JPH063787A - Solid color developing agent for silver halide photographic sensitive material and processing method using that solid color developing agent - Google Patents

Abstract

PURPOSE:To obtain a solid color developing agent for a silver halide photo graphic sensitive material and processing method of this solid color developing agent suitable for environmental conditions by incorporating specified plural compds. CONSTITUTION:This solid color developing agent for a silver halide photographic sensitive material contains at least one kind of compd. expressed by formula I or II, and at least one kind of compd. expressed by formula III. In formula I, A1-A5 are -COOM, -PO3M2, or -CH2OH, and M is a hydrogen atom or alkali metal. In formula II, A1-A4 are -COOM, -PO3M1M2, or -CH2OH, M, M1 and M2 are hydrogen atoms, alkali metals or ammonium, and X is a substd. or unsubstd. alkylene group of 2-6 carbon number. In formula III, X1, X2, Y1, Y2 are hydroxyl groups, halogen atoms, morphorino groups, alkoxy groups, aryloxy groups, alkyl groups, aryl groups, amino groups, alkylamino groups, etc., and M is a hydrogen atom, alkali metal or other cation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid color developing processing agent and processing method for silver halide photographic light-sensitive materials, and more specifically, it has excellent stability in photographic processing performance, has improved fog in unexposed areas, and can be stored in a liquid. It relates to a processing technology with excellent properties.

[0002]

BACKGROUND OF THE INVENTION A color developing solution is usually used in the color development processing of an exposed silver halide photographic light-sensitive material.
This color developing solution is put in a plastic bottle in the form of one or a plurality of concentrated liquid parts in consideration of easiness of handling, and supplied to a 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 laboratories using a small automatic developing machine called a minilab has been rapidly increasing, and the amount of plastic bottles used for processing agents has been rapidly increasing. Since this plastic bottle is light and strong, it is widely used in addition to photoprocessing agent bottles, and the worldwide production of plastics is increasing year by year. It is increasing to exceed the amount.

On the other hand, the amount of discarded plastic is enormous, and about 40% of the production amount is discarded year by year, even in Japan. When such waste plastic is dumped into the ocean, it causes deterioration of the habitat of marine organisms, and in Europe, since it is incinerated in an incinerator that does not have exhaust gas treatment facilities, it causes problems such as acid rain. Is also causing.

For this reason, urgent measures have to be taken, and legal regulations such as plastic recycling and use prohibition, or obligatory use of degradable plastics have become active in Europe and America. It's a reality.

Under these circumstances, it can be said that it is extremely unfavorable to use a large amount of plastic bottles as a processing agent for photographic use, although the present invention is a thick liquid processing method. We tried to reduce the number of plastic bottles by making the agent kit solid.

[0007] In addition, the problem of environmental pollution has begun to be highlighted worldwide, and in 1995, the photographic processing effluent was banned when it was in the ocean, so that it became necessary to reduce the amount of the photographic processing effluent. For this reason, when the replenishing amount of the replenishing liquid is reduced, the replenishing liquid having a high concentration has to be obtained, so that it may be deposited in the replenishing liquid tank. The replenishment solution is required to be low in replenishment for the above-mentioned reason, and as another method, it was considered to solidify the replenishment solution to supplement only the insufficient component.

[0008] Therefore, it was found that powdering was first considered, but the scattering was violent, and the problem of scattering was alleviated but insufficient when using granules, and it was found that tableting is preferable.

However, when tablets are formed, there is a problem that the solubility is not so good and the insoluble substance remains and adheres to the light-sensitive material to cause various problems, and the storage stability against humidity and oxygen is poor. all right.

The inventors of the present invention have made extensive studies and found that the above problem can be solved by incorporating a specific compound in the solid processing agent.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is, firstly, to provide a solid color developing treatment agent for silver halide photographic light-sensitive materials which is suitable for social environment and a processing method using the solid color developing treatment agent. And secondly to provide a solid color developing treatment agent for silver halide photographic light-sensitive materials and a processing method using the solid color developing treatment agent, which does not cause defective dissolution or problems associated therewith, and thirdly, storability. An object of the present invention is to provide a solid color development processing agent for silver halide photographic light-sensitive materials excellent in the above and a processing method using the solid color development processing agent.

[0012]

A solid color developing agent for a silver halide photographic light-sensitive material which achieves the above object is at least one compound represented by the following general formula [I] or [IV] and the following general compound. It is characterized by containing at least one compound represented by the formula [E].

[0013]

Embedded image General formula [I] [In the formula, A _{1 to} A ₅ may be the same or different,
-COOM, -PO ₃ M ₂ or an -CH ₂ OH, M represents a hydrogen atom or an alkali metal. ]

[0014]

Embedded image General formula [IV] [In the formula, A _{1 to} A ₄ may be the same or different and each represents —COOM, —PO ₃ M ₁ M ₂ or —CH ₂ OH, and M, M ₁ and M ₂ are each a hydrogen atom or an alkali metal. Or represents ammonium. X represents a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms. ]

[0015]

Embedded image General formula [E] [Wherein X ₁ , X ₂ , Y ₁ and Y ₂ represent a hydroxyl group, a halogen atom, a morpholino group, an alkoxy group, an aryloxy group, an alkyl group, an aryl group, an amino group, an alkylamino group and an arylamino group, respectively. . M represents a hydrogen atom, an alkali metal or other cation. In a preferred embodiment of the present invention, the following general formula [II] or [III]
Is to contain at least one kind of compound or monosaccharide shown in.

[0016]

Embedded image General formula [II][In the formula, R₁And R_TwoAre hydrogen atom and alkyl
Group, aryl group, alkoxy group, R₃-CO- group, R₃−
CS-group, R₃-SO₂-Group, R₃-SO Represents a group,
R₁And R_TwoAre not hydrogen atoms at the same time. Also
R₁And R_TwoMay combine with each other to form a ring. Furthermore R
₃Is an alkyl group, aryl group, alkoxy group, amino group
Or represents a hydrogen atom. X is a hydrogen atom or a hydrolysis reaction
Is a group capable of becoming a hydrogen atom by. ]

[0017]

Embedded image General formula [III] [In the formula, R ₁₁ , R ₁₂ , and R ₁₃ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R ₁₄ represents a hydroxy group, a hydroxyamino group, a substituted or unsubstituted, It represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group or an amino group. R ₁₅ is -CO-, -SO _2-.
Or

[0018]

[Chemical 15] Represents a divalent group selected from, 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 ₁₁ and R ₁₂ , R ₁₃ and R
₁₄ may together form a heterocyclic group. In still another preferred embodiment, the solid color developing treatment agent is a granule, and the solid color developing treatment agent is a tablet.

In another preferred embodiment, the tablet is granulated and then tableted, and the tablet is separately granulated and then tableted.

Next, a method of processing a silver halide photographic light-sensitive material according to the present invention which achieves the above-mentioned object, is the above-mentioned halogen when the exposed silver halide photographic light-sensitive material is continuously processed by using an automatic processor. It is characterized in that it is processed with a processing solution obtained by dissolving a solid color developing processing agent for silver halide photographic light-sensitive materials.

[0021]

DETAILED DESCRIPTION OF THE INVENTION Preferred processing steps in which the solid processing agent of the present invention is used by dissolving it in a use liquid state include, but are not limited to, the following processing steps. (1) Color development → Bleach fixing → Washing → Stable (2) Color development → Bleach → Fixing → Washing → Stable (3) Color developing → Bleach → Bleach fixing → Washing → Stable (4) Color developing → Bleach fixing → Fixing → Washing → Stable (5) Color development → Bleach fixing → Bleach fixing → Washing → Stable (6) Color development → Fixing → Bleach fixing → Washing → Stable (7) Color development → Bleach → Bleach fixing → Fixing → Washing → Stable (8 ) Black-and-white development → Washing → Inversion → Color development → Washing → Adjustment → Bleach → Fixing → Washing → Stable (9) Black development → Washing → Inversion → Coloring development → Washing → Adjustment → Bleaching fixing → Washing → Stable (10) Coloring development → Bleach fixing → Stable (11) Color development → Bleach → Fix → Stable (12) Color development → Bleach → Bleach fixing → Stable (13) Color development → Bleach fixing → Fix → Stable (14) Color development → Bleach fixing → Bleach Fixing → Stable (15) Color development → Fixing → Bleach fixing → Stable (16) Color development → Bleach → Bleach fixing → Fixing → Stable (17) Black and white development → Wash → Reverse → Color development → Washing → Adjustment → Bleaching → Fixing → Stable (18) Black and white development → Washing → Inversion → Color development → Washing → Adjustment → Bleach fixing → Stable By dissolving the solid color developing agent, the color developing solution is Since it is obtained, in the following description, various compounds contained in the solid color developing treatment may be described as components contained in the processing liquid, but unless otherwise specified, they are contained in the solid color developing treatment. Ingredients are also meant.

The same applies to the case where each of the other processing agents is obtained by dissolving the solid processing agent.

The other treating agents are also preferably those obtained by dissolving the solid treating agent.

In the following description, the treatment liquid obtained by dissolving the solid treatment agent is simply referred to as a tank liquid or a treatment liquid.

Next, the general formula [I] used in the present invention,
The compounds and monosaccharides represented by [IV], [E], [II] and [III] will be described.

The following are specific examples of the compound represented by the general formula [I], but the present invention is not limited thereto.

[0027]

[Outer 1] In the present invention, the above compounds may be used alone or in combination of two or more. Of the above, preferred is I-1 or I-6.

The amount of the compound represented by the general formula [I] added is preferably 0.1 to 20 g, and more preferably 0.2 to 8 g, per liter of the color developing solution.

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

In the formula, A _{1 to} A ₄ are Japanese Patent Application No. 1-2606.
No. 28, page 12, line 15 to page 15, line 3 from line A
Since it is synonymous with _{1 to} A ₄ , detailed description is omitted. The preferred specific examples of the compound represented by the general formula [IV] are shown below.

[0031]

[Outside 2]

As the ferric iron complex salt of the compounds of (IV-1) to (IV-13), sodium salt, potassium salt or ammonium salt of the ferric iron complex salt can be optionally used. From the viewpoint of the effect of the present invention and the solubility, ammonium salts of these ferric complex salts are preferably used.

Of the above-mentioned compound examples, those particularly preferably used in the present invention include (IV-1) and (IV-
3), (IV-4), (IV-5) and (IV-9), with (IV-1) being particularly preferred.

The amount of the compound represented by the general formula [IV] added is preferably 0.05 to 20 g, and more preferably 0.1 to 7 g, per liter of color developer.

Next, the compound represented by the general formula [E] used in the present invention will be explained. For details of each group of the general formula [E] or their substituents, see Japanese Patent Application No. 2-2.
It is synonymous with the description from page 63, line 8 to page 64, line 3 from line 40400. Specific examples of the compound represented by the general formula [E] are shown below.

[0036]

[Outside 10]

[0037]

[Outside 11]

[0038]

[Outside 12]

[0039]

[Outside 13]

[0040]

[Outside 14]

The above compounds can be synthesized by a known method. Among the above exemplified compounds, E-4, E-24, E-34, E-35 and E-3 are particularly preferably used.
6, E-37, E-41, and E-44. The amount of these compounds added is 0.2 g to 1 per liter of color developer.
It is preferably in the range of 0 g, more preferably 0.
It is in the range of 4 to 5 g.

Next, the compound represented by the general formula [II] used in the present invention will be explained. In the general formula [II], R ₁ and R ₂ are an alkyl group, an aryl group, an alkoxy group, a R ₃ —CO— group, a R ₃ —CS— group, a R ₃ —SO ₂ — group,
It represents an R ₃ —SO— group or a hydrogen atom, which may be unsubstituted or substituted. The unsubstituted alkyl group is a straight chain,
It may be branched or cyclic, and preferably has 1 to 1 carbon atoms.
10, for example, methyl group, ethyl group, n-propyl group, i
So propyl group, n-butyl group), unsubstituted aryl group (preferably having 6 to 10 carbon atoms), unsubstituted alkoxy group (preferably having 1 to 10 carbon atoms, for example, methoxy, ethoxy, butoxy group, methoxyethoxy group) Etc.). R
_{When 1} and R ₂ are groups having a substituent, these substituents are preferably a sulfonic acid group, a hydroxy group, an alkoxy group, a sulfo group, a carboxyl group, an amino group, a hydroxylamino group and the like.

Further substituting groups are aryl groups, halogen atoms (chlorine, bromine, etc.), sulfonamide groups, carbamoyl groups, sulfamoyl groups, aryloxy groups, alkylthio groups, acyl groups, nitro groups, cyano groups, ureido groups, sulfinyl. There are groups.

R ₁ and R ₂ may be bonded to each other to form a ring, for example, a heterocycle such as piperidine, pyridine, triazine, morpholine, pyrrolidine, n-alkylpiperazine, indolinyl and the like. R ₃ represents an alkoxy group, an alkyl group, an amino group or an aryl group,
Each may be unsubstituted or substituted, and more specifically, those having the same meanings as R ₁ and R ₂ are preferably mentioned.

X represents a hydrogen atom or a group capable of becoming a hydrogen atom by a hydrolysis reaction.

Specific examples of the case where X represents a group capable of becoming a hydrogen atom by a hydrolysis reaction include the following.

1) Method of protecting with ester bond or urethane bond, that is, X represents --CO--R '. Where R '
As one example, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted amino group can be mentioned.

2) A method of protecting with an imidomethyl blocking group described in JP-A-57-158638, that is, X is

[0049]

[Chemical 20] Represents Here, J represents -CO- or -SO-, and Z
Represents a plurality of atoms necessary for completing a heterocycle having at least one 5-membered ring or 6-membered ring.

Specific examples of the hydroxyamine compound represented by the general formula [II] are shown in US Pat. No. 3,287,12.
No. 5 and No. 3,329,034 and No. 3,287,1
No. 24, etc., but particularly preferred specific exemplified compounds include Japanese Patent Application No. 2-203169, 36 to 38.
(A-1) to (A-39) described in pages and JP-A-3-33.
(1) to (53) described in No. 845, pp. 3 to 6 and JP-A-Hei 3
-63646, pages 1 to 5 (1) to (52) and JP-A-3-184044, pages 4 to 6 (1) to (5).
4), particularly (1) and (7).

The particularly preferred specific exemplified compounds of the general formula [II] are shown below.

[0052]

[Chemical 21]

[0053]

[Chemical formula 22]

[0054]

[Chemical formula 23]

[0055]

[Chemical formula 24]

[0056]

[Chemical 25]

[0057]

[Chemical formula 26]

[0058]

[Chemical 27]

[0059]

[Chemical 28] The compound represented by the general formula [II] is usually used in the form of a free amine, hydrochloride, sulfate, nitrate, oxalate, p-toluenesulfonate, or the like.

Next, the general formula [III] used in the present invention
The compound represented by will be described.

Specific examples of the compound represented by the general formula [III] are shown below.

[0062]

[Chemical 29]

[0063]

[Chemical 30]

[0064]

[Chemical 31] These compounds represented by the general formula [III] are usually used in the form of free amine, hydrochloride, sulfate, nitrate, oxalate, carbonate, p-toluenesulfonate, phosphate, acetate and the like. To be

Next, the monosaccharide used in the present invention will be described.

Generally, saccharides (also called carbohydrates) are composed of monosaccharides and polysaccharides, and most have the general formula C _n H _2n O _n . The monosaccharide generally refers to polyhydric alcohols, aldehydes or ketones, and their reduced derivatives, oxidized derivatives, dehydrated derivatives and amino sugars, thiosugars and the like in a wide range.
Alternatively, the polysaccharide refers to a product obtained by dehydration-condensation of two or more of the above-mentioned monosaccharides.

Among these sugars, the preferable ones are those corresponding to monosaccharides. Specific examples of monosaccharides that can be used in the present invention are shown below, but the present invention is not limited thereto.

S-1) Erythriol S-2) β-D-arabinose S-3) β-L-arabinose S-4) D-Kirosheath S-5) L-Kirosheath S-6) 2-deoxy-β -D-ribose S-7) α-D-lyxose S-8) α-L-lyxose S-9) D-ribose S-10) L-ribose S-11) L-arabitol S-12) D-arabitol. S-13) ribitol S-14) β-D-altrose S-15) β-L-altrose S-16) β-D-allose S-17) β-L-allose S-18) α-D -Galactose S-18) β-D-Galactose S-20) α-L-Galactose S-21) α-D-Quinovose S-22) α-D-Glucose S-23) β-D-Glucose S-24 ) Β-D-full Cuctose S-25) Diquitalose S-26) Dichitoxose S-27) Cimarose S-28) L-sorbose S-29) D-tagatose S-30) α-D-talose S-31) 2-deoxy-D-glucose. S-32) α-D-fucose S-33) α-L-fucose S-34) α-D-mannose S-35) L-mannose S-36) α-L-rhamnose S-37) D-inositol S-38) myo-inositol S-39) galactitol S-40) d-quercitol S-41) D-crucitol S-42) D-mannitol S-43) L-iduronic acid S-44) galactaric acid S-. 45) α-D-galacturonic acid S-46) D-glucaric acid S-47) β-D-glucuronic acid S-48) D-gluconic acid S- 9) L-gluconic acid S-50) 2-deoxy-D-gluconic acid S-51) D-mantalonic acid-6,3-lactone S-52) Methyl = β-D-galactopyranoside S-53) Methyl = α-D-galactopyranoside S-54) Methyl = α-D-glucopyranoside S-55) Methyl = β-D-glucopyranoside S-56) Methyl = α-D-fructofuranoside S-57) Methyl = α-D-mannopyranoside S-58) Methyl = β-D-mannopyranoside S-59) N-acetyl-α-D-galactosamine S-60) N-acetyl-α-D-glucosamine S-61) N- Acetyl-α-D-mannosamine S-62) Muramic acid S-63) α-D-Galactosamine S-64) α-D-Glucosamine S-65) D-Mannosamine S-66 D-glycero-α-galacto
-Heptose S-67) D-glycero-β-L-manno
-Heptose S-68) D-manno-heptulose S-69) D-altro-3-heptulose S-70) D-glycero-D-galacto.
-Heptitol S-71) D-glycero-D-talo-heptitol S-72) D-erythro-D-gateacto
-Octitol S-73) Glyceraldehyde monosaccharides are widespread in nature, and commercial products are easily available. In addition, for various derivatives, reduction, oxidation,
Alternatively, it can be easily synthesized by performing a dehydration reaction or the like.

The amount of each of the compounds represented by the general formulas [II] and [III] or the monosaccharide added is preferably in the range of 0.0006 to 0.6 mol, and more preferably 0.001 mol, per liter of the color developing solution. Is in the range of 0.2 mol.

As the color-developing agent used in the color-developing processing step, a p-phenylenediamine compound having a hydrophilic group is preferably used because the effect of the object of the present invention is excellently exhibited and fogging is small.

The p-phenylenediamine-based compound having a hydrophilic group is free from contamination of the light-sensitive material as compared with the p-phenylenediamine-based compound having no hydrophilic group such as N, N-diethyl-p-phenylenediamine. As for the skin, it has the advantage that the skin is less likely to get rash.

Examples of the hydrophilic group include those having at least one amino group of the p-phenylenediamine compound or on the benzene ring, and specific hydrophilic groups include-(CH ₂ ) _n -CH ₂ OH. _{, - (CH 2) m -NHSO} 2 - (CH 2) n -CH 3, - (CH 2) m -O- (CH 2) n -CH 3, - (CH 2 CH 2 O) n C m H _{2m + 1}

[0073]

[Chemical 32] (M and n each represent an integer of 0 or more.), —COOH, —SO ₃ H and the like are preferable.

Specific examples of the color developing agents preferably used in the present invention include Japanese Patent Application No. 2-203169.
Nos. 26 to 31 (C-1) to (C-1)
6), (1) to (8) described in JP-A-61-289350, pages 8 to 9, and JP-A-3-246543 to 5-.
(1) to (62) described on page 9, JP-A-4-1-1
No. 1255, pages 4 to 6 (1) to (3
0), 1 to 78 described on pages 10 to 17 of JP-A-4-19654, I- (1) to I- (24) described on pages 4 to 5 of JP-A-4-45440, and Japanese Patent Laid-Open No. Hei 4
-68347 No. 7 to 10 (1) to
(49), particularly preferably Japanese Patent Application No. 2-203
Exemplary Compounds (C-1) and (C
-3), Exemplified compound (2) described in JP-A-61-289350, Exemplified compound (1) described in JP-A-3-246543, and JP-A-4-11255. Exemplified compounds (1), (3), (5),
(14), Exemplified Compounds (8) and (9) described in JP-A-4-19654, Exemplified Compound I- (1) described in JP-A-4-45440, and JP-A-4-6.
Exemplified compound (5) described in No. 8347 may be mentioned.

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

[0076]

[Chemical 33]

[0077]

[Chemical 34] The color developing agents may be used alone or in combination of two or more, and if desired, a black and white developing agent such as phenidone,
4-hydroxymethyl-4-methyl-1-phenyl-3
-It may be used in combination with pyrazolidone or metol.

Further, an auxiliary developing agent may be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol hexalphate (meth), phenidone, N, N'-diethyl-p-.
Aminophenol hydrochloride, N, N, N ′, N′-tetramethyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably 0.01 to 1.0 g / l.

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

In the color developer according to the present invention, a slight amount of sulfite can be used as a preservative, and a buffer, a development accelerator and an antifoggant can be added. Further, an auxiliary developing agent can be used together with the developing agent. In addition, various additives such as stain inhibitors, sludge inhibitors, and stacking effect accelerators can be used.

In the present invention, chlorine ions, bromine ions, and iodine ions can be added to the color developer for the purpose of preventing fog.

Furthermore, the color developing agent may contain anionic, cationic, amphoteric and nonionic surfactants.

Further, the solid color-developing agent of the present invention includes 1-
Hydroxyethylidene-1,1-diphosphonic acid and its derivative, and 1,2-dihydroxybenzene and its derivative can also be contained as a chelating agent. Among them, the preferred compound is 1-hydroxyethylidene-1,1.
-Diphosphonic acid, 1,2-dihydroxybenzene-3,
5-diphosphonic acid, 1,2-dihydroxybenzene-
It is 3,5,6-triphosphonic acid and may be used as an alkali metal salt such as sodium salt and potassium salt.

Regarding the bleaching solution, the bleach-fixing solution, the additive used in the fixing solution or the stabilizing solution and each solution used in the present invention, Japanese Patent Application No. 122603, page 2, line 2 to page 31, page 1 is referred to.
What is described in the line can be used.

Further, regarding the light-sensitive material applied to the processing method of the present invention, Japanese Patent Application No. 3-47515, page 31, upper line 2 to page 36, upper line 10, Japanese Patent Application No. 4-73394, paragraph number The light-sensitive materials described in [0124] to [0165] can be used.

The solid photographic processing agent of the present invention is preferably tablets or granules, more preferably tablets.

To solidify the photographic processing agent, a concentrated solution or fine powder or granular processing agent is kneaded and molded with a water-soluble binder, or a water-soluble binder is sprayed onto the surface of the pre-processed processing agent. Arbitrary means such as forming a coating layer can be adopted (Japanese Patent Application No. 2-135887 and 2-2).
03165, 2-203166, 2-2031
67, ibid. 2-203168, ibid. 2-34009).

A method for producing a tablet processing agent is described in, for example, Japanese Patent Application Laid-Open No.
No. 1-61837, No. 54-155038, No. 52-
It can be manufactured by the general method described in 88025 and British Patent 1,213,808.

[0089] The bulk density of the solid photographic processing agent of the present invention, from the viewpoint of its solubility and strength preferably has 0.5 to 6.0 g / cm ^3, in particular of 1.0 to 5.0 g / cm ³ Those are preferably used.

In the present invention, the term "separated granulation" means that when one tablet is made, all the additives are not mixed in advance, alone or by mixing several kinds, and granulated separately. It is said that they are mixed into one tablet.

Mixing all the additives from the beginning and applying the mixture to a tablet machine to form tablets is distinguished from the fractionated granulation of the present invention.

Specific methods of using the solid color developing treatment agent include a method of dissolving it in water once stored in a replenishing tank or the like and replenishing it as a color development replenishing solution in the processing tank, or directly adding it to the processing tank filter layer. And a method of using it as a color developing solution.

In both methods, it is necessary to adjust the feeding frequency and amount so that the concentration becomes equivalent to that of the conventional color developing solution and color developing replenisher. In the case of (1), a replenishment tank is required separately from the processing tank, which takes up space, so that the method of (1) is preferable.

[0094]

The present invention will be described in more detail with reference to the following examples, but the embodiments of the present invention are not limited thereto.

Example 1 The solid color-developing tablet of the present invention was prepared by the method described below and a storage test was conducted. Storage conditions: 75 ° C 6
It was stored at 0% RH, 23 ° C. 60% RH, and 75 ° C. 20% RH for 4 weeks, and then at −5 ° C. for 2 weeks.

Procedure (A) 100.0 g of a developing agent CD-3 [4-amino-3methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] aniline sulfate] was used as an air jet fine pulverizer. It is ground until the average particle size becomes 10 μm. 4.5 m of this fine powder at room temperature for about 5 minutes in a commercial fluidized bed spray granulator.
After granulating by spraying 1 l of water, it is dried at 60 ° C. for 8 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove water.

Operation (B) The additive (c) (see Table 1 for types and amounts) is pulverized and granulated in the same manner as in the operation (A). The amount of water sprayed is 3.0 m
After granulating, the mixture is granulated and dried at 50 ° C. for 10 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove water.

Operation (C) Additives (a) and (b) (see Table 1 for types and amounts), 500 g of potassium carbonate, 0.3 g of potassium bromide,
100 g of sodium p-toluenesulfonate and 200 g of potassium hydroxide are pulverized in the same manner as in the operation (A) and then uniformly mixed with a commercially available mixer. Next, similarly to the operation (A), the amount of water sprayed is set to 200 ml and granulation is performed. After the granulation, the granulated product is dried at 70 ° C for 15 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove water.

Operation (D) The granules prepared in the above operations (A) to (C) are heated at 25 ° C. for 4 hours.
Uniformly mix for 10 minutes using a mixer in a room whose humidity is adjusted to 0% RH or less. Next, the mixture was evenly divided into 300 color-developing replenishing tablets for color paper, and compressed into tablets using a tabletting machine modified from Tuffpress Collect 1527HU manufactured by Kikusui Seisakusho.

The observation items and the results are shown in Table 1.

[0101]

[Table 1]

[0102]

【Evaluation criteria】

 Appearance after storage ○: No change in shape compared to the tablet before storage △: Change in shape due to deliquescence ×: Significant change in shape due to deliquescence Means that the appearance afterwards is bad

Solubility A: Immediately dissolved without caking: Slowly dissolved without caking Δ: Gradually started to dissolve, but solid residue remained and dissolved by vigorous stirring X: Solid residue The larger the number of x that did not readily dissolve even after vigorous stirring, the poorer the solubility.

Example 2 In the same manner as in Example 1, a solid color-developing processing tablet was prepared,
A storage test was conducted. Additives (a), (b) used,
The types and amounts of (c) are as shown in Table 2, and the storage test conditions were the same as in Example 1. Further, the CD-3 residual rate after storage was examined. Table 2 shows the observation items and the results.

[0105]

[Table 2] Example 3 QA paper TypeA5 manufactured by Konica Corporation was exposed by a conventional method, and then CL-PP-1711 was treated with the treatment agent shown below.
A running test was conducted using an automatic developing machine modified as shown in FIG. 7 of Japanese Patent Application No. 4-141425.

1) Replenishing tablet for color development operation (A) CD-3 [4-amino-3methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] aniline sulfate] as a developing agent] 100. Mill 0 g in an air jet mill until the average particle size is 10 μm. 4.5 m of this fine powder at room temperature for about 5 minutes in a commercial fluidized bed spray granulator.
After granulating by spraying 1 l of water, it is dried at 60 ° C. for 8 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove water.

Operation (B) 0.6 mol of the additive (c) (described in Tables 3A to C) is pulverized and granulated in the same manner as in the operation (A). The amount of water sprayed is 3.0 m
After granulating, the mixture is granulated and dried at 50 ° C. for 10 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove water.

Operation (C) Additive (b) (described in Tables 3A to C) 30.0 g, potassium carbonate 500 g, potassium bromide 0.3 g, additive (a)
(Listed in Tables 3A to C) 25.0 g, 100 g of sodium p-toluenesulfonate and 200 g of potassium hydroxide are pulverized in the same manner as in the operation (A) and then uniformly mixed with a commercially available mixer. Next, as in step (A), the amount of water sprayed is 200 ml.
And granulate. After the granulation, the granulated product is dried at 70 ° C for 15 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove water.

Operation (D) The granules prepared in the above operations (A) to (C) were heated at 25 ° C. for 4 hours.
Uniformly mix for 10 minutes using a mixer in a room whose humidity is adjusted to 0% RH or less. Next, the mixture was evenly divided into 300 color-developing replenishing tablets for color paper, and compressed into tablets using a tabletting machine modified from Tuffpress Collect 1527HU manufactured by Kikusui Seisakusho.

2) Bleach-fixing replenishing tablet Operation (E) Ethylenediaminetetraacetic acid ferric potassium monohydrate 550
g and 20 g of ethylenediaminetetraacetic acid are pulverized and granulated in the same manner as in the operation (A). The amount of water sprayed is 25.0 ml,
After granulating, it is dried at 60 ° C. for 15 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove water.

Operation (F) 1770 g of potassium thiosulfate and 200 of sodium sulfite
g, potassium bromide 60 g, p-toluenesulfinic acid 2
0 g is crushed and granulated in the same manner as in the operation (A). The amount of water sprayed is 15.0 ml, and after granulation, it is dried at 60 ° C. for 10 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove water.

Operation (G) The granules prepared in the above operations (E) and (F) were subjected to 4 ° C. at 25 ° C.
Uniformly mix for 10 minutes using a mixer in a room whose humidity is adjusted to 0% RH or less. Next, the mixture was compressed into tablets with a tableting machine modified from Kikusui Seisakusho's Tough Press Collect 1527HU with a filling amount of 8.5 g per tablet to give 300 tablets.
A single bleach-fix replenishment tablet sample for color paper was prepared.

3) Tablet for stable replenishment operation (H) 10 g of potassium carbonate, 1-hydroxyethane-1,1-
200 g of disodium diphosphonate is ground and granulated in the same manner as in the operation (A). The amount of water sprayed is 1.0 ml, and after granulation, the granulated product is dried at 70 ° C. for 3 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove water.

Operation (I) 150 g of Tinopearl SFP (manufactured by Ciba Geigy), 300 g of sodium sulfite, 20 g of zinc sulfate heptahydrate and 150 g of ethylenediaminetetraacetic acid were pulverized in the same manner as in the operation (A).
Granulate. The amount of water sprayed is 10.0 ml, and after granulation, the granulated product is dried at 65 ° C. for 5 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 8 hours to almost completely remove water.

Operation (J) The granules prepared in the above operations (H) and (I) were mixed at 25 ° C. for 4 hours.
Uniformly mix for 10 minutes using a mixer in a room whose humidity is adjusted to 0% RH or less. Next, the mixture was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho, so that the filling amount per tablet was 0.66 g.
00 stable refill tablets for color paper were made.

(Experiment) The color development replenishing tablets prepared as described above were put into an automatic developing machine for a running test.
Before being set, it was stored under the following conditions.

Storage conditions: 70 ° C., 60% RH for 3 weeks -4 ° C., 20% RH for 1 week If the tablets actually used in the running test are insufficient, the same preparation method is repeated, The color development replenishing tablet was used after being stored under the conditions mentioned above.

The following table shows the standard processing conditions of the automatic processing machine.

[0119]

[Table 2A] The stabilizer is replenished in the third tank, and the overflow solution is sequentially flown into the second tank and the first tank in a cascade system.

The processing liquid for the automatic processing machine was prepared by the following method. Color developing tank liquid (23 L) 18 L of 35 ° C. warm water was placed in the automatic developing machine color developing tank, and 628 color developing replenishing tablets were added and dissolved. Next, 23 starters of the following formulation, which were separately tabletted as starter components, were added and completely dissolved, and warm water was added up to the tank mark to complete the tank solution.

Color developing starter for color paper Potassium chloride 4.0 g Potassium hydrogen carbonate 4.8 g Potassium carbonate 2.1 g

Bleach-fixing solution (23 L) 15 L of warm water at 35 ° C. was placed in a bleach-fixing tank for an automatic developing machine, and 720 bleach-fixing replenishing tablets were added and dissolved. After dissolution
Hot water was added up to the tank mark to complete the tank solution.

Stabilizer (15 L for 1 to 3 tanks) 35 ° C. for each of the 1st tank, 2nd tank and 3rd tank of the developing machine stabilizing tank
12 liters of warm water were added, and 60 tablets for stable replenishment were added and dissolved. Next, warm water was added up to the tank mark to complete the tank solution.

Next, during the temperature control of the automatic developing machine, 20 supplementary tablets were set in each of the supplementary tablet supplying devices provided in the automatic developing machine. This supplementary tablet is 3200 cm ² color paper
When processed, they were added one by one, and at the same time, 25.6 ml of supplementary warm water was supplied from the warm water supply device to the color developing tank, 32 ml to the bleach-fixing tank, and 80 ml to the third stabilizing tank. .

The running test was conducted until 2700 tablets for color development replenishment were charged. Observation items and results after the test are shown in Tables 3A to 3C.

[0126]

[Table 3A]

[0127]

[Table 3B]

[0128]

[Table 3C]

[0129]

【Evaluation criteria】

Clogged filter ◎: No problem at all ○: Slightly clogged, circulation was okay △: Initially okay, but gradually clogged, circulation became poor ×: Clogged filter immediately and circulation was bad Example 4 In order to obtain the solid color-developing agent, in Example 3, it was prepared by fractional granulation, but in this Example, as shown below, a method in which all the additives were granulated at once to form tablets was used. It was

Replenishing tablet for color development: 100.0 g of CD-3 [4-amino-3methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] aniline sulfate] as a developing agent, and additive (c ) (Tables 4A-C
0.6 mol, additive (b) (described in Tables 4A to C)
30.0 g, potassium carbonate 500 g, potassium bromide 0.
3 g, additive (a) (described in Table 4A to C) 25.0 g, p
-Sodium toluenesulfonate 100 g, potassium hydroxide 200 g in an air jet pulverizer with an average particle size of 10
After pulverizing to a size of μm, the mixture is uniformly mixed with a commercially available mixer. Next, this fine powder mixture is granulated by spraying 210 ml of water for about 5 minutes at room temperature in a commercially available fluidized bed spray granulator, and then dried at 60 ° C. for 8 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove water. Once removed, the tablets were evenly divided into 300 color-developing replenishing tablets for color paper, and compressed into tablets using a tableting machine modified from Tuffpress Collect 1527HU manufactured by Kikusui Seisakusho.

The bleach-fixing replenishing tablet and the stable replenishing tablet are the same as those used in Example 3.

Next, QA Paper Ty manufactured by Konica Corporation
After exposing peA5 by a conventional method, the bleach-fixing solution tank and the stabilizing solution tank of the CL-PP-1711 automatic developing machine were modified by using the above-described processing agents and modifying the tablet feeding device, the replenishing water replenishing device, and the like. I ran a running test on the actual machine.

The table below shows the standard processing conditions for the automatic processing machine.

[0134]

[Table 4] The stabilizer is replenished in the third tank, and the overflow solution is sequentially flown into the second tank and the first tank in a cascade system.

The processing liquid for the automatic processing machine was prepared by the following method. Color developing tank liquid (23 L) 18 L of 35 ° C. warm water was placed in the automatic developing machine color developing tank, and 628 color developing replenishing tablets were added and dissolved. Next, 23 starters of the following formulation, which were separately tabletted as starter components, were added and completely dissolved, and warm water was added up to the tank mark to complete the tank solution.

Color development starter for color paper Potassium chloride 4.0 g Potassium hydrogen carbonate 4.8 g Potassium carbonate 2.1 g

Bleach-fixing solution (23 L) 15 L of warm water at 35 ° C. was put in a bleach-fixing tank for an automatic developing machine, and 720 bleach-fixing replenishing tablets were added and dissolved. After dissolution
Hot water was added up to the tank mark to complete the tank solution.

Stabilizer (15 liters for 1 to 3 tanks) Develop machine stabilizing tanks 1st, 2nd and 3rd tanks respectively 35 ° C.
12 liters of warm water were added, and 60 tablets for stable replenishment were added and dissolved. Next, warm water was added up to the tank mark to complete the tank solution.

Next, during the temperature control of the automatic developing machine, 2 tablets each for bleach-fixing and stable replenishing tablets were added to the automatic replenishing tablet supplying device.
I set 0 pieces. 3 color papers for this refill tablet
After the treatment of 200 cm ^2, one by one was added, and at the same time, 32 ml of replenishing warm water was supplied from the warm water supply device to the bleach-fixing tank and 80 ml to the stabilizing tank.

The color developing tank was prepared by dissolving a color developing replenishing tablet in water stored in a replenishing tank or the like to replenish the processing tank as a color developing replenishing solution. The replenishing solution in the replenishing tank was made at a ratio of 400 replenishing tablets to 10 L of dissolved water. Replenishment amount is 1.0m
^It was 40 ml per ² pieces. The solid color developing agent was used for dissolution after being stored under the following conditions.

Storage conditions: 60 ° C., 55% RH for 3 weeks −1 ° C., 20% RH for 1 week If the tablets actually used in the running test are insufficient, the same preparation method is repeated, The color development replenishing tablet was used after being stored under the conditions mentioned above.

In the running test, the color developing replenisher was 6
9L, until replenished.

Observation items and results after the test are shown in Tables 4A to 4C.
It was shown to.

[0144]

[Table 4A]

[0145]

[Table 4B]

[0146]

[Table 4C] Example 5 In this example, unlike the above examples, a solid color-forming agent was prepared into granules by the following method.

Granules for replenishing color developing operations (A) 100.0 g of CD-3 [4-amino-3methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] aniline sulfate] as a developing agent was added. Grind in an air jet pulverizer to an average particle size of 10 μm. 4.5 m of this fine powder at room temperature for about 5 minutes in a commercial fluidized bed spray granulator.
After granulating by spraying 1 l of water, it is dried at 60 ° C. for 8 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove water.

Operation (B) 0.6 mol of the additive (c) (same as in Table 4A to C) is pulverized and granulated in the same manner as in the operation (A). The amount of water sprayed is 3.0 m
After granulating, the mixture is granulated and dried at 50 ° C. for 10 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove water.

Operation (C) Additive (b) (as in Tables 4A-C) 30.0 g, potassium carbonate 500 g, potassium bromide 0.3 g, additive (a)
25.0 g (similar to Tables 4A to 4C), 100 g of sodium p-toluenesulfonate, and 200 g of potassium hydroxide are pulverized in the same manner as in the operation (A) and then uniformly mixed with a commercially available mixer. Next, as in the operation (A), the amount of water sprayed is 200 m.
and granulate. After the granulation, the granulated product is dried at 70 ° C for 15 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove water.

Operation (D) The granules prepared in the above operations (A) to (C) were heated at 25 ° C. for 4 hours.
Uniformly mix for 10 minutes using a mixer in a room whose humidity is adjusted to 0% RH or less. The mixture was then evenly divided into 300 packaging materials.

The bleach-fixing replenishing tablet and the stable replenishing tablet are the same as those used in Example 3.

QA Paper TypeA manufactured by Konica Corporation
5 was exposed by a conventional method, and then C using the treating agent shown above was used.
A running test was carried out using an improved L-PP-1711 automatic developing machine (which enables the following replenishment method).

The standard processing conditions for the automatic processing machine and the preparation of the processing liquid for the automatic processing machine are the same as in Example 4, except for the following points.

In this example, the granules for color development replenishment were stored under the following conditions, dissolved in 25.6 ml of warm water per package, and then replenished in the processing tank. still,
The dissolution was carried out at the location where it was attached to the automatic processing machine.

Storage conditions: 50 ° C., 55% RH for 3 weeks -3 ° C., 20% RH for 2 weeks If the granules actually used in the running test are insufficient, the same preparation method is repeated, and color development is performed. The supplementary granules were stored under the above-mentioned conditions before use.

The running test was carried out until the color development replenishing granules were packed in 2700 and replenished.

The state of the granules after storage, the solubility in warm water, and the D _min (Y) and D _max (Y) after the running treatment were observed, and the effect of the present invention was obtained.

It was found that stable photographic performance was obtained regardless of the storage conditions, the form of the solid processing agent and the replenishment method, and the present invention can sufficiently satisfy the object. It can be said that it was possible.

[0159]

According to the present invention, firstly, it is possible to provide a solid color developing treatment agent for a silver halide photographic light-sensitive material which is suitable for social environment and a processing method using the solid color developing treatment agent.
Secondly, it is possible to provide a solid color developing agent for silver halide photographic light-sensitive materials and a processing method using the solid color developing agent, which does not cause poor dissolution or problems associated therewith, and thirdly, halogenation excellent in storage stability. It is possible to provide a solid color developing agent for silver photographic light-sensitive materials and a processing method using the solid color developing agent.

Claims (7)

[Claims] 1. A silver halide containing at least one compound represented by the following general formula [I] or [IV] and at least one compound represented by the following general formula [E]. Solid color developing agent for photographic light-sensitive materials. ## STR00001 ## General formula [I] [In the formula, A _{1 to} A ₅ may be the same or different,
-COOM, -PO ₃ M ₂ or an -CH ₂ OH, M represents a hydrogen atom or an alkali metal. ] [Formula 2] General formula [IV] [In the formula, A _{1 to} A ₄ may be the same or different and each represents —COOM, —PO ₃ M ₁ M ₂ or —CH ₂ OH, and M, M ₁ and M ₂ are each a hydrogen atom or an alkali metal. Or represents ammonium. X represents a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms. ] General formula [E] [Wherein X ₁ , X ₂ , Y ₁ and Y ₂ represent a hydroxyl group, a halogen atom, a morpholino group, an alkoxy group, an aryloxy group, an alkyl group, an aryl group, an amino group, an alkylamino group and an arylamino group, respectively. . M represents a hydrogen atom, an alkali metal or other cation. ] 2. A compound represented by the following general formula [II] or [III]:
Containing at least one compound or monosaccharide
A silver halide photographic light-sensitive material according to claim 1,
Solid color development processing agent. Embedded image General formula [II][In the formula, R₁And R_TwoAre hydrogen atom and alkyl
Group, aryl group, alkoxy group, R₃-CO- group, R₃−
CS-group, R₃-SO₂-Group, R₃-SO Represents a group,
R₁And R_TwoAre not hydrogen atoms at the same time. Also
R₁And R_TwoMay combine with each other to form a ring. Furthermore R
₃Is an alkyl group, aryl group, alkoxy group, amino group
Or represents a hydrogen atom. X is a hydrogen atom or a hydrolysis reaction
Is a group capable of becoming a hydrogen atom by. ] General formula [III][In the formula, R₁₁, R₁₂, R_ThirteenIs a hydrogen atom, substituted or
An unsubstituted alkyl group, aryl group or heterocyclic group
Represent, R₁₄Is a hydroxy group, a hydroxyamino group,
Substituted or unsubstituted alkyl group, aryl group, heterocycle
Group, alkoxy group, aryloxy group, carbamoyl group
Alternatively, it represents an amino group. R₁₅Is -CO-, -SO_Two−
OrRepresents a divalent group selected from, and n is 0 or 1. Special
When n = 0, R₁₄Is an alkyl group, aryl group, hetero
It represents a group selected from ring groups. R₁₁And R₁₂, R_ThirteenAnd R
₁₄May together form a heterocyclic group. ] 3. The solid color developing agent for silver halide photographic light-sensitive materials according to claim 1, wherein the solid color developing agent is a granule. 4. The solid color developing agent for silver halide photographic light-sensitive materials according to claim 1, wherein the solid color developing agent is a tablet. 5. The solid color developing agent for silver halide photographic light-sensitive materials according to claim 1, 2 or 5, wherein the tablets are granulated and then tableted. 6. The solid color developing agent for silver halide photographic light-sensitive materials according to claim 1, 2 or 5, wherein said tablets are tableted after fractional granulation. 7. A solid color developing agent for a silver halide photographic light-sensitive material according to claim 1, when the exposed silver halide photographic light-sensitive material is continuously processed by using an automatic processor. A method for processing a silver halide photographic light-sensitive material, which comprises processing with a processing solution obtained by dissolving