JP3038418B2 - Solid 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 (hereinafter sometimes referred to as a photographic processing agent).
More specifically, the present invention relates to a solid processing agent for a silver halide photographic light-sensitive material having a fixing ability, which prevents scattering of fine particles of a photographic processing agent, has no workability of a plastic bottle, has a work environment suitability and a social environment suitability. Things.

[0002]

BACKGROUND OF THE INVENTION Processing solutions such as black-and-white developing solution, fixing solution, color developing solution, bleaching solution, bleach-fixing solution, and stabilizing solution used in silver halide photographic light-sensitive materials are one for ease of use. Alternatively, it is placed in a plastic bottle in the form of a plurality of concentrated liquid parts and supplied to the user as a treatment agent kit. Users dissolve these treatment agent kits in water to prepare and use working solutions (starting solutions or replenishing solutions).

[0003] In recent years, in the photographic processing industry, the number of small-scale developing laboratories using a small automatic developing machine called a minilab has been rapidly increasing, and with the progress of minilabs, the amount of plastic bottles for processing agents has been increasing year by year. It is increasing rapidly.

[0004] Because of its light and strong properties, this plastic has been widely used in addition to photographic processing agent bottles. The worldwide production of plastics is steadily increasing year by year, to over 100 million tons per year in 1988. On the other hand, the amount of plastic that is discarded is enormous, and even in Japan, about 40% of the production is discarded every year. When such waste plastic is dumped into the ocean, it causes deterioration of the habitat of marine organisms. In Europe, the waste plastic is burned in incinerators with inadequate exhaust gas treatment facilities. The problem has been caused, and it has become a big problem.

[0005] For this reason, urgent countermeasures are urgently required. In Europe and the United States, legislative movements such as prohibition of plastic recycling and use or mandatory use of degradable plastics are becoming active. It is a fact.

[0006] Under such circumstances, it is extremely undesirable to use a large amount of plastic bottles as a processing agent for photographic use, albeit partially.

Therefore, it is conceivable to make a concentrated solution of a photographic processing agent into a powder. However, there is a drawback in that storage over time causes deterioration in solubility due to caking (agglomeration) and fatigue coloring due to moisture, oxygen and the like. Also, there is a high possibility that fine powder will rise when dissolved and workers will inhale it, causing a problem that the effect on health may be affected, or the sowing processing agent component may be mixed into another photographic processing solution. This causes a problem of contamination and trouble. For this reason, the technology of granulating a photographic processing agent to form a granular mixture, for example, JP-A-2-09042, JP-A-2-09043,
It has been proposed in U.S. Pat. The problem of the caking phenomenon of coagulation, coating of the powder with its own wet coating, and disturbing the dispensing workability due to poor dissolution, etc. recurs, and the range of drugs suitable for powdering and granulating is extremely restricted. That is the fact.

[0008] Therefore, as a preferred form of the treatment agent taking advantage of these advantages of the dry state, tableting is disclosed in JP-A-51-61837.
And Canadian Patent No. 831,928.

Against this background, granular fixing agents containing thiosulfate have been proposed in JP-A-3-39735 and JP-A-3-39739.

[0010] Although these have less dust and improved solubility in water as compared with the conventional powdery fixing agent, the fixing solution prepared using the stored fixing agent can be sulfurized in a short time, or can be color-sensitized. When the material is developed, defects in photographic performance tend to occur, such as a decrease in image color density due to poor recoloring and an increase in residual silver in unexposed areas.

These two points are very important in terms of photographic performance, and if these occur, they are so fatal that a product cannot be produced at all. Therefore, the solution of these problems became urgent.

As a result of intensive studies, the present inventors have found that the above problem is related to the ratio of ammonium cation to total cation in the photographic processing agent, and have accomplished the present invention.

Further, as another effect, the friability of the tablet is improved, the fine powder is not scattered, and the work environment suitability is improved. This effect was surprising, as it was completely unpredictable from previous findings.

[0014]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a solid processing agent for a silver halide photographic light-sensitive material having a fixing ability and having the following features.

[0015] The use of packaging materials (especially plastic bottles) is reduced, and it is suitable for social environment.

[0016] The solidification of the processing agent reduces the weight, reduces the transportation cost, and requires less storage space in a developing facility or the like.

The storage stability is improved, and there is no deterioration due to sulfuration and no reduction in image color density during development.

There is no scattering of the fine powder of the photographic processing agent and the work environment is suitable.

Contamination due to contamination can be prevented.

The solubility of the tablet type photographic processing agent is improved,
And tablet friability is reduced.

[0021]

An object of the present invention is to provide a solid processing agent for a silver halide photographic light-sensitive material containing at least one thiosulfate, wherein the ratio of ammonium cation to total cation in the processing agent is 20 %. Mol%
Wherein the solid processing agent is a tablet, and
It was achieved by a silver halide photographic light-sensitive material for the solid processing agent having fixing ability, characterized that you contain Ann salt.

[0022]

Hereinafter, the present invention will be described in detail.

The solid photographic processing agent of the present invention comprises tablets, granules,
Powders, lumps or pastes are used, preferably granules and tablets, most preferably tablets. Production methods for tablet processing agents are described in, for example, JP-A-51-61837,
No. 55038, No. 52-88025, and can be produced by a general method described in British Patent No. 1,213,808, and further, a granule treating agent is disclosed in, for example, Japanese Patent Application Nos. 2-09042, 2-09043, and 3-9. -3973
It can be produced by a general method described in Nos. 5 and 3-39739. Furthermore, powder processing agents are described, for example, in JP-A-54-133332.
No. 725,892, 729,862 and German Patent 3,
It can be produced by a general method as described in, for example, 733,861.

The bulk density of the solid processing agent of the present invention, and in view of its solubility, from the viewpoint of the effect of the object of the present invention, granules of the field
In this case, 0.5 to 0.95 g / cm ³ , and in the case of tablets, 1.1 to 2.5 g / cm ³ are preferably used.

In the present invention, thiosulfates and thiocyanates are used as the main fixing agent used in the solid photographic processing agent having fixing ability. The content of the thiocyanate is preferably at least 0.1 mol / l or more, and more preferably 0.5 mol / l or more, and particularly preferably 1.0 mol / l or more when a color negative film is processed. or,
The thiosulfate content is preferably at least 0.2 mol / l or more, and more preferably 0.5 mol / l or more when a color negative film is processed. In the present invention, the object of the present invention can be more effectively achieved by using a combination of a thiocyanate and a thiosulfate.

The solid photographic processing agent having fixing ability of the present invention may contain, alone or in combination of these fixing agents, pH buffers comprising various salts. Further, it is desirable to contain a large amount of a rehalogenating agent such as an alkali halide or an ammonium halide, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide and the like. In addition, compounds known to be added to ordinary fixing agents or bleach-fixing agents such as alkylamines and polyethylene oxides can be added as appropriate.

In the present invention, the ratio of ammonium cation to total cation in the thiosulfate-containing fixing agent was changed.

The ratio of the ammonium cation to the total cation in the fixing agent is 50 mol% to 0 mol%, preferably 20 mol% to 0 mol%, particularly preferably 10 mol% to 10 mol%.
Mol% to 0 mol%. If the ratio is more than 50 mol%, the tendency of deterioration of solubility due to caking, sulfurization of the fixing solution, lowering of the color image density during the development processing of the color photographic material, increase of residual silver in unexposed areas, etc. is remarkable.

On the other hand, when the ratio exceeds 50 mol%, the strength of the tablet type photographic processing agent is remarkably deteriorated. When the thiocyanate is used in combination, the effect of the present invention is favorably exhibited. The present invention
Combination of monium cation and sodium cation
Combination of ammonium and potassium cations
In the latter case, the effect of the present invention is favorably exhibited.
This is preferable.

The solid photographic processing agent having fixing ability according to the present invention includes a compound represented by the formula [FA] described in Japanese Patent Application No. 2-206120, page 11, and its exemplified compounds (FA-1 to FA-39).
Alternatively, it is preferable to add a compound of the following compound group [FB], which not only exerts the effects of the present invention more, but also occurs in a processing solution having a fixing ability when processing a small amount of photosensitive material over a long period of time. Another effect is that the amount of sludge to be produced is extremely small.

[0032]

Embedded image

In the formula, R ′ and R ″ are each a hydrogen atom,
Represents an alkyl group, an aryl group, an aralkyl group, or a nitrogen-containing heterocyclic group. n 'represents 2 or 3.

Preferred compounds among the exemplified compounds (FA-1 to FA39) are shown below.

[0035]

Embedded image

These compounds represented by the general formula [FA] can be synthesized by a general method as described in US Pat. No. 3,335,161 and US Pat. No. 3,260,718.

The compounds of the compound group [FB] are as follows.

FB-1 Thiourea FB-2 Thiocyanocatechol These compounds represented by the general formula [FA] and compounds of the compound group [FB] may be used alone or in combination of two or more. For example, (FB-
1) and (FA-21), (FB-1) and (FA-12),
(FA-12) and (FA-38), (FA-12) and (FA-
32), (FA-12) and (FA-21) are preferred examples. Of these, the most preferred are
(FB-1).

The amount of the compound represented by the general formula [FA] and the compound of the compound group [FB] was 1
Good results are obtained in the range of 0.1 to 300 g per liter. Especially, the range of 0.2 to 200 g is preferable, and the range of 0.5 to 150 g is particularly preferable.

In the present invention, as a color developing agent used in a color developing solution, a p-phenylenediamine-based compound having a water-soluble group exhibits the desired effects of the present invention.
In addition, it is preferably used because of less fogging.

The p-phenylenediamine compound having a water-soluble group has less contamination of the photosensitive material than a paraphenylenediamine compound having no water-soluble group, such as N, N-diethyl-p-phenylenediamine. The skin has the advantage that the skin is not easily fogged.

Examples of the water-soluble group include those having at least one on an amino group of a p-phenylenediamine compound or a benzene nucleus. Specific examples of the water-soluble group include-(C
_{H 2) nCH 2 OH, -} (CH 2) mNHSO 2 (CH 2) nCH 3, - (CH 2) mO (CH 2) n
CH ₃ , — (CH ₂ CH ₂ O) n CmH ₂ m ₊₁ (m and n each represent an integer of 0 or more), a —COOH group, a —SO ₃ H group, and the like are preferable.

Specific examples of the color developing agent preferably used in the present invention include Japanese Patent Application No. 2-203169 26-31.
(C-1) to (C-16), 4-amino
-3-methyl-N- (3-hydroxypropyl) aniline and the like.

Further, particularly preferred color developing agents include the following compounds Dev-1 to Dev-3.

[0045]

Embedded image

The above color developing agents are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate and the like.

The color developing agent may be used alone or
In combination with at least one kind, and if desired, a black and white developing agent such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl
It may be used in combination with -3-pyrazolidone or methol.

In the present invention, when the color developing solution according to the present invention contains the compounds represented by the following general formulas [A] and [B], not only can the effects of the present invention be exerted more, This is one of the preferable embodiments because the effect of reducing fog generated in the unexposed portion also occurs.

[0049]

Embedded image

In the formula, R ₁ and R ₂ each represent an alkyl group, an aryl group, an R ₃ CO— group or a hydrogen atom. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. Also, R ₁
And R ₂ may form a ring.

In the general formula [A], the alkyl groups represented by R ₁ and R ₂ may be the same or different, and each is preferably an alkyl group having 1 to 3 carbon atoms. Further, these alkyl groups may have a carboxyl group, a phosphate group, a sulfo group or a hydroxyl group. R ₃ represents an alkoxy group, an alkyl group or an aryl group. The alkyl group and the aryl group of R ₁ , R ₂ and R ₃ include those having a substituent,
Examples of the ring which may be formed by R ₁ and R ₂ include a heterocyclic ring such as piperidine, pyridine, triazine and morpholine.

[0052]

Embedded image

[0053] In the formula, each R _11, R _12, R ₁₃ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R ₁₄
Is a hydroxyl group, a hydroxyamino group, an alkyl group,
Represents an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group or an amino group. The heterocyclic group is a 5- to 6-membered ring, is composed of C, H, O, N, S and a halogen atom, and may be saturated or unsaturated. R ₁₅
Is -CO -, - SO ₂ - or -C (= NH) - represents a divalent group selected from, n is 0 or 1. In particular, when n = 0, R ₁₄
Represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R ₁₃ and R ₁₄ may together form a heterocyclic ring.
The alkyl group, aryl group and heterocyclic group represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ include those having a substituent.

Specific examples of the hydroxylamine compound represented by the general formula [A] are described in US Pat. No. 3,287,125.
3,329,034 and 3,287,124, etc.
Particularly preferred specific exemplary compounds include Japanese Patent Application No. 2-2031.
No. 69, pages 36-38 (A-1)-(A-39) and JP-A-Hei.
(1) to (53) described on pages 3 to 6 of 3-33845 and JP-A No. 3-6
No. 3646, pp. 5-7, (1)-(52).

Next, specific examples of the compound represented by the general formula [B] are described in (B-1) to (B-1) of JP-A-2-203169.
(B-33) and (1) to (4) described in JP-A-3-33846, pp. 4-6.
(56).

The compounds represented by the general formulas [A] and [B] are usually free amines, hydrochlorides, sulfates,
It is used in the form of p-toluenesulfonate, oxalate, phosphate, acetate and the like.

A hydroxylamine compound represented by the following general formula [A '] is also preferably used as a preservative in a color developing solution.

[0058]

Embedded image

In the formula, L represents an alkylene group (which may have a substituent); A represents a carboxyl group, a sulfo group, a phosphono group, a phosphino group, a hydroxyl group; It represents an ammonio group, a carbamoyl group or a sulfamoyl group, and R represents a hydrogen atom or an alkyl group (including a substituent).

Specific examples of the compound represented by the general formula [A '] include (1) to (54) described in JP-A-3-84044, page 4, lower left column to page 6, lower right column. But, among others, (1)
And the following compounds represented by (7) are preferred.

(1) HON (CH ₂ CH ₂ COOH) ₂ (7) HON (CH ₂ CH ₂ SO ₃ H) _{2 The} compound represented by the general formula [A ′] is obtained by converting a commercially available hydroxylamine into an alkyl It is obtained by a chemical reaction. For example, West German Patent 1,159,634 and Inorganica Chimica Acta., 93
(1984) pp. 101-108 and the like.

In the color developing solution used in the present invention, a trace amount of sulfite can be used as a preservative. Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like.

It is necessary to use a buffer in the color developer used in the present invention. Examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, and the like. Disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-2-hydroxy Sodium benzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (5
-Potassium sulfosalicylate) and the like.

Examples of the development accelerator include JP-B-37-16088,
No. 37-5987, No. 38-7826, No. 44-12380, No. 45-9019
And thioether compounds represented by U.S. Pat.No. 3,813,247, p-phenylenediamine compounds represented by JP-A-52-49829 and JP-A-50-15554, JP-B-44-30074.
No., JP-A-50-137726, JP-A-56-156826 and JP-A-52-43429
Quaternary ammonium salts represented by US Pat. No. 2,61
P-aminophenols described in Nos. 0,122 and 4,119,462, U.S. Pat.Nos. 2,494,903, 3,128,182, 4,230,79
No. 6, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat.
Amine compounds described in 2,546, 2,596,926 and 3,582,346, etc., JP-B-37-16088, JP-B-42-25201, U.S. Patent 3,128,183, JP-B-41-11431, JP-B-42-23883 and the United States Polyalkylene oxide represented by Patent 3,532,501, etc., other 1-phenyl-3-pyrazolidones,
Hydrazines, mesoionic compounds, ionic compounds,
Imidazoles and the like can be added as needed. Chloride ions and bromine ions may be used in the color developer for the purpose of preventing fog and the like. In the present invention,
Preferably 1.0 × 10 ^{−2 to} 1.5 × 10 ⁻¹ mol, more preferably 3.10 × 10 ⁻² mol, as chlorine ions per color developing agent dissolved in 1 liter.
Contains 5 × 10 ^{-2 to} 1.0 × 10 ^-1 mol. Chloride ion concentration is 1.
If it is more than 5 × 10 ^-1 mol / l, it is not preferable to delay development and quickly obtain a high maximum density. On the other hand, if it is less than 3.5 × 10 ^-2 mol / liter, stain is generated, and photographic performance fluctuations (particularly minimum density) due to continuous processing are undesirably large.

In the present invention, the color developing solution preferably contains bromide ions in an amount of 3.0 × 10 ^{−5 to} 1.0 × 10 ⁻³ mol / l. More preferably, it is 5.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol / liter. Particularly preferred is 1 × 10 ^{−4 to} 3 × 10 ⁻⁴ mol / l. When the bromine ion concentration is higher than 1 × 10 ⁻³ mol / l, the development is delayed, the maximum density and the sensitivity are reduced, and
If it is less than ^-5 mol / l, it is not preferable because stain is generated and photographic characteristics change (especially minimum density) due to continuous processing is caused.

When directly added to a color developing solution, sodium chloride, potassium chloride,
Ammonium chloride, nickel chloride, magnesium chloride,
Manganese chloride, calcium chloride, and cadmium chloride are mentioned, and preferred are sodium chloride and potassium chloride.

Further, it may be supplied in the form of a salt of a fluorescent whitening agent added to the color developing solution.

As a supply substance of bromine ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, Among them, thallium bromide is preferable, and potassium bromide and sodium bromide are preferable.

The color developing solution used in the present invention may optionally contain an antifoggant in addition to chloride ions and bromine ions. As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-
Includes nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine, adenine A nitrogen heterocyclic compound can be mentioned as a representative example.

The color developer used in the present invention preferably contains a triazinylstilbene-based fluorescent whitening agent from the viewpoint of whiteness. As such a fluorescent whitening agent, a compound represented by the following general formula [E] is preferable.

[0071]

Embedded image

In the above formula, X ₁ , X ₂ , Y ₁ and Y ₂ are each a hydroxyl group, a halogen atom such as chlorine or bromine,
Alkyl group, aryl group,

[0073]

Embedded image

Or OR ₂₅ . Here, R ₂₁ and R ₂₂ each represent a hydrogen atom, an alkyl group (including a substituent) or an aryl group (including a substituent), R ₂₃ and R _{24 each} represent an alkylene group (including a substituent), R ₂₅ Represents a hydrogen atom, an alkyl group (including a substituent) or an aryl group (including a substituent),
M represents a cation.

The details of each group of the general formula [E] or a substituent thereof are the same as those described in Japanese Patent Application No. 2-240400, from page 62, below, line 8 to page 64, below, line 3. And specific compounds include E-1 to E-45 described on pages 65 to 67 of the same publication. Among them, particularly preferred is E
-4, E-24, E-34, E-35, E-36, E-37, E-
41. The addition amount of these compounds is preferably in the range of 0.2 to 10 g, more preferably 0.4 to 5 g, per liter of the color developing solution.

Further, an auxiliary developer can be used together with the developing agent. As these auxiliary developers, for example,
N-methyl-p-aminophenol hexalfate (methol), phenidone, N, N-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetramethyl-p-phenylenediamine hydrochloride, etc. It is known, and the addition amount is usually preferably 0.01 to 1.0 g / liter.

Further, various additives such as a stain inhibitor, an anti-sludge agent, and a layering effect promoter can be used.

Also, in the color developing solution, Japanese Patent Application No. 2-240400 No. 69
From the bottom of the page, it is preferable to add a chelating agent represented by the following general formula [K] described on lines 9 to 75 and exemplary compounds K-1 to K-22 thereof.

[0079]

Embedded image

In the formula, E represents an alkylene group, a cycloalkylene group, a phenylene group (each of which may have a substituent), —R ₅ OR ₅ —, —R ₅ OR ₅ OR ₅ — or —R ₅ ZR _5-
R _{1 to} R ₅ represent an alkylene group (including a substituent). Z is = N-R ₅ -A ₅ or = represents NA _5, A ₁ ~A ₅ represents a hydrogen atom, a hydroxyl group, -CO ₂ M group, or -PO ₃ (M) ₂ group. M is a hydrogen atom or an alkali metal atom.

Among these chelating agents, K-2, K-
9, K-12, K-13, K-17, and K-19 are preferably used. Particularly, when K-2 and K-9 are added to a color developing solution, the effects of the present invention are more exerted.

The addition amount of these chelating agents is preferably in the range of 0.1 to 20 g, more preferably 0.2 to 8 g, per liter of the color developing solution.

Further, the color developing solution may contain anionic, cationic, amphoteric and nonionic surfactants. If necessary, various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added.

The bleaching agent of the bleaching solution used in the present invention is a ferric complex salt of an organic acid represented by the following general formula [L].

[0085]

Embedded image

In the formula, A _{1 to} A ₄ may be the same or different and represent —CH ₂ OH, —COOM or —PO ₃ M ₁ M ₂ . M,
M ₁ and M ₂ each represent a hydrogen atom, an alkali metal atom or ammonium. X represents an alkylene group having 3 to 6 carbon atoms which may be substituted.

The groups represented by A _{1 to} A ₄ are described in Japanese Patent Application No. 1-260628.
No. 2, page 15, line 15 to page 15, line 3 have the same meaning as A _{1 to} A _4, and a detailed description thereof will be omitted.

Preferred specific examples of the compound represented by the formula [L] are shown below.

(L-1) 1,3-propanediaminetetraacetic acid (L-2) 2-hydroxy-1,3-propanediaminetetraacetic acid (L-3) 2,3-propanediaminetetraacetic acid (L-4) ) 1,4-butanediaminetetraacetic acid (L-5) 2-methyl-1,3-propanediaminetetraacetic acid (L-6) N- (2-hydroxyethyl) -1,3-propanediaminetriacetic acid (L -7) 1,3-propanediaminetetrakismethylenephosphonic acid (L-8) 2-hydroxy-1,3-propanediaminetetrakismethylenephosphonic acid (L-9) 2,2-dimethyl-1,3-propanediaminetetracarboxylic acid Acetic acid (L-10) 2,4-butanediaminetetraacetic acid (L-11) 2,4-pentanediaminetetraacetic acid (L-12) 2-Methyl-2,4-pentanediaminetetraacetic acid These (L-1) As the ferric complex salts of the compounds of (L to 12), sodium, potassium or ammonium salts of these ferric complex salts It can be used arbitrarily. From the viewpoint of the effects of the object of the present invention and the solubility, ammonium salts of these ferric complex salts are preferably used.

Among the above compound examples, those particularly preferably used in the present invention include (L-1), (L-3),
(L-4), (L-5) and (L-9), and particularly preferably (L-1).

In the present invention, in addition to the iron complex salt of the compound represented by the above formula [L], a ferric complex salt of the following compound can be used as the bleaching agent in the bleaching solution.

(L'-1) ethylenediaminetetraacetic acid (L'-2) trans-1,2-cyclohexanediaminetetraacetic acid (L'-3) dihydroxyethylglycinic acid (L'-4) ethylenediaminetetrakismethylenephosphonic acid ( L'-5) Nitrilotrismethylenephosphonic acid (L'-6) Diethylenetriaminepentakismethylenephosphonic acid (L'-7) Diethylenetriaminepentaacetic acid (L'-8) Ethylenediamine diorthohydroxyphenylacetic acid (L'-9) hydroxy Ethyl ethylenediamine triacetic acid (L'-10) Ethylene diamine dipropionic acid (L'-11) Ethylene diamine diacetic acid (L'-12) Hydroxyethyl iminodiacetic acid (L'-13) Nitrilotriacetic acid (L'-14) Nitrilotri Propionic acid (L'-15) triethylenetetramine 6 Acid amount of (L'-16) ethylenediaminetetraacetic acid said organic acid ferric complex salts, the bleaching solution per liter
It is preferably contained in the range of 0.1 to 2.0 mol, more preferably 0.15 to 1.5 mol / l.

The bleaching solution includes an imidazole derivative described in JP-A-64-295258 or a compound represented by the general formulas [I] to [I] described in the same.
X] and at least one of these exemplified compounds can quickly exert the effect.

In addition to the above accelerators, JP-A-62-123459-5
Illustrative compounds described on pages 1-115 and 22 of JP-A-63-17445.
-Exemplified compounds described on page 25, JP-A-53-95630, 53-2
The compound described in No. 8426 can be used in the same manner.

In addition to the above, the bleaching solution can contain halides such as ammonium bromide, potassium bromide and sodium bromide, various optical brighteners, defoamers and surfactants. In the present invention, the stabilizing solution preferably contains a chelating agent having a chelate stability constant for ferric ion of 8 or more. Here, the chelate stability constant is defined as “Stability” by LGSillen / AEMartell.
Constants of Metal-ion Complexes ”, The Chemical S
ociety, London (1964), by O. Martell, S. Chaberek
rganic Sequestering Agents ”, Willy (1959) and the like.

As chelating agents having a chelate stability constant of 8 or more with respect to ferric ion, Japanese Patent Application No. 2-234776,
No. 1-324507 and the like. The use amount of these chelating agents is preferably from 0.01 to 50 g per liter of the stabilizing solution, and more preferably from 0.05 to 20 g to obtain good results.

[0097] As a preferable compound to be added to the stabilizing solution, an ammonium compound can be mentioned. These are supplied by ammonium salts of various inorganic compounds. The amount of the ammonium compound added is 0.001 per liter of the stabilizing solution.
The range is preferably from 2.0 to 2.0 mol, more preferably from 0.002 to 1.
0 mole. Further, the stabilizer preferably contains a sulfite. Further, the stabilizer preferably contains a metal salt in combination with the chelating agent. As such metal salts, Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb,
There are metal salts of Sn, Zn, Ti, Zr, Mg, Al or Sr, which can be supplied as inorganic salts such as halides, hydroxides, sulfates, carbonates, phosphates, acetates or water-soluble chelating agents. The amount used is 1 × 10 ^-4 to 1 × 10 ^-1 per liter of the stabilizing solution.
The molar range is preferably, more preferably, 4 × 10 ⁻⁴ to 2 ×.
10 ^-2 moles.

To the stabilizing solution, an organic acid salt (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), a pH adjuster (phosphate, borate, hydrochloride, sulfate, etc.) are added. be able to.

In the present invention, known fungicides can be used alone or in combination as long as the effects of the present invention are not impaired.

Next, the photosensitive material to which the processing agent of the present invention is applied will be described.

When the light-sensitive material is a photographic light-sensitive material, silver iodobromide or silver iodochloride having an average silver iodide content of 3 mol% or more is used as silver halide grains. Silver iodobromide containing up to% silver iodide is preferred. Among them,
The preferred average silver iodide content for the present invention is 5 to 12 mol%, most preferably 8 to 11 mol%.

As the silver halide emulsion used in the light-sensitive material processed with the photographic processing agent of the present invention, those described in Research Disclosure No. 308119 (hereinafter abbreviated as RD308119) can be used. The places to be described are shown below.

[Item] [Page of RD308119] Iodine composition 993 IA Item Manufacturing method 993 IA and 994 E Crystal habit Normal crystal 993 IA Twin twin エ ピ タ キ シ ャ ル Epitaxial ハ ロ ゲ ン Halogen composition uniform 993 I- Item B Non-uniform 〃 Halogen Conversion 994 IC Item 置換 Substitution 〃 Metal Containing 994 ID Monodisperse 995 Item IF Addition of Solvent 潜 Latent Image Forming Position Surface 995 IG Inside 〃 Applicable Sensitive Material Negative 995 Section IH Positive (including internal fog grains) 用 い る Use a mixture of emulsions 995 IJ Section Desalting 995 II-A Silver halide emulsions have been subjected to physical ripening, chemical ripening and spectral sensitization. use. Additives used in such a process are Research Disclosure No. 17643, N
o.18716 and No.308119 (hereinafter referred to as RD17643 and RD187, respectively)
16 and RD308119). The places to be described are shown below.

[Item] [RD308119 page] [RD17643] [RD18716] Chemical sensitizer 996 III-A 23 648 Spectral sensitizer 996 IV-AA, B, C, D, E, H, I, J Item 23-24 648-9 Supersensitizer 996 IV-AE, J Item 23-24
648-9 Antifoggants 998 VI 24-25 649 Stabilizers 998 VI 24-25 649 Photographic additives are also described in Research Disclosure, supra. The relevant sections are described below.

[Item] [Page of RD308119] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Whitening agent 998 V 24 UV absorber 1003 VIII C , XIII C 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Static inhibitor 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 Matting agent 1007 XVI Developer (contained in photosensitive material) 1011 XX-B Section Photosensitive processed with photographic processing agent of the present invention Various couplers can be used for the material, and specific examples are described in the above-mentioned Research Disclosure. The relevant sections are described below.

[Items] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D VII C-G Magenta coupler 1001 VII-D VII CG-C Cyan coupler 1001 VII-D VII C-G DIR coupler 1001 VII-F VIIF VIIF BAR coupler 1002 VII-F Other useful residue releasing coupler 1001 VII-F Alkali-soluble coupler 1001 VII-E Section Additives are described in RD308119 XIV It can be added by a method or the like.

In the present invention, RD17643, page 28, R
The supports described in D18716, pages 647-648 and RD308119, XIX can be used.

The light-sensitive material can be provided with an auxiliary layer such as a filter layer or an intermediate layer described in the aforementioned RD308119 VII-K. The light-sensitive material can have various layer constitutions such as a forward layer, a reverse layer, and a unit constitution described in the aforementioned RD308119 VII-K. Next, a preferred color photographic material to which the photographic processing agent of the present invention is applied will be described.

The silver halide particles in the light-sensitive material include
Silver halide grains mainly containing silver chloride containing at least 80 mol% of silver chloride are used, preferably those containing 90 mol% or more, particularly preferably 95 mol% or more, and most preferably 99 mol% or more. .

The silver chloride emulsion mainly containing silver chloride can contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride. In this case, the silver bromide content is 20 mol% or less. Is preferably 10 mol% or less, more preferably 3 mol% or less, and when silver iodide is present, it is preferably 1 mol% or less, more preferably 0.5 mol%.
Hereinafter, it is most preferably zero. Such silver chloride 50
Silver halide grains mainly composed of silver chloride consisting of at least
It may be applied to at least one silver halide emulsion layer, but is preferably applied to all photosensitive silver halide emulsion layers.

The crystal of the silver halide grains may be a normal crystal, a twin crystal or any other crystal, and any ratio of [100] plane to [111] plane can be used. Furthermore, even if the crystal structure of these silver halide grains is uniform from the inside to the outside, the inside and outside are different in layer (phase) -like structure (core / core).
(Shell type). These silver halides may be of a type in which a latent image is mainly formed on the surface or of a type in which a latent image is formed inside a grain. Further, tabular silver halide grains (JP-A-58-113934, Japanese Patent Application No. 59-113934)
170070) can also be used. Also, JP-A-64-268
No. 37, No. 64-26838, No. 64-77047 and the like can be used.

The silver halide grains may be obtained by any preparation method such as an acid method, a neutral method or an ammonia method. Also, for example, seed particles are made by an acid method,
A method of growing by an ammonia method having a high growth rate and growing to a predetermined size may be used. When growing silver halide grains, controlling the pH, pAg, and the like in the reaction vessel, for example, an amount of silver corresponding to the growth rate of silver halide grains as described in JP-A-54-48521. It is preferable that ions and halide ions be sequentially and simultaneously injected and mixed.

When the light-sensitive material processed by the photographic processing agent of the present invention is for color, the silver halide emulsion layer contains a color coupler.

The red-sensitive layer can contain, for example, a non-diffusible cyan coupler for forming a cyan partial color image, generally a phenol or α-naphthol coupler.

The green light-sensitive layer can contain, for example, at least one non-diffusible magenta coupler for producing a magenta partial color image, usually a 5-pyrazolone-based and pyrazolotriazole-based coupler. The blue-sensitive layer can include, for example, at least one non-diffusible yellow coupler that produces a yellow partial color image, generally a coupler having an open chain ketomethylene group. These couplers can be, for example, 6, 4 or 2 equivalent couplers.

In the color light-sensitive material to which the photographic processing agent of the present invention is applied, a 2-equivalent coupler is particularly preferable.

Suitable couplers are disclosed, for example, in the following publications: Agfa Research Report (Mitteilunglnausd)
en Forschungslaboratorien der Agfa), Leverkusen / Munchen Vol.III,
Page 111 (1961) "Color coupler" (Farbkuppler) by W. Pelz; K. Venkataraman, "The Chemistry of Synthetic Soy"
thetic Dyes) Vol.4, pp. 341-387, Academic Press, "The Theory of the Photographic Process"
otographic Process) 4th edition, pages 353-362; and RD17643
VII.

In the color light-sensitive material to which the photographic processing agent of the present invention is applied, in particular, a magenta coupler represented by the general formula [M-1] as described in JP-A-63-106655, p. Examples of magenta couplers include the same
No. 1 to No. 77 described on pages 29 to 34) and 34
Cyan couplers represented by the general formulas [C-I] or [C-II] described on page (specific examples of cyan couplers include (C'-1) to (C'-1) to ( C'-
82), (C "-1) to (C" -36)), and high-speed yellow couplers also described on page 20 (specific examples of yellow couplers are described on pages 21 to 26 of the same publication). (Y′-1) to (Y′39) are preferred from the viewpoint of the effects of the present invention.

[0119]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Comparative Example 1 The following fixing agent for color paper was sufficiently mixed using a commercially available powder mixer to obtain a 10 liter powder treating agent.

<Powder Treatment Agent / Fixing Agent for 10 L> Thiosulfate (potassium salt, ammonium salt) described in Table 3 Thiocyanate (potassium salt, ammonium salt) described in Table 3 anhydrous sodium bisulfite 20 g meta-weight Sodium sulfite 4.0g Disodium ethylenediaminetetraacetate 1.0g Adjust the ratio of thiosulfate (potassium salt, ammonium salt) and thiocyanate (potassium salt, ammonium salt) appropriately to adjust the ratio of ammonium ion to total cation in the fixing agent. By changing the ratio, sample Nos. 1-1 to 1-1
Created 6.

The above-mentioned treating agent was placed in a polyethylene bag and hermetically sealed, and placed in an autoclave at 45.degree.
2.0 kg / cm ^{3 was} added and stored for one month. After storage, the packaging material was cut with a cutter, and the sample was added and dissolved in a chemical mixer filled with water. The state of caking at this time was visually observed. Next, a color paper sample was prepared as follows.

<Color Paper> Each layer having the composition shown in Tables 1 and 2 was coated on a support in which polyethylene was laminated on one side of a paper support and polyethylene containing titanium oxide was laminated on the first layer on the other side. And a color paper sample was prepared. The coating solution was prepared as follows.

First layer coating solution 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), 6.67 g of (ST-2), additive (H
Q-1) 0.67 g was dissolved in 6.67 g of a high boiling solvent (DNP) by adding 60 ml of ethyl acetate, and this solution was ultrasonicated into 220 ml of a 10% aqueous gelatin solution containing 7 ml of a 20% surfactant (SU-1). The mixture was emulsified and dispersed using a homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a hardening agent, (H) was added to the second and fourth layers.
-1) and (H-2) were added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

[0126]

[Table 1]

[0127]

[Table 2]

[0128]

Embedded image

[0129]

Embedded image

[0130]

Embedded image

[0131]

Embedded image

[0132]

Embedded image

[Preparation of Blue-Sensitive Silver Halide Emulsion] In 1000 ml of a 2% aqueous gelatin solution kept at 40 ° C., the following (solution A)
And (solution B) were added simultaneously over 30 minutes while controlling pAg = 6.5 and pH = 3.0, and the following (solution C) and (solution D) were further added to pAg
= 7.3 and pH = 5.5 while simultaneously adding over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Add water 200 ml (Solution B) Add 10 g of silver nitrate water 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Add water 600 ml (D solution) 300 g of silver nitrate was added and 600 ml of water was added. After completion of the addition, desalting was performed using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd. A monodispersed cubic emulsion EMP-1 having a diameter of 0.85 µm, a coefficient of variation of 0.07, and a silver chloride content of 99.5 mol% was obtained.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer (STAB-1) 6 × 10 ^-4 mol / mol AgX sensitizing dye (BS-1) 4 × 10 ^-4 mol / Mol AgX sensitizing dye (BS-2) 1 × 10 ^-4 mol / mol AgX [Preparation of green-sensitive silver halide emulsion] Addition time of (solution A) and (solution B) and (C solution) and (D liquid)
Except for changing the addition time of EMP-1,
A monodispersed cubic emulsion EMP-2 having an average particle size of 0.43 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5 mol% was obtained.

The following compounds were used for EMP-2.
Chemical ripening was performed at 120 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ^-4 mol / mol AgX sensitizing dye (GS-1) 4 × 10 ^-4 mol / Mol AgX [Preparation of red-sensitive silver halide emulsion] Addition time of (Solution A) and (Solution B) and (Solution C) and (Solution D)
Except for changing the addition time of EMP-1,
A monodispersed cubic emulsion EMP-3 having an average particle size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5 mol% was obtained.

The following compounds were used for EMP-3
At 90 ° C. for 90 minutes to obtain a red-sensitive silver halide emulsion (E
mR).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye (RS-1) 4 × 10 ⁻⁴ mol / Mol AgX

[0141]

Embedded image

The thus-prepared sample was exposed to a wedge according to a conventional method, and then subjected to a running process according to the following processing steps.

Processing Step Temperature (° C.) Processing Time (second) Replenisher (ml / m ² ) Color Development 38 20 70 Bleaching 38 20 50 Setting 38 20 40 Stability 30 First Tank 20 120 Drying 60- 80 Second tank 30-30 The first and second tanks of the stabilization tank are of counter current type, and the replenisher was replenished to the second tank.

The following treatment liquids were used in each treatment step.

Color developing solution pure water 800 ml potassium bromide 0.02 g potassium chloride 3.3 g potassium carbonate 25 g potassium sulfite 0.2 g sodium diethylenetriaminepentaacetate 3.0 g 1- (N-ethyl-N-methanesulfonamidoethyl) -3-methyl- p-Phenylenediamine / 3 / 2H ₂ SO ₄ H ₂ O (CD-3) 4.5 g Sodium hydrogen carbonate 3.1 g Diethylhydroxylamine oxalate 6.5 g Tinopearl SFP (Ciba-Geigy) 2.5 g Adjust to 1 liter and PH = 10.00.

Bleach solution Ferric sodium pentaethylenediaminetetraacetate 0.35 mol Potassium bromide 170 g Maleic acid 30 g Succinic acid 30 g Disodium ethylenediaminetetraacetate 1.0 g Water is added to make a total volume of 1 liter, and the pH is adjusted to 4.3.

Fixing Solution A processing solution obtained by dissolving the powder fixing agent sample prepared in advance in water was added to 38
Those stored at 10 ° C. for 10 days were used.

Stabilized water 800 ml 1,2-Benzoisothiazolin-3-one 0.1 g 1-hydroxyethylidene-1,1-diphosphonic acid 5.0 g Ethylenediaminetetraacetic acid 1.0 g Tinopal SFP (Ciba-Geigy) 2.0 g Ammonium sulfate 2.5 g Zinc chloride 1.0 g Magnesium chloride 0.5 g o-Phenylphenol 1.0 g Sodium sulfite 2.0 g Add water to make 1 liter, and adjust to pH 8.0 with 50% sulfuric acid or 25% aqueous ammonia.

After the completion of the three rounds of running, the reflected red density at the maximum density portion and the residual silver amount at the unexposed portion of the processed color paper sample were measured. Further, one liter of the fixing tank solution was taken, placed in a beaker having an opening area ratio of 50 cm ² / liter, stored at 38 ° C., and the number of days until sulfuration was observed.

Table 3 summarizes the ammonium cation ratio in the fixing solution, the state of caking, the reflection red density in the maximum density portion, the amount of residual silver in the unexposed portion, the number of days until sulfuration, and the like.

[0151]

[Table 3]

The caking situation evaluation scale is as follows.

A: No caking at all.

○: slightly caking, but no problem in solubility.

△: There is a caked part,
No problem with solubility.

X: Caked and problematic in solubility.

When the number of “x” increases, it means that the caking is severe and the solubility is deteriorated.

From Table 3, it is found that the ammonium cation ratio (mol%) in the fixing solution is preferably 50 mol% or less.
And, more preferably it can be seen that more than 20 mol%.
Thiocyanate (potassium salt, ammonium salt) in combination with thiosulfate (cationic salt, ammonium salt)
It can be seen that the use of is more preferable.

Further, when the photographic processing agent of the present invention is used, there is no need to use a plastic bottle containing a concentrated photographic processing agent solution which has been conventionally used. Decreased to about 1/5 to 1/30.
The volume of the treatment agent kit could be reduced to 1/3 to 1/10.

Comparative Example 2 The fixing agent used in Comparative Example 1 was granulated using a commercially available fluidized bed spray granulator according to the method described in JP-A-2-09042, and the granulating agent (bulk density 0.80 g / cm ³ ). Otherwise, the experiment was performed in the same manner as in Comparative Example 1. As a result, the situation of caking was further improved, and the liquid preservability (the number of days until sulfurization) was improved.
20-30% improved.

Example 1 The fixing agent mixture used in Comparative Example 1 was converted into a tablet-type processing agent sample No. 3-1 to 3- by using a solid processing agent tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho. 16 were manufactured. Otherwise, the experiment was conducted in the same manner as in Comparative Example 1. As a result, the state of caking was further improved, and the liquid storage stability (days until sulfurization) was also improved to 30 to 45%. Furthermore, it was found that the strength of the tablet was effective. Table 4 summarizes the tablet strength. The tablets were allowed to fall naturally from a height of 1.2 m, and the strength of the tablets was visually observed and evaluated.

Table 4 shows the results.

[0163]

[Table 4]

Tablet strength evaluation scale 良好 Good without any collapse 微量 Very small edge portion collapse (occurrence probability 2%) △ Small edge portion collapse (occurrence probability 10%) × Edge portion collapses It means severe.

From Table 4, it is understood that the content of ammonium cation is preferably 50 mol% or less, more preferably 20 mol% or less as the tablet strength.

Example 2 The following fixing agent for a color negative film was thoroughly mixed to obtain a powder processing agent for 10 liters, and a tableting machine was used to prepare a sample No. 4-1 of 80 tablets each by the general method described in the text. ～4-16 it was was created made <br/>.

<Tablet / fixing agent for 10 liters> Thiosulfate (potassium salt, ammonium salt) described in Table 5 Thiocyanate (potassium salt, ammonium salt) 〃 sodium sulfite 20 g sodium ethylenediaminetetraacetate 5 g metabisulfite 5 g The ratio of the ammonium cation to the total cation in the fixing agent was changed as shown in Table 5 by appropriately adjusting the ratio of the thiosulfate (potassium salt, ammonium salt) and the thiocyanate (potassium salt, ammonium salt).

The tablet strength was evaluated by the method and conditions described in Example 1 .

Next, a color negative film sample was prepared as follows.

The amount of addition in the silver halide photographic light-sensitive material indicates grams per 1 m ² unless otherwise specified. Further, silver halide and colloidal silver are shown in terms of silver.

A triacetyl cellulose film support (thickness: 50 μm) is subjected to an undercoating process on one surface (front surface), and then, on the opposite side (back surface) of the triacetylcellulose film support, with the support interposed therebetween, Each layer of the composition was formed sequentially from the support side.

Backside first layer alumina sol AS-100 (aluminum oxide) 0.8 g (manufactured by Nissan Chemical Industries, Ltd.) Backside second layer diacetylcellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle size 0.2 μm) 50 mg Each layer having the following composition was formed sequentially from the support side on the surface subjected to the above, to prepare a multilayer color photographic light-sensitive material.

First layer: Antihalation layer (HC) Black colloidal silver 0.15 g UV absorber (UV-4) 0.20 g Colored cyan coupler (CC-1) 0.02 g High boiling solvent (Oil-1) 0.20 g High boiling point Solvent (Oil-2) 0.20 g Gelatin 1.6 g Second layer: Intermediate layer (IL-1) Gelatin 1.3 g Third layer: Low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (average particle size 0.3 μm) 0.40 g silver iodobromide emulsion (average particle size 0.4 μm) 0.30 g sensitizing dye (S-1) 3.2 × 10 ^-4 mol / silver 1 mol sensitizing dye (S-2) 3.2 × 10 ^-4 mol / silver 1 mol Sensitizing dye (S-3) 0.2 × 10 ^-4 mol / silver 1 mol Cyan coupler (C-3) 0.50 g Cyan coupler (C-4) 0.13 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006 g DIR compound (D-2) 0.01 g High boiling solvent (Oil-1) 0.55 g Gelatin 1.0 g 4-layer: High speed red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average particle size 0.7 [mu] m) 0.90 g Sensitizing dye (S-1) 1.7 × 10 -4 mol / 1 mol of silver Sensitizing dye (S- 2) 1.6 × 10 ^-4 mol / silver 1 mol Sensitizing dye (S-3) 0.1 × 10 ^-4 mol / silver 1 mol Cyan coupler (C-4) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR Compound (D-2) 0.02 g High boiling solvent (Oil-1) 0.25 g Gelatin 1.0 g Fifth layer: Intermediate layer (IL-2) Gelatin 0.8 g Sixth layer: Low sensitivity green-sensitive emulsion layer (GL) Silver halide emulsion (average particle size 0.4 μm) 0.6 g Silver iodobromide emulsion (average particle size 0.3 μm) 0.2 g Sensitizing dye (S-4) 6.7 × 10 ^-4 mol / silver 1 mol Sensitizing dye (S- 5) 0.8 × 10 ^-4 mol / 1 mol of silver magenta coupler (M-2) 0.17g magenta coupler (M-3) 0.43g colored magenta coupler (CM-1) 0.10g DIR compound (D-3) 0.02 g High boiling solvent (Oil-2) 0.7 g Gelatin 1.0 g Seventh layer: high-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average particle size 0.7 μm) 0.91 g sensitizing dye (S-6) 1.1 × 10 ⁻⁴ mol / silver 1 mol Sensitizing dye (S-7) 2.0 × 10 ⁻⁴ mol / silver 1 mol Sensitizing dye (S-8) 0.3 × 10 ⁻⁴ mol / silver 1 Molar Magenta coupler (M-2) 0.30 g Magenta coupler (M-3) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g High boiling solvent (Oil-2) 0.35 g Gelatin 1.0 g Eighth layer: Yellow filter layer (YC) Yellow colloidal silver 0.1 g Additive (HS-1) 0.07 g Additive (HS-2) 0.07 g Additive (SC-1) 0.12 g High boiling solvent (Oil-2) 0.15 g gelatin 1.0 g ninth layer: low-sensitivity blue-sensitive emulsion layer (BH) silver iodobromide emulsion (average grain size 0.3 μm) 0.25 g iodine odor Silver emulsion (average particle size 0.4 .mu.m) 0.25 g Sensitizing dye (S-9) 5.8 × 10 -4 mol / 1 mol of silver Yellow coupler (Y-2) 0.6 g Yellow coupler (Y-3) 0.32g DIR compound ( D-1) 0.003 g DIR compound (D-2) 0.006 g High boiling solvent (Oil-2) 0.18 g Gelatin 1.3 g Tenth layer: Highly sensitive blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (average particle size) 0.8 μm) 0.5 g Sensitizing dye (S-10) 3.0 × 10 ^-4 mol / silver 1 mol Sensitizing dye (S-11) 1.2 × 10 ^-4 mol / silver 1 mol Yellow coupler (Y-2) 0.18 g Yellow coupler (Y-3) 0.10 g High boiling point solvent (Oil-2) 0.05 g Gelatin 1.0 g Eleventh layer: first protective layer (PRO-1) Silver iodobromide (average particle size 0.08 μm) 0.3 g UV absorption (UV-4) 0.07 g UV absorber (UV-5) 0.10 g Additive (HS-1) 0.2 g Additive (HS-2) 0.1 g High boiling solvent ( Oil-1) 0.07 g High boiling solvent (Oil-3) 0.07 g Gelatin 0.8 g 12th layer: 2nd protective layer (PRO-2) Slip agent (WAX-1) 0.04 g Activator (SU-1) 0.004 g Polymethyl methacrylate (average particle size: 3 μm) 0.02 g Methyl methacrylate: ethyl methacrylate: methacrylic acid = 3: 3: 4 (weight ratio) copolymer (average particle size: 3 μm) 0.13 g Compound SU-
1, SU-4, viscosity modifier, hardener H-1, H-2, stabilizer STAB-2, antifoggant AF-1, AF-2
(With a weight average molecular weight of 10,000 and 1,100,000), dyes AI-4 and AI-5 and compound DI-1 (9.
4 mg / m ² ).

[0174]

Embedded image

[0175]

Embedded image

[0176]

Embedded image

[0177]

Embedded image

[0178]

Embedded image

[0179]

Embedded image

[0180]

Embedded image

[0181]

Embedded image

[0182]

Embedded image

[Preparation of Emulsion] The silver iodobromide emulsion used for the tenth layer was prepared as follows.

A silver iodobromide emulsion was prepared by a double jet method using monodispersed silver iodobromide grains having an average grain size of 0.33 μm (silver iodide content: 2 mol%) as seed crystals.

The solution <G-1> was heated at a temperature of 70 ° C., pAg 7.8, pH 7.0.
, And a seed emulsion equivalent to 0.34 mol was added with good stirring.

(Formation of Internal High Iodine Phase-Core Phase-) Then, while maintaining the flow ratio of <H-1> and <S-1> at 1: 1, the accelerated flow rate (the flow rate at the end was 3.6 of initial flow rate
) And added over 86 minutes.

(Formation of External Low Iodine Phase-Shell Phase-) Subsequently, while maintaining pAg 10.1 and pH 6.0, <H-2> and <S-2
Was added at a flow rate accelerated at a flow ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during particle formation were controlled using an aqueous potassium bromide solution and a 56% acetic acid aqueous solution. After the particles are formed, the particles are subjected to a water washing treatment by a conventional flocculation method, and then gelatin is added and redispersed.
pAg was adjusted to 5.8 and 8.06, respectively.

The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a distribution width of 12.4% and a silver iodide content of 8.5 mol%.

<G-1> Ossein gelatin 100.0 g 10% by weight methanol solution of compound-1 25.0 ml 28% ammonia aqueous solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finish with water 5000.0 ml <H-1> ossein gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide 90.6 g Finish with water 1030.5 ml <S-1> Silver nitrate 309.2 g 28% aqueous ammonia equivalent Finish with water 1030.5 ml <H-2> Ossein gelatin 302.1 g Potassium bromide 770.0 g Iodine 3776.8ml <S-2> Silver nitrate 1133.0g finished with 28% aqueous ammonia solution equivalent water 3776.8Ml compounds _{-1 HO (CH 2 CH 2 O} ) m (CH (CH 3) CH 2 O) k finish with potassium 33.2g water (CH ₂ CH ₂ O) nH (Average molecular weight ≒ 1300) In the same manner, the average grain size, temperature, pAg, pH, flow rate, addition time and halide composition of the seed crystal are changed to obtain the average grain size and silver iodide. Each of the above emulsions having different contents was prepared.

All were core / shell type monodispersed emulsions having a distribution width of 20% or less. Each emulsion is subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, sensitizing dye, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 1-Phenyl-5-mercaptotetrazole was added.

The color film sample prepared as described below was subjected to the following processing steps after wedge exposure according to a conventional method.

Processing Step Processing Temperature Processing Time Color Development 38 ± 0.3 ° C. 3 minutes 15 seconds Bleaching 38 ± 2.0 ° C. 45 seconds Fixed 38 ± 2.0 ° C. 1 minute 30 seconds Stable * 38 ± 5.0 ° C. First tank 30 seconds 2 Tank 30 seconds Drying 60 ± 5.0 ℃ 1 minute * The first and second tanks of the stabilization tank are of counter current type, and the replenisher was replenished to the second tank. The processing liquid used in each processing step is as follows.

Color developing agent (tablet treating agent for 1 liter) Potassium carbonate 30 g Sodium bicarbonate 3.5 g Sodium 1-hydroxyethane-1,1-diphosphonate 2.5 g Sodium diethylenetriaminepentaacetate 2.0 g 4-amino-3-methyl- N-Ethyl-N- (β-hydroxylethyl) aniline sulfate (CD-4) 4.8 g Sodium sulfite 3.5 g Hydroxylamine sulfate 2.8 g Sodium bromide 1.3 g Potassium iodide 0.8 mg Bleach (1 liter tablet processing agent) 1.3-potassium ferric potassium 1.3-propanaminetetraacetate 180 g sodium ferric ethylenediaminetetraacetate 40 g sodium ethylenediaminetetraacetate 5 g potassium bromide 150 g sodium nitrate 35 g maleic acid 28 g fixative (tablet treating agent for 1 liter) Solution at 38 ° C
The one stored for 10 days was used.

Stabilizer (paste treating agent for 1 liter) m-hydroxybenzaldehyde 2 g hexamethylenetetramine 1.5 g polyethylene glycol (molecular weight 1540) 2 g P-octylphenol / ethylene oxide 10 mol adduct 2 g diethylene glycol 5 g Finished after 3 rounds of running With respect to the sample, the transmission red density in the maximum density part (by a photoelectric densitometer) and the residual silver amount in the unexposed part were measured. Further, 1 liter of the fixing solution was taken out from the fixing tank solution, placed in a beaker having an opening area ratio of 50 cm ² / liter, stored at 38 ° C., and the number of days until sulfuration was observed.

Table 5 summarizes the ammonium cation ratio in the fixing solution, the transmission red density in the maximum density part, the residual silver amount in the unexposed part, the number of days until sulfidation, the tablet strength and the like.

[0197]

[Table 5]

From Table 5, it can be seen that Samples Nos. 4-4 to 4-4 of the present invention in which the ammonium cation ratio (mol%) in the fixing solution was 20 mol% or less and thiocyanate (potassium salt, ammonium salt) were used in combination. 11 is excellent.

Comparative Example 3 The fixing agent sample solution No. 4-14 (ammonium cation ratio: 50 mol%) prepared in Example 2 was mixed with the compound represented by the general formula [FA] and the compound group [FB] in Table 6 was added each 5 g / l as shown, the sample No.5-1~5 - 8 were created made <br/>.

In the fixing step in the developing step of the exposed color negative film, the amount of residual silver in the unexposed portion of the processing agent color negative film obtained by using each of the above samples was measured, and the results are shown in Table 6.

[0201]

[Table 6]

The [0202] Table 6, the general formula [FA] compounds and compounds represented by by use of a compound of [FB], it is possible to effect is exhibited as much.

[0203]

According to the present invention, storage stability is improved,
There was obtained a solid processing agent for a silver halide photographic light-sensitive material which did not decrease the image color density after the development processing, improved the solubility, reduced the friability, and had a fixing ability.

As a result, the suitability for the social environment and the working environment was improved by reducing the amount of packaging material (particularly plastic bottles) used, preventing fine powder, and reducing the weight, and the transportation and storage costs were reduced.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 5/26 520 G03C 5/38 G03C 7/42

Claims (1)

(57) [Claims] 1. A solid processing agent for a silver halide photographic light-sensitive material containing at least one thiosulfate, wherein a ratio of an ammonium cation to a total cation in the processing agent is 20 mol% or less. Is a pill
A is, and a silver halide photographic light-sensitive material for the solid processing agent having fixing ability, characterized that you contain thiocyanate.