JPH04338953A - Processing agent kit for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance working environmental and social environmental adapta tion without polluting them and to reduce the volume of the kit by packing the solid photographic processing agents in a packing sack made of a water-solu ble film or in a coat made of a water-soluble binder together with a gas and sealing the sack or coat. CONSTITUTION:The solid photographic processing agents are packed and sealed together with the gas, such as air or nitrogen or NO2, in a sack made of the water-soluble film or the coat made of the water-soluble binder, the form of the solid processing agent is pellets, granules, blocks, or paste, and the solid agents are filled, preferably, in a filling rate of <=90 volume %, and it is preferred that the water-soluble film is made mainly of polyvinyl alcohol or methyl cellulose or their derivatives, and its film thickness is 10-120mmu, the solid processing agents are a color developing agent, a black-and-white developer, a bleaching agent, a fixing agent, and the like, the water-soluble film is made of a thermoplastic resin, and one or all of the alkaline agents in the solid processing agents are coated with the water-soluble binder.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a processing agent (photographic processing agent) kit for silver halide photographic light-sensitive materials, and more specifically, it completely prevents scattering of photographic processing agent fine powder and does not require the use of plastic bottles. The present invention relates to a photographic processing agent kit that has improved suitability for working environments and social environments, and also saves storage space and other labor due to its compact capacity.

0002

[Prior Art and Problems to be Solved by the Invention] Silver halide photographic materials are usually developed using processing solutions such as a black and white developer, a fixer, a color developer, a bleach, a bleach-fix, and a stabilizer. Processing is performed to obtain an image-wise image. Each processing solution used herein is packaged in one or more concentrated liquid parts in a plastic bottle for ease of use and supplied to the user as a processing agent kit. Users dissolve these processing agent kits in water to prepare a working solution (starting solution or replenishing solution) for use.

[0003] In recent years, in the photo processing industry, the number of small-scale photo labs using small automatic processing machines called minilabs has rapidly increased, and as minilabs have become more popular, the amount of plastic bottles used for processing agents has also increased. It is increasing rapidly every year.

[0004] Because of its light and strong properties, this plastic has been widely used in applications other than bottles for photographic processing agents. The global production of plastic continues to increase year by year, reaching over 100 million tons per year in 1988. On the other hand, a huge amount of plastic is discarded, and in Japan as an example, approximately 40% of the plastic produced is discarded every year. When such waste plastics are dumped into the ocean, they cause deterioration of the habitat of marine life, and in Europe, they are burned in incinerators with inadequate exhaust gas treatment equipment, resulting in acid rain and other conditions. It is also causing problems.

[0005] For this reason, there is an urgent need to implement countermeasures, and in Europe and the United States there is an active movement toward legislation such as banning the recycling and use of plastics, or mandating the use of degradable plastics. This is the actual situation.

Under these circumstances, it is extremely undesirable to use a large amount of plastic bottles for processing agents for photographic purposes.

[0007] Therefore, it has been considered to turn the concentrated liquid of the photographic processing agent into a powder, but in this case, there is a high possibility that fine powder will fly up when dissolved and be inhaled by the operator, which poses concerns about the impact on health. or the floating processing agent components may mix into another photographic processing solution, causing contamination and trouble. For this reason, techniques for granulating photographic processing agents to form a granular mixture have been developed, for example, in JP-A No. 2-109042 and JP-A No. 2-10.
No. 9043. However, these techniques are not perfect and have the drawback that a considerable amount of the granular mixture is pulverized during transport of the processing agent.

As a result of various studies, the present inventors have found that the above-mentioned problems can be completely solved by using a solid photographic processing agent packaged with a water-soluble film.

However, when dissolving a solid photographic processing agent packaged in a water-soluble film that is not filled with gas, when it is poured into water, it sinks too quickly due to its own weight and accumulates at the bottom. It has been found that there is a problem in that the film becomes pasty and fixed, and furthermore, the water-soluble film dissolves so as to envelop the solid photographic processing agent, resulting in a caking phenomenon and poor dissolution.

As a result of various studies, the inventors of the present invention have surprisingly found that the above-mentioned problems can be solved by packaging a solid photographic processing agent with a water-soluble film and sealing it together with gas to prepare a photographic processing agent kit. understood.

Furthermore, when developing using the photographic processing agent kit of the present invention as described above, there is another effect that staining is less likely to occur in the unexposed areas of the photosensitive material after storage of the photographic processing agent kit. It turned out that. Furthermore, it has been found that when the photographic processing agent kit of the present invention is used, it also has the effect of improving the crystal precipitation that tends to occur in the air-contact portion of the wall of an automatic developing machine. These were surprising things that could not have been imagined using previous knowledge.

0012

OBJECTS OF THE INVENTION The first object of the present invention is to provide a processing agent kit for silver halide photographic materials that can reduce the use of plastic bottles and is suitable for the social environment, and second, to provide a solid photographic processing agent. An object of the present invention is to provide a processing agent kit for silver halide photographic materials that is suitable for a working environment and does not cause scattering of fine powder. Furthermore, the third object is to provide a processing agent kit for silver halide photographic light-sensitive materials that improves storage stability and reduces stains generated in unexposed areas of the silver halide photographic light-sensitive materials. An object of the present invention is to provide a processing agent kit for silver halide photographic light-sensitive materials, which has improved crystal precipitation properties at the air-contact portion of the vessel wall. Furthermore, fifthly, it is possible to provide a processing agent kit for silver halide photographic light-sensitive materials, which is lightweight, reduces transportation costs, and requires less storage space in a developing laboratory by solidifying the processing agent. An object of the present invention is to provide a processing agent kit for silver halide photographic materials with significantly improved properties.

[0013]

[Means for Solving the Problems] In order to achieve the above object, the present inventors have made extensive studies and found that a solid photographic processing agent is contained in a water-soluble film envelope or a water-soluble binder. It has been found that the above object can be achieved by a processing agent kit for silver halide photographic light-sensitive materials, which is characterized by containing a gas.

A preferred embodiment of the invention comprises a. The solid photographic processing agent is in the form of a tablet, granule, powder, lump or paste; b. The filled gas is air or nitrogen,
being carbon dioxide or an inert gas, c. The filling rate of the solid photographic processing agent is 90% by volume or less; d. The water-soluble film is polyvinyl alcohol-based, methylcellulose-based, polyethylene oxide-based, starch-based, polyvinylpyrrolidone-based, hydroxypropylcellulose-based,
consisting of at least one base material selected from pullulan, dextran, and gum arabic; e. the water-soluble film is polyvinyl alcohol-based; f. The thickness of the water-soluble film is 10 to 120μ; g.
the solid photographic processing agent is at least one selected from a color developing agent, a black and white developer, a bleaching agent, a fixing agent, a bleach-fixing agent, and a stabilizer; h. the water-soluble film is thermoplastic; i. the solid photographic processing agent consists of one mixture; j. Part or all of the alkaline agent in the solid photographic processing agent is covered with a water-soluble binder; k. The alkaline agent is carbonate.

[0015]

[Specific structure of the invention] The technology using a water-soluble film is
Until now, it has been applied to the packaging of agricultural chemicals, water treatment agents, detergents, disinfectants, etc. For example, JP-A No. 2-155999,
It is described in JP-A-62-4800, JP-A-63-12466, and JP-A-61-57700. However, no examples of application of these water-soluble films to photographic processing agents are known, and it is completely surprising that the effects of the present invention as described above can be achieved by applying these water-soluble films to photographic processing agents. Met.

The water-soluble film or binder of the present invention includes:
Polyvinyl alcohol-based, methylcellulose-based, polyethylene oxide-based, starch-based, polyvinylpyrrolidone-based, hydroxypropylcellulose-based, pullulan-based,
Films or binders made of dextran-based, gum arabic-based, polyvinyl acetate-based, hydroxyethylcellulose-based, carboxyethylcellulose-based, carboxymethylhydroxyethylcellulose-based, poly(alkyl)oxazoline-based, and polyethylene glycol-based base materials are preferred. Among these, polyvinyl alcohol-based and pullulan-based ones are particularly preferably used from the viewpoint of the desired effects of the present invention.

The preferred polyvinyl alcohol is a very good film-forming material and has good strength and flexibility under most conditions. Commercially available polyvinyl alcohol compositions cast as films vary in molecular weight and degree of hydrolysis, but preferably have a molecular weight of about 10,000 to about 100,000. The degree of hydrolysis is the rate at which acetate groups of polyvinyl alcohol are substituted with hydroxyl groups. For film applications, the range of hydrolysis is usually about 70% to 100%. Thus, the term polyvinyl alcohol usually includes polyvinyl acetate compounds.

Methods for producing these water-soluble films are described, for example, in JP-A-2-124945 and JP-A-61-9734.
No. 8, No. 60-158245, JP-A-2-86638
No., JP-A-57-117867, JP-A-2-7565
No. 0, JP-A-59-226018, JP-A No. 63-2187
41 and 54-13565.

Furthermore, these water-soluble films are
(manufactured by Aicello Chemical Co., Ltd.), Hi-Selon (manufactured by Nichigo Film Co., Ltd.)
Alternatively, one commercially available under the name Pullulan (manufactured by Hayashibara Co., Ltd.) can be used. Also, Chris Craft
Industries (Chris Craft In
industries) Inc. The 7-000 series polyvinyl alcohol films, available from the MONO-SOL division of , are particularly preferred because they dissolve at water temperatures of about 34 degrees F. to about 200 degrees F., are non-toxic, and exhibit a high degree of chemical resistance. used.

The thickness of the water-soluble film of the present invention is 10 to 1
20μ is preferably used, particularly 15 to 80μ is particularly preferred, and particularly 20 to 60μ is particularly preferred. If it is less than 10μ, the storage stability of the solid processing agent will deteriorate, and if it exceeds 120μ, it will take too long to dissolve the water-soluble film, and the situation of crystal precipitation on the wall of the automatic processor will worsen. This is because they will come to you.

[0021] Furthermore, the water-soluble film of the present invention is preferably thermoplastic. This is because not only the heat sealing process and the ultrasonic welding process become easier, but also the objective effects of the present invention can be better achieved.

Furthermore, the tensile strength of the water-soluble film of the present invention is preferably 0.5 x 106 to 50 x 106 kg/m2, particularly 1 x 106 to 25 x 106 kg/m2.
is preferable, especially 1.5×106 to 10×
106 kg/m2 is preferred. These tensile strengths are measured by the method described in JIS Z-1521.

[0023] In the present invention, the solids filling rate is preferably 90% by volume or less because the kit does not sink to the bottom and there is no problem with solubility. More preferably 7
It is preferably 5% by volume or less. This is because when the kit floats above the upper half of the processing tank and the water-soluble film or binder coating dissolves, the contents are widely dispersed and the solubility is improved. Most preferably it is 50% by volume or less,
This is because the kit almost floats on the liquid surface, resulting in better dispersibility and further increased solubility.

[0024] The gas encapsulation means of the present invention is optional and may be carried out at the time of packaging or covering or at any time thereafter.

In the present invention, in order to solidify the photographic processing agent using a water-soluble binder, the concentrated liquid, fine powder or granular photographic processing agent and the water-soluble binder are kneaded and molded, or temporary molding is performed. Any method can be adopted, such as forming a coating layer by spraying a water-soluble binder onto the surface of the photographic processing agent (Japanese Patent Application Nos. 2-135887, 2-203165,
2-203166, 2-203167, 2-
(See No. 203168 and No. 2-300409). In this case, the gas filling means is also arbitrary as described above.

The solid photographic processing agent of the present invention can be prepared in the form of tablets, granules,
A powder, lump or paste form is used, preferably a granule or powder form. The method for producing the tablet processing agent is described, for example, in JP-A-51-61837 and JP-A-54-15.
No. 5038, No. 52-88025, British Patent No. 1213
It can be produced by a general method described in specifications such as No. 808, and the granule processing agent can be produced by, for example,
It can be produced by a general method described in specifications such as No. 2, No. 2-109043, No. 3-39735, and No. 3-39739. Furthermore, the powder processing agent can be produced by a general method as described in, for example, the specifications of JP-A-54-133332, British Patent No. 725892, British Patent No. 729862, and German Patent No. 3733861.

The bulk density of the solid photographic processing agent of the present invention is 0.4 from the viewpoint of its solubility and the desired effect of the present invention.
0 to 0.95 g/cm3 is preferred, particularly 0.95 g/cm3.
50 to 0.85 g/cm3 is preferably used.

The solid photographic processing agent of the present invention comprises a color developer,
Examples include black and white developers, bleaching agents, fixing agents, bleach-fixing agents, stabilizers, etc., but color developing agents exhibit the effects of the present invention better.

Part or all of the alkaline agents such as potassium carbonate, sodium carbonate, potassium hydroxide, potassium phosphate, potassium bicarbonate, and sodium hydroxide contained in the solid photographic processing agent of the present invention are replaced with a water-soluble binder. (binder) and packaging in a water-soluble film, the deterioration of the water-soluble film due to saponification by an alkaline agent, etc. is improved, and the desired effects of the present invention are also better achieved. The water-soluble binder may be the same as the water-soluble film used in the present invention, or a different type may be used in consideration of slow solubility.

[0030] The gas used in the present invention is preferably carbon dioxide, nitrogen, helium, neon, argon, krypton, or xenon, and more preferably nitrogen or carbon dioxide in view of availability, price, etc. .

As the color developing agent used in the color developer of the present invention, a p-phenylenediamine compound having a water-soluble group satisfactorily exhibits the objective effects of the present invention.
It is preferably used because it causes less fogging.

[0032] p-phenylenediamine compounds having a water-soluble group do not contaminate photosensitive materials and are less harmful to the skin than paraphenylenediamine compounds having no water-soluble group such as N,N-diethyl-p-phenylenediamine. Not only does it have the advantage of not causing rashes on the skin,
In particular, by combining it with the color developing solution of the present invention, the objects of the present invention can be achieved more efficiently.

The water-soluble group is at least one on the amino group or benzene nucleus of the p-phenylenediamine compound.
Specific water-soluble groups include -
(CH2)n'-CH2OH, -(CH2)m'
-NHSO2 -(CH2)n'CH3, -(CH
2) m'-O-(CH2)n'-CH3, -(C
H2 CH2 O) n'Cm'H2m'+1 (m' and n' each represent an integer greater than or equal to 0), -COOH
Preferred examples include a -SO3H group and a -SO3H group.

Specific examples of the color developing agent preferably used in the present invention include those described in Japanese Patent Application No. 2-203169.
(C-1) described on pages 26 to 31 of the specification
(C-16) is mentioned.

The above color developing agent is usually used in the form of a salt such as hydrochloride, sulfate or p-toluenesulfonate.

The above color developing agents may be used alone or in combination of two or more, and if desired, black and white developing agents such as phenidone, 4-hydroxymethyl-4-methyl-1-
It may be used in combination with phenyl-3-pyrazolidone, metol, etc.

Further, in the present invention, when the color developing solution according to the present invention contains compounds represented by the following general formulas [A] and [B], the desired effects of the present invention can be better achieved. In addition, this is one of the preferred embodiments of the present invention because it also has the effect of reducing fog in unexposed areas.

[0038]

embedded image In the formula, R1 and R2 each represent an alkyl group or a hydrogen atom. However, both R1 and R2 are not hydrogen atoms at the same time. Further, R1 and R2 may form a ring.

In the general formula [A], R1 and R2
are alkyl groups, aryl groups, and aryl groups, respectively, which are not hydrogen atoms at the same time.

[0040]

[Image Omitted] Alternatively, it represents a hydrogen atom, and the alkyl groups represented by R1 and R2 may be the same or different, and each is preferably an alkyl group having 1 to 3 carbon atoms. Furthermore, these alkyl groups may have a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, or a hydroxyl group.

R' represents an alkoxy group, an alkyl group or an aryl group. The alkyl groups and aryl groups of R1, R2 and R' include those having substituents, and R1
and R2 may be combined to form a ring, for example a heterocyclic ring such as piperidine, pyridine, triazine or morpholine.

[0042]

embedded image In the formula, R11, R12, R13 represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R14 represents a hydroxy group, a hydroxyamino group, a substituted or unsubstituted, Alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group,
Represents an amino group. The heterocyclic group is a 5- to 6-membered ring, composed of C, H, O, N, S, and halogen atoms, and may be saturated or unsaturated. R15 is -CO-, -SO2
-or

[0043]

It represents a divalent group selected from the following, and n is 0 or 1. In particular, when n=0, R14 represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R13 and R14 may jointly form a heterocyclic group.

Specific examples of the hydroxylamine compounds represented by the general formula [A] are described in US Pat. No. 3,287,125, US Pat. No. 3,329,3034, US Pat. (A-1) to (A-39) described on pages 36 to 38 of Japanese Patent Application No. 2-203169 and JP-A-3-338
(1) to (53) described on pages 3 to 6 of the specification of No. 45 and (1) to (53) described on pages 5 to 7 of the specification of JP-A-3-63646
(52) is mentioned.

Next, specific examples of the compound represented by the general formula [B] are described in Japanese Patent Application No. 40-4 of Japanese Patent Application No. 2-203169.
(B-1) to (B-33) described on page 3 and JP-A-3-3
Examples include (1) to (56) described on pages 4 to 6 of Specification No. 3846.

The compounds represented by the general formula [A] or the general formula [B] are usually free amines, hydrochlorides, sulfates,
It is used in the form of p-toluenesulfonate, oxalate, phosphate, acetate, etc.

A small amount of sulfite can be used as a preservative in the color developer and black-and-white developer according to the present invention. Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like.

[0048] It is necessary to use a buffering agent in the color developer and black-and-white developer according to the present invention.
Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (boric acid) , potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-2-hydroxybenzoate Examples include potassium acid (potassium 5-sulfosalicylate).

As a development accelerator, Japanese Patent Publication No. 37-160
88, No. 37-5987, No. 38-7826, No. 44-12380, No. 45-9019, and U.S. Pat. No. 3,813,247, etc.
p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554;
-137726, JP 44-30074, JP 56-156826 and JP 52-43429, etc., quaternary ammonium salts, U.S. Patent No. 2610122
p-aminophenols described in US Pat. No. 2,494,903 and US Pat. No. 3,128,182,
No. 4230796, No. 3253919, Special Publication No. 41
-11431, U.S. Patent No. 2482546, U.S. Patent No. 259
Amine compounds described in Japanese Patent Publications No. 6926 and No. 3582346, Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 42-2520
No. 1, U.S. Patent No. 3128183, Special Publication No. 41-114
No. 31, No. 42-23883 and U.S. Patent No. 35325
Polyalkylene oxide represented by No. 01 etc., other 1-phenyl-3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles,
etc. can be added as necessary.

The color developer preferably contains substantially no benzyl alcohol. Substantially means 2.0 ml or less per liter of color developer, more preferably not at all. Substantially no content causes less variation in photographic properties during continuous processing, particularly an increase in stain, and more favorable results can be obtained.

Chloride ions and bromine ions are necessary in the color developer for the purpose of preventing fog. In the present invention, the chlorine ion is preferably 1.0 x 10-2 to 1.
5 x 10-1 mol/liter, more preferably 4 x 10
-2 to 1×10 −1 mol/liter. If the chloride ion concentration is more than 1.5 x 10-1 mol/liter,
It is not preferable to advance development and quickly obtain a high maximum density. Also, if it is less than 3.5 x 10-2 mol/liter,
Staining occurs, and furthermore, photographic properties change due to continuous processing (
In particular, the minimum concentration) becomes large, which is undesirable.

In the present invention, preferably 3.0×10-3 to 1.0×10-3 bromine ions are contained in the color developer.
Contains moles/liter. More preferably 5.0×10
-3 to 5 x 10-4 mol/liter. Particularly preferred is 1 x 10-4 to 3 x 10-4 mol/liter. If the bromide ion concentration is greater than 1 x 10-3 mol/liter, development will be delayed, maximum density and sensitivity will be reduced, and 3
．． If it is less than 0 x 10-3 mol/liter, it is not preferable because it causes staining and also causes fluctuations in photographic properties (particularly minimum density) due to continuous processing.

When added directly to the color developer, sodium chloride, potassium chloride,
ammonium chloride, nickel chloride, magnesium chloride,
Examples include manganese chloride, calcium chloride, and cadmium chloride, of which sodium chloride and potassium chloride are preferred.

[0054] It may also be supplied in the form of a color developer and a counter salt of an optical brightener added to the developer. Sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide,
Examples include magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, and thallium bromide, of which potassium bromide and sodium bromide are preferred.

[0055] In addition to chlorine ions and bromide ions, any antifoggant can be added to the color developer and developing agent of the present invention, if necessary. As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Representative examples include nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

From the viewpoint of the desired effects of the present invention, it is preferable that the color developer and developing agent of the present invention contain a triazinylstilbene fluorescent brightener. As such a fluorescent brightener, a compound represented by the following general formula [E] is preferable.

[0057]

[Image Omitted] In the above formula, X2, X3, Y1 and Y2 each represent a hydroxyl group, a halogen atom such as chlorine or bromine, an alkyl group, an aryl group,

[0058]

embedded image Or represents -OR25. Here, R21 and R22 each represent a hydrogen atom, an alkyl group (including substituents), or an aryl group (including substituents), R23 and R24 represent an alkylene group (including substituents), and R25 represents a hydrogen atom, an alkyl group, or an aryl group (including substituents). It represents a group (including substituents) or an aryl group (including substituents), and M represents a cation.

The details of each group in general formula [E] or their substituents are the same as those described in Japanese Patent Application No. 2-240400, line 8 from the bottom of page 63 to line 3 from the bottom of page 64. It is.

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

[0061]

[C7]

[0062]

[Chemical formula 8]

[0063]

[Chemical formula 9]

[0064]

[Chemical formula 10]

[0065]

[Chemical formula 11]

The above compounds can be synthesized by known methods. Among the above exemplified compounds, E-4, E-24, E-34, E-35, and E-3 are particularly preferably used.
6, E-37, and E-41. The amount of these compounds added is preferably in the range of 0.2 g to 10 g, more preferably 0.4 g to 10 g per liter of color developer.
It is in the range of 5g.

Furthermore, the color developer and black-and-white developer used in the present invention may optionally contain methyl cellosolve,
Methanol, acetone, dimethylformamide, β-
Cyclodextrin and other compounds described in Japanese Patent Publication Nos. 47-33378 and 44-9509 can be used as organic solvents to increase the solubility of the developing agent.

Furthermore, an auxiliary developer can be used together with the developing agent. These auxiliary developers include, for example, N-methyl-p-aminophenol hexulfate (methol), phenidone, N,N-diethyl-p-
Aminophenol hydrochloride, N,N,N',N'-tetramethyl-p-phenylenediamine hydrochloride, etc. are known, and the amount added is usually 0.01 to 1.0 g /
Liters are preferred.

Furthermore, various other additives such as anti-stain agents, anti-sludge agents, interlayer effect promoters, etc. can be used.

[0070] Regarding color developing agents and black and white developing agents, Japanese Patent Application No. 2-240400, page 63, lines 8 to 6 from the bottom,
From the viewpoint of effectively achieving the object of the present invention, the chelating agent represented by the following general formula [K] and its exemplary compounds K-1 to K-22 described in the third line from the bottom of page 4 are added. preferable.

[0071]

[Chemical formula 12]

Among these chelating agents, K
-2, K-9, K-12, K-13, K-17, K-1
9, are preferably used, especially K-2 and K
-9 is added to the color developing solution, the effects of the present invention are exhibited well.

The amount of these chelating agents added is preferably in the range of 0.1 to 20 g, more preferably in the range of 0.2 to 8 g per liter of the color developer and black and white developer.

Furthermore, the color developer and the black and white developer may contain anionic, cationic, amphoteric, or nonionic surfactants.

[0075] Also, if necessary, alkyl sulfonic acid,
Various surfactants such as arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added.

The main bleaching agent preferably used in the bleach or bleach-fixing agent of the present invention is a ferric complex salt of an organic acid represented by the following general formula [IV].

[0077]

[In the formula, A1 to A4 may be the same or different,
Represents -CH2OH, -COOM or -PO3M1M2. M, M1 and M2 each represent a hydrogen atom, an alkali metal or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms. ] The compound represented by the general formula [IV] will be explained in detail below. In the formula, A1 to A4 are Japanese Patent Application No. 1-2606.
No. 28, page 12, line 15 from the top to page 15, line 3 from the top A
Since it is synonymous with 1 to A4, detailed explanation will be omitted.

Preferred specific examples of the compound represented by the general formula [IV] are shown below.

[0079]

[Chemical formula 14]

[0080]

[Chemical formula 15]

As the ferric complex salts of these compounds (IV-1) to (IV-12), sodium salts, potassium salts or ammonium salts of these ferric complex salts can be arbitrarily used. From the viewpoint of the desired effect and solubility of the present invention, ammonium salts of these ferric complex salts are preferably used.

Among the above compound examples, those particularly preferably used in the present invention are (IV-1) and (IV-3).
), (IV-4), (IV-5), and (IV-9), and particularly preferred is (IV-1).

In the present invention, in addition to the iron complex salt of the compound represented by the above general formula [IV], ferric complex salts of the following compounds and the like can be used as the bleaching agent or bleach-fixing agent. [A'-1] Ethylenediaminetetraacetic acid [A'-2] Trans-1,2-cyclohexanediaminetetraacetic acid [A'-3] Dihydroxyethylglycinate [A'-4]
] Ethylenediaminetetrakismethylenephosphonic acid [A'-5] Nitrilotrismethylenephosphonic acid [A'
-6] Diethylenetriaminepentakismethylenephosphonic acid [A'-7] Diethylenetriaminepentaacetic acid [A'-8]
Ethylenediaminediorthohydroxyphenylacetic acid [A'-9] Hydroxyethylethylenediaminetriacetic acid [A'-10] Ethylenediaminedipropionic acid [A'
-11] Ethylenediaminediacetic acid [A'-12] Hydroxyethyliminodiacetic acid [A'-13] Nitrilotriacetic acid [A'-14] Nitrilotripropionic acid [A'-15]
Triethylenetetraminehexaacetic acid [A'-16]ethylenediaminetetrapropionic acid The amount of the ferric complex salt of the organic acid added is 0.1 mol to 1 liter of bleach solution or bleach-fix solution.
The content is preferably in the range of 2.0 mol, more preferably in the range of 0.15 to 1.5 mol/liter.

Bleaching agents, bleach-fixing agents and fixing agents include imidazole and its derivatives described in JP-A No. 64-295258, or general formulas [I] to [IX] described therein.
] and at least one of these exemplified compounds can have an effect on rapidity.

In addition to the above accelerators, JP-A-62-1234
Exemplary compounds described in pages 51 to 115 of the specification of No. 59 and No. 22 of the specification of JP-A-63-17445
Exemplary compounds described on pages 25 to 25, JP-A-53-95
Compounds described in No. 630 and No. 53-28426 can also be used in the same manner.

In addition to the above, the bleach or bleach-fix agent may also contain halides such as ammonium bromide, potassium bromide, and sodium bromide, various optical brighteners, antifoaming agents, or surfactants. can.

As the main fixing agent used in the fixing agent or bleach-fixing agent according to the present invention, thiocyanates and thiosulfates are preferably used. The content of thiocyanate is preferably at least 0.1 mol/liter or more, and more preferably 0.1 mol/liter or more when processing a color negative film.
5 mol/liter or more, particularly preferably 1.0
moles/liter or more. Further, the content of thiosulfate is preferably at least 0.2 mol/liter or more, and more preferably 0.2 mol/liter or more when processing a color negative film.
5 mol/liter or more. Further, in the present invention, the object of the present invention can be achieved more effectively by using a thiocyanate and a thiosulfate in combination.

The fixing agent or bleach-fixing agent according to the present invention may contain, in addition to these main fixing agents, one or more pH buffering agents consisting of various salts. Furthermore, it is desirable to contain a large amount of a rehalogenating agent such as an alkali halide or ammonium halide, such as potassium bromide, sodium bromide, sodium chloride, or ammonium bromide. Further, compounds known to be added to ordinary fixing agents or bleach-fixing agents, such as alkylamines and polyethylene oxides, can be appropriately added.

[0089] For the fixing agent or bleaching fixing agent, JP-A-64
- It is preferable to add a compound represented by the following general formula [FA] described on page 56 of Specification No. 295258, and its exemplified compounds, which not only improves the effect of the present invention but also allows a small amount of light-sensitive material to last for a long time. Another effect is obtained in that very little sludge is generated in the processing liquid having fixing ability during processing over a period of time.

[0090]

[Chemical formula 16]

The compound represented by the general formula [FA] described in the same specification can be prepared by a general method as described in US Pat. No. 3,335,161 and US Pat. No. 3,260,718. Can be synthesized. These, the general formula [
The compounds represented by FA] may be used alone or in combination of two or more.

[0092] The amount of the compound represented by the general formula [FA] to be added is 0.1 g to 200 g per liter of treatment liquid.
Good results are obtained within the range of g.

In the present invention, the stabilizer preferably contains a chelating agent having a chelate stability constant of 8 or more with respect to ferric ions. Here, the chelate stability constant is defined as L. G. Sillen A. E. Martell
Author, “Stability Constants of
Metal-ion Complexes”,The
Chemical Society, London (
1964). S. Chaberek A. E. Mart
ell, “Organic Sequester”
ing Agents'', Wiley (1959), etc.

As a chelating agent having a chelate stability constant of 8 or more for ferric ions, Japanese Patent Application No. 2-2347
Examples include those described in No. 76 and No. 1-324507.

The amount of the above-mentioned chelating agent used is preferably 0.01 to 50 g, more preferably 0.05 to 20 g per liter of the stabilizing solution to obtain good results.

[0096] Preferred compounds to be added to the stabilizer include ammonium compounds. These are supplied by ammonium salts of various inorganic compounds. The amount of ammonium compound added is 0 per liter of stabilizing solution.
．． The range is preferably from 0.001 mol to 1.0 mol, more preferably from 0.002 to 2.0 mol.

Further, it is preferable that the stabilizer contains a sulfite.

Furthermore, it is preferable that the stabilizer contains a metal salt in combination with the chelating agent. Such metal salts include Ba, Ca, Ce, Co, In,
La, Mn, Ni, Bi, Pb, Sn, Zn
, Ti, Zr, Mg, Al or Sr, and can be supplied as inorganic salts such as halides, hydroxides, sulfates, carbonates, phosphates, acetates, or water-soluble chelating agents. The amount used is 1 x 10-4 per liter of stabilizer.
The range is preferably from 1 x 10-1 mol, more preferably from 4 x 10-4 to 2 x 10-2 mol.

Stabilizers include organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH adjusters (
Phosphate, borate, hydrochloric acid, sulfate, etc.) can be added. In the present invention, known antifungal agents may be used alone or in combination as long as the effects of the present invention are not impaired.

Next, the photosensitive material to which the processing agent of the present invention is applied will be explained.

When the light-sensitive material is a photographic light-sensitive material, silver iodobromide or silver iodochloride having an average silver iodide content of 3 mol % or more is used as silver halide grains, particularly 4 mol %. Silver iodobromide containing up to 15 mole percent silver iodide is preferred. Among them, the average silver iodide content preferred in the present invention is 5 mol% to 12 mol%, most preferably 8 mol% to 11 mol%.
It is mole%.

In the light-sensitive material processed with the photographic processing agent of the present invention, silver halide emulsions described in Research Disclosure No. 308119 (hereinafter abbreviated as RD308119) can be used. The table below shows the locations. [item]
[RD308119 page] Iodine tissue
993
I-A manufacturing method
Section 993I-A and 9
94 E-term crystal habit Normal crystal habit
9
93 I-A term twin crystal

〃Epitaxial

〃 Uniform halogen composition
993 Section I-B
not uniform
〃
halogen conversion
994 I-C section
〃 Replacement

〃 Metal content

994 I-D term monodisperse

995 I-F term solvent addition

〃
Latent image formation position surface
995 I-G term
internal

〃 Applicable photosensitive material Negative

995 I-H terms Positive (including internal fog particles)
〃 Mix and use emulsions

995 I-J section desalination

995 II-A silver halide emulsion is:
Use materials that have undergone physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are based on research and
Disclosure No. 17643, No. 18716 and no. 308119 (hereinafter referred to as RD17643)
, RD18716 and RD308119).

[0103] The descriptions are shown in the table below. [Item] [RD308119 page]
[RD 17643] [RD 1871
6] Chemical sensitizer 996 Section III-A
23
648 Spectral sensitizer 996 IV-A-A,
B, C, D, E, H, I, J items 23-24
648-9 Supersensitizer 996 IV-A-
E, J sections 23-24
648-9 Antifoggant 998 VI
24-25
649 Stabilizer 998 V
I 24
~25 649 photographic additives are also described in the above Research Disclosure. The relevant entries are shown in the table below. [Item] [RD308119 page] [RD 17643] [RD 1871
6] Color clouding prevention agent 1002 Section VII-I 25
650 Dye image stabilizer 1001 VII-J
Section 25 Brightener
998V
24 Ultraviolet absorber 1003 VI
II C, XIII Section C 25-26 Light absorber 1003 VIII
25-26 light scattering agent
1003 VIII Filter Dye
1003 VIII 2
5-26 binder 1003 IX
26
651 Static inhibitor 1006 X
III 27
650 hardener
1004 x 2
6 651 Plasticizer
1006 XII
27 650 Lubricant 1006 XII
27
650 Activator/Coating Aid 1005 XI
26-27 65
0 Matting agent 1007 Described in Research Disclosure. The relevant entries are shown in the table below. [Item] [
RD308119 page] [RD 17643] [
RD 18716] Yellow coupler
1001 Section VII-D
VII C-G Section Magenta Coupler
1001 Section VII-D
VII C-G Cyan coupler
1001 VII-D Section VII C-G Section DIR Coupler 1001 VI
I-F term VII F term
BAR coupler 10
02 Section VII-F Other useful residue-releasing couplers
1001 Section VII-F alkali soluble coupler
1001 Section VII-E additives are RD3
It can be added by the dispersion method described in 08119 XIV.

[0104] In the present invention, the aforementioned RD17643 page 28, RD18716 pages 647-648 and RD
The supports described in No. 308,119 XIX can be used.

[0105] The photosensitive material includes the aforementioned RD308119.
Auxiliary layers such as filter layers and interlayers as described in Section VII-K can be provided. In addition, the photosensitive material is
Various layer configurations such as forward layer, reverse layer, and unit configuration described in Section VII-K of D308119 can be adopted.

Next, preferred color light-sensitive materials to which the photographic processing agent of the present invention is applied will be explained.

As the silver halide grains in the light-sensitive material, silver halide grains mainly consisting of silver chloride containing at least 80 mol% or more of silver chloride are used, preferably 90 mol% or more, particularly preferably 95 mol% or more. What it contains;
Most preferably, those containing 99 mol% or more are used.

The above-mentioned silver halide emulsion containing mainly silver chloride may contain silver bromide and/or silver iodide as a silver halide composition in addition to silver chloride, and in this case, the silver bromide content is 20 mol %.
The following is preferable, more preferably 10 mol% or less, still more preferably 3 mol% or less, and when silver iodide is present, 1 mol% or less is preferable, more preferably 0.
5 mol% or less, most preferably zero. Such silver halide grains consisting mainly of silver chloride containing 50 mol% or more of silver chloride may be applied to at least one silver halide emulsion layer, but are preferably applied to all photosensitive silver halide emulsion layers. It is to be applied.

The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and have [1.0.0 ] planes and [1
．． 1.1] Any ratio of the surface can be used. Furthermore, even if the crystal structure of these silver halide grains is uniform from the inside to the outside, the inside and outside have different layers (
It may have a phase-like structure (core-shell type). Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. In addition, tabular silver halide grains (JP-A-58-1139
No. 34 and Japanese Patent Application No. 170070/1983) may also be used. Further, silver halides described in JP-A-64-26837, JP-A-64-26838, JP-A-64-77047, etc. can be used.

[0110] Further, the silver halide grains can be prepared by an acid method,
It may be obtained by any preparation method such as the neutral method or the ammonia method.

[0111] Alternatively, for example, a method may be used in which seed particles are produced by an acidic method and further grown by an ammonia method, which has a high growth rate, to grow to a predetermined size. When growing silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled, and the amount of silver ions commensurate with the growth rate of silver halide grains is controlled, for example, as described in JP-A-54-48521. It is preferable to implant and mix the and halide ions sequentially and simultaneously.

When the photographic material to be processed with the photographic processing agent of the present invention is a color photosensitive material, the silver halide emulsion layer contains a color coupler.

The red-sensitive layer may contain, for example, a non-diffusive color coupler, generally a phenolic or alpha-naphthol coupler, which produces a cyan partial color image. The green light-sensitive layer contains at least one non-diffusive color coupler, usually 5, which produces a magenta partial color image, for example.
- Can include pyrazolone color couplers and pyrazolotriazoles. The blue-sensitive layer may contain, for example, at least one non-diffusive color coupler that produces a yellow color image, generally a color coupler having open-chain ketomethylene groups. For example, the color coupler is 6,
It can be a 4 or 2 equivalent coupler.

In color light-sensitive materials to which the photographic processing agent of the present invention is applied, 2-equivalent couplers are particularly preferred. Suitable couplers are disclosed, for example, in the following publications: Agfa Research Report (Mitteilunglnau)
sden Forschungslaboratori
ender Agfa), Leverkusen/Munchen (Leverkusen/Munchen),
Vol. III. p. 111 (1961) "Color coupler" by W. Pelz
(Farbkuppler); K. Venkataraman, “The Chemistry of Synthetic Soybeans” (The Che
mirsry of Synthetic Dyes),
Vol. 4, 341-387, Academic Press (
Academic Press), “The Theory of the Photographic Process” (TheTh
theory of the Photographic
Process), 4th edition, pp. 353-362; and Research Disclosure.
Disclosure) No. 17643, Section VII.

[0115] In the color photosensitive material to which the photographic processing agent of the present invention is applied, especially
General formula [M-1] as described in the specification, page 26
Magenta couplers shown in (Specific examples of these magenta couplers include No. 1 to No. 77 described in JP-A-63-106655, pages 29 to 34); The general formula [C
-I] or [C-II] (specific examples of cyan couplers include the same specification, 37
(C'-1) to (C'-82), (C'-82) described on page 42
''-1) to (C''-36)), high-speed yellow couplers also described on page 20 (specific examples of yellow couplers include (Y') described on pages 21 to 26 of the same specification) -1) to (Y'-39)) are preferred from the viewpoint of the desired effects of the present invention.

[0116]

EXAMPLES The present invention will now be illustrated by way of examples.

Example 1 The following color developer for color paper was thoroughly mixed, and 1
It was used as a powder processing agent for 0 liters.

<10 liter powder processing agent, color developer> Potassium bromide

0.2g potassium chloride

33g potassium carbonate

250
g potassium sulfite

2g sodium diethylenetriaminepentaacetate
30g 1-(N-ethyl-N-methanesulfonamidoethyl)-3-methyl-p-phenylenediamine・3/2H2SO4・H2O(CD
-3) 45g Chino Pearl SF
P (manufactured by Ciba Geigy)
25g sodium bicarbonate
31g
Diethylhydroxylamine oxalate
65g above,
A color developer (powder processing agent for 10 liters) was placed in a bag as shown in Table 1 below, and a gas as shown in Table 1 was sealed in the bag to conduct a storage test. Storage test condition is 50℃
The sample was stored at 20% RH for one month, dissolved in a chemical mixer, and developed. Add the inner bag to the water,
During dissolution, the state of powder scattering and dissolution was observed, and the reflective green density of the unexposed area of the color paper sample after development was measured. Furthermore, 1 liter of the dissolved color developing solution was taken out and the opening area was 20 cm2.
After storing the sample in a hard vinyl chloride container for three weeks at room temperature, the state of crystal precipitation at the developer interface on the container wall inside the container was observed. The above results are summarized in Table 1. However, the following color paper was used.

<Color paper> Each layer of the composition shown below is coated on a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the first layer side of the other side. A paper sample was prepared. The coating solution was prepared as follows.

First layer coating liquid Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, (ST-2) 6.67 g
, 0.67 g of additive (HQ-1) was added to high boiling point solvent (DNP
) and 60 ml of ethyl acetate to dissolve it, and this solution was emulsified and dispersed in 220 ml of a 10% gelatin aqueous solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer to obtain a yellow coupler dispersion. was created. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The second to seventh layer coating solutions were also prepared in the same manner as the first layer coating solution.

[0122] Also, as a hardening agent, (
H-1) and (H-2) were added to the seventh layer. As coating aids, surfactants (SU-2) and (SU-3) were added to adjust the surface tension.

[0123]

[Table 1]

[0124]

[Table 2]

[0125]

[Chemical formula 17]

[0126]

[Chemical formula 18]

[0127]

[Chemical formula 19]

[0128]

[C20]

[Method for preparing blue-sensitive silver halide emulsion] 4
In 1000 ml of a 2% aqueous gelatin solution kept at 0°C, the following (solution A) and (solution B) were added with pAg=6.5 and pH=3.
0 over 30 minutes, and then added the following (C
Liquid) and (Liquid D) were added simultaneously over 180 minutes while controlling pAg=7.3 and pH=5.5.

[0130] At this time, the control of pAg is as described in JP-A-59-4
The method described in No. 5437 was used, and the pH was controlled using sulfuric acid or an aqueous solution of sodium hydroxide. (Liquid A) Sodium chloride

3.42g potassium bromide

Add 0.03g water

200
ml (B solution) Silver nitrate

Add 10g water

200ml (
Solution C) Sodium chloride

102.7g potassium bromide

Add 1.0g water

600
ml (solution D) silver nitrate

Add 300g water

600ml

0
131] After the addition, Demol N 5 manufactured by Kao Atlas Co., Ltd.
After desalting using a 20% aqueous solution of magnesium sulfate and a 20% aqueous solution of magnesium sulfate, the mixture is mixed with an aqueous gelatin solution to obtain an average particle size of 0.
A monodisperse cubic emulsion EMP-1 having a diameter of 85 μm, a coefficient of variation (σ/r) of 0.07, and a silver chloride content of 99.5 mol % was obtained.

The above emulsion EMP-1 was subjected to chemical ripening at 50° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate
0.8mg/mol AgX
Chloroauric acid
0.5mg/
Mol AgX Stabilizer (STAB-1)
6 x 10-4 mol/mol A
gX Sensitizing dye (BS-1)
4 x 10-4 mol/mol AgX
〃 (BS-2)
1 x 10-4 mol/mol Ag
X

[Method for preparing green-sensitive silver halide emulsion]
Addition time of (Liquid A) and (Liquid B) and (Liquid C) and (Liquid D)
Same as EMP-1 except for changing the addition time.
Average particle size 0.43 μ, coefficient of variation (σ/r) = 0.08,
Monodispersed cubic emulsion EMP with silver chloride content of 99.5 mol%
-2 was obtained.

[0135] EMP-2 was treated with 5 using the following compound.
Chemical ripening was performed at 5° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate
1.5mg/mol AgX
Chloroauric acid
1.0mg/
Mol AgX Stabilizer (STAB-1)
6 x 10-4 mol/mol A
gX Sensitizing dye (BS-1)
4 x 10-4 mol/mol AgX

[Method for preparing red-sensitive silver halide emulsion] (
The average particle size was 0.50 μ, the coefficient of variation (σ/r ) = 0.08, monodisperse cubic emulsion EMP- with silver chloride content of 99.5 mol%
I got 3.

[0138] EMP-3 was treated with 6 using the following compound.
Chemical ripening was performed at 0° C. for 90 minutes to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate
1.8mg/mol AgX
Chloroauric acid
2.0mg/
Mol AgX Stabilizer (STAB-1)
6 x 10-4 mol/mol A
gX Sensitizing dye (BS-1)
4 x 10-4 mol/mol AgX

[0140]

[C21]

[0141] The sample thus prepared was exposed to wedge light according to a conventional method, and then subjected to a running process according to the following processing steps.

[0142]

[Table 3] *The stabilization tank consists of three tanks, and the replenisher is replenished in the third tank (the final tank), and each overflow liquid sequentially flows into the previous tank using a countercurrent method.

[0143] The following treatment liquids were used in each treatment step.

[0144] The color developer used was a solution in which the above-mentioned stored color developer was dissolved.

The following bleach-fix solution was used. water

700g ferric ammonium ethylenediaminetetraacetate
75g ethylenediaminetetraacetic acid
2g ammonium thiosulfate
50
g Ammonium thiocyanate

30g potassium sulfite

10g sulfinic acid


5g ammonium bromide

Add 10g water to make 1 liter,
The pH was adjusted to 6.5 using acetic acid or sodium hydroxide.

The following stabilizing solution was used. water

800g 1,2-benzisothiazolin-3-one
0.1g 1-hydroxyethylidene-1,1-diphosphonic acid
5.0g ethylenediaminetetraacetic acid

1.0g Chino Pearl SFP (manufactured by Ciba Geigy)
2.0g ammonium sulfate

2.5g zinc chloride


1.0g Magnesium chloride

0.5g o-phenylphenol
1.0g sodium sulfite
2.0g
Water was added to make up to 1 liter, and the pH was adjusted to 8.0 using 50% sulfuric acid or 25% ammonia water.

[0147]

[Table 4]

In Table 1 above, PVA-1 means a water-soluble film of polyvinyl alcohol (Hi-Selon S type 30μ, manufactured by Nichigo Film Co., Ltd.), and PVA-2 means a water-soluble film of polyvinyl alcohol (Solblon PH 30μ,
PVA-3 is a polyvinyl alcohol water-soluble film (Solblon PW 40 μ, manufactured by Aicello Chemical Co., Ltd.), PVA-4 is a polyvinyl alcohol water-soluble film (Hi-Selon C type 30 μ, manufactured by Nichigo Film Co., Ltd.) , PL-1 means pullulan film (20μ natural polysaccharide whose minimum unit is glucose, manufactured by Hayashibara Co., Ltd.). In Table 1, regarding the crystal precipitation status, ○ means that no crystal precipitation is observed and it is good, △ means that some crystal precipitation is observed but it is at a level that does not pose a practical problem, × means that it is clearly observed to the extent that it causes a problem. Also, the greater the number of x's, the worse the degree.

Regarding the powder scattering during melting, ◯ means that there is no scattering at all, × means that scattering is observed, and the greater the number of × means that the degree of scattering is worse.

Furthermore, regarding the solubility of the processing agent, ○ means that it dissolves rapidly, × means that it takes time to dissolve, and ×
The larger the number, the worse the degree.

[0151] From Table 1 above, when the solid photographic processing agent is packaged with a water-soluble film and nitrogen, carbon dioxide, or an inert gas is sealed at that time, there is no scattering of powder during dissolution.
It can be seen that the solubility is good, crystal precipitation is improved, and a photographic processing agent kit with less fogging even after storage of the processing agent can be obtained. It can be seen that a filling rate of 50% or less is particularly preferable.

Furthermore, when using the photographic processing agent kit of the present invention, there is no need to use a conventionally used plastic bottle containing a concentrated photographic processing agent solution, and the volume of the processing agent kit is reduced to 1/2. It was possible to reduce it by 3 to 1/10.

Example 2 The following bleach-fixing agent for color paper was thoroughly mixed to prepare a powder processing agent for 1 liter. <1 liter powder processing agent, bleach fixing agent> Ferric sodium ethylenediaminetetraacetate
65g Sodium ethylenediaminetetraacetate
2g sodium thiosulfate
7
0g potassium thiocyanate

30g potassium sulfite

10g potassium bromide

20g sodium sulfinate

5g of the bleach-fixer thus prepared was placed in the same bag as listed in Table 1 of Example 1, and a similar storage experiment was conducted with the bag further sealed with gas. As a result, almost the same results as in Example 1 were obtained regarding the state of crystal precipitation, the state of scattering of powder during dissolution, and the solubility of the processing agent.

Example 3 The color developer used in Example 1 was
According to the method described in No. 2, granulation was performed using a commercially available fluidized bed spray granulator to produce a granular treatment agent. An experiment was conducted in the same manner as in Example 1, and the solubility of the processing agent was further improved, and the fog density of the color paper was also improved by 20 to 30%.

Example 4 The film thickness of PVA-2 (water-soluble polyvinyl alcohol film) used in Example 1 was changed as shown in Table 2 below, and the other conditions were as in Experiment No. 1 of Example 1. The experiment was conducted in the same manner as in 1-10. The results are summarized in Table 2.

[0156]

[Table 5]

From Table 2 above, the thickness of the water-soluble film is preferably 10 to 120 μm in the present invention, particularly preferably 15 to 80 μm, particularly preferably 20 to 80 μm.
It can be seen that a 60μ water-soluble film is good.

Example 5 Experiment No. 1 of Example 1. Regarding 1-4, JP-A-2-10
A granule processing agent (color developer of Example 1) was prepared and used according to the method described in No. 9043 and No. 3-39739. However, the bulk density was set as shown in Table 3 below. An experiment similar to Example 1 was conducted using this granule treatment agent. The results are summarized in Table 3.

[0159]

[Table 6]

[0160] From Table 3 above, when the bulk density of the solid processing agent of the photographic processing agent kit of the present invention is 0.4 to 0.95 g/cm2, it is particularly good, especially 0.5 to 0.85 g.
/cm2, it is found to be good.

Example 6 In the following examples, the amount added in the silver halide photographic material is expressed in grams per m2 unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver.

Color negative film triacetyl cellulose film support (thickness 50μ)
A subbing process was applied to one side (front side) of the sample, and then a support was sandwiched between the two sides, and each layer having the composition shown below was sequentially formed from the support side on the opposite side (back side) to the subbed side. .

[0163] Back side first layer Alumina sol AS-100 (aluminum oxide) (
(manufactured by Nissan Chemical Industries, Ltd.)

0
．． 8g Back side 2nd layer diacetyl cellulose

100mg stearic acid

10mg Silica fine particles (average particle size 0.2μ)
50mg

[0164] Next,
A multilayer color photographic material (a-1) was prepared by sequentially forming layers having the compositions shown below on the surface of a subbed triacetylcellulose film support from the support side. 1st layer; antihalation layer (HC) black colloidal silver

0.15g UV absorber (UV-1)

0.20g colored cyan coupler (CC-1)
0.02g High boiling point solvent (Oil-1)

0.20g (
Oil-2)
0.20g gelatin

1.6 g

2nd layer; intermediate layer (IL-1) gelatin

1.3 g

Third layer; low sensitivity red-sensitive emulsion layer (R-L) Silver iodobromide emulsion (average grain size 0.3μ)
0.4 g
(Average particle size 0.4μ)
0.3 g
Sensitizing dye (S-1)
3.2×10-4 (mol/silver 1 mol)
〃 (S-2)
3.2×10-4 (mol/1 mole of silver)
(S-3)
0.2×10-4 (mol/silver 1 mol) Cyan coupler (C-1)
0.50g
〃 (C-2)
0
．． 13g colored cyan coupler (CC-1)
0.0
7g DIR compound (D-1)
0
．． 006g (D-2)

0.01g High boiling point solvent (Oil
-1)
0.55g gelatin

1.
0g

4th layer; High sensitivity red-sensitive emulsion layer (R-H) Silver iodobromide emulsion (average grain size 0.7μ)
0.9 g sensitizing dye (
S-1) 1.7
×10-4 (mol/silver 1 mol) 〃 (S
-2) 1.6×
10-4 (mol/1 mol of silver) 〃 (S-
3) 0.1×1
0-4 (mol/silver 1 mol) Cyan coupler (C-2
)
0.23g colored cyan coupler (CC-1)
0.03g DIR compound (D-2
)
0.02g high boiling point solvent (
Oil-1)
0.25g gelatin

1.0 g

5th layer; intermediate layer (IL-2) gelatin

0.8g

6th layer; low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.4μ)
0.6 g
(Average particle size 0.3μ)
0.2 g
Sensitizing dye (S-4)
6.7 x 10-4 (mol/1 mol of silver)
〃 (S-5)
0.8 x 10-4 (mol/silver 1 mol) Magenta coupler (M-A)
0.17g
〃 (M-B)
0
．． 43g colored magenta coupler (CM-1)
0.10
g DIR compound (D-3)

0.02g High boiling point solvent (Oil-2)

0.7 g gelatin

1.0 g

017
0] 7th layer; High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average grain size 0.7μ)
0.9 g sensitizing dye (
S-6) 1.1
×10-4 (mol/silver 1 mol) 〃 (S
-7) 2.0×
10-4 (mol/1 mol of silver) 〃 (S-
8) 0.3×1
0-4 (mol/silver 1 mol) Magenta coupler (M-
A)
0.30g 〃
(M-B)
0.13g
Colored magenta coupler (CM-1)
0.04g DIR
Compound (D-3)
0.004g
High boiling point solvent (Oil-2)
0.35
g Gelatin

1.0 g

8th layer; Yellow filter layer (YC) Yellow colloidal silver
0.1
g Additive (HS-1)

0.07g (HS-2)

0.07g (S
C-1)
0.12g
High boiling point solvent (Oil-2)
0.1
5g gelatin

1.0 g

9th layer; low-speed blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (average grain size 0.3μ)
0.25g
(Average particle size 0.4μ)
0.25g Sensitizing dye (S-9)
5.8×10-4 (mol/silver 1 mol) Yellow coupler (Y-1)
0.6 g
〃 (Y-2)
0
．． 32 DIR compound (D-1)

0.003g (D-2)

0.006g High boiling point solvent (Oil
-2)
0.18g gelatin

1.
3g

10th layer; Highly sensitive blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (average grain size 0.8μ)
0.5 g Sensitizing dye (S-10)
3×10-4 (mol/1 mole of silver)
(S-11) 1.2
×10-4 (mol/1 mole of silver) Yellow coupler (
Y-1)
0.18g
〃 (Y-2)
0.10g
High boiling point solvent (Oil-2)
0.
05g gelatin

1.0 g

11th layer; First protective layer (PRO-1) Silver iodobromide (average grain size 0.08μ)
0.3
g Ultraviolet absorber (UV-1)
0
．． 07g 〃 (UV-2)

0.10g additive (HS-1)

0.2 g
(HS-2)
0.1
g High boiling point solvent (Oil-1)

0.07g (Oil-3)

0.07g gelatin

0.8g

12th layer; second protective layer (PRO-2) Compound A

0.04g Compound B

0.004g polymethyl methacrylate (average particle size 3μ)
0.02g Methyl methacrylate: Ethyl methacrylate: Methacrylic acid =
3:3:4 (weight ratio) copolymer (average particle size 3μ)
0.13g

017
6] The above color negative film further contains compounds Su-1, Su-2, viscosity modifier, hardener H-1, H-
2. Stabilizer ST-1, antifoggant AF-1, AF-2
(weight average molecular weight 10,000 and 1,100,
000), dyes AI-1, AI-2 and compound DI-1 (9.4 mg/m2).

[0177]

[C22]

[0178]

[C23]

[0179]

[C24]

[0180]

[C25]

[0181]

[C26]

[0182]

[C27]

[0183]

[C28]

[0184]

[C29]

[0185]

[C30]

[0186]

[Chemical formula 31] Component A: Component B: Component C = 50:46:40 (molar ratio)

[Preparation of Emulsion] The silver iodobromide emulsion used in the 10th layer was prepared in the following manner.

A silver iodobromide emulsion was prepared by a double jet method using monodispersed silver iodobromide grains (silver iodide content 2 mol %) having an average grain size of 0.33 μm as seed crystals.

Solution <G-1> was heated to a temperature of 70°C and a pAg of 7.
8. While maintaining the pH at 7.0 and stirring well, a seed emulsion equivalent to 0.34 mol was added. (Formation of internal high iodine phase - core phase) Then <H-1>
and <S-1> were added at an accelerated flow rate (the final flow rate was 3.6 times the initial flow rate) over a period of 86 minutes while maintaining a flow ratio of 1:1. (Formation of external low iodine phase - shell phase) Subsequently, pAg1
<H-2> and <S- while keeping the pH at 0.1 and pH 6.0.
2> was added at an accelerated flow rate (end flow rate 5.2 times the initial flow rate) at a flow rate ratio of 1:1 over a period of 65 minutes.

The pAg and pH during particle formation were controlled using a potassium bromide aqueous solution and a 56% acetic acid aqueous solution. After the particles were formed, they were washed with water by a conventional flocculation method, and then gelatin was added to redisperse them, and the pH and pAg were adjusted to 5.8 and 8.06, respectively, at 40°C.

The obtained emulsion had an average grain size of 0.80 μm,
It was a monodisperse emulsion containing octahedral silver iodobromide grains with a distribution width of 12.4% and a silver iodide content of 8.5 mol%. <G-1> Ossein gelatin

100.0g 10% by weight methanol solution of compound-1 25.0
ml 28% ammonia aqueous solution
440
．． 0ml 56% acetic acid aqueous solution

Finish with 660.0ml water

5000.0ml <H-1> Ossein gelatin

82.4g potassium bromide

151.6g potassium iodide

90.6g
finish with water
103
0.5ml <S-1> Silver nitrate

309.2g 28% ammonia aqueous solution

Equivalent Finish with water
1030.5ml<
H-2> Ossein gelatin

302.1g potassium bromide

770.0g Potassium iodide

33.2g
finish with water
3776
．． 8ml <S-2> Silver nitrate

1133.0g 28% ammonia aqueous solution

Equivalent Finish with water
3776.8ml

0
192]

[C32]

[0193] In a similar manner, the average particle size of the seed crystal, temperature,
The above emulsions having different average grain sizes and silver iodide contents were prepared by varying pAg, pH, flow rate, addition time, and halide composition.

All of them were core/shell type monodispersed emulsions with a distribution width of 20% or less. Each emulsion was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and the sensitizing dye, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene ,
1-phenyl-5-mercaptotetrazole was added.

The color film sample prepared as follows is processed in the following processing steps.

[0196]

[Table 7] *The first and second rows of the stabilization tank were of a counter current type, and the replenisher was replenished in the second row. The treatment liquid used in each treatment step is as follows.

<Color developer> (1 liter powder processing agent) Potassium carbonate

30g sodium bicarbonate

3.5g 1-hydroxyethane-1,1
-Sodium diphosphonate 2.5g Sodium diethylenetriaminepentaacetate
2.0g 4-amino-3-methyl-N-(β-hydroxyethyl)aniline sulfate (CD-4)

4.8g Sodium sulfite

3.5g Hydroxylamine sulfate
2.8g sodium bromide
1.
3g potassium iodide

0.6mg

<Bleach> (Powder processing agent for 1 liter) Ferric potassium 1,3-propylenediaminetetraacetate
180g Sodium ferric ethylenediaminetetraacetate
40g Sodium ethylenediaminetetraacetate

5g potassium bromide

150g sodium nitrate

35g maleic acid

28g

<Fixer> (Powder processing agent for 1 liter) Sodium thiosulfate
200g
sodium sulfite

20g potassium thiocyanate

100g Sodium ethylenediaminetetraacetate
5g

<Stabilizer> (1 liter slurry processing agent) Hexamethylenetetramine
10g
Polyethylene glycol (molecular weight 1540)
2g

[0201]

[Chemical formula 33] Diethylene glycol

5g of the stabilizer was used in the form of a slurry using a commercially available kneader.

[0202] As in Example 1, each treatment agent prepared in this manner was placed in an inner bag of water-soluble film, and gases as shown in Table 4 were sealed therein, and the same experiment as in Example 1 was carried out. I did it. However, the density of the unexposed area was measured using a photoelectric densitometer to measure the transmitted green density. The results are summarized in Table 4.

[0203]

[Table 8]

The descriptions in Table 4 above are the same as those in Table 1 of Example 1. From Table 4 above, the effects of the present invention are clear.

[0205]

[Effects of the Invention] According to the present invention, there is no need to use plastic bottles or the number of plastic bottles is greatly reduced, so it is suitable for the social environment, and there is no scattering of fine powder of the solid photographic processing agent, so the work environment is improved. Demonstrates suitability and improves storage stability.
The stain that occurs in the unexposed areas of silver halide photographic light-sensitive materials has been improved, and the crystal precipitation in the air-contact parts of the walls of automatic processors has also been improved.Furthermore, the solidification of processing agents has led to lighter weight and reduced transportation costs. It is possible to provide a processing agent kit for silver halide photographic light-sensitive materials which is reduced in size and requires less storage space in a developing laboratory.

Claims (12)

[Claims] 1. A processing agent kit for silver halide photographic materials, characterized in that a gas is sealed together with a solid photographic processing agent in a water-soluble film envelope or a water-soluble binder coating. 2. The processing agent kit for silver halide photographic materials according to claim 1, wherein the solid photographic processing agent is in the form of a tablet, granule, powder, block, or paste. 3. The processing agent kit for silver halide photographic light-sensitive materials according to claim 1 or 2, wherein the sealed gas is air, nitrogen, carbon dioxide, or an inert gas. 4. The processing agent kit for silver halide photographic light-sensitive materials according to claim 1, wherein the filling rate of the solid photographic processing agent is 90% by volume or less. 5. The water-soluble film is polyvinyl alcohol-based, methyl cellulose-based, polyethylene oxide-based,
The silver halide according to any one of claims 1 to 4, comprising at least one base material selected from starch, polyvinylpyrrolidone, hydroxypropylcellulose, pullulan, dextran, and gum arabic. Processing agent kit for photosensitive materials. 6. The processing agent kit for silver halide photographic materials according to claim 5, wherein the water-soluble film is polyvinyl alcohol-based. 7. The processing agent kit for silver halide photographic materials according to claim 1, wherein the water-soluble film has a thickness of 10 to 120 μm. 8. Any one of claims 1 to 7, wherein the solid photographic processing agent is at least one selected from a color developer, a black-and-white developer, a bleach, a fixing agent, a bleach-fixing agent, and a stabilizer. A processing agent kit for silver halide photographic light-sensitive materials described in the above. 9. The processing agent kit for silver halide photographic materials according to claim 1, wherein the water-soluble film is thermoplastic. 10. The processing agent kit for silver halide photographic light-sensitive materials according to claim 1, wherein the solid photographic processing agent consists of one mixture. 11. The silver halide photographic material according to claim 1, wherein a part or all of the alkaline agent in the solid photographic processing agent is covered with a water-soluble binder. Treatment kit. 12. The processing agent kit for silver halide photographic materials according to claim 11, wherein the alkaline agent is a carbonate.