JPH04229856A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To provide such a silver halide photosensitive material that has a good spectral absorptive characteristic, while being photographically inactive in the photosensitive material, decoloring and/or flowing out easily during photographic processing, and contains water-soluble dyes extremely less in contamination after the processing. CONSTITUTION:This silver halide photosensitive material contains at least one type of the compounds shown in a general formula [R<1>, R<2> in this expression show a hydrogen atom, an alkyl group, an aryl group and an alkenyl group, R<3>, R<5> show the alkyl group and the alkenyl group, and R<4>, R<6> show the aryl group. L1-L5 show a methyl chain, and n1, n2 show 0, 1 or 2 integers].

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material containing a dye, and more particularly to a silver halide photographic material containing a hydrophilic colloid layer colored with a dye useful as a light-absorbing dye.

0002

BACKGROUND OF THE INVENTION Dyes are incorporated into silver halide photographic materials for the purpose of absorbing light of specific wavelengths for use as filters, antihalation, antiirradiation, or sensitivity adjustment. are well known, and these dyes are used to color hydrophilic colloid layers.

[0003] A filter layer is usually located above a photosensitive emulsion layer or between two emulsion layers, and plays the role of converting the incident light that reaches the emulsion layer into light having a preferable spectral composition. In addition, in order to improve the sharpness of photographic images, an antihalation layer is provided between the emulsion layer and the support or on the back side of the support to prevent harmful effects at the interface between the emulsion layer and the support or on the back side of the support. It is common practice to prevent halation by absorbing reflected light, or to prevent irradiation by coloring the emulsion layer to absorb harmful reflected light or scattered light from silver halide grains, etc. There is.

[0004] Dyes used for such purposes should have good absorption spectrum characteristics depending on the purpose of use;
It must be completely decolorized during photographic processing or easily eluted from the silver halide photographic light-sensitive material, so that there is no residual color staining caused by the dye after processing, and there is no adverse effect such as fog or desensitization on the photographic emulsion. It must also satisfy various conditions, such as not causing any adverse effects, having excellent stability over time in solutions or silver halide photographic materials, and not discoloring or fading.

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, U.S. Patent No. 3,247
, No. 127, Japanese Patent Publication No. 39-22069, Japanese Patent Publication No. 55-10059, etc., are known.

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

In particular, as oxonol dyes, those of carbamoyl type at the 3rd position are disclosed in British Patent No. 1,338,79.
Specification No. 9 and JP-A Nos. 51-77327 and 58-
No. 143342, No. 59-111641, No. 63-1
Among them, the dyes described in British Patent No. 1,338,799 and Japanese Patent Application Laid-open No. 77327/1983 have water-soluble properties in their molecular structure. Since it does not have a functional group, it is insoluble or poorly soluble in water.

[0008] Since photographic development processing is usually carried out for a short time and under low alkaline conditions, it is difficult for these dyes to be completely eluted from the photographic material. Furthermore, dyes that have been bleached may restore color over time, or even if they do not restore color, it may have an adverse photographic effect. Therefore, when using dyes for the above-mentioned purposes, especially in photographic materials coated in multiple layers, For this purpose, 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,
A water-soluble dye has the advantage that it can be dissolved in water and added as an aqueous solution, but when using a poorly water-soluble dye, an organic solvent or the like must be used, which is undesirable in terms of toxicity.

In this respect, the dyes described in JP-A-58-143342, JP-A-59-111641 and JP-A-63-139944, and JP-A-1-126646 each have a water-soluble group. It is an oxonol dye having a carbamoyl group in the position and is preferable, but it still has poor performance.
In particular, the bleaching properties were insufficient, and further improvements were required.

[0011] Furthermore, although JP-A-2-93534 discloses a dye having a heterocycle at the 3,3'-position of pyrazolone, this patent publication discloses that a carbamoyl group at the 3,3'-position is There are few examples in which both of the substituents for the nitrogen atom are other than hydrogen atoms, and only one example of a methyl group and a pyridyl group is shown.

[0012] Furthermore, the compounds described in the above patent publication are:
Performances such as bleaching properties are also insufficient.

Therefore, the present inventors continued intensive research in order to improve some of the drawbacks of the above-mentioned dyes and satisfy all the conditions as a light-absorbing dye. Only when the combination of substituents on the nitrogen atom of the carbamoyl group is set as specified in the present invention can a light-absorbing dye that is particularly excellent in decolorization and dissolution properties and is photographically inert be obtained. This discovery led to the completion of the present invention.

[0014]

OBJECTS OF THE INVENTION Therefore, it is an object of the present invention to have good spectral absorption properties, to be photographically inactive in photographic materials, and to be easily decolorized and/or washed out during photographic processing. An object of the present invention is to provide a silver halide photographic material containing a water-soluble dye that causes extremely little staining after processing.

[0015]

[Structure of the Invention] The above object of the present invention is based on the following general formula [I]
This was achieved by a silver halide photographic material containing at least one compound represented by: General formula [I]

[0016]

[Case 2]

[In the formula, R1 and R2 represent a hydrogen atom, an alkyl group, an aryl group, or an alkenyl group.

R3 and R5 represent an alkyl group and an alkenyl group, and R4 and R6 represent an aryl group.

L1 to L5 represent methine chains, n1 and n2
represents an integer of 0, 1 or 2. ] Hereinafter, the present invention will be explained in more detail.

The oxonol dye according to the present invention is represented by the general formula [I], in which R
1. The group represented by R2 may have a substituent or may not have a substituent.

Specific examples of R1 and R2 will be illustrated below.

The alkyl group represented by R1 and R2 includes a cycloalkyl group, such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, cyclopentyl group, and cyclohexyl group. Can be mentioned. These alkyl groups can further include hydroxy groups, cyano groups, sulfo groups, carboxyl groups, and halogen atoms (e.g.
fluorine atom, chlorine atom, bromine atom), alkoxy group (e.g. methoxy group, ethoxy group), aryloxy group (
For example, phenoxy group, 4-sulfophenoxy group, 2,
4-disulfophenoxy group), aryl group (e.g. phenyl group, 4-sulfophenyl group, 2,5-disulfophenyl group), alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group), aryloxycarbonyl group groups (e.g. phenoxycarbonyl groups)
, carbamoyl group (e.g., phenylcarbamoyl group,
ethylcarbamoyl group), amide group (e.g., anilinocarbonyl group, methylaminocarbonyl group), sulfamoyl group (e.g., methylaminosulfone group, anilinosulfone group), sulfonamide group (e.g., methanesulfonamide group, benzenesulfonamide group) group), etc. may be substituted.

[0023] Examples of the aryl group represented by R1 and R2 include phenyl group and naphthyl group.

These groups can have as substituents the same groups as the alkyl groups represented by R1 and R2 and the groups represented as substituents for the alkyl groups.

[0025] Examples of the alkenyl group represented by R1 and R2 include a vinyl group and an allyl group. It can have the same group as the above group as a substituent.

Examples of the alkyl and alkenyl groups represented by R3 and R5 include the alkyl and alkenyl groups described for R1 and R2.

[0027] Examples of the aryl group represented by R4 and R6 include the aryl groups described for R1 and R2.

The methine chains represented by L1, L2, L3, L4 and L5 include those having substituents, such as alkyl groups (for example, methyl group, ethyl group, i-propyl group, t-butyl group, 3-hydroxypropyl group, benzyl group), aryl group (e.g. phenyl group), halogen atom (e.g. chlorine atom, bromine atom, iodine atom, fluorine atom), alkoxy group (e.g. methoxy group, ethoxy group), acyloxy group (eg, methylcarbonyloxy group, phenylcarbonyloxy group), and the like.

In the present invention, it is preferable that R1 and R2 are an alkyl group or a phenyl group, and it is particularly preferable that R1 and R2 are a phenyl group.

[0030] Below, the general formula [I] used in the present invention
Specific examples of dyes represented by (referred to as exemplified compounds in the examples) are given below, but the present invention is not limited to these dyes.

[0031]

[Chemical formula 3]

[0032]

[C4]

[0033]

[C5]

[0034]

[C6]

[0035]

[C7]

[0036]

[Chemical formula 8]

[0037]

[Chemical formula 9]

[0038]

[Chemical formula 10]

[0039]

[Chemical formula 11]

[0040]

embedded image The oxonol dye according to the present invention is disclosed in JP-A-58-143
No. 342, JP 2-193973, JP 2-19397
It can be easily synthesized by the same method as described in Publication No. 4.

Specific synthesis examples of the compounds of the present invention are listed below, but other compounds can be synthesized in the same manner.

<Synthesis example> (Synthesis of Exemplary Compound 1) Scheme 1

[0043]

[Chemical formula 13]

-Synthesis of compound (3) (protection reaction) 300
30.6 g of compound (1), 150 ml of dimethylformamide (DMF), and 20.2 g of triethylamine were added to a ml conical beaker, and 14 g of benzoyl chloride was slowly added dropwise at 40° C. or lower while stirring.

After the addition was completed, the mixture was stirred at room temperature for 2 hours, and then 500 ml of acetone was added to precipitate crystals. The target compound (3) was obtained by filtration and drying. Yield 33g
, yield 80%

・Synthesis of compound (5) (condensation reaction) 41 g of compound (3) obtained previously, 10.7 g of compound (4),
150 ml of DMF and 13.8 g of pyridine were added, and 21 g of dicyclohexylcarbodiimide (DCC) was added little by little at room temperature.

After the addition was completed, the mixture was stirred at room temperature for 5 hours, the precipitated solid was filtered, and 500 ml of acetone was added to precipitate crystals.

[0048] The crystals were filtered and dried to obtain the target compound (5). Yield 26.9g, yield 54%

00
49] Synthesis of Compound (6) (Deprotection) 150 ml of methanol was added to 50 g of the compound (5) obtained previously, and 30 g of triethylamine was quickly added at room temperature.

After the addition was completed, the mixture was stirred at room temperature for 1 hour, and then methanol was distilled off under reduced pressure. Add 150ml of acetone to the residual solid.
The target compound (
6) was obtained. Yield 38g, yield 96%

・Synthesis of exemplified compound (1) (dye formation) The previously obtained compound (
6) 4.0g, compound (7) 1.3g, DMF 25ml
, and 2 g of triethylamine were added thereto, followed by stirring at room temperature for 7 hours.

The reaction solution was poured into (150 ml of ethanol + 3 g of sodium acetate), and the precipitated solid was filtered and dried to obtain the desired product. Yield: 2.4 g, yield: 64% The target product was identified by IR, NMR, and mass spectrometry.

Scheme 1 (7) is shown below as (8)
, (9), the trimethine form and monomethine form can also be easily obtained.

[0054]

[Chemical formula 14]

[0055]

[Chemical formula 15]

In the photographic material of the present invention, the general formula [
The oxonol dye represented by [I] can be incorporated into a silver halide photographic emulsion and used as an irradiation-preventing dye, or it can be incorporated into a non-photosensitive hydrophilic colloid layer and used as a filter dye. Alternatively, it can also be used as 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. In order to incorporate the dye according to the present invention into a silver halide photographic emulsion layer or other hydrophilic colloid layer, a conventional method can be adopted and it can be easily carried out. Generally, a dye or an organic or inorganic alkali salt of the dye is dissolved in water to form an aqueous dye solution of an appropriate concentration, and the solution is added to a coating solution and coated by a known method to incorporate the dye into the photographic material. I can do it. Although these dyes vary depending on the purpose of use, they are generally applied in an amount of 1 to 800 mg per square meter 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, and polyolefin-coated paper. , polypropylene synthetic paper, glass plate, metal, 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 agar, casein or alginic acid, polyvinyl alcohol and polyvinylpyrrolidone. synthetic resins, cellulose derivatives such as carboxymethyl cellulose, etc., and these can be used alone or in combination.

The silver halide emulsion in the photographic material of the present invention may be a conventional silver halide emulsion such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, or silver chloroiodobromide emulsion. Any used in emulsions is included.

The silver halide emulsion used in the photographic material of the present invention can be produced by various methods including the usual method, for example, the method described in Japanese Patent Publication No. 7772/1983, or the method described in US Pat. No. 592,250, that is, forming an emulsion of silver salt grains consisting of a silver salt having at least a higher solubility than silver bromide, and then at least a portion of the grains being treated with silver bromide salt or iodine. It can also be produced by a method of producing a so-called conversion emulsion, such as converting it into a silver bromide salt, or by a method of producing a Lippmann emulsion consisting of fine-grained silver halide having an average grain size of 0.1 μm or less. This silver halide emulsion may contain chemical sensitizers such as sulfur sensitizers such as thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, active or inactive selenium sensitizers, potassium chloride sensitizers, etc. Gold compounds such as aurate, auric trichloride, potassium auric thiocyanate, 2-aurothiabenzthiazole methyl chloride etc., palladium compounds such as ammonium chloroparatate, sodium chloroparatate etc., platinum such as potassium chloroplatinate Noble metal sensitizers such as compounds, ruthenium compounds, rhodium compounds, iridium compounds, etc. or combinations of such sensitizers can be used for sensitization. In addition to the chemical sensitization mentioned above, this emulsion can also be reduced sensitized using a reducing agent such as triazoles, imidazoles, azaindenes, benzthiazolium compounds, zinc compounds, cadmium compounds, mercaptans, or these. Mixtures can be used and sensitizing compounds of thioethers, quaternary ammonium salts or polyalkylene oxides can 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 dyes such as streptocyanin dyes can be used, and one type or a combination of two or more types of sensitizing dyes can be used.

In the photographic material of the present invention, glycerin, 1,
Dihydroxy alkanes such as 5-pentanediol, esters of ethylene bisglycols, bis-ethoxydiethylene glycol succinate, wetting agents such as water-dispersible particulate polymer compounds obtained by emulsion polymerization, plasticizers, film property improvers, etc. It can also contain N- such as aldehyde compounds and N,N'-dimethylol urea.
Active halogen compounds such as methylol compounds, mucohalogen acids, divinyl sulfones, 2,4-dichloro-6-hydroxy-5-triazine, hardeners and saponins such as dioxane derivatives, divinyl ketones, isocyanates, and carbodiimides, Polyalkylene glycol, polyalkylene glycol ether, alkyl sulfonate,
Surfactants such as alkylbenzenesulfonates and alkylnaphthalenesulfonates, and photographic additives such as optical brighteners, antistatic agents, antistain agents, ultraviolet absorbers, and stabilizers can be contained.

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 release a colored coupler for masking or a development inhibitor. It may be a coupler that As yellow-forming couplers, open-chain ketomethylene compounds such as acylacetamide-based couplers, as magenta-forming couplers, pyrazolone-based compounds, and as cyan-forming couplers, phenol-based or naphthol-based compounds are usually advantageously used.

[0064]

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

The compounds used in the following Reference Examples and Examples are shown below.

[0066]

[Chemical formula 16]

[0067]

[Chemical formula 17]

[0068]

[Chemical formula 18]

[0069]

[Chemical formula 19]

[0070]

[C20]

[0071]

[C21]

[0072]

[C22]

[0073]

[C23]

[0074]

[C24]

Reference Example 3.5 g of gelatin was added and dissolved in 35 ml of distilled water, and 5 ml of an aqueous solution containing 2.0 x 10 -4 mol of the dyes according to the present invention or comparative dyes shown in Tables 1 and 2 was prepared. After adding 1.25 ml of a 10% saponin aqueous solution and 0.75 ml of a 1% formalin aqueous solution, water was added to make the total volume 50 ml. This aqueous dye solution was applied onto an acetyl cellulose support and dried to produce samples 1-1 to 1-64, respectively, and treated with a model fatigue solution in which the following dyes were accumulated.

Each sample was added to an aqueous sodium hydroxide solution (pH 10.4) containing the same dye compound used when preparing each sample at a molar concentration of (10/molar extinction coefficient) at 30° C. under stirring. immersed for 30 seconds, washed for 15 seconds in a water bath containing dye at a concentration of (1/molar extinction coefficient),
Dry.

The visible spectra of each of the above samples before and after immersion were measured, and the elution rate was determined from the absorbance at the maximum absorption wavelength using the following formula and is shown in Tables 1 and 2.

[0078]

[Math 1]

E1 represents the absorbance before immersion in an aqueous sodium hydroxide solution, and E2 represents the absorbance after immersion.

[0080] Each sample was placed in a developer having the following composition at 30°C.
The sample was immersed in water for 30 seconds, washed for 15 seconds in a water bath containing a molar concentration of dye (1/mol 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 Tables 1 and 2.

[0082]

[Math 2]

E3 represents the absorbance before immersion in the developer, and E4 represents the absorbance after immersion in the developer.

[Composition of developer] Metol
3.0g Sodium sulfite (anhydrous)
45.0g Sodium carbonate (monohydrate)
80.0g potassium bromide
2.0g dye
Add (molecular weight) x (10/molar extinction coefficient)g water to make 1 liter.

[0085]

[Table 1]

[0086]

[Table 2]

As is clear from Tables 1 and 2, the samples of the present invention exhibit extremely high values for both the elution rate and the decolorization rate, compared to the comparative samples.

As described above, the dye according to the present invention is easily eluted from the gelatin layer and exhibits excellent decolorizing properties.

Example 1 Color photosensitive material sample 2- for printing was prepared in the manner described in (1) below.
7 was produced.

(1) Preparation of sample A paper support whose surface is coated with polyethylene containing anatase titanium oxide as a white pigment is pretreated with gelatin undercoating, and then the following layers are sequentially coated to prepare the sample. 2-7 was produced.

Layer 1: Blue-sensitive silver chlorobromide emulsion layer A blue-sensitive silver chlorobromide emulsion containing 5 mol % of silver chloride, and yellow couplers Y-1 and 2,5-di-t-octylhydroquinone. Coating was performed using an emulsified dispersion prepared by dissolving in dioctyl phthalate.

Layer 2: First intermediate layer was coated using an emulsified dispersion prepared by dissolving 2,5-di-t-octylhydroquinone in dioctyl phthalate.

Layer 3: Green-sensitive silver chlorobromide emulsion layer Silver chloride 15
A green-sensitive silver chlorobromide emulsion containing mol % and an emulsified dispersion prepared by dissolving magenta coupler M-1 and 2,5-di-t-octylhydroquinone in dioctyl phthalate were used for coating.

Layer 4: Second intermediate layer The layer was coated using an emulsified dispersion prepared by dissolving UV absorbers UV-1 and 2,5-di-t-octylhydroquinone in dioctyl phthalate.

Layer 5: Red-sensitive silver chlorobromide emulsion layer Silver chloride 25
Coating was carried out using a red-sensitive silver chlorobromide emulsion containing mol % and an emulsion dispersion prepared by dissolving the following cyan coupler C-1 and 2,5-di-t-octylhydroquinone in dioctyl phthalate. .

Layer 6: Protective layer was coated with gelatin, a hardener, and an anti-bacterial agent-1 added thereto.

Table 3 shows the amount of each component (amount per 100 cm2) in the sample.

[0098]

[Table 3]

In Sample 2-7, the dyes shown in Table 4 were added to Layer 3 (green-sensitive silver chlorobromide emulsion layer) to form Samples 2-1 to 2-6 and 2-8 shown in Table 4. ~2-28 was prepared,
In addition, the dyes shown in Table 5 were added to layer 5 (red-sensitive silver chlorobromide emulsion layer) to prepare samples 3-1 to 3-33 shown in Table 5, and the following evaluations were performed on these samples. .

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

(2) Residual color stain (stain) In order to investigate the degree of color stain due to the residual color of the dye after the development process in the sample, N- Ethyl-N-β-methanesulfonamidoethyl-
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 Tables 4 and 5.

[0103] Processing step (38°C) Color development
2 minutes 30 seconds bleach fixing
Wash with water for 1 minute
1
Minute drying 60-80℃
The composition of each 2-minute treatment solution is as follows.

<Color developer> Pure water

800ml benzyl alcohol

15ml triethanolamine
10g
hydroxyamine sulfate

2.0g potassium bromide

1.5g sodium chloride

1.0g potassium sulfite
2.0
g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate
4.
5g 1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution)

1.5ml potassium carbonate

32g White
x BB (50% aqueous solution) (fluorescent brightener, manufactured by Sumitomo Chemical Co., Ltd.)
Add 2 ml of pure water to make 1 liter and adjust the pH to 10 with 20% potassium hydroxide or 10% dilute sulfuric acid.
．． Adjust to 1.

<Bleach-fix solution> Pure water

600ml ethylenediaminetetraacetate iron(III) ammonium
65g ammonium thiosulfate

85g sodium bisulfite

10g sodium metabisulfite
2g sodium bromide

Add 10g of pure water to make 1 liter, and adjust the pH to 7 with dilute sulfuric acid.
．． Adjust to 0.

[0106]

[Table 4]

[0107]

[Table 5]

[0108] In Tables 4 and 5 above, each number attached to the label indicating the dye indicates the coating amount (mg) of each dye per 100 cm2.

It is clear from Tables 4 and 5 that the desired whiteness for a color photosensitive material for printing requires a fog of 0.005 or less, and the samples according to the present invention satisfy this requirement. It is. In addition, color contamination due to residual color of the dye, which is observed in samples containing comparative dyes, is hardly observed in the samples according to the present invention. That is, it was found that the dye according to the present invention has extremely little adverse effect on the emulsion.

Example 2 A multilayer color photosensitive material sample 4-14 was prepared 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 shown in g/m2. However, silver halide emulsions and yellow colloidal silver are shown in silver equivalent values.

First layer; antihalation layer ultraviolet absorber U-1

0.3 Ultraviolet absorber U-2

0.4 High boiling point solvent O-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 O-1
0.2
gelatin

1.0

Third layer; low-sensitivity red-sensitive silver halide emulsion layer Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes (S-1, S-2) (AgI 4.30 mol%, average grain size 0.25μ
m,) 0.5 Coupler C-2

0.1 mole
High boiling point solvent O-2

0.6 Gelatin

1.3

4th layer: Highly sensitive red-sensitive silver halide emulsion layer Red sensitizing dyes (S-1, S
-2) Silver iodobromide emulsion spectrally sensitized (AgI 2 mol%, average grain size 0.6 μm)
0.8 Coupler C-2
0.2
Mol High boiling point solvent O-2

1.2 Gelatin

1.8

5th layer; middle layer 2,5-di-t-octylhydroquinone
0.1 High boiling point solvent O-1
0.2
gelatin

0.9

6th layer; low-sensitivity green-sensitive silver halide emulsion layer Silver iodobromide emulsion spectrally sensitized with green sensitizing dyes (S-3, S-4) (AgI 4 mol %, average grain size 0. 25μm)
0.6 Coupler C
-3
0.04
Mol coupler C-4

0.01 mol High boiling point solvent O-3

0.5 gelatin

1.4

7th layer: High-sensitivity green-sensitive silver halide emulsion layer Silver iodobromide emulsion spectrally sensitized with green sensitizing dyes (S-3, S-4) (AgI 2 mol %, average grain size 0. 6μm)
0.9 Coupler C-3
0.1
0 mol coupler C-4

0.02 mol High boiling point solvent O-3

1.0 Gelatin

1.
5

8th layer; middle layer Same as 5th layer

9th layer; yellow filter layer yellow colloidal silver

0.1 gelatin

0.9 2,5-di-t-
octylhydroquinone
0.1 High boiling point solvent O-1

0.2

[0120] 10th layer;
Low-speed blue-sensitive silver halide emulsion layer Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (S-5) (AgI 4 mol%, average grain size 0.35 μm)
0.6 Coupler C
-5
0.3 mol High boiling point solvent O-3

0.6 Gelatin

1.3

Eleventh layer: Highly sensitive blue-sensitive silver halide emulsion layer Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (S-5) (AgI 2 mol%, average grain size 0.9 μm)
0.9 Coupler C-5
0.5
Mol High boiling point solvent O-3

1.4 Gelatin

2.1

12th layer; first protective layer ultraviolet absorber U-1

0.3 Ultraviolet absorber U-2

0.4 High boiling point solvent O-3

0.6 Gelatin

1.2 2
,5-di-t-octylhydroquinone
0.1

13th
Layer: second protective layer non-photosensitive fine-grain silver halide emulsion made of silver iodobromide with an average grain size of 0.08 μm and containing 1 mol% of silver iodide
Silver amount 0.3
Polymethyl methacrylate particles (1.5 μm in diameter)
0.05 Surfactant-1 Gelatin

0.7

[0124] In addition to the above compounds, a hardening agent, a surfactant, and an anti-build agent-1 were added to each layer.

[0125] 0.01 g/m2 of the dye shown in Table 6 was added to the 13th layer (second protective layer) of Sample 4-14, and Samples 4-1 to 4-13 and 4-15 shown in Table 6 were added. -4-30 were produced. These samples were evaluated as shown below.

[Fog] After storing the unexposed sample at 55°C for 20 days, it was treated according to the following processing steps.
Increase the maximum blue density increase (ΔDmax) from sample 4-1 to 1.
It is shown as a relative value set to 00.

[Processing process] Process Processing time Processing temperature
1st development 6 minutes
38℃ water
Wash 2 minutes
38℃ anti
2 minutes
38℃ color development
6 minutes
38℃ adjustment
2 minutes
38℃ bleaching
6 minutes
Fixed at 38℃
4 minutes
38℃ water washing
4 minutes
38℃ stable
1 minute
Room temperature 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
．． 5g potassium thiocyanate

1.2g potassium iodide (0.1% solution)

Add 2ml water

1000ml [Reversal solution] Nitrilotrimethylenephosphonic acid hexasodium salt 3g Stannous chloride (2
water salt)
1g p-aminophenol
0.1g sodium hydroxide

8g glacial acetic acid

Add 15ml water

1000ml

012
9] [Color developer] Sodium tetrapolyphosphate

3g sodium sulfite

7g Sodium phosphate (dihydrate)

36g potassium bromide

1g potassium iodide (0
．． 1% solution)
90ml sodium hydroxide
3g citradinic acid
1.
5g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate

11g 2,2-ethylenedithiodiethanol
Add 1g water

1000ml

[Adjustment liquid] Sodium sulfite

12g Sodium ethylenediaminetetraacetate (2
water salt) 8g
thioglycerin
0
．． 4ml glacial acetic acid

Add 3ml water

1000ml

0
131] [Bleach solution] Sodium ethylenediaminetetraacetate (dihydrate)
2g Iron(III) ammonium ethylenediaminetetraacetate (dihydrate)
120g ammonium bromide

Add 100g water

1000ml

[Fixer] Ammonium thiosulfate

80g sodium sulfite

5g sodium bisulfite

Add 5g water

1000ml

013
3] [Stabilizing liquid] Formalin (37% by weight)

5ml Konidax (manufactured by Konica Corporation)
5
Add ml water

The 1000ml results are shown in Table 6.

[0134]

[Table 6]

As is clear from the results in Table 6, the dyes according to the present invention have almost no effect on photographic emulsion properties. That is, it can be seen that it is inactive with respect to emulsions.

[0136]

Effects 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 properties. It has excellent effects in that it has no adverse effects in photographic light-sensitive materials (inert to emulsions), easily decolorizes and/or flows out during photographic processing, and causes very little contamination after processing. It is.

Claims (1)

[Claims] 1. A silver halide photographic material containing at least one compound represented by the following general formula [I]. General formula [I] [Formula, R1 and R2 represent a hydrogen atom, an alkyl group, an aryl group, and an alkenyl group. R3 and R5 represent an alkyl group and an alkenyl group, and R4 and R6 represent an aryl group. L1 to L5 represent methine chains, and n1 and n2 represent integers of 0, 1 or 2. ]