JPH03204637A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material small in dye stains, high in sensitiv ity, and improved in storage stability in raw samples by incorporating a speci fied pentamethine dye to sensitize silver halide in a red region. CONSTITUTION:At least one of the silver halide emulsion layers contains the photosensitive dye (pentamethine dye) spectrally sensitizing the silver halide grains represented by formula I in which each of Y<1> and Y<2> is an O, S, or Se atom; each of R<1> and R<2> is 1 - 10 C alkyl or 3 - 10 alkenyl; R<3> is optionally substituted methine or 2 - 10 C alkyl or the like; Z<1> is a nonmetallic atomic group necessary to form a 5- or 6-membered ring; each of L<1> - L<5> is methyl; X<1> is an acid anion; and l is 0 or 1, thus permitting the obtained silver halide photographic sensitive material to be small in dye stains, high in sensitivity, and superior in storage stability of raw samples.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material), and more specifically, a silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material). The present invention relates to a photosensitive material that has excellent storage stability (hereinafter referred to as "raw sample storage stability").

[Background of the Invention] In recent years, there has been an increasing demand for highly sensitive photosensitive materials from various viewpoints, and research on sensitization techniques has been conducted from various angles.

Research on sensitization technology related to silver halide grains includes, for example, research that theoretically calculates the grain efficiency of silver halide and considers the influence of grain size distribution.
Proceedings of the 1980 Tokyo Symposium “Interactions Between Light and Materials for Photographic Applications 291”
It is written on the page. This research suggests that creating a monodisperse emulsion is effective in improving quantum efficiency, that is, it is possible to increase sensitivity.

On the other hand, as part of research on sensitization technology, studies are also being conducted to apply optimal chemical sensitization to these silver halide emulsions. As sensitizers used for chemical sensitization, sulfur sensitizers, selenium sensitizers, reduction sensitizers, noble metal sensitizers, etc. are well known. These chemical sensitizers may be used alone or in combination of two or more.

Furthermore, it is a well-known technique to add a sensitizing dye to a silver halide emulsion to expand the sensitive wavelength range specific to the silver halide emulsion and to spectrally sensitize it. It is also known that selecting a sensitizing dye with high spectral sensitization efficiency as the sensitizing dye used at this time can significantly contribute to increasing the sensitivity of the light-sensitive material.

The sensitizing dye used for the above purpose should have an appropriate spectral sensitizing wavelength range and should not diffuse into other photosensitive layers or interact with additives other than the sensitizing dye. Those with desirable properties are selected.

Further, more preferable conditions include that when the photosensitive material containing the sensitizing dye is stored, there is little decrease in sensitivity, occurrence of fogging, or occurrence of dye staining after sensitization processing. is required. In particular, when a sensitizing dye is used in a multilayer color photographic material, it has higher sensitivity and excellent brown color reproducibility, and these photographic properties can be stably maintained even when stored for a long period of time. This is a necessary condition.

It is known that certain pentamethine dyes are very effective as spectral sensitizing dyes used in red-sensitive emulsions, but these sensitizing dyes have the following drawbacks depending on the conditions of use. Ta.

1) Residual color contamination after processing is large, and the amount used must be reduced at the expense of spectral sensitivity.

2) High sensitivity can be obtained immediately after manufacture, but as time passes, the initial sensitivity decreases and fog occurs.

Photographic properties required of recent photosensitive materials are high sensitivity, high image quality, and suitability for rapid processing.

Even with dyes with low color sensitization efficiency, it is possible to sensitize by increasing the amount of dye up to a certain coating amount, but with conventional dyes, residual color contamination occurs in the finished photograph and the product image deteriorates. Therefore, the amount of sensitizing dye added is limited.

For this reason, a sensitizing dye with better color sensitization efficiency or less residual color staining has been sought.

Furthermore, the various properties of photosensitive materials must always be stable, and when photosensitive materials are stored under various atmospheres, if sensitivity changes or fog occurs depending on the storage conditions, image quality may deteriorate. This results in the loss of commercial value as a photosensitive material.

As a technology to improve the preservation of such raw samples, JP-A No. 6
No. 0-202438 and No. 63-284743 propose a technique of using a pentamethine dye in combination with a certain compound, but further improvements have been desired.

The present inventors have conducted various studies to improve the drawbacks of the pentamethine dye described above, and have discovered that by using a pentamethine dye with a specific structure, a photosensitive material with high sensitivity and good preservation of raw samples can be obtained. The present invention has now been completed.

[Object of the Invention] An object of the present invention is to provide a photosensitive material that has less dye staining, high sensitivity, and improved raw sample storage stability by containing a specific pentamethine dye that sensitizes in the red region. That's true.

[Structure of the Invention] The object of the present invention is to provide a silver halide photographic material having at least one photographic constituent layer including a light-sensitive silver halide emulsion layer on a support, in which at least one layer of the silver halide emulsion layer is provided. This was achieved by a silver halide photographic material characterized in that the silver halide grains contained therein have been spectrally sensitized with at least one photosensitive dye represented by the following general formula [IF].

General Formula [1] [In the formula, Yl and Y2 each represent an oxygen atom, a sulfur atom or a selenium atom.

R1 and R2 each represent an alkyl group having 10 or less carbon atoms or an alkenyl group having 3 or more and 10 or less carbon atoms,
R3 is a methyl group having a substituent, an alkyl group having 2 to 10 carbon atoms, a cyclopentyl group, a cyclohexyl group, a methoxy group having a substituent, an ethoxy group having a substituent, or an alkoxy group having 3 to 10 carbon atoms. represents. zl represents a nonmetallic atomic group necessary to form a 5- or 6-membered ring or a condensed ring containing these rings, and LI
L2 1. ff , R4 and R5 each represent a methine group, and Xl represents an acid anion.

2 represents an integer of 0 or 1, and 2 represents 0 when the compound forms an inner salt. ] Hereinafter, the present invention will be explained in more detail.

In the compound represented by the general formula [I] used in the present invention, R1 and R2 each represent a branched or straight-chain alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group). group, l5o-pentyl group, 2-ethylhexyl group, octyl group, decyl group) or an alkenyl group having 3 to 10 carbon atoms (e.g. 2-propenyl group, 3-butenyl group, 1-methyl-3-propenyl group, 3 -pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group). These groups include /XX rosin atoms (e.g. fluorine atom, chlorine atom, bromine atom), hydroxy group, alkoxy group (e.g. methoxy group, ethoxy group), aryloxy group (e.g. phenoxy group, p-tolyloxy group), cyano group , carboxy group, carbamoyl group (e.g. carbamoyl group, N-methylcarbamoyl group, N,N-tetramethylenecarbamoyl group), sulfamoyl group (e.g. sulfamoyl group, N,N-3-oxapentamethyleneaminosulfonyl group), sulfonyl group (e.g. methanesulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (e.g. ethoxycarbonyl group, n-butoxycarbonyl group), aryl group (
For example, phenyl group, carboxyphenyl group), acyl group (e.g. acetyl group, benzoyl group), acylamino group (e.g. acetylamino group, benzoylamino group), sulfonamide group (e.g. methanesulfonylamino group, benzenesulfonamino group), cyclo It may be substituted with a substituent such as an alkyl group (eg, cyclopentyl group, cyclohexyl group).

Substituents for the substituted methyl group, substituted methoxy group, and substituted ethoxy group represented by R3 include halogen atoms (e.g., fluorine atoms, chlorine atoms,
bromine atom), hydroxy group, alkoxy group (e.g. methoxy group, ethoxy group), aryloxy group (e.g. phenoxy group, p-)lyloxy group), cyano group, carboxy group, carbamoyl group (e.g. carbamoyl group, N-methylcarbamoyl group) group, N,N-tetramethylenecarbamoyl group), sulfamoyl group (e.g. sulfamoyl group, N,N-3-oxapentamethyleneaminosulfonyl group), sulfonyl group (e.g. methanesulfonyl group, p-
toluenesulfonyl group), alkoxycarbonyl group (e.g. ethoxycarbonyl group, butoxycarbonyl group),
Aryl groups (e.g. phenyl, p-tolyl, p-chlorophenyl), acyl groups (e.g. acetyl, benzoyl), acylamino groups (e.g. acetylamino, benzoylamino), sulfonamide groups (e.g. methanesulfonylamino) group, benzenesulfonamino group)
, cycloalkyl groups (eg, cyclopentyl group, cyclohexyl group), and the like.

11jff represents an alkyl group having 2 to 10 carbon atoms (
For example, ethyl group, propyl group, 15o-propyl group, butyl group, t-butyl group, 1so-amyl group) or an alkoxy group having 3 to 10 carbon atoms (for example, propoxy group,
(1so-propoxy group, butoxy group), cyclopentyl group, and cyclohexyl group can have the same substituents as R1 and R2.

Examples of the ring formed by Zl include a benzoxazole ring, a naphthoxazole ring, a benzthiazole ring, a naphthothiazole ring, a tetrahydrobenzthiazole ring, a benzselenazole ring, a naphthoselenazole ring, and a tetrahydrobenzselenazole ring. Examples include a hydrocarbon ring to complete the ring, and a heterocycle to complete the ring such as a chenothiazole ring and a pyridothiazole ring.

For example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group (methyl group, ethyl group,
1so-propyl group, unsubstituted alkyl group such as butyl group,
cyanomethyl group, benzyl group, methoxyethyl group, phenethyl group, substituted alkyl group such as chloromethyl group), alkoxy group (unsubstituted alkoxy group such as methoxy group, ethoxy group, butoxy group, 2-methoxyethoxy group, benzyloxy group) hydroxyl group, aryloxy group (substituted or unsubstituted aryloxy group such as phenoxy group, tolyloxy group, etc.), or aryl group (substituted or unsubstituted aryl group such as phenyl group, p-chlorophenyl group, etc.) Any group such as (group) may be substituted.

At least one of the methine groups represented by LI R2, R3, R4, and R5 is preferably a substituted methine group, and examples of the substituent include, for example, a methyl group, an ethyl group, a butyl group, and a 1so- Examples include pentyl group and phenyl group. In addition, R2 and R4 are bonded via a substituent, and [,2,LI R4 and the substituent are 2-cyclopentene ring, 5.5-dimethyl-2-cyclohexene ring, 5
, 5-diethyl-2-cyclohexene ring and 4,4,6.
A hydrocarbon ring such as a 6-tetramethyl-2-cyclohexene ring may also be formed.

The acid anion represented by
, p-toluenesulfonate ion, perchlorate ion, 4
Specific examples include boron fluoride ions.

The compound of the present invention represented by the general formula [I] (1) Preferred compounds are represented by the following general formula [nl].

General formula [■] Z2 is 2! , X2° is synonymous with XIo, and m is synonymous with g. ] In general formula [I] and general formula [11F, YIY2,
It is preferable that Y3 and Y4 are sulfur atoms.

Specific examples of the sensitizing dye represented by the general formula [N are shown below, but the sensitizing dye used in the present invention is not limited to these compounds.

The following margin [where R4 and R5 are the general formula [R1 in 1F]
and R2, and similarly R6 is Ririto, Y
3 and Y4 are Yl and Y2, -8 I-9 ■-10 ■-11 CF12C:H= to H2 r CH2COOF! ll-28 ff-31 ■-29 ■-30 Margin below The sensitizing dye represented by the general formula [I] used in the present invention is described, for example, in The Chemistry, written by F.M. Palmer.
of Heterocyclic Compounder (The C
hemistry or heterocycle
Cogpounds) Volume 18, The Cyanine Soybean and Related Compounder (The Cy
anine DyesandRe1ated Com
(^Jeissherger ed,
Published by Interscence, New York 1
964).

The optimal concentration of the sensitizing dye of general formula [I] can be determined by methods known to those skilled in the art.

For example, a method may be used in which the same emulsion is divided, each emulsion contains a different concentration of sensitizing dye, and the performance of each emulsion is measured.

The amount of the sensitizing dye added in the present invention is not particularly limited, but ranges from 2XLO-'mol to I
Preferably, 10-' moles of X are used, and even 5
Preferably, 10-' moles to 5 x 10-' moles are used.

Methods well known in the art can be used to add the sensitizing dye to the emulsion. For example, these sensitizing dyes can be dispersed directly in the emulsion or in single solvents such as pyridine, methyl alcohol, ethyl alcohol, n-propanol, methyl cellosolve, fluorinated alcohols, dimethylformamide, etc., or mixtures thereof. It can be dissolved in a water-soluble solvent consisting of and added to the emulsion as it is or diluted with water and in the form of a solution.

Ultrasonic vibrations can also be used during the dissolution process.

Furthermore, as described in US Pat. No. 11,469.987, the dye is dissolved in a volatile organic solvent, this solution is dispersed in a hydrophilic colloid, and this dispersion is added to an emulsion. A method is also used in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and this dispersion is added to an emulsion, as described in Japanese Patent Publication No. 4B-241115.

The dye can also be added to the emulsion by the protonation dissolution method. Other methods of addition to emulsions include U.S. Patent No. 2,912.345, U.S. Pat.
The methods described in each specification of No. 5 can also be used.

The sensitizing dye represented by the general formula [11] used in the present invention may be added to the emulsion at any time during the manufacturing process from the time of silver halide grain formation to just before coating on the support. Can be added.

Specifically, before the formation of silver halide grains, during the formation of silver halide grains, after the completion of silver halide grain formation until the start of chemical sensitization, at the start of chemical sensitization, during chemical sensitization, and during chemical sensitization. Any time selected from the end of chemical sensitization and the time of application may be used. It may also be added in multiple portions. Further, the sensitizing dye represented by the general formula [11] can also be used in combination with other sensitizing dyes as a so-called supersensitizing combination. In this case, the respective sensitizing dyes may be dissolved in the same or different solvents, and the solutions may be mixed or separately added to the emulsion prior to addition to the emulsion. When adding them separately, the order and time interval can be arbitrarily determined depending on the purpose.

Higher spectral sensitivity can be obtained by using the sensitizing dye used in the present invention in combination with a compound that provides supersensitizing action. Examples of compounds having such a supersensitizing effect include those described in U.S. Pat. No. 2,933.390, U.S. Pat.
Specification of No. 3.1ll15.613, Specification of No. 3,615,632, No. 3,635.72L
Compounds having a pyrimidylamino group or triazinylamino group described in the specification of British Patent No. 1.137.58
Aromatic organic formaldehyde condensate described in specification No. 0,
Halogenated benzotriazole derivatives described in U.S. Pat. No. 4,030,927, JP-A-59-14254
1, bispyridinium compounds described in JP-A No. 59-188641, aromatic heterocyclic quaternary salt compounds described in JP-A-59-191032, JP-A-60-79348
The electron-donating compound described in the US patent jf! 4,
Polymer containing aminoallylidene malononitrile units described in No. 307.183, JP-A-55-149937
1,3-oxadiazole derivatives described in U.S. Patent No. 3,615,633, amino group-substituted derivatives described in U.S. Patent No. 4,780,404 Examples include 1,2,34-thiatriazole derivatives.

There is no particular restriction on the timing of addition of these supersensitizers, and they can be added at any time according to the timing of addition of the sensitizing dyes. The amount added is from I x 10-' to I x 1 per mole of silver halide.
The sensitizing dye is selected in the range of 0-' mole, and the sensitizing dye is 1/10 to
A molar addition ratio of 10/1 is used.

The silver halide grains contained in the silver halide emulsion according to the present invention may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver chloroiodobromide, and these grains It may be a mixture of Among these, emulsions containing at least silver chloride are more preferred, and emulsions containing substantially silver chloride are particularly preferred. It is preferable that the photosensitive material assembled using the silver chloride emulsion be processed quickly, with the processing time from development to completion of water washing being within 3 minutes, since a greater improvement effect can be obtained.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples, but these are just one embodiment of the present invention, and the present invention is not limited thereto.

Example 1 On a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the other side on the first layer side, each layer having the structure shown below was sequentially coated to form a multilayer halogenated paper support. Silver color photographic materials (Samples 1 to 38) were produced. The coating solution was prepared as follows.

1st layer coating liquid Yellow coupler (Y-1) 26.5g, dye image stabilizer (ST-1) IO, Or, additives (HQ-1
) and high boiling point organic solvent (DNP) LO+r were added and dissolved in 60 ml of ethyl acetate, and this solution was added to 220 ml of 10% gelatin solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer. The mixture was emulsified and dispersed to prepare a yellow coupler dispersion. A blue-sensitive silver halide emulsion (
(containing 10 g of silver) to prepare a first layer coating solution.

The second to seventh layer coating solutions were also prepared in the same manner as the first layer coating solution.

1st layer (blue-sensitive layer) Gelatin blue-sensitive silver chlorobromide emulsion (in terms of silver) Yellow coupler (Y-1) Dye image stabilizer (ST-1) Additive (HQ-1) NP 2nd layer (intermediate layer) Gelatin additive (HQ-1) Additive (HQ-2) IDP 3rd layer (green-sensitive layer) Gelatin green-sensitive silver chlorobromide emulsion (in terms of silver) Addition amount (g:/a) 1.4 0.3 0.8 0.3 0.0L5 0.3 1.0 0.02 0.06 0.13 1.3 0.28 Magenta coupler (M-1) Dye Image stabilizer (ST-2) Dye image stabilizer (ST-3) Dye image stabilizer (ST-4) Additive (HQ-2) IDP Anti-irradiation dye (AI-1) 4th layer (Ultraviolet absorption layer) Gelatin ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) Additive (HQ-1) NP Anti-irradiation dye (AI-2) Catechol derivative (CA-1) 5th layer (Red-sensitive layer) Gelatin red-sensitive silver chlorobromide emulsion 0.35 0.1 0.2 0.015 01 O128 4,OXIG-' ■, 1 0.52 0.18 0.04 0.45 0 .015 7, OXl0-' 1.4 (in terms of silver) Cyan coupler (C-1) Cyan coupler (C-2) Dye image stabilizer (ST-1) Additive (HQ-1) OP No. 6 layers (UV absorption layer) Gelatin UV absorber (UV-1) UV absorber (UV-2) Additive (HQ-1) NP Anti-irradiation dye (AI-2) Anti-irradiation dye (AI- 3) Catechol derivative (CA-1) 7th layer gelatin 0.23 0.13 0.26 0.20 5.5xlG O120 0,50 0,23 0,07 0,01B 0.2 5.2x to-3 1,2X 1G-' 3, Ox 10-' 1.0 Silicon dioxide 3. OX 10-'
Note that 5U-2 and 5U-3 were used as coating aids, and H-1 and H-2 were used as hardeners.

Blue-sensitive silver chlorobromide emulsion Average grain size: 0.7 μm 1 A silver chlorobromide emulsion with a silver bromide content of 90 mol % was subjected to optimal chemical ripening at 57°C using sodium thiosulfate to produce a sensitizing dye. (SD-1) and stabilizer (Z-
1) was added.

Green-sensitive silver chlorobromide emulsion A silver chlorobromide emulsion with an average grain size of 0.5 μm and a silver bromide content of 70 mol% was subjected to optimal chemical ripening at 59°C using sodium thiosulfate, and sensitized. Dye (SD-2) and stabilizer (Z
-1) was added.

Red-sensitive silver chlorobromide emulsion A silver chlorobromide emulsion (shown in Table 2) was heated at 60°C using a polycondensation compound of sodium thiosulfate, a sensitizing dye (shown in Table 2) and phenol-formalin. Optimum chemical ripening was carried out, and a stabilizer (Z-1) was added.

In addition, silver chlorobromide emulsions Em-A and Em-B shown in Table 2
SEm-C and Em-D were produced as follows.

The amounts of additives used in preparing emulsions are per mole of silver halide, unless otherwise specified.

A solution containing a silver nitrate solution, potassium bromide, and sodium chloride was added to an inert gelatin aqueous solution using the double jet method in Table 1.
It was added under the conditions described in .

Next, desalting and washing with water were carried out by a conventional method to prepare silver chlorobromide emulsions Em-A, Em-B, Em-'C and Em-D, respectively.

Margin below -1 I -1 1 -1 T-1 T-2 T-3 T-4 V-1 0H V-2 I D.

(Dioctyl phthalate) NP (Dinonyl phthalate) DP (Diisodecyl phthalate) I H I-1 C3I% CH2C00CH2CHC4H9 N103S CI COOCH2CHC4H92H
5 I-2 CI2 COOCH2 (CF2CF2)2HN! 03
5 CM C00Ct12(ChCFz)JU-3 -1 I-1 I-3 A-1 I -2 C(CHzSOzCH=CHz)4 ・NH2CH2CH2SO3 adduct I-1 -1 H (1) Evaluation of relative sensitivity Each sample 3 using a photosensitive needle KS-7 type (manufactured by Konica).
After being exposed to red light using a primary color separation filter, it was processed according to the development process shown below.

After the treatment was completed, sensitometric measurements were performed using a PD^-65 type densitometer (manufactured by Konica). The results are shown in Table 2 as relative sensitivities, with the sensitivity of Sample 1 being 100.

(2) Evaluation of residual color contamination Each "sample" was treated unexposed according to the processing steps shown below, and was measured at 840 nm using a Hitachi spectrophotometer model 32Q.
The reflection density at 700 nm was measured and determined from the difference from the cyan fog density. The results are shown in Table-2.

(3) Evaluation of raw sample storage stability Raw sample storage stability is evaluated by the change in sensitivity before storage and after storage at 25°C and 60% (relative humidity) for one month, and is calculated by the rate of change in sensitivity expressed by the following formula. I showed it. The sensitivity was determined by performing the same exposure as above, then performing the development process shown below, and measuring the cyan density.

Sensitivity change due to storage (%) The results are shown in Table-2.

Color development process〉 Color development, bleaching, fixing water Washing and drying Processing solution composition〉 (Color developer) Benzyl alcohol Ethylene glycol Potassium sulfite Potassium bromide Sodium chloride Potassium carbonate Hydroxylamine sulfate Polyphosphoric acid (TPPS) 3-Methyl- 4-Amino-N- 38°C 83°C 25-30°C 75-80°C 3 minutes 30 seconds 1 minute 30 seconds 3 minutes Approximately 2 minutes 5m1 5m1 2, Og 1.3g 0.2g 30.0g 3, Og 2. 5g Ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water to bring the total amount to 1fI and adjust the pH to 10.20.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 80g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust to pH 7.1 with potassium carbonate or glacial acetic acid and add water to bring the total volume to Ll.
shall be.

Margin S-1 below As is clear from Table 2, the samples using the sensitizing dye of the present invention have excellent sensitivity and raw sample storage stability, which are the effects of the present invention, and have improved residual color staining. I understand.

Example 2 In the same manner as in Example 1, the following seven layers were sequentially coated on a polyethylene resin-coated paper to prepare a silver halide photographic material 39 having rapid processing compatibility.

In the following margin, H-1 shown in Example 1 was used as a hardening agent.

D-1 HBS-1 vP (Polyvinylpyrrolidone) T-6 I-4 I-5 -2 cノ T-5 -1 Each sensitive emulsion was prepared as follows.

The blue-sensitive silver chlorobromide emulsion Em-D was optimally sensitized at 57°C using sodium thiosulfate to obtain a sensitizing dye (D-1) and a stabilizer (SB-1).
) was added.

Green-sensitive silver chlorobromide emulsion Em-D was optimally sensitized at 59°C using sodium thiosulfate to obtain a sensitizing dye (D-2) and a stabilizer (SB-1).
) was added.

Red-sensitive silver chlorobromide emulsion Em-D was optimally sensitized at 60°C using sodium thiosulfate, a sensitizing dye (S-4) and a phenol resin, and a stabilizer (SB-1) was added. .

Furthermore, the sensitizing dye (S-4) of the red-sensitive emulsion of Sample 39 is shown in the table below.
Samples 40 to 47 were prepared in the same manner except for the changes shown in No. 3.

This sample was evaluated in the same manner as in Example 1 for relative sensitivity, residual color contamination, and raw sample storage stability. Note that the treatment was performed according to the following treatment steps.

<Processing process> Color development, bleaching, fixing, stabilization, drying (color developer) Pure water triethanol treatment temperature 35.0±0.3 35.0±0.5 30-34℃ 80-80℃ Time "C45 seconds" 0 45 seconds 90 seconds 60 seconds Min 00ml 0g N,N-diethylhydroxylamine 5g Potassium bromide
0.02g potassium chloride
2g potassium sulfite
0.3g 1-hydroxyethylidene-1゜1-diphosphonic acid 1.0g ethylenediaminetetraacetic acid 1.0g catechol-
Disodium 3,5-disulfonate 1.0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5° Fluorescent brightener (4,4'-diaminostilbendisulfone Acid derivative) 10g Potassium carbonate 27g Add water to bring the total amount to 1g, and adjust the pH to -10, io.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml Ammonium sulfite (40% aqueous solution) Add 27.5ml water to bring the total volume to 1
g, and adjust the pH to -5.7 with potassium carbonate or glacial acetic acid.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one L, 0g ethylene glycol 1.0g 1-hydroxyethylidene-1°1-diphosphonic acid 2,0g ethylenediaminetetraacetic acid 1.0g ammonium hydroxide (20% aqueous solution) 3.0g optical brightener (4
, 4'-diaminostilbendisulfonic acid derivative) Add 1.5 g of water to make the total volume II, and adjust the pH with sulfuric acid or potassium hydroxide.
Adjust to -7,0.

The results obtained are shown in Table 3.

Table - *1; 4XIQ-' mole added per 1 mole of emulsion (in terms of silver).

*2; Sensitivity is expressed as relative sensitivity with the sensitivity of sample 39 as 100.

As is clear from Table 3, the samples using the sensitizing dye of the present invention are excellent in sensitivity, residual color staining, and raw sample storage stability.

It can be seen that a particularly large effect can be obtained in terms of raw sample storage stability, and that an emulsion consisting essentially of silver chloride is preferable in terms of raw sample storage stability.

[Effects of the Invention] The color light-sensitive material of the present invention has little dye staining, high sensitivity, and excellent raw sample storage stability.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one photographic constituent layer including a light-sensitive silver halide emulsion layer on a support, wherein a halogenated material is contained in at least one of the silver halide emulsion layers. A silver halide photographic material, characterized in that silver grains are spectrally sensitized with at least one photosensitive dye represented by the following general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, Y^1 and Y^2 represent an oxygen atom, a sulfur atom, or a selenium atom, respectively. R^1 and R^2 each represent an alkyl group having 10 or less carbon atoms or an alkenyl group having 3 or more and 10 or less carbon atoms, and R^3 represents a methyl group having a substituent, or a methyl group having 2 or more and 10 or less carbon atoms. It represents an alkyl group, a cyclopentyl group, a cyclohexyl group, a methoxy group having a substituent, an ethoxy group having a substituent, or an alkoxy group having 3 or more and 10 or less carbon atoms. Z^1 represents a nonmetallic atomic group necessary to form a 5- or 6-membered ring or a condensed ring containing these rings, and L^1, L^2, L^3, L^4, and L^ 5 each represents a methine group, and X^1^■ represents an acid anion. 1 represents an integer of 0 or 1, and 1 represents 0 when the compound forms an inner salt. ]