JP2001330934A - Processing method for silver halide color photographic sensitive material and color photographic processing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method for a color photographic sensitive material in which a desilvering step can rapidly be carried out without impairing image stability and a processing solution is stable and does not cause turbidity during use. SOLUTION: In the processing method, a silver halide color photographic sensitive material is processed with a processing solution containing a heterocyclic compound substituted by a sulfonic acid group or a phosphonic acid group and a mercapto group, an aryl compound or an aliphatic compound, in particular an azole ring, pyrimidine ring or triazine ring compound substituted by a sulfonic acid group and a mercapto group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, to secure image stability even if the silver halide color photographic light-sensitive material is rapidly processed. The present invention relates to an improved processing method and a processing agent used for the method.

[0002]

2. Description of the Related Art In general, processing of a silver halide color photographic light-sensitive material comprises, as basic steps, a color developing step (particularly a color developing step), a desilvering step and an image stabilizing step such as washing with water. In the color development step, an image-like dye and developed silver are generated by a reaction between the color developing agent and the silver salt. In the desilvering step, the developed silver generated in the color developing step is oxidized (bleached) to a silver salt by a bleaching agent having an oxidizing action, and is further removed from the photosensitive layer by a fixing agent that forms soluble silver together with unused silver halide. Is done. Alternatively, oxidation to a silver salt and its removal are performed in one step by a bleach-fix solution. The image stabilization step is a step of adjusting the atmosphere of the image layer in order to secure long-term stability of the formed image,
Either a rinsing and image stabilizing bath or a stabilizing bath instead of rinsing is performed. Each processing step is basically a step of immersion in an aqueous solution of a chemical (referred to as a processing liquid), so that the steps are complicated and a long processing time is required.

The simplification and speeding up of processing of silver halide photographic light-sensitive materials has been an important issue in the past. However, in recent years, practical use of non-silver salt recording materials, especially magnetic recording materials, With the commercialization of electronic recording materials such as cameras, there is a stronger demand. Regarding the speeding up of processing, measures such as increasing the processing temperature, activating the processing solution, and strengthening the stirring in the processing tank have been actively taken over the respective steps of color development, desilvering and image stabilization. . Among them, the desilvering step is a step that requires a relatively long processing time, and therefore requires particularly rapid processing.

Conventionally, the speed of the desilvering process has been described in JP-A-8-201997, JP-A-9-5964 and JP-A-9-2964.
Japanese Patent No. 11820 discloses that the processing can be speeded up by including a specific thione compound, a mercapto compound, particularly a mercaptoazole in a processing solution having a fixing ability. Although the processing time can be shortened by the effect of promoting the fixation of these sulfur-containing compounds, the effect is limited and it is still not enough to meet the demand for speeding up from the market. That is, even if these sulfur-containing compounds are added, if the processing time is shortened and fixing is not completed, silver halide remains in the light-sensitive material and the stability of the processed image is significantly impaired, and If the amount of the compound is increased, an adverse effect such as precipitation of an insoluble silver compound appears in the processing solution, so that the effect of speeding up to a sufficient level cannot be obtained.

To solve this problem, Japanese Patent Application Laid-Open No. H11-316
According to Japanese Patent No. 445, there is a compound in which the residual silver halide in the light-sensitive material does not adversely affect the aging stability of the image even if the fixing time is shortened and the fixing is not completed. It is disclosed that if used, the desilvering step can be shortened because the image stability over time is maintained even if the desilvering is not completed. Although this disclosed technique is an effective means, the time required for the desilvering step is still longer than the time required for color development, and the time required for the desilvering step accounts for a large proportion of the entire processing step. Therefore, speeding up the desilvering process is still strongly demanded.

Further, in the above-mentioned disclosed technologies, during the continuous processing, the desilvering-promoting compound causes turbidity, coloration, precipitation, etc. of the insoluble silver salt in the processing solution during the continuous processing. With the secondary defect of impairing the stability of the liquid,
This limits the long-term stable development work in a development facility. This defect is particularly noticeable in the off-season when the processing solution tends to stay for a long time in the processing tank of the developing machine. For this reason, it is required that the accelerator added for accelerating the desilvering has high stability during use of the processing solution.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above background, and an object thereof is to shorten a desilvering step in processing a silver halide color photographic light-sensitive material. It is an object of the present invention to provide a method for processing a color photographic light-sensitive material, which can speed up the desilvering process without deteriorating the image stability. It is a further object of the present invention to provide a method for processing a color photographic light-sensitive material, which can speed up the desilvering step while maintaining the stability of a processing solution in use in addition to the image stability. Another object of the present invention is to provide a processing agent for a color photographic light-sensitive material which can solve the above-mentioned problems and can be easily used in a store development shop.

[0008]

The present inventor has found that, for the above-mentioned object, the addition of a water-soluble group to a fixing accelerating compound reduces the adverse effect on image stability. As a result of further study based on the above, the present invention has been reached. That is, the object of the present invention is achieved by the following.

1. A method for processing a silver halide color photographic light-sensitive material, comprising processing with a processing solution containing a compound represented by the general formula (1). General formula (1) An-L-SM (A is a sulfonic acid group or a phosphonic acid group, L is a heterocyclic group, an aryl group or an aliphatic hydrocarbon group, M is a hydrogen atom or an alkali metal atom, and n is Represents an integer of 1 or 2).

[0010] 2. Wherein the compound of the general formula (1) is a compound represented by the general formula (2).
The method for processing a silver halide color photographic light-sensitive material described in 1 above.

[0011]

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(Z forms a 5- or 6-membered nitrogen-containing unsaturated heterocyclic group having at least one sulfonic or phosphonic acid group or a group containing a sulfonic or phosphonic acid group as a substituent; And M represents a hydrogen atom or an alkali metal atom, respectively).

3. 3. The method for processing a silver halide color photographic light-sensitive material as described in 1 or 2, wherein the compound represented by the general formula (1) is a compound represented by the general formula (3).

[0014]

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(X and Y each represent CW or N, W represents a hydrogen atom, an aliphatic hydrocarbon group, an amino group, an alkyloxy group,
Aryloxy group, alkylthio group, arylthio group,
Represents a heterocyclic thio group, a ureido group, a thioureido group, an aminosulfamoyl group, a sulfo group, a phosphono group, a carbamoyl group, an amide group or a hydroxyl group. However, at least one of X and Y represents N. R has the same meaning as W. Provided that at least one of R and W is a group substituted with a sulfonic acid group).

4. Wherein the processing solution containing the compound represented by the general formula (1) is a processing solution selected from a processing solution having a bleaching ability, a processing solution having a fixing ability, a stabilizer and a washing water. 4. The method for processing a silver halide color photographic light-sensitive material as described in any one of 1 to 3 above.

5. A processing agent for a silver halide color photographic light-sensitive material, comprising a compound represented by the general formula (1).

6. Core / shell type granular particles having a surface layer having a critical relative humidity of 80% or less or a critical relative humidity of 8
6. The processing agent for a silver halide color photographic light-sensitive material as described in the above item 5, which is a single-phase granular particle of 0% or less.

7. 6. The processing agent for a silver halide color photographic light-sensitive material as described in 5 above, which is a concentrated solution having a one-part constitution consisting of a homogeneous phase having a concentration magnification of at least 5 times.

A feature of the present invention is that a compound represented by the general formula (1) having a mercapto group and a sulfonic acid group or a phosphonic acid group is used for accelerating desilvering. As described above, in the conventionally known desilvering accelerating compound, if the desilvering time is excessively shortened, coloring with the lapse of time due to residual silver and image instability are caused. And compounds that can reduce the desilvering time due to relatively little coloring over time and image instability even if there is residual silver even if the desilvering reaction accelerating property is not particularly large, The compound of the general formula (1) of the present invention has a conventionally known desilvering time in that it has both of the above two accelerating effects, that is, it has a large desilvering promoting effect and little adverse effect even if there is residual silver. This is a feature not found in compounds for shortening purposes.

In the present invention, the desilvering is promoted by adding the compound represented by the general formula (1) having such properties to the processing solution to increase the stain (Dmin).
And its increase with time is reduced, and even if the desilvering time is shortened so that residual silver is generated, the stain and its adverse effect on the increase over time are small, so that the desilvering step is greatly performed while maintaining image stability. Shortening has been achieved. The image stability mentioned here mainly includes temporal coloring caused by residual silver, fading of a cyan image, and a change in color balance (color tone). .

Among the compounds represented by the general formula (1), a compound having a large effect is substituted by a sulfonic acid group or a phosphonic acid group represented by the general formula (2) or a group containing the same, and nitrogen Azoles and azines having a mercapto group at the o-position with respect to are preferably substituted with a sulfonic acid group or a phosphonic acid group represented by the general formula (3) or a group containing them. 2,4
-Dimercapto-1,3 diazine or 2,4-dimercapto-1,3,5 triazine. The processing solution to which these compounds are added for use in the present invention may be any of a processing solution having a bleaching ability, a processing solution having a fixing ability and a stabilizer, and may be added to a plurality of processing solutions. It is particularly preferable to add to the processing solution and / or the stabilizing solution having a fixing ability, and particularly to the stabilizing solution because the effect of maintaining the image stability with time is large.

In the color photographic processing market, over-the-counter processing of photo shops called so-called mini labs has become widespread, and preparation processing agents have been used in response to this situation. The compound added to the processing solution in the desilvering step used in the present invention is a stable compound, and is suitable for use as a preparation agent.

[0024]

Embodiments of the present invention will be described below in detail. First, a compound having both a mercapto group and a sulfonic acid group or a phosphonic acid group characteristic of the present invention will be described. In the compound represented by the general formula (1), A is a sulfonic acid group or a phosphonic acid group, or a group containing a sulfonic acid group or a phosphonic acid group, and L is a heterocyclic residue substituted with A, aryl A residue or an aliphatic hydrocarbon residue (hereinafter, “residues” of these residues are omitted), M represents a hydrogen atom or an alkali metal atom, and n represents an integer of 1 or 2.

When A is a group containing a sulfonic acid group or a phosphonic acid group, preferred A is a sulfoalkylamino group having 1 to 4 carbon atoms, a sulfoalkylthio group having 1 to 4 carbon atoms,
Sulfophenylamino group, disulfophenylamino group,
Sulfoanilino-5-mercapto-2,4,6-triazinothio group, 3- (2,4-disulfoanilino) -5
(3,5-dimercapto-2,4,6-triazinothio) -2,4,6-triazinothio group, sulfophenylureido group, sulfophenylacylamino group, sulfoanilinosulfonylamino group, sulfo having 1 to 4 carbon atoms Alkylamide group, sulfoalkylcarbonylaminoalkyl group having 2 to 6 carbon atoms, phosphonoaminophenylamino group, phosphonoalkylamino group having 1 to 4 carbon atoms, phosphonoalkylthio group having 1 to 4 carbon atoms, 2 carbon atoms To 6 phosphonoalkylaminoalkyl groups and 2 to 8 phosphonoalkylthioalkyl groups. When A is a group containing an amino group, the amino group may be substituted with one or two phenyl groups, methyl groups or ethyl groups. Further, the sulfonic acid group or phosphonic acid group contained in A may be an alkali metal salt or an ammonium salt.

When L is a heterocyclic group, preferred L is a 5- or 6-membered nitrogen-containing unsaturated heterocyclic group, and when L is an aryl group, preferred L is a phenyl group. Is an alkyl group having 1 to 2 carbon atoms such as a methyl group and an ethyl group, and a carbon atom having 1 to 2 carbon atoms such as a methoxy group and an ethoxy group.
It may have 2 alkoxy groups, amino groups or acylamino groups having 1 to 2 carbon atoms as substituents. When L is an aliphatic group, preferred L is an aminoalkyl group having 1 to 4 carbon atoms, an alkylaminoalkyl group having 2 to 4 carbon atoms, or an alkyl group having 2 to 4 carbon atoms. Particularly preferably, L is 5
And a 6- or 6-membered nitrogen-containing unsaturated heterocyclic group. Further preferred compounds of the general formula (1) are compounds represented by the general formula (2) or the general formula (3).

In the compound represented by the general formula (2),
Z is necessary for forming a 5- or 6-membered nitrogen-containing unsaturated heterocyclic group having at least one sulfonic acid group or phosphonic acid group or a group containing a sulfonic acid group or a phosphonic acid group as a substituent. M represents a hydrogen atom or an alkali metal atom, respectively. The atomic group Z is an atomic group necessary for forming a 5- or 6-membered nitrogen-containing unsaturated hetero ring containing preferably 2 or 3 nitrogen atoms, and has at least one sulfonic acid group. Or an atomic group having, as a substituent, a group containing a phosphonic acid group, a sulfonic acid group, or a phosphonic acid group. The group containing a sulfonic acid group or a phosphonic acid group which is substituted on the atomic group Z has the same meaning as the group containing a sulfonic acid group or a phosphonic acid group in the above A. Further, the SM group has an o
-Position.

In the general formula (3), X and Y represent CW or N, and W is a hydrogen atom, an aliphatic hydrocarbon group, an amino group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a heterocyclic ring. Thio groups (for example, 3,
5-dimercapto-2,4,6-triazinothio group), ureido group, thioureido group, aminosulfamoyl group, sulfo group, phosphono group, carbamoyl group, amide group or hydroxyl group. However, at least one of X and Y represents N. R has the same meaning as W. However, at least one of R or W is a sulfonic acid group, a phosphonic acid group, or a group substituted with a sulfonic acid group or a group containing a sulfonic acid group, and the group containing a sulfonic acid group or a phosphonic acid group is It has the same meaning as the group containing a sulfonic acid group or a phosphonic acid group in A above. Preferably, W is a substituted amino group. Preferably, X is an N atom and R is a sulfonic acid group or a group containing a sulfonic acid group as defined above. More preferred R is a substituted amino group containing a sulfonic acid group.

Specific examples of the compounds represented by the general formulas (1), (2) and (3) are shown below.

[0030]

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[0031]

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[0032]

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[0033]

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Many of these compounds can be easily obtained, and can be obtained by known methods such as the method described in De. J. Brown (DJBrawn), The Chemistry of Heterocyclic Compounds Series (Th
e Chemistry of Heterocyclic Compounds, Series),
(Interscience Publishers (interscienc
e Publishers, Inc.), etc.).

When a compound represented by the above general formula (1), and especially the compound represented by the general formula (2) or (3) is used in the present invention, a bleaching solution, a fixing solution, a bleach-fixing solution and an image stabilizing solution It is effective if added to both the stable liquid and the washing water. Further, for example, it may be used by adding to two or more processing solutions such as both a bleach-fix solution and a stabilizing solution. However, when it is added to the developer, the development is suppressed and the photographic characteristics are inhibited, so that the desired effect cannot be obtained. A preferred application form is to use the above compound in a process after fixing, specifically, a fixing solution,
This is a form added to at least one of a bleach-fix solution, a stabilizing solution, and washing water. A particularly preferred form is a form added to a stabilizing solution or washing water. When added to the stabilizing solution or washing water, adverse effects due to residual silver such as image stains, coloring over time, and changes in color balance over time are particularly effectively prevented, and desilvering during processing from the photosensitive material is incomplete. Even in this case, the effect of stably maintaining the finished image quality and its aging property becomes remarkable. It is considered that the adverse effect of the residual silver in the color processing is more likely to occur in the stabilizing solution and the washing water than in the fixing solution containing a relatively large amount of sulfite.
In the case of the addition of the stabilizer, the action of the compound of the general formula (1), the general formula (2) or the general formula (3) according to the present invention is not simply promoted by desilvering, but marked by the fact that silver is added. Even if it remains, it is colored stain and its aging,
Suppress changes in color balance (especially changes over time). That is, it has an effect related to color processing, which is different from the fixing promotion (desilvering promotion) function that is also effective in black-and-white development.

As described above, the compound of the general formula (1), among which the compound of the general formula (2) or (3) accelerates the desilvering speed, but shortens the processing time and the residual silver remains in the compound material. Even if it does, it prevents the deterioration of the stain and the aging stability of the image, so that an increase in the amount of silver remaining in the photosensitive material is acceptable. In the processing method of the present invention, when the residual silver amount is such that 10% of the coated silver amount of the original photosensitive material remains,
There is almost no effect on the temporal stability of the image, and even if 50% remains, the temporal stability of the image at the required level is secured,
Depending on the purpose of storing the image, even if 70% of silver remains, it is acceptable. Therefore, the effect of the present invention is remarkable even when the compound of the present invention is added to a stabilizing solution in which the fixing action of the silver salt should be small. Thus, in the present invention, the addition of the compound of the general formula (1), especially of the general formula (2) or (3), enhances the desilvering speed, and also detoxifies the residual silver remaining in the image stability of the image stability. Can exert a remarkable effect. The amount of the residual silver can be quantified by either the atomic absorption method or the X-ray fluorescence analysis, and the quantified values agree within the range of allowable accuracy.

The amount of the above compound to be added to any of the above solutions can be 0.001 mol / L or more. Yes, but practically 0.00
1 to 1.0 mol / L, more preferably 0.005 to
Use at a concentration of 0.10 mol / L. 0.0
If it is less than 01 mol / L, the effect of the invention is poor.
Even if the concentration is increased to 0 mol / L or more, the effect of the invention is hardly further improved, and this compound itself remains, and adverse effects such as economic disadvantages also occur. As described above, the general formula (1)
The description of the compound of (2) or (3) is finished.

Next, processing of a color photographic light-sensitive material using a compound of the general formula (1), in particular, a compound of the general formula (2) or (3), a developing device, a light-sensitive material, and the like will be sequentially described. The processing step comprises the steps of color development, desilvering, washing and / or stabilization. In the case of color reversal film development, additional steps such as black-and-white development (first development), fogging bath, and neutralization bath are involved.

In the color development step, a color development replenisher and a color developer are used. Among them, a color developing agent is contained, and a preferred example is a known aromatic primary amine color developing agent, particularly a p-phenylenediamine derivative. Representative examples are shown below, but are not limited thereto. is not. In recent years, some black-and-white photosensitive materials have been added with a coupler so as to form a black color, and a black-and-white image is formed using a general-purpose general color developing solution. Is also applicable to this type of photosensitive material processing.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-3-methyl-N, N-diethylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-
Methylaniline 4) 4-Amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-Amino-3-methyl-N-ethyl-N- (β-
Hydroxyethyl) aniline 6) 4-amino-3-methyl-N-ethyl-N- (3-
Hydroxypropyl) aniline 7) 4-amino-3-methyl-N-ethyl-N- (4-
Hydroxybutyl) aniline 8) 4-amino-3-methyl-N-ethyl-N- (β-
Methanesulfonamidoethyl) aniline 9) 4-amino-3- (β-hydroxyethyl) -N,
N-diethylaniline 10) 4-amino-3-methyl-N-ethyl-N- (β
-Methoxyethyl) aniline 11) 4-amino-3-methyl-N- (β-ethoxyethyl) -N-ethylaniline 12) 4-amino-3-methyl-N- (3-carbamoylpropyl) -NN -Propylaniline 13) 4-Amino-3-methyl-N- (4-carbamoylbutyl) -N- (n-propyl) aniline 15) N- (4-amino-3-methylphenyl) -3-
Hydroxypyrrolidine 16) N- (4-amino-3-methylphenyl) -3-
(Hydroxymethyl) pyrrolidine 17) N- (4-amino-3-methylphenyl) -3-
Pyrrolidine carboxamide

Among the above-mentioned p-phenylenediamine derivatives, particularly preferred principal compounds are exemplified compounds 5), 6),
7), 8) and 12), among which compounds 5) and 8) are frequently used. Moreover, these p-phenylenediamine derivatives are usually in the form of salts such as sulfate, hydrochloride, sulfite, naphthalenedisulfonic acid, p-toluenesulfonic acid salt in a solid material state. The color developing composition is used in the form of a development replenisher (or a further diluted developer) by mixing it with water at a predetermined ratio at the time of use. The concentration of the secondary amine developing agent is preferably 2 to 200 mmol, more preferably 12 to 200 mmol, and still more preferably 12 to 15 mmol per liter of developer.
0 mmol.

Usually, a hydroxylamine derivative or a salt thereof or an N-alkylhydroxylamine or a salt thereof is often added to a color developing solution. Hydrazides, phenols,
α-hydroxy ketones, α-amino ketones, sugars,
Polyethyleneimines, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds,
Condensed amines are particularly effective. These are described in JP-A-63-4235, JP-A-63-30845, JP-A-63-21647, and JP-A-63-446.
No. 55, No. 63-53551, No. 63-43140, No. 63-56654, No.
63-58346, 63-43138, 63-146041, 63-446
No. 57, No. 63-44656, U.S. Pat.No. 3,615,503, No. 2,49
4,903, JP-A-52-143020 and JP-B-48-30496. When configuring the treatment composition, it is often convenient to configure these preservatives as a separate treatment agent part from the active ingredient.

The color developing solution usually contains bromine ions in an amount of 0.2 ×.
10 ^{-2 to} 15.0 × 10 ^-2 mol / l, preferably 0.5 × 10
^{-2 to} 5.0 × 10 ^-2 mol / l
Since bromine ions are usually released into a developer as a by-product of development, it is often unnecessary to add them to a replenisher. Bromide ion generic in the color developing solution is about 1～5X10 ^-3 mol / l in the processing of photographic materials, the processing of the print material is less 1.0 × 10 ^-3 mol / liter. Also,
In the case of color developers for photographic materials, iodine ions are reduced to 0.
2 × 10 ^{-3 to} 15.0 × 10 ^-3 mol / l, preferably 0.5
The content is usually from × 10 ^{-3 to} 5.0 × 10 ^-3 mol / l, but iodine ions are usually released to the developing solution as a by-product of development, and conversely adsorbed on undeveloped silver halide. Depending on the nature of the photosensitive material, it may not be necessary to add it to the replenisher or may be added to the replenisher in order to maintain the iodine ion concentration in the developing tank.

A color developing solution (especially a developing solution for color printing materials) usually contains chloride ions at 3.5 × 10 ^{-2 to} 1.5 × 10 ^-1.
Although it often contains mol / liter, chloride ion
Usually, it is released to the developer as a by-product of the development, so that it is often unnecessary to add it to the replenisher. Regarding the content of bromide ion, the situation is the same as in the case of chlorine ion. The bromine ion in the color developing solution is 1 to 5 × 10 ^{−3 in} the processing of the photographic material.
Mol / l, 1.0 ×
10 ^-3 mol / l or less.

When the photosensitive material to be developed is color photographic paper, it is important that the white background of the screen is white. Therefore, stilbene-based fluorescent whitening agents, especially di (triazylamino) stilbene-based, 4,4'-diamino-2,
A 2'-disulfostilbene-based fluorescent whitening agent may be added to the color developer. This stilbene-based fluorescent whitening agent can be added to any of a desilvering solution and a photosensitive material in addition to a color developing solution. When it is contained in a color developing solution, the preferred concentration is 1 × 10 ^{−4 to} 5 × 10 ⁻² mol / l, more preferably 2 × 10 ⁻⁴ to 1 × 10 ⁻² mol / l. .

The color developing solution and the developing replenisher are used at pH 9.5 or more, more preferably at 10.0 to 12.5.
In order to stably maintain the pH, it is preferable to use various buffers. As a buffer, in addition to carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt,
Norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt,
Lysine salts and the like can be used. The amount of the buffer is
The concentration in the diluted color development replenisher is 0.01 to 2
Mol / l, especially 0.1 mol / l to 0.5 mol / l
It is added to the composition to make up a liter.

The color developing composition may contain other components of the color developing solution, for example, various chelating agents which are precipitation inhibitors for calcium and magnesium or improve the stability of the color developing solution. . For example,
Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid, ethylenediamine-N, N-disuccinic acid, N, N-di (carboxylate) -L-aspartic acid, β-alanine disuccinic acid, transsirohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, -Phosphonobutane-1,
2,4-tricarboxylic acid, 1-hydroxyethylidene-
1,1-diphosphonic acid, N, N′-bis (2-hydroxybenzyl) ethylenediamine-N, N′-diacetic acid,
1,2-dihydroxybenzene-4,6-disulfonic acid and the like. These chelating agents may be used as needed.
More than one species may be used in combination. The amount of these chelating agents may be an amount sufficient to block metal ions in the color developing solution. For example, it is added so as to be about 0.1 g to 10 g per liter.

An optional development accelerator can be added to the color developer if necessary. Examples of the development accelerator include known thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, amine compounds, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, imidazoles described in various publications. , Etc. can be added as needed.

Further, an optional antifoggant can be added to the color developing solution, if necessary. As the antifoggant, alkali metal halides and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be mentioned as typical examples. In addition, various surfactants such as polyalkylene glycols, alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added.

The processing temperature for color development is 30 to 75 ° C., preferably 35 to 55 ° C., and more preferably 3 to 55 ° C. when the photosensitive material to be developed is a color print material.
8 to 45 ° C. The development processing time is 5 to 90 seconds, and preferably 15 to 60 seconds. The replenishment amount is preferably smaller, but is suitably 15 to 600 ml, preferably 15 to 120 ml, and particularly preferably 30 to 60 ml per m ^{2 of} the photographic material.

On the other hand, in the case of color development of a color negative or color reversal film, the development temperature is 20 to 55 ° C.
, Preferably from 30 to 55 ° C, more preferably from 38 to 45 ° C. The development processing time is 20 seconds to 6 minutes, preferably 30 to 200 seconds, and more preferably 60 to 150 seconds. Also, for color reversal, the time is preferably 1 to 4 minutes. The replenishment amount is preferably smaller, but is suitably from 100 to 800 ml, preferably from 200 to 500 ml, and particularly preferably from 250 to 400 ml, per m ^{2 of} the light-sensitive material.

The desilvering step is started after the color developing step. The structure of the desilvering step can take various forms as shown below.

Structure of desilvering step of typical color development processing (Step 1) Bleaching and fixing (Step 2) Bleaching and bleaching and fixing (Step 3) Bleaching and bleaching and fixing (Step 4) Bleaching and fixing (Step 5) Fixing-Bleaching-Fixing (Step 6) Bleaching-Fixing-Fixing Each of the bleaching, bleach-fixing, and fixing steps may be divided into a plurality of baths as necessary, and a cascade method may be employed.

The bleaching solution and the bleach-fixing solution having a bleaching ability contain a bleaching agent and oxidize the developed silver to convert it into a soluble silver salt. In the present invention, any of known bleaching agents may be used, but it is preferable to use an iron (III) -aminopolycarboxylic acid complex salt. In the present invention, it is preferable to use a bleaching solution or a bleach-fixing solution. Any known iron (II
I) -polyaminopolycarboxylic acid complex salts and iron (III) -monoaminopolycarboxylic acid complex salts can also be used. Polyaminopolycarboxylic acids which are organic acid components of these iron complex salts include, for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cis-cyclohexanediaminetetraacetic acid, ethylenediamine-N, N'-disuccinic acid, ethylenediamine-N, N ' Diglutamic acid, ethylenediamine-N, N'-dimalonic acid, 1,3-propylenediamine-N, N'-disuccinic acid, 1,3-propylenediamine-N, N, N ', N'-tetraacetic acid, 1,3-propylenediamine-N, N′-dimalonic acid, N, N′-di (carboxylate) -L-glutamic acid, transsiloxanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid,
1,4-butylenediaminetetraacetic acid, o-xylenediaminetetraacetic acid, ethylenediamine-N, N'-bis-orthohydroxyphenylacetic acid, diethylenethioetherdiaminetetraacetic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine- N, N'-diacetic acid, ethylenediamine-N, N'-di (2-acetamido) diacetic acid and the like. Iron (III) / monoaminopolycarboxylic acid complex salts include iminodiacetic acid, methyliminodiacetic acid, β-alaninediacetate, ethylenediaminemonosuccinic acid, β-alaninemonosuccinic acid, diethylenetriaminemonosuccinic acid, triethylenetetraminemonosuccinic acid, nitrilotriacetic acid And the like.

In addition, JP-A-4-121439, EP-A-461413, JP-A-4-174432
And various kinds of iron (III) / aminopolycarboxylic acid complex salts described in JP-A-3-144446 and the like can also be used in the present invention. Among these iron (III) -aminopolycarboxylic acid complex salts, particularly preferred complex salts are iron (III) complex salts of ethylenediaminetetraacetic acid, ethylenediamine-N, N'-disuccinic acid and ethylenediamine-N, N'-digglutamic acid. It is. Among them, ethylenediamine-N, N'-disuccinic acid and ethylenediamine-
It is an iron (III) complex salt of N, N'-diglutamic acid. If necessary, two or more of these iron (III) / aminopolycarboxylic acid complex salts may be used in combination.

In the present specification, the description of the bleaching agent of iron (III) polyaminomonosuccinate complex and iron (III) aminopolycarboxylic acid complex indicates the form of the salt of the carboxyl group in the molecule. Did not, but both complex salts,
The carboxyl group may be any of an alkali metal salt, an ammonium salt or a non-salt type in which a hydrogen atom remains as it is, but the description of the form of these salts is omitted in the following description for simplification of the description.

The total concentration of the iron (III) -aminopolycarboxylic acid complex salt and the iron (III) -polyaminomonosuccinic acid complex salt in the bleaching solution and the bleach-fixing solution depends on the amount of silver and halogen in the photosensitive material to be processed. It depends on the silver halide composition and the replenishment rate of the bleach-fix solution. Preferably from 0.01 to 1 per liter of working solution.
The amount is 5 mol, more preferably 0.05 to 1.0 mol, and particularly preferably 0.10 to 0.5 mol.

The components other than the iron (III) complex salt of the bleaching solution and the bleach-fixing solution used in the present invention will be described. The bleaching solution and the bleach-fixing solution contain a compound selected from the group consisting of a hydroxycarboxylic acid and a polycarboxylic acid represented by the following general formula (I) and an imidazole derivative represented by the following general formula (II). Insoluble matter generated in the processing solution is reduced, the desilvering action is promoted, and the stability when the processing solution is used for a long time is also improved. Although the mechanism of action of these compounds is unknown, it is presumed that these compounds are weakly complexing with iron (III) ions, which is related to the effect of strengthening the chelate structure of bleach. are doing.

Formula (I) R⁰COOM In the general formula (I), R⁰Is a hydroxyalkyl
Group, hydroxyalkenyl group, hydroxyalkoxya
Alkyl group, hydroxyalkylthioalkyl group, hydro
Xycycloalkyl group, hydroxyphenyl group, carbo
Xyalkyl group, carboxyalkenyl group, carboxy
Alkoxyalkyl group, carboxyalkylthioalkyl
Group, carboxycycloalkyl group and
Phenyl group. These substituents R⁰Has a carbon number of R⁰
Is an aliphatic substituent, 1 to 8, R ⁰Is cycloalkyl
6 to 10 for a group, R⁰Is 6-1 when is a phenyl group
0 and R⁰Hydroxyl or carboxyl groups contained in
May be plural (2 or 3). Also these
Substituent R⁰Has an alkyl group of 1 to 1
May have 1 or 2 alkoxy groups. M is hydrogen
Represents an atom, alkali metal or ammonium group.

Specific examples of the polycarboxylic acid represented by the general formula (I) include glycolic acid, citric acid, tartaric acid, glyceric acid and lactic acid, and the following exemplified compounds I-1 to I-17.
The compound of the general formula (I) used in the present invention is not limited to these. These may be used in combination of two or more compounds.

[0061]

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Formula (II) (R ¹ ) _n A ^{0 In the} formula (II), R ¹ is a hydrogen atom, having 1 to 3 carbon atoms.
Represents an alkyl group or alkenyl group and a halogen atom, and the alkyl group or alkenyl group may be substituted with an amino group or a hydroxyl group. When a plurality of R ¹ are present, they may be the same or different. The amino group represented by R ¹ may be substituted with one or two methyl groups or ethyl groups. When an alkyl group and an alkenyl group are substituted with an amino group, the amino group may be further substituted with an alkyl group having 1 to 3 carbon atoms. n is an integer of 1 to 3. A ⁰ represents an imidazolyl group.

Specific examples of the imidazole compound represented by the general formula (II) are shown below, but the compound of the general formula (II) used in the present invention is not limited to these. 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 4- (2-hydroxyethyl) imidazole, 4- (2-aminoethyl) imidazole, 2- (2
-Hydroxyethyl) imidazole, 2-ethylimidazole, 2-vinylimidazole, 4-propylimidazole, 2,4-dimethylimidazole, 2-chloroimidazole, 4,5-di (2-hydroxyethyl) imidazole, imidazole, 4- (2-Dimethylaminoethyl) imidazole.

When the polycarboxylic acid of the general formula (I) is added to the bleach-fixing solution, it may be allowed to coexist with acetic acid which is usually added as a buffering salt. It may be replaced by a carboxylic acid. When coexisting, the compound of the general formula (I) is added in an amount of 0.2 to 1.5 times (molar ratio) the amount of acetic acid. Preferably, 0.5 to
1.0 times. When replacing, the amount of acetic acid to be replaced is 0.4 to 2.5 times (molar ratio), preferably,
It is 0.8 to 1.5 times. The total amount of acetic acid and polycarboxylic acid can be added in a wide concentration range as long as the buffering capacity is sufficient, but the preferable molar ratio is iron (III).
It is 0.1 to 2.0 for 1.0 ion. Preferably, it is 0.5 to 2.0 times. When the compound of the general formula (II) is added to the bleaching solution or the bleach-fixing solution, the preferred molar ratio is from 0.2 to 2.0 to 1.0 of iron (III) ion.
0. Preferably, it is 0.5 to 1.5 times. In addition, the iron (III) -aminopolycarboxylic acid complex salt composition such as a bleaching solution or a bleach-fixing solution usually contains an aminopolycarboxylic acid in an excess of about 1 to 10 mol% with respect to iron (III) ions. The same applies to the present invention.

The fixing agents used in the bleach-fixing solution and the fixing solution are known fixing agents, that is, alkali metal salts and ammonium salts of thiosulfates such as sodium thiosulfate and ammonium thiosulfate. To the bleach-fix solution, other silver halide dissolving agents may be added in a secondary manner for the purpose of promoting fixing. Suitable silver halide solubilizers that can be added as a secondary are:
Sodium thiocyanate, thiocyanates such as ammonium thiocyanate, ethylenebisthioglycolic acid,
A water-soluble silver halide dissolving agent such as a thioether compound such as 3,6-dithia-1,8-octanediol and a thiourea such as thiourea and ethylenethiourea. It can be used by being added as a component. Also, JP-A-55-155354
A special bleach-fixing solution comprising a combination of a fixing agent described in Japanese Patent Application Laid-Open Publication No. HEI 7-163, and a large amount of a halide such as potassium iodide can also be used.

In the bleach-fixing solution and the fixing solution, the amount of thiosulfate, which is the main fixing agent, is from 60 to 100 mol% of the total amount of the fixing agent and the silver halide dissolving agent which may be added as a secondary addition.
And the silver halide dissolving agent which may be added as a secondary component does not exceed 40 mol% of the total amount. Further, among thiosulfates, it is particularly preferable to use ammonium thiosulfate. The amount of the fixing agent per liter of the bleach-fixing solution is 0.1%.
5 to 4 mol is preferable, and more preferably 0.5 to 3.0 mol.
Range of moles.

To the bleach-fixing solution and the fixing solution, a compound having a desilvering promoting property other than the compounds of the general formulas (1), (2) and (3) according to the present invention is added to speed up the processing. The silver removal performance can be improved. Compounds suitable for this purpose include JP-A-8-297356 and JP-A-8-297356.
JP-A-137070 discloses 1,2,4-triazolium-3-sulfide-type mesoionic compounds (representative examples: 1,4,5-trimethyl-1,2,4-triazolium-3-sulfide) and JP-A-Hei. RSO ₂ M disclosed in JP-A-8-292510 (R represents an alkyl, cycloalkyl, alkenyl, aralkyl or aryl group;
M is a hydrogen atom, an alkali metal atom, an ammonium group) type of sulfinic acids (typically, phenylsulfinic acid), and one or more of these are treated at a concentration of 0.001 to 0.1 mol / L. Can be added inside.

In order to prevent the formation of silver sludge, a compound capable of forming a silver salt can be added to the bleach-fixing solution and the fixing solution. Compounds suitable for this purpose include N-amino-substituted or N-alkoxy-substituted derivatives of guanidine disclosed in JP-A-8-204980 (otherwise, an alkyl group or the like may be substituted); N
-(Di-n-butylaminopropyl) guanidine, N-
(Di-n-propylaminoethyl) guanidine), 2-mercaptoazole derivatives and 2-mercaptopyrimidine derivatives (representative examples, 2-mercapto-5-acetamidothiadiazole, 2-mercapto) disclosed in JP-A-9-212820. -4-methyl-5-amino-pyrimidine);
It can be added to the processing solution at a concentration of 0.1 mol / liter.

Further, the bleach-fixing solution and the fixing solution may contain other various types of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol. In the bleach-fixing solution and the fixing solution, sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) are used as preservatives. Or a metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.), a compound capable of releasing sulfite ions, p-toluenesulfinic acid, m-carboxybenzenesulfinic acid as described above And arylsulfinic acid. In such a case, the amount of these compounds to be added is preferably about 0.02 to 0.8 mol / liter in terms of sulfite ions or sulfinate ions.

As a preservative for the bleach-fix solution, in addition to the above, ascorbic acid, carbonyl bisulfite adduct or other carbonyl compounds may be added. Further, a buffer, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary.

The pH of the bleaching solution, bleach-fixing solution and fixing solution according to the present invention is preferably from 3.0 to 8.0, and preferably from 4.0 to 4.0.
7.5 is more preferable, and 4.5 to 7.0 is still more preferable. When the pH is lower than 3, the bleaching ability is improved, but deterioration of the solution such as consumption of sulfite ions is promoted. Conversely, pH 8
If it is higher, bleaching will be delayed and stain will easily occur. To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary. Ammonia water is especially needed to increase the pH,
It is preferable to use dilute sulfuric acid to correct the pH.

When the light-sensitive material to be processed is a color negative or color reversal film, the processing time for each of the bleaching, bleach-fixing and fixing processes, ie, the desilvering process, is usually 10 seconds to 6 minutes 30 minutes. Seconds, preferably 15 seconds to 4 minutes 30 seconds, more preferably 30 to 120 seconds,
The bleaching process for color print materials takes 10 seconds to 1 minute. Each of the bleaching, bleaching, and fixing steps can take a wider variety of forms during each of the above process times. For example, for the processing of the color negative film in the desilvering step (4) described above, a more specific preferred processing time is 10 to 45 seconds for the bleaching step, and more preferably 15 to 40 seconds.
Seconds, particularly preferably 20 to 35 seconds, and for the fixing step, 20 to 90 seconds, more preferably 30 to 80 seconds.
Seconds, particularly preferably 40 to 70 seconds, and for the stabilizing solution treatment step, 20 to 65 seconds, and more preferably 25 to 70 seconds.
60 seconds, particularly preferably 30 to 55 seconds. As described above and as can be seen from the examples, the processing time can be reduced as described above because the compound of the general formula (1), (2) or (3) simply promotes fixing to remove residual silver. In addition to the decrease, the residual silver is stabilized and the stain is hardly increased. The processing temperature is 25 ° C to 60 ° C.
° C, preferably 30 ° C to 50 ° C. The replenishing rate is 20 to 750 ml, preferably 30 to 500 ml, and particularly preferably 35 to 300 ml per m ² of the photosensitive material.

The bleaching solution and the bleach-fixing solution used in the present invention may be subjected to aeration for long-term continuous processing. Any means known in the art can be used for aeration, and air can be blown or absorbed using an ejector. When blowing air, it is preferable to discharge air into the liquid through an air diffuser having fine pores. Such a diffuser,
Widely used for aeration tanks in activated sludge treatment. However, excessive aeration must be avoided because it results in unnecessary oxidation of the processing solution components. Regarding aeration, Z-Manufactured by Eastman Kodak Company
121, USING PROCESS C-41 3rd edition (19
1982), and the items described on pages BL-1 and BL-2 can be used. In the processing using a processing solution having bleaching ability,
It is preferable that stirring is performed, and the contents described on page 8, upper right column, line 6 to lower left column, and line 2 of JP-A-3-33847 can be used as it is.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening the stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a light-sensitive material, or a method using a rotating means described in JP-A-62-183461, is used. A method for improving the effect, a method for moving the photosensitive material while bringing the wiper blade provided in the solution into contact with the emulsion surface, and making the emulsion surface turbulent to improve the stirring effect, and a circulation of the entire processing solution. There is a method of increasing the flow rate. Such a stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective in any of the fixing solutions. It is considered that improving the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed.

After desilvering processing such as fixing or bleach-fixing, a stabilizing solution treatment for water washing alternative, a stabilizing solution treatment for image stabilization, or a stabilizing solution treatment for both purposes, and a stabilizing solution treatment for water washing alternative are followed. In the present invention, a stabilizing solution treatment for image stabilization is performed, but in the present invention, the general formula (1)
The compounds of (2) and (3) exert their effects even when added to any of these stabilizing solutions. Therefore, in the present specification, they are collectively referred to as a stabilizing solution. As described above, in the present invention, the general formulas (1) and (2)
The compounds of (3) and (3) may be contained in any processing solution such as a bleaching solution, a bleach-fixing solution, and a stabilizing solution. The residual silver has an excellent feature that, at most, there is little coloring or fading during storage of the image, and rather the image stability is high.

A compound having an image stabilizing function is added to the stabilizing solution, and examples thereof include an aldehyde compound typified by formalin, a buffering agent for adjusting the membrane pH to a level suitable for stabilizing the dye, and an ammonium compound. Can be Also,
Aldehydes such as formaldehyde, acetaldehyde and pyruvaldehyde which inactivate the remaining magenta coupler to prevent color fading and stain formation, methylol compounds and hexamethylenetetramine described in U.S. Pat. No. 4,786,583, JP-A-2-153348 No. 492, US Patent No. 492
The formaldehyde bisulfite adduct according to 1779,
Azolylmethylamines described in European Patent Publication Nos. 504609 and 519190 are added. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, an optical brightener and a hardener can be added. In the treatment according to the present invention, when the stabilization is directly performed without going through a water washing step, all known methods described in JP-A-57-8543, JP-A-58-14834, JP-A-60-220345 and the like are used. Can be used. In addition, it is also a preferable embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound. The replenishment amount in the stabilizing solution processing step can be set in a wide range depending on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the purpose, the processing solution temperature, the number of processing tanks (the number of stages), and various other conditions. Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in Journal of the Society of Motion Picture and Television Engineers (Journal
of the Society of Motion Picture and Television En
gineers), Vol. 64, pp. 248-253 (May, 1955). Usually, the number of stages in the multistage countercurrent system is preferably 2 to 15, and particularly preferably 3 to 10.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced. However, due to an increase in the residence time of water in the tank,
There is a problem that bacteria proliferate and the generated suspended matter adheres to the photosensitive material. As a solution to such a problem,
The method for reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, chlorine bactericides such as isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorinated sodium isocyanurate described in JP-A-61-120145, JP-A-61-26761. Benzotriazole, copper ions, and others described in the gazette, Hiroshi Horiguchi, "Bactericidal and antifungal chemistry"
(1986) Sankyo Shuppan, edited by the Sanitary Technology Society, "Microbial Sterilization,
Sterilization and fungicide technology ”(1982) Industrial Technology Association, and the fungicide described in“ Encyclopedia of Fungicide and Fungicide ”edited by the Japan Society of Antifungal and Fungicide (1986) can also be used.

Further, in the stabilizing solution, a surfactant as a draining agent and a chelating agent represented by EDTA as a water softener can be used.

The rinsing bath used after the desilvering treatment also functions in the same manner as the stabilizing solution. In the present invention, the compounds of the general formulas (1), (2) and (3) are used in the case where they are added to the stabilizing solution. It can be used under the same conditions, and the effect of its addition is the same as when it is added to the stabilizer. The preferred pH of the stabilizer is 4-10, more preferably 5-8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but is generally 20 ° C to 50 ° C, preferably 25 ° C to 45 ° C. Drying is performed following the stabilizing solution treatment step. From the viewpoint of reducing the amount of water carried into the image film, it is possible to speed up drying by absorbing water with a squeeze roller or cloth immediately after leaving the washing bath. As a means of improvement from the dryer side, as a matter of course, it is possible to speed up the drying by increasing the temperature or changing the shape of the spray nozzle to increase the drying air. Further, JP-A-3-15
As described in Japanese Patent No. 7650, drying can be accelerated by adjusting the blowing angle of the drying air to the photosensitive material or by removing the discharged air.

The processing method of the present invention is often performed using an automatic developing machine. The automatic developing machine preferably used in the present invention is described below. In the present invention, it is preferable that the linear speed of conveyance of the automatic developing machine is 5000 mm / min or less. More preferably, 200 mm / min to 4500
mm / min, particularly preferably 500 to 3000 mm / min. The treatment liquid according to the present invention is a treatment tank and a replenisher tank,
The area where the liquid comes into contact with air (opening area) is preferably as small as possible. For example, assuming that the value obtained by dividing the opening area (cm ² ) by the liquid tank (cm ³ ) in the tank is the opening ratio, the opening ratio is 0.0
It is preferably 1 (cm ^-1 ) or less, more preferably 0.005 or less, and most preferably 0.001 or less.

In order to reduce the area in contact with air, it is preferable to provide a solid or liquid air non-contact means floating on the liquid surface in the processing tank and the replenishing tank. Specifically, it is preferable to float a float made of plastic or the like on the liquid surface, or to cover with a liquid that does not mix with the processing liquid and does not cause a chemical reaction. Preferred examples of the liquid include liquid paraffin and liquid saturated hydrocarbon.

In the present invention, in order to perform the processing quickly, the shorter the air time, ie, the crossover time, when the photosensitive material moves between the processing solutions, the better, preferably 10 seconds or less, more preferably 7 seconds or less. The time is not more than seconds, more preferably not more than 5 seconds. In order to achieve the above-mentioned short-time crossover, the present invention preferably employs a cine-type automatic developing machine, and particularly preferably employs a leader transport system. Such a system has been developed using an automatic processor FP-56 manufactured by Fuji Photo Film Co., Ltd.
0B. Japanese Patent Laid-Open Publication Nos. 60-191257 and 60-19
No. 1258 and No. 60-191259 are preferred.
-265794, 1-266915, 1-26
It is preferable to adopt each system described in No. 6916.
Further, in order to shorten the crossover time and prevent the mixing of the processing solution, the crossover rack preferably has a mixing prevention plate described in Japanese Patent Application No. 1-265975.

It is preferable to perform so-called evaporation correction for supplying each processing solution in the present invention with water corresponding to the amount of evaporation of the processing solution. In particular, a color developing solution, a bleaching solution or a bleach-fixing solution is preferable. The specific method for replenishing such water is not particularly limited. Among them, a monitor water tank different from the bleaching tank described in JP-A Nos. 1-254959 and 1-254960 is installed. The evaporation amount of water in the inside is obtained, the evaporation amount of water in the bleaching tank is calculated from the evaporation amount of water, and the water is replenished to the bleaching tank in proportion to the evaporation amount. 2-4
No. 7777, No. 2-47778, No. 2-47779
And an evaporation correction method using a liquid level sensor and an overflow sensor described in JP-A-2-117972. The most preferable evaporation correction method is to predict and add water corresponding to the amount of evaporation.
As described in JP-A-4-49925, page 1, right column, line 26 to page 3, left column, line 28, and Japanese Patent Application No. 2-103894, the operation time, stop time and temperature control time of the automatic developing machine are described. The amount of water calculated by a coefficient obtained in advance based on the information is added.

It is also necessary to take measures to reduce the amount of evaporation, and it is necessary to reduce the opening area and adjust the air volume of the exhaust fan. For example, the preferable aperture ratio of the color developing solution is as described above, but it is preferable to similarly reduce the opening area in other processing solutions. As means for reducing the amount of evaporation, it is particularly preferable to “maintain the humidity of the upper space of the processing tank at 80% RH or more” described in JP-A-6-110171, and the evaporation prevention rack described in FIGS. It is particularly preferable to have a roller automatic cleaning mechanism. Exhaust fan is mounted in order to prevent dew condensation at the temperature control, preferred emissions, per minute 0.1 m ³ to 1 m ^3, a particularly preferred displacement volume,
It is a 0.2m ³ ~0.4m ^3. The drying conditions of the photosensitive material also affect the evaporation of the processing liquid. The drying method is preferably a ceramic hot air heater is preferably min 4m ³ to 20 m ³ as feed air volume, particularly 6 m ³ through 10m ³ preferred. The thermostat for heating prevention of the ceramic hot air heater is preferably operated by heat transfer,
It is preferable that the mounting position is attached to the leeward or upwind side through the radiation fins or the heat transfer portion. The drying temperature is preferably adjusted according to the water content of the photosensitive material to be processed,
The optimum temperature is 45 to 55 ° C for a 35 mm wide film and 55 to 65 ° C for a brownie film. When replenishing the processing solution, a replenishing pump is used, but a bellows type replenishing pump is preferable. As a method of improving the replenishment accuracy, it is effective to reduce the diameter of the liquid feeding tube to the replenishment nozzle in order to prevent a backflow when the pump is stopped. A preferable inner diameter is 1 to 8 mm, and a particularly preferable inner diameter is 2 to 5 mm.

Various parts materials are used in the automatic developing machine. Preferred materials are described below. The tank material such as the treatment tank and the temperature control tank is preferably a modified PPO (modified polyphenylene oxide) or a modified PPE (modified polyphenylene ether) resin. The modified PPO includes "Noryl" manufactured by Nippon GE Plastics Co., Ltd., and the modified PPE includes "Zylon" manufactured by Asahi Kasei Kogyo, "Iupiece" manufactured by Mitsubishi Gas Chemical, and the like. In addition, these materials are suitable for parts that may come into contact with the processing liquid, such as processing racks and crossovers.

As the roller material of the processing section, resins such as PVC (polyvinyl chloride), PP (polypropylene), PE (polyethylene), and TPX (polymethylpentene) are suitable. These materials can also be used for other treatment liquid contact parts. The PE resin is also preferable for the material of the replenishment tank formed by blow molding. Materials such as processing parts, gears, sprockets and bearings include PA (polyamide), PBT (polybutylene terephthalate), UH
Resins such as MPE (ultra high molecular weight polyethylene), PPS (polyphenylene sulfide), and LCP (fully aromatic polyester resin, liquid crystal polymer) are suitable. The PA resin is a polyamide resin such as 66 nylon, 12 nylon, 6 nylon, and the like, and a resin containing glass fiber, carbon fiber, or the like is strong against swelling due to the processing solution and can be used.

A high molecular weight product such as MC nylon or a compression-formed product can be used without fiber reinforcement. Unreinforced products are suitable for UHMPE resin. Mitsui Petrochemical Co., Ltd. "Lybuma", "HIZEX Million" Sakushin Kogyo Co., Ltd. "New Light", Asahi Kasei Kogyo Co., Ltd. "Sun Fine" etc. Are suitable. The molecular weight is preferably 1,000,000 or more, more preferably 100
10,000 to 5 million. The PPS resin is preferably glass fiber or carbon fiber reinforced. The LCP resin includes “Victrex” by ICI Japan Co., Ltd., “Econol” by Sumitomo Chemical Co., Ltd., “Zyder” by Nippon Oil Co., Ltd., and “Vectra” by Polyplastics Co., Ltd. Particularly, as the material of the transport belt, an ultra-high-strength polyethylene fiber or polyvinylidene fluoride resin described in Japanese Patent Application No. 2-276886 is preferable. As a soft material such as a squeeze roller,
A foamed vinyl chloride resin, a foamed silicone resin, and a foamed urethane resin are suitable. Examples of the urethane foam resin include “Rubicel” manufactured by Toyo Polymer Co., Ltd. As a rubber material such as a pipe joint, an agitation jet pipe joint, or a sealing material, EPDM rubber, silicon rubber, viton rubber, or the like is preferable.

The passage time of the drying unit is preferably designed to be 30 seconds to 2 minutes, and is particularly designed to be dried in 40 seconds to 80 seconds. As mentioned above, although the continuous processing by the replenishment method has been mainly described, in the present invention,
It is also possible to preferably use a batch processing method in which the processing is performed without replenishment with a certain amount of the processing liquid, and then the whole or a part of the processing liquid is replaced with a new liquid and the processing is performed again.

The treating agent applicable to the present invention may be supplied as a concentrate having a single or plural part composition, or may be supplied in the form of powders, tablets, granules, pastes and the like.
Also, it may be supplied in the state of use liquid, concentrated solution, powder, tablet,
Any combination of granules, pastes, and use solutions may be used. The compounds of the general formulas (1), (2) and (3) can be added to bleaching agents, bleach-fixing agents and fixing agents in any of these forms, and can also be added singly as additives. It may be. In particular, in the case of a stabilizer, it can be added and dissolved in water or a stabilizer in the form of a solid as an additive having a single composition. When adding to bleach, bleach-fixer and fixer,
Each part may be included in either part.

Particularly advantageous when the treating agent according to the present invention is a concentrated liquid treating agent, is that the compounds of the general formulas (1), (2) and (3) have a relatively low water solubility due to the water-soluble mercapto group. Since it is large and does not become a restriction when increasing the concentration of the treating agent, a compact treating agent having a high concentration can be obtained. For example, a compound of the above general formula is made to coexist in a high-concentration ammonium thiosulfate solution to form a concentrated liquid fixing agent having a one-part structure, or generally used as a solid processing agent or as a solid / liquid multi-part processing agent. Even the treating agent for the stabilizing liquid used can be a single-part concentrated liquid treating agent. The liquid processing agent is advantageous in terms of simplicity because the processing liquid can be adjusted only by dilution.

On the other hand, the compounds of the general formulas (1), (2) and (3) are advantageous because they can be adjusted to an appropriate critical relative humidity which does not easily cause the composition to absorb and dehumidify even in a solid processing agent. Since this compound also has an organic hydrophobic group, it also has a water-soluble mercapto group, so that it has a critical relative humidity that does not easily absorb or release moisture in the storage environment, and furthermore, it has a treatment agent component and Is excellent in miscibility, so that it is convenient to adjust the composition of the composition so that the solid composition has a critical relative humidity at which the composition is stably stored in the environment, that is, the average relative humidity of the storage environment. The advantage of this property is particularly exhibited for granular processing agents. That is, even in the case of single-phase granules, the granules are stabilized by controlling the critical relative humidity of the compound of the above general formula. In the case of a core / shell type granule, the compound of the above general formula is added to the shell layer with a hygroscopic component having a low critical relative humidity as a core to increase the critical relative humidity (preferably 70%).
As described above), the stability over time of the granules can be improved. The method of the present invention is described, for example, in Japanese Patent Laid-Open No. 6-130571.
No. 5,939,911 and the like, and can be preferably applied to the granular treatment agent having a core / shell structure disclosed in JP-A-5-93911.

In the preparation of the granular treating agent, both granules having a single-phase constitution and a core / shell structure are described in “Granulation Handbook (edited by the Japan Powder Industry Association)”.
It can be produced according to each method described on page 470. In particular, for the production of core / shell type granules, the core granulation is performed by a compression granulation method (p.199 of the above handbook).
And compacting method. Rolling granulation method (p. 133) and coating granulation method (p.
09) is preferred.

A preferred embodiment of the processing carried out by an automatic developing machine using a condensing agent will be described. In the case of a one-part concentrated treatment agent, it is diluted and used as a replenisher. In this case, by setting the concentrate in the developing machine,
It is preferred to automatically dilute with water in the replenisher tank. As this water, it is preferable to use water from a washing water replenishing tank. Alternatively, the replenisher may be directly replenished to the treatment tank as it is, and water suitable for the dilution ratio may be directly replenished to the treatment tank. It is particularly preferable for a compact developing machine having no replenishing tank.

The same applies to the concentrated solution having a plurality of parts. It is preferable that the concentrated solution is set in the developing machine and automatically diluted with water in the replenisher tank. As this water, it is preferable to use water from a washing water replenishing tank. Further, the processing tank may be directly replenished for each part, and water corresponding to the dilution rate may be directly replenished to the processing tank.

Similarly, in the case of powders, tablets, granules, and pastes, it is also preferable to add a chemical directly to the treatment tank and simultaneously add water suitable for the dilution ratio to the treatment tank. It is also preferable to use a system which is automatically dissolved and diluted in a replenishing tank and used as a replenishing solution.

In a preferred embodiment of the present invention, the compounds of the general formulas (1), (2) and (3) are used by being contained in these treating agents as constituents. In over-the-counter developing laboratories and the like, processing that is easy to handle and requires less work is desired. From that viewpoint, a compounding agent is desired. The form of the processing agent may be selected from the above-mentioned powdery, tablet, granule, and paste-like processing agents, and a combination thereof in accordance with the working environment of the developing laboratory. The treating agent containing the compound according to the present invention may be a regenerating agent.
The bleach-fixing solution and the fixing solution include a regenerating agent having a composition mainly composed of components consumed and reacted during processing in a used processing solution overflowing from a processing tank in a processing process. There is also a mode in which the replenisher is used as a regenerated bleach-fix replenisher or a regenerated replenisher. The pH of the regenerating bleach-fix replenisher or regenerating fix replenisher is 4.0 to 6.5,
Preferably, the regenerant has a p-value of 4.5-6.0.
An H-regulating acid has been added.

For example, the preferred composition of the regenerant for the bleach-fix replenisher is thiosulfate, aminopolycarboxylic acid,
It contains the components of the above-mentioned bleach-fixing solution such as iron (III) complex salts and sulfites, and also contains many components consumed during processing. Since the compounds of the general formulas (1), (2) and (3) prevent the generation of insolubles and turbidity in the processing solution,
It is a convenient additive component for such a regenerant.

The replenishing agent and the regenerating agent used in the present invention can be easily handled in the form of a cartridge in which containers filled with the treating agent used in each step are collectively stored. It is preferably used. Although any material such as paper, plastic, and metal can be used as the material of the treatment agent container, a plastic material having an oxygen permeability coefficient of 50 ml / m ² · atm · day or less is particularly preferable. The oxygen permeability coefficient is “O ₂ permeation of plastic container, modern packing” (O ₂ permeation of plastic container, Modern
Packing; NJ Calyan, 1968), December 143-1
It can be measured by the method described on page 45. Preferred plastic materials include, specifically, vinylidene chloride (PVDC), nylon (NY), polyethylene (PE), polypropylene (PP), polyester (PES), ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl Alcohol copolymer (EVAL), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), polyethylene terephthalate (P
ET) and the like. In the present invention, in order to reduce oxygen permeability, PVDC, NY, PE, EVA, EVAL and PE
The use of T is preferred.

These container materials may be used singly and molded and used, or a method in which a film is formed and a plurality of kinds are bonded and used (so-called composite film) may be used. Further, as the shape of the container, various shapes such as a bottle type, a cubic type, and a pillow type can be used, but the present invention provides a cubic type which is flexible, easy to handle, and can be reduced in volume after use. A structure similar to the above is also preferable.

The thickness of the composite film is about 5 to 1500 microns, preferably about 10 to 1000 microns. The content of the completed container is 100 ml to 20 liters, preferably 500 ml to
It is about 10 liters. The container may have a cardboard or plastic outer box, or may be formed integrally with the outer box. Various treatment liquids can be filled in the container of the treatment agent used in the present invention. For example, a color developing solution, a bleaching solution, an adjusting solution, a reversing solution, a fixing solution, a bleach-fixing solution, a stabilizing solution, and the like can be exemplified. Is preferred.

Preferred containers for treating agents include high-density polyethylene (HDPE) and polyvinyl chloride resin (PV
C), a rigid container using a one-layer material such as polyethylene terephthalate (PET) or a multilayer material such as nylon / polyethylene (NY / PE) can be used. Further, after the contents are discharged and emptied, the volume of the container can be reduced, that is, a liquid container having flexibility that can easily reduce the required space can be used. As a specific example of the flexible container, there is provided a liquid container in which a hard mouth projecting upward from a flexible container body is opened and closed by a lid member engaged with the flexible body, and the container body and the mouth And a container having a bellows portion in at least a part of the height of the container body (FIGS. 1 and 2 described in JP-A-7-5670).

When a polyethylene container is used as a container for the treatment agent used in the present invention, low-density polyethylene (hereinafter abbreviated as LDPE), medium-density polyethylene (hereinafter abbreviated as MDPE) and high-density polyethylene (hereinafter HDPE) ) Can be used. In a preferred embodiment, the container main body is formed of HDPE, and the cap and the packing member are preferably formed of another HDPE or LDPE. HDPE preferably used in the present invention has a density of 0.941 to 0.9.
69. Polyethylene in this density range is produced by a polymerization method belonging to the so-called medium-pressure method and low-pressure method such as the Ziegler method and the Phillips method, and is known to be a linear molecule having few branches and a high degree of crystallinity. LDPE is synthesized by a high-pressure polymerization method and has a density of 0.910 to 0.925. Since it has a structure with more branches than HDPE, it is bulky, and is rich in flexibility and impact resistance. It is convenient for parts such as caps to be combined with the above-mentioned HDPE container body.

As the container used in the present invention, it is preferable to use HDPE having the above-mentioned density range.
DPE melt index (extruded at a temperature of 190 ° C according to the method specified in ASTM D1238;
16-kg), but 0.3-7.0 g / 10 min,
Preferably, it is 0.3 to 5.0 g / 10 min. When the value of the melt index is in this range, a relatively thin wall of 0.5 to 3.0 suitable for minilab applications.
It is easy to mold a small bottle of about 1 liter. Therefore, a container having excellent uniformity of container thickness and high dimensional accuracy suitable for the purpose of the present invention can be molded. However, the polyethylene container for the bleach-fixing agent of the present invention is made of the above-mentioned HDPE material.
It is not limited to. The preferred thickness of the container in the present invention varies depending on the material, but is preferably from 0.1 to
It is 2.0 mm, particularly preferably 0.3 to 1.5 mm, and more preferably 0.4 to 1.0 mm.

The molding of polyethylene bottles is performed by injection molding,
There are molding methods such as blow molding (including injection blow molding and extrusion blow molding), extrusion molding, vacuum molding and the like, and a molding method according to the purpose can be adopted. The main body of the HDPE bottle used in the present invention is preferably manufactured by a blow molding method, and particularly preferably manufactured by an injection blow molding method. Further, it may be stretched after injection blow molding. Preferably, the cap is manufactured by injection molding or injection blow molding.

HD used in the container for the bleach-fixing composition
In PE, when an additive is added to the resin material, HDPE using an additive that does not adversely affect the bleach-fix processing composition or the alkaline development processing composition is considered from the viewpoint of the possibility of sharing the processing container. preferable. Examples of such additives include pigments such as carbon black, titanium white, calcium silicate, and silica; calcium carbonate;
Additives such as di-t-butyl-4-methylphenol (BHT), dicetyl sulfide, tris (laurylthio) phosphite, other known antioxidants such as amines, thioethers and phenols, stearic acid or stearic acid Sliding agents such as metal salts, 2-hydroxy-
A known ultraviolet absorber compatible with polyethylene, such as 4-n-octyloxybenzophenone, a known plasticizer compatible with polyethylene, and the like may be added as necessary. The total amount of these additives is desirably 50% or less of the total amount of the mixture of plastic raw materials. Preferably, the ratio of polyethylene is 85% or more and no plasticizer is contained, and more preferably, the ratio of polyethylene is 95% or more and no plasticizer is contained.

The shape and structure of the container for filling the concentrated liquid developer composition of the present invention can be arbitrarily designed according to the purpose.
Nos. 7046 and 63-50839, JP-A-1-235
No. 950, JP-A-63-45555, etc .;
Nos. 61 and 62-134626 and the like having a flexible partition can also be used.

It is also preferable to use a polyethylene terephthalate container as the container for the bleach-fixing solution regenerant. This resin is also vulnerable to acid or alkali hydrolysis, which is a common weakness with other polyester resins.Bleach-fixing agents are neither strongly acidic nor strongly alkaline, and therefore hydrolyze even polyester resins such as polyethylene terephthalate. And has sufficient physical strength as a treatment agent container. Blow molding makes it possible to make a container suitable for a concentrated bleach-fixing agent.
Among them, a molded container obtained by performing injection molding to form a shape called a preform, then transferring to a mold, blow molding, and biaxially stretching is preferable. This resin can be used as a coloring container by adding a coloring dye. Although additives such as plasticizers are not usually used, glass fibers may be added for reinforcement. Excellent as a photographic container in terms of physical strength and impact resistance.

The bleach-fixing agent of the present invention is combined with a color developing agent and, in some cases, a stabilizing solution agent to constitute a kit. One form suitable for a minilab is to form a kit in which the kit is collectively housed and integrated into one container from the viewpoint of handleability and transportability. The material of the cartridge is preferably made of corrugated cardboard, wooden or plastic, which is shock-resistant, lightweight and low-cost.

The color photographic light-sensitive material to which the developing method using the bleach-fix solution of the present invention is applied will be described. The processing method of the present invention can be applied to color photographic light-sensitive materials in general, regardless of whether they are for photography or printing. Color negative film, color reversal film,
The present invention can be applied to any development processing of color photographic paper, and can be applied to any of general, movie, and professional use. The effects of the present invention are particularly large, and the preferred applications are color negative and color reversal films, and especially color negative films.

The light-sensitive material is provided with at least one light-sensitive layer on a support. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer unit comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is.
The photosensitive layer unit has color sensitivity to any of blue light, green light, and red light. In a multilayer silver halide color photographic material, the photosensitive layer units are layered. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

These may contain a coupler, a DIR compound, a color mixing inhibitor and the like described below. The plurality of silver halide emulsion layers constituting each photosensitive layer unit are DE1,
121,470, GB923,045, JP-A-57-1
No. 12751, No. 62-200350, No. 62-20
Various arrangements can be formed on the support as described in JP-A-6541 and JP-A-62-206543. As a specific example, from the side farthest from the support, a low-sensitivity blue photosensitive layer (BL) / a high-sensitivity blue photosensitive layer (BH) / a high-sensitivity green photosensitive layer (GH) / a low-sensitivity green photosensitive layer (GL) / a high-sensitivity red Photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH
/ BL / GH / GL / RL / RH or BH / BL /
They can be installed in the order of GH / GL / RH / RL. In addition, as described in JP-B-55-34932, JP-A-56-25738, and JP-A-62-63936, it is necessary that the respective constituent layers of GL, RL, and BL are not necessarily integrated into an integrated multilayer structure. However, a layer configuration in which a low-sensitivity layer or a high-sensitivity layer is separated can be adopted.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a layer having a lower sensitivity than the middle layer. Further, there is an arrangement in which a silver halide emulsion layer having a low sensitivity is disposed and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even in the case of such three layers having different sensitivities, different configurations are possible as in JP-A-59-202264. To improve color reproducibility, US 4,6
63,271, 4,705,744, 4,70
7,436, JP-A-62-160448, JP-A-63-160448.
A donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, and RL described in the specification of 89850 may be arranged adjacent to or close to the main photosensitive layer.

Tabular grains having a silver iodobromide internal structure and non-tabular multi-structure grains are mainly used in color photographic materials for photographing purposes, for example, multilayer color negative films and color reversal films. Preferred silver halide is about 3
Silver iodobromide, silver iodochloride, or silver iodochlorobromide containing 0 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystalline forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The light-sensitive silver halide emulsion in the light-sensitive material as a positive material such as color paper has a silver chloride content of at least 95 mol%, the balance being silver bromide, and substantially no silver iodide. It preferably comprises silver halide grains. Here, “substantially free of silver iodide” means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less, more preferably 0 mol%. From the viewpoint of rapid processing, the above silver halide emulsion is particularly preferably a silver halide emulsion having a silver chloride content of 98 mol% or more.
Among such silver halides, those having a silver bromide localized phase on the surface of silver chloride grains are particularly preferable because high sensitivity can be obtained and photographic performance can be stabilized.

The silver halide emulsion contained in at least one light-sensitive silver halide emulsion layer has a coefficient of variation in grain size distribution (standard deviation of grain size distribution divided by average grain size) of 15% or less. Some are preferred and 1
Monodispersed emulsions of 0% or less are more preferred. It is preferable to use two or more of the above monodispersed emulsions in the same layer for the purpose of obtaining a wide latitude. At this time, the monodispersed emulsions preferably differ in average grain size by 15% or more, more preferably differ by 20 to 60%, and particularly preferably differ by 25 to 50%. The sensitivity difference between the monodispersed emulsions is preferably from 0.15 to 0.50 logE, more preferably from 0.20 to 0.40 logE, even more preferably from 0.25 to 0.35 logE. .

To obtain a positive image, iron and / or ruthenium and / or osmium compounds are added per mole of silver halide to silver chlorobromide having a silver chloride content of not less than 95 mol% which is substantially free of silver iodide. 1 × 10 ^-5 to 1 × 10 ^-3
It is effective to use a silver halide emulsion containing the iridium compound in an amount of 1 × 10 ⁻⁷ to 1 × 10 ⁻⁵ mol per mol of silver halide in the silver bromide localized phase.

Although the preferred range of the silver content in the light-sensitive material varies depending on the type of the light-sensitive material, it is generally 10 g / m ^2.
Is less than. Preferably it is less than 8 g / m ² . In the case of photographic paper, the level is preferably less than 1.5 g / m ² , more preferably less than 0.8 g / m ² , but preferably less than 0.8 g / m ² .
It is at least 05 g / m ² . In the case of a photosensitive material for photographing with a camera, the level is preferably less than 10.0 g / m ² , more preferably less than 8.0 g / m ² , and even more preferably less than 5.0 g / m ² , 0.5 g / m ² or more.

The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-
Page 23, "I. Emulsion preparation and t
ypes) "and No. 18716 (November 1979).
Mon.), p. 648, ibid. 307105 (1989 l
January, pp. 863-865, and Grafkid, "Physics and Chemistry of Photography," published by Paul Montell (P. Glafkides, C.
hemie et Phisique Photographique, Paul Montel, 1
967), "Photographic Emulsion Chemis" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion Chemis)
try, Focal Press, 1966), Zeligman et al., "Manufacture and Coating of Photographic Emulsion," Focal Press (VLZelikm)
an, et al., Making and Coating Photographic Emulsio
n, Focal Press, 1964).

US Pat. Nos. 3,574,628 and 3,655.
Monodisperse emulsions described in 394 and GB 1,413,748 are also preferred. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are by Gatoff, Photographic Science and Engineering (Gutoff, Photographic Sciencean
d Engineering), Vol. 14, pp. 248-257 (197
0); US Pat. Nos. 4,434,226 and 4,414,31
0, 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, or the inside and outside may be composed of different halogen compositions,
It may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, or may be joined to a compound other than silver halide, such as, for example, silver rhodanate or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grains, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used.
This preparation method is described in JP-A-59-133542. Although the thickness of the shell of this emulsion varies depending on the development process and the like, it is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

For the silver halide photographic light-sensitive material to be processed by the processing method and the processing agent of the present invention, conventional photographic materials and additives can be used. For the purpose of the present invention, polyethylene terephthalate, polyethylene naphthalate, transparent film support such as cellulose triacetate, and polyethylene terephthalate, polyethylene naphthalate,
A reflection-type support provided with a light reflection layer on cellulose triacetate, paper, or the like is preferable. The former is preferable for a photographic material, and the latter is mainly preferable for a positive material for printing or the like. In the latter case, a reflective support laminated with a plurality of polyethylene layers or polyester layers and containing a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferred.

It is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, preferably, benzoxazole type, coumarin type,
A pyrazoline-based fluorescent whitening agent can be used, and a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is more preferable. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by weight, more preferably 0.001 to 0.5% by weight, based on the resin.

The photosensitive material to which the method of the present invention is applied includes:
For the purpose of improving image sharpness, etc., a hydrophilic colloid layer is coated on the hydrophilic colloid layer in the manner described in EP-A-0,337,490 A2, Nos. 27-7.
Addition of a dye capable of being decolorized by processing (among which is an oxonol dye) described on page 6 so that the optical reflection density at 680 nm of the photosensitive material becomes 0.70 or more;
The water-resistant resin layer of the support preferably contains 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with a divalent to tetravalent alcohol (for example, trimethylolethane).

Further, a fungicide such as that described in JP-A-63-271247 is added to the light-sensitive material in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. Is preferred.

The light-sensitive material may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferred.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material, and the processing methods and processing additives applied for processing this light-sensitive material As the agent, European Patent EP355
660A2, JP-A-2-33144 and JP-A-62-215272
Those described in the specification of the item or those listed in the following Table 1 are preferably used.

[0127]

[Table 1]

In the light-sensitive material to which the present invention is applied, a color image preservability improving compound as described in European Patent No. EP277589A2 is used in combination with a pyrazoloazole coupler, the above pyrrolotriazole coupler, or an acylacetamide type yellow coupler. Is preferred.

Examples of the cyan coupler include phenol couplers and naphthol couplers described in the publicly known documents in the above table, as well as JP-A-2-33144.
JP, EP 333185 A2, JP-A-64
-32260, European Patent EP 456226 A1, European Patent EP 484909, European Patent EP 488
The cyan couplers described in JP-A-248-248 and EP0491197A1 may be used. In particular, Japanese Patent Laid-Open No. 5-1
No. 50423, No. 5-255333, No. 5-2020
Application to silver halide color photographic light-sensitive materials containing a pyrrolotriazole derivative as a cyan coupler described in JP-A Nos. 04, 7-048376 and 9-189988 is also effective. However, the method of the present invention can of course be applied to photosensitive materials containing cyan couplers other than pyrrolotriazole type couplers.

Examples of the magenta coupler include 5-pyrazolone-based magenta couplers as described in the publicly known documents in the above table, as well as those described in WO92 / 18901, WO92 / 18902 and WO92 / 18903. Are also preferred. In addition to these 5-pyrazolone magenta couplers, known pyrazoloazole-type couplers are used in the present invention, among which hue and image stability,
The use of pyrazoloazole couplers described in JP-A-61-65245, JP-A-61-65246, JP-A-61-14254, European Patent Nos. EP226849A and 294785A is preferred from the viewpoint of color development and the like. .

As the yellow coupler, known acylacetanilide type couplers are preferably used. Among them, European Patent EP 449,969A and JP-A-5-10-10 are particularly preferable.
7701, Japanese Patent Application Laid-Open No. Hei 5-113462, European Patent EP
The couplers described in 482552A and EP524540A are preferably used.

The color negative film to which the present invention is applied preferably has a magnetic recording layer. The magnetic recording layer used in the present invention will be described. The magnetic recording layer used in the present invention is obtained by coating a support with an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder. The magnetic particles used in the present invention are γF
ferromagnetic iron oxide such as e ₂ O ₃ , Co-coated γFe ₂ O ₃ , Co
Deposited magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy and the like can be used.

The binder used for the magnetic particles may be a thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, a natural material described in JP-A-4-219569. Combinations (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. For example, polyurethane resin, polyurethane
Examples thereof include polyester resins, vinyl copolymers, cellulose derivatives, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, antiadhesion, and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. Abrasives of the above non-spherical inorganic particles are preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide, silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. US Pat. No. 5,336,589 and US Pat. No. 5,250,4 have disclosed a photosensitive material having a magnetic recording layer.
04, 5,229,259, 5,215,874,
It is described in EP 466,130.

[0135]

[Example-1]

(1) Light-sensitive Material Used A light-sensitive material sample 001 used in Examples was prepared by the following emulsion, support and coating layer constitution.

[Constituent Emulsions] Each constituent silver halide emulsion Em
-A to Em-O were prepared by the following method. (Preparation of Em-A) An aqueous solution 1200 containing 1.0 g of low molecular weight gelatin having a molecular weight of 15,000, 1.0 g of KBr and 1.0 g of KBr
Milliliter (hereinafter referred to as “mL”) at 35 ° C.
And stirred vigorously. 30 mL of an aqueous solution containing 1.9 g of AgNO ₃ and 30 mL of an aqueous solution containing 1.5 g of KBr and 0.7 g of low-molecular-weight gelatin having a molecular weight of 15,000 were added over 30 seconds by the double jet method to form nuclei.
At this time, the excess concentration of KBr was kept constant. 6 KBr
g was added and the temperature was raised to 75 ° C. to ripen. After ripening, 35 g of succinated gelatin was added. The pH was adjusted to 5.5. 150 mL of aqueous solution containing 30 g of AgNO ₃ and KB
The r aqueous solution was added over 16 minutes by the double jet method. At this time, the silver potential is set to −25 with respect to the saturated calomel electrode.
mV. Further, an aqueous solution containing 110 g of AgNO ₃ and an aqueous KBr solution were added over a period of 15 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, an AgI having a size of 0.03 μm
The fine grain emulsion was simultaneously added at an accelerated flow rate so that the silver iodide content became 3.8%, and the silver potential was kept at -25 mV. 132 mL of an aqueous solution containing 35 g of AgNO ₃ and K
An aqueous Br solution was added over 7 minutes by the double jet method. KBr so that the potential at the end of the addition becomes -20 mV.
The addition of the aqueous solution was adjusted. After the temperature was adjusted to 40 ° C., 5.6 g of Compound 1 in terms of KI was added, and 64 cc of a 0.8 M aqueous sodium sulfite solution was further added. Furthermore, Na
The pH was raised to 9.0 by adding an aqueous OH solution and maintained for 4 minutes to rapidly generate iodide ions.
Returned to 5.

After the temperature was returned to 55 ° C., 1 mg of sodium benzenethiosulfonate was added, and 13 g of lime-treated gelatin having a calcium concentration of 1 ppm was added. After completion of the addition, an aqueous solution 25 containing 70 g of AgNO ₃
0 mL and an aqueous KBr solution were added over 20 minutes while maintaining the potential at 60 mV. At this time, 1.0 × 10 ⁻⁵ mol of yellow blood salt was added to 1 mol of silver. After washing with water, 80 g of lime-processed gelatin having a calcium concentration of 1 ppm was added, and the mixture was adjusted to pH 5.8 and pAg 8.7 at 40 ° C.

[0138]

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The content of calcium, magnesium and strontium in the above emulsion was measured by ICP emission spectroscopy to be 15 ppm, 2 ppm and 1 ppm, respectively.

The temperature of the above emulsion was raised to 56 ° C. First, 1 g of a pure AgBr fine grain emulsion having a size of 0.05 μm was added thereto in terms of Ag and shelled. Next, sensitizing dyes 1, 2, 3
In the form of a solid fine dispersion,
5.85 × 10 ^-4 mol, 3.06 × 10 ^-4 mol, 9.0
0 × 10 ^-6 mol was added. As shown in Table 2, the inorganic salt was dissolved in ion-exchanged water, and then a sensitizing dye was added.
By dispersing at 0 rpm for 20 minutes, sensitizing dye 1,
A few solid fine dispersions were made. When the sensitizing dye is added and the adsorption of the sensitizing dye reaches 90% of the adsorption amount in the equilibrium state, the calcium nitrate is reduced to a calcium concentration of 250 ppm.
Was added so that The amount of sensitizing dye adsorbed is determined by separating the solid layer and the liquid layer by centrifugal sedimentation, measuring the difference between the amount of sensitizing dye added first and the amount of sensitizing dye in the supernatant, and adsorbing the sensitizing dye. The amount of dye was determined. After addition of calcium nitrate, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N,
N-dimethylselenourea and Compound 4 were added for optimal chemical sensitization. N, N-dimethylselenourea was added in an amount of 3.40 × 10 ⁻⁶ mol per mol of silver. At the end of the chemical sensitization, Compound 2 and Compound 3 were added to prepare Em-A.

[0141]

[Table 2]

[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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(Preparation of Em-B) In the preparation of Em-A, the amount of KBr added after nucleation was changed to 5 g, and the succinated gelatin was converted to a trimellitization ratio of 98,000 having a molecular weight of 100,000 containing 35 μmol methionine per gram. %
The compound 1 was replaced with the compound 6, and the added amount of the compound 6 was 8.0 in terms of KI.
g, and the amount of the sensitizing dye added before the chemical sensitization was 6.50 × 10 ^-4 mol, 3.40 × 10 ^-4 mol, and 1.40 × 10 ^-4 mol, respectively, with respect to sensitizing dyes 1, 2, and 3, respectively. Em-B in the same manner as Em-A, except that the amount was changed to 00 × 10 ⁻⁵ mol and the amount of N, N-dimethylselenourea added during chemical sensitization was changed to 4.00 × 10 ⁻⁶ mol. Was prepared.

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(Preparation of Em-C) In the preparation of Em-A, the amount of KBr added after nucleation was changed to 1.5 g, and the succinated gelatin was converted into a phthalate having a molecular weight of 100,000 containing 35 μmol of methionine per gram. 97
% Phthalated gelatin and compound 1 was replaced with compound 7
And the amount of compound 7 added was changed to 7.1 g in terms of KI, and the amount of sensitizing dye added before chemical sensitization was 7.80 × 10 ^{− with} respect to sensitizing dyes 1, 2, and 3, respectively. ⁴ moles,
Except that the amounts were changed to 4.08 × 10 ⁻⁴ mol and 1.20 × 10 ⁻⁵ mol, and the amount of N, N-dimethylselenourea added during chemical sensitization was changed to 5.00 × 10 ⁻⁶ mol. Is E
Em-C was prepared in the same manner as mA.

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(Preparation of Em-E) 1200 mL of an aqueous solution containing 1.0 g of low molecular weight gelatin having a molecular weight of 15,000 and 1.0 g of KBr was kept at 35 ° C. and stirred vigorously. AgN
30 mL of an aqueous solution containing 1.9 g of O ₃ and 30 mL of an aqueous solution containing 1.5 g of KBr and 0.7 g of low molecular weight gelatin having a molecular weight of 15,000 were added over 30 seconds by a double jet method to form nuclei. At this time, the excess concentration of KBr was kept constant. 6 g of KBr was added, and the temperature was raised to 75 ° C. to ripen. After ripening, 15 g of succinated gelatin and 20 g of the above-mentioned trimellitated gelatin were added. The pH was adjusted to 5.5. Aqueous solution 15 containing 30 g of AgNO ₃
0 mL and KBr aqueous solution were added by a double jet method over 16 minutes. At this time, the silver potential was kept at -25 mV with respect to the saturated calomel electrode. Further, AgNO ₃ 110
g and an aqueous solution of KBr were added by a double jet method over 15 minutes while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, the size is 0.03
μm AgI fine grain emulsion was simultaneously added at a flow rate acceleration of 3.8% so that the silver iodide content became 3.8%.
It was kept at 25 mV. Aqueous solution 13 containing 35 g of AgNO ₃
2 mL and KBr aqueous solution were added by a double jet method over 7 minutes. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition became -20 mV. Add KBr,
After adjusting the potential to −60 mV, 1 mg of sodium benzenethiosulfonate was added, and the calcium concentration was reduced to 1 p.
13 g of pm-treated gelatin were added. After the addition, an aqueous solution of low molecular weight gelatin having a molecular weight of 15,000 and Ag
AgI having a particle size (sphere equivalent diameter) of 0.008 μm prepared by premixing an aqueous solution of NO _{3 and an} aqueous KI solution immediately before addition in a separate chamber having a magnetic coupling induction type stirrer described in JP-A-10-43570. Fine particle emulsion KI
While continuously adding 8.0 g in conversion, 70 g of AgNO ₃
250 mL of an aqueous solution containing
It was added over 20 minutes while maintaining 0 mV. At this time, 1.0 × 10 ⁻⁵ mol of yellow blood salt was added to 1 mol of silver. After washing with water, 80 g of lime-processed gelatin having a calcium concentration of 1 ppm was added, and the pH was adjusted to 5.8 and pAg at 40 ° C.
Adjusted to 8.7.

The contents of calcium, magnesium and strontium in the above emulsion were measured by ICP emission spectroscopy.
ppm.

In the chemical sensitization, sensitizing dyes 1, 2, and 3 were changed to sensitizing dyes 4, 5, and 6, and the added amount was 7.73.
× 10 ^-4 mol, 1.65 × 10 ^-4 mol, 6.20 × 10
Em-E was prepared by performing chemical sensitization in the same manner as Em-A except that the amount was changed to ^-5 mol.

[0155]

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[0156]

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[0157]

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(Preparation of Em-F) 1200 mL of an aqueous solution containing 1.0 g of low-molecular-weight gelatin having a molecular weight of 15,000 and 1.0 g of KBr was kept at 35 ° C. and stirred vigorously. AgN
30 mL of an aqueous solution containing 1.9 g of O ₃ and 30 mL of an aqueous solution containing 1.5 g of KBr and 0.7 g of low molecular weight gelatin having a molecular weight of 15,000 were added over 30 seconds by a double jet method to form nuclei. At this time, the excess concentration of KBr was kept constant. 5 g of KBr was added, and the temperature was raised to 75 ° C. to ripen. After ripening, 20 g of succinated gelatin and 15 g of phthalated gelatin were added. The pH was adjusted to 5.5. A
150 mL of an aqueous solution containing 30 g of gNO ₃ and an aqueous KBr solution were added over 16 minutes by a double jet method. At this time, the silver potential was kept at -25 mV with respect to the saturated calomel electrode. Further, an aqueous solution containing 110 g of AgNO ₃ and KB
The r aqueous solution was added over a period of 15 minutes by a double jet method at an accelerated flow rate such that the final flow rate was 1.2 times the initial flow rate. At this time, an AgI fine grain emulsion having a size of 0.03 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 3.8%, and the silver potential was kept at −25 mV.
132 mL of an aqueous solution containing 35 g of AgNO ₃ and an aqueous KBr solution were added over 7 minutes by a double jet method. KB
After adjusting the potential to −60 mV by adding an aqueous solution of r, 9.2 g of an AgI fine grain emulsion having a size of 0.03 μm in terms of KI was added. 1 mg of sodium benzenethiosulfonate was added, and 13 g of lime-treated gelatin having a calcium concentration of 1 ppm was further added. After the addition is completed, AgN
250 mL of an aqueous solution containing 70 g of O ₃ and an aqueous KBr solution were added over 20 minutes while maintaining the potential at 60 mV. At this time, yellow blood salt was added in an amount of 1.0 × 10
^-5 mol was added. After washing with water, calcium concentration 1ppm
80 g of lime-processed gelatin were added at 40 ° C. and pH5.
8, pAg was adjusted to 8.7.

The contents of calcium, magnesium and strontium in the above emulsion were measured by ICP emission spectroscopy.
ppm.

In chemical sensitization, sensitizing dyes 1, 2, and 3 were replaced with sensitizing dyes 4, 5, and 6, and the added amount was 8.50 ×
10 ^-4 mol, 1.82 x 10 ^-4 mol, 6.82 x 10 ^-5
Chemical sensitization was carried out in the same manner as in Em-B except for using mol, to prepare Em-F.

(Preparation of Em-G) 1200 mL of an aqueous solution containing 1.0 g of low-molecular-weight gelatin having a molecular weight of 15,000 and 1.0 g of KBr was kept at 35 ° C. and stirred vigorously. AgN
30 mL of an aqueous solution containing 1.9 g of O ₃ and 30 mL of an aqueous solution containing 1.5 g of KBr and 0.7 g of low molecular weight gelatin having a molecular weight of 15,000 were added over 30 seconds by a double jet method to form nuclei. At this time, the excess concentration of KBr was kept constant. 1.5 g of KBr was added, and the temperature was raised to 75 ° C. to ripen. After ripening, the above-mentioned trimellitized gelatin 1
5 g and 20 g of the above-mentioned phthalated gelatin were added. pH
Was adjusted to 5.5. 150 mL of an aqueous solution containing 30 g of AgNO ₃ and an aqueous KBr solution were added over 16 minutes by a double jet method. At this time, the silver potential was kept at -25 mV with respect to the saturated calomel electrode. Furthermore, AgNO ₃ 1
An aqueous solution containing 10 g and an aqueous KBr solution were added over 15 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, the size is 0.
An AgI fine grain emulsion of 03 µm was prepared by using a silver iodide content of 3.8.
% While simultaneously accelerating the flow and adding the silver potential at -25 mV. 132 mL of an aqueous solution containing 35 g of AgNO ₃ and an aqueous KBr solution were added over 7 minutes by the double jet method. K so that the potential becomes -60 mV
The addition of the aqueous Br solution was adjusted. 7.1 g of an AgI fine grain emulsion having a size of 0.03 μm was added in terms of KI. 1 mg of sodium benzenethiosulfonate is added, and 13 g of lime-treated gelatin having a calcium concentration of 1 ppm is further added.
Was added. After completion of the addition, 250 mL of an aqueous solution containing 70 g of AgNO ₃ and an aqueous KBr solution were added over 20 minutes while maintaining the potential at 60 mV. At this time, 1.0 × 10 ⁻⁵ mol of yellow blood salt was added to 1 mol of silver. After washing with water, 80 g of lime-treated gelatin with a calcium concentration of 1 ppm
Was added at 40 ° C. to adjust the pH to 5.8 and the pAg to 8.7.

The contents of calcium, magnesium and strontium in the above emulsion were measured by ICP emission spectroscopy.
ppm.

Sensitizing dyes 1, 2, and 3 were replaced with sensitizing dyes 4, 5, and 6
Was changed to 1.00 × 10 ^-3 mol,
Em-G was prepared in the same manner as Em-C except that 2.15 × 10 ⁻⁴ mol and 8.06 × 10 ⁻⁵ mol were used.

(Preparation of Em-J) In the preparation of Em-B, the sensitizing dyes added before chemical sensitization were changed to sensitizing dyes 7 and 8, and the added amount of each was 7.65 × 10 ^-4. Mole,
Em-J was prepared in the same manner as Em-B except that the amount was 2.74 × 10 ⁻⁴ mol.

[0165]

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[0166]

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(Preparation of Em-L) <Preparation of silver bromide seed emulsion> Average sphere equivalent diameter: 0.6 μm
A silver bromide tabular emulsion containing an aspect ratio of 9.0, 1.16 mol of silver per kg of emulsion, and 66 g of gelatin was prepared.

<Growth Process 1> An aqueous solution 1 containing 1.2 g of potassium bromide and a succinated gelatin having a succinating rate of 98%.
0.3 g of modified silicone oil was added to 250 g.
After the silver bromide tabular emulsion containing 0.086 mol of silver was added, the mixture was stirred at 78 ° C. An aqueous solution containing 18.1 g of silver nitrate and the silver iodide fine particles having a particle size of 0.037 μm were added so as to be 5.4 mol based on silver to be added. Further, at this time, the pAg was 8.1 by double jetting the aqueous potassium bromide solution.
It was added while adjusting to be.

<Growth Process 2> After adding 2 mg of sodium benzenethiosulfonate, 0.45 g of 3,5-disulfocatechol disodium salt and 2.5 mg of thiourea dioxide were added. Further, an aqueous solution containing 95.7 g of silver nitrate and an aqueous potassium bromide solution were added over 66 minutes while accelerating with a double jet. At this time, the above 0.037μ
m of silver iodide fine grains was added in an amount of 7.0 mol with respect to the added silver. At this time, the amount of potassium bromide in the double jet was adjusted so that the pAg became 8.1.
After the addition is completed, sodium benzenethiosulfonate 2m
g was added.

<Growth Process 3> An aqueous solution containing 19.5 g of silver nitrate and an aqueous solution of potassium bromide were mixed with a double jet to obtain a solution.
Added over minutes. At this time, the amount of the aqueous potassium bromide solution was adjusted so that the pAg became 7.9.

<Addition of sparingly soluble silver halide emulsion 4> After adjusting the host particles to pAg 9.3 with an aqueous potassium bromide solution, the above 0.037 μm silver iodide fine grain emulsion 2 was prepared.
5 g was added rapidly within 20 seconds.

<Outer Shell Layer Forming Step 5> Further, silver nitrate 3
An aqueous solution containing 4.9 g was added over 22 minutes.

This emulsion was tabular grains having an average aspect ratio of 9.8, an average equivalent sphere diameter of 1.4 μm, and an average silver iodide content of 5.5 mol.

<Chemical sensitization> After washing with water, the modification rate was 98%.
Add succinic acid-introduced gelatin and calcium nitrate at 40 ℃
And adjusted to pH 5.8 and pAg 8.7. The temperature was raised to 60 ° C., 5 × 10 ⁻³ mol of a 0.07 μm silver bromide fine grain emulsion was added, and sensitizing dyes 9, 10 and 11 were added 20 minutes later. Thereafter, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N-dimethylselenourea, compound 4
Was added for optimal chemical sensitization. Compound 3 was added 20 minutes before the end of the chemical sensitization, and Compound 5 was added at the end of the chemical sensitization. Here, the optimal chemical sensitization means that the sensitizing dye and each compound are added in an amount of 10 ^-1 to 10 ^-8 mol per mol of silver halide so that the sensitivity at the time of exposure at 1/100 becomes the highest. Means you have selected from a range.

[0175]

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[0176]

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[0177]

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[0178]

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[0179]

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(Preparation of Em-O) An aqueous gelatin solution (1250 mL of distilled water, 48 g of deionized gelatin, 0.75 g of KBr) was placed in a reaction vessel equipped with a stirrer, and the temperature of the solution was kept at 70 ° C. To this solution was added 276 mL of an aqueous solution of AgNO ₃ (containing 12.0 g of AgNO ₃ ) and an aqueous solution of KBr having an equimolar concentration while maintaining the pAg at 7.26 over 7 minutes by a controlled double jet addition method. Then, the temperature was lowered to 68 ° C., and thiourea dioxide (0.05 wt.
%) Was added.

Subsequently, 592.9 mL of an AgNO ₃ aqueous solution
(Including 108.0 g of AgNO ₃ )
A mixed aqueous solution of r and KI (2.0 mol% KI) was added over 18 minutes and 30 seconds by a controlled double jet addition method while maintaining the pAg at 7.30. Five minutes before the end of the addition, 18.0 m of thiosulfonic acid (0.1 wt%) was added.
L was added.

The obtained grains were cubic grains having an equivalent sphere diameter of 0.19 μm and an average silver iodide content of 1.8 mol%.

Em-O was re-dispersed by subjecting it to desalting and washing with a normal flocculation method,
It adjusted to 6.2 and pAg7.6.

Subsequently, Em-O was subjected to the following spectral and chemical sensitization.

First, sensitizing dye 10, sensitizing dye 11, and sensitizing dye 12 were each added in an amount of 3.37 × 10 ^-4 per mol of silver.
Mol / mol, KBr 8.82 × 10 ^-4 mol / mol, sodium thiosulfate 8.83 × 10 ^-5 mol / mol, aqueous potassium thiocyanate 5.95 × 10 ^-4 mol / mol and potassium chloroaurate 3. Aging was performed at 68 ° C. by adding 07 × 10 ⁻⁵ mol / mol. The aging time is 1/10
Adjustment was made so that the sensitivity at 0 second exposure was the highest.

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For the preparation of (Em-D, H, I, K, M, N) tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. According to the examples of JP-A-3-237450, gold sensitization was carried out in the presence of the spectral sensitizing dyes and sodium thiocyanate shown in Table 3.
Sulfur sensitization and selenium sensitization are applied. Emulsions D, H,
I and K contain optimum amounts of Ir and Fe. Emulsion M, N
Is subjected to reduction sensitization during grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.

[0188]

[Table 3]

[0189]

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[0190]

[Table 4]

In Table 4, dislocation lines as described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope.

[Coating of Support and Constituent Layers] In this example, a polyethylene naphthalate support having a thickness of 90 μm was used. The first, second, and third backing layers are coated on one side of the support, an undercoat layer on the other side, and a series of photosensitive layers described below are further coated thereon to form a silver halide emulsion layer. A photosensitive material sample having a transparent magnetic recording medium layer was prepared.

1) Coating of a first backing layer and an undercoat layer A processing atmosphere pressure of 0.2 Torr was applied to both sides of the support.
r, partial pressure of H ₂ O in atmosphere gas 75%, discharge frequency 30
The glow discharge treatment was performed at a frequency of 2500 kHz, an output of 2500 W, and a treatment intensity of 0.5 kV · A · min / m ² . On this support, a coating solution having the following composition was used as a first backing layer.
It was applied at a coating amount of 5 mL / m ² using the bar coating method of JP-A No. 4589.

Conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₅ particle concentration 50 parts by weight 10% aqueous dispersion. Secondary aggregate having a primary particle diameter of 0.005 μm and an average particle diameter of 0.05 μm) Gelatin 0.5 parts by weight Water 49 parts by weight Polyglycerol polyglycidyl ether 0.16 parts by weight Poly (degree of polymerization 20) oxyethylene 0.1 parts by weight Sorbitan monolaurate.

Further, after the first backing layer was applied, it was wound around a stainless steel core having a diameter of 20 cm, and was heated at 110 ° C. (PE
(Tg of N support: 119 ° C.), heat-treated for 48 hours, heat-annealed, and then annealed with the support sandwiched between the first layer and a coating solution of the following composition as an undercoat layer for emulsion. Using a coating method, coating was performed at a coating amount of 10 mL / m ² .

Gelatin 1.01 parts by weight Salicylic acid 0.30 parts by weight Resorcin 0.40 parts by weight Poly (degree of polymerization 10) oxyethylene nonylphenyl ether 0.11 parts by weight Water 3.53 parts by weight Methanol 84.57 parts by weight n -Propanol 10.08 parts by weight.

2) Second Backing Layer (Transparent Magnetic Recording Layer) Dispersion of Magnetic Material Co-Coated γ-Fe_TwoO_ThreeMagnetic material (average length
Shaft length: 0.25 μm, S _BET: 39m^Two/ G, Hc: 8
31 Oe, σs: 77.1 emu / g, σr: 37.
4emu / g) 1100 parts by weight, 220 parts by weight of water and
Run coupling agent [3- (poly (degree of polymerization 10) oxy
Ethynyl) oxypropyltrimethoxysilane] 165
Add parts by weight and mix thoroughly with an open kneader for 3 hours.
Kneaded. This viscous liquid roughly dispersed is heated at 70 ° C for 24 hours.
After drying and removing water, heat treatment at 110 ° C. for 1 hour,
Surface-treated magnetic particles were produced.

Further, the mixture was kneaded again in an open kneader for 4 hours according to the following formulation. The above-mentioned surface-treated magnetic particles 855 g Diacetyl cellulose 25.3 g Methyl ethyl ketone 136.3 g Cyclohexanone 136.3 g

Furthermore, a sand mill (1/1 /
(4G sand mill) at 2,000 rpm for 4 hours. As the medium, glass beads having a diameter of 1 mm were used. The kneading liquid 45 g Diacetyl cellulose 23.7 g Methyl ethyl ketone 127.7 g Cyclohexanone 127.7 g Further, a magnetic substance-containing intermediate liquid was prepared according to the following formulation.

Preparation of Magnetic Substance-Containing Intermediate Solution 674 g of the above magnetic substance fine dispersion liquid 24280 g (solid content: 4.34% by weight, solvent: methyl ethyl ketone / cyclohexanone = 1/1) cyclohexanone 46 g After mixing these Then, the mixture was stirred with a disper to prepare a "magnetic substance-containing intermediate liquid".

The α-alumina abrasive dispersion used in the present invention was prepared according to the following formulation. (A) Preparation of Sumicorundum AA-1.5 (average primary particle size: 1.5 μm, specific surface area: 1.3 m ² / g) particle dispersion A ceramic-coated sand mill (1/1 /
(4G sand mill) at 800 rpm for 4 hours. As the media, zirconia beads having a diameter of 1 mm were used. Sumicorundum AA-1.5 152 g Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone Co., Ltd.) 0.48 g Diacetyl cellulose solution 227.52 g (solid content: 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1).

(B) Colloidal silica particle dispersion (fine particles) As the colloidal silica particle dispersion (fine particles), "MEK-ST" manufactured by Nissan Chemical Industries, Ltd. was used. this is,
It is a dispersion liquid of colloidal silica having an average primary particle diameter of 0.015 μm using methyl ethyl ketone as a dispersion medium, and has a solid content of 30%.

Preparation of Second Backing Layer Coating Solution The above magnetic substance-containing intermediate solution 19053 g Diacetyl cellulose solution 264 g (solid content: 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Colloidal silica dispersion “MEK-ST” [Dispersion b] 128 g (solid content 30%) AA-1.5 dispersion [dispersion a] 12 g Millionate MR-400 (manufactured by Nippon Polyurethane Co., Ltd.) Diluent 203 g (solid content 20%, diluent solvent: Methyl ethyl ketone / cyclohexanone = 1/1) methyl ethyl ketone 170 g cyclohexanone 170 g

The coating solution obtained by mixing and stirring the above was applied by a wire bar so as to have an application amount of 29.3 mL / m ² . Drying was performed at 110 ° C. The thickness of the dried magnetic layer was 1.0 μm.

3) Third backing layer (higher fatty acid ester slip agent-containing layer) Preparation of a stock solution of a slip agent The following solution A was heated and dissolved at 100 ° C, added to the solution A, and dispersed with a high-pressure homogenizer.
A dispersion stock of a slip agent was prepared.

Solution A The following compound 399 parts by weight C ₆ H ₁₃ CH (OH) (CH ₂ ) ₁₀ COOC ₅₀ H _{101 The following} compound 171 parts by weight nC ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H Cyclohexanone 830 Parts by weight

Liquid A Cyclohexanone 8600 parts by weight

Preparation of Spherical Inorganic Particle Dispersion A spherical inorganic particle dispersion [c1] was prepared according to the following formulation.

Isopropyl alcohol 93.54 parts by weight Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone) Compound 1-1: (CH ₃ O) ₃ Si— (CH ₂ ) ₃ —NH ₂ ) 5.53 parts by weight Compound 2-1 2.93 parts by weight

[0210]

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Sea Hosta KEP50 (amorphous spherical silica, average particle size 0.5 μm, manufactured by Nippon Shokubai Co., Ltd.) 88.00 parts by weight

After stirring for 10 minutes with the above formulation, the following is further added. 252.93 parts by weight of diacetone alcohol

While the above solution was cooled with ice and stirred, an ultrasonic homogenizer “SONIFIER450 (BRANSON)
(Manufactured by Co., Ltd.) for 3 hours to obtain a spherical inorganic particle dispersion c1.

Preparation of Spherical Organic Polymer Particle Dispersion A spherical organic polymer particle dispersion [c2] was prepared according to the following formulation. XC99-A8808 (manufactured by Toshiba Silicone Co., Ltd., spherical crosslinked polysiloxane particles, average particle size 0.9 μm) 60 parts by weight methyl ethyl ketone 120 parts by weight cyclohexanone (solid content 20%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) 120 parts by weight

While cooling with ice and stirring, an ultrasonic homogenizer “SONIFIER450 (BRANSON CORPORATION)
(2) for 2 hours to obtain a dispersion liquid c2 of spherical organic polymer particles.

Preparation of Coating Solution for Third Backing Layer
The following was added to 542 g of the slip agent dispersion stock solution to prepare a third layer coating solution.

Diacetone alcohol 5950 g Cyclohexanone 176 g Ethyl acetate 1700 g The above-mentioned Seahosta KEP50 dispersion [c1] 53.1 g The above-mentioned spherical organic polymer particle dispersion [c2] 300 g FC431 (manufactured by 3M Corporation, solid content) 50%, solvent: ethyl acetate) 2.65 g BYK310 (manufactured by BYK Kemi Japan KK, solid content 25%) 5.3 g

The above third layer coating solution was coated on the second layer by 10.3
It was applied at a coating amount of 5 mL / m ² , dried at 110 ° C., and further dried at 97 ° C. for 3 minutes.

4) Coating of Photosensitive Layer Next, on the side opposite to the back layer obtained above, each layer having the following composition was applied in a multi-layer manner to prepare a color negative film.

(Composition of Photosensitive Layer) The main materials used for each layer are classified as follows: ExC:
Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin hardener In the following description, specific compounds of each of the above classification symbols are given numerical values following the symbols, Each chemical formula is given later).

The number corresponding to each component indicates the coating amount in g / m ² , and the coating amount in terms of silver is shown for silver halide.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.122 0.07 μm Silver Iodobromide Emulsion Silver 0.01 Gelatin 0.919 ExC-1 0.002 ExC-3 0.002 Cpd -2 0.001 HBS-1 0.005 HBS-2 0.002

Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.055 Gelatin 0.425 ExF-1 0.002 Solid Disperse Dye ExF-9 0.120 HBS-1 0.074

Third layer (low-sensitivity red-sensitive emulsion layer) Em-D silver 0.577 Em-C silver 0.347 ExC-1 0.188 ExC-2 0.011 ExC-3 0.075 ExC-40 .121 ExC-5 0.010 ExC-6 0.007 Cpd-2 0.025 Cpd-4 0.025 Cpd-7 0.050 Cpd-8 0.050 HBS-1 0.114 HBS-5 0.038 Gelatin 1.474

Fourth Layer (Medium Speed Red Sensitive Emulsion Layer) Em-B Silver 0.431 Em-C Silver 0.432 ExC-1 0.154 ExC-2 0.068 ExC-3 0.018 ExC-40 .103 ExC-5 0.023 ExC-6 0.010 Cpd-2 0.036 Cpd-4 0.028 Cpd-7 0.010 Cpd-8 0.010 HBS-1 0.129 Gelatin 1.086

Fifth layer (high-sensitivity red-sensitive emulsion layer) Em-A silver 1.108 ExC-1 0.180 ExC-3 0.035 ExC-6 0.029 Cpd-2 0.064 Cpd-40 077 Cpd-7 0.040 Cpd-8 0.040 HBS-1 0.329 HBS-2 0.120 Gelatin 1.245

Sixth layer (intermediate layer) Cpd-1 0.094 Cpd-9 0.369 Solid disperse dye ExF-4 0.030 HBS-1 0.049 Polyethyl acrylate latex 0.088 Gelatin 0.886

Seventh Layer (Layer that Gives Layering Effect to Red Sensitive Layer) Em-J Silver 0.293 Em-K Silver 0.293 Cpd-4 0.030 ExM-2 0.120 ExM-3 0.016 ExY -1 0.016 ExY-6 0.036 Cpd-6 0.011 HBS-1 0.090 HBS-3 0.003 HBS-5 0.030 Gelatin 0.610

Eighth layer (low-sensitivity green-sensitive emulsion layer) Em-H silver 0.329 Em-G silver 0.333 Em-I silver 0.088 ExM-2 0.378 ExM-3 0.047 ExY-1 0.017 HBS-1 0.098 HBS-3 0.010 HBS-4 0.077 HBS-5 0.548 Cpd-5 0.010 Gelatin 1.470

Ninth Layer (Medium Speed Green Sensitive Emulsion Layer) Em-F Silver 0.457 ExM-2 0.032 ExM-3 0.029 ExM-4 0.029 ExY-1 0.007 ExC-6 010 HBS-1 0.065 HBS-3 0.002 HBS-5 0.020 Cpd-5 0.004 Gelatin 0.446

Tenth layer (high-sensitivity green-sensitive emulsion layer) Em-E silver 0.794 ExC-6 0.002 ExM-1 0.013 ExM-2 0.011 ExM-3 0.030 ExM-40 017 ExY-5 0.003 Cpd-3 0.004 Cpd-4 0.007 Cpd-5 0.010 HBS-1 0.148 HBS-5 0.037 Polyethyl acrylate latex 0.099 Gelatin 0.939

Eleventh layer (yellow filter layer) Cpd-1 0.094 Solid disperse dye ExF-2 0.150 Solid disperse dye ExF-5 0.010 Oil-soluble dye ExF-7 0.010 HBS-1 0.049 Gelatin 0.630

Twelfth layer (low-sensitivity blue-sensitive emulsion layer) Em-O silver 0.112 Em-M silver 0.320 Em-N silver 0.240 ExC-1 0.027 ExY-1 0.027 ExY-2 0.890 ExY-6 0.120 Cpd-2 0.100 Cpd-3 0.004 HBS-1 0.222 HBS-5 0.074 Gelatin 2.058

Thirteenth layer (high-sensitivity blue-sensitive emulsion layer) Em-L silver 0.714 ExY-2 0.211 Cpd-2 0.075 Cpd-3 0.001 HBS-1 0.071 Gelatin 0.678

Fourteenth layer (first protective layer) 0.07 μm silver iodobromide emulsion Silver 0.301 UV-1 0.211 UV-2 0.132 UV-3 0.198 UV-4 0.026 F -18 0.009 S-1 0.086 HBS-1 0.175 HBS-4 0.050 Gelatin 1.984

Fifteenth layer (second protective layer) H-1 0.400 B-1 (1.7 μm in diameter) 0.050 B-2 (1.7 μm in diameter) 0.150 B-3 0.050 S- 1 0.200 Gelatin 0.750

Further, in order to improve the storability, processability, pressure resistance, fungicide / antibacterial properties, antistatic properties and coatability of each layer, W-1 to W-6, B-4 to B -6, F
-1 to F-17, and lead salts, platinum salts, iridium salts, and rhodium salts.

Preparation of Dispersion of Organic Solid Disperse Dye No. 11
The layer ExF-2 was dispersed in the following manner.

ExF-2 wet cake (containing 17.6% by weight of water) 2.800 kg Sodium octylphenyldiethoxymethanesulfonate (31% by weight aqueous solution) 0.376 kg F-15 (7% aqueous solution) 011 kg water 4.020 kg total 7.210 kg (adjusted to pH = 7.2 with NaOH)

After the slurry having the above composition was coarsely dispersed by stirring with a dissolver, using an agitator mill LMK-4,
Circumferential speed 10m / s, discharge rate 0.6kg / min, 0.3m
The dispersion was dispersed until the absorbance ratio of the dispersion became 0.29 at a filling rate of zirconia beads of m diameter of 80% to obtain a solid fine particle dispersion. The average particle size of the fine dye particles was 0.29 μm.

Similarly, ExF-4 and ExF-9
Was obtained. The average particle size of the fine dye particles was 0.28 μm and 0.49 μm, respectively. ExF-5
Was dispersed by a microprecipitation dispersion method described in Example 1 of European Patent No. 549,489A. The average particle size was 0.06 μm.

The compounds used for forming each layer are shown below.

[0243]

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[0244]

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[0245]

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[0246]

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[0247]

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[0248]

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[0249]

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[0250]

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[0251]

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[0252]

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[0253]

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The color negative photosensitive material prepared as described above is designated as Sample 001.

[0255] 2. Method of photographic property test In order to perform the test when the processing solution has reached the running equilibrium, the photosensitive material sample 001 is developed by the CIE standard C light source light and the neutral color light amount control filter, so that 30% of the coated silver amount is developed. After giving a uniform exposure of a corresponding exposure amount, each processing tank was subjected to continuous development processing of 10 turnovers while replenishing each processing tank in the following processing steps. One turnover occurs when the replenisher amount becomes the same volume as the processing solution in the processing tank in the unit of the processing amount of the processing). The evaluation of photographic properties, desilvering properties, and stability of the processing solution were performed on the sample and the processing solution processed at the time of 10-turnover.

For the treatment test, the sample 001 was subjected to ISO5
800 (a method for measuring the sensitivity of a color negative film) and a standard C light source and a continuous light wedge with a neutral color (density gradient 0.4
Sensitometric exposure was carried out through ΔD / cm, density range 0.02 to 4.8). As shown in Table 5, the compounds of the general formulas (1), (2) and (3) used in the present invention were subjected to photographic processing using this exposed sample for the development treatment of 30 mmol or less per liter of the stabilizing solution. Sensitivity, gradation and fog) and desilverability (remaining silver amount) were determined. At the same time, the stability of the processing liquid was evaluated by visually observing the liquid state of the running liquid in the processing tank at that time.

[0257] 3. Developing Process The developing process was performed using the following color negative developing machine and processing specifications. As a processor, an experimental machine obtained by modifying the processing time of an automatic developing machine FP-363SC manufactured by Fuji Photo Film Co., Ltd. was used. This machine is equipped with an automatic opening and dispensing type refilling system. The outline is as follows. The plastic (HDPE) bottles described in the specification text are installed side by side, and The plastic sheet acting as the lid of the bottle is pierced, and the treating agent solution inside flows into the replenishment tank. After that, a certain amount of washing water is jetted out from the nozzle hole of the squeezing nozzle to wash the inside of the bottle, and the washing water also flows down to the replenishment tank and becomes part of the dilution water for preparing the replenisher. Used (the squeeze nozzle is designed to play two roles: lid opening and cleaning). The following treatment was performed using the replenisher thus prepared.

The processing steps and the composition of the processing solution are shown below. (Processing step) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 2 minutes 30 seconds 41.0 ° C 15 ml 10.3 L Bleaching 25 seconds 40 ° C 5 ml 3.6 L Setting (1) 25 seconds 40 ° C -3. 6L fixed (2) 25 seconds 40 ° C 7.5ml 3.6L stable (1) 14 seconds 40 ° C-1.9L stable (2) 13 seconds 40 ° C-1.9L stable (3) 13 seconds 40 ℃ 30ml 1.9L Drying 30 seconds 60 ℃ * Replenishment amount per photosensitive material 35mm width 1.1m (equivalent to 24 Ex. 1 bottle)

The stabilizing solution is of a counterflow type (3) → (2) → (1), and the fixing solution is also connected from (2) to (1) by a counterflow pipe. Also, 15 ml of the tank solution of the stabilizing solution (2) flows into the fixing solution (2), which corresponds to the replenishing amount. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were all 2.0 ml per 1.1 mm width of 35 mm photosensitive material. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing solution is shown below. (Color developing solution) Tank solution Replenisher Diethylenetriaminepentaacetic acid 2.0 g 4.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.4 g 0.5 g Disodium-N, N-bis (sulfonateethyl ) Hydroxylamine 10.0 g 15.0 g Sodium sulfite 4.0 g 9.0 g Potassium bromide 1.4 g-2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 5. 5 g 8.0 g Potassium carbonate 39 g 59 g Hydroxylamine sulfate 2.0 g 4.0 g Add water 1.0 L 1.0 L pH (adjusted with sulfuric acid and KOH) 10.15 10.35

(Bleaching solution) Tank solution Replenisher 1,3-diaminopropanetetraacetic acid ammonium ferric ammonium monohydrate 130 g 220 g Ammonium bromide 50 g 70 g Succinic acid 30 g 50 g Maleic acid 40 g 60 g Imidazole 20 g 30 g Add water. 0L 1.0L pH (adjusted with ammonia water and nitric acid) 4.6 4.0

(Fixing solution) Tank solution Replenisher Ammonium thiosulfate (750 g / L) 280 ml 780 ml Ammonium bisulfite aqueous solution (72%) 20 g 80 g Imidazole 5 g 45 g Ethylenediaminetetraacetic acid 8 g 12 g Water was added to add 1 L 1 L pH (aqueous ammonia and nitric acid Adjusted with 7.0) 7.0

(Stabilizing solution) Common to tank solution and replenishing solution Sodium p-toluenesulfinate 0.03 g p-nonylphenoxypolyglycidol (glycidol average polymerization degree 10) 0.4 g disodium ethylenediaminetetraacetate 0.05 g 1,2 1,4-triazole 1.3 g 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 g 1,2-benzisothiazolin-3-one 0.10 g Desilvering accelerator (see Table 5) ) Add 30 mmol water and add 1.0 L pH 8.5

[0264]

[Table 5]

(4) Evaluation Method When the cumulative replenishment amount of the development replenisher reached 10 turns over, the photographic material sample subjected to sensitometric exposure was evaluated. Among them, the photographic performance was evaluated by the following two items. Stain density: A value (Dmin (B)) obtained by measuring the light density of the blue filter in the unexposed portion of the processed sample using a reflection densitometer FSD103 (manufactured by Fuji Photo Film Co., Ltd.) according to the specifications of International Standard (ISO-5). ). The measured value is a value obtained by correcting the density of the support. Colorability with time (to the extent that the background is colored during the lapse of time after the treatment): After the sample was forcibly aged at 70 ° C. and a temperature and humidity of 70% RH for 5 days, the blue filter light of the unexposed portion was observed. The concentration was determined, and the increase from the measured value before the forced aging (indicated by ΔDmin (B)) was obtained, which was used as a measure of the coloring with time.

The evaluation of the desilvering property was performed based on the following residual silver amount. Desilvering performance: As an evaluation scale for desilvering performance, it was indicated by a value obtained by quantifying the amount of residual silver in the highest density portion of the gray exposed portion after processing with a fluorescent X-ray analyzer. The smaller the measured value, the better the desilvering property.

Evaluation of stability of treatment liquid: The presence or absence of precipitates and the degree of coloring were observed by visual observation of the appearance of turbidity and precipitation due to accumulation of insolubles in the treatment liquid.異常 indicates no abnormality at all, slightly opaque or slight coloring is recognized, but さ れ る is judged to be acceptable, × if the degree of precipitation or coloring exceeds the allowable level. Displayed.

(5) Test results The results are shown in Table 5. Each of the samples of the present invention in which the exemplified compounds of the general formulas (1), (2) or (3) according to the present invention were added to the stabilizing solution was more photographic, that is, more stainable than the comparative example without these compounds. It is excellent in terms of concentration and coloring with time. Further, the amount of residual silver was also reduced, indicating that the desilvering property was also improved. Further, no abnormality was recognized in the liquid, indicating that the stability of the treatment liquid was sufficient. On the other hand, known 2-mercaptotriazole and 2-mercapto-5-aminotriazole, which were mentioned as other comparative examples, have a high stain concentration, a large increase over time, and an increase in the amount of residual silver. This shows that silveriness has also declined. In addition, slight turbidity has also occurred for liquids,
This indicates that an insoluble silver salt has been formed. As described above, the general formulas (1) and (2) having both a mercapto group and a sulfonic acid group or a phosphonic acid group or a group containing the same.
The excellent effects of the compounds of (3) and (3) on stain concentration, coloring with time, promotion of desilvering and stability of the processing solution during use are apparent.

[Reference Example] (Example of Standard Development) The processing of the present invention is a processing for the purpose of preventing weak points such as defective desilvering, stain, coloring with time, and deterioration of liquid in rapid processing in which processing time is shortened. Therefore, the results were compared with the results obtained by using the photosensitive material sample 001 used in the examples and performing general-purpose processing (standard processing) capable of commonly processing color negative films of various photosensitive material manufacturers in the world market.
In the standard processing, development processing was performed according to the following color negative developing machine and processing specifications. That is, as an automatic developing machine, an automatic developing machine FP-363 manufactured by Fuji Photo Film Co., Ltd. is used.
Using SC, the processing steps and the composition of the processing solution are as follows. (Processing process) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 20 ml 10.3 liter Bleaching 50 seconds 38.0 ° C 5 ml 3.6 liters Fixed (1) 50 seconds 38.0 ° C-3.6 liters Fixed (2) 50 seconds 38.0 ° C 7.5 ml 3.6 liters Stable (1) 20 seconds 38.0 ° C-1.9 liters Stable (2) 20 seconds 38.0 ° C-1.9 liters Stable (3) 20 seconds 38.0 ° C 30 ml 1.9 liters Drying 1 minute 30 seconds 60 ° C * Replenishment amount per 0.039m2 of photosensitive material

The stabilizing solution is of a counterflow type (3) → (2) → (1), and the fixing solution is also connected from (2) to (1) by a countercurrent pipe. The amount of developer brought into the bleaching process,
The amount of the bleaching solution brought into the fixing step and the amount of the fixing solution brought into the washing step were 2.5 ml, 2.0 ml and 2.0 ml, respectively, per 0.039 m2 of the light-sensitive material. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing solution is shown below. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 4.0 4,5-Dihydroxybenzene-1,3-disulfonic acid sodium 0.4 0.5 Hydroxylamine 10.0 15.0 Sodium sulfite 4.0 9.0 Diethylene glycol 10.0 17.0 Potassium carbonate 39.0 59.0 Ethylene urea 3.0 5.5 Potassium bromide 1.4-2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.7 11.4 Add water and add 1.0 liter 1.0 liter pH (with potassium hydroxide Adjusted with sulfuric acid) 10.05 10.25

(Bleaching solution) Tank solution (g) Replenisher (g) 1,3-diaminopropanetetraacetic acid ferric ammonium ammonium monohydrate 128 180 Ammonium bromide 50 70 Succinic acid 30 50 Imidazole 20 30 Maleic acid 40 60 Add water 1.0 liter 1.0 liter pH (prepared with aqueous ammonia) 4.4 4.0

(Fixing solution) Tank solution (g) Replenisher (g) Ammonium bisulfite (72% solution) 20 80 Ammonium thiosulfate aqueous solution (750 g / l) 280 ml 1000 ml imidazole 5 45 2- (N, N-dimethyl) ) Ethylaminomercaptotetrazole 1.0 3.0 Ethylenediaminetetraacetic acid 8 12 Add water 1.0 liter 1.0 liter pH (prepared with aqueous ammonia and acetic acid) 7.0 7.0

(Stabilizing solution) Common to tank solution and replenisher (unit g) Sodium p-toluenesulfinate 0.03 p-nonylphenoxypolyglycidol (glycidol average polymerization degree 10) 0.4 Disodium ethylenediaminetetraacetate 0.05 1,2,4 -Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1,2-benzisothiazolin-3-one 0.10 1.0 liter with water pH 8.5

The results obtained by the same evaluation method as in Example 1 were as follows: the residual silver amount was 3.1 μm / cm ² , the stain [Dmin
(B)] 0.06, coloring with time [ΔDmin (B)]
06, and by comparing this value with Table 5, it can be seen that, despite rapid processing by the processing method of the present invention, at least the same processing performance and image storage stability over time as standard processing widely used worldwide. You can see that it has been achieved. Also,
The treatment solution of the standard treatment has a weak point that a sediment of △ tends to occur on an evaluation scale during long-term continuous treatment in a quiet period in some regions, but in this embodiment, No turbidity or precipitation of the treatment solution was observed during the treatment period of 10 turns, and it was judged that the treatment solution was sufficiently stable (evaluation scale ○).

Example 2 The same test as in Example 1 was conducted except that the desilvering accelerator according to the present invention was added to the fixing solution instead of the stabilizing solution. Table 6 shows the exemplary compounds of the general formulas (1), (2) and (3) added to the fixing solution, and also shows the test results.
Table 5 also shows the results. In Table 6, in each of the samples of the present invention in which the exemplified compounds of the general formulas (1), (2) and (3) according to the present invention were added to the fixing solution, all of the samples were more stained than the comparative examples in which these compounds were not added. It is excellent in terms of concentration and coloring with time, and also shows that the amount of residual silver was reduced and the desilverability was improved. Further, no abnormality was recognized in the liquid, indicating that the stability of the treatment liquid was sufficient. On the other hand, the comparative examples to which a known desilvering accelerator, 2-mercaptotriazole or 2-mercapto-5-aminotriazole was added, had a high stain concentration, a large increase over time, and a large amount of residual silver. This indicates that desilvering ability has also declined. Further, slight turbidity (evaluation scale △ to ×) also occurred in the liquid state, indicating that an insoluble silver salt was generated.

[0277]

[Table 6]

Also, by comparing the results of Table 6 with the above-mentioned reference example of the general-purpose processing, the processing method of the present invention, despite the rapid processing, is at least equivalent to the standard processing widely used worldwide. It can be seen that the performance and the storage stability of the image over time have been achieved.

Example 3 Examples of the present invention in which Exemplified Compound 1 was added to a bleaching solution, a fixing solution, and a stabilizing solution as shown in Table 7 and Comparative Examples in which none of the processing solutions were added, and other operations, etc. Was tested in the same manner as in Example 1. The test results are also shown in Table 7. The display format is also shown in Table 5 of the first embodiment. In Table 7, even when the exemplified compound was added to any of the baths, the desilvering property, the stain, the coloring property over time, and the liquid were at least equivalent to those of the comparative examples.
The evaluation in which the respective characteristics are integrated shows a result superior to the comparative example. Further, the properties when added to the fixing solution or the stabilizing solution are better than those when added to the bleaching solution. When added to the stabilizer, the desilvering property and the stability of the fixer are slightly inferior to those of the fixer, but are less than those of the fixer in that the coloring with time, which is an important evaluation characteristic in image quality, is small. Is also excellent. Furthermore, it is also shown that the addition of both the fixing solution and the stabilizing solution improves all the evaluation characteristics and further enhances the effects of the invention.

[0280]

[Table 7]

Example 4 Example 4 is an example in which the present invention is applied to a bleach-fixing solution. The effect of imidazoles and hydroxycarboxylic acids, which increase when added together with the exemplified compounds according to the present invention, is shown. It is an example shown. The same sample as in Example 1, except that the bleaching step and the fixing step were collectively referred to as a bleach-fixing step in the color developing treatment formulation shown in Example 1, and the following steps and a processing solution composition were used,
Tests and evaluations were performed.

(Processing step) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 05 seconds 38.0 ° C. 15 ml 10.3 L Bleaching (1) 50 seconds 38 ° C. 5 ml 3.6 L Bleaching (2) 50 38 ° C-3.6L Bleaching (3) 50 seconds 38 ° C 7.5ml 3.6L Stability (1) 30 seconds 38 ° C-1.9L Stability (2) 20 seconds 38 ° C-1.9L Stability (3) 20 seconds 38 ° C. 30 ml 1.9 L Drying 1 minute 30 seconds 60 ° C. * Replenishment amount per photosensitive material 35 mm width 1.1 m (equivalent to 24 Ex. 1 bottle)

The stabilizing solution is of a counterflow type (3) → (2) → (1), and the fixing solution is also connected from (2) to (1) by a countercurrent pipe. Also, 15 ml of the tank solution of the stabilizing solution (2) flows into the fixing solution (2), which corresponds to the replenishing amount. Further, the color developing solution is replenished by dividing the replenishing solution of the color developing solution (A) and the replenishing solution of the color developing solution (B) of the following formulation into 12 ml and 3 ml, respectively, corresponding to the replenishing amount, to a total of 15 ml. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were all 2.0 ml per 1.1 mm width of 35 mm photosensitive material.
The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the bleach-fix solution is shown below. [Bleach-fixing solution A] [Tank solution] [Replenisher] Water 800 ml 800 ml ammonium thiosulfate (750 g / l) 107.0 ml 214.0 ml m-carboxymethylbenzene sulfinic acid 8.3 g 16.5 g ethylenediaminetetraacetic acid Ammonium iron (III) 65.0 g 130.0 g Iron (III) ethylenediaminetetraacetate 5.0 g 10.0 g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Glycolic acid 20.0 g 30.0 g Exemplified Compound 1 30.0 mmol 60.0 mmol Imidazole 14.6 g 29.2 g Add water 1000 ml 1000 ml pH (adjusted at 25 ° C / acetic acid and ammonia) 6.5 6.5

[Bleach-fixing solution B] A formulation obtained by removing glycolic acid from the formulation of bleach-fixing solution A and adding an equimolar amount of acetic acid. [Bleach-fixing solution C] A formulation obtained by removing imidazole from the formulation of the bleach-fixing solution A. [Bleach-fixing solution D] A formulation obtained by removing imidazole from the formulation of the bleach-fixing solution B.

The results are shown in Table 8. Both are examples of the present invention, but the use of Formulation A to which both hydroxycarboxylic acid and imidazole are added shows excellent results in desilvering, stain inhibiting properties, and coloring with time. It can be seen that no prescription D was inferior among the three. The effect of adding hydroxycarboxylic acid (comparison between Formulation D and Formulation C) and the effect of adding imidazole (comparison between Formulation D and Formulation B) were observed, and the results of Formulation A showed that the effects of both were additive. It turns out that there is. The result is
The processing solution for desilvering is represented by the general formula (1),
When the compounds (2) and (3) are used in combination with an imidazole derivative or a hydroxy group-containing carboxylic acid, they show that the stain, the image stability and the desilverability are further excellent, and the effect of the invention is increased. Is shown.

[0287]

[Table 8]

Example 5 Formulation A of the bleach-fixing solution used in Example 4 was combined into the following three-part (one-part, two-part) processing agents. The following description is based on the equivalent of 1 liter of the bleach-fix replenisher, but in each part, the prepared volume was 10 liters, and the injection centrifugal molding HDP described above in the text of the specification was used.
E (melt index is 190 ° C., 2.1 × 10 ⁴
Filled into a columnar bottle (0.4 g / 10 min in Pa) (average thickness of the columnar portion: 0.4 mm), and the mouth was LDPE
(Thickness: 0.2 mm).

• Part 1 (Solution Part) Ammonium Thiosulfate (750 g / l) 214.0 ml

Part 2 (bleach part, powder) Ammonium iron (III) ethylenediaminetetraacetate 130.0 g Iron (III) ethylenediaminetetraacetate 10.0 g

Part 3 (Auxiliary Part, Powder) m-carboxymethylbenzenesulfinic acid 16.5 g glycolic acid 30.0 g exemplified compound (1) 60.0 mmol imidazole 29.2 g ammonium sulfite 32.0 g potassium metabisulfite 46.2 g A replenisher was prepared from the bottle filled with the treating agent by the operation described in Example 1. Preparation of the replenisher was performed almost automatically, the quality of the processing solution was normal, and a processing agent suitable for simple and rapid processing could be obtained. Processing solutions other than the bleach-fix replenisher are the same as in Example 4 in both preparation and processing operations.

[0292]

According to the process of the present invention in which the processing solution containing the compound of the general formula (1), (2) or (3) is used in the desilvering step, the desilvering property is promoted and the residual silver is reduced. Furthermore, even if the desilvering is insufficient, the stain value and its increase over time (coloring over time) are suppressed, and the generation of turbidity, insoluble matter, and precipitates due to long-term continuous use of the processing solution is suppressed. And stable processing becomes possible. Incorporation of this compound into a compounding agent also enables stable operations in a storefront development laboratory such as a so-called minilab. The above effects of the present invention can be more remarkably exhibited by including a hydroxycarboxylic acid or an imidazole derivative of the general formula (I) in the bleach-fix solution.

Claims (7)

[Claims] 1. A method for processing a silver halide color photographic light-sensitive material, comprising processing with a processing solution containing a compound represented by the general formula (1). General formula (1) An-L-SM (A is a sulfonic acid group or a phosphonic acid group, L is a heterocyclic group, an aryl group or an aliphatic hydrocarbon group, M is a hydrogen atom or an alkali metal atom, and n is Represents an integer of 1 or 2). 2. A compound represented by the general formula (1):
2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, which is a compound represented by the formula: Embedded image (Z represents a 5-membered or 6-membered nitrogen-containing unsaturated heterocyclic group having at least one sulfonic acid group or phosphonic acid group or a group containing a sulfonic acid group or a phosphonic acid group as a substituent. The necessary atomic group, M represents a hydrogen atom or an alkali metal atom, respectively). 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the general formula (3). Processing method. Embedded image (X and Y represent CW or N, W represents a hydrogen atom, an aliphatic hydrocarbon group, an amino group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, a ureido group, a thioureido group, Represents an aminosulfamoyl group, a sulfo group, a phosphono group, a carbamoyl group, an amide group or a hydroxyl group, provided that at least one of X and Y represents N. R has the same meaning as W, provided that R or W
At least one is a group substituted with a sulfonic acid group). 4. The processing solution containing the compound represented by the general formula (1) is a processing solution selected from a processing solution having a bleaching ability, a processing solution having a fixing ability, a stabilizing solution and washing water. The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 3, wherein 5. A processing agent for a silver halide color photographic light-sensitive material, comprising a compound represented by the general formula (1). 6. Core / shell type granular particles having a surface layer having a critical relative humidity of 80% or less or a critical relative humidity of 80%
The silver halide color photographic light-sensitive material processing agent according to claim 5, which is a single-phase granular particle of 0.1% or less. 7. The processing agent for a silver halide color photographic light-sensitive material according to claim 5, which is a concentrated solution having a one-part constitution consisting of a homogeneous phase having a concentration ratio of at least 5 times.