JP2979355B2 - Processing kit for silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing agent (photographic processing agent) kit for a silver halide photographic light-sensitive material, and more particularly, to completely preventing the fine powder of the photographic processing agent from scattering and eliminating the need for using a plastic bottle. And a photographic processing agent kit having suitability for working environment and social environment.

[0002]

BACKGROUND OF THE INVENTION Silver halide photographic materials are usually black-and-white developers, fixers, color developers, bleachers, bleach-fixers,
Development processing is performed using a processing liquid such as a stabilizing liquid, and an image-wise image is obtained. Each processing solution used here is put in a plastic bottle in the form of one or a plurality of concentrated liquid parts for ease of use, and is supplied to the user as a processing agent kit. Users dissolve these treating 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. With the progress of the minilab, 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, but in that case, there is a high possibility that the fine powder will fly up during the dissolution and be inhaled by the worker, and there is a concern that the effect on health may be affected. Or the sowing of the processing agent component is mixed into another photographic processing solution, thereby causing a problem of contamination and trouble.
For this reason, a technique for granulating a photographic processing agent to form a granular mixture has been proposed in, for example, JP-A-2-09042, JP-A-2-09043, U.S. Pat.No. 2,843,484 and JP-A-3-39735.
Occupational health and safety issues still due to flying chemical dust,
Problems such as mixing into other processing liquids as impurities, or caking phenomena that settle and condense on the bottom of the container when dissolving, and disturb the dispensing work due to coating defects caused by coating the powder with its own wet coating. In fact, the range of drugs suitable for pulverization and granulation is extremely limited.

[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.
No. has been proposed.

However, when these photographic processing agents are made into tablets, they are extremely useful for dispensing workability or occupational safety and health. However, these tablets are extremely weak to humidity. For example, the tablet surface absorbs moisture during the rainy season. It turned out to be poorly soluble, and this caused a reaction inside the tablet, resulting in a drawback that sufficient photographic performance could not be obtained.

As a result of various studies, the present inventors have found that, when a photographic tablet is stored in a packaging material, the above performance greatly depends on the humidity in the packaging material. ) Was found to have criticality, and the present invention was constituted.

[0011]

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

[0012] The use of packaging materials (especially plastic bottles) is reduced, and it is suitable for social environment.

The tableting 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 generation of stain during development and no contamination of the photosensitive material after processing.

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

[0016] Contamination due to contamination can be prevented.

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

[0018]

The object of the present invention is to achieve a bulk density of 1.0 to 5.0 g /
This was achieved by a processing kit for silver halide photographic light-sensitive materials, in which a tablet-shaped photographic processing agent of cm ³ was packaged in a moisture-proof packaging material so that the internal relative humidity was 20% or less. In addition, (a) the tablet-shaped photographic processing agent has the general formula [A] or
A small amount of the compound represented by [B] (“Chemical A” or “Chemical B”)
A color developing agent containing at least one kind . (b) the moisture-proof packaging material polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polyvinylidene chloride, polyamides, polycarbonates, be selected from polyacrylates <br/> Ronitoriru and aluminum are both exert more effects of the present invention This is a preferred embodiment because it is possible.

In the present specification, the relative humidity is a temperature of 25 ° C.
Shows the value of

In the present invention, it is necessary to keep the relative humidity (RH) in the packaging material at 20% or less, particularly preferably at 10% RH or less, most preferably at 5% RH or less. The moisture proof packaging material of the present invention can be used to protect solid photographic processing agents packaged or bound or coated with a water-soluble film during storage, transport, and handling in air, such as high humidity, rain, and fog. Moisture, and to prevent damage from splashing or sudden contact with water by wet hands, a film with a film thickness of 10 to 150 μm is preferable, and the moisture-proof packaging material is polyethylene terephthalate, polyethylene, polypropylene, or the like. polyolefin films, kraft paper, which may have a moisture effects with polyethylene, wax paper, moisture resistance cellophane, glassine, polyester, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polycarbonate, acrylonitrile and such metal foil aluminum, metalized Preferably at least one selected from polymer films Ku, or may be a composite material using the same.

However, in the present invention, the moisture-proof packaging material is preferably a degradable plastic, particularly a biodegradable or photodegradable plastic.

Examples of the biodegradable plastic include those composed of natural polymers, microorganism-produced polymers, synthetic polymers having good biodegradability, and the incorporation of biodegradable natural polymers into plastics. Examples include those in which a group which is excited by ultraviolet rays and is linked to cleavage is present in the main chain. Further, in addition to the polymers listed above, those having both functions of photodegradability and biodegradability are also included in the present invention. Specific examples of these are as follows.

Examples of biodegradable plastics include natural polymer polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, and modified products thereof. Microbial polymers PHB-PHV (3-hydroxybutyrate and 3-hydroxyvale) "Polypol", which is a component of "Polyol"), bio-degradable synthetic polymers Polyvinyl alcohol, polycaprolactone, etc., or their copolymers or mixtures Biodegradable natural polymers into plastics Formulation of natural polymers having good biodegradability include starch and cellulose, which are plastics and have a shape-disintegrating property.

Examples of the photodegradability include the introduction of a carbonyl group for photodisintegration, and an ultraviolet absorber may be added for accelerating the disintegration.

For such degradable plastics,
"Science and Industry," Vol. 64, No. 10, pp. 478-484 (1990),
The materials generally described in "Functional Materials", July 1990, pp. 23-34 can be used. Also, Biopol
(ICI), Eco (Union Carbide),
Ecolite (Eco Plastic), Ecostar
Commercially available degradable plastics such as (Ecostar) (St. Lawrence Starch) and Knuckle P (Nippon Unicar) can be used.

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

The solid photographic processing agent of the present invention comprises tablets, granules,
Powders, lumps or pastes are used, preferably tablets. The method for producing a tablet processing agent can be produced by a general method described in, for example, JP-A-51-61837, JP-A-54-155038, JP-A-52-88025, British Patent No. 1,213,808, and further, a granulation agent. Is, for example, JP-A-2-09042,
It can be produced by a general method described in JP-A Nos. 2-109043, 3-39735 and 3-9739. Furthermore, the powder processing agent,
For example, JP-A-54-133332, UK Patents 725,892 and 729,8
No. 62 and German Patent 3,733,861 and the like, it can be produced by a general method.

The bulk density of the solid photographic processing agent of the present invention is from 1.0 to 1.0 from the viewpoint of its solubility and the effect of the object of the present invention.
Those having 5.0 g / cm ³ are preferably used.

The solid photographic processing agent of the present invention comprises a color developing agent,
Examples thereof include a black-and-white developer, a bleaching agent, a fixing agent, a bleach-fixing agent, and a stabilizer. Among them, a color developing agent that more effectively exerts the effects of the present invention is provided.

As a color developing agent used in the color developing agent of the present invention, a p-phenylenediamine compound having a water-soluble group is preferably used because it exhibits the desired effects of the present invention and generates less fog. Can be

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 not only has the advantage that the skin is less susceptible to fogging, and the object of the present invention can be more effectively achieved by combining it with the color developing agent of the present invention.

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

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.

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.

[0037]

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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.

[0040]

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[0041] 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 form a heterocyclic ring together. R
_11, R _12, R _13, the alkyl group represented by R _14, an aryl group, a heterocyclic group may have 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] include (B-1) to (B-1) described in Japanese Patent Application No. 2-203169, pp. 40-43.
(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.

[0046]

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

In the color developer and black-and-white developer according to 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 for the color developing agent and the black-and-white developer according to the present invention. Examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, and phosphoric acid. Tripotassium, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo- Two
And sodium 5-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

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, 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Patent 2,48
Amine compounds described in 2,546, 2,596,926 and 3,582,346, etc., JP-B-37-16088, JP-B-42-25201, U.S. Pat. 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 as chlorine ions per color developer dissolved in 1 L (liter),
More preferably, the content is 3.5 × 10 ^{-2 to} 1.0 × 10 ^-1 mol. If the chloride ion concentration is more than 1.5 × 10 ^-1 mol / L, it is not preferable to delay development and quickly obtain a high maximum concentration.
On the other hand, if it is less than 3.5 × 10 ^-2 mol / L, stain is generated, and photographic property fluctuation (especially minimum density) accompanying continuous processing is undesirably large.

In the present invention, bromine ions are contained in the tablet such that the color developer preferably contains 3.0 × 10 ^{−5 to} 1.0 × 10 ⁻³ mol / L. More preferably 5.0 × 10 ^-5
55 × 10 ⁻⁴ mol / L. Particularly preferably 1 × 10 ^-4 or more
3 × 10 ^-4 mol / L. When the bromine ion concentration is higher than 1 × 10 ⁻³ mol / L, the development is delayed and the maximum concentration and sensitivity are lowered. When the bromine ion concentration is lower than 3.0 × 10 ⁻⁵ mol / L, stain is generated and the process is accompanied by continuous processing. It is not preferable in that a change in photographic characteristics (particularly, minimum density) occurs.

When directly added to a color developing agent, 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 counter salt of a color developing agent and a fluorescent whitening agent added to the developing agent.

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 agent and the developing agent of 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. It is preferable that a triazinylstilbene-based fluorescent whitening agent is contained in the color developer and the developer of the present invention from the viewpoint of the effects of the present invention. As such a fluorescent whitening agent, a compound represented by the following general formula [E] is preferable.

[0058]

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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, -N (R ₂₁ ) (R ₂₂ ) group,

[0060]

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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.

The above compounds can be synthesized by known methods. Representative compounds are shown below, and particularly preferably used are E-4, E-24, E-34,
E-35, E-36, E-37 and 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.

[0064]

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[0065]

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Further, the color developer and the black-and-white developer used in the present invention may include, if necessary, methylcellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other JP-B Nos. 47-33378 and 44-333. The compound described in No. 9509 can be used as an organic solvent for increasing the solubility of a developing agent.

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 / L.

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

Also, a color developing agent and a black-and-white developer include a chelating agent represented by the following general formula [K] described in Japanese Patent Application No. 2-240400, from page 69 below, line 9 to page 75, and an exemplified compound thereof. K-
Addition of 1 to K-22 is preferred from the viewpoint of effectively achieving the object of the present invention.

[0070]

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In the formula, E is 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
Represents = NR ₅ -A ₅ or = NA ₅ , A _{1 to} A ₅ represent a hydrogen atom,
It represents 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 per liter of the color developer and the black-and-white developer.
More preferably, it is 0.2 to 8 g.

Further, the color developing agent and the black-and-white developing agent 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 preferably used in the bleaching agent or the bleach-fixing agent according to the present invention is a ferric complex salt of an organic acid represented by the following general formula [L].

[0076]

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In the formula, A _{1 to} A ₄ may be the same or different and each represents —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 an ammonium group. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.

Hereinafter, the compound represented by formula [L] will be described in detail.

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 general 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, as the bleaching agent or the bleach-fixing agent, besides the iron complex salt of the compound represented by the above general formula [L], a ferric complex salt of the following compound can be used as a bleaching agent.

(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) Diethylenetriamine pentakismethylenephosphonic 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 (L'-16) Ethylenediaminetetrapropionic acid The amount of the ferric organic acid complex salt to be added is preferably 0.1 to 2.0 mol, more preferably 0.15 to 1.5 mol per 1000 ml of the bleaching solution or the bleach-fixing solution. Mol / L.

Examples of the bleaching agent, bleach-fixing agent and fixing agent include imidazoles and derivatives described in JP-A-64-295258, compounds represented by the general formulas [I] to [IX] described in the same, and examples thereof. By containing at least one of the compounds, the effect is achieved quickly.

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.

The bleaching agent or bleach-fixing agent may contain, in addition to the above, halides such as ammonium bromide, potassium bromide and sodium bromide, various optical brighteners, defoamers and surfactants. it can. As the fixing agent used in the fixing agent or the bleach-fixing agent according to the invention, thiocyanates and thiosulfates are preferably used. The thiocyanate content 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 when processing a color negative film.
L or more. Also, the content of thiosulfate is at least 0.
It is preferably at least 2 mol / L, and more preferably at least 0.5 mol / L when processing a color negative film. 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 fixing agent or bleach-fixing agent according to the present invention includes:
In addition to these fixing agents, a single or two or more pH buffers comprising various salts can be contained. Further alkali halides or ammonium halides, such as potassium bromide,
It is desirable to contain a large amount of a rehalogenating agent such as sodium bromide, sodium chloride, and ammonium bromide.
Further, a compound known to be added to a compound to be added to a normal fixing agent or a bleach-fixing agent such as alkylamines and polyethylene oxides can be appropriately added.

A fixing agent or a bleach-fixing agent is described in JP-A-64-295.
It is preferable to add a compound represented by the following general formula [FA] described on page 56 of No. 258 and the exemplified compounds (FA-1 to FA-39), and not only exert the effect of the present invention more, but also a small amount. Another effect is obtained that the amount of sludge generated in the processing solution having a fixing ability when processing the photosensitive material for a long period is extremely small.

[0090]

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

The compound represented by the general formula [FA] described in the same can be synthesized by a general method as described in US Pat. Nos. 3,335,161 and 3,260,718. These compounds represented by the general formula [FA] may be used alone or in combination of two or more. Good results can be obtained when the added amount of these compounds is in the range of 0.1 to 200 g per liter of the processing solution.

In the present invention, the stabilizer 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 Constants” by LGSillen and AE Martell.
of Metal-ion Complexes ”, The Chemical Society, Lon
don (1964), "Organic Seq" by S. Chaberek and AE Martell
uestering Agents ”, Willy (1959) and the like. A chelating agent having a chelate stability constant of 8 or more for ferric ion is disclosed in Japanese Patent Application No. 2-2347.
Nos. 76 and 1-3324507. The amount of these chelating agents used is 0.01 to 50 g per liter of the stabilizing solution.
And more preferably in the range of 0.05 to 20 g to obtain good results.

As a preferable compound to be added to the stabilizer, an ammonium compound can be mentioned. These are supplied by ammonium salts of various inorganic compounds. The amount of the ammonium compound to be added is 0.001 to 1 liter of the stabilizing solution.
A range of 2.0 moles is preferred, more preferably 0.002-1.0.
Is a mole. Further, the stabilizer preferably contains a sulfite. Further, the stabilizer preferably contains a metal salt in combination with the chelating agent. Such metal salts include Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, S
There are metal salts of n, 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 preferably in the range of 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 4 × 10 ^-4 to 2 × 10 ^-1 mol per liter of the stabilizing solution.
^-2 moles.

Further, organic acid salts (such as citric acid, acetic acid, succinic acid, oxalic acid, and benzoic acid), pH adjusters (such as phosphate, borate, hydrochloride, and sulfate) are added to the stabilizer. 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.

[Items] [Page of RD308119] Iodine composition 993 IA Item Production method 993 IA and 994 E Crystal habit Normal crystal 993 IA Twin twin {epitaxial} 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, No. 1
8716 and No.308119 (hereinafter referred to as RD17643 and RD18716, respectively)
And RD308119). The places to be described are shown below.

[Item] [RD308119 page] [RD17643] [RD18716] Chemical sensitizer 996 Section 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 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 It is described in the disclosure. The relevant sections are described below.

[Item] [RD308119] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Brightener 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.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 Sections VII-D VII C to G Magenta coupler 1001 VII-D VII C to G Cyan coupler 1001 VII-D VII C to 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 light-sensitive material to which the photographic processing agent of the present invention is applied will be described.

The silver halide grains 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 halide emulsion mainly composed of silver chloride may 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 crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, 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, and 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), "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, a magenta coupler represented by the general formula [M-1] (particularly described in JP-A-63-106655, page 26) can be used. 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.

[0116]

The present invention will now be illustrated by way of examples.

Example 1 The following color paper color developer was thoroughly mixed, and 10 L
As a powder processing agent for use, 80 tablets were prepared using a tableting machine by the general method described in the text.

<Powder processing agent / color developing agent for 10 L> Potassium bromide 0.2 g Potassium chloride 33 g Potassium carbonate 250 g Potassium sulfite 2 g Sodium diethylenetriaminepentaacetate 30 g 4-Amino-3-methyl-N-ethyl-N- (methanesulfone Amidoethyl) Aniline sulfate (CD-3) 48 g Tinopearl SFP (manufactured by Ciba Geigy) 25 g Sodium hydrogen carbonate 31 g Diethylhydroxylamine / sulfate 70 g (Hereinafter referred to as wrapping material), the internal humidity was changed, and the container was hermetically sealed and subjected to a storage test. Storage test condition is 50 ℃
-Stored at 70% RH for 3 months.

The packaging material after storage was cut with a cutter, and the tablets were added into a water-filled chemical mixer to dissolve the tablets. At this time, the state of the tablet, the dissolution state, and the presence or absence of insoluble matter were observed. Further, the reflection green density of the unexposed portion of the color paper sample treated with this color developing solution was measured, and the stain on the color paper was visually observed.

The above results are summarized in Table 1 below. However, the following color paper was used.

[0121]

[Table 1]

The evaluation scale in Table 1 is as follows.

<Tablets after storage>: All of the tablets are not adhered at all.

{Circle around (2)} Several tablets are adhered, but easily peeled off.

X: Adhered.

The larger the number of “x”, the more difficult it is for the attached tablet to peel off.

<Solubility of tablet> ○: dissolves quickly.

X: Time is required for dissolution.

The larger the number of “x”, the longer the dissolution time.

<Presence or absence of insoluble matter after dissolution>: There is no insoluble matter at all.

△: There are some fine particles.

X: There are various insolubles, large and small.

The larger the number of “x”, the larger the amount of insoluble matter.

<Stain on Paper>: There is no stain at all.

△: There is some dirt, which is a problem as a product.

X: There is dirt.

The larger the number of “x”, the more severe the dirt condition.

In this experiment, it was confirmed that no dust was generated when the packaging material was cut with a cutter and dissolved, no treatment chemicals remained in the packaging material, and there was no problem in the working environment. . Table 1 shows that the effects of the present invention can be obtained when the internal humidity is 20% RH or less.

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

<Color Paper> Each layer having the composition shown in Tables 2 and 3 was coated on a support obtained by laminating polyethylene on one side of a paper support and polyethylene containing titanium oxide 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 Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, (ST-2) 6.67 g, additive (HQ
-1) 0.67 g of ethyl acetate was added to 6.67 g of a high boiling point solvent (DNP).
Add 60 ml to dissolve and add this solution to a 20% surfactant (SU
-1) A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of a 10% aqueous gelatin solution containing 7 ml using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions.
A layer coating solution was prepared. The coating liquid for the second to seventh layers is also the first layer.
It was prepared in the same manner as the layer coating solution.

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.

[0143]

[Table 2]

[0144]

[Table 3]

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[0146]

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[0148]

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[0149]

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[Preparation of Blue-Sensitive Silver Halide Emulsion] 40 ° C.
In 1000 ml of a 2% aqueous gelatin solution kept warm in
Solution) and (solution B) while controlling pAg = 6.5 and pH = 3.0.
At the same time, and further add the following (Solution C) and (Solution D)
The co-addition was performed over 180 minutes while controlling pAg = 7.3 and pH = 5.5. 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 Water was added to 200 ml (Solution B) 10 g of silver nitrate was added to 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added to 600 ml (D solution) Silver nitrate 300g Water was added and after the addition of 600ml, desalting was performed using 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 compounds 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] (Solution A) and (Solution B)
The average particle diameter was 0.43 μm in the same manner as EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
A monodispersed cubic emulsion EMP-2 having 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] (Solution A) and (Solution B)
The average particle size was 0.50 μm in the same manner as EMP-1, except that the addition time of (C) and (C solution) and (D solution) were changed.
A monodisperse cubic emulsion EMP-3 having 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

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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 Processing time Color development 38 ± 0.3 ° C 30 seconds Bleaching and fixing 38 ± 3 ° C 30 seconds Stable * 38 ± 5 ° C 20 seconds × 3 Drying 60 ± 5 ° C 45 seconds * 3 stabilization tanks The replenisher is replenished in the third tank (final tank), and each overflow liquid is of a counter current type in which it sequentially flows into the previous tank. The following treatment liquid was used in each treatment step.

As the color developing solution, a solution in which the above-described stored color developing agent (tablet) was dissolved was used.

Bleaching / fixing solution Water 700 g Ammonium ferric ethylenediaminetetraacetate 75 g Ethylenediaminetetraacetic acid 2 g Ammonium thiosulfate 50 g Ammonium thiocyanate 30 g Potassium sulfite 10 g p-Toluenesulfinic acid 5 g Ammonium bromide 10 g Adjusted to pH 6.5 with sodium oxide.

Stabilized liquid water 800 g 1,2-benzisothiazolin-3-one 0.1 g 1-hydroxyethylidene-1,1-diphosphonic acid 5.0 g ethylenediaminetetraacetic acid 1.0 g Tinopearl SFP (manufactured by 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 L, adjust to pH 8.0 with 50% sulfuric acid or 25% aqueous ammonia.

Example 2 The following bleach-fixing agent for color paper was thoroughly mixed, and 1 L
30 tablet processing agents were prepared. <1L powder processing agent / bleach-fixing agent> Sodium ferric diethylenetriaminepentaacetate 65g Sodium ethylenediaminetetraacetate 2g Sodium thiosulfate 70g Potassium thiocyanate 30g Potassium sulfite 10g Potassium bromide 20g p-Toluenesulfinic acid 5g Prepared in this way The bleach-fixing tablet thus obtained was placed in the same packaging material as described in Table 1 of Example 1, and the humidity was adjusted and a similar storage experiment was performed. As a result, almost the same results as in Example 1 were obtained for the adhesion state of the tablet after storage, the solubility, the presence or absence of insoluble matter after dissolution, and the scattering state of the powder during dissolution.

Example 3 The procedure of Example 1 was repeated, except that the fluorescent whitening agent (Tinopearl SFP) in the color developer used in Experiment No. 1-5 of Example 1 was changed to that shown in Table 4. An experiment was performed.

Table 4 summarizes the results.

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[Table 4]

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From the results shown in Table 4, it can be seen that the effects of the present invention can be more remarkably exhibited by using a specific fluorescent brightener in combination with the treating agent kit of the present invention.

Example 4 The procedure of Example 1 was repeated, except that the packaging material (polyethylene) used in Example 1 was packed with Knucknal P manufactured by Nippon Unicar and Ecostar manufactured by St. Lawrence Starch. The experiment was performed in the same manner. The results were almost the same as those in Example 1, but it was confirmed that the photographic processing agent kit could be packaged with the degradable polymer bag, and the product could be a product having social environment suitability.

Example 5 Experiment No. 1 of Example 1 The pressure at the time of tableting was changed for 1-5, and tablets having different bulk densities were prepared as shown in Table 5. The same experiment as in Example 1 was performed using this tablet. Table 5 summarizes the results.

[0172]

[Table 5]

There were no significant differences in the tablet adhesiveness, the presence or absence of insolubles, and the stain on the paper. According to Table 5, the bulk density is 1.0
It can be seen that the effect of the present invention is favorably exhibited in the range of 5.05.0 g / cm ³ .

Example 6 In the following Examples, the amount added in the silver halide photographic light-sensitive material indicates grams per 1 m ² unless otherwise specified. Silver halide and colloidal silver are shown in terms of silver.

(Color negative film) One side (front surface) of a triacetyl cellulose film support (thickness: 50 μm) is subjected to an undercoating process, and then the other surface (back surface) of the triacetyl cellulose film support opposite to the undercoated process is sandwiched by the support. ), Each layer having the following 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 point 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 grain size 0.3 μm) 0.42 g silver iodobromide emulsion (average particle size 0.4 μm) 0.28 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) 0.91 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 grain size: 0.4 μm) 0.6 g Silver iodobromide emulsion (average grain 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 10th layer: High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (average grain 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 11th layer: 1st protective layer (PRO # 1) Silver iodobromide (average particle size 0.08 μm) 0.3 g UV absorption (UV # 4) 0.07g UV absorber (UV # 5) 0.10g Additive (HS-1) 0.2g Additive (HS-2) 0.1g High boiling solvent ( Oil No. 1) 0.07 g High boiling solvent (Oil No. 3) 0.07 g Gelatin 0.8 g 12th layer: Second protective layer (PRO No. 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 ).

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[0180]

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[0181]

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[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 particle diameter 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) Thereafter, 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 increased). 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 Finished with water 1030.5 ml <S-1> Silver nitrate 309.2 g 28% ammonia aqueous solution Equivalent Finished 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 area 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 processed in the following processing steps.

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 / IL tablet processing agent> 20 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 <Tablets for bleach / IL Treatment agent> 20 potassium ferric potassium 1,3-propanediaminetetraacetate 180 g sodium ferric ethylenediaminetetraacetate 40 g sodium ethylenediaminetetraacetate 5 g potassium bromide 150 g sodium nitrate 35 g maleic acid 28 g <fixing agent / IL tablet treatment agent > 20 pcs Sodium thiosulfate 200 g Sodium sulfite 20 g Potassium thiocyanate 100 g Ethylene diamine Sodium tetraacetate 5 g <Stabilizer / slurry treating agent> m-hydroxybenzaldehyde 2 g polyethylene glycol (molecular weight 1540) 2 g hexamethylenetetramine 1.5 g p-octylphenol / ethylene oxide (10 mol adduct) 2 g diethylene glycol 5 g The slurry was used in a machine.

The same experiment as in Example 1 was conducted for each of the treating agents thus prepared.

The density of the unexposed portion was measured using a photoelectric densitometer, and the transmission magenta density was measured.

Table 6 summarizes the results.

[0201]

[Table 6]

The contents described in Table 6 are the same as those in Table 1 of Example 1. Table 6 shows the effect of the present invention.

Example 7 The same as Example 1 except that the preservative (diethylhydroxylamine / sulfate) in the color developing agent used in Experiments 1-5 of Example 1 was changed to that shown in Table 7 The experiment was performed. Table 7 summarizes the results.

[0204]

[Table 7]

[0205]

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From the results shown in Table 7, it can be seen that the effects of the present invention can be more remarkably exhibited by using a specific preservative in combination with the treating agent kit of the present invention.

[0207]

According to the present invention, sufficient photographic performance is provided, and stains generated in the unexposed portions of the photographic light-sensitive material are suppressed, and no plastic bottle is used or the amount is greatly reduced. So we have social environment aptitude,
In addition, since there is no scattering of fine powder of the solid processing agent, it has work environment suitability, excellent storage stability and solubility, stains of automatic processing machine processing are improved, and further, the processing agent is made into tablets to reduce weight, It is possible to provide a processing agent kit for a silver halide photographic light-sensitive material, in which the transportation cost is reduced and the storage space in the developing lab is reduced.

Claims (3)

(57) [Claims] 1. A tablet-type photographic processing agent having a bulk density of 1.0 to 5.0 g / cm ³ is packaged in a moisture-proof packaging material so that the relative humidity inside is 20% or less (25 ° C.). Processing kit for silver halide photographic materials. 2. The tablet- type photographic processing agent has the following general formula:
At least one of the compounds represented by [A] or [B]
2. A processing kit for a silver halide photographic light-sensitive material according to claim 1 , which is a color developing agent . [A] Wherein R ₁ and R ₂ are each an alkyl group, an aryl group,
R ₃ represents a CO— group or a hydrogen atom. Provided that both R ₁ and R ₂
They cannot be hydrogen atoms at the same time. Also, a ring is formed by R ₁ and R ₂
It may be formed. ] [Of B] [Wherein R ₁₁ , R ₁₂ and R ₁₃ are each a hydrogen atom, an alkyl
R ₁₄ represents a hydroxy group, an aryl group or a heterocyclic group;
Group, hydroxyamino group, alkyl group, aryl group,
Heterocyclic group, alkoxy group, aryloxy group, carbamo
Represents an yl group or an amino group. R ₁₅ is -CO, -SO ₂ -or
Represents a divalent group selected from -C (= NH)-, wherein n is 0 or
It is one. When n = 0, R ₁₄ is an alkyl group, an aryl
Group, a group selected from the heterocyclic group, R ₁₃ and R ₁₄ are jointly
To form a heterocyclic ring. ] Wherein the moisture-proof packaging material polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polyvinylidene chloride, polyamide, polycarbonate, silver halide of claim 1, wherein a is selected from polyacrylonitrile and aluminum Processing kit for photographic photosensitive materials.