JP2939674B2 - Processing agents for silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solid processing agent for a silver halide photographic light-sensitive material.

[0002]

BACKGROUND OF THE INVENTION Conventionally, processing agents for silver halide photographic light-sensitive materials are classified into a liquid type and a powder type. However, in the case of a liquid type processing agent, since it is stored in a thick liquid state, it can be used over time. In some cases, the activity of the treating agent changes depending on storage conditions and the like, so that it takes time and effort to dissolve in water at the time of use in 2-3 liquids. In the case of powder, the stability in the storage state is better than that of liquid, but the conventional powder type has poor solubility at the time of liquid preparation, and the temperature is increased and stirring is required, which is troublesome. there were. Therefore, there is a demand for a form of a processing agent which can be easily prepared and can provide stable photographic performance.

In the case of adding an organic compound that is hardly soluble in water to a treating agent, conventionally, the organic compound was once dissolved in a solvent and then added to the treating solution. For this reason, it was difficult to solidify the treating agent containing such an organic compound.

Further, in a silver halide photographic light-sensitive material using a tetrazolium compound or a hydrazine derivative, which is generally used as a high contrast agent in a printing plate-making light-sensitive material, the sensitivity may fluctuate when running with a conventional processing agent. However, there is a problem that fog increases.

[0005]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to solidify a processing agent for a silver halide photographic light-sensitive material, to enhance the stability of the processing agent, and to simplify the preparation during use.
It is still another object of the present invention to provide a processing agent for a silver halide photographic light-sensitive material which has a small fluctuation in performance even when a light-sensitive material containing a tetrazolium compound, a hydrazine derivative or the like is processed.

[0006]

The object of the present invention is to provide a processing agent for a silver halide photographic light-sensitive material, characterized in that at least one organic compound is dissolved in a solvent and at least one kind of capsule containing a liquid built-in substance is contained. Achieved. Preferably, the capsule is made of an alkali-soluble substance.

The present invention is preferably applied to a silver halide photographic light-sensitive material containing a tetrazolium compound or a hydrazine derivative in order to improve the stability of running performance of such a light-sensitive material.

Hereinafter, the present invention will be described specifically.

[0009] The capsule used in the present invention can be prepared by a known method.

For example, US Pat. Nos. 2,800,457 and 2,800,4
No. 58, No. 3,111,407, No. 3,287,154, No. 3,418,250
No. 3,660,304, 3,796,696, 3,914,511,
No. 4,001,140, No. 4,087,376, No. 4,089,802, No. 4,0
25,455, UK Patents 990,443, 952,807, 965,07
No. 4, No. 930, 422, No. 36-9168, No. 38-19574,
Nos. 42-446 and 42-771 and JP-A-51-9079. Specifically, phase separation method, drying method in liquid, melting dispersion cooling method, spray drying method, pan coating method, air suspension coating method, powder bed method, interfacial polymerization method, in situ polymerization method, curing coating in liquid And an interfacial reaction method.

Various resins can be used as a material constituting the capsule shell. For example, polyamide resin, polyester resin, polyurea resin, polyacrylic acid resin, polymethacrylic acid resin, polyurethane resin, aminoaldehyde resin, epoxy resin, novolak resin, composite resin,
Gelatin, starch and the like.

The capsule of the present invention is preferably water-soluble or alkali-soluble as a solid processing agent. As the alkali-soluble group, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a sulfate group and the like are preferable, and it is preferable to introduce these alkali-soluble groups into the resin. Although the solvent of these resins is not particularly limited, polyhydric alcohol, methylene chloride, chloroform, diethyl ether, hexane, benzene, ethyl acetate and a mixture thereof are preferable, and the viscosity of the solution is 10 to 500 cps (25 ° C.). preferable.

The organic compound of the present invention includes all of photographic additives and processing additives.

The solvent for dissolving the organic compound is not particularly restricted but includes, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols, methanol, ethanol, acetone, ether, dimethylformamide and the like.

The solid of the solid processing agent used in the present invention refers to a general solid, and includes powders, granules, tablets,
It contains a paste or the like, and may be a mixture thereof.

Next, the method for dissolving the solid processing agent of the present invention may be manual or mechanical, as in the case of the ordinary liquid preparation method. It may be. As a method of supplying the treating agent,
Except for the capsules of the present invention, any form may be used as long as each component of the treatment agent does not scatter.For example, a method in which a solid treatment agent is wrapped in a water-soluble polymer film and charged as it is, or a paper surface-treated with a material such as polyethylene. There is a method of packaging, preventing scattering and residue of powder, and adding the powder to a tank. In consideration of the solubility of the treating agent in water, the solid form is preferably granules or tablets, but in order to form granules or tablets, it is preferable to use commonly used granulating auxiliaries, and Alternatively, an alkali or acid soluble polymer is used. Specifically, gelatin, pectin, polyacrylic acid, polyacrylate, polyvinyl alcohol, polyvinylpyrrolidone, vinyl acetate copolymer, polyethylene oxide, sodium carboxymethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, alginate, chitanic acid Gum, gum arabic, tragacanth gum,
Karaya gum, carrageenan, methyl vinyl ether, maleic anhydride copolymer, polyoxyethylene alkyl ether such as polyoxyethylene ethyl ether and polyoxyethylene stearyl ether, polyoxyethylene alkyl phenol such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether Ethers or one or more water-soluble binders described in Japanese Patent Application No. 2-203165 can be used in combination.

Further, in order to increase the preservability of the treatment agent in the kit, the treatment agent may be enclosed in two or more types in the kit.

The combination of a dihydroxybenzene chain and 1-phenyl-3-pyrazolidones is most preferred as the developing agent used in the developer used in the present invention, since good performance is easily obtained. Needless to say, a p-aminophenol-based developing agent may also be contained.

The dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone,
Bromohydroquinone, isopropylhydroquinone,
Methylhydroquinone, 2,3-dichlorohydroquinone,
There are 2,5-dichlorohydroquinone, 2,3-dipromhydroquinone, 2,5-dimethylhydroquinone and the like, with hydroquinone being particularly preferred.

The developing agent of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention is 1-phenyl-4,4-
Examples include dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone.

The p-aminophenol developing agents used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxy Phenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol, etc., among which N-methyl-p-aminophenol is preferred.

The developing agent is usually 0.01 mol / l to 1.2 mol / l.
Preferably it is used in an amount of 1.

As the sulfite preservative used in the present invention, sodium sulfite, potassium sulfite, lithium sulfite,
Examples include ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. The amount of sulfite is preferably 0.2 mol / 1 or more and 0.4 mol / 1 or more. The upper limit is preferably up to 2.5 mol / 1.

The pH of the developer used in the present invention is preferably in the range of 9 to 13. More preferably, the pH is in the range of 10 to 12. Alkaline agents used for setting the pH include pH adjusters such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate tribasic, and potassium phosphate tribasic.

JP-A-61-28708 (borate), JP-A-60-28708
No. -93439 (for example, saccharose, acetoxime, 5-
Buffering agents such as sulfosulfylic acid), phosphates and carbonates may be used.

Additives other than the above-mentioned components include development inhibitors such as sodium bromide, potassium bromide and potassium iodide; further, if necessary, a color tone agent, a surfactant,
It may contain a fire fighting agent, a water softener, an amino compound described in JP-A-56-106244, and the like.

In the present invention, a silver stain inhibitor is added to the developer.
For example, compounds described in JP-A-56-24347 can be used. Amino compounds such as alkanolamines described in JP-A-56-106244 can be used in the developer of the present invention.

In addition, L. F. A. Meson, "Photographic Processing Chemistry", Focal,
Press (1966) pages 226-229, U.S. Patent No. 2,193,01
Nos. 5, 2,592, 364 and JP-A-48-64933 may be used.

The fixing solution is an aqueous solution containing thiosulfate,
It has a pH of 3.8 or more, preferably 4.5 to 5.5.

As the fixing agent, there are sodium thiosulfate and ammonium thiosulfate, and thiosulfate ion and ammonium ion are essential components. Ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed.

The amount of the fixing agent to be used can be appropriately changed.
Generally, it is about 0.1 to about 6 mol / 1.

The fixing solution may contain a water-soluble aluminum salt acting as a hardener, and examples thereof include aluminum chloride, ammonium sulfate, potassium alum and the like.

Tartaric acid, citric acid or their conductors can be used alone or in combination of two or more in the fixing solution. It is effective to use 0.005 mol or more of these compounds per fixing solution 11, particularly 0.01 mol / l to 0.03 mol / l.
1 is valid.

Specifically, there are tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate, ammonium citrate and the like.

If necessary, a preservative (for example, sulfite or bisulfite), a pH buffer (for example, acetic acid or nitric acid), a pH adjuster (for example, sulfuric acid), a chelating agent having a water softening ability, Compounds described in Japanese Patent Application No. 60-213562 can be included.

Next, the tetrazolium compound that can be used in the present invention will be described.

The tetrazolium compound has the following general formula [T]
Can be indicated by

[0038]

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In the present invention, the substituents R ₁ , R ₂ and R ₃ of the phenyl group of the triphenyltetrazolium compound represented by the general formula [T] are hydrogen atoms or Hammett's sigma value (σP ) Are preferably negative or positive. Particularly, a negative one is preferable.

Hammett's sigma values for phenyl substitution are described in many publications, for example, Journal of Medical Chemistry, Volume 20,
As can be seen in the report of C. Hansch et al., P. 304, 1977, a particularly preferred group having a negative sigma value is, for example, a methyl group (σP = −0.17 or less). σP value), ethyl group (-0.15), cyclopropyl group (-
0.21), n-propyl group (-0.13), iso-propyl group (-0.1
5), cyclobutyl group (-0.15), n-butyl group (-0.16), is
o-butyl group (-0.20), n-pentyl group (-0.15), cyclohexyl group (-0.22), amino group (-0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group ( -
0.27), ethoxy group (-0.24), propoxy group (-0.25),
Butoxy group (-0.32), pentoxy group (-0.34) and the like.

Specific examples of the compound of the general formula [T] used in the present invention include, for example, JP-A-2-226143, pages (8) to (8).
(9) IV-1 to IV-18 described on page 9, but the compound of the present invention is not limited thereto. The following are representative examples.

[0042]

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Next, the structure of the hydrazine derivative used in the present invention is preferably represented by the following general formula [H].

[0044]

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In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and G represents-
[C (O)] _n -group, sulfonyl group, sulfoxy group,-
A represents a P (O) (R)-group or an iminomethylene group, n represents an integer of 1 or 2, and both A ₁ and A ₂ are a hydrogen atom or one of them is a hydrogen atom and the other is a substituted or unsubstituted alkyl. Represents a sulfonyl group, or a substituted or unsubstituted acyl group, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group,
It represents an oxycarbonyl group or -O-R ₃ group, R ₃ represents an alkyl group or a saturated heterocyclic group.

Further, the following general formulas [A] and [B] are preferable.

[0047]

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In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and n represents an integer of 1 or 2. When n = 1, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, Or, it represents a heterocyclic oxy group, and R ₁ and R ₂ may form a ring together with a nitrogen atom. When n = 2, R ₁
And R ₂ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group. Represents a group. However, when n = 2, at least one of R ₁ and R ₂ is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group. Represents a group. R ₃ represents an alkynyl group or a saturated heterocyclic group.

The compound represented by the general formula [A] or [B] includes a compound in which at least one H of -NHNH- in the formula is substituted with a substituent.

The details of A, R ₁ and R ₂ are the same as those described in Japanese Patent Application No. 2-222638.

In the general formulas [A] and [B], H of -NHNH-, that is, the hydrogen atom of hydrazine is a sulfonyl group (eg, methanesulfonyl, toluenesulfonyl, etc.), an acyl group (eg, acetyl, trifluoroacetyl, The compound represented by the general formulas [A] and [B] may be substituted with a substituent such as ethoxycarbonyl or the like, or an oxalyl group (for example, ethoxylyl or pyruvoyl).

More preferable compounds in the present invention are a compound of the general formula [A] when n = 2 and a compound of the general formula [B]
Is a compound of

In the compound of the formula (A) where n = 2,
R ₁ and R ₂ are a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group or an alkoxy group, and R ₁ and R ₂
At least one of which is an alkenyl group, an alkynyl group,
Compounds representing a saturated heterocyclic group, a hydroxy group or an alkoxy group are more preferred.

Representative compounds represented by the above general formulas [A] and [B] are exemplified by compounds (I-1) to (I-I) described in JP-A-2-120852, pp. 3-6. 59), Japanese Patent Application No. 2-222638
Nos. H-1 to H-130 on pages 20 to 44, and the following. However, needless to say, specific compounds of the general formulas [A] and [B] that can be used in the present invention are not limited to these compounds.

Specific examples of compounds

[0056]

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The silver halide used in the silver halide photographic light-sensitive material according to the present invention should contain silver chloride, silver chlorobromide, silver chloroiodobromide, etc. of any composition and contain at least 50 mol% of silver chloride. Is preferred. The average grain size of the silver halide grains is 0.
A range of 025 to 0.5 μm is preferably used, but 0.05
~ 0.30 µm is more preferred.

The silver halide grains according to the present invention are preferably prepared so that the value of the monodispersity thereof is 5 to 60, more preferably 8 to 30. The grain size of the silver halide grains according to the invention is conveniently represented by the ridge length of the cubic grains, and the monodispersity is represented by a value obtained by multiplying the standard deviation of the grain size by the average grain size by 100.

As the silver halide that can be used in the present invention, a silver halide having a multilayer structure of at least two layers can be preferably used. For example, silver chlorobromide particles having silver chloride in the core, silver bromide in the shell, silver bromide in the core and silver chloride in the shell may be used. At this time, iodine can be contained in any layer within 5% mol.

Further, at least two kinds of particles can be used as a mixture. For example, the main grains are cubic, octahedral or tabular silver chloroiodobromide grains containing 10 mol% or less of silver chloride and 5 mol% or less of iodine, and the secondary grains are iodine 5 or less.
The mixed grains can be cubic, octahedral or tabular silver chloroiodobromide grains containing not more than 50 mol% of silver chloride and not less than 50 mol%. When mixing and using particles like this,
The chemical sensitization of the primary and secondary grains is optional, but the secondary grains may have lower sensitivity by reducing chemical sensitization (sulfur sensitization or gold sensitization) than the primary grains, The sensitivity may be reduced by adjusting the amount of a noble metal such as rhodium to be doped. Also, the inside of the sub-particles may be fogged with gold,
The composition of the core and the shell may be changed and fogged by the core / shell method. The primary particles and the secondary particles are preferably as small as possible, but may have any value of, for example, 0.025 μm to 1.0 μm.

At the time of preparing the silver halide emulsion used in the present invention, a rhodium salt can be added to control the sensitivity or gradation. In general, the rhodium salt is preferably added at the time of grain formation, but may be added at the time of chemical ripening or at the time of preparing an emulsion coating solution.

The rhodium salt added to the silver halide emulsion used in the present invention may be a simple salt or a double salt. Typically, rhodium chloride, rhodium trichloride, rhodium ammonium chloride and the like are used.

The addition amount of the rhodium salt depends on the required sensitivity,
Although it can be freely changed depending on the gradation, the range of 10 ^-9 mol to 10 ^-4 mol per mol of silver is particularly useful.

When a rhodium salt is used, other inorganic compounds such as iridium salt, platinum salt, thallium salt, cobalt salt, gold salt and the like may be used in combination. Iridium salts are often used for the purpose of improving high-light properties, with 10 ^-9 per mole of silver.
It can be preferably used in the range of from mol to 10 ^-4 mol.

The silver halide used in the present invention can be sensitized by various chemical sensitizers. Examples of sensitizers include active gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiocyanate, etc.), selenium sensitizers (N, N-dimethylselenourea, selenoureas, etc.), Reduction sensitizers (triethylenetetramine, stannous chloride, etc.) such as potassium chloroaulite, potassium aurithiocyanate, potassium chloroaurate, 2-aurosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroplatinate, Various noble metal sensitizers represented by sodium chloroparadite and the like can be used alone or in combination of two or more. When a gold sensitizer is used, rhodamonmon can be used as an auxiliary agent.

The silver halide emulsions used in the present invention are described, for example, in US Pat. Nos. 3,567,456, 3,615,639,
579,345, 3,615,608, 3,598,596, 3,598,955,
3,592,653, 3,582,343, JP-B40-26751, 40-273
Desensitizing dyes and / or ultraviolet absorbers described in the specifications such as Nos. 32, 43-13167, 45-8833, and 47-8746 can be used.

Further, the silver halide emulsions used in the present invention include, for example, US Pat. Nos. 2,444,607, 2,716,062, 3,512,982, West German Application Publication No. 1,189,380, and US Pat. 2,058,626, 2,118,411
No., Japanese Patent Publication No. 43-4133, U.S. Pat.
No. 47-4417, West German Application Publication No. 2,149,789, Japanese Patent Publication No. 39-2
No. 825, compounds described in JP-B-49-13566, etc.,
Preferably, for example, 5,6-trimethylene-7-hydroxyn-
S-triazolo (1,5-a) pyrimidine, 5,6-tetramethylene-7-hydroxy-S-triazolo (1,5-a) pyrimidine, 5-
Methyl-7-hydroxy-S-triazolo (1,5-a) pyrimidine, 5-methyl-7-hydroxy-S-triazolo (1,5-a) pyrimidine, 7-hydroxyne-S-triazolone (1,5 -a) pyrimidine, 5-methyl-6-bromo-7-hydroxy-S-triazolo
(1,5-a) pyrimidine, gallate (e.g. isoamyl gallate, dodecyl gallate, propyl gallate,
Sodium gallate), mercaptans (1-phenyl-5-
It can be stabilized using mercaptotetrazole, 2-mercaptobenzthiazole), benzotriazoles (5-bromobenztriazole, 5-methylbenztriazole), benzimidazoles (6-nitrobenzimidazole) and the like.

The silver halide photographic light-sensitive material and / or the developer according to the present invention preferably contain an amino compound.

The amino compound preferably used in the present invention includes all primary to quaternary amines. Preferred examples of amino compounds include alkanolamines.

Preferred specific examples are listed below, but the present invention is not limited to these.

Diethylaminoethanol diethylaminobutanol diethylaminopropane-1,2-diol dimethylaminopropane-1,2-diol diethanolamine diethylamino-1-propanol triethanolamine dipropylaminopropane-1,2-diol dioctylamino-1-ethanol dioctyl Aminopropane-1,2-diol dodecylaminopropane-1,2-diol dodecylamino-1-propanol dodecylamino-1-ethanol aminopropane-1,2-diol diethylamino-2-propanol dipropanolamine glycine triethylamine triethylenediamine amino The compound is contained in at least one of the coating layers on the photosensitive layer side of the silver halide photographic material (for example, a silver halide emulsion layer, a protective layer, a hydrophilic colloid layer of an undercoat layer) and / or a developer. A preferred embodiment is an embodiment in which it is contained in a developer. Although the content of the amino compound varies depending on the object to be contained, the type of the amino compound, and the like, a contrast promoting amount is required.

In order to enhance the developability, a developing agent such as phenidone or hydroquinone and an inhibitor such as benzotriazole can be contained in the emulsion. Alternatively, in order to increase the processing ability of the processing solution, the backing layer may contain a developing agent or an inhibitor.

The hydrophilic colloid particularly preferably used in the present invention is gelatin. Examples of the hydrophilic colloid other than gelatin include colloidal albumin, agar, acacia, alginic acid, hydrolyzed cellulose acetate, acrylamide, and the like. Imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, gelatin derivatives, for example, U.S. Pat.No. 2,614,928,
Phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin, as described in the same 2,525,753,
Alternatively, a polymerizable monomer having an ethylene group such as styrene acrylate, acrylate, methacrylic acid, or methacrylic acid ester, as described in U.S. Pat.Nos. 2,548,520 and 2,831,767, graft-polymerized on gelatin. These hydrophilic colloids can be applied to a layer containing no silver halide, such as an antihalation layer, a protective layer, and an intermediate layer.

Examples of the support used in the present invention include polyester film such as baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate such as polyethylene terephthalate, polyamide film, polypropylene film, and polycarbonate film. , Polystyrene films and the like are included as typical examples. These supports are appropriately selected depending on the purpose of use of the silver halide photographic light-sensitive material.

[0075]

EXAMPLES The effects of the present invention will now be illustrated by examples.

Example 1 (Preparation of Capsule Internal Liquid) As shown in Table 1, the following solvents were used as organic compounds in each solvent: 5-nitroindazole, 5-methylbenztriazole, 2-mercaptobenzothiazole, 5-nitrobenzimidazole, -Phenyl-5-mercaptotetrazole was respectively dissolved to give a capsule internal liquid.

(Preparation of Capsule) As shown in Table 1, each resin was used as a shell of the capsule and ethyl acetate: chloroform = 1:
One solution was dissolved in 100 cc, and the above internal solution was added by a submerged drying method, followed by stirring with a homoblender and then 600 ml of 4% Tween20.
% Aqueous solution, and the mixture was stirred for 30 minutes with a homoblender to evaporate the solvent, thereby preparing capsules.

The average particle size was 3.5 mm.

The following comparative developer D-1 and the present developer D-
2 were each granulated by a compression granulation method to a particle size of about 2.5 mm to obtain a solid processing agent.

(Preparation of Comparative Developer D-1) Polyethylene glycol (Mw 600) 1.3 g 5-nitroindazole 0.06 g phenidone 0.5 g hydroquinone 15 g 1-phenyl-5-mercaptotetrazole 0.02 g 5-methylbenzotriazole 0.16 g bromide Potassium 4.5 g Sodium carbonate 9.3 g Caustic soda 7.4 g Sodium sulfite 18 g (Prescription of developer D-2 of the present invention) Potassium bromide 4.5 g Sodium carbonate 9.3 g Caustic soda 7.4 g Sodium sulfite 18 g Hydroquinone 15 g Phenidone 0.5 g Made with

A capsule for 0.06 g of 5-nitroindazole and a capsule for 0.02 g of 1-phenyl-5-mercaptotetrazole A capsule for 0.16 g of 5-methylbenzotriazole was added to obtain a D-2 developer.

However, the capsules shown in Table 1 were used for 5-nitroindazole, 1-phenyl-5-mercaptotetrazole and 5-methylbenzotriazole used in D-2.

The time required for dissolving D-1 and D-2 in 1 liter of water at 25 ° C. was measured.

Table 2 shows the results. The number of each capsule in Table 2 indicates the No. of Table 1.

[0085]

[Table 1]

[0086]

[Table 2]

From the results in Table 2, it was found that D of the capsule of the present invention was
It can be seen that the dissolution time was shorter in the case of the formulation of the D-2 developer than in the formulation of the comparative D-1.

Example 2 (Preparation of Emulsion Samples Em-1 and Em-2) An average grain size containing ^10-5 mol of a rhodium salt per mol of silver by a controlled double jet method under an acidic atmosphere of pH 3.0. 0.20
μm, silver halide composition monodispersity 20, silver bromide 2 mol%
A silver chlorobromide particle containing was prepared. The particles were grown in a system containing 30 mg of benzyladenine per liter of 1% aqueous gelatin solution. After mixing silver and halide, 6-methyl-4-hydroxy-1,3,3a, 7 tetrazaindene is added to silver halide 1
600 mg was added per mole, and then washed with water and desalted. Next, sodium thiosulfate was added to sensitize sulfur.

Additives were prepared and added to the obtained emulsion in the following amounts, and coated on the subbed polyethylene terephthalate support used in Example 1.

Latex polymer: styrene-butyl acrylate acrylic acid terpolymer 1.0 g / m ² phenol 1 mg / m ² saponin 200 mg / m ² sodium dodecylbenzenesulfonate tetrazolium compound ☆ Compound (N) shown below 40 mg / m ² compound (O) 50 mg / m ² Styrene-maleic acid copolymer 20 mg / m ² Alkali-treated gelatin (isoelectric point 4.9) 2.0 g / m ² Silver amount 3.5 g / m ² Formalin 10 mg / m ²

[0091]

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☆ Tetrazolium compound T-2 50m
The sample in the case of g / m ² was Em-1 T-3 and the sample in the case of 40 mg / m ² was Em-2.

The coating solution was previously sodium hydroxide
It was applied after adjusting the pH to 6.5. As an emulsion protective film, an additive was prepared so as to have the following amount, and was simultaneously coated with an emulsion coating solution.

(Protective film layer) Fluorinated dioctyl sulfosuccinate 100 mg / m ² Dioctyl sulfosuccinate 100 mg / m ² Matting agent: amorphous silica 50 mg / m ² Compound (O) 30 mg / m ² 5-methylbenzotriazole 20 mg / m ² compound (P) 500 mg / m ² propyl gallate ester 300 mg / m ² styrene - maleic acid copolymer 100 mg / m ² alkali-treated gelatin (isoelectric point 4.9) 1.0 g / m ² formalin 10 mg / m ² still After the pH was adjusted to 5.4 with citric acid in advance, it was applied.

[0095]

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Next, a backing layer was provided on the support opposite to the emulsion layer in exactly the same manner as in Example 2 of JP-A-2-226143. Thus, the photosensitive material samples Em-1, Em-
2 was prepared.

<Preparation of Samples Em-3 and Em-4> (Emulsion) According to the method described in Example 2, silver chlorobromide particles having an average particle size of 0.11 μm, a monodispersity of 15, and 5 mol% of silver bromide were used. Prepared,
After treatment, washing and desalting, sulfur sensitization was performed in the same manner as in Example 2.

Next, 60 mg of silver halide per mole was used.
After adding 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene, 15 mg of sodium thiosulfate was added per 1 mol of silver halide, and sulfur sensitization was performed at 60 ° C. After sulfur sensitization, 600 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer per mole of silver halide.

Additives were added to the resulting emulsions in the following amounts, and the resulting emulsions were coated on a subbing layer of a 100 μm-thick polyethylene terephthalate support coated with a conductive layer.

Latex polymer: styrene-butyl acrylate-acrylic acid terpolymer 1.0 g / m ² tetraphenylphosphonium chloride 30 mg / m ² saponin 200 mg / m ² polyethylene glycol 100 mg / m ² hydroquinone 200 mg / m ² styrene-male Acid copolymer 20 mg / m ² hydrazine compound ☆ 5-methylbenzotriazole shown below 30 mg / m ² Desensitizing dye (M) 20 mg / m ² Alkali-treated gelatin (isoelectric point 4.9) 1.5 g / m ² bis (vinyl Sulfonylmethyl) ether 15 mg / m ² Silver amount 2.8 g / m ² ☆ The hydrazine compound was added to Em-3H-1 50 mg / m ² Em-4H-2 80 mg / m ² .

[0101]

Embedded image

(Emulsion Protective Film) An emulsion layer protective film was prepared so as to have the following coating weight, and was simultaneously coated with the emulsion.

Fluorinated dioctylsulfosuccinate 200 mg / m ² Sodium dodecylbenzenesulfonate 100 mg / m ² Matting agent: polymethyl methacrylate (average particle size 3.5 μm) 100 mg / m ² Lithium nitrate 30 mg / m ² Propyl gallate Ester 300mg / m ² 2-Mercaptobenzimidazole-5-sodium sulfonate 30mg / m ² Alkaline-treated gelatin (isoelectric point 4.9) 1.3g / m ² Colloidal silica 30mg / m ² Styrene-maleic acid copolymer 100mg / m The support on the opposite side of the ² bis (vinylsulfonylmethyl) ether 15 mg / m ² emulsion layer is the same as Em-2.

In this way, the photosensitive material samples Em-3, Em
-4 was prepared.

(Preparation of solidified fixing solution F-1) Solidification was carried out in the same manner as in the case of the developing solution.

(1) 4.2 g of water 135 g of ammonium thiosulfate 5.0 g of sodium sulfite were solidified.

(2) Polyethylene glycol (MW 600) 2.6 g Boric acid 6.7 g Potassium alum 20 g Citric acid 16 g Sodium citrate 45 g was solidified.

The fixing solution F-1 was prepared by dissolving (1) and (2) in 1 liter of water.

(Preparation of Solidified Developer D-3) Polyethylene glycol (MW 600) 2 g Trisodium phosphate (12-hydrate) 26.1 g Hydroquinone 19.2 g Potassium bromide 1.2 g Sodium phosphate 15.6 g N, N- Diethanolamine 5.5ml Ethylenediaminetetraacetic acid disodium salt 1g Sodium pyrosulfite 63.5g Sodium chloride 2.4g Sodium hydroxide 33.8g Capsule No.12 (addition amount 0.19g) Capsule No.24 (addition amount 0.025g) It was dissolved in 1 liter of water.

(Preparation of Developer D-4) 0.19 g of 5-methylbenzothiazole instead of Capsule No. 12 in the above D-3 formulation 0.025 g of 2-mercaptobenzothiazole instead of Capsule No. 24 and 1 liter of water Was dissolved.

The dissolution rate was higher than that of D-4 in the solidified developer D.
-3 was faster.

The light-sensitive material samples Em-1 and Em-2 were exposed by a conventional method, and were exposed to 28 ° C.,
Treated for 0 seconds. The fixing solution used was F-1.

As a result, there was no difference in performance between the developing solutions D-1 and D-2, and the same sensitivity and fog were obtained.

Further, photosensitive material samples Em-3 and Em-
4 was exposed by a conventional method, and treated with D-3 and D-4 at 34 ° C. for 30 seconds. The fixing solution used was F-1.

As a result, there was no difference in performance between the developing solutions D-3 and D-4, and the developing solutions D-3 and D-4 had the same sensitivity and fog.

As described above, those using capsules have the same photographic performance as conventional processing agents, and have excellent solubility.

The conventional product was prepared by dissolving the substance contained in the capsule and the other components separately using a treating agent of D-2, forming a concentrated solution, preparing the concentrate at the time of use, and diluting with water.
By using 21 to 23, one concentrated solution can be prepared.

Example 3 E containing tetrazolium compound or hydrazine derivative
m Sample Nos. 1, 2, 3, and 4 were converted into 1
000 sheets were processed in the same manner as in Example 3, and the sensitivity of
The fluctuation when 0 and fog were set to 0 was measured. The replenishment rate of the processing solution was 100 ml per large piece. Each comparative developing solution did not contain a capsule, and a concentrated solution was prepared by mixing the internal components of the capsule like a conventional developing solution, and diluted with water at the time of use.

[0119]

[Table 3]

From the results shown in Table 3, when the photosensitive material containing a tetrazolium compound or a hydrazine derivative was treated with the capsule-containing developer of the present invention, the sensitivity and fogging performance were more stable in running processing than in the conventional method. You can see that.

[0121]

According to the present invention, a processing agent for a silver halide photographic light-sensitive material is solidified, the stability of the processing agent is increased, the preparation during use is simplified, and a tetrazolium compound, a hydrazine derivative and the like are further contained. Thus, a processing agent for a silver halide photographic light-sensitive material having little fluctuation in performance even when the light-sensitive material is processed was provided.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 5/26 520 G03C 5/26 510

Claims (3)

(57) [Claims] 1. A processing agent for a silver halide photographic light-sensitive material, comprising at least one kind of capsule containing at least one organic compound dissolved in a solvent and containing a liquid built-in substance. 2. The processing agent for a silver halide photographic light-sensitive material according to claim 1, wherein the capsule is an alkali-soluble substance. 3. The processing agent for a silver halide photographic material according to claim 1, wherein a silver halide photographic material containing at least one tetrazolium compound or hydrazine derivative is processed.