JP2003327865A - Near infrared light-absorbing pigment and near infrared light-absorbing material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a near infrared light-absorbing pigment which has an excellent near infrared light-absorbing ability and high heat resistance, and to provide a near infrared light-absorbing material using the same. <P>SOLUTION: This near infrared light-absorbing pigment comprises a diimmonium salt represented by general formula (1) (R<SP>1</SP>to R<SP>4</SP>are each H, an alkyl, an aminoalkyl, an aryl, or the like; X is an ion of a halogen or an inorganic acid, an organic acid or the like) and a benzenedithiol nickel complex represented by general formula (2) (R<SP>5</SP>is H, an alkyl, an aminoalkyl, an aryl, or the like; A is an ammonium ion or a phosphonium ion). The near infrared light-absorbing material is obtained by polymerizing and curing a composition comprising the near infrared light-absorbing pigment and monomer. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a near-infrared absorbing dye and a near-infrared absorbing material using the same. More specifically, it relates to a near-infrared absorbing dye comprising a diimonium salt and benzenedithiol metal complexes and a near-infrared absorbing material using the same.

[0002]

2. Description of the Related Art In recent years, plasma displays have been developed and commercialized as large displays. Near-infrared rays are generated from such a plasma display at the time of plasma discharge, and the wavelengths of the generated near-infrared rays are used for TV, video,
Since it is similar to the wavelength of near-infrared rays used by home appliances such as coolers, it is a problem that these devices may malfunction. Therefore, the near infrared region 800-
A near-infrared absorbing material using a dye that absorbs near-infrared rays having a wavelength of 1200 nm, particularly 850 to 1000 nm has been proposed.

As such a near-infrared absorbing dye, a diimonium salt can be mentioned, and a near-infrared absorbing filter using this diimonium salt is known (WO97 /
38855, JP-A-11-323121,
JP 2001-158762 A). However,
The near-infrared absorbing film placed on the front surface of the plasma display is exposed to high temperature for a long time due to the heat generated from the plasma display, but the diimonium salt is inferior in heat resistance, and the wavelength of the infrared remote controller is 800 to 90.
There is a problem that absorption of near infrared rays of 0 nm is insufficient.

On the other hand, a method of adding a benzenedithiol copper complex to a diimonium salt in order to improve the heat resistance of the near-infrared absorbing film (Japanese Unexamined Patent Publication No. 2001-174626), A method of adding a benzyl nickel complex to supplement absorption (Japanese Patent Laid-Open No. 2000-206323) and the like are known. However, the benzenedithiol copper complex does not absorb near infrared rays, and the benzylnickel complex has a
Although it absorbs near-infrared rays of 0 to 900 nm, it has a low heat resistance improving effect on diimonium salts.

Therefore, in order to obtain a near-infrared absorbing dye having high heat resistance and excellent near-infrared absorbing ability,
A means of adding a benzenedithiol copper complex and a benzylnickel complex to a diimonium salt can be considered,
Since both the benzenedithiol copper complex and the benzylnickel complex have a green color and have absorption in the visible region, adding a large amount of both at the same time causes a decrease in the transmittance in the visible region.

[0006]

SUMMARY OF THE INVENTION The present invention has been conceived under such circumstances, and the object of the present invention is to provide a near-infrared ray which has excellent near-infrared absorption ability and high heat resistance. An object is to provide an absorbing dye and a near-infrared absorbing material using the same.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a near-infrared absorbing dye and a near-infrared absorbing material using the same as shown below.

(1) The following general formula (1);

[0009]

[Chemical 5]

(In the formula, R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkylamino group having 1 to 8 carbon atoms or an aryl group, and X ⁻ is A diimonium salt represented by a halogen ion, an inorganic acid ion, or an organic acid ion) and the following general formula (2);

[0011]

[Chemical 6]

(In the formula, R ⁵ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkylamino group having 1 to 8 carbon atoms, an aryl group, a halogen atom or the following general formula (3);

[0013]

[Chemical 7]

Alternatively, the following general formula (4):

[0015]

[Chemical 8]

(Wherein R ⁶ and R ⁷ are an alkyl group having 1 to 6 carbon atoms, an alkylamino group having 1 to 8 carbon atoms, an aryl group, a halogen atom, and a morpholino group which may have a substituent, Also shows a piperidino group, a pyrrolidino group, a thiomorpholino group, or a piperazino group.)
Represents a group represented by. m represents an integer of 1 to 4. A ⁺ represents a quaternary ammonium ion or a quaternary phosphonium ion. ) Near-infrared absorbing dye consisting of benzenedithiol nickel complexes represented by. (2) A near-infrared absorbing material obtained by coating and forming the near-infrared absorbing dye according to (1) on a substrate. (3) A near infrared absorbing material obtained by curing the composition containing the near infrared absorbing dye according to (1) and a monomer by polymerization of the monomer.

The near-infrared absorbing dye composed of the diimonium salt represented by the above general formula (1) and the benzenedithiol nickel complex represented by the above general formula (2) has excellent heat resistance and is suitable for solvents, monomers and the like. High solubility. Therefore,
An amount sufficient to block near infrared rays can be dissolved in a solvent, a monomer or the like. Therefore, the near-infrared absorbing material using the near-infrared absorbing dye of the present invention can exhibit a sufficient near-infrared absorbing ability.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The near-infrared absorbing dye of the present invention comprises a diimmonium salt which is a near-infrared absorbing dye represented by the general formula (1) and a benzenedithiol nickel complex represented by the general formula (2).

The diimonium salt represented by the above general formula (1), which is used as a near infrared ray absorbing dye in the present invention, is synthesized by a method similar to the method described in JP-B-43-25335. be able to. That is, a diimonium salt can be obtained by oxidizing a 1,4-phenylenediamine derivative with inorganic acid silver or the like. As the near-infrared absorbing dye, those commercially available from various companies can be used.

In the above general formula (1), R ¹ , R ² ,
R ³ and R ⁴ are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
An alkylamino group or an aryl group having 1 to 8 carbon atoms is shown. Further, X ⁻ represents a halogen ion, an inorganic acid ion, or an organic acid ion.

Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- Pentyl group, isopentyl group, sec-pentyl group, neo-pentyl group, n-
A hexyl group, an isohexyl group, a cyclohexyl group and the like can be mentioned.

Examples of the alkylamino group having 1 to 8 carbon atoms include N-methylamino group, N-ethylamino group, N-isopropylamino group, Nn-propylamino group and Nn-butylamino group. , N, N-dimethylamino group, N, N-methylethylamino group, N, N-diethylamino group, N, N-ethyl-isopropylamino group,
N, N-di-isopropylamino group, N, N-di-n-
Examples thereof include a propylamino group and N, N-di-n-butylamino group.

As the aryl group, for example, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4
-Methylphenyl group, 2,6-dimethylphenyl group, 4
-Ethylphenyl group, 2-n-propylphenyl group, 4
-N-butylphenyl group, 2-chlorophenyl group, 4-
Chlorophenyl group, 2,4-dichlorophenyl group, 2-
Bromophenyl group, 4-bromophenyl group, 2-chloro-4-bromophenyl group, 4-aminophenyl group, 2,
4-diaminophenyl group, 2,4-dinitrophenyl group, 2-acetylphenyl group, 4-acetylphenyl group, 2-hydroxyphenyl group, 4-hydroxyphenyl group, 2-methoxyphenyl group, 4-methoxyphenyl group, Examples thereof include a 2-methylthiophenyl group and a 4-methylthiophenyl group.

Examples of the halogen ion include iodine ion, bromine ion, chlorine ion, fluorine ion and the like.

Examples of the inorganic acid ions include hexafluoroantimonate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion,
Examples thereof include nitrate ions.

Examples of the organic acid ion include acetate ion, trifluoroacetate ion, methanesulfonate ion, trifluoromethanesulfonate ion, benzenesulfonate ion and the like.

The above-mentioned diimonium salt is, for example, CIR-1080, CIR, trade name of Nippon Carlit Co., Ltd.
-1081, trade name IRG-02 of Nippon Kayaku Co., Ltd.
2, what is marketed as IRG-023 and IRG-040 can be used.

On the other hand, the benzenedithiol nickel complexes represented by the above general formula (2) used in the present invention are described in, for example, J. Am. Chem. Soc. , 88 volumes,
It can be synthesized by a method similar to the method described on page 43 (1966). That is, benzenedithiols are reacted with a nickel halide, and then
The benzenedithiol nickel complexes can be obtained by reacting with an ammonium salt or a phosphonium salt. Further, it can be synthesized by a method similar to the method described in JP-A-9-309886 and JP-A-10-45767. That is, first, halogenobenzenes and hydrosulfides are reacted in the presence of sulfur and iron powder in a polar organic solvent to form iron complexes of benzenedithiols. The benzenedithiol nickel complexes can be obtained by reacting the obtained iron complex of benzenedithiols with a nickel halide, and then with an ammonium salt or a phosphonium salt.

In the above general formula (2), R ⁵ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkylamino group having 1 to 8 carbon atoms, an aryl group, a halogen atom or the following general formula (3);

[0031]

[Chemical 9]

Alternatively, the following general formula (4):

[0033]

[Chemical 10]

The groups shown are shown below. m represents an integer of 1 to 4. A ⁺ represents a quaternary ammonium ion or a quaternary phosphonium ion.

Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- Pentyl group, isopentyl group, sec-pentyl group, neo-pentyl group, n-
A hexyl group, an isohexyl group, a cyclohexyl group and the like can be mentioned.

Examples of the alkylamino group having 1 to 8 carbon atoms include N-methylamino group, N-ethylamino group, N-isopropylamino group, Nn-propylamino group and Nn-butylamino group. , N, N-dimethylamino group, N, N-methylethylamino group, N, N-diethylamino group, N, N-ethyl-isopropylamino group,
N, N-di-isopropylamino group, N, N-di-n-
Examples thereof include a propylamino group and N, N-di-n-butylamino group.

As the aryl group, for example, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4
-Methylphenyl group, 2,6-dimethylphenyl group, 4
-Ethylphenyl group, 2-n-propylphenyl group, 4
-N-butylphenyl group, 2-chlorophenyl group, 4-
Chlorophenyl group, 2,4-dichlorophenyl group, 2-
Bromophenyl group, 4-bromophenyl group, 2-chloro-4-bromophenyl group, 4-aminophenyl group, 2,
4-diaminophenyl group, 2,4-dinitrophenyl group, 2-acetylphenyl group, 4-acetylphenyl group, 2-hydroxyphenyl group, 4-hydroxyphenyl group, 2-methoxyphenyl group, 4-methoxyphenyl group, Examples thereof include a 2-methylthiophenyl group and a 4-methylthiophenyl group.

Examples of the halogen atom include iodine atom, bromine atom, chlorine atom, fluorine atom and the like.

R ⁶ in the general formula (3) and R ⁷ in the general formula (4) are each an alkyl group having 1 to 6 carbon atoms, an alkylamino group having 1 to 8 carbon atoms, an aryl group,
A halogen atom, a morpholino group which may have a substituent, a piperidino group, a pyrrolidino group, a thiomorpholino group or a piperazino group.

C1-C6 alkyl group, C1-C8
The alkylamino group, aryl group and halogen atom of are the same as R ⁵ in the above general formula (2).

The morpholino group which may have a substituent is, for example, a morpholino group, a 2-methylmorpholino group,
3-methylmorpholino group, 4-methylmorpholino group, 2
-Ethylmorpholino group, 4-n-propylmorpholino group, 3-n-butylmorpholino group, 2,4-dimethylmorpholino group, 2,6-dimethylmorpholino group, 4-phenylmorpholinyl group and the like can be mentioned.

Examples of the piperidino group which may have a substituent include a piperidino group, a 2-methylpiperidino group,
3-methylpiperidino group, 4-methylpiperidino group, 2
-Ethylpiperidino group, 4-n-propylpiperidino group, 3-n-butylpiperidino group, 2,4-dimethylpiperidino group, 2,6-dimethylpiperidino group, 4-phenylpiperidino group, etc. Can be mentioned.

Examples of the pyrrolidino group which may have a substituent include a pyrrolidino group, a 2-methylpyrrolidino group,
3-methylpyrrolidino group, 4-methylpyrrolidino group, 2
-Ethylpyrrolidino group, 4-n-propylpyrrolidino group, 3-n-butylpyrrolidino group, 2,4-dimethylpyrrolidino group, 2,5-dimethylpyrrolidino group, 4-phenylpyrrolidino group, etc. Can be mentioned.

Examples of the thiomorpholino group which may have a substituent include, for example, a thiomorpholino group, a 2-methylthiomorpholino group, a 3-methylthiomorpholino group, a 4-methylthiomorpholino group, a 2-ethylthiomorpholino group and a 4-methylthiomorpholino group.
n-propylthiomorpholino group, 3-n-butylthiomorpholino group, 2,4-dimethylthiomorpholino group, 2,
Examples thereof include 6-dimethylthiomorpholino group and 4-phenylthiomorpholino group.

Examples of the piperazino group which may have a substituent include, for example, piperazino group, 2-methylpiperazino group,
3-methylpiperazino group, 4-methylpiperazino group, 2
-Ethylpiperazino group, 4-n-propylpiperazino group, 3-n-butylpiperazino group, 2,4-dimethylpiperazino group, 2,6-dimethylpiperazino group, 4-phenylpiperazino group, 2 -Pyrimidyl piperazino group etc. are mentioned.

In the above general formula (2), R ⁵ is a tert-butyl group, N, N among the various substituents described above.
-Diethylamino group, morpholinocarbonyl group, pyrrolidinocarbonyl group, piperidinocarbonyl group, piperazinocarbonyl group, phenylcarbonyl group, N, N-diethylaminocarbonyl group, morpholinosulfonyl group, pyrrolidinosulfonyl group, piperidinosulfonyl group Base, 4-
It is preferable to use a methylpiperazinosulfonyl group, a 4-chlorophenylsulfonyl group, or a chlorine atom.

Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetra-n-butylammonium ion, tetraphenylammonium ion, tetrabenzylammonium ion, trimethylbenzylammonium ion, N-methylpyridinium ion. Etc.

Examples of the quaternary phosphonium ion include tetramethylphosphonium ion, tetraethylphosphonium ion, tetra-n-butylphosphonium ion, tetraphenylphosphonium ion, tetrabenzylphosphonium ion and trimethylbenzylphosphonium ion.

The near-infrared absorbing dye comprising the diimonium salt represented by the general formula (1) and the benzenedithiol nickel complex represented by the general formula (2) of the present invention is a diimmonium salt and a benzenedithiol nickel complex. To
It can be produced by a simple mixing method, a method of dissolving after dissolving in a solvent or a monomer described below, a method of simultaneously dissolving in a solvent or a monomer, and the like.

The mixing ratio of the diimonium salt and the benzenedithiol nickel complex is not particularly limited, but the benzenedithiol nickel complex is 0.1 to 500 parts by weight, preferably 10 parts by weight, relative to 100 parts by weight of the diimonium salt.
˜100 parts by weight, more preferably 20 to 70 parts by weight. When the amount of benzenedithiol nickel complexes is less than 0.1 parts by weight, heat resistance may be reduced. In addition, benzenedithiol nickel complexes are 50
If it exceeds 0 parts by weight, the transmittance of the visible portion may decrease.

In the present invention, when the near-infrared absorbing dye composed of the diimonium salt represented by the general formula (1) and the benzenedithiol nickel complex represented by the general formula (2) is used, Dissolve the absorbing dye in a solvent or monomer. Then, it is formed into various forms depending on the use, purpose, etc. and used as a near-infrared absorbing material. The embodiment will be described below.

(1) First Embodiment (Application of Dye Solution to Substrate) A solution obtained by dissolving a near-infrared absorbing dye and a binder resin in a solvent is applied to a glass or resin substrate,
Dry to remove solvent. After the solvent is removed, the layer containing the near infrared absorbing dye remains on the substrate.

Examples of the binder resin include polycarbonate resin, polymethacrylate resin, polyacrylate resin, polyethylene resin, polyethylene terephthalate resin, and cellulose acetate resin.
These resins may be used alone or in combination of two or more.

Examples of the solvent include hydrocarbons such as toluene, xylene, pentane, hexane, heptane, and cyclohexane; alcohols such as methanol, ethanol, and isopropanol; cellosolves such as methyl cellosolve and ethyl cellosolve; ethyl acetate, Examples thereof include esters such as propyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; halogenated hydrocarbons such as methylene chloride and chloroform. You may use these solvent individually or in mixture of 2 or more types.

As the substrate, a base material such as glass or resin is used. As the resin, a highly transparent resin such as polyethylene terephthalate resin, polymethylmethacrylate resin, polycarbonate resin, polyethylene resin, polysulfone resin, polyether sulfone resin, polyamide resin, polyvinyl chloride resin, polyacrylate resin is preferable. The substrate may be flexible or hard, and may be plate-shaped, sheet-shaped, or film-shaped.

Examples of the method of applying the near-infrared absorbing dye solution to the substrate include a bar coating method and a spin coating method.

The amount of the near infrared absorbing dye used is 0.01 to 200 parts by weight, based on 100 parts by weight of the binder resin.
It is preferably 0.1 to 60 weight. When the amount of the near infrared absorbing dye used is less than 0.01 part by weight,
There is a risk that the absorption capacity of near infrared rays will not be sufficient.
Further, when the amount of the near-infrared absorbing dye used exceeds 200 parts by weight, the transmittance in the visible portion may decrease.

(2) Second Embodiment (Curing of Composition Containing Dye and Monomer) Whether or not a curable composition containing a near-infrared absorbing dye, a monomer and a polymerization initiator is injected into a mold for polymerization and curing. ,
Alternatively, the near-infrared absorbing material is obtained by applying it on the above-mentioned substrate and polymerizing and curing it. This near infrared absorbing material is, for example,
A sheet-shaped or plate-shaped structure can be adopted.

As the above-mentioned monomer, methacrylic acid esters, acrylic acid esters, aromatic and aliphatic vinyls, glycidyl ethers, vinyl sulfides,
Examples thereof include vinyl ethers.

Examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate, ethylene glycol dimethacrylate, glycidyl methacrylate, bis (4-methacryloylthiophenyl) sulfide, bis (2-methacryloylthioethyl) sulfide and the like. Can be mentioned.

Examples of the acrylic acid esters include methyl acrylate, ethyl acrylate, ethylene glycol diacrylate, glycidyl acrylate and the like.

Examples of the aromatic and aliphatic vinyls include styrene, chlorostyrene, hydroxystyrene, α-methylstyrene, divinylbenzene and 4-vinylstyrene.
Examples thereof include vinylcyclohexene and 1,5-cyclooctadiene.

Examples of the glycidyl ethers include allyl glycidyl ether, phenyl glycidyl ether, trimethylolpropane glycidyl ether,
1,6-hexanediol glycidyl ether and the like can be mentioned.

Examples of the vinyl sulfides include propyl vinyl sulfide, phenyl vinyl sulfide, bis (4-vinylthiophenyl) sulfide and the like.

Examples of the vinyl ethers include:
Examples include propyl vinyl ether, phenyl vinyl ether, bis (4-vinyloxyphenyl) sulfide, and the like.

These monomers may be used alone or in admixture of two or more.

The curing method is not particularly limited, and may be appropriately selected from a heat curing method, a photo-curing method using an ultraviolet ray, an electron beam, etc., depending on the application.

The amount of the near infrared absorbing dye used is 10
It is desirable that the amount is 0.01 to 200 parts by weight, preferably 0.1 to 60 parts by weight, relative to 0 parts by weight. If the amount of the near-infrared absorbing dye used is less than 0.01 part by weight, the near-infrared absorbing ability may be insufficient. When the amount of the near infrared absorbing dye used exceeds 200 parts by weight,
There is a risk that the transmittance of the visible portion will decrease.

Examples of the polymerization initiator used in the thermosetting reaction include 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2-isobutyronitrile) and 2,2 '. Azo compounds such as'-azobis (2,4-dimethylvaleronitrile); and peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, tert-butyl peroxyisobutyrate, and benzoyl peroxide.

Examples of the polymerization initiator used in the photo-curing reaction include 2,2-diethoxyacetophenone, 2,2-diethoxy-2-phenylacetophenone, benzophenone and 1- (4-isopyropyrphenyl) -2. -Hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio)
Phenyl] -2-morpholinopropan-1-one, benzoin isopropyl ether, 2,4-dimethylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like can be mentioned.

The polymerization initiator is used in an amount of 0.01 to 2 parts by weight, preferably 0.1 to 100 parts by weight of the monomer.
It is desirable that the amount is 1 part by weight. The curing temperature and the curing time vary depending on the use and shape of the near-infrared absorbing material of the present invention, the type of the polymerization initiator used, and in the case of the thermosetting method, the curing temperature is 0 to 200 ° C., preferably 10 to 150. It is desirable that the temperature is ° C. The curing time is 0.5 minutes to 50 hours,
It is preferably 1 minute to 10 hours. In the case of the photo-curing method, the irradiation energy is 0.1 to 50.
It is preferably J / cm ² .

[0072]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples.

Synthesis Example 1 To 59.2 g (0.2 mol) of 4- (morpholinosulfonyl) -1,2-dibromobenzene, 183 g of N, N-dimethylformamide and 33.6 g (0% of 70% by weight aqueous sodium hydrosulfide solution) were added. 0.42 mol) and added at 65 ° C for 3
Reacted for hours. To this solution, 5.9 g (0.11 mol) of iron powder and 6.7 g (0.21 mol) of sulfur powder were added,
The reaction was carried out at 90 to 95 ° C for 6 hours.

The obtained reaction solution was added with methanol 108 at room temperature.
After the addition of 0 g, 77.2 g of a 28% by weight sodium methylate solution (0.21 mol as sodium methylate) was added and stirred for 1 hour to obtain nickel (II) chloride 6
22.9 g (0.1 mol) of the hydrate was added, and the reaction was further performed at room temperature for 3 hours. Then, tetra-
32.2 g of n-butylammonium bromide (0.1
Mol) was added, and the mixture was reacted at room temperature for 2 hours while blowing air.

The reaction solution thus obtained was concentrated and purified by silica gel column chromatography to obtain 36.3 g of the target green benzenedithiol nickel complex D1 (see Table 1 below). The maximum absorption wavelength (λmax) in the near infrared region of this complex was 858 nm when measured with a spectrophotometer, and the molar absorption coefficient was 15500 when measured with a spectrophotometer.

Synthesis Examples 2 to 8 Various benzenedithiol nickel complexes D2 to D8 were synthesized in the same manner as in Synthesis Example 1. The structural formula of each benzenedithiol nickel complex is shown in Table 1 together with the benzenedithiol nickel complex D1.

Synthesis Example 9 31.7 g (0.16 mol) of 4-tert-butylbenzene in 28% by weight sodium methylate solution 121.3
g (0.33 mol as sodium methylate) was added and stirred at room temperature for 1 hour, and a solution of 36.6 g (0.16 mol) of nickel (II) chloride hexahydrate in 200 g of methanol was added. Then, the mixture was further reacted at room temperature for 1 hour. Then, 25.8 g (0.8 mol) of tetra-n-butylammonium bromide was added to this reaction liquid, and the reaction was carried out at room temperature for 1 hour while blowing air.

The reaction solution thus obtained was filtered, washed with methanol, and then dried to obtain the desired yellow-green benzenedithiol nickel complex D9 (see Table 1 below).
Obtained 3.6 g.

Synthesis Example 10 Further, a benzenedithiol nickel complex D10 was synthesized in the same manner as in Synthesis Example 9. Table 1 shows the structural formula of the obtained benzenedithiol nickel complex.

[0080]

[Table 1]

The position of R ⁵ in Synthesis Examples 1 to 9 is 4,
It is in the 4'position and m is 1. Further, the position of R ⁵ in Synthesis Example 10 is 4, 4 ′, 5, 5 ′ position, and m is 2.

Example 1 N, N, N ', N'-tetrakis (4-di-n-butylaminophenyl) -1,4-benzoquinone-bis (immonium hexafluoroantimonic acid) (produced by Nippon Carlit Co., Ltd.) Trade name: CIR-1081) 1.2 g and nickel complex (D1) 0.4 g were mixed to obtain 1.6 g of near infrared absorbing dye.

Example 2 N, N, N ', N'-Tetrakis (4-di-n-butylaminophenyl) -1,4-benzoquinone-bis (immonium / perchloric acid) (a product of Nippon Carlit Co., Ltd.) Name; CIR-1080) 1.2 g and nickel complex (D
2) 0.4 g was mixed to obtain 1.6 g of near infrared absorbing dye.

Example 3 N, N, N ', N'-tetrakis (4-di-n-butylaminophenyl) -1,4-benzoquinone-bis (imonium hexafluoroantimonic acid) (Nippon Kayaku Co., Ltd.) Trade name; IRG-022) 1.2 g and nickel complex (D3) 0.8 g are mixed, and near infrared absorbing dye 2.0
g was obtained.

Example 4 N, N, N ', N'-tetrakis (4-di-n-butylaminophenyl) -1,4-benzoquinone-bis (imonium hexafluoroantimonic acid) (Nippon Kayaku Co., Ltd.) Trade name; IRG-022) 2.4 g and nickel complex (D4) 0.8 g are mixed to obtain a near-infrared absorbing dye 3.2.
g was obtained.

Example 5 N, N, N ', N'-tetrakis (4-di-n-butylaminophenyl) -1,4-benzoquinone-bis (immonium hexafluoroantimonic acid) (Nippon Kayaku Co., Ltd.) Trade name; IRG-022) 1.2 g and nickel complex (D9) 0.4 g are mixed to obtain a near infrared absorbing dye 1.6.
g was obtained.

Example 6 N, N, N ', N'-tetrakis (4-di-n-butylaminophenyl) -1,4-benzoquinone-bis (immonium hexafluoroantimonic acid) (produced by Nippon Carlit Co., Ltd.) 0.4 g of trade name; CIR-1081) and 0.1 g of nickel complex (D5) were mixed to obtain 0.5 g of near infrared absorbing dye.

Example 7 N, N, N ', N'-tetrakis (4-di-n-butylaminophenyl) -1,4-benzoquinone-bis (immonium hexafluoroantimonic acid) (produced by Nippon Carlit Co., Ltd.) Trade name: CIR-1081) 0.4 g and nickel complex (D6) 0.1 g were mixed to obtain a near infrared ray absorbing dye 0.5 g.

Example 8 N, N, N ', N'-tetrakis (4-di-n-butylaminophenyl) -1,4-benzoquinone-bis (immonium hexafluoroantimonic acid) (produced by Nippon Carlit Co., Ltd.) 0.4 g of trade name; CIR-1081) and 0.2 g of nickel complex (D7) were mixed to obtain 0.6 g of near infrared absorbing dye.

Example 9 N, N, N ', N'-tetrakis (4-di-n-butylaminophenyl) -1,4-benzoquinone-bis (immonium hexafluoroantimonic acid) (Nippon Kayaku Co., Ltd.) Trade name; IRG-022) 0.8g and nickel complex (D8) 0.2g are mixed, and near infrared absorption dye 1.0
g was obtained.

Example 10 N, N, N ', N'-tetrakis (4-di-n-butylaminophenyl) -1,4-benzoquinone-bis (immonium hexafluoroantimonic acid) (Nippon Kayaku Co., Ltd.) Trade name; IRG-022) 0.4 g and nickel complex (D10) 0.1 g are mixed, and near infrared absorbing dye 0.
5 g was obtained.

Example 11 100 g of a polycarbonate resin and 1.6 g of the near-infrared absorbing dye obtained in Example 1 were dissolved in a mixed solvent of 390 g of methyl ethyl ketone and 390 g of methylene chloride. The solution of the obtained near-infrared absorbing dye is 100 μm thick
Was coated on the above polyester film by the bar coating method and dried at room temperature to obtain a near-infrared absorbing material having a film thickness of 15 μm.

Example 12 100 g of polymethylmethacrylate resin and 1.6 g of the near infrared absorbing dye obtained in Example 2 were dissolved in 780 g of methyl ethyl ketone. The solution of the obtained near-infrared absorbing dye is applied on a polyester film having a thickness of 100 μm by a bar coating method and dried at room temperature to give a film thickness of 15 μm.
To obtain a near infrared ray absorbing material.

Example 13 100 g of a polycarbonate resin and 2.0 g of the near infrared absorbing dye obtained in Example 3 were dissolved in a mixed solvent of 390 g of methyl ethyl ketone and 390 g of methylene chloride. The solution of the obtained near-infrared absorbing dye is 100 μm thick
Was coated on the above polyester film by the bar coating method and dried at room temperature to obtain a near-infrared absorbing material having a film thickness of 15 μm.

Example 14 In a mixed solvent of 390 g of methyl ethyl ketone and 390 g of methylene chloride, 100 g of a polycarbonate resin and 3.2 g of the near infrared absorbing dye obtained in Example 4 were dissolved. The solution of the obtained near-infrared absorbing dye is 100 μm thick
Was coated on the above polyester film by the bar coating method and dried at room temperature to obtain a near-infrared absorbing material having a film thickness of 15 μm.

Example 15 100 g of a polycarbonate resin and 1.6 g of the near infrared absorbing dye obtained in Example 5 were dissolved in a mixed solvent of 390 g of methyl ethyl ketone and 390 g of methylene chloride. The solution of the obtained near-infrared absorbing dye is 100 μm thick
Was coated on the above polyester film by the bar coating method and dried at room temperature to obtain a near-infrared absorbing material having a film thickness of 15 μm.

Example 16 0.5 g of the near infrared absorbing dye obtained in Example 6 and 0.1 g of 2,2'-azobis (2-isobutyronitrile) were dissolved in 100 g of styrene. The solution of the obtained near-infrared absorbing dye was applied on a polyester film having a thickness of 100 μm by a bar coating method, and the mixture was heated at 65 ° C. for 3 hours and then at 80 ° C.
It was cured by heating at 0 ° C for 2 hours. After cooling, a near infrared ray absorbing material having a film thickness of 50 μm was obtained.

Example 17 0.5 g of the near infrared absorbing dye obtained in Example 7 and 0.1 g of 2,2'-azobis (2-isobutyronitrile) were dissolved in 100 g of methyl methacrylate. . The solution of the obtained near-infrared absorbing dye was applied on a polyester film having a thickness of 100 μm by a bar coating method, and heated at 65 ° C. for 3 hours and at 80 ° C. for 2 hours to be cured. After cooling, a near infrared ray absorbing material having a film thickness of 50 μm was obtained.

Example 18 0.6 g of the near-infrared absorbing dye obtained in Example 8 and 0.1 g of 2,2'-azobis (2-isobutyronitrile) were dissolved in 100 g of methyl methacrylate. . The solution of the obtained near-infrared absorbing dye was applied on a polyester film having a thickness of 100 μm by a bar coating method, and heated at 65 ° C. for 3 hours and at 80 ° C. for 2 hours to be cured. After cooling, a near infrared ray absorbing material having a film thickness of 50 μm was obtained.

Example 19 To 100 g of methyl methacrylate, 1.0 g of the near infrared absorbing dye obtained in Example 9 and 2-hydroxy-2-
0.1 g of methyl-1-phenylpropan-1-one was dissolved. A solution of the obtained near-infrared absorbing dye is applied to a thickness of 10
It was coated on a polyester film of 0 μm by the bar coating method, and it was coated with a metal halide lamp in a nitrogen atmosphere for 10 minutes.
It was irradiated with ultraviolet rays of J / cm ² and cured. After cooling, a near infrared ray absorbing material having a film thickness of 50 μm was obtained.

Example 20 0.5 g of the near-infrared absorbing dye obtained in Example 10 and 2-hydroxy-2 were added to 100 g of methyl methacrylate.
0.1 g of -methyl-1-phenylpropan-1-one was dissolved. Thickness of the obtained solution of near-infrared absorbing dye is 1
It was applied by bar coating method on a polyester film of 00 μm, and it was used in a nitrogen atmosphere using a metal halide lamp.
UV rays of 0 J / cm ² were radiated to cure. After cooling, a near infrared ray absorbing material having a film thickness of 50 μm was obtained.

Comparative Example 1 100 g of a polycarbonate resin and N, N, N ', N'-tetrakis (4-di-n-butylaminophenyl) -1,4-in a mixed solvent of 390 g of methyl ethyl ketone and 390 g of methylene chloride. 1.2 g of benzoquinone-bis (immonium hexafluoroantimonic acid) (trade name of Japan Carlit Co .; CIR-1081) was dissolved. A solution of the obtained near-infrared absorbing dye is applied to a thickness of 10
It was applied on a 0 μm polyester film by a bar coating method and dried at room temperature to obtain a near infrared absorbing material having a film thickness of 15 μm.

Comparative Example 2 100 g of a polycarbonate resin and N, N, N ', N'-tetrakis (4-di-n-butylaminophenyl) -1,4-in a mixed solvent of 390 g of methyl ethyl ketone and 390 g of methylene chloride. Benzoquinone-bis (immonium hexafluoroantimonate) (trade name of Japan Carlit Co .; CIR-1081) 1.2 g and bis (4-morpholino-1,2-benzenedithiolate)
0.4 g of copper-tetrabutylammonium (trade name of Sumitomo Seika Chemicals Co., Ltd .; EST5-Cu) was dissolved. The solution of the obtained near-infrared absorbing dye was applied on a polyester film having a thickness of 100 μm by a bar coating method and dried at room temperature to obtain a near-infrared absorbing material having a thickness of 15 μm.

Comparative Example 3 With respect to 100 g of methyl methacrylate, N, N, N ',
0.4 g of N'-tetrakis (4-di-n-butylaminophenyl) -1,4-benzoquinone bis (immonium hexafluoroantimonate) (trade name of Japan Carlit Co., Ltd .; CIR-1081) and bisdithiobenzyl Nickel (trade name of Hayashibara Institute of Biochemistry; NK-14
14) 0.1 g and 2,2'-azobis (2-isobutyronitrile) 0.1 g were dissolved. The solution of the obtained near-infrared absorbing dye was applied on a polyester film having a thickness of 100 μm by a bar coating method, and heated at 65 ° C. for 3 hours and at 80 ° C. for 2 hours to be cured. After cooling, a near infrared ray absorbing material having a film thickness of 50 μm was obtained.

[Evaluation] Examples 11 to 20 and Comparative Example 1
The transmittance (%) at each wavelength of 850 nm and 1050 nm of each of the near-infrared absorbing materials obtained in Nos. 3 to 3 was measured with a spectrophotometer (U-3410, manufactured by Hitachi Ltd.) (transmittance before the test). Next, a constant temperature bath (Nagano Scientific Co., Ltd., LH-20
Mold), the near-infrared absorbing material obtained in
The transmittance (%) after standing for a time was measured in the same manner as above (transmittance after the test). The results are shown in Table 2.

[0106]

[Table 2]

From Table 2, it can be seen that the near-infrared absorbing materials obtained in Examples 11 to 20 have a small difference between the transmittance before the test and the transmittance after the test and are excellent in heat resistance. On the other hand, it is understood that the near infrared ray absorbing materials obtained in Comparative Examples 1 and 3 are inferior in heat resistance. Further, it can be seen that the near-infrared absorbing material obtained in Comparative Example 2 has excellent heat resistance but high transmittance.

[0108]

INDUSTRIAL APPLICABILITY The near-infrared absorbing dye of the present invention has excellent near-infrared absorbing ability and high heat resistance by using a diimonium salt and benzenedithiol nickel complexes in combination. Therefore, the near-infrared absorbing material using the near-infrared absorbing dye of the present invention is a near-infrared blocking film for electronic devices represented by plasma displays, a heat-ray blocking film for construction, a recording medium utilizing near-infrared absorption. It is preferably used for optical devices and the like.

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Claims (3)

[Claims] 1. The following general formula (1): (In the formula, R ¹ , R ² , R ³ , and R ⁴ are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkylamino group having 1 to 8 carbon atoms or an aryl group, and X ⁻ is a halogen ion, An inorganic acid ion or an organic acid ion is shown) and a diimonium salt represented by the following general formula (2); (In the formula, R ⁵ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
An alkylamino group having 1 to 8 carbon atoms, an aryl group, a halogen atom or the following general formula (3); Alternatively, the following general formula (4); (In the formula, R ⁶ and R ⁷ are an alkyl group having 1 to 6 carbon atoms, an alkylamino group having 1 to 8 carbon atoms, an aryl group, a halogen atom, a morpholino group which may have a substituent, and a piperidino group. , Also represents a pyrrolidino group, a thiomorpholino group, or a piperazino group.). m represents an integer of 1 to 4. A ⁺ represents a quaternary ammonium ion or a quaternary phosphonium ion. )
A near-infrared absorbing dye composed of benzenedithiol nickel complexes represented by. 2. A near-infrared absorbing material obtained by coating and forming the near-infrared absorbing dye according to claim 1 on a substrate. 3. A near infrared absorbing material obtained by curing the composition containing the near infrared absorbing dye according to claim 1 and a monomer by polymerizing the monomer.