⁵A group represented by the formula (R³⁵Is mentioned above
Is the same as³²Are hydrogen and al
A kill group, an alkoxy group, a hydroxy group, an amino group or
Represents a logen atom. n represents an integer of 0 to 3. R³³Passing
And R³⁴Represents an alkyl group, an aryl group or an ar
Represents a kill group;³³And R³⁴And or R³²And R³³as well as,
Or R³²And R³⁴Combine with each other to form a 5- or 6-membered ring
May be. 2. The near-infrared absorption filter according to claim 1, wherein the dye is contained in a solid fine particle dispersion. 3. The infrared absorption filter according to claim 1, wherein the resin contains a dye and is formed from a monomer and a polymerization initiator. 4. A display device using the near-infrared absorption filter according to claim 1 and a plasma display device.