JPH02171746A - Development processing method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To lessen the fluctuation in the performance of a developing soln. by long-term use by reducing the grain sizes of the silver halides in the red photosensitive layers of an internal latent image type direct positive photosensitive material and negative type photosensitive material. CONSTITUTION:The internal latent image type direct positive photosensitive material and negative type photosensitive material are subjected to a development processing within the same development processing bath. Both the internal latent image type direct positive photosensitive material and negative type photosensitive material are so formed as to have at least one layer of the red photosensitive layers contg. the silver halide particles having <=0.3mum average grain size. The fluctuation in the performance of the developing soln. by the long-term use is lessened in this way.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an internal latent image type direct positive silver halide photographic material (hereinafter referred to as an internal temperature type direct positive photographic material) and a negative type silver halide photographic material. The present invention relates to a development method for processing materials (hereinafter referred to as negative-tone sensitive materials) with a common developer.

[Background of the invention]

Methods used to create positive images using internal temperature type direct positive light-sensitive materials can be mainly divided into two types in consideration of practical usefulness, excluding special methods.

One type uses a silver halide emulsion that has been fogged in advance and uses solarization or the Burschel effect to destroy fog nuclei (latent images) in exposed areas, thereby obtaining a positive image after development. .

Another embodiment is to use an unfogged internal latent image type silver halide emulsion, and to obtain a positive image by performing surface development after or while performing fogging treatment after image exposure.

The above-mentioned internal latent image type silver halide emulsion refers to a silver halide photographic emulsion which has photosensitive nuclei mainly inside the silver halide grains and forms a latent image inside the grains upon exposure.

This latter type of method generally has higher sensitivity than the former type of method and is suitable for image formation that requires high sensitivity, and the present invention is a technology related to this latter type of method. .

Various techniques are known to date in this technical field. For example, U.S. Patent No. 2,592,250;
, 466.957, 2,497.875, 2,
No. 588.982, No. 3,761.266, No. 3,7
The main methods are those described in No. 61,276, No. 3,796.577, British Patent No. 1.151.363, etc., and using these methods, relatively high sensitivity can be achieved as a direct positive type. photosensitive materials can be made.

Although it cannot be said that a clear explanation has been given regarding the details of the direct positive image formation mechanism, for example, in ``The Theory of the Photographic Process'' by Mies and James,
of the Photographic Process
ss), 3rd edition, p. 161, the process by which a positive image is formed can be understood to some extent by the "desensitizing effect due to internal latent images."

In other words, fog nuclei are selectively generated only on the surface of unexposed silver halide grains due to the surface desensitization effect caused by the so-called internal latent image created inside the silver halide grains by the first image exposure, and then normally It is thought that a photographic image is formed in the unexposed area by development.

As mentioned above, as a means of selectively generating fog nuclei, there is a method called "chemical fogging" in which fogging is performed using a chemical such as a fogging agent, and a method called "optical fogging" in which the entire surface is exposed to light. There is a known method of putting it on.

By the way, when processing internal temperature type direct positive photosensitive materials in a photo processing laboratory, a dedicated processing line for internal temperature type direct positive photosensitive materials is set up separately from the conventional processing line for negative type photosensitive materials. It is common for there to be.

For example, a processing line for negative-tone photosensitive materials has three types of equipment installed separately: an automatic developing machine for negative film, an automatic developing machine for negative paper, and an automatic printing device. The photosensitive material processing line consists of two types of equipment: a dedicated automatic printing device and a dedicated automatic developing machine. Generally, a certain amount of work space is required around each of these devices, and the space necessary for adjusting the refill cock, correcting evaporation, replacing tank fluid, and refilling must also be secured around these devices. Must be.

Therefore, if the above-mentioned equipment is placed separately, it is necessary to ensure that the work spaces around each equipment do not overlap, which may hinder work in narrow spaces such as small-scale color photo labs. , there is a strong desire to standardize processing methods.

Against this background, the present inventor continued research into processing an internal temperature type direct positive light-sensitive material and a negative tone sensitive material with a common developer, but it was found that the following drawbacks were present.

When processing an internal temperature type direct positive photosensitive material alone while replenishing a developer appropriate for the photosensitive material, the leg gradation changes between when preparing a new solution and when using a fatigued solution after long-term use. It has been found that this problem (the more fatigued the liquid is, the softer the tone) occurs regardless of "optical fog" or "chemical fog." Furthermore, it has been found that when a negative-tone photosensitive material is processed alone under the same conditions, the shoulder gradation changes (the more the liquid becomes fatigued, the higher the contrast becomes).

Then, by using a combination of an internal temperature direct positive sensitive material and a negative sensitive material,
If processing is continued while replenishing the developer appropriate for each photosensitive material, the gradation balance of both photosensitive materials will fluctuate, especially the cyan image gradation will greatly vary from the magenta image gradation. It has been found that the problem arises that it becomes more susceptible to the influence of the pH of the developer, making it difficult to obtain stable images.

As described above, it is possible to process internal temperature type direct positive and negative sensitive materials using a common developer, but if the developer is used for a long time and is tired, the performance will be worse than when preparing a new solution. There is a problem. This variation in performance occurs between when preparing a new developer solution and when using a tired solution after long-term use.
This is a serious problem in the industry, and is an important problem that must be solved especially when internal temperature type direct positive and negative materials are processed with a common developer.

[Purpose of the invention]

The purpose of the present invention is to develop an internal temperature type direct positive photosensitive material and a negative photosensitive material using a common developer, thereby achieving stable photographic performance (particularly when preparing a new developer solution and reducing the fatigue fluid after long-term use). It is an object of the present invention to provide a method for developing a poor silver halide photographic material, which provides a method for developing a poor quality silver halide photographic material.

[Structure of the invention]

The above-mentioned object of the present invention includes a step of developing an internal temperature type direct positive photosensitive material and a negative type photosensitive material in the same development processing bath, and All of these are achieved by a method for developing a silver halide photographic light-sensitive material, which is characterized by having at least one red light-sensitive layer containing silver halide grains with an average grain size of 0.3 μm or less. .

[Action of the invention]

When we investigated the cause of performance fluctuations in internal temperature type direct positive and negative type photosensitive materials, we found that the developability of the red photosensitive layer had deteriorated, and silver halide grains in the core layer By reducing the particle diameter, an improvement effect was obtained in a single system. However, it was surprisingly discovered that when the improved internal temperature type direct positive light-sensitive material and the negative-tone light sensitive material were used in combination, a remarkable improvement effect that was not expected from the results of each system alone was obtained, and the present invention has been made. It's arrived.

[Specific structure of the invention]

In the present invention, an internal temperature type direct positive photosensitive material and a negative type photosensitive material are developed using a common processing solution, and an internal temperature type direct positive photosensitive material using a "light fog" method is carried into a processing tank. When a chemical fog type internal temperature type direct positive sensitive material and a negative tone sensitive material are brought into the processing tank, the entire surface exposure is controlled so that the entire surface is not exposed. It is possible to use an automatic developing machine that allows for this.

In the present invention, negative photosensitive material means color photographic paper, color negative film, color reversal film, and color reversal paper.

The processing step used in the present invention is preferably a color development process as a development step.

In particular, as a color development process, it is preferable to perform a color development process, a bleaching process, a fixing process, and a washing alternative stabilization process. Alternatively, the bleach-fixing process can be carried out using a 1-bath bleach-fixing solution.

In addition, in combination with these treatment steps, a pre-hardening treatment step,
A neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development process, an activator process may be performed in which a color developing agent or its precursor is contained in the sensitive material and the development process is performed using an activator solution.

Representative examples of these processes are shown below.

Incidentally, in these treatments, as a final step (final bath), any one of (1) water washing treatment step, (2) water washing alternative stabilization treatment step, or (2) water washing treatment step and stabilization treatment step is performed.

In the processing steps of the present invention, the developing tank is substantially common, and the processing tanks can be made into a unit and connected as needed.

The configuration of the processing tank in the processing method of the present invention is as follows: Preferred representative examples of the processing steps of the present invention *→ (Final melting (A)) *-(Final melting (B)) *→ (Fixing (A)) → (Final melting) Melting (A)) *→ (Fixing (B)
)) → (Final solution (B)) (7) [Color development] - [Bleaching]
- [Fixing] - [Final solution] (8) [Color development] → [Bleach-fixing] - [Final solution] (9) [Color development] → [Neutralization] → [Bleach] → [Fixing] → [Final solution] ] (IOX color development] - [Neutralization] → [Bleach-fixing] - [Final solution] (ll) [Pre-during film] →
[Neutralization] - [Color development] - [Neutralization] → [Washing] - [Bleach] - *※ → [Fixing] → [Washing] → [Post-hardening] → [Final solution] (12X black and white development (B) )) - (, Neutralization (B)) - (Water washing (B)) - (Color development] - *※ - [Bleaching] - [Fixing]
- [Final bath] Among the above treatment steps (1) to (12), the steps enclosed in [ ] represent a common treatment step, while the steps enclosed in () are separate treatment steps, and A is B is for internal temperature direct positive photosensitive materials, and B is for negative photosensitive materials. The ratio of the number of processed sheets of positive-tone photosensitive material and negative-tone photosensitive material can be selected arbitrarily, but it is 20:80 to 80:2.
It is particularly preferable that it be 0.

In the present invention, "substantially common processing tank" usually refers to l
Although it means a tank, it also includes a countercurrent system (cascade system) partitioned into two or three tanks. The countercurrent method also includes a countercurrent method, a forward flow method, which is parallel to the moving direction of the photosensitive material to be processed in plan view, and a parallel overflow method, which is perpendicular to the moving direction of the photosensitive material. It also includes a treatment tank in which two tanks are connected to each other by providing piping or holes. Details of these are described in JP-A No. 60-280207.

The development processing solution of the present invention preferably contains hydroxylamine as a preservative. Hydroxylamine is usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, and acetate.

The concentration of hydroxylamine used in the above-described invention in the color developing solution is usually, for example, 0.05 g/Q or more, more preferably 0.07 g/Q to 4 g/Q, particularly preferably 0.07 g/Q to 4 g/Q. It is 2g/12 to 4g/ff.

Furthermore, the hydroxylamine used in the present invention may be used alone or in combination with other antioxidants such as hydroxylamine derivatives.

In the present invention, it is particularly preferred to use a sulfite or a sulfite ion-releasing compound in combination.

That is, the above-mentioned effect of preventing coloration of the processing liquid becomes even more remarkable in the presence of sulfite or a sulfite ion-releasing compound.

Specific examples of sulfites or sulfite ion releasing compounds include potassium sulfite, sodium sulfite, ammonium sulfite, sodium metabisulfite, potassium metabisulfite,
Examples include bisulfite adducts of formaldehyde, bisulfite adducts of acetaldehyde, bisulfite adducts of propionaldehyde, and bisulfite adducts of glutaraldehyde.

The concentration of the above compound is 1.0X per 112 of the color developing solution.
10-'~1. OX may be in the range of 10-' mole, but
If a large amount of sulfite and sulfite ion-releasing compounds are present, the coloring density of the dye in the light-sensitive material tends to decrease, so 5. OX 10-'~5. OX1
0-" mole.

The color developing solution used in the present invention means a surface developing solution that does not substantially contain a silver halide solvent,
The color developing agent contained in the color developing solution is an aromatic primary amine color developing agent, aminophenol type and p-
722-diamine derivatives are included. These color developing agents can be used as salts of organic acids and inorganic acids, such as hydrochloride, sulfate, p-toluenesulfonate, sulfite, oxalate, and benzenesulfonate.

These compounds are generally about 0.0% in color developer lQ.
Concentrations from 1 g to about 200 g, more preferably from about 1 g to 50 g.
Use at a concentration of g. Also, the processing temperature with the color developer is IO'c! ~65°C is preferred, more preferably 25°C
Processed between °C and 45 °C.

Examples of the aminophenol-based developer include 0-aminophenol, p-aminophenol, 5-aminophenol,
2-hydroxy-toluene, 2-amino-3-hydroxy-toluene, 2-hydroxy-3-amino-1,4-
Dimethyl-benzene and the like are included.

Particularly useful aromatic primary amine color developers include N, N-
A dialkyl-p-phenylenediamine compound,
Alkyl groups and phenyl groups may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N,N-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, NlN-dimethyl-p-7-phenylenediamine hydrochloride. , 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline Ram
, N-ethyl-N-β~hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline -p-toluenesulfonate and the like can be mentioned.

Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials. For example, US Patent 3,7
No. 19,492, a method of incorporating a color developing agent into a metal salt, US Pat. No. 3,342.559, and Research Disclosure.
Sure is hereinafter abbreviated as RD. ) 1976 No. 151
59, a method of incorporating a color developing agent into a Schiff salt, JP-A-58-65429 and JP-A-58-65429;
A method of incorporating it as a dye precursor as shown in No. 24137, etc., a method of incorporating it as a color developing agent precursor as shown in US Pat. No. 3,342,597, etc. can be used. In this case, it is also possible to process the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution, and the bleach-fixing process is carried out immediately after the alkaline solution treatment.

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. Furthermore, various additives such as benzyl alcohol, alkali metal halides, such as potassium bromide or potassium chloride, etc. can be contained.

Further, it may contain a development regulator such as citradinic acid, and a preservative such as a sulfite. Furthermore, various antifoaming agents, surfactants, and organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide can be appropriately contained.

The pH of the color developing solution used in the present invention is usually 7 or more, preferably about 9-13.

In addition, the color developing solution used in the present invention may contain tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary
Alcohol, hydroxamic acid, pentose or hexose, pyrogallol-1,3-dimethyl ether, etc. may be contained.

In the color developing solution used in the present invention, various chelating agents can be used in combination as metal ion sequestering agents. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminopentaacetic acid,
Organic phosphonic acids such as l-hydroxyethylidene-1,1-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphonic acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane-1 , phosphonocarboxylic acids such as 2,4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexamethanoic acid, and polyhydroxy compounds.

The entire surface exposure used in the present invention is preferably carried out at the beginning of development from the viewpoint of shortening the development time. In this case, it is advantageous to start exposure after the developer has sufficiently penetrated the emulsion layer.

In the present invention, means for controlling flashing of the entire surface exposure include Utility Model Application No. 56-130935 and No. 56-1
No. 45049, No. 59-87051, No. 59-870
The exposure apparatus described in No. 52 and JP-A No. 61-114237 can be used.

In the present invention, in order to control the blinking of the entire surface exposure, for example, the operator of an automatic processing machine determines in advance which of the above-mentioned photosensitive materials the photosensitive material to be processed is, and If the photosensitive material to be processed is of the image type, the exposure device can be switched on manually before the photosensitive material to be processed enters the developer solution, or if the photosensitive material to be processed is of the negative type, It is also possible to manually cut off the photosensitive material to be processed before it enters the developer, and instead of manually switching a switch on the reversal exposure device by an operator, a notch or a bar code on the photosensitive material can be used as a detection mark. It can automatically determine whether the photosensitive material is an internal latent image type or a negative type, and can automatically control the flashing of full exposure. Furthermore, the identification determination may be automatic, and the operator may be notified of the determination result by sound or mark display, and the operator may manually switch the flashing of the full exposure.

As the light source for light fog used in the present invention, at least one light source within the wavelength range to which the photographic light-sensitive material is sensitive may be used.
It is desirable to use at least one light source having a wide spectral distribution over the range of 00 nm to 700 nm. For example, a fluorescent lamp with high color rendering properties as described in JP-A-56-17350 may also be used. Furthermore, a combination of two or more types of light sources with different emission distributions and color temperatures may be used, and various filters such as color temperature conversion filters may be used.

The illuminance of the entire surface exposure used in the present invention, that is, the optical fog, is as follows:
It is preferable to use an illuminance that does not cause illuminance failure during photofogging, and although it varies depending on the photosensitive material, it is generally 0.01 to 2000 lux, preferably 0.05 to 30 lux, and more preferably 0.1 to 5 lux. Can be used. Adjustment of the light fog illuminance may be performed by changing the luminous intensity of the light source, or by using various filters to reduce the light, the distance between the light-sensitive material and the light source, the angle between the light-sensitive material and the light source, and the like. Further, in order to shorten the exposure time for light fogging, a method may be adopted in which the light fogging is caused to be fogged with weak light at the beginning of the exposure, and then with stronger light. Furthermore, a method of exposing the entire surface to light while increasing the illuminance as described in Japanese Patent Publication No. 58-1172486 can also be advantageously carried out.

Exposure apparatuses that can be used for full-surface exposure include Utility Model Application Nos. 56-130935, 56-145049, 59-87051, 59-870521, and 61.
-61542 and the apparatus described in JP-A-61-114237 can be referred to.

As the fogging agent that can be used in the present invention, all compounds conventionally developed for the purpose of nucleating endothermic silver halide can be used. Two or more types of fogging agents may be used in combination. To explain in more detail, as a nucleating agent,
For example, RD No. 22534 (January 1983, 50
(pages 1 to 54), and these are broadly classified into three types: hydrazine compounds, quaternary heterocyclic compounds, and other compounds.

First, examples of hydrazine compounds include RDNo,
15162 (November 1976, pp. 76-77) and the same magazine No. 23510 (November 1983, No. 346~
Examples include those described on page 352). More specifically, those described in the following patent specifications can be mentioned. First, as an example of a hydrazine fogging agent having a silver halide adsorption group, for example, U.S. Patent No. 4,030,9
No. 25, No. 4,080,207, No. 4,031,12
No. 7, No. 3,718,470, No. 4,269.929
No. 4,276.364, No. 4,278,748, No. 4,385,108, No. 4,459,347,
British Patent No. 2,011゜391, JP 54-7472
Examples include those described in No. 9, No. 55-163533, No. 55-74536, and No. 60-179734.

Other hydrazine-based fogging agents include, for example, JP-A-57-86829, U.S. Pat. No. 4,560,638,
4゜478.928, and also 2,563.785
No. 2,588.982.

Next, as the quaternary heterocyclic compound, for example, the above-mentioned RD
No. 22534 and Special Publication No. 49-38164, No. 52
-No. 19452, No. 52-47326, JP-A-52-
No. 69613, No. 52-3426, No. 55-1387
No. 42, No. 60-11837, U.S. Patent No. 4°306.
No. 016 and RD No. 23213 (August 1983
May, pp. 267-270).

The fogging agent useful in the present invention preferably has the following general formula (
1), (U) or CI[I).

General formula [C], -Z- In the formula, Z represents a group of nonmetallic atoms necessary to form a 5- to 6-membered heterocycle, and Z may be substituted with a substituent. R
11 is an aliphatic group, and R1□ is a hydrogen atom, an aliphatic group, or an aromatic group.

However, among the groups represented by Rll+ R12 and Z,
At least one contains an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R11 and R1□ form a 6-membered ring to form a dihydropyridinium skeleton.

More specifically, the heterocyclic group completed by Z is, for example, quinolinium, benzothiazolium, benzimidazolium, pyridinium, thiazolium, naphthothiazolium, benzoselenazolium, naphthoxacillium and penzooxazolium. One example is the ram nucleus.

At least one of the groups represented by R11, R11 and Z has an alkyl group, an acyl group, a hydrazine group, or a hydrazone group, or R11, R1! and form a 6-membered ring to form a dihydropyridinium skeleton, but the hydrazine group preferably has an acyl group or a sulfonyl group as a substituent.

The hydrazone group preferably has an aliphatic group or an aromatic group as a substituent.

As the acyl group, for example, a formyl group and an aliphatic or aromatic ketone are preferred.

Some of the alkynyl substituents possessed by either R++, Rt□ or 2 have already been described, but to explain in more detail, they are preferably those having 2 to 181 carbon atoms.
'EH's, such as ethynyl, propargyl, 2-
These groups include phthynyl, 1-methylpropargyl, 1,1-dimethylpropargyl, 3-butynyl, and 4-pentynyl.

R+ At least one of the groups or substituents on the ring represented by R, 2 and Z is an alkynyl group or an acyl group, or when R11 and R12 are linked to form a dihydropyridinium skeleton is preferable, and R1□, R
1! It is most preferable that the group or ring represented by and Z contains at least one alkynyl group as a substituent.

Specific examples of the compound represented by general formula (I) are listed below, but the invention is not limited thereto.

C,Fll CH. CmiCH ■ - Formula (II) "CH2GHz CHO The above-mentioned compounds are, for example, RD No. 22.534
(Published January 1983, pp. 50-54) and US Pat. No. 4,471.044, and similar methods thereof can be used.

Ac-NH-NH-R,.

R2 represents an aryl group or a heterocyclic group, and the nitrogen atom of hydrazine is bonded to the tertiary carbon group of these groups.

Examples of the aryl group of R□ include phenyl group, naphthyl group, etc., and examples of the heterocyclic group include pyridyl, quinolinyl, thiazolyl, benzothiazolyl, naphthothiazolyl,
Examples include groups such as oxasilyl, benzoxasilyl, naphthoxasilyl, imidazolyl, benzimidazolyl, and naphthoimidazolyl (the 3rd position of these heterocyclic groups).
(the nitrogen atom of hydrazine is bonded to the carbon atom).

Up to 20 alkyl groups, alkenyl groups, alkynyl groups, each optionally having substituents, aryl groups optionally having substituents (for example, phenyl, naph and Rls each have a hydrogen atom, 1 to 1 carbon atoms) (20 represents an alkyl group or an aryl group. However, R14 and Rls may form a heterocycle.) R13 represents the same group as R12 or a hydroxyl group.

Typical examples of R22 include a hydrogen atom and a methyl group,
Examples include groups such as ethyl, octyl, trifluoromethyl, perfluoropropyl, phenyl, tolyl, chlorophenyl, nitrophenyl, naphthyl, and substituted naphthyl.

Typical R24 and Rzs include a hydrogen atom, a methyl group, an alkyl group having up to 20 carbon atoms such as an ethyl group, R24
and Rls to form a heterocyclic group such as morpholino, piperazino, pyrrolidino, etc.

- Specific examples of the compound represented by formula (n) are shown below.

However, the present invention is not limited to the following compounds.

Poem I [-4 II -12 II-13 Tomo R 1 [-14 ■-10 S)! ■ The method for synthesizing the compound represented by the general formula (U) used in the present invention is described, for example, in RD No. 15162 (1976
November, pp. 76-77), same magazine No. 22534 (1
January 983, pp. 50-54) and same magazine No. 235
10 (November 1983, pp. 346-352), US Pat. No. 4,080.207, US Pat. No. 4,269,924, US Pat.

Other preferred fogging agents include the following general formula CII:
There is a compound represented by I).

General Formula CI , represents an alkylsulfamoyl group, an arylsulfamoyl group, or an alkoxycarbonyl group, and Rsg and R33 each represent a hydrogen atom, a saturated or unsaturated aliphatic group, an aryl group, or a heterocyclic group. However, R31 may form a methylidene group together with R32, and R6゜ may form a methylidene group together with R and l, and the methylidene group may be substituted with an alkyl group, an aryl group, a heterocyclic group, etc. ,or,
R31 may form a 5- to 6-membered ring together with R34,
For example, a heterocycle such as a 1,2,3,4-tetrazolidine-5-thione ring or a hexahydro-1,2,4,5-tetrazine-3-thione ring may be formed. The group necessary for forming these heterocycles is generally a methylene group, but this methylene group may be mono- or di-substituted, and examples of substituents in this case include alkyl groups, cycloalkyl groups, etc. , an aralkyl group, and an aryl group.

Further, two such substituents (for example, two alkyl groups) may form a ring together with the carbon atoms of the methylene group, and examples of this ring include, for example, cyclopentane, cyclohexane, 3 .3.5-trimethylcyclohexane,
Included are carbocycles such as cyclododecane, indane, and heterocycles such as piperidine.

Examples of such saturated aliphatic groups include alkyl groups, which may be straight chain, branched or cyclic alkyl groups having up to 18 carbon atoms. Further, the alkyl group may have a substituent, and examples of the substituent include a carboxyl group, a carbamoyl group, and a nitrile group.

Moreover, an allyl group is mentioned as an example of the above-mentioned reflexine type unsaturated aliphatic group.

A particularly preferred example of the aryl group is a phenyl group. This phenyl group may be substituted with, for example, a halogen atom, a hydroxyl group, a carboxyl group, a sulfamoyl group, an amino group, an alkyl group, or a combination of two or more types.

Examples of the acyl group, alkylsulfonyl group, arylsulfonyl group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, and alkoxycarbonyl group listed in R31 and R34 include formyl, acetyl, , benzoyl, phenylcarbamoyl, dimethylcarbamoyl,
Examples include groups such as dimethylsulfamoyl and ethoxycarbonyl.

Examples of the heterocyclic group include 5- to 6-membered groups containing atoms such as nitrogen, oxygen, and sulfur, such as furyl.

Specific examples of the compound represented by the formula [■] are listed below.

I[[-2 I[[-4 II[-5 ll-7 I[I-8 +11-9 ■ ll-11 H! NNHC3NHNH2 The method for synthesizing the fogging agent represented by formula CI above is described in U.S. Pat. No. 4,139,387, RD No. 15.
750 (1977), etc.

The above-mentioned fogging agent may be added to the developer or the photographic light-sensitive material, but is preferably added to the photographic light-sensitive material.

- The amount of the fogging agent represented by the formula CI), (I[) or (I[[) when added to a photographic light-sensitive material varies depending on the chemical structure of the compound, and also depends on the silver halide emulsion used. Although it can vary over a wide range depending on the characteristics and development conditions, it is usually preferably in the range of 0.5 mg to 5 g, more preferably 1 mg to 3 g, per mole of internal latent image type silver halide. It is.

In addition, it is preferably contained in the silver halide emulsion layer,
It may also be contained in other hydrophilic colloid layers adjacent to the emulsion layer. In this case, the amount added may be the same as when added to the emulsion layer.

In the present invention, the bleaching process refers to a process of bleaching the developed silver image after the color development process using an oxidizing agent (bleaching agent).

As a bleaching agent, a metal complex salt of an organic acid is used, for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid, oxalic acid, citric acid, etc., coordinated with a metal ion such as iron, cobalt, copper, etc. is used. .

Among the above organic acids, the most preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific examples of these include the following. That is, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, diethylenetriaminepentaacetic acid pentasodium salt, and the like.

These bleaches are used at 5 to 4509/+2, more preferably from 20 to 250 y/Q.

In addition to the bleaching agent mentioned above, it is preferable to add a halide such as ammonium bromide to the bleaching solution. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

In the present invention, the fixing process refers to a process of desilvering and fixing using a fixing solution containing a silver halide fixing agent. Silver halide fixing agents used in the fixing solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes. Typical examples include thiosulfates such as, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and the like.

These fixing agents are used in an amount of 5 g/Q or more, within the range that can be dissolved, but are generally used in an amount of 70 g/Q to 250 g/Q.

In the present invention, it is preferable that the bleaching process and the fixing process are performed in one process using a bleach-fix solution,
The metal complex salt of an organic acid as a bleaching agent used in the bleach-fix solution is an organic acid such as aminopolycarboxylic acid, oxalic acid, citric acid, etc., coordinated with metal ions such as iron, cobalt, copper, etc. .

The most preferred organic acid used to form such a metal complex salt of an organic acid is one similar to a bleaching solution.

As the silver halide fixing agent contained in the bleach-fix solution, there is used a compound which reacts with silver halide to form a water-soluble complex salt, such as those used in ordinary fixing processing.

After the treatment with a treatment liquid having fixing ability, a normal water washing treatment may be performed, but particularly in the present invention, it is preferable to perform a stabilization treatment that does not substantially include a water washing step.

In the present invention, a stabilization treatment that does not substantially include a water washing step refers to a stabilization treatment that is an alternative to water washing using a single tank or multiple tank countercurrent method immediately after treatment with a treatment liquid having fixing ability. It may also include processing steps other than general washing, such as rinsing, auxiliary washing, and known washing promotion baths.

In the stabilization treatment step of the present invention, the method of bringing the stabilizing solution into contact with the silver halide photosensitive material is preferably by immersing the silver halide photographic material in a bath as in a general processing solution. It may be applied to the emulsion surface of the silver halide photographic material, both sides of the transport leader, and the transport belt using a synthetic fiber cloth, or it may be sprayed onto the transport belt.

The case where a stabilizing bath by the immersion method is used will be mainly explained below.

The stabilizing solution preferably contains a chelating agent having a chelate stability constant of 6 or more with respect to iron ions.

Examples of the chelating agent having a chelate stability constant of 6 or more for iron ions include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. Note that the above-mentioned iron ion means ferric ion (Fe'').

Specific examples of chelating agents having a chelate stability constant of 6 or more with ferric ions include diethylenetriaminepentaacetic acid, nitrilotriacetic acid, l-hydroxyethylidene-1,1-diphosphonic acid, and the like.

The amount of the above-mentioned chelating agent used is 0.00% per 112 ml of stabilizing liquid.
The amount is in the range of 0.01 to 50 g, preferably 0.05 to 20 g.

Furthermore, preferred compounds to be added to the stabilizing solution include:
Examples include anti-spill agents, water-soluble metal salts, ammonium compounds, and the like.

The above-mentioned anti-spill agents include hydroxybenzoic acid compounds, phenol compounds, inthiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds, and urea compounds. , inoxazole compounds, propatoolamine compounds, sulfamide compounds, amino acid compounds, and benzotriazole compounds.

Furthermore, as metal salts, Ba, Ca, Ce, Go
, In.

La, Mn, Ni, Pb, Sn, Zn, T
i, Mg, Al1. It is a metal salt of Sr, and can be supplied as an inorganic salt such as a halide, hydroxide, sulfate, carbonate, phosphate, or acetate, or as a water-soluble chelating agent.

The amount used is 1 x 10-' per 112 of the stabilizing liquid.
~ I x 10-' mol, preferably 4
X 10-' to 2×lO 7 moles, more preferably 8 X
It ranges from 10-' to 1×1 O-2 mol.

In addition to the above compounds, the stabilizing liquid also contains optical brighteners, organic sulfur compounds, onium salts, hardeners, quaternary salts, water droplet blocking agents such as polyethylene oxide derivatives, siloxane derivatives, etc.
pH adjusters such as boric acid, citric acid, phosphoric acid, acetic acid, or sodium hydroxide, sodium acetate, potassium citrate, organic solvents such as methanol, ethanol, dimethyl sulfoxide, dispersants such as ethylene glycol, polyethylene glycol, and other color tones. Adjustment agents, etc., improve processing effects,
Addition of various additives for expansion is optional.

The above compounds and other additives can be added to the stabilization tank as a concentrated liquid, or the above compounds and other additives are added to the stabilizing liquid supplied to the stabilization tank and then stabilized. There are various methods, such as using it as a supply solution to the solution, or adding it to the pre-bath of the stabilization treatment process and making it present in the stabilization tank by including it in the silver halide photographic light-sensitive material to be processed. It may be added by any method.

As for the method of supplying the stabilizing liquid in the stabilization treatment step, when a multi-tank countercurrent system is used, it is preferable to supply the stabilizing liquid to the rear bath and overflow from the front bath.

The pH value of the treatment liquid in the stabilizing bath is preferably in the range of 4 to 8.

Further, the pH can be adjusted using the above-mentioned I)H adjusting agent.

The treatment temperature during the stabilization treatment is, for example, 20°C to 50°C.
°C1 is preferably in the range of 25°C to 40°C. In addition, from the viewpoint of rapid processing, a short treatment time is preferable, but it is usually 20 seconds to 5 minutes, most preferably 30 seconds to 2 minutes, and in the multi-vessel countercurrent method, the pre-stage treatment can be performed in a short time. ,
It is preferable that the post-stage treatment time is long.

In the present invention, washing with water may not be necessary before and after the stabilization treatment, but the surface may be cleaned by rinsing with a small amount of water in a short period of time or with a sponge, stabilizing the image, and improving the surface properties of the silver halide photographic light-sensitive material. Providing a treatment tank for adjustment is optional.

Formalin and its derivatives, siloxane derivatives, polyethylene oxide compounds,
Examples include surfactants such as quaternary salts.

In the present invention, it is optional to provide additional processing steps in addition to the above processing steps. Further, silver may be recovered by a known method not only from the above-mentioned stabilizing solution but also from a processing solution containing a soluble silver complex salt such as a stabilizing solution or a bleach-fixing solution.

In addition, if the above-mentioned stabilization treatment is carried out, the washing process is virtually unnecessary, and therefore, there is no need for piping equipment for washing.
This has the advantage that the device itself can be easily installed at any location.

In addition to these treatments, there are methods in which the developer produced by color development is subjected to halogenation bleaching and then color development is performed again, and various intensification treatments (amplification treatments) described in JP-A-58-154839, etc. It may be processed using a development method that increases the amount.

Each processing step is usually carried out by immersing the photosensitive material in a processing solution, but other methods are also available, such as a spray method that supplies the processing solution in the form of a spray, or contacting it with a carrier impregnated with the processing solution. A web method using viscous development processing, a method using viscous development processing, etc. may also be used.

The internal latent image type silver halide emulsion used in the present invention is an emulsion having silver halide grains that mainly form a latent image inside the silver halide grains and has most of the photosensitive nuclei inside the grains. Silver halides such as silver bromide, silver chloride, silver iodochloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide and the like are included. In particular, silver chloride, silver chlorobromide, silver chloroiodobromide, and silver iodochloride are preferred from the viewpoint of grains with a high development speed.

It is preferable that the internal latent image type silver halide grains used in the present invention have their surfaces not chemically sensitized, or even if they are sensitized, the sensitization is only slight.

Specifically, for example, conversion-type silver halide emulsions described in U.S. Pat. Core/shell type silver halide emulsion doped with nuclear sensitive or polyvalent metal ions, JP-A-1973
-8524, 50-38525, 53-240
Laminated silver halide emulsion described in No. 8, and others, JP-A-52-156614, JP-A-55-127549
Examples include the emulsions described in this issue.

The silver halide grain composition of the negative-working silver halide emulsion used in the present invention is not particularly limited, but includes silver chlorobromide, silver iodobromide,
Silver chloroiodobromide is preferred.

Hereinafter, the term "silver halide emulsion of the present invention" generally refers to an internal temperature type direct positive silver halide emulsion and a negative type silver halide emulsion, unless otherwise specified.

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method.

The particles may be grown all at once, or may be grown after seed particles are produced. The method of making and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into consideration the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling the pH in the mixing tank and 1) Ag. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. After growth, a conversion method may be used to change the halogen composition of the particles.

During production of the silver halide emulsion of the present invention, it is possible to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains by using a silver halide solvent as necessary. can.

In the process of forming and/or growing grains, silver nitride grains contain cadmium salts, zinc salts, lead salts, thallium salts,
Metal ions are added using at least one selected from iridium salts (complex salts containing), rhodium salts (complex salts containing), and iron salts (complex salts containing), and these metals are added inside the particles and/or on the particle surfaces. It is possible to contain elements, and by placing them in a suitable reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in RD No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the grain interior and the surface layer. There may be.

Halogen used in the silver halide emulsion of the present invention The silver halide grains used in the silver halide emulsion of the present invention may have regular crystal shapes such as cubic, octahedral, or dodecahedral. It may also have an irregular crystal shape, such as a spherical or plate-like shape.

In these particles, any ratio of the (lO01 plane to the (111) plane) can be used.Also, they may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. .

The average grain size (grain size: defined below) of silver halide grains used in areas other than the red-sensitive layer of the present invention is preferably 5 μm or less, and particularly preferably 3 μm or less.

Further, it is particularly preferable that the ratio of the average grain size of silver halide in the blue-sensitive layer to the average grain size of silver halide in the red-sensitive layer is 1.2:1 or more.

The silver halide emulsion of the present invention may have any grain size distribution. 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). When divided by the average grain size, the value is 0.20 or less, preferably 0.15 or less.In the case of spherical silver halide, the grain size is the diameter of non-spherical silver halide. In the case of shaped particles, the diameter is the diameter when the projected image is converted into a circular image of the same area.) may be used alone or in combination of several types. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

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

The silver halide emulsion of the present invention can be chemically sensitized by conventional methods. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. Sensitizing dyes may be used alone, but
Two or more types may be used in combination. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
During chemical ripening, at the end of chemical ripening, and/or after chemical ripening, until silver halide emulsion is applied, for the purpose of preventing fog during storage or photographic processing, or to maintain stable photographic performance. Compounds known in the photographic industry as anti-capri agents or stabilizers can be added to.

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
Hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, and synthetic hydrophilic polymer substances such as other proteins, sugar derivatives, cellulose derivatives, and single or copolymers can also be used.

The photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention contains one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be used to harden the membrane.

The hardening agent can be added in an amount capable of hardening the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

A plasticizer may be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention for the purpose of increasing flexibility.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer for the purpose of improving dimensional stability.

In the emulsion layer of the light-sensitive material of the present invention, a dye is formed by a coupling reaction with an oxidized form of an aromatic primary amine developer (e.g., p-) unilene diamine derivative, aminophenol derivative, etc.) during the color development process. A dye-forming coupler is used that forms .

The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer.

However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either equivalence may be used, but the magenta dye-forming coupler has the following formula CM-I.
) is particularly preferred.

-Formula CM-I) In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent.

In general formula (M-I), there are no particular restrictions on the substituent represented by R, but typically polygroups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, etc. In addition, halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino , alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylaminolkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, as well as spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

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

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

The cycloalkenyl group represented by R has 3 to 3 carbon atoms.
12, especially those of 5 to 7 are preferred.

Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, aryloxyphosphonyl groups, etc. Nyl group, arylphosphonyl group, etc.; Acyl group includes alkylcarbonyl group, arylcarbonyl group, etc.; carbamoyl group includes alkylcarbamoyl group, arylcarbamoyl group, etc.; sulfamoyl group includes alkylsulfamoyl group,
Arylsulfamoyl group, etc.; Acyloxy group includes alkylcarbonyloxy group, arylcarbonyloxy group, etc.; carbamoyloxy group includes alkylcarbamoyloxy group, arylcarbamoyloxy group, etc.; ureido group includes alkylureido group, arylureido group. etc.; As the sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc.; as a heterocyclic group, a 5- to 7-membered one is preferable; specifically, a 2-furyl group, a 2-thienyl group , 2-pyrimidinyl group, 2-benzothiazolyl group, etc.; as the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferable, such as 3,
4,5.6-tetrahydrobilanyl-2-oxy group, ■
-Phenyltetrazole-5-oxy group, etc.; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1 , 3,5-triazole-6 monothio group, etc.; Siloxy groups include trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide groups include succinimide group, 3-hebutadecylsuccinimide group, 7-thalimide group, glutarimide group, etc.; spiro compound residues include spiro[3,3]hebutan-1-yl; bridged hydrocarbon compound residues include bicyclo[2°2.1
1 hebutan-1-yl, tricyclo [3,3,1,1
3.1]decane-1-yl, 7,7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy General formula (M-11 ) (R1' is the same as the above R, Z' is the same as the above Z, and R, / and R1' are hydrogen atoms, aryl groups,
Represents an alkyl group or a heterocyclic group. ) and the like, preferably a norogen atom, especially a chlorine atom.

Further, examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and examples of the substituents that the ring may have include those mentioned above for R. Things can be mentioned.

More specifically, what is represented by the general formula CM-1 is, for example, the following -Satsuri CM-n) to -General formula M-■] General formula CM-Ill) General formula (M-IV) General formula (M- V) General formula CM-Vl) General formula [M-■] -N-N R in the above-mentioned -slaughter [M-III to [M-■].

~R8 and X have the same meanings as R and X above.

Moreover, among -M-Il, preferred is the one represented by -M-Il below.

In the formula, R, , X and Zl represent the general formula [R in M-Il,
It is synonymous with X and Z.

Among the magenta couplers represented by the above-described formulas [M-n] to [M-■], particularly preferable ones have the general formula [M-■].
-n ] is a magenta coupler.

- Substituents which the ring formed by Z in M-Il and Z in - M-Il may have, and - M-II [M-I[]
R1 to R in ~[M-VI], the following -
It is preferable to use the expression [M-ff].

-Salting [M-II] -R'-SO, -R' In the formula, R1 represents an alkylene group, and R2 represents an alkyl group, a cycloalkyl group, or an aryl group.

The alkylene group represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and does not matter if the straight chain has 9 branches.

The cycloalkyl group represented by R2 is preferably a 5- to 6-membered one.

In addition, when used for positive image formation, the substituent R on the heterocycle
And the most preferable as R1 is the following - killing [M-
X].

-Slaughter [M-X] R.

R+o-C R1 dish formula Rs, R+. and R11 each have the same meaning as R above.

Also, the above R,,R,. and two of R11, for example R9
and R. may be combined to form a whole saturated or unsaturated ring (e.g. cycloalkane, cycloalkene, heterocycle), and R11 may be further combined to the ring to form a bridged hydrocarbon compound residue. .

- Among the killing [M-X], (i) R9-
When at least two of R1 are alkyl groups, (i
i) One of R1-R11, for example R1+, is a hydrogen atom, and the other two, R3 and R1°, combine to form a cycloalkyl together with the root carbon atom.

Furthermore, in (i), it is preferable that two of R9 to R11 are alkyl groups and the other one is a hydrogen atom or an alkyl group.

In addition, when used for negative image formation, the substituent R on the heterocycle
And the most preferable as R1 is the following - killing [M
-XI].

-Slaughter [M XI] R+2CH2-R1 in the formula
□ has the same meaning as R above.

Preferred as R12 is a hydrogen atom or an alkyl group.

Specific examples of such compounds include JP-A No. 62-166339.
Compounds N011 to N0.223 described on pages 66 to 122 of the No. 1 specification can be mentioned.

Also, the coupler is described in the Journal of the Chemical
Society 4 (Journal of the Ch
chemical Society), Perki
n) I (1977), 2047-2052, U.S. Patent No. 3,725.067, Japanese Patent Application Publication No. 59-99437,
No. 5842045, No. 59-162548, No. 59
-171956, 6033552, 60-43
No. 659, No. 60-172982 and No. 60-190
It can be synthesized by referring to No. 779 and the like.

The couplers of the invention typically have lX per mole of silver halide.
It can be used in a range of 10-3 mol to 1 mol, preferably IX 10-'' mol to 8 X 10-' mol.

The couplers of the present invention can also be used in combination with other types of magenta couplers.

Dye-forming couplers can be used as development accelerators, bleach accelerators, developing agents, silver halide solvents, toning agents, hardeners, fogging agents, antifoggants,
Compounds that release photographically useful fragments such as chemical sensitizers, spectral sensitizers, and desensitizers can be included.

These dye-forming couplers may be combined with colored couplers that have a color correction effect or DIR couplers that release a development inhibitor during development and improve image sharpness and image graininess.

In this case, it is preferable that the dye formed from the DIR coupler is of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not noticeable, a different type of dye may be used. It may also be one that forms a pigment.

In place of, or in conjunction with, the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

A colorless coupler that undergoes a coupling reaction with an oxidized aromatic primary amine developer, but does not form a dye, can also be used in combination with a dye-forming coupler.

The support used in the photosensitive material of the present invention includes α-thin polymers (e.g. polyethylene, polypropylene,
Flexible reflective supports such as paper laminated with ethylene/butene valve type), synthetic paper, etc., semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. These include films made of materials, flexible supports made of these films with reflective layers, glass, metals, ceramics, etc.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material has sensitivity. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser beams, light emitting diode lights, electron beams, X-rays, and gamma rays. Any known light source can be used, such as light emitted from a phosphor excited by alpha rays or the like.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 <Preparation of internal temperature type silver halide emulsion> A core/shell type silver chloride content silver halide emulsion DP-1 as shown in Table 1 was prepared according to the method described in JP-A-55-127549. -12 were prepared.

(Silver chloride content was kept constant) Silver chlorobromide negative-working silver halide emulsions NE-1~
6 was prepared.

Table 2 * Add 5 mg of sodium thiosulfate and 6 mg of chloroauric acid (tetrahydrate) per mole of silver in the core to 80 °C at 75 °C.
Heat for a minute.

<Preparation of negative silver halide emulsion> According to the method described in Japanese Patent Publication No. 46-7772, the following formulas are shown in Table 2.
Internal temperature type direct positive color photosensitive material sample 1 using “optical fogging” method
Preparation of Sample 6> Sample 1 was prepared by sequentially applying the following layers onto a resin-coated paper support from the support side.

Layer 1: Red-sensitive silver halide emulsion layer 2,4-dichloro-3-methyl-6-Ca-(
Mix and dissolve 70 g of 2,4-di-L-amylphenoxy)butyramide]phenol, 2 g of 2.5-';-octylhydroquinone, 50 g of dibutyl phthalate, and 140 g of ethyl acetate, and add to the gelatin solution containing sodium isobrobylnaphthalene sulfonate. Emulsified and dispersed.

Next, the dispersion was added to the emulsion DP-3 which had been spectrally sensitized with the following sensitizing dye and
-Dihydroxy-4-sec-octadecylbenzenesulfonate potassium Ig was added, bis(vinylsulfonylmethyl)ether was added as a hardening agent, and the amount of silver was 400 m.
g/m" and the coupler amount was 460 mg/m".

Layer 2: Intermediate layer 100 mQ of a 2.5% gelatin solution containing 5 g of gray colloidal silver and 10 g of 2,5-di-octylhydroquinone dispersed in dibutyl phthalate was mixed with an amount of colloidal silver of 400 mQ.
It was coated at a concentration of mg/112.

Layer 3: green-sensitive silver halide emulsion layer containing 1-(2,4,6-trichlorophenyl)- as a magenta coupler
3-(2-chloro-5-octadecylsuccinimideanilino)-5-pyrazolone 40g52.5-di-L-octylhydroquinone 1g1 Dioctyl phthalate 7
5 g and 30 g of ethyl acetate were mixed and dissolved, added to a gelatin solution containing sodium isopropylnaphthalene sulfonate, and emulsified and dispersed.

Next, the dispersion was added to the emulsion DP-7 which had been spectrally sensitized with the following sensitizing dye and
- Add 1 g of potassium di-hydroxy-4-sac-octadecylbenzenesulfonate, add bis(vinylsulfonylmethyl) ether as a hardening agent, and reduce the amount of silver to 400.
mg/m", and the coupler amount was 400 mg/m2.

Layer 4...Yellow filter layer Yellow 5 g of colloidal silver and 5 g of 2,5-di-t-octylhydroquinone dispersed in dibutyl 7 tallate.
2.5% gelatin solution containing 200mg/colloidal silver
It was applied so that it became m2.

Layer 5: Blue-sensitive silver halide emulsion layer containing α-(4-(1-benzyl-2.phenyl-
3,5-dioxo-1,2,4-triaziridinyl)]
-]α-pivalyl-2-chloro-5-γ-(2,4-di-monoamylphenoxy)butyramide]acetanilide 80 g 12.5-di-L-octylhydroquinone I
gs dibutyl phthalate 80g 1 ethyl acetate 200g
The mixture was mixed and dissolved, added to a gelatinner solution containing sodium isopropylnaphthalene sulfonate, and emulsified and dispersed.

Next, the dispersion was added to the emulsion DP-9 which had been spectrally sensitized with the following sensitizing dye, and 2.5
-Dihydroxy-4-sec-octadecylbenzenesulfonate potassium Ig was added, bis(vinylsulfonylmethyl)ether was added as a hardening agent, and the amount of silver was 380 m
g/m", and the amount of coupler was 530 mg/m".

Layer 6: Ultraviolet absorbing layer 0.54 g/m'' of gelatin, 0-12 g/m'' of O dissolved in the following solvent, 1 g/m'' of the following ultraviolet absorber (
UV-1) and 0.12 g/m' of ultraviolet absorber (UV
-2) A layer containing.

Preparation of negative color photographic material samples I to ① The negative silver chlorobromide emulsions NE-1, -3, and -4 were each chemically sensitized using sodium thiosulfate pentahydrate to stabilize them. As an agent, 4-hydroxy=1,3°3a,7-chitrazaindene was added.

Regarding NE-1, the following sensitizing dye layer 7 was coated so that the amount of gelatin applied to the protective layer was 1.23 g/m<2>.

Sample 1 was prepared by containing saponin as a coating aid in Layer 1, Layer 2, Layer 3, Layer 4, Layer 5, and Layer 6.

Sample 2 was prepared in exactly the same manner except that the emulsions of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer were changed as shown in Table 3.
~6 was created.

was added to prepare a blue-sensitive silver chlorobromide emulsion (NE-IB).

For NE-3, the two sensitizing dyes used in layer 3 of the direct positive light-sensitive material were further added to form a green-sensitive silver chlorobromide emulsion (NE-3).
3G).

For NE-4, the two sensitizing dyes used in layer 1 of the direct positive light-sensitive material were further added to form a red-sensitive silver chlorobromide emulsion (NE-4).
4R).

On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side.

Incidentally, unless otherwise specified, the amount added indicates the amount applied per llm2 of the sensitive material.

Layer 1: 1.2 g of gelatin, 0.32 g (in terms of silver, the same applies hereinafter) of blue-sensitive silver chlorobromide emulsion (NE-IB), 0
．． 0.80g dissolved in 50g dioctyl phthalate
A layer containing a yellow coupler (Y-1').

Layer 2...0.70g gelatin, 12+++g anti-irradiation dye (AI-1), 6mg (AI-
2) The middle layer consists of:

Layer 3: 0.62 g of magenta coupler (M-1) dissolved in 1.25 g of gelatin, 0.25 g of green-sensitive silver chlorobromide emulsion (NE-3c), 0.30 g of dioctyl phthalate. Containing layer.

Layer 4: Intermediate layer consisting of 0.20 g of gelatin.

Layer 5...1.20g gelatin, 0-30g red-sensitive silver chlorobromide emulsion (NE-4R), 0.45g cyan coupler (C) dissolved in 0.20g dioctyl phthalate.
-1) A layer containing.

Layer 6: Layer containing 0.30 g of ultraviolet absorber (UV-2) dissolved in 1.00 g of gelatin and 0.20 g of dioctyl 7-talate.

Layer 7: Layer containing 0.50 g of gelatin.

As a hardening agent, sodium 2,4-dichloro-6-hydroxy-S-triazine was added to layers 2, 4 and 7 in an amount of 0.017 g per 1 g of gelatin, respectively.

Cθ ff C-1 Samples (1) to (2) were prepared in exactly the same manner except that the emulsion used in the optical layer was changed as shown in Table 4.

Cα I-1 I-2 Negative color photosensitive material sample I was prepared as described above.

Separately, the blue photosensitive layer, green photosensitive layer, and red sensitivity direct positive samples 1 to 6 and negative samples I to ■ were cut to a width of 82 mm, and for samples 1 to 6, color reversal film was photographed with a camera using ASAloo. Then, using the positive obtained by color development, uniform image exposure was applied using an auto color printer, and color negative film was applied to AS for sample processing ~
A negative image was photographed with an Aloo camera and subjected to color development processing, and uniform image exposure was applied using an autocolor printer, and a test was conducted using an automatic processor shown in FIG. 1.

Incidentally, FIG. 1 is a schematic diagram showing an example of an automatic processor that can be used in the processing of the present invention. As shown in the figure, the automatic processor main body l is composed of a paper feed section 2, a photographic processing section 3, and a drying section 4. Ru.

Silver halide photographic light-sensitive material 5, which is a sample according to this example
is formed into a roll and stored in a dark box 6.

The silver halide photographic light-sensitive material 5 pulled out from the dark box 6 is developed in the photographic processing section 3 while being conveyed by a series of pressure-contact rotating rollers.

In this embodiment, the photo processing section 3 has four processing tanks, namely:
Development processing tank 7, bleach-fixing processing tank 8 and stabilization tank 9, 9'
It consists of The stabilization tank 9°9' is of a two-way countercurrent type. Further, the exposure device 11 is detected by the sensor 13 when the silver halide photographic light-sensitive material 5 is an internal temperature image type direct positive light-sensitive material of the "light fog" type, and the fluorescent light 1 is detected by the sensor 13.
By turning on 2, fog exposure is provided during development processing, but fog exposure is not provided when a negative-tone photosensitive material is used.

In the photographic processing section 3, the exposed silver halide photographic material 5 is processed for a predetermined time in each processing tank, and then sent to the drying section 4 where it is dried, and then cut into a predetermined length by a cutting member 14. It is cut and discharged from the device.

In the figure, 15 is a waste liquid storage section, and 16 is a replenishment liquid storage section.

The processing conditions are as follows.

Processing process Processing temperature Processing time 1, Color development (Note 1) 38°C 2 minutes 2, Bleach fixing 35°C 50 seconds 3, Stable 32°C 1 minute (Note 1) Full-surface exposure is performed when the sample is in the color developing solution. The setting was such that the light was irradiated for 10 seconds.

A processing solution having the following composition was used as the processing solution.

Color developer Benzyl alcohol 16I112 Ethylene glycol 16m12 Hydroxylamine sulfate 3,0 g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) Aniline sulfate 5.7 g 3-Methyl-4-amino -N-Ethyl-N-β-hydroxyethylaniline sulfate Potassium carbonate Potassium sulfite (50% solution) Potassium bromide polyphosphoric acid (TPPS) Finished to IQ with water. (pH 10,20) Color developer replenisher Benzyl alcohol Ethylene glycol Hydroxylamine sulfate 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) Aniline sulfate (Kodak CD-3) 3- Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate (Kodak CD-4) Potassium carbonate Potassium sulfite (50% solution) Polyphosphoric acid (TPPS) Finished with water to IQ, potassium hydroxide 2 .4g 5g 7-5ra (1 4, Og rum or sulfuric acid g 5g 6+a4 1, Og 3.0g 20+iff 0IIIa 3.0g 6.8g Adjusted to pH 10,60.

Bleach-fix solution Ethylenediaminetetraacetic acid iron(III) Ammonium salt 70g Ammonium sulfite 5.0g Ammonium thiosulfate 150g Aqueous ammonia (28%
) It was finished to 1Q with 10ml of water and adjusted to pH 7.5 with acetic acid and aqueous ammonia.

Bleach-fix replenisher ethylenediaminetetraacetic acid iron (I [I) Ammonium salt 80g Ammonium sulfite 10g Ammonium thiosulfate 180g Aqueous ammonia (28%)
The pH was adjusted to 112 with 10 ml of water, and the pH was adjusted to 7.0 with acetic acid and aqueous ammonia.

Stabilizer and stabilizer replenisher 2-methyl-4-isothiazolin-3-one 0.0
1g1~Hydroxyethylidene-1,1-diphosphonic acid 1.5g Finished to IQ with water and adjusted to pH 7.0 using potassium hydroxide.

3.2 tons of color developer replenisher per 100 cm of photosensitive material
a(1) 3.2 mff of bleach-fixing replenisher is replenished per 100 cm' of light-sensitive material to the bleach-fixing bath. Also, 3.2 mff of stable replenisher is replenished per LOOcm' of light-sensitive material. There are also 2 tanks of stabilizing solution. A countercurrent system is used, and the final tank is replenished.

In the processing line a, sample 1 was continuously processed (hereinafter referred to as 2 rounds) until the total amount of color developer replenisher became twice the amount of the color developer tank for 10 days.

Hereinafter, the samples to be continuously processed in the same manner were changed to form processing lines b-g.

Processing line b: Continuously processes sample I for 2 rounds over 10 days Processing line C: Continuously processes sample 3 for 2 rounds over 10 days Processing line d: Continuously processes sample ■ for 2 rounds over 10 days Processing line e...Sample 33m" and Sample I3+++"
2 rounds of continuous processing for 10 days while alternating processing Processing line f...Sample 13+a" and Sample] I3m"
2 rounds of continuous processing on IO days while alternating processing Processing line g...Sample 33IIlffi and Sample ll
3m" was processed in two consecutive rounds for 10 days, alternating with each other. Samples were wedge-exposed to view the photographic properties.

3 and Samples I and II were processed at the beginning of each line and at the end of the second round. Table 5 shows similar values (relative values) at the end of the second round, assuming that the ratio of the cyan gradation to the magenta gradation at the start of processing of the image obtained by processing is 100.

As is clear from Table 5, the processing line g according to the present invention is
It can be seen that there is almost no variation in the ratio of cyan gradation to magenta gradation between the start of processing and the end of continuous processing, indicating excellent processing stability.

Example 2 The pH of the color developer and replenisher used in Example 1 was adjusted to 9.5.
．． 10.2.11.5 was obtained by processing in exactly the same manner as in Example 1, and when the ratio of cyan gradation to magenta gradation at the start of processing was set to 100, 2
Similar values (relative values) at the end of the round are shown in Table 6.

As is clear from the results in Table 6, it can be seen that the processing line g according to the present invention has a small pH dependence of the color developer and is excellent in processing stability.

Example 3 Processing lines a, c, e, f used in Example 1
The internal temperature type direct positive light-sensitive material used in , g is transferred to processing line a.

Example 1 was carried out in exactly the same manner as in Example 1, except that the combination of f to sample 2 and processing line C+e+g to sample 40 was changed, and as a result, only processing line g according to the present invention had excellent processing stability. obtained similar results.

Example 4 The same procedure as in Example 2 was carried out except that the treatment lines a''g of Example 3 were used, and the same results were obtained.

Example 5 The procedure was carried out in exactly the same manner as in Example 1, except that the following developing agents were added at 1.0 g/12 and 1.2 g/l to the color developer and color developer replenisher used in Example 1, respectively. Similar results were obtained.

Example 6 Except for changing the treatment liquid used in Example 1 as follows,
It was carried out in exactly the same manner as in Example 1, and similar results were obtained.

(Processing liquid composition) Color developer benzyl alcohol 15+12Ce
z(SO2)s O,0
15g ethylene glycol 8111
Potassium bisulfite 2.5g Potassium bromide 0.8g Sodium chloride 0.2g Potassium carbonate
25.0g4-hydroxy-6-
Methyl-1,3,3a,7-chitrazaindene 0.
1g hydroxylamine sulfate 5.0g diethylenetriaminepentaacetic acid 2g developing agent (C
D-1) 4.2g optical brightener (
4,4'-diaminostilbendisulfonic acid derivative)
1.0g potassium hydroxide
2.0g diethylene glycol
Add 15mff water to make a total volume of 1f2, and adjust the pH to 10.20.
Adjust to.

CD-1 Benzyl alcohol Ce3(SOa)s Ethylene glycol Potassium sulfite Potassium bromide Sodium chloride Potassium carbonate 19+4 0.019g 10ff10°3.1g 0.2g O,1g 31.3g 4-Hydroxy-6-methyl-1,3 , 3a, 7-titrazaindene hydroxylamine sulfate diethylenetriaminepentaacetic acid developing agent (CD-1) Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) Potassium hydroxide diethylene glycol water was added to make the total amount If, Bleach-fix solution Ferric ammonium dihydrate ethylenediaminetetraacetate Ammonium thiosulfate ethylenediaminetetraacetate (70% solution) Ammonium sulfite (40% solution) Add water to bring the total volume to lα, and adjust the pH to 7.1 with potassium carbonate glacial acetic acid. .

Bleach-fix replenisher Ethylenediaminetetraacetic acid 1.25g 2.5g 9mn Adjust the pH to 10.60.

0.13g 6.3g 2.5g 5.3g 0g g 00mff 27.5mI2 Rum or ferric ammonium dihydrate 70g ethylenediaminetetraacetic acid 3.5g ammonium thiosulfate (70% solution) 120m + 2 ammonium sulfite (40% solution) 50mff Add water to bring the total volume to 1Q, adjust the pH to 6 with potassium carbonate or glacial acetic acid,
Adjust to 7.

Stabilizing and Stable Replenisher 5-chloro-2-methyl-4-inthiazolin-3-one 1.0 g Ethylene glycol 10 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.5 g Bismuth chloride 0.2 g Magnesium chloride 0 .1g ammonium hydroxide (28% aqueous solution) 2.0g sodium nitrilotriacetate Add 1.0g water to bring the total amount to 112
and adjust the pH to 7.0 with ammonium hydroxide or sulfuric acid.

Note that the stabilization treatment was performed using a countercurrent method with a two-tank configuration.

Example 7 A treatment line h shown below was installed and compared with treatment line g of Example 1 in the same manner as in Example 1. Table 7 shows the results.

Processing line h...Continuous processing for 2 rounds for 10 days while alternately processing sample 53m2 and sample ■3■2.

Sample 7 was prepared in exactly the same manner as Sample 3 in Example 1, except that the magenta coupler was changed to the following compound (MC-1).

As shown in Table 7, in the present invention, Sample 5 and Sample 2, in which the ratio of the more preferable blue-sensitive silver halide grain size to red-sensitive silver halide grain size is 1.2:1.0 or more, are continuously used. It can be seen that the treated treatment line h has better treatment stability. Furthermore, similar results were obtained when sample 6 was used instead of sample 5 and when sample 2 was used instead of sample 2 in the processing line h.

Example 8 A processing line i shown below was installed, and the results were compared with the processing line g of Example 1 in the same manner as in Example 1. Table 8 shows the results.

Processing line i...sample 73a+' and sample I [3m"
Two consecutive rounds of treatment were carried out on IO days, with alternating treatments.

As shown in Table 8, in the present invention, processing line i, in which sample 7 was continuously processed using the more preferred magenta coupler MC-1, had better processing stability.

Example 9 Sample V was prepared in exactly the same manner as Sample ① of Example 1, except that the magenta coupler was changed to the following compound (MC-2).

MC-2 A treatment line j shown below was installed, and the results were compared with the treatment line g of Example 1 in the same manner as in Example 1. Table 9 shows the results.

Processing line j...Sample 33ffi2 and sample V3m"
2 rounds of continuous treatment for 10 days with alternating treatments.

As is clear from Table 9, in the present invention, processing line j in which sample V was continuously processed using the more preferred magenta coupler MC-2 exhibits better processing stability.

Example 1O Blue photosensitive layers of Samples 1 to 6 prepared in Example 1.

The above fogging agent I [-
9 per mole of Ag, respectively. Positive silver halide color photographic light-sensitive materials 1' to 6' were prepared in the same manner except that 0 mg of each was added.

Example 1 was carried out in exactly the same manner as in Example 1, except that the positive-tone sensitive materials processed in Example 1 were changed to the corresponding samples 1' to 6', respectively, and the same results were obtained.

Example 11 Except for using samples 1' to 6' prepared in Example 1O,
It was carried out in exactly the same manner as in Example 2, and the same results were obtained.

Example 12 Except for using the color developer and color developer replenisher used in Example 5, the same procedure as in Example 10 was carried out to obtain the same results.

Example 13 Example 1O except that the treatment liquid used in Example 6 was used.
The procedure was carried out in exactly the same manner as above, and the same results were obtained.

Example 14 Table 1O shows the results obtained when the number of sheets of internal temperature type direct positive light-sensitive material and negative-tone light-sensitive material to be processed was varied as shown in Table IO in the processing line g used in Example 1.

FIG. 1 is a schematic diagram showing an example of an automatic developing machine that can be used in the processing of the present invention.

l...Automatic processor main body 3...Photographic processing section 5...Photosensitive material 7...Development processing tank 9.9'...Stabilization tank 12...Fluorescent lamp 14...Cutting member 16...Replenisher storage section 2...Paper feed section 4...Drying section 6...Dark box 8...Bleach-fixing treatment tank 11...Exposure device 13...Sensor 15...Waste liquid Storage Department Taganhito Konica Corporation As is clear from the results in Table IO, the treatment in the present invention with a more preferable number of sheets to be treated has better treatment stability.

[Brief explanation of the drawing]

hand Continued Supplementary Positive book Heisei November 24, 1 year

Claims (1)

[Claims] In a method for processing a silver halide photographic material in which an internal latent image type direct positive silver halide photographic light sensitive material and a negative working silver halide photographic light sensitive material are developed in the same development bath, the internal latent image type direct Both the positive silver halide photographic light-sensitive material and the negative silver halide photographic light-sensitive material have at least one red light-sensitive layer containing silver halide grains having an average grain size of 0.3 μm or less. A method for developing a silver halide photographic material, characterized by: