JPH02140740A - Image forming method - Google Patents

Abstract

PURPOSE:To increase the rate of release of a development inhibitor and to improve shelf stability by carrying out development in the presence of a specified development inhibitor releasing compd. CONSTITUTION:When a silver halide photographic sensitive material is developed in the presence of a development inhibitor releasing compd. represented by formula I or II, an image having superior graininess, sharpness and color reproducibility is obtd. In the formulae I, II, each of R1-R8 is H or a substituent, at least one of them is a group which is released in a developing stage and can form a development inhibitor, preferably a group bonding to a benzene ring through S or N, and each of A1 and A2 is H or a group protecting a phenolic hydroxyl group and enabling deprotection in a developing stage.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for developing silver halide photographic materials.
More specifically, the present invention relates to a method of developing a silver halide photographic material in the presence of a compound that imagewise dissociates and releases a development inhibitor in the development process.

[Background of the invention]

In recent years, in silver halide photographic light-sensitive materials (hereinafter simply referred to as light-sensitive materials), compounds have been developed that generate a development inhibitor in the emulsion layer in an amount that corresponds to the progress of development during development.
It is well known that it greatly contributes to improving the sharpness and graininess of photosensitive materials and, especially in color photosensitive materials, to improving color reproduction through color correction effects.

Such compounds typically include development inhibitor-releasing couplers (which release a development inhibitor as development progresses).
DIR couplers) and development inhibitor-releasing hydroquinone compounds (hereinafter referred to as DIR-hydroquinone compounds) are known.

DIR-coupler generally has a development inhibitor bonded to the active site of the coupler directly or via a timing group, and undergoes a coupling reaction with an oxidized form of an aromatic primary amine developing agent to release the development inhibitor. It is a compound that is released and has effects such as adjusting image gradation, making images finer, improving image sharpness, and improving color reproducibility. However, D.I.R.
- Since couplers utilize a cuff-pulling reaction as a means for releasing a development inhibitor, their use is essentially limited to color photographic materials.

On the other hand, DIR-hydroquinone compounds are hydroquinone derivatives substituted with development inhibitors, and examples of such compounds include U.S. Pat.
No. 20,746, JP-A-49-129536, JP-A No. 50
-37435, 56-153342, 61-1
Compounds described in No. 8946, No. 61-156043, etc. are known.

In addition, the former R-hydroquinone compound causes a cross-oxidation reaction with the oxidized product of a black and white developing agent and/or the oxidized product of an aromatic primary amine developing agent, or by directly reducing silver halide. It is a compound that becomes an oxidant and releases a development inhibitor through a nucleophilic substitution reaction caused by attack of the oxidant by nucleophilic species such as sulfite ions and hydroxide ions present in the developer. Thus, the IR-hydroquinone compound has the same excellent effect on photographic properties as the above-mentioned DIR-coupler, and also
While DIR couplers are essentially applicable only to color photographic materials, they have the advantage of being applicable to black and white photographic materials as well, and have therefore been extensively studied.

The mechanism of detachment of the development inhibitor from the IR-hydroquinone compound is a cross-oxidation reaction with the oxidized form of the developing agent and a nucleophilic substitution between the generated oxidized form of DIR-hydroquinone and the nucleophilic species present in the developer. It is made up of reactions. The above first reaction can be promoted by substituting the DIR-hydroquinone compound with an electron donating group to lower the oxidation potential of the compound;
R-hydroquinone compounds have the disadvantage that they are susceptible to autooxidation due to oxygen in the air, resulting in poor long-term storage stability. Regarding the second reaction, substituting the DIR-hydroquinone compound with an electron-withdrawing group lowers the electron density of the oxidized form of the compound, making it more susceptible to nucleophilic attack, and therefore reducing the rate of release of the development inhibitor. growing. In this way, in the development inhibitor separation reaction in the DIR-hydroquinone compound, it is preferable to add an electron donating group to the compound in order to promote the first reaction, promote the second reaction, and improve storage stability. They have contradictory properties in that it is preferable to add an electron-withdrawing group to increase the properties. Therefore, it is still difficult to develop a DIR-hydroquinone compound having a sufficient development inhibitor release rate, and the activity of the old R-hydroquinone compound described in the above patent was still insufficient.

[Purpose of the invention]

In view of the above-mentioned circumstances regarding DIR-hydroquinone compounds, the first object of the present invention is to provide a novel photographic development inhibitor-releasing compound having excellent inhibitor release rate and storage stability. .

A second object of the present invention is to provide an image forming method in which development processing is carried out in the presence of a novel photographic development inhibitor-releasing compound.

Furthermore, a third object of the present invention is to provide an image forming method with excellent image granularity, image sharpness, and color reproducibility.

[Structure of the invention]

The above object of the present invention is achieved by an image forming method in which a silver halide photographic material is developed in the presence of a compound represented by the following general formula [I] or (II).

General formula [I] General formula (11) A2 In the formula, R□, R2, Rs, R4, Rs, Rs
, R a and R8 each represent a hydrogen atom or a substituent,
At least one of these represents a group that can be separated during the development process to form a development inhibitor. Also, R1, R2 and R7
and R8 may be bonded to each other to form a hydrocarbon ring.

A1 and A each represent a hydrogen atom or a protecting group for a phenolic hydroxyl group that can be deprotected during the processing step.

[Specific structure of the invention]

The compounds represented by general formulas [I] and (II) will be explained.

The group represented by R1-R6 that can be separated in the development process to form a development inhibitor is preferably a group that is bonded to the benzene nucleus I through a sulfur atom or a nitrogen atom.

Groups bonded via a sulfur atom include arylthio groups and heterocyclic thio groups.

Typical examples of arylthio groups include phenylthio groups (e.g. 2-carboxyphenylthio, 2-nitrophenylthio), and examples of heterocyclic thio groups include tetrazolylthio groups (e.g. 1-7enyltetrazolyrunyl). tetrazolyl-5-thio, -ethyltetrazolyl-5-thio), oxadiazolylthio group (e.g. 3-ethyl-1.2.4-year-old oxadiazolyl-5-thio, 3-methylthio-1.2.4) -oxadiazolyl-5-thio)
, thiadiazolylthio group (e.g. 3-amino-1,2.
4-thiadiazolyl-5-thio,3-methyl-1.2.
4-thiadiazolyl-5-thio), triazolylthio groups (e.g. l,2).

4-triazolyl-5-thio) and the like.

Furthermore, as the group bonded via a nitrogen atom, a benzotriazolyl group is particularly preferable, such as 5-methylbenzotriazolyl, 5-bromobenzotriazolyl, 5-octanamidobenzotriazolyl, 5-phenoxycarbonyl Examples include various groups such as benzotriazolyl and 5-(3-methylbenzothiazonylidene)aminobenzotriazolyl.

Among the substituents represented by R1-R8, groups other than those that can be separated in the development process to form a development inhibitor include hydrogen, halogen atoms, hydroxyl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, Alkynyl, aryl, heterocycle, acyl, sulfonyl, sulfinyl, phosphonyl, carbamoyl, sulfamoyl, cyan, alkoxy, aryloxy, heterocycleoxy, acyloxy, carbamoyloxy, amino, acylamino, sulfonamide, imide, ureido, sulfamoylamino , alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, alkylthio, and arylthio, but are not limited thereto. Moreover, these groups may have a substituent.

R, and R4 and R7 and R. Examples of the hydrocarbon ring that may be formed with are the following.

These hydrocarbon rings further include halogen atoms and alkyl, aryl, alkoxy, cyano, carboxyl,
formyl, amide, carbamoyl, sulfonamide, sulfamoyl, acyloxy, nitro, alkoxycarbonyl, aryloxycarbonyl, acyl, amino,
Six groups such as imino, alkenyl, alkynyl, alkylthio, arylthio, ureido, sulfonyl, and sulfo may be substituted with one or more arbitrary groups.

A and the protecting group for the phenolic hydroxyl group that can be deprotected during the treatment step represented by A can be removed under alkaline conditions with a pH value of 9 to 14, preferably 10 to 13, and such Examples of the group include six groups such as acetyl, chloroacetyl, trichloroacetyl, trifluoroacetyl, and benzoyl.

Preferred compounds in the present invention are those in which R1 and R3 or R2 and R6 in general formula (I) are groups that can be separated in the development process to form a development inhibitor, and in general formula (n), R , and R6, R2 and R1, or R1 and R2 are groups that can be separated in the development process to form a development inhibitor.

Among the hydrocarbon rings formed by bonding R3 and R4 and R7 and R6, the following rings are preferred.

A and A2 are preferably hydrogen atoms.

Next, typical specific examples of the development inhibitor-releasing compound represented by the general formula [I] or (I[) (hereinafter referred to as the compound of the present invention) will be shown, but the present invention is limited to these ■ ■ ■ ■ ■ OOH ■ ■ ■ ■ ■ ■ H ゝNO□ ■ ■ ■ ■ N -N ■ CH2C00C3Hr CH2C00C3H7 The compound of the present invention can be used in various photosensitive materials,
It can be equally used for black and white light-sensitive materials and color light-sensitive materials.

In particular, improvement of sharpness in X-ray sensitive materials, improvement of graininess, sharpness and color reproducibility in multilayer color photographic materials,
It is also effectively used to improve halftone gradation in light-sensitive materials for photolithography without deteriorating halftone dot quality, and is also used in light-sensitive materials that form ultra-high contrast negative images through the action of hydrazine derivatives and tetrazolium salts. It can be used for effect.

The compound of the present invention can be contained in the silver halide emulsion layer, in the hydrophilic colloid layer provided above or below the emulsion layer, or in both layers.

Silver halide emulsions using the compounds of the present invention include:
Any silver halide emulsion used as a normal silver halide emulsion containing silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, silver chloride, etc. may be used as the silver halide. Can be done.

For the compound of the present invention, the above-mentioned exemplified compounds may be used alone or in combination of two or more, but the amount used can be arbitrarily selected depending on the purpose, and is preferably 1 mole of silver.
O-4 to 1 mole, particularly preferably 10-1 mole of silver
'' to 10-'' moles.

Further, the compound of the present invention can also be included in developing solutions for various photosensitive materials. For example, it can be added to color developing solutions such as color negative films and color reversal films, black and white developers for color reversal films, X-ray sensitive materials, and photolithographic materials.

〔Example〕

Synthesis examples and examples of the compounds of the present invention will be described in detail below, but the present invention is limited to these aspects.Synthesis example-1 (synthesis of exemplified compound I) ] Reaction■(1)
After dissolving 33.2g in 500n12 of chloroform, add 23.4g (2) and further add 11g of aluminum chloride.
After adding 4.7 g little by little, the mixture was reacted at room temperature for 4 hours. After filtering the residue, almost all of the solvent chloroform was distilled off under reduced pressure, and then ethyl acetate 500 + nQ - ice water 500
m<1 was added and extracted. Dilute the organic phase with 500 m of water + 2
After washing twice, the solvent was distilled off under reduced pressure to obtain a solid product.

This was purified by column chromatography to obtain 29.7 g of pale brown crystals. (Yield 58%) This substance was identified by FD mass spectrum, 'HNMR, and IR [3
] was confirmed.

Reaction■ [3] Dissolve 25.4g in 500m(2) of DMF,
Furthermore, 32 g of metal steel was added, and the mixture was reacted for 3 hours at a solution temperature of 100°C.

After removing metallic copper by filtration, it was poured into 2Q ice water and the produced solid was collected by filtration. This was recrystallized from acetonitrile to obtain 11.7 g of pale yellow crystals. (Yield 61%) This substance was identified by FT) mass spectrometry, '1 (NMR, IR) and it was confirmed to be Exemplified Compound I-1 Synthesis Example 2 (Synthesis of Exemplified Compound I-4) Synthesis Route > Reaction ■ [4] 28.8 g was dissolved in 600 mff of chloroform, and 46.8 g of (2) was further added, and then 29.3 g of aluminum chloride was added little by little. After reacting at room temperature for 3 hours, the remaining liquid was filtered and almost all of the chloroform was removed.
After distilling off under pressure, add 500ml of ethyl acetate (2-500ml of ice water)
It was extracted by adding mQ. This organic phase was mixed with 500 mQ of water for 3
After washing twice, the solvent was distilled off under reduced pressure to obtain a solid product.

This was purified by column chromatography to obtain 34.5 g of gray crystals. (Yield 54%) This substance was identified by FD mass spectrum, 'HNMR, and IR [5]
It was confirmed that

Reaction (5) To 30.0 g were added 1000+n12 of benzene and 300 g of cupric chloride supported on diatomaceous earth (cupric chloride content: about 15 g), and the mixture was reacted at 50°C for 4 hours.

After filtering off the residue, benzene was distilled off under reduced pressure, and the resulting solid was purified by column chromatography to obtain pale brown crystals 1.
9.1 g was obtained. (Yield 64%) This substance was identified by FD mass spectrometry, HNMR, and IR, and it was confirmed to be Exemplified Compound I-4 Synthesis Example 3 (Synthesis of Exemplified Compound 2) .

(6) 55.3 g was dissolved in 800 mQ of chloroform, 78.3 g of N-bromosuccinimide was added little by little under water cooling, and the mixture was reacted at 5°C for 2 hours. After the residue was filtered off, it was washed five times with 1a water and the organic phase was dried over magnesium sulfate.

85.1 g of (2) was added to this solution, and further 53.3 g of aluminum chloride was added little by little, and the mixture was reacted at room temperature for 3 hours. After the residue was filtered off, chloroform was distilled off under reduced pressure, and 700 mQ of ethyl acetate and 700 mQ of ice water were added to extract the organic matter. This organic phase was washed three times with 50 On+Q water,
Furthermore, after ethyl acetate was distilled off under reduced pressure, the residue was purified by column chromatography to obtain 62.5 g of pale brown crystals. (yield 4
0%) This substance was identified by FD mass spectrometry and 'HNMRSIR and was confirmed to be [8].

Reaction■ (8) Add 600ml of DMF to 59g12. 95 g of metallic copper was added and reacted for 4 hours at a solution temperature of 100°C. After removing metallic copper by filtration, the DMF solution was poured into 3α ice water, and the resulting solid was collected by filtration. This was recrystallized from acetonitrile to obtain 32.6 g of pale yellow crystals. (Yield: 69%) This substance was identified by FD mass spectrometry, 'HNMR, and IR, and was confirmed to be Exemplified Compound 11-2.

Example-1 Subbing processing I: l-hydroxy-N-(
4-(2,4-di-t-amylphenoxy)butyl]-
2-naphthamide io, 6 g tricresyl phosphate
) was dissolved in 30 m4 of ethyl acetate, mixed with 20 m+2 of a 10% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by Davon) and 200 m2 of a 5% aqueous gelatin solution, and emulsified and dispersed in a colloid mill to form an emulsion. This dispersion was mixed into a red-sensitive silver iodobromide emulsion (
Added to Nkg containing 6 mol% silver iodide, as a hardening agent, 1
．． 2% aqueous solution of 2-bis(vinylsulfonyl)ethane 4
0mQ was added and coated and dried. (Coated silver amount 12mg/1
00 cm'', coupler mole/Ag mole -0.1) The silver halide color photographic light-sensitive material thus obtained is designated as Sample 1.

Compounds (I-6) and (n
Samples 2 and 3 are those to which -8) was added.

Comparative Compound a 0M Comparative Compound b U Comparative compound a 0M Comparative compound b u After applying wedge exposure to each of these samples using an intensity scale sensitometer, color development was performed according to the following processing steps. The treatment was carried out and the results shown in Table 1 were obtained.

Processing process (38°C) Processing time Color development 3 minutes 15 seconds Bleaching
Wash with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
3 minutes and 15 seconds Stabilization bath 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step was as follows.

Color developer composition 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.75 g Anhydrous sodium sulfite 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate
37.5 g sodium bromide
1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make IQ, and adjust to pH 1O60 using potassium hydroxide.

Bleach solution composition Ethylenediaminetetraacetic acid iron ammonium salt 100.0
g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 mQ Add water to make 1Q, and adjust to pH 6.0 using aqueous ammonia.

Fixer composition Ammonium thiosulfate (50% aqueous solution) 162 mQ Anhydrous sodium sulfite 12.4 g Add water to make 1Q, and adjust to pH 6.5 using acetic acid.

Stabilizing liquid composition Formalin (37% aqueous solution) 5.0 mQ
Konidax (manufactured by Konica Corporation) 7.5m (Table 2-1 The same sample was stored at 60°C and 80% RH (relative humidity) for 2 days, and then exposed to light at the same time and the same development process was performed -2 Table- 1 and Table 2, the compound of the present invention has a conventional DIR
It can be seen that gamma can be adjusted with a small amount added compared to couplers, and that it is extremely stable with almost no change even under storage conditions of 60° C., 180% RH, and 2 days.

Example-2 (Preparation of photosensitive silver halide emulsion) 1. containing 4.0 g of potassium iodide and 80 g of potassium bromide.
A 6% aqueous gelatin solution was kept at 56°C, and silver nitrate was added.
The ammoniacal silver ion solution containing g was divided into three equal parts, and these were added in three parts using a single jet method and a positive mixing method, respectively. The average particle size was controlled by changing the interval time between adding the ammoniacal silver ion solution divided into three equal parts.

Incidentally, during the second and third additions of the ammoniacal silver ion solution, partial neutralization was performed with acetic acid. After the third addition was completed, Ostwald ripening was carried out, the pH was adjusted to 6, and desalination was carried out by the usual flocculation method, resulting in an irregular potato-like shape with a silver iodide content of 4.0 mol%. An emulsion of silver iodobromide grains was obtained. This emulsion had an average grain size (?) of 1.1 μm and a dispersion coefficient (σ/r) of 0.26.

To this emulsion, sodium thiosulfate, chloroauric acid and ammonium thiocyanate were added to perform gold/sulfur sensitization, and 4-
Hydroxy-6-methyl-1,3,3a.

7-chitrazaindene and trimethylolpropane were added to obtain a photosensitive silver iodobromide emulsion.

A coating aid (dodecylbenzenesulfonate) and a thickener (polypotassium p-vinylbenzenesulfonate) were added to the photosensitive silver halide emulsion prepared by the above method, and the compound of the present invention (I -1).

(I-2), (II-8), comparative compound (a),
Both sides of the polyethylene terephthalate support were undercoated with (b) and (c) as shown in Table 3, with a silver coating amount of 4.0 g/m'' per side and a gelatin amount of 2.
．． It was coated at a coating weight of 6 g/m''.

Comparative compound (a) Comparative compound (b) Comparative compound (c) Furthermore, gelatin, a thickener (sodium polystyrene sulfonate, and a matting agent (average particle size 3.0) were added on these emulsion layers.
μm polymethyl methacrylate 1/fine particles), hardening agent (
2-hydroxy-4,6-dichloro-1,3゜5-triazine sodium salt), coating aid (sodium t-octylphenoxyethoxysulfonate), antistatic agent (liquid mixture of dinonylphenol ether and polyethylene oxide) ) was applied to form a protective layer, and samples 6 to 1 were coated with
2 was created.

The amount of gelatin per side was 1.3 g/m' and was coated on both sides.

Both sides of these samples were sandwiched between fluorescent intensifying screens containing calcium tungstate, and a rectangular wave chart of the aluminum group was placed in close contact with them as a subject. After xma light was applied so that the density was 1.0, the following processing was performed. The film was developed with a solution at 35° C. for 25 seconds, further fixed, washed with water, and dried, and the CTF was measured using a microphotometer. These results are shown in Table 3.

Developer composition Potassium hydroxide 29.14g Glacial acetic acid 10.96g sub-WtH
Power! J Lamb 44.20g Sodium bicarbonate 7.50g Boric acid 1.00g Diethylene glycol 28.96g Ethylenediaminetetraacetic acid 1.67g 5-Methylbenzotriazole 0.06g 5-Ditroindazole 0.25g Hydroquinone
30.00g 1-phenyl-3-pyrazolidone 1.50g glutaraldehyde
4.93g Sodium Metabisulfite
12.60g potassium bromide
Add 7.00g of water to make up to 1Q, fixer composition: ammonium thiosulfate, sodium sulfite (anhydrous), ammonium sulfate borate, sulfate, glacial acetic acid water to make up to 1Q, and adjust pH to 10.25.

200.0g 20.0g 8.0g 15.0g 2.0g 22.0g Adjust pH to 4.2.

From Table 3, sample 1O11111 using the compound of the present invention
2 has a sharpness of 1 compared to samples using conventional DIR compounds.
It turns out that it is excellent.

Example 3 In this example, the amounts of sensitizing dyes and couplers added are per mole of silver halide unless otherwise specified.

Multilayer color photosensitive material sample 13 was prepared by sequentially coating each layer having the composition shown below on a subbed triacetylcellulose film support from the support side.

1st layer: Antihalation layer UV absorber - 10.3g/m" UV absorber -20.4g/n+" Black colloidal silver 0.24g/+i
”Gelatin 2.7 g/m
Second layer: Intermediate layer 2.5-di-t-octylhydroquinone Ool g
/m”gelatin l-Og/
m'' third layer: low sensitivity red-sensitive silver halide emulsion layer average grain size 0.35 μm, AgBr containing 2.5 mol% Agl
1 Emulsion (Emulsion-1) Silver amount 0-5g/m”
Sensitizing dye-17,6x1. O-' mole coupler C-10, 1 mole gelatin 0.9 g/m2 4th layer: High sensitivity red-sensitive silver halide emulsion layer average grain size 0.7
5 μm, AgBrI emulsion containing 2.5 mol% Agl (emulsion-2) Silver amount (L 8 g/m" Sensitizing dye - 13,2X 10-'Mo4 Coupler C-10,2 mol Gelatin 0.75 g/m"
5th layer: Intermediate layer 2.5-di-mo-octylhydroquinone 0.1g/
m” gelatin 0.9g/m
"6th layer: Low sensitivity green-sensitive silver halide emulsion layer Emulsion - 1 silver amount 1.0 g 7 m" Sensitizing dye - 26,6X 10-' molar Sensitizing dye - 30,6x 10-' molar coupler M -10,05 Morgelatin 0.8 g/m” 7th layer: High sensitivity green sensitive silver halide emulsion layer Emulsion-2 Silver amount 1
．． 0g7m” Sensitizing dye-22,76X 10-'Mole Sensitizing dye-30
, 23 m”2.
5-di-t-octylhydroquinone 0.1g/m2
1st O layer: low sensitivity blue sensitive silver halide emulsion layer average grain size 0
．． 6 p m, AgBr containing 2.5 mol% Agl
Emulsion 1 (Emulsion-3) Silver amount 0-4g/m
"Coupler Y -10,3M gelatin 1.3g/m" 11th layer: High sensitivity blue sensitive silver halide emulsion layer Average grain size: 1.
0 μm, AgBr 1 emulsion containing 12.5 mol% Ag (emulsion-4) Silver amount 0.8/m" Coupler Y - 10.3 mol Gelatin 2.1 g/m" 12th layer: 1st protective layer UV absorber -10.3g/m" Ultraviolet absorber -20.4g/m" Gelatin 1.2g/m"2
．． 5-G-octylhydroquinone O, 1g/m
``13th layer: second protective layer average particle size 0.08 μm, Ag containing 1 mol% Agl
Non-photosensitive fine grain silver halide emulsion consisting of Br I Silver amount: 0.3 g/m" Polymethyl methacrylate particles (diameter: 1.5 μm) Gelatin: 0.7 g/m2 In addition to the above composition, each layer contains a gelatin hardener. -1, surfactant-1 was added. Also, tricresyl phosphate was used as a coupler solvent.

Next, Sample 14 was prepared with the same structure as Sample 13 except that 0501 mol of the compound of the present invention (Ni 9) was added per 1 mol of silver halide to the third and fourth layers of Sample 13. 1 Sensitizing dye-3 Ultraviolet absorber C, H.

Coupler C-1 Sensitizing dye-1 C,H.

Coupler M-1 Sensitizing dye (CH2hSOx' (CH2)3sO3Na Coupler Y g Gelatin hardening agent ■ Na Surfactant-1 NaOsS CHCOOCHz (CFzCFz) JC
)bcOOcHz(CF2CFz)xH Samples 8 and 9 prepared in this manner were processed into 35 mm color reversal photosensitive materials, photographed with a still camera, and then subjected to the following development process, and the resulting samples were compared. Sample 14 containing the compound (I-9) of the present invention was better than the sample 14 containing the compound (I-9) of the present invention.
Compared to Sample 13 to which 1-9) was not added, sharpness was improved and red color reproducibility was excellent.

Processing process Processing time Processing temperature First development
6 minutes 38°C (±0.3°C) water washing
2 minutes 〃Reversal
2 minutes // Color development 6
Minutes Adjustment 2 minutes //
Bleach 6 minutes
//Constant M 4 minutes
//Wash with water 4 minutes
// Stable 1 minute Constant rotation The composition of the treatment liquid used in the above treatment step is as follows.

First developer Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (l hydrate)
30g1-7enyl-4-methyl-4 pyrazolidone 2g 2.5g Lium 1.2g (0.1% solution) 2mQ1,000
mff Hydroxymethyl-3 Potassium bromide thiocyanate Add potassium iodide water and invert the solution Nitrilotrimethylenephosphonic acid 6-sodium salt Stannous chloride (dihydrate) p-Aminophenol Sodium hydroxide Add glacial acetic acid water Color developer Sodium tetrapolyphosphate Sodium sulfite Sodium tertiary phosphate (dihydrate) Potassium bromide Potassium iodide (0.1% solution) Sodium hydroxide antig g 0.1g g 5mff 1, OOOmQ g g 6g g 0m12 g Ntrazinic acid 1.5g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amine aniline sulfate 11g2.2-ethylenedithiogetanol 1g Add water
l, OOOmQ solution Sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin 0.4mQ Glacial acetic acid
Add 3m+2 water
l, 000m12 bleaching
Liquid sodium ethylenediaminetetraacetate (dihydrate) 2g ethylenediaminetetraacetate iron (Ilff) ammonium (2
water salt) 120g potassium bromide
Add 100g water
1.0OOn+I2 preparation Liquid ammonium thiosulfate 80g Sodium sulfite 5g Sodium bisulfite 5g Water
, 000m12 Stable liquid formalin (37% by weight) 5m
(2 Konidax (manufactured by Konica Corporation) 5m1
2 Add water, l, OOO
mR Example-4 On a subbed transparent polyester base, the following layers were sequentially installed from the support side to prepare sample 15 having the structure shown in Table-4.

1st layer (antihalation layer) A gelatin aqueous solution containing black colloidal silver was mixed with 0.5 g of silver/
Coat at a ratio of m2 to a dry film thickness of 3.0 μm.
child .

Second layer (intermediate layer) An aqueous gelatin solution was applied to give a dry film thickness of 1.0 μm.

Third layer (red-sensitive, low-sensitivity silver halide emulsion layer) silver iodobromide emulsion (silver iodobromide emulsion containing 4 mol% of silver iodide with an average grain size of 0.6 μm and silver iodide with an average grain size of 0.3 μm) A silver iodobromide emulsion containing 4 mol % was mixed in a ratio of 2:1) was chemically sensitized with gold and sulfur sensitizers, and further as a red-sensitive sensitizing dye,
After adding 5DR-1 and 5DR-2, 5DR-1 and 5DR-2 were added as stabilizers.
A red-sensitive, low-sensitivity emulsion containing 0.0 g of T-11 and 0.0 mg of 5T-2 was obtained.

Then, the cyan coupler, DIR compound, colored cyan coupler, antifoggant and high boiling point solvent were added to ethyl acetate 150n+12 and heated to dissolve, 7.5% containing 5g of sodium triisopropylnaphthalene sulfonate.
Added to 500ml of gelatin aqueous solution (2) and emulsified and dispersed in a colloid mill. After heating the dispersion and removing ethyl acetate, the above red-sensitive and low-sensitivity emulsion was added to it to obtain a dry film thickness of 4.
．． It was coated to a thickness of 0 μm (containing 100 g of gelatin per mole of silver halide).

Fourth layer (red-sensitive, high-sensitivity silver halide emulsion layer) A silver iodobromide emulsion (average grain size: 1.2 μm, containing 7 mol% of silver iodide) is chemically sensitized with gold and sulfur sensitizers, and further red After adding 5DR-1 and 5DR-2 as sensitizing dyes, 5T-11,
0g and ST-210mg were added to obtain a red-sensitive and highly sensitive emulsion.

Furthermore, cyan coupler DIR compound, antifoggant and high boiling point solvent were added to 60 mQ of ethyl acetate, dissolved by heating, and sodium triisopropylnaphthalene sulfonate was added.
．． It was added to 30 mα of a 7.5% gelatin aqueous solution containing 5 g and emulsified and dispersed using a colloid mill. The above-mentioned red-sensitive high-sensitivity emulsion was added to this dispersion and coated to give a dry film thickness of 2.0 μm (containing LOOG of gelatin per mole of silver halide).

Fifth Layer (Intermediate Layer) A high boiling point solvent and an antifoggant were added to 2 mQ of ethyl acetate, added to a 7.5% gelatin aqueous solution containing sodium triisopropylnaphthalene sulfonate, and emulsified and dispersed using a colloid mill. Add this to gelatin 1. The coating was applied at a rate of 1.0 g/m'' to a dry film thickness of 1.0 μm.

6th layer (green-sensitive low-sensitivity silver halide emulsion layer) average grain size 0
．． 6 μm, a silver iodobromide emulsion containing 4 mol% of silver iodide, and a silver iodobromide emulsion containing 7 mol% of silver iodide with an average grain size of 0.3 μm,
They were chemically sensitized with gold and sulfur sensitizers, and 5DG-1, 5DG-2, and 5DG-3 were added as green-sensitive sensitizing dyes.
, 0 mg was added and adjusted in the usual manner.

The two types of silver halide emulsions obtained in this way were
: 1 to obtain a green-sensitive and low-sensitivity silver halide emulsion.

Furthermore, magenta coupler, DIR coupler, colored magenta coupler, anti-stick agent, and high boiling point solvent were added to 240 m4 of ethyl acetate, dissolved by heating, and added to a 7.5% aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate to form a colloid. The above-mentioned green-sensitive low-sensitivity emulsion was added to the dispersion emulsified and dispersed in a mill to obtain a dry film thickness of 4.
It was coated to a thickness of 0 μm (contains long gelatin per mole of silver halide).

7th layer (green-sensitive high-sensitivity silver halide emulsion layer) A silver iodobromide emulsion (average grain size 1.2 μm, containing 7 mol% of silver iodide) is chemically sensitized with gold and sulfur sensitizers, and further green 5DG-1% 5DG-2 and 5DG-3 were added as sensitizing dyes, and then 11.0 g of 5T-2 and 10.0 mg of 5T-2 were added to obtain a green-sensitive high-sensitivity silver halide emulsion.

Furthermore, magenta coupler, DIR coupler, colored magenta coupler, antifoggant, and high boiling point solvent were added to ethyl acetate 200i12, dissolved by heating, added to a 7.5% aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate, and placed in a colloid mill. The above-mentioned green-sensitive high-sensitivity emulsion was added to the emulsified and dispersed dispersion to obtain a dry film thickness of 2.
It was coated to a thickness of 0 μm (containing 100 g of gelatin per mole of silver halide).

8th layer (intermediate layer) Same as 2nd layer - 9th layer (yellow filter layer) 2,
3 g of 5-di-1 octyl hydroquinone and 1.5 g of di-2-ethylhexyl phthalate, vinegar H-c 9-1
Add a dispersion of gelatin dissolved in 0 m (2) and dispersed in an aqueous gelatin solution containing 0.3 g of sodium triisopropylnaphthalene sulfonate, and add 0.9 g/m of gelatin.
”, 2,5-di-t-octylhydroquinone 0.10
It was applied at a ratio of g/ml to a dry film thickness of 1.2 μm.

First O layer (blue-sensitive, low-sensitivity silver halide emulsion layer) A silver iodobromide emulsion (average grain size 0.6 μm, containing 6 mol% silver iodide) is chemically sensitized with gold and sulfur sensitizers, and then 5 as a sensitizing dye
Add DB-1, then ST-11,0g5ST-2
20.0 mg was added and adjusted in a conventional manner to prepare a blue-sensitive, low-sensitivity silver halide emulsion.

Furthermore, yellow coupler and high boiling point solvent were added to 30% ethyl acetate.
Add the above blue-sensitive low-sensitivity emulsion to the dispersion that was added to 0m (2), heated and dissolved, added to a 7.5% aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate, and emulsified and dispersed in a colloid mill. Dry film thickness 4.0μm
(24% per mole of silver halide)
Contains 0g gelatin).

Eleventh layer (blue-sensitive, high-sensitivity silver halide emulsion layer) A silver iodobromide emulsion (average grain size 1.2 μm, containing 7 mol% of silver iodide) was chemically sensitized with gold and sulfur sensitizers, and further sensitized. 5 as a sensitive dye
Add DR-1, then 5T-11,0g and 5T-2
10.0 mg was added and adjusted in a conventional manner to prepare a blue-sensitive and highly sensitive silver halide emulsion.

Furthermore, the yellow coupler high boiling point solvent was added to ethyl acetate 24
0+n12, heated and dissolved, added to a 7.5% gelatin aqueous solution containing sodium triisopropylnaphthalene sulfonate, and emulsified and dispersed in a colloid mill.The above blue-sensitive high-sensitivity emulsion was added to the dispersion, and a dry film was formed. Thickness 2. Op
m (1 mole of silver halide)
Contains 60g gelatin).

12th Layer (Intermediate Layer) A high boiling point solvent and an ultraviolet absorber were added to 2 ml of ethyl acetate, added to a 7.5% gelatin aqueous solution containing sodium triisopropylnaphthalene sulfonate, and emulsified and dispersed using a colloid mill. This was coated at a rate of 1.0 g/n+'' of gelatin to give a dry film thickness of 1.0 μm.

13th layer (protective layer) A gelatin aqueous solution containing 4 g% of gelatin and 0.2 g of 1.2-bisvinylsulfonylethane per Loom<2 was added at a rate of 1.3 g/m2 of gelatin to a dry film thickness of 1.2 μm. In Table 4, the amount added is the amount added per mol of silver halide, the coupler and former R coupler colored coupler are expressed in mol%, and the high boiling point solvent and antifoggant are expressed in weight% relative to the amount of coupler. The weight of the agent was measured per unit m2, and the high boiling point solvent used in the 12th layer was used in the same weight (g) (per m'') as the ultraviolet absorber.
The weight of the antifoggant used in the layer (g) per m2
The high boiling point solvent was used in the same weight as the antifoggant.

DR-1 DG-1 DG-2 DG-3 DR-2 DB-1 SOJ-N(C2Hs)s ST-] 5T-2 (Same as Example-3) ■ (Same as Example-3) m2 C11゜ N=N B5-1 J8 ■ 2H5 B5-2 ■ 0M CH.

After 0M CC-1 light was applied, color development was performed according to the same processing steps as in Example-1. The color density of the sample after development was measured using a green filter to obtain data on photographic characteristics. Also, the granularity (RMS) at the image density of Capri+0.7
was measured. , these results are shown in Table-5.

Table-5 H H U-1 (same as ultraviolet absorber-1 of Example-3) Sample 1
The DIR coupler D-2 in the sixth layer of No. 5 was replaced with the comparative compound (c) described in Example-2, the compound Cl-4) of the present invention, (1
Samples 16.17°18 and 19 were prepared in the same manner as sample 15 except that -6) and (II-2) were replaced.

Wedge exposure Table 5 for these samples according to a conventional method shows that the compound of the present invention can improve graininess compared to conventional DIR couplers and conventional DIR compounds without adversely affecting sensitivity and gamma. It turns out.

In addition, the sensitivity and maximum color density are for PDA manufactured by Konica Corporation.
-Measurement was made using a densitometer type 65.

〔Effect of the invention〕

As described above in detail, by using the development inhibitor-releasing compound of the present invention in a silver halide photographic light-sensitive material, an excellent development inhibitor release rate can be obtained in the development process, and an effective development inhibitory effect can be obtained. It became possible to give

Furthermore, even when the development inhibitor-releasing compound of the present invention is incorporated into a silver halide photographic light-sensitive material, it does not adversely affect the photographic properties and storage stability of the light-sensitive material, and improves sharpness, graininess, color reproducibility, etc. was able to improve.

Claims (1)

[Scope of Claims] An image forming method characterized by developing a silver halide photographic material in the presence of a compound represented by the following general formula [I] or [II]. General formula [I] General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, R_3, R_4, R_5, R
_6, R_7 and R_8 each represent a hydrogen atom or a substituent, and at least one of these represents a group that can be separated in the development process to form a development inhibitor. Also, R_3 and R
_4, R_7 and R_8 may be combined with each other to form a hydrocarbon ring. A_1 and A_2 each represent a hydrogen atom or a protecting group for a phenolic hydroxyl group that can be deprotected during the treatment process. ]