JPH04230748A - Product for color development processing - Google Patents

Abstract

PURPOSE:To obtain a color developing agent product free from deterioration due to storage, capable of forming an image good in photographic performance by using this and low in conveyance cost due to compactness, and simple in preparation. CONSTITUTION:The constituents of the color development processing agents including an aromatic primary amine color developing agent are contained in >=3 different solid constituent layers and sealed to provide a vacuum packaged product for color development processing. At that time, an intermediate layer 3 composed essentially of at least one of a group an organic acid, a fluorescent whitening agent, a polymer compound, a surfactant, and a neutral salt.

Description

Description: FIELD OF THE INVENTION This invention relates to color development processing products used in preparing color development solutions. [0002] Silver halide color photographic light-sensitive materials (hereinafter referred to as light-sensitive materials) are processed through steps such as color development, desilvering, water washing, and stabilization after exposure. Color developing solution is used for color development, bleach solution, bleach-fix solution, fixer solution is used for desilvering processing,
Tap water or ion-exchanged water is used for washing, and a stabilizing solution is used for stabilization. Each treatment solution is usually 30 to 40
The temperature is adjusted to .degree. C., and the photosensitive material is immersed in these processing solutions for processing. [0003] The processing performance of these processing liquids deteriorates due to processing and aging, so a replenishment system or a batch system is applied to replace them with fresh ones. In such cases, the user is required to prepare a processing solution prior to processing. Although many of the chemicals used in preparation are solid, they may come into contact with each other and react, producing undesirable reaction products. For this reason, they cannot be handed to users in the form of a mixture. [0004] Therefore, chemicals that react with each other must be packaged separately and handed to the user, but this not only increases packaging and transportation costs, but also makes it easy for inexperienced users to mix the chemicals incorrectly. A problem arises. [0005] Therefore, in principle, the components of the processing liquid are divided into parts to prevent reactions, and these concentrated liquids are handed to the user so that the only operation required is dilution. For example, in a color developer, there are usually three parts: a part containing a color developing agent, a part containing an alkaline agent, and a preservative such as hydroxylamine sulfate.
A product made from a concentrated solution of parts is used. However, even in concentrated liquids, substances that react with each other are stored in separate containers, which does not allow for sufficient compactness. In addition, even if it is a concentrate, it is still a liquid, which requires a complicated dissolution operation at the manufacturing stage. Furthermore, since it is a liquid, there are many problems in terms of transportation. In addition to this, precipitation may occur in the concentrate during transportation, making it difficult to redissolve it. Therefore, European Patent Publication No. 196551 discloses that two of the constituent components of photographic processing agents react with each other.
A method has been proposed in which more than one type of particles are stacked with an inert layer interposed therebetween to prevent them from reacting with each other, and then vacuum packaged. This publication describes, as a specific example, a case where a black and white developing agent is used. However, regarding color developing agents for color photography, there is no mention of how best to stack them. OBJECTS OF THE INVENTION [0008] The object of the present invention is to provide a material that has excellent storage stability, has a compact shape, is easy to prepare, and has good photographic properties when processed using the same. The object of the present invention is to provide a processing product for color development that allows the formation of images. [Means for Solving the Problems] Such objects are achieved by the present invention as described in (1) to (4) below. (1) The constituent components of a color developing agent containing an aromatic primary amine color developing agent are stored in a container as three or more solid layers of different components, and this is sealed. A vacuum-packaged color development processing product, in which a compound selected from the group consisting of an organic acid, an optical brightener, a polymer compound, a surfactant, and a neutral salt is provided adjacent to the color developing agent-containing layer. A color development processing product characterized by having a layer containing at least one main component. (2) The color developing product as described in (1) above, wherein the color developing agent-containing layer is configured so as not to be adjacent to the preservative-containing layer. (3) The color developing agent-containing layer is located as the outermost layer, and one to three constituent layers containing a preservative and an alkaline agent are arranged through the layer (1) or The color development processing product described in (2). (4) Laminated on the color developing agent-containing layer, a group consisting of the layer, a preservative-containing layer, an organic acid, an optical brightener, a polymer compound, a surfactant, and a neutral salt. The color development processing product according to (3), which sequentially comprises a second layer containing at least one compound selected from the following as a main component and an alkali agent-containing layer. [Operation] In the present invention, the constituent components of a color developing agent containing an aromatic primary amine color developing agent are generally stored in layers for each different component in a container, and the containers are sealed under reduced pressure to form a solid. Because it is formulated into a formulation, it has a compact shape. Also, as a result of vacuum packaging, the constituent layers retain this shape and do not mix with each other. At this time, an intervening layer containing an organic acid, a fluorescent whitening agent, a polymer compound, a surfactant, and a neutral salt as main components is interposed as an adjacent layer to the layer containing the color developing agent. Since contact between the color developing agent and the alkaline agent is prevented, the promotion of oxidation of the color developing agent by the alkali is prevented, and there is no deterioration in processing performance even after long-term storage. In this case, the neutral salt may be an antifoggant or may be added separately as an inert substance. Furthermore, the layer structure of the present invention prevents contact between the color developing agent and the preservative, thereby improving storage stability. [0017] Further, since a vacuum-packaged, integral-shaped product is simply taken out of the container each time and dissolved in a predetermined amount of water, the liquid preparation operation is easy. Therefore, when processed using a color developing solution prepared using this, an image with good photographic performance can be obtained. [Specific Configuration] The specific configuration of the present invention will be explained in detail below. As shown in FIG. 1, the vacuum-packed color development processing product of the present invention contains components contained in a color development processing agent containing an aromatic primary amine color developing agent in a container 1. It is obtained by storing the container in layers and sealing it under reduced pressure so that the pressure inside the container is lower than atmospheric pressure. The container 1 in this case is not particularly limited as long as it is made of a material that can withstand vacuum packaging and does not react upon contact with the color developing agent. Specifically, resins such as polyethylene, polypropylene, nylon, polyvinylidene chloride, polyethylene terephthalate,
Metal foils made of aluminum or the like whose surfaces are coated with these materials are preferably used. [0021] The internal pressure of the container is 100 mmHg or less, preferably 50 to 1 mmHg, particularly preferably 30 to 1 mmHg.
g. By creating such a vacuum state, the influence of oxygen and moisture on the color developing agent can be eliminated. [0022] To form the package, the above-mentioned components are fed into the container 1 from 15 to form a predetermined amount of layers of uniform thickness, which are successively laminated, and then according to a known method,
For example, supply may be carried out by heat sealing 15 and vacuum packaging. As a result of the vacuum packaging, each of the constituent layers indicated by 2 to 6 in the figure forms a clear interface with the adjacent layer, and moreover, forms a rigid integrated body as a whole. In addition, there is almost no mutual diffusion of components between layers over time, and even if there is, it is negligible in terms of photographic performance. The number of layers in the present invention is three or more, and an intervening layer 3 is provided adjacent to the color developing agent-containing layer 2 in order to prevent the color developing agent and the alkaline agent from coming into contact and reacting. As the compound constituting such an intervening layer 3, even if it is a chemical as a constituent component contained in a color developing agent, a component that does not affect the photographic performance may be intentionally used. Specifically, at least one of a neutral salt, an organic acid, a fluorescent brightener, a polymer compound, and a surfactant is used. As neutral salts, alkali metal halides (sodium chloride, potassium chloride, potassium bromide,
Examples include sodium bromide, etc.), alkali metal sulfates (sodium sulfate, potassium sulfate, etc.), alkali metal nitrates (sodium nitrate, potassium nitrate, etc.). These include anti-fogging agents that fall under the category of processing chemicals, and additions such as sodium chloride in the processing of silver iodobromide sensitive materials (mainly photographic materials), whose presence or absence affects developing performance. There are some ingredients that are not functional agents and have no substantial effect. In addition, such components account for 10 wt% or less, preferably 5 to 1 wt% of the total weight.
It is preferable to set it as t%. Even if used within this range, photographic performance will not be affected. [0027] Organic acids are mainly used as chelating agents, and fluorescent brighteners are mainly used in processing photosensitive materials for printing. Examples of organic acids include diethyleneaminepentaacetic acid, catecholdisulfonic acid, catecholtrisulfonic acid, ethylenediaminetemethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1
．． 1-diphosphonic acid, EDTA, NTA, TTHA,
Examples include hydroxyethyliminodiacetic acid iminoacetic acid. Among these, those having a total stability constant with Fe(III) ions of 10 or more, particularly 15 or more are preferable, and in these cases, the stability of the main drug when adjacent to each other is high. Among these, diethyleneamine pentaacetic acid, catechol disulfonic acid, catechol trisulfonic acid, ethylenediamine tetramethylene phosphonic acid, nitrilotrimethylene phosphonic acid, and 1-hydroxyethylidene-1,1-diphosphonic acid are preferred, particularly diethylenetriamine pentaacetic acid and catechol Disulfonic acid is preferred. The organic acid is 0.5 to 1 liter of color developing solution.
Used in the range of 10g. As the fluorescent whitening agent, it is preferable to use a triazylstilbene type fluorescent brightening agent shown in the following formula 1, since the occurrence of fogging is further reduced. ##STR1## In the formula, X1, X2, Y1 and Y2
Each represents a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholino group, an alkoxy group (e.g. methoxy, ethoxy, methoxyethoxy, etc.), an aryloxy group (e.g. phenoxy, p-sulfophenoxy, etc.), an alkyl group (e.g. methyl, ethyl, etc.) ), aryl groups (e.g. phenyl, methoxyphenyl, etc.), amino groups, alkylamino groups (e.g. methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino, β-hydroxyethylamino, di(β-hydroxyethyl)amino) , β-sulfoethylamino, N-(β-sulfoethyl)-N'-methylamino, N-(β-hydroxyethyl-N'-methylamino, etc.), arylamino groups (e.g. anilino, o-, m-, p-sulfoanilino, o-,
m-, p-chloroanilino, o-, m-, p-toluidino, o-, m-, p-carboxyanilino, o-, m-
, p-hydroxyanilino, sulfonaphthylamino, o
-, m-, p-aminoanilino, o-, m-, p-anidino, etc.). M represents a hydrogen atom, sodium, potassium, ammonium or lithium. Specifically, the following chemical formulas 2, 3, 4, and 5
and compounds of formula 6, but are not limited thereto. [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 4] [Chemical 5] [Chemical 6] [Chemical] It can be synthesized by the usual method described in "Fluorescent Brighteners" edited by Japan Industrial Association (published in August 1976), page 8. These triazylstilbene brighteners are
It is preferably used in an amount of 0.2 to 6 g, particularly preferably 0.4 to 3 g, per liter of color developer. Furthermore, the molecular weight of the polymer compound used in the present invention is not particularly limited, but is between 1000 and 500.
00 degree, degree of polymerization 100-5000, especially 200-20
00 is preferred. These polymer compounds are mainly used for purposes such as preventing crystallization of color developing agents. An example of such a polymer compound is one in which vinyl alcohol or vinyl pyrrolidone is used as a copolymer. , vinylmethylimidazole,
Ionene, acrylic, acrylic acid, methacrylic acid, maleic anhydride, maleic acid, styrene sulfonic acid, vinylbenzoic acid, phenol, polyester silicone, vinyl succinimide, acrylonitrile, vinyl ester,
Examples include acrylic esters, vinyl alcohol, and vinylpyrrolidone. Among these, those containing 20 mol% or more of vinyl alcohol or vinylpyrrolidone are preferred, and those containing 40 mol% or more of vinyl alcohol or vinylpyrrolidone are particularly preferred. The copolymer contains 70 mol% or more, and it is practically desirable that these copolymers be water-soluble so that they can be uniformly dissolved. Preferred specific examples of the polymer compound as the polymer are shown below, but the present invention is not limited thereto. B-1 Polyvinyl alcohol B-2
Vinyl alcohol-vinyl acetate/copolymer B-3
Vinyl alcohol-acrylic acid/copolymer B-4 Vinyl alcohol-vinylpyrrolidone/copolymer B-5 Vinyl alcohol-methacrylic acid/copolymer B-6 Vinyl alcohol-maleic acid/copolymer B-7 Vinyl Alcohol-acrylonitrile/copolymer B-8 Vinyl alcohol-acrylic ester/copolymer B-9 Vinyl alcohol-acrylic ester-acrylic acid/copolymer B-10 Polyvinylpyrrolidone B-11 Vinylpyrrolidone-acrylic ester /
Copolymer B-12 Vinylpyrrolidone-vinyl acetate/copolymer B-13 Vinylpyrrolidone-methacrylic acid/copolymer B-14 Vinylpyrrolidone-maleic acid/copolymer B-15 Vinylpyrrolidone-acrylamide/copolymer Combined B-16 vinylpyrrolidone-methacrylamide/
Copolymer B-17 Vinylpyrrolidone-acrylic acid/Copolymer B-18 Vinylpyrrolidone-acrylic acid ester-
Acrylic/copolymer B-19 Vinylpyrrolidone-vinyl alcohol-acrylic acid/copolymer B-20 Vinylpyrrolidone-vinyl alcohol-acrylic acid ester/copolymer Addition of these polymer compounds to the color developer The amount is preferably 0.05g/l to 2g/l,
More preferably 0.1 g/l to 1 g/l. Furthermore, as a surfactant, the following chemical formulas 7 and 8 are used.
, Formula 9 is preferred. The surfactant may be either anionic or nonionic. Specific examples of surfactants are listed below. ##STR7## The amount of the surfactant used per liter of color developing solution is about 0.1 to 10 g/liter. [0051] Two or more of the above compounds may be mixed and blended in advance to form the intervening layer. For example, the combination of neutral salts such as potassium bromide and sodium chloride, the combination of chelating agents and optical brighteners such as diethylenetriaminepentaacetic acid and diaminostilbene optical brighteners, and the combination of ethylenediaminetetraacetic acid and ethylenediaminetemethylene phosphorus. Examples include the combined use of chelating agents such as acids. In the case of pre-mixing, the number of times the container is filled is reduced, time can be shortened, manufacturing equipment is simplified, and productivity is improved. Furthermore, since the amount of filling per time increases, the accuracy of the filling amount improves, and the accuracy of weighing improves, so productivity also improves in this respect. [0052] These compounds also have a 5wt content in the intervening layer.
% or more. Furthermore, multi-layering of these is also possible. Note that this intervening layer may have a thickness of at least 3 mm or more. The color developing agent-containing layer is usually a layer consisting only of a color developing agent, and such a layer is preferred in order to obtain good photographic performance. However, in some cases, optical brighteners, neutral salts, polymer compounds, surfactants,
It is also possible to mix with chelating agents. Furthermore, when multiple types of color developing agents are used in combination, a layer may be formed for each type of color developing agent, or a layer containing a mixture of multiple types may be formed. By forming the intervening layer adjacent to the color developing agent-containing layer as described above, not only contact with the alkali agent-containing layer but also contact with the preservative is prevented. As preservatives, sulfites, solid hydroxylamines, and hydrazines are used, and these are usually used in combination. However, sulfites are used in only trace amounts in printing sensitive materials containing high silver chloride emulsions. [0056] Contact between sulfite and color developing agent is prevented because the color developing agent is usually in the form of sulfate or hydrochloride, which is actually quite acidic, and sulfite decomposes to produce sulfur dioxide gas. This is because similar sulfur dioxide gas is generated when dissolved in water. Furthermore, there arises the problem of accelerating deterioration of the main drug. It was unexpected that such a problem would arise. Preservatives such as hydroxylamines and hydrazines undergo redox reactions with color developing agents and produce various intermediate components, so it is preferable for long-term storage that they do not come into contact with each other in the processing agent container. . Furthermore, desensitization and formation of fog substances when combined with organic preservatives such as hydroxylamine over a long period of time are unexpected from the conventional concept that preservatives protect developing agents. Was that. Some hydroxylamines are originally solid, and even if they are liquid by themselves, such as diethylhydroxylamine, they can be turned into powder by converting them into sulfates, hydrochlorides, etc. In this way, the layer can be constructed as a solid. If it is to be used as a liquid, it may be removed from the vacuum package and stored in a separate container. However, in the present invention, it is preferable to use a solid material. This also applies to hydrazines. Hydroxylamines and hydrazines which can be used as preservatives for color developing agents are used in color developing agents and are not used in black and white developing agents. With the exception of the above-mentioned limitations, the adjoining layers of hydroxylamines and hydrazines may be determined depending on whether the compound is acidic, neutral, or alkaline. Hydroxylamines are not preferable if they are included in or adjacent to the alkali agent layer because they will increase fogging. This phenomenon is particularly noticeable with hydroxylamine. [0059] The alkaline agent-containing layer in the present invention is usually a layer consisting only of an alkaline agent, but the alkaline agent also includes a pH buffering agent. For this reason, it is common to use multiple types of compounds together, and in this case, it is possible to form a layer for each type of compound or a layer for a mixture of multiple types. In order to increase productivity, it is preferable to mix a plurality of types in advance to form a layer. [0060] It may also be mixed with a sulfite, and in some cases, a neutral salt, an alkali metal salt of a chelating agent, a 1-
It is also possible to mix with organic antifoggants such as phenyl-5-mercaptotetrazole and benzotriazole. In the present invention, the layers may be laminated under the above-mentioned restrictions, but in principle, a layer of an acidic compound is placed on the color developing agent side, a layer of an alkaline compound is placed on the alkaline agent side, and then an acidic compound layer is placed on the alkaline agent side. At least one layer composed of a neutral compound (e.g., a neutral salt, an optical brightener, a near-neutral salt of a chelating agent) is interposed between the layer of the compound and the layer of the alkaline compound. It is preferable to laminate them in such a manner. Examples of the acidic compound include organic acids such as hydroxylamines represented by hydroxylamine sulfate, and as a general rule, the closer the layer is to the color developing agent, the more acidic the compound is. However, it is preferable that the closer the layer is to a neutral compound, the less acidic it is. On the other hand, other alkaline compounds of the alkaline agent include sulfites, diethylenetriaminepentaacetic acid 5
Examples include alkaline salts of chelating agents such as sodium salts, and as a general rule, keep the most alkaline layer of alkaline agents away from neutral compounds.
It is preferable that the closer the layer is to a neutral compound, the lower the degree of alkalinity is. [0064] It is preferable to arrange the layers as described above in order to improve storage stability. As mentioned above, it is preferable to blend the layer constituents in each of the constituent layers 2 to 6 in advance, but as shown in the figure, the color developing agent-containing layer is located at the outermost layer (preferably the lowermost layer). , it is preferable to have the following 3-layer to 5-layer structure. 1) A three-layer structure in which an intervening layer 3 is interposed between a layer containing an alkaline agent and a preservative and a color developing agent-containing layer 2.2) In 1), an alkaline agent and a preservative are provided. A four-layer structure in which the preservative is a separate layer, an intervening layer 3 is placed on the color developing agent-containing layer 2, and a preservative-containing layer and an alkali agent-containing layer are placed on top of that in sequence. 3) 2 ), using the second intervening layer, as shown in the figure, the intervening layer 3 is arranged on the color developing agent-containing layer 2, the preservative-containing layer 4 is arranged thereon, and the intervening layer 3
A five-layer structure in which an alkali agent-containing layer 6 is arranged through a second intervening layer 5 similar to the above.Among these, the five-layer structure 3) is particularly preferable. [0070] It is preferable to stack the sulfite in contact with an acidic compound, especially since generation of sulfite gas during dissolution can be prevented. A layer made of a neutral compound may be appropriately provided between each layer made of an acidic compound or between each layer made of an alkaline compound. It is particularly preferable that a layer made of such a neutral compound be provided between layers made of an acidic compound. In particular, by installing such an intermediate layer,
Storage stability is improved by increasing the interlayer distance between the color developing agent and the hydroxylamines. [0071] In the above, acidic compounds, neutral compounds and alkaline compounds are defined by the acid dissociation constant (
In order, pKa (ionic strength 0.1 mol/l, 25°C) is less than 6,
Refers to those whose number is 6 or more and less than 8, and those whose number is 8 or more. For example, in the case of polybasic acids such as organic acids, the first acid dissociation constant is used as a guide. [0072] There is no particular restriction on the order in which each compound is supplied into the container during lamination, but it is preferable to supply the color developing agent first, and it is preferable that the color developing agent is added to the water last during liquid preparation. It is better to do so. [0073] In order to prevent the color developing agent from being oxidized by oxygen dissolved in water during solution preparation, preservatives such as sodium sulfite and hydroxylamines may be added first. This is because it is preferable that the alkaline agent is added before the color developing agent in order to prevent sodium sulfite from being decomposed by the acidic color developing agent. This is because by doing so, this becomes possible. [0074] The powder used in the present invention may be produced by freeze-drying. Further, the powder may be in the form of granules. The particle size of the powder is, for example, 150 to 3000.
μm is preferred. More preferably 500-1500μ
It is m. [0075] The thickness of each layer of the color developing agent in a vacuum-packed state usually corresponds to the amount of each chemical used when preparing one batch of color developing solution. For example, 10 l
For commercial use, the total thickness is about 50 to 300 mm, the color developing agent-containing layer is about 5 to 30 mm, and the alkaline agent-containing layer is about 10 to 250 mm. In addition, in the case of multiple layers, the total thickness of the layer composed of a neutral compound (including the above-mentioned intervening layer) that fundamentally separates each layer of acidic compound from each layer of alkaline compound is 2 to 2.
It is about 50mm. Furthermore, the total thickness of the layers composed of acidic compounds is about 2 to 30 mm, and the total thickness of the layers composed of alkaline compounds is about 2 to 30 mm. If there is a layer composed of a compound, this is included. Furthermore, in the present invention, the same compound can be added to a plurality of layers in a divided manner. Note that the total capacity is compact, about 200 to 1000 ml. When using the color development processing product of the present invention, it is usually sufficient to cut open a container such as a bag, add it to a predetermined amount of water, and dissolve it. At this time, it is preferable to cut the alkali agent-containing layer side and pour it into the water from this side. In principle, the present invention can be applied to solid chemicals, and as mentioned above, for those that require a liquid such as diethylhydroxylamine, only the liquid component is stored in a separate container, and only the solid component is stored in a separate container. The present invention may also be applied. However, the present invention can also be applied by impregnating a large amount of liquid components with low volatility and a small amount of liquid. Examples of such compounds include alkanolamines such as triethanolamine and diethanolamine, alcohols and glycols such as benzyl alcohol and diethylene glycol. Compounds to be impregnated include alkaline agents or pH buffering agents such as potassium carbonate and sodium bicarbonate, neutral salts such as sodium chloride and potassium bromide, and organic acids such as diethylenetriaminepentaacetic acid. Further, even if it is a liquid, if it can be pulverized by, for example, converting diethylhydroxylamine into a salt with an acid as described above, it can be pulverized and used as a solid. Silver halide color photographic light-sensitive materials that can be processed with a color developer prepared using the color development processing product of the present invention include color paper, color reversal paper, color negative film for photography, color reversal film, and movies. Known color photosensitive materials such as color negative films or color positive films, transmission type (film) or reflection type (paper) direct positive photosensitive materials can be used. As color papers, commercially available Fuji Color Paper Super FA Paper and Super HG Paper manufactured by Fuji Photo Film Co., Ltd., 2001 Paper manufactured by Eatsman Kodak Co., Ltd., and Koni Color QA manufactured by Konica Corporation are used.
Paper, Agfa Color Paper Type 9 manufactured by Agfa Gewald, etc. can also be mentioned. Color negative films include Fujicolor Super HRII100, Fujicolor Super HG100, Fujicolor Super HG200, Fujicolor Super HG400, Fujicolor Super HRII1600, Fujicolor Super HG1600, Fujicolor Reala, Eastman Kodak Co., Ltd., manufactured by Fuji Photo Film Co., Ltd., and Kodacolor manufactured by Eastman Kodak Company. Examples include Gold 100, Gold 200, Gold 400, Gold 1600, Ector 25, Ector 100, and Ector 1000. Next, the components constituting the color developing agent will be explained. The amounts shown below are for use as a color developer. The color developing agent used in the present invention is an aromatic primary amine compound, and includes known compounds widely used in various color photographic processes. However, in the present invention, preferred color developing agents are: (1) 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate
88] (2) 4-(N-ethyl-N-β-methanesulfonamidoethylamino)-2-methylaniline sulfate (3) 4-(N-ethyl-N-β-methoxyethylamino) -2-Methylaniline-p-toluenesulfonate (4) 4-(N,N-diethylamino)-
2-Methylaniline hydrochloride [0091] (5) 4-(N-ethyl-N-dodecylamino)-2-methylaniline sulfate [0092] (6) N,N-diethyl-p-phenylenediamine hydrochloride [ (7) 4-(N-ethyl-N-β-hydroxypropylamino)aniline sulfate (8) 4-(N-ethyl-N-γ-hydroxypropylamino)-2-methylaniline Sulfate, [
These are N,N-dialkyl-p-phenylenediamine color developing agents such as ##STR2##. [0096] The above color developing agent can be used in 1 liter of color developing solution.
The amount is used in the range of 0.013 to 0.065 mol, but from the viewpoint of speeding up, 0.016 to 0.048 mol is preferable, and 0.019 to 0.032 mol is particularly preferable. Normally, only one type of these color developing agents is used, but they can be used in combination depending on the purpose, such as discrimination or improvement of hue.The effects of the present invention are as follows.
The same effect can be obtained even when such a color developing agent is used in combination. As a preferable example of combined use, (1) and (2) above,
(1) and (3), (2) and (3), (1) and (7), (
Examples include 2) and (7). Further, in addition to (1) above, in color photosensitive materials for photographing, and (2) above, in color photosensitive materials for printing, (1) and (7) are mainly used. Preservatives used in color developing solutions include:
Hydroxylamine, diethylhydroxylamine, N
, N-disulfoethylhydroxylamine, N,N-dicarboxyethylhydroxylamine, etc., and sulfites are preferred. Further, hydrazines can be used, and specific examples include those described in JP-A-63-146041. In the present invention, hydroxylamine and diethylhydroxylamine are used in solid form, so they are used in the form of salts such as sulfate, hydrochloride, p-toluenesulfonate, oxalate, and citrate. Ru. [0100] The amount of hydroxylamine and diethylhydroxylamine added is 0.01 to 1 liter of color developer.
The amount of sulfite added is 0.1 mol, preferably 0.03 to 0.07 mol, and the amount of sulfite added is 0.005 to 0.08 mol, preferably 0.01 to 0.05 mol. however,
Sulfites are highly competitive in the color development reaction, and reducing this is a preferred embodiment in order to promote and speed up color development. Such a preferable addition amount is from 0.03 mol to no additive per liter of developer, particularly from 0.02 to 0.0 mol.
05 mol. Such an amount of sulfite added is particularly preferable for processing high-silver chloride (for example, 95 mol % or more silver chloride) type photosensitive materials. As the hydroxylamine, it is preferable to use a hydroxylamine compound represented by the following formula 10. Use of these compounds prevents decomposition of the color developing agent and ensures stable finishing performance. Further, the generation of tar due to decomposition of the color developing agent is also prevented, and the generation of stain can also be suppressed. Furthermore, these compounds have less effect on their own photographic performance, making the finishing performance more stable. ##STR10## In the formula, L represents an optionally substituted alkylene group, preferably a straight chain or branched chain having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms. preferable. Specifically, preferred examples include methylene, ethylene, trimethylene, and propylene. Examples of the substituent include a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, and an ammonio group which may be substituted with an alkyl group, and preferred examples include a carboxy group, a sulfo group, a phosphono group, and a hydroxy group. . A is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be substituted with alkyl, an ammonio group which may be substituted with alkyl, a carbamoyl group which may be substituted with alkyl, or an alkyl group. It represents an optionally substituted sulfamoyl group or an optionally substituted alkylsulfonyl group, and preferable examples thereof include a carboxy group, a sulfo group, a hydroxy group, a phosphono group, and a carbamonyl group that may be substituted with an alkyl group. Preferred examples of -LA include carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, and hydroxyethyl group. , carboxymethyl group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group, and phosphonoethyl group are particularly preferred examples. R represents a hydrogen atom or an optionally substituted alkyl group, and when it is an alkyl group, it is preferably a straight chain or branched chain having 1 to 10 carbon atoms, and more preferably a straight chain or branched chain having 1 to 10 carbon atoms.
5 is preferred. Examples of substituents include a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be substituted with alkyl, an ammonio group which may be substituted with alkyl, a carbamoyl group which may be substituted with alkyl, and an alkyl group. An optionally substituted sulfamoyl group, an optionally substituted alkylsulfonyl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonyl group, an optionally substituted amino group, an arylsulfonyl group, a nitro group, cyano group,
Represents a halogen atom. There may be two or more substituents. [0107] R is a hydrogen atom, a carboxymethyl group,
Preferred examples include carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, and hydroxyethyl group, and hydrogen atom, carboxymethyl group, carboxyethyl group, sulfoethyl group, Particularly preferred examples include a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group. L and R may be connected to form a ring. [0108] Furthermore, these may be in the form of salts. Next, specific compounds are shown as chemical formulas 11, 12 and 13. [Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13] [Chemical Formula 13] The amount of the compounds represented by the above Formulas 11, 12 and 13 is preferably 0 per liter of color developer. ．．
The amount is 1 to 50 g, more preferably 0.2 to 20 g. In the present invention, various chelating agents are used for the purpose of water softening and metal hiding. [0115] The chelating agent in the present invention is a solid. Such compounds include diethylenetriaminepentaacetic acid, nitrilotrimethylenephosphonic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid, 1,2
-dihydroxybenzene-3,5-disulfonic acid, catecholtrisulfonic acid, ethylenediaminetetraacetic acid, ethylenediaminetetramethylenephosphonic acid, and diaminopropanoltetraacetic acid are preferred. These may be in the form of free acids, alkali metal salts such as sodium or potassium salts, or ammonium salts. [0118] However, when it is a free organic acid, it is an acidic compound, and when it is in the form of a salt, it is acidic.
Many are neutral or alkaline compounds. [0119] Generally, in the present invention, the organic acid is more often used in the form of an organic acid. The antifoggant used in the present invention includes alkali metal halides, and alkali metal bromides such as potassium bromide, sodium bromide, and lithium bromide are preferably used. [0121] Potassium chloride and the like can also be used. [0122] Not more than 0.02 mol/l is added to the color developing solution for purposes such as fog suppression and gradation adjustment, but it is preferably not more than 0.015 mol/l in order to speed up development. is preferred. [0123] Various antifoggants can also be used to suppress fog and improve discrimination. Preferred examples of the antifoggant include benzotriazole, 5-methylbenzotriazole, 6-nitrobenzimidazole, 5-phenyltetrazole, 1-phenyl-5-mercaptotetrazole, L.I. F. A. Mason, Photographic Processing Chemistry 2nd Edition (published in 1975), 3
The organic antifoggants described on pages 9 to 42 can be mentioned, and the amount used is preferably the same as that described in the same publication. [0124] Also, T. H. 4-Hydroxy-6-methyl-1,3,3a,7-tetraazaindene, etc., described in The Theory of Photographic Process, 4th edition, pages 398 to 399 by James, are also preferred, and the amount used is the same as the above-mentioned organic antifoggant. Among these antifoggants, halides are neutral salts, while organic antifoggants are solid, neutral compounds. [0126] In order to speed up development, it is also preferable to use various development accelerators in the color developing solution. Examples of these development accelerators include the above-mentioned L. F. A. Compounds described on pages 41 to 44 of Mason's book, and from page 15 of the same book
Examples include the use of various black and white developing agents described on page 29, among which pyrazolidones such as 1-phenyl-3-pyrazolidone, p-aminophenols,
Tetramethyl-p-phenylenediamine and the like. The preferred usage amount of these development accelerators is 1 liter of color developing solution.
The amount is 0.001g to 0.1g, particularly preferably 0.003 to 0.05g. [0127] These are generally solid and approximately neutral compounds, and in the present invention, they are preferably placed adjacent to the color developing agent, organic acid, or neutral salt layer. In the present invention, the pH of the color developer is 9.
It is set in the range of 5 to 12, but from the point of view of speeding up, 10
．． It is preferably 2 or more, particularly preferably 10.5 to 11.5. By increasing the pH, it is possible to promote both silver development and color development reaction, and is particularly effective in promoting color development of cyan dye. [0129] In order to achieve such a pH, an alkali agent is added, and examples of the alkali agent used in the present invention include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide. . [0130] In order to raise the pH, it is preferable to increase the amount of alkali metal hydroxide added as an alkaline agent and to increase the amount of pH buffering agent as an alkaline agent. The amount of alkali metal hydroxide added is 0.02 to 0.4 mol, preferably 0.02 to 0.4 mol per liter of color developing solution.
．． The amount of pH buffer is from 0.2 mol to 1.0 mol, preferably from 0.3 mol to 0.8 mol, particularly preferably from 0.35 mol per liter of color developer. mole to 0.5 mole. [0132] The color development step may be carried out using two or more baths with different pH values; for example, the first bath is treated as a developer solution with a pH of 9 or less for a very short time, followed by a high pH solution with a pH of 10.5 or more. By processing with a developer, it is also possible to adjust the balance of development progress between the upper layer and the lower layer. [0133] When processing with a color developer prepared using the vacuum-packed color developer of the present invention, the development temperature is 2.
A range of 5 to 50°C is selected, but for the purpose of speeding up,
Preferably the temperature is 33-48°C, especially 35°C.
~45°C is preferred. [0134] Furthermore, the development time is 3 minutes and 30 seconds or less. Here, the development time is the time from when the leading edge of the photosensitive material is first immersed in the color developer until it is first immersed in the processing solution of the next step, and includes the time in the air during which the tip of the photosensitive material moves between steps. do. [0135] Generally, the time in the air is 1 second to 30 seconds,
To speed up the process, which is the objective of the present invention, it is preferable that the time in the air is short, specifically 15 seconds or less, particularly 10 seconds or less. [0136] The above color developing solution is preferably used continuously by supplying a replenisher. The replenisher has
It contains an amount necessary to replenish components consumed during development or consumed over time. Therefore, it usually contains a slightly larger amount of components than the developing mother liquor. The ratio thereof is generally 10 to 50% greater than the mother liquor. [0137] However, since bromide is eluted from the photosensitive material during development, it is preferable to set the content of the replenisher to be smaller than that of the mother liquor, and as the amount of replenishment is reduced, the content can be further reduced. preferable. For example, 1m2 of photosensitive material
When the replenishment amount per liter is set to 700 ml or less, the bromide content is preferably 0.004 mol or less per 1 liter, and when the replenishment amount is 500 ml or less, it is preferably 0.003 mol or less. preferable. When further reducing the amount of replenishment, it is also preferable not to include bromide. [0138] The present invention can also be applied to the preparation of such a replenisher, and the ratio of each component may be set in consideration of the composition of the replenisher. The light-sensitive material after color development using the present invention is processed according to predetermined processing steps. [0140] After the color development process, a desilvering process is performed. Desilvering may be carried out simultaneously with bleaching and fixing (bleach-fixing) or separately. Furthermore, in order to speed up the processing,
The processing method described in No. 2, which involves bleaching and then bleach-fixing, may also be used. Furthermore, processing with a two-tank continuous bleach-fixing bath described in JP-A No. 62-91952, JP-A-61-51
A fixing treatment may be performed before the bleach-fixing treatment described in No. 143, or a bleaching treatment may be performed after the bleach-fixing treatment, depending on the purpose. As a bleaching agent, for example, iron (III
), cobalt (III), chromium (VI), copper (I
Compounds of polyvalent metals such as I), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3- Aminopolycarboxylic acids such as diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Of these, iron ethylenediaminetetraacetate (III
) Aminopolycarboxylic acid iron(III) including complex salts
) Complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. In addition, iron aminopolycarboxylate (III
) Complex salts are particularly useful in both bleach and bleach-fix solutions. These aminopolycarboxylic acid iron (II
I) The pH of the bleaching solution or bleach-fixing solution using a complex salt is usually 5.5 to 8, but in order to speed up the processing, the pH can be lowered. Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, especially ammonium thiosulfates. is the most widely used. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred. In the present invention, when a bleaching solution and/or a bleach-fixing solution is used, the amount of replenishment is 200 to 1500 ml per 1 m2 of color photosensitive material for photography, but from the viewpoint of simplifying processing, it is preferably 800 ml or less. Particularly preferably, the volume is 500 ml or less. In addition, for color photosensitive materials for printing, 25~
The volume is preferably 500 ml, but it is also preferably 250 ml or less, particularly preferably 150 ml or less. [0144] When a bleach-fix solution is used, the fixing agent is preferably thiosulfate, and its concentration is 0.5 to 2 per liter.
It is in the molar range. [0145] The temperature of bleaching, fixing, and bleach-fixing treatment is 25~
The temperature is 50℃, but for speeding up the temperature, it should be 30℃ or higher, especially 35℃.
℃ or higher is preferable. [0146] In addition, the bleach-fix solution used in the present invention preferably contains bromide in order to promote bleaching. It is also a preferred embodiment to use an iodide ion trapping means such as an anion exchange resin in order to remove iodide ions accumulated in the bleach, bleach-fix, and fixer solutions and promote bleaching and fixing reactions. [0147] Furthermore, the bleaching solution, fixing solution, and bleach-fixing solution may contain fungicides and fungicides such as isothiazolones, thiabendazoles, benzotriazoles, and quaternary ammonium compounds. Further, after the desilvering treatment, a water washing treatment and/or a stabilization treatment are performed. It is preferable to use deionized water as described in Japanese Patent Application No. 61-131632 as the washing liquid or stabilizing liquid in the washing treatment and stabilization treatment. Also, JP-A-57-
Including isothiazolone compounds described in No. 8542,
Thiabendazoles, benzotriazoles, chlorinated isocyanurates, and the like can be added as fungicides or fungicides. Additionally, water softeners such as ethylenediaminetetraacetic acid, optical brighteners, and the like can also be added. In addition to the above, an image stabilizer such as formalin or ammonium salt is added to the stabilizing solution. [0151] Furthermore, it is preferable to use a surfactant, particularly a nonionic surfactant as shown in the following formula 14, in the washing liquid and the stabilizing liquid. ##STR14## This improves the washing or stabilization efficiency. [0154] It is preferable that the water washing or stabilization treatment process be configured with a plurality of tanks, and a multistage countercurrent system in which the last tank is replenished. The number of tanks is usually 2 to 6, preferably 2.
~4. [0155] The pH of the washing liquid and stabilizing liquid is generally in the range of 5 to 9, preferably 6 to 8. The processing time in the washing tank or stabilization tank can be set arbitrarily depending on the purpose.
Generally, it is in the range of 30 seconds to 5 minutes, and if speeding up is required, it is set in the range of 30 seconds to 1 minute and 30 seconds. Further, the processing temperature is 20 to 40°C, but in rapid processing, it is set to around 35°C from the viewpoint of promoting cleaning. [0156] In the present invention, the amount of replenishment of the washing tank or stabilizing tank is 100 to 100 per m2 of color photosensitive material for printing.
500ml, 200 per m2 of color photosensitive material for photography
Although it is set in the range of ~1200 ml, it can also be set to 400 ml or less per 1 m 2 of color photosensitive material for printing, and 800 ml or less per 1 m 2 of color photosensitive material for photographing. [0157] The color development process in the present invention can also be applied to reversal development process. In this case, a reversal bath or the like may be used in combination after the first black-and-white development process. [0158] In addition, in the present invention, when preparing not only a color developing solution but also other processing solutions such as a bleach solution, a bleach-fix solution, a fixer solution, and a stabilizer solution, it is possible to use a method for each processing solution according to the present invention. A vacuum packaging treatment agent may also be used. [Examples] Hereinafter, specific examples of the present invention will be shown to explain the present invention in further detail. Example 1 The constituent components of the color developing solution used are shown below. [0161] All of these components are powders (solids). (Components) Alkaline agent: Potassium hydroxide
12.5g
potassium carbonate
345g Sodium bicarbonate 20g Preservative: Sodium sulfite
40g Hydroxylamine sulfate (monohydrate) 24g Water softener: diethylenetriaminepentaacetic acid 40
g Aromatic primary amine color developing agent: 4-amino-3-
Methyl-N-ethyl-N- (β-hydroxyethyl)aniline sulfate 46g
Antifoggant: Potassium bromide
14 g [0163] The above components were each housed in an aluminum foil bag whose surface was coated with a low-density polyethylene resin having a thickness of 120 μm by the following method. [0164] These can be stored as items 1 to 8 depending on the storage method.
shall be. Stored item 1 (comparative example): The above components were sufficiently blended in the above amounts, and the bag was placed in a bag and then sealed. Contained Item 2 (Comparative Example): The above components were thoroughly blended in the above amounts, and the bag was placed in a bag and sealed under reduced pressure of 20 mmHg. Stored Items 3 to 11: Stored in layers with the following configuration and then sealed under reduced pressure of 20 mmHg. Note that I added the ingredients starting from the bottom. Also, in these
Unless otherwise specified, each of the above components was laminated in layers in the above amounts. In addition, the number of layers in these is also noted. These materials have a total thickness of about 15 to 20 cm in the layer direction. Containment 3 (Number of layers: 8: Comparative example) Potassium hydroxide Potassium carbonate Sodium bicarbonate Color developing agent Potassium bromide Hydroxylamine sulfate Diethylenetriamine Pentaacetic acid Sodium sulfite Containment 4 (Number of layers: 8: Invention ) Potassium hydroxide Potassium carbonate Sodium bicarbonate Sodium sulfite Potassium bromide hydroxylamine sulfate Diethylenetriaminepentaacetic acid Color developing agent 0170 Storage item 5 (Number of layers: 9: present invention) Potassium hydroxide Potassium carbonate Sodium bicarbonate Sodium sulfite bromide Potassium 7g*1) Hydroxylamine sulfate Diethylenetriaminepentaacetic acid Potassium bromide 7g*1) Color developing agent Storage 6 (Number of layers: 9: present invention) Potassium hydroxide Potassium carbonate Sodium bicarbonate Sodium sulfite Potassium bromide Hydroxyl Amine sulfate diethylenetriamine pentaacetic acid sodium chloride 20g*2) Color developing agent Storage item 7 (Number of layers: 10: present invention) Potassium hydroxide Potassium carbonate Sodium bicarbonate Sodium sulfite Potassium bromide Sodium chloride 10g*2) Hydroxylamine Sulfate diethylenetriaminepentaacetic acid sodium chloride 10g *2) Color developing agent 0173] Contains 8 (number of layers: 5: the present invention) 5th layer Potassium hydroxide *3) Potassium carbonate *3) Sodium hydrogen carbonate *3) Sodium sulfite *3) 4th layer potassium bromide 7g*1) 3rd layer hydroxylamine sulfate*4) diethylenetriaminepentaacetic acid*4) 2nd layer potassium bromide 7g*1) *5) Sodium chloride 10g*2)*5 ) 1st layer color developing agent 0174] Storage 9 (number of layers: 4: present invention) 4th layer Potassium hydroxide *3) Potassium carbonate *3) Sodium bicarbonate *3) Sodium sulfite *3) Third layer Odor Potassium chloride *4) Sodium chloride *4) 2nd layer color developing agent 1st layer hydroxylamine sulfate *5) Diethylenetriaminepentaacetic acid *5) Contents 10 (number of layers: 6: present invention) 6th layer water Potassium oxide *3) Potassium carbonate *3) Sodium hydrogen carbonate *3) 5th layer Potassium bromide 4th layer Hydroxylamine sulfate 3rd layer Diethylenetriaminepentaacetic acid 2nd layer Color developing agent 1st layer Sodium sulfite 0176] Storage Product 11 (Number of layers: 4 according to the invention) 4th layer Potassium hydroxide *3) Potassium carbonate *3) Sodium bicarbonate *3) Sodium sulfite *3) 3rd layer Hydroxylamine sulfate 2nd layer Potassium bromide *4 ) Diethylenetriaminepentaacetic acid *4) First layer color developing agent *1) Potassium bromide was divided into two parts and placed in two places. *2) A component used as an intervening layer that does not affect development performance. *3) , *4) , *5) The respective parts are blended in advance. [0178] The above stored items 1 to 8 were kept at 60°C and relative humidity 8.
After storage for 4 weeks under 0% conditions, each was dissolved in water to make a total volume of 10 liters. The color developing solutions prepared in this way are designated as color developing solutions I to XI, corresponding to the stored items 1 to 11. In this case, for storage items 3 to 11, after adding and dissolving in 8 liters of water from the upper layer side, add water again to make 10 liters.
And so. [0180] Next, a color negative film manufactured by Fuji Photo Film Co., Ltd., Fuji Color Super HG400, with a color temperature of 48
Wedge exposure at 00° C. and 5 CMS was applied, and processing was performed according to the following processing steps using each of the above color developing solutions I to XI. Processing process time Temperature Color development 3 minutes 15 seconds 38.0°C
Bleach 45 seconds 38.
0°C fixed 1 minute 30 seconds 3
8.0℃ water washing (1) 20 seconds
38.0℃ water washing (2) 20 seconds Stable at 38.0℃
Dry at 38.0℃ for 20 seconds
1 minute 00 seconds 55.0°C [0182] The compositions of processing solutions other than the color developing solution used in the above steps are described below. (Bleach solution) Mother liquor (g) Ferric ammonium 1,3-propanediaminetetraacetate 0.25 mol/l ammonium bromide
140.0 Ammonium nitrate
30.0 Acetic acid (98%)

25.0ml glycolic acid
70.0 Add water
1.0
l pH
3.3 (Fixer)

Mother liquor (g) 1-hydroxyethylidene-1,1-diphosphonic acid


1.0 Ammonium sulfite
1
2.0 Ammonium thiosulfate
Add 1.5 mol/l water
1
．． 0 l pH

6.7 (Washing liquid) Tap water
Calcium and magnesium ion concentrations were determined by passing water through a mixed bed column packed with a strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH anion exchange resin (Amberlite IR-400). was treated to 3 mg/l or less, and then 20 mg/l of sodium isocyanurate dichloride and sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5. (Stable solution) Mother liquor (g) Triethanolamine
2.0 Formalin (37%)
2.0ml
Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10%)
0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water
1.
0 pH
5.0 ~ 8.0 01
[87] In addition, a color developing solution (standard solution) was prepared by newly blending the above components to a volume of 10 liters, and treated in the same manner according to the above steps. [0188] For the color negative films processed using each of the color developing solutions I to XI, those processed using the standard solution were used as standard samples, and the differences in magenta dye sensitivity, average gradation, and fog with respect to these were compared. Find Table 1
Published in. In this case, the above photographic properties were determined as follows. Fog: The minimum density of magenta was defined as fog. Sensitivity: The logarithm of the exposure amount corresponding to the density of fog+0.2 was defined as the sensitivity. Average gradation: The gradation was defined as the value obtained by subtracting fog +0.2 from the density corresponding to the exposure amount obtained by adding 1.5 logarithmically to the exposure amount at the above sensitivity point. [Table 1] [0194] As is clear from Table 1, all of the samples processed according to the present invention have good photographic properties. Although the stored item 9 is of the present invention, since it is adjacent to a layer containing hydroxylamine sulfate (preservative), the sensitivity decreases significantly, which is not very preferable. Moreover, although the stored items 10 and 11 are of the present invention,
In the storage item 10, sodium sulfite (preservative) is adjacent, and in the storage item 11, hydroxylamine sulfate is adjacent to the alkaline agent layer. If sodium sulfite is adjacent to the main agent, the gradation difference will increase, and if hydroxylamine is adjacent to the alkaline agent layer, fog will increase, which is not very preferable. Example 2 The constituent components of the color developing solution used are shown below. [0197] All of these are powders (solids). (Components) Alkali agent: Potassium hydroxide
50g
potassium carbonate
263g sodium bicarbonate

20g Preservative: Disulfoethylhydroxylamine 60g
sodium sulfite
0.2g water softener: nitrilotrimethylenephosphonic acid 30g
diethylenetriaminepentaacetic acid
20g optical brightener: triazinylstilbene optical brightener

20g Aromatic primary amine color developing agent: 4-amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl) 3/2 aniline sulfate (monohydrate)
60g Antifoggant: Potassium chloride
40g 01
[99] The above components were each housed in an aluminum foil bag whose surface was coated with a low-density polyethylene resin having a thickness of 100 μm by the following method. [0200] These are stored items a to k depending on the storage method.
shall be. Stored item a (comparative example): The above components were sufficiently blended in the above amounts, and the mixture was stored in a bag and sealed. Storage item b (comparative example): The above components were thoroughly blended in the above amounts and sealed under reduced pressure of 10 mmHg. Stored items c to k: After being stored in layers with the following configuration, the items were sealed under reduced pressure of 10 mmHg. Note that I added the ingredients starting from the bottom. Also, in these
Unless otherwise specified, each of the above components was laminated in layers in the above amounts. In addition, the number of layers in these is also noted. [0204] These materials have a total thickness of 1 in the layer direction.
It is about 5 to 20 cm. Storage c (Number of layers: 10: comparative example) Color developing agent Potassium carbonate Sodium bicarbonate Sodium sulfite Potassium hydroxide Optical brightener (Compound A-13) Di(sulfoethyl)hydroxylamine Nitrilotrimethylenephosphonic acid Diethylenetriaminepentaacetic acid Potassium chloride d (Number of layers: 10: invention) Potassium hydroxide Potassium carbonate Sodium bicarbonate Sodium sulfite Optical brightener (Compound A-13) Di(sulfoethyl)hydroxylamine Nitrilotrimethylenephosphonic acid Diethylenetriamine Pentaacetic acid chloride Potassium color developing agent Contents e (Number of layers: 10: present invention) Potassium hydroxide Potassium carbonate Sodium bicarbonate Sodium sulfite Optical brightener (Compound A-13) Di(sulfoethyl)hydroxylamine Potassium chloride Nitrilotrimethylenephosphonic acid Diethylenetriaminepentaacetic acid Color developing agent 0208 Contains f (Number of layers: 10: present invention) Potassium hydroxide Potassium carbonate Sodium bicarbonate Sodium sulfite Potassium chloride Di(sulfoethyl)hydroxylamine Nitrilotrimethylenephosphonic acid Diethylenetriaminepentaacetic acid Fluorescent brightener (Compound A-13) Color developing agent 0209] Storage g (Number of layers: 10: present invention) Potassium hydroxide Potassium carbonate Sodium bicarbonate Sodium sulfite Optical brightener (Compound A-13) Di(sulfoethyl)hydroxylamine nitrilotrimethylene phosphone Acid diethylene triamine pentaacetic acid chloride Potassium chloride Color developing agent h (Number of layers: 11: present invention) Potassium hydroxide Potassium carbonate Sodium bicarbonate Sodium sulfite Optical brightener (Compound A-13) Di(sulfoethyl)hydroxylamine chloride potassium
20g*6) Nitrilotrimethylenephosphonic acid diethylenetriaminepentaacetic acid Potassium chloride 20g*6) Color developing agent*6) Potassium chloride was divided into two parts and placed in two places. Storage item i (number of layers: 5 according to the invention) 5th layer Potassium hydroxide *7) Potassium carbonate *7) Sodium hydrogen carbonate *7) Sodium sulfite *7) 4th layer Fluorescent brightener (Compound A- 13) Third layer di(sulfoethyl)hydroxylamine Second layer Potassium chloride *8) Nitrilotrimethylenephosphonic acid *8) Diethylenetriaminepentaacetic acid *8) Potassium chloride *8) First layer color developing agent 0212] Storage items j ( Number of layers: 5: present invention) Fifth layer Potassium hydroxide *7) Potassium carbonate *7) Sodium hydrogen carbonate *7) Sodium sulfite *7) Fourth layer optical brightener (Compound A-13) *8) Potassium chloride *
8) 3rd layer nitrilotrimethylenephosphonic acid *9) Diethylenetriaminepentaacetic acid *9) 2nd layer color developing agent 1st layer di(sulfoethyl)hydroxylamine *7), *8)
, *9): Each is blended in advance. Stored items k (number of layers: 4 according to the invention) 4th layer Potassium hydroxide *7) Potassium carbonate *7) Sodium hydrogen carbonate *7) Sodium sulfite *7) 3rd layer Di(sulfoethyl)hydroxylamine 2nd layer Layer optical brightener (compound A-13) *8) Potassium chloride *
8) Nitrilotrimethylenephosphonic acid *8) Diethylenetriaminepentaacetic acid *8) First layer color developing agent
After storage for 4 weeks under 0% conditions, each was dissolved in water to make a total volume of 10 liters. The color developing solutions prepared in this manner are designated as color developing solutions A to K in correspondence with the stored items a to k. In this case, the stored items c to k were put into water from the upper layer side, as in Example 1. Next, silver chloride color paper manufactured by Fuji Photo Film Co., Ltd., color temperature 2850K, 250
CMS wedge exposure was applied, and processing was performed according to the following processing steps using the color developing solutions A to H, respectively. Processing process temperature time color development 38.5°C 45
Second bleach fixing 38.0℃ 4
Wash with water for 5 seconds 1 38.0℃
Wash with water for 15 seconds 2 38.0℃
Wash with water for 15 seconds 3 38.0℃
Wash with water for 15 seconds 4 38.0
Dry for 15 seconds at ℃ 7
5.0° C. 50 seconds [0217] The compositions of processing solutions other than the color developing solution used in the above steps are described below. Bleach-fix solution Mother liquor Water

700ml ammonium thiosulfate solution (700g/
l) 100ml
ammonium sulfite
18g ethylenediaminetetraacetic acid ferric ammonium dihydrate
55g Ethylenediaminetetraacetic acid disodium dihydrate 3g Ammonium bromide
40g glacial acetic acid

Add 8g water

1000ml pH (25
℃)
5.5 0219
]Washing liquid tap water (calcium 23mg/l, magnesium 3mg
/l content, conductivity 170 μs/cm) [0220] In addition, a color developing solution (standard solution) was prepared by newly blending the above components to a volume of 10 liters, and according to the above steps,
Treated in the same way. [0221] Regarding the color paper processed using each of the color developing solutions A to K, the one processed using the standard solution was used as a standard sample, and the difference in sensitivity and fog of the cyan color image with respect to this was determined. Listed in Table 2. Further, the concentration of the color developing agent in the color developing solutions A to K at the time of preparation was measured, and the residual rate (%) of the color developing agent after storage was determined. This is also listed in Table 2. [0223] The above photographic properties were determined as follows. Fog: The minimum density of cyan was defined as fog. Sensitivity: Expressed as the logarithm of the exposure amount corresponding to the density of fog + 0.5. [0225] [Table 2] [0226] As is clear from Table 2, in the stored product to which the present invention is applied, the amount of color developing agent hardly changes due to storage, and when processed using this, good photographic properties can be obtained. images are obtained. [0227] Although the stored item j is of the present invention, since it is adjacent to the preservative layer, the deterioration of the main ingredient is accelerated contrary to expectations, and the sensitivity decrease is large, which is not desirable. Although the stored product i was pre-blended, the performance was good. Furthermore, although stored article k is of the present invention, since the preservative di(sulfoethyl)hydroxylamine is adjacent to the alkaline agent layer, fogging increases and the sensitivity decreases somewhat, which is not preferable. [0228] As described above, in the structure in which the preservative layer was provided adjacent to the color developing agent layer, a decrease in photographic properties was observed. Further, when the preservative is a sulfite salt, the sulfite decomposes during storage or when dissolved in water, resulting in the generation of sulfur dioxide gas. Example 3 In Example 2, 1.5 g of polymer compound B-9 was mixed into the layer adjacent to the main drug. [0230] Storage contents l (invention) 5th layer Potassium hydroxide *10) Potassium carbonate *10) Sodium hydrogen carbonate *10) Sodium sulfite *10) 4th layer Optical brightener (Compound A-13) 3rd layer Layer Di(sulfoethyl)hydroxylamine 2nd layer Potassium chloride *11) Nitrilotrimethylenephosphonic acid *11) Diethylenetriaminepentaacetic acid *11) High molecular compound B-9 *11) 1st layer color developing agent *10), *11) : Each pre-blended 0231
] As a result, the remaining active ingredient was 94%, and the fog difference was +0.01.
, the sensitivity difference was -0.03, which was good. Example 4 In Example 2, the following vacuum-packaged bleach-fixer and acetic acid solution were dissolved in 10 liters of water to prepare a bleach-fixer, and the following treatments were carried out in the same manner.The results were substantially the same as in Example 2. there were. [0233] <Vacuum packaging agent> Ammonium thiosulfate 700g
Pre-blended ammonium sulfite 180g
Pre-blended sodium p-toluenesulfinate
150g Ethylenediaminetetraacetic acid disodium dihydrate
30g ferric ammonium ethylenediaminetetraacetate 2
Water salt 550g 〈Acetic acid solution〉 Water 100ml Glacial acetic acid
80g Example 4 In Example 2, surfactant C-3 was added to the layer adjacent to the main ingredient.
10 g was mixed and evaluated in the same manner as in Example 2. 6th layer Potassium hydroxide *12) Potassium carbonate *12) Sodium bicarbonate *12) Sodium sulfite *12) 5th layer optical brightener (compound A-13) 4th layer di(sulfoethyl)hydroxylamine 3rd layer Potassium chloride 2nd layer Nitrilotrimethylenephosphonic acid *13) Diethylenetriaminepentaacetic acid *13) Surfactant c-13 *13) 1st layer Color developing agent *12), *13) are pre-blended.
] The results showed that the residual active ingredient was 94%, the fog difference was ±0, and the sensitivity difference was -0.03, which were good. Example 5 A color developer for silver chloride color paper having the following composition was placed in a 150 micron thick low-density polyethylene bag, sealed under a reduced pressure of 10 mmHg, and then placed at 40°C and at a relative humidity of 70°C.
% environment for 8 weeks. 5th layer Potassium hydroxide 45g*14) Potassium carbonate 280g*14) Sodium hydrogen carbonate 25g*14) 4th layer Potassium chloride 45g*15) High molecular compound (B-8) 10g*
15) Fluorescent brightener (compound A-15) 20g*
15) Potassium bromide 0.
1g*15) Third layer N,H-diethylhydroxylamine sulfate 7
0g Second layer 1,2-dihydroxybenzene-3.5-disulfonic acid 20g*16) Ethylenediaminetetraacetic acid 10g*16) Surfactant D-3 30g*16
) 1st layer (β-methanesulfonamidoethyl)aniline 3/2
Sulfate (monohydrate) 60g 0240] Storage item X is *14), *15), *16)
are blended in advance and then formed into the above layered structure (the present invention), and stored item Y is one in which everything is blended and then stored without the layered structure. After saving, store items X and Y to 10
When dissolved in 1 liter of water and analyzed for its composition, it was found to be as follows. [0241]
Storage item X Storage item Y

(Present invention) (Comparative example) Color developing agent residual rate 96% 7
4% N,N-diethylhydroxyl 92%
65% amine sulfate [0242] Also, using this developer, the same processing as in the example was carried out, and as a result, the fog density difference with respect to the separately prepared new solution was +0.007 for stored item X, and +0.007 for stored item Y. +0
．． 04, and the increase in fog was also very small for stored item X of the present invention. As shown in the above results, it can be seen that in the packaged article X of the present invention, the residual rate of the color developing agent and diethyl hydroxylamine sulfate as a preservative is high, and the preservability is excellent. [0244] According to the present invention, images with good photographic properties can be obtained without deterioration due to storage. Also,
It is compact and advantageous in terms of transportation costs. Furthermore, the liquid preparation work is easy.

[Brief explanation of the drawing]

FIG. 1 is a partially cutaway front view of a color development processing product of the present invention.

[Explanation of symbols]

1 Container 2 Color developing agent containing layer 3 Intervening layer

Claims (2)

[Claims] Claim 1: The components of a color developing agent containing an aromatic primary amine color developing agent are stored in a container as three or more solid layers of different components, and this is sealed and vacuum-treated. A packaged color development product, in which at least one compound selected from the group consisting of an organic acid, an optical brightener, a polymer compound, a surfactant, and a neutral salt is provided adjacent to the color developing agent-containing layer. A color development processing product characterized by having a layer mainly composed of: 2. The color development processing product according to claim 1, wherein the color developing agent-containing layer is configured not to be adjacent to the preservative-containing layer.