JPH0293535A - Silver halide photographic sensitive material containing oxonol dye - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material which is extremely less contaminated after processing by incorporating a specific water soluble oxonol dye into the material. CONSTITUTION:The water soluble oxonol dye expressed by the formula I is incorporated into the silver halide photographic sensitive material. In the formula I, R1 to R6 denote a hydrogen atom, alkyl group, aryl group, alkenyl group, or heterocyclic group, etc.; L1 to L3 respectively denote a substd. or unsubstd. methyne group; m1, m2, n denote 0, 1 or 2 integer. This oxonol dye is prepd. by dissolving the org. and inorg. alkaline salts of the dye in water to prepare an aq. dye soln. of a proper concn., and adding this soln. to a coating liquid. This coating liquid is applied onto the photographic material by which the dye is incorporated therein. Such excellent silver halide photographic sensitive material which allows easy decoloring and/or outflow and extremely decreases the contamination after the processing is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material containing a dye, and in particular a silver halide photographic material containing a hydrophilic colloid layer colored with a dye useful as a light-absorbing dye. This invention relates to silver oxide photographic materials.

[Background of the invention]

It is well known that dyes are included in silver halide photographic materials for the purpose of absorbing light of a specific wavelength for filters, antihalation, antiirradiation, or sensitivity adjustment. These dyes color the hydrophilic colloid layer.

The filter layer is usually located above the light-sensitive emulsion layer or between the emulsion layers, and serves to adjust the incident light reaching the emulsion layer to have a preferable spectral composition, and also to improve the sharpness of the photographic image. An antihalation layer is provided between the emulsion layer and the support or on the back side of the support to improve the
Harmful reflected light from the interface between the emulsion layer and the support, the back surface of the support, etc. is absorbed to prevent halation, and the emulsion layer is colored to absorb harmful reflected light and scattered light from silver halide grains, etc. It is common practice to prevent irradiation by absorbing

Dyes used for such purposes must have good absorption spectrum characteristics depending on the purpose of use, be completely decolorized during photographic processing, be easily eluted from silver halide photographic materials, and be free after processing. There is no residual color staining caused by dyes, there is no negative effect on photographic emulsions such as fogging or desensitization, and there is also excellent stability over time in solutions or silver halide photographic materials, and there is no discoloration or fading. The following conditions must be met.

To date, many efforts have been made and a large number of dyes have been proposed with the aim of finding dyes that satisfy the above conditions. For example, US Pat. No. 3,247.127, Japanese Patent Publication No. 39-22069, Japanese Patent Publication No. 55-1
Oxonol dyes described in JP-A No. 0059 and the like are known.

However, the reality is that there is still no dye that satisfies all of the above conditions and has such good properties that it can be used in photographic materials.

Particularly, as oxonol dyes, those having a carbamoyl type at the 3rd position are described in British Patent No. 1,338,799, as well as in JP-A-51-77327 and JP-A-58-1433.
No. 42, JP-A-59-111641, JP-A-63-1
Among them, the dyes described in British Patent No. 1,338,799 and Japanese Patent Application Laid-Open No. 77327/1980 have water-soluble dyes in their molecular structure. Since it does not have a functional group, it is insoluble or poorly soluble in water.

However, since photographic processing is usually carried out in a short period of time under low alkaline conditions, it is difficult for these dyes to be completely eluted from photographs. It is also conceivable that dyes that have been decolorized may restore color over time, or even if they do not restore color, they may have an adverse photographic effect.Therefore, dyes are used for the above purpose, especially in photographic materials coated in multiple layers. In some cases, it is desirable to make a water-soluble dye by introducing a water-soluble group into the dye. As a result, water-soluble dyes are easily eluted during the development process and do not remain in the photographic material.

Furthermore, when incorporating a dye into a photographic material, if it is a water-soluble dye, it has the advantage of being dissolved in water and added as an aqueous solution, but when using a poorly water-soluble dye, an organic solvent etc. must be used. It is also undesirable in terms of toxicity.

In this regard, JP-A-58-143342 and JP-A-59-1
The dyes described in JP-A No. 11541 and JP-A-63-139944 are oxonol dyes having a water-soluble group and a carbamoyl group at the 3-position, but their performance, especially bleaching properties, are still insufficient. However, further improvements were required.

Therefore, the inventors of the present invention aimed to improve some of the drawbacks of the above-mentioned dyes and to satisfy all the conditions as a light-absorbing dye (as a result of intensive research, we found that, in particular, the ability to improve decolorizing and elution properties and photographically inertness). We have discovered a light-absorbing dye that is excellent in these points, and have now completed the present invention.

[Purpose of the invention]

It is therefore an object of the present invention to have good spectral absorption properties as well as to be photographically inert in photographic light-sensitive materials, to be easily bleached and/or washed out during photographic processing, and to be highly susceptible to post-processing contamination. An object of the present invention is to provide a silver halide photographic material containing a small amount of water-soluble dye.

[Structure of the invention]

The above objects of the present invention have been achieved by a silver halide photographic material containing a water-soluble oxonol dye represented by the general formula [I].

General formula (1) [wherein R1 and Rg may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, or a heterocyclic group. However, a small number of R1 and R1 (one of which represents a heterocyclic group. R3, R4, R5
, Ra may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group or a heterocyclic group. Further, R3 and R4 or RS and Rh may be bonded to each other to form a heterocycle.

Further, each of the substituents R1 and R6 may be substituted or unsubstituted, but at least one of these substituents has a water-soluble group.

L+, Lx, Ls each represent a substituted or unsubstituted methine group, mi Sm, , n is 0, 1 or 2
represents an integer. ] Hereinafter, the present invention will be explained in more detail.

The water-soluble oxonol dye used in the present invention is represented by general formula (1), and R1 in this formula
, R1 may further have a substituent or no substituent, and the group represented by RI,
A specific example of R& will be given.

Examples of the alkyl group represented by R1 and Ra include methyl group, ethyl group, propyl group, isopropyl group, n-
Butyl group, tert-butyl group, cyclopropyl group,
Examples include cyclohexyl group. These alkyl groups further include hydroxy groups, cyano groups, sulfo groups, carboxyl groups, halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, etc.), alkoxy groups (e.g., methoxy groups, ethoxy groups, etc.), and aryl groups. Oxy groups (e.g., phenoxy groups, etc.), aryl groups (e.g., phenyl groups, etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl groups, ethoxycarbonyl groups, etc.), aryloxycarbonyl groups (e.g., phenoxycarbonyl groups, etc.), etc. may be replaced by

Examples of the aryl group represented by Rl and R6 include phenyl group, 2-methoxyphenyl group, 4-nitrophenyl L3-chlorophenyl group, 4-aminophenyl group, 4-hydroxyphenyl group, 4-methanesulfonylphenyl group. group, 4-sulfophenyl group, 3-sulfophenyl group, 2-sulfophenyl group, 2-methyl-4-sulfophenyl group, 2-chloro-4-sulfophenyl group, 4-chloro3-sulfophenyl group, 2 -Chloro-5-sulfophenyl group, 2-methoxy-5-sulfophenyl group, 2-
Hydroxy-4-sulfophenyl group, 2.5-dichloro-4-sulfophenyl group, 2゜6-diethyl-4-sulfophenyl group, 2.5-disulfophenyl group, 3.5-
Disulfophenyl group, 2,4-disulfophenyl group, 4
-phenoxy-3-sulfophenyl group, 2-chloro-6
-Methyl-4-sulfophenyl group, 3-carboxy-2
-Hydroxy-5-sulfophenyl group, 4-carboxyphenyl group, 2.5-dicarboxyphenyl group, 3.5
-Dicarboxyphenyl L2゜4-dicarboxyphenyl group, 3,6-disulfo-α-naphthyl group, 8-hydroxy-3,6-disulfo-α-naphthyl group, 5-hydroxy-7-sulfo-β-naphthyl group group, 6,8-disulfo-β-naphthyl group, and the like.

Examples of the alkenyl group represented by R+ and Ra include a vinyl group and an allyl group, and these groups may further have a substituent.

Examples of the heterocyclic group represented by R3 to R& include a pyridyl group (2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 5-sulfo-2-pyridyl group, 5-carboxy-
2-pyridyl group, 3.5-dichloro-2-pyridyl group,
4.6-dimethyl-2-pyridyl group, 6-hydroxy-
2-pyridyl group, 2.3,5.6-tetrafluoro-4
-pyridyl group, 3-nitro-2-pyridyl group, etc.), oxasilyl group (5-sulfo-2-penzoxazolyl group,
2-benzoxasilyl group, 2-oxasilyl group, etc.),
Thiazolyl group (5-sulfo-2-benzthiazolyl group,
2-benzthiazolyl group, 2-thiazolyl group, etc.), imidazolyl group (l-methy7L/-2-imidazolyl group,
1-methyl-5-sulfo-2-benzimidazolyl group, etc.), furyl group (3-furyl group, etc.), pyrrolyl group (3-pyrrolyl group, etc.), thienyl group (2-thienyl group, etc.), pyrazinyl group (2-thienyl group, etc.) -pyrazinyl group, etc.), pyrimidinyl group (2
-pyrimidinyl group, 4-chloro-2-pyrimidinyl group, etc.), pyridazinyl group (2-pyridazinyl group, etc.), purinyl group (8-purinyl group, etc.), isoxazolinyl group (3
-isoxazolinyl group, etc.), selenazolyl group (5-sulfo-2-selenazolyl group, etc.), sulfolanyl group (3-
sulfolanyl group, etc.), piperidinyl group (1-methyl-3
=piperidinyl group, etc.), pyrazolyl group (3-pyrazolyl group, etc.), tetrazolyl group (1-methyl-5=tetrazolyl group, etc.), etc.

In R3 to R-, the rings that can be formed by R3 and R4 and R5 and R6 each represent a piperazyl group, a piperidyl group, a morpholyl group, etc., and these groups can also have a substituent.

At least one of the groups R' to Bb has a water-soluble group, and the water-soluble group includes, for example, a sulfo group,
Examples include carboxyl group, phosphono group, phosphoryl group, hydroxyl group, and sulfate ester group.

In the present invention, more preferable substituents include R
1 or R2 are heterocyclic groups which may be the same or different, and more preferably R1 and R1 are the same heterocyclic group.

Specific examples of dyes represented by general formula [1] used in the present invention (referred to as exemplified compounds in the examples) are given below.

), but the present invention is not limited to these dyes.

3Na MEJ3K SJ3 1, uJtl Uλm Tobiru s03 Memu h W3: A3 JJ le LLII Mushroom hK υV Illusion 5U3K SU3K S stop 13 $3 1oO6 (Hereafter the margin) This invention The oxonol dye used in
It can be easily synthesized in the art in a manner similar to the method described in Japanese Patent No. 143342.

In the photographic material of the present invention, the oxonol dye represented by the above general formula can be incorporated into a silver halide photographic emulsion and used as an irradiation-preventing dye, or can be used as an anti-irradiation dye in a non-photosensitive hydrophilic colloid layer. It can also be used as a filter dye or an antihalation dye. Furthermore, depending on the purpose of use, two or more types of dyes may be used in combination, or in combination with other dyes. The dye according to the present invention can be easily incorporated into a silver halide photographic emulsion layer or other hydrophilic colloid layer by a conventional method. Generally, a dye or an organic/inorganic alkali salt of a dye is dissolved in water to make an aqueous dye solution of an appropriate concentration.
The dye can be added to a coating solution and applied by a known method to incorporate the dye into the photographic material. Although the content and L7 of these dyes vary depending on the purpose of use, they are generally used by coating them in an amount of 1 to 800 square meters per rrf of area on the photosensitive material.

Supports in the photographic material of the present invention include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyolefin films such as polyethylene, polystyrene films, polyamide films, polycarbonate films, baryta paper, polyolefin-coated papers, polypropylene synthetics, etc. paper,
There are glass plates, metals, etc., and these supports are appropriately selected depending on the intended use of the photographic material.

Hydrophilic colloids in the photographic material of the present invention include gelatin, derivative gelatin such as phthalated gelatin and benzenesulfonylated gelatin, water-soluble natural polymers such as phthalated gelatin, casein, and alkinoic acid, and polyvinyl alcohol and polyvinylpyrrolidone. Examples include synthetic resins and cellulose derivatives such as carboxymethylcellulose, and these can be used alone or in combination.

The silver halide emulsion in the photographic material of the present invention includes:
Any compounds commonly used in silver halide photographic emulsions are included, such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide.

The silver halide emulsion used in the photographic material of the present invention can be manufactured by various manufacturing methods including the usual manufacturing method, for example,
6-7772 or as described in U.S. Pat. No. 2,592.250, i.e. from at least some silver salts whose solubility is greater than that of silver bromide. A method for producing a so-called conversion emulsion, such as forming an emulsion of silver salt grains, and then converting at least a part of the grains to silver bromide salt or silver iodobromide salt, or
It can be manufactured by a manufacturing method such as a Lippmann emulsion manufacturing method consisting of fine-grained silver halide having an average grain size of 0.1 μm or less. The silver halide emulsion may contain chemical enhancers such as thiosulfate, allylthiocarbamide,
Sulfur sensitizers such as thiourea, allyl isothiocyanate, cystine, active or inactive selenium sensitizers, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, 2-aurothiabenzthiazole methyl chloride, etc. Noble metal sensitizers like gold compounds, palladium compounds like ammonium chloropalatate, sodium chloropalatite etc., platinum compounds like potassium chloroplatinate, ruthenium compounds, rhodium compounds, iridium compounds etc. or this Sensitization can be performed using combinations of sensitizers such as:

In addition to chemical sensitization, this emulsion can also be reduced sensitized using a reducing agent, such as triazoles, imidazoles, azaindenes, benzthiazolium compounds, zinc compounds, cadmium compounds, mercaptans, or mixtures thereof. It can also be stabilized with thioethers,
A quaternary ammonium salt type or polyalkylene oxide compound may be included.

The photographic emulsion used in the photographic material of the present invention may be spectrally sensitized with a sensitizing dye, if necessary.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merostyryl dyes,
Various sensitizing dyes such as streptocyanin can be used, and one or more sensitizing dyes can be used in combination.

In the photographic material of the present invention, in the photographic emulsion layer and other hydrophilic colloid layers, glycerin, dihydroxyalkanes such as 1°5-bentanediol, esters in the ethylene bisglycol layer, bis-ethoxydiethylene glycol succinate, etc., are added by emulsion polymerization. The obtained water-dispersible particulate polymer compound can contain a wetting agent, a plasticizer, a film property improver, etc., and can also contain an aldehyde compound, an N-methylol compound such as N,N'-dimethylol urea, Mucohalogenic acid, divinyl sulfones, 2.4-
Active halogen compounds such as dichloro-6-hydroxy-5-triazine, dioxane derivatives, divinyl ketones,
Hardening agents such as isocyanates and carbodiimides, surfactants such as saponins, polyalkylene glycols, polyalkylene glycol ethers, alkyl sulfonates, alkylbenzene sulfonates, and alkylnaphthalene sulfonates, and optical brighteners, Photographic additives such as antistatic agents, antistain agents, ultraviolet absorbers, and stabilizers can be included.

In the photographic material of the present invention, the photographic emulsion layer may contain a color coupler, and the coupler may be either 4-equivalent or 2-equivalent, and may be a colored coupler for masking or a coupler that releases a development inhibitor. There may be. Yellow-forming couplers include open-chain ketomethylene compounds such as acylacetamide, magenta-forming couplers include pyrazolone compounds, and cyan-forming couplers include phenolic or naphthol compounds.
Usually used to advantage.

〔Example〕

Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto.

Example 1 3.5 g of gelatin was added and dissolved in 35II11 of distilled water, and 2.5 g of gelatin was added to the solution to dissolve the dye used in the present invention or comparative dye.
Add an aqueous solution of 5d containing 0x10-' moles, and then add 10%
Saponin aqueous solution 1.257 and 1% formalin aqueous solution 0.
After adding 751d, add water to bring the total amount to 50d.
And so. This aqueous dye solution was applied onto an acetylcellulose support and dried to prepare samples 1 to 32, respectively.
The treatment was carried out using a model fatigue solution in which the following dyes were accumulated.

Each sample was prepared using sodium hydroxide (pH=10) containing a molar concentration (101 molar extinction coefficient) of the same dye compound as the sample.
．． 4) for 30 seconds under stirring at 30° C., washed with water for 15 seconds in a water bath containing a dye at a concentration of (11 molar extinction coefficient), and dried.

The visible spectrum of each sample was measured before and after immersion, and the elution rate was determined from the absorbance at the maximum absorption wavelength, which is shown in Table 1.

E represents the absorbance before immersion in an aqueous sodium hydroxide solution, and E2 represents the absorbance after immersion.

Further, the sample was immersed in a developer having the following composition at 30° C. for 30 seconds, washed with water for 15 seconds in a water tank containing a dye having a molar concentration of 11 molar extinction coefficient, and then dried.

The visible spectrum of each sample was measured before and after immersion in the developer, and the decolorization rate was determined from the absorbance at the maximum absorption wavelength.

The results are shown in Table-1.

E is the absorbance before immersion in the developing solution, and represents the absorbance after immersion in the E4 developing solution.

[Composition of developer]

Metol 3.0 Sodium sulfite (anhydrous) 45.0 Sodium carbonate (
Monohydrate) SO, O Potassium Bromide 2.0 Dye
(Molecular weight) x (101 molar extinction coefficient) Add water to 1
1! , and so on.

Current Comparative Dye A Comparative Dye B SO, K OffK As is clear from Table 1, the sample of the present invention showed extremely high values for both the elution rate and the decolorization rate, and the exemplary dye according to the present invention can be easily removed from the gelatin layer. It also shows superior decolorizing properties compared to comparative dyes.

Example 2 Color photosensitive materials for printing were prepared as described in (1) below, and after these samples were imagewise exposed, they were processed using the following color developer and bleach-fix solution to form each dye image. We measured the performance related to

(1) Preparation of sample A paper support whose surface was coated with polyethylene containing anatase-type titanium oxide as a white pigment was pretreated with gelatin subbing, and then the following layers were sequentially coated to prepare a sample. .

Layer 1: Blue-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 5 mol % of silver chloride, as well as the following yellow coupler (Y-1) and 2°5-diter
Coating was performed using an emulsified dispersion prepared by dissolving t-octylhydroquinone in dioctyl phthalate.

Layer 2: First intermediate layer was coated using an emulsified dispersion prepared by dissolving 2.5-tert-octylhydroquinone in dioctyl phthalate.

Third layer: Green-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 15 mol% of silver chloride, as well as the following magenta coupler (M-1) and 2°5-di-te
An emulsified dispersion prepared by dissolving rt-octylhydroquinone in dioctyl phthalate, and Table 3 below
The aqueous dye solution shown in Figure 1 was added and applied.

Layer 4: Second intermediate layer The following ultraviolet absorber (UV-1) and 2.5-GTE
An emulsified dispersion prepared by dissolving rt-octylhydroquinone in dioctyl phthalate and an aqueous dye solution shown in Table 3 were added for coating.

Layer 5: Red-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 25 mol% of silver chloride, and the following cyan coupler (C-1) and 2°5-diter
Coating was performed using an emulsified dispersion prepared by dissolving t-octylhydroquinone in dioctyl phthalate.

Layer 6: Protective layer Coating was done mainly by adding gelatin and a hardening agent.

(Y-1) I (C-1) (UV-1) 1;l (M-1) Amount of each component in the sample (mg amount per 100 CI”)
are shown in Table-2.

Based on the above layer structure, the dyes in the green-sensitive silver chlorobromide emulsion layer and layer 4 (intermediate layer) were changed to prepare the samples shown in Table 3. Layer and Layer 4 (
Samples shown in Table 4 were prepared by changing the dye in the intermediate layer), and the evaluations shown below were performed on these samples.

(2) Fog The unexposed sample was processed using the following processing steps, and the magenta and cyan densities of the obtained sample were measured using a Breturf D-122 densitometer.

(2) In order to investigate the degree of color contamination due to residual color of the dye after development processing in samples with residual color contamination, N-ethyl-N-βmethanesulfonamidoethyl- A solution was prepared without using 3-methyl-4 aminoaniline sulfate, and the same test as in ① was conducted. The results are shown in Table-3 and Table-4.

Comparative dye E Comparative dye F Processing step (38°C) Color development 2 minutes 30 seconds Bleach-fixing 1 minute Water Washing 1 minute Drying 60-80'C 2 minutes The composition of each processing solution is as follows.

[Color developer]

Pure water Benzyl alcohol Triethanolamine Sulfate Hydroxyamine Potassium bromide Sodium chloride Potassium sulfite N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 1-hydroxyethylidene-1,1-diphosphone Acid (60% aqueous solution) Potassium carbonate 00IR1 5d 0g 2.0g 1.5g 1.0g 2.0g 4.5g 1.5d 2g Whitex B B (50% aqueous solution)
2d (fluorescent brightener, manufactured by Sumitomo Chemical Co., Ltd.) Add pure water to make 11 and 20% potassium hydroxide or 10%
Adjust the pH to 10.1 with dilute sulfuric acid.

[Bleach-fix solution]

Pure water 600mg Ethylenediaminetetraacetic acid iron (III) Ammonium 65g Ethylenediaminetetraacetic acid 2-sodium salt 5g Ammonium thiosulfate 85g Sodium bisulfite 10g Sodium metabisulfite 2g Sodium ethylenediaminetetraacetic acid-2 20g Sodium bromide 10g Color developer 2
oomI! Add pure water to bring the solution to 11 and adjust the pH to 7.0 with dilute sulfuric acid.

In Tables 3 and 4 above, each number of dyes is 1
The coating amount (mg) per 00cm" is shown.

The desired whiteness for a color photosensitive material for printing requires a capri of 0.005 or less, and the samples of the present invention satisfy this requirement as shown in Tables 3 and 3.
It is clear from 4. It was also found that color contamination due to residual color of the dye, which was observed in samples containing comparative dyes, was hardly observed in the samples of the present invention, that is, the dyes of the present invention had extremely little adverse effect on the emulsion.

Example 3 Sample 57 was prepared as a comparative sample of a multilayer color light-sensitive material by sequentially coating each layer having the composition shown below on a subbed triacetyl cellulose film support from the support side. The coating amount of each component is expressed in g/m''.

1st layer (antihalation layer) Ultraviolet absorber U -10,3 Ultraviolet absorber U -20,4 High boiling point solvent 0-1 1.0 Black colloidal silver 0.24 Gelatin
2.0 Second layer (middle layer) 2.5-di-t-octylhydroquinone 0.1 High boiling point solvent 0-1 0.2 Gelatin
1.0 Third layer: low sensitivity red-sensitive silver halide emulsion layer red sensitizing dye (S-1, 5-2)
8gBrI (AgI 4.
0 mol%, average grain size 0.25 μ) 0.5 Coupler C-10, 1 mol High boiling point solvent Q -20,6 Gelatin 1.3 4th layer: High sensitivity red-sensitive silver halide emulsion layer Red mulching dye (S-
AgBr1 (1,5-2) spectrally sensitized by
Agl 2 mol%, average particle size 0.6 μ) 0.8 Coupler C-10, 2 mol High boiling point solvent 0-2 1.2 Gelatin 1.8 5th layer (middle layer) 2.5-G is also 1 octyl Hydroquinone 0.1 High boiling point solvent 0-1 0.2 Gelatin
0.9 6th layer (low sensitivity green-sensitive silver halide emulsion layer) Green sensitizing dye (S-3,5-4
) was spectrally sensitized by AgBrI (8gI 4
Mol%, average particle size 0.25μ) 0.6 Coupler-C-20.04 mole Coupler C-30.01 mole High-boiling solvent 0-3 0.5 Gelatin 1.4 7th layer (high-sensitivity green-sensitive halogenated Silver emulsion layer) Green sensitizing dye (S-3,
8gBrl (Ag
I 2 mol%, average particle size 0.6 μ) 0.9 Coupler C-20, 10 mol Coupler C-30, 02 mol High boiling point solvent 0-3 1.0 Gelatin 1.5 8th layer (intermediate layer) 5th 9th layer (yellow filter layer) same as layer Yellow colloidal silver 0.1 gelatin 0.92.5-di-
t-octylhydroquinone 0.1 high boiling point solvent 0-1
0.2 10th layer (low sensitivity blue-sensitive silver halide emulsion layer) AgBr1 spectrally sensitized with blue sensitizing dye (S-5) (Agl 4 mol%, average grain size 0.35 a) 0.6 Coupler C-40.3 mol High-boiling solvent 0-3 0.6 Gelatin 1.3 11th layer (high sensitivity blue-sensitive silver halide emulsion layer) Blue sensitizing dye (S-5
) spectrally sensitized by AgBrI (Agl 2 mol%, average particle size 0.9 u) 0.9 Coupler C-40.5 mol High boiling point solvent 0-3 1.4 Gelatin 2.1 12th layer: 1 Protective layer UV absorber U-10,3 UV absorber U-20,4 High boiling point solvent 0-3 0.6 gelatin 1.22.5-G-t'-octylhydroquinone UV absorber U-1 UV absorber U-2 0,1 13th N: Second protective layer average grain size (lower) 0.08 μm Non-photosensitive fine grain silver halide emulsion made of silver iodobromide containing 1 mol% of silver iodide
Silver amount 0.3 Polymethyl methacrylate particles (diameter 1.5 μm) Surfactant-1 Gelatin 0.7
In addition to the above composition, gelatin hardener-1 and a surfactant were added to each layer. Additionally, tricresyl phosphate was used as a coupler solvent.

Exacerbating pigment S-1 Exacerbating pigment S-2 BoC! Hs Sensitizing dye S Coupler C-1 Sensitizing dye S-4 Coupler C-2 Sensitizing dye S-5 Coupler C-3 Coupler C-4 l Gelatin hardener-1 Surfactant-1 NaOsS-CHCOOCHz (CFtCFz) J
CHzCOOCHz (CFzCFz) Jzos Js After adding 0.01 g/rrl of the compound of the present invention to the 13th layer (second protective layer) of sample 57 to prepare the samples shown in Table 5, the following evaluations were performed. Ta.

[Fog]

After storing the unexposed sample at 55°C for 17 days, the increase in maximum blue density (Δ
Dmax) is expressed as a relative value with sample 57 set as 100.

[Processing process]

Process Processing time Processing temperature First development
6 minutes Wash with water at 38℃ 2 minutes
38℃ inversion 2 minutes
38℃ color development 6 minutes 38
℃ adjustment 2 minutes 38℃ drift
White 6 minutes 38°C fixation 4 minutes 38°C water washing
4 minutes Stable at 38°C 1 minute
Normal humidity drying The composition of the treatment liquid used in the above treatment step is as follows.

[First developer] Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-phenyl-4-methyl-4
-Hydroxymethyl-3-pyrazolidone
2g potassium bromide 2.5
g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 211ti Add water
1000 relative [reversed solution] Nitrilotrimethylenephosphonic acid, hexasodium salt 3 g Stannous chloride (dihydrate) Igp-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid
Add 15rd water
1000d [Color developer] Sodium tetrapolyphosphate 3g Sodium sulfite 7g Sodium tertiary phosphate (dihydrate) 36g Potassium bromide
1g potassium iodide (0.1% solution) 90mf! Sodium hydroxide
3g citradinic acid
1.5g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4 - aminoaniline sulfate 1
g 2.2-ethylenedithiogetanol Add 1g water 1000. +d [Adjustment solution] Sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin 0.4 dI1
1000d Add glacial acetic acid water [bleaching solution] Sodium ethylenediaminetetraacetate (dihydrate) 8g (III) ammonium 20g 00g 1000d Ethylenediaminetetraacetate iron (dihydrate) Add ammonium bromide water [fixing solution] ] Ammonium thiosulfate Sodium sulfite Add sodium bisulfite water [Stabilizing solution] Formalin (37% by weight) 5d Konidax (manufactured by Konica Corporation) 5 Add water
1000 m10g 8g 8g 1000 Relative Table-5 As is clear from the results in Table 5, the dye of the present invention has almost no effect on emulsion properties. That is, it can be seen that it is inactive with respect to emulsions.

〔Effect of the invention〕

Since the present invention contains a water-soluble oxonol dye represented by the general formula (I) as a light-absorbing dye, the obtained silver halide photographic material has good spectral absorption characteristics and is photosensitive. It has excellent effects in that it does not have any adverse effect on the material (it is inert to the emulsion), easily decolorizes and/or flows out during photographic processing, and causes very little contamination after processing.

Sender: Konica Corporation

Claims (1)

[Claims] A silver halide photographic material containing a water-soluble oxonol dye represented by the general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. represents a group or a heterocyclic group, provided that R^1, R
At least one of ^2 represents a heterocyclic group. R^3,
R^4, R^5, and R^6 may be the same or different, and each represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, or a heterocyclic group. Also R^3 and R^
4 or R^5 and R^6 may be bonded to each other to form a heterocycle. Further, each of the substituents R^1 to R^6 may be substituted or unsubstituted, but at least one of these substituents has a water-soluble group. L_1, L_2, and L_3 each represent a substituted or unsubstituted methine group, and m_1, m_2, and n represent an integer of 0, 1, or 2. ]