JPH11194461A - Color developer composition and development processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent precipitation of insoluble matter and deterioration of photographic performance during storage by using a concentrated color developer composition specified in pH containing a specified amount of potassium carbonate or sodium carbonate and a specified amount of color developing agent and a specified fluorescent whitening agent. SOLUTION: One part of the concentrated color developer composition contains the potassium carbonate or the sodium carbonate or both in the total amount of 0.45-2 mol and the color developing agent in an amount of 0.08-1 mol and at least one of the fluorescent whitening agents represented by formulae I and II, and it has a pH of >=12.5. In formulae I and II, each of X1 , X2 , Y1 , Y2 , Z1 , and Z2 is an amino or morpholino group optionally substituted with a group except a hydroxy, methoxy and sulfo groups and a Cl atom; and M is an H or alkali metal atom; (n) is 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color developing agent used for processing a silver halide color photographic light-sensitive material and a development processing method using the same. The present invention relates to a concentrated developer composition having high suitability and storage stability, and a developing method using an automatic developing machine.

[0002]

BACKGROUND OF THE INVENTION Generally, processing of silver halide photographic light-sensitive materials, for example, processing of silver halide color photographic light-sensitive materials,
The basic steps include 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 the 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,
Further, it is removed from the photosensitive layer by a fixing agent which forms soluble silver together with unused silver halide. 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 in which the atmosphere of the image layer is adjusted in order to ensure the stability of the generated image for a long period of time. Is performed. Each processing step is performed using an aqueous solution (called a processing liquid) containing one or more processing chemicals except for washing with water. Since each processing solution has a relatively low concentration, it is generally economical, storage space-consuming to manufacture a processing solution ready for use by a processing chemical manufacturer, transport it to a lab, and store it. Or, it is inappropriate from the viewpoint of work.

Conventionally, two methods have been used to solve this problem. One is to prepare a powder chemical mixture in which the processing chemicals constituting the processing liquid are mixed at a ratio according to the processing liquid composition, and supply it to a developing laboratory in the form of a so-called solid processing agent in which it is packaged. This is a method of dissolving in water and diluting it to an appropriate concentration and using it as a processing liquid. Is supplied to a developing station, and is diluted with water or the like to a predetermined concentration in the developing station and used as a processing solution. The former is specifically described in U.S. Pat.
No. 43484, No. 2846308, Canadian Patent No. 8
No. 31,928 and the like, and the latter discloses a concentrated liquid processing agent for color development in US Pat.
9, No. 3,647,461 and No. 3,814,606 and British Patent Specification No. 2016723.

[0004] Solid processing agents are advantageous in terms of transportation cost and storage space, but are inconvenient in terms of dissolving work in a developing laboratory, scattering of chemical dust, uniformity of the composition of mixed chemicals, and the like. Further, it is disadvantageous in that a chemical which is liquid at room temperature must be put in a separate processing agent container and combined with a powder in a separate package. On the other hand, the concentrated liquid processing agent has a great advantage that the dissolving work in the developing laboratory can be omitted,
Convenience in transportation and storage is inferior to solid processing agents. As described above, the solid processing agent and the liquid processing agent each have advantages and disadvantages, and the volume of the processing agent is reduced, the amount of the waste container is reduced,
Economical, such as saving storage space, reducing transportation costs,
No treating agent excellent in both environmental aspects, simplicity of working aspects such as labor saving of processing solution preparation work, and safety aspects has been obtained.

However, with respect to processing agents for color developing laboratories, the convenience of liquid processing agents has been highly evaluated from the viewpoint of simplicity of work such as labor saving of processing liquid preparation work, productivity and safety. For this reason, liquid processing agents are widely used, and therefore, it is desired that the liquid processing agent be as compact as a solid processing agent. Therefore, it is required to further increase the concentration of the developing processing solution. However, in order to ensure that the liquid thickening agent is stored stably and does not hinder use, it should be basically a homogeneous solution with a saturation solubility or less, and there is very little room for further volume reduction and thickening. In the situation.

As liquid thickening agents, for example, pasting of black-and-white developing solutions has been known for a long time in, for example, Italian Patent No. 427967 and US Pat. No. 2,735,774.
Pasting of color developers has also been performed for thickening and various other purposes. US Patent No. 278
No. 4086 attempts to make a paste using an alginic acid derivative as a viscosity-imparting agent, that is, a thickener. Japanese Patent Application Laid-Open No. 57-500485 discloses a technique for making a concentrated liquid developer for color into a paste. However, pasting does not increase the degree of concentration by increasing the solubility of the treatment chemical, but only delays the precipitation, or even if the precipitation starts, the effect of agglomeration and solidification of insoluble matter is slowed and the service life is slightly extended. Nevertheless, this does not solve the essential problem of volume reduction, and the advantage of the liquid developer is not exhibited.

A liquid developer for a color photographic light-sensitive material comprises a color developing agent, a bleaching agent and a fixing agent or a bleach-fixing agent, a stabilizing solution and the like. Among these processing agents, a color developer contains a p-phenylenediamine derivative as a developing agent, and since this agent has relatively low solubility, there is a large restriction on thickening. In addition, when a fluorescent whitening agent is contained in the developer, its solubility is also insufficient, and if the amount of addition is within a range that does not cause precipitation, the white background of the image of the developed photosensitive material will be white. Is unsatisfactory, and when the required amount of the optical brightener is added, precipitation occurs from the treating agent. Therefore, in order to increase the convenience of the liquid developer by increasing its concentration, it is necessary to prevent the precipitation of the fluorescent whitening agent as in the case of the color developing agent. In particular, one color developer
In the case of a part configuration, it is particularly necessary to suppress the precipitation of the fluorescent whitening agent.

Regarding the prevention of precipitation of the color developing agent,
JP-A-6-194797, JP-A-7-043873, JP-A-7-043874, JP-A-7-043875 and JP-A-7-4-1
No. 14163, No. 7-239541, No. 7-3114
No. 53, a method of adding an N, N-disubstituted aniline derivative, combining this compound with addition of alkyldiphenyl ether disulfonates, anionic surfactants, aromatic sulfonic acids, paratoluenesulfonic acid, alkanolamines, etc. There is disclosed a method of adding such a compound, and although their effects are recognized, they are still insufficient for solving a substantial problem. On the other hand, regarding the prevention of precipitation of the fluorescent whitening agent, there is no suitable means other than selecting a fluorescent whitening agent having high solubility having many water-soluble groups such as sulfonic acid groups. There is a further need to develop means for enriching the fluorescent whitening agent in the developer.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a color photographic apparatus which does not cause any precipitation of insoluble matter during storage and does not deteriorate the photographic performance despite containing a fluorescent whitening agent. An object of the present invention is to provide a liquid concentrated developer composition for a photosensitive material. A second object of the present invention is to provide the above-mentioned liquid concentrated developer composition in the form of a one-part structure, particularly in a plastic container. A third object of the present invention is to
An object of the present invention is to provide a color developing method in which the operation using the above-mentioned liquid concentrated developer composition in a plastic container is easy and the quality can be stably maintained.

[0010]

To achieve the above object, the present inventors studied a fluorescent whitening agent from both the solubility and the whitening effect, and added an additive for improving the solubility of the fluorescent whitening agent. As a result of intensive studies, they found that the specific combination of the two sides maintained the solubility of the fluorescent whitening agent and color developing agent and prevented precipitation, and based on this discovery, conducted further research based on this discovery. The invention has been reached. That is,
The object of the present invention is achieved by the following color developing liquid concentrate processing composition.

1. Potassium carbonate and / or sodium carbonate in a total amount of 0.45 to 2 M; a color developing agent of 0.08 to 1 M; Containing p and
A color developer composition for a silver halide color photographic light-sensitive material, characterized by comprising one part of a concentrated solution in which H is 12.5 or more.

[0012]

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(Wherein, X ₁ , X ₂ , Y ₁ and Y ₂ each represent an amino group or a morpholino group which may have a substituent other than a hydroxyl group, a chlorine atom, a methoxy group and a sulfo group. M represents a hydrogen atom or an alkali metal atom).

[0014]

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(Wherein n is 1 or 2;₁, Z
_TwoIs X of the general formula (I)₁, X_Two, Y ₁, Y_TwoSynonymous with
And M represents a hydrogen atom or an alkali metal atom).

2. 2. The color developing composition as described in 1 above, comprising a polyalkylene glycol.

3. 3. The color developer composition as described in 1 or 2 above, further comprising at least one alkanolamine selected from the group represented by the following general formula (A) in the composition. [H (R′O) _m R] _n NH _(3-n) (A) (wherein m is 0 or 1, n is an integer of 1 to 3, and R is hydroxy having 2 to 4 carbon atoms) Substituted alkylene group, R '
Is an alkylene group having 1 to 4 carbon atoms or a hydroxy-substituted alkylene group. However, when m is 0, n is 2 if R has 2 carbon atoms, and n is 1, 2 or 3 if R has 3 to 4 carbon atoms. When m is 1, n is 1, 2 or 3 regardless of the type of R).

4. A color developing composition for a silver halide color photographic light-sensitive material as described in any one of the above items 1 to 3, characterized by comprising a concentrated solution having a one-part constitution.

5. 5. The silver halide color photographic light-sensitive material as described in any one of the above items 1 to 4, which contains both of the optical brighteners represented by the general formulas (I) and (II). A color developing composition.

6. A method for developing a silver halide color photographic light-sensitive material, comprising performing color development using the color developer composition according to any one of the above 1 to 5.

[0021]

Embodiments of the present invention will be described below in detail. The present invention relates to the constitution of a liquid concentrated developer composition for a color photographic light-sensitive material, wherein (1) potassium carbonate or sodium carbonate or both are contained in a total amount of 0.1 to 0.1.
45-2M, and (2) 0.08-1M of color developing agent
And (3) at least one of the optical brighteners represented by the general formula (I) or (II), and (4) a pH of 1
The color developer composition for a silver halide color photographic light-sensitive material is characterized by being constituted by a concentrated solution having a concentration of 2.5 or more (the upper limit is not particularly limited, but the pH is substantially about 14).

If the total concentration of the carbonates exceeds 0.45M, the pH of the color developer, which is in the ordinary pH range of a general color developing solution, is adjusted to pH1.
In the vicinity of 0 to 11, the solubility of the color developing agent reaches the solubility limit due to the salt effect, and precipitation occurs. However, under the above-mentioned high pH specified in the present invention, no precipitation occurs even when the carbonate concentration exceeds 0.45M,
It has been found that the stability of the color developing agent can be dissolved in high concentrations over a range of ~ 2M. When the concentration of the carbonate is higher than 2M, precipitation of the color developing agent tends to occur. This can be presumed to be due to the salt effect.

In this range, many optical brighteners do not have sufficient solubility to exhibit a brightening effect, but the optical brighteners represented by the above-mentioned general formulas (I) and (II) cannot be used. The required amount is stably dissolved under the salt concentration and the pH conditions described below. The carbonate may be either a potassium salt or a sodium salt, or may include both of them. However, in the concentration range of potassium ions from equimolar to 4 times the sodium ions with respect to the ratio of both,
In particular, precipitation of the color developing agent hardly occurs, which is advantageous. The region where both the solubility of the color developing agent and the fluorescent whitening agent is high has a pH of 12.5 or more (pH 14 or less) in the above-mentioned carbonate concentration range. Therefore, the above composition conditions are indispensable ranges for increasing the concentration of the color developing agent in the developer composition to reduce the volume of the composition.

The above conditions are based on a color developing agent and a fluorescent whitening agent.
It is a favorable condition on the solubility of both components,
However, use a stilbene-based optical brightener with sufficient whiteness on a white background.
It is generally difficult to dissolve them. Key to the Invention
One is the optical brighteners of the general formulas (I) and (II).
It is possible to dissolve the required amount under the conditions of
It is to have found. And the basics of optical brighteners
Fluorescence intensity, which is the target performance, is maintained. Especially the general formula
Precipitation when using (I) and the optical brightener of the general formula (II) together
Both the stability against precipitation and the fluorescence intensity characteristics are used alone.
Increases when used. In the general formula (I), X₁, X
_Two, Y₁, Y_TwoRepresents a hydroxyl group and a chlorine atom, respectively.
May have a substituent other than a methoxy group, a sulfo group
Represents either an amino group or a morpholino group. Other than sulfo group
The amino group which may have one or more substituents is preferably one
Or an amino group having two hydroxy groups. M
Is a hydrogen atom, sodium, potassium, lithium, etc.
Represents an alkali metal atom. X₁, X _Two, Y₁, Y_TwoIn table
At least two (preferably 2 to 4) of the groups
An amino group having a substituent other than a ruho group is preferable.
As the amino group, a hydroxyalkyl group having 1 to 4 simple primes
Or a hydroxyalkoxyalkyl group having 4 to 8 primaries
One or two substituted amino groups are particularly preferred. Like
New substituted amino groups include 2-hydroxyethylamino
Group, di (2-hydroxyethyl) amino group, di (2-h
Droxypropyl) amino group, di (3-hydroxypro
Pill) amino group, 2-hydroxypropylamino group, 3
-Hydroxypropylamino group, N- (2-hydroxy
Ethyl) -N-methylamino group, [2- (2-hydroxy
[Ciethoxy) ethyl] amino group, di [2- (2-hydro
[Xyethoxy) ethyl] amino group, N- (2-hydroxy
(Siethyl) -N- (2-hydroxypropyl) amino
And a diethylamino group. Component of general formula (I)
Examples of physical compounds are shown below.

[0025]

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In the general formula (II), n is 1 or 2, and Z ₁ and Z ₂ are X ₁ , X ₂ ,
M has the same meaning as Y ₁ and Y ₂ , and M represents a hydrogen atom or an alkali metal atom such as sodium or potassium. When Z ₁ or Z ₂ is a substituted amino group, the substituent has the same meaning as the substituent represented by the general formula (I), and preferred substituted amino groups are the same as the substituted amino group represented by the general formula (I). Is the same. Examples of specific compounds of the general formula (II) are shown below.

[0027]

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When both the fluorescent whitening agents of the general formula (I) and the general formula (II) are used in combination, the solubility as a whole is increased and the whitening effect is improved. The effect of reducing the stain (called residual color) due to the residual color is obtained. The preferred concentration of the optical brightener of the general formula (I) in the developing replenisher prepared from the developing composition is 1.0 × 1
0 ^{−3 to} 5 × 10 ⁻² mol / l, more preferably 2 × 10 ^{−3 to} 2.5 × 10 ⁻² mol / l,
The preferred concentration of the optical brightener of the general formula (II) is 1 × 10 ⁻³ to
5 × 10 ^-2 mol / l, more preferably ² × 10 ^-2 mol / l
It is 10 ^{−3 to} 2.5 × 10 ⁻² / liter. When both are used in combination, the respective concentrations may be lower than in the case where they are used alone, but the respective preferred concentration ranges are the above ranges. The amount of the developer composition of the present invention is determined so that the replenisher in use contains the fluorescent whitening agent at this concentration level.

When the color developing composition of the present invention contains a polyalkylene glycol, the solubility of the fluorescent whitening agent is further improved and the concentration of the fluorescent whitening agent can be increased.
Preferred polyalkylene glycols are those having 2 to 3 carbon atoms in the alkylene group, that is, polyethylene glycol,
It is a block copolymer of polypropylene glycol and polyethylene glycol and polypropylene glycol. When the number of carbon atoms of the alkylene group is 4 or more, the effect is reduced. Among these polyalkylene glycols, polyethylene glycol is particularly preferred. Preferred polyethylene glycols have a molecular weight of 200-800, more preferably 200-600. When the molecular weight exceeds 800, the effect decreases, and as the molecular weight increases, the viscosity of the developer composition increases, and the handling aptitude becomes inappropriate. Preferred propylene glycol has a molecular weight of 300 to 700, and more preferably 300 to 450. The block copolymer of polyethylene glycol and polypropylene glycol has a molecular weight of 2
A range of 00 to 800, preferably 200 to 600 is effective. The addition amount of the above polyalkylene glycols is 2 to 100 g, preferably 5 to 80 g, more preferably 10 to 7 g per liter of the treatment composition.
0 g. If the addition amount is too large, the viscosity of the liquid increases and the handling aptitude is impaired. If it is too low, the dissolution promoting effect is lost.

The incorporation of an alkanolamine into the color developing composition of the present invention also improves the solubility of both the developing agent and the fluorescent whitening agent, thereby preventing precipitation and precipitation, and concomitantly coloring the developer composition. In addition, contamination of the developed photosensitive material is also prevented. Effective alkanolamines are represented by the general formula (A), wherein m is 0 or 1, n is 1 to 3, R is a linear or branched hydroxy-substituted alkylene group having 2 to 4 carbon atoms, R ′ Is a linear or branched alkylene group having 1 to 4 carbon atoms or a hydroxy-substituted alkylene group. However, when m is 0, n is 2 if R has 2 carbon atoms, and R has 3 to 4 carbon atoms.
Then, n is 1, 2 or 3. When m is 1, n is 1, 2 or 3 regardless of the type of R.

Particularly effective alkanolamines are shown below. A-1 triisopropanolamine, A-2 diisopropanolamine, A-3 monoisopropanolamine, A-4 diethanolamine, A-5 2,3 dihydroxypropylamine, A-6 di (2,3 Dihydroxypropyl) amine, A-7 di (4-butanol) amine,

Particularly effective alkanolamines are triisopropanolamine, diisopropanolamine and diethanolamine, among which triisopropanolamine is preferred. The alkanolamines effective for the purpose of the present invention seem to have an appropriate balance of hydrophilic groups and hydrophobic groups. But the effect is small even if it is too large. For example, triethanolamines, which are conventionally known organic solvents for adding a developing solution, have no effect on the purpose of the present invention.

The amount of the alkanolamines added is
The amount is 0.02 to 3 mol, preferably 0.05 to 1 mol, and more preferably 0.08 to 0.5 mol per liter of the treatment composition. The above addition amount and the above addition amount or content are all represented by the addition amount or content in the concentrated liquid clogged developer composition.

It is already a feature of the concentrated developer composition of the present invention that it is particularly highly concentrated, and that it is a technical feature that it overcomes the restrictions of thickening. explained. The degree of thickening is 1.5 to 1.5 times the concentration of the solution in actual use, that is, the replenisher for development.
It is about 10 times, preferably 2 to 8 times, more preferably 3 to 5 times, or 5 to 30 times, especially 6 to 25 times, especially 10 to 10 times the so-called mother liquor of the developing tank. 16 times. The developer is prepared by diluting a replenisher prepared by diluting the composition, further diluting the replenisher according to a prescribed formulation, adding components not included in the replenisher such as potassium chloride and potassium bromide, and adjusting the pH. You.

It is advantageous that the concentrated developer composition of the present invention has a form in which all the components contained in the working solution are contained in one composition, that is, a so-called one-part constitution. When it is not desirable to keep the components in contact with each other, the components may be separated into two or more liquids to form a two- or three-part developer composition (usually international standard IS
According to the name of O 5989, the composition is referred to as a one, two, three part composition, etc.), in which case one part is composed of the composition under the composition conditions specified in the present invention. By dividing into parts, the effects and features of the present invention are not lost. However, a particularly great advantage of the present invention is that by finding a technique that can dissolve both the color developing agent and the optical brightener at a sufficient concentration as described above,
That is, a concentrated developer composition having a one-part structure can be prepared without having to divide it into a plurality of parts. The one-part configuration is advantageous in various aspects, such as transportation cost, packaging material cost, and simplicity of attachment to the development processing apparatus, in terms of workability of the developing station.

A one-part developer composition can be prepared by simply diluting the composition in a single container (eg, one bottle) with water to prepare a developing solution or a developing replenisher. The addition of an alkali for correcting the pH of the replenisher is not excluded, and an alkali may be added to the developing tank or the replenisher as needed.

There are several methods for producing the treatment composition of the present invention, and the following three methods give good results. However, in the practice of the present invention, the manufacturing method is not limited to the following three methods. [Method A] A method in which a small amount of water is introduced into a mixing tank in advance, and constituent chemicals are sequentially charged therein while stirring. [Method B] A method in which constituent chemical powders are preliminarily mixed and then poured at once into a small amount of water in a mixing tank. [Method C] A method in which constituent chemicals are divided into two or more groups in which components that can be conveniently combined in advance are dissolved in water or a hydrophilic mixed solvent to form a concentrated solution, and then each concentrated liquid is mixed. Further, a combined manufacturing method partially incorporating each method can also be implemented.

Next, the container for the concentrated liquid developer of the present invention will be described. The present invention is characterized in that the developer can be supplied while being stored in a polyethylene container, which is an advantage.

Usually, the liquid developer composition is transported, stored and used in a suitable container. It goes without saying that the first requirement for the material of the developer container is that it must be inert and sufficiently stable with respect to the developer composition (Requirement 1). Aside from this, an important requirement is sufficient oxygen barrier properties to prevent air oxidation during the period from the production of the developer composition to the use thereof (requirement 2). It must be recyclable (Requirement 3). In addition, since the concentrated liquid developer lowers the developing activity when the pH decreases during storage, it is preferable to avoid contact with carbon dioxide in the air. Therefore, the material of the container must be such that carbon dioxide is difficult to permeate through the vessel wall together with the oxygen barrier property (Requirement 4). Many materials that meet Requirement 2 also meet Requirement 4.

From the viewpoints of Requirements 2 and 4, the developer composition is filled and stored in an oxygen and carbon dioxide gas barrier container.
It is effective to store and transport. From the practical useful life of the developer composition, the material and thickness of the container are such that the air permeation rate per unit area per unit time in air at normal temperature and normal pressure is 2.5 × 10 ⁻⁷ cm ³ / cm ² / sec / sec. atm or less, preferably 2.5 × 10 ⁻⁸ cm ³ / cm ² / sec / atm
It is desirable to design to be as follows. On the other hand, from the viewpoint of Requirement 4, it is desirable that the vessel be made of a material having a permeation rate of carbon dioxide of the vessel wall of ⁷ × 10 ⁻⁷ cm ³ / cm ² / sec / atm or less.

From the viewpoint of gas impermeability, liquid treatment agents were often supplied in a sealed state in a glass bottle at the beginning of practical use. However, bottles made of a laminated material of a plastic having high gas barrier properties and plastics stable against an alkaline developer have recently been used because of their disadvantages such as being heavy and being easily broken. Is being used. Although this known composite plastic material effectively blocks air to prevent air (oxygen) oxidation and enhances the storage stability of the liquid developer, the composite material is difficult to recycle. However, they are discarded after each use, increasing the environmental burden.

A color developing solution containing a compound of the general formula (I) or (II) within a specific pH range and a carbonate concentration range hardly precipitates and precipitates as described above, and is also subject to air oxidation. It has been found that it has a difficult advantage, and therefore, practical storage stability can be obtained without using such a composite material container. The material of the plastic container suitable for the present invention may be a single-piece plastic having an air permeation speed exceeding the above-mentioned value. For example, even if a plastic bottle has an air permeation speed one digit higher, the above-mentioned requirements 1 and 3 If it satisfies, it can be preferably used. Therefore, it is a characteristic advantage of the present invention that a single plastic material (not a composite material) can be selected, and that the requirement 3 can be easily satisfied. One of the most significant advantages is that polyethylene, which had previously been considered to have insufficient air barrier properties despite the widespread use of recycling systems,
The liquid developer of the present invention has preservability that can be practically used as a container.

From the viewpoint of requirements 2 and 4, preferred container materials are polyester resins, acrylic resins, ABS resins, epoxy resins, polyamide resins such as nylon, polyurethane resins, polystyrene resins, polycarbonate resins,
It is preferable to use PVA, polyvinyl chloride, polyvinylidene chloride, polyethylene resin or the like in a single structure or as a laminated composite material. Among these, practically preferable materials in consideration of the requirement 1 are polyethylene terephthalate, polyethylene naphthalate, a laminate of polyethylene, polypropylene and nylon, and a laminate of polyethylene, polypropylene and aluminum. . In particular, the above two polyester materials are suitable because the oxygen permeability coefficient is as small as ³ × 10 ⁻¹² cm ³ / cm · sec · cmHg.

On the other hand, from the viewpoint of recycling the waste container of the requirement 3, a container made of a single material is preferable. In particular, a container made of polyethylene, polypropylene, polyethylene terephthalate, or polyethylene naphthalate as a single material is preferable. Among them, polyethylene is preferable, and high density type among polyethylene,
So-called HDPE is preferred as the container material. Although a single-piece molded article of polyethylene or polypropylene is advantageous in terms of requirement 3, it has not been used in a developer composition container which conventionally requires preservation due to restrictions of requirements 2 and 4,
The developing composition of the present invention, which has excellent stability over time, is characterized in that these can be used.

The polyethylene may be added with pigments such as carbon black and titanium white which do not adversely affect the alkaline developing composition, calcium carbonate, and a plasticizer compatible with polyethylene, if necessary. 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 filled with 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
950, JP-A-63-45555, etc .;
Nos. 61 and 62-134626 can be used.

When filling the container with the developer composition, in order to further enhance the safety against air oxidation,
It is better to fill the mouth of the container as much as possible to minimize the head space, or to replace the head space with nitrogen and fill it so as to cut off contact with oxygen in the air,
The present invention is not necessarily limited to such a filling method.

The developer compositions of the present invention are particularly advantageous for use in automatic processors. After mounting the container filled with the developer composition into the developing machine and injecting the composition inside the container into the developing replenishment tank or directly into the developing tank, the inside of the container is washed with a certain amount of water, and at the same time, the water used for washing is removed. The developing operation system which is introduced into the replenishing tank and used as water for preparing a replenishing solution is a system in which the advantages of the present invention are particularly effectively utilized. In order to wash the inside of the container with a certain amount of water, spray-type washing is particularly preferable, but is not necessarily limited to this. With this replenisher preparation method, the washing water is effectively used, and the wastewater is not discharged.

A further advantage of the developer composition of the present invention is that
The incorporation of this developer makes it possible to realize a developing system that is simple and has high environmental and operational safety. For example, using an automatic developing machine, a container filled with the developing developer composition of the present invention is mounted on the developing machine, and the contents are transferred into a developing replenishing tank. The chemical components adhering to the walls are washed away, and the water used for the washing can be subjected to a developing treatment of the silver halide color light-sensitive material by a method used for preparing a replenisher or the like. In this case, when the container of the developer composition is loaded into the automatic developing machine,
A mechanism is provided for automatically opening the lid of the container and smoothly discharging the fluid content. Also, Japanese Unexamined Patent Publication No.
988, JP-A-8-220722, etc., the inside of the container is cleaned without the need for human labor by spraying the washing water, and the container can be handled cleanly and recycling of the waste container becomes easy. In addition, the washing water is used as a part of the water for dissolving the developer, and is not a waste liquid. The concept of such a system can be realized only by a highly concentrated small-volume developer composition embodied in the present invention which has sufficient fluidity for easy handling and long-term maintenance.

Next, the components of the developer composition of the present invention other than the factors directly related to the above-mentioned components of the present invention will be described. The developer composition is an alkaline continuous phase liquid containing components contained in a normal color developer in a dissolved state. 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, and typical examples are shown below, but are not limited thereto. is not.
In recent years, some black-and-white light-sensitive 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. Developers are also applied to this type of photosensitive material processing.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-N, N-diethyl-3-methylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-
Methylaniline 4) 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-amino-N-ethyl-N- (β-hydroxyethyl) -3-methylaniline 6) 4-amino- N-ethyl-N- (3-hydroxypropyl) -3-methylaniline 7) 4-amino-N-ethyl-N- (4-hydroxybutyl) -3-methylaniline 8) 4-amino-N-ethyl- N- (β-methanesulfonamidoethyl) -3-methylaniline 9) 4-amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-amino-N-ethyl-N- (β -Methoxyethyl) -3 methyl-aniline 11) 4-Amino-N- (β-ethoxyethyl) -N-
Ethyl-3-methylaniline 12) 4-amino-N- (3-carbamoylpropyl-
Nn-propyl-3-methylaniline 13) 4-amino-N- (4-carbamoylbutyl-N
-N-propyl-3-methylaniline 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 compounds 5), 6), 7), 8) and 12), among which compounds 5) and 8) are preferred. Further, these p-phenylenediamine derivatives are:
In the state of solid materials, usually sulfate, hydrochloride, sulfite,
It is in the form of a salt such as naphthalenedisulfonic acid and p-toluenesulfonic acid. The processing agent composition is used as a working solution in the form of a developing replenisher (or a further diluted developing solution) by mixing it with water at a predetermined ratio at the time of use, and the aromatic primary amine in the working solution is used. The developing agent is diluted to a concentration of preferably 2 to 200 mmol, more preferably 12 to 200 mmol, and still more preferably 12 to 150 mmol per liter of the developing solution.

The developer composition of the present invention may or may not contain a small amount of sulfite ion depending on the type of the light-sensitive material to be treated. This is because sulfite ions have a remarkable preservative action, but may adversely affect the photographic performance in the color development process depending on the target photosensitive material. Hydroxylamine may or may not be included in the components of the composition depending on the type of the photosensitive material. This is because the photographic properties may be affected because the developer itself has silver developing activity at the same time as the function as a preservative of the developer.

The concentrated developer composition of the present invention preferably contains an inorganic preservative such as hydroxylamine or sulfite ion or an organic preservative. What is an organic preservative?
It refers to all organic compounds that reduce the deterioration rate of an aromatic primary amine color developing agent by being included in a processing solution for a photosensitive material. That is, organic compounds having a function of preventing air oxidation and the like of a color developing agent. Monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused amines, and the like are particularly effective organic preservatives. These are disclosed in JP-A-63-4235, JP-A-63-30845, and JP-A-63-21647.
Nos. 63-44655, 63-53551, 63-43140, 63
-56654, 63-58346, 63-43138, 63-146041
No. 63-44657, No. 63-44656, U.S. Pat.
No. 3, 2,494,903, JP-A-52-143020, JP-B-48
No. -30496 and other publications or specifications.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
No. 0588, salicylic acids, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat.
An aromatic polyhydroxy compound described in the specification of JP-A No. 4 and the like may be contained as necessary. In particular, in addition to the alkanolamines described above as formula (A), other alkanolamines such as triethanolamine, and substituted or unsubstituted dialkylhydroxylamines such as disulfoethylhydroxylamine and diethylhydroxylamine It is preferable to add a hydroxylamine derivative of the above general formula [I] or an aromatic polyhydroxy compound. Among the above organic preservatives, hydroxylamine derivatives are particularly preferred.For details, refer to JP-A-1-97953, JP-A-1-186939, and JP-A-1-186940.
And No. 1-187557. In particular, when the hydroxylamine derivative of the general formula [I] and the amines of the general formula (A) are used in combination,
It is more preferable in terms of improving the stability of the color developer and the stability during continuous processing. Examples of other amines include cyclic amines described in JP-A-63-239447, amines described in JP-A-63-128340, and other amines described in JP-A-1-186939. Examples thereof include amines described in JP-A-1-1187557.

If necessary, chloride ions may be added to the concentrated developer composition of the present invention. Color developers (especially developers for color print materials) usually use chloride ions for 3.
Although it is often contained in an amount of 5 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / l, chlorine ions are usually released into a developing solution as a by-product of development, so that it is often unnecessary to add them to a replenishing solution. The amount of chloride ions in the replenisher, and hence in the base developer composition, is set such that the chloride ion concentration in the developing tank when the running equilibrium composition is reached is at the above-mentioned concentration level. If the chloride ion concentration is more than 1.5 × 10 ^-1 mol / l, it has the disadvantage of delaying the development and is unfavorable because the speed and color density are impaired. Also,
If it is less than 3.5 × 10 ^-2 mol / l, it is often not preferable in preventing fog.

With respect to the developer composition, the content of bromine ions is the same as in the case of chlorine ions. The bromine ion in the color developer is 1 to
5x10 ^-3 mol / l approximately, in the processing of the print material is preferably not more than 1.0 × 10 ^-3 mol / liter. If necessary, bromine ions may be added to the developer composition so that the bromine ion concentration falls within this range. When included in the developer composition, as a chloride ion supplying substance, sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride,
Manganese chloride and calcium chloride are mentioned, and preferred are sodium chloride and potassium chloride. Examples of the bromine ion supply material include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cerium bromide, and thallium bromide. Among them, preferred are potassium bromide and sodium bromide.

When the photosensitive material to be processed is color photographic paper, it is an important image quality characteristic that the white background of the screen is white. To increase the amount of light perceived by the sight,
It is important to finish it white. The fluorescent whitening agent may be included in the photosensitive material depending on its properties, but the fluorescent whitening agent in the developer composition of the present invention is to be penetrated from the processing solution into the photosensitive material during the development processing. is there.
Although the stilbene-based fluorescent whitening agent contained in the developing composition of the present invention has already been described, the developing composition of the present invention may include a known fluorescent whitening agent other than the above-described ones.

In addition to a color developing solution, a known brightener such as a stilbene-based brightener can be added to any of the desilvering solution and the photosensitive material.

The concentrated liquid developer composition of the present invention has a pH of
As mentioned above, the color developer prepared therefrom has a pH
It is used in a range of 9.5 or more, more preferably 9.8 to 12.5. In order to maintain this pH, it is preferable to use various buffers. As the buffer, in addition to the above-mentioned potassium carbonate and sodium carbonate, other carbonates, phosphates, borates, tetraborates, hydroxybenzoates, glycyl salts, N, N-dimethylglycine salts, 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 Salts, lysine salts and the like can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent buffering capacity in the high pH range of pH 9.0 or higher, and have an adverse effect on photographic performance (such as fog) even when added to color developers. )
The use of these buffers is particularly preferred because they have the advantage of being free of cost and being inexpensive.

Specific examples of these buffers include sodium bicarbonate, potassium carbonate and sodium bicarbonate.
Potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, o-hydroxybenzoate Sodium (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like Can be mentioned. However, the invention is not limited to these compounds. The amount of the buffer is included in the composition such that the concentration in the diluted color development replenisher is 0.04 to 2.0 mol / l, particularly 0.1 mol / l to 0.4 mol / l, in total. Can be made.

The developer composition of the present invention may contain other color developing solution components, for example, various chelating agents which are precipitation inhibitors for calcium and magnesium, or which are also agents for improving the stability of the color developing solution. it can. 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, ethylenediamine
N, N, N ', N'-tetramethylenesulfonic acid, transsilohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2 , 4-Tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-
Bis (2-hydroxybenzyl) ethylenediamine-
N, N'-diacetate, 1,2-dihydroxybenzene-
4,6-disulfonic acid and the like. These chelating agents may be used in combination of two or more as necessary. The amount of these chelating agents may be an amount sufficient to block metal ions in the color developer. For example, it is added to the composition such that the concentration of the developer or replenisher is about 0.1 g to 10 g per liter.

The developer composition of the present invention can optionally contain an optional development accelerator. As development accelerators, JP-B-37-16088, JP-B-37-5987, JP-B-38-7826, and JP-B-44-123
No. 80, No. 45-9019 and U.S. Pat.No. 3,813,247, etc. and thioether compounds described in the specification and JP-A Nos. 52-49829 and 50-15554.
Phenylenediamine compounds, quaternary ammonium salts disclosed in JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, U.S. Pat.
No. 2,494,903, No. 3,128,182, No. 4,230,796, No. 3,
No. 253,919; Japanese Patent Publication No. 41-11431; U.S. Pat.No. 2,482,546
Nos. 2,596,926 and 3,582,346, etc.
No. 42-25201, U.S. Pat.No. 3,128,183, Japanese Patent Publication No. 41-11431
No. 42-23883 and U.S. Pat.No.3,532,501.
In addition, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as needed.

The treatment composition of the present invention may optionally contain
Optional antifoggants can be added. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole,
5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2
Nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be mentioned as typical examples.
In addition to the surfactant in the present invention, various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary. The color developing composition of the present invention and the color developing replenisher or developing solution prepared therefrom have been described above.

The processing temperature of color development applied to the present invention is 30 to 55 ° C., preferably 35 to 55 ° C., more preferably 38 to 55 ° C. when the photosensitive material to be developed is a color print material. 45 ° C. The development processing time is 5 to 90 seconds, preferably 15 to 60 seconds. The replenishment amount is preferably small, but is suitably ^{20 to} 600 ml per 1 m ^{2 of} the light-sensitive material, preferably 30 to 600 ml.
It is 120 ml, particularly preferably 15 to 60 ml. 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.
, 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. Also, for color reversal, the time is preferably 1 to 4 minutes. While replenishing amount is desirably small, the photosensitive material 1 m ² per 20
500 ml is suitable, preferably 30 to 200 ml, particularly preferably 50 to 160 ml.

In practicing the present invention, a desilvering step is carried out after a developing step using a color developing solution prepared by using the developer composition of the present invention, and processing with a bleaching solution and a bleach-fixing solution is performed. . In the case of a light-sensitive material to be subjected to color printing, this processing solution often contains an appropriate compound of the above-described fluorescent whitening agent, preferably a stilbene-based fluorescent whitening agent. As the bleaching agent used in the bleaching solution or the bleach-fixing solution, a known bleaching agent can be used. In particular, organic complex salts of iron (III) (for example, complex salts of aminopolycarboxylic acids) or citric acid, tartaric acid, malic acid Organic acids, such as persulfates and hydrogen peroxide, are preferred.

Of these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Iron (III)
Examples of aminopolycarboxylic acids or salts thereof useful for forming an organic complex salt of the following are biodegradable ethylenediaminedisuccinic acid (SS form), N- (2-carboxylateethyl) -L-asparagine Acid, beta-alanine diacetate, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3
-Diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid,
In addition to iminodiacetic acid, glycol ether diamine tetraacetic acid, etc., compounds represented by the general formula (I) or (II) of European Patent 0789275 can be exemplified. These compounds may be any of the sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediaminedisuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, beta-alaninediacetic acid, ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methylimino Diacetic acid is the iron (II
I) Complex salts are preferred because of their good photographic properties. These ferric ion complex salts may be used in the form of a complex salt.
Ferric ion in a solution using an iron salt such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate and a chelating agent such as aminopolycarboxylic acid; Complex salts may be formed. In addition, the chelating agent
The iron ion complex salt may be used in excess of the iron salt complex. Among the iron complexes, iron aminopolycarboxylate complexes are preferred, and the amount of addition is 0.01 to 1.0 mol / l, preferably 0.05 to 0.50 mol / l, and more preferably 0.10 to 0 mol / l. .50 mol / l, more preferably 0.15 to 0.40 mol / l.

The bleaching time is usually 30 seconds to 6 minutes and 30 seconds, preferably 1 to 4 minutes and 30 seconds. In the case of bleaching for color printing materials, it is 30 seconds to 2 minutes.

The fixing agent used in the bleach-fixing solution or the fixing solution includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate;
Ethylenebisthioglycolic acid, 3,6-dithia-1,
Thioether compounds such as 8-octanediol and water-soluble silver halide dissolving agents such as thioureas;
These can be used alone or in combination of two or more. Also, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per liter is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol.

The pH range of the bleach-fixing solution or fixing solution used in the present invention is preferably from 3 to 8, and more preferably from 4 to 7. When the pH is lower than this, the desilverability is improved, but the deterioration of the solution and the leuco formation of the cyan dye are promoted. Conversely p
If H is higher than this, desilvering will be delayed and stain will easily occur. The pH range of the bleaching solution used in the present invention is 8 or less, preferably 2 to 7, and particularly preferably 2 to 6.
If the pH is lower than this, the deterioration of the solution and the leuco conversion of the cyan dye are promoted, and if the pH is higher than this, desilvering is delayed,
Stain is likely to occur. To adjust the pH,
If necessary, hydrochloric acid, sulfuric acid, nitric acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added.

Further, the bleach-fixing solution may contain various other types of fluorescent whitening agents, defoamers or surfactants, and organic solvents such as polyvinylpyrrolidone and methanol. Bleach-fixing solutions and fixing solutions include sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives, Sulfite ion releasing compounds such as metabisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and arylsulfinic acids such as p-toluenesulfinic acid and m-carboxybenzenesulfinic acid It is preferable to contain the like. These compounds are preferably contained in an amount of about 0.02 to 1.0 mol / liter in terms of sulfite ion or sulfinate ion.

As a preservative, in addition to the above, ascorbic acid, carbonyl bisulfite adduct, carbonyl compound and the like may be added. Further, a buffer, an optical brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary. The bleach-fix processing according to the present invention requires a processing time of 5
２４０240 seconds, preferably 10-60 seconds. The processing temperature is from 25C to 60C, preferably from 30C to 50C.
The replenishing rate is ²⁰ ml to 250 per m ² of the photosensitive material.
ml, preferably 30 ml to 100 ml, particularly preferably 15 ml to 60 ml.

After desilvering such as fixing or bleach-fixing, washing and / or stabilization are generally performed. The amount of rinsing water in the rinsing 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 use, the rinsing water temperature, the number of rinsing tanks (the number of stages), and various other conditions.
Among them, 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 Engineers) Vol. 64, pp. 248-253 (1955
May issue). Usually, the number of stages in the multistage countercurrent system is preferably 3 to 15, and particularly preferably 3 to 10.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, and the increase in the residence time of water in the tank causes the bacteria to propagate and the resulting suspended matter to adhere to the photosensitive material. Occurs. As a solution to such a problem, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively.
Further, chlorinated fungicides such as isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorinated sodium isocyanurate described in JP-A-61-120145, and JP-A-61-26761. Benzotriazole, copper ion, and others described in the official gazette.
1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Fungicide, "Encyclopedia of Antifungal Agents" (1986) Can be used.

Also, aldehydes such as formaldehyde, acetaldehyde and pyruvaldehyde which inactivate the remaining magenta coupler to prevent color fading and stain formation, methylol compounds described in US Pat. No. 4,786,583 and hexamethylentetramine Hexahydrotriazines described in JP-A-2-153348, formaldehyde bisulfite adduct described in U.S. Pat. No. 4,921,779, seized patent publication 504609
And azolylmethylamines described in JP-A Nos. 519190 and 519190 are added.

Further, in the washing water, a surfactant as a draining agent and a chelating agent represented by EDTA as a hardening agent can be used. Continue with the above washing process or
Alternatively, the treatment can be performed directly with the stabilizing solution without going through the washing step. A compound having an image stabilizing function is added to the stabilizing solution, and examples thereof include an aldehyde compound represented by formalin, a buffering agent for adjusting a membrane pH suitable for stabilizing a dye, and an ammonium compound. 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 processing of the light-sensitive material of the present invention, when the stabilization is directly performed without going through a washing step, a known method described in JP-A-57-8543, JP-A-58-14834, JP-A-60-220345, etc. 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.

A so-called rinsing solution is also used as a washing solution or a stabilizing solution used after the desilvering treatment. The preferred pH of the washing step or the stabilizing step is 4 to 10, and more preferably 5 to 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 washing and / or stabilizing 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, as described in Japanese Patent Application Laid-Open No. 3-157650, drying can be accelerated by adjusting the blowing angle of the drying air to the photosensitive material and removing the exhaust air.

A color photographic light-sensitive material to which a developing method using the developer composition of the present invention is applied will be described. The method of the present invention can be generally applied to color photographic light-sensitive materials regardless of whether they are for photography or printing. That is, the present invention can be applied to any development processing of a color negative film, a color reversal film, and a color photographic paper, and can be applied to any of general use, movie use, and professional use. In particular, the effect of application to the development processing of color photographic paper in which whiteness on a white background is important is great. Further, it is effective to apply to a silver halide color photographic light-sensitive material containing a pyrrolotriazole derivative as a cyan coupler for development processing. Cyan dyes obtained from pyrrolotriazole derivatives have excellent hues with little tailing on the short wavelength side of the spectral absorption curve, but have the disadvantage that they tend to cause color mixing and stain, It is susceptible to stability over time. The color developer composition of the present invention has an advantage that color mixture and stain are less likely to occur when applied to the development processing of a color photographic light-sensitive material using a pyrrolotriazole derivative as a cyan coupler. The use of a pyrrolotriazole derivative as a coupler is described in JP-A-5-150423, JP-A-5-255333, JP-A-5-202004, and JP-A-5-2004.
Nos. 8376 and 9-189988.

Next, the constitution of the photosensitive material other than the above pyrrolotriazole type cyan coupler will be described. A light-sensitive silver halide emulsion in a 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 is preferable that the particles consist of particles. 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 silver halide emulsion is 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 photosensitive silver halide emulsion layer,
The dispersion coefficient of the particle size distribution (the standard deviation of the particle size distribution divided by the average particle size) is preferably 15% or less, more preferably 10% or less. 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 of each monodispersed emulsion is 0.15 to
0.50 logE, preferably 0.20-0.
More preferably, it is 40 logE, and 0.25-0.
More preferably, it is 35 logE.

This positive material is prepared by adding iron and / or ruthenium and / or osmium compound to silver chlorobromide having a silver chloride content of 95 mol% or more, which does not substantially contain silver iodide, in an amount of 1 to 1 mol per mol of silver halide. Silver halide containing 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol and 1 × 10 ⁻⁷ to 1 × 10 ⁻⁵ mol of iridium compound per mol of silver halide in a silver bromide localized phase It is effective to use an emulsion.

For a color photographic material for photographing purposes, for example, a multilayer color negative film or a color reversal film, tabular grains having a silver iodobromide internal structure or non-tabular multi-structure grains are mainly used. Preferred silver halide is about 30
Silver iodobromide, silver iodochloride, or silver iodochlorobromide containing not more than mol% 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 silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), pp. 22-23, "I. Emulsion Production (Emulsion p.
reparation and types) ”and No. 18716
(November 1979), p. 648, ibid. 30710
5, pp. 863-865, and Physics and Chemistry of Photography by Grafkid, published by Paul Montel (P.Glafkides, Chemie et Phisique Photographique,
Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, Focal Press (GFDuffin, Photographi)
c Emulsion Chemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions", by Zeligman et al., published by Focal Press (VLZelikman, et al., Making and Coating Ph.
otographic Emulsion, 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 written 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.

The silver halide emulsion usually used is one subjected to physical ripening, chemical ripening and spectral sensitization. The additive used in such a process is RD No. 17643,
No. No. 18716 and the same No. 307105, and the corresponding portions are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions different in at least one property of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the photosensitive silver halide emulsion,
They can be mixed and used in the same layer. US4,0
82,553, fogged silver halide grains, US Pat. No. 4,626,498, JP-A-59-214.
It is preferable to apply the silver halide grains and the colloidal silver having the inside of the grains described in 852 to a light-sensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The term “silver halide particles having a fogged interior or surface” refers to silver halide particles that can be uniformly (non-imagewise) developed regardless of the unexposed portions and exposed portions of the photosensitive material. The preparation method is US 4,626,49
8, described in JP-A-59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. Any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used as the silver halide having the inside or the surface of the grain fogged. The average grain size of these fogged silver halide grains is 0.1.
It is preferably from 0.01 to 0.75 μm, particularly preferably from 0.05 to 0.6 μm. The grains may be regular grains or polydispersed emulsions, but may be monodisperse (at least 95% of the weight or the number of silver halide grains is ± 40% of the average grain size).
Having a particle diameter within the range described above).

For the silver halide photographic light-sensitive material for printing and photographing which is the object of the present invention, conventional photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as a photographic support. As the transmission type support, a transparent film such as a cellulose acetate film or polyethylene terephthalate, and further, 2,6-naphthalenedicarboxylic acid (NDC)
The one in which an information recording layer such as a magnetic layer is provided on a polyester of A) and ethylene glycol (EG) or a polyester of NDCA, terephthalic acid and EG is preferably used. The positive material to which the present invention is applied is preferably a reflection-type support, and in particular, is laminated with a plurality of polyethylene layers or polyester layers. Reflective supports containing pigments are 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 in the case of mixing with the water-resistant resin is preferably 0.0005 to 3% by weight with respect to the resin, and more preferably 0.1 to 3% by weight.
001 to 0.5% by weight. Instead of including the fluorescent whitening agent in the water-resistant resin layer, a hydrophilic colloid layer containing a white pigment may be provided on the support. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.

The light-sensitive material according to the present invention may be coated with a hydrophilic colloid layer in order to improve the sharpness and the like of an image by a process described in EP 0,337,490A2, pages 27 to 76, which is described in the specification of EP 0,337,490A2. Dyes (especially oxonol dyes) so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or when dihydric alcohols are added to the water-resistant resin layer of the support. (For example, trimethylolethane) or the like
It is preferable that the content be at least 10% by weight (more preferably at least 14% by weight).

The photosensitive material used in the present invention includes:
In order to prevent various fungi and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add a fungicide as described in JP-A-63-271247.

The light-sensitive material according to the present invention 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 according to the present invention, and processing methods applied for processing this light-sensitive material And processing additives, EP 0,355,660 A2, JP-A-2-33144 and JP-A-62
Those described in the specification of U.S. Pat. No. 215272 or those listed in Table 1 below are preferably used.

[0091]

[Table 1]

Further, when the photographic material of the present invention contains the above-mentioned pyrrolotriazole type coupler, the effect of the invention such as improvement of whiteness on a white background is great. Materials are also applicable to the method of the present invention. The cyan, magenta or yellow coupler is impregnated with a loadable latex polymer (eg, US Pat. No. 4,203,716) in the presence (or absence) of a high boiling organic solvent as described in the preceding table, or It is preferable to dissolve it together with a water-insoluble and organic solvent-soluble polymer and emulsify and disperse in a hydrophilic colloid aqueous solution. Preferred water-insoluble and organic solvent-soluble polymers are described in U.S. Pat. No. 4,857,449, columns 7 to 15 and WO 88/00723, pages 12 to 30. Copolymers or copolymers are mentioned. In particular, a methacrylate or acrylamide polymer is particularly preferred in terms of color image stability and the like.

The light-sensitive material to which the present invention is applied includes a pyrazoloazole coupler, a color image preservability improving compound described in European Patent EP 0,277,589A2,
It is preferable to use in combination with the above pyrrolotriazole coupler and acylacetamide type yellow coupler.

Examples of the cyan coupler include phenol type couplers and naphthol type couplers described in the publicly known documents listed in the above table, as well as JP-A-2-33144.
JP, EP 0333185 A2, JP-A-6
4-32260, European Patent EP 0 456 226 A1, European Patent EP 0 484 909, European Patent EP
You may use the cyan coupler of the specification of 0488248 and EP0491197A1.

The magenta couplers used in the present invention include 5-pyrazolone-based magenta couplers described in the publicly known documents listed in the above table, as well as WO92.
/ 18901, WO92 / 18902 and WO9
The thing described in 2/18903 is also preferred. These 5
In addition to pyrazolone magenta couplers, known pyrazoloazole type couplers can be used in the present invention. Among them, in terms of hue, image stability, color developing property and the like, JP-A-61-652 is known.
No. 45, JP-A-61-65246, JP-A-61-65246
No. 14254, European Patent Nos. 226,849A and 2nd.
The use of pyrazoloazole couplers described in 94,785A is preferred.

As the yellow coupler, known acylacetanilide-type couplers are preferably used. Among them, European Patent EP0447969A and JP-A-5-15-1 can be used.
07701, JP-A-5-113462, European Patent E
The couplers described in P-0482552A and EP-0524540A are preferably used.

Examples of couplers in which a coloring dye has an appropriate diffusivity include US Pat. No. 4,366,237, GB 2,125,
570, EP 96,873B, DE 3,234,533
Are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (particularly Y on page 84).
C-86), yellow colored magenta coupler ExM-7 (p. 202) and EX-1 (249) described in the EP.
EX-7 (page 251), US Pat. No. 4,833,069.
Magenta colored cyan couplers CC-9 (column 8), CC-13 (column 10), US Pat.
7,136 (2) (column 8), WO92 / 1157
Colorless masking couplers of formula (A) of claim 1 of claim 5 (especially the exemplified compounds on pages 36 to 45) are preferred.

Examples of compounds (including couplers) which react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound: E
Formulas (I), (II), and P378, 236A1.
Compounds represented by (III) and (IV) (particularly T-101
(Page 30), T-104 (page 31), T-113 (36
Page), T-131 (page 45), T-144 (page 51),
T-158 (p. 58)), EP 436, 938 A2, 7
Compounds represented by formula (I) described on page (particularly D-49)
(Page 51)), the compound represented by the formula (1) of EP568,037A (especially (23) (page 11)), EP44
Formulas (I), (II) and (II) described on pages 5 to 6 of U.S. Pat.
Compounds represented by I) (especially I- (1) on page 29);

Bleaching accelerator releasing compound: EP 310,12
Compounds of formulas (I) and (I ') on page 5 of 5A2 (especially (60) and (61) on page 61) and JP-A-6-59.
411. The compound represented by the formula (C) according to claim 1 (particularly (7) (p. 7); Ligand releasing compound: US 4,55)
Compound represented by LIG-X described in claim 1 of US Pat.
Compounds 1 to 6 of columns 3 to 8; fluorescent dye releasing compounds:
C0UP-DY of claim 1 of US 4,774,181
Compound represented by E (particularly, compound 1 in columns 7-10)
-11); Development accelerator or fogging agent releasing compound: US
Formulas (1), (2) in column 3 of 4,656,123,
The compound represented by (3) (particularly, (I-2) in column 25
2)) and EP450, 637A2, page 75, 36-38.
ExZK-2 in row: Compound that releases a group that becomes a dye only after leaving: a compound represented by formula (I) in claim 1 of US Pat. No. 4,857,447 (especially, Y-1 to Y- 19).

As the additives other than the coupler, the following are preferable. Dispersion medium of oil-soluble organic compound: JP-A-62-215272
P-3, 5, 16, 19, 25, 30, 42, 49,
54, 55, 66, 81, 85, 86, 93 (140 to
144)); Latex for impregnation of oil-soluble organic compound: U
Latex described in S4, 199, 363; oxidized developing agent scavenger: a compound represented by the formula (I) in column 2, lines 54 to 62 of US Pat. , (6), (12) (columns 4-5),
US Pat. No. 4,923,787, columns 5 to 10 of formula (particularly compound 1 (column 3);
Formulas (I) to (II) on page 4, lines 30 to 33 of 98321A
I), especially I-47, 72, III-1, 27 (24-48
Page); Anti-fading agent: A-6,7, of EP298321A
20, 21, 23, 24, 25, 26, 30, 37, 4
0, 42, 48, 63, 90, 92, 94, 164 (6
9-118), column 25 of US 5,122,444.
II-I to III-23, especially III-10, EP47
1347A, pages 1 to 12 I-1 to III-4, especially II-
2, US 5,139,931 Columns 32-40 A-
Nos. 1 to 48, especially A-39, 42; a material for reducing the amount of a color-enhancing agent or color-mixing inhibitor used: EP 411324A
I-5 to I-15 on pages 5 to 24, especially I-46; Formalin scavenger: 24-47 of EP 477932A.
SCV-1 to 28 on page 9, especially SCV-8;

Hardener: H-1, 4, 6, 8, 14, US Pat. No. 4,618,573 on page 17 of JP-A-1-214845.
(H-1 to 54) represented by formulas (VII) to (XII) in columns 13 to 23 of JP-A-2-214852.
Compounds represented by the formula (6) at the lower right of the page (H-1 to 7)
6), particularly compounds described in claim 1 of H-14, US Pat. No. 3,325,287; development inhibitor precursors: P-24, 37, 39 of JP-A-62-168139 (6-7)
Compounds described in claim 1 of US Pat. No. 5,019,492, especially 28, 29 of column 7; preservative, fungicide: U
I-4 to I-3 of columns 3 to 15 of S4,923,790
-43, especially II-1, 9, 10, 18, III-25; stabilizers, antifoggants: I-1 to (14) of columns 6 to 16 of US 4,923,793, especially I-1,60 ,
(2), (13), column 25 of US 4,952,483
Compounds 1 to 65, especially 36: Chemical sensitizer: triphenylphosphine selenide, JP-A-5-40324
Compound 50 of the formula:

Dye: 15-1 of JP-A-3-156450
A-1 to b-20 on page 8, especially a-1, 12, 18, 2
7, 35, 36, b-5, pp. 27 to 29, V-1 to V-2
3, especially F-1, I-F-II-43 on pages 33 to 55 of EP 445627A, especially F-I-11 and F-II.
VIII, pages III-I to EP-157153A, pages 17-28.
36, especially III-1,3, WO88 / 04794, 8-
26, a fine crystal dispersion of Dye-1 to 124, EP319
Compounds 1 to 22 of 999A, pages 6 to 11, especially compounds 1, compounds D-1 to 87 of formulas (1) to (3) of EP519306A (pages 3 to 28), US Pat.
68,622 compounds of formula (I) 1-22
(Columns 3 to 10), compounds (1) to (31) represented by formula (I) of US Pat. No. 4,923,788 (column 2
9); UV absorber: Formula (1) of JP-A-46-3335
Compounds (18b) to (18r), 101-
427 (pages 6 to 9), compounds (3) to (66) (pages 10 to 44) represented by formula (I) and compounds HBT-1 to 10 (1) represented by formula (III) in EP520938A.
4), compounds (1) to (31) represented by the formula (1) in EP521823A (columns 2-9).

The present invention can be applied to general-purpose or movie general-purpose color negative films. It is also suitable for a film unit with a lens described in Japanese Patent Publication No. 2-3615 and Japanese Utility Model Publication No. 3-39784. Suitable supports that can be used in the present invention are described, for example, in RD. N
o. No. 17643, page 28; 647 of 18716
From the right column of page 648 to the left column of page 648, and the same No. 307105
On page 879, it is preferable to use a polyester support.

The color negative film used in the present invention 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 liquid in which magnetic particles are dispersed in a binder. The magnetic particles used in the present invention are γFe
Ferromagnetic iron oxide such as ₂ O ₃ , Co-coated γFe ₂ O ₃ , Co-coated magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite and the like can be used. Co such as γFe ₂ O ₃
Deposited ferromagnetic iron oxide is preferred. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g. The saturation magnetization (σs) of the ferromagnetic material is preferably from 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, and particularly preferably from 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-16032. JP-A-4-259911, 5
Magnetic particles having a surface coated with an inorganic or organic substance described in JP-A-81652 can also be used.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, anti-adhesion 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. The 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. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. US Pat. Nos. 5,336,589 and 5,25 for photosensitive materials having a magnetic recording layer
0,404, 5,229,259, 5,215,8
74, EP 466,130.

The polyester support used in the present invention will be described. For details including photosensitive materials, treatments, cartridges and examples which will be described later, see Japanese Patent Publication No.
4-6023 (Invention Association; 1994. 3.15.). The polyester used in the present invention is formed with diol and aromatic dicarboxylic acid as essential components,
2,6-, 1,5-, 1,4 as aromatic dicarboxylic acids
-And 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and diols include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferred. The average molecular weight ranges from about 5,000 to 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, preferably 90 ° C. or higher.

Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more and less than Tg in order to make it difficult to form a curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is from 0.1 hour to 1500 hours, and more preferably from 0.5 hour to 200 hours. The heat treatment of the support may be performed in a roll form, or may be performed while transporting the support in a web form. The surface is provided with irregularities (for example, Sn
(Conductive inorganic fine particles such as O ₂ and Sb ₂ O ₅ are applied), and the surface state may be improved. It is also desirable to take measures such as applying knurls to the ends and making the ends slightly higher so as to prevent the cut end of the core from appearing. These heat treatments may be performed at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), and after the application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. In order to prevent light piping, the purpose can be achieved by kneading a commercially available dye or pigment for polyester, such as Diaresin manufactured by Mitsubishi Kasei or Kayaset manufactured by Nippon Kayaku.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less.
Further, the film swelling speed T _1/2 is preferably 30 seconds or less, and more preferably 20 seconds or less. T _1/2 is a color developer at 30 ° C., 3
When 90% of the maximum swelled film thickness reached when the treatment is performed for 15 minutes is defined as the saturated film thickness, it is defined as the time until the film thickness itself reaches １ ／. The film thickness means a film thickness measured at 25 ° C. and a relative humidity of 55% under humidity control (2 days), and T _1/2 is a value obtained by Photographic Science and Engineering (A. Green) et al. Photogr.Sci.En
g.), Vol. 19, pages 2, 124-129, using a serometer (swelling meter). T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. In addition, the swelling ratio is 150 ~
400% is preferred. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness-film thickness) / film thickness. The photosensitive material of the present invention has a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
It is preferable to provide a hydrophilic colloid layer (referred to as a back layer). In this back layer, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener,
It is preferable to include a binder, a plasticizer, a lubricant, a coating aid, and a surfactant. The swelling ratio of this back layer is 1
50-500% is preferred.

[0109]

The present invention will be described in more detail with reference to the following Examples, which by no means limit the present invention.

Example 1 Stability to Precipitation Precipitation To test the stability to precipitation, 14 types of color developing compositions were prepared by changing the factors in the following composition table. Table 2 shows the changing factors of the fourteen compositions. Table 2 also shows the test results. (1) Test Formulation of Color Developer Composition Fluorescent Whitening Agent of General Formula (I) (see Table 2) 7.5 g Fluorescent Whitening Agent of General Formula (II) (see Table 2) 12.0 g dimethyl Polysiloxane surfactant 0.35 g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Ethylenediaminetetraacetic acid 15.0 g Tri (isopropanol) amine 30.0 g Potassium hydroxide 18.5 g Sodium hydroxide 24.0 g Sodium sulfite 0.60 g Potassium bromide 0.04 g Other additives (see Table 2) 4-amino-3-methyl-N-ethyl-N- (β-methanesulfamidoethyl) aniline / 3/2 sulfate aqueous solution Monohydrate 60.0 g Potassium carbonate 100.0 g pH 13.0 Add water and add 1 liter

(2) Stability Test Conditions and Evaluation Criteria The prepared color developer composition was placed in a glass bottle, and
Each was stored at 0 and -5 ° C for one week. Evaluation of test results
The liquid after the lapse of time was visually judged, and x indicating that a precipitate was formed even when stored at 5 ° C, ○ indicating that a precipitate was formed after storage at 0 ° C, and stored at −5 ° C. A five-point evaluation was performed in which a transparent and excellent product was evaluated as A, a product that did not cause precipitation was evaluated as A, and a product that was cloudy was evaluated as A.
Table 2 shows the results. Further, in Comparative Examples 2 to 5 using other than the fluorescent whitening agent other than the fluorescent whitening agent according to the present invention, precipitation was observed even at 5 ° C. storage, whereas the general formula (I) or (II) Inventive Examples 6 to 14 using either or both of them all have at least the rank of ○,
Further, a comparison between Samples 7 and 8 and Samples 10 and 12 shows that the stability is increased by using the compounds of the general formulas (I) and (II) together. Sample 15 and Sample 1
Comparison of 2 shows the stabilizing effect of polyethylene glycol. In particular, Samples 9 and 12 are standards that do not contain an optical brightener and show the same stability as Comparative Sample 1 which is also the target.

[0112]

[Table 2]

In Table 2, the optical brighteners RA-1, RA-2 and RB-1 not used in the present invention and used for comparison were used.
And RB-2 have the following structures.

[0114]

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[0115]

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Example 2 Stability of Fluorescent Whitening Agent to Storage over Time Samples 4, 5, 9, 12, and 13 were selected from the 14 color developing compositions used in the above-described stability test for precipitation, and the resultant was treated with water. Samples 4D, 5D, 9D, 12D, diluted 6 times
13D. The original samples 4, 5, 9, 12, and 13 and the diluted samples 4D, 5D, 9D, 12D, and 13D were placed in a glass bottle and aged at 50 ° C. for 8 weeks in a bright room. Samples 4, 5, 9, 12, and 13 are:
It was aged even under conditions of low temperature (5 ° C.) with shading. The heat-aged samples 4, 5, 9, 12, 13 and the samples 4, 5, 9, 12, 13 which were kept at a low temperature as a standard were each diluted 12-fold, and potassium carbonate 16
g and adjust the pH to 10.15, while sample 4
D, 5D, 9D, 12D, and 13D are diluted 2-fold to obtain 1
Add 16 g of potassium carbonate per liter and bring the pH to 1
It was adjusted to 0.15 to prepare a developer. Using these developing solutions, the photosensitive material sample B shown in Example 3 was developed without being exposed, and the fluorescence intensity of the developed sample was measured. The measurement was performed using an M-850 fluorescence spectrophotometer manufactured by Hitachi, Ltd., with an excitation wavelength of 350 nm and a measurement wavelength of 4 nm.
50 nm was chosen. The evaluation of the fluorescence intensity was performed based on the relative value of the fluorescence intensity of the light-sensitive material developed after the lapse of low-temperature light-shielding, that is, the relative intensity of the fluorescence spectrum represented by the following formula. (Fluorescence intensity of photosensitive material treated with high-temperature aged sample) / (fluorescence intensity of photosensitive material treated with light-shielded low-temperature aged sample) Table 3 shows the obtained results.

[0117]

[Table 3]

In Table 3, the developing composition of the present invention (samples 9, 12, and 13) in a 12-fold concentration state exhibited a strong fluorescence intensity, but the 2-fold concentrated sample and the fluorescent brighteners other than the present invention exhibited a strong fluorescence intensity. The developing composition using the agent had a low fluorescence intensity.

Example 3 Photographic quality characteristics (1) Preparation of photosensitive material sample A corona discharge treatment was applied to the surface of a support having both sides of paper coated with polyethylene resin, and then gelatin containing sodium dodecylbenzenesulfonate was used. An undercoat layer was provided, and first to seventh photographic constituent layers were sequentially applied to prepare a silver halide color photographic light-sensitive material sample having the following layer structure (referred to as sample sample B). . The coating solution for each photographic constituent layer was prepared as follows. The average grain size of the emulsion shown below is the average value of the converted diameter of the grain area measured by the so-called projection area method.

(Preparation of Coating Solution) Preparation of Coating Solution for Fifth Layer 300 g of cyan coupler (using the following pyrrolotriazole coupler), 250 g of color image stabilizer (Cpd-1),
10 g of a color image stabilizer (Cpd-9), a color image stabilizer (Cpd-9)
-10) 10 g, a color image stabilizer (Cpd-12) 20 g,
14 g of UV absorber (UV-1), UV absorber (UV
-2) 50 g, an ultraviolet absorber (UV-3) 40 g and an ultraviolet absorber (UV-4) 60 g were mixed with a solvent (Solv-
6) Dissolve in 230 g and 350 ml of ethyl acetate, and add 10% sodium dodecylbenzenesulfonate 2
Emulsified dispersion C was prepared by emulsifying and dispersing in 6500 g of a 10% aqueous gelatin solution containing 00 ml.

[0121]

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On the other hand, silver chlorobromide emulsion C (cubic, 1: 4 mixture of large-size emulsion C with an average grain size of 0.50 μm and small-size emulsion C with an average grain size of 0.41 μm (silver molar ratio). Coefficients of variation were 0.09 and 0.11, respectively, and 0.5 mol% of silver bromide was locally contained in a part of the surface of the silver chloride-based grain in each size emulsion.) . This emulsion contains the following red-sensitive sensitizing dyes G and H in an amount of 6.0 × 10 ⁻⁵ mol per mol of silver for the large-size emulsion C, and 6.0 × 10 ^-5 mol for the small-size emulsion C per mol of silver. 9.0 × 10 ^-5 mol is added. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. Emulsified dispersion C and silver chlorobromide emulsion C
Were mixed and dissolved to prepare a fifth layer coating solution having the composition described below. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the first to fourth layers and the sixth to seventh layers were prepared in the same manner as the coating solution for the fifth layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Ab-1, Ab-2 , Ab-3 and Ab-4 the total amount respectively 15.0 mg / m ² in each layer, 60.0mg / m ^2,
It was added to a 5.0 mg / m ² and 10.0 mg / m ^2.

[0124]

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The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0126]

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(The sensitizing dyes A, B and C were used in an amount of 1.4 ×
^10-4 moles, ^1.7x each for small size emulsions
10 ^-4 mol was added. Green sensitive emulsion layer

[0128]

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(Sensitizing dye D was added per mole of silver halide,
3.0 × 10 for large emulsions ^-FourMol, small size
3.6 × 10 for emulsion^-FourMol and sensitizing dye E
Per mole of silver halide and for large emulsions
4.0 × 10^-Five7.0 × for mole, small size emulsions
10^-FiveMol of sensitizing dye F per mol of silver halide.
2.0 × 10 for large emulsions^-FourMole, small
2.8 × 10 for size emulsion^-FourMole was added. ) Red-sensitive emulsion layer

[0130]

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(Sensitizing dyes G and H were converted to silver halide 1
6.0 × 1 per mole for large size emulsions
0 ^-5 mol, respectively 9.0 × 1 to the small size emulsion
0 ^-5 mol was added. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide. )

[0132]

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Further, a blue-sensitive emulsion layer, a green-sensitive emulsion layer and
1- (3-methylureidophenyl) was added to the red-sensitive emulsion layer.
) -5-mercaptotetrazole
3.3 × 10 per mole of silver halide^-FourMol, 1.0 × 10^-3
Mol and 5.9 × 10^-FourMole was added. Furthermore, the second
Layer, the fourth layer, the sixth layer and the seventh layer, respectively.
mg / m ^Two 0.2 mg / m^Two , 0.6 mg / m^Two ,
0.1mg / m^Two Was added so that Blue sensitivity
4-hydroxy-6 to the emulsion layer and the green-sensitive emulsion layer
-Methyl-1,3,3a, 7-tetrazaindene
1 × 10 per mol of silver halide^-FourMole, 2
× 10^-FourMole was added. Also, methacrylate is added to the red-sensitive emulsion layer.
Copolymer of phosphoric acid and butyl acrylate (weight ratio 1: 1, flat
Average molecular weight of 200,000 to 400,000) is added to 0.05 g /
m2 was added. In addition, the second, fourth and sixth layers
Catechol-3,5-disulfonate disodium
6mg / m each^Two, 6mg / m^Two, 18mg / m^TwoBecomes
Was added as follows. Also, to prevent irradiation
In addition, the following dyes are shown in the emulsion layer
Was added.

[0134]

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(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion is
It represents the silver equivalent coating amount. Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ;
Content of 16% by weight, ZnO; content of 4% by weight) and a fluorescent whitening agent (4,4'-bis (benzoxazolyl) stilbene and 4,4-bis (5-methylbenzoxazolyl) stilbene) 8/2 (weight ratio): 0.05% by weight), including bluish dye (ultramarine)

First Layer (Blue-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 3: 7 mixture of large-size emulsion A having an average grain size of 0.72 μm and small-size emulsion A having an average grain size of 0.60 μm (silver molar ratio) The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion. ) 0.26 Gelatin 1.35 Yellow coupler (ExY) 0.62 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0 .08 Solvent (Solv-1) 0.23

Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention agent (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large-size emulsion B having an average grain size of 0.45 μm and small-size emulsion B having an average grain size of 0.35 μm (silver mole The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively. In each size emulsion, 0.4 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride.) 0.14 Gelatin 1.36 Magenta coupler (ExM) 0.15 UV absorber (UV-1) 0.05 UV absorber (UV-2) 0.03 UV absorber (UV-3) 0.02 UV absorption Agent (UV-4) 0.04 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 0.002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer ( Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Image stabilizer (Cpd-10) 0.01 Color Image Stabilizer (Cpd-11) 0.0001 solvent (Solv-3) 0.11 solvent (Solv-4) 0.22 solvent (Solv-5) 0.20

Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention agent (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 1: 4 mixture of large emulsion C having an average grain size of 0.50 μm and small emulsion E of 0.41 μm (silver mole) The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.20 Gelatin 1.11 Cyan coupler (A or B) 0.30 Ultraviolet absorber (UV-1) 0.14 Ultraviolet absorber (UV-2) 0.05 Ultraviolet absorber (UV-3) 0.04 UV absorber (UV-4) 0.06 Color image stabilizer (Cpd-1) 0.25 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer Agent (Cpd-12) 0.02 Solvent (Solv-6) 0.23

Sixth layer (ultraviolet absorbing layer) Gelatin 0.66 Ultraviolet absorbing agent (UV-1) 0.19 Ultraviolet absorbing agent (UV-2) 0.06 Ultraviolet absorbing agent (UV-3) 0.06 Ultraviolet absorbing Agent (UV-4) 0.05 Ultraviolet absorber (UV-5) 0.09 Solvent (Solv-7) 0.25

Seventh layer (protective layer) Gelatin 1.00 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

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2. Developing process (Preparation of developing solution for developing process) The above-mentioned photosensitive material sample B was processed into a 127 mm wide roll, and a minilab printer processor PP72 manufactured by Fuji Photo Film Co., Ltd.
Photosensitive material sample B was exposed imagewise from an average density negative film using 8AR, and was continuously processed (running test test) in the following processing steps until the replenishment amount was four times the capacity of the color developing tank. . The developer composition sample 9 shown in Table 2 was diluted 4-fold to adjust the pH to 12.50 to prepare a developing replenisher, and then put into a replenishing tank. Was satisfied, and continuous development processing was performed by an automatic developing machine.

Processing Step Temperature Time Replenishment amount ^* Color development 38.5 ° C. 45 seconds 45 ml Bleaching and fixing 38.0 ° C. 45 seconds 35 ml Rinse (1) 38.0 ° C. 20 seconds-rinse (2) 38.0 ℃ 20 seconds-Rinse (3) ** 38.0 ° C 20 seconds-Rinse (4) ** 38.0 ° C 20 seconds 121 ml Drying 80 ° C 30 seconds (Note) * Replenishment amount per 1 m ^{2 of} photosensitive material ** The rinse screening system RC50D manufactured by Fuji Photo Film Co., Ltd. is attached to the rinse (3), and the rinse liquid is taken out from the rinse (3) and sent to the reverse osmosis module (RC50D) by a pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. Rinsing was performed in a 4-tank countercurrent system from (1) to (4).

The composition of each processing solution is as follows. [Color developer] [Tank solution] Water 800 ml Dimethyl polysiloxane surfactant (Silicone KF351A, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1 g Polyethylene glycol (molecular weight 300) 10.0 g Fluorescent brightening of general formula (I) Agent A-1 1.0 g Optical brightener B-1 of the general formula (II) 2.0 g Ethylenediaminetetraacetic acid 4.0 g Tri (isopropanol) amine 8.8 g 4,5-dihydroxybenzene-1,3- Sodium disulfonate 0.5 g Potassium chloride 10.0 g Sodium sulfite 0.1 g N-hydroxy-N. N-di (sulfoethyl) amine disodium salt 8.5 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline / 3/2 sulfate monohydrate 5.0 g Carbonic acid 26.3 g of potassium 1000 ml of water by adding water pH (adjusted with potassium hydroxide and sulfuric acid at 25 ° C.) 10.15

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 800 ml 800 ml ammonium thiosulfate (750 g / l) 107.0 ml 214.0 ml m-carboxymethylbenzenesulfinic acid 8.3 g 16.5 g ethylenediamine Ammonium iron (III) tetraacetate 47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4 g 2.8 g Nitric acid (67%) 16.5 g 33.0 g Imidazole 14.6 g 29.2 g Ammonium sulfite 16.0 g 32.0 g Meta heavy Potassium sulfite 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted at 25 ° C / acetic acid and ammonia) 6.5 6.5

[Rinse solution] [Tank solution] [Replenisher] Dechlorinated sodium isocyanurate 0.02 g 0.02 g Deionized water (conductivity of 5 μs / cm or less) 1000 ml 1000 ml pH 6.5 6.5

The liquid exchange rate of the developing tank was up to four times, but the photographic quality characteristics were excellent in stain, fluorescence intensity (whiteness), gradation, and color reproducibility. It was normal.

[0156]

The pH and carbonate concentration as defined in claim 1
The developer composition having a developing agent concentration and containing a fluorescent sensitizer selected from the general formula (I) and the general formula (II) has no precipitate during storage over time or during the development process. The properties are stably maintained without deterioration of the processing agent performance such as strength. Therefore, the volume of the developer composition can be reduced, and the composition can be incorporated in an automatic developing system. Further, it is possible to use a single-part polyethylene container which could not be used for a color developing composition having a one-part configuration.

Claims (6)

[Claims] 1. A fluorescent enhancer represented by the following general formula (I) or (II): potassium carbonate or sodium carbonate or both in a total amount of 0.45 to 2M, a color developing agent in a range of 0.08 to 1M, Containing at least one whitening agent, and having a pH
A color developing composition for a silver halide color photographic light-sensitive material, characterized by comprising a concentrated solution having a pH of 12.5 or more. Embedded image (Wherein, X ₁ , X ₂ , Y ₁ and Y ₂ each represent an amino group or a morpholino group which may have a substituent other than a hydroxyl group, a chlorine atom, a methoxy group and a sulfo group.
Represents a hydrogen atom or an alkali metal atom). Embedded image (In the formula, n is 1 or 2, Z ₁ and Z ₂ have the same meanings as X ₁ , X ₂ , Y ₁ and Y _{2 in the} general formula (I), respectively, and M is a hydrogen atom or an alkali. Represents a metal atom). 2. The color developing composition according to claim 1, comprising a polyalkylene glycol. 3. The color developer composition according to claim 1, wherein the composition further comprises at least one alkanolamine selected from the group represented by the following general formula (A). [H (R′O) _m R] _n NH _(3-n) Formula (A) (where m is 0 or 1, n is an integer of 1 to 3, and R is a group having 2 to 4 carbon atoms) Hydroxy-substituted alkylene group, R '
Is an alkylene group having 1 to 4 carbon atoms or a hydroxy-substituted alkylene group. However, when m is 0, n is 2 if R has 2 carbon atoms, and n is 1, 2 or 3 if R has 3 to 4 carbon atoms. When m is 1, n is 1, 2 or 3 regardless of the type of R). 4. The color developer composition for a silver halide color photographic light-sensitive material according to claim 1, wherein the composition is constituted by a concentrated solution of one part. 5. The silver halide according to claim 1, which contains both of the optical brighteners represented by the general formulas (I) and (II). A color developer composition for a color photographic light-sensitive material. 6. A method for developing a silver halide color photographic light-sensitive material, comprising performing color development using the color developing composition according to claim 1.