JPH0478848A - Vacuum packed photographing processing agent - Google Patents

Abstract

PURPOSE:To eliminate deterioration of the processing agent due to storage and to enhance handling efficiency by adding a liquid compound to a solid powder to form a layer. CONSTITUTION:This processing agent is prepared by filling a vessel with constituents contained in the photographic processing agent in layers and sealing it in reduced pressure. At least one of the layers is formed by adding the liquid compound in a liquid state, and this compound is liquid in normal pressure, and added to the other solid constituent. This liquid compound is a liquid amine compound to be used for a development promotor, such as 6-dimethylamino-1- hexanol, and a surfactant, a deforming agent, and the like, and the solid powder to be used is hydroquinones for use in a black-and-white developer, sulfites for use in preservatives, are enumerated.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a vacuum-packed photographic processing agent used in preparing a photographic processing solution for silver halide photographic materials (hereinafter referred to as "photosensitive materials").

<Prior art> Black and white photosensitive materials are processed through steps such as black and white development, fixing, and water washing after exposure, while color photosensitive materials are processed through steps such as color development and water washing after exposure.
It is processed through processes such as desilvering, water washing, and stabilization.

Black and white developer for black and white development, fixer for fixing, color developer for color development, bleach, bleach-fix, fixer for desilvering, tap water or ion exchange water for washing, Stabilizing solutions are used in each stabilization process.

The temperature of each processing solution is usually adjusted to 30 to 40°C, and the photosensitive material is immersed in these processing solutions to be processed.

Since the processing performance of these processing liquids deteriorates due to processing and aging, a replenishment method or a batch method 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 the 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.

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 more likely that inexperienced users will mix the chemicals incorrectly. A problem arises.

Therefore, as a general rule, 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, a black-and-white developer may consist of a concentrated solution consisting of two parts: a part containing a developing agent or alkaline agent, and a part containing a hardening agent, or a three-part concentrate containing a part containing an auxiliary developing agent in a separate room. Those made of concentrated liquid are used.

Furthermore, the fixing solution used is one that is composed of a two-part concentrated solution, a part containing a hardening agent and a part containing other components.

However, even in concentrated liquids, substances that react with each other are stored in separate containers, which does not allow for sufficient compactness.

Moreover, even if it is a concentrate, it is still a liquid, and liquid preparation work is required at the manufacturing stage, which is complicated. 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 a method in which two or more types of particles that react with each other among the constituent components of a photographic processing agent are laminated with an inert layer interposed to prevent them from reacting with each other, and then vacuum packaged. Proposed.

This publication describes, as a specific example, a case where a black and white developing agent is used.

Although solid powder can be applied to this product, in some cases it may be necessary to add a liquid compound.

Among such liquid compounds, the amount added is often small. As such,
Examples include alkanolamines used as development accelerators, surfactants, antifoaming agents, and the like.

In this case, for fishing on a boat, it is necessary to prepare a separate container separate from the above-mentioned package and store it in this container.

Therefore, in such a method, the number of containers increases, which goes against the goal of compactness. Also, because it is in a separate container, it is easy to forget to add it. Furthermore, since it is a liquid, it may leak during storage or spill when added.

Also, some substances easily evaporate. Such problems are particularly noticeable when the amount added is small.

For this reason, there is a problem in that correct liquid preparation cannot be carried out, and that good photographic images cannot be obtained when processed using this solution.

By the way, some liquid compounds, such as aldehydes used as hardening agents, can be pulverized as bisulfite adducts, and it is also possible to pulverize and layer them. People are also trying.

However, not all compounds can be pulverized, and some liquid compounds that are added in small amounts cannot be pulverized. In addition, even if it can be powdered, if the amount added is relatively large, such as the aldehydes mentioned above, powdering is advantageous, but if the amount is small, powdering is the method. In addition, since it is a small amount, errors tend to occur when converting the amount of liquid into the amount of powder and adding it.

Furthermore, when powdered, the original properties may be lost.

For these reasons, some kind of improvement is desired.

Furthermore, the above-mentioned publication does not mention processing agents for color photography at all, and even if it is a processing agent for black and white photography, there is no specific mention of how to optimally stack fixing agents. Not suggested.

The above-mentioned problems commonly occur in all photographic processing agents.

<Problems to be Solved by the Invention> The objects of the present invention are to provide a product that has excellent storage stability, has a compact shape, is easy to handle, facilitates liquid preparation work, and is also effective in solving container pollution. Furthermore, it is an object of the present invention to provide a vacuum-packaged photographic processing agent which is advantageous in terms of transportation and storage, and which allows images with good photographic properties to be obtained at all times when processed using the same.

Means for Solving the Problems> The above object is achieved by the present invention having the following configuration (1).

(1) In a vacuum-packed photoprocessing agent in which a small amount of photoprocessing agent (both two types of components are housed in separate solid layers), a layer in which a liquid compound is added to a solid powder is used. A vacuum packaging photographic processing agent comprising:

<Function> In the present invention, the constituent components of the photographic processing agent are, in principle, stored in layers for each different component and sealed under reduced pressure to form a single solid product, so it has a compact shape. Also,
As a result of vacuum packaging, the constituent layers retain this shape and there is no intermixing.

At this time, in the present invention, compounds that are liquid at normal pressure, such as alkanolamines as development accelerators, surfactants, and antifoaming agents, are added in small amounts (Log/j or less in the processing solution). If the compound is a solid compound that is added in a large amount among the constituent components of the photographic processing agent and does not react with the liquid compound mentioned above, it is added and laminated. Therefore, there is no need to store this liquid compound in a separate container, and the processing agent can be made more compact. In addition, there is no need to worry about the amount of addition (there is no leakage or spillage of liquid, and there is no need to worry about vaporization.Also, although the liquid compound and the solid powder compound to which it is added do not react when they come into contact with each other, Since they can be selected as a combination, there are no problems with processing performance in processing solutions prepared using them.

Furthermore, since the components that are solid and react upon contact are separated and stacked, there is no deterioration in processing performance even after long-term storage.

Further, since one vacuum-packed product is simply taken out of the container each time and dissolved in a predetermined amount of water, the liquid preparation work is easy.

Therefore, when processed using a processing solution prepared using this, an image with good photographic properties can be obtained.

<Specific configuration> Hereinafter, a specific configuration of the present invention will be explained in detail.

The vacuum-packaged photographic processing agent of the present invention is obtained by storing the components contained in the photographic processing agent in layers in a container and sealing the container under reduced pressure so that the pressure inside the container is lower than atmospheric pressure. be.

The container 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 photographic processing agent.

Specifically, metal foils such as aluminum whose surfaces are coated with resins such as polyethylene, polypropylene, nylon, and vinylidene chloride, and pressure-resistant thick resin materials, etc.
Preferably used.

By creating a vacuum state, the effects of oxygen and moisture on the photographic processing agent can be eliminated.

To form a package, the above-mentioned components may be supplied into a container, formed into a predetermined amount of layers of uniform thickness, successively laminated in this manner, and then vacuum-packaged according to a known method.

In the above, when supplying the material into the container, it is preferable to drop the material while applying vibration or the like.

As a result of vacuum packaging, each constituent layer forms a distinct interface with the adjacent layer, and yet forms a rigid integral body as a whole.

Further, over time, there is almost no mutual diffusion of components between the eyebrows, and even if there is, it is negligible in terms of photographic performance.

In the present invention, at least one layer of the laminate is a layer to which a liquid compound is added in a liquid state.

This liquid compound is a liquid compound at normal pressure and cannot be laminated by itself, so it is added to other solid components.

Further, the amount of this liquid compound added to the processing liquid is small, usually less than Log/l.

On the other hand, the solid compound is a component that forms a layer by itself in the laminate, and the liquid compound is added to this solid powder compound. This powder compound is added in a large amount when used as a processing liquid, and the amount added is about 40 to 300 g/R.

Further, this powder compound hardly dissolves in the above-mentioned liquid compound, and has a solubility of 0.1 or less, and furthermore, these compounds do not react with each other even when they come into contact.

In the above, the liquid compound may be mixed and dispersed in the powder compound, coated with the powder compound, or impregnated with the powder compound by addition. , Such a state is realized depending on the properties of the compound, the addition ratio, the addition method, etc.

At this time, the mixed dispersion may be in the form of a paste.

Although the addition is generally carried out before laminating the above-mentioned components, it may also be carried out by an appropriate method such as adding a liquid after the powder compounds are laminated.

Moreover, when laminating as a mixed dispersion, the layer adjacent to this layer needs to be composed of a component that does not react upon contact with both the powder compound and the liquid compound. In such cases, the liquid compound may diffuse into adjacent layers.

Examples of the liquid compound mentioned above include, for example, a black-and-white developing agent, an amine compound as a development accelerator, a surfactant, an antifoaming agent, and the like.

As a liquid amine compound, JP-A-56-10624
No. 4, European Patent Publication No. 0136582, etc., alkanolamines (e.g., 6-dimethylamino-1
-hexanol, N-methylaminoethanol, 3-diethylamino-1,2-propanediol, 2-aminoethylethanolamine, butyljetanolamine)
etc.

Examples of the surfactant include nonionic surfactants, specifically those having an ethylene oxide group as a parent group, such as polyethylene glycol (trade name polyethylene glycol-400, -1500, -2000), Polyoxyethylene alkyl ether, polyoxyethylene alkylphenol, having an ether-type lipophilic group,
It is a polyethylene glycol having an ester type lipophilic group.

Also included are those in which the hydrophilic group is a monoglyceride of a glycerin derivative.

Further examples include trialkyl phosphate esters, and the alkyl group in this case is a linear or branched alkyl group having 1 to 10 carbon atoms, and specifically includes an octyl group.

Examples of antifoaming agents include silicone compounds, and a specific example is the product name Silicone L-76 (manufactured by Nippon Unica).
There are some commercially available.

And, as a powder compound to which a liquid compound is added,
Hydroquinones and ascorbic acids used as black and white developing agents, sulfites used as preservatives (e.g. sodium sulfite, potassium sulfite, sodium bisulfite), carbonates used as pH buffers (e.g. potassium carbonate, sodium carbonate). ), phosphates (e.g. sodium phosphate), organic acid salts (e.g. sodium acetate, sodium citrate, sodium sulfone), water-soluble polymers used as thickeners, specifically celluloses (e.g. Hydroxyethyl cellulose, carboxymethyl cellulose), which easily react with each other 2
Examples include photographically inert substances (for example, sugars) used in reaction inhibiting layers (intermediate layers) provided between solid layers of photographic processing agent components.

In addition, when using such an inert substance, the amount added is:
The method may be adjusted as appropriate depending on the amount of the liquid compound to be added.

The liquid compound and the powder compound to which it is added may be appropriately selected from the above, and any combination thereof may be used.

However, combinations that reduce their functionality by coming into contact with each other and reacting should be broken.

Specific examples of preferred combinations are listed below.

Liquid compound Powder compound ■6-dimethylamino-1-K,SOsHexanol ■Polyethylene glycol Hydroquinone ■Butyljetanolamine Na2SOx ■Polyethylene glycol Saccharide ■6-Simethylamino-1-Hexanol Saccharide ■Polyethylene glycol K, So.

Of the liquid compounds mentioned above, the amine compound used as a development accelerator can be solidified or powdered by forming an adduct with it using an acid, etc., and then stacked as a powder, as described below. Yes (see Japanese Patent Application No. 138858/1999).
Therefore, when laminating, it can be appropriately selected whether to use the liquid as described above or to use the powder. - For boat fishing, as mentioned above, when the amount added is small or when formation of adducts is expensive or difficult, it is preferable to use it in a liquid state.

Next, a case will be described in which, in a fixing agent used in combination with a black and white developing agent, a method is adopted in which a liquid compound is added to a powder compound in a liquid state and laminated.

Liquid compounds in this case include wetting aids (surfactants), antifoaming agents, etc., and powder compounds include thiosulfates, sulfites, organic acid salts (e.g., sodium acetate, citric acid, etc.). (sodium) and photographically inert substances (for example, sodium sulfate, etc.).

Further, preferred combinations of these liquid compounds and powder compounds are as follows.

Liquid compound Powder compound ■ Polyethylene Glycol Thiosulfate 400 Sodium ■ Antifoaming agent Sodium acetate ■ Antifoaming agent Sodium sulfate Since the liquid compound can be added in liquid form and laminated in this way, it is not only easy to operate but also , - Since it can be made into a formulation, it is advantageous in terms of handling.

In the present invention, although having the above configuration, a poorly soluble compound or a trace additive that is poorly soluble in water even if it is solid is coated on the particle surface of an easily soluble compound and contained in the laminate. It is preferable. Regarding the details, please refer to the patent application No. 2-1
No. 19537.

Furthermore, in the present invention, an intermediate layer containing an inert substance that does not function as a photographic processing agent and does not substantially affect photographic performance is provided between the eyebrows, each of which contains constituent components that react with each other. Good too. Such inert substances include sugars (glucose, glucose, etc.), NaCf
Examples include inorganic salts such as 1, KCj2, and N az S 04, and water-soluble polymers such as hydroxyethyl cellulose. The details are described in Japanese Patent Application No. 2-120612.

A laminate using a layer to which the liquid compound described above is added,
The case where it is applied to a black and white developer will be described.

Black and white processing agents mainly consist of a developing agent which is a reducing agent, an alkaline agent, a preservative, and a development inhibitor (antifogging agent), and may also contain additives as necessary. be.

When obtaining a laminate using such components, it goes without saying that solid powder is used (compounds that undergo a solid phase reaction when they come into contact in a solid state should be avoided from coming into contact with each other). Layer them together.

Compounds that should be avoided from contact are typically a developing agent and an alkaline agent.

As black and white developing agents, hydroquinones are mainly used, but from the viewpoint that it is easy to obtain good performance, combinations of idowaquinones and 1-phenyl-3-pyrazolidones, or combinations of hydroquinones and p-aminophenols are used. combinations are used. Further, ascorbic acids may be used as a developing agent.

Among these, it is particularly preferable that hydroquinones not come into contact with the alkali agent.

On the other hand, 1-phenyl-3 used as an auxiliary developing agent
-Pyrazolidones and p-aminophenols exhibit some degree of stability against the above-mentioned alkaline compounds, but it is still preferable to avoid contact with these compounds.

In addition, it is generally advisable to avoid contact between acidic compounds and alkaline compounds, and between reducing compounds and oxidizing compounds.

As a combination of such compounds, for example, 5-
Examples include sulfosalicylic acid and sulfites.

Alkaline compounds include alkaline agents, pH buffering agents such as alkali metal carbonates and borates, and sulfite preservatives.

In addition, contact with acid should be avoided because sulfites decompose and generate sulfur dioxide gas when they come into contact with acids.

In the laminate of the present invention, an inert layer made of a compound that does not react with any compound that does not react with any compound is interposed between the eyebrows, which contains compounds that should be avoided.

As such a laminate, there is one in which an alkali agent-containing layer is arranged on one side and a developing agent-containing layer is arranged on the other side so as to be partitioned by an inert layer.

In the above, in principle, on the alkali agent-containing layer side,
A layer of an alkaline (pKa of 9 or higher) compound is disposed.

At this time, a plurality of layers may be formed, or a single layer may be formed by mixing these compounds.

For example, in the case of a plurality of layers for each compound, it is preferable that the strongly alkaline compound be placed at the farthest position from the inactive layer, and the closer to the inactive layer the layer of the compound is weakly alkaline.

On the other hand, on the developing agent-containing layer side, an acidic compound with a pKa of 6 or less, a neutral compound, or a compound with antioxidant ability is arranged.

Note that, according to the above classification, preservatives such as sulfites are generally arranged as a layer located on the developing agent-containing layer side.

In the developing agent-containing layer, since two types of developing agents including an auxiliary developing agent are usually used as the developer, these may be mixed to form a single layer or separate layers.

Usually, they are separate layers, and the 1-phenyl-3-pyrazolidones auxiliary developing agent layer and the sulfite layer are often laminated in contact with each other.

Note that the sulfite preservative layer can also be provided on the alkali agent-containing layer side.

In the present invention, there is no particular restriction on the order in which each compound is supplied into the container during lamination, as long as the above-mentioned laminate can be obtained, but it is preferable to supply the alkaline agent first.

The reason for this is that when using the laminate by cutting open the container such as a bag and dissolving it in a predetermined amount of water, it is preferable to pour the water softener or chelating agent into the water from the water softener or chelating agent side. This is because this is possible with a laminate having the lowest layer. Further, it is preferable to do this from the viewpoint of preventing oxidation of the developing agent under an alkaline solution.

Generally, the laminate in the present invention includes, in order from the bottom layer, an alkali agent, a preservative, a developer, and a water softener or chelating agent.

Furthermore, it is also possible to add the same compound in a divided manner to a plurality of layers.

The thickness of each layer of the black-and-white developer in a vacuum-packed state usually corresponds to the amount of each chemical when preparing one batch of black-and-white developer, and depends on the size of the container.

As described above, the constituent components that are solid powders and the liquid compounds added to the layer as described above are applied, and the liquid compound is either added to the layer as described above or pulverized. Although it is preferable to use the compound as a liquid, if it is necessary to add a liquid compound, it can also be used by storing it in a separate container.

Some of these overlap with the liquid compounds listed above, but include ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol,
Organic solvents such as methanol, JP-A-56-10624
Examples include amino compounds such as alkanolamines, glycerin, and liquid surfactants described in European Patent Publication No. 4 and European Patent Publication No. 0136582.

Next, the components constituting the black and white developer will be described.

The amounts shown below are for use as a black and white developer.

Developing agents are generally used in combination as described above, but hydroquinone developing agents include hydroquinone,
Chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2.3
-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, etc., with hydroquinone being particularly preferred.

There are liquid p-aminophenol developing agents, such as N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminephenol, N-(4-hydroxy phenyl)glycine, 2-methyl-p-aminophenol, p-benzylaminophenol, among others, N-methyl-
p-Aminophenol is preferred.

As a 3-pyrazolidone developing agent, 1-phenyl-3
-pyrazolidone, ■-phenyl-4,4-dimethyl-3
-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,
4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-
p-Tolyl-4,4-dimethyl-3-pyrazolidone, 1
-p-tolyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone, etc.

Furthermore, ascorbate may be used as a developing agent.

Hydroquinone developing agents are usually 0.01 mol/l ~
1,5 mol/j, preferably o, 05 mol/i~1
．． It is used in an amount of 2 mol/1.

In addition to this, the p-aminophenol developing agent or 3-pyrazolidone developing agent is usually 0.0005 mol/
i~0.2 mol/8, preferably 0.001 mol/i~0
．． It is used in an amount of 1 mol/j.

Sulfite preservatives include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, and potassium metabisulfite. Sulfites are 0. It is preferably 2 mol/j or more, particularly 0.4 mol/j or more. Further, the upper limit is preferably up to 2.5 mol/j.

Alkaline agents used for setting pH include pH adjusting agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate.

JP-A-62-186259 (Borate), JP-A-60
Buffers such as No.-93433 (eg, sucrose, acetoxime, 5-sulfosalicylic acid), phosphates, carbonates, etc. may be used.

The black and white developer set by these has a pH of 8.5 to 1.
A range of up to 3 is preferred. More preferably p
It ranges from H9 to H12.

A dialdehyde hardening agent or its bisulfite adduct is used as a hardening agent, and specific examples thereof include gel taraldehyde and its bisulfite adduct.

Among these, the bisulfite adduct is a solid and can be used as an inert layer. Those that are not additives are generally liquids, and can be used by storing them in a Kariya container as described above.

The amount of the inorganic salt used as an antifoggant or a development inhibitor is about 0.01 to 50 g/l,
On the other hand, the amount of organic matter added is about 0.001 to 1.0 g/j.

Furthermore, Re5earch Disclosure 1st
Volume 76, No. 17643, Section XXI (December issue,
(1978); furthermore, if necessary, a toning agent, the above-mentioned surfactants, antifoaming agents, water softeners, and the amino compounds described in JP-A-56-106244; For example, JP-A No. 56-24347 and JP-A No. 5
The silver stain preventive agent described in No. 6-46585, as well as F
, A. Mason, "Photographic Processing Chemistry", Focal Press (1966), pp. 226-229, U.S. Patent No. 2,193°01.
No. 5, No. 2,592,364, JP-A-48-6493
Those described in No. 3 etc. can be used.

Among these additives, liquid compounds that can be added to the layer in a liquid state and solid compounds, including those that can be pulverized, serve as constituent components of the laminate.

Next, a case will be described in which a laminate using a layer to which the above-mentioned liquid compound is added is applied to a fixing agent.

During this lamination, a layer of thiosulfate as a fixing agent and a layer of a hardening agent are separated.

Furthermore, sulfites used as preservatives in fixing agents are also weakly alkaline, and contact with hardeners should be avoided.

For this reason, an intermediate layer made of a compound that does not react even if it comes into contact with the compound in the adjacent layer is interposed between the eyebrows of the compound whose contact is unfavorable.

Specific examples of compounds constituting such an intermediate layer include inorganic acid salts such as boric acid, tartaric acid, and acetate, and organic acid salts.

The general combination of compounds that should be avoided in contact is the same as for black and white processing agents.

Further, when using a liquid, it is possible to add it to the layer in liquid form or turn it into powder as described above, and it is preferable to use it in this way, but it can also be used by storing it in a Kariya vessel.

A preferable layer structure of the vacuum packaging fixing treatment agent is preferably a hardening agent, a pH buffering agent, and a preservative fixing agent in order from the bottom layer.

When using a plurality of types of fixing agents, a mixed layer including only the negative layer or a plurality of layers may be used. It is also possible to mix it with a preservative.

In addition, lamination may be carried out in accordance with the black and white developing agent.

Next, the case where the components constituting the fixing treatment agent are used as a fixing solution will be mainly described.

The fixer is an aqueous solution containing thiosulfate and has a pH of 3.8 or more, preferably 4.2 to 7.0.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of the fixing agent used can be changed as appropriate, and is generally about 0.1 to about 3 mol/P.

The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride, aluminum sulfate, potassium alum, and the like.

The amount of this aluminum salt added is A! 0 to 3.5 in terms of conversion
g/j.

The fixing solution contains tartaric acid, citric acid, gluconic acid, or their derivatives alone or in combination as stabilizers for An.
More than one species can be used. It is effective to contain these compounds in an amount of 0.005 mol or more per fixer 12, and particularly 0.01 to 0.3 mol/i.

The fixing solution may optionally contain preservatives (e.g. sulfites, bisulfites), pH buffers (e.g. acetic acid, boric acid, citric acid, tartaric acid, malic acid, succinic acid, glycolic acid),
pH adjusters (for example, sulfuric acid), fixing accelerators, image protectants, chelating agents with water softening ability, and JP-A-62-785
The compound described in No. 51 may be included.

Among these additives, liquid compounds that can be added to the layer in a liquid state and solid compounds, including those that can be pulverized, serve as constituent components of the laminate.

Note that sodium hydroxide and potassium hydroxide used as alkaline agents in the laminate of the present invention are disclosed in U.S. Pat. Nos. 2,649,376 and 2,639,221.
As described in the above issue, a stabilized product coated with phthalic anhydride may be used.

In addition, when obtaining a laminate, in the constituent components of each layer, as described in U.S. Pat. No. 2,384,592,
Alkali metasulfite, phthalic anhydride, maleic anhydride,
A method of stabilizing developer components using benzoic acid, salicylic acid, phthalimide, etc., as described in U.S. Pat. No. 2,606,118, B.
A method of stabilizing a developer component using boric anhydride, a method of stabilizing a developer component using a combination of boric anhydride and phthalic anhydride, as described in U.S. Pat. a method of stabilizing developer components with metaboric acid, as described in U.S. Pat. No. 2,666.703; a method of stabilizing developer components with metaboric acid, as described in U.S. Pat. As described in U.S. Pat. No. 2,685,513, a developer component is stabilized using metaboric acid hydrate stabilized with phthalic anhydride, boric anhydride, metaboric acid, etc. A method of stabilizing components can be applied.

Further, as the ammonium thiosulfate used as a fixing agent in the fixing treatment agent, one manufactured according to Japanese Patent Publication No. 16948/1982 may be used.

A black and white developer prepared using the vacuum packaging processing agent of the present invention,
Photographic materials that are processed using fixing solutions, other stabilizing solutions, rinsing solutions, and the like include general black and white light-sensitive materials. In particular, negative photosensitive materials and black-and-white photographic paper for general photography, photographic materials for laser printers for medical images, photosensitive materials for printing, medical direct photography X-ray photosensitive materials, medical indirect photography X-ray photosensitive materials, and CRT images. Recording sensitive material, industrial X-
It can be used as a light-sensitive material.

In this case, the present invention can be applied to all the waves or only to a part of the waves, which can be selected as appropriate.

Next, water washing and/or stabilization treatment, which is usually performed after development and fixing treatment, will be described.

In the process described in 2, it is also possible to use washing water or stabilizing solution at a replenishment amount of 3 f2 or less (including 0, ie, reservoir water washing) per 1 m'' of the silver halide photosensitive material.

For the above-mentioned water-saving treatment or piping-free treatment, it is preferable to apply anti-mold means to the washing water or the stabilizing liquid.

In the development process in the present invention, the development time is 5 seconds to 3 minutes,
Preferably, the developing time is 8 seconds to 2 minutes, and the developing temperature is preferably 18 to 50°C, more preferably 20 to 40°C.

The fixing temperature and time in the present invention are about 18 to about 50°C.
The temperature is preferably 5 seconds to 3 minutes, and more preferably 6 seconds to 2 minutes at 20 to 40°C.

The temperature and time in water washing (or stabilization bath) are 0 to 5
Preferably 6 seconds to 3 minutes at 0°C, 6 seconds to 2 minutes at 10 to 40°C
minutes is more preferred.

Further, the photosensitive material that has been developed, fixed, and washed (or stabilized) is often dried by squeezing out the washing water, that is, passing through a squeeze roller. Drying is approximately 0℃ to approximately 1
The drying time is suitably changed depending on the surrounding conditions, but is usually about 5 seconds to 3 minutes, particularly preferably about 5 seconds to 2 minutes at 40 to 80''C.

The method for producing a vacuum packaging processing agent using the coating of the present invention can be applied not only to a processing agent for black and white light-sensitive materials as described above, but also to a processing agent for color light-sensitive materials.

Examples include color development processing agents, bleaching processing agents, bleach-fixing processing agents, fixing processing agents, processing agents for stabilizers, and the like.

Similar effects can be obtained in these cases as well.

<Example> Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 The constituent components of the black and white developer used below are shown below.

All of these components are powders (solids) unless otherwise specified.

(Components) Alkaline agent: Sodium hydroxide HIX 20g pH buffer diboric acid 20X 20g5
-Sulfosalicylic acid 30X 20g Preservative: Potassium sulfite 110X 20g Development accelerator = 6-dimethylamino-l-hexanol (liquid) 4x
20g Antifoggant or development inhibitor: Potassium bromide lOX10X20 methylbenztriazole 0.4X20g Developing agent: Hydroquinone 50X 20g4-
Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 0.1 x 20g Water softening agent or chelating agent: ethylenediaminetetraacetic acid, disodium,
Dihydrate salt (EDTA ・2 Na ・2 Hz O) 1
．． 0x20g 8g of 5-methylbenztriazole to 101g of methanol
00O, added to 200 g of potassium bromide, mixed with stirring, and evaporated to dryness while stirring in a mixing dryer.

Hereinafter, this will be expressed as KBr15-MBT.

(2) 6-Dimethylamino-1-hexanol The liquid 6-dimethylamino-1-hexanol was added during the layering of potassium sulfite or glucose, which was the substance to be added, and then the layer was further layered.

Such items are displayed as additive substance + liquid.

The components listed above were placed in an aluminum foil bag (width 10 cm x width 10 cm x height 20 cm) whose surface was coated with polyethylene resin.
am) was stored in layers with the following configuration, and then sealed under reduced pressure to obtain a stored item.

These are designated as storage items 1.2 according to the layer structure.

Storage item 1 (invention) EDTA ・2Na ・2H,0 Hydroquinone 4-methyl-4-hydroxymethyl-1-phenyl-3
-Pyrazolidone K B r / 5- M B T 23 on 5-sulfosalicylic acid + 6-dimethylamino-1-hexanol borate Sodium hydroxide storage 2 (invention) E D T A ・2 N a ・2 H * 0 Hydroquinone 4 -Methyl-4-hydroxymethyl-1-phenyl-3
-Pyrazolidone K B r / 5-M B T -8Os Boric acid 5-sulfosalicylic acid Glucose (120 g) + 6-dimethylamino-1-hexanol Sodium hydroxide Also, remove 6-dimethylamino-1-hexanol (blend each component) A bag was also produced that was sealed under reduced pressure.This will be referred to as stored item 3.

In addition, in Storage Item 3, 6-dimethylamino-1-hexanol was added as it was, blended into the entire bag, and sealed in a bag. This is storage item 4
shall be.

After storing the above stored items 1 to 4 for 4 weeks under the conditions of 60° C. and 70% RH, each was dissolved in water to give a total amount of 20 g. In case of stored item 1.2, it was put into water from the upper layer side.

The black and white developing solutions prepared in this way are designated as developing solutions I to II, corresponding to the stored items 1 to 4.

In storage item 3, 6-dimethylamino-1-hexanol was stored in a Kariya vessel and used for the above liquid preparation.

In the above, five pieces of each of stored items 1 to 4 were prepared, and developer solutions 1 to 2 were prepared corresponding to the stored items.

Next, black and white photosensitive material GA-10 manufactured by Fuji Photo Film ■
After exposing 0, using each of the above developer ~■,
Processed according to the following process steps.

[1 step 1 1--1 1-1 Development 30 seconds 34℃
Fixation 30 seconds 33℃
Wash with water 30 seconds 25
Dry at ℃ 40 seconds 60
℃The fixing solution and washing solution used had the following composition.

(Fixer) Ammonium thiosulfate 120 g Sodium thiosulfate 30 g Sodium sulfite
10 g boric acid
8g Shun Tarseki 1.0g Aluminum sulfate 15g Add water
1.0Q pH 4,5 (Washing liquid) Tap water In addition, a developing solution (standard solution) with a concentration of 20ρ was prepared by newly blending the above-mentioned components.

At this time, 5-methylbenztriazole was dissolved in methanol and uniformly added to the developer.

A sensitive material was also processed using this standard solution in the above processing step, and this was used as a standard sample.

The photographic properties (sensitivity) of each photosensitive material and standard sample after processing were examined.

As a result, the sensitivity of developers ① and ② showed performance equivalent to that of the standard sample. In addition, it is easy to prepare liquids, and it is easy to prepare! ! There was no variation in photographic properties from liquid to liquid (all showed good results equivalent to the standard sample.

On the other hand, in developer m, 6-dimethylamino-1-
Because hexanol was used in a separate container, the preparation work was complicated, and there were cases of liquid leakage during storage and spillage during operation, resulting in variations in photographic properties depending on the prepared liquid.

Furthermore, in developer IV, the contents were discolored and partially formed into lumps, and the photographic properties (sensitivity) were significantly lowered.

Example 2 (Preparation of Fixer Solution) The constituent components of the fixer solution described above were stored in layers in the following configuration, and then sealed under reduced pressure to obtain a stored product.

Fixing contents Ammonium thiosulfate iso g Sodium thiosulfate 10 g Sodium sulfite 15 g Na 2 S O4 (1
0g) + Silicone L-76 (Liquid: 0.05g) Boric acid 4g Tartaric acid
0.8g aluminum sulfate
12 gIn the above, Nag SO
J+ silicone L-76, as in Example 1,
It was added during the stacking of Na 2 S Oa.

After storing this for 4 weeks at 60°C and 70%RH,
It was dissolved in water to make a total amount of 1.02.

Using this fixer, batch type C0M5000 processing machine (
412,000 pieces of Mini Copy Microfilm HR-II (manufactured by Fuji Photo Film ■) were processed using Ficiesa (manufactured by Fuji Photo Film ■). This product had good performance without causing any fixing failure or bubbling.

As described above, when a vacuum package is used for the fixing process, it is advantageous in terms of ease of handling compared to the conventional method, and it can be said that the processing work is further improved.

On the other hand, if the liquid is placed in a separate container, it will have a two-part configuration, which is less suitable for manufacturing and will be more expensive. Also,
It is easy to forget to add it.

Example 3 The constituent components of the black and white developer used below are shown below.

All of these components are powders (solids) unless otherwise specified.

(Components) Alkaline agent: Potassium hydroxide 12X 20g pH buffer: Potassium carbonate 8X 20g Preservative: Potassium sulfite 60X 20g Surfactant: Polyethylene glycol-1500 (liquid) X 20g Antifoggant or development inhibitor: Brominated Potassium 3X20g5-nitroindazole 0. 1 x 20 g Developing agent: Hydroquinone 25 x 20 g Chelating agent or water softening agent: Propylene diamine tetraacetic acid (PDTA) The mixture was mixed by stirring and evaporated to dryness while stirring in a mixing table dryer. Potassium bromide coated with 5-nitroindazole was thus obtained.

Hereinafter, this will be expressed as KBr/5-NID.

Polyethylene gutukol (
80 g of PGE) were added and kneaded to obtain a homogeneous mixture thereof (package item a).

This is displayed as S03+PGE.

Further, in the same manner as in Example 1, a method was also carried out in which PGE was added during the layering of K and SOx and the layering was continued (package item b).

The components listed above were placed in an aluminum foil bag (width 10 cm x width 10 cm x height 30 cm) whose surface was coated with polyethylene resin.
cm) with the following configuration, and then sealed under reduced pressure to obtain a stored item.

These are designated as stored objects a to C according to the layer structure.

Storage item a (invention) PDTA Hydroquinone KBr / 5-NID Kg SOs +PEG zSOs Potassium carbonate hydroxide gallium boric acid Storage item b (invention) PDTA Hydroquinone KBr / 5-NID K, So, +PEG Potassium carbonate Potassium hydroxide stored item C (comparative example) PDTA Hydroquinone K B r / 5-N I D Potassium sulfite Potassium carbonate Potassium hydroxide Each component except polyethylene glycol was blended, stored in a bag, and sealed. We also created a product that was sealed under reduced pressure. This is referred to as stored item d.

In addition, polyethylene glycol was added as is to the stored item d, blended throughout, and stored in a bag and sealed. This is referred to as stored item e.

The above stored items a to e were stored at 60℃ and 70% RH.
After storage for a week, each was dissolved in water to make the total amount 2012. In addition, stored items a to C were put into water from the upper layer side.

The black and white developing solutions prepared in this manner are designated as developing solutions A to E, corresponding to the storage areas a to e.

In addition, in storage items c and d, polyethylene glycol is
It was stored in a separate container and used for the above liquid preparation.

In the above, ten stored items a to e were each prepared, and developers A to E were prepared in correspondence with the stored items.

Next, the photosensitive material KU for black and white plate making manufactured by Fuji Photo Film ■
After exposing V-100, processing was performed according to the following processing steps using the above-mentioned developers A to E, respectively.

En IJ, Cheng Xiu - 1 Yi Yan'-1 Black and white development 20 seconds 38℃ fixation
Wash with water at 37℃ for 20 seconds
Dry at 25℃ for 20 seconds
30 seconds at 60℃.
The washing liquid used had the same composition as in Example 1.

In addition, a developing solution (standard solution) was prepared by newly blending the above-mentioned components and keeping the temperature at 20°C.

At this time, 5-nitroindazole was dissolved in methanol and uniformly added to the developer.

A sensitive material was also processed using this standard solution in the above processing step, and this was used as a standard sample.

The photographic properties of each photosensitive material and standard sample after processing were examined.

Photographic properties are evaluated in terms of sensitivity and gradation. Sensitivity is the specific sensitivity with the standard solution as 100, and gradation is the density D = 0.3 and D = 3.
．． It is shown by the slope at 0.

The results are shown in Table 1. Table 1 also shows the properties of the developer.

With the developing solutions A and B, the preparation work was easy, there was no variation in photographic properties between the prepared solutions, and the results were as good as those of the standard sample.

On the other hand, developers C and D use polyethylene glycol in a separate container, making the preparation work complicated and having poor solubility. There were variations in photographic properties depending on the preparation solution.

Furthermore, with developer E, the photographic properties deteriorated significantly.

<Effects of the Invention> According to the present invention, there is no deterioration due to storage and ease of handling is improved. Further, it becomes possible to prepare the processing solution in a constant manner, and images with good photographic properties can be obtained.

It is also compact and advantageous in terms of transportation costs.

Furthermore, the liquid preparation work is easy.

Proceedings (spontaneous) Patent Application No. 192259 of 1990 2, Name of the invention Vacuum packaging photographic processing agent 3, Person making the amendment June 3, 1OE 4, Representative patent applicant Fuji Photo Film Co., Ltd. Patent Attorney Ishii Seikan Patent Attorney
Increase 1) Tatsuya 6, Contents of the amendment (1) “(Japan Uni Power)” on page 14, line 14 of the specification.
(manufactured by Nippon Uni-Riki Co., Ltd.) J will be corrected to "(manufactured by Nippon Uniriki Co., Ltd.) or Dishome (manufactured by NOF Corporation)."

(2) rPGEJ on page 48, line 13 of the same page is rPEG
Correct it with J.

(3) Page 48, line 15 (7) rK, So.

Correct +PGEJ with rK, So, /PEGJ.

(4) rPGEJ on page 48, line 17 of the same page is rPEG
Correct it with J.

(5) Correct the lines 10 and 19 of page 49 (D rK, So, +PEGJ 'ir, 'f:h as rK, SOs /PEGJ, respectively).

Claims (1)

[Claims] (1) A vacuum-packed photographic processing agent in which at least two constituent components of the photographic processing agent are housed as separate solid layers in a container, which has a layer in which a liquid compound is added to solid powder. A vacuum packaging photo processing agent featuring: