JPH05142708A - Tablet for processing silver halide photosensitive material and production thereof - Google Patents

Abstract

PURPOSE:To improve preservable stability, sticking, adaptability to social environment, adaptability to working environment, etc., by granulating the compsn. of the tablet, then solidifying the granules by compression under pressurization. CONSTITUTION:The plural solid chemicals used for photographic processing are uniformly mixed and pulverized by a mixer and the pulverized chemicals are granulated by using a fluidized bed spray granulating machine. The granules are mixed with the granules consisting of the plural solid chemicals separately prepd. by the same method. The mixture is tableted to produce the tablet type processing agent. The granules having 100 to 800mum average grain sizes are used. The preservable property is poor if the average grain size is <=100mum. The preservable property is insufficient if the average grain size is >=800mum and, therefore, the effective total amt. is decreased by the long-term preservation. Troubles, such as generation of insoluble matter, are then generated and such case is undesirable. The moisture content per tablet is 0.5 to 10wt.%. The strength is insufficient if the moisture content is below 0.55. The content of the main materials in the tablets decreases if the moisture content exceeds 10%. The preferable grain size distribution is such that >=60% of the particles are within a deviation from + or -100 to 150mum.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing agent for silver halide photographic light-sensitive materials (photographic processing agent) and a method for producing the same, more specifically, storage stability, insoluble matter, sticking, social environment suitability, work environment suitability, etc. Relates to an improved tablet for processing a silver halide photographic light-sensitive material.

[0002]

BACKGROUND OF THE INVENTION Silver halide photographic light-sensitive materials are usually black-and-white developing solution, fixing solution, color developing solution, bleaching solution, bleach-fixing solution,
Development processing is performed using a processing solution such as a stabilizing solution to obtain an imagewise image. Each processing solution used here is put in a plastic bottle in the form of one or a plurality of concentrated solution parts for ease of use and supplied to the user as a processing agent kit. The user dissolves these treating agent kits in water to prepare a working solution (starting solution or replenishing solution) for use.

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 minilabization, the amount of plastic bottles for processing agents used is increasing year by year. It is increasing rapidly.

Because of its light and strong properties, this plastic has been widely used in addition to bottles for photographic processing agents. The worldwide production of plastics has been increasing year by year, and in 1988, the annual production amount exceeded 100 million tons. On the other hand, the amount of plastics discarded is enormous, and even in Japan, about 40% of the production is discarded year by year. When such waste plastic is dumped into the ocean, it causes deterioration of the habitat of marine organisms, and in Europe, because it is burned in an incinerator with insufficient exhaust gas treatment equipment, acid rain, etc. Has also become a major problem.

For this reason, urgent countermeasures are urgently required. In Europe and America, legal regulations such as plastic recycling and use prohibition, or obligatory use of degradable plastics are becoming active. It is the actual situation.

Under such circumstances, it is extremely unfavorable to use a large amount of plastic bottles as a processing agent for photographic use, although it is a part.

Therefore, it is considered to make the concentrated liquid of the photographic processing agent into a powder, but in that case, there is a high possibility that fine powder will fly up when the solution is dissolved and the worker may inhale it, which may cause a health problem. Occurs, or the raised processing agent component is mixed into another photographic processing solution, which causes contamination and causes a problem.
Therefore, a technique of granulating a photographic processing agent to form a granular mixture is proposed in, for example, JP-A-2-09042, JP-A-2-09043, U.S. Patents 2,843,484 and 3-39735.
Occupational health and safety issues due to scattered drug dust,
Problems such as mixing into other types of treatment liquids as impurities, or caking phenomenon in which sedimentation / condensation occurs at the bottom of the container during dissolution, powder coating with its own wet coating, and poor dissolution resulting in poor mixing workability. In reality, the range of drugs suitable for pulverization and granulation is extremely limited.

Therefore, tableting is a preferable form of the treating agent which takes advantage of the advantages of these dry conditions.
No. 2-109042, No. 2-109043, and the like.

Tableting of the treatment agent is very useful in terms of reliability of preparation, workability of workability, and occupational hygiene, but the number of small packages is reduced as much as possible, and at most several types of tablet packages are used. In order to reduce the amount of the drug, several drugs will coexist in the tablet, and the stability during storage and the mutual reactivity at the time of preparation, solubility, dissolution order, pll, Binders that are irrelevant to behavior against oxidation, exothermicity, endotherm, technical treatment for changes in dissolved concentration of components and total amount of dissolution, or dissolution rate as tablets, abrasion resistance, and photographic characteristics for maintaining tablet form. The technical considerations for selection of disintegrants and lubricants, and the amount used, etc. must all be incorporated without mutual conflict.

Among them, the storage stability cannot be completely solved even by solidification such as granulation and tableting, and at present, the stability of performance during storage with time and the development of a developer are not possible. Oxidants of developing agents, bleach-fixing agents, fixing agents to prevent the formation of insoluble matter such as sulfur and sulfide,
Further improvement is desired.

As a result of earnest studies, the present inventors have found that the above problems can be solved by granulating to a specific particle size, and then compressing under pressure and tableting, and accomplished the present invention. It was In addition, by applying a specific particle size distribution, the adhesion of fine powder to the tableting machine punch (hereinafter referred to as sticking)
Therefore, it was found that the obstacles during continuous tableting were extremely reduced. This was surprising and unexpected from our previous knowledge.

[0012]

OBJECTS OF THE INVENTION Accordingly, the object of the present invention is to improve storage stability, to prevent the formation of insoluble matter, to eliminate sticking and to significantly reduce obstacles during continuous tableting. It is an object of the present invention to provide a tablet for processing a silver halide color light-sensitive material having a social environment suitability and a work environment suitability without using a plastic bottle, and a method for producing the same.

[0013]

The present inventors have conducted extensive studies in order to achieve the above object, and as a result, in a tablet for processing a silver halide color light-sensitive material containing at least two compounds, a composition of the tablet was obtained. It has been found that the above object can be achieved by the tablet characterized by being granulated to have an average particle size of 100 to 800 μm, and then being pressed and solidified, and a method for producing the same.

The tablet type treating agent of the present invention is disclosed in, for example, Japanese Patent Application Laid-Open No.
-61837, 52-88025, 54-155038, British patents 1,2
It can be produced by a general method described in the specification such as 13,808.

That is, a plurality of solid chemicals used in the photographic processing according to the present invention are uniformly mixed in a mixer, pulverized, and then granulated in a fluidized bed spray granulator. This granulated product is mixed with a granulated product composed of a plurality of solid drugs separately prepared by the above method, and the mixture is tableted to produce a tablet-type treatment agent. In this case, it is particularly preferable for the present invention to use a granulated product having an average particle size of 100 to 800 μm. When the average particle size is 100 μm or less, the storage stability is deteriorated, and when the average particle size is 800 μm or more, the storage stability is insufficient.

It is preferably 200 to 750 μm, particularly preferably 3
It is from 00 to 600 μm.

This granulated product is, for example, disclosed in JP-A 2-10
It can be produced by a general method described in 9042, 2-09043, 3-39735, 3-39739 and the like.

The water content per tablet of the tablet-type treatment agent of the present invention is 0.5 to 10 wt%, preferably 1.0 to 10 wt%, and particularly preferably 2.0 to 8.0 wt%.

If the water content is less than 0.5 wt%, the strength will be insufficient, and if it exceeds 10 wt%, the content of the main ingredient in the tablet will be reduced.

Further, the particle size distribution is ± 10 for 60% or more of the particles.
Those within a deviation of 0 to 150 μm are preferred.

A method for producing a tablet processing agent is described in, for example, JP-A-51.
-61837, 54-155038, 52-88025, British Patents 1,2
It can be produced by a general method described in 13,808 and the like, and the granule treating agent is, for example, JP-A-2-09042 and 2-09043.
No. 3-39735, No. 3-39739, etc. Further, the powder processing agent can be produced by a general method as described in, for example, JP-A-54-133332, British Patents 725,892, 729,862 and German Patent 3,733,861.

The bulk density of the solid photographic processing agent of the present invention is 0.5 to 5 from the viewpoint of its solubility and the effect of the object of the present invention.
Preferably having 6.0 g / cm ^3, it is preferably used especially 1.0 to 5.0 g / cm ^3.

The solid photographic processing agent of the present invention is a color developing agent,
The black-and-white developer, the bleaching agent, the fixing agent, the bleach-fixing agent, the stabilizer and the like can be mentioned, but the one which more effectively exhibits the effect of the present invention is the color developing agent.

When the processing agent in the present invention is a color developing agent, as the color developing agent to be used, a p-phenylenediamine compound having a water-soluble group exerts the desired effect of the present invention favorably and causes fog. It is preferably used because it has a small amount.

The p-phenylenediamine-based compound having a water-soluble group has less contamination of the photosensitive material than the para-phenylenediamine-based compound having no water-soluble group such as N, N-diethyl-p-phenylenediamine, and As for the skin, not only has the advantage that the skin is less susceptible to rash, but the object of the present invention can be achieved more effectively 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 of the p-phenylenediamine compound or on the benzene nucleus. Specific water-soluble groups 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) nCmH 2 m +1 (m and n each represents an integer of 0 or more.), - COOH group, and as -SO ₃ H group and the like.

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 described on page
-3-Methyl-N- (3-hydroxypropyl) aniline and the like can be mentioned.

The color-developing agent is usually used in the form of a salt such as hydrochloride, sulfate or p-toluenesulfonate.

The color developing agent may be used alone or in a mixture of 2
In combination with one or more kinds, 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 metol.

Further, in the present invention, when the color developer according to the present invention contains the compounds represented by the following general formulas [A] and [B], not only the effects of the present invention are exhibited more effectively. This is also one of the preferable modes because it also produces the effect of causing less fog in the unexposed portion.

[0031]

[Chemical 1]

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.

Further, 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 phosphoric acid 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 aryl group of R ₁ , R ₂ and R ₃ include those having a substituent, and
Examples of the ring that may be formed by R ₁ and R ₂ include heterocycles such as piperidine, pyridine, triazine and morpholine.

[0035]

[Chemical 2]

In the formula, R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group, and R ₁₄ represents a hydroxyl group, a hydroxyamino group, a substituted or unsubstituted group. It represents a substituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group or amino group. The heterocyclic group is a 5- or 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 a divalent group selected from -C (= NH)-, and n is 0
Or 1. Particularly 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 heterocycle.

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

Specific examples of the compound represented by the general formula [B] are described in Japanese Patent Application No. 2-203169, pages 40 to 43 (B-1) to
(B-33) and (1) to JP-A-3-33846, pages 4 to 6
(56) is mentioned.

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

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

[0041]

[Chemical 3]

In the formula, L represents an alkylene group which may be substituted, A is a carboxyl group, a sulfo group, a phosphono group, a phosphino group, a hydroxyl group, an amino group which may be alkyl-substituted, an ammonio group and a carbamoyl group, respectively. Alternatively, it represents a sulfamoyl group, and R represents a hydrogen atom or an optionally substituted alkyl group.

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 above all (1)
And the following compounds represented by (7) are preferable.

(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 an alkylation reaction of commercially available hydroxylamines. It is obtained by doing. For example, West German Patent 1,159,634 and Inorganica Chimica Acta., 93
(1984) 101 to 108 and the like according to the synthesis method.

A small amount of sulfite can be used as a preservative in the color developer and the black and white developer according to the present invention. Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite and the like.

It is necessary to use a buffering agent in the color developing agent and the black and white developing agent according to the present invention. As the buffering agent, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, phosphoric acid is used. Tripotassium, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo- 2
-Sodium hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned.

As a development accelerator, Japanese Examined Patent Publication No. 37-16088,
37-5987, 38-7826, 44-12380, 45-9019
And thioether compounds represented by U.S. Pat. No. 3,813,247, p-phenylenediamine compounds represented by JP-A-52-49829 and 50-15554, and JP-B-44-30074.
No. 5, JP-A-50-137726, JP-A-56-156826 and JP-A-52-43429
Quaternary ammonium salts represented by U.S. Pat.
0,122 and 4,119,462 described p-aminophenols, U.S. Patents 2,494,903, 3,128,182, 4,230,79
No. 6, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2,48
Amine compounds described in 2,546, 2,596,926 and 3,582,346 etc., Japanese Patent Publication Nos. 37-16088, 42-25201, U.S. Patents 3,128,183, 41-11431, 42-23883, and U.S.A. Polyalkylene oxides represented by patents 3,532,501 and the like, other 1-phenyl-3-pyrazolidones,
Hydrazines, mesoionic compounds, ionic compounds,
Imidazoles and the like can be added as necessary. 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, chlorine ions are 1.0 × 10 ^{-2 to} 1.5 × 10 ^-1.
Mol / l, more preferably 3.5 × 10 ^-2 to 1 × 10 ^-1 mol / l
Contains l. When the chlorine ion concentration is more than 1.5 × 10 ^-1 mol / l, it is not preferable to delay the 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 variation (particularly minimum density) due to continuous processing becomes large, which is not preferable.

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

When added directly to the color developing agent, sodium chloride, potassium chloride,
Ammonium chloride, nickel chloride, magnesium chloride,
Examples thereof include manganese chloride, calcium chloride and cadmium chloride, of which sodium chloride and potassium chloride are preferred.

It may also be supplied in the form of a salt of the color developing agent and the optical brightening agent added to the developing agent.

As the bromine ion supplying substance, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, Thallium bromide may be mentioned, of which potassium bromide and sodium bromide are preferred.

To the color developing agent and developer of the present invention, an optional antifoggant can be added in addition to chlorine ion and bromine ion, if necessary. As the antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-
Includes such as nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine and adenine. A nitrogen heterocyclic compound can be mentioned as a typical example. The color developer and developer of the present invention preferably contain a triazinyl stilbene-based optical brightening agent from the viewpoint of the effect of the object of the present invention. As the fluorescent whitening agent, a compound represented by the following general formula [E] is preferable.

[0053]

[Chemical 4]

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,
An alkyl group, an aryl group, a -N (R ₂₁ ) (R ₂₂ ) group,

[0055]

[Chemical 5]

Or OR ₂₅ . Here, R ₂₁ and R ₂₂ are each a hydrogen atom, an alkyl group (including a substituent) or an aryl group (including a substituent), R ₂₃ and R ₂₄ are 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 their substituents are the same as those described in Japanese Patent Application No. 2-240400, from page 62 down to line 8 to page 64 down to line 3. As specific compounds, E-1 to E-45 described on pages 65 to 67 of the same item can be mentioned.

The above compounds can be synthesized by a known method. Representative compounds are exemplified below, and among them, particularly preferably used are E-4, E-24, E-34,
E-35, E-36, E-37 and E-41. The amount of these compounds added is preferably in the range of 0.2 to 10 g, and more preferably 0.4 to 5 g, per 1000 ml of color developing solution.

[0059]

[Chemical 6]

[0060]

[Chemical 7]

Further, in the color developing agent and the black and white developing agent used in the present invention, if necessary, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other Japanese Patent Publication Nos. 47-33378, 44-33378. The compounds described in No. 9509 can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developing agent may be used together with the developing agent. Examples of these auxiliary developers include, for example,
N-methyl-p-aminophenol hexalphate (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.

Furthermore, various additives such as stain inhibitors, sludge inhibitors, and stacking effect accelerators can be used.

Further, for the color developing agent and the black and white developing agent, a chelating agent represented by the following general formula [K] and its exemplified compounds described in Japanese Patent Application No. 2-240400, page 69, bottom, line 9 to page 74, can be used. K-
Addition of 1 to K-22 is preferable from the viewpoint of effectively achieving the object of the present invention.

[0065]

[Chemical 8]

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

The amount of these chelating agents added is preferably in the range of 0.1 to 20 g, and more preferably 0.2 to 8 g, per 1000 ml of the color developing agent and the black and white developing agent.

Furthermore, 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 alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added.

When the processing agent according to the present invention is a bleaching agent or a bleach-fixing agent, the bleaching main agent preferably used is an organic acid represented by the following general formulas [L], [M], [N] and [P]. It is a ferric complex salt.

[0070]

[Chemical 9]

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.

The compound represented by the general formula [L] will be described in detail below.

The groups represented by A _{1 to} A ₄ are Japanese Patent Application No. 1-260628.
Since it has the same meaning as A _{1 to} A ₄ described on page 12, line 15 to page 15, line 3, detailed description thereof will be omitted.

Preferred specific examples of the compound represented by the above 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-6) -7) 1,3-Propanediamine tetrakismethylenephosphonic acid (L-8) 2-Hydroxy-1,3-propanediamine tetrakismethylenephosphonic acid (L-9) 2,2-Dimethyl-1,3-propanediamine Acetic acid (L-10) 2,4-butanediaminetetraacetic acid (L-11) 2,4-Pentanediaminetetraacetic acid (L-12) 2-Methyl-2,4-pentanediaminetetraacetic acid (L-1) As the ferric iron complex salts of the compounds (L to 12), sodium, potassium or ammonium salts of these ferric iron complex salts can be used. It can be used arbitrarily. From the viewpoint of the effect and solubility of the object of the present invention, ammonium salts of these ferric complex salts are preferably used.

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

Next, the compound represented by the general formula [M] will be described in detail.

[0078]

[Chemical 10]

A _{1 to} A ₄ are as defined above, and n is 1 to 8
Represents the integer. B ₁ and B ₂ may be the same or different and each represents a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms (for example, ethylene, propylene, butylene, pentamethylene, etc.). Hydroxyl group as the substituent, carbon number 1 to
3 lower alkyl groups (methyl group, ethyl group, propyl group) and the like.

Preferred specific examples of the compound represented by the above general formula [M] are shown below.

[0081]

[Chemical 11]

As the ferric iron complex salts of the compounds (M-1) to (M-7), sodium salts, potassium salts or ammonium salts of the ferric iron complex salts of these compounds can be optionally used.

Among the ferric iron complex salts of the organic acid of the present invention, the ferric iron complex salt of the organic acid represented by the general formula [L] or [M] is most preferably used for exhibiting the effect of the present invention, and particularly (L
-1), (L-3), (L-4), (L-5), (L-
9), (M-1), (M-2) and (M-7), and particularly preferably (L-1) or (M-1).

Next, compounds represented by the general formula [N] are shown.

[0085]

[Chemical 12]

In the formula, R ₁ represents a hydrogen atom or a hydroxyl group,
n is 1 or 2, x is 2 or 3, y is 0 or 1, and the sum of x and y is always 3.

Preferred compounds represented by the general formula [N] are [N-1] and [N-2].

[0088]

[Chemical 13]

Next, the compound represented by the general formula [P] is shown.

[0090]

[Chemical 14]

In the formula, A _{1 to} A ₄ may be the same or different and each represents —CH ₂ OH, —PO ₃ M ₁ M ₂ or —COOM ₃ . M ₁ , M ₂ or M ₃ represents a hydrogen atom, an alkali metal atom (eg sodium, potassium) or another cation (eg ammonium, methylammonium, trimethylammonium etc.). X is an alkylene group of a substituted or unsubstituted 2-6 carbon atoms _{- (B 1 O) n-} B 2 - represents a. B ₁ and B ₂ may be the same or different and each represents a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms.

Examples of the alkylene group represented by X include ethylene, trimethylene, tetramethylene and the like.
Examples of the alkylene group represented by B ₁ or B ₂ include methylene, ethylene, trimethylene and the like. X, B
Examples of the substituent of the alkylene group represented by ₁ or B ₂ include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group, etc.) and the like. n represents an integer of 1 to 8, and preferably 1 to 4. Specific preferred examples of the compound represented by formula [P] are shown below, but the invention is not limited thereto.

[0093]

[Chemical 15]

[0094]

[Chemical 16]

As the bleaching agent, a ferric iron complex salt of the following compound can be used in addition to the iron complex salt of the compound represented by the above general formula [A].

(A'-1) Ethylenediaminetetraacetic acid (A'-2) Trans-1,2-cyclohexanediaminetetraacetic acid (A'-3) Dihydroxyethylglycinic acid (A'-4) Ethylenediaminetetrakismethylenephosphonic acid (A'-4) A'-5) Nitrilotrismethylenephosphonic acid (A'-6) Diethylenetriamine pentakismethylenephosphonic acid (A'-7) Diethylenetriaminepentaacetic acid (A'-8) Ethylenediaminedioltohydroxyphenylacetic acid (A'-9) Hydroxy Ethyl ethylenediamine triacetic acid (A'-10) ethylenediamine dipropionic acid (A'-11) ethylenediamine diacetic acid (A'-12) hydroxyethyliminodiacetic acid (A'-13) nitrilotripropionic acid (A'-14) tri Ethylenetetramine hexaacetic acid (A'-15) ethylenedi The addition amount of the amine tetra acid said organic acid ferric complex salts are preferably contains in the range of the bleaching solution or the bleach-fixing solution 1000ml per 0.1 to 2.0 moles, more preferably from 0.15 to 1.5 mol / l.

Examples of the bleaching agent, the bleach-fixing agent and the fixing agent include imidazoles and derivatives described in JP-A No. 64-295258 or compounds represented by the general formulas [I] to [IX] described in the same article, and their examples. By containing at least one kind of compound, the effect of rapidity is exerted.

In addition to the above-mentioned accelerators, JP-A-62-123459, 5
Exemplified compounds described on pages 1 to 115 and 22 of JP-A-63-17445
Pp. 25 to the exemplified compounds, JP-A Nos. 53-95630 and 53-2.
The compounds described in No. 8426 and the like can be used as well.

In addition to the above, the bleaching agent or bleach-fixing agent may contain a halide such as ammonium bromide, potassium bromide or sodium bromide, various fluorescent whitening agents, defoaming agents or surfactants. it can. When the processing agent according to the present invention is a fixing agent or a bleach-fixing agent, thiocyanates and thiosulfates are preferably used as the fixing main agent used. The content of thiocyanate is preferably at least 0.1 mol / l or more, more preferably 0.5 mol / l or more, and particularly preferably 1.0 mol / l or more when processing a color negative film. The content of thiosulfate is preferably at least 0.2 mol / l or more, more preferably 0.5 mol / l when processing a color negative film.
It is 1 or more. In the present invention, the object of the present invention can be more effectively achieved by using thiocyanate and thiosulfate together.

The fixing agent or bleach-fixing agent according to the present invention includes
In addition to these fixing base agents, pH buffer agents composed of various salts may be used alone or in combination of two or more kinds. Furthermore, alkali halides or ammonium halides such as potassium bromide,
It is desirable to add a large amount of a rehalogenating agent such as sodium bromide, sodium chloride or ammonium bromide.
Further, a compound known to be added to a compound which is usually added to a 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 the compound represented by the following general formula [FA] described in No. 258, page 56 and the exemplified compounds thereof, and not only the effect of the present invention is more exerted but also a small amount of a light-sensitive material is processed for a long period of time. Another effect is that the amount of sludge generated in the processing liquid having fixing ability is extremely small during the process.

[0102]

[Chemical 17]

The compound represented by the general formula [FA] described in the above item 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 kinds. The addition amount of these compounds is 0.1 to 200 g per 1000 ml of treatment liquid.
Good results are obtained in the range.

In the present invention, the stabilizer preferably contains a chelating agent having a chelate stability constant for ferric ions of 8 or more. Here, the chelate stability constants are the Stability Constants by LG Sillen / AEMartell.
of Metal-ion Complexes ”, The Chemical Society, Lon
don (1964) by S. Chaberek AEMartell "Organic Seq"
Uestering Agents ”, Wiley (1959), etc. means a constant generally known. As a chelating agent having a chelate stability constant for ferric ions of 8 or more, Japanese Patent Application No. 2-2347
No. 76, No. 1-324507, etc. are mentioned. The amount of these chelating agents used is 0.01 to 50 per 1000 ml of stabilizer.
g is preferable, and more preferably 0.05 to 20 g, and good results are obtained.

Further, as a preferable compound added to the stabilizer, an ammonium compound can be mentioned. These are supplied by ammonium salts of various inorganic compounds. Addition amount of ammonium compound is 0.001 per 1000 ml of stabilizer.
To 2.0 mol is preferable, and more preferably 0.002 to 1.
It is 0 mol. Further, the stabilizer preferably contains sulfite. Furthermore, 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,
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 1000 ml of stabilizer.
A molar range is preferable, and more preferably 4 × 10 ⁻⁴ to 2 ×
It is 10 ^-2 mol.

Further, as the stabilizer, an organic acid salt (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), a pH adjusting agent (phosphate salt, borate salt, hydrochloride salt, sulfate salt, etc.) are added. be able to.

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

Next, a light-sensitive material to which the processing agent of the present invention is applied will be described.

When the light-sensitive material is a light-sensitive material for photographing, silver iodobromide or silver iodochloride having an average silver iodide content of 3 mol% or more is used as the silver halide grain, but particularly 4 to 15 mol. Silver iodobromide containing up to 5% silver iodide is preferred. Above all,
The average silver iodide content of the present invention is preferably 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 following shows the locations of description.

[Item] [Page of RD308119] Iodine composition 993 IA Item Production method 993 I-A item and 994 E Item Crystal habit Normal crystal 993 I-A Twin twin 〃 Epitaxial 〃 Halogen composition Uniform 993 I- Item B Non-uniform 〃 Halogen conversion 994 IC item 〃 Substitution 〃 Metal-containing 994 Item ID Monodisperse 995 Item IF Addition of solvent 〃 Latent image forming position Surface 995 Item Internal 〃 Applied Sensitive Negative 995 Item I-H Positive (including internal fog grains) 〃 Mix and use emulsions 995 Item I-J Desalting 995 Item II-A Silver halide emulsions are those that have undergone physical ripening, chemical ripening and spectral sensitization. use. Additives used in such processes are Research Disclosure No.17643, No.1
8716 and No.308119 (hereinafter RD17643, RD18716, respectively)
And RD308119). The following shows the locations of description.

[Item] [Page of RD308119] [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 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 It is described in the disclosure. Below are the relevant locations.

[Items] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Whitening agent 998 V 24 UV absorber 1003 VIII C , XIII C Item 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricants 1006 XII 27 650 Activators and coating aids 1005 XI 26 to 27 650 Matting agents 1007 X VI Developers (contained in light-sensitive materials) 1011 XX-B Photosensitized by the photographic processing agent Various couplers can be used in the material, specific examples of which are described in Research Disclosure above. Below are the relevant locations.

[Items] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VII C to G magenta coupler 1001 VII-D item VII C to G item Cyan coupler 1001 VII-D item VII C to G item DIR coupler 1001 VII-F section VII F section BAR coupler 1002 VII-F other useful residue releasing coupler 1001 VII-F section Alkali-soluble coupler 1001 VII-E section Additives are dispersions described in RD308119 XIV It can be added by a method or the like.

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

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

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

The silver halide 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 preferable, more preferably 10 mol% or less, further preferably 3 mol% or less, and when silver iodide is present, 1 mol% or less is preferable, and more preferably 0.5 mol%.
Below, it is most preferably zero. Such silver chloride 50
The silver halide grains mainly composed of silver chloride containing more than mol% are
It may be applied to at least one silver halide emulsion layer, but is preferably applied to all light-sensitive silver halide emulsion layers.

The crystal of the silver halide grains may be normal crystal, twin crystal or other crystal, and any ratio of [1.0.0] plane to [1.1.1] plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layer (phase) -like structure (core / shell type) having different inside and outside. Good. Further, these silver halides may be of a type that forms a latent image mainly on the surface or a type that forms inside of grains. Further, tabular silver halide grains (Japanese Patent Application Laid-Open No. 58-113934, Japanese Patent Application No.
9-170070) can also be used. In addition, JP-A 64-2
The silver halides described in 6837, 64-26838, 64-77047 and the like can be used.

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

[0121]

The present invention will be described in more detail below with reference to examples of the present invention, but the present invention is not limited to these examples.

Example 1 A color developing tablet for a color negative film was prepared according to the following procedure.

Operation (1) 3.5 g of hydroxylamine sulfate is ground in an air jet pulverizer until the average particle size becomes 10 μm. The fine powder is granulated in a commercially available fluidized bed spray granulator at room temperature for about 7 minutes to granulate it to an average particle diameter of 95 μm, and then the granulated product is dried at an air temperature of 63 ° C. for 8 minutes. .. Then granulate in vacuum
Dry at 90 ° C for 90 minutes to almost completely remove the water content of the granular material.

Operation (2) 6.2 g of the developing agent CD-4 [4-amino-3methyl- (N-ethyl-N-β-hydroxylethyl) aniline sulfate] 6.2 g of air jet finely ground as in the operation (1) After crushing in the machine, granulate while spraying water. After granulation, it is dried at 60 ° C. for 7 minutes. The granulate is then dried in vacuum at 40 ° C. for 90 minutes to remove water almost completely.

Operation (3) 1-Hydroxyethane-1,1-diphosphonate sodium 2.5
After homogenizing g, 1.75 g of sodium sulfite, 15.4 g of potassium carbonate, 0.75 g of sodium hydrogen carbonate and 0.35 g of sodium bromide in a commercially available mixer, pulverize in an air jet fine pulverizer as in step (1). Then, granulate. After granulation, dry at 70 ° C for 10 minutes. Next, the granular material is dried in vacuum at 40 ° C. for 90 minutes to almost completely remove water.

Procedure (4) 1.75 g of sodium sulfite, 2.0 g of sodium diethylenetriaminepentaacetate, 15.4 g of potassium carbonate, 0.75 g of sodium hydrogencarbonate and 0.35 g of sodium bromide are granulated in the same manner as in the procedure (3). The drying temperature was 80 ° C. and the time was 10 minutes.

Operation (5) The granulated product granulated by the above operations (1) to (4) is uniformly mixed for about 10 minutes by a mixer in a room where the relative humidity is 40% or less at 25 ° C. .. Next, the mixture is tableted by a processing agent tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho. In tableting, 5.00 g of the above mixture was charged into the above tableting machine and molded. This operation was repeated to prepare 10 color-developing tablet samples 1 for color film from the mixture.

Operation (6) The same operation was performed except that the average particle size of the granulated product was adjusted to the value shown in Table 1 in the operation (1), and the operations (2) to (5) were performed. The same operation as above was repeated to prepare tablet samples 2 to 11.

Experiment Two tablet samples obtained by the above operation were put in a polyethylene bag, sealed, and stored at 65 ° C. for 2 months. After storage, the content of CD-4 in one tablet was measured, and the value before storage was set to 100% to determine the residual rate. The results are shown below.

[0130]

[Table 1]

From Table 1 above, when tablets were made from granules having an average particle size of less than 100 μm or more than 800 μm, the storability of the obtained tablets was poor, and the tablets of the present invention had a good preservation. It can be seen that it has the property.

(Example 2) Operation (7) 160 g of sodium thiosulfate, 10 g of sodium sulfite, 37.5 g of potassium thiocyanate and 1.0 g of sodium ethylenediaminetetraacetate are granulated in the same manner as in the operation (3). 77 after drying
The time was 10 minutes at ° C.

Operation (8) The granulated product granulated in the above operation (7) was tableted in the same manner as in the operation (5). Twenty-five color fixing film fixing tablet samples 12 to 22 were prepared in the same manner as in the operations (5) and (6) except that the filling amount in the processing agent tableting machine was 9.0 g.

Next, the 10 samples thus obtained were stored under the same conditions as in Example 1 and then dissolved in 250 ml of water to examine the presence or absence of insoluble matter.

The results are shown below. The evaluation of insoluble materials in the table is as follows.

X: There are various sizes of insoluble matter.

(The larger the number x, the larger the amount of insoluble matter.) Δ: Insoluble matter is slightly observed.

◯: There is no insoluble matter at all.

[0139]

[Table 2]

From the above table, it can be seen that the fixing treatment tablet of the present invention does not generate insoluble matter and has good storability.

Example 3 Operation (9) 200 g of diethylhydroxylamine oxalate and 55 g of sodium hydrogen carbonate are granulated in the same manner as in operation (1). The drying temperature was 70 ° C. and the time was 70 minutes.

Operation (10) 270 g of CD-3 [1- (N-ethyl-N-methanesulfonamidoethyl) -3-methyl-p-phenylenediamine sesquisulfadede monohydrate as a developing agent was operated (2) Granulate as in.
Operation (2) except that the drying temperature was 63 ° C and the time was 8 minutes
Same as.

Operation (11) Granules of 6 g of sodium sulfite, 450 g of potassium carbonate, 22.5 g of sodium hydrogen carbonate and 75 g of Tinopearl SFP are granulated in the same manner as in the operation (3). The same operation (3) was performed except that the drying temperature was 73 ° C. and the time was 10 minutes.

Operation (12) 450 g of potassium carbonate, 120 g of sodium diethylenetriamine pentaacetate, 22.5 g of sodium hydrogen carbonate, Pluronic F
Granulate 60 g of -68 (manufactured by Asahi Denka) in the same manner as in step (4).
Operation (4) except that the drying temperature was 73 ° C and the time was 10 minutes.
Same as.

Operation (13) The granulated product granulated in the above operations (9) to (12) is operated (5).
After mixing in the same manner as in (1), the mixture was placed in a processing agent tableting machine and tableted. Color-developing tablets for color paper, 50 each, were prepared in the same manner as in steps (5) and (6) except that the amount of the processing agent tableting machine filled was 7.0 g.

Then, the same storage test as in Example 1 was conducted.
As a result, the same result as in Example 1 was obtained.

Example 4 A bleach-fixing tablet sample for color paper was prepared according to the following procedure.

Operation (14) 600 g of ferric sodium ethylenediaminetetraacetate, 10.8 g of ethylenediaminetetraacetic acid and 6.25 g of sodium hydrogencarbonate are granulated in the same manner as in the operation (3). Drying temperature is 80 ℃ and time is 10
Minutes.

Operation (15) Sodium thiosulfate 730 g, potassium thiocyanate 271 g
Then, 216 g of sodium sulfite, 27 g of sulfinic acid and 54 g of potassium bromide are granulated in the same manner as in step (3). Drying temperature is 77
The time was 10 minutes at ° C.

Operation (16) The granulated product granulated in the above operations (14) and (15) was mixed in the same manner as in the operation (5), and then tableted. Bleach-fixing tablet sample 4 for 100 color papers in the same manner as in steps (5) and (6), except that the filling amount in the processing tableting machine was 5.0 g.
Created 2 to 51.

After the same storage as in Example 1, the presence or absence of insoluble matter and the residual ratio of thiosulfate were examined. The results are shown below.

[0152]

[Table 3]

From Table 3 above, it can be seen that the bleach-fixing tablet of the present invention has good storability.

(Example 5) Exemplified compound C-17 was used in place of CD-3 in Example 3, and the deviation of the particle size was adjusted to the value shown in Table 4 in each granulation operation. Conducted the same operation experiment as in Example 3. The results are shown below.

[0155]

[Table 4]

From Table 4 above, the particle size distribution of the granulated product is ± 100 to 1
It can be seen that when it is 50 μm or less and 60% or more, there is no adhesion (sticking) of fine powder to the punches of the tableting machine, and there are very few obstacles during continuous tableting.

[0157]

INDUSTRIAL APPLICABILITY According to the present invention, storage stability (reduction of effective content, prevention of insoluble matter generation, etc.) is improved, and sticking is eliminated so that obstacles during continuous tableting are significantly reduced. It is possible to provide a tablet for processing a silver halide color light-sensitive material having a social environment suitability and a work environment suitability without using a plastic bottle, and a method for producing the same.

Claims (2)

[Claims] 1. A tablet for processing a silver halide color light-sensitive material containing at least two compounds, wherein the composition of the tablet is granulated to have an average particle size of 100 to 800 μm, and then compressed under pressure to be solidified. A method for producing the tablet, comprising: 2. A tablet for processing a silver halide color light-sensitive material produced by the method according to claim 1.