JPS62299848A - Method for preserving color developing solution without deteriorating characteristics - Google Patents

Abstract

PURPOSE:To enable a color developing solution to be preserved stable for a long term not accompanied by deterioration of characteristics by preserving the color developing solution containing a color developing agent, a specified preservative, and an alkali agent in a receptacle made of a plastic package material specified in oxygen permeability coefficient. CONSTITUTION:The color developing solution contains the color developing agent made of an aromatic primary amine, the preservative made of alkylated hydroxylamine represented by the formula shown on the right (each of R<1> and R<2> is H or 1-3C nonsubstituted alkyl, and either of them is said alkyl), and the alkali agent for keeping the color developing solution in a pH of >=9.5. This solution is preserved in the receptacle made of the plastic packaging material having an oxygen permeability coefficient of <=50ml/m<2>.atm.day at a temperature of 20 deg.C and in a relative humidity of 65%, and as the receptacle, flexible pillow type ones are preferable from the viewpoint of compactness and easiness in handling. Such a receptacle 10 is obtained, for example, by sticking and fixing a pair of outside walls 21, 22 each made of a flexible rectangular sheet to each other so as to overlap each other at each outer border.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for preserving a color developing solution used in the development of color silver halide photographic light-sensitive materials, and particularly relates to a method for preserving a color developing solution that does not cause deterioration of properties. This invention relates to a method for preserving color developing solutions.

[Background of the invention]

Generally, when forming a photograph, a process is required to form a negative or positive image by subjecting the silver halide photographic light-sensitive material after photography to processing such as development and fixing. In the case of photosensitive materials, color negative or positive images are formed through processes such as color development, bleach-fixing (bleaching and fixing may be performed separately), and water washing. be done.

Conventionally, processing of such silver halide photographic materials is
This process used to be carried out in photo labs with large-scale equipment, known as large lab systems, but recently, so-called in-house mini-lab systems, which can easily carry out processing at camera stores, offices, etc. has been developed, and opportunities for processing silver halide photographic light-sensitive materials are increasing even for so-called amateurs who have little or no experience in developing processing.

A color developer is required in the development of color silver halide photographic light-sensitive materials, but in the development process using a so-called in-house mini-lab system, the processor is an amateur, so the color developer is used as a color developer. It is desirable that the required component strength is already determined and that it can be used immediately.

However, color developing solutions have conventionally contained components that act as both oxidizing agents and reducing agents, so their properties tend to deteriorate due to internal redox reactions during storage. Also, it has the disadvantage that reducing substances are easily degraded by air oxidation. Therefore, there was a drawback that long-term storage was difficult.

For this reason, the supply of color developer to users has traditionally been
It was done as follows.

(1) A means of dividing and supplying a color developing solution prepared by experts at a photo lab called a large laboratory system to users immediately before use.

(2) A means for supplying each component of the color developer to the user in the form of a kit in which each component is separately packaged in several sachets.

However, with the method (1) above, when a user who operates a minilab system receives an order for a photograph, or the amount of the order is usually undefined, the necessary amount of mixed color developer is provided to the user for use. It is quite difficult to quickly and smoothly supply the color developer at the last minute, and in some cases, the color developer may not be supplied in time and the photograph cannot be formed within the time required by the orderer. On the other hand, it is conceivable to estimate the required amount and order a larger amount of color developer in advance, but in this case there is a problem that the characteristics of the color developer deteriorate.

On the other hand, in the method (2) above, there are a large number of components to be prepared, and it is necessary to dissolve each component in a solvent. After that, it is necessary to start dissolving the next component, and it is usually necessary to wait for several minutes to several tens of minutes with continuous stirring, which takes a considerable amount of time. It takes time and effort. In addition, in-house processing minilab systems installed in camera stores or offices are usually operated by amateurs, so when preparing color developing solutions, it is difficult to distinguish between individually packaged components, and color development is difficult. The developer may be mixed incorrectly, and a color developer with appropriate performance may not be obtained.

[Problem that the invention seeks to solve]

For this reason, the present inventors have conducted extensive research into containers that can store color developing solutions without deteriorating their properties.

For example, one idea is to prevent the properties of the color developer from deteriorating due to oxidation by storing the color developer sealed in a container made of plastic packaging material with extremely low oxygen permeability. It will be done.

However, color developing solutions conventionally contain hydroxylamine or its sulfate or hydrochloride as a preservative to prevent air oxidation and suppress redox reactions between components, and this hydroxylamine is alkali-based. It easily decomposes in liquid, and releases ammonia gas and nitrogen gas when it decomposes, which can cause a breakdown in photographic performance, and nitrogen gas can fill the sealed container, eventually causing the seal of the plastic packaging material to fail. Problems arise such as the color developer leaking due to breakage or damage to the color developer entrance/exit provided in the container.

On the other hand, it is conceivable to use a container made of plastic packaging material that easily permeates nitrogen gas, and to allow the nitrogen gas generated inside the container to escape outside the container. There is a problem in that oxygen gas enters the container, causing deterioration of the color developer due to oxidation.

In addition, by storing the color developer in a concentrated paste form in a container, the generation of nitrogen gas is suppressed, and during the development process, a fixed amount of color developer is removed from the container and automatically poured into water. A method was proposed in which the method was used while being dissolved in
7-500485).

However, with this technical means, the color developer is stored in a concentrated paste form in the container, so the color developer becomes highly alkaline, and as a result, the color developer is easily oxidized in the air, and prematurely caused by redox reactions. There is a problem that the characteristics tend to deteriorate.

For this reason, in reality, the color developing agent, the preservative made of hydroxylamine, and the alkaline agent must be packaged and stored separately, which makes it difficult for users to carry out the development process. When doing this, it was necessary to mix each component by oneself to create a color developing solution.

Furthermore, although unsubstituted hydroxylamine and its sulfate salts have excellent preservative properties, they are highly toxic in themselves, so they should not be used when users handle color developing solutions in home-processing minilab systems. However, there is a problem that there is a great possibility that it will have an adverse effect on the human body. For this reason, there is a strong desire for a preservative with less toxicity and superior performance.

In this way, we developed a color developer that does not require the work of mixing each component, has low toxicity and is safe to handle, and can be stored stably for a long period of time without deterioration of its properties. The reality is that a method for preserving it has not yet been discovered.

[Purpose of the invention]

The present invention was made based on the above-mentioned circumstances, and its purpose is to provide a color developing solution that does not require the work of blending each component, has low toxicity, and is safe to handle, while preventing deterioration of its properties. It is an object of the present invention to provide a method for storing a color developing solution, which can be stored stably for a long period of time without any liquid.

[Means for solving problems]

The method for preserving the color developing solution of the present invention includes the following components (1) to (3).
) with an oxygen permeability coefficient of 50 m
ff1/(+s2・atm-day) (Temperature 20°C
It is characterized by being stored in a container made of plastic packaging material with a relative humidity of 65% or less.

Component (1): Color developing agent consisting of an aromatic primary amine Component (2): Preservative consisting of an alkyl-substituted hydroxylamine represented by the following general formula (1) General formula (1) R1 (R', R ” each represents a hydrogen atom or an unsubstituted alkyl group having 1 to 3 carbon atoms;
3 is an unsubstituted alkyl group. ) Ingredient ■: Alkaline agent for adjusting the pH of the color developer to 9.5 or higher (effects of the invention) According to the present invention, in the color developer, component ■ contained as a retention agent is a specific alkyl Since it is a substituted hydroxylamine, it has low toxicity and is safe to handle, and has excellent performance as a preservative.
It has low reactivity with the alkaline agent (component (2)), so it can coexist extremely stably in the container, and even if it decomposes, it generates little ammonia gas, nitrogen gas, etc., so the container is less likely to be damaged. Furthermore, since the container containing the color developer is made of plastic packaging material with an oxygen passage coefficient below a certain level, oxidation of the color developer stored in the container can be effectively prevented, and these As a result, the color developing solution, which has low toxicity and is safe to handle, can be stored stably for a long period of time without deterioration of its properties.

Therefore, users of in-house processing type minilab systems can store color developing solution in a stable state at all times, and can quickly and properly develop color silver halide photographic materials. can.

[Specific structure of the invention]

The present invention will be specifically explained below.

In the present invention, a color developing solution containing the above-mentioned components (1) to (3) has an oxygen permeability coefficient of 50m! /(m2・a
tm-day) (temperature 20°C, relative humidity 65%) or less, more preferably 25mZ/(m”・atm-day)
) Store in containers made of the following plastic packaging materials:

In addition, the oxygen permeability coefficient is [02 permeation of plastic container, modern backing J (02 permeation of plastic container, modern backing J
iccontainer, Modern Packi
12 of ng; N, J., Calyyan, 196B)
It can be measured by the method described on pages 143 to 145 of the issue.

As the plastic packaging material forming the container used in the present invention, for example, a sheet 1 or Sheets made by laminating metal foil such as aluminum on these sheets or sheets made by vapor-depositing metals such as aluminum; also sheets made by laminating these sheets to sheets made of polyethylene or ethylene-vinyl acetate copolymer, etc. A laminated sheet consisting of; etc. can be used. Further, a container may be formed using one of these sheets, or a container may be formed using a combination of a plurality of sheets.

Among these plastic packaging materials, polyvinylidene chloride, nylon, and ethylene-vinyl acetate copolymer are particularly preferred because of their low oxygen permeability coefficient, high strength when formed into containers, and ease of processing into containers. A combined saponified product can be preferably used.

The specific form of the container is not particularly limited, but may be any form such as a bottle type, cubic type, pillow type, etc. For example, when obtaining a cubic type container, it is also possible to mold the container into a laminate by coextrusion using the above-mentioned plastic packaging materials.

In particular, flexible pillow-type containers are preferred because they are compact and easy to handle. An example of such a pillow type container is shown in FIGS. 1 and 2. FIG. 1 shows an example in which a container 10 is constructed by airtightly adhering and fixing a pair of outer walls 21 and 22 each made of a single flexible rectangular sheet, overlapping each other at their outer edges. FIG. 2 shows a container 10 constructed by a pair of outer walls 31 and 32 made of two independent flexible rectangular sheets, which are overlaid on each other at their outer edges and hermetically bonded and fixed. This is an example having an outer wall of a sheet.

40 is a storage chamber for a color developer, and 50 is an entrance/exit for the color developer.

If there is only one sheet forming the outer wall of the container 10 as in the example shown in FIG. However, if there are two sheets forming the outer wall of the container 10 as in the example shown in FIG.
``atm'day) or less.

As the sheet forming the outer wall, a single-layer plastic sheet, a multi-layer plastic sheet formed by laminating a plurality of plastic sheets, etc. can be used. In addition, the plastic sheet may be a sheet made only of plastic, a sheet made by laminating metal foil or paper, etc. on a plastic sheet, or a plastic sheet coated with a metal vapor-deposited film. It may be a sheet made of

Examples of single-layer plastic sheets include plastic sheets made of polyvinylidene chloride, nylon, saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyvinylidene chloride, etc.; metal foil made of aluminum etc. on these plastic sheets; Sheet made by laminating paper etc.; Sheet made by vapor depositing metal such as aluminum on the above plastic sheet;
etc. can be mentioned.

Plastic sheets with a multilayer structure made by laminating multiple plastic sheets include, for example, a three-layer structure of polyethylene terephthalate/polyvinyl alcohol/ethylene copolymer/polyethylene, Combined/3N structure of polyethylene, 3-layer structure of unstretched polypropylene/polyvinyl alcohol/ethylene copolymer/polyethylene, 3-layer structure of nylon/aluminum foil/polyethylene, 3-layer structure of polyethylene terephthalate/aluminum foil/polyethylene, cellophane/ 4-layer structure of polyethylene/aluminum foil/polyethylene, 3-layer structure of aluminum foil/paper/polyethylene, 4-layer structure of polyethylene terephthalate/polyethylene/aluminum foil/polyethylene, 4-layer structure of nylon/polyethylene/aluminum foil/polyethylene, paper /Polyethylene/aluminum foil/polyethylene 4-layer structure, polyethylene terephthalate/aluminum foil/polyethylene terephthalate/polypropylene 4-layer structure, polyethylene terephthalate/aluminum foil/polyethylene terephthalate/high-density polyethylene 4N structure, polyethylene terephthalate/aluminum foil/polyethylene /4-layer structure of low-density polyethylene, 2-layer structure of polyvinyl alcohol/ethylene copolymer/polypropylene, 3-layer structure of polyethylene terephthalate/aluminum foil/polypropylene
The layer structure is a three-layer structure of paper/aluminum foil/polyethylene, particularly preferably a four-layer structure of polyethylene/nylon coated with polyvinylidene chloride/polyethylene/ethyl vinyl acetate/polyethylene condensate, and a four-layer structure of polyethylene/nylon coated with polyvinylidene chloride/polyethylene. 3-layer structure, ethyl vinyl acetate/polyethylene condensate/polyethylene/aluminum-deposited nylon/polyethylene/
5-layer structure of ethyl vinyl acetate/polyethylene condensate, 4 layers of aluminum-deposited nylon/nylon/polyethylene/ethyl vinyl acetate/polyethylene condensate
Layer structure: 3-layer structure: oriented polypropylene/nylon coated with polyvinylidene chloride/PoIJ Knee 1-L/N; 3-layer structure: oriented polypropylene/nylon coated with polyvinylidene chloride/polyethylene; oriented polypropylene/polyvinyl alcohol/ethylene copolymer/ 3N low density polyethylene
Composition, 3-layer structure of oriented polypropylene/polyvinyl alcohol/ethylene copolymer/unoriented polypropylene, 3-layer structure of polyethylene terephthalate/polyvinyl alcohol/ethylene copolymer/low-density polyethylene, oriented nylon/polyvinyl alcohol/ethylene copolymer /
Examples include a three-layer structure of low-density polyethylene, a three-layer structure of unstretched nylon/polyvinyl alcohol/ethylene copolymer/low-density polyethylene, and the like.

In addition, the oxygen permeability coefficient is 501All (aa"-atra-
day) A container is formed using a multilayered plastic sheet made by laminating a plastic sheet with a high oxygen permeability coefficient but high flexibility made of polyethylene, ethylene-vinyl acetate copolymer, etc. to a plastic sheet having the following properties: In this case, a container with sufficient oxygen impermeability and excellent durability against pinhole formation can be obtained.

The thickness of the sheet forming the outer wall of the container varies depending on its constituent materials and cannot be generally specified, but is preferably about 5 to 1500 pm, particularly preferably 10 to 500 pm.

In the present invention, the color developing solution stored in the container contains components (1) to (2) as described above.

As the aromatic primary amine which is component (2), for example, N,
N'-dialkyl-p-phenylenediamine compounds may be used, and the alkyl group and phenyl group may be substituted with any substituent. Specifically, for example, N,N'-diethyl-p-phenylenediamine hydrochloride,
N-methyl-p-phenylenediamine hydrochloride, N,
N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amino Aniline sulfate, N-ethyl-N-β-hydroxyethylaniline, 4-amino-
3-Methyl-N,N'-diethylaniline, 4-amino-3-N-(2-methoxyethyl)-N-ethyl-3-
Methylaniline-p-toluenesulfonate, N-ethyl-N-propylparaphenylenediamine sulfate, 4-
Amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate, 4-amino-3-methyl-N.

No-diethylaniline sulfate, 4-amino-N-(β
-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate, N,N'-diethyl-3
-(β-methanesulfonamidoethyl)-4-aminoaniline sulfate and the like can be preferably used.

The content ratio of the aromatic primary amine is usually preferably 0.005 to 0.2 mol based on 11 moles of the color developing solution.

Aromatic primary amines that are particularly effective as color developing agents are
It is a phenylenediamine-based aromatic primary amine having at least one water-soluble group (hydrophilic group) in the amino group. Examples of such water-soluble groups include the following.

0 water-soluble group (CHz), CHzOH (CHt”)-NHSO2(CH2)-CHI3- (
CHI), -0-(C)12)Il-CHI3(C
HzCHzO) -C-Hz--rC00H -5O,H (However, m and n are integers of 0 or more.) Typical aromatic primary amines of the phenylenediamine type having such a water-soluble group For example, those represented by the following formula can be mentioned.

HsCz CzHaNH3OzCHx12 HsCg CgH40CH+H2 HOH,C,C,H40H H9C4CnHsSC)+H Hq C4Cs Hb S Os H NB2 HCH2C0OH th HsCz (CHzCH Particularly useful aromatic primary amines include (CHz )llCIl□0H1-(C112
)lI-NH30□-(CB2)-CHs, (CHI
)IlIO(Ctl□)□-CH3, (CthCHzO
) -C-B2--1, and specific examples include the formula Tl), (2), (3), (
4), (6) and (7).

Note that m and n are integers greater than or equal to 0, preferably 0.
It is an integer of ~5.

Particularly preferred among these compounds are those represented by the formula (
11, (3) and (4),
Among these, compounds represented by formulas (11 and (3)) can be particularly preferably used.

Examples of the alkyl-substituted hydroxylamine represented by the general formula (1) as component (1) include monomethylhydroxylamine, dimethylhydroxylamine, diethylhydroxylamine, methylethylhydroxylamine, monopropylhydroxylamine, monoethylhydroxylamine, dipropyl Hydroxylamine, methylpropylhydroxylamine, ethylpropylhydroxylamine, etc. can be mentioned.

Among these, monomethylhydroxylamine, dimethylhydroxylamine, diethylhydroxylamine, dipropylhydroxylamine, monoethylhydroxylamine, and monopropylhydroxylamine can be particularly preferably used.

The alkyl-substituted hydroxylamine acts as a preservative in the color developer, and the content of the alkyl-substituted hydroxylamine is usually preferably 0.01 to 150 g based on II2 of the color developer.
Particularly preferably 0.5 to 30 g.

The alkaline agent (component) lowers the pH of the color developer to 9.5.
These are the components used to achieve the above, and for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, tribasic potassium phosphate, etc. can be used. Some of these alkaline agents act as pl+ regulators or buffers.

In addition to the above-mentioned components (1) to (2), various additives may be added to the color developing solution used in the present invention, if necessary. Such additives include a preservative made of tJ1 sulfite, an antifogging agent, a development inhibitor, a development accelerator, an organic solvent, a cleaning agent that acts as a water softener or a heavy metal sequestering agent, and an auxiliary developer. Can be used.

Preservatives made of sulfite include sodium sulfite,
Examples include potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. The content ratio of the sulfite is generally preferably 0.4 to 2.5 mol, particularly preferably 0.5 to 2.5 mol, based on 11 of the color developing solution.

Examples of antifoggants include mercapto compounds such as 1-phenyl-5-mercaptotetrazole and 2-mercabuthenzimidazole-5-sulfonic acid sodium salt; indazole compounds such as 5-nitroindazole, and 5-methylbenzole. Penztriazole compounds such as triazole; inorganic halide compounds such as potassium bromide and potassium iodide; 6-nitrobenzene imidazole described in U.S. Patent No. 2,496,940; U.S. Patent No. 2,497 , No. 917 and No. 2', 656.
, 5-nitropenzimidazole; 0-phenylenediamine, mercaptobenzoxazole, thiouracil;
Heterocyclic compounds described in Japanese Patent No. 675; etc. can be used. The content ratio of such antifoggant is
Usually 0.001 to 30g for 11 of color developer
is preferable, particularly preferably 0.001 to 5 g.

As the development inhibitor, for example, sodium bromide, potassium bromide, potassium iodide, etc. can be used. The content ratio of the development inhibitor is 11 to 11 in the color developing solution.
Generally, the amount is preferably 0.001 to 30 g, particularly preferably 0.05 to 5 g.

As the development accelerator, for example, U.S. Pat.
Various pyridium compounds, other cationic compounds, cationic dyes such as phenosafranine, and thallium nitrate described in Japanese Patent Publication No. 604, No. 3,671.247, and Japanese Patent Publication No. 44-9503. Neutral salts such as U.S. Patent Nos. 2,533,990, 2,531,832, and 2,95o, 970
Specification of No. 2.577, Specification of No. 127, Special Publication No. 1977
Nonionic compounds such as polyethylene glycol or its derivatives and polythioethers described in Japanese Patent Publication No. 4-9504, organic solvents or organic amines, ethanolamine, ethylenediamine, and jetanol described in Japanese Patent Publication No. 44-9509. Includes amines, triethanolamine, etc. Also, U.S. Patent No. 2,304
In addition to benzyl alcohol and phenethyl alcohol, which are described in , No. 925, acetylene glycol, methyl ethyl ketone, cyclohexane, thioethers, pyridine, ammonia, hydrazine, amines, and the like can also be effectively used as development accelerators. The content ratio of such a development accelerator is usually preferably 0.05 to 150 g, particularly preferably 0.5 to 30 g, based on 11 of the color developing solution.

Examples of solvents include ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl sesolv, hexylene glycol, ethanol, methanol, acetone, dimethylformamide, and the like, as disclosed in Japanese Patent Publication No. 47-33378, No. 44- Compounds described in Japanese Patent No. 9509 can be used.The content ratio of such an organic solvent is 1p of the color developer, and jffi is usually 0.05 to 1.
100g is preferred, particularly preferably 0.5-30g.

Examples of chelating agents that act as water softeners or heavy metal sequestrants include phosphates such as polyphosphate; nitrilotriacetic acid, 1,3-diaminob1]panoltetraacetic acid,
Aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid and hydroxyethyliminodiacetic acid; aminopolyphosphonic acids such as acids); 1.
Polyhydroxy compounds such as 2-dihydro-r1-xybenzene-3,5-disulfonic acid; etc. can be used. The content ratio of such a chelating agent is usually preferably 0.05 to 160 g per 1e of the color developing solution, and the content ratio of the chelating agent is usually 0.05 to 160 g.
: The weight is 0.1 to 50 g.

Examples of the auxiliary developer include N-methyl-p-aminophenol sulfate (methol), phenidone, N,
N-diethyl-p-aminophenol hydrochloride, N,N,
N,N-tetramethyl-p-phenylenediamine hydrochloride and the like can be used. The content ratio of such auxiliary developer is usually 0.01 to 30 g per 1/1 of the color developing solution.
is preferred.

Furthermore, if necessary, a competitive coupler such as citradinic acid, a tin chelate compound such as N, N, Nl rimedylene phosphonate, tin citrate, tert-
Borohydride compounds such as butylamine borane, colored couplers, development-inhibited release type couplers (so-called DIR couplers), development inhibitor-releasing compounds, and the like can also be used.

As the antifoaming agent, for example, a silicone antifoaming agent or the like can be used. The content ratio of such antifoaming agent is preferably 5 x 10-' to 5 g per 1 p of the color developing solution.

The aromatic primary amine used as component (2) has a pH of 9.5.
It is preferable to use p
H9.6~]3, particularly preferably pH9.8~1
It is 2.5. The temperature of color development processing is 25-75℃.
is preferable, particularly preferably 30 to 62°C.

[Specific examples]

Hereinafter, specific examples of the present invention will be described, but the present invention is not limited to these examples.

One week of color developing solution (1) Color developing solution 1 (for comparison) 0 benzyl alcohol 8go ethylene glycol IOgo polyvinylpyrrolidone 1. OgO potassium sulfite
5.0gON-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.0gON-ethyl-N-β-human[]xyethylaniline sulfate
5.0 go potassium carbonate
30 go potassium bromide
1.2go1-hydroxyethylidene-1,]~diphosphonic acid 0.3gopotassium hydroxide Star 0 water with a pl+ of 10.35
The total amount is 1 p (in addition, water contains 0
．． It contained 5 ppm of iron ions and 0.05 ppa of copper ions. ) Mix and dissolve the above substances, add hydroxylamine sulfate as a preservative at a ratio of 3 g/p, mix and dissolve, and then adjust the pH of the liquid to 10.3.
5, thereby obtaining a color developing solution for comparison. This is referred to as "color developer I."

(2) Color developer 2 (for the present invention) In the preparation of color developer 1, 3 g/ml of monomethyl human L1 xylamine was added instead of hydroxylamine silicate.
A color developing solution was obtained in the same manner using Hoga, which was used at a ratio of lt. This is referred to as [color developer 2-1].

(3) Color developer 3 (for the present invention) In the preparation of color developer 1, 3 g/dimethylhydroxylamine was added in place of hydroxylamine sulfate.
A color developing solution was obtained in the same manner except that the ratio of It was used. This is referred to as "color developer 3."

(4) Color developer 4 (for the present invention) In the preparation of color developer 1, 3 g of monoethylhydroxylamine was added instead of hydroxylamine sulfate.
A color developing solution was obtained in the same manner except that the ratio of 1/Il was used. This is referred to as "color developer 4".

(5) Color developer 5 (for the present invention) In the preparation of color developer 1, 3 g of diethylhydroxylamine was added instead of hydroxylamine sulfate.
A color developing solution was obtained in the same manner except that the ratio of 1/R was used. This is referred to as "color developer 5."

(6) Color developer 6 (for the present invention) In the preparation of color developer 1, 3 g of monopropyl hydroxylamine was added instead of hydroxylamine sulfate.
A color developing solution was obtained in the same manner except that it was used at a ratio of /ρ. This is referred to as "color developer 6."

(7) Color developer 7 (for the present invention) In the preparation of color developer 1, 3 g/dipropyl hydroxylamine was added in place of hydroxylamine sulfate.
A color developing solution was obtained in the same manner as in Hakaba, which was used at a ratio of 1. This is referred to as "color developer 7."

Guest 3a Harvest 1 Temporary (1) Container 1 (for comparison) A pair of rectangular sheets D having a one-layer structure made of polyethylene (200, m) were prepared, and the outer edges of these pair of rectangular sheets were adhesively fixed to each other, One rectangular sheet has an entrance and exit, and it has a pillow-type container (capacity:
51) was prepared. This will be referred to as "container 1." The oxygen permeability coefficient of this container 1 is 480m! /(m”・atIIl−
day) (temperature 20°C, relative humidity 65%).

(2) Container 2 (for comparison) A pair of single-layer rectangular sheets E made of polyethylene-vinyl acetate copolymer (250μ) were prepared, and the outer edges of these pair of rectangular sheets were adhesively fixed to each other, and one A pillow-type container (capacity: 57 mm) was created by providing an entrance and exit in the rectangular sheet.
”. The oxygen permeability coefficient of this container 2 is 100mff1
/(m''·atm-day) (temperature 20°C, relative humidity 65%).

(3) Container 3 (for comparison) One-layer square sheet F made of polyethylene (50p) and polyethylene-vinyl acetate copolymer (100n)
) and a rectangular sheet G with a one-layer structure consisting of polyethylene.
A pair of rectangular multi-sheets are prepared by independently stacking a single-layer rectangular sheet H made of vinyl acetate copolymer (100 μm), and the outer edges of these pairs of rectangular multi-sheets are adhesively fixed to each other. At the same time, an entrance/exit was provided in one of the rectangular multiple sheets, thereby producing a pillow-type container (capacity=51). This will be referred to as "container 3."

The oxygen permeability coefficient of this container 3 is 200m7/(m”・at
m-day) (temperature 20°C, relative humidity 65%).

(4) Container 4 (for the present invention) Saponified polyethylene-vinyl acetate copolymer (20n)
A rectangular sheet A with a three-layer structure made of /nylon (15n)/polyethylene (15n) and a rectangular sheet B with a one-layer structure made of polyethylene-vinyl acetate copolymer (80IIm) are stacked independently. A pair of rectangular multi-sheets was prepared, the outer edges of the pair of rectangular multi-sheets were adhesively fixed to each other, and an entrance/exit was provided in one of the rectangular multi-sheets, thereby producing a pillow-type container (capacity: 5J). is called “container 4”.The oxygen permeability coefficient of this container 4 is 6 mJ/(n”・atm-d
ay) (Temperature 20℃.

The relative humidity was 65%).

(5) Container 5 (for the present invention) A pair of rectangular sheets C having a two-layer structure made of nylon (75Q)/polyethylene (75n) are prepared, and the outer edges of the pair of rectangular sheets C are bonded and identified to each other, One rectangular sheet was provided with an inlet/outlet [1], and a billow-type container (capacity: 5/liter) was prepared. This is referred to as "container 5". The oxygen permeability coefficient of this container 5 is 20 ml/(
mz-atm-day) (Temperature 20°C.

The relative humidity was 65%).

<Test on storage stability of color developer (1)> - Container 1
Seven container groups were prepared for each of 5 to 5 to prepare 5 container groups. Pour the above color developing solutions 1 to 7 into each set of 7 containers for 4.91 yen! Then, each inlet and outlet were sealed airtight. All of the containers containing the color developer in this way were stored for two months in a laboratory adjusted to a temperature of 38° C., a relative humidity of 65%, and a pressure of 1 atmosphere.

When the state of the containers after storage was examined, it was found that color developing solutions 2 to 7 for the present invention were prepared using containers 4 and 5 for the present invention.
When each container is stored, the gas pressure inside the container does not become very high after being left unused, and no damage to the container is observed.
The storage condition of the color developing solution was extremely good.

On the other hand, when color developer 1 for comparison was stored, nitrogen gas was generated and the gas pressure inside the container was high, so there was a high possibility that the container would be damaged.

Next, a silver halide photographic light-sensitive material for color paper (manufactured by Konishiroku Photo Industry Co., Ltd.), which had been exposed through a stepped exposure wedge for sensitometry, was actually processed using each of the stored color developing solutions according to the following conditions. A test was conducted in which a photograph was formed using the same method, and the minimum density (fogging) and maximum density in the obtained photograph were examined. The results are shown in Table 1 below.

The density was determined by measuring the density of the yellow pigment (maximum density) using an optical densitometer rPDA-60, J (manufactured by Konishiroku Photo Industry Co., Ltd.) using a blue filter, and also measuring the minimum density using the same method. did.

[Conditions for photo formation]

-i no February Halogen 41 Forge 11 1↑L "Sakura Color SR Paper" (manufactured by Konishi Roku Photo Industry Co., Ltd.) Standard treatment process: +l) Color development treatment (38°C, 3 minutes 30 seconds) (2) Bleaching Fixing treatment (38°C, 1 minute 30 seconds) (3) Stabilization treatment (2
5-35℃, 3 minutes) (4) Drying treatment (75-100℃,
Approximately 2 minutes) U constant 1 solution: 0 ethylenediaminetetraacetic acid ferric ammonium dihydrate 60. Ogo ethylenediaminetetraacetic acid 3.0 gO ammonium thiosulfate (70% aqueous solution) 100 mIO ammonium sulfite (40% aqueous solution) 27.5 dO water
Mix and dissolve the above substances in an amount that makes a total of 1 p, and adjust the pl+ to 7.1 with potassium carbonate or glacial acetic acid.
Adjusted to.

Hiroshi 1J is: 0 ethylene glycol 1.0g01-
Hydroxyethylidene-1,1-niphosphonic acid (60%
aqueous solution) 1.0 go ammonia water (ammonium hydroxide 25% aqueous solution) 2.0 g
o Water The above substances were mixed and dissolved in a total amount of 11, and the pH was adjusted to 7.0 with sulfuric acid.

<Test on storage stability of color developer (2)> In the above test for storage stability of color developer (1), each color developer was stored in the same manner except that the temperature in the laboratory was changed to 58°C. did.

When the state of the containers after storage was examined, it was found that color developing solutions 2 to 7 for the present invention were prepared using containers 4 and 5 for the present invention.
When each container is stored, the gas pressure inside the container does not become very high after being left unused, and no damage to the container is observed.
The storage condition of the color developing solution was extremely good.

On the other hand, when Comparative Color Developer 1 was stored, ammonia gas and nitrogen gas were generated, the gas pressure inside the container was high, and there was a high possibility that the container would be damaged.

Next, a photoformation test was conducted in the same manner using each of the color developing solutions after storage, and the same results as in Table 1 were obtained.

Test of storage stability of color developing solutions (3) - Test of storage stability of color developing solutions (1), except that the temperature in the laboratory was changed to 78°C. Saved.

When the state of the containers after storage was examined, it was found that color developing solutions 2 to 7 for the present invention were prepared using containers 4 and 5 for the present invention.
When each container is stored, the gas pressure inside the container does not become very high after being left unused, and no damage to the container is observed.
The storage condition of the color developing solution was extremely good.

On the other hand, when Comparative Color Developer 1 was stored, ammonia gas and nitrogen gas were generated, the gas pressure inside the container was high, and there was a high possibility that the container would be damaged.

Next, a photoformation test was conducted in the same manner using each of the color developing solutions after storage, and the same results as in Table 1 were obtained.

As can be understood from the results in Table 1, when applying the method of the present invention, it is possible to store the color developer stably for a long period of time without deteriorating its performance or damaging the container. As a result, good development processing can be performed using the color developing solution after storage.

On the other hand, when the color developer is stored using Comparative Containers 1 to 3, the performance of the color developer decreases due to oxidation due to the high oxygen permeability coefficient of the container, resulting in a poor performance. Development processing cannot be performed.

In addition, when storing color developer 1 for comparison, the color developer 1 decomposes and generates ammonia gas and nitrogen gas, resulting in a decrease in the performance of the color developer.As a result, good development processing is not possible. Furthermore, there is a high risk that the container will be damaged due to the generation of nitrogen gas while the color developer is being stored.

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 are explanatory cross-sectional views each showing a specific example of the structure of a container used in the present invention. 10... Container 21.22... Outer wall 3
1.32...Outer wall 40...Storage room 50.
・Entrance/exit

Claims (1)

[Claims] 1) A color developing solution containing the following components (1) to (3) with an oxygen permeability coefficient of 50 ml/(m^2・atm・d
ay) (Temperature: 20° C., relative humidity: 65%) A method for storing a color developer, characterized by storing it in a container made of plastic packaging material. Component (1): Color developing agent consisting of an aromatic primary amine Component (2): Preservative consisting of an alkyl-substituted hydroxylamine represented by the following general formula (I) General formula (I) ▲Mathematical formula, chemical formula, table etc. ▼ (R^1 and R^2 are each hydrogen atom or carbon number 1 to
3 represents an unsubstituted alkyl group, one of which is an unsubstituted alkyl group having 1 to 3 carbon atoms. ) Component (3): Alkaline agent to adjust the pH of the color developer to 9.5 or higher