JPH11202459A - Color developer composition for silver halide color photographic sensitive material and developing processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the liquid concentrated developer composition, for the silver halide color photographic sensitive material, containing no hydroxylamine but one having at least similar preservability to this and the same photographic performance as this and to provide the development processing method by using this composition. SOLUTION: This color developer composition contains an alkoxylamine compound specified in structure but substantially no hydroxylamine, and it contains the above alkoxyamine compound together with an N- alkylhydroxylamine compound specified in structure.

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,
Generally, the basic steps include a color developing step (particularly a color developing step), a desilvering step, and an image stabilizing step such as washing with water. In the color development step, an image-like dye and developed silver are generated by the reaction between the color developing agent and the silver salt. In the desilvering process,
The developed silver generated in the color development step is oxidized (bleached) to a silver salt by a bleaching agent having an oxidizing action, and is removed from the photosensitive layer by a fixing agent that 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 to ensure long-term stability of the generated image.
Alternatively, either a washing with water and an image stabilizing bath, or a stabilizing bath instead of washing with water are 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, 3,647,461 and 3,814,606 and published 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,
Satisfactory treating agents have not been obtained in both environmental aspects, simplicity of working aspects such as labor saving of processing solution preparation work, and safety aspects.

[0005] In recent years, in view of improvement of solid processing agents, a method of forming the processing agent into tablets has been disclosed (for example, Canadian Patent No. 8).
Despite some progress such as the development of a liquid developer, a concentrated liquid processing agent is desired as a developing agent for a color developing plant from the viewpoint of easiness of operation and improvement in productivity of developing processing. Therefore, there is a demand for further increasing the degree of concentration of the liquid processing agent to provide compactness comparable to a solid processing agent. 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 forming a concentrated liquid treating agent for color into 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 does not extend the advantages of the liquid treating agent.

The liquid processing agent for color photographic light-sensitive materials 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, the color developing agent contains a p-phenylenediamine derivative as a developing agent, and the main agent is easily susceptible to air oxidation. The developing agent becomes tar-like and adheres to the container wall, which hinders the recycling and reuse of the container.

In order to prevent the color developing agent from deteriorating with time, hydroxylamine (usually used as a sulfate or hydrochloride, but for convenience sake, the salt portion is omitted) as a preservative or an alkali such as sulfurous acid is used. A metal salt has been added to the developer composition. However, since hydroxylamine is specified as a deleterious substance, it must be handled with care in terms of safety and compliance with laws and regulations, and it also reacts with sulfite to reduce sulfite, Since the components of the processing agent composition fluctuate, it was difficult to use a developing agent having a one-component configuration (also referred to as a one-part configuration). Many alternative N-preservatives for hydroxylamine, such as Japanese Patent Application Laid-Open No.
Alkyl-substituted hydroxylamine derivatives are disclosed. JP-A-4-443 discloses dialkylhydroxylamines and hydroxylalkylhydrazines having a large preservative effect. Although these alternative compounds are advanced compounds in terms of improving preservation, they also have disadvantages in maintaining the performance of photographic image characteristics.

In other words, these hydroxylamine derivatives or hydrazine derivatives intended to substitute for hydroxylamine have photographic characteristics that do not completely match those of hydroxylamine, and are disadvantageously similar to similar photosensitive materials (eg, color negative films). ), The degree of difference in photographic properties from hydroxylamine differs depending on the type and brand, and therefore, for example, even in the case of developing color negative films, color negative films of each type of each company are developed with the same developing machine and the same developing machine. In the normal color processing laboratory development method where development is carried out using a processing agent, the change in photographic properties due to the replacement with the hydroxylamine derivative is subtly changed by each film, and the performance that all the films have is sufficient. Problems that cannot be exhibited . Therefore, one of the necessary conditions as a substitute for hydroxylamine is to have the same photographic behavior as that of hydroxylamine for each type of photosensitive material of each company. Are strongly desired.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material which does not contain hydroxylamine but has a preservative property which can substitute for hydroxylamine and has the same photographic behavior as hydroxylamine. And a developing method using the same. A second object of the present invention is to provide a liquid concentrated developer composition in a plastic container which is stored so that the developer composition filled with the liquid concentrated developer composition is stably stored for a long period of time. It is to be. A third 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.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on the above-mentioned objects by paying attention to the characteristics of a specific alkoxyamine compound, and have found that this compound satisfies the above-mentioned requirements. The present inventors have found that the present invention can function as a liquid developer, and utilized this fact for stabilization of a concentrated liquid developer to arrive at the present invention. That is, the object of the present invention is achieved by the following liquid-concentrating processing agent composition for color development, the form of accommodation in a container, and the developing method.

1. A color developing composition for a silver halide color photographic light-sensitive material, comprising a compound represented by the following general formula (I) and substantially free of hydroxylamine.

[0013]

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In the general formula (I), R ₁ represents an alkyl group which may have a substituent, and R ₂ and R ₃ each represent a hydrogen atom or an alkyl group which may have a substituent. R ₂ and R ₃ may be linked to each other to form a ring.

2. The color developer composition according to the above item 1, further comprising a hydroxylamine derivative represented by the following general formula (II) in addition to the compound represented by the general formula (I):

[0016]

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In the general formula (II), L represents an alkylene group or a single bond which may be substituted, and A represents a carboxyl group, a sulfo group, a phosphono group or a phosphinic acid residue when L is an alkylene group. A hydroxyl group, an amino group which may be substituted with alkyl, an ammonio group which may be substituted with alkyl, a carbamoyl group which may be substituted with alkyl, a sulfamoyl group which may be substituted with alkyl or an alkylsulfonyl group which may be substituted, When L is a single bond, it represents an alkyl group which may be substituted with alkoxy, and R represents a hydrogen atom or an alkyl group which may be substituted. Further, L and R may be linked to form a ring.

3. 3. The color developer composition as described in 1 or 2 above, which is contained in a container made of a material containing 95% or more of polyethylene.

4. 4. A method for developing a silver halide color photographic light-sensitive material, comprising performing color development using a color developing replenisher obtained by diluting the color developing composition according to any one of the above 1 to 3.

[5] A container filled with the developer composition according to any one of the above 1 to 3 is attached to an automatic developing machine, and the contents of the container are poured into a developing replenishing tank. 5. The developing method according to the above item 4, wherein washing is performed, water used for the washing is introduced into a replenishing tank, used as water for preparing a replenishing solution, and development is performed using the obtained replenishing solution.

[0021]

Embodiments of the present invention will be described below in detail. In the present invention, by adding the compound represented by the general formula (I) to a liquid concentrated developer composition for a color photographic light-sensitive material, preservation is sufficiently ensured,
In addition, it is based on the fact that the same photographic behavior can be obtained for various common light-sensitive materials.

The compound represented by formula (I) will be described. In the general formula (I), R ₁ is a linear or branched alkyl group having 1 to 12 carbon atoms which may have a substituent, and a preferable alkyl group is a linear or branched alkyl group having 1 to 6 carbon atoms. It is. The substituent is a hydroxy group, a carboxy group, a sulfonic acid group or an alkoxy group having 1 to 5 carbon atoms. Particularly, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a t-butyl group are preferable. Preferred alkyl groups having a substituent include a hydroxyethyl group,
A carboxyethyl group, an n-4-sulfobutyl group, and a methoxyethyl group. When R ₂ and R ₃ represent an alkyl group, it is a straight-chain or branched alkyl group having 1 to 12 carbon atoms, preferably a straight-chain or branched alkyl group having 1 to 8 carbon atoms. Particularly preferred alkyl groups include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-
Butyl group, t-butyl group, pentyl group, hexyl group and octyl group. When the alkyl group has a substituent, the substituent is a hydroxy group, a carboxy group, a sulfonic acid group, or an alkoxy group having 1 to 5 carbon atoms. Preferred substituted alkyl groups include a hydroxyethyl group, a carboxyethyl group, an n-4-sulfobutyl group, a methoxyethyl group, a sulfoethyl group, and a carboxymethyl group. When R ₂ and R ₃ are bonded to each other to close the ring, a pyrrolidine ring, a piperidine ring, a morpholine ring and the like can be mentioned.

Hereinafter, specific examples of the compound represented by formula (I) of the present invention will be shown, but the present invention is not limited thereto.

[0024]

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[0025]

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Particularly preferred among the compounds of the general formula (I) are the compounds I-1, I-2 and I-12 of the above specific examples.
It is. The amount of these compounds to be added to the color developing solution is 0.001 to 0.1 mol, preferably 0.005 to 0.05 mol, per liter of the processing solution. Usually 1.0 to 1.8 of the amount added to the developer.
And more generally 1.1-1.4 times. The concentration in the processing agent composition is determined from the above-mentioned addition concentration and the concentration ratio so that a developer or a developer replenisher is obtained by dilution.

It goes without saying that the alkoxyamino compound of the general formula (I) has a performance that can substitute for hydroxylamine as a preservative, but its feature is that it is characterized by a conventionally known hydroxylamine derivative or hydrazine derivative. Unlike hydroxylamine-substituted compounds such as these, the effect on photographic properties other than preservation, that is, on sensitivity and gradation, tends to be the same as the effect of hydroxylamine. Therefore, the photographic behavior of the photosensitive material to be processed is different from that of hydroxylamine due to the difference in the type and manufacturer of the photosensitive material. Also, development processing can be performed without problems even with brand photosensitive materials.

The color developing composition of the present invention has the general formula (I)
By substantially containing hydroxylamine, which is a preservative conventionally used, is contained. Substantially free means that even if it contains a small amount of hydroxylamine that does not maintain its original function as a preservative, it is equivalent to "not included", and Even if such a small amount of hydroxylamine is contained, the compound of the general formula (I) is included in the present invention. The specific amount is 3 to 5 per liter of a conventional color developing solution as an amount in which hydroxylamine exhibits an effect as a sole preservative.
g, and even if hydroxylamine is contained in an amount of 1 g or less per liter of the color developing solution, the effect as a preservative is insufficient. Such a small amount of hydroxylamine, for example, 0.5 g per liter of developer
Is included in the scope of the present invention, when it does not substantially contribute to the preservative property of the developer and the preservative property is given by the general formula (I) of the present invention. It is. Also,
The compounds of the general formula (I) are included in the compounds described in JP-T-61-501343 and JP-B-48-39168, the former being used as a component of a black-and-white tanning developer, and the latter being It is disclosed that it is used as an aldehyde neutralizing agent after hardening treatment, and has nothing to do with the usage of the present invention.

In the present invention, by further including the compound represented by the general formula (II) in addition to the compound of the above (I) in the developer composition, the photographic behavior of hydroxylamine can be further brought closer. it can. General formula (II)
Some of the compounds are known as hydroxylamine replacement compounds, but these compounds, when used alone as a preservative, show different photographic behavior from hydroxylamine, The homeostasis between each product type and each brand cannot be obtained. However, the general formula (I)
When used in combination with any of the compounds, the homeostasis is improved as compared with the case of using any of the compounds alone.

The compound of the formula (II) will be described.
In the formula (II), when L represents an alkylene group, it is a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. Specifically, methylene, ethylene, trimethylene, and propylene are preferred examples. As the substituent, a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue,
Hydroxyl group, alkyl (preferably 1-5 carbon atoms)
It represents an amino group which may be substituted, and preferred examples thereof include a carboxyl group, a sulfo group, a phosphono group and a hydroxyl group.

A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxyl group, an alkyl (preferably having 1 to carbon atoms) when L is an alkylene group.
5) optionally substituted amino group, alkyl (preferably 1 to 5 carbon atoms) optionally substituted ammonio group, alkyl (preferably 1 to 5 carbon atoms) optionally substituted carbamoyl group, alkyl (preferably C1-5) represents a sulfamoyl group which may be substituted, an alkylsulfonyl group which may be substituted, and a carboxyl group, a sulfo group, a hydroxyl group, a phosphono group, and a carbamoyl group which may be alkyl-substituted are mentioned as preferred examples. Can be When A represents an ammonium group, the compound of the general formula (II) may have a sulfate ion, a p-toluenesulfonic acid ion, a chloride ion, a sulfite ion, or the like as a counter ion of the ammonium group. L and A are a carboxyl group, a sulfonic acid group,
When a substituent having an acid group such as a phosphono group, a phosphinic acid residue, or a hydroxyl group is involved, the hydrogen may be replaced with an alkali metal atom or an ammonium atom group. Preferred examples of -LA include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. Groups, carboxyethyl groups, sulfoethyl groups, sulfopropyl groups, phosphonomethyl groups, and phosphonoethyl groups can be mentioned as particularly preferred examples.

When L is a single bond, A has 1 carbon atom.
To 5, especially a methyl group, an ethyl group,
An n-propyl group and an i-propyl group are preferred. This alkyl group may be substituted with an alkoxy group having 1 to 3 carbon atoms. Preferred alkoxy-substituted alkyl groups are methoxyethyl, ethoxyethyl, ethoxyethyl, and methoxy-n-propyl.

R represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. As the substituent, a carboxyl group,
Sulfonic acid group, phosphono group, phosphinic acid residue, hydroxyl group, amino group optionally substituted with alkyl, carbamoyl group optionally substituted with alkyl, sulfamoyl group optionally substituted with alkyl, alkylsulfonyl group optionally substituted , Acylamino group, alkylsulfonylamino group,
An arylsulfonylamino group, an alkoxycarbonyl group, an amino group which may be substituted with alkyl, an arylsulfonyl group, a nitro group, a cyano group, and a halogen atom.
Two or more substituents may be substituted on one R. Among them, preferred R includes a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. Particularly preferred examples include a hydrogen atom. Carboxymethyl group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group and phosphonoethyl group.

L and R may combine to form a ring. L
When R and R form a ring, L and R directly form a ring to have A as a substituent, or A represents an amino group which may be alkyl-substituted, and L represents a nitrogen atom of the amino group. And R can also form a ring (eg, a piperazine ring). Next, specific compounds of the present invention are described, but are not limited thereto.

[0035]

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[0036]

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[0037]

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The compound represented by the general formula (II) can be synthesized by subjecting commercially available hydroxylamines to an alkylation reaction (nucleophilic substitution reaction, addition reaction, Mannich reaction, etc.). West German Patent 1159634, `` Inorganica Chemica Acta '' (Inorganica
Chimica Acta), 93, (1984) 101-108, and the like. A more specific method for synthesizing a compound is described in JP-A-3-266837.

Particularly preferred among the compounds of the general formula (II) are the compounds II-2, II-57 and II-5 of the above specific examples.
8 Among them, I-1 and II-57, I-2 and II-5
7, a combination of I-2 and II-58 is preferred. The amount of the hydroxylamine derivative represented by the general formula (II) to be added to the color developing solution of the present invention is 0.001 to 1.0 mol, preferably 0.01 to 0.5 mol per liter as a composition of the processing tank solution.
Mol, and the amount added to the replenisher is 1.0 to 1.8.
Times, preferably 1.0 to 1.4 times. The amount of addition to the developer composition is set so that the above-mentioned developer and development replenisher can be obtained by dilution corresponding to the concentration ratio.

By adding a compound represented by the general formula (I) or a compound represented by the general formula (II) to a color developing solution, a processing composition having excellent preservation property and high concentration is obtained. It became possible to design. More advantageously, the compounds of formula (I) or (II) have the effect of preventing the coloration of the solution and the vessel walls of the container by the air oxidation of the developer. Although the mechanism for preventing coloration is not sufficiently clear, it is presumed that the prevention of precipitation of the developing agent results in the elimination of the insoluble agent which is easily oxidized. In addition, since the developing agent in the color developing solution does not precipitate and is not oxidized, it is stably maintained in the concentrated processing agent composition. Stability can be improved.

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 concentration is about 1.5 to 10 times, preferably 2 to 8 times, and more preferably 2.3 times the concentration of the solution in actual use, that is, the developing replenisher or the mother liquor (tank solution). It is up to 5.0 times. The concentration of the compound of the general formula (I) or the general formula (II) in the concentrated developer composition is from 0.01 to 1M, preferably from 0.02 to 0.4M, more preferably
0.02-0.2M when the concentration ratio is 2.3-5.0
It is.

The developer composition of the present invention has the following general formula (II)
When the compound represented by the formula (I) is contained, the solubility is increased and the concentration can be further increased.

[0043]

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In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and these groups are connected to each other to form a ring. You may. In the general formula (III), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄
Represents a hydrogen atom and an aliphatic hydrocarbon group having 1 to 3 carbon atoms, respectively. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an alkyl group such as n-propyl and i-propyl,
An alkenyl group such as a vinyl group and an allyl group is preferable, and an alkyl group is particularly preferable. Further, the alkyl group may be substituted with a hydroxy group, a carboxyl group or a sulfonic acid group. Particularly preferred R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are a hydrogen atom, a methyl group and a propyl group.

Any two of R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ may be linked to each other to form a ring. When a ring is formed, the ring may be a pyrrole ring, a 2-pyrroline ring,
A 5- to 7-membered ring containing one nitrogen atom such as a pyrroline ring, a pyrrolidine ring, a piperidine ring, or a 2-oxoimidazolidine ring, or a urea structure containing two nitrogen atoms incorporated into the ring.
It is a structure of a 7-membered ring. Further, the carbon atoms constituting these rings may have a substituent. In such a case, the substituents may be the same as those described above for R ₁₁ , R ₁₂ , R ₁₃ and R _14, and May be a 2-oxoimidazolidine ring formed by bonding a ureylene group to an adjacent carbon atom. When the compound of the general formula (III) has the above-mentioned ring structure, particularly preferred compounds are a compound having one 2-oxoimidazolidine ring and a compound having two fused 2-oxoimidazolidines. .

By adding the compound represented by the general formula (III) to the color developing solution, precipitation of the color developing agent is prevented, and as a result, a processing composition having a high concentration can be designed. became. More advantageously, the compounds of formula (III) have the effect of preventing the developer from being oxidized by air oxidation and discoloration of the container and vessel walls. Although the mechanism for preventing coloration is not sufficiently clear, it is presumed that the prevention of precipitation of the developing agent results in the elimination of the insoluble agent which is easily oxidized. In addition, since the developing agent in the color developing solution does not precipitate and is not oxidized, it is stably maintained in the concentrated processing agent composition. Stability can be improved. Hereinafter, specific examples of the compound represented by formula (III) of the present invention are shown, but the present invention is not limited thereto.

[0047]

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[0048]

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Particularly preferred among the compounds of the general formula (III) are the compounds III-11 and III-15 of the above specific examples.

The developer composition of the present invention can further increase the solubility of the color developing agent by further adding a surfactant in addition to the above, and therefore, has stability against air oxidation and a tar-like colored material. Can be more effectively suppressed. Many of the known anionic surfactants have such an effect, but especially the following general formula (I
An anionic surfactant containing a repeating structure of an alkylene oxide group as shown in V) is particularly effective.

R ¹⁰ O (CH ₂ CH ₂ O) _p [CH ₂ CH (OH) CH ₂ O] _q (CH ₂ ) _r V [IV] In the general formula [IV], R ¹⁰ represents an alkyl group or an alkenyl group. , An aryl group or an alkylcarbonyl group, and p and q represent 0 or an integer of 1 to 100. However, p + q is 1
This represents the above. r represents 0 or an integer of 1 to 50. V is r
Is 0, it represents a sulfonic acid group or a phosphoric acid group. Also, r
Is 1 or more, represents a sulfonic acid group, a phosphoric acid group, a sulfonic acid ester group, and a phosphoric acid ester group.

R^TenIs an alkyl group having 1 to 20 carbon atoms.
A chain or branched alkyl group, and a preferred simple prime number is 3 to 1
2. Particularly preferred alkyl groups are linear or branched
Butyl group, pentyl group, hexyl group, octyl group,
A nonyl group and a dodecyl group. R^TenIs an alkenyl group
When represented, they may be straight-chain or branched and have 1 to 1 carbon atoms.
20 and a preferred number of carbon atoms is 3-16. Especially
Preferred alkenyl groups are allyl, pentenyl,
A xenyl group. R^TenRepresents an aryl group,
A phenyl group and a substituted phenyl group;
, Preferably 1-2 carbon atoms, more preferably 1 carbon atom
1-20 linear or branched alkyl groups,
The prime number is 3 to 12. Particularly preferred aryl groups
Is a 4-nonylphenyl group, a 4-octylphenyl group,
4-dodecylphenyl group, 2,5-di-t-amylfe
And a 2,5-di-t-octylphenyl group.
R ^TenWhen represents an alkylcarbonyl group, preferred
A kill carbonyl group has a single prime number of the alkyl group of 4-1.
6 is preferred, especially octylcarbonyl group, nonylka
Rubonyl group, dodecylcarbonyl group, amylcarbonyl
Groups are preferred. The sum of p and q is 1 or more, and r is
It represents 0 or an integer of 1 to 50. V is the case where r is 0
Represents a phonic acid group and a phosphoric acid group. When r is 1 or more,
Phonic acid group, phosphoric acid group, sulfonic acid ester group, phosphoric acid group
Represents a stele group. R^TenIs particularly preferred when is an aryl group
Most preferably, p + q is in the range of 2 to 30. Ma
In addition, r is most preferably 0 to 10.

Specific examples of the anionic surfactant represented by the general formula (IV) are shown below, but the anionic surfactant which can be used in the present invention is not limited thereto.

[0054]

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[0055]

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The amount of these compounds to be added to the washing water or the stabilizing bath is approximately 0.002 g to 1.0 g / l, preferably about 0.005 g to 0.2 g / l. These compounds can be easily obtained as commercial products.

It is advantageous that the 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-component constitution. If you do n’t want to keep it,
The components may be separated into two or more liquids to form a two- or three-part developer composition (usually international standard ISO 59
89, it is referred to as a 1, 2, 3 part configuration, etc.), and dividing into parts does not lose the effects and features of the invention. The developer composition of the present invention preferably has a one-part structure.

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. Typically, liquid developer compositions are 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 are Requirement 4
Also satisfies.

In view of the requirements 2 and 4, the developer composition is filled in an oxygen and carbon dioxide gas barrier container and stored.
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, the permeation rate of carbon dioxide through the vessel wall is
A container made of a material of ⁷ × 10 ⁻⁷ cm ³ / cm ² / sec / atm or less has been considered desirable. For this reason, material restrictions were great.

In view of gas impermeability, liquid developing 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. Formula (I) or (I
As described above, the color developing solution containing the compound of the formula (I) has the advantage of being less susceptible to air oxidation, as described above, so that it can be stored practically without using such a composite material container. It has been found that stability is obtained. The material of the plastic container suitable for the present invention may have an air permeation rate eight times higher than the above-mentioned value, and a single-piece plastic that satisfies the above requirements 2 and 4 can be selected. It is a characteristic advantage of the present invention that requirement 3 can be easily satisfied by using a single product. A particularly great advantage is that polyethylene, which was previously unusable due to insufficient air barrier properties while being easy to recycle, has a protective property that can be practically used as a container in the liquid developer of the present invention. .

Preferred container materials for the color developing agent of the present invention include polyester resins, acrylic resins, ABS resins, epoxy resins, polyamide resins such as nylon, polyurethane resins, polystyrene resins, polycarbonate resins, PVA, and poly (vinyl alcohol). Vinyl chloride, polyvinylidene chloride,
It is a polyethylene resin, and among them, a container composed of a polyester resin such as polyethylene terephthalate and polyethylene naphthalate and a polyolefin resin such as polyethylene and polypropylene as a single material is preferable. Among them, polyethylene is preferable, and among polyethylene, a high-density type, so-called HDPE, is preferable as the container material.

The polyethylene used for the container of the concentrated liquid developer composition of the present invention may contain 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. May be. 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 plastic bottle can be molded by injection, hollow (blow), injection blow, injection → hollow, compressed air, extrusion, vacuum, etc., and a molding method according to the purpose is adopted. The most commonly used is hollow molding. The bottles according to the invention are often made by injection molding of the cap and of the bottle by hollow molding.
In the case where the strength is obtained by stretching such as an ET bottle, it is manufactured by injection → hollow molding.

The shape and structure of the container for filling the concentrated liquid developer composition of the present invention can be arbitrarily designed according to the purpose.
Nos. 7046 and 63-50839, JP-A-1-235
950, JP-A-63-45555, etc .;
Nos. 61 and 62-134626 and the like with flexible partition walls can also be used.

When filling the container with the developer composition, in order to further enhance the safety against air oxidation, the space above the container should be filled as much as possible to minimize the upper space, or the upper space should be filled with nitrogen. It is preferable to perform the filling so as to eliminate the contact with the oxygen in the air, but the present invention is not necessarily limited to such a filling method.

When the developer composition of the present invention is used in an automatic developing machine, a container filled with the developer composition is mounted on the developing machine, and the composition inside the container is placed in a developing replenishing tank or directly in a developing tank. After the injection, the container is washed with a certain amount of water, and the water used for washing is introduced into a replenishing tank, used as water for preparing a replenishing solution, and developed using the replenishing solution thus obtained. The operation method is a method that effectively utilizes the advantages of the present invention. 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. This replenisher preparation method makes it possible to effectively use the washing water and reduce the amount of wastewater discharged from the developer.

Accordingly, a particularly advantageous embodiment of the present invention is a development processing system which is simple and has high environmental and operational safety by incorporating the above-mentioned developer composition. 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, the contents are transferred into a developing replenishing tank, and the inside of the container is sprayed.
After washing, the chemical components adhering to the vessel wall are washed away, and the water used for washing can be subjected to development processing of the silver halide color photographic 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 in which the lid of the container is automatically opened and the fluid content is smoothly discharged. In addition, Japanese Unexamined Patent Publication No.
According to the methods disclosed in Japanese Patent Application No. 82988, JP-A-8-220722 and the like, the inside of the container can be cleaned without the need for manual operation by spraying the washing water, and the container can be handled cleanly and the recycling of the waste container is simplified. 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, as one embodiment of the present invention, the structure of a bottle 300 as a container for a photographic processing agent suitable for the processing method of the system incorporating a processing agent composition described above will be described with reference to FIG. However, the container for the composition of the present invention is not limited to this bottle. As shown in FIG. 1, the bottle 300 includes a container body 302. The container main body 302 is formed in a hollow box shape by a resin material. The upper end of the container body 302 has a tapered shape whose diameter is gradually reduced, and a cylindrical neck portion 306 formed with a male screw 304 is formed on the outer peripheral portion. This neck 30
The upper end of 6 is open, and the above-mentioned replenisher can be taken in and out through this opening. In addition, a polyethylene (LDPE) sheet member 308
Is arranged. The sheet 308 member is provided with a cross-shaped thin notch, which is designed to be easily broken by a constricted hole nozzle for pouring out the contents of the bottle.

The bottle 300 has a cap 310 as a fixing member. This cap 310
It is formed in a cylindrical shape with a bottom opening toward the neck portion 306, and has a male screw 30 formed on the neck portion 306 on its inner peripheral portion.
The female screw 318 corresponding to 4 is cut and can be screwed to the neck 306. By screwing to the neck 306, the polyethylene sheet 308 can be pressed by the bottom 312 of the cap 310 and the polyethylene sheet 308 can be fixed to the neck 306. Further, a circular opening 314 is formed in the bottom 312 of the cap 310 so that the sheet 308 can be perforated with the cap 310 fitted.

This bottle is mounted upside down in the replenishing section of the developing machine, and the constricted nozzle breaks the polyethylene sheet member 308 from below and puts the contents into the replenishing tank. After the injection, a fixed amount of washing water is sprayed from the constricted nozzle to wash the inside of the bottle. The washing water is also injected into the replenishing tank, and the developing composition is used as dilution water to prepare a replenisher (FIG. 2). reference).

Next, the developer compositions of the present invention other than the compounds of the general formulas (III) and (IV) which are effective when used in combination with the aforementioned general formulas (I) and (II) 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. Recently, couplers have been added to black-and-white photographic materials so as to develop a black color.
Although some black and white images are formed using a developing solution, the color developing solution of the present invention is also applicable to processing of this type of photosensitive material.

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

Of 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 processing composition of the present invention may contain a small amount of sulfite ion or may not substantially contain a sulfite ion depending on the kind 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. Further, as described above, hydroxylamine is not contained in the constituent components of the composition, or even if it is contained, it is an addition amount having no photographic effect and substantially not contained. If hydroxylamine is contained, it has a function as a preservative of the developer as described above, but at the same time, it itself has silver developing activity, which may affect photographic characteristics.

The thickening agent composition of the present invention preferably contains an inorganic preservative such as the above-mentioned hydroxylamine derivatives and sulfite ions, and an organic preservative. The organic preservative refers to any organic compound that reduces 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, among which, among the above-mentioned hydroxylamine derivatives, hydroxamic acids, hydrazides, phenols, α-hydroxyketones, α-aminoketone , Sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines and the like are particularly effective organic preservatives. These are disclosed in JP-A-63-4235,
63-30845, 63-21647, 63-44655, 63-53551
Nos. 63-43140, 63-56654, 63-58346, 63
-43138, 63-146041, 63-44657, 63-44656
No. 3,615,503, U.S. Pat.
52-143020 and JP-B-48-30496.

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, it is preferable to add alkanolamines such as triethanolamine and triisopropanolamine, substituted or unsubstituted dialkylhydroxylamine such as disulfoethylhydroxylamine and diethylhydroxylamine, or aromatic polyhydroxy compounds. Among the organic preservatives, the details of the hydroxylamine derivative are described in JP-A-1-97953, JP-A-1-86939, JP-A-1-186940,
No. 1-187557, and the like. In particular, the use of a hydroxylamine derivative and an amine in combination is more preferable in terms of improving the stability of the color developing solution and the stability during continuous processing. Examples of the amines include:
Cyclic amines as described in JP-A-63-239447, amines as described in JP-A-63-128340, and others described in JP-A-1-186939 and JP-A-187557. Examples include amines as described.

The thickening agent composition of the present invention may optionally contain chlorine ions, for example, for color paper. A color developing solution (especially a developing solution for color printing materials) usually contains chloride ions of 3.5 × 10 ^{-2 to} 1.5 ×.
Although it is often contained at 10 ^-1 mol / l, chloride ions are usually released to a developer as a by-product of development, and therefore, it is often unnecessary to add them to a replenisher. In compositions for color paper, etc., in the replenisher so that the chloride ion concentration in the developing tank when the running equilibrium composition is reached is the above-mentioned concentration level, and therefore in the processing agent composition from which it is based. The chloride ion amount is set. Chloride ion concentration
If it is more than 1.5 × 10 ⁻¹ mol / l, it has a disadvantage of delaying the development, and the speed and color density are unfavorably deteriorated. On the other hand, if it is less than 3.5 × 10 ^-2 mol / l, it is often not preferable for preventing fog.

Regarding the treating agent composition, the content of bromine ions is the same as that of chlorine ions. The bromine ion in the color developing solution is 1 to 5 in the processing of the photographic material.
It is preferably about ^10-3 mol / l, and in the processing of print material, it is preferably ^1.010-3 mol / l or less. If necessary, bromine ions may be added to the treatment composition so that the bromine ion concentration falls within this range. When the target photosensitive material is obtained from a silver iodobromide emulsion such as a color negative film or a color reversal film, the situation is the same for iodine ions, but usually iodine ions are released from the photosensitive material. As a result, the iodine ion concentration becomes about 0.5 to 10 mg per liter of the developing solution, so that the iodine ion is usually not contained in the developing composition or the replenisher made therefrom. When included in the treating agent composition, as the chloride ion supplying material, sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and the like, of which sodium chloride is preferred , Potassium chloride. As bromine ion supply substances, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide,
Cerium bromide and thallium bromide are mentioned, and potassium bromide and sodium bromide are preferred.
Sodium iodide and potassium iodide are used as iodine ion supply materials.

When the photosensitive material to be developed is color photographic paper, it is important that the white background of the screen is white, so that it is important that the white background is apparently finished with a fluorescent whitening agent. Depending on the nature of the fluorescent whitening agent, the fluorescent whitening agent is contained in the light-sensitive material. In some cases, the fluorescent whitening agent permeates the light-sensitive material from the processing solution during the development processing. In that case, an appropriate treatment liquid to be added is selected according to the properties of the fluorescent brightening agent so that a high whitening effect is obtained. Therefore, it may be added to a color developing solution having a high pH. Generally, stilbene-based fluorescent brighteners are frequently used, and among them, di (triazylamino)
Stilbene-based and 4,4'-diamino-2,2'-disulfostilbene-based optical brighteners are preferred. In particular, a preferred stilbene-based optical brightener is 4,4'-ditriazinylamino-2,2'-disulfostilbene, but the present invention is not limited thereto.

The stilbene-based fluorescent whitening agent used is a known one, and can be easily obtained or can be easily synthesized by a known method. This stilbene-based fluorescent whitening agent can be added to any of a desilvering solution and a photosensitive material in addition to a color developing solution. When it is contained in a color developing solution, its preferable concentration is 1 × 10 ^{−4 to} 5 ×.
10 ^-2 mol / l, more preferably 2 × 10
⁻⁴ to 1 × 10 ⁻² mol / l. The amount of the processing agent composition of the present invention is determined so that development in use contains the optical brightener at this concentration level.

The concentrated liquid processing composition of the present invention preferably has a pH of 9.5 to 13.5, but a color developer prepared therefrom has a pH of 9.0 to 12.2, more preferably 9 to 12.2. 0.9 to 11.2, and may further contain other known compounds of a developer component. In order to maintain the above pH, it is preferable to use various buffers.
Examples of the buffer include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4- Dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-
1,3-propanediol salt, valine salt, proline salt,
Trishydroxyaminomethane salt, lysine salt and the like can be used. Especially carbonates, phosphates, tetraborate,
Hydroxybenzoate has excellent buffering ability in the high pH range of pH 9.0 or higher, and has the advantage of being inexpensive without any adverse effect on photographic performance (such as fog) even when added to a color developer. It is particularly preferred to use these buffers.
The concentration is added to the composition so as to be 0.01 to 2 mol, preferably 0.1 to 0.5 mol per liter of the developing replenisher.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, and sodium borate. , Potassium borate, sodium tetraborate (borax),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
Potassium 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 so that the concentration in the diluted color developing replenisher is 0.1 mol / L or more, particularly 0.1 mol / L to 0.4 mol / L.

The processing composition of the present invention may contain other color developing solution components, for example, various chelating agents which are calcium or magnesium precipitation inhibitors or color developing solution stability improvers. it can. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid, transsilohexanediaminetetraacetic acid, , 2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediaminedisuccinic acid (SS
), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetate, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid, 1,2-dihydroxybenzene-4,6-disulfonic acid, and the like. These chelating agents may be used 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 so as to be about 0.1 g to 10 g per liter.

The processing composition of the present invention may optionally contain any 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. when the photosensitive material to be developed is a color print material.
And more preferably 38 to 45 ° C. The development processing time is 5 to 90 seconds, preferably 15 to 60 seconds.
Seconds. Although it is preferable that the replenishment amount is small, the photosensitive material 1
^{20 to} 600 ml per m ² is suitable, preferably 30 to 120 ml, particularly preferably 15 to 60 ml.
Milliliters. On the other hand, color negative, color river
In the case of monkey film color development, the development temperature is 20
~ 55 ° C, preferably 30-55 ° C,
More preferably, it is 38 to 45 ° C. The development processing time is 20 seconds to 6 minutes, preferably 30 to 200 seconds. Also, in the case of a color negative, the time is preferably 1 to 4 minutes. The replenishment amount is preferably small, but it is suitably ^{20 to} 1000 ml per m ^{2 of} the light-sensitive material, and preferably 50 to 1000 ml.
~ 600 ml, particularly preferably 100-400
Milliliters. This replenishing amount is the total amount of the replenisher composition and water when the concentrated replenisher composition and water are separately added to the developing tank.

There are several methods for producing the developer composition of the present invention. 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.

In practicing the present invention, a desilvering step is carried out after a developing step using a color developing solution prepared 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,
Iminodiacetic acid, glycol ether diamine tetraacetic acid, and the like. 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, β-alanine diacetate, ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because their iron (III) complex salts have good photographic properties. These ferric ion complex salts may be used in the form of a complex salt, or a ferric salt such as ferric sulfate,
A ferric ion complex salt may be formed in a solution using ferric chloride, ferric nitrate, ammonium ferric sulfate, ferric phosphate and a chelating agent such as aminopolycarboxylic acid. In addition, the chelating agent may be used in excess of forming a ferric ion complex salt. Among the iron complexes, iron aminopolycarboxylate complexes are preferred, and the amount added is 0.01 to
1.0 mol / liter, preferably 0.05 to 0.50
Mol / l, more preferably 0.10 to 0.50 mol / l, even more preferably 0.15 to 0.40 mol / l.

The bleaching time is generally 30 seconds to 6 minutes and 30 seconds, preferably 1 to 4 minutes and 30 seconds, particularly preferably 30 seconds to 2 minutes. Various known organic acids (eg, glycolic acid, succinic acid, maleic acid, malonic acid, citric acid, sulfosuccinic acid, etc.) and organic bases (eg, imidazole, dimethylimidazole, etc.) may be used in the bleaching solution, bleach-fixing solution or fixing solution. Or the general formula (Aa) described in JP-A-9-212819, including 2-picolinic acid.
It is preferable to contain a compound represented by the general formula (Bb) described in the same publication, such as a compound represented by the formula (I) or cordic acid. The addition amount of these compounds is preferably from 0.005 to 3.0 mol, more preferably from 0.05 to 1.5 mol, per liter of the treatment liquid.

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, 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 other various 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 the water in the tank causes a problem that bacteria proliferate and the generated suspended matter adheres 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 for inactivating remaining magenta couplers to prevent fading of dyes and formation of stains, 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, a fluorescent whitening agent and a hardening agent may 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 liquid is also used as a washing liquid or a stabilizing liquid 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.

The photosensitive material that can be used in the present invention will be described. As the silver halide used in the light-sensitive material according to the present invention, silver chloride, silver bromide, silver (iodo) chlorobromide, silver iodobromide and the like can be used. It is preferable to use a silver chlorobromide or silver chloride emulsion containing substantially no silver and having a silver chloride content of 98 mol% or more. The phrase "substantially free of silver iodide" means that the silver iodide content is preferably 0.1 mol% or less, more preferably 0.0 mol% or less.
It is preferably at most 1 mol%, and particularly preferably contains no silver iodide at all. For a color light-sensitive 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. The light-sensitive material according to the present invention is coated with a hydrophilic colloid layer in order to improve the sharpness of an image and the like, as described in EP-A-0,337,490 A2, Nos. 27-76.
A dye (e.g., oxonol-based dye) which can be decolorized by treatment described on page 3 is added so that the optical reflection density at 680 nm of the photosensitive material becomes 0.70 or more, or a water-resistant resin layer of a support is used. 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with dihydric or tetrahydric alcohols (for example, trimethylolethane) or the like.
It is preferable to include them.

The light-sensitive material according to the present invention is provided with a protective agent such as that described in JP-A-63-271247 in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferred to add a fungicide. In the case of a photographic film photosensitive material, cellulose triacetate, poly (ethylene terephthalate) or poly (ethylene naphthalate) is used as a support for the photosensitive material according to the present invention. Is a paper (resin-coated paper) laminated with white pigment-kneaded polyethylene,
A support such as a poly (ethylene terephthalate) film kneaded with a white pigment for display is used.

The light-sensitive material according to the present invention may be exposed to visible light or, depending on the purpose, may be exposed to other radiation such as 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.

[0105]

[Table 1]

Further, as a cyan coupler, JP-A-2-33
No. 144, EP 0,333,185 A2 and JP-A-64-32260 can also be used. Cyan, magenta or yellow couplers can be loaded in the presence (or absence) of high boiling organic solvents as described in the preceding table (see, for example, U.S. Pat. No. 4,203,716).
It is preferable to emulsify or disperse in a hydrophilic colloid aqueous solution by dissolving with a water-insoluble and organic solvent-soluble polymer. Preferred water-insoluble and organic solvent-soluble polymers are described in US Pat. No. 4,857,449.
Nos. 7 to 15 of the specification and International Publication WO88 / 00
No. 723, pages 12 to 30 of the homopolymer or copolymer. In particular, a methacrylate or acrylamide polymer is particularly preferred in terms of color image stability and the like.

The light-sensitive material according to the present invention includes European Patent E
It is preferable to use a color image storability improving compound as described in P0,277,589A2 in combination with a pyrazoloazole coupler, a pyrrolotriazole coupler, or an acylacetamide type yellow coupler.

Examples of the cyan coupler include phenol couplers and naphthol couplers described in the publicly known documents in the above table, as well as JP-A-2-33144.
JP, EP 0333185 A2, JP-A-6
4-32260, European Patent EP 0 456 226 A1, European Patent EP 0 484 909, European Patent EP
Preference is given to using the cyan couplers described in US Pat. No. 4,488,248 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 No. 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 diffusibility 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 formula (I) of 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).

The following are preferred as additives other than the coupler. 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 on page 17 of JP-A-1-214845, US Pat. No. 4,618,573
(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:

Dyes: 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.

The binder used for the magnetic particles may be a thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, a natural material described in JP-A-4-219569. Combinations (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. Tg of the above resin is −40 ° C. to 300 ° C.,
The weight average molecular weight is from 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. As the isocyanate-based crosslinking agent, isocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate,
Reaction products of these isocyanates with polyalcohols (for example, a reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane), and polyisocyanates formed by condensation of these isocyanates are mentioned. No. 6-59357.

As a method for dispersing the above-mentioned magnetic substance in the binder, a kneader, a pin type mill, an annular type mill and the like are preferably used, as in the method described in JP-A-6-35092. JP-A-5-088283
And other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to
3 μm. The weight ratio of the magnetic particles to the binder is preferably 0.5: 100 to 60: 100, and more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably 0.01 to ³ g / m ² .
2 g / m ^2, more preferably from 0.02 to 0.5 g / m ^2. The transmission yellow density of the magnetic recording layer is 0.01 to 0.5.
50 is preferable, and 0.03 to 0.20 is more preferable.
0.04 to 0.15 is particularly preferred. The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. As a method for applying the magnetic recording layer, air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion, etc. can be used. The coating solution described in 341436 or the like is preferable.

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 below.
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.

Next, in the present invention, it is preferable to perform a surface treatment in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, preferred are an ultraviolet irradiation treatment, a flame treatment, a corona treatment, and a glow treatment. Next, the undercoating method is described.
It may be more than layers. As a binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, including a copolymer starting from a monomer selected from maleic anhydride, as a starting material,
Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcinol and p-chlorophenol. In the undercoat layer, gelatin hardeners such as chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, and active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine) And the like, epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

In the present invention, an antistatic agent is preferably used. Examples of such antistatic agents include polymers containing carboxylic acid and carboxylate and sulfonate, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Zn
O, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , Si
A particle size of at least one selected from O ₂ , MgO, BaO, MoO ₃ and V ₂ O ₅ having a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. .00
Fine particles of crystalline metal oxides or composite oxides thereof (Sb, P, B, In, S, Si, C, etc.), furthermore, sol-like metal oxides or composite oxides thereof Particles. 5 to 5%
500 mg / m ² is preferred, particularly preferably 10 to 350 mg / m ²
a m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably from 1/300 to 100/1, more preferably from 1/100 to 100/5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25 ° C., 60% PH). In this evaluation, even when the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level. Examples of the slipping agent usable in the present invention include polyorganosiloxane, higher fatty acid amide, higher fatty acid metal salt, ester of higher fatty acid and higher alcohol, and polyorganosiloxane as polydimethylsiloxane, polydiethylsiloxane, polystyrylmethyl. Siloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is also preferably narrow. It is preferable that 90% or more of the total number of particles is contained between 0.9 and 1.1 times the average particle size. . It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm) ), Polystyrene particles (0.25
μm) and colloidal silica (0.03 μm).

Next, the film cartridge used in the present invention will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone of the present invention may contain various antistatic agents, carbon black, metal oxide particles, nonions, anions,
Cationic and betaine-based surfactants or polymers can be preferably used. These anti-charged patrones are disclosed in JP-A Nos. 1-312537 and 1-31253.
8. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be 135 size at present,
To reduce the size of the camera, it is also effective to reduce the diameter of the current 135-size 25 mm cartridge to 22 mm or less.
The volume of the patrone case is 30 cm ³ or less, preferably 2
It is preferred to be 5 cm ³ or less. Weight of plastic used for patrone and patrone case is 5g
~ 15 g is preferred.

Further, a patrone used in the present invention to feed a film by rotating a spool may be used. Further, a structure may be employed in which the leading end of the film is accommodated in the cartridge body, and the leading end of the film is sent out from the port of the cartridge by rotating the spool shaft in the film sending direction. These are US 4,834,306 and 5,2
26, 613. The photographic film used in the present invention may be a so-called raw film before development,
A photographic film that has been processed may be used. Further, the raw film and the developed photographic film may be stored in the same new patrone, or may be different patrones.

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.

[0131]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 In Example 1, an example is shown in which photographic performance was examined when four types of color negative film samples having different constitution materials and sensitivities of photosensitive materials were processed with the same development processing formula. (Photosensitive Material) (1) Sample 101 On a cellulose triacetate film support undercoated,
Samples 101, which are multilayer color photosensitive materials, were prepared by applying each layer having the composition shown below in multiple layers. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.10 Silver Iodobromide Emulsion P Silver 0.03 Gelatin 0.44 ExC-1 0.004 ExC-3 0.006 Cpd-20 0.001 HBS-1 0.008 HBS-2 0.004 Second layer (second antihalation layer) Black colloidal silver Silver 0.117 Gelatin 0.691 ExM-1 0.050 ExF-1 2.0 × 10 ^{− 3} HBS-1 0.074 Solid disperse dye ExF-2 0.015 Solid disperse dye ExF-3 0.020

Third layer (intermediate layer) ExC-2 0.045 polyethyl acrylate latex 0.20 gelatin 0.515 fourth layer (low-sensitivity red-sensitive emulsion layer) silver iodobromide emulsion A silver 0.20 iodine odor Silver halide emulsion B Silver 0.40 ExS-1 2.7 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 2.8 × 10 ^-4 ExS-4 2.7 × 10 ^-4 ExC- 1 0.18 ExC-3 0.036 ExC-4 0.12 ExC-5 0.018 ExC-6 0.003 Cpd-2 0.025 HBS-1 0.17 Gelatin 1.26

Fifth Layer (Medium Speed Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.20 Silver Iodobromide Emulsion D Silver 0.60 ExS-1 2.2 × 10 ^-4 ExS-2 8 × 10 ^-5 ExS-3 2.3 × 10 ^-4 ExS-4 2.2 × 10 ^-4 ExC-1 0.18 ExC-2 0.040 ExC-3 0.042 ExC-4 0.12 ExC-50 .015 ExC-6 0.010 Cpd-2 0.055 Cpd-4 0.030 HBS-1 0.15 Gelatin 1.04

Sixth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion E 1.17 ExS-1 4.0 × 10 ^-4 ExS-2 1 × 10 ^-5 ExS-3 2.1 × 10 ^-4 ExC-1 0.08 ExC-3 0.09 ExC-6 0.037 ExC-7 0.010 Cpd-2 0.046 Cpd-4 0.03 HBS-1 0.22 HBS-2 0.10 Gelatin 1.14

Seventh layer (intermediate layer) Cpd-1 0.094 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 0.89 Eighth layer (to red sensitive layer) Layer giving multilayer effect) Silver iodobromide emulsion F silver 0.40 Silver iodobromide emulsion G silver 0.90 ExS-6 2.0 × 10 ^-4 ExS-10 8.4 × 10 ^-4 Cpd-40 0.030 ExM-2 0.23 ExM-3 0.049 ExY-1 0.054 HBS-1 0.20 HBS-3 0.007 Gelatin 1.29

Ninth Layer (Low-Sensitivity Green-Sensitive Emulsion Layer) Silver Iodobromide Emulsion H 0.16 ExS-4 2.4 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 6.5 × 10 ^-4 ExM-2 0.13 ExM-3 0.047 HBS-1 0.10 HBS-3 0.04 Gelatin 0.38 10th layer (Medium speed green-sensitive emulsion layer) Silver iodobromide emulsion H silver 0.08 silver iodobromide emulsion I silver 0.21 silver iodobromide emulsion J silver 0.08 ExS-4 3.3 × 10 ^-5 ExS-5 3.0 × 10 ^-5 ExS-6 1.4 × 10 ^-4 ExS-7 7.2 × 10 ^-4 ExS-8 1.6 × 10 ^-4 ExC-6 0.015 ExM-2 0.093 ExM-3 0.037 ExM-4 0.045 ExY-5 0.004 HBS-1 0.08 HBS-3 4.0 × 10 ^-3 gelatin 0.41

Eleventh layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion K silver 1.10 ExS-4 4.3 × 10 ^-5 ExS-7 1.0 × 10 ^-4 ExS-8 4.7 × 10 ^-4 ExC-6 0.005 ExM-3 0.070 ExM-4 0.028 ExM-5 0.026 Cpd-3 0.010 Cpd-4 0.050 HBS-1 0.23 Polyethyl acrylate latex 0.15 gelatin 1.18

Twelfth Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.047 Cpd-1 0.18 Solid Disperse Dye ExF-5 0.060 Solid Disperse Dye ExF-6 0.060 Oil-soluble Dye ExF-7 010 HBS-1 0.094 Gelatin 1.204 13th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L silver 0.15 Silver iodobromide emulsion M silver 0.20 Silver iodobromide emulsion N silver 0 .15 ExS-9 8.0 × 10 ^-4 ExC-1 0.067 ExC-8 0.013 ExY-1 0.047 ExY-2 0.50 ExY-3 0.20 ExY-4 0.010 Cpd- 2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.23 Gelatin 1.45

Fourteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion O silver 0.96 ExS-9 3.6 × 10 ^-4 ExC-1 0.013 ExY-2 0.42 ExY-30 .05 ExY-6 0.104 Cpd-2 0.07 Cpd-3 1.0 × 10 ^-3 HBS-1 0.14 Gelatin 1.20

Fifteenth Layer (First Protective Layer) Silver Iodobromide Emulsion Q Silver 0.10 UV-1 0.12 UV-2 0.10 UV-3 0.16 UV-4 0.025 HBS-10 .10 HBS-4 4.0 × 10 ^-2 gelatin 2.0 Sixteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (Diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 gelatin 0.75

Further, in order to improve the storability, processing property, pressure resistance, fungicidal / bactericidal property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B -6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
Contains palladium, iridium and rhodium salts.

Table 2 below shows the AgI content, grain size, and the like of the emulsions represented by the above-mentioned abbreviations.

[0145]

[Table 2]

In Table 2, (1) Emulsions L to O were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to O were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Have been. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of 0.5 g of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) were put into a 700 ml pot mill. , Dye ExF-
2 and 5.0 g of zirconium oxide beads (diameter 1 mm)
500 ml was added and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After the dispersion, the contents were taken out, added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles is 0.4
It was 4 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameter of the fine dye particles is 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
m. ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of EP-A-549,489A. The average particle size was 0.06 μm.

The compounds used for forming each of the above layers are as shown below.

[0150]

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[0164]

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[0166]

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(2) Sample 102 The photosensitive material of Example 1 of JP-A-9-166854 was prepared and used as Sample 102. (3) Sample 103 The photosensitive material of Example 3 of JP-A-9-43792 was prepared and used as Sample 103. (4) Sample 104 The photosensitive material of Example 1 of JP-A-7-152133 was prepared to be Sample 104.

(Exposure) Each sample film was subjected to ISO5800
(Method for measuring sensitivity of color negative film) Standard C light source and neutral color continuous light wedge (density gradient 0.4 △ D /
sensitometric exposure was carried out through a cm, density range of 0.02 to 4.8). In the following development processing, photographic characteristics (sensitivity, gradation and fog) were obtained using this exposed sample.

(Color Developer Composition) A color developer composition having the following composition was prepared and filled in a plastic bottle (HDPE) containing 1300 ml. At that time, the head space was 26 cc. Diethylenetriaminepentaacetic acid 9.0 4, Sodium 5-, 5-dihydroxybenzene-1,3-disulfonate 0.8 Sodium sulfite 14.0 Potassium carbonate 100.0 Compounds of general formulas (I) to (IV) and comparative examples (see Table 3) 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 15.0 Add water and add 1.0 liter pH (potassium hydroxide) 10.25

(Development treatment) The above-described color developer bottle for color negative which was not heated and aged (also referred to as fresh, and described as Fr in Tables 3 and 5) was heated at 50 ° C. for 2 days and forcibly aged. (Hereinafter referred to as forced aging) were diluted 3.3 times with water, and potassium bromide and potassium iodide were added to prepare the following color developing solution, which was used in a small experimental developing machine. Development processing was performed according to the following color negative development processing specifications.

[0171]

The composition of the processing liquid is shown below. (Color developing solution) Tank solution (g) The above developer composition was diluted 3.3 times, and the following amounts (per liter) of potassium bromide and potassium iodide were added to adjust the pH. Potassium bromide 1.3 Potassium iodide 1.3 mg pH (adjusted with potassium hydroxide and sulfuric acid) 10.05

(Bleaching solution) Tank solution (g) Ferric ammonium 1,3-diaminopropanetetraacetate monohydrate 118 Ammonium bromide 50 Ammonium nitrate 14 Succinic acid 40 Imidazole 20 Maleic acid 10 Add water and add 1.0 L pH [ Prepared with aqueous ammonia) 4.4

(Fixing solution) Tank solution (g) Ammonium metabisulfite (50% solution) 25 Aqueous ammonium thiosulfate solution (700 g / L) 280 mL Imidazole 7 Ethylenediaminetetraacetic acid 15 2- (N, N-dimethyl) ethylaminomercapto Add tetrazole 1 water and add 1.0 liter pH (prepared with ammonia water and acetic acid) 7.4

(Washing water) Tap water is used.

(Stabilizing solution) Tank solution (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1,2,4- Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1,2-benzoisothiazolin-3-one 0.10 1.0 liter with water pH 8.5

[0177]

[Table 3]

(Tests and Test Results)
The concentration was measured using a densitometer conforming to the regulations of O5-2 and 5-3. As the representative value of the photographic characteristics, the maximum density (Dmax) of the sample due to the red filter light (status A)
R), the difference between the maximum concentration of the developer containing hydroxylamine (DmaxR) and the freshness of green filter light (status A) sensitivity and forced aging determined according to the sensitivity measurement method of ISO5800 as a representative value of storage stability. And the results are shown in Table 3. In addition, the concentrations of the color developing agent and sodium sulfite of the developing replenisher that had been freshly and forcibly aged were analyzed. Under the conditions of the present invention, it can be seen from the difference in color density that each photosensitive material behaves the same as the developer containing hydroxylamine. In addition, there was little change in sensitivity due to forced aging, indicating that storage stability was excellent. In addition, the analytical values supported this.

Example-2 In Example-2, the above four kinds of photosensitive material samples 10
Using Nos. 1 to 104, 1, 2, 4,
6 shows the results of a running test performed by selecting No. 6. (Development processing) Development processing was carried out using the following color negative developing machine and processing specifications. As a processing machine, an experimental developing machine which was modified from an automatic developing machine FP-560B manufactured by Fuji Photo Film Co., Ltd. and used an automatic opening and automatic blending system was used. The contents of the remodeling are as follows: a replenisher preparation section is provided at the upper part of the developing machine, and three 1300 ml plastic bottles described in the text of the specification containing a preparation composition of a developer, a bleaching agent, and a fixing agent respectively in this section. (HDPE) 300 are placed side by side with the mouth of the bottle facing down, and the door of the mixing section is closed.
The plastic sheet 308 acting as a bottle lid with the piercing nozzle 188 moving upward from below as shown in FIG.
And drain the internal composition solution into the refill tank. Thereafter, a certain amount of washing water is jetted out from the nozzle hole 214 of the piercing nozzle to wash the inside of the bottle, and the washing water also flows down to the replenishment tank and is used as dilution water for preparing the replenisher. It is a method. The development processing was performed using the following processing steps and processing solutions.

(Processing step) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 20 ml 17 liter Bleaching 50 seconds 38.0 ° C 5 ml 5 liters Fixing (1) 50 seconds 38.0 ° C -5 Liter Settling (2) 50 seconds 38.0 ° C 8 ml 5 liter Washing water 30 seconds 38.0 ° C 17 ml 3.5 liter Stability (1) 20 seconds 38.0 ° C-3 liter Stability (2) 20 seconds 38.0 ° C 15 ml 3 liter Dry Drying 1 minute 30 seconds 60 ° C * Replenishment amount is 35 mm width of photosensitive material 1.1 m (equivalent to 24 Ex. 1 bottle) Stabilizing solution is countercurrent method from (2) to (1). All were introduced into fixing (2). The fixing solution is also connected from (2) to (1) by a countercurrent pipe. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 2.5 ml and 2.0 ml, respectively, per 1.1 mm width of 35 mm photosensitive material. , 2.0 ml.
The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.7 4.1 4,5-Dihydroxybenzene-1,3-disulfonic acid sodium 0.42 0.64 Sodium sulfite 4.8 7.3 Potassium carbonate 30.0 47.0 Ethylene urea 3.0 4.7 Bromide Potassium 1.3-Potassium iodide 1.3 mg-Hydroxylamine sulfate (described in Table 4) (described in Table 4) 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.9 Compound of general formula (I) or (II) (See Table 4) (See Table 4) 1.0 liter 1.0 liter pH by adding water (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.25

(Bleaching solution) Tank solution (g) Replenisher (g) Ferric ammonium 1,3-diaminopropanetetraacetate monohydrate 118 180 Ammonium bromide 80 115 Ammonium nitrate 14 21 Succinic acid 40 60 Imidazole 20 30 Maleic Acid 10 15 1.0 liter with water 1.0 liter pH (prepared with aqueous ammonia) 4.4 4.0

(Fixing solution) Tank solution (g) Replenisher (g) Ammonium metabisulfite (50% solution) 25 80 Aqueous ammonium thiosulfate (700 g / L) 280 mL 840 mL Imidazole 7 20 2- (N, N- Dimethyl) ethylaminomercaptotetrazole 0.8 2.0 Ethylenediaminetetraacetic acid 15 45 Add water 1.0 liter 1.0 liter pH (prepared with aqueous ammonia and acetic acid) 7.4 7.45

(Stabilizing solution) Common to tank solution and replenisher (unit g) Sodium p-toluenesulfinate 0.03 p-nonylphenoxypolyglycidol (glycidol average polymerization degree 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1,2,4 -Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1,2-benzoisothiazolin-3-one 0.10 1.0 liter with water pH 8.5

[0185] 4. Tests and Test Results The results are shown in Table 4. Table 4 shows that the running tests showed that Samples 2 and 6 of the present invention performed the same photographic behavior as Sample 1 containing hydroxylamine, and that the photographic performance was stable. Also, in the comparison between the present invention,
In Sample 6, the difference between the light-sensitive materials became smaller, and the effect of the combined use of the compounds of the general formulas (I) and (II) was observed.

[0186]

[Table 4]

Example 3 (Color Negative Film) The following experiment was carried out using the sample 101 shown in Example 1. (Color developer composition) Developer samples 1 to 10 in the same bottle (HDPE) used in Example 1 were used.
A polyethylene bottle aged at 40 ° C. for 8 weeks (forced aged sample) and a freshly prepared fresh sample filled in a polyethylene bottle were used.

(Storage stability over time) The liquid state of each of the samples subjected to heating and aging was visually judged, and those which did not cause coloring in any of the container and the developer composition were evaluated as ◎. A five-point evaluation was performed, in which the resulting color was evaluated as ○, the color of the bottle was slightly recognized as Δ, the color of the bottle was clearly x, and the color of the bottle was marked as xx. Table 5 shows the results.

[0189]

[Table 5]

In all of Samples 2, 3 and 6 to 10 to which the compound of the present invention was added, some coloring was observed in the treating agent composition, but no coloring was observed in the bottle. A clear effect was observed for 1, 4, and 5.
Above all, it was shown that Sample 10 to which both the compounds of the general formulas (III) and (IV) were added was excellent.

(Photographic Properties) The above-mentioned color developing bottle for color negative was heated and aged for 2 days at 50 ° C. without heating and aging (referred to as “fresh” and indicated in Table 5 as Fr). (Referred to as “forced aging”) were diluted with potassium bromide to prepare the color developing solution shown in Example 1, which was used in a small developing machine for experiments to develop the following color negative. Development processing was performed according to the processing specifications. The difference between the fresh sample and the forced aging sample was determined for the maximum density (DmaxG) of the color density measured with the green filter light density, and the results are also shown in Table 5. Samples 2, 3, and 6 to 10 of the present invention were all shown to have excellent storage stability from the viewpoint of photographic properties. Sample 1 to which both compounds of general formulas (III) and (IV) are added
0 was shown to be excellent.

Example 4 The photographic properties were evaluated using the following photosensitive materials in the same manner as in Example 3 of the present application. As a result, the same effects as those obtained for Sample 101 in Example 3 were confirmed for all the photosensitive materials. done. Tested photosensitive material Kodak Gold 100 (Serial No .: 22104)
12) Kodak ADVANTix 100 (Serial No .: 10)
47058) Fujimana Negative Super V100 manufactured by Eastman Kodak Co., Ltd. (Production number: S36)
149) Fujicolor negative nexia F (Production number: AAO2
-302) Fuji Photo Film Co., Ltd.

[0193]

By adding an alkoxyamine derivative of the general formula (I) instead of hydroxylamine to a color developer composition for a silver halide color photographic light-sensitive material, differences in photographic properties due to differences in varieties and brands are obtained. It is possible to produce a processing agent having high storage stability without causing the generation of the treatment agent. Further, when the hydroxylamine of the general formula (II) is added in combination, the effect is further enhanced. The general formula (II
Addition of the urea compound of the formula (I) or the surfactant of the formula (IV) can prevent precipitation and produce a more stable developer composition. Further, it is possible to use a polyethylene container which could not be used for a color developing composition in the past.

[Brief description of the drawings]

FIG. 1 shows a treatment agent composition container (bottle) according to one embodiment of the present invention.

FIG. 2 shows a state where a piercing nozzle breaks a seal portion of a treatment agent composition container (bottle) according to one embodiment of the present invention.

[Explanation of symbols]

 188 Hole Nozzle 214 Nozzle Hole 300 Bottle (Photo Processing Agent Container) 302 Container Main Body 304 Male Thread (Screw) 308 Polyethylene Sheet with Notched Groove 310 Cap (Fixing Member) 312 Bottom (When Loaded) 314 Opening

Claims (5)

[Claims] 1. A color developing composition for a silver halide color photographic light-sensitive material, comprising a compound represented by the following general formula (I) and substantially free of hydroxylamine. Embedded image (In the formula, R ₁ represents an alkyl group which may have a substituent, R ₂ and R ₃ represents an alkyl group which may each have a hydrogen atom or a substituent. Also, R ₂ and R ₃ is
May be linked to each other to form a ring). 2. The color developing agent according to claim 1, further comprising a hydroxylamine derivative represented by the following general formula (II) in addition to the compound represented by the general formula (I). Composition (In the formula, L represents an alkylene group or a single bond which may be substituted, and A represents a carboxyl group, a sulfonic acid group, a phosphono group, a phosphinic acid residue, a hydroxyl group, an alkyl group when L is an alkylene group. An amino group which may be substituted, a carbamoyl group which may be alkyl-substituted, a sulfamoyl group which may be alkyl-substituted or an alkylsulfonyl group which may be substituted, or, when L is a single bond, an alkoxy-substituted group. R represents a hydrogen atom or an alkyl group which may be substituted, and L and R may combine to form a ring. 3. The color developer composition according to claim 1, wherein the color developer composition is contained in a container made of a material containing 95% or more of polyethylene. 4. A silver halide color photographic light-sensitive material comprising performing color development processing using a color development replenisher obtained by diluting the color developer composition according to claim 1. Material development processing method. 5. A container filled with the developing agent composition according to claim 1, which is mounted on an automatic developing machine, and the contents of the container are poured into a developing replenishing tank. Is washed with a fixed amount of water, the water used for the washing is introduced into a replenishing tank, used as water for preparing a replenishing solution, and development is performed using the obtained replenishing solution. The development processing method described in 1. above.