JP3481802B2 - Silver halide photographic material, developer for silver halide photographic material and processing method thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, a developer for silver halide photographic light-sensitive material and a processing method thereof.

[0002]

2. Description of the Related Art Conventionally, it has been important to improve the coverage of a silver halide photographic light-sensitive material (hereinafter also referred to as a light-sensitive material or a light-sensitive material) because it saves the amount of silver. on the other hand,
In recent years, low replenishment processing and rapid processing have become the mainstream in order to reduce the amount of waste liquid while the environmental load is required to be reduced. Under the influence of, the technology for improving the coverage rate is becoming more and more important.

However, when a high silver covering power is given, the color tone of developed silver almost always depends on the grain size and grain thickness, but is yellowish and gives an unpleasant impression to an image observer.

Japanese Unexamined Patent Publication No. 5-66525 discloses a technique in which a photosensitive material containing tabular grains having an aspect ratio of 3 or more is processed with a developing solution containing a nitrogen-containing heterocyclic mercapto compound to improve the silver tone while maintaining the sensitivity and Dm. However, the degree of improvement in silver color tone is insufficient, and silver sludge property, Dm during long-term running treatment (state of being subjected to oxidation fatigue for a long time), and stability of color tone are not mentioned.

Japanese Unexamined Patent Publication (Kokai) No. 7-114153 discloses a technique of using a mercapto-containing compound in a developer containing a dihydroxybenzene-free auxiliary developer and potassium carbonate to prevent silver sludge, improve sensitivity of rapid processing, and improve γ. However, as well as the constitution of the present invention in which a peculiar mercapto compound is used in combination, silver tone and the above long-term stability are not mentioned as effects.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to improve the silver tone and at the same time a long-term running process which is affected by oxidative fatigue, particularly a process state in which a large amount of water is evaporated in a small amount of process and the process liquid is concentrated. It is another object of the present invention to provide a silver halide photographic light-sensitive material, a developing solution for a silver halide photographic light-sensitive material, and a processing method thereof, which can improve the stability of Dm, γ, and silver tone.

[0007]

The present invention which solves the above-mentioned problems includes: In a silver halide photographic light-sensitive material in which a hydrophilic colloid layer containing at least one silver halide emulsion layer is provided on a support, the hydrophilic colloid layer has the following general formula (1)
A silver halide photographic light-sensitive material comprising a compound represented by: and a compound represented by the general formula (2).

[0008]

[Chemical 3] In the formula, Y and Z are N or CR ₂ (R ₂ represents a hydrogen atom and a substituted or unsubstituted alkyl group or aryl group.) R ₁ is at least one or more sulfo group, carboxy group,
It represents an amino group, a hydroxy group or a salt thereof, or an aryl group substituted with a boron residue. When two or more of these substituents are present, they may be the same or different. M represents a hydrogen atom, an alkali metal atom, quaternary ammonium, and a group in which M can be a hydrogen atom or an alkali metal under alkaline conditions.

[0009]

[Chemical 4] In the formula, P and Q are N or CR ₄ (R ₄ represents a hydrogen atom and a substituted or unsubstituted alkyl group or aryl group.) R ₃ is at least one or more sulfo group, carboxy group,
It represents an alkyl group substituted with an amino group, a hydroxy group or a salt thereof, or a boron residue.

When there are two or more substituents, they may be the same or different. M ₁ represents a hydrogen atom, an alkali metal atom, a quaternary ammonium, or a group in which M can be a hydrogen atom or an alkali metal under alkaline conditions.

2. 2. A developer for a silver halide photographic light-sensitive material, comprising a compound represented by the general formula (1) and a compound represented by the general formula (2). A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a silver halide emulsion layer on a support is used for the presence of the compound represented by the general formula (1) and the compound represented by the general formula (2). 3. A method for processing a silver halide photographic light-sensitive material, which is characterized in that development processing is performed below. 4. The developing solution for silver halide photographic light-sensitive material as described in 2 above, wherein the developing solution contains reductones. 5. The method for processing a silver halide photographic light-sensitive material as described in 3 above, wherein the developer contains a reductone. 6. The developing solution for silver halide photographic light-sensitive materials as described in 2 or 4 above, wherein the developing solution contains substantially no dihydroxybenzenes. 7. The method for processing a silver halide photographic light-sensitive material as described in 3 or 5 above, wherein the developer does not substantially contain dihydroxybenzenes. 8. A solid developer for a silver halide photographic light-sensitive material, containing a compound represented by the general formula (1) and a compound represented by the general formula (2). 10. The developer for a silver halide photographic light-sensitive material according to 2, 4, or 6, wherein the developer is prepared by dissolving the solid developer according to claim 8. 9. The method for processing a silver halide photographic light-sensitive material as described in 3, 5, or 7, wherein a developer is prepared by dissolving the solid developer according to claim 8.

[0012]

The present inventor has conducted extensive studies on nitrogen-containing heterocyclic mercapto compounds, and as a result, by using the compound of the general formula (1) and the compound of the general formula (2) in combination, the silver color tone was surprisingly improved. At the same time, the stability of Dm, γ, and silver tone is greatly improved in the long-running compound treatment that is affected by oxidative fatigue, especially in the treatment state where a small amount of treatment causes a large amount of water vaporization and influences the concentration of the treatment liquid. What to do was a surprising discovery.

The compound of the general formula (1) of the present invention alone,
The compound of the general formula (2) alone does not provide the effects of the present invention, and the combined use of the compounds has the invention of the constitution of the present invention.

Further, even if two or more compounds corresponding to the compound of the general formula (1) of the present invention are used, the effect of the invention cannot be observed. Even if two or more compounds corresponding to the compound of the general formula (2) of the present invention are used, the effect of the invention cannot be seen. If the compound of the general formula (1) and the compound of the general formula (2) of the present invention are used in combination, two or more kinds of each compound may exist.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The addition amount of the compound of the general formula (1) of the present invention is 20 mg to 1500 mg / l in a developing solution.
Is preferable, and more preferably 100 mg to 700 mg /
It is l. On the other hand, the addition amount of the compound of the general formula (2) is preferably 5 mg to 500 mg / l, and more preferably 10 mg to 200 mg / l in the developer.

When it is contained in the silver halide photographic light-sensitive material, both the compound represented by the general formula (1) and the compound represented by the general formula (2) may be contained in any position in the hydrophilic colloid layer.
It is preferably a silver halide photographic emulsion layer or a protective layer, more preferably added to the protective layer. Addition to the protective layer is preferable because it has less effect on the storage stability of the light-sensitive material (desensitization, etc.). The amount of the compound of the general formula (1) added to the light-sensitive material is preferably 5 mg to 200 mg, and the compound of the general formula (2)
Is preferably added at 1 mg to 100 mg.

Specific examples of the compounds of the general formula (1) and the general formula (2) are shown below, but the compounds of the general formulas (3) and (4) are preferable.

[0018]

[Chemical 5] R ₅ is at least one or more sulfo group, carboxy group,
It represents an amino group, a hydroxy group or a salt thereof, or an aryl group substituted with a boron residue. When two or more of these substituents are present, they may be the same or different. M represents a hydrogen atom, an alkali metal atom, quaternary ammonium, and a group in which M can be a hydrogen atom or an alkali metal under alkaline conditions.

[0019]

[Chemical 6] R ₆ is at least one or more sulfo group, carboxy group,
It represents an alkyl group substituted with an amino group, a hydroxy group or a salt thereof, or a boron residue.

When there are two or more substituents, they may be the same or different. M ₁ represents a hydrogen atom, an alkali metal atom, a quaternary ammonium, or a group in which M can be a hydrogen atom or an alkali metal under alkaline conditions.

More specifically, R ₃ is one or more sulfo group, carboxy group or hydroxy group, a linear or branched alkyl group having 1 to 20 carbon atoms substituted with a boron residue (eg, methyl group, ethyl group). , Propyl group, hexyl group, dodecyl group, isopropyl group, etc.), C 1-2
A cycloalkyl group of 0 (eg cyclopropyl group, cyclohexyl group, etc.), R ₁ is a sulfo group, a carboxy group,
6 to 20 carbon atoms substituted with a hydroxy group or a boron residue
Represents an aryl group (eg, phenyl group, naphthyl group, etc.).

The alkyl group (straight chain, branched alkyl group, cycloalkyl group) and aryl group may be further substituted, and specifically, a halogen atom (F, Cl, Br, etc.), an alkyl group (methyl group). , Ethyl groups, etc.), aryl groups (phenyl groups, etc.), alkoxy groups (methoxy groups,
Ethoxy group), aryloxy group (phenoxy group, etc.), sulfonyl group (methanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (unsubstituted carbamoyl group, diethylcarbamoyl group, etc.), amide group (acetamide group, benzamide group) Groups), alkoxycarbonylamino groups (methoxycarbonylamino groups, etc.), allyloxycarbonylamino groups (phenoxycarbonylamino groups, etc.), alkoxycarbonyl groups (methoxycarbonyl groups, etc.), aryloxycarbonyl groups (phenoxycarbonyl groups, etc.), Cyano group, niloto group, amino group (unsubstituted amino group, dimethylamino group, etc.), alkylsulfinyl group (methylsulfinyl group, etc.), arylsulfinyl group (phenylsulfinyl group, etc.), alkylthio (Such as methylthio group), an arylthio group (phenylthio group) can be exemplified. The alkyl group and aryl group represented by R ₂ and R ₄ have the same meanings as R ₃ and R ₁ , and the substituents can also be the same as those of R ₃ and R ₁ . Particularly preferred as R ₁ is a phenyl group substituted with at least one sulfo group, a carboxy group or a hydroxy group, and particularly preferred as R ₃ is a methyl group substituted with a sulfo group, a hydroxy group or a carboxy group, and ethyl. Group, a propyl group. R ₂ , R
Particularly preferred as ₄ is a hydrogen atom, M is a hydrogen atom, an alkali metal atom (eg, sodium atom, potassium atom, etc.), a quaternary ammonium group (eg, trimethylammonium group, dimethylammonium group, tributylammonium group, etc.) and an alkali. A group in which M can be a hydrogen atom or an alkali metal under certain conditions (eg, acetyl group,
Cyanoethyl group, methanesulfonyl group, etc.).

Specific examples of the compound represented by the general formula (1) used in the present invention are shown below, but the present invention is not limited to these compounds.

[0024]

[Chemical 7]

[0025]

[Chemical 8]

[0026]

[Chemical 9]

[0027]

[Chemical 10]

[0028]

[Chemical 11]

[0029]

[Chemical 12]

Specific examples of the compound represented by formula (2) used in the present invention are shown below, but the present invention is not limited to these compounds.

[0031]

[Chemical 13]

(Regarding Light-Sensitive Material) As the silver halide photographic light-sensitive material, any publicly-known and publicly-known materials can be used as long as they satisfy the constitutional requirements of the present invention.

The silver halide grains in the silver halide emulsion layer are preferably tabular grains having an aspect ratio of 3 or more, more preferably 5 or more and 10 or less. The effects of improving the silver color tone and the coverage (CP) in the present invention are more remarkably exhibited. The silver halide grains are preferably selenium or tellurium sensitized grains. The silver halide composition may be any of silver chloroiodobromide, silver bromide, silver iodobromide, silver chloride and silver chlorobromide. Iodine content is preferably 1 mol
% Or less, and more preferably 0.5 mol% or less. Within this range, rapid processing (dty to
sry 30 seconds treatment). Further, it is preferable to contain a natural polymer such as dextran and dextrin and / or a synthetic polymer such as polyacrylamide in the silver halide emulsion layer and / or the hydrophilic colloid layer including the protective layer and the crossover cut layer.

(Regarding Reductones) The reductones used in the silver halide photographic light-sensitive material of the present invention and / or the processing method thereof will be described. Examples of the reductones used in the development treatment of the present invention include enediol type, enaminol type, enediamine type, thiolenol type and enaminethiol type. Preferable examples include compounds represented by the following general formulas (A) and (B-1) to (B-4).

[0035]

[Chemical 14]

In the formula, R ₄ represents a hydrogen atom or a hydroxyl group,
R ₅ represents a hydroxyl group or a hydrogen atom, and a represents an integer of 1 to 4.

[0037]

[Chemical 15]

[0038]

[Chemical 14]

The reductones used in the present invention can also be used in the form of alkali metal salts such as lithium salt, sodium salt and potassium salt. The most preferable reductones in the present invention include ascorbic acid and erythorbic acid represented by A-1 above.

The content of reductones is 3 to 80 g / l.
Is good. When used as a main drug, it is preferably 25 to 5
It is 0 g.

(Regarding Developer) The developer of the present invention contains p
H is 9.0 to 11.0, preferably pH 9.5
˜10.5. In the case of a developer containing a reductone, it is particularly preferably 10.0 to 9.5, which is effective in improving running stability.

The developer of the present invention preferably contains substantially no dihydroxybenzenes. The term "substantially free from" means, for example, that a trace amount such as 5 × 10 ⁻⁴ mol / l or less is limited, and dihydroxybenzene is not contained at all. Since dihydroxybenzenes, especially hydroquinone used in a developing solution, are environmentally harmful compounds, they are desired, and at the same time, the degree of effect varies.

It is preferable that glutaraldehyde or a bisulfite adduct thereof is added to the developer as a development hardening agent.
As a result, the improvement of the silver color tone of the present invention is greatly exhibited.

The developer of the present invention preferably contains iodide ions as a replenisher as well, and it is 2 × 10 ⁻⁴ to 2 ×.
It is particularly preferred to contain 10 ⁻³ mol / l. By containing the iodide ion, the effect of improving CP is highly exerted. This effect is particularly great in the developer of the present invention containing reductones. The amount of developer replenishment is
Replenishment is preferably 200 ml or less per 1 m ^{2 of the} light-sensitive material. Replenishment amount 2 as well as reduction of waste liquid
The improvement effect of the present invention is great when the amount is 00 ml or less. The replenishing amount of the fixing solution is preferably 200 ml / m ² or less.

The developing solution of the present invention contains boric acid, benzoates, alkanolamines, phosphates as buffer agents,
Bicarbonates and carbonates can be used, but it is preferable to contain carbonates. 0.35 mol as the content concentration
/ L or more, more preferably 0.5
It is 0 to 1.00 mol / l, and is effective for improving long-term stability in the developer of the present invention containing reductone. As the carbonate and bicarbonate, potassium carbonate and potassium bicarbonate are preferred. This is Dm, γ from the salts of Na and Li.
It is effective in terms of stability.

Regarding the developing solution of the present invention, Japanese Patent Application No. 4-5
The chelating agent and biodegradable chelating agent described in 86232 (paragraph 20) can be used.

Further, as a silver sludge-preventing agent, Japanese Unexamined Patent Publication No.
It is preferable to use the compounds described in No. 13303 (general formulas [1] and [2]).

The developer of the present invention may contain a sulfite such as sodium or potassium sulfite and metabisulfite. Sulfite is used as a preservative, but it has an appropriate amount depending on the type of developer because it has a defect that silver sludge is generated when the amount is too large. For the above reason, in the case of the developer containing reductone as in the present invention, 0.0
1 to 0.30 mol / l is preferable, and especially 0.05 to
0.20 mol / l is preferred.

In the developer of the present invention, as a development accelerator,
For example, thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, amine compounds, polyalkylene oxide compounds, hydrazines can be used.

Further, KBr or an organic inhibitor can be used as the inhibitor. For example, benzotriazole, 6
-Nitrogen-containing heterocyclic compounds such as nitrobenzimidazole, 5-nitroindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolyl-benzotriazole, azaindenes, adenine and thiadiazole Can be mentioned.

Cyclodextrins are preferably added to the developer of the present invention. In particular, in the case of a reductone-containing developer, the oxidation resistance is improved and the color tone is greatly contributed, which greatly contributes to the effect of the present invention.

The developing solution and fixing solution of the present invention are preferably solutions prepared by dissolving in water from a solid agent kit. The solid agent kit is effective in that the storage stability of the kit state (change in the amount of components and composition during long-term storage) is significantly improved and the space in the kit form is reduced. In the present invention, long-term stability is mentioned as a problem to be solved, but the effect can be made more remarkable by using a solidification kit.

The developer and fixer of the present invention are preferably supplemented with water so as to avoid concentration due to evaporation of the processing solution in order to stabilize long-term processing. For water replenishment, a sensor detects the drop in the liquid level due to evaporation, and a method of adding water until the original liquid level is returned, a method of adding a certain amount daily instead of the amount of evaporation, and detecting the number of processed sheets per day. A method of determining the amount of water replenishment depending on the number of sheets can be adopted.

The processing temperature of the developing solution is 25 to 50 ° C.,
It is preferably 30 to 40 ° C. The developing time is 5 to 25 seconds, more preferably 5 to 15 seconds. The processing temperature of the fixing solution is 25 to 50 ° C., preferably 30 to 40
℃. The fixing time is 5 to 25 seconds, preferably 5 to 15 seconds.

The total processing time in the present invention is Dry to Dry which is 12 after development, fixing, washing with water and drying.
It is preferably 0 to 30 seconds. Particularly, 40 seconds to 15 seconds is preferable.

Prior to the treatment, it is preferable to add a starter, and it is preferable to solidify and add the starter. As the starter, in addition to an organic acid such as a polycarboxylic acid compound, an alkali metal halide such as KBr, an organic inhibitor, or a development accelerator can be used.
The developer replenishment rate is 300 ml / m ^{2 to} 50 ml /
m ² is preferable, but especially 200 ml / m ^{2 to} 80 ml / m
² is preferred. As the content is limited to this preferred range, the effect of the present invention is more remarkably exhibited.

(Regarding Auxiliary Developer) In the developer of the present invention, in addition to the above reductones, 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, as an auxiliary developer,
1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-4,
4-dimethyl-3-pyrazolidone, 1-phenyl-4-
Methyl-4-hydroxymethyl-3-pyrazolidone, 1
-Phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-
p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1-p
-Hydroxyphenyl-4,4-dimethyl-3-pyrazolidone, 1- (2-benzothiazolyl) -3-pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone, etc., 3-aminopyrazolines (for example, 1 -(P-
Hydroxyphenyl) -3-aminopyrazoline, 1-
(P-Methylaminophenyl) -3-aminopyrazoline, 1- (p-amino-m-methylphenyl) -3-aminopyrazoline, etc.) and phenylenediamines (for example, 4-amino-N, N-diethyl). Aniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline,
3-Methyl-4-amino-N-ethyl-N-β-methoxyethylaniline etc.) and the like can be added. Preferred are 1-phenyl-3-pyrazolidones.

Furthermore, even when aminophenols are used as an auxiliary developing agent, a high contrast image can be obtained. As aminophenol developing agents, 4-aminophenol, 4-amino-3-methylphenol, 4- (N-methyl) aminophenol, 2,4-diaminophenol, N- (4-hydroxyphenyl) glycine, N-
(2'-hydroxyethyl) -2-aminophenol,
Examples thereof include 2-hydroxymethyl-4-aminophenol, 2-hydroxymethyl-4- (N-methyl) aminophenol, and hydrochlorides and sulfates of these compounds.

The amount of these compounds added is 0.2 g to 40 g, preferably 0.5 g to 2 per liter of the developing solution.
It is 5 g.

(Regarding Fixing Agent) Next, the fixing solution used in the present invention will be described. The fixing solution used in the present invention is preferably prepared by preparing a solid processing agent, dissolving it, and preparing a solution. The fixing agent preferably contains thiosulfate. The thiosulfate is specifically used as a salt of lithium, potassium, sodium or ammonium, but preferably used as ammonium thiosulfate or sodium thiosulfate to obtain a fixing solution having a high fixing rate.

In addition, iodide salts, thiocyanates and the like can be used as fixing agents. The fixer used in the present invention contains sulfite. As the sulfite, solid lithium, potassium, sodium, ammonium salt or the like is used. As the type, sodium sulfite, sodium metabisulfite, or the like can be used.

The fixing solution used in the present invention 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, aluminum nitrate and the like.

The solid (powdered) water-soluble aluminum salt generally has a plurality of crystal waters, and examples thereof include 18-hydrate and 14-hydrate. When used as a component of a solid treating agent, the crystal water is used. The aluminum salt may be hardened by migration or may have a bad effect on coloring (such as sulfur coloring due to the reaction between acid and hypo).
(° C.): MAX temperature when assuming practical storage conditions), and it is preferable to use an aluminum salt from which a part of the water of crystallization has been removed until the amount of water of crystallization reaches an equilibrium state. For example, aluminum of 18 to 14 hydrate is 6 to 6 by the above treatment.
It is preferable to use a tetrahydrate. In addition, it is not preferable because it is adversely affected by excessive dehydration or complete decrystallization by water, which lowers the solubility and, on the contrary, absorbs water.

The fixing solution used in the present invention contains acetate ions. The type of the acetate ion is arbitrary, and the present invention can be applied to any compound that dissociates the acetate ion in the fixing solution, but acetic acid and lithium, potassium, sodium, ammonium salts of acetic acid are preferably used, and particularly, Sodium salt and ammonium salt are preferable.

Further, β-alanine and succinic acid can be used as the buffer agent. Further, citric acid, tartaric acid, malic acid, phenylacetic acid and optical isomers thereof may be contained.

Examples of these salts include potassium citrate, lithium citrate, sodium citrate, ammonium citrate, lithium hydrogen tartrate, potassium hydrogen tartrate, potassium tartrate, sodium hydrogen tartrate, sodium tartrate, ammonium hydrogen tartrate, ammonium tartrate. Potassium, potassium sodium tartrate, sodium malate, ammonium malate, sodium succinate,
Lithium, potassium, sodium, ammonium salts represented by ammonium succinate and the like are preferable.

Of the above compounds, more preferred are citric acid, isocitric acid, malic acid, phenylacetic acid and salts thereof. Examples of other acids include salts of inorganic acids 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, with boric acid and aminopolyacid being preferred. Acids and salts such as carboxylic acids.

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 sulfuric acid esterified products and sulfonated compounds, nonionic surfactants such as polyethylene glycol-based and ester-based surfactants,
Examples include amphoteric activators.

Examples of the lubricant include alkanolamine and alkylene glycol.

Examples of fixing accelerators include thiourea derivatives, alcohols having a triple bond in the molecule, and thioethers.

The fixing solution has a pH of 3.8 or more, preferably 4.
2 to 5.5. 300 for fixer replenisher
ml ^{/ m 2} ~50ml ^/ m 2 are preferred, especially 200m
1 / m ^{2 to} 80 ml / m ² is preferable.

(Solidification) Next, solidification (solidification) of the photographic processing agent will be described.

To solidify the photographic processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or a water-soluble binder is preliminarily formed on the surface of the photographic processing agent. Arbitrary means such as forming a coating layer by spraying (see JP-A-4-29136 and 4-8)
No. 5535, No. 4-85536, No. 4-85533
Nos. 4-85534 and 4-172341).

A preferable tablet manufacturing method is a method in which a powdery solid processing agent is granulated and then a tableting step is performed. There is an advantage that the solubility and storability are improved and the photographic performance becomes stable as compared with the solid processing agent formed by the tableting process by simply mixing the solid processing agent components.

As the granulation method for tablet formation, known methods such as rolling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation and spray drying granulation are used. You can
In order to form tablets, the average particle size of the obtained granules is 100 to 800 μm in that when the granules are mixed and compressed under pressure, nonuniformity of the components, so-called segregation does not easily occur.
It is preferable to use the above-mentioned one, and more preferably 200
˜750 μm. Furthermore, the particle size distribution is 6 for granulated particles.
It is preferable that 0% or more is within a deviation of ± 100 to 150 μm. A known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a pre-ketching machine can be used for compressing the obtained granulated product under pressure. The solid processing agent obtained by compression under pressure can have any shape, but from the viewpoint of productivity and handleability, or from the problem of dust when used on the user side, a cylindrical type, a so-called tablet is used. preferable.

More preferably, at the time of granulation, each component, for example, an alkali agent, a reducing agent, a preservative and the like is separately granulated.

The method for producing the tablet treating agent is described in, for example, JP-A Nos. 51-61837, 54-155038 and 52-52.
-88025, British Patent No. 1,213,808 and the like can be produced by the method described in the specification, and the granule treating agent is
For example, JP-A Nos. 2-109042 and 2-10904.
No. 3, No. 3-39735, and No. 3-39739 can be produced by the method described in the specification. Further, the powder processing agent can be prepared by a method described in, for example, JP-A-54-133332, British Patents 725,892 and 729,862, and German Patent 3,733,861. Can be manufactured.

[0079] The bulk density of the solid processing agent, and in view of its solubility, if a tablet from the viewpoint of the effect of the object of the present invention 1.0g ^/ cm ³ ~2.5g ^/ cm 3 is preferably 1. 0
In terms of the strength of the solid obtained when it is larger than g / cm ³ ,
It is more preferable that the solid content is less than 2.5 g / cm ³ in terms of solubility of the obtained solid. When the solid processing agent is granules or powder, the bulk density is preferably 0.40 to 0.95 g / cm ³ .

It is within the scope of the present invention to solidify only one part of a certain treating agent in the solid treating agent used in the present invention, but preferably all components of the treating agent are solidified. is there. It is desirable that each component be molded as a separate solid processing agent and packaged in the same manner. It is also desirable that the individual components are packaged in the order in which they are periodically added repeatedly in a package.

It is preferable to add all the processing agents to be replenished to the respective processing tanks as solid processing agents according to the processing amount information.
When replenishment water is required, it is replenished based on the throughput information or other replenishment water control information. In this case, the liquid to be replenished in the treatment tank can be only replenishing water. That is, when there are two or more types of processing tanks that need to be replenished, only one tank is required to store the replenishing liquid by sharing the replenishing water, and the automatic developing machine can be made compact. The replenishing water tank may be placed outside or may be built in the automatic developing machine, and it is preferable to install the replenishing water tank from the viewpoint of space saving.

When the developer is solidified, all of the alkali agent, reducing agent and the like are solidified, and in the case of the tablet, at least 3 agents, that is, 1 agent, or 2 or more agents can be used. When divided into solid processing agents, it is preferable that the plurality of tablets and granules be packed in the same package.

The following materials can be used for the package of the solid processing agent used in the present invention. Synthetic resin materials include polyethylene (either high pressure method or low pressure method), polypropylene (either unstretched or stretched), polyvinyl chloride, polyvinyl acetate, nylon (stretched or unstretched), polyvinylidene chloride, polystyrene , Polycarbonate, vinylon, eval, polyethylene terephthalate (PET), other polyesters, acrylonitrile butadiene copolymer, epoxy-phosphoric acid resin (polymers described in JP-A-63-63037, JP-A-57-32952). Any of the listed polymers). Alternatively, it may be pulp.

Although these are preferably made of a single material, when they are used as a film, the films are laminated and adhered, but may be a coating layer or a single layer.

Further, it is more preferable to use various gas barrier films such as using aluminum foil or aluminum vapor deposition synthetic resin between the above synthetic resin films.

The oxygen permeability of these packaging materials is 50 ml in order to preserve the solid processing agent and prevent stains from being generated.
/ M ² 24hr · atm or less (20 ° C, 65% RH
), More preferably 30 ml / m ² 24 hr · atm
The following is preferable.

The total thickness of these laminated films or single layers is 1 to 3000 μm, more preferably 10 to 2000.
μm, and more preferably 50 to 1000 μm.

The above synthetic resin film may be a single layer (polymer) resin film, or a laminate of two or more (polymer)
It may be a resin film.

Examples of the one-layer polymer resin film suitable for the conditions of the present invention include (1) polyethylene terephthalate (PET) having a thickness of 0.1 mm or more, and (2) a thickness of 0.3 mm.
The acrylonitrile butadiene copolymers described above and (3) hydrochloric acid rubber having a thickness of 0.1 mm or more can be mentioned. Among them, polyethylene terephthalate is excellent in alkali resistance and acid resistance, and thus can be suitably used in the present invention.

Next, as the laminated polymer resin film which meets the conditions of the present invention, for example, (4) PET / polyvinyl alcohol / ethylene copolymer (Eval) / polyester (PE), (5) stretched polypropylene ( OPP) / Eval / PE, (6) unstretched polypropylene (CPP) /
EVAL / PE, (7) Nylon (N) / Aluminum foil (Al) / PE, (8) PET / Al / PE, (9)
Cellophane / PE / Al / PE, (10) Al / Paper / P
E, (11) PET / PE / Al / PE, (12) N /
PE / Al / PE, (13) Paper / PE / Al / PE,
(14) PET / Al / PET / polypropylene (P
P), (15) PET / Al / PET / high density polyethylene (HDPE), (16) PET / Al / PE / low density polyethylene (LDPE), (17) Eval / P
P, (18) PET / Al / PP, (19) paper / Al /
PE, (20) PE / PVDC coated nylon / PE /
Ethyl vinyl acetate / polyethylene condensate (EV
A), (21) PE / PVDC coated N / PE, (2
2) EVA / PE / Aluminum deposition nylon / PE / EV
A, (23) Aluminum vapor deposition nylon / N / PE / EVA,
(24) OPP / PVDC coat N / PE, (25) P
E / PVDC coated N / PE, (26) OPP / Eval / LDPE, (27) OPP / Eval / CPP,
(28) PET / EVAL / LDPE, (29) ON
(Stretched nylon) / Eval / LDPE, (30) CN
(Unstretched nylon) / Eval / LDPE and the like, among which (20 to (30)) is preferably used.

As a more specific constitution of the packaging material, if the side in contact with the treating agent is the inner surface, PE /
Main board / PE / Al / epoxy-phosphoric acid resin layer / polyester resin layer / PE PE / K-nylon / PE or adhesive / Al / PE /
Paperboard / PE, PE / Vinlon / PE or adhesive / Al
/ PE / paperboard / PE, PE / vinylidene chloride / PE or adhesive / Al / PE / paperboard / PE, PE / polyester / PE or adhesive / Al / PE / paperboard / PE, polypropylene / K-nylon / polypropylene / Examples include Al / polypropylene / paperboard / polypropylene.

As a method for moisture-proof packaging of tablets and granules,
There are four-sided seals, three-sided seals, sticks (pillow packaging, gusset packaging), PTP, and cartridges.

The four-sided seal, the three-sided seal, and the stick (pillow, gusset) packaging have different forms, and the above materials are used. However, when using the peel open method, a sealant agent is laminated to give the peel open aptitude.

The peel-open method generally includes a cohesive failure method, an interfacial peeling method, and an interlayer peeling method.

The cohesive failure method is an adhesive called hot melt, which is used as a sealant in a heat seal lacquer, and peels off due to internal cohesive failure of the sealant layer at the time of opening.

The surface-active peeling method is a method of peeling at the interface between films, in which the sealing film (sealant) and the adherend are not completely fused and can be peeled off with appropriate strength. The sealant is a film in which an adhesive resin is mixed, and polyethylene, polypropylene or a copolymer thereof, a polyester type or the like can be selected depending on the material of the adherend.

Further, the delamination method is one in which the sealant is peeled between the layers of the laminate film by using a multilayer coextrusion film such as a laminate film.

In the peel open method using the film of the present invention, the interlaminar peeling method or the interfacial peeling method is preferable.

Since such a sealant is thin,
Usually, other films such as polyethylene, polypropylene, polystyrene, polycarbonate, polyester (polyethylene terephthalate), polyvinyl chloride, nylon, eval, aluminum are laminated and used, but considering moisture resistance, environmental friendliness and matching with contents. Polyethylene, polypropylene, polyester, EVAL and the like are preferable. In consideration of printability, the outermost surface is preferably unstretched polypropylene, polyester, paper or the like.

As the sealant film, for example, CMPS film manufactured by Tohcello, Diffran PP-100, PS-300 manufactured by Dainippon Ink and LTS film manufactured by Toppan Printing, Sunseal FR, Sunseal M manufactured by San-A Chemical Co., Ltd.
There are S etc., and as a type already laminated with polyester, Declan C-1600T, C-16
02T and so on.

PTP is a packaging form in which a solid processing agent is put into a sheet of PVC, CPP or the like which is molded as a kind of blister packaging and heat sealed with an aluminum sealing material.

Environmentally, PVC is not used as a forming material, and recently, A-PET and highly moisture-proof PP (for example, TA
S-1130, TAS-2230, TAS-3230:
Taisei Kako Co., Ltd. is preferably used.

When the treating agent is packaged or bound or coated with a water-soluble film or binder, the water-soluble film or binder may be polyvinyl alcohol, methyl cellulose, polyethylene oxide, starch, polyvinyl pyrrolidone, Hydroxypropyl cellulose system,
Film or binder consisting of pullulan-based, dextran-based, gum arabic-based, polyvinyl acetate-based, hydroxyethyl cellulose-based, carboxyethyl cellulose-based, carboxymethyl hydroxyethyl cellulose sodium salt-based, poly (alkyl) oxazoline-based, polyethylene glycol-based substrates Agents are preferably used, and among these, polyvinyl alcohol-based and pullulan-based agents are more preferably used from the viewpoint of the effect of coating or binding.

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

The method for producing these water-soluble films is described in, for example, JP-A-2-124945 and JP-A-61-1934.
No. 8, 60-158245, and JP-A-2-86638.
JP-A-57-117867 and JP-A-2-7565.
No. 0, JP-A-59-226018, 63-2187.
No. 41 and No. 54-13565, and the like.

Further, as these water-soluble films, those commercially available under the names of Solbron (manufactured by Aicello Chemical Co., Ltd.), Hi-Selon (manufactured by Nigo Film Co., Ltd.) or Pullulan (manufactured by Hayashibara Co., Ltd.) can be used. Also, Chris Craft Industries (Chris Craft I)
ndustries) Inc. The 7-000 series polyvinyl alcohol films available from the MONO-SOL Division of the Company dissolve in water temperatures of about 34 ° F. to about 200 ° F., are harmless and exhibit a high degree of chemical resistance, and are particularly preferred. Used.

The thickness of the water-soluble film is preferably 10 to 120 μm, particularly 15 to 80 μm, from the viewpoints of storage stability of the solid processing agent, dissolution time of the water-soluble film and crystal precipitation in an automatic processor. Those having a thickness of 20 to 60 μm are particularly preferably used.

The water-soluble film is preferably thermoplastic. This is because not only the heat sealing process and the ultrasonic welding process are facilitated, but also the covering effect is more excellently achieved.

Further, the tensile strength of the water-soluble film is 0.
5 × 10 6 to 50 × 10 6 kg / m ² is preferable, 1 × 10 6 to 25 × 10 6 kg / m ² is particularly preferable, and 1.5 × 10 6 to 10 × 10 6 kg / m ² is particularly preferable. These tensile strengths are measured by the method described in JIS Z-1521.

Further, the photographic processing agent packaged or bound or coated with a water-soluble film or a binding agent is used in storage, transportation, and handling during storage, transportation, and handling, and humidity in the atmosphere such as high humidity, rain, and fog, and In order to prevent water from splashing or accidental contact with water due to wet hands, it is preferable to be packaged in a moisture-proof packaging material, and the moisture-proof packaging material has a film thickness of 10 to 1
A film having a thickness of 50 μm is preferable, and a moisture-proof packaging material is a polyolefin film such as polyethylene terephthalate, polyethylene or polypropylene, kraft paper, wax paper, moisture-resistant cellophane, which can have a moisture resistance effect with polyethylene.
At least one selected from glassine, polyester, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polycarbonate, acrylonitrile-based metal foil such as aluminium, and metallized polymer film is preferable, and a composite using these is also used. It may be a material.

In the practice of the present invention, the moisture-proof packaging material is preferably a degradable plastic, particularly a biodegradable or photodegradable plastic.

Examples of the biodegradable plastic include those made of natural polymers, polymers produced by microorganisms, synthetic polymers having good biodegradability, blending of biodegradable natural polymers with plastics, and photodegradable plastics are ,
Examples thereof include a group that is excited by ultraviolet rays and has a group that is linked to cleavage in the main chain. Further, other than the above-mentioned polymers, those having two functions of photodegradability and biodegradability at the same time can be favorably used.

The specific representative examples are as follows.

Examples of biodegradable plastics include natural high molecular polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, and modified products thereof such as PHB-PHV (3-hydroxybutyrate and 3-hydroxyvalerate), which are polymers produced by microorganisms. (Copolymer with rate) as a component
pol ", microbial-produced cellulose and other biodegradable synthetic polymers such as polyvinyl alcohol, polycaprolactone, etc., or their copolymers or mixtures of the biodegradable natural polymer into plastics. , Starch, and cellulose, which have shape-disintegrating properties in addition to plastic.

Further, examples of the photodegradability include introduction of a carbonyl group for photodisintegration, and an ultraviolet absorber may be added to accelerate the disintegration.

Regarding such degradable plastics, "Science and Industry", Vol. 64, No. 10, No. 478-484.
Page (1990), "Functional Materials," July 1990, Issue 2
What is generally described on pages 3 to 34 can be used.
Also, Biopol (manufactured by ICI),
Eco (made by Union Carbide),
Ecolite (Eco Plasti)
c company), Ecostar (Ecostar) (St. La
Commercially available degradable plastics such as Wrence Starch) and Knuckle P (Nippon Unicar) can be used.

The moisture-proof packaging material preferably has a moisture permeability coefficient of 10 g · mm / m ² 24 hr or less, more preferably 5 g · mm / m ² 24 hr or less.

In the present invention, as a means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, JP-B-63-137783 and 63-975.
Although there are known methods such as No. 22, No. 22 and Jitsukaihei 1-85732, any method may be used as long as it has at least the function of supplying tablets to the processing tank. Further, when the solid processing agent is granules or powders, it is used in the practical method of Sho 62-81964.
No. 63-84151, the gravity drop method described in JP-A-1-292375 and the like, Japanese Utility Model Publication No. 63-105159,
Although a method using a screw or a screw described in JP-A-63-195345 and the like is a known method, the method is not limited thereto.

However, a preferable method is, as a supply means for supplying the solid processing agent to the processing tank, for example, a predetermined amount of the solid processing agent which has been previously weighed and divided and packaged is opened according to the processing amount of the light-sensitive material, and the package is opened. A method of taking it out is possible. Specifically, the solid processing agent is sandwiched and housed in a package composed of at least two packaging materials by a predetermined amount, preferably one replenishment amount, and the package is separated in two directions or the package A part of it is opened so that it can be taken out. The solid processing agent that can be taken out can be easily supplied to the processing tank having the filtering means by spontaneous fall. A predetermined amount of the solid processing agent is housed in a package that is divided and hermetically sealed so that the air permeability between the solid processing agent and the adjacent solid processing agent is blocked. Therefore, moisture resistance is guaranteed unless the package is opened.

As an embodiment, it is conceivable that a package composed of at least two packaging materials sandwiching the solid processing agent is closely adhered or adhered to each other so that the periphery of the solid processing agent can be separated. . By pulling each packaging material sandwiching the solid processing agent in different directions, the closely contacted or adhered contact surfaces are separated, and the solid 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 means a cut or break that leaves a part of the packaging material. As the unsealing method, the solid processing agent is forcibly pushed out by applying a compressive force from the packaging body on the non-opening side through the solid processing agent in the direction of the packaging body that can be opened, or on the packaging body on the openable side. It is considered 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 the processing amount information. The supply stop signal is obtained by detecting the information that the supply of the predetermined amount is completed. Further, when the treatment agent is packaged and needs to be opened, the driving means for separating or opening based on the obtained supply start signal operates, and the driving means for separating or opening based on the supply stop signal is It can be controlled to stop.

It is preferable that the means for supplying the solid processing agent has a control means for supplying a fixed amount of the solid processing agent according to information on the processing amount of the photosensitive material. That is, in the automatic processor of the present invention, it is necessary to keep the concentration of components in each processing tank constant and to stabilize the photographic performance. The processing amount information of the silver halide photographic light-sensitive material is the processing amount of the silver halide photographic light-sensitive material processed by the processing liquid, or the processing amount of the processed silver halide photographic light-sensitive material or the silver halide photograph during the processing. It is a value proportional to the processing amount of the light-sensitive material, and indirectly or directly indicates the reduction amount of the processing agent in the processing liquid. It may be detected at any timing before or after the photosensitive material is carried into the processing liquid, or during the immersion in the processing liquid. Further, it may be a physical parameter such as the concentration of the composition in the treatment liquid or a change in the concentration, pH and specific gravity. Further, it may be the amount that has been discharged to the outside after the treatment liquid is dried.

The solid processing agent of the present invention may be put in a processing tank, but preferably, it is connected to a processing section for processing a light-sensitive material, and a processing solution flows between the processing section and the processing section. It is preferable that the structure is such that the dissolved components move to the processing section because there is a certain amount of processing liquid circulation between the processing section and the processing section. The solid processing agent is preferably added to the temperature-controlled processing liquid.

Generally, since the temperature of the automatic processor is adjusted, the temperature of the processing liquid is adjusted by an electric heater. As a general method, a heat exchange section is provided in an auxiliary tank connected to the processing tank, a heater is installed, and a pump is arranged in this replenishment tank to pump the liquid from the processing tank in a constant circulation amount and to keep the temperature constant. There is.

[0126] Usually, a filter is arranged for the purpose of removing the crystalline foreign matter that is mixed into the processing liquid or is generated by crystallization, and plays a role of removing the foreign matter.

The most preferable method is to add the solid processing agent to a place where the temperature is adjusted, such as a place communicating with the processing section such as this auxiliary tank. This is because the insoluble component in the processing agent that has been added is blocked from the processing section by the filter section, and it is possible to prevent solids from flowing into the processing section and adhering to photosensitive materials, etc., and the solubility of the solid processing agent is also very high. It will be good.

Further, when the treatment agent input portion is provided in the treatment tank together with the treatment portion, it is preferable to devise a shield or the like so that the insoluble portion does not come into direct contact with the film or the like.

As for the material of the filter, the filtering device, etc., all the materials used for general automatic processors can be used in the present invention, and the special structure and material do not influence the effect of the present invention.

The number of cycles of the processing solution circulated by the circulation means in the present invention is preferably 0.5 to 2.0 times / min, particularly 0.8 to 2.0 times / min, and further 1.0 to
2.0 times / min is preferable. 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 unevenness of the density of the processed photosensitive material can be prevented, and the generation of an insufficiently processed photosensitive material can be prevented. It can be prevented. Here, the number of circulations indicates the flow rate of the liquid to be circulated, and it is defined as once when the liquid amount corresponding to the total liquid amount in the processing tank flows.

The solid processing agent used in the present invention is added to the processing tank separately from the replenishing water, and the replenishing water is supplied by the replenishing water tank.

The antifungal means of the refill water tank in this case will be described. When the replacement rate in the replenishment tank decreases and the residence time of water becomes long, water stains occur, and the water rots for 2-3 weeks, causing a bad odor. Further, when the generated water scale is replenished as it is, it adheres to the surface of the photographic light-sensitive material or the solid processing agent, and in the case of a developing tank, uneven development,
In the case of a fixing tank, there is a big problem that fixing failure occurs and the commercial value is significantly reduced. Therefore, in order to remove this water stain, it has to be washed regularly, which is very troublesome. Therefore, the water supply tank used in the present invention has an antifungal means. This antifungal means can be achieved by at least one means selected from the following group. (Group) 1) Chelating agent addition means 2) Antifungal agent addition means 3) Deionization treatment means 4) Ultraviolet irradiation means 5) Magnetic treatment means 6) Ultrasonic treatment means 7) Electrolytic sterilization means 8) Silver ion release means 9 ) Air-foaming means 10) Active oxygen releasing means 11) Means by contact with porous material Means for preventing harmful bacteria from growing by adding harmless other fungi. These means will be specifically described. As the chelating agent and bactericidal agent used as the antifungal means in the present invention, known ones can be arbitrarily used.

Examples of the chelating agent include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), 2-hydroxy-4-sulfophenol and 2-hydroxy-3. , 5-disulfophenol is preferable, and as the bactericide, phenol compounds, thiazole compounds and benztriazole compounds are preferable. Specifically, 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-one
3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, sodium o-phenylphenol, and benztriazole are mentioned as preferable compounds.
It is preferable that these compounds are in the form of tablets if they are packaged in a package, and if they are divided and weighed in advance, they are individually packaged in an amount to be added at one time.

Means for adding these may be added manually by the pharmacist, but it is preferable to install a solid processing agent supply device, and to add by this, and more preferably to add a detector to the rehydration tank. However, it is preferable from the viewpoint of maintenance-free that water is automatically added when water is replenished up to a certain amount in the tank.

The means for modifying water with an ion exchange resin can be carried out based on the means described in JP-A-61-131632.

As the ion exchange resin, various publicly known cation exchange resins described in, for example, Kokai Giho, Kogi No. 90-473 (strongly acidic cation exchange resin, weakly acidic cation exchange resin).
And various anion exchange resins (strongly basic anion exchange resins)
And these can be used alone or in combination. Usually, it is preferable to use a strongly acidic H type cation exchange resin and a weakly basic OH type anion exchange resin. It may be attached to the water replenishment tank or the water may be improved elsewhere.

Preferred ion exchange resins for strong acid are DIAION SK1B SK102, SE104, S.
K106, SK110, SK112, and SK116 (Mitsubishi Kasei Co., Ltd.), and preferred OH type strongly basic anion exchange resins are DIAION PA406 and PA40.
8, PA412, PA416, PA418 (Mitsubishi Kasei Co., Ltd.).

The means for irradiating with ultraviolet rays is disclosed in JP-A-60-2.
It can be carried out by the means described in Japanese Patent No. 63939. As the ultraviolet irradiation device, a product manufactured by Kindai Bio Research Institute (headquarters Kobe City) is small and can be preferably used. The means for applying the magnetic field of the present invention can be implemented by the means described in JP-A-60-263939. The means for applying ultrasonic waves can be implemented by the means described in JP-A-60-263940. Further, means for applying electrolysis is disclosed in JP-A-3-
It can be carried out by the means described in Japanese Patent No. 22468.
Further, means for releasing silver ions include means for putting a silver foil or a silver plate in a water replenishing tank, means for coating the inner wall with silver, and means for putting a silver ion releasing compound.

On the other hand, the air bubbling means may be a very simple means for blowing bubbles into the replenishment tank, and is appropriately selected according to the size of the replenishment tank. From the viewpoints of compactness and economy, the means for preventing the formation of water stains and mildew-proofing materials is preferably the above 1), 2), 3), 7), 8), and more preferably 1), 3), 8 ) Is selected.

The silver ion-releasing compound of the means 8) is, for example, silver chloride, silver bromide, silver iodide, silver oxide, silver sulfate, silver nitrate or silver acetate, silver oxalate, silver behenate or silver maleate. Specific examples thereof include organic acid silver.

These silver compounds have SiO ₂ —Na ₂ O type glass bodies having a network structure as a chemical structure as a base structure component, or SiO ₄ tetrahedra having a methane type structure and A.
zeolite having a three-dimensional skeleton structure in the form of lO ₄ tetrahedra shared oxygen atoms one by one to each other, those obtained by containing the silver compound, in the present invention, is preferably used.

These silver compounds and the zeolite bodies and glass bodies containing the compounds can be obtained as commercially available products. For example, bio-sure SG (Bio-Sure SG) manufactured by Kinki Pipe Giken Co., Ltd., Opa Pharma (Switzerland) Opagent Tablets (Opargent
Tablets and Zeomic (Ze manufactured by Sinanen Zeomic Co., Ltd.)
mic) and the like.

Further, the silver compound and the zeolite body or glass body containing the compound can be used in various shapes. For example, it may be in the form of powder, spheres, pellets, fibers, or filters, or these may be kneaded into fibers such as cotton, wool, polyester, etc. before use. Specific examples thereof include Saniter 30 manufactured by Kuraray Co., Ltd. and the like. Among these, the filter-like and spherical ones are one of the preferable embodiments in the present invention.

Furthermore, it is also one of the preferred embodiments of the present invention to use the silver compound or the zeolite or glass body containing the silver compound in a water permeable container such as a plastic case or a tea bag. . In addition, Clinker 205 manufactured by Nichiban Kenkyusho Co., Ltd. or racking manufactured by Pacific Chemical Co., Ltd. can be preferably used.

On the other hand, the solid processing agent used in the present invention is
It contains at least one saccharide and / or a compound represented by the following general formulas (B) and (C). The content of saccharides in the solid processing agent is preferably 0.5% or more and less than 30% of the total weight, and particularly preferably 3% or more and less than 20%.

The saccharides in the present invention refer to monosaccharides, polysaccharides in which a plurality of these are glycosidic-bonded to each other, and degradation products thereof.

The monosaccharide means a single polyhydroxyaldehyde, polyhydroxyketone and their reduced derivatives,
It is a general term for a wide range of derivatives such as oxidized derivatives, deoxy derivatives, amino derivatives, and thio derivatives. Although many sugars are represented by the general formula CnH ₂ nOn, they are defined as monosaccharides in the present invention, including compounds derived from the sugar skeleton represented by this general formula. Among these monosaccharides, preferred are sugar alcohols obtained by reducing the aldehyde group and the ketone group of sugar to form primary and secondary alcohol groups, respectively.

The polysaccharides include celluloses, starches,
Glycogen, etc. are included, and celluloses include derivatives such as cellulose ethers in which some or all of the hydroxyl groups are etherified, and starches are various decomposition products until they are hydrolyzed to maltose. Contains certain dextrin sugars. Cellulose may be in the form of an alkali metal salt from the viewpoint of solubility. Of these polysaccharides, those preferably used are celluloses and dextrins, more preferably dextrins.

Preferred compounds as monosaccharides are: -Elitrit (trade name, Mitsubishi Kasei Foods erythritol) -D-sorbit-L-sorbit-D-mannite-L-mannite-D-idit-L-idit-D -Talit, L-Talit, Zulsit, Allozulsit.

Preferred compounds are shown below as specific examples of the polysaccharides and sugar-decomposed products.

Α-cyclodextrin ・ Β-Cyclodextrin ・ Γ-Cyclodextrin ・ Hydroxypropyl-α-cyclodextrin ・ Hydroxypropyl-β-cyclodextrin ・ Hydroxypropyl-γ-cyclodextrin ·Maltodextrin Is.

The dextrin used in the present invention may have any weight average molecular weight, but is preferably 10
~ 1000.

[0153] Saccharides exist widely in nature, and commercial products are easily available. Also, various derivatives can be easily synthesized by performing reduction, oxidation or dehydration reaction.

As a commercially available product, a decomposed product of starch is Pine Flow, Paindex series, Foodtex, Max 100, Glister P, TK-16, MPD, H-PDX, Stacodex manufactured by Matsutani Chemical Industry Co., Ltd. , Oil Q series manufactured by Nippon Oil & Fats Co., Ltd.

Next, the compound represented by formula (B) in the present invention will be specifically described.

General formula (B) HO- (A ₁ -O) l _1- (A ₂ -O) l _2- (A _3-
O) l in ₃ -H _{formula, A 1, A 2, A} 3 is substituted independently represent an unsubstituted straight-chain or branched alkylene group, which may optionally be the same or different.

Examples of the substituent include a hydroxy group, a carboxy group, a sulfonyl group, an alkoxy group, a carbamoyl group and a sulfamoyl group. Those preferably used are those in which A ₁ , A ₂ and A ₃ are each unsubstituted. Most preferred are A ₁ , A
_{2, A 3} is _{-CH 2 CH 2 -, - CH} (CH 3) -CH
_2- .

L ₁ , l ₂ , and l ₃ are 0 or 0, respectively.
Represents an integer of ˜500. However, l ₁ + l ₂ + l ₃ ≧ 5
Is.

Of these, at least one of l ₁ , l ₂ and l ₃ is preferably used 15 or more, and more preferably 20 or more.

When the compound represented by the general formula (B) in the present invention is, for example, a copolymer obtained by mixing two kinds of monomers A and B and copolymerizing them, those having the sequences shown below are also included. To be done.

-A-B-A-B-A-B-A-B-A-B-A-A-B-A-B-B-B-A-A-B-A-A-B- B-A--A-A-A-A-A-A-B-B-B-B-B-B-A-A-A-A-A- Among these copolymers, especially Preferred compounds are represented by the following general formula (B-1). It is a block polymer of ethylene glycol and propylene glycol (Pluronic type nonionic).

[0162] Formula _{(B-1) HO- (CH} 2 CH 2 -O) l 4 [CH _(CH 3) CH
₂ -O] _l 5 _- in _{(CH 2 CH 2 -O) l} 6 -H _{formula, l 4, l 5, l} 6 is _l 1 in the foregoing formula (B),
It is synonymous with l ₂ and l ₃ .

In the compound represented by the general formula (B-1) in the present invention, the content (% by weight) of ethylene oxide in the total molecular weight is preferably 70% by weight or more, particularly preferably 80% by weight or more. It is a thing.

The general formula (B) and the general formula (B-
Specific compounds represented by 1) are shown below.

[0165] _{HO- (CH 2 -CH 2 -O)} n'-H -average molecular weight B-1 300 B-2 600 B-3 1000 B-4 1500 B-5 2000 B-6 3000 B-7 4000 B- 8 6000 B-9 10000 B- 10 15000 B-11 20000 B-12 30000 HO- (CH 2 CH 2 -O) a '- _{[CH (CH} 3) _-CH 2 -O] b' - _(CH 2 _{CH 2-} O) c'-H Content of ethylene oxide average molecular weight in total molecule (% by weight) B-1-1 80 8350 B-1-2 80 10800 B-1-3 50 4600 B-1-4 70 6500 B-1-5 80 5000 B-1-6 50 3500 B-1-7 70 7850 B-1-8 50 4150 In the above formula, n'represents an integer of 5 or more, a ', b',
c'is synonymous with l ₁ , l ₂ , and l ₃ .

Among the compounds represented by the general formula (B) and the general formula (B-1) in the present invention, the most preferable one is polyethylene glycol (sometimes referred to as PEG).

In the case of polyethylene glycol,
Those having an average molecular weight of 2,000 to 20,000 are preferable, and those of 3,000 to 15,000 are particularly preferable.

The average molecular weight in the present invention is the molecular weight calculated from the hydroxyl value. The compound represented by the general formula (B) may be used alone or in combination of two or more kinds.

General formula (C) R-SxOyM [In the formula, R is an aliphatic group, an aromatic group or a heterocyclic group, x is 1 or 2, y is an integer of 2 to 8, and M is a cation. Next, the organic sulfur oxide represented by the general formula (C) will be described.

The solid processing composition according to the present invention contains the organic oxide represented by the general formula (C) in an amount of 0.01% to 3.0% of the total weight. Preferably 0.1% or more, 2.
It is 5% or less, more preferably 0.5% or more and 2.0% or less.

In the general formula (C), the aliphatic group represented by R includes an alkyl group, an alkenyl group and an alkynyl group, and examples of the alkyl group include methyl, ethyl, i-propyl, butyl and t. -Butyl, pentyl,
Each group such as cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl and the like can be mentioned. These alkyl groups further include a halogen atom (eg chlorine, bromine, fluorine, etc.), an alkoxy group (eg methoxy, ethoxy, 1,
1-dimethylethoxy, hexyloxy, dodecyloxy, etc.), aryloxy groups (eg, phenoxy, naphthyloxy), aryl groups (eg, phenyl, naphthyl, etc.), alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-
Ethylhexylcarbonyl etc.), aryloxycarbonyl group (eg phenoxycarbonyl, naphthyloxycarbonyl etc.), alkenyl group (eg vinyl, allyl etc.), heterocyclic group (eg 2-pyridyl, 3-pyridyl,
4-pyridyl, morpholyl, piperidine, piperazil,
Pyrimidine, pyrazoline, furyl, etc.), alkynyl group (eg propargyl), amino group (eg amino,
It may be substituted with N, N-dimethylamino, anilino), a cyano group, a sulfonamide group (eg, methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino, etc.).

Examples of the alkenyl group include vinyl and allyl, and examples of the alkynyl group include propargyl.

Examples of the aromatic group represented by R include phenyl and naphthyl.

Examples of the heterocyclic group represented by R include a pyridyl group (2-pyridyl, 3-pyridyl, 4-pyridyl, etc.), a thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group, a cenyl group, a pyrrolyl group, Pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulforanyl group, piperidinyl group, pyrazolyl group,
Examples thereof include a tetrazolyl group.

The above alkenyl group, alkynyl group, aromatic group and heterocyclic group can be substituted with the same groups as the alkyl group represented by R and the groups shown as the substituents of the alkyl group.

The group represented by M is preferably a metal ion or an organic cation. Examples of the metal ion include lithium ion, sodium ion, potassium ion and the like, and examples of the organic cation include ammonium ion (ammonium, tetramethylammonium,
Tetrabutylammonium, etc.), phosphonium ion (tetraphenylphosphonium), guanidyl and the like.

The compound represented by the general formula (C) is contained when the solid processing agent containing the saccharide of the present invention and / or the compound represented by the general formula (B) is formed into tablets by compression molding. It was found that by doing so, lubricity, tablet hardness, and friability were dramatically improved.

Specific examples of the compound represented by formula (C) are shown below, but the invention is not limited thereto.

[0179] _{C-1 C 2 H 5 SO} 3 Na C-2 CH 3 (CH 2) 6 SO 3 Na C-3 CH 3 (CH 2) 7 SO 3 Na C-4 CH 3 (CH 2) 5 OSO _{3 Na C-5 CH 3 (} CH 2) 6 OSO 3 Na C-6 CH 3 (CH 2) 7 OSO 3 Na C-7 CH 3 O (CH 2) 2 SO 3 Na

[0180]

[Chemical 16]

[0181]

【Example】

Example 1 <Preparation of coated sample><< Preparation of photosensitive material >> Seed emulsion-1 was prepared as follows. A1 ossein gelatin 24.2 g water 9657 ml S-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 2825 ml D1 1.75N Potassium bromide aqueous solution Silver potential control amount below

No. 58-58288 and 5 at 42 ° C.
Solution A using the mixing stirrer shown in No. 8-58289.
464.3 ml of each of solution B1 and solution C1 was added to 1 by the simultaneous mixing method over 1.5 minutes to perform nucleation.

After stopping the addition of solution B1 and solution C1, it took 60 minutes to raise the temperature of solution A1 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then re-solution. B1 and solution C1 were each mixed by the simultaneous mixing method at 55.4.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase from 42 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was made + using the solution D1.
It was controlled to be 8 mv and +16 mv.

After completion of the addition, the pH was adjusted to 6 with 3% KOH, and desalting and washing with water were immediately performed. In this seed emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The hexagonal tabular grains have an average thickness of 0.064 μm and an average diameter. (Circle diameter conversion)
Was confirmed to be 0.595 μm with an electron microscope. The variation coefficient of thickness was 40%, and the variation coefficient of distance between twin planes was 42%.

<Preparation of Em-1 to Em-4> Seed emulsion-1
A tabular silver halide emulsion Em-1 was prepared using the following four solutions. A2 ossein gelatin 34.03 g S-3 (10% ethanol aqueous solution) 2.25 ml seed emulsion-1 1.218 mol equivalent Water is made up to 3150 ml. B2 Potassium bromide 1734 g Make up to 3644 ml with water. C2 Silver nitrate 2478 g Water to make 4165 ml. D2 Fine grain emulsion composed of 3% by weight of gelatin and silver iodide grains (average particle size: 0.05 μm) (equivalent to 0.080 mol) * 5.0% by weight of gelatin containing 0.06 mol of potassium iodide To 66.4 liters of the aqueous solution, 2 liters each of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. The pH during fine particle formation was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After forming the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

Solution A2 was vigorously stirred in the reaction vessel while maintaining it at 60 ° C., and part of solution B2, part of solution C2 and half of solution D2 were added thereto by the simultaneous mixing method over 5 minutes, After that, half of the remaining amount of the solution B2 and the solution C2 was added over 37 minutes, and then a part of the solution B2, a part of the solution C2 and the remaining whole amount of the solution D2 were added over 15 minutes. Solution B2 and solution C2 with the remaining total amount of 33
Added over minutes. During this period, the pH was kept at 5.8 and the pAg was kept at 8.8 throughout. Here, the addition rates of the solution B2 and the solution C2 were changed in a function-like manner with respect to the time corresponding to the critical growth rate.

Further, the above solution D2 was added in an amount corresponding to 0.15 mol% of the total amount of silver for halogen substitution.

After the addition is complete, the emulsion is cooled to 40.degree.
1800 ml of a 13.8% (weight) modified gelatin aqueous solution modified with a phenylcarbamoyl group (substitution rate 90%) was added as an aggregating polymer, and the mixture was stirred for 3 minutes. Thereafter, a 56% (weight) aqueous acetic acid solution was added to adjust the pH of the emulsion to 4.
After adjusting to 6, the mixture was stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation. Then 4
Distilled water (9.0 liters) at 0 ° C was added, and the mixture was left to stir, and the supernatant was drained. Further, 11.25 liters of distilled water was added, and the mixture was left standing to stir, and then the supernatant was drained. Subsequently, a gelatin aqueous solution and a 10% (weight) aqueous solution of sodium carbonate were added to adjust the pH.
Was adjusted to 5.80, stirred at 50 ° C. for 30 minutes and redispersed. After redispersion, the pH was adjusted to 5.8 at 40 ° C, p
Ag was adjusted to 8.06.

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.
The tabular silver halide grains had an average aspect ratio of about 4.5 and a width of grain size distribution of 18.1%. or,
The average distance between twin planes is 0.020 μm and 97% (number) of all tabular silver halide grains have a ratio of distance between twin planes to 5 or more and 49 or more are 49 or more. %, 15
The above particles accounted for 17%. Also, AgNO ₃ , K
Br, potassium iodide, pH and pAg are changed to
The particles were prepared in the same manner as in -1, and as shown in Table 1, Em-2, Em-3, E having different aspect ratios and AgI contents were used.
An m-4 silver halide emulsion was prepared.

Next, after each of the above-mentioned emulsions Em-1 to Em-4 was heated to 60 ° C., 10 minutes after adding a predetermined amount of the spectral sensitizing dye as a solid fine particle dispersion, adenine and ammonium thiocyanate were added. , A mixed aqueous solution of chloroauric acid and sodium thiosulfate, and a dispersion liquid of triphenylphosphine selenide were added, and after 30 minutes, a silver iodide fine grain emulsion was added, and ripening was performed for a total of 2 hours. 4-hydroxy-6-methyl-1,3,3 as a stabilizer at the end of aging
A predetermined amount of a, 7-tetrazaindene (TAI) was added.

The above additives and their addition amounts (AgX1
(Per mole) is shown below. 5,5'-Dichloro-9-ethyl-3,3'-di- (sulfopropyl) -oxacarbocyanine sodium salt anhydrous 400 mg 5,5'-di- (butoxycarbonyl) -1,1'-diethyl- 3,3'-di (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydride 4.0 mg adenine 15 mg potassium thiocyanate 95 mg chloroauric acid 2.5 mg sodium thiosulfate 2.0 mg triphenylphosphine selenide 0. 2 mg Silver iodide fine particles 280 mg 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 500 mg

A solid fine particle dispersion of a spectral sensitizing dye was prepared by a method according to the method described in Japanese Patent Application No. 4-99437. That is, a predetermined amount of the above-mentioned spectral sensitizing dye is added to water whose temperature has been adjusted to 27 ° C. in advance, and the mixture is stirred at a high speed (dissolver) for 3,5
Obtained by stirring at 00 rpm for 30-120 minutes.

A dispersion liquid of the above selenium sensitizer was prepared as follows. That is, triphenylphosphine selenide 1
20 g was added to 30 kg of ethyl acetate at 50 ° C., and the mixture was stirred and completely dissolved. On the other hand, 3.8 kg of photographic gelatin was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzene sulfonate was added thereto.
Next, these two liquids were mixed and dispersed at a peripheral speed of the dispersing blade of 40 m / sec for 30 minutes at 50 ° C. by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm. Immediately after that, the residual concentration of ethyl acetate was 0.3 wt.
Ethyl acetate was removed while stirring until the amount became less than or equal to%. Then, this dispersion was diluted with pure water to obtain 80 kg. A part of the thus obtained dispersion was collected and used in the above experiment.

(Preparation of Coating Solution for Emulsion Layer) The following various additives were added to the emulsion obtained above.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² 1,1-dimethylol-1-bromo-1- Nitromethane 70 mg t-Butyl-catechol 130 mg / m ² Polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² 1,3-Dihydroxybenzene-4-sulfonate ammonium 500 mg / m ² 2-Mercaptobenzimidazole-5-sulfonate sodium 5 mg / m ² compound (H) 0.5 mg / m ² n-C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² General formula (1) Table 1 amount described General formula (2) Amount shown in Table 1 Colloidal silica (Ludox AM: particle size 0.013 μm manufactured by DuPont) 0.5 g / m ² However, as gelatin, 1.5 g / m ² by mixing an emulsion.
I adjusted it to be.

(Preparation of Protective Layer Coating Liquid) Gelatin 0.8 g / m ² Polymethylmethacrylate Matting Agent (Area Average Particle Diameter 7.0 μm) 50 mg / m ² Hardener (CH ₂ = CHSO ₂ CH ₂ ) ₂ O 36 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² latex (L) 0.2 g / m ² polyacrylamide (average molecular weight 10000) 0.2 g / m ² sodium polyacrylate 30 mg / m ² polysiloxane (SI) 20 mg / m ² compound (I) 12 mg / m ² compound (J) 2 mg / m ² compound (S-1) 7 mg / m ² compound (K) 15 mg / ^{m 2} compound (O) 50 mg / ^{m 2} compound ^{(S-2) 5mg / m} 2 compound ^{(F-1) 3mg / m} 2 compound (F-2) 2mg m ² Compound (F-3) 1 mg / ^{m 2} Formula (1), compounds shown in Table 1 of the general formula (2) In addition, the amount with the material is one-sided 1 m ² per silver coverage as one side component It was adjusted to be 1.6 g / m ² .

(Creation of Crossover Cut Layer) Glycidyl Methacrylate 50 wt%, Metriacrylate 1
Copolymer dispersion obtained by diluting the copolymer consisting of three monomers of 0 wt% and 40 wt% of butyl methacrylate so as to have a concentration of 10 wt% was applied as an undercoat liquid to give a blue color with a thickness of 175 μm. A support sample was prepared by coating a crossover cut layer on both sides of a polyethylene terephthalate support such that the coating amount per 1 m ^{2 on} one side was the following composition.

[0198]   Solid fine particle dispersion dye (AH) 50 mg   Gelatin 0.2g   Sodium dodecylbenzene sulfonate 5mg   Compound (I) 5 mg   2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt                                                           5 mg   Colloidal silica (average particle size 0.014 μm) 10 mg   Polystyrene potassium sulfonate 50mg

[0199]

[Chemical 17]

[0200]

[Chemical 18]

[0201]

[Chemical 19]

(Coating) Using these coating solutions, two slide hopper type coaters were used so that the coating amount was 1.6 g / m ^{2 on} one side and the coating amount on gelatin was 2.5 g / m ^2. Was simultaneously coated on both surfaces of the above-mentioned support sample at the speed of 120 M per minute with the following layer structure and dried for 2 minutes and 20 seconds to prepare a coated sample.

Layer position Layer type Gelatin amount per one side (g / m ² ) Upper layer Protective layer 0.8 Intermediate layer Emulsion layer 1.5 Lower layer Filter layer 0.2

[0204] <Preparation of monodisperse cubic seed emulsion Em-B> <Solution A>   Ocein gelatin 30g   KBr 1.25g   Nitric acid (0.1N) 150 ml   Make up to 7700 ml with distilled water

[0205] <Solution B>   KBr 6g   KI 0.16g   Make up to 740 ml with distilled water

[0206] <Solution C>   KBr 680g   KI 20g   Make up to 2480 ml with distilled water

[0207] <Solution D>   Silver nitrate 8.4g   Nitric acid (0.1N) 32 ml   Make up to 740 ml with distilled water

[0208] <Solution E>   Silver nitrate 991.6g   Nitric acid (0.1N) 80 ml   Make up to 2480 ml with distilled water

Solution A stirred vigorously at 60 ° C. was added to solution B.
And Solution D were added by the double jet method over 10 minutes. Then, the solution C and the solution E were added by the double jet method over 140 minutes. At this time, the initial addition flow rate was 1/8 of the final addition flow rate, and linear sensitization was performed with time. While adding these solutions, pH = 2,
It was constantly adjusted to pAg = 8. After the addition was completed, the pH was raised to 6 with sodium carbonate, 150 g of KBr was added, and then desalting and washing with water were carried out immediately to obtain a monodispersion of silver iodobromide containing 2 mol% of silver iodide having an average particle size of 0.3 μm. Cubic seed emulsion E
m-B was obtained. According to an electron microscope, the generation rate of twins was 1% or less in number.

(Preparation of Normal Crystal Core / Shell Emulsion Em-5) A normal crystal emulsion Em-5 containing 2.0 mol% AgI was prepared using the following 5 kinds of solutions. <Solution A> ossein gelatin _{75.5g 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 Em-B equivalent to 0.40 mol Distilled water to 4000 ml

<Solution B> AgNO ₃ 46.2 g AgNO ₃ and an equimolar amount of ammonia solution and distilled water are added to make 259 ml.

<Solution C> AgNO ₃ 647.6 g AgNO ₃ and an equimolar amount of ammonia solution and distilled water were added to make 1088 ml.

[0213] <Solution D>   KBr 22.6g   KI 13.5g   Make up to 259 ml with distilled water

[0214] <Solution E>   KBr 453.3g   Make up to 1088 ml with distilled water

The solution A was kept at 40 ° C. in the reaction vessel, and ammonia water and acetic acid were further added to adjust the pH to 9.5. After adjusting pAg to 7.3 with ammoniacal silver ion solution, p
Solution B and solution D were added by the double jet method while H and pAg were kept constant to form a silver iodobromide layer containing 30 mol% of silver iodide. The pH was adjusted to 9.0 using acetic acid and KBr,
After the pAg was adjusted to 9.0, the solution C and the solution E were added at the same time and grown, and then grown until the particle diameter reached 90%.
At this time, the pH was gradually lowered from 9.0 to 8.20. A KBr solution was added to adjust the pAg to 11, and solutions C and E were further added to grow while gradually lowering the pH to 8 to obtain a silver iodobromide emulsion containing 2 mol% of silver under iodine. After the addition was completed, precipitation desalting was carried out by the following method in order to remove excess salts.

1. The reaction mixture after mixing is brought to 40 ° C.,
Add 20g / AgX1mol of coagulated gelatin agent, 56wt
% Acetic acid is added to adjust the pH, and the mixture is left standing and decanted. After adding 1.8 liter / AgX1 mol of pure water at 2.40 ° C. and stirring for 10 minutes, the mixture is left standing and decanted. 3. Repeat step 2 above once more. 4. An aqueous gelatin solution containing 92.2 g of ossein gelatin was added to 2500 ml with stirring and redispersion to give Em-5.

Approximately 1000 particles of Em-5 were observed and measured by an electron microscope and the shape was analyzed. As a result, the particles were monodisperse spherical particles having an average particle diameter of 0.51 μm and a distribution width of 12%.

Next, the obtained emulsion was spectrally and chemically sensitized by the following methods. After the emulsion was heated to 50 ° C., the solid fine particle dispersion described above was added so that the sensitizing dye (A) was 40 mg per mol of silver, and then 7.0 × 10 ⁻⁶ mol of the following selenium sensitizer was added. Ammonium thiocyanate salt of 4.0 × 10 ⁻⁴ mol per mol of silver, 3.2 × 10 ⁻⁶ mol of chloroauric acid and 3.4 of sodium thiosulfate.
X 10 ^-5 mol was added, and 40 minutes after that, the above silver iodobromide fine grain emulsion was added with 1.7 x 10 ^-3 mol / Ag 1 mol, and then
4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was stabilized with 1.2 × 10 ⁻² mol.

[0219]

[Chemical 20]

(Preparation of Sample) To each of the obtained emulsions, the following various additives were added to prepare emulsion solutions (photosensitive silver halide coating solutions). The addition amount is indicated by the amount per mol 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 1,3-dihydroxybenzene sodium-4-sulfonic acid ammonium 4g 2-mercaptobenzimidazole indazole-5-sulfonic acid _{1.5mg n-C 4 H 9 OCH} 2 CH (OH) CH 2 n (CH 2 COOH) 2 1g

[0222]

[Chemical 21]

Compound of General Formula (1) Amount Described in Table 1 Compound of General Formula (2) Amount Described in Table 1 The additives used in the protective layer are as follows. The added amount is shown as an amount per 1 g of gelatin. Coating liquid for protective layer Matting agent composed of polymethylmethacrylate having an area average particle size of 7 μm 7 mg Colloidal silica (average particle size 0.013 μm) 70 mg 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 30 mg

[0224]

[Chemical formula 22]

(CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardener) 36 mg Compound of general formula (1) Table 1 amount of compound of general formula (2) Compound of table 1 A sample was prepared by uniformly coating an emulsion layer and a protective layer on both sides on a blue-colored polyethylene terephthalate film base having an undercoating treatment of 175 μm and drying the layer. The silver coverage of the silver halide emulsion layer was 2.20 g / m ² per side.

The solid agent and liquid agent of the developer according to the present invention are prepared below. <Solid developer α used as hydroquinone developing agent> Preparation of 100 liter amount as a developing solution.

[Granulated product (A)] 3000 g of hydroquinone as a developing agent, 400 g of phenidone, 1000 of boric acid.
g, N-acetyl-D, L-penicillamine 10 g, and glutaraldehyde sodium bisulfite 500 g are ground in a commercially available bandam mill to an average of 10 μm. The amount of reductones listed in Table 1 in this fine powder,
700 g of sodium sulfite, 2 parts of binder D-sorbit
After adding 00 g and mixing for 30 minutes in a mill and granulating by adding 30 ml of water for about 5 minutes at room temperature in a commercial stirring granulator, the granulated product was dried at 40 ° C. in a fluid bed dryer. At 2
The granules are dried for an hour to almost completely remove water.

[Preparation of Solid Developer A] The granulated product (A) thus obtained was mixed with 100 g of sodium 1-octanesulfonate in a room conditioned at 25 ° C. and 40% RH or less. After uniformly mixing for 10 minutes, the resulting mixture is toughly pressed collect 15 manufactured by Kikusui Seisakusho KK
The filling amount per tablet is 1 by the tablet machine modified from 27HU.
The tablets were compressed to 0 g and compressed to give a hydroquinone-based developing tablet having a cylindrical shape with a diameter of 30 mm.

[Granulated product (B)] 10000 potassium carbonate
g, 1000 g of sodium bicarbonate, and 200 g of KBr are ground in a commercially available bandam mill to an average of 10 μm. LIOH to each fine _· H 2 0 200g,
DTPA · 5H 250 g, 1-phenyl-5-mercaptotetrazole 5 g, sodium sulfite 4000 g,
General formula (1) The amount described in Table 1 of general formula (2), the amount described in Table 2 of general formula (2), and 1000 g of a binder mannitol were added and mixed in a mill for 30 minutes, and then in a commercially available stirring granulator at room temperature for about 15 minutes at 30 m.
After granulating by adding 1 liter of water, the granulated product is dried at 40 ° C. for 2 hours in a fluid dryer to almost completely remove the water content of the granulated product.

[Preparation of Solid Developer B] The granulated product (B) thus obtained was mixed with 200 g of sodium 1-octanesulfonate in a room conditioned at 25 ° C. and 40% RH or less. After uniformly mixing for 10 minutes, the resulting mixture is toughly pressed collect 15 manufactured by Kikusui Seisakusho KK
The filling amount per tablet is 1 by the tablet machine modified from 27HU.
Alkali developed tablets were prepared by compression compression to 0 g.

<Solid developer β containing the reductone of the present invention as a main component> Preparation of 100 l of a developer. [Granulate (A)] 1-phenyl-3-pyrazolidone 3
00 g, N-acetyl-D, L-penicillamine 10 g,
500 g of glutaraldehyde sodium bisulfite is ground in a commercial Van Dam mill to an average of 10 μm. 1500 g of sodium metabisulfite was added to this fine powder.
g, the amount of the reductone of the present invention shown in Table 1 and 600 g of the binder D-sorbitite were added and mixed in a mill for 30 minutes, and 30 ml of water was added in a commercially available stirring granulator at room temperature for about 10 minutes. After granulating with the
The granulated product is dried at 0 ° C. for 2 hours to almost completely remove water.

[Preparation of Solid Developer A] The granulated product (A) thus obtained was mixed with 80 g of sodium 1-octanesulfonate in a room conditioned at 25 ° C. and 40% RH or less. After uniformly mixing for 10 minutes, the obtained mixture is toughly pressed collect 152 manufactured by Kikusui Seisakusho KK
Filling amount per tablet is 10 with a tablet machine modified from 7HU.
Then, the tablet was compressed to g to prepare a reductone-based developing tablet.

[Granulated product (B)] Potassium carbonate 9,000
g and 100 g of sodium bicarbonate are ground in a commercially available bandam mill to an average of 10 μm. 250 g of DTPA · 5H in each fine powder, the amount described in General Formula (1) Table 1, the amount described in General Formula (2) Table 1, KI Table 1, 200 g of methyl-β-cyclodextrin, 2000 g of binder mannitol, D- After 700 g of sorbit was added and mixed in a mill for 30 minutes, and granulated by adding 30 ml of water in a commercially available stirring granulator at room temperature for about 15 minutes, the granulated product was dried at 40 ° C. in a fluidized dryer. And dried for 2 hours to almost completely remove the water content of the granulated product.

[Preparation of Solid Developer B] The granulated product (B) thus obtained was mixed with 150 g of sodium 1-octanesulfonate in a room conditioned at 25 ° C. and 40% RH or less. After uniformly mixing for 10 minutes, the resulting mixture is toughly pressed collect 15 manufactured by Kikusui Seisakusho KK
The filling amount per tablet is 1 by the tablet machine modified from 27HU.
Alkali developed tablets were prepared by compression compression to 0 g.

The developer of hydroquinone base and the developer of reductone base were both packaged in a pillow bag containing aluminum for the purpose of preventing moisture in both developers A and B in an amount of 4.0 liters.

A solid fixing agent having a volume of 100 liters was prepared as a fixing solution by the following operation.

[Granulate (C)] Ammonium thiosulfate /
Sodium thiosulfate (90/10 weight ratio) 15000g
Are ground in a commercial bander mill to an average of 10 μm. To this fine powder, 500 g of sodium sulfite, Na ₂ S ₂
0 ₅ 750 g and binder pine flow 1300 g are added and the amount of water added is set to 50 ml to carry out stirring granulation, and the granulated product is dried at 40 ° C. in a fluid bed dryer to remove water almost completely.

[Granulate (D)] Boric acid 400 g, aluminum sulfate octadecahydrate 1200 g, succinic acid 1200 g, tartaric acid 3
00 g is ground in a commercial Van Dam mill to an average of 10 μm. 250g of D-Masonite, D-
Sorbit (120 g) and PEG # 4000 (160 g) were added, and water was added in an amount of 30 ml to carry out stirring granulation, and the granulated product was dried at 40 ° C. in a fluid bed dryer to completely remove water.

[Solid-fixing agent] To the granulated product (C) thus obtained, 3,000 g of β-alanine, 4330 g of sodium acetate, and 1-octanesulfonic acid sodium were added so as to be 1.5% of the total weight. In addition, 750 g of sodium metabisulfite and sodium 1-octanesulfonate are added to the granulated product (D) so as to be 1.0% of the total weight, and the humidity is adjusted to 25 ° C and 40% RH or less, respectively. After uniformly mixing for 10 minutes using a mixer in the designated room,
The obtained mixture was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., so that the filling amount per tablet was (C) 10.2 g and (D) 11.2 g. A cylindrical fixed tablet having a diameter of 30 mm was prepared. Each of the solid agents was sealed and packed in a pillow bag containing aluminum for moisture prevention in an amount of 4.0 liters.

<Treatment Method> As the automatic developing machine, SRX-201 (manufactured by Konica Corporation) was modified and used. Development temperature 35 ° C., fixing temperature 35 ° C., drying temperature 55 ° C., processing time dry to
dry The treatment was carried out under the conditions shown in Table 1. Replenishment was done in the amounts listed in Table 1.

At the start, the developer in the developing tank was mixed with hydroquinone-based solid developer α and reductone-based solid developer β of respective solid developers A and B, and diluted with diluted water with a modified chemical mixer described later. Dissolve and adjust. The tablets were completely dissolved and no precipitate was observed. 7.8 liters of this developing solution was put into SRX-201 (manufactured by Konica Corporation), and a starter described later was added to fill a developing tank as a starting solution to start the processing. The amount of starter added was 35 ml / 1 liter. The fixing agent is prepared by diluting the solid fixing agents (C) and (D) with diluted water with a modified chemical mixer described later. The tablets were completely dissolved and no precipitate was observed. 5.6 liters of this adjusted fixing solution was put into the fixing processing tank of SRX-201 to be used as a starting solution.

[0242] Starter formulation _{KBr 5.5g HO (CH 2) 2} S (CH 2) 2 S (CH) 2 OH 0.05g N- acetyl -D, L-penicillamine 0.10g sodium metabisulfite following starting solution pH The amount of water to be finished 35 ml Incidentally, the built-in chemical mixer for dissolving the solid agent was modified by providing a modified chemical mixer inlet so that each solid agent could be charged during development and fixing of SRX-201.

For development and fixing, each packaging bag was manually opened in each solid agent charging port, and the tablets were dropped into the built-in chemical mixer and at the same time warm water (25 to 3
(0 ° C) is poured and dissolved with stirring with a dissolution time of 25 minutes.
Adjust to 0 liter. This was used as a developing / fixing replenisher. The adjusted replenisher is supplied to the developing tank and the fixing tank to satisfy the above-mentioned amount.

The pH when the development is dissolved is 10.55 for the hydroquinone type development, and pH 1 for the reductone base type.
Fine adjustment was carried out with acetic acid and KOH so as to be 0.15. The solution replenisher pH of the fixer was 4.80.

The built-in chemical mixer is divided into a preparation tank and a reserve tank tank, and the preparation tank capacity is 3.0 liters and the reserve tank capacity is 3.0 liters. The film is prepared in the preparation tank during the running process. A spare tank was provided so that the replenisher was supplied so that the replenisher was not consumed and the replenisher was not replenished during the stirring and dissolving time (about 25 minutes).

The pH of the developer when the starter was added was α of 10.45 and β of 9.90.

A starter is also added to the replenishment developer γ prepared by SRX-201 modified from the concentrated solution kit of the following three-part composition to prepare the built-in CM in the three-part composition instead of the above solid agent. Starting liquid (starting pH 9.90)
And processed. As the fixing solution, the same solution as prepared above was used.

Adjustment of Developer γ [Composition of Concentrated Solution Development Kit] Developer 1 liter Finishing amount (A part) Reductones Amount described in Table 1 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 4 g Sulfurous acid Potassium 50% 70 g Potassium bicarbonate 3 g Potassium carbonate 100 g General formula (1) Amount described in Table 1 General formula (2) Amount described in Table 1 Diethylene glycol 70 g 50% Potassium hydroxide pH adjusted to 550 ml with pure water for pH adjustment 10.80 Was prepared.

[0249] (Part B)   Acetic acid (90%) 22 g   Triethylene glycol 10g   N-acetyl-D, L-penicillamine 0.2 g   1-phenyl-3-pyrazolidone 2.0 g   4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone                                                                 4 g   5-nitroindazole 0.02g

(Part C) 50% glutaraldehyde solution 5.0 g Incidentally, when 1 liter of the developer is prepared, the pH is 10.1.
It was 0.

The following evaluations were carried out using the obtained coated sample, treating agent and automatic developing machine.

<Long-term stability> Table 1 shows the presence or absence of water replenishment. In order to suppress the effect of concentration due to long-term running, the SRX-201 automatic developing machine was modified to add water to the developing tank and / or fixing tank. A mechanism for replenishment was provided.

A liquid level sensor is provided in each processing tank, and water is added to make up the liquid level sensor so that the liquid level sensor is turned on before the start of processing, and every 1 or 2 hours during operation of the automatic processing machine. The liquid level was checked and the decreased amount was replenished with water. However, for replenishment to fixing, the current-constant Watarilac wash water was included in the replenishment.

Further, the developer replenisher and the fixer replenisher are cut into four pieces before the start of processing, and a quantity equivalent to the processing of four pieces is cut into four pieces per hour during operation to suppress a decrease in the liquid level and concentration. The method also went.

[Evaluation of Sensitometric Variation] The photosensitive material prepared above was cut into a large-angle size, uniformly exposed to light so that the optical density after development was 1.0, and running was performed. During running, the amount of replenishment for developing and fixing per one sheet (0.077 m ² ) of four-cut photosensitive material was as shown in Table 1. For running, 50 sheets are processed per day, and the first day (start liquid state) and 500 sheets (20 sheets)
The sensitometry of 1000 sheets (40 days), 1500 sheets (60 days) was obtained and shown in Table 1.

Sensitometry was determined as follows. The obtained film was sandwiched between fluorescent intensifying screens KO-250 (manufactured by Konica Corp.), tube voltage 90 KVP, current 20 m.
X-ray irradiation was performed under the conditions of A and time of 0.05 seconds, and a sensitometric curve was created by the distance method to determine the sensitivity. The sensitivity value was obtained as the reciprocal of the X-ray dose required to obtain Fog + 1.0. Fog + 0.25-Fog + as γ value
The density difference in the density range of 2.0 was expressed as the slope which is the value obtained by dividing the logarithmic difference in the exposure amount required to obtain the density. The maximum density that can be obtained by increasing the exposure dose is shown in Table 1 as Dm.

[Evaluation of Remaining Coloring Property]
It was cut into a size of 0.5 × 25.4 cm, and developed by the above-mentioned processing method while being unexposed. The degree of residual color was visually evaluated according to the following criteria.

[0258] A: Almost no residual color B: The color remains slightly, but it does not bother me C: Remaining color, but practically acceptable D: Many residual colors are not possible

[Evaluation of Silver Tone] The large size of the obtained film was sandwiched between fluorescent intensifying screens KO-250 (manufactured by Konica Corp.), tube voltage 90 KVP, current 200 mA, time 0.0.
X-ray irradiation was performed with the phantom as a subject under the condition of 5 seconds. This was processed in the above run. The obtained image was visually evaluated according to the following ranks.

Rank 5: Color tone is black tone Rank 4: Color tone is warm black tone Rank 3: Color tone is slightly yellowish Rank 2: Color tone is slightly yellowish, NG level rank 1: Clearly yellowish

[Evaluation of Silver Sludge] The density after the treatment was 1.
After processing 200 sheets of quadrants of the coated sample uniformly exposed to a solid of 0 ± 0.1, stains in the developing tank and the transport roller were visually evaluated.

[0262] Rank 3: No problem Rank 2: Acceptable level Rank 1: Problematic level

[0263]

As can be seen from the description and evaluation in Table 1, the composition of the present invention significantly improves the sensitivity (γ, Dm variation) due to running (long-term running including aging). In particular, the improvement in fluctuations in γ and Dm is remarkable. Further, silver tone and silver sludge are also greatly improved by the present invention.

Further, the developer and the fixing agent of the present invention can be solidified and can be compacted by reducing the space by nearly 70%, and at the same time, the solidification from the concentrate kit results in long-term stability (sensitometry, silver tone). You can see that it is improving.

In particular, when a developing solution containing a reductone as a main component is used, the improvement effect of the present invention is greatly exerted by replenishing water by adopting the constitution of the present invention. It was a surprising invention that was especially exhibited in residual color.

[0266]

[Table 1]

[0267]

[Table 2]

[0268]

[Table 3]

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Claims (10)

(57) [Claims] 1. A silver halide photographic light-sensitive material comprising a support and a hydrophilic colloid layer containing at least one silver halide emulsion layer, wherein the hydrophilic colloid layer is represented by the following general formula (1). And a compound represented by the general formula (2). [Chemical 1] In the formula, Y and Z are N or CR ₂ (R ₂ represents a hydrogen atom and a substituted or unsubstituted alkyl group or aryl group.) R ₁ is at least one or more sulfo group, carboxy group,
It represents an amino group, a hydroxy group or a salt thereof, or an aryl group substituted with a boron residue. When two or more of these substituents are present, they may be the same or different. M represents a hydrogen atom, an alkali metal atom, quaternary ammonium, and a group in which M can be a hydrogen atom or an alkali metal under alkaline conditions. [Chemical 2] In the formula, P and Q are N or CR ₄ (R ₄ represents a hydrogen atom and a substituted or unsubstituted alkyl group or aryl group.) R ₃ is at least one or more sulfo group, carboxy group,
It represents an alkyl group substituted with an amino group, a hydroxy group or a salt thereof, or a boron residue. When there are two or more such substituents, they may be the same or different. M ₁ represents a hydrogen atom, an alkali metal atom, a quaternary ammonium, or a group in which M can be a hydrogen atom or an alkali metal under alkaline conditions. 2. A developer for a silver halide photographic light-sensitive material, containing a compound represented by the general formula (1) and a compound represented by the general formula (2). 3. A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a silver halide emulsion layer provided on a support is represented by the compound represented by the general formula (1) and the general formula (2). The method for processing a silver halide photographic light-sensitive material, which comprises performing development processing in the presence of the compound described above. 4. The developer for a silver halide photographic light-sensitive material according to claim 2, wherein the developer contains reductones. 5. The method of processing a silver halide photographic light-sensitive material according to claim 3, wherein the developer contains reductones. 6. The developing solution for silver halide photographic light-sensitive materials according to claim 2, wherein the developing solution contains substantially no dihydroxybenzenes. 7. The method of processing a silver halide photographic light-sensitive material according to claim 3, wherein the developing solution contains substantially no dihydroxybenzenes. 8. A solid developer for a silver halide photographic light-sensitive material, containing a compound represented by the general formula (1) and a compound represented by the general formula (2). 9. The developer is prepared by dissolving the solid developer according to claim 8.
The developer for a silver halide photographic light-sensitive material as described above. 10. The method for processing a silver halide photographic light-sensitive material according to claim 3, 5 or 7, wherein a developing solution is prepared by dissolving the solid developer according to claim 8.