JPH06332100A - Photographic spectral sensitizing dye - Google Patents

Abstract

PURPOSE:To enhance sensitivity and to reduce color stains due to residual dyes and fog and to enhance storage stability by combining a phenylpyrazoliding group directly with or through a specified bonding group with a methine chain for connecting a specified N-containing hetero ring. CONSTITUTION:This spectral sensitizing dye is formed by combining the 1- phenyl-3-pyrazolidino group directly with or through the divalent bonding group with the methine chain for connecting the 5- or 6-membered N-containing heterocycle and it is, preferably, represented mainly by formulae I and II in which Y is the 1-phenyl-3-pyrazolidino group directly with or through the divalent bonding group with the methine chain; each of Z<1>-Z<4> an atomic group necessary to form a 5- or 6-membered N-containing hetero ring; each of R<1>-R<3> is alkyl or alkenyl; R<3> is alkyl, aryl, or the like; each of L1-L11 is, independently, an optionally substituted methine group; each of m-p is 0 or 1; and X1 is a counter ion.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a spectral sensitizing dye for photography, and more particularly to a dye useful as a sensitizing dye used in a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material is required to have high sensitivity in different specific wavelength ranges depending on its intended use. As one of the manufacturing techniques for such a silver halide photographic light-sensitive material, various types of cyanine dyes and merocyanine dyes are added to a silver halide photographic emulsion, and a wavelength longer than the unique light-sensitive wavelength region of the silver halide is used. It is generally well known that, in the range, the sensitivity in a specific wavelength range is extremely effectively increased.

When the color sensitization is applied to a silver halide photographic emulsion, not only the increase due to the spectrum but also the following requirements must be satisfied. (1) The spectral sensitization range is proper. (2) Stable photographic characteristics are maintained during storage of the light-sensitive material. (3) No contamination or fog due to the residual sensitizing dye is left after the development processing.
(4) No bad interaction with other photographic additives.
Although quite a number of cyanine dyes are known to date,
In reality, few satisfy the above requirements such as sensitization and photographic characteristics.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an excellent photographic spectral sensitizing dye for photographic products which satisfies the above-mentioned various requirements.

[0005]

Means for Solving the Problems As a result of various investigations, the present inventors have found that the methine chain that connects a 5- or 6-membered nitrogen-containing heterocycle is 1
It has been found that a photographic spectral sensitizing dye having a -phenyl-3-pyrazolidino group directly or via a divalent linking group is an excellent dye satisfying the above object.

The sensitizing dye of the present invention is preferably represented by the following chemical formulas 1 to 3.

[0007]

[Chemical 1]

[0008]

[Chemical 2]

[0009]

[Chemical 3]

[In the formula, Y represents a 1-phenyl-3-pyrazolidino group bonded to a carbon atom of a methine chain directly or via a divalent linking group. Z ^{1 to} Z ⁷ are each 5
Alternatively, it represents an atomic group necessary for forming a 6-membered nitrogen-containing heterocycle. R ¹ , R ² , R ³ , R ⁵ , and R ⁷ represent an alkyl group and an alkenyl group, respectively, and R ⁴ and R ⁶ represent an alkyl group, an alkenyl group, and an aryl group, respectively. L _{1 to} L ₁₉ each independently represent a substituted or unsubstituted methine group. m,
n, o, p, q, r, and s independently represent a positive number of 0 or 1. X ₁ and X ₂ represent counter ions. ]

Examples of the divalent group connecting the 1-phenyl-3-pyrazolidino group and the methine chain include -X ₁ -AX _2.
A group, wherein X ₁ and X ₂ may be the same or different, —S—, —O—, —NR ₀ — (R ₀ is a hydrogen atom,
Alkyl group, an aryl _{group), - NR 0 -CO- (R} 0 represents a hydrogen atom, an alkyl group, an aryl group), A represents an alkylene group or an arylene group having 1 to 6 carbon atoms.

The bonding position of the 1-phenyl-3-pyrazolidino group is the meta position or para position of the phenyl substituent, and the 2, 3 or 4 position of the 3-pyrazolidino group.

Z ^{1 to} Z ⁷ each represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. Z ₁ , Z ₂ ,
Specific examples of the heterocycle containing Z ₃ , Z ₅ and Z ₇ include, for example, an oxazoline ring, an oxazole ring, a benzoxazole ring, a naphthoxazole ring, a thiazoline ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, a selenazoline ring, Selenazole ring, benzoselenazole ring,
There are naphthoselenazole ring, tetrazole ring, benzotetrazole ring, naphthotetrazole ring, pyridine ring, quinoline ring, benzoquinoline ring, indolenine ring, benzoindolenine ring, benzimidazole ring, naphthimidazole ring, pyrroline ring, etc. The heterocyclic ring and condensed benzene ring or naphthalene ring have halogen atoms (for example,
Chlorine, bromine, iodine, etc.), alkyl group (for example, methyl, ethyl, n-propyl, n-butyl, t-butyl,
n-amyl, etc.), an alkoxy group (eg, methoxy,
Ethoxy, n-propoxy, etc.), hydroxy group, trifluoromethyl group, cyano group, alkanesulfonyl group (eg, methanesulfonyl, ethanesulfonis, etc.), sulfamoyl group (eg, sulfamoyl,
Substituents such as N, N-dimethylsulfamoyl, piperidinosulfamoyl, morpholinosulfamoyl, etc.) and aryl groups (eg, phenyl, methoxyphenyl, etc.) may be attached. Specific examples of Z ⁴ and Z ⁶ include 3 (2H) thianaphthenone ring, 3 (2H) benzofuranone ring, 1,3-indandioneone ring, 2,4-thiazolidinedione ring, 2-thio-2,4- Oxazolidinedione ring, 2-thio-2,4-thiazodidinedion ring, 5
-Pyrazolone ring, oxindole ring, 5 (4H) isoxazolone ring, barbituric acid ring, 2-thiobarbituric acid ring and the like.

R ¹ , R ² , R ³ , R ⁵ and R ⁷ are each independently a substituted or unsubstituted alkyl group (for example,
Methyl, ethyl, n-propyl, i-propyl, n-butyl, n-amyl group, β-hydroxyethyl, γ-hydroxypropyl, β-acetoxyethyl, γ-acetoxypropyl, β-methoxyethyl, γ-methoxypropyl, Carboxymethyl, β-carboxyethyl, γ-carboxypropyl, δ-carboxybutyl, ω-carboxypentyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, β-methoxycarbonylethyl, γ-
Methoxycarbonylpropyl, δ-methoxycarbonylbutyl, β-sulfoethyl, γ-sulfopropyl, γ-
Sulfobutyl, δ-sulfobutyl, benzyl, phenethyl, p-carboxybenzyl, p-sulfophenethyl group and the like) and alkenyl group (eg, allyl).
R ⁴ and R ⁶ represent an alkyl group, an alkenyl group, or an aryl group (for example, phenyl, tolyl, methoxyphenyl, chlorophenyl, carboxyphenyl, sulfophenyl, naphthyl, etc.) as described above.

L _{1 to} L ₁₉ each independently represent a substituted or unsubstituted methine group, which are crosslinked with each other to form 5
Alternatively, a 6-membered substituted or unsubstituted carbocyclic ring may be formed. m, n, o, p, q, r and s each independently represent 0 or 1. X ₁ and X ₂ are counter ions (eg, chlorine, bromine, iodine, perchloric acid, benzenesulfonic acid, p, etc.) necessary for balancing the charge of the dye molecule.
-Toluenesulfonic acid, methylsulfuric acid, ethylsulfuric acid, potassium, sodium, pyridinium, triethylammonium ion, etc.), which forms an inner salt when it is part of the dye molecule itself.

Specific examples of the sensitizing dye used in the present invention are shown below. However, the sensitizing dye used in the present invention is not limited to these.

[0017]

[Chemical 4]

[0018]

[Chemical 5]

[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

[Chemical 8]

[0022]

[Chemical 9]

[0023]

[Chemical 10]

[0024]

[Chemical 11]

[0025]

[Chemical 12]

[0026]

[Chemical 13]

Next, of the dyes represented by Chemical Formulas 1, 2 and 3 of the present invention, typical synthesis examples will be described. The synthetic method is shown in Chemical formula 14. The intermediates (C) and (D) are described in Yakuhin, 94 , 702 (1974), B. et al. P. 623,9
90 (1940).

[0028]

[Chemical 14]

Synthesis of Chemical Formula 5

To 60 ml of THF, 1.0 g of sodium hydride, 6.1 g of the starting material (A) and 6.0 g of carbon disulfide were added, and the mixture was heated under reflux on a water bath. The color of the solution immediately changed from yellow to red. After 2 hours, the reaction was stopped, the solvent was distilled off, cold water was poured into the residue, and insoluble matter was removed by extraction with benzene. 5.0 g of carbon disulfide was added to the aqueous layer while stirring, and the precipitated crystal was repeatedly washed with water, and then recrystallized from benzene to obtain 4.5 g of the intended intermediate (B). (Melting point 14
7 ° C)

To 3.21 g of the above intermediate (B) was added 1.8 g of dimethylsulfate, and the mixture was reacted at 110 ° C. for 15 minutes on an oil bath.
The precipitated crystals were collected by filtration and recrystallized from isopropanol to obtain 3.9 g of the intended intermediate (C). (Melting point 1
88-189 ° C)

3.25 g of the intermediate (C) and 2.52 g of the starting material (A) were dissolved in 10 ml of methanol, 4.0 g of triethylamine was added, and the mixture was heated under reflux on a water bath for 30 minutes. After the reaction was completed, the reaction solution was cooled with water and the precipitated crystals were collected by filtration.
Repeated washing with ethanol and washing with ether gave 4.5 g of the intended intermediate dye (D). The absorption maximum values of the methanol solution were 543.0 and 582.5 mm. Melting point 216-219 ° C. (decomposition) ^' H-NMR (δ ppm, DMSO-d ₆ ) 1.42
(T, 6H), 2.75 (s, 3H), 4.53 (q,
4H), 6.64 (s, 2H), 7.43 (dd, 2)
H), 8.03 (d, 2H)

Phenylhydrazine (0.5 ml) was added to the intermediate dye (D) (150 mg), and the mixture was heated on a water bath at 60 ° C. for 1.5 hours. After the reaction was completed, ether was added, the supernatant was removed by decantation, and the residue was added with acetonitrile.
It was dissolved in 0 ml. Under ice-cooling, triethylamine 0.
5 ml and β-chloropivaloyl chloride 65 mg were sequentially added, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was separated and purified by column chromatography (eluent CHCl ₃ : MeoH = 20: 1) to obtain 21 mg of the desired compound 5. The absorption maximum of the methanol solution was 560.0 mm. ^' H-NMR (δ ppm, CDCl ₃ ) 1.43
(T, 6H), 1.61 (s, 6H), 3.46 (s,
2H), 4.18 (q, 4H), 6.28 (s, 2)
H), 6.77 (d, 2H), 6.87 (d, 1H),
6.90 (dd, 1H), 7.21 to 7.26 (m, 3
H), 7.41 (dd, 2H), 7.68 (d, 2H)

The silver halide photographic emulsion in which the sensitizing dye of the present invention is used is a silver chloride produced by a conventional method,
Any of silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and the like may be used.

To add the sensitizing dye of the present invention to these silver halide photographic emulsions, an organic solvent such as methanol, ethanol, acetone, cellosolve, pyridine or dimethylformamide, which is optionally miscible with an aqueous solution or water, is used alone. Alternatively, it can be added as a solution of a mixed solvent. Also,
It is generally preferable to add these sensitizing dyes to the silver halide photographic emulsion after the completion of chemical ripening. The amount added varies depending on the type of sensitizing dye or the type of silver halide photographic emulsion, but is 10 in terms of silver nitrate.
It can be used in a wide range of approximately 4 to 1,200 mg per 0 g.

The silver halide photographic emulsion in which the sensitizing dye of the present invention is used is subjected to noble metal sensitization, sulfur sensitization, reduction sensitization and a combination thereof, or addition of a polyalkylene oxide compound or the like. May be.

The silver halide photographic emulsion in which the sensitizing dye of the present invention is used may be spectrally sensitized with other sensitizing dyes, for example, known cyanine and merocyanine dyes, if necessary. Stabilizer, surfactant,
Hardener, optical brightener, UV absorber, filter dye,
Additives such as anti-irradiation dyes, anti-halation dyes, preservatives, plasticizers, matting agents, color couplers and the like can be contained. Further, when used in a light-sensitive material for stabilizing processing, a developing agent or its precursor can be contained.

As protective colloids for silver halide photographic emulsions in which the sensitizing dye of the present invention is used, gelatin derivatives such as phthalated gelatin and malonated gelatin, cellulose derivatives, soluble starch, water-soluble polymers and the like can be used in addition to gelatin. Is mentioned.

The support to which the silver halide photographic emulsion containing the sensitizing dye of the present invention is applied is, for example, baryta paper, plastic-laminated paper, synthetic paper, resin film such as cellulose triacetate or polyethylene terephthalate. Can be used. If necessary, an undercoat layer and an antihalation layer may be provided on these supports by a known method.

[0040]

EXAMPLES The present invention will be described in detail below based on examples, but of course the present invention is not limited thereto.

Example 1 A silver bromide emulsion prepared by the double jet method was added to the sensitizing dye (Chemical formula 5) of the present invention, and the sensitizing dyes 15, 15
A 0.05% methanol solution of each of 6 and 17 was converted into silver nitrate and added in various amounts per g as shown in Table 1.

This emulsion was aged in a bath at 40 ° C. for 45 minutes to stabilize the spectral sensitizing effect. Then, after adding a predetermined amount of a stabilizer, a surfactant and a hardener, it was coated on a polyethylene-laminated paper support, dried and left overnight at 40 ° C. Then, it was cut into an appropriate size to obtain a test sample and exposed according to the ISO method. Then D each sample
After development with a -72 developer (developing solution of Eastman Kodak Company, USA) at 20 ° C for 90 seconds, the solution was stopped and fixed, washed with water and dried to obtain strips having a predetermined black-and-white image. The density was measured using a MACHBETHTD-504 densitometer manufactured by Macbeth Corporation in the United States to obtain sensitivity and fog. The reference point of the optical density for which the sensitivity was determined was 0.75. The sensitivity was shown as a relative value with the sensitivity of the sample not added with the sensitizing dye being 100. The results obtained are shown in Table 1.

[0043]

[Chemical 15]

[0044]

[Chemical 16]

[0045]

[Chemical 17]

[0046]

[Table 1]

As is clear from Table 1, the sensitizing dye of the present invention is superior to the comparative sensitizing dye in both sensitivity and fog. At the added amount of 3.6 ml, the sensitizing dye of the present invention showed no coloring and showed no residual color.

Example 2 A sample was prepared in the same manner as in Example 1 except that the silver halide was silver chloride. However, as a sensitizing dye, a 0.05% DMF solution was converted to silver nitrate and 1.2 ml was added per 1 g. In addition, the red sensitivity is based on the Eastman Kodak Ratten Gelatin Filter No. 29 was used. The white light sensitivity is shown as a relative value with the sensitivity of the sample not added with the sensitizing dye as 100, and the red sensitivity as 100 with the red sensitivity of Comparative Sensitizing Dye 20 as 100. On the other hand, a part of this sample (fresh) was aged for 3 days under the conditions of 50 ° C. and 80% relative humidity to prepare a sample (thermo). The red sensitivity was shown as a relative value with the fresh red sensitivity of Comparative Sensitizing Dye 19 being taken as 100. The obtained results are shown in Table 2.

[0049]

[Chemical 18]

[0050]

[Chemical 19]

[0051]

[Chemical 20]

[0052]

[Table 2]

As is clear from the above, the sensitizing dyes of the present invention are superior to the comparative sensitizing dyes in terms of sensitivity, fog and storability.

[0054]

By using the sensitizing dye of the present invention,
It is possible to obtain a silver halide photographic light-sensitive material which has high sensitivity, has less residual color and fog due to dye contamination, and is excellent in storage stability.

Claims (1)

[Claims] 1. A photographic spectrum characterized by having a 1-phenyl-3-pyrazolidino group in a methine chain connecting a 5- or 6-membered nitrogen-containing heterocycle directly or through a divalent linking group. Sensitizing dye.