JPS63301888A - Oxanol compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I {L is (substituted) methine, trimethine formed by bonding methines by conjugated double bond or pentamethine; E is O, S or N-R<4> [R<1> and R<4> are (substituted)alkyl or (substituted) alkenyl; R<2> is (substituted)alkyl or (substituted)alkynyl; R<3> is H, halogen, cyano, nitro, OH, (substituted)alkyl or (substituted)aryl}. USE:Useful as an optical information recording medium, photographic sensitized material (for preventing halation and irradiation especially in photographic sensitized material of silver halide), optical filtration and coloring composition for heat-sensitve paper. Having an absorption band in a wide wavelength range reaching a near infrared range. PREPARATION:A dioxopyrazolopyridine compound shown by formula II is reacted with a proper methine source, trimethine source or pentamethine source compound in a solvent such as methanol.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to novel oxonol compounds.

More specifically, the present invention relates to a novel oxonol compound having a pyrazolopyridine nucleus.

Regarding information recording media.

[Conventional technology]

Conventional oxonol compounds having a pyrazolopyridine nucleus include JP-A-52-135335 and JP-A-60-719.
No. 25, and the compounds described in Japanese Patent Publication No. 58-35544 were known.

However, these compounds have a problem in that their absorption wavelength range is relatively narrow.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a novel oxonol compound having an absorption band in a wide wavelength range up to the near infrared region.

[Means for solving problems]

The novel compound of the present invention is represented by the following general formula (I).

General formula (I) [The formula represents an optionally substituted methine group, or a trimethine chain or pentamethine chain formed by connecting these with a conjugated double bond, and E is O, S, N-
R' represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, an optionally substituted aryl group, and an optionally substituted aryl group. R1 represents an optionally substituted heterocyclic group, an optionally substituted amino group, an optionally substituted hydrazino group, or an optionally substituted diazenyl group; R1 is an optionally substituted alkyl group, a substituted represents an optionally substituted aryl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted heterocyclic group; R″ is a hydrogen atom, a halogen atom, a cyano group , nitro group, hydroxyl group, carboxyl group, optionally substituted alkyl group, optionally substituted aryl group, optionally substituted alkenyl group, optionally substituted heterocyclic group, unsubstituted optionally substituted alkoxy group, optionally substituted aryloxy group, optionally substituted alkoxycarbonyl group, optionally substituted aryloxycarbonyl group, optionally substituted amino group, optionally substituted a good acyloxy group, an optionally substituted carbamoyl group, an optionally substituted sulfamoyl group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted alkylsulfonyl group, represents an optionally substituted arylsulfonyl group or an optionally substituted alkynyl group, and R1
and R4 may be linked to each other to form a ring. ] The structural difference between the compound of the present invention and conventional oxonol compounds containing a pyrazolopyridine nucleus is that the group represented by Rt is not a hydrogen atom. It is presumed that the compound has favorable properties such as absorption of near-infrared light, ease of synthesis, and excellent stability.

It should be noted that, as a matter of course, the compound of the general formula (I) may exist as a tautomeric mixture with the compounds of the following general formulas (Ia) and (Ib), but in this specification, for convenience, the compound of the general formula (I)
Described using the structural formula.

(Ia) As the methine chain formed by connecting L with a conjugated double bond, those represented by general formulas (a) to 1) are particularly preferred.

General formula (a) General formula (b) Tomi CH-CI = C-CH= CI -■ General formula (C) General formula (el General formula (fl General formula (phantom general formula (h) General formula (I) % Formula % In general formula (a) or 1), Y represents a hydrogen atom or a monovalent group, and p and q are independently 0 or 1.
In this case, the monovalent group includes a lower alkyl group such as a methyl group, an aralkyl group, a lower alkoxy group such as a methoxy group, a dimethylamino group, a diphenylamino group, a methylphenylamino group, a morpholino group, an imidazolidino group. , a di-substituted amino group such as an ethoxycarbonylpiperazino group, an alkylcarbonyloxy group such as an acetoxy group, an alkylthio group such as a methylthio group, a cyano group, a nitro group, and a halogen atom such as FS CA' and Br.

Among the connecting groups represented by the above, particularly preferred are those represented by the general formula (a) or (b), especially those in which Y represents a hydrogen atom and at least one of p or q represents O. .

Preferred substituents on L in general formula (I) have 30 or less carbon atoms and are selected from the groups listed below, even if these groups further have a substituent. Good, that is, alkyl group, aralkyl group, aryl group, hydroxy group, FS C&, BrS L cyano group, nitro group, alkoxy group, aralkyloxy group, aryloxy group, acyl group, acyloxy group, acylamino group, sulfonamido group , aryloxycarbonyl group, aralkyloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, carboxyl group or carboxylad group, sulfonic acid group or sulfonato group, carbamoylamino group, sulfamoylamino group, alkylsulfonyl group, aralkyl group They are a sulfonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aralkylsulfinyl group, an arylsulfinyl group, an alkylthio group, an aralkylthio group, or an arylthio group.

Among the groups represented by E, preferred are 0 or NR'
and preferred as R4 are an optionally substituted alkyl group, an optionally substituted alkenyl group,
An optionally substituted aryl group, an optionally substituted amino group, an optionally substituted hydrazino group, an optionally substituted diazo group, and especially when E is NR', R4 is R1 It is preferable to form a ring by linking with. Preferred rings formed by connecting R1 and R4 are imidazole, pyrazole, triazole, and tetrazole rings, and these rings may have a substituent or form a fused ring with another ring. You may do so.

Among the groups represented by R1, preferable groups have 1 carbon atom.
an optionally substituted alkyl group having 6 to 30 carbon atoms; an optionally substituted phenyl group having 6 to 30 carbon atoms;
An optionally substituted heterocyclic group having 5 or 6 ring members and 1 to 30 carbon atoms (heteroatoms include, for example, B
Specific examples of the heterocyclic group (including SN, 0, S, Ses Te) include an optionally substituted pyrrolidyl group, morpholino group, 2-bora-1,3-dioxolanyl group, 1.3 saturated heterocycles such as thiazolidinyl groups,
Examples include unsaturated heterocycles such as optionally substituted imidazolyl, thiazolyl, benzothiazolyl, benzoxasilyl, penzotellazolyl, penzeselenazolyl, pyridyl, pyrimidinyl, and quinolinyl. Preferred substituents that may be substituted on these bases include halogen atoms (e.g. F, C1Br5 I), cyano groups, nitro groups, carboxyl groups, sulfonic acid groups, hydroxyl groups, alkoxy groups (e.g. methoxy groups, isopropoxy group, hexadecyloxy group), aryloxy group (e.g. phenoxy group, 2,4-di-t-pentylphenoxy group, m-pentadecylphenoxy group, p-methoxyphenyl group, 3,5-dichlorophenyl group) , 3-sulfophenyl group, 3゜5-disulfophenyl group, etc.), alkyl group (methyl group, 4-sulfobutyl group, 2-methoxyethyl group, trifluoromethyl group, etc.), aryl group (
For example, phenyl group, 4-sulfophenyl group, 3-chlorophenyl group, 4-hexylphenyl group, 2-naphthyl group, etc.), substituted or unsubstituted amino group (for example, amino group, methylamino group, phenylamino group) , acetylamino group, methanesulfonylamino group, methylcarbamoylamino group, phenylthiocarbamoylamino group, benzenesulfonylamino group, etc.), carbamoyl group (e.g. carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, octadecylcarbamoyl group, diethyl group) carbamoyl group, pyrrolidinocarbonyl group) sulfamoyl group (e.g. sulfamoyl group, dimethylsulfamoyl group, t-butylsulfamoyl group, phenylsulfamoyl group, pyrrolidinosulfonyl group, 3-(
(2,4-cy to monopentylphenoxy)butylsulfamoyl group, etc.), alkyl or arylthio groups (such as methylthio group, phenylthio group, benzylthio group,
octadecylthio group), alkylsulfonyl group (e.g. methanesulfonyl group, 2-ethoxyethylsulfonyl group, etc.), irisulfonyl group (e.g. benzenesulfamoyl group, dodecylbenzenesulfonyl group, 2-(2
-methoxyethoxy)-5-(4-hydroxyphenylazo)-benzenesulfonyl group, etc.).

Among the groups represented by R1, particularly preferred are an optionally substituted alkyl group having 1 to 20 carbon atoms (which may be substituted with the above-mentioned preferred substituents), and a substituted alkyl group having 6 to 20 carbon atoms. Phenyl group (which may be
2-pyridyl, 4-pyridyl, 2-benzthiazolyl, 2-(I-methylimidazolyl), 6- or 6-membered heterocyclic groups having 1 to 20 carbon atoms (e.g. ), 4,6-diethylamino-2-triazinyl, etc.).

Specific examples of the optionally substituted alkyl group include methyl group, isopropyl group, n-butyl group, t-pentyl group, cyclohexyl group, 2-ethylhexyl group, benzyl group, 3-(2,4-di- t-pentylphenoxy)
Propyl group, octadecyl group, carboxymethyl group, 4
-Sulfobutyl group, 2-sulfobenzyl group, 2-methoxyethoxy group, trifluoromethyl group, examples of the optionally substituted phenyl group include phenyl group, 4-methoxyphenyl group, 3-chlorophenyl group! , 4-hexylphenyl group, 3-sulfophenyl group, 4-1-octylphenyl group, 2-sulfobenzyl group, 4-methanesulfonamido-2-sulfamoylphenyl group, etc. -pyridyl group, 2-imidazolyl group, 1
Examples include -methylbenzothiazol-2-yl group, 2-imidazolidinyl group, and 2-pyrimidinyl group.

Among the groups represented by R2, preferred are an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted phenyl group having 6 to 30 carbon atoms, and an optionally substituted phenyl group having 1 to 30 carbon atoms. Optionally substituted heterocyclic group (number of ring members is 5 or 6, heteroatom is BS
N, 0.51SeSTe). Preferred groups for substituting these bases are:
Preferred substituents on R1 include the groups mentioned above.

Among the groups represented by R2, preferred are optionally substituted alkyl groups having 1 to 20 carbon atoms (e.g., methyl group, 4-sulfobutyl group, 2-methoxyethyl group, trifluoromethyl group, benzoyloxymethyl group). groups), optionally substituted phenyl groups having 6 to 20 carbon atoms (e.g. phenyl group, 4-sulfophenyl group, 4-methoxyphenyl group, 3-chlorophenyl group,
(3-trifluoromethylphenyl group, 2-methanesulfonyl-4-nitrophenyl group, 2-nitro-4-dimethylsulfamoylphenyl group, 4-methanesulfonylphenyl group, etc.), ring having 1 to 20 carbon atoms Heterocyclic groups having 5 or 6 members (e.g. 2-pyridyl, 4-pyridyl, 3-pyridyl, 2-benzthiazolyl, 2-(I
-methyl-imidazolyl), 4,6-sibutylamino-
2-triazinyl, etc.).

Specific examples of optionally substituted alkyl groups include methyl group, isopropyl group, n-butyl group, t-pentyl group, cyclohexyl group, 2-ethylhexyl group, benzyl group, 3-(2,4-di- t-pentylphenoxy)propyl group, octadecyl group, carboxymethyl group, 2-
Examples of optionally substituted phenyl groups such as methoxyethoxy group and trifluoromethyl group include phenyl group, 4-methoxyphenyl group, 3-chlorophenyl group,
-hexylphenyl group, 3-sulfophenyl group, 4-t
-octylphenyl group and the like.

Among the groups represented by R3, preferred are a hydrogen atom,
An optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted phenyl group having 6 to 3 o carbon atoms, an optionally substituted carbamoyl group having 1 to 30 carbon atoms, a carbon atom An optionally substituted alkoxycarbonyl group having 2 to 30 carbon atoms, an optionally substituted phenoxycarbonyl group having 7 to 30 carbon atoms, a carboxyl group, or a hydroxyl group.

Preferred groups to substitute on these bases are R
Preferred substituents on 1 include the groups mentioned above.

Among the groups represented by R3, particularly preferred are optionally substituted alkyl groups having 1 to 20 carbon atoms (
(e.g., methyl group, t-butyl group, trifluoromethyl group, etc.), optionally substituted phenyl group having 6 to 20 carbon atoms (e.g., phenyl group, 4-methoxyphenyl group, L3,5-dichlorophenyl group, etc.), carboxyl group groups and salts thereof, optionally substituted carbamoyl groups having 1 to 20 carbon atoms (e.g. carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, pyrrolidinocarbonyl group, 2-ethylhexylcarbamoyl group, etc.), carbon atoms It is an alkoxycarbonyl group of number 2 to 20 (eg, ethoxycarbonyl group, hexadecyloxycarbonyl group, t-butoxycarbonyl group, cholesteryloxycarbonyl group, etc.), a carboxyl group or a salt thereof, or a hydroxyl group.

Preferred examples of the optionally substituted alkyl group include methyl group, t-butyl group, trifluoromethyl group, 2
- Preferred examples of ethylhexyl group, pentadecyl group, and optionally substituted phenyl group include phenyl group,
4-methoxyphenyl group, 4-nitrophenyl group, etc.
Preferred examples of the optionally substituted carbamoyl group include carbamoyl group, methylcarbamoyl group, butylcarbamoyl group, diethylcarbamoyl group, pyrrolidinocarbonyl group, morpholinocarbonyl group, hexadecylcarbamoyl group, phenylcarbamoyl group, N-methyl -N-Phenylcarbamoyl group, 2-methoxyethoxycarbamoyl group, 2-ethylhexylcarbamoyl group, and other preferred examples of optionally substituted alkoxycarbonyl groups include ethoxycarbonyl group, butoxycarbonyl group, and benzinioxycarbonyl group. group, 2-methoxyethoxycarbonyl group, 2-dodecyloxy-ethoxycarbonyl group, and the like.

Table 1 lists specific examples of the compound represented by the general formula (I), but the scope of the present invention is not limited thereto.

Sentry
B (I:l
C1) The compound of the present invention is prepared by mixing a dioxopyrazolopyridine compound represented by the following general formula (n) with a suitable methine source, trimethine source, or pentamethine source compound (for example, ethyl orthoformate, 1. 5-diphenyl-1
, 5-diaza-1°3-pentadiene, 1.5.5-trialkoxy-1,3-pentadiene, 1,7-diphenyl-1,7-diaza-1,3,5-hebutatriene, etc.) It can be synthesized by At this time, the reaction may be accelerated by adding a basic substance such as triethylamine and an acid anhydride such as acetic anhydride.

More specifically, Special Publication No. 39-22069, No. 43-3
No. 504, No. 52-38056, No. 54-38129
No. 55-10059, JP-A No. 49-99620, JP-A No. 59-16834, or U.S. Patent No. 4,18
1.225, etc., can be used for synthesis.

General formula (n) [In the formula, R', R", R', and E represent the same groups as defined in general formula (I).] -i The compound represented by formula (If) has the following general formula (II
It can be synthesized by heating the compound represented by I) and the compound represented by general formula (IV) under acidic conditions.

General formula (I[[) [wherein RISR2, E are R1, R in general formula (I)]
1, represents a group with the same meaning as E] General formula (IV) [In the formula, R3 represents a group with the same meaning as R3 in general formula (I), and R4 represents an alkyl group or an aryl group] General formula (II) The compound represented by
-112626, the dioxopyrazolopyridine compound (general formula (■)) is alkylated, arylated,
Alternatively, it can also be synthesized by acylation.

General formula (■): In the formula, R'SR''%E is R1, R3 of general formula (I),
Represents a group having the same meaning as E. Of course, the general formula (
The functional group on the compound represented by I) or general formula (II) can be converted into another functional group by a known method.

Specific examples of methods for synthesizing the compounds of the present invention are listed below.

Synthesis example 1. Synthesis of Compound 2 1-Phenyl-3-anilino-2-pyrazolin-5-one (25 g), ethyl acetoacetate (18 g), and acetic acid (150 ml) were heated under reflux for 6 hours. The reaction solution was diluted with water and the resulting solid was crystallized from acetonitrile to yield 10.9 g of 2,7-diphenyl-4-.
Methylpyrazolo(3,4-b)pyridine-3,6-dione was obtained.

Melting point: 145-147°C This 2,7-diphenyl-4-methylpyrazolo(3,4
-b) Pyridine-3,6-dione (3,17 g), methanol (50 mj) and triethylamine (2,8++/
1,7-diphenyl-1,7 to the solution made by adding
-Diaza-1,3,5-heptatriene hydrochloride (2,8
5 g) was added and dissolved, and then acetic anhydride (I, 88n1
1) was added and stirred at room temperature for 1 hour. The resulting precipitate was collected by filtration, washed with methanol, and dried to give 5-(5-(N-acetylanilino)-2,3-pentadienylidene)-2.
,7-diphenyl-4-methylpyrazolo(3,4-b
) Pyridine-3,6-dione (I, 9 g) was obtained. This crystal (I, 5 g) was added to N,N-dimethylformamide (6
0ml), 2,7-diphenyl-4-methylpyrazolo(3,4-b)pyridine-3,6-dione (0.95g
), and triethylamine (0.42 mjt) were added, and the mixture was stirred at 50°C for 2 hours. After filtering off a trace amount of insoluble matter, 10 times the volume of ethyl acetate was added to the mixture while stirring to cause crystallization. The obtained crystals were again dissolved in a small amount of N,N-dimethylformamide, and then 10 times the volume of ethyl acetate was added to crystallize, collected by filtration, and dried to obtain Compound 2 (I, 3 g). Golden crystals, melting point 300°C or higher, Synthesis Example 2 Synthesis of Compound 1 3-Methylamino-1-phenyl-2-pyrazoline-5
-one (I, 9g), ethyl acetoacetate (I, 4g),
and acetic acid (8++) were heated under reflux for 6 hours. The reaction solution was diluted with water, the resulting crystals were collected by filtration, washed with isopropyl alcohol, and 1.8 g of 4°7-dimethyl-2-phenylpyrazolo (3,4 -b) Pyridine-3,6-dione (
(melting point 179-181°C) was obtained. This crystal (Ig>) was mixed with methanol (20 mJ) and triethylamine (0.7 mJ).
Add 1,7-diphenyl- to the solution prepared by adding A.
1,7-Diaza-1,3,5-heptatriene hydrochloride (
0.7 g) was added and dissolved, and then acetic anhydride (0.6 m
j2) was added and stirred at room temperature for 1 hour.

The resulting precipitate was collected by filtration, washed with methanol, and dried.
- (5-(N-acetylanilino)-2,3-pentadienylidene)-4,7-dimethyl-2-phenylpyrazolo(3,4-b)pyridine-3,6-dione (0,
2g) was obtained. To this crystal (0.15 g) was added N,N-dimethylformamide (5 ml) and 4.7-dimethyl-2-
Phenylpyrazolo(3,4-b)pyridine-3,6-dione (0.08g) was added and stirred at 50°C for 2 hours.

The reaction solution was filtered, diluted with water, crystallized, collected by filtration, washed with water, and dried to obtain Compound 1 (0.2 g).

Synthesis Example 3 Synthesis of Compound 4 3-(3-chlorophenylamino)-1-phenyl-2
- Add ethyl acetoacetate (2.8 g) and acetic acid (40111) to pyrazolin-5-one (5.7 g) and add 6
The mixture was heated to reflux for an hour. The resulting crystals were collected by filtration and washed with isopropyl alcohol to give 2 g of 7-(3-chlorophenyl)-4-methyl-2-phenylpyrazolo (3,4-b).
Pyridine-3°6-dione was obtained (melting point 278-282
℃).

1,7-diphenyl-1,7-diaza-1,3,5-
Add and dissolve hebutatriene hydrochloride (I, 13 g),
Then, acetic anhydride (<0.75 ml) was added and stirred at room temperature for 1 hour. The resulting precipitate was collected by filtration, washed with methanol, and dried to give 5-(5-(N-acetylanilino)-
2,3-Pentadienylidene)-7-(3-chlorophenyl)-4-methyl-2-phenylpyrazolo(3,4-
b) Pyridine-3,6-dione was obtained. This crystal (0,
5 g) and N,N-dimethylformamide (30 mj)
, 8-(3-chlorophenyl)-4-methyl-2-phenylpyrazolo(3,4-b)pyridine-3,6-dione (0,32g), and triethylamine (0,13a
+J) and stirred at 50°C for 2 hours.

After the reaction solution was filtered, 10 times the volume of ethyl acetate was added to the solution while stirring for crystallization. The obtained crystals are again treated with a small amount of N, N
- After dissolving in dimethylformamide, 10 times the amount of ethyl acetate was added to crystallize, collected by filtration, washed with ethyl acetate, and dried to obtain Compound 4 (0.4 g).

Melting point 300℃ or higher Ae*sx'/bZnl1
Synthesis Example 4 Synthesis of Compound 3 3-(4-methoxyphenylamino)-1-phenyl-
Ethyl acetoacetate (8.5 g) and acetic acid (75I111) were added to 2-pyrazolin-5-one (I4 g).
The mixture was heated to reflux for an hour. The reaction solution was poured into 150 ml of water, and the resulting solid was mixed with methanol (500 mA') and acetone (I
50 ml) and then cooled to give 8.4 g.
7-(4-methoxyphenyl)-4-methyl-2-phenylpyrazolo(3,4-b)pyridine-3,6-dione (melting point 189-190°C) was obtained. This crystal (3,4
7g), methanol (40a+A') and triethylamine (2,8n+1),
Diphenyl-1,7-diaza-1,3゜5-hebutatriene hydrochloride (2.85 g) was added and dissolved, and then acetic anhydride (I, 88 mj) was added and stirred at room temperature for 1 hour. The resulting precipitate was It is filtered, washed with methanol, and dried to give 5-
(5-N-acetylanilino)-2,3-pentadienylidene]-7-(4-methoxyphenyl)-4-methyl-2-phenylpyrazolo(3,4-b)pyridine-
3,6-dione (4.1 g) was obtained. This crystal (3,8
g) N,N-dimethylformamide (40 ml), 7
-(4-Methoxyphenyl)-4-methyl-2-phenyl-pyrazolo(3,4-b)pyridine-3,6-dione and 0.98 ml of triethylamine were added and heated at 50℃ for 2 hours.
Stir for hours. After filtering the reaction solution, 10
Crystallization was carried out by adding twice the volume of ethyl acetate. The obtained crystals were recrystallized from acetonitrile to give compound 3 (I,0,g
) was obtained.

Synthesis Example 5 Synthesis of Compound 5 In Synthesis Example 1, 1-phenyl-3-anilino-2-
Instead of pyrazolin-5-one, 3-(3-methyl-4
Compound 5 was prepared in the same manner except that -methoxyphenylamino)-1-phenyl-2-pyrazolin-5-one was used.
I got it.

(Melting point 300°C or higher) Synthesis Example 6 Synthesis of Compound 6 In Synthesis Example 1, 1-phenyl-3-anilino-2-
3-(4-n-hexylphenylamino)-1-phenyl-2-pyrazoline- instead of pyrazolin-5-one
Compound 6 was obtained in the same manner except that 5-one was used.

(Melting point 220-223°C) Synthesis Example 7 Compounds 12-16.27.30.33-
35.44-60 were synthesized. The melting points of these compounds were all 300°C or higher.

Various uses can be considered for the compounds of the present invention. For example, optical information recording media such as optical discs,
These include photographic light-sensitive materials (particularly for preventing halation or irradiation in silver halide photographic light-sensitive materials), optical filters, inks, coloring compositions for thermal paper, and the like.

When the compound of the present invention is used in an optical recording medium, it may be used alone, in combination of two or more kinds, or in combination with a dye other than the oxonol compound of the present invention. It is also effective to use various antioxidants and singlet oxygen quenchers in combination to improve durability. Moreover, various resins may be used in combination.

Alternatively, durability can be increased by adding transition metal ions to form a chelate.

When the compound of the general formula (I) of the present invention is used as an optical filter, the compound represented by the general formula (I) is
It can be used by appropriately incorporating it into a binder. As a binder, it can be used regardless of whether it is organic or inorganic.
For example, in the case of optical filters, examples include polymeric materials such as plastics and inorganic materials such as glass.

Preferably, a binder having excellent transparency and mechanical properties is used as the binder. Examples of such binders include polyethylenes such as polyethylene terephthalate, cellulose esters such as cellulose diacetate, cellulose triacetate, and cellulose acetate butyrate, polyolefins such as polyethylene and polypropylene, polyvinyl chloride, and polypropylene. Known materials such as vinylidene chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl compounds such as polystyrene, acrylic addition polymers such as polymethyl methacrylate, polycarbonates made of polycarbonate esters, hydrophilic binders such as urethane resins or gelatin, etc. Mention may be made of film-forming binders.

Particularly preferred are cellulose esters such as cellulose triacetate because of their excellent transparency and mechanical properties.

As a method for forming a film by adding and retaining the compound of general formula (I) to the above-mentioned plastic material, there is first a method of blending it into the plastic at the time of film production. That is, if the compound of formula (I) is mixed with various additives into a polymer powder or pellet, melted and extruded by T-die method or inflation method, or formed into a film by calender method, the compound is uniformly dispersed. A film is obtained. In addition, when producing a film from a polymer solution by a casting method, the general formula (I) is added to the solution.
) may be contained.

The second method is to form a light absorption layer by applying a polymer solution or dispersion containing the compound of general formula (I) to the surface of various plastic films or glass plates manufactured by an appropriate method. be. As the binder used in the coating solution, one is selected that dissolves the compound of general formula (I) as well as possible and has excellent adhesiveness to the plastic phenyl or glass plate serving as the support. Polymethyl methacrylate, cellulose acetate butyrate, polycarbonate, etc. are suitable for this purpose. The support film may be pre-applied with a suitable primer to improve adhesion.

The third method is to mix the compound of general formula (I) and a polymerizable polymer in the light incident window frame of the element to be cut in a specific wavelength region, add a suitable polymerization initiator, and heat or One method is to add light to cause polymerization, and then use the resulting polymer to form a filter on the window frame. In this method, the entire device can also be embedded in plastics made from ethylenically unsaturated polymerizable monomers or polyaddition compositions such as epoxy resins.

A fourth method is a method in which the compound (I) according to the present invention is vapor-deposited on a suitable support. In this process, a suitable film-forming binder layer may also be provided as a protective layer at a position remote from the support.

The optical filter obtained from the compound of general formula (I) of the present invention is disclosed in JP-A-57-58107 and JP-A-59-9317.
It can also be used in combination with color separation filters such as those described in No. 1 and No. 59-30509.

When the compound of the general formula (I) of the present invention is used as an optical filter, the compound represented by the general formula (I) is
More than one species may be used in combination.

When the compound of general formula (I) of the present invention is used as an optical filter, an ultraviolet absorber may be further used in combination,
Resorcin monobenzoate, substituted or unsubstituted benzoic acid esters such as methyl salicylate, 2-oxy-3
- cinnamate esters such as butyl methoxycinnamate,
2. Benzophenones such as 4-dioxybenzophenone, α, β-unsaturated ketones such as dibenzalacetone,
5. Coumarins such as 7-cyoxycoumarin, l.

Carbostyryls such as 4-dimethyl-7-oxycarbostyryl, 2-phenylbenzimidazole, 2-
Azoles such as (2-hydroxyphenyl)benzotriazole and the like are used.

Furthermore, the compound of the present invention can be used in combination with other yellow dyes, magenta dyes, and cyan dyes.

In addition, in the case of a film made by a coating method using a compound of the general formula (R) of the present invention, a thin plastic film is pasted on the surface of the coating layer for the purpose of protecting the coating layer and imparting distribution properties.
It can be painted.

For example, by stacking polyvinyl chloride films with a thickness of 0.05 mm and heat-pressing them at 120 to 140°C, a laminated film can be obtained.

Next, embodiments in which the compound of general formula (I) of the present invention is used in inkjet inks will be described.

Inkjet printer inks that use organic solvents as solvents are mainly used in electrostatic acceleration type and electrostatic air flow type, both of which require applying high-pressure pulses to the ink to enable ink flow or ink droplet formation. This problem involves not only the electrical properties of the ink, but also the physical properties related to fluidity such as surface tension and viscosity.
It can be carried out according to the methods described in No. 35 and Japanese Patent Application Laid-Open No. 56-135568.

Ink for inkjet printers may include, in addition to the compound of general formula (I) of the present invention, solvents such as ethyl cellosolve, toluene, ethanol, n-butanol, ethyl methyl ketone, methyl isobutyl ketone, dichloromethane, triethanolamine, and dimethyl formamide. An organic solvent such as isoamyl acetate is used, and glycerin, metal soap, etc. are added to adjust the viscosity.

The content has a viscosity of 1Ocp at room temperature and a resistivity of 1×1.
The composition ratio of the organic solvent and the viscosity modifier is selected so that it becomes 04 to 1×1 OLlΩ·(to).

The content ratio of the compound of the general formula (I) to the solvent is 0, 1 to 0.8 parts of the compound of the general formula (I) per 1 part by weight of the solvent, and preferably dissolves at room temperature, or at least has an average particle size. The ink must be finely dispersed to a size of 0.8 μm or less. In some cases, a pigment that absorbs visible light or near-infrared light may be added to the ink.

The compound of general formula (I) of the present invention can also be used in combination with known near-infrared absorbers of organic or metal complex type.

In particular, when used in combination with absorbers having different absorption maximums, the absorption wavelength range can be expanded.

Although the compound of the present invention has sufficiently high light resistance even when used alone,
In order to further improve the light resistance, JP-A-50-87649, JP-A-54-62826, JP-A-54-62987, JP-A-54-65185, JP-A-54-69580, JP-A-54-72780, 1973-82234, Japanese Patent Publication No. 5
4-82384, Japanese Patent Publication No. 54-82385, Japanese Patent Application Publication No. 1973
-82386, US Patent -4268605, US Patent -
4246330, JP-A-55-12129, JP-A-56
It can also be used in combination with metal complexes, various singlet oxygen etchers, or various antioxidants described in Japanese Patent Application No. 167138 and Japanese Patent Application No. 13396/1982.

〔Effect of the invention〕

The novel compounds of the present invention can set absorption bands in a wide range of wavelengths up to the near infrared region depending on the selection of substituents, and are therefore useful for optical information recording media that use laser beams, photographic materials, optical filters, etc. It can be used for many purposes, including:

In particular, a filter with excellent fastness to light and heat can be obtained, and a low-cost optical filter can be obtained.

Furthermore, by appropriately selecting and combining the substituents in the compound represented by the general formula (I) of the present invention, the solubility in solvents can be adjusted, so that it has the advantage that a wide variety of binders can be employed.

The optical filter obtained from the compound of general formula (I) of the present invention can be used as a near-infrared absorbing material, as a safelight filter for infrared-sensitive materials, for controlling plant growth, for blocking heat rays, and for human eye tissue. Harmful infrared cut filters, infrared cut filters for semiconductor photodetectors and color solid-state image sensors, infrared light cut filters for optoelectronic integrated circuits that incorporate elements with both electrical and optical functions on the same substrate. In addition to this, it can be used for various purposes.

Furthermore, the compound of general formula (I) of the present invention can be used in laser recording media and inks for inkjet printers.

Furthermore, the compound of the present invention has the property of converting absorbed light into heat, and can be used as a radiation/heat exchange agent. Typical examples include: 1) JP-A-57-14095 or JP-A-57-14095;
It can be added to a laser thermosensitive recording material such as that described in No. 14096 to enhance the mixed color reaction caused by the heat generated by irradiation with an infrared laser. 2) It can be included in resist materials whose solubility changes due to the action of heat generated by laser light, such as those described in JP-A-57-40256.

3) As described in JP-A-56-143242,
When the compound of the present invention is included in a heat-drying or thermosetting composition, the reaction can be accelerated.

The compound according to the present invention is further disclosed in Japanese Patent Application Laid-Open No. 58-2141.
As described in No. 62, it can also be used as an electrophotographic photosensitive coating for an electrophotographic printer using a semiconductor laser as a light source. It can also be incorporated into electrophotographic toner compositions to improve heat fixability.

Of course, the above description does not limit the uses of the compounds according to the present invention.

"Reference Example" Next, the present invention will be explained in more detail based on a reference example. Note that "parts" indicate "parts by weight."

Reference Example 1 Using Exemplified Compound 3, the following near-infrared absorbing composition was prepared to create an optical filter. That is, after mixing each component with the composition shown below in parts by weight and stirring well, after filtration,
It is coated on a metal support by a casting method and peeled off after film formation.
°The desired optical filter was obtained. Dry film pressure 0.0
Several optical filters were obtained varying between 2 and 0.3 mm+. The optical density of the optical filter thus obtained (thickness: 25 microns) is shown in FIG.

〔Composition〕

Cellulose triacetate 170 parts Triphenyl phosphate 10 parts Methylene chloride
160 parts 2.2,3.3-tetrafluoropropanol 800 parts Exemplary compound 3
As can be seen from Figure 1 of Part 10, an optical filter with high transmittance in the visible light range and low transmittance in near-infrared light was obtained.

Reference example 2 Exemplary compound 3 0.8 parts Oil-soluble blue dye 0.7 parts Ethyl cellosolve
5 parts 1.2-pentisobutiazolone (antifungal agent) 0.001 part Glycerin 3 parts The above components were mixed homogeneously, and the resulting composition had a specific resistance of 103Ω and a viscosity of 5c.
p. When this ink composition was recorded on an inkjet recording device, a good image was obtained. This could be read with a reading device using a semiconductor laser (780 nm) as a light source.

Reference Example 3 Isoamyl acetate 7 parts Exemplary Compound 6 0.4 parts Oil-soluble dye (Oil Black HB B) 0.5 parts Metal soap 0.05 parts The above components were mixed homogeneously, and the resulting ink composition had a specific resistance. 10″Ω・1
A good image was obtained when recording was performed using an inkjet recording device with a viscosity of 4.5 cp. This could be read with a reading device using a semiconductor laser (780 nm) as a light source.

Reference example 4 2-anilino-3-methyl-6-N-cyclohexyl-
2.4 parts of N-methylaminofluorane, 2-anilino-
2.4 parts of 3-chloro-6-dinithylaminofluorane (
A solution serving as a core substance was prepared by dissolving 60.3 parts of the exemplified compound (dileuco dye) in 25 parts of diisopropylnaphthalene.

Furthermore, 18 parts of xylylerane diisocyanate/trimethylolpropane (3:1) adduct and 17 parts of methylene chloride were added and dissolved.

This color former solution was mixed with 3.5 parts of polyvinyl alcohol,
It was added to an aqueous solution containing 1.7 parts of gelatin and 2.4 parts of 1,4-di(hydroxyethoxy)benzene dissolved in 58 parts of water and emulsified and dispersed at a temperature of 20°C to obtain an average particle size of 3μ.
An emulsion of m was obtained. 100 parts of water was added to the emulsion and heated to 60° C. while stirring, and after 2 hours, a microcapsule liquid containing a color former, a color inhibitor, and an ultraviolet absorber in the core substance was obtained.

Separately, 20 parts of bisphenol A as a color developer was added to 100 parts of a 5% polyvinyl alcohol aqueous solution and dispersed in a sand mill for about 24 hours to obtain a dispersion of bisphenol A with an average diameter of 3 μm.

Five parts of the obtained microcapsule liquid and three parts of the bisphenol 8 dispersion were mixed to prepare a coating liquid.

This coating liquid was applied to the surface of smooth high-quality paper (50 g/rrr) and dried at a temperature of 40° C. for 30 minutes to provide a heat-sensitive recording layer having a dry weight of 1 g/rd.

In this way, thermosensitive recording sheet A containing microcapsules containing Exemplified Compound 6 was produced.

Separately, a thermosensitive recording sheet B to which Exemplified Compound 6 was not added was prepared.

Next, thermal recording was performed using each of the obtained thermal recording sheets.

When the thermal recording sheet was loaded into a G mode thermal printer (Banafa Sox 7200, manufactured by Hitachi, Ltd.) and the thermal head was activated to record heat on the recording sheet, the product containing Exemplary Compound 6 developed color as shown in the product below. An image with high density was obtained.

Heat-sensitive recording sheet) A Heat-sensitive recording sheet B (with exemplified compound) (Exemplary compound heat) Color density 1.23
1.09 coloring (turnip 0.11 0
．． 10W) Concentration Reference Example 5 80.5 g of the exemplary compound was added to a visible light transmitting resin containing 70 g of hexahydrophthalic acid, 20 g of tetraglycidyl isocyanurate, 30 g of CX-221 (manufactured by Chisso Corporation, trade name), and 0.15 g of imidazole. A silicon diode for a photodetector of a camera was molded using the dissolved resin composition (A).

The mold was prepared by setting a silicon diode in a mold heated to about 150°C, pouring the resin composition (A) onto the surface of the diode to a thickness of about 2111111 mm, curing for 5 minutes, and pouring the resin composition (A) into the mold. ) was removed from the mold and further cured at 150° C. for about 2 hours.

Reference Example 6 Exemplary compound 4 was placed on a transparent glass objective plate with a thickness of 0.5 mm.
Thermosetting acrylic resin and dimethylformamide
．． A composition liquid containing 3:8:3 (weight ratio) was applied to form a near-infrared absorbing resin film with a thickness of 3 μm, and heated at 150°C.
The infrared ray blocking layer was formed by heating and curing for 20 minutes.

A chromium nitride layer was deposited on this infrared blocking layer to a thickness of 500 nm by sputtering, and a chromium layer was further deposited thereon to a thickness of 1500 nm. Next, AZ-1450 resist (manufactured by Silapray, USA) was applied on this chromium layer.
After coating, the film was exposed to light using a predetermined photomask, developed and dried, and then the exposed chromium layer and chromium nitride layer were removed by etching with a cerium ammonium nitrate based etching solution. Thereafter, the resist layer is peeled off to form a photoshield layer having a predetermined pattern on the infrared blocking layer. Since this photoshield layer has a reflectance from the glass surface of 15% or less, the problem of flare is eliminated.

Next, a water-soluble photosensitive solution consisting of casein-ammonium dichromate was applied to a thickness of 0.8 μm on the infrared blocking layer with the photoshield layer, and after drying, a predetermined photomask was accurately aligned. Close contact, expose, develop with warm water,
A dyed layer having a predetermined pattern is formed, and this dyed layer is dyed with a red dyeing bath to form an R colored layer. Next, after carrying out a predetermined resist dyeing treatment, a water-soluble photosensitive liquid was applied to a film thickness of 0.8 μm by the same method as above, dried, and
After exposure and development, dyeing was performed using a green dyeing bath to form a G colored layer having a predetermined pattern, and a second color colored layer was formed. Furthermore, a third color B colored layer having a predetermined pattern was formed using a blue dyeing bath in the same manner as the method for forming the second color colored layer. In this way, a single layer color separation filter consisting of R, G, and B colored layers having a predetermined pattern was obtained. Thereafter, an acrylic resin was applied to a thickness of 1 μm on one layer of the color separation filter to form a protective film. The chip size of the color separation filter was set to be the size of the photosensitive area of the solid-state image sensor. This color separation filter had an excellent ability to block long wavelength light of 700 nm or more.

The compositions of the R, G, and B dye baths used above are as follows.

Red dyeing bath Kayanol Milling Red R3 (manufactured by Nippon Kayaku Co., Ltd.) 1 part acetic acid
3 parts water
100 parts Green dye bath Brilliant in Blue (manufactured by Hoechst) 1 part Suminol Yellow MR (manufactured by Sumitomo Chemical) 1 part Vinegar #1
3 parts water
100 parts Blue dyeing bath Kayanolcyanine 6B (manufactured by Nippon Kayaku Co., Ltd.) 1 part acetic acid
3 parts water
100 copies

[Brief explanation of the drawing]

FIG. 1 shows the relationship between wavelength and absorbance of the optical filter obtained in Example 1. Part 7 Super Showa Year Month Day 3. Person making the amendment Relationship to the case Applicant name (520) Fuji Photo Film Co., Ltd. 4, Agent 5, Date of amendment order Initiator 6, Subject of amendment Detailed explanation of the invention in the specification column 7, Amendment Content (I) "Carboxymethyl group" on page 16, line 11 of the specification is corrected to "carboxymethyl group." (2) "Benzinioxy" on page 21, line 6 of the same book is corrected to "benzyloxy." (3) The formula corresponding to R2 of compound 25 in Table 1 on page 24 of the circular is corrected as follows. (4) The formula corresponding to R2 of compound 40 in Table 1 on page 25 of the same book is corrected as follows. "0-CH,CCH3" (5) The formula corresponding to R2 of compound 43 in Table 1 on page 26 of the circular is corrected as follows. r -CH2CmiCHJ (6) The formula corresponding to R2 of compound 52 in Table 1, page 27 of the same book is corrected as follows. 'CHzCHzOHJ

Claims (1)

[Claims] An oxonol compound represented by the following general formula (I). General Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. Representation: E is O, S, N-
R^4 represents; R^1 and R^4 are independently an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group; group, an optionally substituted heterocyclic group,
represents an optionally substituted amino group, an optionally substituted hydrazino group, or an optionally substituted diazenyl group; R^2 is an optionally substituted alkyl group,
an optionally substituted aryl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group,
or represents an optionally substituted heterocyclic group; R^3
is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group, an optionally substituted alkenyl group, and an optionally substituted alkenyl group. A good heterocyclic group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted alkoxycarbonyl group, an optionally substituted aryloxycarbonyl group, an optionally substituted aryloxycarbonyl group an optionally substituted acyloxy group, an optionally substituted carbamoyl group, an optionally substituted sulfamoyl group, an optionally substituted alkylthio group, an optionally substituted arylthio group, a substituted represents an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, or an optionally substituted alkynyl group; R^1 and R^4 may be linked to each other to form a ring; good. ]