JP2890065B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photographic light-sensitive material, and more particularly, to a photographic light-sensitive material containing a blocked precursor compound that releases a useful photographic group in the course of photographic processing.

[Background of the Invention]

Various effects can be exerted by incorporating the useful group for photography into the photosensitive material in a blocked form. When the photographically useful group is a coupler, storage stability can be improved by forming a precursor. When the useful group for photography is a dye, a silver halide photographic light-sensitive material having a corresponding light-sensitive spectral region is obtained by blocking the chromophore or auxiliary chromophore of the dye to temporarily make the colorless or short-wavelength, and thereby have a corresponding light-sensitive spectral region. Even if they coexist in the same layer, the sensitivity can be prevented from lowering due to the filter effect.

When the useful group for photographic use is an anti-irradiation dye, it is desirable that the dye is allowed to flow out of the light-sensitive material during processing. Therefore, when it is added to a photosensitive material, it is difficult to contain it only in a specific layer, and a great decrease in sensitivity has been unavoidable. In this way, by blocking the diffusible photographically useful group with the group having the ability to resist diffusion, it can be immobilized only on a specific layer.

When the useful group for photography is a development inhibitor or an antifoggant, by blocking, the influence on the silver halide during storage can be suppressed, and the development can be suppressed without lowering the sensitivity or the fog can be reduced. Can be prevented.

When the photographic useful group is a component in the processing solution, the composition of the processing solution can be simplified by blocking and incorporating it into the photosensitive material.

As described above, the precursor technology of blocking useful photographic groups and including them in the photographic material to release the useful photographic groups in the photographic processing process is expected to be extremely effective. During processing, it is necessary to release useful photographic groups promptly, and it is not easy to satisfy both.

Several blocking groups for such precursor compounds are already known. Representative examples are, for example, JP-B-54-39,727, JP-B-63-616,6493,
JP-A-63-61,6563 and JP-A-58-209,736 disclose a block group which releases a useful photographic group upon formation of quinone methide and a similar compound by electron transfer.
No. 55-53,330. A blocking group which releases a useful photographic group by an intramolecular nucleophilic substitution reaction described in JP-A-57-76,541.
Nos. 57-135,949 and 57-179,842, and a blocking group utilizing 5- or 6-membered ring cleavage, JP-B Nos. 54-39,723, 55-96,963 and 55-34,927. And a blocking group utilizing the reverse Michael reaction.

However, these blocking groups have poor storage stability or a slow release rate, and are far from practically used in conventional photographic light-sensitive materials having a low processing pH.

On the other hand, the blocking group described in JP-A-60-35,729 can release useful photographic groups not only by hydroxyl ions in the processing solution but also by hydroxylamine, sulfite ions, etc. There is some advantage in terms of compatibility between the properties and the release during processing. In addition, European Patent Publication 394,
The blocking group described in No. 974 hardly releases useful photographic groups by hydroxyl ion,
This is a significant advantage over previous blocking groups in that it releases photographic useful groups only by nucleophiles. However, these blocking groups are still insufficient in terms of compatibility between stability during storage and release during processing, and further improvement is desired.

[Object of the invention]

Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material containing a precursor compound which is completely stable under storage conditions and rapidly releases a useful photographic group even during processing at a low pH during processing. Is to provide.

[Configuration of the invention]

The above object of the present invention has been achieved by a silver halide photographic material containing a compound represented by the following general formula [I].

General formula [I] [In the formula, Z is a nonmetallic atom group necessary for forming a 5- to 7-membered ring containing at least one of an oxygen atom, a sulfur atom, and a nitrogen atom, or a nonmetallic group necessary for forming indanone. Represents an atomic group. R represents a substituent. Time represents a timing group, and PUG represents a useful group for photography.
n represents the integer of 0-2. Hereinafter, the present invention will be described in detail.

In the general formula [I], examples of the substituent represented by R include a halogen atom, nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, alkylthio, arylthio, heterocyclic, and alkyl. Groups such as amino and arylamino; Of these, preferred are alkyl, aryl and cycloalkyl groups, and more preferred are alkyl groups.
Examples of the ring formed together with Z include the following.

In the general formulas [I-1] to [I-8], Time, n,
PUG and R represent the same groups as in formula [I]. R ₁ , R ₂ , R
₃ represents a hydrogen atom, a substituent, and as the substituent, a halogen atom, nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy,
Represents a group such as alkoxycarbonyl, aryloxycarbonyl, arylthio, alkylthio, heterocycle, alkylamino, arylamino, amide, sulfonamide, ureido, acyl, aroyl and the like. Among them, when R ₁ may be substituted by a complex, they may be the same or different. X represents an oxygen atom, a nitrogen atom, or a sulfur atom.

As the group represented by Time, for example, (1) a group that causes a cleavage reaction using an electron transfer reaction along a conjugated system,
(2) a group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction, (3) a group that uses a cleavage reaction of hemiacetal, (4) a group that uses a cleavage reaction of imino ketal,
(5) A group using a hydrolysis cleavage reaction of an ester.

Regarding the group (1), for example, JP-A-56-114946,
No. 57-154234, No. 57-188035, No. 58-98728, No. 5
8-160954, 58-209736, 58-209737, 58
-209738, 58-209739, 58-209740, 62-
86361 and 62-87958, for the group (2), for example, JP-A-57-56837,
In U.S. Pat. No. 4,248,962, for the group (3), for example, JP-A-60-249148,
No. 60-249149, U.S. Pat. No. 4,146,396, the group (4) is described in, for example, U.S. Pat. No. 4,546,073, and the (5) group is described in, for example, West German Patent 2,626,
No. 315 describes it in detail.

 Of the groups represented by Time, those shown below are preferred.

In the structural formula, * 2 indicates a site that binds to PUG.

Ra represents a substituent, Rb, Rc represents a hydrogen atom or a substituent, p represents 0, 1 or 2, and when p is 2, Ra may be the same or different from each other. A ring may be formed. q represents 0, 1 or 2.

Examples of the substituent represented by Ra include a halogen atom,
Alkyl, alkenyl, alkoxy, alkoxycarbonyl, anilino, acylamino, ureido, cyano, nitro, sulfonamide, sulfamoyl, carbamoyl, aryl, carboxyl, sulfo, cycloalkyl , An alkanesulfonyl group, an arylsulfonyl group or an acyl group, including those further having a substituent.

Examples of the substituent represented by Rb and Rc include an alkyl group, an alkenyl group, a cycloalkyl group and an aryl group, and these include those further having a substituent.

PUGs which are useful groups for photography include, for example, antifoggants, development inhibitors, color and black and white developing agents, auxiliary developers, development accelerators, fogging agents, image forming couplers, competing couplers, DIR couplers, colored couplers, Color coupler, black coupler, dye, dye, bleach accelerator,
Bleach inhibitors, silver halide solvents, silver complexing agents, fixing agents,
Examples include a curing agent, a DP 'scavenger, and an image stabilizer. Specific examples of the antifoggant and the development inhibitor include a benzotriazole compound, a benzimidazole compound, a mercaptoimidazole compound, a mercaptothiazole compound, a mercaptotetrazole compound, a mercaptothiadiazole compound, a mercaptotriazole compound, and a mercaptooxadiazole compound. Specific examples of the developing agent, auxiliary developer, and development accelerator include hydroquinone compounds, catechol compounds, aminophenol compounds, p-phenylenediamine compounds, pyrazolidone compounds, ascorbic acid compounds, and the like. Specific examples of the fogging agent include hydrazine compounds, hydrazide compounds, and tetrazolium salts. Specific examples of image forming couplers include benzoylacetanilide-based and pivaloylacetoanilide-based yellow couplers, phenol-based, naphthol-based, imidazole-based and pyrazoloazole-based cyan couplers, pyrazolone-based, indazolone-based, cyanoacetyl-based, and pyrazoloazole-based couplers. There are magenta couplers and the like. Specific examples of DIR couplers, U.S. Pat.Nos. 3,227,554, 3,384,657, 3,615,506,
3,617,291, 3,733,201, JP-B-61-27738,
JP-A-56-114946, JP-A-57-111536, JP-A-57-154234
No. 58-160954, No. 58-162949, No. 60-185950
Nos. 61-233741 and 57-151944. Examples of the colored coupler include a colored magenta coupler and a colored cyan coupler. Representative examples of non-colored couplers include indanone-type compounds. Specific examples of the dye include an azo aromatic dye, an azomethine dye, an anthraquinone dye, and an indophenol dye. Specific examples of dyes include azo dyes, azomethine dyes, azopyrazolone dyes, indoaniline dyes, indophenol dyes, anthraquinone dyes, triarylmethane dyes, alizarin dyes, quinoline dyes, oxanol dyes, phthalocyanine dyes, merocyanine dyes, arylidene dyes And styryl dyes. Specific examples of the bleaching accelerator include an aminoethanethiol compound, a sulfoethanethiol compound, an aminoethanethiocarbamate compound, and a carboxyethanethiol compound. Specific examples of the silver halide solvent include a thioether compound, rhodanine compound, hypo, and methylenebissulfone compound. There is a hypo as a fixing agent. Preferred as PUGs are development inhibitors, color and black and white developing agents, auxiliary developers, fogging agents, image forming couplers, competing couplers, DI
R couplers, colored couplers, dyes, dyes and bleaching accelerators.

In the general formulas [I-1] to [I-8], preferably,
General formulas [I-1], [I-2], [I-5] and [I-6], and particularly preferable are general formulas [I-1] and [I-6].

Hereinafter, typical examples of the compound of the general formula [I] are shown,
The present invention is not limited to these.

Hereinafter, typical synthesis examples of the present invention will be described.

Synthesis Example (Synthesis of Exemplified Compound 3) At room temperature Put 1 20.8 g 2 19.0 g of Exemplified Compound 3 ethyl acetate 200 ml,
Dimethylaniline (14.9 g) was added in 1 hour, and 50 ° C
Stirred at 6060 ° C. for 2 hours. After cooling, the mixture was washed with water, and the ethyl acetate was removed by distillation under reduced pressure. Then, 28 g of 3 was obtained by column chromatography (SiO ₂ ). 150 ml of acetone
And 16.0 g of 4 was added at room temperature for 1 hour, and the mixture was further heated under reflux for 2 hours. After removing acetone under reduced pressure, ethyl acetate
After adding 200 ml and extracting and washing with water, ethyl acetate was removed under reduced pressure. The residue was purified by column chromatography (SiO ₂ ) to obtain 26 g of the desired compound.

Fixation was performed by NMR, IR, and MS spectra, and it was confirmed that the compound was Exemplified Compound 3.

Other compounds of the present invention can be synthesized by the same synthesis method.

The amount of the compound of the present invention added to the light-sensitive material may be
It is not uniform depending on the type of PUG, but silver halide 1
It is 10 ^-9 to 10 mol, preferably 10 ^-5 to 1 mol per mol.

The light-sensitive material of the present invention can be applied to various types of light-sensitive materials described below.

For example, for color positive, color negative, color paper, reverse color, direct positive, color diffusion transfer,
It can be used for photosensitive materials for thermal development and the like, and is particularly advantageous for application to color photosensitive materials having a multilayer structure.

The silver halide emulsion used in the present invention may be any silver halide emulsion such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide or silver chloride. Can be used.

The silver halide grains used in the silver halide emulsion are:
The grains may have a uniform silver halide composition distribution within the grains, or may be core / shell grains having different silver halide compositions between the inside of the grains and the surface layer.

The silver halide grains may be grains whose latent image is mainly formed on the surface, or grains whose latent image is mainly formed inside the grain.

The silver halide emulsion having any grain size distribution may be used. Emulsions having a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions having a narrow grain size distribution (referred to as monodisperse emulsions) may be used alone or as a mixture of several kinds. Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The silver halide emulsion may be a mixture of two or more kinds of silver halide emulsions formed separately.

The emulsion can be chemically sensitized by a conventional method,
By using a sensitizing dye, it can be optically sensitized to a desired wavelength range.

Antifoggants, stabilizers and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as a binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened, and can contain a plasticizer and a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer.

In the emulsion layer of the color light-sensitive material, a coupler is generally used. Further, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, by coupling with a competitive coupler having a color correction effect and an oxidized form of the developing agent.
Compounds that release photographically useful fragments such as hardeners, foggants, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers can be used.

As the yellow dye-forming coupler, known acylacetanilide-based couplers can be preferably used. Of these, benzoylacetanilide and pivaloylacetoanilide compounds are advantageous.

As the magenta dye-forming coupler, a 5-pyrazolone coupler, a pyrazoloazole coupler, a pyrazolobenzimidazole coupler, a closed acylacetonitrile coupler, an indazolone coupler and the like can be used.

As the cyan dye-forming coupler, a phenol or naphthol coupler is generally used.

Photosensitive materials include filter layers, antihalation layers,
An auxiliary layer such as an irradiation prevention layer can be provided. In these layers and / or the emulsion layers, dyes which flow out of the light-sensitive material or are bleached during the development processing may be contained.

Matting agents, lubricants, image stabilizers, formalin scavengers, ultraviolet absorbers, fluorescent brighteners, surfactants, development accelerators, development retarders and bleach enhancers can be added to the photosensitive material.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

〔Example〕

Example 1 (Preparation of coating solution) After dissolving 35 g of gelatin in water of 1.0, a coating aid (Su
-1) and a hardener (H-1) was added to prepare a coating solution.

(Dye precursor dispersion) 2.5 × 10 ^-3 mol of the comparative compound (A) was mixed with a high boiling solvent (Oil).
-1) The solution was dissolved in 1.6 ml and 6 ml of ethyl acetate, and this solution was added to 44 g of a 10% aqueous gelatin solution containing a surfactant (Su-2) and emulsified and dispersed.

The coating liquid and the dye dispersion were mixed and dissolved to have the following composition, and a coating aid (Su-1) and a hardener (H-1) were added to prepare a coating liquid for an emulsion layer.

(Preparation of Sample) Sample 101 was prepared by applying the above coating solution for an emulsion layer on a 100 μm polyethylene terephthalate film base which had been subjected to a latex subbing process described in JP-A-59-19941 and dried. The amount of the dye precursor (compound) applied was 3 × 10 ⁻⁴ mol / m ² .

(Processing) Each of these samples was processed using a developing solution having the following composition and a developing solution having the following composition, in which only hydroxylamine sulfate was removed.

Development processing conditions Development processing 30 seconds 38 ° C Water washing 30 seconds Drying 2 minutes 60-80 ° C [Color developing solution] Pure water 800 ml Benzyl alcohol 15 ml Triethanolamine 10.0 g Hydroxyamine sulfate 2.0 g Potassium bromide 1.5 g Sodium chloride 1.0 g Potassium sulfite 2.0 g N-ethyl-N-β-methanesulfonamidoethyl-
3-methyl-4-aminoaniline sulfate 4.5 g potassium carbonate 32.0 g 1-hydroxyethylidene-1,1-disulfonic acid (60
% Aqueous solution) 1.5ml Whitex BB (50% aqueous solution) (Fluorescent brightener, manufactured by Sumitomo Chemical Co., Ltd.) Add pure water to make 1 and add 20% potassium hydroxide or 10%
Adjust to pH 10.1 with dilute sulfuric acid.

(Evaluation) The following evaluation was performed for the presence or absence of residual color after the treatment. The visible spectrum of each sample after the treatment was measured, and the decolorization rate was obtained from the difference between the absorbance (E ₂ ) at the absorption maximum and the following E ₁ by the following formula.

(E ₁ represents the absorbance at the absorption maximum of the sample before treatment.) The results are shown in Table 1.

In the same manner, samples were prepared in the same manner as in Sample 101 except that the compounds used in Sample 101 were replaced with the compounds shown in Table 1.
2 to 106.

As is apparent from Table 1, the compounds of the present invention release dyes only in the presence of hydroxylamine. This means that the disadvantages of the conventional precursors, which are attacked by hydroxide ions during storage before treatment and release the dye, have been improved. The release of the comparative compound (B) is certainly suppressed in the system without hydroxylamine, but the release of the dye in the presence of hydroxylamine is insufficient. In comparison, the compounds of the present invention show sufficient values, indicating that the objects of the present invention have been sufficiently achieved.

Example 2 On a support in which polyethylene was laminated on one side of a paper support and polyethylene containing titanium oxide was laminated on the other side, each layer having the following structure was applied on the side of the polyethylene layer containing titanium oxide. Thus, a silver halide color photographic light-sensitive material was prepared. The coating solution was adjusted as described below.

(First layer coating solution) 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), 6.67 of dye image stabilizer (ST-2)
g, additive (HQ-1) 0.67 g, and high boiling organic solvent (DN
P) To 6.67 g, add and dissolve 60 ml of ethyl acetate.
A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of a 10% gelatin aqueous solution containing 7 ml of a 10% surfactant (SU-1) using an ultrasonic homogenizer. This dispersion was prepared under the following conditions using a blue-sensitive silver halide emulsion (silver 10 g).
And the first layer coating solution.

(Second layer coating solution) Surfactant (SU-2), (SU-3) in gelatin aqueous solution
And hardeners (H-1), (H-2), fungicides (F-1)
Was added and mixed to prepare a second layer coating solution.

Second layer (protective layer) Addition amount (g / m ² ) Gelatin 2.0 First layer (blue-sensitive layer) Gelatin 2.5 Blue-sensitive silver chlorobromide emulsion 0.26 Yellow coupler (Y-1) 0.69 Dye image stabilizer (ST -1) 0.26 (ST-2) 0.17 Stain inhibitor (HQ-1) 0.02 Support Polyethylene laminated paper However, the amount of silver halide emulsion is shown in terms of silver.

A blue-sensitive emulsion is prepared by a conventional method by preparing a silver chlorobromide emulsion having an average particle size of 0.70 μm and a silver bromide content of 90 mol%, and optimally increasing the temperature at 57 ° C. using 1.5 mg / mol AgX sodium thiosulfate. Feel,
The sensitizing dye (BS-1) was adjusted by adding 5 × 10 ^-4 mol / mol AgX and (STAB-1) as a stabilizer by adding 5 × 10 ^-4 mol / mol AgX. Each compound was added by dissolving in a high boiling point solvent in the same manner as in Example 1. The addition amount is 5 ×
10 ^-4 mol / mol AgX.

(Evaluation) After exposure by a conventional method, the following processing was performed, and the obtained yellow dye image was subjected to density measurement with a PDA-65 densitometer (manufactured by Konica Corporation).

Developing conditions Color development 38 ° C for 3 minutes and 30 seconds Bleaching and fixing 33 ° C for 1 minute and 30 seconds Washing process 25-30 ° C for 3 minutes Drying 75-80 ° C for about 2 minutes The results are shown in Table 2. In the table, the amounts of the compounds added to Samples 202 to 205 are the same as STAB-1 of Sample 202.

Processing solution composition (color developing solution) Benzyl alcohol 15 ml Ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide 0.7 g Sodium chloride 0.2 g Potassium carbonate 30.0 g Hydroxylamine sulfate 3.0 g Polyphosphoric acid (TPPS) 2.5 g 3-Methyl-4- Amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate 5.5 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Adjust the pH to 10.20.

(Bleaching-fixing solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid. Add water to bring the total volume to 1.

As is evident from Table 2, it is found that the compound of the present invention suppresses fog without lowering the sensitivity.

A blue-sensitive emulsion and a silver chlorobromide emulsion having an average particle size of 0.7 μm and a silver bromide content of 0.5 mol% were prepared, and sodium thiosulfate 0.8 m
g / mol AgX, chloroauric acid 0.5 mg / mol AgX, optimally sensitized at 50 ° C., sensitizing dye BS-14 × 10 ⁻⁴ mol / mol AgX, sensitizing dye BS-21 × 10 ^-4 mol / mol AgX and ST as stabilizer
AB-2 3 × 10 ^-4 mol / mol AgX, STAB-3 3 × 10 ^-4
It was adjusted by adding mol / mol AgX. These were coated and dried in the same manner as above and evaluated, and the effects of the present invention were obtained.

Example 3 The results are shown in Table 3, which are the same as those of the silver halide emulsion used in Example 2, except that only the compounds are changed as shown in Table 3 and samples are 301 to 306.

As is evident from the results in Table 3, the compounds of the present invention increase gamma and sensitivity without increasing fog.

Example 4 A multilayer color photographic element sample was prepared by sequentially forming layers having the following compositions on a film support from the support side.
No.401 was created. However, the amount of application was shown by weight per 1 m ² unless otherwise specified.

First layer: Antihalation layer Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Colored coupler (CC-1) 0.02 g High boiling solvent (Oil-1) 0.20 g High boiling solvent (Oil-2) 0.20 g Gelatin 1.6g Second layer; Intermediate layer Gelatin 1.3g Third layer; Low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (Em-1) 0.4g Silver iodobromide emulsion (Em-2) 0.4g Sensitizing dye (S-1) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ^-4 (Mol / silver 1 mol) Cyan coupler (C-1) 0.50 g Cyan coupler (C-2) 0.13 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006 g DIR compound (D-1) 0.01g Additive (SC-1) 0.003g High boiling solvent (Oil-1) 0.55g Gelatin 1.0g 4th layer; High sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (Em-3) 0.9g Sensitizing dye (S-1) 1.7 × 10 ^{− 4} (mol / silver 1 mol) Sensitizing dye (S-2) 1.6 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.1 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High boiling solvent (Oil-1) 0.25 g Additive (SC-1) 0.003 g Gelatin 1.0 g Fifth Layer: Intermediate layer Gelatin 0.8 g Sixth layer: Low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (Em-1) 0.6 g Silver iodobromide emulsion (Em-2) 0.4 g Sensitizing dye (S-4) 6.7 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-5) 0.8 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.17 g Magenta coupler (M-2) 0.43 g Colored Magenta coupler (CM-1) 0.10 g DIR compound (D-3) 0.02 g High boiling solvent (Oil-2) 0.7 g Additive (SC-1) 0.003 g Gelatin 1.0 g 7th layer; high-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (Em 3) 0.9 g Sensitizing dye (S-6) 1.1 × 10 -4 ( mol / mole of silver) Sensitizing dye (S-7) 2.0 × 10 -4 ( mol / mole of silver) Sensitizing dye (S- 8) 0.3 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g High boiling solvent (Oil-2) 0.35 g Additive (SC-1) 0.003 g Gelatin 1.0 g Eighth layer: Yellow filter layer Yellow colloidal silver 0.1 g Additive (HS-1) 0.07 g Additive (HS-2) 0.07 g Additive (SC-2) 0.12 g High boiling solvent (Oil-2) 0.15 g Gelatin 1.0 g Ninth layer; low-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (Em-1) 0.25 g Iodobromide Silver emulsion (Em-2) 0.4 g Sensitizing dye (S-9) 5.8 × 10 ^-4 (mole / silver 1 mol) Yellow coupler (Y-1) 0.6 g Yellow coupler (Y-2) 0.32 g DIR compound ( D-1) 0.003 g DIR compound (D-2) 0.006 g High boiling solvent (Oil-2) 0.18 g Additive (SC-1) 0.004 g Gelatin 1.3 g 10th layer; high-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (Em- 4) 0.5 g sensitizing dye (S-10) 3 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-11) 1.2 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 g Yellow coupler (Y-2) 0.10 g DIR compound (D-4) 0.002 g High boiling solvent (Oil-2) 0.05 g Additive (SC-1) 0.002 g Gelatin 1.1 g 11th layer; 1st protection Layer Silver iodobromide emulsion (Em-5) 0.3 g UV absorber (UV-1) 0.07 g UV absorber (UV-2) 0.10 g High boiling solvent (Oil-1) 0.07 g High boiling solvent (Oil-3) 0.07 g Formalin Scavenger (HS-1) 0.2 g Formalin Scavenger (HS-2) 0.1 g Gelatin 0.8 g 12th layer; 2nd protective layer Surfactant (SU-1) 0.004 g Surfactant (SU-2) 0.02g Alkaline soluble polymer 0.13 g Polymethyl methacrylate (average particle size 3 μm) 0.02 g Cyan dye (No. 9) 0.005 g Magenta dye (No. 7) 0.01 g Slip agent (WAX-1) 0.04 g Gelatin 0.5 g In addition to the above composition, coating aid SU-4 and dispersing aid SU-
3. Stabilizer ST-1, preservative DI-1, antifoggant AF-1,
AF-2 was added as needed.

The emulsions used in the above samples are as follows.
Em-1 to Em-4 are core / shell type monodisperse emulsions having an internal high iodine degree.

Em-1: average AgI content 7.5 mol%, octahedron 0.55 μm Em-2: average AgI content 2.5 mol%, octahedron 0.36 μm Em-3: average AgI content 8.0 mol%, octahedron 0.84 μm Em− 4: Average AgI content of 8.5 mol%, octahedral 0.95 μm Em-5: Average AgI content of 2.0 mol%, octahedral 0.08 μm Each of the above emulsions is added after being chemically and spectrally sensitized according to the purpose. Was.

 The compounds used in Sample No. 201 are shown below.

Colored cyan coupler C of the third and fourth layers of sample 401
A sample 402 was prepared in exactly the same manner except that C-1 was changed to the compound 2 of the present invention.

Samples 401 and 402 were exposed to sensitometry exposure according to a conventional method, and were subjected to a development process described later. The density of the treated sample was measured with green light to determine the sensitivity. The sample containing the compound of the present invention showed a 10% increase in sensitivity as compared with the sample containing the comparative colored coupler, and the mask characteristics were good.

Next, Sample 403 was prepared in exactly the same manner as Sample 401 except that the magenta coupler M-1 in the sixth and seventh layers was changed to the compound 28 of the present invention. The sixth layer and the seventh layer
The magenta coupler M-1 in the layer was changed to the compound 28 of the present invention, and the addition amounts of the HS-1 and HS-2 in the eighth and eleventh layers were each reduced by half in the same manner as in the sample 401. Sample 404 was produced. After subjecting samples 401, 403 and 404 to wedge exposure according to a conventional method, the following treatments were performed.

Treatment 1 A 300% aqueous 35% glycerin solution is placed on the bottom of a closed container, and the sample is kept at 30 ° C. for 3 days in air kept in equilibrium with this.

Treatment 2 3% per 300ml of 35% glycerin aqueous solution
A solution containing 6 ml of a 5% aqueous formaldehyde solution is placed, and the sample is kept at 30 ° C. for 3 days in air kept in equilibrium therewith.

The samples that had been subjected to the above two types of processing were subjected to the development processing described below. For each sample, determine the magenta color density by Konica Corporation.
Was measured from green light using an optical densitometer PDA-65, and a sample subjected to treatment 1 was compared with a sample subjected to treatment 2.
Samples 403 and 404 containing the compounds of the present invention correspond to sample 401
The change in the processing 1 and the processing 2 was smaller than that of the processing.

 The development processing was performed in the following processing steps.

Processing step (38 ° C) Color development 3 minutes 10 seconds Bleaching 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Used in each processing step The composition of the processing solution is as follows.

<Color developing solution> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 (PH = 10.1) <Bleaching solution> Iron ammonium salt of ethylenediaminetetraacetic acid 100.0 g Diammonium salt of ethylenediaminetetraacetic acid 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Add water to 1 to make pH = 6.0 using aqueous ammonia.
Adjust to

<Fixing solution> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1 and adjust the pH to 6.0 using acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica) 7.5 ml Add water to make 1.

Claims (1)

(57) [Claims] 1. A silver halide photographic material comprising a compound represented by the following general formula [I]. General formula [I] [In the formula, Z is a nonmetallic atom group necessary for forming a 5- to 7-membered ring containing at least one of an oxygen atom, a sulfur atom, and a nitrogen atom, or a nonmetallic group necessary for forming indanone. Represents an atomic group. R represents a substituent. Time represents a timing group, and PUG represents a useful group for photography. n
Represents an integer of 0 to 2. ]