JPH10133338A - Solid developer for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid developer for developing the silver halide photographic sensitive material superior in storage stability. SOLUTION: This developer comprises reductions and an alkali metal carbonate and an alkali metal bicarbonate in a molar ratio of 0.3-0.8, or reductions and >=40% carbonates, and Na<+> and K<+> ions in a Na<+> /K<+> ratio of 0-0.3. It is preferred that this developer is formed into tablets each having a carbonate content of 40-70%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solid developer for processing a silver halide photographic material, and more particularly to a solid developer having improved storage stability.

[0002]

2. Description of the Related Art A developer containing reductones is more advantageous at a lower pH in view of its oxidation stability. However, when the pH is lowered, the oxidation-reduction potential becomes high, and the developing activity becomes insufficient. Therefore, the processing system (for example, the difference between the processing machines of a large machine, a medium machine, and a small machine and the replenishment amount in a medical treatment system) There is a lower limit pH value depending on the difference. In addition, it is desirable that the kit solution storage stability in the state of a concentrated solution before preparing the developer is as low as possible. Therefore, the pH is set so as to be balanced with the developing activity. This principle is the same for a solid developer obtained by solidifying a developer.

Further, in order to improve the preservability of a solid developer containing reductones, a method in which a solid agent is contained in a moisture-proof bag so as not to absorb moisture, an alkali agent and a reductone are separately used.
Although a method of dividing into solid preparations is disclosed, it is not yet satisfactory, and there is no disclosure of improving storage stability by changing the composition of the solid preparation itself as in the constitution of the present invention.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a solid developer for processing a silver halide photographic material having excellent storage stability.

[0005]

SUMMARY OF THE INVENTION In view of the above circumstances, the present inventors have considered that a solid developer containing reductones may be heated to a high temperature (4%).
Investigation of storage properties including short-term storage at 0-60 ° C) and long-term storage at room temperature (20-25 ° C), and adopting the constitution of the present invention, specifically, sensitometric performance and hardness of the solid agent using the preservation solid agent. Was found to be improved. This is the storage of developing agents and auxiliary agents including reductones (heat and oxidation)
This is attributable to the fact that fatigue was suppressed and the softening was suppressed. This is an effect peculiar to a solid agent, and the improvement effect is small even if a similar configuration is employed in a concentrated kit solution or a concentrated developer in a working solution state. Further, the inventors of the present invention have found that the solubility of the solid developer of the present invention is improved during the study, but this was an unexpected finding.

That is, the above object of the present invention has been attained by the following constitutions.

(1) A solid developer containing reductones, an alkali metal carbonate and an alkali metal bicarbonate, and having a molar ratio of bicarbonate to carbonate of 0.3 to 0.8.

(2) It contains reductones, carbonates, Na ⁺ and K ⁺ , and the ratio of Na ⁺ to K ⁺ (Na / K) is 0 to
0.3, a solid developer having a carbonate content of 40% or more.

(3) It contains Na ⁺ and K ⁺ and contains Na ⁺
The solid developer according to (1), wherein the ratio of (Na / K) to K ⁺ is 0 to 0.3 and the content of carbonate is 40% or more.

(4) The solid developer is in the form of a tablet (1),
The solid developer according to (2) or (3).

(5) The content of carbonate in one tablet is from 40 to
The solid developer according to (4), which is 70%.

Hereinafter, the present invention will be described in more detail.

The reductones contained in the solid developer of the present invention are preferably those represented by the following general formula (I).

[0014]

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In the formula, R ₁ and R ₂ each represent a hydroxyl group, an amino group (including those substituted with an ethyl group, a butyl group, a hydroxyethyl group, an alkyl group having 1 to 10 carbon atoms), an acylamino group (Acetylamino, benzoylamino, etc.), alkylsulfonylamino group (methanesulfonylamino, etc.), arylsulfonylamino group (benzenesulfonylamino, p-toluenesulfonylamino, etc.), alkoxycarbonylamino group (methoxycarbonylamino, etc.), mercapto group Or an alkylthio group (methylthio, ethylthio, etc.).

Preferred examples of R ₁ and R ₂ include a hydroxyl group, an amino group, an alkylsulfonylamino group and an arylsulfonylamino group.

X is a group of atoms necessary for forming a 5- to 6-membered ring, and is preferably composed of a carbon atom, an oxygen atom or a nitrogen atom, and two vinyl carbon atoms substituted by R ₁ and R _2. And a carbonyl carbon atom to form a 5- to 6-membered ring.

Specific examples of the structure of X include -O- and -C-
_{(R 3) (R 4)} -, - C (R 5) =, - C (= O) -,
—N (R ₆ ) — and —N =. Here, R ₃ , R ₄ , R ₅ and R ₆ are each a hydrogen atom and a carbon atom 1
Represents 10 to 10 alkyl groups which may be substituted (including a hydroxyl group, a carboxyl group, and a sulfo group as a substituent), a hydroxyl group and a carboxyl group. Further, the 5- or 6-membered ring may form a saturated or unsaturated condensed ring.

Examples of the 5- or 6-membered ring include dihydrofuranone, dihydropyrone, pyranone, cyclopentenone,
Each ring includes pyrrolinone, pyrazolinone, pyridone, azacyclohexenone, uracil and the like. Preferred 5
The 6-membered ring includes dihydrofuranone, cyclopentenone, cyclohexanone, pyrazolinone, azacyclohexenone,
Each ring of uracil.

The compound represented by the general formula (I) may form a salt of lithium, sodium, potassium, ammonium and the like.

Specific examples of the reductone represented by the general formula (I) (referred to as the compound of the present invention) are shown below, but it should not be construed that the invention is limited thereto.

[0022]

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[0023]

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[0024]

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Among the above specific examples, preferred is ascorbic acid or erythorbic acid (stereoisomer) (I-1).

The content of the compound of the present invention in the solid treating agent is preferably at least 30%, more preferably at least 50% of the total weight of the treating agent. The developer of the present invention may contain only one type of the compound of the present invention or two or more types.

Next, the solid processing agent of the present invention will be described.

Specific developers may contain the following developing agents in addition to reductones. Examples of black-and-white developing agents include dihydroxybenzenes (hydroquinone, chlorohydroquinone, bromohydroquinone, dichlorohydroquinone, i-propylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, methoxyhydroquinone, 2,5-dimethylhydroquinone, hydroquinone monosulfonic acid) Salts), 3-pyrazolidones (1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl-
4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone,
1-p-tolyl-3-pyrazolidone, 1-phenyl-2
-Acetyl-4,4-dimethyl-3-pyrazolidone, 1
-(2-benzothiazolyl) -3-pyrazolidone, 3-
Acetoxy-1-phenyl-3-pyrazolidone, etc.), aminophenols (o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-
Methyl-p-aminophenol, 2,4-diaminophenol, etc., 1-allyl-3-aminopyrazolines (1
-(P-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-amino-m-methylphenyl)-
3-aminopyrazolone), pyrazolones (such as 4-aminopyrazolone), and the like, and mixtures thereof.

Alkali metal carbonates are K ₂ CO ₃ , Na ₂
CO ₃ and Li ₂ CO _3, but preferably K ₂ CO 3
₃ In addition, as a bicarbonate of an alkali metal, KHC is used.
O ₃ , NaHCO ₃ , and LiHCO ₃ are mentioned, but KHCO ₃ is preferable. These are both superior in solubility.

It is necessary that the molar concentration ratio of bicarbonate to carbonate is 0.3 to 0.8 in order to exert the effect of the present invention, but it is preferably 0.4 to 0.7. .
When it is less than 0.3, the effect of the present invention, particularly on sensitometry in storage, is large, and when it is higher than 0.7, the effect on storage hardness is large, and it becomes easy to soften.

The solid developer exerts its effects as long as it is a solid developer including granules, but is preferably in the form of a tablet because the effects (preservability) of the present invention are more exhibited.

Further, the developer of the present invention contains Na ⁺ and K ⁺ , and the ratio (Na / K) is from 0 to 0.3, preferably from 0 to 0.2. The fact that this ratio is 0 means that the amount of Na ⁺ is substantially smaller than K ^{+ as} it is substantially closer to 0. For example, when Na ⁺ / K ⁺ is less than 0.0001, it is included in 0. I do. If the ratio is higher than 0.3, the effect of improving the storage stability of the developer as well as the solubility is poor.

The content of the carbonate is at least 40%, preferably 40 to 70%. If it is less than 40%, the effect on sensitometry during storage of a solid developer is particularly large and unstable. If it is higher than 70%,
Among the effects of the present invention, the effect of improving the solid agent hardness is small.

Further, when the solid developer is a tablet, the content of carbonate in one tablet is more preferably 40 to 70%.

The developer may further include a preservative (sulfite, bisulfite, etc.), a buffer (carbonate, a salt, a borate, an alkanolamine, etc.), an alkali (carbonate, etc.), if necessary. Etc.), dissolution aids (polyethylene glycols and their esters, etc.), pH adjusters (organic acids such as citric acid and tartaric acid), sensitizers (quaternary ammonium salts, etc.), development accelerators, hardening Agents (dialdehydes such as glutaraldehyde), surfactants and the like. Further, as an antifoggant, an azole organic antifoggant (indazole type, imidazole type, penzoimidazole type, triazole type, benzotriazole type, tetrazole type, thiadiazole type), and masks calcium ions mixed in tap water. (Sodium hexametaphosphate, calcium hexametaphosphate, polyphosphate, etc.) may be added. Also, as a silver stain inhibitor
For example, compounds described in JP-A-56-24347 can be used.

The pH of the developer used in the present invention after dilution or dissolution is preferably in the range of 9 to 12, more preferably 9.0 to 10.0.

As the developer, amino compounds such as alkanolamines described in JP-A-56-106244 can be used. In addition, L. F. A. Mason, Photographic Processing Chemistry, Focal Press (1966), pp. 22-229,
U.S. Pat. Nos. 2,193,015 and 2,592,364
And those described in JP-A-48-64933.

The fixing solution and the solid fixing agent (hereinafter, both are collectively abbreviated as a fixing agent) used in the present invention will be described.

The fixing agent preferably contains a thiosulfate. Thiosulfates are usually lithium, potassium,
It is used as a sodium or ammonium salt, preferably sodium thiosulfate or ammonium thiosulfate. More preferably, a fixing solution having a high fixing speed can be obtained by using the compound as an ammonium salt, but a sodium salt is preferable from the viewpoint of retention.

The concentration of thiosulfate is preferably 0.1 to 5
Mol / l, more preferably 0.5 to 2 mol / l, even more preferably 0.7 to 1.8 mol / l. In addition, iodide salts, thiocyanates and the like can also be used as fixing agents.

The fixing agent contains a sulfite, and the concentration of the sulfite is 0.2 mol / liter or less when the thiosulfate and the sulfite are dissolved and mixed in an aqueous solvent. As the sulfite, a solid lithium, potassium, sodium, ammonium salt or the like is used, which is dissolved and used together with the solid thiosulfate.

The fixing agent may contain a water-soluble chromium salt or a water-soluble aluminum salt. Examples of the water-soluble chromium salt include chromium alum, and examples of the water-soluble aluminum salt include aluminum sulfate, potassium aluminum chloride,
Aluminum chloride and the like can be mentioned. The amount of the chromium salt or aluminum salt to be added is 0.2 to 3.0 g, preferably 1.2 to 2.5 g, per liter of the fixing solution.

The fixing agents include acetic acid, citric acid, tartaric acid,
Malic acid, succinic acid, phenylacetic acid, and optical isomers thereof may be included. These salts include, for example, potassium citrate, lithium citrate, sodium citrate, ammonium citrate, lithium hydrogen tartrate, potassium hydrogen tartrate, potassium tartrate, sodium bitartrate, sodium tartrate, ammonium bitartrate, tartaric acid Lithium, potassium represented by ammonium potassium, sodium potassium tartrate, sodium malate, ammonium malate, sodium succinate, ammonium succinate, etc.
Sodium and ammonium salts are preferred.

Among the above compounds, more preferred are acetic acid, citric acid, isocitric acid, malic acid, phenylacetic acid and salts thereof. The amount of the compound added is 0.2 to 0.1.
6 mol / l is preferred.

Examples of the acid include inorganic acids and salts such as sulfuric acid, hydrochloric acid, nitric acid and boric acid, and organic acids such as formic acid, propionic acid, oxalic acid and malic acid. Preferably, boric acid and aminopolycarboxylic acid are used. Acids and salts such as acids. Particularly preferred aminocarboxylic acids include β-alanine and piberidic acid. The preferred addition amount of the acid is 0.5 to 40 g / liter.

Examples of the chelating agent include aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, and salts thereof.

Examples of the surfactant include anionic surfactants such as sulfated and sulfonated compounds, nonionic surfactants such as polyethylene glycol and ester, and amphoteric surfactants described in JP-A-57-6840. Is mentioned. Examples of the wetting agent include alkanolamine and alkylene glycol.

Examples of the fixing accelerator include, for example, those described in
No. 35754, No. 58-122535, No. 58-
No. 122536, thiourea derivatives, alcohols having a triple bond in the molecule, and thioethers described in U.S. Pat. No. 4,126,459.

The pH of the fixing agent after dissolution or dilution is usually 3.8 or more, preferably 4.2 to 5.5.

In the present invention, the solid fixing agent refers to a solid fixing agent having a pH of less than 7 after being dissolved in water and having a fixing ability. When the tablet is a tablet, a tablet prepared by dividing the tablet into a fixing agent and an acid agent is also included.

To solidify the photographic processing agent, a concentrated liquid, a fine powder, or a granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is added to the surface of the temporarily molded photographic processing agent. Any means can be adopted, such as forming a coating layer by spraying on the surface (Japanese Patent Laid-Open Nos. 4-29136 and 4-85).
No. 535, No. 4-85536, No. 4-85533,
4-85534 and 4-172341).

As a preferred method for producing a tablet, there is a method in which a powdery solid processing agent is granulated and then subjected to a tableting step to form the tablet. There is an advantage that solubility and storage stability are improved as compared with a solid processing agent formed by a tableting step by simply mixing a solid processing agent component, and as a result, photographic performance is also stabilized. Granulation methods for tablet formation include rolling granulation, extrusion granulation, compression granulation,
Known methods such as crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation can be used. For tablet formation,
The average particle size of the obtained granules is preferably 100 to 800 μm in that, when the granules are mixed and pressed / compressed, non-uniformity of components, that is, so-called segregation is unlikely to occur. , More preferably 200 to 750 μm.
Furthermore, the particle size distribution is such that 60% or more of the granulated particles are ± 100.
Those having a deviation of １５０150 μm are preferred.

Next, when the obtained granules are pressed and compressed, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a pricketting machine is used. be able to. The solid processing agent obtained by pressurization and compression can take any shape, but from the viewpoint of productivity and handling, or from the problem of dust when used on the user side, a cylindrical type, so-called tablet Is preferred.

More preferably, at the time of granulation, the above effect is further remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative, and the like.

A method for producing a tablet processing agent is described in, for example,
Nos. 1-61837, 54-155038 and 52-
No. 88025, British Patent No. 1,213,808, etc., and can be produced by a general method. Further, granulating agents are described in, for example, JP-A Nos. 2-109042 and 2-109043.
And JP-A-3-39735, JP-A-3-39939, and the like. Further, powder processing agents are disclosed in, for example, JP-A-54-133332, British Patent
It can be produced by a general method as described in JP-A Nos. 25,892 and 729,862 and German Patent 3,733,861.

From the viewpoint of the solubility and the effect of the present invention, the bulk density of the solid processing agent is 1.0 to 2.5 in the case of a tablet.
preferably g / cm ^3, in terms of the strength of the resulting solids greater than 1.0 g / cm ^3, also preferred from the viewpoint of solubility of the solid product obtained as 2.5 g / cm ³ less than.
When the solid processing agent is granules or powder, the bulk density is 0.4
It is preferably from 0 to 0.95 g / cm ³ .

The solid processing agent is used for all photographic processing agents such as a developer, a fixing agent, and a rinsing agent, but the effect of the present invention, particularly the effect of stabilizing photographic performance, is great for the developer. . Although it is within the scope of the present invention that the solid processing agent solidifies only some components of a certain processing agent, it is preferable that all components of the processing agent be solidified. It is desirable that each component is molded as a separate solid processing agent and is mounted in the same unit. It is also desirable that the separate components are packaged in the order in which they are periodically charged repeatedly.

It is preferable that all the processing agents to be replenished into each processing tank according to the processing amount information are charged as solid processing agents. When replenishing water is required, replenishing water is replenished based on the processing amount information or other replenishing water control information. In this case, the liquid to be replenished to the processing tank can be only replenishing water.
That is, when two or more kinds of processing tanks need replenishment, only one tank for storing the replenishing liquid by sharing the replenishing water is required, and the size of the automatic developing machine can be reduced. The replenishing water tank may be placed outside or may be built in an automatic processor, and is preferably built in from the viewpoint of space saving and the like.

When the developer is solidified, all of the alkali agent and the reducing agent are solidified, and in the case of a tablet, it is preferable to use at least three agents, most preferably one agent. Is a preferred embodiment. In the case of solidifying two or more tablets, it is preferable that the plurality of tablets and granules are packaged in the same manner.

As a supply means for supplying the solid processing agent containing the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, Japanese Unexamined Utility Model Publication No. 63-137783 and 63-975.
There are known methods such as No. 22 and Japanese Utility Model Application Laid-Open No. 1-85732, but any method may be used as long as the function of supplying tablets to the processing tank is provided at a minimum. When the solid processing agent is in the form of granules or powder, the gravity drop method described in Japanese Utility Model Application Laid-Open Nos. 62-81964 and 63-84151, Japanese Patent Application Laid-Open No. 1-292375, and Japanese Utility Model Application Laid-Open No. 63-105159, 6
The method using a screw or a screw described in 3-195345 or the like is known, but is not limited thereto.

However, as a preferable solid processing agent supply means, for example, a predetermined amount of the solid processing agent weighed in advance and divided and packaged is opened in a package according to the processing amount of the photosensitive material.
There is a way to take it out. Specifically, the solid processing agent is sandwiched and stored by a predetermined amount, preferably by a single replenishment amount, in a package composed of at least two packaging materials. The part is opened so that it can be removed. The solid processing agent in a removable state can be easily supplied to a processing tank having a filtering means by natural fall. A predetermined amount of the solid processing agent is housed in a separately sealed package so that the air permeability between the outside air and the adjacent solid processing agent is shut off. ing.

As an embodiment, a configuration is conceivable in which a package made of at least two packaging materials sandwiches the solid processing agent and is closely adhered or adhered to each other so that the periphery of the processing agent can be separated. . By pulling each packaging material sandwiching the solid processing agent in different directions, the close contact or adhesion surface is separated, and the processing agent can be taken out.

As another embodiment, it is conceivable that at least one of the packages made of at least two packaging materials can be opened by an external force so as to sandwich the solid processing agent. The term “opening” as used herein refers to a cut or break that leaves a part of the packaging material. As an opening method, the solid processing agent is forcibly extruded by applying a compressive force from the non-opening side package to the openable package through the solid processing agent, or the package is opened. It is conceivable that the solid processing agent can be taken out by making a cut with a sharp member.

The supply start signal is obtained by detecting information on the processing amount. The supply stop signal is obtained by detecting information indicating that the supply of a predetermined amount has been completed. Further, when the processing agent is packaged and opening is required, a driving unit for separating or opening based on the obtained supply start signal operates,
It is possible to control so that the driving means for separating or opening is stopped based on the supply stop signal.

The supply means of the solid processing agent has a control means for supplying a fixed amount of the solid processing agent in accordance with the processing amount information of the photosensitive material, which is an important requirement. That is, in an automatic developing machine, it is necessary to keep the component concentration in each processing tank constant and to stabilize photographic performance. The processing amount information of the photosensitive material is a value proportional to the processing amount of the photosensitive material processed by the processing solution, the processing amount of the processed photosensitive material, or the processing amount of the photographic photosensitive material being processed. The reduction amount of the treatment agent is indicated indirectly or directly. The detection may be performed at any timing before or after the photosensitive material is carried into the processing solution, or during immersion in the processing solution. Further, physical parameters such as the concentration of the composition in the processing solution or a change in the concentration, pH and specific gravity may be used. Alternatively, the amount of the processing liquid that has come out after drying may be used.

The place where the solid processing agent is charged may be in the processing tank, but is preferably in communication with the processing section for processing the photosensitive material, and the processing liquid flows between the processing section and the processing section. It is preferable that there is a constant processing liquid circulation amount between the processing part and the processing part, and the dissolved component move to the processing part.
The solid processing agent is preferably introduced into a processing liquid whose temperature is controlled.

Generally, in an automatic developing machine, the temperature of a processing solution is controlled by an electric heater to control the temperature. As a general method, a heat exchange unit is provided in the auxiliary tank connected to the processing layer, a heater is installed, and a pump is arranged in this replenishment tank so that the liquid is sent from the processing tank at a constant circulation rate and the temperature is kept constant. Have been. Usually, a filter is disposed for the purpose of removing crystal foreign substances mixed in the processing liquid or generated by crystallization, and plays a role of removing the foreign substances. It is most preferable that the solid processing agent is introduced into a place where the temperature is controlled, such as a place communicating with the processing section, such as the auxiliary tank. This is because the insoluble components in the input processing agent are blocked from the processing unit by the filter unit, so that the solid content can be prevented from flowing into the processing unit and adhering to the photosensitive material, and the solubility of the solid processing agent can be improved. Very good.

In the case where a processing agent charging section is provided together with the processing section in the processing tank, it is preferable to devise a shield or the like so that the insoluble component section does not directly contact the film or the like. As the material of the filter, the filtration device, and the like, those used in general automatic developing machines can be used, and the special structure and material do not affect the effects of the present invention.

The number of circulations of the treatment liquid circulated by the circulation means is preferably 0.5 to 2.0 times / min, and particularly preferably 0.8 to 2.0 times / min.
~ 2.0 times / min, more preferably 1.0 ~ 2.0 times / min
Is preferred. As a result, the dissolution of the solid processing agent is promoted, the occurrence of agglomeration of the high-concentration liquid can be prevented, the occurrence of concentration unevenness in the processed photographic material can be prevented, and the generation of insufficiently processed photographic material can be prevented. Can be prevented. Here, the number of circulations indicates the flow rate of the circulated liquid, and the time when the liquid amount corresponding to the total liquid amount in the processing tank flows is defined as one time.

The solid treating agent is added to the treatment tank separately from the replenishing water, and the replenishing water is supplied from a refilling tank. In the solid processing agent, Japanese Patent Application No. 6-91987, 2 discloses a binder.
The saccharides described on pages 3 to 30 (monosaccharides, polysaccharides in which a plurality of monosaccharides are linked to each other, and their decomposed products) are preferable, and among them, those selected from dextrins and sugar alcohols are particularly preferably used. . There is little change in shape during long-term storage, and trouble during addition and usability are improved.

The solid processing agents include lubricants as disclosed in Japanese Patent Application No.
It is preferred to use the acylated amino acids described in 186254, pages 9-15. The solid processing agent can be manufactured stably without impairing the strength, the solubility is less deteriorated, and the storage stability and dust generation are improved.

The solid processing agents include, as a coating agent, hydroxylamines, phenylcarboxylic acids, phenylsulfonic acids, alkyl (to which a hydroxyl group or a carboxyl group is introduced) described in Japanese Patent Application No. 6-70860, pp. 14-33. Or alkenyl) carboxylic acids, sulfites, water-soluble polymers (eg, polyalkylene glycols, methacrylic acid-based betaine polymers), and saccharides. The generation of fine powder is small, the deterioration of solubility is small, and excellent storability can be maintained and stable photographic performance can be maintained.

In the developer of the present invention, in addition to dihydroxybenzenes, aminophenols and pyrazolidones described in Japanese Patent Application No. 4-286232, pp. 19-20, developing agents are described in JP-A-5-165161. Are also preferably used. Of the pyrazolidones used, particularly those substituted at the 4-position (dimesone, dimesone S
And the like) are particularly preferable since the water-soluble and solid processing agents themselves hardly change with time.

The photosensitive material processed by the developer of the present invention is not particularly limited, but preferred examples of elements constituting the photosensitive material are described below.

The emulsion used for the light-sensitive material can be produced by a known method. For example, Research Disclosure (R
D) 17643 (December 1978) I on pages 22-23
"Emulsion preparation method (Emulsion preparati
on and types) and RD18716 (19
(November 1979) page 648. Also, T. H. James "The theo
ry of the photographic pr
process, 4th edition, published by Macmillan (197
7), pages 38 to 104; F. Dau
"Photographic Emulsion Chemistry", Photographi
cemslon chemistry ”, Foc
al press (1966); Glafk
"Physics and Chemistry of Photography" by Chides et al.
physique photographiqu
e ", published by Paul Montel (1967),
V. L. "Manufacturing and Coating of Photographic Emulsions," Zelikman et al., "Making and Coating Pho."
graphical Emulsion ", Focal
It is prepared by the method described in Press, etc. (1964).

Examples of preferably used silver halide emulsions include, for example, JP-A-59-177535 and JP-A-61-8.
No. 02237, No. 61-132943, No. 63-49
No. 751 and JP-A-2-85846. Silver chlorobromide or silver chloride having a silver chloride content of 50 mol% or more is also preferable.

The crystal structure of silver halide is preferably a core / shell type monodispersed emulsion having a two-layer structure comprising a low iodine shell layer in a high iodine core portion. The silver iodide content of the high iodine part is 20 to 40 mol%, particularly preferably 20 to 30 mol%. Examples of these include, for example, Pho
t. Sci. 12, 242 to 251 (1963), JP-A-48-36890, JP-A-52-16364, and 5
Nos. 5-142329, 58-49938, British Patent 1,413,748, U.S. Patent 3,574,628
No. 3,655,394, British Patent 1,027,1
No. 46, U.S. Pat. Nos. 3,505,068 and 4,44
4,877 and JP-A-60-14331.

The silver halide emulsion preferably used is
Tabular grains having an average aspect ratio of greater than 1. The advantage of such particles is that they provide improved spectral sensitization efficiency, improved image graininess and sharpness, and the like, for example, in UK Patent 2,112,157, US Patent 4,439,520.
Nos. 4,433,048 and 4,414,310
No. 4,434,226, JP-A-58-11392.
No. 7, 58-127921, 63-138342
And JP-A-63-284272 and JP-A-63-305343, and can be prepared by the methods described therein.

The silver halide emulsion may be prepared at the stage of physical ripening or grain preparation at a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iridium salt (including a pyramid salt), a rhodium salt (including a pyramid salt), an iron salt. (Including pyramidal salt) and the like may be used. The emulsion may be subjected to a washing method such as a noodle washing method or a flocculation sedimentation method to remove soluble salts. For example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086,
A method using a flocculant polymer agent (exemplified G3, G8) described in JP-A-63-158644 is a particularly preferred desalting method.

As a method for chemically ripening a silver halide emulsion, gold sensitization, sulfur sensitization, reduction sensitization, sensitization with a chalcogen compound, and a combination thereof are preferably used.

In the emulsion, various photographic additives can be used before and after physical ripening or chemical ripening.
A hydrazine compound can also be added.
No. 34743 is preferred, and particularly preferred are compounds of the general formula (5) and compounds of the general formulas (7) and (8) as the nucleation accelerator. A tetrazolium salt can be added, and those described in JP-A-2-25050 are preferred. Others
Known additives include the aforementioned RD17643, 23-
29, 18716, 648-651 and 308
119, 996-1009.

Examples of the support that can be used for the light-sensitive material include RD17643, page 28 and RD3081.
19, page 1009.
A suitable support is a plastic film or the like, and the surface of the support may be provided with an undercoat layer to improve the adhesion of the coating layer, or may be subjected to corona discharge, ultraviolet irradiation, or the like. Further, a crossover cut layer or an antistatic layer may be provided.

An emulsion layer may be present on both sides of the support,
Only one side may be used. In the case of both sides, both sides may have the same performance or different performances.

[0084]

The present invention will be described in more detail with reference to the following examples.

Example 1 (Preparation of Seed Emulsion-1) Seed Emulsion-1 was prepared as follows.

A1 Ossein gelatin 24.2 g Water 9657 ml Compound (SU-3) (10% ethanol aqueous solution) 6.78 ml Potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 Potassium bromide 841 g Water 2.25 ml D1 1.75N aqueous potassium bromide solution Silver potential control amount SU-3: HO (CH ₂ CH ₂ O) _n [CH (CH ₃ ) CH
₂ O] ₁₇ (CH ₂ CH ₂ O) _m H At 42 ° C., JP-B-58-58288, 58-582
Using a mixing stirrer described in No. 89, 464.3 ml of each of the solution B1 and the solution C1 was added to the solution A1 by a simultaneous mixing method over 1.5 minutes to form nuclei.

After stopping the addition of the solution B1 and the solution C1, the temperature of the solution A1 was raised to 60 ° C. in 60 minutes, the pH was adjusted to 5.0 with a 3% aqueous solution of potassium hydroxide, and then again. The solution B1 and the solution C1 were respectively added at a flow rate of 55.4 ml / min for 42 minutes by a simultaneous mixing method. This 4
The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature rise from 2 ° C. to 60 ° C. and re-mixing with the solutions B1 and C1 was determined using the solution D1
Control was performed so as to be +8 mV and +16 mV, respectively.

After the addition was completed, the pH was adjusted to 6 with a 3% aqueous solution of potassium hydroxide, and then immediately desalted and washed with water. In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.064 μm. It was confirmed with an electron microscope that the diameter (in terms of circular diameter) was 0.595 μm. The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

(Preparation of Emulsion Em-1) A tabular silver halide emulsion Em-1 was prepared using the above seed emulsion-1 and the following four kinds of solutions.

A2 Ossein gelatin 34.03 g Compound (SU-3) (10% aqueous ethanol solution) 2.25 ml Seed emulsion-1 1.218 mol equivalent with water 3150 ml B2 Potassium bromide 1734 g with water 3644 ml C2 Silver nitrate 2478 g with water 4165 ml D2 3% by weight of gelatin and fine grain emulsion comprising silver iodide grains (average particle size: 0.05 μm) (*) Equivalent to 0.080 mol * 5.0% by weight containing 0.06 mol of potassium iodide To 6.64 liters of an aqueous gelatin solution, 2 liters of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After particle formation, pH is adjusted using aqueous sodium carbonate solution.
Adjusted to 6.0.

In the reaction vessel, the solution A2 was vigorously stirred while maintaining it at 60 ° C., and a part of the solution B2, a part of the solution C2 and half of the solution D2 were added thereto by a double jet method over 5 minutes. Subsequently, half of the remaining amount of the solution B2 and the solution C2 is
Over a period of 15 minutes, and then a part of the solution B2, a part of the solution C2 and the entire remaining amount of the solution D2 are added over 15 minutes, and finally, the entire remaining amount of the solution B2 and the solution C2 are added over 33 minutes. Was added. During this time, the pH was 5.8 and the pAg was 8.8.
I kept it at 8. Here, the addition rates of the solution B2 and the solution C2 were changed like a function with respect to the time corresponding to the critical growth rate.

Further, the solution D2 was added in an amount corresponding to 0.15 mol% based on the total silver amount to perform halogen substitution.

After the addition was completed, the emulsion was cooled to 40 ° C.
13.8 wt% aqueous solution of modified gelatin modified with a phenylcarbamoyl group (substitution rate 90%) as an aggregated polymer 1
800 ml was added and stirred for 3 minutes. Then, acetic acid 5
The pH of the emulsion was adjusted to 4.6 by adding a 6 wt% aqueous solution, stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was removed by decantation. Thereafter, 9.0 liters of distilled water at 40 ° C. was added, and the mixture was stirred and allowed to stand. The supernatant was removed, and 11.25 liters of distilled water was further added, and the mixture was stirred and allowed to stand.
The supernatant was removed. Subsequently, an aqueous gelatin solution and a 10 wt% aqueous sodium carbonate solution were added to adjust the pH to 5.80, followed by stirring at 50 ° C. for 30 minutes to redisperse. After redispersion, the pH was adjusted to 5.8 and pAg to 8.06 at 40 ° C.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.11 μm and the average thickness was 0.2.
Tabular silver halide grains having a size of 5 μm, an average aspect ratio of about 4.5, and a particle size distribution of 18.1% were obtained. The average of the twin plane distance is 0.020 μm, and the grains having a ratio of twin plane distance to thickness of 5 or more are 97% (number) of all tabular silver halide grains and 10 or more grains. Occupied 49%, and 15% or more of the particles occupied 17%.

Next, after the temperature of the emulsion Em-1 was raised to 60 ° C., a predetermined amount of the spectral sensitizing dyes (SD-1, SD-2 ⁾ was added as ^a solid particulate dispersion ^(a) for 10 minutes. Later, a mixed solution of adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate and a selenium sensitizer (Se-
The dispersion liquid ^(b) of 1) was added, and after 30 minutes, a silver iodide fine grain emulsion was added, followed by ripening for a total of 2 hours. At the end of aging, a predetermined amount of the stabilizer (ST-1) was added.

The structures and amounts (per mole of silver halide) of the above additives are shown below.

SD-1: 5,5'-dichloro-9-ethyl-3,3'-di- (sulfopropyl) -oxacarbocyanine sodium salt anhydrous SD-2: 5,5'-di- ( Butoxycarbonyl)-
1,1'-diethyl-3,3'-di (4-sulfobutyl) benzimidazolocarbocyanine sodium salt anhydride Se-1: triphenylphosphine selenide ST-1: 4-hydroxy-6-methyl-1 , 3,3
a, 7-Tetrazaindene SD-1 400 mg SD-2 4.0 mg Adenine 15 mg Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Se-1 0.2 mg Fine silver iodide 280 mg ST-1 500 mg (A) Solid fine particle dispersion of spectral sensitizing dye is disclosed in
It was prepared according to the method described in -99437. That is, a predetermined amount of the spectral sensitizing dye is added to water previously adjusted to 27 ° C.,
30 at 3,500 rpm with high-speed stirring (dissolver)
Obtained by stirring for ~ 120 minutes.

(B) A dispersion of the selenium sensitizer was prepared as follows. That is, 120 g of Se-1 was added to 30 kg of ethyl acetate at 50 ° C. and completely dissolved by stirring. On the other hand, 3.8 kg of photographic gelatin was added to 38 kg of pure water.
And 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto.

Next, these two liquids were mixed to form a mixture having a diameter of 10%.
cm disperser with a high-speed stirring type disperser,
The dispersion was performed at 50 ° C. for 30 minutes at a peripheral speed of the dispersion blade of 40 m / sec. Thereafter, the ethyl acetate was removed while rapidly stirring under reduced pressure until the residual concentration of ethyl acetate became 0.3 wt% or less. Thereafter, the dispersion is diluted with pure water to obtain 8
Finished to 0 kg. A part of the dispersion thus obtained was fractionated and used in the above experiment.

(Preparation of Emulsion Coating Solution) The following various additives were added to the emulsion obtained above (shown in an amount per 1 m ^{2 of the} coated area).

Compound (G) 0.5 mg 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg 1,1-dimethylol-1-bromo-1-nitromethane 70 mg t-butylcatechol 130 mg polyvinylpyrrolidone (molecular weight 10,000) 35 mg styrene-maleic anhydride copolymer 80 mg sodium polystyrenesulfonate 80 mg trimethylolpropane 350 mg diethylene glycol 50 mg nitrophenyl / triphenylphosphonium chloride 20 mg resorcin-4-ammonium ammonium 500 mg 2-mercaptobenz imidazole-5-sulfonic acid sodium 5mg compound _{(H) 0.5mg C 4 H 9} OCH 2 CH (OH) CH 2 N (CH 2 COOH) 2 350m g Colloidal silica (Ludox AM: manufactured by DuPont, particle size: 0.013 μm) 0.5 g However, as gelatin, 1.5 g / g
It was adjusted to m ^2.

(Preparation of Coating Solution for Protective Layer) Gelatin 0.8 g Matt agent composed of polymethyl methacrylate (area average particle size 7.0 μm) 50 mg Bis (vinylsulfonylmethyl) ether (hardening agent) 36 mg 2,4-dichloro Sodium 6-hydroxy-1,3,5-triazine (hardener) 10 mg Latex (L) 0.2 g Polyacrylamide (average molecular weight 10,000) 0.2 g Sodium polyacrylate 30 mg Polysiloxane (SI) 20 mg Compound ( I) 12 mg compound (J) 2 mg compound (SU-1) 7 mg compound (K) 15 mg C ₁₁ H ₂₃ CONH (CH ₂ CH ₂ O) ₅ H 50 mg compound (SU-2) 5 mg C ₉ H ₁₉ O (CH _{2) CH 2 O) 11 H 3mg C} 8 F 17 SO 2 N (C 3 H 7) (CH 2 CH 2 O) 15 _{2mg C 8 F 17 SO 2 N} (C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 SO 3 Na 1mg Incidentally, the amount with the material is one-sided 1 m ² per silver coverage simplex It was adjusted to 1.6 g / m ² as a minute.

(Formation of Crossover Cut Layer) Thickness of a dispersion of glycidyl methacrylate / methyl acrylate / butyl methacrylate copolymer (50:10:40 wt%) (diluted to a concentration of 10 wt%) applied as a subbing liquid on both sides of a blue-colored polyethylene terephthalate (PET) support 175 .mu.m, was prepared a support samples coated with the cross-over cut layer as the coating amount per surface 1 m ² is the following composition.

Solid fine particle dispersion dye (SF) 50 mg Gelatin 0.2 g Sodium dodecylbenzenesulfonate 5 mg Compound (I) 5 mg 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium (hardener 5 mg colloidal silica (average particle size 0.014 μm) 10 mg potassium polystyrene sulfonate 50 mg J: 12 mol adduct of p-nonylphenol / ethylene oxide SU-1: i-amyl decyl sodium sulfosuccinate SU-2: sulfoamber Acid bis (2,2,3,3,4,
4,5,5,6,6,7,7-dodecylfluoroheptyl) sodium

[0105]

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[0106]

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(Preparation of Samples of Photosensitive Material) Using these coating solutions, two units were prepared such that the coating amount was 1.6 g / m ² per one side and 2.5 g / m ² with gelatin. The slide hopper type coater was used to simultaneously coat both sides of the above support sample at the speed of 120 m / min with the following layer constitution, and dried in 2 minutes and 20 seconds to prepare a photosensitive material sample-1.

Position of layer Layer type Layer amount of gelatin per side (g / m ² ) Upper layer Protective layer 0.8 Intermediate layer Emulsion layer 1.5 Lower layer Filter layer 0.2 (Monodispersed cubic seed emulsion-2) preparation) <solution a _1> ossein gelatin 30g potassium bromide 7700ml with 1.25 g 0.1 N nitric acid 150ml distilled water <solution B _1> 740 ml potassium bromide 6g potassium iodide 0.16g distilled water <solution C ₁ > Potassium bromide 680 g potassium iodide 20 g distilled water 2480 ml <solution D ₁ > silver nitrate 8.4 g 0.1 N nitric acid 32 ml distilled water 740 ml <solution E ₁ > silver nitrate 991.6 g 0.1 N nitric acid 80 ml distilled water 2480 ml 60 solution a ₁ which was vigorously stirred at ° C., a solution B ₁ and solution D ₁
Was added by the double jet method over 10 minutes. Then, the solution C ₁ and the solution E ₁ are mixed with _{each other} by a double jet method.
Added over 0 minutes. At this time, the initial addition flow rate was 1/8 of the final addition flow rate, and the sensitivity was linearly sensitized with time. During the addition of these solutions, the pH was constantly adjusted to 2 and pAg to 8. After the addition is completed, adjust the pH to 6 with sodium carbonate.
And 150 g of potassium bromide was added thereto. Immediately after desalting and washing with water, a monodispersed cubic seed emulsion Em-B of silver iodobromide containing 2 mol% of silver iodide having an average grain size of 0.3 μm was obtained. Obtained. According to the electron microscope, the twin generation rate was 1% or less in number.

(Preparation of Normal Crystal Core / Shell Emulsion Em-2) A normal crystal emulsion Em-2 containing 2.0 mol% of silver iodide was prepared using the following five kinds of solutions.

<Solution A ₂ > 75.5 g of ossein gelatin HO (CH ₂ CH ₂ O) n [CH (CH ₃ ) CH ₂ O] (CH ₂ CH ₂ O) mH (n + m = 5.7) 10% Methanol aqueous solution 15 ml Seed emulsion-2 equivalent to 0.40 mol 4000 ml with distilled water <Solution B ₂ > 46.2 g of silver nitrate Add an equimolar amount of ammonia solution and distilled water 259 ml <Solution C ₂ > 647.6 g of silver nitrate equimolar ammonia solution and distilled water was added 1088Ml <solution D _2> in potassium bromide 22.6g potassium iodide 13.5g distilled water in 259 mL <solution E _2> potassium bromide 453.3g distilled water 1088Ml reaction kettle maintaining the solution a ₂ in 40 ° C., and adjusted to 9.5 and the pH addition of ammonia water and acetic acid. After adjusting the pAg to 7.3 with an ammoniacal silver ion solution, the solution B and the solution D are added by a double jet method while keeping the pH and the pAg constant, and a silver iodobromide layer containing 30 mol% of silver iodide is added. Was formed. The pH was adjusted to 9.0 and the pAg was adjusted to 9. using acetic acid and potassium bromide.
After adjusting to 0, the solution C and the solution E were added at the same time, and after growing, the solution was grown to reach 90% of the particle size. P at this time
H gradually decreased from 9.0 to 8.20. After adding a potassium bromide solution to adjust the pAg to 11, solutions C and E were further added to grow the solution while gradually lowering the pH to 8, to obtain a silver iodobromide emulsion containing 2 mol% of silver iodide. After completion of the addition, precipitation and desalting were carried out by the following method in order to remove excess salts.

The reaction mixture after completion of the mixing is adjusted to 40 ° C., 20 g / AgX of 1 mol of agglomerated gelatin agent is added, the pH is lowered by adding 56 wt% acetic acid, and the mixture is left to stand for decantation. 1.8 liters of pure water at 40 ° C. Add AgXl mole,
After stirring for 10 minutes, the mixture is allowed to stand and decanted. The above steps are repeated once more. A gelatin aqueous solution containing 92.2 g of ossein gelatin was added to 2500 ml, and the mixture was stirred and redispersed to obtain Em-2.

About 1000 Em-2 particles were observed and measured with an electron microscope, and the shape was analyzed. As a result, monodispersed spherical particles having an average particle diameter of 0.51 μm and a distribution width of 12% were obtained.

Next, the emulsion Em-2 was subjected to spectral sensitization and chemical sensitization in the following manner.

After the emulsion was heated to 50 ° C., the sensitizing dye (SD-
1: The above-mentioned solid fine particle dispersion was added so that the above-mentioned amount became 40 mg per mol of silver, and then the following selenium sensitizer (S
e-2) was added in an amount of 7.0 × 10 ^-6 mol, and ammonium thiocyanate was added in an amount of 4.0 × 10 ^-4 mol per mol of silver, 3.2 × 10 ^-6 mol of chloroauric acid, and sodium thiosulfate 3 mol .
4 × 10 ^-5 mol was added, and 40 minutes later, the above silver iodobromide fine grain emulsion was added at 1.7 × 10 ^-3 mol / Ag 1 mol.
It was stabilized with 1.2 × 10 ^-2 mol of ST-1.

Se-2: diphenyl pentafluorophosphine selenide (Preparation of photosensitive material sample) The following various additives were added to each of the obtained emulsions to form emulsion solutions (photosensitive silver halide coating solutions). . The amount of addition is shown in an amount per mole of silver halide.

T-butyl-catechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.5 g trimethylolpropane 10 g diethylene glycol 5 g nitrophenyl / triphenylphosphonium chloride 50 mg resorcin-4-sulfonic acid ammonium 4g 2-mercapto sodium-5-sulfonic acid _{1.5mg C 4 H 9 OCH 2 CH} (OH) CH 2 N (CH 2 COOH) 2 1g compound (G) 150 mg compound (H) 70 mg The protection layer The additives used are as follows. The amount of addition is shown in an amount per 1 g of gelatin.

Matting agent (polymethyl methacrylate having an area average particle diameter of 7 μm) 7 mg Colloidal silica (average particle diameter 0.013 μm) 70 mg 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium (hardening agent 30 mg Compound (I) 12 mg Compound (K) 2 mg Compound (SU-1) 7 mg Compound (K) 15 mg C ₉ F ₁₉ O (CH ₂ CH ₂ O) ₁₀ CH ₂ CH ₂ OH 3 mg Compound (SU-2) 5 mg (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardener) 36 mg K: 2,4-dinonylphenol / ethylene oxide 1
2 mol adduct The above coating solution is uniformly coated and dried on both sides of an emulsion layer and a protective layer on a 175 μm-thick undercoated blue-colored polyethylene terephthalate film base and dried to obtain a photosensitive material sample. -2 was produced. The silver coverage of the silver halide emulsion layer was 2.20 g / m ² per side.

A solid developer and a developer according to the present invention were prepared below.

<Solid developer α using hydroquinone as a developing agent> 100 liter amount of developer Granulated product (A) 3000 g of hydroquinone, 400 g of phenidone, 1000 g of boric acid, N-acetyl-D, L-penicillamine 10
g and glutaraldehyde sodium bisulfite 500
g in an average of 10 μm
Crush until it becomes The reductones described in Table 1 were added to the fine powder in the amounts described in Table 1, 700 g of sodium sulfite, and binder D
-Add 200 g of sorbit, mix for 30 minutes in a mill, granulate in a commercial stirred granulator at room temperature for about 5 minutes by adding 30 ml of water, then granulate the fluidized bed dryer At 40 ° C. for 2 hours to substantially completely remove the water content of the granulated material. This is designated as granulated product (A).

Phenidone: 1-phenyl-5-pyrazolidone Granulated product (B) Carbonate, bicarbonate (type and amount shown in Table 1, and in Table 3, carbonate content, K ⁺ , Na ⁺ Carbonate so that the amount
Adjust the type and amount of bicarbonate), 200 g potassium bromide
Are ground in a commercially available bandam mill to an average of 10 μm. 200 g of lithium hydroxide hydrate, 250 g of DTPA / 5H, 1-phenyl-5 were added to each fine powder.
-5 g of mercaptotetrazole, 40 of sodium sulfite
After adding 100 g of binder and 1000 g of binder mannitol, mixing in a mill for 30 minutes and granulating by adding 30 ml of water for about 15 minutes at room temperature in a commercially available stirring granulator, the granulated material is fluid-dried. It is dried at 40 ° C. for 2 hours with a machine to substantially completely remove the water content of the granulated product. This is designated as granulated product (B).

DTPA · 5H: diethylenetriaminepentaacetic acid << Preparation of granular solid developer α-1 >> The above granulated materials (A) and (B) were mixed in a room conditioned at 40% RH or less using a mixer. After mixing uniformly for 10 minutes, the mixture was sealed and packaged in a pillow bag containing aluminum for moisture prevention in an amount of 3.5 liters.

<< Preparation of tablet-like solid developer α-2 >> The granules (A) and (B) were mixed with 200 g of sodium 1-octanesulfonate in a room conditioned at 25 ° C. and 40% RH or less. After mixing uniformly using a mixer for 10 minutes, the resulting mixture was subjected to Kikusui Seisakusho's Tough Presto Collect 1527HU.
Was subjected to compression tableting using a modified tableting machine with a filling amount per tablet of 10 g to prepare alkali-developed tablets. This was sealed and packaged in a pillow bag containing aluminum for moisture prevention under an environment of 40% RH.

<Solid developer β using reductone of the present invention as a developing agent> 100 liter amount of developer Granulated product (C) 300 g of phenidone, 10 g of N-acetyl-D, L-penicillamine, glutaraldehyde bisulfite Sodium 5
00 g in an average of 10 μm each in a commercially available bandam mill.
pulverize to m. To this fine powder, 1500 g of sodium metabisulfite, the amount described in Table 1 of reductones, binder B
-Add 600 g of sorbit, mix in a mill for 30 minutes, granulate in a commercial stirred granulator for about 10 minutes at room temperature by adding 30 ml of water, then granulate the granulated product in a fluid bed dryer At 40 ° C. for 2 hours to substantially completely remove the water content of the granulated material. This is designated as granulated product (C).

Granulated product (D) Carbonate, bicarbonate (type and amount described in Table 1, and in Table 3, carbonate content such as carbonate content, K ⁺ and Na ⁺ in the table,
(Adjust the type and amount of bicarbonate) in a commercially available bandam mill until the average is 10 μm. 250 g of DTPA · 5H in each fine powder, the following compound (AF-1) 4
0 g, compound (AF-2) 10 g, potassium iodide 7 g,
200 g of methyl-β-cyclodextrin, 2000 g of a binder mannitol, and 700 g of D-sorbitol were added,
After mixing in a mill for 30 minutes and granulating in a commercial stirred granulator at room temperature for about 15 minutes by adding 30 ml of water, the granulated product is fluidized at 40 ° C. for 2 hours. After drying, the water content of the granulated material is almost completely removed. This is granulated (D)
And

AF-1: 1- (3-sulfophenyl)-
5-mercaptotetrazole sodium AF-2: 5-mercapto- (1H) -tetrazolylacetate sodium <Preparation of granular solid developer β-1> The above granulated products (C) and (D) are not more than 40% RH. The mixture was uniformly mixed for 10 minutes using a mixer in a humidified room, and then sealed in a pillow bag containing aluminum for 3.5 liters in order to prevent moisture.

<< Preparation of Tablet-like Solid Developer β-2 >> The granules (C) and (D) were mixed with 150 g of sodium 1-octanesulfonate in a room conditioned at 25 ° C. and 40% RH or less. After mixing uniformly using a mixer for 10 minutes, the resulting mixture was subjected to Kikusui Seisakusho's Tough Presto Collect 1527HU.
Was subjected to compression tableting using a modified tableting machine with a filling amount per tablet of 10 g to prepare alkali-developed tablets. This was sealed and packaged in a pillow bag containing aluminum for moisture prevention under an environment of 40% RH.

A solid fixing tablet having a fixing liquid amount of 100 liters was prepared by the following operation.

Granulated product (E) Ammonium thiosulfate / sodium thiosulfate (90/1
(Weight ratio) of 15000 g in a commercially available banda mill on average 1
Grind to 0 μm. 500 g of sodium sulfite, 750 g of sodium pyrosulfate, and 1300 g of binder pine flow were added to the fine powder, and the mixture was stirred and granulated to a water addition amount of 50 ml. The granulated product was dried at 40 ° C. with a fluidized bed drier to remove water. Almost completely removed. This is designated as granulated product (E).

Granulated product (F) 400 g of boric acid, 1200 g of aluminum sulfate octahydrate,
1200 g of succinic acid and 300 g of tartaric acid are pulverized in a commercially available bandam mill until the average becomes 10 μm. D
-Mannit 250g, D-Sorbit 120g, PE
G # 4000 (160 g) is added, water is added in an amount of 30 ml, and stirring granulation is carried out. This is designated as granulated product (F).

<< Solid Fixing Tablet >> 3000 g of β-alanine, 4330 g of sodium acetate, and further, sodium 1-octanesulfonate were added to the granulated product (E) thus obtained in an amount of 1.5% of the total weight. 750 g of sodium metabisulfite and sodium 1-octanesulfonate are added to the granulated product (F) so as to be 1.0% of the total weight, and each is adjusted to 25 ° C. and 40% RH or less. After mixing uniformly for 10 minutes using a mixer in a wet room,
The obtained mixture is tough pre-collect 1 manufactured by Kikusui Seisakusho
Using a modified tableting machine of 527HU, the filling amount per tablet was set to 10.2 g for (E) and 11.2 g for (F), and compression tableting was performed to produce a cylindrical fixing tablet having a diameter of 30 mm. Each solid agent was sealed and packed in a pillow bag containing aluminum in an amount of 3.5 liters in order to prevent moisture. These are designated as solid fixing tablets (E) and (F).

(Treatment method) The automatic processing machine used was a modified SRX-201 (manufactured by Konica). Processing time dry to d at a developing temperature of 36 ° C., a fixing temperature of 35 ° C., and a drying temperature of 55 ° C.
Processing was performed in ry60 seconds. The replenishment amount is 1 for both development and fixing.
It was 80 ml / m ² .

The developing solution in the developing tank at the start is prepared by diluting and dissolving both the hydroquinone-based solid developer α and the reductone-based solid developer β with dilution water using a modified chemical mixer described later. The tablet was completely dissolved, and no precipitate was observed.

7.8 liters of this developing solution was added to SRX-20.
1 (manufactured by Konica Corp.), a starter described below was added thereto, and the processing was started by filling the developing tank as a starting solution. The starter addition amount was 35 ml / 1 liter.

The fixing agent is prepared by diluting the solid fixing tablets (E) and (F) with dilution water using a modified chemical mixer described later. The tablet was completely dissolved, and no precipitate was observed. 5.6 liters of the prepared fixing solution was applied to SRX-201.
Was used as a start solution in a fixing tank.

Starter formulation Potassium bromide 5.5 g HOCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ OH 0.05 g N-acetyl-D, L-penicillamine 0.10 g Sodium metabisulfite 35 ml with water A modified chemical mixer inlet was provided so that each solid agent could be charged for both development and fixing of SRX-201, and the built-in chemical mixer for dissolving the solid agent was modified.

For both development and fixing, the packaging bags each opened by hand were set at the inlet of each solid agent, and the solid processing agent of the present invention was dropped into the built-in chemical mixer, and simultaneously with hot water (25 to 30 ° C.). ) Is poured into the mixture, and the mixture is adjusted to 3.5 liters with a dissolution time of 25 minutes while stirring and dissolving. Develop this
Used as a fixing replenisher. The replenisher thus prepared is supplied to a developing tank and a fixing tank to satisfy the above-mentioned amount.

The pH when the developer was dissolved was 10.55 for the hydroquinone-based developer and p.
Fine adjustment was made with acetic acid and potassium hydroxide so as to obtain H10.15. The pH of the dissolution replenisher for the fixer was 4.80.

The built-in chemical mixer is divided into a liquid preparation tank and a spare tank tank. The capacity of the liquid preparation tank is 3.5 liters and the capacity of the spare tank is 3.0 liters. A spare tank was provided so that the replenisher could be supplied so that the replenisher would not be in a non-replenished state during the stirring and dissolving time (about 25 minutes) even when the prepared replenisher disappeared.

When the starter was added, the pH of the developer was adjusted so that α was 10.45 and β was 9.90.

A starter was similarly added to the replenishment developer γ prepared with the SRX-201 modified so that the built-in CM could be prepared in the three-part composition from the following three-part concentrate kit instead of the solid agent. And the starting solution (starting pH 9.9)
0) and processing was performed. As the fixing solution, the same solution as prepared above was used.

(Preparation of Developing Solution γ) Composition of Concentrated Solution Developing Kit (1 liter of developing solution finished amount) (Part A) Reductones Tables 1 and 3 Dimezone S 4 g Potassium sulfite (50% aqueous solution) 70 g Bicarbonate Amounts described in Tables 1 and 3 * Potassium carbonate Amounts described in Tables 1 and 3 * Compound (AF-1) 0.4 g Compound (AF-2) 0.10 g Diethylene glycol 70 g 50% aqueous potassium hydroxide solution pH adjustment To 550 ml with pure water Finishing, pH adjusted to 10.80.

Dimesone S: 4-hydroxymethyl-4-
Methyl-1-phenyl-3-pyrazolidone * In Table 3, the types and amounts of carbonate and bicarbonate were adjusted so that the carbonate content, K ⁺ , and Na ⁺ amounts in the table were obtained.

(B part) Acetic acid (90%) 22 g Triethylene glycol 10 g N-acetyl-D, L-penicillamine 0.2 g Phenidone 2.0 g Dimezone S 4 g 5-Nitroindazole 0.02 g (C part) 50% glutar Aldehyde solution 5.0 g The pH of the above developer when adjusted to 1 liter was 1
0.10.

(Evaluation of Examples) The solid developers (granules and tablets) prepared by enclosing and packaging in a pillow bag first were used at 25 ° C for 1 year, 50 ° C for 1 month, and 40 ° C for 3 months, respectively. After storage, the following evaluation was performed on the sample before and after storage. The results are shown in Tables 1 to 4.

{Sensitometric fluctuation} The photosensitive material prepared above was cut into large-sized pieces, subjected to uniform exposure over the entire surface so that the optical density after development processing became 1.0, and subjected to running processing (100 sheets). Was.

Sensitometry was determined as follows.

The film was sandwiched between fluorescent intensifying screens KO-250 (manufactured by Konica Corporation), irradiated with X-rays under the conditions of a tube voltage of 90 kVp, a current of 20 mA and a time of 0.05 second, and the sensitometric curve was measured by the distance method. Created and determined the sensitivity. Sensitivity value (S
₂ ) was determined as the reciprocal of the X-ray dose required to obtain a density of fog + 1.0. Sample No. The relative sensitivity is shown with 1 as 100.

Fog + 0.25 to Fog +
In the density range of 2.0, the gradient was indicated by a slope obtained by dividing the density difference by the logarithmic value difference of the exposure amount required to obtain the density.
Also, the maximum density at which the exposure amount can be increased is shown as Dm.

{Solubility of Solid Developer} Take each solid developer (granules, tablets) in an amount of 0.3 liter,
Dissolve in tap water (an amount of 300 ml in a dissolved state) at a constant temperature of 30 ° C. using a magnetic stirrer, and measure the time from when the solid developer is charged to when all the solid developer is completely dissolved visually. Were evaluated comparatively.

{Hardness of Solid Developer} Five samples of each tablet were measured using a hardness tester (TS-50N manufactured by Okada Seiko Co., Ltd.), and the average value was taken as the hardness (strength) of the tablet sample.

[0151]

[Table 1]

[0152]

[Table 2]

[0153]

[Table 3]

[0154]

[Table 4]

[0155]

As is clear from the results shown in Tables 1 to 4, adoption of the constitution of the present invention provides excellent sensitometric fluctuation and solubility after storage at room temperature and at high temperature. In particular, it can be seen that the effect is more remarkable and the hardness characteristics after storage are improved by making the tablet form.

Claims (5)

[Claims] 1. A method comprising the steps of: containing a reductone, an alkali metal carbonate and an alkali metal bicarbonate, wherein the molar concentration ratio of bicarbonate to carbonate is 0.3 to 0.8. Solid developer. 2. It contains reductones, carbonates, Na ⁺ and K ⁺ , and the ratio of Na ⁺ to K ⁺ (Na / K) is 0 to 0.3.
Wherein the content of carbonate is 40% or more. 3. It contains Na ⁺ and K ⁺ , and Na ⁺ and K ⁺
The solid developer according to claim 1, wherein the ratio (Na / K) is 0 to 0.3 and the content of carbonate is 40% or more. 4. The solid developer according to claim 1, wherein the solid developer is in the form of a tablet. 5. The content of carbonate in one tablet is from 40 to 70.
% Of the solid developer.