JPH04330438A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To make compatible both of stability at the time of storage and reliesability of a photographic useful group at the time of processing by incorporating a specified compound. CONSTITUTION:The compound to be added is represented by formula I in which Z is a nonmetallic atomic group necessary for forming a 5-7 membered ring containing at least one of O, S, and N atoms or an alicyclic hydrocarbon ring or cyclopentyl group; R is a substituent; Time is a timing group; PUG is a photographic useful group; and (n) is 0, 1, or 2. As the timing group Time, a group for causing cleavage reaction by utilizing electron transfer reaction along conjugated series, a group for causing cleavage reaction by utilizing intramolecular nucleophilic substitution reaction, groups utilizing cleavage reaction of hemiacetal or iminoketal and hydrolytic cleavage reaction of esters are enumerated.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to photographic materials, and more particularly to photographic materials containing blocked precursor compounds that release photographically useful groups during photographic processing.

[Background of the invention]

By incorporating a photographically useful group in a blocked form into a photographic material, 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 to create a silver halide photographic light-sensitive material with the corresponding photosensitive spectral region. It is possible to prevent a decrease in sensitivity due to the filter effect even if the filter is present in the same layer as the filter.

In addition, if the photographic useful group is an irradiation-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, blocking it can suppress the effect on silver halide during storage, inhibit development without reducing sensitivity, and prevent fogging. It 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 the photographic processing process, is expected to be extremely effective, but it is not 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 being practical in conventional photographic materials where the processing pH is low.

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 ion, 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 objects of the present invention have been achieved by a silver halide photographic material characterized by containing a compound represented by the following general formula [I].

General formula [I] In the formula, Z is a group of nonmetallic atoms necessary to form a 5- to 7-membered ring containing at least one of an oxygen atom, a sulfur atom, and a nitrogen atom, and an aliphatic cyclic group having an oxo group. Represents a group of nonmetallic atoms necessary to form a hydrocarbon or cyclopentyl. R represents a substituent.

Time represents a timing group and PUG represents a photographically useful group. n represents 0-2.

The present invention will be explained in detail below. In general formula [I],
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,
No. 58-209736, No. 58-209737, No. 58-209738, No. 58-209739, No. 5
No. 8-209740, No. 62-86361 and No. 62
-87958, for the group (2), see, for example, JP-A No. 57-56837 and US 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*2
indicates a site that binds to PUG.

Ra represents a substituent, Rb 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, and Ra may be condensed with each other. It may form a ring. q represents 0, 1 or 2.

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

Examples of the substituent represented by Rb and Rc 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-forming couplers, competitive couplers, DIR couplers, colored couplers, and non-fogging agents. Color forming couplers, black couplers, pigments, dyes, bleach accelerators, bleach inhibitors, silver halide solvents, silver complex forming agents, fixing agents, hardening agents, DP' scavengers, image stabilizers and the like can be mentioned. Specific examples of antifoggants and development inhibitors include benzotriazole compounds, benzimidazole compounds, mercaptoimidazole compounds, mercaptothiazole compounds, mercaptotetrazole compounds, mercaptothiadiazole compounds, mercaptotriazole compounds, mercaptooxadiazole compounds, and the like. Specific examples of the developing agent, auxiliary developer, and development accelerator include hydroquinone compounds, catechol compounds, aminophenol compounds, p-phenylenediamine compounds, 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 and pivaloylacetanilide yellow couplers, phenolic, naphthol, imidazole and pyrazoloazole cyan couplers, pyrazolone, indazolone, cyanoacetyl, and pyrazoloazole. There are magenta couplers, etc. Specific examples of DIR couplers include U.S. Pat. Nos. 3,227,554 and 3,384,657.
No. 3,615,506, No. 3,617,291, No. 3,733,201, JP 61-27738, JP 56-114
No. 946, No. 57-111536, No. 57-1542
No. 34, No. 58-160954, No. 58-16294
No. 9, No. 60-185950, 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 an indanone type compound. Specific examples of dyes include azo aromatic dyes, azomethine dyes, anthraquinone dyes,
There are indophenol pigments, etc. Specific examples of dyes include azo dyes, azomethine dyes, azopyrazolone dyes, indoaniline dyes, indophenol dyes, anthraquinone dyes, triarylmethane dyes, alizarin dyes,
Examples include quinoline dyes, oxonol dyes, phthalocyanine dyes, merocyanine dyes, arylidene dyes, and styryl dyes. Specific examples of bleach accelerators include aminoethanethiol compounds, sulfoethanethiol 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. PUG
Preferred are development inhibitors, color and black and white developing agents, auxiliary developers, fogging agents, imaging couplers, competitive couplers, DIR couplers, colored couplers,
Pigments, dyes, and bleach accelerators.

In general formula [I], the substituent represented by R is a hydrogen atom, a halogen atom, nitro, cyano, alkyl,
alkenyl, cycloalkyl, aryl, alkoxy,
Represents groups such as aryloxy, alkoxycarbonyl, aryloxycarbonyl, alkylthio, arylthio, heterocycle, alkylamino, arylamino, amide, sulfonamide, ureido, acyl, and aroyl.

Among these, preferred are alkyl and aryl.

Examples of the 5- to 7-membered ring containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom represented by Z include tetrahydrofuryl, pyrrolidinyl, nil, pyrrolinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperidinyl, piperazinyl, chromanyl, Examples include isochromanyl, morpholinyl, indolinyl, isoindolinyl, thiomorpholinyl, dioxanyl, tetrahydropyranyl, pentamethylene sulfide, pentamethylene sulfone, and tetrahydrothienyl groups. Examples of the aliphatic cyclic hydrocarbon having an oxo group include cyclopentanonyl, cyclohexanonyl, and cycloheptanonyl groups.

Preferred as Z are tetrahydrofuryl, tetrahydropyranyl, cyclohexanonyl, and pentamethylenesulfonyl groups.

Typical exemplified compounds of general formula I according to the present invention are shown below, but the present invention is not limited thereto.

Typical synthesis examples of the present invention are shown below.

Synthesis Example (Synthesis of Exemplified Compound 4) 17.29 was dissolved in 100 cc of chloroform, 12 g of thionyl chloride was added, and the mixture was heated under reflux for 3 hours. Further distillation under reduced pressure was performed, and the resulting residue contained 150% ethyl acetate.
cc was added, and 19.39 was added. Dimethylaniline was added to this at room temperature over 1 hour, and the mixture was stirred at 50 to 60°C for 2 hours. After cooling, the mixture was washed with water, ethyl acetate was removed under reduced pressure, and purified by column chromatography (SiO2) to obtain 28.39 pieces of ■. Add acetone 200 to this
cc, (17 g) was added, and the mixture was heated under reflux for 2 hours. After acetone was removed under reduced pressure, 200 cc of ethyl acetate was added, washed with water, and ethyl acetate was removed under reduced pressure. The obtained residue was purified by column chromatography (SiO2) to obtain 35.6 g of the target compound.

Identification was performed using NMR spectrum, MS spectrum, IR spectrum, and MS spectrum, and it was confirmed that it was Exemplary Compound 3.

Other compounds of the present invention can also be synthesized using similar synthetic methods.

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
-5 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 in photosensitive materials such as color positive, color negative, 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 such that the latent image is mainly formed on the surface, or may be such that the 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. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be 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 hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

Coupler is generally used in the emulsion layer of color light-sensitive materials. Furthermore, by coupling with a competing coupler having a color correction effect and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, Compounds that release photographically useful fragments such as 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, pyrazolobenzimidazole couplers, open-chain acylacetonitrile couplers, indazolone couplers, etc. can be used.

Phenol or naphthol couplers are commonly used as cyan dye-forming couplers.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layers may contain dyes that are leached from the light-sensitive material or bleached during the development process.

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

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

〔Example〕

The present invention will be explained below with reference to Examples.

Example 1 (Preparation of coating liquid) After dissolving 35 g of gelatin in 1.0 ml of water, a coating aid (Su-1) and a hardening agent (H-1) were added to prepare a coating liquid.

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

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) The above emulsion layer coating solution was applied onto a 100 μm polyethylene terephthalate film base subjected to latex undercoating described in JP-A-59-19941, and dried to prepare Sample 301. The dye precursor (compound) loading was 3 x 10-4 mol/m2.

(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 [color developer] Pure water 800m ■ Benzyl alcohol 15m ■ Triethanolamine 10.0g 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 sulfate 4.5g Potassium carbonate 32.0g 1-hydroxyethylidene-1,1-disulfonic acid (60% aqueous solution) 1.5m Whit
ex 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 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.

(E1 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.
02 to 106.

Comparative Compound A Comparative Compound B As is clear from Table 1, the compounds of the present invention release dye only in the presence of hydroxylamine.

This means that the drawback of conventional precursors, which release dyes due to attack by hydroxyl ions during storage before processing, has been improved. 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) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST
-2) 60ml of ethyl acetate was added to 6.67g of additive (HQ-1), 0.67g of additive (HQ-1), and 6.67g of high boiling point organic solvent (DNP) and dissolved, and this solution was mixed with 20% surfactant (
SU-1) 10% gelatin aqueous solution containing 7 m■22
A yellow coupler dispersion was prepared by emulsifying and dispersing the mixture 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) Surfactant (SU-2) (SU-3) in gelatin aqueous solution
A second layer coating solution was prepared by adding and mixing hardeners (H-1), (H-2), and fungicide (F-1).

2nd layer (protective layer) Added 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 laminate paper However, the amount of silver halide emulsion is shown in terms of silver.

A blue-sensitive emulsion was prepared by 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 heated to an optimum temperature of 57°C using sodium thiosulfate at 1.5 mg/mol AgX. sensitized with sensitizing dye (BS-1) 5 x 10-4 mol/mol Ag
Adjustment was made by adding 10-4 mol/mol AgX. Further, each compound was added by dissolving it in a high boiling point solvent in the same manner as in Example 1. The amount added is 5 x 10-4 mol/mol AgX.

(Evaluation) After exposure by a conventional method, the following processing was performed and the density of the obtained yellow dye image was measured using a PDA-65 densitometer (manufactured by Konica Corp.).

The results are shown in Table 2. The amount of compound added in samples 202 to 205 in the table is the same as that of sample 202 STAB-1.

Processing solution composition (color developer) Benzyl alcohol 15m Ethylene glycol 15m Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2 .5g 3-Methyl-4-amyl-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Optical brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water to make a total volume of 1 ml, and adjust the pH to 10.20.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100m Ammonium sulfite (40% solution) 27.5m Adjust pH to 7.1 with potassium carbonate or glacial acetic acid Adjust and add water to make a total volume of 1.

As is clear from Table 2, it can be seen that the compounds of the present invention suppress fog without reducing sensitivity.

Blue-sensitive emulsion, average grain size 0.7 μm, silver bromide content 0.
A 5 mol% silver chlorobromide emulsion was prepared, sodium thiosulfate 0.8 mg/mol AgX, chloroauric acid 0.5 mg/mol A
Optimally sensitize using gX at 50°C and sensitizing dye BS-
14 x 10-4 mol/mol AgX, sensitizing dye BS-2
1 x 10-4 mol/mol AgX and STA as stabilizer
B-2 at 3 x 10-4 mol/mol AgX, STAB-3
was adjusted by adding 3×10 −4 mol/mol AgX. When these were coated and dried in the same manner as before and evaluated, the effects of the present invention were obtained.

Example 3 Samples were prepared in the same manner as the silver halide emulsion used in Example 2, except that the compounds were changed as shown in Table 2.
The results of 06 are shown in Table 3.

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

Comparative Compound E Comparative Compound F Exemplified Compound 36 Exemplified Compound 37 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 coating amount was expressed in weight per 1 m2.

1st layer; antihalation layer Black colloidal silver 0.15g UV absorber (UV-1) 0.20g Colored coupler (CC-1) 0.02g High boiling point solvent (Oi■-1) 0.20g (Oi■- 2) 0.20
g Gelatin 1.6g 2nd layer; Intermediate layer gelatin 1.3g 3rd layer; Low sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (Em-1) 0.4g (Em-2) 0.4g Sensitizing dye ( S-1) 3.2 x 10-4 (mol/silver 1 mol) (S-2) 3.2 x 10-4 (〃) (S-3) 0.2 x 10-4 (〃) Cyan coupler (C-1) 0.50g (C-2) 0
．． 13g colored cyan coupler (CC-1) 0.07gDI
R compound (D-1) 0.006gDIR compound (D-
1) 0.01g Additive (SC-1) 0.003g High boiling point solvent (Oi■-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 x 10-4 (mol/silver 1 mol) (S-2 ) 1.6 x 10-4 (〃) (S-3) 0.1 x 10-4 (〃) Cyan coupler (C-2) 0.23g Colored cyan coupler (CC-1) 0.03gDIR compound (D −
2) 0.02g high boiling point solvent (Oi■-1) 0.25g additive (SC
-1) 0.003g Gelatin 1.0g 5th layer; Intermediate layer gelatin 0.8g 6th layer; Low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (Em-1) 0.6g (Em-2) 0. 4g Sensitizing dye (S-4) 6.7 x 10-4 (mol/silver 1 mol) (S-5) 0.8 x 10-4 (〃) Magenta coupler (M-1) 0.17 g (M -2)
0.43g Colored magenta coupler (CM-1) 0.10gD
IR compound (D-3) 0.02g High boiling point solvent (Oi■-2) 0.7g Additive (SC-1) 0.003g Gelatin 1.0g 7th layer: High-sensitivity green-sensitive emulsion layer perspiration silver bromide Emulsion (Em-3) 0.9g Sensitizing dye (S-6) 1.1 x 10-4 (mol/silver 1 mol) (S-7) 2.0 x 10-4 (〃) (S-8 ) 0.3×10-4 (〃) Magenta coupler (M-1) 0.30g (M-2)
0.13g Colored magenta coupler (CM-1) 0.04gD
IR compound (D-3) 0.004g high boiling point solvent (Oi
■-2) 0.35g Additive (SC-1) 0.003g Gelatin 1.0g 8th layer: Yellow filter layer Yellow colloidal silver 0.1g Additive (HS-1) 0.07g (BS-2) 0 .07g (SC-2) 0.12g High boiling point solvent (Oi■-2) 0.15g Gelatin 1.0g 9th layer: Low sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (Em-1) 0.25g ( Em-2) 0.4g Sensitizing dye (S-9) 5.8 x 10-4 (mol/silver 1 mol) Yellow coupler (Y-1) 0.6g (Y-2) 0.32g DIR compound ( D-1) 0.003g (D-2) 0.006g High boiling point solvent (Oi■-2) 0.18g Additive (SC-1) 0.004g Gelatin 1.3g 10th layer: High sensitivity blue-sensitive emulsion Layered silver iodobromide emulsion (Em-4) 0.5g Sensitizing dye (S-10) 3 x 10-4 (mol/silver 1 mol)
(S-11) 1.2 x 10-4 (″) Yellow coupler (Y-1) 0.18 g (Y-2) 0.
10g DIR compound (D-4) 0.002g High boiling point solvent (Oi■-2) 0.05g Additive (SC-1) 0.002g Gelatin 1.1g 11th layer: First protective layer silver iodobromide emulsion (Em-5) 0.3g UV absorber (UV-1) 0.07g (UV-2) 0.10g High boiling point solvent (Oi■-1) 0.07g (Oi■-3) 0.07g Formalin scaven Shear (HS-1) 0.2g (HS
-2) 0.1g Gelatin 0.8g 12th layer: 2nd protective layer Surfactant (SU-1) 0.004g (SU-2) 0.02g Alkali-soluble matting agent (average particle size 2 μm) 0. 13g Polymethyl methacrylate (average particle size 3μm) 0.02g Cyan dye (No. 9) 0.005g Magenta dye (No. 7) 0.01g Sliding agent (WAX-1) 0.04g Gelatin 0.5g In addition, above In addition to the composition, coating aid SU-4 and dispersion aid SU
-3, stabilizer ST-1, preservative DI-1, and antifoggants AF-1 and AF-2 were added as necessary.

The emulsions used in the above samples are as follows. E
All of m-1 to m-4 are core/shell type monodisperse emulsions with high internal iodine content.

Em-1. Average AgI content 7.5 mol%, octahedral 0.
55 μmEm-2: average AgI content 2.5 mol%, 8
Hedron 0.36 μm Em-3, average AgI content 8.0 mol%, octahedron 0.84 μm Em-4: average AgI content 8.5 mol%, octahedron 0.95 μm Em-5: average Ag
Each of the above emulsions having an I content of 2.0 mol % and an octahedral diameter of 0.08 μm was added after being chemically sensitized and spectrally sensitized depending on the purpose.

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

Sample 402 was prepared in exactly the same manner as Sample 401 except that the colored cyan coupler CC-1 in the third and fourth layers was changed to Compound 10 of the present invention.

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 1 of the present invention. In addition, the magenta coupler M-1 in the sixth and seventh layers of sample 401 was replaced with compound 1 of the present invention.
HS-1 and HS of the 8th and 11th layers.
Sample 40 except that the amount of addition of −2 was reduced by half.
Sample 404 was prepared in the same manner as in Example 1. Sample 401, 4
03 and 404 were subjected to wedge exposure according to a conventional method, and then subjected to the following treatments.

Treatment 1: Add 300 m 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 A solution containing 6 ml of a 35% formaldehyde aqueous solution per 300 ml of a 35% glycerin aqueous solution is placed at the bottom of a closed container, and the sample is held in air at 30° C. for 3 days in equilibrium with this.

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 Corporation.
A sample subjected to treatment 1 and a sample subjected to treatment 2 were compared. Samples 403 and 404 containing the compound of the present invention had smaller changes between treatment 1 and treatment 2 than sample 401.

The development process was performed using the following processing steps.

Processing steps (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 The composition of the processing solution used in each processing step is as follows. It is as follows.

<Color developer> 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine 1/2 sulfate 2.0g anhydrous Potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1. (pH = 10.1) <Bleach solution> Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid 2 ammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0m■ Add water to make 1■, ammonia pH = 6 using water.
Adjust to 0.

<Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to make 1 liter, and the pH was adjusted to 6.0 using acetic acid.

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

Applicant: Konica Corporation

Claims (1)

[Scope of Claims] A silver halide photographic material characterized by containing a compound represented by the following general formula [I]. General formula [I] [In the formula, Z is a group of nonmetallic atoms necessary to form a 5- to 7-membered ring containing at least one of an oxygen atom, a sulfur atom, and a nitrogen atom, and an aliphatic group having an oxo group. Represents a group of nonmetallic atoms necessary to form a cyclic hydrocarbon or cyclopentyl. R represents a substituent. Time represents a timing group and PUG represents a photographically useful group. n represents 0-2. ]