JPH11212229A - Color developer composition for silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the concentrated liquid color developer composition prevented from color staining of a processing solution and a processing agent vessel due to air oxidation and deterioration of photographic performances and capable of recycling its plastic containers. SOLUTION: This concentrated liquid color developer composition contains a color developing agent and 0.5-2 M carbonate and a concentration of potassium ions is at least higher than that of sodium ions. A bottle to be filled with this composition is substantially composed of a single polyolefin polymer and a ratio of the thickness of the bottle wall in contact to the gas in the bottle the thinnest in the bottle to that of the wall in contact to the processing liquid the thinnest in the bottle is controlled to 1.1-8.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

BACKGROUND OF THE INVENTION Generally, processing of silver halide photographic light-sensitive materials, for example, processing of silver halide color photographic light-sensitive materials,
The basic steps include a color developing step (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 necessary for a processing chemical manufacturer to manufacture a processing solution that can be used as it is, transport it to a lab, and store it, in terms of transportation costs and storage space. 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,
No treatment agent has been obtained that satisfies both environmental aspects, simplicity of operation aspects such as labor saving of treatment liquid preparation, 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 a liquid treatment agent to have a higher concentration and to be as compact as a solid treatment agent. However, in order to ensure that the liquid-concentrated treatment agent is stored stably and does not interfere with use, it should be basically a homogeneous solution having a saturation solubility or less.
There is very little room for further volume reduction and enrichment.

As a liquid thickening agent, for example, it has long been known that a black-and-white developing solution is used in the form of paste in Italian Patent No. 427967 and US Pat. No. 2,735,774. Also, in the case of a color developer, the formation of a paste has been performed for the purpose of thickening the developer and various other purposes. U.S. Pat. No. 2,784,086 attempts to form a paste using an alginic acid derivative as a viscosity-imparting or thickening agent. 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 coagulation and solidification of the insoluble material is delayed and the service life is somewhat extended However, this is not an essential solution to volume reduction and does not extend the advantages of the liquid treatment 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. However, since the developing agent is easily susceptible to air oxidation, deterioration over time during storage of the processing agent proceeds, and The developed developing agent becomes tar-like and adheres to the container wall, which hinders the recycling and reuse of the container. As described above, the concentrated liquid developer has problems such as precipitation of the color developing agent due to solubility restrictions, air oxidation of the color developing agent during storage of the processing agent, coloring contamination of the container, and stain on the photosensitive material. ing.

In order to prevent air oxidation of the color developing solution, development of preservatives which are more effective than hydroxylamine salts conventionally used as preservatives has been promoted. JP-A-4-443 discloses dialkylhydroxylamine and hydroxylalkylhydrazines having a large preservative effect. Despite these advances, their effects have not been able to adequately meet the increasing demands of the market, and there is a need for further improvements in preservation.

Liquid color developing agents have a weak point in terms of such storage stability.
Although filled in a glass container, it has drawbacks such as heavy weight, inconvenient handling, and easy breakage. For this reason, plastic bottles having a multilayer structure in which a plastic material having low gas permeability is added to the constituent materials have begun to be used. However, this bottle has a high manufacturing cost and cannot be recycled because it is made of a composite material, which wastes resources and is not preferable in terms of environmental conservation. Among the single-component plastic materials that are easy to recycle, some are used for general purposes, but as containers for developer compositions, for example, polyolefin resin has excessive air permeability and the Poor storage stability, polyester resin is hydrolyzable, poor in chemical stability to withstand strong alkaline aqueous solution such as color developer, and polyvinyl chloride resin and similar chlorine-containing resin can be recycled However, it has drawbacks such as no method for treating non-recyclable residues (residues). As described above, improvement of the storage stability of the developer composition by using a container having low air permeability also results in a new defect. As described above, in order to improve the suitability of using the concentrated liquid developing agent, it is strongly desired to improve the storage stability of the color developing agent. There is no means at present.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to prevent a processing solution or a processing agent container from being colored by air oxidation during storage even though it contains a high concentration of a color developing agent, and An object of the present invention is to provide a liquid concentrated developer composition for a color photographic light-sensitive material which does not generate stains on the light-sensitive material to be processed and does not deteriorate photographic performance. It is a further object of the present invention to provide a liquid concentrated developer composition of the above object wherein the containing plastic container is recyclable. 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 As a result of intensive studies on the above objects, the present inventor has discovered a phenomenon that the air permeability of a plastic material is affected by the composition of a developer, and this phenomenon has been found. The present invention has been achieved based on a technical idea that the fact is utilized for stabilizing a concentrated liquid developer. That is, the object of the present invention can be attained by the following liquid-concentrating processing agent composition for color development, the material and shape of the container thereof, and the developing method.

1. A color developer composition comprising a color developing agent, a concentrated liquid having a carbonate concentration in the range of 0.5 to 2 M, a potassium ion concentration higher than at least a sodium ion concentration, and loaded in a plastic bottle. In the product, the plastic bottle is substantially composed of polyolefin as a single polymer constituent material, and a color developer composition (hereinafter, as long as the meaning is clear,
The ratio of the thickness of the thinnest wall surface in contact with the gas in the bottle to the thickness of the thinnest wall surface in contact with the "treatment liquid" is 1.1 to 8 times. A color developing composition for a silver halide color photographic light-sensitive material, comprising:

2. 2. The color developer composition as described in 1 above, wherein the volume ratio of the head space portion to the total internal volume of the bottle is 0.2 to 10%.

3. 3. The color developing composition according to any one of the above 1 or 2, wherein the bottle is made of a material containing 95% or more of polyolefin.

4. Bottles made of high density polyethylene (HDP
4. The color developing composition as described in 3 above, comprising a material containing 95% or more of E).

5. The body of the bottle is made of a material containing 95% or more of high-density polyethylene (HDPE), and at least a portion of the cap of the bottle in contact with the upper end of the bottle body is made of a material containing 95% or more of low-density polyethylene (LDPE). 5. The color developer composition according to any one of the above items 1 to 4, wherein

The color developing composition according to any one of the above 1 to 5, which is suitable for being mounted on an automatic developing machine having an automatic washing mechanism and used for a specific plastic bottle and a developing agent having a specific composition. This is a feature of the present invention in which the agent composition is combined.

The color developing treatment of a silver halide color photographic light-sensitive material can be carried out using a color developing replenisher or a developing solution obtained by diluting these color developing compositions. After the bottle filled with the color developer composition is mounted on an automatic developing machine, the contents of the bottle are poured into a developing replenishing tank, the inside of the bottle is washed with a certain amount of water, and used for the washing. It is also a feature of the present invention that it is suitable for a developing method in which the added water is introduced into a replenishing tank and used as water for preparing a replenisher, and development is performed using the obtained replenisher.

[0019]

Embodiments of the present invention will be described below in detail. The essential point of the color developer composition for a silver halide photographic light-sensitive material of the present invention is a plastic bottle substantially comprising polyolefin as a single polymer constituent material, and being in contact with the processing solution of the bottle. A plastic bottle in which the ratio of the thickness of the thinnest wall surface in contact with the gas in the bottle to the thickness of the thinnest wall surface in the wall is 1.1 to 8 times is used, and the concentration of the carbonate is 0.1%.
In the range of 5 to 2 M, the concentration of potassium ions is at least higher than the concentration of sodium ions, and is filled with a liquid developer composition containing a color developing agent,
That is, it is characterized by a specific combination with the container material, the shape element, and the composition of the treatment agent composition.

As described above, it is well known that polyolefin resins have high air permeability and therefore have poor protection against air oxidation of the contents, and are not suitable for containers for developing compositions. I have. However, in a system in which potassium ions are present in excess with respect to the high carbonate concentration and sodium ions described above, even if the content is an alkaline aqueous solution containing a color developing agent, the air oxidation rate may be significantly reduced. found. Although the mechanism is unknown, it is thought that the solubility of the permeated gas in the liquid treatment agent other than the gas permeability of the plastic material is affected by the carbonate concentration of the treatment agent and the ratio of potassium ion and sodium ion. ing. In the present invention, in addition to the above,
As will be described later, the balance between the thickness of the narrowed portion at the top of the plastic bottle and the portion of the bottle mouth that is in contact with the gas and the thickness of the portion that is in contact with the processing liquid on the side surface is set to an appropriate range and the contents are set. Successfully reduce the amount of bottle material used without increasing the air oxidation and without reducing the strength of the bottle.

Therefore, the container used for the concentrated liquid developer of the present invention will be described first. 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 also meet Requirement 4.

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 life of the developer composition, the material and thickness of the container are such that the oxygen 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.

From the viewpoint of gas impermeability, it has already been mentioned that liquid developing agents are often supplied in a sealed state in a glass bottle at the beginning of practical use. However,
Bottles made of laminated materials of plastics with high gas barrier properties and plastics that are stable against alkaline developer have recently been used because of their drawbacks, such as their heavy weight and easy breakage. It is becoming. 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.

The color developer composition having a specific composition with respect to the carbonate concentration and the potassium ion / sodium ion ratio of the present invention is a thin HD which inherently permeates air and undergoes oxidative deterioration.
Even PE bottles have the advantage of being less susceptible to air oxidation, so that practical storage stability can be obtained without using such a composite material container. The material of the polyolefin container suitable for the present invention may have an air permeation speed eight times higher than the above-mentioned value, and a single plastic that satisfies the above requirements 2 and 4 can be selected. Requirement 3 as a single item
Is a characteristic advantage of the present invention. 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. .

The preferred bottle has a generally cylindrical or prismatic side surface and a shape in which a shoulder is narrowed toward an upper bottle mouth. Not limited. The essence of the present invention is based on the finding that the oxygen permeation rate of a plastic material changes depending on the composition of a content liquid.If the plastic material bottle has the same thickness, it is in contact with a processing solution, that is, a concentrated developer. Based on the finding that the oxygen permeation rate is smaller in the part that is in contact with the gas than in the part that is in contact with the gas, it is necessary to make the thickness relatively large even though the area of the gas contact part is small. It has been found that it is effective in reducing the amount of oxygen permeation. Therefore, in the present invention, the ratio of the thickness of the thinnest wall surface in contact with the gas in the bottle to the thickness of the thinnest wall surface in contact with the processing liquid is at least 1.1 times, preferably 1. By increasing the ratio by five times, the amount of bottle material used has been successfully reduced without increasing the air oxidation of the contents and without reducing the strength of the bottle. In other words, in order to reduce material costs, transportation costs, and in particular, recycling costs, it is preferable to reduce the thickness of the bottle as long as it meets the practically acceptable level of air oxidation deterioration of the developer composition. If the thickness of the wall in contact with the gas inside the bottle at the top is equal to the thickness of the wall in contact with the processing liquid (concentrated developer), the wall from the gas in contact with the bottle inside the bottle, that is, into the headspace Contribution of the permeated air to the oxidative deterioration of the developer composition, that is, the processing solution, cannot be ignored, and the shoulder strength and rigidity of the plastic bottle are reduced, thereby resulting in impaired handling aptitude. Therefore, the thickness of the thinnest wall surface in contact with the internal gas at the top of the bottle is at least 1.1 times, preferably 1.5 times or more the thickness of the thinnest wall surface in contact with the processing liquid. Is good. Further, it is not preferable that the thickness ratio is excessive. That is, if the amount of plastic material used is constant, increasing the ratio means reducing the thickness of the part in contact with the processing solution, increasing the permeability and increasing the overall oxygen transmission rate If the deterioration of the entire bottle due to air permeation is suppressed to an allowable level or less, the amount of plastic material used will increase. Therefore, the upper limit of the thickness ratio is 8, and
Preferably, the range is 3. This range balances the air oxidation from the wall surface in contact with the processing liquid and the air oxidation from the portion in contact with the gas inside the headspace, and has good handling suitability.

The thickness of the wall in contact with the processing liquid is
Reduce the amount of plastic material used and design the ratio of the thickness of the thinnest wall on the wall in contact with the gas in the bottle to the thickness of the thinnest wall on the wall in contact with the processing solution within the above range In general, it is generally determined that the thickness is 0.1 to 1.5 mm, preferably 0.3 to 0.8 mm.
mm is better. Thicknesses above this range increase the protection against air permeation, but in many cases are already sufficient and increase the weight, inferior handleability and waste resources.
If the thickness is less than this range, the protection against air permeation is often insufficient.

Preferred container materials for the color developing agent include polyester resins, acrylic resins, ABS resins, epoxy resins, polyamide resins such as nylon, polyurethane resins, polystyrene resins, polycarbonate resins, and PV resins.
A, polyvinyl chloride, polyvinylidene chloride, and polyethylene resin. Among them, the material satisfying the object of the present invention is a container composed of a polyolefin resin such as polyethylene or polypropylene as a single polymer material. Among them, polyethylene is preferable, and among polyethylene, a high-density type, so-called HDPE, is preferable as the container material. HDPE suitable for the container material has a density of 0.94 to 0.97.

The polyethylene used for the container of the concentrated liquid developer composition of the present invention is a pigment such as carbon black, titanium white, calcium silicate or silica, which does not adversely affect the alkaline developing composition, calcium carbonate, 2,6-
Additives such as di-t-butyl-4-methylphenol (BHT), dicetyl sulfide, tris (laurylthio) phosphite, other known antioxidants such as amines, thioethers and phenols, stearic acid or stearic acid Sliding agents such as metal salts, 2-hydroxy-
A known ultraviolet absorber compatible with polyethylene, such as 4-n-octyloxybenzophenone, a known plasticizer compatible with polyethylene, and the like may be added as necessary. The total amount of these additives is desirably 50% or less of the total amount of the mixture of plastic raw materials. Preferably, the ratio of polyethylene is 85% or more and no plasticizer is contained, and more preferably, the ratio of polyethylene is 95% or more and no plasticizer is contained.

In the present invention, it is preferable to select an appropriate material for the cap in order to increase the airtightness of the fitting portion between the bottle and the cap and to provide a buffer against external impact. In the present invention, the “cap” is expressed as a cap including the sealing member at the opening of the bottle. While a material containing 95% or more of high-density polyethylene (HDPE) is used for the main body of the bottle, a material containing 95% or more of low-density polyethylene (LDPE) is preferably used for the cap of the bottle. Alternatively, even if the cap is mainly made of high-density polyethylene (HDPE), a material containing 95% or more of low-density polyethylene (LDPE) is used as a material (for example, packing) in contact with the bottle body. It is good to increase the confidentiality between the bottle and the cap. The preferred density of LDPE for the cap and seal material is 0.91 to 0.94.

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

When filling the container with the developer composition, in order to further increase the safety against air oxidation,
It is preferable to minimize the space above the container so as to fill the mouth of the container as much as possible. However, it is preferable to provide a certain amount of space from the viewpoint of filling workability, safety in transportation, and workability in a developing station. This space is usually called the headspace. In the present invention, since measures are taken on both sides of the developer composition and the bottle so as to enhance the storage stability of the developer composition, the head space is more various than the storage stability in the above-described various workability and safety. You can choose a suitable headspace. Thus, a preferred headspace is between 0.2 and 10% of the internal volume of the bottle, preferably between 1.0 and 6.0.
%. The upper space of the bottle should be further filled with nitrogen to eliminate contact with oxygen in the air,
The present invention is not necessarily limited to such a filling method.

Next, the developer composition of the present invention will be described. The color developing agents which are the object of the present invention are those for general silver halide color photographic light-sensitive materials, and include materials for photographing such as color negative films and color reversal films, and materials for printing such as color positive films and color papers. It can be used for general amateurs, business photographers, movies, and news photographs.

The color developer composition is a concentrated processing agent containing a color developing agent, an alkali carbonate, a preservative and other necessary development aids, and is usually made into a replenisher for development by diluting with a fixed amount of water. Alkali carbonate is a carbonate of an alkali metal such as a sodium salt and a potassium salt.
0.5-2.0M is preferable, 0.5-1.5M is more preferable, and 0.6-1.0M is especially preferable. When the concentration is lower than this, air oxidation easily proceeds in a bottle having the material and thickness specified in the present invention, and storage stability is impaired. Similarly, the potassium ion concentration needs to be at least higher than the sodium ion concentration. Precipitation is likely to occur, and the precipitate promotes air oxidation of the developing solution to cause deterioration. Therefore, the ratio of potassium ion to sodium ion as well as the range of carbonate concentration has an essential effect on the storage stability. The molar ratio of potassium ion to sodium ion is preferably 1.1 or more, more preferably 1.7 or more, and the upper limit is that the constituent of the alkali metal salt in the composition is substantially a potassium salt. It does not have to contain sodium ions, but preferably not more than 10. on the other hand,
When the concentration of the carbonate exceeds 2.0 M, precipitation tends to occur and storage stability is similarly impaired. The potassium ion is not particularly limited as long as the concentration thereof is higher than that of the sodium ion. For example, except for a small amount of an additive in the form of a sodium salt, the alkali metal element substantially composed of potassium salt is potassium. It may be a treatment agent composed only of the above.

When the pH of the color developing composition is diluted with a predetermined amount of water to form a developing replenisher, it can be preferably used as it is without adjusting the pH, or it can be used with a slight pH adjustment. It is good to set as follows.
Such a pH varies depending on the photosensitive material and the developing method, but generally, in the case of a developer composition for color paper, the pH is 10.0 to 14.0, preferably 1 to 4.
1.5 to 13.5. In the case of a color negative developer composition, the pH is 10.0 to 12.5, preferably 10.
2-12.0.

The concentrated developer composition of the present invention is characterized in that it is particularly highly concentrated and that the potassium ion concentration is higher than the sodium ion concentration (on a molar basis), and It has already been described that the technical feature is that storage stability is ensured even when combined with a bottle having high air permeability. The degree of concentration is about 1.5 to 10 times, preferably 2 to 8 times, and more preferably 3 to 5 times the concentration ratio to the liquid in actual use, that is, the developing replenisher or the mother liquor (tank liquid). It is twice.

It is advantageous that the concentrated developer composition of the present invention has a form in which all the components contained in the working solution are contained in one composition, that is, a so-called one-component constitution. When it is not desirable to keep the components in contact with each other, the components may be separated into two or more liquids to form a two- or three-part developer composition (usually international standard IS
According to the name of O 5989, it is called a 1, 2, 3 part structure, etc.), and the effect and features of the invention are not lost by dividing into parts. In the case of a developer composition composed of a plurality of parts, the present invention is applied to a part containing a color developing agent.

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, etc., the inside of the container is cleaned without human labor by spraying the washing water, and the container can be handled cleanly and recycling of the waste container becomes easy. In addition, the washing water is used as a part of the water for dissolving the developer, and is not a waste liquid. The concept of such a system can be realized only by a highly concentrated small-volume developer composition embodied in the present invention which has sufficient fluidity for easy handling and long-term maintenance.

Next, 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 a 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 portion of the container body 302 is a tapered narrowing portion having a gradually reduced diameter, and a cylindrical bottle mouth portion (also referred to as a neck portion) 30 having an external thread 304 formed on an outer peripheral portion.
6 are formed. The upper end of the bottle mouth 306 is open, and the above-mentioned replenisher can be taken in and out through this opening. Further, a polyethylene (LDPE) sheet member 308 is arranged at the upper end of the bottle opening 306. 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 bottle mouth portion 306, and has a male screw 3 formed in the bottle mouth portion 306 on an inner peripheral portion thereof.
The female screw 318 corresponding to 04 is cut and can be screwed into the bottle mouth 306. By screwing into the bottle mouth 306,
The polyethylene sheet 30 is provided at the bottom 312 of the cap 310.
8 and the polyethylene sheet 308
Can be fixed to A circular opening 314 is formed in the bottom 312 of the cap 310, and the cap 310
The sheet 308 can be pierced in a state where is fitted. Further, it is preferable to use LDPE in a portion where the cap bottom 312 is in contact with the upper end of the bottle mouth (eg, polyethylene sheet 308) in order to keep the bottle main body and the cap tightly connected. HDPE is preferable as the material of the cap.

FIG. 2 shows a state in which the bottle is mounted upside down on the replenishing section of the developing machine, the hole opening nozzle breaks the polyethylene sheet member 308 from below, and the contents are charged into the replenishing tank. . As a specific embodiment, three 1300 ml plastic bottles (HDPE) 300 each containing a preparation composition of a developer, a bleaching agent, and a fixing agent are placed in the replenisher preparation section of the upper part of the developing machine. When the door of the dispensing section is closed, the piercing nozzle 188 moves upward from below and breaks through the plastic sheet 308 serving as a bottle lid as shown in FIG. Pour the 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. .

Next, the components of the developer composition of the present invention other than the above-mentioned carbonate concentration and the concentration ratio of potassium ion and sodium ion 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,
Although a color developing agent is contained, a preferred example is a known aromatic primary amine color developing agent, particularly a p-phenylenediamine derivative. Representative examples are shown below, but are not limited thereto. In recent years, in black-and-white photosensitive materials, a coupler has been added so as to form black.
Although some black and white images are formed using a general-purpose general color 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 it 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. Hydroxylamine may or may not be included in the components of the composition depending on the type of the photosensitive material. This is because the photographic properties may be affected because the developer itself has silver developing activity at the same time as the function as a preservative of the developer.

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

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
No. 0588, salicylic acids, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat.
An aromatic polyhydroxy compound described in the specification of JP-A No. 4 and the like may be contained as necessary. In particular, other than the above-mentioned alkanolamines, for example, alkanolamines such as triethanolamine and triisopropanolamine, substituted or unsubstituted dialkylhydroxylamine such as disulfoethylhydroxylamine and diethylhydroxylamine, or aromatic polyamines The addition of a hydroxy compound is preferred. Among the above organic preservatives, hydroxylamine derivatives are particularly preferred.For details, refer to JP-A-1-97953, JP-A-1-186939, and JP-A-1-186940.
And No. 1-187557. In particular, it is more preferable to use a hydroxylamine derivative and an amine in combination from the viewpoint of improving the stability of the color developer and the stability during continuous processing. Examples of the amines include cyclic amines described in JP-A-63-239447, amines described in JP-A-63-128340, and other amines described in JP-A-1-186939. Examples thereof include amines described in JP-A-1-1187557.

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

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

When the photosensitive material to be developed is color photographic paper, it is important that the white background of the screen is white, so that it is important to make it seem white 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 whitening agents are frequently used, and among them, di (triazinylamino) 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 contain other known compounds of developer components. 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 various color developing solution components, for example, various chelating agents which are precipitation inhibitors for calcium and magnesium, or which are also agents for improving the stability of the color developing solution. it can. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid, 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 to which the present invention is applied is 30 to 55 ° C., preferably 35 to 55 ° C., more preferably 38 to 55 ° C. when the photosensitive material to be developed is a color print material. 45 ° C. The development processing time is 5 to 90 seconds, preferably 15 to 60 seconds. The replenishment amount is preferably small, but is suitably ^{20 to} 600 ml per 1 m ^{2 of} the light-sensitive material, preferably 30 to 600 ml.
It is 120 ml, particularly preferably 15 to 60 ml. On the other hand, in the case of color development of a color negative or color reversal film, the development temperature is 20 to 55.
, Preferably from 30 to 55 ° C, more preferably from 38 to 45 ° C. The development processing time is 20 seconds to 6 minutes, preferably 30 to 200 seconds. Also, in the case of a color negative, the time is preferably 1 to 4 minutes. It is preferable that the replenishing amount is small, but 20 to 100 per m ^{2 of} the light-sensitive material.
0 ml is suitable, preferably 50-600 ml, particularly preferably 100-400 ml. 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, and the following three methods give good results. However, in the practice of the present invention, the manufacturing method is not limited to the following three methods. [Method A] A method in which a small amount of water is introduced into a mixing tank in advance, and constituent chemicals are sequentially charged therein while stirring. [Method B] A method in which constituent chemical powders are preliminarily mixed and then poured at once into a small amount of water in a mixing tank. [Method C] A method in which constituent chemicals are divided into two or more groups in which components that can be conveniently combined in advance are dissolved in water or a hydrophilic mixed solvent to form a concentrated solution, and then each concentrated liquid is mixed. Further, a combined manufacturing method partially incorporating each method can also be implemented.

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

Of these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Iron (III)
Examples of aminopolycarboxylic acids or salts thereof useful for forming an organic complex salt of the following are biodegradable ethylenediaminedisuccinic acid (SS form), N- (2-carboxylateethyl) -L-asparagine Acid, beta-alanine diacetate, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3
-Diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid,
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 usually 30 seconds to 6 minutes and 30 seconds, preferably 1 to 4 minutes and 30 seconds. In the case of bleaching for color printing materials, it is 30 seconds to 2 minutes. Various known organic acids (for example, glycolic acid, succinic acid, maleic acid, malonic acid, citric acid,
Organic bases (eg, imidazole,
Dimethylimidazole, etc.) or 2-picolinic acid and other compounds represented by general formula (A-a) described in JP-A-9-212819, and general formulas described in the same publication including cordic acid and the like. It is preferable to contain the compound represented by (Bb). 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 contained in the bleach-fixing solution or the fixing solution used in combination with the developer composition of the present invention includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, and sodium thiocyanate. Water-soluble silver halide dissolving agents such as thiocyanates such as ammonium thiocyanate, thioether compounds such as ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol, and thioureas; 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 also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per liter is 0.1.
It is preferably 3 to 2 mol, more preferably 0.5 to 1.0 mol.
Range of moles.

The pH range of the bleach-fixing solution or the fixing solution is 3 to 8
Is preferable, and 4-7 are especially preferable. 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, if the pH is higher than this, desilvering will be delayed and stain will easily occur. The pH range of the bleaching solution used with the developer composition of the present invention is 8
It is the following, 2-7 are preferred, and 2-6 are especially preferred. When the pH is lower than this, the deterioration of the solution and the leuco-formation of the cyan dye are promoted. To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

Further, the bleach-fixing solution may contain various other types of fluorescent whitening agents, antifoaming agents, 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 processing time for bleach-fixing is 5 to 240 seconds,
Preferably, it is 10 to 60 seconds. Processing temperature is 25 ℃ ～ 6
0 ° C., preferably 30 ° C. to 50 ° C. The replenishing amount is ²⁰ ml to 250 ml, preferably 30 ml to 100 ml, particularly preferably 15 ml to 1 m ² per 1 m ² of the light-sensitive material.
60 ml.

After desilvering such as fixing or bleach-fixing, washing and / or stabilization are generally performed. The amount of rinsing water in the rinsing step can be set in a wide range depending on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (the number of stages), and various other conditions.
Among them, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in Journal of the Society of Motion Picture and Television Engineers (Journal of the Society of Motion Picture).
and Television Engineers) Vol. 64, pp. 248-253 (1955
May issue). Usually, the number of stages in the multistage countercurrent system is preferably 3 to 15, and particularly preferably 3 to 10.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, and the increase in the residence time of water in the tank causes the 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 which inactivate the remaining magenta coupler to prevent color fading and stain formation, methylol compounds described in US Pat. No. 4,786,583 and hexamethylentetramine Hexahydrotriazines described in JP-A-2-153348, formaldehyde bisulfite adduct described in U.S. Pat. No. 4,921,779, seized patent publication 504609
And azolylmethylamines described in JP-A Nos. 519190 and 519190 are added.

Further, in the washing water, a surfactant as a draining agent and a chelating agent represented by EDTA as a hardening agent can be used. Continue with the above washing process or
Alternatively, the treatment can be performed directly with the stabilizing solution without going through the washing step. A compound having an image stabilizing function is added to the stabilizing solution, and examples thereof include an aldehyde compound represented by formalin, a buffering agent for adjusting a membrane pH suitable for stabilizing a dye, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, a fluorescent whitening agent and a hardening agent may be added. When the stabilization is performed directly without going through a washing step, JP-A-57-8543, JP-A-58-14834,
All known methods described in JP-A-60-220345 and the like can be used. In addition, 1-hydroxyethylidene-
It is also a preferred embodiment to use a chelating agent such as 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 to which the developer composition of the present invention can be applied 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. To be substantially free of silver iodide
The silver iodide content is preferably 0.1 mol% or less, more preferably 0.01 mol% or less, 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. In the light-sensitive material to which the present invention is applied, a dye capable of being decolorized by a process described in European Patent EP 0,337,490 A2, pp. 27-76, is coated on a hydrophilic colloid layer for the purpose of improving image sharpness and the like. (Among others, oxonol dyes) of 680
Titanium oxide added so that the optical reflection density in nm becomes 0.70 or more, or surface-treated with a divalent or tetravalent alcohol (for example, trimethylolethane) in the water-resistant resin layer of the support At least 12% by weight (more preferably 1%
4% by weight or more).

Further, the photosensitive material to which the developer composition of the present invention is applied is described in JP-A-63-271247 in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image.
It is preferable to add an antifungal agent as described in JP-A No. 2-2,028.
Further, as a support used for the photosensitive material, in the case of a film-forming photosensitive material, cellulose triacetate, poly (ethylene terephthalate), and poly (ethylene naphthalate) are used. A support such as paper (resin-coated paper) laminated with kneaded polyethylene or a poly (ethylene terephthalate) film kneaded with white pigment for display is used.

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

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material 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.

[0076]

[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 to which the developer composition of the present invention is applied may include a pyrazoloazole coupler or a pyrrolotriazole coupler as described in EP 0,277,589A2. And an acylacetamide type yellow coupler.

Examples of the cyan coupler include phenol type couplers and naphthol type 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.

As magenta couplers, in addition to 5-pyrazolone-based magenta couplers described in the publicly known documents in the above table, international publications WO92 / 18901, WO92 / 18902 and WO92 / 18903. Are also preferred. In addition to these 5-pyrazolone magenta couplers, known pyrazoloazole-type couplers are used in the present invention, among which hue and image stability,
The pyrazolo described in JP-A-61-65245, JP-A-61-65246, JP-A-61-14254, and EP-A-226,849A and EP-A-294,785A in terms of coloring properties and the like. The use of azole couplers is preferred.

As the yellow coupler, known acylacetanilide-type couplers are preferably 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 the 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:
215272 P-3, 5, 16, 19, 25, 30,
42, 49, 54, 55, 66, 81, 85, 86, 9
Latex for impregnating an oil-soluble organic compound: Latex described in US Pat. No. 4,199,363; Oxidized developing agent scavenger: US Pat.
606, column 54, lines 54 to 62, compounds of formula (I) (especially I-, (1), (2), (6), (12) (columns 4 to 5), US Pat. No. 4,923,787 Column 2 of 5
Formulas on lines 10 to 10 (especially compound 1 (column 3); Stain inhibitor: Formulas (I) to (III) on page 4, lines 30 to 33 of EP298321A, especially I-47, 72, III-1, 27
(Pages 24 to 48); Anti-fading agent: A-6, 7, 20, 21, 23, 24, 25, 26, 3 of EP298321A
0, 37, 40, 42, 48, 63, 90, 92, 9
4,164 (pp. 69-118), US 5,122,44
4, columns 25-38 II-1 to III-23, especially III-
10, EP 471347A, pages 8 to 12 I-1 to III
Column 4, especially II-2, US 5,139,931
A-1 to 48 of 2 to 40, especially A-39 and 42; a material for reducing the amount of a color-enhancing agent or color-mixing inhibitor used: EP
I1 to II-15, especially I-46 on pages 5 to 24 of 411324A; formalin scavenger: EP 47793
SCV-1 to 28 on page 24 to 29 of 2A, especially SCV-
8;

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

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

The present invention can be applied to general-purpose or cinema-use 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 to which the present invention is applied preferably has a magnetic recording layer. The magnetic recording layer used in the present invention will be described. The magnetic recording layer used in the present invention is obtained by coating a support with an aqueous or organic solvent-based coating 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 for the light-sensitive material will be described. For details including the light-sensitive material, processing, cartridges and examples described later, refer to Published Technical Report, Official Technique No. 94-6023 (Invention Association; 1994. 15.)). The polyester used in the present invention is formed with diol and aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, as aromatic dicarboxylic acid.
Examples of 1,4- 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 2,6
-50 mol% to 100 mol% of naphthalenedicarboxylic acid
Polyester. 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, and 9
0 ° C. or higher is preferred.

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

In order to adhere the support and the light-sensitive material constituting layer,
Surface treatment is preferred. Chemical treatment, mechanical treatment,
Corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment,
Surface activation treatments such as glow discharge treatment, active plasma treatment, 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 will be described. It may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, including copolymers starting from monomers 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 (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S)
-Triazine, etc.), 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.

An antistatic agent is preferably used in the light-sensitive material. 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 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 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 will be described. Book
The main material of the patrone of the film to which the invention is applied is metal
However, it may be a synthetic plastic. Preferred plastic
The material is polystyrene, polyethylene, polypropylene,
And polyphenyl ether. Further, the patrol of the present invention
May contain various antistatic agents.
, Metal oxide particles, nonions, anions, cations
And betaine surfactants or polymers are preferably used
Can be. These antistatic patrones
Are described in JP-A Nos. 1-312537 and 1-312538.
Have been. In particular, the resistance at 25 ° C. and 25% RH is 10¹²
Ω or less is preferable. Normally plastic patrones are shaded
Knead carbon black and pigments to give
Manufactured using embedded plastic. Patrone's
The size may be 135 size at present or the camera
For miniaturization, the current 135 mm 25 mm cartridges
It is also effective to set the diameter of the die to 22 mm or less. Patrol
The case volume is 30cm ^ThreeLess than 25cm^ThreeLess than
It is preferable that Patrone and Patroneque
The weight of the plastic used for the base is 5 g to 15 g
preferable.

Further, a patrone for feeding 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 disclosed in US Pat. Nos. 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development or a photographic film that has been subjected to development processing. Also, raw film and developed photographic film may be stored in the same new patrone,
A different patrone may be used.

In the light-sensitive material, 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, further preferably 18 μm or less, and particularly 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 the time required for the film thickness to reach 1/2 when the saturated film thickness is 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds. Define. The film thickness was adjusted at 25 ° C and 55% relative humidity (2
T _1/2 is the film thickness measured in days), and T _1/2 is the value of A. Green et al.
And Engineering (Photogr.Sci.Eng.), 19
Vol. 2, pages 124 to 129, can be measured by using a serometer (swelling meter) of the type described in the volume. T
_{The ratio} of _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is 150 to 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 light-sensitive material of the present invention preferably has a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-described light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling ratio of this back layer is 150 to
500% is preferred.

[0102]

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

Example 1 Bottle Shape Factors and Stability to Air Oxidation The relationship between the bottle shape factors and the stability to air oxidation of the treatment composition 1 (Comparative Example) and Formulation 2 (Example of the present invention) was shown. The evaluation was made according to the degree of coloring of the composition with time and the degree of stain of the photosensitive material sample when development processing was performed using a developer prepared from the composition with aging.

1. Bottles The bottles tested were all made of HDPE containing 1300 ml as shown in FIG. The thickness ratio was 0.2 to 0.6 mm, and the thickness ratio of the thinnest wall surface in contact with the internal gas at the top of the bottle was changed as shown in Table 2. When the developer composition was filled, the head space ratio was 6%, and the filling amount of the processing agent was 1,300 ml.

2. Preparation of the photosensitive material for the test After performing corona discharge treatment on the surface of the support obtained by coating both sides of the paper with a polyethylene resin, a gelatin undercoat layer containing sodium dodecylbenzenesulfonate was provided, and further a first layer to A silver halide color photographic light-sensitive material sample 10 having the following layer structure was formed by sequentially applying a seventh photographic constituent layer.
1 was produced. The coating solution for each photographic constituent layer was prepared as follows. The average grain size of the emulsion shown below is the average value of the converted diameter of the grain area measured by the so-called projection area method.

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

[0107]

Embedded image

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

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

[0110]

Embedded image

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

[0112]

Embedded image

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

[0114]

Embedded image

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

[0116]

Embedded image

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

[0118]

Embedded image

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

[0120]

Embedded image

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

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

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

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

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

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

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

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

[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136] 3. Preparation of color developer composition (per bottle filling amount) (1) Common component dimethylpolysiloxane-based surfactant 0.1 g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Ethylenediaminetetraacetic acid 4.0 g Fluorescent brightener (Hakor BSU- PN, manufactured by Sumitomo Chemical Co., Ltd.) 20.0 g Ethylenediaminetetraacetic acid 4.0 g Disodium-N, N-bis (sulfonateethyl) 15.0 g Hydroxylamine Polyethylene glycol 300 (average molecular weight 300) 10.0 g Sodium sulfite 0.2 g N-ethyl-N (Β-methanesulfonamidoethyl) 14.0 g -3-Methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate pH (adjusted with potassium hydroxide and sodium hydroxide) 13.2 (2) Factors for change changed. Carbonates
Potassium carbonate and sodium carbonate are used and the ratio is K
The ratio of salt to Na salt was 2.0. The pH was adjusted by adding potassium hydroxide and sodium so that the total K / Na ratio was 2.0. Formulation 1 Formulation 2 K / Na ratio 2.0 2.0 Carbonate concentration (M) 0.2 1.0 Remarks Comparative example Inventive example

4. Test Method and Evaluation Method The prepared color developer composition was filled in a 1300 ml HDPE bottle shown in FIG. (1) Coloring of composition The samples filled in eight kinds of polyethylene (HDPE) bottles shown in Table 2 and sealed were stored at 40 ° C for 8 weeks. 490 of each sample before and after performing the heating aging.
The spectral absorption concentration at 1 nm (cell thickness 1 cm) was measured, and the difference between the measured values of the spectral concentration before and after the heat aging (# 45)
0 nm) was used as an evaluation scale for coloring the composition.

(2) Stain of developed photosensitive material The photosensitive material sample 101 of the above 2 was used without exposure.
The color developing replenisher was prepared by diluting each of the eight composition-filled bottle samples described in 4 above with heating and aging at 40 ° C. for 8 weeks and newly prepared ones with a 2.0-fold dilution with water. Was prepared. Also, add it to the water 25
%, And 0.01 g of potassium bromide was added per liter to prepare a color developer. Sample 101 was processed while the color developing solution was placed in a developing tank and a replenisher was added, and the blue filter light density (DminB) of the obtained developed sample was measured. Difference (△ DminB) in blue filter light density (DminB) between a photosensitive material sample treated with a developer prepared from a composition aged after heating and a photosensitive material sample treated with a developer prepared from a newly prepared composition
Was used as the stain evaluation scale.

[0139] 5. Using a small developing machine for development processing experiments, the composition samples of the above bottles were developed according to the following development processing steps.

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

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

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

6. Results The results are shown in Table 2. (1) Coloring of Composition In the case of Formulation 1 in which the carbonate concentration and the K / Na ratio are out of the range of the developer composition of the present invention (Comparative Samples 1-1, 2, and 3), the wall surface / treatment liquid in contact with the internal gas Even with a bottle having a wall thickness ratio in contact with the present invention within the range of the present invention, remarkable coloring with time was observed. In the case of Formulation 2 in which the developer composition falls within the range of the present invention, Comparative Sample 1-4 having a small ratio of the wall thickness in contact with the internal gas to the wall surface in contact with the processing liquid of 1.0 has a large coloring with time and is stable with time. Inferior properties, but on the contrary, the wall /
Comparative sample 1 having a large wall thickness ratio of 10 in contact with the processing liquid
8 also shows that the coloring with time tends to increase somewhat, indicating that there is an appropriate range in the thickness ratio of the wall surface in contact with the internal gas / the wall surface in contact with the treatment liquid. Moreover, the handling is not good. In each of Inventive Examples 1-5 to 7, the coloring density with time was 0.02 or less, which was within the allowable range.

(2) Stain of Developed Photographic Material Stain which adheres to the developed photographic material and has the same developer composition outside the scope of the present invention in the case of Formula 1 (Comparative Samples 1-1, 2, and 3) 3) is the wall in contact with the internal gas /
Even if a bottle having a wall thickness ratio in contact with the processing liquid within the range of the present invention is used, and in the case of Formulation 2 in which the developer composition is within the range of the present invention, in the case of Formulation 2, the wall surface in contact with the internal gas / the wall surface in contact with the processing liquid Comparative sample 1-4 having a small thickness ratio of 1.0 has a large stain, and comparative sample 1-8 having a large thickness ratio of 10
Is lighter than Comparative Sample 1-1, but still produces stains. On the other hand, in Examples 1-5 to 7 of the present invention, no adhesion of stain was observed.

[0145]

[Table 2]

Example 2 Stability of Bottled Developer Composition against Air Oxidation The storage stability test of the bottled developer composition over time was performed by examining the degree of coloring of the composition over time and the developer prepared from the aged composition. The evaluation was performed according to the degree of stain of the light-sensitive material sample when the development processing was performed using. For the photosensitive material for the test, the sample 101 shown in Example 1 was used, and the developer bottle was the one of the present invention example 1-5 (thickness ratio 1.5) shown in Table 2 of Example 1. used. The common parts of the formulation of the developer composition are the same as those shown in Example 1, and the changed parts are shown in Table 3. As in the case of Example 1, potassium carbonate and sodium carbonate were used as the carbonate, and the ratio was set to a ratio of K salt to Na salt of 2.0. The pH was adjusted by adding potassium hydroxide and sodium so that the total K / Na ratio was 2.0. The developer was diluted to prepare a color developing replenisher and a developing solution, and the developing process was performed using a small experimental developing machine. Table 3 shows the stain concentration values selected as representative values of the results. The evaluation test was performed in the same manner as in Example 1, except for the degree of coloring with time of heating of the composition in the bottle, the above-described stain concentration during development, and disodium-n, a preservative in the developer composition. The results are also shown by analysis of the content of n-bis (sulfonatoethyl) hydroxylamine. In addition, the analysis of the content of disodium-n, n-bis (sulfonatoethyl) hydroxylamine was performed by separating this compound by a reversed-phase column using a high-performance liquid chromatograph.
It was measured by measuring the spectral density with an ultraviolet spectrophotometer (210 nm).

Table 3 also shows the test results. Comparative Example 2-1 with low carbonate concentration and Comparative Example 2- with low K / Na ratio
No. 2 shows that the coloring over time and the stain concentration are high, and the preservative is reduced at a high rate. On the other hand, Comparative Examples 2-7 and 2-
No. 2 cannot be put to practical use due to precipitation of a precipitate. The developer compositions 2-3 to 2-6 within the scope of the present invention all show good results in coloration with time, stain concentration, and reduction rate of preservative, and no precipitation of precipitates was observed. Was.

[0148]

[Table 3]

[0149]

According to the present invention, a color developing composition obtained by filling a color developing composition having the above-mentioned carbonate concentration and cation ratio in the above-mentioned HDPE bottle is also capable of oxidizing a developing agent. Aging of the composition and coloring of the container with aging, and therefore no contamination of the photosensitive material to be processed. Therefore, the volume of the developer composition can be reduced, the handling in a developing station can be simplified, and the developer composition can be incorporated in an automatic developing machine system. In particular, it is possible to use a polyethylene container which could not be used conventionally for a color developer composition.

[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 concentrated liquid containing a color developing agent, wherein the concentration of carbonate is in the range of 0.5 to 2M, and the concentration of potassium ion is at least higher than the concentration of sodium ion, and is filled in a plastic bottle. In the color developer composition, the plastic bottle is substantially composed of a polyolefin as a single polymer constituent material, and the thickness of the thinnest wall surface among the wall surfaces in contact with the color developer composition. A color developer composition for a silver halide color photographic light-sensitive material, wherein the ratio of the thickness of the thinnest wall surface among the wall surfaces in contact with the gas in the bottle is 1.1 to 8 times. 2. The color developer composition according to claim 1, wherein the volume ratio of the head space portion to the total internal volume of the bottle is 0.2 to 10%. 3. The color developing composition according to claim 1, wherein the bottle is made of a material containing 95% or more of polyolefin. 4. The bottle is made of high density polyethylene (HDP).
The color developer composition according to claim 3, comprising a material containing 95% or more of E). 5. The bottle body is made of high-density polyethylene (H
DPE), wherein at least a portion of the bottle cap that contacts the upper end of the bottle body is made of a material containing 95% or more of low density polyethylene (LDPE). 5. The color developing composition according to any one of 4.