JPH04177247A - 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 to R4 stand for a hydrogen atom or a substituent, Timing for a timing group and PUG for a useful group for a photograph. R1 and R3, R3 and R5 or R4 and R5 may respectively form an annulus. l and (m) are an integer of 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 [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, 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.

When the photographically useful group is an irradiation-preventing dye, it is desirable that it flow out from the light-sensitive material during processing, so it is usually provided with 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 can be immobilized 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, suppress 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 a block 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-
5-membered or I; described in No. 135949 and No. 57-179842 is a blocking group utilizing 6-membered ring cleavage,
There are blocking groups utilizing the reverse Michael reaction described in Japanese Patent Publication Nos. 54-39723, 55-96963, and 55-34927.

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 photographically useful group is released with hydroxyl ion, and d i nuc 1e such as hydroxylamine.
It is considerably advantageous over previous blocking groups in that it releases a photographically useful group only through ophile. 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 a photographically useful group even in a low pu processing solution during processing. Our goal is to provide the following.

[Structure of the invention]

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

General formula [I] R.

In the formula, Rl+ R2, Rs, R4+ Rs are hydrogen atoms or substituents, Ti+ge is a timing group,
PUG is a photographically useful group. R1 and R8, R3 and R3
, R1 and R5 may each form a ring. ! and I is 0
or an integer of 1.

General formula CI) will be further explained.

Substituents represented by R+, Rz, Rs, R4, and Rs include alkyl (methyl, dodecyl, etc.), aryl (phenyl, naphthyl, etc.), heterocycle (pyridyl, furyl, etc.)
, hydroxy, alkoxy (methoxy, etc.) and the like. R and R3 may form a ring such as pyridine, pyrimidine, or triazine.

R8 and R5, R4 and R, may form a ring such as cyclopentane or cyclohexane.

These also include those having substituents.

When f=1, an onium salt is formed.

Examples of the group represented by Ti■e 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. (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 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*2
indicates a site that binds to PUG.

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; A fused ring may be formed. 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.

PLIG, which is a photographically useful group, includes, for example, antifoggants, development inhibitors, color and black and white developing agents, auxiliary developers, development accelerators, fogging agents, image-forming couplers, competitive couplers, Dll? Couplers, colored couplers, colorless couplers, black couplers, pigments, dyes, bleach accelerators, bleach inhibitors, silver halide solvents, silver complex forming agents, fixing agents, curing agents, DP' scavengers, image stabilizers, etc. 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,
Examples include virazolidone 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, indacylon, cyanoacetyl, and pyrazoloazole. There are magenta couplers, etc. Specific examples of DIR couplers include U.S. Pat. No. 3,227.554;
384.657, 3,615, 506, 3,
No. 617.291, No. 3,733.201, Special Publication No. 6
No. 1-27738, JP-A-56-114946, No. 5
No. 7-111536, No. 57-154234, No. 58
-160954, 58-162949, 60-
No. 185950, No. 61-233741, No. 57-1
There are issues such as No. 51944. 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,
There are azomethine dyes, anthraquinone dyes, indophenol dyes, etc. Specific examples of dyes include azo dyes, azomethine dyes, azopyrazolone dyes, indoaniline dyes, indophenol dyes, anthraquinone dyes, triarylmethane dyes, alizarin dyes, quinoline dyes,
Examples include oxonol dyes, phthalocyanine dyes, meonanine dyes, azomethine dyes, and styryl dyes. Specific examples of bleach accelerators include aminoethanethiol compounds,
Examples include 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.

Preferred as PIGs 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.

Preferred specific examples of the compounds represented by the general formula (1) are shown below. However, the present invention is not limited to the following compounds.

specific compound shi41'Iri CH3 to CR3 words 2H5 CH.

OCH.

2H6 ! ShirI3 CH.

SO, C8H, and CR3 Next, a specific synthesis example of a compound represented by the general formula CI] will be shown.

Synthesis Example (Synthesis of Exemplary Compound (1)) Synthesis was carried out according to the above scheme. Compound (A) 6.7g
Dissolve 1 of triethylamine in 30 ml of acetonitrile.
．． 2 g of 2-pyridylacetyl chloride was added to the solution while stirring. After reacting at room temperature for 3 hours, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water, dried and concentrated, and the residue was separated and purified by column chromatography to obtain 5.1 g of compound (1).

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 −9 to 10 mol per mol, preferably 10
-'-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. You can use any of the following.

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. 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, indacylon 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-1 ultraviolet absorber, a fluorescent whitening agent, a surfactant, a development accelerator, a development retardant, and a bleach accelerator 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 1 (Preparation of coating liquid) After dissolving 35 g of gelatin in 1.01 g of water, a coating aid (Su-1) and a hardening agent (H-1) were added to prepare a coating liquid.

(Dye precursor dispersion) 2.5X 10-3 mol of comparative compound (A) was mixed with high boiling point solvent (Oil-1) 1.6 mA', ethyl acetate 611
17, and this solution was added to 44 g of a 10% aqueous gelatin solution containing a surfactant (Su-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) The above emulsion layer coating solution was applied onto a 10 hour polyethylene terephthalate film base subjected to latex undercoating described in JP-A-59-19941, and dried to prepare Sample 101. . Dye precursor (compound)
The loading was 3X 10-'mol/la2.

(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℃ water washing
Dry for 30 seconds Dry 2 minutes 60-80℃ [Color developer] Pure water 800ml Benzyl alcohol 15ml Triethanolamine 10.0g Hydroxyamine sulfate 260g 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
32.0g1-hydroxyethylidene-1
,1-disulfonic acid (60% aqueous solution) 1.5■1White
x BB (50% aqueous solution) (fluorescent brightener, manufactured by Sumima Kagaku Kogyo Co., Ltd.) Add pure water to make 1z, and add 20% potassium hydroxide or 10%
Adjust the pH to 1o, I with % dilute sulfuric acid.

(Evaluation) The presence or absence of residual color after treatment was evaluated as shown below. 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.

E, -E2 Decolorization rate = -x 1 (10 (%) E.

(E 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 (S u-1) (S u-2) Na As is clear from Table 1, it can be seen that 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 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 liquid) Yellow coupler (Y-1) 26.7g, dye image stabilizer (ST-1) 1O,Og, dye image stabilizer (ST-2) 6J7g, additive (HQ-1) )
0.67g, and high boiling point organic solvent (DNP) 6.
Add and dissolve 60 ml of ethyl acetate (2) to 67 g, and mix this solution with 10 ml containing 20% surfactant (SOl).
% gelatin aqueous solution using an ultrasonic homogenizer to prepare a yellow coupler dispersion. 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
), 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 (5-cho-2)
O17 stain inhibitor (HQ
-1) 0.02 Support polyethylene laminated paper However, the amount of silver halide emulsion is expressed 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 then heated at 57°C using 1.5 sodium thiosulfate + 1 mol of agX.
Optimally sensitize with sensitizing dye (BS-1') 5 x 1
0-4 mol 1 mol AgX and as stabilizer (STAB-
1) was prepared by adding 5X 10-'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 5 x 1
0-'mol 1 mol 8gX.

(HQ-1) 0 ■ (DNP) Dinonyl phthalate (SU-2) C ((JIzSO2CH=CH2)4 (H-2) QNa (F-1) Mixture of the following three components Component A: Component B: Component c -50: 46: 4 (molar ratio) (STAB-1) Comparative Compound C Comparative Compound Exemplary Compound (27) CH.

Exemplary Compound (28) (Evaluation) After exposure by a conventional method, the following treatment was performed and the density of the obtained yellow dye image was measured using a PDA-65 densitometer (manufactured by Konica Corp.).

Development processing conditions Color development 38°0 3 minutes 30 seconds Bleach fixing
33℃ 1 minute 30 seconds water washing treatment 25-30℃
Dry for 3 minutes 75-80℃
Approximately 2 minutes The results are shown in Table 2. The amount of compound added in Samples 202 to 206 in the table is the same as that of 5TAB-1 in Sample 202.

Processing solution composition (color developer) Benzyl alcohol 15a+Q ethylene glycol 15n++2 Potassium sulfite 2.0g Potassium bromide
0.7g sodium chloride
0.2g potassium carbonate
30.0g Hydroxylamine sulfate 3.0
g Polyphosphoric acid (TPPS) 2.5
g3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) -aniline sulfate 5.5g optical brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g hydroxide Add 2.0 g of potassium water to bring the total volume to 11, and adjust pnlQ to 20.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (
70% solution) 100ml ammonium sulfite (4
(0% solution) Adjust the pH to 7.1 with 27.5 μl potassium carbonate or glacial acetic acid, and add water to make a total volume of 11.

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 0.7μ, silver bromide content 0.
Prepare a 5 mol% silver chlorobromide emulsion, add 0.8 g of sodium thiosulfate to 1 mol of sodium thiosulfate, and 0.5 to 1 mol of auric acid chloride
Optimally sensitize using gX at 50°C and sensitizing dye BS-
14x 10” mol/mol AgX, sensitizing dye B5-2
1 X 10-'mol 1 mol^gX and 5 as stabilizer
TAB-2 3 x 10-'-T-ru/mol AgX
, 5TAB-3 3 x IQ-4 mol 1 mol^gX
Added and adjusted. 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, but with only the compounds changed as shown in Table 3.
The results of 6 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 (29) C, H6 ■ Exemplified Compound (30) Example 4 On a film support, each layer having the composition shown below was sequentially formed from the support side to produce a multilayer color photograph. Element sample N
O,401 was created. However, unless otherwise noted,
The coating amount was expressed in weight per l wa2.

1st layer; antihalation layer black colloidal silver 0.15gUV
Absorbent (UV-1) 0.20g
Colored coupler (CC-1) 0.0
2g high boiling point solvent (Oill-1)
0.20gtt (Oin -2)
0-20g gelatin
1.6 g Second layer; Intermediate layer gelatin 1.3 g Third layer; Low sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (Em-1) 0.4 g
// (E-12) 0.4g
Sensitizing dye (S-1') 12X 10-' (mol/1 mol of silver) // (S-2) 3.2X10-' (//
)” (S 3) 0.2XlO-4(t
t) Cyan coupler (C-1)
0.50gtt (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 (Oiff -1)
0.55g gelatin
1. Og 4th layer; High sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (Em-3) 0.9g
Sensitizing dye (S-1) 1.7X 10-' (mol/silver 1 mol) 1/ (S-2) 1.6XlO-' (//
)tt (S-3)0.1xlO-'(/
/ ) Cyan coupler (C-2)
0.23g colored cyan coupler (CC-1)
0.03gDIR compound (D-2)
0.02g high boiling point solvent (Oig -1)
0-25g additive (SC-1)
(LOO3g gelatin
1.0g Fifth layer: Intermediate layer gelatin 0.8g Sixth layer: Low sensitivity emulsion layer Silver iodobromide emulsion (Em-1) 0.6g
tt (E-gut-2) 0.4g sensitizing dye (S-4) 6.7X 10-'C mol/silver 1
mol)” (S 5)0.8XlO-'(//
) Magenta coupler (M-1) O
,17g// (M-2) 0.4
3g colored magenta coupler (CM-1)
0. lOgDIR compound (D-3)
0.02g high boiling point solvent (Oi(1-2)
0.7g additive (SC-1)
0.003g gelatin
1.0g 7th layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (EIll-3) 0.9
g Sensitizing dye (S-6) 1. lX 10-' (mol/
1 mole of silver)II (S-7)2.0X10-'(/
/ )II (S-8)0.3XIO-'(
// ) Magenta coupler (M-1)
0.30g” (M-2) O
, 13g colored magenta coupler (CM-1)
0.04gDIR compound (D-3)
0-004g high boiling point solvent (OiQ-2)
0.35g additive (SC-1)
0.003g gelatin
1.0g 8th layer; Yellow filter layer Yellow colloidal silver 0.1° Additive (H5-1) 0.07g//
(MS-2)
0.07g// (SC-2)
0-12g high boiling point solvent (Oi12-2
) 0.15g gelatin
l -0g 9th layer: Low-frequency sensitivity emulsion layer Silver iodobromide emulsion (Em -1) 0.25
g// (Es -2) 0.4
g Sensitizing dye (S-9) 5.8X 10-' (mol/
1 mole of silver) Yellow coupler (Y-1) 0
．． 6g// (Y-2) 0.32
gDIR compound (D-1) 0.
003gt/ (D-2) 0
．． 006g high boiling point solvent (OiIl-2)
0.18g additive (SO-1)
0.004g gelatin
l・3g 1st θ layer; Highly sensitive emulsion layer Silver iodobromide emulsion (Em-4) 0.5g
Sensitizing dye (S-10) 3X to-' (mol/silver 1 mol) 1/ (S-11) 1.2X lO-
'(1/) Yellow coupler (Y -1)
0.18g// (Y 2)
0-100-1O compound (D4
) 0.002g high S point solvent (Oi
Q-2) 0.05g additive (SC-
1) 0.002g gelatin
1.1g 11th layer; 1st protective layer silver iodobromide emulsion (E, m-5) 0.3
guv absorber (UV-1)
0.07g// (UV-2)
0. lOg high boiling point solvent (OiQ-1)
0.07gtt (OiQ-3)
0.07g formalin scavenger (MS-
1) 0.2gtt (Is -2)
0.1g gelatin
0.8g 12th layer: 2nd protective layer surfactant (SU-1) 0.00
1gtt (SU-2)
0.02g alkali-soluble matting agent (average particle size 2μm) 0.13g polymethyl methacrylate (average particle size 3μm) 0.02g/Undye (No. 9) 0.005g
Magenta dye (No. 7) O,
Olg slip agent (WAX-1) 0
．． 04g gelatin 0.5
g In addition to the above composition, coating aid 5U-4, dispersion aid 5
Add U-3, stabilizer 3 to 11, preservative DI-1, and antifoggants AF-1 and AF-2 as necessary.

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

Em-1: average Agl content 7.5 mol%, octahedron 0.
55μmEm-2: average Agl content 2.5 mol%, 8
Face piece 0.36μmEm-3: Average Agl content 8.0
Mol%, octahedron 0.84 μm Em-4: Average Agl content 8.5 mol%, octahedron 0.95 μm Em-5: Average A
Each of the above emulsions having a gl 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.

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

(S-1) (S-2) (S-3) (S-4) (S-5) (S-6) (S-7) (S-8) (S~9) (S-10) (S-11) u, fl.

C-2 C-2C I u-4 H NaO,5-C-COoC,H,.

CHz C00CaHrt (average molecular weight -30,000) T-1 IT AF-IAF-2 I-1 Colored cyan coupler CC-1 in the third and fourth layers of sample 401 was changed to compound (5) of the present invention All except (
Sample 402 was prepared in the same manner.

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 the same manner except that the magenta coupler M-1 in the sixth and seventh layers of sample 401 was changed to the compound (1) of the present invention. Except that the magenta coupler M-1 in the layer and the seventh layer was changed to the compound (1) of the present invention, and the amounts of US-1 and Its-2 added in the eighth and eleventh layers were respectively halved. Sample 404 was prepared in the same manner as sample 401. Samples 401, 403, and 404 were subjected to wedge exposure according to a conventional method, and then subjected to the following treatments, respectively.

Treatment 1: Add 300 mQ of 35% glycerin aqueous solution to the bottom of a sealed container.
and keep the sample at 30° C. in air for 3 days.

Treatment 2 A solution containing 35% formaldehyde aqueous solution 6a+Q per 300 mQ of 35% glycerin aqueous solution is placed at the bottom of a closed container, and the sample is held at 30° C. for 3 days in air kept 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 with 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 404 containing compounds of the invention
Compared to sample 401, the change between treatment 1 and treatment 2 was smaller.

The development process was performed using the following processing steps.

Processing process (38℃) Color development 3 minutes 10 seconds Bleaching 6 minutes 30 seconds Water
Washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds Washing with water
Stabilization for 3 minutes and 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 l/2 sulfate 2.0g Anhydrous potassium carbonate 37.5 g Sodium bromide
1.3 g Nitrilotamaacetic acid trisodium salt (l hydrate) 2.5
g Potassium hydroxide 1.0 g Add water to make IQ. (pH = 10.1) Bleaching solution> Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Ice Vinegar fil
Add 10.0 mff water to make 112, and adjust to p)I-6,0 using ammonia water.

Fixer> Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make IQ, and adjust to pH=6.0 using acetic acid.

Stabilizer> Formalin (37% aqueous solution) 1.5m<
1 Konidax (manufactured by Konica) 7.5m1
2 Add water to make IQ.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one silver halide emulsion layer, characterized in that it contains a compound represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1, R_2, R_3, R_4, R_5 are hydrogen atoms or substituents, Time is a timing group, and PUG is a useful group for photography. be. R_1 and R_3, R_
3 and R_5, and R_4 and R_5 may each form a ring. l and m are integers of 0 or 1.