JPH04177245A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To ensure a silver halide photosensitive material to be completely stable in a storage condition, and enable a useful group for a photograph to be quickly released even during processing in a solution having a low pH value by causing the material to contain a specified compound. CONSTITUTION:A compound expressed by the formula I is contained in at least one of silver halide emulsifier layers. In the formula, R1 and R2 stand for an alkyl group, an aryl group, an alkenyl group and a cycloalkyl group. R3 stands for a hydrogen atom or a substituent, EWG for an electron attractive group, Time for a timing group, PUG for a useful group for a photograph, and (n) for 0 or 1. The addition of the compound to a photosensitive material depends upon the type of the material, PUG or the like, but is generally 10<-9> to 10mol per mol of silver halide. According to this construction, the photosensitive material becomes completely stable during storage, and can quickly release a useful group for a photograph even during processing in a solution having a low pH value.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photographic material, and more particularly to a photographic material containing a blocked precursor compound that releases a photographically useful group during a photoprocessing process.

[Background of the invention]

By incorporating photographically useful groups in a blocked form into photosensitive materials, various effects can be exerted. When the photographically useful group is a coupler, storage stability can be improved by converting it into a precursor. When the photographically useful group is a dye, by blocking the chromophore or auxochrome of the dye, it can be temporarily made colorless or short-wavelength, allowing silver halide photography to be exposed to the corresponding photosensitive spectral region. Even if the material coexists with the material in the same layer, it is possible to prevent the sensitivity from decreasing due to the filter effect.

In addition, if the photographic useful group is an irradiation compound-preventing dye, it is desirable that it flow out from the light-sensitive material during processing.
It usually has a large diffusivity.

Therefore, when added to a photosensitive material, it is difficult to contain it only in a specific layer, and a large decrease in sensitivity is unavoidable. In this way, by blocking a diffusible photographically useful group with a group having anti-diffusion ability, it is possible to immobilize it only in a specific layer.

If the photographic useful group is a development inhibitor or antifoggant, by blocking it, the effect on silver chloride during storage can be suppressed, and development can be suppressed without reducing sensitivity. Fog can be prevented.

When the photographically useful group is a component in the processing solution, the composition of the processing solution can be simplified by forming it into blocks and incorporating it into the light-sensitive material.

Precursor technology, which blocks photographically useful groups and incorporates them into light-sensitive materials and releases them during photographic processing, is expected to be extremely effective, and is stable and stable during storage. It is necessary to release photographically useful groups quickly during processing, and it is not easy to satisfy both requirements.

Several types of blocking groups for such precursor compounds are already known. Typical examples include, for example, Special Publication No. 54-39727 and No. 63-6166.
No. 493, No. 63-616563, JP-A-58-20
A blocking group that releases a photographically useful group with the production of quinone methide and similar compounds through electron transfer, as described in No. 9736, and a blocking group that releases a photographically useful group through the production of quinone methide and similar compounds, as described in JP-A No. 55-53330; Blocking group releasing useful group JP-A No. 57-76541, No. 57-
Block groups utilizing 5- or 6-membered ring cleavage as described in Japanese Patent Publications No. 135949 and No. 57-179842, Japanese Patent Publications Nos. 54-39723, 55-96963, and 5
There are blocking groups using the reverse Michael reaction described in No. 5-34927.

However, these blocking groups have poor storage stability or slow release rate, and their performance is far from practical in conventional photographic materials with low fi/pH values.

On the other hand, the blocking group described in JP-A No. 60-35729 can release useful groups for photography not only by hydroxyl ions in the processing solution but also by hydroxylamine, sulfite ions, etc., so it is stable during storage. It is somewhat advantageous in terms of both performance and release properties during processing.

In addition, the blocking group described in European Patent Publication No. 394.974 is such that almost no photographic useful groups are released with hydroxyl ions, and dinucleophores such as hydroxylamine are used as blocking groups.
It has a considerable advantage over previous blocking groups in that it releases photographically useful groups only through ile. However, these blocking groups are still insufficient in achieving both stability during storage and release during processing, and further improvements are desired.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material containing a precursor compound that is completely stable under storage conditions and that rapidly releases photographically useful groups even in a low pH processing solution during processing. Our goal is to provide the following.

[Structure of the invention]

The above object of the present invention is achieved by a silver halide photographic material characterized by containing a compound represented by the general formula CI).

General formula I
．． represents an electron-withdrawing group of 3 or more, Ti-e represents a timing group, PUG represents a photographically useful group, n is O
or represents l. 1. The present invention will be explained in more detail below.

The alkyl groups represented by RI and R2 in general formula [11] preferably have 1 to 32 carbon atoms, and may be linear or branched, such as methyl, n-octyl, 2-ethylhexyl, etc. Can be mentioned.

Examples of the aryl group include phenyl group and naphthyl group.

The alkenyl group preferably has 2 to 32 carbon atoms, such as vinyl group, allyl group, 2-putenyl group, lO-
Examples include undecenyl group.

The cycloalkyl group has 3 to 12 carbon atoms, especially 5 to 7 carbon atoms.
Preferred examples include cyclopentyl group and cyclohexyl group.

The substituent represented by R3 in general formula [I] is not particularly limited, but typically includes multiple groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl. In addition, halogen atoms, cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, sulfonyloxy, aryloxy, heterocyclicoxy, siloxy, acyloxy, carbamoyloxy, Amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio,
thioureido, carboxy, hydroxy, mercapto,
Also included are polygroups such as nitro and sulfonic acid, as well as spiro compound residues, bridged hydrocarbon compound residues, and the like.

Among the substituents represented by R1, the alkyl group preferably has 1 to 32 carbon atoms, and may be linear or branched.

As the aryl group, a phenyl group is preferred.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group include the alkyl group and aryl group represented by R8 above.

The alkenyl group preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group has 3 to I2 carbon atoms, especially 5
-7 is preferred.

Sulfonyl groups include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alcoquinephosphonyl groups, aryloquinephosphonyl groups, and arylphosphonyl groups. Nyl group, etc.; Acyl group includes alkylcarbonyl group, arylcarbonyl group, etc.; carbamoyl group includes alkylcarbamoyl group, arylcarbamoyl group, etc.; sulfamoyl group includes alkylsulfamoyl group,
Arylsulfamoyl groups, etc.; Acyloxy groups include alkylcarbonyloxy groups, arylcarbonyloxy groups; Carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc. Examples of the sulfamoylamino group include an alkylsulfamoylamino group and an arylsulfamoylamino group; as the heterocyclic group, a 5- to 7-membered one is preferable;
This includes 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, l-pyrrolyl group, 1-tetrazolyl group, etc.; heterocyclic ox7 group includes those having a 5- to 7-membered heterocycle are preferred, such as 3.4.5.6-tetrahydropyranyl-2-oxy group, l-phenyltetrazole-5-
Oxy group, etc.; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2.4-cyphenoki7-1.3.5- Triazole-6 monothio group, etc.; Siloxy group includes triethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide group includes succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group etc.; as a spiro compound residue, spiro[3,3]hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2°2.1
] heptan-1-yl, tricyclo[3,3,1,1”
]]Decan-1-yl7,7-dimethyl-bicyclo[2
,2,1]butan-1-yl and the like.

The above group may further have a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue.

In general formula [I], the substituent represented by EWG is a substituent having a Hammett's substituent constant σp of 0.3 or more, and typically includes a cyano group, a nitro group, a sulfonyl group (for example, an octylsulfonyl group, phenylsulfonyl group, trifluoromethylsulfonyl group, pentafluorophenylsulfonyl group), β-carboxyvinyl group, sulfinyl group (e.g. t-butylsulfinyl group, tolylsulfinyl group, trifluoromethylsulfinyl group, pentafluorophenylsulfinyl group) ), β, β-dicyanovinyl group, halogenated alkyl group (e.g. trifluoromethyl group, perfluorooctyl group, ω-hydroperfluorododenyl group, etc.), formyl group, carboxyl group, carbonyl group (e.g. acetyl group, etc.) groups, pivaloyl groups, benzoyl groups, trifluoroacetyl groups, etc.), alkyl and aryloxycarbonyl groups (e.g. ethoxycarbonyl groups, phenoxycarbonyl groups, etc.), 1-tetrazolyl groups, 5-chloro-1-tetrazolyl groups, carbamoyl groups ( Examples include dodecylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (eg, trifluoromethylsulfamoyl group, phenylsulfamoyl group, ethylsulfamoyl group, etc.).

Preferred among these substituents are a cyano group, a sulfonyl group, and a sulfamoyl group.

The most preferred of these substituents is the cyano group.

Examples of the group represented by Time include (1) a group that causes a cleavage reaction using an electron transfer reaction along a conjugated system, and (2) a group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction. group, (3) a group that utilizes the cleavage reaction of hemiacetal, (4) a group that utilizes the cleavage reaction of iminoketal, (5)
) A group using an ester hydrolytic cleavage reaction can be mentioned.

Regarding the group (1), for example, JP-A-56-11494
No. 6, No. 57-154234, No. 57-188035
No. 58-98728, No. 58-160954,
5g-209736, 5g-209737, 58-209738, 5g-209739, 5
No. 8-209740, No. 62-86361 and No. 62
-87958, for the group (2), see, for example, JP-A No. 57-56837 and U.S. Pat. No. 4,248,962, and for the group (3), see, e.g.
No. 8, No. 60-249149, U.S. Patent No. 4.146.
No. 396, for the group (4), for example, U.S. Pat.
．． 546゜073, and regarding group (5), for example, West German Published Patent Application No. 2, 6
No. 26.315 describes this in detail.

Among the groups represented by Time, the following are preferred.

In the structural formula, Nel is and *2 is P
The site that binds to UG is shown.

b Ra represents a substituent, Rh and Rc represent 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; may form a fused ring. q represents 0, 1 or 2.

Examples of the substituent represented by Ra include a norogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, anilino group, an acylamino group, a ureido group, a cyano group, a nitro group, a sulfonamide group, and a sulfamoyl group. , carbamoyl group, aryl group, carboxyl group, sulfo group, cycloalkyl group, alkanesulfonyl group, arylsulfonyl group or acyl group,
These also include those having substituents.

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

PUG, which is a useful group for photography, includes, for example, antifoggants, development inhibitors, color and black and white developing agents, auxiliary developers, development accelerators, fogging agents, image layer forming couplers, competitive couplers, DIR couplers, and colored couplers. , colorless couplers, black couplers, dyes, dyes, bleach accelerators, bleach inhibitors, silver halide solvents, silver complex forming agents, fixing agents, hardening agents, DP' scavengers, image stabilizers, etc. . Specific examples of antifoggants and development inhibitors include benzotriazole compounds, benzimidazole compounds, mercaptoimidazole compounds, mercaptothiazole compounds, mercaptotetrazole compounds,
Examples include mercaptothiadiazole compounds, mercaptotriazole compounds, and mercaptooxadiazole compounds. Specific examples of the developing agent, auxiliary developer, and development accelerator include a hydroquinone compound, a catechol compound, an aminofuninol compound, a p-7 unilene diamine compound,
Examples include pyrazolidone compounds and ascorbic acid compounds.

Specific examples of fogging agents include hydrazine compounds, hydrazide compounds, and tetrazolium salts. Specific examples of image-forming couplers include benzoylacetanilide-based and pivaloylacetanilide-based yellow couplers, phenol-based, nuthol-based, imidazole-based, and pyrazoloazole-based cyan couplers, pyrazolone-based, indacylon-based, cyanoacetyl-based, and pyrazolone-based couplers. There are zoroazole magenta couplers, etc. Specific examples of DIR couplers include U.S. Pat. Nos. 3,227,554 and 3,384,6
No. 57, No. 3,615.506, No. 3,617.29
No. 1, No. 3,733.201, Special Publication No. 61-2773
No. 8, JP-A-56-114946, JP-A No. 57-1115
No. 36, No. 57-154234, No. 5g-16095
No. 4, No. 58-162949, No. 6G-185950
No. 61-233741, No. 57-151944, etc. Colored couplers include colored magenta couplers, colored cyan couplers, and the like. A typical example of a colorless coupler is a compound manufactured by Indanone. Specific examples of dyes include azo aromatic dyes, azomethine dyes, anthraquinone dyes, and indophenol dyes. Specific examples of dyes include azo dyes, azomethine dyes, azopyrazolone dyes, indoaniline dyes, indophenol dyes, anthraquinone dyes, triarylmethane dyes, alizarin dyes, quinoline dyes, oxonol dyes, phthalocyanine dyes, merocyanine dyes, and azomethine dyes. , styryl dye, etc. Specific examples of bleach accelerators include aminoethanethiol compounds, sulfoethanethiotb compounds, aminoethanethiocarbamate compounds, and carboxyethanethiol compounds.

Specific examples of silver halide solvents include thioether compounds, rhodanine compounds, hypo, methylene bissulfone compounds, and the like. Hypo is used as a fixing agent.

Preferred PUGs include development inhibitors, color and black-and-white developing agents, auxiliary developers, fogging agents, image-forming couplers, competitive couplers, DIR couplers, colored couplers, dyes, dyes, and bleach-accelerating exemplified compounds. Synthesis of Exemplified Compound 23) [Synthesis Route] (Intermediate 1) (Intermediate 2) Synthesis of Intermediate 2 1.13.0 g of the intermediate was dissolved in 40 mQ of CH3CN, 4.2 g of cyanoamide was added thereto, and the mixture was boiled and refluxed. The reaction was continued for 5 hours. After the reaction was completed, ethyl acetate and water were added and the organic layer was extracted, dried over anhydrous sodium sulfate, and the solvent ethyl acetate was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 105 g of Intermediate 2. The structure was confirmed by 'HNMRIRSMASS spectrum.

15.2 g of oxalyl chloride to 2.9.2 g of synthetic intermediate of Exemplified Compound 23
After adding 1 drop of triethylamine and stirring at room temperature for 24 hours, excess oxalyl chloride was distilled off under reduced pressure. (
Intermediate 2') Intermediate 3.17.0 g was dissolved in 200 ml of ethyl acetate, 3.9 g of anhydrous sodium acetate and 50 mff of water were added thereto, and the mixture was stirred under water cooling and brought to 5°C. 50ml ethyl acetate solution was added dropwise. After the addition was completed, the organic phase was stirred at room temperature for 3 hours, and the organic phase was separated into 3%
After washing with an aqueous sodium hydrogen carbonate solution, it was washed with water. After drying this organic phase over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 18.0 g of Exemplary Compound 23.

The structure was confirmed by IHNMRI R and MASS spectra.

The amount of the compound of the present invention to be added to the photosensitive material and P
Although it varies depending on the type of UG, silver halide 1
10-' to 10 mol per mol, preferably 10
-' to 1 mole.

The photosensitive material of the present invention can be applied to the following various types of photosensitive materials.

For example, it can be used for photosensitive materials such as color positive, color paper, color reversal, direct positive, color diffusion transfer, and heat development, but it is especially suitable for color photosensitive materials with multilayer structures. It's advantageous.

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

The silver halide grains used in silver halide emulsions may have a uniform silver halide composition distribution within the grain, or they may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain. good.

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

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone or in combination. Alternatively, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

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

The emulsion can be chemically sensitized by conventional methods, or optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other wood-philic colloid layers can be hardened, or can be hardened by containing a plasticizer or a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is generally used in the emulsion layer of color light-sensitive materials. Furthermore, by force/combination with a competing coupler and an oxidized form of a developing agent, which have the effect of color correction, a development accelerator, a bleach accelerator, a developer, a silver saponide solvent, a toning agent, a hardening agent, Compounds that release photographically useful 7-ragments such as fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

As the magenta dye-forming coupler, 5-pyrazolone couplers, pyrazoloazole couplers, virazolobennymidazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, etc. can be used.

- Phenol or naphthol couplers are generally used as 7-an dye-forming couplers.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an anti-halation layer, an anti-irradiation layer, and the like. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process.

A mitotic agent, a lubricant, an image stabilizer, a formalin scavenger, an ultraviolet absorber, a fluorescent brightener, a surfactant, a development accelerator, a development retardant, and a bleach enhancer can be added to the photosensitive material.

The support can be laminated with polyethylene, etc., second grade polyethylene terephthalate film, baryta paper,
Cellulose triacetate etc. can be used.

〔Example〕

Example I (Preparation of coating solution) 35 g of Seratin was mixed into 1. After dissolving Oa in water, a coating aid (Su-1) and a hardening agent (H-1) were added to prepare a coating solution.

(Dye Precursor Dispersion) 2.5×10-” moles of Comparative Compound (A) were mixed with 1.6 ml of high boiling point solvent (Oil-1) 12.6 ml of ethyl acetate (
2, and this solution was added to 44 g of a 10% gelatin aqueous solution containing a surfactant (S u-2) to emulsify and disperse.

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

(Preparation of Sample) Sample 101 was prepared by coating the above emulsion layer coating solution on a 100 μm polyethylene terephthalate film base subjected to latex undercoating described in JP-A-59-19941 and drying. The dye precursor (compound) loading was 3X 10-'mol/mZ.

(Processing) Each of these samples was processed with a developer having the following composition and a developer having the following composition except that only hydroxylamine sulfate was removed.

Development processing conditions Development processing 30 seconds 38°C Washing 30 seconds Drying 2 minutes 60~8
0°C [color developer 1 pure water 800mQ benzyl alcohol 15mQ triethanolamine lo, 0g hydroxyamine sulfate 2.0g potassium bromide
1.5g sodium chloride
1.0g potassium sulfite
2.0g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfur salt
4.5g potassium carbonate
32.0g 1-hydroxyethylidene-1,1-disulfonic acid (60% aqueous solution) 1.5ml
2Whitex B B (50% aqueous solution) (fluorescent brightener, manufactured by Sumima Kagaku Kogyo Co., Ltd.) Add pure water to make 1Q, and add 20% potassium hydroxide or 10% potassium hydroxide.
Adjust the pH to 10.1 with % dilute sulfuric acid.

(Evaluation) The presence or absence of residual color after treatment was evaluated as follows. The visible spectrum of each sample after treatment was measured, and the decolorization rate was determined from the difference between the absorbance at the absorption maximum (E2) and the following E1 using the following formula.

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

Similarly, samples were prepared by replacing the compound used in Sample 101 with the compounds shown in Table 1, and each of these samples was added to Sample 1.
It was set as 01-106.

Group 5 white [F] (Su -1) (S
u-2) Comparative Compound A Comparative Compound B Exemplified Compound 5 Exemplified Compound 6 Exemplified Compound 7 Exemplified Compound 8 Table 1 As is clear from Table=1, the compound of the present invention releases dye only in the presence of hydroxylamine. Recognize.

This means that the drawback of conventional precursors, which release dyes when attacked by hydroxyl ions during storage before processing, has been overcome. Furthermore, although the comparative compound (B) does indeed suppress dye release in the system without hydroxylamine, the dye release in the presence of hydroxylamine is insufficient.

In comparison, the compounds of the present invention both show sufficient values, indicating that the objects of the present invention have been fully achieved.

Example 2 On a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the other side, each layer having the composition shown below was coated on the side of the polyethylene layer containing titanium oxide. A silver halide color photographic material was prepared. The coating solution was prepared as follows.

(First layer coating solution) Yellow coupler (Y-1) 26.7g, dye image stabilizer (ST-1) 1O,og, dye image stabilizer (ST-2) 647g, additive (HQ-1) ) 0.
Add and dissolve ethyl acetate (iQmQ) to 67 g and 6.67 g of high boiling point organic solvent (DNP), and dissolve this solution to 20%
A yellow coupler dispersion was prepared by emulsifying and dispersing 220 ml of a 10% gelatin aqueous solution containing 7 ml of surfactant (SU-1) using an ultrasonic homogenizer.

This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.

(Second layer coating solution) Surfactants (Su-2) and (Su-3) are added to gelatin aqueous solution.
), hardeners (H-1), (H-2), antifungal agents (F-1
) were added and mixed to prepare a second layer coating solution.

2nd layer (protective layer) addition amount (g/m2)
Gelatin 2.0 1st 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.

The blue-sensitive emulsion was prepared using a conventional method to prepare a silver chlorobromide emulsion with an average grain size of 0.70 μm and a silver bromide content of 90 mol%, and was optimally sensitized at 57°C using 15 mg of sodium thiosulfate and 1 mol of AgX. and sensitizing dye (B s −, l ) 5 x
lO-'mol 1 mol AgX and as stabilizer (STAB
-1) was prepared by adding 5XlO-'mol 1 mol AgX. Further, each compound was added by dissolving it in a high boiling point solvent in the same manner as in Example 1. Addition amount is 5X 10
-' mol 1 mol AgX.

(ST-1) Sun (DNP) dinonyl 7-thalerate (SU-1) (SU-2) C (CH2SO2CH=CH2) 4 (F-1) Mixture of the following three components Component A: Component B: Component C = 50 : 46 : 4 (molar ratio) (STAB-1) Comparative compound C Exemplary compound 11 (Evaluation) After exposure by a conventional method, the yellow dye image obtained by performing the following processing was measured using a PDA-65 densitometer (Konica (manufactured by Co., Ltd.) to measure the concentration.

Development conditions Color development 38°C 3 minutes 30 seconds Bleach fixing 33°C 1 minute 30 seconds Washing process
Drying at 25-30°C for 3 minutes. Drying at 75-80°C for about 2 minutes. The results are shown in Table 2. The amounts of compounds added in Samples 202 to 205 in the table are as follows: Sample 2
It is the same amount as 5TAB-1 of 02.

Processing solution composition (color developer) Benzyl alcohol 15mQ ethylene glycol l 5m12 Potassium sulfite 2.0g Potassium bromide
0.7g sodium chloride
0.2g potassium carbonate 3
0, 0g hydroxylamine sulfate 3.0
g Polyphosphoric acid (TPPS) 2.
5g3-Methyl-4-amino-N-ethyl-N-(β-
Methanesulfonamidoethyl) -Aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water to make total IQ and adjust pH to 10,20 do.

(Bleach-fix solution) 1g ethylenediaminetetraacetic acid 60g 2-iron ammonium dihydrate 3g ammonium thiosulfate (
70% solution) 100mQ sub-Wt ammonium (
40% solution) 27.5m0° Adjusted to pH 7.1 with potassium carbonate or glacial acetic acid, Table 2 As is clear from Table 2, it can be seen that the compound of the present invention suppresses fog without reducing sensitivity. .

A blue-sensitive emulsion with an average grain size of 0.7μ11 and a silver bromide content of 0.
A 5 mol % silver chlorobromide emulsion was prepared and optimally sensitized at 50°C using sodium thiosulfate 0.811 g 1 mol Ag
-14×1O-4 mol 1 mol Agx1 Sensitizing dye B5-2
1X10-'mol 1 mol AgX and 5TA as stabilizer
B-2 was prepared by adding 3X IQ-4 mol 1 mol 1 1 O-4 mol 1 mol AgX. When these were coated and dried in the same manner as before and evaluated, the effects of the present invention were obtained.

(STAB-2) (STAB-3) Example 3 Samples were prepared using the same silver halide emulsion as used in Example 2, except that the compounds were changed as shown in Table 2.
Table 3 shows the results of 6.

As is clear from the results in Table 3, the compounds of the present invention increase comma sensitivity without increasing fog.

Comparative Compound E Comparative Compound F Exemplified Compound 19 Exemplified Compound 16 Example 4 On a film support, each layer having the composition shown below was sequentially formed from the support side, and multilayer color photographic element sample N
O. 401 was created. However, unless otherwise noted,
The amount of coating is expressed in weight per square meter.

1st layer; antihalation layer black colloidal silver 0.15gUV
Absorbent (UV-1) 0.20g Colored coupler (CC-1) 0.02
g High boiling point solvent (O IQ-1)
0.20g// (O 1I2- 2 )
0.20g gelatin
1.6g 2nd layer; Intermediate layer gelatin 1.3g 3rd layer: Low sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (Em-1) 0.4gt
t (Em-2) 0.4g Sensitizing dye (S-1') 3.2X 10-' (mol/silver 1 mol) // (S-2) 3.2xlO-'
(tt) // (S-3)0.2
X10-'(//) uncoupler (C-1
) 0.50g” (C-2)
0.13g colored cyan coupler (
CC-1) 0.07gDIR compound (D-1)
0.006gDIR compound (D-2)
0.01g additive (SC-1)
0.003g high boiling point solvent (OiJ-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) 1.7X10-' (mol/silver 1 mol)〃 (S- 2) 1.6XlO-'()〃(S-3)
0. lX10-'() Cyan coupler (C-2) 0.23g
Colored cyan coupler (CC-1) 0.03gD
IR compound (D-2) 0.02g High boiling point tX (Oi/ -1) 0.25
g additive (SC-1) 0.003
g Gelatin 1.0g 5th
Layer: Middle layer' Seratin 0.8g
6th layer: Low sensitivity green sensitive emulsion layer Silver iodobromide emulsion (Em-1) 0.6g1
/ (Em-2) 0.4g sensitizing dye (s -4) 6.7x 1O-4 (mol/silver 1 mol) tt (S-5) 0.8xlO (/l
) Magenta coupler (M-1) O, 17
g// (M-2) 0.43g colored magenta coupler (CM-1) 0.10gD
IR compound (D-3) 0.02g High boiling point solvent (Oi12-2) 0.7g
Additive (S C-1) 0.003
g Seratin l・0g No. 7
Layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (Em-3) 0.9g Sensitizing dye (S-6)1. lX10 (mol/1 mole of silver)/
/ (s-7)2.0xlO-'(// )
tt (s-8)0.3xlO-'(//
) Magenta coupler (M-1) 0.30
g1l (M-2)
0.13g colored magenta coupler (CM-1)
0.04gDIR compound (D-3)
0.004g high boiling point solvent (Oi12-2)
0.35g additive (SC-1)
0.003g gelatin
l・0g 8th layer: Yellow filter layer Yellow colloidal silver 0.1g Additive (HS-1), 0.07g//
(HS-2) 0.07g/
/ (SC-2) O, 12g high boiling point solvent (Oi (22) 0.15g gelatin 1.0g 9th layer;
Low-speed blue-sensitive emulsion layer Silver iodobromide emulsion (Em -1) 0.25
g// (Em-2) 0.4g
Sensitizing dye (s-9) 5.8x lo-'('mol/
1 mole of silver) Yellow coupler (Y-1)
0.6g// (Y-2) 0.3
2gDIR compound (D-1) 0.0
03gy (D2)
0-006g high boiling point solvent (Oif2-
2) 0.18g additive (S C
-1) 0.004g Seratin
1.3g 1st O layer; high sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (Em-4) 0.5g sensitizing dye (s-10) 3x 1O-4 (mol/silver 1
mole) N (S -11) 1.2X 10-'(
// ) Yellow coupler (Y-1)
O, 18gtt (Y-2)
0. lQgDIR compound (D-4)
0.002g high boiling point solvent (Oi12-2)
0゜05g additive (SC-1)
0.002g gelatin
l・1g 11th layer; 1st protective layer silver iodobromide emulsion (Em-5) 0.3gU
V absorber (UV-1) 0.07g//
(UV-2) 0.10g High boiling point solvent (Oiff-1) 0.07g
// (Oi(2-3) 0.07
g Formalin scavenger (HS-1) 0.2
gtt (H52) O, 1g Seratin 0.8g 12th layer; 2nd protective layer surfactant (SU-1) 0.00
4g// (SU-2) 0.02
g Alkali-soluble matting agent (average particle size 2 μm) 0.13 g Polymethyl methacrylate (average particle size 3 μm) 0.02 g Cyan dye (No. 9) 0.005 g
Magenta dye (No. 7) O,
Olg slip agent (WAX-1) 0.
04g gelatin 0.5g
In addition to the above composition, coating aid SU-4 and dispersion aid 5U are also used.
-3, stabilizer ST-1, preservative DI-i, and antifoggants AF-1 and AF-2 may be added as appropriate.

The emulsions used in the above samples were as follows.

Em-1 to Em-4 are all core/fel type monodispersed emulsions with high internal iodine content.

Em-1: average Agl content 7.5 mol%, octahedron 0.
55 μmEm-2: average AgI content 2.5 mol%, 8
Face piece 0.3677 mEm-3: Average Agl content 8.
0 mol%, octahedron 0.84. umEm-4: Average Ag+
Content 8.5 mol%, octahedron 0.95. u mEm-5
: Average Agl content 2.0 mol%, octahedron 0.08 μm
Each of the above emulsions was added after being chemically sensitized and spectrally sensitized depending on the purpose.

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

(S-1) (S-2) (S-3) (S-4) (S-5) (S-6) (CH2)ssO3” (CHzJsS
U3H”N(1;2B5]3(S-7) (S-8) (S-9) (S-10) (S-11) c-2 M-1 l C!H.

Sample 402 was prepared in the same manner as above, except that Compound 23 of the present invention was used as the colored cyan coupler CC-1 in the third and fourth layers of WAX-1 AF-IAF-2 mixture sample 401.

Samples 401 and 402 were exposed to light for sensitometry according to a conventional method, and were subjected to the development treatment described below.

The density of the treated sample was measured using green light to determine the sensitivity. The sample containing the compound of the present invention showed a 10% increase in sensitivity compared to the comparative sample containing a colored coupler, and had good mask characteristics.

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 compound 29 of the present invention. Also, the sixth sample of sample 401
Sample 401 except that the magenta coupler M-1 in the layer and the seventh layer was changed to Compound 29 of the present invention, and the amounts of H5-1 and H5-2 added in the eighth and eleventh layers were each reduced by half. Sample 404 was prepared in the same manner as above. Sample 401
．． After applying wedge exposure to samples 403 and 404 according to a conventional method, the following treatments were performed on each sample.

Treatment 1: Add 300 mQ of 35% glycerin aqueous solution to the bottom of a sealed container.
The samples are kept at 30° C. for 3 days in air equilibrated with this.

Treatment 2: Add 300mff of 35% glycerin aqueous solution to the bottom of a sealed container.
A solution containing 6 ml (l) of a 35% formaldehyde aqueous solution was placed and kept in equilibrium with the sample.The sample was kept in air at 30°C for 3 days.

The samples subjected to the two types of treatments described above were subjected to the development treatment described below. The magenta color density of each sample was measured under green light using an optical densitometer PDA-65 manufactured by Konica Corp., and the samples subjected to treatment 1 and the samples subjected to treatment 2 were compared. Samples 403 and 40 containing compounds of the invention
Compared to sample 401, sample No. 4 had smaller changes between treatment 1 and treatment 2.

The development process was performed using the following processing steps.

Processing process (38°C) Color development 3 minutes 10 seconds Bleaching 6 minutes 30 seconds Water
Wash for 3 minutes and 15 seconds
Arrived 6 minutes 30 seconds Washed with water Stabilized for 3 minutes 15 seconds
Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

<Color developer> 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl) aniline sulfate 4, 75g anhydrous sodium sulfite 4.25g hydroquineluamine 1/2 sulfate 2 .0g anhydrous potassium carbonate 37, 5g sodium bromide 1.3g nitrilotriacetic acid trisodium salt (l hydrate) 2.5g
Potassium hydroxide 1.0g Add water to make 112. (pH = 10.1) Bleaching solution> Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Water Vinegar
Acid 10. Or
Add nQ water to set IQ, and use ammonia water to adjust pH=
Adjust to 6.0.

<Fixer> Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Water was added to make IQ, and the pH was adjusted to 6.0 using acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5ml
2 Konidax (manufactured by Konica) 7.5mQ
Add water to make 112.

Claims (1)

[Scope of Claims] A silver halide photographic material containing a compound represented by the general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 are alkyl groups, aryl groups,
represents an alkenyl group or a cycloalkyl group, R_3 represents a hydrogen atom or a substituent, and EWG represents Hammett's σp
represents an electron-withdrawing group of 0.3 or more, Time represents a timing group, PUG represents a photographically useful group, and n
represents 0 or 1. ]