JP2002275134A - Infrared light-absorbing compound and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new infrared light-absorbing compound, and develop a photo-recording medium and an infrared light-cutting filter by using the same compound. SOLUTION: This infrared light-absorbing compound is obtained by oxidizing a compound expressed by the following formula (1) [wherein, R1 to R16 are each H, a (substituted) alky, cycloalkyl alkenyl or aryl, and may be the same or different; and also rings A, B, C each may have substituents], and its use.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel compound having an absorption in the infrared region (hereinafter referred to as an infrared absorption compound) and its use. Specifically, dyes for optical recording materials, dyes for infrared cut filters, dyes for data codes, dyes for light-shielding filters, dyes for blocking heat rays, dyes for laser printers, singlet oxygen quencher, anti-fading agents, organic electric field elements The present invention relates to an infrared absorber used for a hole transport material and the like in the above. In particular, the present invention relates to an optical recording medium containing the infrared absorbing compound in a recording layer, and an infrared cut filter containing the infrared absorbing compound.

[0002]

2. Description of the Related Art Hitherto, a diimmonium salt compound as an infrared absorber has been widely used for heat insulating films, sunglasses and the like. Various organic dyes such as cyanine dyes have been proposed as dyes used in optical recording media containing organic dyes, particularly optical disks such as CD-Rs and DVD-Rs that can be recorded only once, optical cards, and the like. However, generally, there is a problem that the recording / reproducing characteristics and the storage stability are deteriorated due to the fact that the substance is easily changed by heat and light. As a solution to such a problem, Japanese Patent
It is known to add an aminium salt, a diimonium salt or the like as described in JP-A-26028, JP-A-1-99885 and the like.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and an object of the present invention is to provide a novel infrared absorbing compound which can be used in the same manner as conventional diimonium salts and aminium salts. An object of the present invention is to provide an optical recording medium using a compound and an infrared cut filter.

[0004]

Means for Solving the Problems The present inventors have made intensive efforts to solve the above-mentioned problems, and as a result, the following formula (1) has been obtained.
The present invention was completed by synthesizing a novel infrared absorbing compound having the following structure. That is, the present invention provides (1) the following formula (1)

[0005]

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(In the formula (1), R1 to R16 represent a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, which may be the same or different. Rings A, B and C may have a substituent.) An infrared absorbing compound obtained by oxidizing a compound represented by the formula (2): Rings A, B and C are unsubstituted or substituted The compound according to claim 1, wherein the group has 1 to 4 halogen atoms, lower alkyl groups, lower alkoxy groups, cyano groups, and hydroxyl groups, and (3) R1 to R16 each independently represent an unsubstituted alkyl group or halogen substitution. The compound according to claim 2, which is an alkyl group, an alkoxy-substituted alkyl group, a cyano-substituted alkyl group, or a substituted or unsubstituted alkynyl group, and the compound according to any one of (4) (1) to (3). (5) An infrared cut filter comprising the compound according to any one of (1) to (3), (6) An oxidation precursor of the compound according to any one of (1) to (3).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The compound obtained by oxidizing the compound of the formula (1) according to the present invention is an infrared-absorbing compound having an absorption in the infrared region, and various functional dyes such as optical recording Material dye, infrared cut filter dye, data code dye, light shielding filter dye, heat ray blocking dye, laser printer dye, singlet oxygen quencher, anti-fading agent, hole transport material in organic electric field element, etc. Can be used.

The infrared absorbing compound of the present invention can be obtained by oxidizing a compound having the structure represented by the above formula (1). A typical example of such an infrared absorbing compound is represented by the following chemical formula (2). The compound of formula (1) is an oxidation precursor of the compound of formula (2).

[0009]

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(In the formula (2), R1 to R16, rings A and B,
C is the same as above. X is an anion, and n is an integer from 1 to 6. In the formula (2), [] indicates an even oxidation state.
It becomes a diimmonium salt having a quinone structure as described in 2000-80071. For example, in the case of divalent, any of the rings A, B and C can have a quinone structure, and in the case of tetravalent, a structure such as two rings A and C and two quinone structures of ring B can be considered. In the case of hexavalent, a structure having three quinone structures in ring A and two rings C is considered. In the case of an odd oxidation state, a structure in which a radical cation exists, such as an aminium salt described in JP-A-2000-229931, can be considered. For example, 1
In the case of valence, the radical cation can be present on any nitrogen atom, and in the case of trivalent, it can be present on any nitrogen atom other than the quinone structure present in the above-mentioned divalent form.
In terms of valency, it can also have a radical cation on a nitrogen atom other than the quinone structure present in the tetravalent form. Of course, all of these structures can take many structures, considering conjugation.

Rings A, B and C may or may not have from 1 to 4 substituents. Examples of the substituent that can be bonded include a halogen atom, a hydroxyl group, an alkoxy group, a cyano group, and a lower alkyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group include a C1 to C5 alkoxy group such as a methoxy group and an ethoxy group. Examples of the lower alkyl group include a C1 to C5 alkyl group such as a methyl group and an ethyl group. Preferably, A, B and C have no substituent or are substituted with a halogen atom (particularly a chlorine atom or a bromine atom), a methyl group or a cyano group.

In the general formula (1), R1 to R16 each represent a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, which may be the same or different. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, tert-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group,
an alkyl group having 1 to 20 carbon atoms such as an n-octadecyl group,
Preferably, an alkyl group having 1 to 10 carbon atoms, more preferably, an alkyl group having 1 to 6 carbon atoms is used. Examples of the cycloalkyl group include a cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. As the alkenyl group, a vinyl group,
Allyl group, 1-propenyl group, isopropenyl group, 2-
An alkenyl group having 2 to 10 carbon atoms such as a butenyl group, a 1,3-butadienyl group and a 2-pentenyl group is exemplified. Aryl groups include phenyl, tolyl, xylyl,
An aryl group having 6 to 12 carbon atoms such as a naphthyl group is exemplified.

Examples of the substituents bonded to these groups include a cyano group; a nitro group; a hydroxy group; a tetrahydrofuryl group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; a methoxy group, an ethoxy group and an n-propoxy group. , Isopropoxy group, n-butoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, n-
C1-C10 alkoxy groups such as hexyloxy group, n-heptyloxy group, n-octyloxy group, n-decyloxy group; methoxymethoxy group, ethoxymethoxy group, propoxymethoxy group, methoxyethoxy group, ethoxyethoxy group An alkoxyalkoxy group having 2 to 12 carbon atoms such as a propoxyethoxy group, a methoxypropoxy group, an ethoxypropoxy group, a methoxybutoxy group, an ethoxybutoxy group; a methoxymethoxymethoxy group, a methoxymethoxyethoxy group, a methoxyethoxymethoxy group,
C3 such as methoxyethoxyethoxy, ethoxymethoxymethoxy, ethoxymethoxyethoxy, ethoxyethoxymethoxy, ethoxyethoxyethoxy, etc.
Aryloxy group having 6 to 12 carbon atoms such as phenoxy group, tolyloxy group, xylyloxy group, naphthyloxy group; methylsulfonylamino group, ethylsulfonylamino group, n-propylsulfonylamino Group, isopropylsulfonylamino group, n-butylsulfonylamino group, tert-butylsulfonylamino group, sec-
1 carbon atom such as butylsulfonylamino group, n-pentylsulfonylamino group, n-hexylsulfonylamino group, etc.
Alkylsulfonylamino groups of methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, sec-
C 2-7 carbon atoms such as a butoxycarbonyl group, an n-pentyloxycarbonyl group and an n-hexyloxycarbonyl group
Alkoxycarbonyl group; methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, tert-butylcarbonyloxy group, sec-butylcarbonyloxy group, n- An alkylcarbonyloxy group having 2 to 7 carbon atoms such as a pentylcarbonyloxy group and an n-hexylcarbonyloxy group; a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an isopropoxycarbonyloxy group, and an n-butoxy group Carbonyloxy group, tert-butoxycarbonyloxy group, s
Examples thereof include an alkoxycarbonyloxy group having 2 to 7 carbon atoms such as an ec-butoxycarbonyloxy group, an n-pentyloxycarbonyloxy group, and an n-hexyloxycarbonyloxy group.

Among these substituents of R1 to R16, preferred are, for example, unsubstituted (C1 to C16) groups such as an ethyl group, an n-propyl group and an n-butyl group.
8) alkyl group or trifluoromethyl group, 1,1,
Halogen substitution such as a 2,2,2-pentafluoroethyl group, a 3-chloropropyl group, a 2-chloroethyl group (C1-
C8) Alkyl group or (C1-C4) alkoxy substitution (C1-C8) such as methoxymethyl group, methoxyethyl group, methoxypropyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl group, ethoxybutyl group, propoxymethyl group and the like. ) Alkyl, or cyanomethyl,
2-cyanoethyl group, 3-cyanopropyl group, 2-cyanopropyl group, 4-cyanobutyl group, 3-cyanobutyl group, 2-cyanobutyl group, 5-cyanopentyl group, 6-
Cyano substitution such as cyanohexyl group (C1 to C8)
Unsubstituted alkynyl groups such as an alkyl group and an allyl group are preferred.

X is an anion, and examples thereof include an organic acid anion and an inorganic anion. Examples of the organic acid anion include organic carboxylate ions such as acetate ion, lactate ion, trifluoroacetate ion, propionate ion, benzoate ion, oxalate ion, succinate ion, and stearate ion, methanesulfonic acid ion, and toluene. Organic sulfonic acid ions such as sulfonic acid ion, naphthalene monosulfonic acid ion, chlorobenzenesulfonic acid ion, nitrobenzenesulfonic acid ion, dodecylbenzenesulfonic acid ion, benzenesulfonic acid ion, ethanesulfonic acid ion, trifluoromethanesulfonic acid ion, etc., and tetraphenyl Organic borate ions such as borate ion and butyltriphenyl borate ion, etc., are preferred. Halogenoalkyls such as trifluoromethanesulfonic acid ion and toluenesulfonic acid ion are preferred. Acid ion or alkyl arylsulfonate ion.

Examples of the inorganic anions include halogen ions such as fluorine ion, chloride ion, bromine ion and iodine ion, thiocyanate ion, hexafluoroantimonate ion, perchlorate ion, periodate ion, nitrate ion and tetrafluoro ion. Borate ion, hexafluorophosphate ion, molybdate ion, tungstate ion, titanate ion, vanadate ion, phosphate ion, borate ion, etc., and preferred are perchlorate ion, iodine ion and the like. , Tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion and the like.

Of these anions, preferred are, for example, perchlorate ion, iodine ion, tetrafluoroborate ion, hexafluorophosphate ion,
Hexafluoroantimonate ion, trifluoromethanesulfonic acid ion, toluenesulfonic acid ion and the like can be mentioned.

Next, specific examples of the infrared absorbing compound represented by the general formula (2) of the present invention are shown in Tables 1 to 4. Table 1
In ~ 4, TsO represents toluenesulfonic acid ion. When A, B, and C are unsubstituted, “4H” and R 1 to R
When all 16 are cyanoethyl groups, "8 (CH2
CH2CN, CH2CH2CN) "and, for example, when one of R1 to R16 is an n-butyl group and the remaining is a cyanoethyl group," 7 (CH2CH2CN, CH2CH2C)
N) (CH2CH2CN, n-C4H9) "and the like.

Table 1 No. (R1, R2) (R3, R4) (R5, R6) (R7, R8) (R9, R10) (R11, R12) (R13R14) (R15, R16), ABCX n 18 (n-C4H9, n-C4H9), 4H 4H 4H SbF6 1 2 8 (n-C4H9, n-C4H9), 4H 4H 4H SbF6 2 3 8 (n-C4H9, n-C4H9), 4H 4H 4H SbF6 3 4 8 (n-C4H9, n-C4H9), 4H 4H 4H SbF6 4 5 8 (n-C4H9, n-C4H9), 4H 4H 4H SbF6 5 6 8 (n-C4H9, n-C4H9), 4H 4H 4H SbF6 6 7 8 (n-C3H6CN, n-C3H6CN), 4H 4H 4H SbF6 18 8 (n-C3H6CN, n-C3H6CN), 4H 4H 4H SbF6 298 (n-C3H6CN, n-C3H6CN), 4H 4H 4H SbF6 3 10 8 (n-C3H6CN, n-C3H6CN), 4H 4H 4H SbF6 4 11 8 (CH2CH2OCH3, CH2CH2OCH3), 4H 4H 4H SbF6 2 12 8 (CH2CH2OCH3, CH2CH2OCH3), 4H 4H 4H SbF6 4

Table 2 No. (R1, R2) (R3, R4) (R5, R6) (R7, R8) (R9, R10) (R11, R12) (R13R14) (R15, R16), ABCX n138 (n-C4H9, n-C4H9), 4H 4H 4H ClO4 1 14 8 (n-C4H9, n-C4H9), 4H 4H 4H PF6 215 8 (n-C4H9, n-C4H9), 4H 4H 4H BF4 3 16 8 (n-C4H9, n-C4H9), 4H 4H 4H Cl04 4 17 8 (n-C4H9, n-C4H9), 4H 4H 4H ClO4 5 18 8 (n-C4H9, n-C4H9), 4H 4H 4H BF4 6 198 (n-C3H6CN, n-C3H6CN), 4H 4H 4H PF6 1 208 (n-C3H6CN, n-C3H6CN), 4H 4H 4H BF4 221 8 (n-C3H6CN, n-C3H6CN), 4H 4H 4H ClO4 3 22 8 (n-C3H6CN, n-C3H6CN), 4H 4H 4H BF4 4 23 8 (CH2CH2OCH3, CH2CH2OCH3), 4H 4H 4H ClO4 2 24 8 (CH2CH2OCH3, CH2CH2OCH3), 4H 4H 4H ClO4 4

Table 3 No. (R1, R2) (R3, R4) (R5, R6) (R7, R8) (R9, R10) (R11, R12) (R13R14) (R15, R16), ABCX n258 (n-C4H9, n-C4H9), 4H 4H 4H TsO 2 268 (n-C4H9, n-C4H9), Cl 4H 4H ClO4 2 278 (n-C4H9, n-C4H9), 4H Cl 4H ClO4 1 28 8 (n-C4H9, n-C4H9), CH3 4H 4H ClO4 229 8 (n-C4H9, n-C4H9), 4H 4H Cl ClO4 3 30 8 (n-C4H9, n-C4H9), Cl CH3 4H ClO4 4 31 8 (n-C3H6CN, n-C3H6CN), Cl 4H 4H SbF6 2 328 (CH2CH = CH2, CH2CH = CH2), 4H 4H 4H ClO4 238 (n-C3H7, n-C3H7), 4H 4H 4H ClO4 2 348 (C2H5, C2H5), 4H 4H 4H ClO4 435 8 (CH2CH2OCH3, CH2CH2OCH3), Cl 4H 4H ClO4 236 8 (CF2CF3, CF2CF3), 4H 4H 4H ClO4 4

Table 4 No. (R1, R2) (R3, R4) (R5, R6) (R7, R8) (R9, R10) (R11, R12) (R13R14) (R15, R16), ABCX n 37 7 (n-C4H9, n-C4H9) (n-C4H9, CH2CH2OCH3), 4H 4H 4H ClO4 138 7 (n-C4H9, n-C4H9) (n-C4H9, CH2CH2OCH3), 4H 4H 4H PF6 2 39 7 (n -C4H9, n-C4H9) (n-C4H9, CH2CH2OCH3), Cl 4H 4H BF4 3 40 7 (n-C4H9, n-C4H9) (n-C4H9, CH2CH2OCH3), 4H 4H 4H Cl04 4 41 7 (n-C4H9 , n-C4H9) (n-C4H9, n-C3H6CN), 4H 4H 4H ClO4 3 427 (n-C4H9, n-C4H9) (n-C4H9, n-C3H6CN), CH3 4H 4H BF4 443 7 (n -C4H9, n-C4H9) (n-C4H9, n-C3H6CN), 4H 4H 4H PF6 144 7 (n-C4H9, n-C4H9) (n-C4H9, n-C3H6CN), 4H 4H 4H ClO4 2 45 7 (n-C3H6CN, n-C3H6CN) (n-C3H6CN, n-C4H9), 4H 4H 4H ClO4 3 46 7 (n-C3H6CN, n-C3H6CN) (n-C3H6CN, n-C4H9), 4H 4H 4H BF4 4 47 7 (CH2CH2OCH3, CH2CH2OCH3) (CH2CH2OCH3, n-C4H9), 4H 4H 4H ClO4 2 48 7 (CH2CH2OCH3, CH2CH2OCH3) (CH2CH2OCH3, n-C4H9), 4H 4H 4H ClO4 4

The compound represented by formula (2) of the present invention can be obtained, for example, by the following method described in JP-B-43-25335. The following formula (3) obtained by the Ullmann reaction and the reduction reaction

[0024]

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(In the formula (3), R1-16, rings A, B, C
Is the same as above. ) Is again subjected to the Ullmann reaction and the reduction reaction of the amino compound represented by the following formula (4):

[0026]

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(In the formula (4), R1-16, rings A, B, C
Is the same as above. )) In an organic solvent, preferably in a water-soluble polar solvent such as DMF, DMI or NMP, at 30 to 160 ° C, preferably 50 to 140 ° C. Is C4H9), it is possible to obtain an all-substituted compound of the general formula (1). When a compound other than the all-substituted compound is synthesized (for example, No. 37 compound), it is first reacted with a predetermined number of moles of a reagent (15 moles of C4H9Cl) and then reacted with the remaining moles of halogenated moles. With 1 mol of ClC3H6CN to give a compound of formula (1).

Thereafter, the compound of the formula (1) is added with a corresponding silver salt in an organic solvent, preferably in a water-soluble polar solvent such as DMF, DMI, NMP at 0 to 100 ° C., preferably 5 to 70 ° C. Then, by oxidation, the compound represented by the general formula (2) of the present invention is obtained. Here, by arbitrarily changing the number of moles of the oxidizing agent from 1 equivalent to 6 equivalents, 1 to 6 oxidized products can be obtained. Further, the compound of the formula (1) is oxidized with an oxidizing agent such as silver nitrate, silver perchlorate, cupric chloride or the like, and a salt exchange is performed by adding an acid or salt of a desired anion to the reaction solution. Can also synthesize the compound represented by the general formula (2).

The optical recording medium of the present invention has a recording layer on a substrate, and the recording layer contains the above-mentioned infrared absorbing compound of the present invention. This recording layer may be formed of the infrared absorbing compound of the present invention alone, or may be formed by mixing with various additives such as a binder. In this case, information is recorded by the infrared absorbing compound of the present invention.

Further, by including the infrared absorbing compound of the present invention in a recording layer of an optical recording medium on which information is recorded by an organic dye, the light resistance of the optical recording medium can be improved. Such an optical recording medium is also a kind of the optical recording medium of the present invention. As the optical recording medium, organic dyes that can be used in combination with the infrared absorbing compound of the present invention include commonly known dyes such as cyanine dyes, squarylium dyes, indoaniline dyes, phthalocyanine dyes, and azo dyes. And merocyanine dyes, polymethine dyes, naphthoquinone dyes, and pyrylium dyes. The infrared absorbing compound of the present invention is generally used in an amount of 0.01 to 10 mol, preferably 0.03 to 3 mol, per 1 mol of these organic dyes.

The optical recording medium of the present invention comprises a substrate on which a recording layer containing the infrared absorbing compound of the present invention and, if desired, a dye is provided. If necessary, a reflective layer and a protective layer are provided. Any known substrate can be used. For example, a glass plate, a metal plate or a plastic plate or a film may be mentioned, and as a plastic for producing these, acrylic resin, polycarbonate resin, methacrylic resin, polysulfone resin, polyimide resin, amorphous polyolefin resin, polyester resin,
Examples include polypropylene resin. The shape of the substrate includes various shapes such as a disk shape, a card shape, a sheet shape, and a roll film shape.

The recording layer in the present invention may be formed, for example, by adding a compound represented by the general formula (2) and more preferably a compound represented by the general formula (2) and another organic dye to a known organic solvent such as tetrafluorocarbon. It is dissolved in propanol (TFP), octafluoropropanol (OFP), diacetone alcohol, methanol, ethanol, butanol, methyl cellosolve, ethyl cellosolve, dichloroethane, isophorone, cyclohexanone, etc., and if necessary, an appropriate binder is added. The solution can be obtained by coating the solution on a substrate with a spin coater, bar coater, roll coater or the like. Other methods include a vacuum deposition method, a sputtering method, a doctor blade method, a casting method, and a dipping method in which a substrate is immersed in a solution. The thickness of the recording layer is preferably set at 0.0 in consideration of recording sensitivity and reflectance.
1 μm to 5 μm, more preferably 0.02 μm to 3 μm
It is.

In the optical information recording medium of the present invention, an undercoat layer can be provided below the recording layer, and a protective layer can be provided on the recording layer, if necessary. Further, a reflective layer is provided between the recording layer and the protective layer. Can be provided. When providing a reflective layer, the reflective layer is gold,
It is composed of silver, copper, aluminum or the like, preferably gold, silver or aluminum, and these metals may be used alone or as an alloy of two or more. This is formed by a vacuum deposition method, a sputtering method, an ion plating method, or the like. The thickness of such a reflective layer is
0.02 to 2 μm. The protective layer, which may be provided on the reflective layer, is generally formed by applying an ultraviolet curable resin by a spin coating method and then irradiating ultraviolet rays to cure the coating film. In addition, an epoxy resin, an acrylic resin, a silicone resin, a urethane resin, or the like is also used as a material for forming the protective film. The thickness of such a protective film is
Usually, it is 0.01 to 100 μm.

Recording of information on the optical recording medium of the present invention,
Alternatively, the image is formed by a laser, for example, a semiconductor laser, a helium-neon laser, a He-Cd laser,
It is performed by irradiating the recording layer with a focused high-energy beam such as a YAG laser or Ar laser through the substrate or from the opposite side of the substrate. Reading of information or images is performed by irradiating a low-output laser beam. This is performed by detecting the difference between the amount of reflected light or the amount of transmitted light between the pit portion and the portion where no pit is formed.

The infrared cut filter of the present invention may have the above-mentioned infrared absorbing compound-containing layer provided on a substrate, or the substrate itself may be an infrared absorbing compound-containing layer. The substrate is not particularly limited, but usually a resin substrate is used. The thickness of the infrared-absorbing compound-containing layer is about 0.1 μm to 10 mm, but is appropriately determined according to the purpose such as the infrared cut rate. Also, the content of the infrared absorbing compound is appropriately determined according to the intended infrared cut ratio.

The resin used as the base is preferably as transparent as possible when formed into a resin plate or resin film. Specific examples include polyethylene, polystyrene, polyacrylic acid, polyacrylate, polyvinyl acetate, and polyvinyl acetate. Vinyl compounds such as acrylonitrile, polyvinyl chloride and polyvinyl fluoride, and addition polymers of those vinyl compounds, polymethacrylic acid, polymethacrylic acid esters, polyvinylidene chloride, polyvinylidene fluoride, polyvinylidene fluoride, vinylidene fluoride / trivinylidene Copolymers of vinyl compounds or fluorine compounds, such as fluoroethylene copolymers, vinylidene fluoride / tetrafluoroethylene copolymers, vinylidene cyanide / vinyl acetate copolymers, polytrifluoroethylene, polytetrafluoroethylene, Fluorine-containing resins such as hexafluoropropylene, polyamides such as nylon 6, nylon 66, polyimides, polyurethanes, polypeptides, polyesters such as polyethylene terephthalate, polycarbonates, polyethers such as polyoxymethylene, epoxy resins, polyvinyl alcohol, polyvinyl Butyral and the like.

The method for producing the infrared cut filter of the present invention using the above compound is not particularly limited, but for example, the following method can be used. For example, (1) a method in which a resin plate or a film is prepared by kneading the above-mentioned infrared-absorbing compound into a resin and heat-molding the mixture.
(2) A method of producing a resin plate or film by cast polymerization of a compound and a resin monomer or a prepolymer of a resin monomer in the presence of a polymerization catalyst. (3) A method of preparing a paint containing a compound and coating it on a transparent resin plate, a transparent film, or a transparent glass plate. (4) The compound is contained in the adhesive, and a laminated resin plate, a laminated resin film,
Alternatively, it is a method of producing a laminated glass plate.

As the production method (1), although the processing temperature, film formation (resin plate formation) conditions and the like are slightly different depending on the resin to be used, the compound of the present invention is usually added to base resin powder or pellets. After heating and melting at 150 to 350 ° C., a method of forming a resin plate by molding, a method of forming a film (resin plate) by an extruder, and the like can be given. The amount of the infrared absorbing compound to be added varies depending on the thickness, absorption intensity, and visible light transmittance of the resin plate or film to be produced, but is generally from 0.01 to 30%, preferably to the weight of the binder resin. 0.03 to 15% is used.

In the method (2) in which the above compound and the resin monomer or the prepolymer of the resin monomer are cast-polymerized in the presence of a polymerization catalyst, the mixture is poured into a mold, reacted and cured. Alternatively, it is poured into a mold and solidified in the mold until a hard product is formed. Many resins can be molded in this process, such as acrylic resin, diethylene glycol bis (allyl carbonate) resin, epoxy resin, phenol-formaldehyde resin, polystyrene resin, silicone resin,
And the like. Among them, a casting method by bulk polymerization of methyl methacrylate, which gives an acrylic sheet excellent in hardness, heat resistance and chemical resistance, is preferable.

As the polymerization catalyst, known radical thermal polymerization initiators can be used. For example, benzoyl peroxide, p-
Examples include peroxides such as chlorobenzoyl peroxide and diisopropyl peroxycarbonate, and azo compounds such as azobisisobutyronitrile. The amount used is generally from 0.01 to 5% by weight, based on the total amount of the mixture. The heating temperature in the thermal polymerization is generally 40 to 200.
° C, and the time is generally about 30 minutes to 8 hours.
In addition to the thermal polymerization, a method of adding a photopolymerization initiator or a sensitizer and performing photopolymerization can also be used.

Examples of the method (3) include a method in which the compound of the present invention is dissolved in a binder resin and an organic solvent to form a coating, and a method in which the compound of the present invention is formed into fine particles and dispersed to obtain an aqueous coating. . In the former method, for example, aliphatic ester resin, acrylic resin, melamine resin, urethane resin, aromatic ester resin, polycarbonate resin, polyvinyl resin, aliphatic polyolefin resin, aromatic polyolefin resin, polyvinyl alcohol resin, polyvinyl modified resin Or a copolymer resin thereof can be used as a binder.

As the solvent, a halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvent, or a mixture thereof can be used. The concentration of the infrared absorbing compound of the present invention, the thickness of the coating to be produced, the absorption intensity,
Although it depends on the visible light transmittance, it is generally 0.1 to 30% based on the binder resin.

The paint prepared as described above can be obtained by coating a transparent resin film, a transparent resin plate, a transparent glass or the like with a spin coater, a bar coater, a roll coater, a spray or the like.

In the method (4), the adhesive is
A known transparent adhesive for laminated glass such as a general silicone-based, urethane-based, acrylic-based resin, or a laminated glass such as a polyvinyl butyral adhesive or an ethylene-vinyl acetate-based adhesive can be used. A transparent resin plate, a resin plate and a resin film, a resin plate and a glass, a resin film and a resin film, a glass and a glass are bonded to each other using an adhesive containing 0.1 to 30% of the compound of the present invention. , To make a filter.

In kneading and mixing by the respective methods, additives such as an ultraviolet absorber and a plasticizer which are used for ordinary resin molding may be added.

The infrared cut filter of the present invention may be composed of only the compound represented by the general formula (2), or may be prepared by mixing it with another near infrared absorbing compound. Examples of other near-infrared absorbing compounds include phthalocyanine-based and cyanine-based dyes. Examples of the inorganic metal near-infrared absorbing compound include metallic copper or a copper compound such as copper sulfide and copper oxide, a metal mixture containing zinc oxide as a main component, a tungsten compound, ITO, and ATO.

Further, in order to change the color tone of the filter, it is preferable to add a dye having absorption in the visible region as long as the effect of the present invention is not impaired. Alternatively, a filter containing only a toning dye may be prepared and then laminated later.

When such an infrared cut filter is used for a front panel of a display or the like, the higher the transmittance of visible light, the better and the transmittance is required to be at least 40%, preferably at least 50%. Near infrared cut area is 800 ~
It is preferably 900 nm, more preferably 800 to 1000 nm, and the average transmittance in that region is 50% or less, more preferably 30% or less, further preferably 20% or less, and particularly preferably 10% or less.

[0049]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, parts are parts by weight unless otherwise specified.

Example 1 <Synthesis of N, N, N ′, N′-tetrakis-di (p-nitrophenyl) aminophenyl} -p-phenylenediamine N, N, N ′, N ′ in 90 parts of DMF -Tetrakis (aminophenyl) -p-phenylenediamine 1
0.6 part, 42 parts of p-nitrochlorobenzene, 14 parts of potassium carbonate and 1 part of copper powder are added and reacted at 160 ° C. for 24 hours. After cooling, it was filtered. The crystals were washed with 200 parts of warm water and dried to obtain 72 parts of orange crystals.

<Synthesis of N, N, N ′, N′-tetrakis {di (p-aminophenyl) aminophenyl} -p-phenylenediamine> 23 parts of the nitro compound synthesized above in 70 parts of DMF, 5% palladium After adding 1.3 parts of carbon and heating to 90 ° C., a hydrogenation reaction was carried out for 1 hour by applying a pressure of 8 kg / cm 2 of hydrogen. After cooling methanol 20
0 parts was cooled to 5 ° C. or lower, the whole amount of the reaction solution was added, and the mixture was stirred for 1 hour. After filtration, the crystals were dried to obtain 20 parts of black crystals.

<Synthesis of N, N, N ′, N′-tetrakis [di {p-di (n-butyl) aminophenyl} aminophenyl] -p-phenylenediamine> The amino compound synthesized above in 130 parts of DMF 20 parts, 91 parts of 1-bromobutane and 61 parts of potassium carbonate are added, and the mixture is reacted at 90 ° C. for 3 hours and at 130 ° C. for 2 hours. After cooling, liquid filtration,
100 parts of methanol is added to the reaction solution, and
Stir for hours. The generated crystals were washed with methanol and dried to obtain 5.2 parts of light brown crystals. Melting point 111-121 ° C (DSC) Decomposition temperature 300 ° C (TG-DTA)

<NO. Synthesis of 1 Compound> 0.4 part of the compound synthesized above was added to 6 parts of DMF, dissolved by heating at 60 ° C., and then 0.53 part of silver hexafluoroantimonate dissolved in 6 parts of DMF (4 molar equivalents) ) And react for 30 minutes. After cooling, the precipitated silver is filtered off. Water 1
0 parts is slowly added dropwise, and the mixture is stirred for 15 minutes after the addition. The formed dark green crystals were filtered, washed with 50 parts of water, and the obtained cake was dried. 0.5 part of one compound was obtained. λmax 1043 nm (dichloromethane) Absorption coefficient 114,000 Decomposition temperature 245 ° C (TG-DTA)

Example 2 Synthesis was performed in the same manner as in Example 1 except that the amount of silver hexafluoroantimonate was changed to 0.26 parts (2 molar equivalents) in the reaction of Example 1 above. 0.5 part of compound 2 was obtained. λmax 1051 nm (dichloromethane) Absorption coefficient 100,000 Decomposition temperature 239 ° C (TG-DTA)

Other examples of compounds are also described in Synthesis Example 1 above.
To synthesize the corresponding phenylenediamine derivative,
It can be synthesized by oxidizing it with the corresponding oxidizing agent such as the corresponding silver salt and then reacting with the corresponding anion.

Example 3 (Example of Recording Medium) 0.02 part of compound (1) and a cyanine dye (OM-57, manufactured by Fuji Photo Film Co., Ltd.)
0.10 part was dissolved in 10 parts of tetrafluoropropanol, and passed through a 0.2 μm filter to obtain a coating solution. 5 ml of this solution was dropped on a 5-inch polycarbonate resin substrate with grooves by a pipette, applied by a spin coater, and dried to form an organic thin film recording layer. The maximum absorption wavelength of the coating film was 716 nm. Gold was formed on the obtained coating film by a sputtering method to prepare an optical recording medium as a reflection layer. When the obtained optical recording medium was evaluated by a CD-R recording / reproducing apparatus, recording and reproduction were possible.

Example 4 (Test for light stability of recording medium) Cyanine dye (O) was added to 67 parts of tetrafluoropropanol.
M-57) was dissolved in 3 parts, and the solution of No. No. 1 (sample 1) or No. 1 0.4 part of the compound (Sample 2) was added to prepare a coating solution. The obtained coating liquid is spin-coated on a polycarbonate substrate,
A dye film was formed. The obtained dye film was put into an ultraviolet long life carbon arc light resistance tester (black panel temperature: 63 ° C.) manufactured by Suga Test Machine, and irradiated with light from the substrate side to obtain 10
The light stability test was performed for 20 hours. Thereafter, the residual ratio of the cyanine dye was measured with a spectrophotometer. Table 4 shows the results. In addition, No. A dye film (Comparative 1) was prepared and evaluated in the same manner except that the compound was dissolved without containing one compound, and the results were shown in Table 5.

Table 5 (Light Stability Test) Residual Rate of Cyanine Dye (%) Initial 10 hours After 20 hours After 30 hours Sample 1 100 75 61 41 Sample 2 100 67 380 Comparative 1 100 27 0

Example 5 (Example of infrared cut filter and light / heat stability test) No. 10 obtained in Example 1 was added to 10 parts of tetrafluoropropanol. No. 1 (sample 3) or No. 1 0.1 part of Compound 2 (Sample 4) was dissolved, and about 1 mg of the solution was spin-coated on a polycarbonate substrate at a rotation speed of 2000 rpm to obtain an infrared cut filter of the present invention. The obtained infrared cut filter was put into an ultraviolet long life carbon arc light resistance tester (black panel temperature: 63 ° C.) manufactured by Suga Test Instruments, irradiated with light from the substrate side, and subjected to a light resistance stability test in 5 hours, 10 hours, and 20 hours. went. Further, the obtained infrared cut filter was subjected to a heat stability test with a hot air dryer at 80 ° C. for 1, 4, and 7 days. After the test, the residual dye ratio was measured using a spectrophotometer.
Table 6 shows the results of the light resistance test, and Table 7 shows the results of the heat resistance test.

Table 6 (Light Stability Test) Dye Residual Rate (%) Initial 5 hours After 10 hours After 20 hours Sample 3 100 85 77 54 Sample 4 100 61 56 36

Table 7 (Heat Stability Test) Dye Residual Rate (%) Initial 1 day 4 days later Sample 3 100 59 28 Sample 4 100 47 22

Example 6 (Example of infrared cut filter) Compound 1 was added at 0.03% to PMMA and injection-molded at a temperature of 200 ° C. to obtain filters having a thickness of 1 mm and 3 mm. When the average light transmittance at 800 to 1000 nm of the obtained filter was measured by a spectrophotometer, it was 20% for a 1 mm thick filter and 3% for a 3 mm thick filter.

[0063]

The infrared-absorbing compound of the present invention is an excellent infrared-absorbing compound having a maximum absorption wavelength of 900 nm or more and an absorption coefficient having a large absorption peak of about tens of thousands to hundreds of thousands. Further, it can be used as a material for a recording layer of an optical recording medium, and can greatly improve the light resistance of an organic dye.For example, the organic dye thin film corresponding to the recording layer of the optical recording medium contains the infrared absorbing compound of the present invention. In this case, it is possible to provide an optical recording medium in which durability and light stability in repeated reproduction are significantly improved. Further, since the infrared absorbing compound of the present invention has a maximum absorption in an infrared region, it is used for an infrared cut film, a heat insulating film, sunglasses, and the like.

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Claims (6)

[Claims] (1) The following formula (1): (In the formula (1), R1 to R16 represent a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, which may be the same or different. And B and C may have a substituent.). 2. The method according to claim 1, wherein the rings A, B and C are unsubstituted or have 1 to 4 halogen atoms, lower alkyl groups, lower alkoxy groups, cyano groups or hydroxyl groups as substituents. Compound. 3. The compound according to claim 2, wherein R1 to R16 are each independently an unsubstituted alkyl group, a halogen-substituted alkyl group, an alkoxy-substituted alkyl group, a cyano-substituted alkyl group, or a substituted or unsubstituted alkynyl group. 4. An optical recording medium comprising a recording layer containing the compound according to claim 1. 5. An infrared cut filter comprising the compound according to any one of claims 1 to 3. 6. An oxidation precursor of the compound according to any one of claims 1 to 3.